1986 Book ScYLa-LuRareEarthElements

Pariodic Table of the Elements with the Gmelin System Numbers
I ! I I
I i I I
H 2 I I H2 ~e . l
i .I II II II I I
5 6 7 8 9 10
3 4 : !
LJ 20 Be 26 l! I B 13 c 14 N 4 0 3 F5 Ne I
t I I
.. ! I II 13 14 16 16 17 18
II 12 i I I I
J I I
I
: Al 35 Si 15 p 16 s 9 Cl 6 Ar I
Na21 Mg 27 !
I
ii l!!
... I i : I ! !
<>
f 19 * 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
c;')
K 22 Ca 28 Sc 39 Ti 41 V 48 Cr 52 Mn 56 Fe 59 Co 58 Ni 57 Cu 60 Zn 32 Ga 36 Ge 45 As 17 Se 10 Br 1 Kr I
l
!r
37 38 39 40 41 42 43 44 45 46 47 48 49 50 61 62 53 54
Rb24 Sr 29 y 39 Zr 42 Nb 49 Mo 53 Tc 69 Ru 63 Rh 64 Pd 65 Ag 61 Cd 33 l n 37 Sn 46 Sb 18 Te II I 8 Xe I
f
a·
81 82 83 84 85 86
55 56 57** 72 73 74 75 76 71 78 79 80
l Cs 25 Ba 30 La 39 Hf 43 Ta 50 w54 Re 70 Os 66 Ir 67 Pt 68 Au 62 Hg 34 Tl 38 Pb 47 Bi 19 Po 12 At Rn I
~
f 87 88 89*** 104 105
Fr Ra 31 Ac 40 71 71
I I~H..31
i
(")
!*•Lanthan ides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
I 39 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
I*** Actini des 90 44 91 51 93 71 94 71 95 71 96 71 97 71 99 71 100 71 102 71 103 71

Th Pa ~ 55 Np Pu Am Cm Bk ~~ 71 Es Fm ~~ 71 No Lr
_ L__ -- - L__
Gmelin Handbook of lnorganic Chemistry
8th Edition
Gmelin Handbook
of lnorganic Chemistry
8th Edition
Gmelin Handbuch der Anorganischen Chemie
Achte, völlig neu bearbeitete Auflage
Prepared Gmelin-lnstitut für Anorganische Chemie

and issued by der Max-Planck-Gesellschaft
zur Förderung der Wissenschaften
Director: Ekkehard Fluck
Founded by Leopold Gmelin

8th Edition 8th Edition begun under the auspices of the
Deutsche Chemische Gesellschaft by R. J. Meyer
Continued by E. H. E. Pietsch and A. Kotowski, and by
Margot Becke-Goehring
Springer-Verlag Berlin Heidelberg GmbH 1987

Gmelin-lnstitut für Anorganische Chemie
der Max-Planck-Gesellschaft zur Förderung der Wissenschaften
ADVISORY BOARD
Dr. G. Breil, Chairman (Ruhrchemie AG, Oberhausen-Holten), Prof. Dr. K. Dehnicke (Philipps-
Universität Marburg), Prof. Dr. N. N. Greenwood (University of Leeds), Prof. Dr. H. Grünewald
(Bayer AG, Leverkusen), Prof. Dr. H. Harnisch (Hoechst AG, Frankfurt/Main-Höchst), Prof. Dr.
H. Nöth (Universität München), Prof. Dr. H. Ottermanns (Degussa AG, Frankfurt/Main), Prof.
Dr. G. zu Putlitz (Universität Heidelberg), Prof. Dr. A. Rabenau (Max-Planck-lnstitut für Fest-
körperforschung, Stuttgart), Prof. Dr. A. Sirnon (Max-Planck-lnstitut für Festkörperforschung,
Stuttgart), Prof. Dr. Dr. A. H. Staab (Präsident der Max-Planck-Gesellschaft, München), Prof.
Dr. Dr. h.c. mult. G. Wilke (Max-Planck-lnstitut für Kohlenforschung, Mülheim/Ruhr)
DIRECTOR DEPUTY DIRECTOR

Prof. Dr. Dr. h.c. Ekkehard Fluck Dr. W. Lippert
CHIEF-EDITORS
Dr. K.-C. Buschback - Dr. H. Bergmann, J. Füssel, 8. Heibel, Dr. H. Katscher, Dr. R. Keim,
Dr. E. Koch, Dipl.-Phys. D. Koschel, Dr. U. Krüerke, Dr. H. K. Kugler, Dr. P. Merlet, Dr. E.
Schleitzer-Rust, Dr. F. Schröder, Dr. A. Slawisch, Dr. B. v. Tschirschnitz-Geibler, Dr. R. Warncke
CORRESPONDENT MEMBERS OF THE SCIENTIFIC STAFF Dr. H. C. Andersen, Dr. J. R. Clark,

Dr. J. L. Grant, Dr. V. Haase,
Dipl.-lng. G. Kirschstein, Dr. K. Rumpf,
Dr. U. Trobisch, Dr. 8. Vance
EMERITUS MEMBER OF THE INSTITUTE Prof. Dr. Dr. E.h. Margot Becke
CORRESPONDENT MEMBERS OF THE INSTITUTE Prof. Dr. Hans Bock

Prof. Dr. Dr. Alois Haas, Sc. D. (Cantab.)
STAFF GMELIN HANDBOCK
D. Barthel, Dr. N. Baumann, Dr. W. Behrendt, Dr. L. Berg, Dipl.-Chem. E. Best, K. D. Bonn,
Dipl.-lng. V. A. Chavizon, E. Cloos, Dipl.-Phys. G. Czack, I. Deim, Dipl.-Chem. H. Demmer,
R. Dowideit, Dipl.-Chem. M. Drößmar, U. Duggen, M. Engels, Dr. H.-J. Fachmann, Dr. J. Faust,
Dr. Chr. Fianda, Dr. W.-D. Fleischmann, V. Frick, G. Funk, Dipl.-lng. N. Gagel, Dr. U. W.
Gerwarth, C. Gorr, Dipl.-Phys. D. Gras, Dipl.-Bibl. W. Grieser, H. Hartwig, Dr. R. Haubold,
Dipl.-Min. H. Hein, G. Heinrich-Sterzel, H.-P. Hente, H. W. Herold, U. Hettwer, Dr. I. Hinz, Dr.
W. Hoffmann, Dipl.-Chem. K. Holzapfel, Dipl.-Chem. E.-M. Horn, Dr. W. Huisl, Dr. S. Jäger, Dr.
R. Jotter, Dr. J. von Jouanne, Dr. B. Kalbskopf, Dipl.-Chem. W. Karl, H.-G. Karrenberg, Dipl.-
Phys. H. Keller-Rudek, A. Klusch, Dipl.-Phys. E. Koch, Dipl.-Chem. K. Koeber, Dipl.-Chem. H.
Köttelwesch, R. Kolb, E. Kranz, Dipl.-Chem. I. Kreuzbichler, Dr. A. Kubny, Dr. P. Kuhn, Dr. W.
Kurtz, M. Langer, Dr. B. Leduc, Dr. A. Leonard, Dipl.-Chem. H. List, H. Mathis, E. Meinhard,
K. Meyer, Dr. M. Mirbach, Dipl.-Chem. B. Mohsin, Dr. U. Neu-Becker, K. Nöring, Dipl.-Chem.
R. Nohl, Dipl.-Min. U. Nohl, Dr. W. Petz, Dr. L. Psotta, I. Rangnow, Dipl.-Phys. H.-J. Richter-
Ditten, Dipl.-Chem. H. Rieger, B. Riegert, E. Rieth, A. Rosenberger, E. Rudolph, G. Rudolph,
Dipl.-Chem. S. Ruprecht, Dr. B. Sarbas, Dr. K. D. Scherfise, V. Schlicht, Dipl.-Chem. D.
Schneider, Dipl.-Min. P. Schubert, Dr. B. Schwager, A. Schwärzet, Dipl.-lng. H. M. Somer, E.
Sommer, M. Teichmann, Dr. W. Töpper, Dipl.-lng. H. Vanecek, Dipl.-Chem. P. Velic, Dipl.-lng.
U. Vetter, H.-M. Wagner, Dipl.-Phys. J. Wagner, R. Wagner, Dr. E. Warkentin, Dr. C. Weber, Dr.
B. Wöbke, K. Wolff, U. Ziegler
STAFF GMELIN ONLINE DATA SYSTEM
Dr. L. Kießling - Dr. R. Froböse, Dr. B. Roth

Dipl.-Min. M.-B. Cinarz, Dr. J. Fippinger, Dr. G. Friedrich, Dr. B. Fröhlich, M. Klöffler, R.
Lohmeyer, Dr. M. Pauluth, Dr. H.-J. Schröder, Dr. K. Schücke
Volumes published on "Rare Earth Elements" (Syst. No. 39)
A1 Introductory Review. History. Occurrence - 1938
A2 Scandium: History. Occurrence - 1973
A3 Y, La to Lu: Cosmochem istry - 1980
A4 Y, La to Lu: Crystal Chemistry- 1979
A5 Y, La to Lu: Geochemistry - Total Earth. Magmatic Cycle - 1981
*A7 Y, La to Lu: Minerals (Excluding Silicates) - 1984
•A 8 Y, La to Lu: Minerals (Silicates). Deposits. Mineralindex - 1984
o B 1 Sc, Y, La to Lu: History, Position in the Periodic System. Separation from Raw
Materials - 1976
B2 Sc, Y, La to Lu: Separation of the Rare Earth Elements from One Another. Preparation
of the Pure Metals. Uses. Toxicology - 1976
B3 Sc, Y, La to Lu: Physical Properties of the Metals - 1974
oB 4 Sc, Y, La to Lu: Nuclear, Atomic, and Molecular Properties - 1976
B5 Sc, Y, La to Lu: Preparation, Enrichment, and Separation of Isotopes (Sc, Y, La to Sm)
- 1978
B6 Sc, Y, La to Lu: Preparation, Enrichment, and Separation of Isotopes (Eu to Lu).
Detection and Determination of Isotopes. Chemical Reactions of the Elements - 1978
B7 Sc, Y, La to Lu: Reactions of the Ions in Solution. Electrochemical Behavior - 1979
C1 Sc, Y, La to Lu: Hydrides. Oxides - 1974
C2 Sc, Y, La to Lu: Compounds with H + 0, Alkali Metals + 0, N, as well as the Related
Alkali DoubleSalts - 1974
C3 Sc, Y, La to Lu: Fluorides, Fluoride Oxides, and the Related Alkali Double Salts -
1976
• C 4a Sc, Y, La to Lu: Chlorides. Comparative Data - 1982
• C 4b Sc, Y, La to Lu: Data on Individual Chlorides - 1982
C5 Sc, Y, La to Lu: Oxide Chlorides, Hydroxide Chlorides, Salts of Oxoacids of Chlorine,
and Alkali Chlorometallates - 1977
C6 Sc, Y, La to Lu: Bromides. Iodides, Corresponding Basic Halides. Salts of Halogen
Oxoacids and Alkali DoubleSalts - 1978
•C 7 Sc, Y, La to Lu: Sulfides, Oxide Sulfides, Alkali Thiometallates - 1983
o C8 Sc, Y, La to Lu: Sulfide Halides. Sulfates, Salts of Other Sulfuric Acids and Gorre-
spanding Alkali Double Compounds - 1981
•C 9 Sc, Y, La to Lu: Compounds with Se - 1986
• C 10 Sc, Y, La to Lu: Compounds with Te, Po - 1987 (present volume)
•D 1 Sc, Y, La to Lu: Coordination Compounds 1 - 1980
•D 5 Sc, Y, La to Lu: Carboxylates - 1984
*D6 Sc, Y, La to Lu: Ion Exchange and Solvent Extraction Reactions. Organametallic
Compounds - 1983
* Completely or o partly in English

Gmelin Handbock
of lnorganic Chemistry
8th Edition
Sc, V, La-Lu
RARE EARTH ELEMENTS
C10
Compounds with Te, Po
With 149 illustrations
AUTHORS lngeborg Hinz, Peter Kuhn, Ursula Vetter, Eberhard Warkentin
EDITORS Hartmut Bergmann, Hiltrud Hein, lngeborg Hinz, Ursula Vetter
CHIEF EDITOR Hartmut Bergmann
System Number 39
Springer-Verlag Berlin Heidelberg GmbH 1987

LITERATURE CLOSING DATE: 1985
IN MANY CASES MORE RECENT DATA HAVE BEEN CONSIDERED
Library of Congress CataLog Card Number: Agr 25-1383
ISBN 978-3-662-06368-2 ISBN 978-3-662-06366-8 (eBook)

DOI 10.1007/978-3-662-06366-8
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In data banks Under §54 of the German COPYright Law where caples are made for other than private use, a fee IS payabLe to
"VerwertungsgeseLLschaft Wort", MUnich
© by Springer-Verlag Berlin Heidelberg 1986

Originally published by Springer-Verlag Berlin Heidelberg New York London Paris Tokyo in 1986
Soflcover reprint of the hardcover 8th edition 1986
The use of registered names, trademarks, etc., In this pubLication does not ImpLy, even in the absence of a specific statement, that
such names are exempt from the relevant protective laws and regulations and therefore free for general use.
Preface
The volume "Rare Earth Elements" C10 deals with the rare earth tellurides, oxide
tellurides, tellurates, telluride halides, tellurate halides, sulfide tellurides, selenide tellurides,
and alkali rare earth tellurates. Another topic of this volume are the compounds of the rare
earth elements with polonium. Sofaras meaningful and as in all earlier volumes of "Rare
Earth Elements" Series C ("Seltenerdelemente" Reihe C), comparative data are presented
in sections preceding treatment of the individual compounds and systems.
Gaseous telluride molecules are described in the first section. The subsequent sections
deal mainly with the chemical and physical properties of the solid tellurides, of which SmTe,
EuTe, and TmTe play the most important rote. The most prominent feature of SmTe is the
pressure-induced valence transition from divalent Sm to the intermediate valence state,
similar to SmSe (see "Rare Earth Elements" C9). Main topics of the section on EuTe are the
magnetic and spectroscopic investigations, which show only antiferromagnetic ordering at
low temperatures, unlike the complex magnetic properties of EuSe. The magnetic phase
diagram, magnetic resonances, exchange interactions, and anisotropies have been ex-
tensively studied. A pressure-induced valence change is also observed in TmTe with divalent
Tm under ambient conditions. The valence changewas also reached by alloying with TmSe.
The oxide tellurides have been studied less intensively than the other oxide chalcogenides
and only the type M2 0 2Te is known. Data on preparation, crystallographic, and magnetic
properties dominate this section. Main topics of the section on the tellurates are the prepara-
tion and the crystallographic and optical properties. Systematic studies of the M 20 3-Te0 2
systems throughout the whole concentration regions have not yet been made and the reported
compositions of some compounds are still under discussion. lnteresting compounds among
the tellurates(IV) are the so-called anti-glass phases, which are metastable nonstoichiometric
compounds with a crystal structure related to that of fluorite. There are only a few data on
alkali rare earth tellurates(VI).
The compounds of rare earth elements and polonium have been studied only poorly. The
generally used formula MPo for the polonides describes the composition only roughly; the
M: Po ratios of the prepared compounds vary strongly. Data on preparation, crystallographic
properties, and the thermal stability are reported.
Frankfurt am Main Hartmut Bergmann

December 1986
XI
Table of Contents
Page
30 Rare Earth Elements and Tellurium .
30.1 Tellurides
General References .
30.1.1 Gaseous Molecules 2

lonization Energies . . . 2
lnternuclear Distaoces r. Vibrational Frequencies. 2
Dissociation Energies . . 2
Enthalpies of Formation . 4
Thermodynamic Functions 4
30.1.2 Solid Tellurides . . 6

Comparative Data for MTe 6
Formation and Preparation . 6
Crystallographic Properties 8
Density and Microhardness 11
Thermal Properties . . . . 13
Thermodynamic Properties . 13
Melting Point and Debye Tamperature. 13
Thermal Conductivity 14
Magnetic Properties . 15
Mössbauer Spectra . . 18
Electrical Properties . . 19
Comparative Data for M3Te 4 and M'M 2Te 4 21
M3Te 4 . . . . . • • • . . . 21
Existence and Preparation . 21
Density and Microhardness 22
Melting Point . . . . . . . 23
Heat Capacity, Entropy, and Debye Tamperature 23
Thermal Conductivity 25
Mössbauer Effect . . 26
Electrical Properties . 26
M'M 2Te4 . . . . . . . 30
Comparative Data for M2Te3 31
Preparation . . . . . . . 31
Crystallographic Properties. Density 32
Thermal Properties . . . . . . . . 36
Magnetic and Electrical Properties . 39
Comparative Data for M4Te 7 (= MTeu±xl 43
Formation and Preparation . . . . . 43
XII
Page
Additional Physical Properlies 46
Comparative Data for MTe2 _x· . 47
Formation and Preparation . . 47
Mössbauer Spectra and Electrical Properties 51
Chemical Reactions . . . 51
Comparative Data for M 2Te 5 53
Comparative Data for M 4Te 11 56
Comparative Data for MTe 3 57
Rare Earth Metals in Malten Te . 60
Data for Individual Tellurides . 61
Scandium Tellurides . 61
ScTe . . . . . 61
Sc2Te3 . . . . . . 62
Yttrium Tellurides . . 63
Y2Te 3 and Phases in the Y2Te 3-YTe System. 63
Lanthanum Tellurides 65
The La-Te System . . . . . . . . . 65
LaTe . . . . . . . . . . . . . . . 68
Homogeneity Region. Preparation 68
Crystallographic and Mechanical Properties 69
Thermal Properlies . . 69
Magnetic Susceptibility 70
Electrical Properties . . 70
Optical Properties . . . 71
Solid Salutions La 3Te4-La2Te 3 and Terminal Garnpounds 73
La 3Te 4 . . . . . . . . . . . 73
Solid Salutions La 3Te4-La 2Te 3 . 77
La2Te 3 . . . . . . • • 81
Lanthanum Polytellurides 84
LaTeu±x· LaTe 2 _x. 84
La3Te7±x . 88
La2Te 5 ±x . 88
La 4Te 11±x. 89
LaTe3 _x . 89
(La0 .8Y0 .2 )aTe 4 90
Cerium Tellurides 91
The Ce-Te System. 91
CeTe . . . . . . . 93
Preparation and Crystallographic Properties . 93
Cerium Valence . . . . . . . . . . 93
Mechanical and Thermal Properties 94
Magnetic Properties . . . . . . . . 95
Crystal Field Effects and Electrical Properties 96
Optical Properties . . . . . . . . . . . . . 98
X-Ray Absorption Spectrum. Photoemission . 98
Solid Salutions Ce3Te4-Ce 2Te 3 and Terminal Garnpounds 99
Cerium Polytellurides . . . . . 102
Cela 2Te 4-La 2Te 3 Solid Salutions 104
Praseodymium Tellurides . . . . 104
XIII
Page
The Pr-Te System . . . 104
Phase Diagram . . . 104
Additional Physical Properties 106
PrTe . . . . . . . . . . . . . 107
Solid Solutions Pr3Te 4-Pr2Te 3 and Terminal Compounds . 110
Praseodymium Polytellurides . . 113
PrTeu±x· PrTe 2 _x . . . . . . 113
Pr3Te7 • Pr2Te 5 . Pr4Te 11 • PrTe 3 . 114
Neodymium Tellurides . 115
The Nd-Te System . . . . . . . 115
NdTe . . . . . . . . . . . . . 118
Solid Solutions Nd 3Te4-Nd 2Te 3 and Terminal Compounds 122
Nd3Te4 and Nd3 _yTe4 . 122
Nd2Te3 . . • • • • . • 124
Neodymium Polytellurides 126
Samarium Tellurides 128
The Sm-Te System . . . 128
SmTe . . . . . . . . . 130
Homogeneity Range. Preparation . 130
Valency and Bonding . 133
Mössbauer Spectra . . 134
Mechanical Properties . 134
Thermal Properties . 136
Electronic Structure 139
Band Structure of Low-Pressure SmTe (NaCl Type) . 139
Band Structure of High-Pressure SmTe (CsCl Type) 142
Theoretical Models on the Valence lnstability . 143
Electrical Conductivity . . . . . . . . . . . . 145
Magnetoelectric and Thermoelectric Properlies 147
Optical and Dielectric Properlies 148
General . . . . . . . . . . . . 148
Raman Spectra . . . . . . . . . 149
Absorption and Reflection Spectra 149
Dielectric Properties . . . . . . 151
Pressure Dependance of the Optical Spectra 152
Magnetic Circular Dichroism (MCD) . . . . 152
Photoemission and X-Ray Absorption Spectra 153
ESR Spectra of SmTe Doped with Eu and Gd 154
The SmTe-NdTe System . 155
Sm 3Te4 . Sm 2Te3 . . • . . 155
Samarium Polytellurides . 157
Europium Tellurides . 158
The Eu-Te System . . . . 158
EuTe . . . . . . . . . . 159
XIV
Page
lonicity. Bonding 166
Lattice Vibrations 166
Mössbauer Effect 167
Nuclear Magnetic Resonance (NMR) 169
Hyperfine Fields . . . . . . . . . 171
At the Eu 2 + Nuclei . . . . . . . 171
At the Sn 2 + Nuclei in Sn-Doped EuTe 173
At the Te 2 - Nuclei 173
Thermal Expansion . 177
Melting Point . . . . 177
Vaporization. Sublimation 177
Thermodynamic Data of Formation 178
Heat Capacity and Additional Thermodynamic Functions 178
Debye Temperature . 180
Thermal Conductivity . . 180
Magnetic Properties . . . . 181
lntroduction and General 181
Magnetic Structure. Magnetic Phase Diagram 182
Anisotropies . . . . . . . . . . . . . . . 186
Exchange Field, Exchange Interaction Parameters 187
Magnetization and Low Temperature Susceptibility . 190
Paramagnetic Susceptibility . . . . . . . . . . . 192
Magnetic Resonance . . . . . . . . . . . . . . 193
Magnetic Properties of Doped or Nonstoichiometric EuTe Samples 196
Electrical Properties . . . 198
Electronic Structure . . 198
Conduction Mechanism 200
Electrical Conductivity . 203
Magnetoresistance . . 204
Hall Effect . . . . . . 205
Thermoelectric Properties 206
Photoelectric Effects . 206
Optical Properties . 207
Color 207
Raman Spectra . 208
lntroduction 208
Paramagnetic Range 208
Antiferromagnetic Range 210
Raman Scattering in Applied Magnetic Fields 211
Theoretical Models . . . . . . 212
Additional Light Scattering Studies 214
Absorption. Reflection 214
Below E9 . . . . . . . . . . . 214
Absorption Edge E9 . . . . . . 214
Absorption and Reflection Above E9 216
Modulated Reflection and Transmission . 218
Interpretation . . . . . . . . 218
Optical and Dielectric Constants . . . . . 220
XV
Page
Faraday Effect . . . . . . . . . . . . . . . . . . . . . . . . . . 222
Magnetic Circular Dichroism (MCD). Magnetic Linear Dichroism (MLD). 225
Luminescence . . . . . . . . . . . . . 226
Photoemission. Electron Energy Loss Spectra 227
Compounds EuTe. with x > 1 229
Gadolinium Tellurides 231
The Gd-Te System 231
GdTe . . . . . . 233
Preparation and Crystallographic Properties . 233
Mechanical and Thermal Properties. 233
Magnetic and Electrical Properties 234
Optical and Dielectric Properties . . 235
The GdTe-EuTe System . . . . . . . 236
Solid Solutions Gd3Te4-Gd 2Te 3 and Terminal Compounds 237
Gd 2Te 3-Nd 2Te 3 and Gd 2Te 3-Nd 3Te 4 Systems. 239
Gadolinium Polytellurides 240
Terbium Tellurides 242
TbTe. . . . . . . . . . 242
Dysprosium Tellurides . . . 242
Phase Diagram of the Dy-Te System 243
Compounds of the Dy-Te System 243
The DyTe-TbTe System 246
Holmium Tellurides . . . . . . . 246
Erbium Tellurides . . . . . . . . 247
Phase Diagram of the Er-Te System 247
Compounds of the Er-Te System . 248
ErTe-TbTe and ErTe-DyTe Systems 250
Thulium Tellurides . . . . . 251
Studies in the Tm-Te System 251
TmTe 253
lntroduction . . . . . . 253
Preparation . . . . . . 254
Valence . . . . . . . 257
Lattice Vibrations . . . 258
Thermal Properties . . 260
Mössbauer Spectra, Magnetic Hyperfine Field, and Crystal Field. 262
Magnetic Properties . . . . . . . . . . . . . . . . . 264
Magnetic Ordering . . . . . . . . . . . . . . . . . . 264
Susceptibility and Magnetization at Ambient Pressure . . 264
Pressure Dependence of Susceptibility and Magnetization 266
Magnetostriction and Thermal Expansion in Magnetic Fields 267
Electronic Structure . . . . . . . . . . . . . . . 268
General Features . . . . . . . . . . . . . . . 268
Gap E9 Between 4f States and Conduction Band . 269
Photoemission Spectra 270
Optical Properties . . . . . 27 4
XVI
Page
Color 274
Raman Spectrum . . . 274
Reflection and Absorption Spectra 274
Magnetooptical Properties 276
TmTe-MTe Systems 276
Ytterbium Tellurides . 278
The Yb-Te System . 278
YbTe . . . . . . . 278
Preparation 278
Magnetic and Electrical Properties . . . . 279
Electronic Structure and Optical Properties 280
General . . . . . . . . . . . . . . . 280
Reflection and Absorption Spectra . . . 281
Raman Spectra and Photoluminescence . 282
Additional Optical Properties . 282
Chemical Reactions 283
YbTe-MTe Systems . 285
Yb 2Te 3 (?). YbTe 2 (?). 287
Lutetium Tellurides . . 287
The LuTe-TmTe System 287
30.2 Hydride Tellurides MHx Te 288
30.3 Oxide Tellurides . . . . . 288
30.3.1 Comparative Data for M 2 0 2 Te 288

Formation. Preparation . . . . . 288
Properties . . . . . . . . . . . 289
Thermal Properties . . . . . . . 291
Optical Properties . 292
Chemical Reactions . . . . . . 293
30.3.2 Lanthan um Oxide Tellurides. 294

30.3.3 Ce 2 0 2 Te . 295
30.3.4 Nd 2 0 2Te . 296
30.3.5 Eu 2 0 2Te . 297
30.3.6 Dy 2 0 2Te . 298
30.3.7 Ho2 0 2Te. Er 2 0 2Te 298
30.4 Tellurates 298

30.4.1 Tellu rates(IV) 298
General ..... 298
XVII
Page
M20 3-Te0 2 Systems . . . . . . . . 299
The Y20 3-Te0 2 System . . . . . . 299
The La20 3 (La2(S0 4 )s)-Te0 2 System 299
The Sm 20 3-Te02 System 299
The Er20 3-Te0 2 System . . . . . 300
M2Te05 . . . . . . . . . . . . . . 300
M 4Te3 0 12 . Anti-Glass Phases with Similar Garnpositions. 301
M 2 (Te0 3 )s . . · · · · · · : 301
Physical Properlies . . . . 302
M2(Te03 )s · nH 20 . . . . . . 304
Physical Properlies 305
Chemical Reactions . . . . 306
M2Te4011 . . . . . . . . . . 307
Physical Properlies . . . . 308
Anti-Glass Phases M2Te6 0 15 to M 4Te 70 20 . 309
30.4.2 Compounds in the Cerium(lll, IV)-Tellurium(IV, VI)-O(-H 20) System 310

The Ce0 2-Te02 System 310
(Ce,Te)0 2 Solid Salutions 311
Cerium(IV) Tellurates(IV) . 311
CeTe04 (?) . 311
Ce(Te0 3b . . . . . 312
CeTe 3 0 8 (?) . . . . . 313
Cerium(lll) Tellurates(VI) 313
Ce2(Te04 )s . . . . . 313
Ce 20 3 · 2Te0 3 · 10H20 313
30.4.3 Tellurates(VI) 314

M6Te0 12 . 314
M2Te06 . . . . . . 314
M2(Te04 )s . . . . . 316
Cerium(IV) Tellurates(VI) . 317
Ce(Te0 4 ) 2 . . . . . 317
Ce0 2 · Te03 · 4.5H 20 318
Ce0 2 · Te0 3 · H20 . . 318
30.5 Telluride Halides. Tellurate Halides . 318
Compounds Containing Fluorine 318

NdTeF . . . . . 318
M1-xTex01+xF1-x . . 319
M 4Te0 7 F4 . . . . . · 319
Nd 2Te0 5F2. NdTe 20 7 F 319
XVIII
Page
Compounds Containing Chlorine 320
The NdCl3 -TeCl4 System 320
M2 (TeCL")s · 24 H20 . 320
MCl3-Te0 2 Systems . . 320
Compounds Containing Bromine 321

M 2 (TeBr 6)s · 24H 20 321
The LaBr 3 -Te0 2 System 321
The YbTe-1 2 System . . . 322
30.6 Sulfide Tellurides 322

The SmTe-SmS System 322
M2Te 3-M 2S3 Systems . 323
M2Te1+xS 2 Phases . . 323
Preparation and Polymorphism . 323
Orthorhombic Phases 323
Monoclinic Phases 324
Chemical Reactions . . 325
30.7 Selenide Tellurides 326

30.7.1 MTe-MSe Systems 326
CeTe 0 .5Se 0 _5 . . . . . . 326
The EuTe-EuSe System 326
The TmTe-TmSe System 328
General . . . . . . 328
Preparation . . . . . 329
Valency . . . . . . . . . 332
General . . . . . . . . 332
Results and Interpretation 332
Semiconductor-Metal Transition 333
Mechanical Properties . . 334
Density . . . . . . . 334
Pressure-Volume Data . 335
Magnetic Properties . . . 338
lntroduction . . . . . 338
Semiconducting TmTexSe 1 _x 338
Metallic TmTexSe 1 _x 339
Magnetic Structure . . . 339
Low Temperature Magnetization. Magnetic Moments . 340
Susceptibilities . . . . . . . . . . . . . . . . . . 341
lnelastic and Quasi-Elastic Lines in Magnetic Neutron Scattering 341
Theoretical Models . . . . . . . . . . . . . . . . . . . . . . 342
XIX
Page
Electrical Properties . . . 343
Electronic Structure . . 343
Optical Properties . . . . 348
30.7.2 The La 3Te4 -La 3 Se4 System 349

30.7.3 M2Te 3-M 2Se 3 Systems 350
Sc 2Te 0 _33Se 2.67 . . . · · · · 350
The La 2Te 3-La 2Se 3 System . 350
Phases in the Dy2Te 3-Dy 2Se 3 System 352
30.8 Alkali Rare Earth Tellurates . . 352

30.8.1 Alkali Rare Earth Tellurates(IV) 352
30.8.2 Alkali Rare Earth Tellurates(VI) 353
Li 3 M 3Te 20 12 . 353
LiDy(Te0 4 ) 2 . 354
NaDy(Te04 b 354
31 Rare Earth Elements and Polonium . 355
31.1 Polonides . . . . . . 355

31.1.1 Gaseous Molecules 355
31.1.2 Solid Polonides 355
General . . . . . . 355
M~........ ~
Melting Point. Vaporization . 358
Chemical Reactions . . . . . . . . . . . 359
31.2 Polonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
Table of Conversion Factors . . . . . . . . . . . . . . . . . . . . . . . . . . 361

30 Rare Earth Elements and Tellurium
30.1 Tellurides
General References:
A. A. Eliseev, The Crystal-Chemical Characteristics of Chalcogenides of Lanthanides with

Variable Valency, Zh. Neorgan. Khim. 30 [1985] 1111/20; Russ. J. lnorg. Chem. 30 [1985]
627/33.
X. Oudet, Structures Cristallines et Liaison, Ann. Chim. [Paris] [15]8 [1983]483/507.
Landolt-Börnstein New Ser. Group 11112 Pt. c [1982] 159/371. ·
A. A. Eliseev, 0. A. Sadovskaya, G. M. Kuz'micheva, Synthesis and Crystal Chemistry of Rare
Earth Semiconductor Chalcogenides, Zh. Vses. Khim. Obshchestva 26 No. 6 [1981]12/21;
Mendeleev Chem. J. 26 No. 6 [1981]15/27.
V. P. Zhuze, P. G. Rustamov, Redkozemel'nye Poluprovodniki, lzd. Elm, Baku 1981, pp. 1/182.
V. P. Zhuze, Optical Properties of Rare Earth Semiconductors, Zh. Vses. Khim. Obshchestva
26 No. 6 [1981]95/102; Mendeleev Chem. J. 26 No. 6 [1981]135/48.
J. Flahaut in: K. A. Gschneidner, LeRoy Eyring, Handbook on the Physics and Chemistry of
Rare Earths, Vol. 4, North-Holland, Amsterdam 1979, pp. 1/88.
S. Pokrzywnicki, Scientific Papers of the Institute of lnorganic Chemistry and Metallurgy of
Rare Elements of Wroclaw Polytechnic Institute No. 45, Wyd. Politech., Wroclaw 1979,
pp. 1/69; C.A. 92 [1980] No. 87141.
S. P. Gordienko, 8. V. Fenochka, G. Sh. Viksman, Termodinamika Soedinenii Lantanidov,
Naukova Dumka, Kiev 1979, pp. 1/373, 340/71.
V. P. Zhuze, I. A. Smirnov, Redkozemel'nye Poluprovodniki, Nauka, Leningrad 1977, pp.1/201.
E. I. Yarembash, A. A. Eliseev, Khal'kogenidy Redkozemel'nykh Elementov: Sintez i
Kristallokhimiya [Rare Earth Chalcogenides: Synthesis and Crystal Chemistry], Nauka,
Moscow 1975, pp. 1/260, 169/256; C.A. 83 [1975] No. 125545.
K. C. Mills, Thermodynamic Data for lnorganic Sulphides, Selenides, and Tellurides,
Butterworth, London 1974, pp. 1/854.
V. P. Zhuze, et al., Fizicheskie Svoistva Khal'kogenidov Redkozemel'nykh Elementov [Physical
Properties of Rare Earth Chalcogenides], Nauka, Leningrad 1973, pp. 1/304.
I. A. Smirnov, Thermal Properties of Rare Earth Chalcogenides, Phys. StatusSolidiA 14 [1972]
363/404.
J. Flahaut, Les Elements des Terres Rares, Masson, Paris 1969, pp. 1/165, 126/32.
J. Flahaut, P. Laruelle, Chimie Cristalline des Sulfures, Seleniures, et Tellurures Binaires
des Elements des Terres Rares, Progr. Sei. Technol. Rare Earth 3 [1968]149/208.
For additional generat references see "Rare Earth Elements" C9, 1986, p. 1.
Gmelin Handbook
RE Main Vol. C 10
2 Mo~w~s
30.1.1 Gaseous Molecules

Gaseaus rare earth tellurides exist in the vapors above the refractory solids in an anal-
ogaus manner to the sulfides and selenides; see "Rare Earth Elements" C7, 1983, p. 2, and
C9, 1986, p. 2. The available information on gaseaus tellurides, however, is comparatively
scarce. The diatornie molecules of only Sc, Y, La, Nd to Gd, Ho, and Lu have been detected
so far by high temperature mass spectrometry.
lonization Energies
The appearance potential in mass spectra only of YTe +, 6.0 ± 1.0 eV, has been obtained
so far by Uy, Drowart [1].
lnternuclear Distances r. Vibrational Frequencies OJ

No experimental values appear to have been determined. Empirical relations, viz.
r(MTe)- r(MO) = 0.79 A, are used by Uy, Drowart [1] and Bergman et al. [2], or 0.74 A by
Mills [3], and OJ(MO)/OJ(MTe) = 2.80 [2 to 4], where M is any of the elements Sc, Y, and La to
Lu, to obtain the following set of molecular constants:
M in MTe Sc y La Ce Pr Nd Sm Eu
r in A. 2.44 2.47 2.62 2.49 2.51 2.57 2.51 2.78

OJ in cm- 1 . 344 304 280 300 280 280 280 250
Ref. [3] [3] [2, 3] [3] [3] [2, 3] [3] [2, 3]
M in MTe Gd Tb Dy Ho Er Tm Yb Lu
r in A. 2.55 2.51 2.51 2.51 2.51 2.51 2.94 2.49

OJ in cm- 1 . 280 280 280 280 280 280 250 280
Ref. [2, 3] [3] [3] [2, 3] [3] [3] [3] [2, 3]
A considerably lower vibrational frequency for La Te of 219 cm- 1 was estimated by Goodfriend
[4] by another semiempirical extrapolation from LaO and LaS. The values r = 2.53, 2.63, and
2.68 A for Sc Te, YTe, and LaTe, respectively, were estimated by considering regularities of
bond lengths in diatornie molecules when one of the atoms changes through a group or period
of the periodic system, Spiridonov, Tatevskii [10].
Dissociation Energies D
The dissociation energies of several diatornie MTe molecules, namely with M = Sc, Y, La,
Nd to Gd, Ho, and Lu, have been determined, as for the rare earth sulfides and selenides, by
the Knudsen effusion method combined with mass spectrometry. Also, as for the rare earth
sulfides and selenides, the high temperature equilibria were of two main types, either sublima-
tion equilibria where two vaporization processes occur simultaneously:
MTe(s) ~ MTe(g), MTe(s) ~ M(g) + Te(g),
or gas-phase exchange equilibria:
MTe(g) + M'(g) ~ M(g) + M'Te(g) .
Gmelm Handbock
RE Mam Val. C 10
Dissociation 3
Here, MTe(g) is the gaseous rare earth telluride molecule for which D is to be determined
and which sublimes from the solid (s). M'Te(g) is any other gaseous metal telluride whose
known D value serves as a calibration standard. Either a solid telluride of the metal M' or
elemental M' is placed tagether with a telluride of M in the Knudsen cell, cf. "Rare Earth
Elements" C7, 1983, pp. 5/6, and C9, 1986, pp. 2/4. Dissociation energies were estimated for
the MTe molecules of the remaining rare earth elements on an empirical basis. The values
obtained for D are presented in Table 30.1.1/1.
Table 30.1.1/1
Dissociation Energies of Rare Earth Monotelluride Molecules MTe from High Temperature
Equilibria.
M equilibrium Tin K method og Ref.

in kcaUmol
Sc ScTe(g) + M'(g) ~ Sc(g) + M'Te(g)a) 70.4± 1.5 [2]

y (no details given) 80.25 [1]
La LaTe(g) + Sc(g) ~ La(g) + ScTe(g) 1900to2196 3rd law 90.3± 1.6 [2]
LaTe(s) ~ La(g) + Te(g) 1831to2100 2nd law 86.9± 1.5 [5]
Ce 92 ± Sb) [2]
Pr 77 ± Sb) [2]
Nd NdTe(g) + Sc(g) ~ Nd(g) + ScTe(g) 1866 to 2124 3rd law 72.0 ± 1.6 [2]
Pm 60 ± 1Sc) [7]
Sm SmTe(s) ~ Sm(g) + Te(g) 3rd law 64.2 ± 3.5 [6]
Eu EuTe(g) + Te(g) ~ Eu(g) + Te 2 (g) 1905 to 1904 3rd law 56.6 ± 1.3 [2]
(sie)
EuTe(s) ~ Eu(g) + Te(g) 3rd law 59.1 ± 3.5 [6]
Gd GdTe(g) + Sc(g) ~ Gd(g) + ScTe(g) 2015 to 2073 3rd law 80.3± 1.6 [2]
GdTe(g) + La(g) ~ Gd(g) + LaTe(g) 2012 to 2303 3rd law 80.4 ± 1.6 [2]
GdTe(g) + Nd(g) ~ Gd(g) + NdTe(g) 1952to2103 3rd law 80.9± 1.6 [2]
mean: 80.5 [2]
Tb 79 ± Sb) [2]
Dy 55 ± Sb) [2]
Ho HoTe(g) + Ti(g) ~ Ho(g) + TiTe(g) 2155 3rd law ~58.2 ± 1.6 [2]
Er 56 ± Sb) [2]
Tm 43 ± 10b) [2]
Yb 10d) [2]
23 ± 12e) [3]
Lu LuTe(g) + La(g) ~ Lu(g) + LaTe(g) 1952 to 2239 3rd law 76.7 ± 1.6 [2]
a) Any isomolecular exchange equilibrium, not specified further in the original reference [2]. -
b) Calculated from the empirical relation Dg(MSe)- Dg(MTe) = 21 ± 2 kcaUmol (88 ± 7 kJ/mol),
found to hold true for all molecules studied, except EuTe and EuSe. Dg(EuSe)- Dg(EuTe) =
14.5 kcaUmol (60.6 kJ/mol) [2]. - c) lnterpolated [7] from data in [2]. - d) Estimated from
og(YbO) by assuming Dg(YbO)- Dg(YbTe) = 76 kcaUmol (316 kJ/mol), same difference asthat
found for the EuO-EuTe pair [2]. - e) Obtained by comparison with other gaseaus rare earth
tellurides (sie) [3].
Dissociation energies obtained by Fenochka and Gordienko [8] from a model of electron
distribution in diatornie rare earth chalcogenide molecules are larger than those given in
Table 30.1.1/1 by 10 to 30 kcaUmol throughout.
Gmelin Handbook 1.
RE Mam Vol. C 10
4 Molecules
The trend with atomic number of the dissociation energies of the rare earth tellurides is
very similar tothat for the sulfides and selenides, i. e., it is closely parallel to the trend obeyed,
e. g., by the heats of Sublimation of the rare earth metals; cf. "Rare Earth Elements" C7, 1983,
p. 9, and C9, 1986, p. 4 [2].
Enthalpies of Formation
Values in kcal/mol from the compilations of thermodynamic data of Mills [3] and Gordienko
et al. [7] are as follows:
molecule ScTe YTe LaTe CeTe PrTe NdTe
LlHf2ss [7] 70.2 ± 4a) 70 ± 5a) 61.6 ± 3.5a) 64.2 52.7 57.0
LlHf2ss [3] 70.2 ± 4 70±5 61.6 ± 3.5 69.2 ± 5 61.7 ± 5 56.9
molecule Pm Te Sm Te Eu Te GdTe Tb Te DyTe HoTe
LlHf2ss [7] 65 ± 16 34.8 33.8 65.7 56.6 54.0 63.7

LlHf2ss [3] 44.2 ± 10 34.9 ± 4 64.8±4 64.2 ± 5 65.5 ± 5 ;;;62.0
molecule ErTe Tm Te YbTe Lu Te
LlHf2ss [7] 58.4 75.5

LlHf298 [3] 75.5 ± 5 65.2 ± 10 63 ± 12 75.1 ± 4
a) ln [7] adopted from [3].
For gaseaus EuTe, Schumm et al. [9] give LlHf0 = 41 kcaUmol.
Thermodynamic Functions
Selected values of the enthalpy H~-Hg, entropy S~, and free-energy function (G~-Hg)/T,
which have been calculated within the rigid-rotor and harmonic-oscillator approximations,
are compiled in the following Table 30.1.1/2. The assumed molecular constants, except for
the multiplicities of the electronic states (not given here), are presented on p. 2. The free-
energy functions for LaTe through LuTe were represented by a series expansion in powers
ofT and the coefficients given, Kovalevskaya, Fesenko [11].
Table 30.1.1/2
Thermodynamic Functions of Gaseaus Rare Earth Monotellurides MTe.
M Tin K H~-Hg s~ -(G~-Hg)/T Ref.

in kcaUmol in cal · mol- 1 • K- 1 in cal· mol- 1 · K- 1
Sc 298 2.305 61.4 53.67 [3, 7] a)

2000 17.414 78.22 69.51 (3, 7]a)
2000 69.36 [2]b),d)
y 298 2.334 63.23 55.40 [3, 7]a)

2000 17.466 80.09 71.35 [3, 7]a)
2100 72.04 [1]c).d)
Gmelm Handbock
RE Mam Vol. C10
Thermodynamic Functions 5
Table 30.1.1/2 (continued)
M Tin K H~-Hg s~ -(G~-Hg)/T Ref.

in kcaUmol in cal · mol- 1 • K- 1 in cal · mol- 1 · K- 1
La 298 2.346 64.72 56.85 [3, 7] 8)

2000 17.486 81.59 72.85 [3, 7] 8)
2000 72.82 [2]b),d)
Ce 298 2.337 66.58 58.74 (3, 7]8)

2000 17.473 83.45 74.71 [3, 7] 8)
Pr 298 2.353 67.31 59.41 [3, 7] 8l
2000 17.498 84.19 75.44 [3, 7] 8l
Nd 298 2.353 67.90 60.00 (3, 7]8)
2000 17.500 84.79 76.03 [3, 7] 8)
2000 76.03 [2]b),d)
Sm 298 2.353 68.59 60.69 [3, 7]8)

2000 17.498 85.47 76.72 [3, 7] 8l
Eu 298 2.379 69.48 61.50 (3, 1]8)
2000 17.358 86.39 77.62 [3, 7]8)
2000 77.62 [2]b),d)
Gd 298 2.353 67.89 59.99 [3, 7] 8l

2000 17.498 84.77 76.02 [3, 7]8)
2000 76.02 [2]b),d)
Tb 298 2.353 68.42 60.52 [3, 7]8)

2000 17.498 85.30 76.55 (3, 1]8)
Dy 298 2.353 68.12 60.60 [3, 7]8)
2000 17.498 85.00 76.65 [3, 7] 8)
Ho 298 2.353 68.52 60.62 [3, 7] 8)
2000 17.498 85.40 76.65 [3, 7]8)
2000 76.64 [2] b).d)
Er 298 2.353 67.17 59.27 (3, 7] 8 )

2000 17.498 84.05 75.30 [3, 7] 8l
Tm 298 2.353 66.40 58.50 (3, 1]8)
2000 17.498 83.28 74.53 [3, 7] 8l
Yb 298 2.379 65.90 57.92 [3, 7] 8)
2000 17.538 82.81 74.04 [3, 7] 8)
Lu 298 2.353 65.07 57.17 (3, 7]8),e)
2000 17.498 81.95 73.20 (3, 7]a),e)
2000 73.20 [2]b).d)
a) At 400 to 2000 Kin 100 K intervals, including calculated heat capacities [3, 7]. Values from
[3] have been adopted in [7]. All thermodynamic functions have been converted here from a
reference temperature 298 K, as used in the original reference [3], to 0 K. - bJ At 1800 to
2400 K in 200 K intervals. - c) At 2100 to 2500 K in 100 K intervals. - dl Original references
[1, 2] use units of kJ instead of kcal throughout. - e) Ref. [7] gives S~98 = 65.87, S~000 = 82.75,
-(G~ 98 -Hg)/298 = 57.97 cal· mol- 1 · K- 1 (misprint?).
Gmelin Handbook
RE M8in Vol. C10
6 MTe
Reterences:
[1] 0. M. Uy, J. Drowart (High Temp. Sei. 2 [1970]293/8).
[2] C. Bergman, P. Coppens, J. Drowart, S. Smoes (Trans. Faraday Soc. 66 [1970] 800/8).
[3] K. C. Mills (Thermodynamic Data for lnorganic Sulphides, Selenides, and Tellurides,
Butterworth, London 1974).
[4] P. L. Goodfriend (Spectrochim. Acta A 40 [1984]283/5).
[5] S. P. Gordienko, B. V. Fenochka (lzv. Akad. Nauk SSSR Neorgan. Materialy 18 [1982]
1811/5; lnorg. Materials [USSR]18 [1982]1554/8).
[6] S. I. Nagai, M. Shinmei, T. Yokokawa (J. lnorg. Nucl. Chem. 36 [1974]1904/5).
[7] S. P. Gordienko, B. V. Fenochka, G. Sh. Viksman (Termodinamika Soedinenii Lantanidov,
Naukova Dumka, Kiev 1979, pp. 1/373, 340/71).
[8] B. V. Fenochka, S. P. Gordienko (Konfigurats. Predstavleniya Elektron. Str. Fiz.
Materialoved. Mater. 2nd Nauchn. Semin. Konfigurats. Modeli Kondens. Sostoyaniya
Veshchestva, Lvov 1976 [1977]. pp. 67/70; C.A. 88 [1978] No. 177425).
[9] R. H. Schumm, D. D. Wagman, S. Bailey, W. H. Evans, V. B. Parker (NBS-TN-270-7 [1973]
1/75, 35).
[10] V. P. Spiridonov, V. M. Tatevskii (Zh. Fiz. Khim. 36 [1962] 2024/9; Russ. J. Phys. Chem.
36 [1962]1086/9).
[11] E. I. Kovalevskaya, V. V. Fesenko (Tezisy Dokl. 2nd Vses. Konf. Fiz. Khim. Redkozem.
Poluprovodn., Leningrad 1979, p. 3; C.A. 93 [1980] No. 55269).
30.1.2 Solid Tellurldes

Comparative data are given for MTe, M3Te4 , M2Te3 , M4Te7 , MTe2 _x, M2Te 5, M4Te 11 , and
MTe3 , but not for the poorly characterized phases M3Te 7 (M =La to Eu).
30.1.2.1 Comparative Data for M Te
30.1.2.1.1 Formation and Preparation

The rare earth monotellurides MTe were prepared like the other chalcogenides (see, e.g.,
"M 2Te3", p. 31, or in connection with the M-Te systems) by reacting appropriate quantities of
Te and M in the form of chips in a sealed evacuated quartz tube at about 600°C for 18 to 24 h,
followed by further reaction near 900°C for 3 to 4 h and repeatedly melting the thoroughly
homogenized material in a sealed Ta tube, Jayaraman [1]. After the element mixtures or
pellets have violently reacted at 320 to 350°C in Ar-filled quartz ampules, heating was
maintained at 800°C for 2 to 4 h. The cooled products were compacted and the pellets were
refired under Ar, preferably at 1000°C for 6 h, Brixner [2]. The monotellurides formed are
metallic gray, Brixner [3]. For the reaction in evacuated ampules the temperature was held
for 2 to 3 d at 400 to 450°C. After cooling, the brown powders are pressed under C02 followed
by annealing in quartz ampules. M3Te4 , formed intermediately via M2Te3 , transforms at 1100°C
slowly into MTe. The prepared MTe (M = La, Ce, Pr, Nd) are dark and shiny violet, landelli
[4]. At first, turnings of the metals (Y to Yb) reacted with Te vapor by slow heating to about
600°C; then the brown powders, which contain M3Te4 at the surtace, were pressed and heated
under Ar at 1100°C (M = Y to Eu) or at 1450°C (M = Gd to Yb), landelli [5].
The reaction is less violent when direct contact between the metals and Te is prevented.
The tube containing Te was placed in a glass ampule containing the metal (La, Pr, or Nd).
Then the ampule was evacuated, filled with H2 (1 atm), and slowly heated to 600°C. The solid-
vapor reaction is greatly accelerated in the presence of H2 and the products are more
Gmelin Handbock
RE Main Vol. C 10
Preparation 7
homogeneous. Heat-resistant glass is preferable to quartz because it remains impermeable

to gas up to 600°C. The products obtained at 600°C were pressed in dry Ar or C0 2 and
annealed in Mo or Ta crucibles in vacuum ( -5 x 10- 5 Torr) at 1600 to 1800°C. From the
macrocrystaLLine specimens single crystals could be picked out. They have metaLLic Luster
and are violet-red, Golubkov et al. [6]. ln a Later work, the preparation of scandium teLLuride
was carried out in evacuated quartz ampules in a two-zone furnace. Then peLLets were
annealed in sealed Mo bombs at 1700 to 1800°C and single crystals were grown from the
melts by the horizontal Bridgman method in sealed cylindrical Ta crucibles, Zhuze et al. [7].
By heating YbCL3 with an excess of Te in a stream of H2 for 8 hat 950°C, a black powder
of YbTe was formed. EuTe can be prepared in the same manner (see p. 160), while SmCL3
reacts very slowly, Senff, Klemm [8].
Single crystals of MTe (M = Nd, Sm, Eu, Gd, Ho, Er, Yb) were grown by high temperature
vapor growth in sealed Mo (or W) crucibles, for example, at a temperature gradient of
1960-+ 1915°C and a growth rate of approximately 12.5 mg/h. The chemicaL transport takes
place via the formation of M-Mo complexes. lodine was used as a transporting agent for YbTe,
and iodine, Eul 2 , or EuBr2 were used in the case of EuTe, Kaldis [9]. The chemical transport
reaction with iodine as the carriergaswas used by Khan et aL. [10 to 12] to prepare MTe with
M = Tb, Dy, Er [10], Dy, Er [11], Tm, Lu [12], or to prepare mixed crystals (M, M') Te with
(M, M') = (Dy, Tb), (Dy, Er), (Er, Tb) [10], or (Lu, Tm) [12]. The transport took place, for example,
at a temperature gradient ßt between 25 and 75°C within the range 1000 to 900°C in ampules
of ca. 25 mL volume and an iodine concentration of (5 to 6.5) mg/mL [11] or 7 and 9.3 mg/mL
[10]. Elementmixtures of 0.5 to 1 g were transported within 72 h [10 to 12].
Films were prepared by evaporating the metals from a Ta crucible at < 10- 8 Torr onto an
inert substrate (glass, quartz, MgO) in a chamber under vacuum, then introducing H2Te at
atmospheric pressure and room temperature, Schueler [13]. Films of MTe (M = Eu, Sm, Yb)
of 100 to 5000 A thickness were prepared by Co-evaporation of M and Te from Knudsen ceLL
type crucibles made of Ta and graphite, respectively. The substrates (Pyrex glass, NaCL, or
CaF2 ) were kept at temperatures between 400 and 500°C. On (111) CaF2 substrates the films
show epitaxy, Paparoditis, Suryanarayanan [14]. For the preparation of EuTe and YbTe films
by the same method, see also Suryanarayanan, Paparoditis [15]. Rare earth monoteLLuride
films were prepared by evaporation (with heating in some cases with an electron beam) of
sintered samples in a sealed chamber at < 10- 5 Torr onto a 200°C substrate within the
chamber, Holtzberg, Methfessel [16].
References:
[1] A. Jayaraman (in: K. A. Gschneidner, LeRoy Eyring, Handbock on the Physics and
Chemistry of Rare Earths, VoL. 2, North-HoLLand, Amsterdam 1979, pp. 575/611, 577).
[2] L. H. Brixner, E. I. Du Pont de Nemours & Co. (Can. 649834/5 [1960/62]; C. 1965 No. 41-
2217).
[3] L. H. Brixner (J. lnorg. NucL. Chem. 15 [1960]199/201).
[4] A. landeLLi (Gazz. Chim. ltal. 85 [1955] 881/7).
[5] A. landeLLi (Proc. 1st Conf. Rare Earth Res., Lake Arrowhead, Calif., 1960 [1961], pp. 135/41).
[6] A. V. Golubkov, I. B. Zhukova, V. M. Sergeeva (lzv. Akad. Nauk SSSR Neorgan. Materialy
2 [1966]77/81; lnorg. Materials [USSR]2 [1966] 66/9).
[7] V. P. Zhuze, A. V. Golubkov, M. G. Karin, K. K. Sidorin, A. I. Shelykh (Fiz. Tverd. Tela
[Leningrad]24 [1982]1017/25; Soviet Phys.-Solid State 24 [1982]577/82).
[8] H. Senff, W. KLemm (Z. Anorg. ALLgem. Chem. 242 [1939] 92/6).
Gmelin Handbook
RE Main Vol. C10
8 MTe
[9] E. Kaldis (in: C. H. L. Goodman, Crystal Growth, Theory and Techniques, Plenum, New
York 1974, pp. 49/191, 93/111).
[10] A. Khan, C. Garcia (Proc. 12th Conf. Rare Earth Res., Vail, Colo., 1976, Vol. 2, pp. 953/60;
C.A. 85 [1976] No. 134614).
[11] A. Khan, L. Manzi (Proc. 5th Conf. Chem. Vap. Deposition Intern. Conf., Slough, Engl.,
1975, pp. 317/30).
[12] A. Khan, C. Vallaneilla (Proc. 5th Conf. Chem. Vap. Deposition Intern. Conf., Slough,
Engl., 1975, pp. 331/43).
[13] C. Schueler, Intern. Business Machines Corp. (Brit. 1084696 [1965/67]; C.A. 68 [1968] No.
54878).
[14] C. Paparoditis, R. Suryanarayanan (J. Cryst. Growth 13/14 [1972] 389/92).
[15] R. Suryanarayanan, C. Paparoditis (Colloq. Intern. Centre Natl. Rech. Sei. No. 180
[1969/70]149/55).
[16] F. Holtzberg, S. I. Methfessel, Intern. Business Machines Corp. (Brit. 1061949 [1965/67];
C.A. 66 [1967] No. 120027).
30.1.2.1.2 Crystallographic Properties

The structure of ScTe is hexagonal; see p. 61. The other monotellurides have the cubic
NaCl structure, space group Fm3m-O~ (No. 225), Z = 4, landelli [1]. Composition-dependent
distortions are observed at the Neel temperature: NdTe may become tetragonal and TbTe
may become rhombohedral. GdTe undergoes a rhombohedral distortion and is monoclinic at
still lower temperatures; see p. 16 and the individual sections. CeTe, Leger et al. [37] as well
as PrTe, SmTe, and EuTe, Chatterjee et al. [2] exhibit a phase transition from NaCl-type to
CsCl type structure at high pressure (8 to 11 GPa) [2, 37], and TmTe transforms at -15 GPa
into a hexagonal phase (see p. 256); furthermore an isostructural pressure-induced valence
transition M2 +--> M 3 + is observed in MTe with M = Sm, Tm, and Yb, see pp. 133, 256, and
279, respectively. The existence of monoclinic LaTe and GdTe at room temperature (and
possibly of PrTe, NdTe, and SmTe), reported by Brixner [12, 13], was not confirmed in more
recent papers; see for example "La Te", p. 69.
The lattice constants of the NaCl type compounds are shown in Fig.1. They decrease with
increasing atomic number for MTe with trivalent cations, and show maxima for MTe with
divalent cations (M = Sm, Eu, Tm, Yb), Jayaraman [3]. Similar curves are shown by Campagna
et al. [4], Jayaraman et al. [5, 6], and Flahaut [7]. The lattice constants in dependence of the
effective ionic radii (M 2 + for Sm, Eu, Tm, Yb, and M 3 + for the others) decrease Linearly with
decreasing radii, Fritzler, Katdis [8].
6_6 La Pr Pm Eu Tb Ho Tm Lu
6.4 I r\
""'~V \
.D-
oc(
.5
tl 6.2
r~
I I
~ ....,._I I
I
6.0
Ce Nd Sm Gd Dy Er Yb
Fig. 1. Lattice constants of MTe forM= La to Lu.

Gmelm Handbook
RE Mam Val. C 10
Lattice constants in A for the NaCL type MTe:
YTe 6.080 [1], 6.095 [12], 6.093 [20]

LaTe 6.422 [1]. 6.429 [9], 6.436 [21]
Ce Te 6.359 [1], 6.361 [30], 6.342 [22]
PrTe 6.322 [1], 6.317 [9], 6.315 [2]
NdTe 6.262 [1], 6.282 [9], 6.30 [10]
Pm Te 6.24 8 ) [17]
SmTebl 6.594 [1]. 6.595 [2, 11]. 6.60 [6], 6.58 [10]
EuTebl 6.585 [1]. 6.591 [2, 11]. 6.594 [23], 6.60 [6]
GdTe 6.139 [1]. 6.14 [10], 6.1238 [31]
Tb Te 6.021 [33], 6.101 [1, 12], 6.102 [32], 6.115 [24]
DyTe 6.075 [1], 6.092 [12]. 6.077 [25]
HoTe 6.049 [1, 34]. 6.053 [33]. 6.072 [12]
ErTe 6.021 [1], 6.063 [12], 6.010 [27]
TmTebl 6.355 or 6.366 [39]dl, 6.361 [26], 6.042c) [12, 35]
YbTe 6.361 [1, 11, 14], 6.37 [10]
Lu Te 5.953 [20], 5.96 8 ) [17]. 6.006(2) [35]
a)Estimated values. - b) For details see pp. 132, 163, and 254/5, respectively. - c) Tm deficient,
no NaCl type, see p. 251. - d) Quenched or slowly cooled crystal, respectively.
Similar or the same values: forMTe with M = La, Ce, Pr, Nd, landelli [15]. M = Ce and Pr,
Zhuze et al. [16], M = Tm, Yb [6], M = Tb to Tm, Brixner [13]. Measured values for two Tb-
deficient TbTe samples are 6.019(8) and 6.070(8) at 293 K and 5.996(8) and 6.069(8) A at 4.2 K
(however, TbTe is rhombohedrally distorted below TN; see p. 242). For HoTe is a = 6.055(8) A
at 293 K and 6.035(8) A at 4.3 K by neutron diffraction, Fischer et al. [33]. For computer
calculation of cation vacancies in HoTe, see Kutolin et al. [36].
Experimental and calculated atomic distances M-Te in A for the NaCL type compounds
[15]:
LaTe CeTe PrTe Nd Te
M-Te (exp) . . . . . . . . . . . . 3.211 3.181 3.161 3.131

M-Te (calc) . . . . . . . . . . . . 3.276 3.236 3.216 3.196
The mean anion radius in MTe was calculated tobe 2.135 A (maximum deviation + 0.013 and
-0.007 A) by subtraction of the M3+ radius from the cation-anion distances, Allbutt, Dell [18].
According to Haase et al. [19], the X-ray powder patterns as well as single crystal patterns
of LaTe, NdTe, and ErTe do notshow lines with h, k,l odd. lt was concluded thatthese structures
have primitive cells (Z = 1 M0 .5Te0 _5) with a = 3.218 A for LaTe, 3.125 A for NdTe, and 3.005 A
for ErTe [19]. This conclusion was later revised in favor of the NaCl structure; see for example
[21, 27] and Li n et al. [28].
Regarding the homogeneity range of MTe, there generally exists no large NaCl type solid
solution range; see the individual sections for M = La, Sm, Eu, Gd, Tb, Ho, and Yb. YTe is
said to form orthorhombic solid solutions with Y2Te3 with a = 12.45, b = 8.63, c = 25.62 A for
YTe, Norman [29] (see p. 63). Analogous orthorhombic solid solutions, which have a cubic
Gmelin Handbock
RE Main Vol. C10
10 MTe
subcell, were originally also observed between NaCl type MTe and orthorhombic M 2Te 3 for
M = Er, Haase et al. [27], and M = Tm, Eliseev et al. [26]. However, later Observations cast
some doubt upon the existence for such a solid solution with MTe as an end member; see
pp. 247 and 252, respectively. (The relations between the cubic subcell (a 0 ) and the
orthorhombic cell, a = 2 a 0 , b = a 0 · V2.and c = 3 a 0 · V2
[27], are not strictly fulfilled in
the case of the above given lattice parameters for orthorhombic YTe.) The change of the
lattice constants of the cubic cell or cubic subcell as a function of the lanthanide valence and
possible homogeneity regions are derived from Literature data on the lattice constants of MTe
with M = Sm, Eu, Tm, and Yb, Eliseev [38].
The high-pressure phases CeTe, PrTe, SmTe, and EuTe have the CsCl structure, space
group O~-Pm3m (No. 221), Z = 1. Lattice constants a for the NaCl and the CsCl phases at the
pressure Ptr of NaCl-CsCl transition and volume change !J.V!V associated with the transition
of Ce Te [37] and the tellurides of Pr, Sm, and Eu [2, 11):
Ce Te PrTe Sm Te Eu Te
Ptr in GPa. 8±1 9±1 11 ± 1 11 ± 1

a (NaCl) in A 6.192(10) 6.218(20) 5.992(20) 6.222(20)
a (CsCl) in A 3.773(10) 3.761(10) 3.656(10) 3.739(10)
!J.V!V in% -8.5 -11.5 -9.1 -13.2
References:
[1) A. landelli (Proc. 1st Conf. Rare Earth Res., Lake Arrowhead, Calif., 1960 [1961), pp.135/41).
[2) A. Chatterjee, A. K. Singh, A. Jayaraman (Phys. Rev. [3) B 6 [1972) 2285/91).
[3) A. Jayaraman (in: K. A. Gschneidner, LeRoy Eyring, Handbock on the Physics and
Chemistry of Rare Earths, Val. 2, North-Holland, Amsterdam 1979, pp. 575/611, 578).
[4) M. Campagna, G. K. Wertheim, E. Sucher (Struct. Bonding [Berlin)30 [1976]99/140, 114).
[5] A. Jayaraman (Comments Solid State Phys. 7 No. 6 [1977)135/48, 136).
[6) A. Jayaraman, P. D. Dernier, L. D. Longinotti (High Temp.-High Pressures 7 [1975] 1/28,
2/3).
[7] J. Flahaut (Les Elements des Terres Rares, Masson, Paris 1969, pp. 1/165, 146).
[8) B. Fritzler, E. Kaldis (Valence lnstab. Proc. Intern. Conf., Zürich, Switz., 1982, pp. 173/8,
175).
[9) A. V. Golubkov, T. B. Zhukova, V. M. Sergeeva (lzv. Akad. Nauk SSSR Neorgan. Materialy
2 [1966] 77/81; lnorg. Materials [USSR] 2 [1966] 66/9).
[10] J. F. Miller, L. K. Matson, R. C. Himes (Proc. 2nd Conf. Rare Earth Res., Glenwood
Springs, Cola., 1961 [1962], pp. 233/48, 239).
[11] A. Jayaraman, A. K. Singh, A. Chatterjee (Proc. 9th Conf. Rare Earth Res., Blacksburg,
Va., 1971, Val. 1, pp. 360/360i).
[12) L. H. Brixner (J. lnorg. Nucl. Chem. 15 [1960]199/201).
[13) L. H. Brixner, E. I. Du Pont de Nemours & Co. (Can. 649834 [1960/62]; C. 1965 No. 41-
2217).
[14] E. Sucher, V. Narayanamurti, A. Jayaraman (J. Appl. Phys. 42 [1971]1741/5).
[15] A. landelli (Gazz. Chim. ltal. 85 [1955] 881/7).
[16] V. P. Zhuze, A. V. Golubkov, E. V. Goncharova, V. M. Sergeeva (Fiz. Tverd. Tela
[17] A. 0. Finogenov (Zh. Fiz. Khim. 46 [1972]286/9; Russ. J. Phys. Chem. 46 [1972]172/4).
Gmelin Handbook
RE Ma1n Vol. C10
Mechanical Properlies 11
[18] M. Allbutt, R. M. Deli (J. lnorg. Nucl. Chem. 30 [1968] 705/10).

[19] D. J. Haase, H. Steinfink, E. J. Weiss (Proc. 4th Conf. Rare Earth Res., Phoenix, Ariz.,
1964 [1965], pp. 535/44, 537/9; C.A. 65 [1966]14821).
[20] F. Hull, G. W. Hulliger Jr. (Solid State Commun. 8 [1970]1379/82).
[21] T. H. Ramsey, H. Steinfink, E. J. Weiss (lnorg. Chem. 4 [1965]1154/7).

[22] V. I. Chukalin, E. I. Yarembash, A. I. Villenskii (lzv. Akad. Nauk SSSR Neorgan. Materialy
3 [1967]1538/45; lnorg. Materials [USSR]3 [1967]1341/7).
[23] A. A. Eliseev, 0. A. Sadovskaya (lzv. Akad. Nauk SSSR Neorgan. Materialy 13 [1977]
[24] F. Hulliger, F. Stucki (Z. Physik 8 31 [1978] 391/3).
[25] N. Kh. Abrikosov, K. A. Zinchenko (Redkozem. Metally lkh Soedin. Mater. Vses. Simp.,
Kiev 1968 [1970], pp. 173/80; C.A. 76 [1972] No. 7748).
[26] A. A. Eliseev, K. A. Zinchenko, V. M. Zemlyanukhina, Nguyen Chin Tarn (Zh. Neorgan.
Khim. 21 [1976] 2603/5; Russ. J. lnorg. Chem. 21 [1976]1431/3).
[27] D. J. Haase, H. Steinfink, E. J. Weiss (lnorg. Chem. 4 [1965] 541/3).
[28] W. Lin, H. Steinfink, E. J. Weiss (lnorg. Chem. 4 [1965] 877/81).
[29] L. D. Norman (U.S. Bur. Mines Rept. lnvest. No. 6851 [1966] 1/19, 5; C.A. 66 [1967]
No. 14966).
[30] D. Ravot, P. Burlet, J. Rossat-Mignod, J. L. Tholence (J. Phys. [Paris]41 [1980]1117/20).
[31] W. Beckenbaugh, J. Evers, G. Güntherodt, E. Kaldis, P. Wachter (J. Phys. Chem. Solids
36 [1975] 239/48).
[32] G. L. Olcese (Atti Accad. Nazi. Lincei Rend. Classe Sei. Fis. Mat. Nat. [8] 30 [1961]
195/200).
[33] P. Fischer, P. Schobinger-Papamantellos, E. Kaldis, A. Ernst (J. Phys. C 10 [1977]
3601/11 ).
[34] G. Bruzzone (Atti Accad. Nazi. Lincei Rend. Classe Sei. Fis. Mat. Nat. [8] 30 [1961]
208/13).
[35] A. Khan, C. Vallaneilla (Proc. 5th Conf. Chem. Vap. Deposition Intern. Conf., Slough,
Engl., 1975, pp. 331/43).
[36] S. A. Kutolin, S. N. Komarova, Yu. A. Frolov (Zh. Fiz. Khim. 56 [1982]996/9; Russ. J. Phys.
Chem. 56 [1982]606/8).
[37] J. M. Leger, R. Epain, J. Loriers, D. Ravot, J. Rossat-Mignod (Phys. Rev. [3] 8 28 [1983]
7125/9).
[38] A. A. Eliseev (Zh. Neorgan. Khim. 29 [1984] 1650/4; Russ. J. lnorg. Chem. 29 [1984] 945/8).
[39] E. Kaldis, E. Jilek, H. Spychiger (J. Less-Common Metals 93 [1983] 399/409).
30.1.2.1.3 Density and Microhardness
The following calculated X-ray densities Deale in g/cm 3 for the NaCl type MTe (Z = 4) from
the lattice constants in landelli [1] were reported by Sergeeva, Golubkov [2] and in part by
Gschneidner [3]; the density of Tm Te was calculated by landelli, Palenzona [4]:
MTe YTe La Te Ce Te PrTe NdTe Sm Te Eu Te

Deale 6.397 6.683 6.914 7.057 7.352 6.438 6.502
MTe GdTe TbTe DyTe HoTe ErTe Tm Te YbTe

Deale 8.178 8.330 8.593 8.777 8.971 7.640 7.757
Gmelin Handbock
RE Main Vol. C10
12 MTe
Measured densities Dexp and some calculated densities for the cubic MTe:
LaTe CeTe PrTe NdTe EuTe DyTe ErTe
Dexp 6.66 6.55 6.91 6.89 6.89 7.40 6.40 7.93 8.6
Deale 6.68 6.68 7.01 7.11 6.50
Ref. [14) [5] [6) [7) [8) [15] [9) [10) [11)
For LaTe, NdTe, and ErTe with an assumed primitive cubic cell (Z = 0.5) the densities 6.68,
7.40, and 9.02, respectively, were calculated by Haase et al. [13].
Values for the hexagonal ScTe, see p. 61. The molar volumes of MTe with M = Ce to Yb
show maxima for the MTe with divalent cations (or minima, respectively, in the reciprocal
molar volumes, called the packing density), Zaslavskii, Samsonov [12].
The microhardness of polycrystalline samples in 107 N/m 2 at a Load of 0.2 N is 200 to 215
for GdTe and TbTe, Rustamov, Geidarova [16), and 145 to 150 for DyTe, Murguzov et al. [17].
References:
[1) A. landelli (Proc. 1st Conf. Rare Earth Res., Lake Arrowhead, Calif., 1960 [1961], pp.135/41).
[2) V. M. Sergeeva, A. V. Golubkov (in: V. P. Zhuze et al., Fizicheskie Svoistva Khal'kogenidov
Redkozemel'nykh Elementov, Nauka, Leningrad 1973, pp. 5/57, 15; C.A. 80 [1974) No. 75014).
[3) K. A. Gschneidner (Rare Earth Alloys, Princeton, New York 1961, p. 298).
[4) A. landelli, A. Palenzona (Colloq. Intern. Centre Natl. Rech. Sei. No. 157 [1967]397/405;
C.A. 68 [1968] No. 63803).
[5] A. A. Eliseev, E. I. Yarembash, V. G. Kuznetsov, et al. (lzv. Akad. Nauk SSSR Neorgan.
Materialy 1 [1965)1027/38; lnorg. Materials [USSR)1 [1965]943/52).
[7] E. I. Yarembash, A. A. Eliseev, E. S. Vigileva, L. I. Antonova (lzv. Akad. Nauk SSSR
Neorgan. Materialy 3 [1967] 2184/9; lnorg. Materials [USSR] 3 [1967)1905/9).
[8) A. landelli (Gazz. Chim. ltal. 85 [1955] 881/7).
[9) 0. A. Sadovskaya, E. P. Stepanov, V. V. Khrapov, E. I. Yarembash (lzv. Akad. Nauk SSSR
Neorgan. Materialy 8 [1972] 815/20; lnorg. Matertals [USSR] 8 [1972] 708/12).
[10) N. Kh. Abrikosov, K. A. Zinchenko (Redkozem. Metally lkh Soedin. Mater. Vses. Simp.,
Kiev 1968 [1970], pp. 173/80; C.A. 76 [1972) No. 7748).
[11) D. J. Haase, H. Steinfink, E. J. Weiss (lnorg. Chem. 4 [1965]541/3).

[12) I. I. Zaslavskii, G. V. Samsonov (Ukr. Khim. Zh. 35 [1969] 675/80; C.A. 71 [1969]
No. 128918).
1964 [1965], pp. 535/44; C.A. 65 [1966]14821).
[14) T. H. Ramsey, H. Steinfink, E. J. Weiss (J. Appl. Phys. 36 [1965] 548/53).
[15] K. A. Zinchenko, N. P. Luzhnaya, E. I. Yarembash, A. A. Eliseev (lzv. Akad. Nauk SSSR
Neorgan. Materialy 2 [1966]1747/56; lnorg. Materials [USSR)2 [1966]1506/14).
[16) P. G. Rustamov, E. A. Geidarova (Zh. Neorgan. Khim. 29 [1984] 2982/4; Russ. J. lnorg.
Chem. 29 [1984]1706/7).
[17) M. I. Murguzov, A. P. Gurshumov, Kh. V. Kadyrly, et al. (Zh. Neorgan. Khim. 29 [1984)
2965/7; Russ. J. lnorg. Chem. 29 [1984]1695/7).
Gmel1n Handbock
RE Ma1n Val. C 10
Thermal Properties 13
30.1.2.1.4 Thermal Properties
Thermodynamic Properlies
Estimated values by Mills [1] for the standard enthalpy of formation ~H298 in kcallmol
(± 15) and the absolute entropy S298 in cal · mol- 1 · K- 1 ( ± 2 to 3) obtained by comparison
with other rare earth chalcogenides:
ScTe YTe La Te Ce Te PrTe NdTe Pm Te Sm Te
-~H2ss 72 72 72 ± 10 72 72 72 72 74
S2ss 18.2 20.7 (21.1 ± 1) •) 23.4 23.3 23.3 23.2 23.2
Eu Te GdTe Tb Te DyTe Ho Te Er Te Tm Te YbTe Lu Te
-~H2ss 65 75 75 75 75 75 75 72 75
S2sa 23.2 23.2 23.2 23.2 23.2 23.2 23.2 21.2 19.7
·> The value for LaTe was obtained from CP measurements; see p. 69.
Melting Point and Debye Temperature

Melting points (in K) for the congruently melting monotellurides:
LaTe 1993 ± 25 [23], 2023 [27] GdTe 2098± 15 [10], 2143±30 [7], 2173 [24]
Ce Te 2093 [2] Tb Te 1573 [24]
PrTe 2223 ±50 [3] DyTe ~2093 [25], 2123 [11]
Nd Te 2028 ± 15 [4], 2278 [26], 2298 ± 15 [5], HoTe 1643 ± 25 [12]
2313 ± 10 [6], 2318 ± 30 [7] ErTe ~ 1763 [14], 1798 [13]
Sm Te 2133 [8], ~ 2193 [7] Tm Te 2143 ± 5 [30]
EuTe*l 2456 ± 2 [9] YbTe 2003 ± 10 [15], ~2013 [7], 2260 [28]
•> Additional values see p. 177.
Values calculated by Tikhonov et al. [16] and Smirnov [17] deviate considerably (up to 300 K)
from the above tabulated measured values. The melting points and the Debye temperatures
0 0 have been approximately calculated from the linear dependence of 0 0 on the average
atomic weight of the monochalcogenides, using 0 0 values experimentally determined from
the heat capacity of some compounds. For tabulated values of the calculated melting points,
see the papers; values of 0 0 in Kare as follows [16, 17]:
MTe . . LaTe Ce Te PrTe NdTe GdTe Tb Te

0 0 in K. 184 183 182 180 170 167
MTe . . DyTe HoTe ErTe Tm Te

0 0 in K. 165 163 160 159
The compound LaTe has 0 0 = 175 K from CP measurements, Sucher et al. [18], and 0 0 =
170 K based on Tm = 1993 K, Golubkov et al. [19]. For graphs of melting points and Debye
temperatures of rare earth chalcogenides, estimated from crystal chemicalliterature data for
the NaCl type, see Kuz'micheva et al. [29].
Gmelm Handbook
RE Main Vol. C10
14 MTe
Characteristic Mössbauer temperatures which generally differ from Debye temperatures

are given on p. 18.
Thermal Conductivity
Values at room temperature (for La Te at 400 K) for the total and lattice thermal conductivity
Atot and A181 in cal · s- 1 • cm- 1 • K- 1 :
La Te Ce Te PrTe NdTe GdTe DyTe YbTe
~0.050 0.027 0.019 0.0153 0.0124 0.017 0.0048

0.0126 0.013 0.007 0.0027 0.0012
[19] [20] [20] [21] [10] [22] [15]
Relerences:
Butterworth, London 1974, pp. 1/854).
[3] E. I. Yarembash, E. S. Vigileva (lzv. Akad. Nauk SSSR Neorgan. Materialy 6 [1970] 1572/8;
lnorg. Materials [USSR] 6 [1970] 1388/93).
[4] N. Kh. Abrikosov, V. Sh. Zargaryan (lzv. Akad. Nauk SSSR Neorgan. Materialy 1 [1965]
Neorgan. Materialy 2 [1966]1747/56; lnorg. Materials [USSR]2 [1966]1506/14).
[6] W. Lin, H. Steinfink, E. J. Weiss (lnorg. Chem. 4 [1965]877/81).
[7] J. F. Miller, L. K. Matson, R. C. Hirnes (Proc. 2nd Conf. Rare Earth Res., Glenwood
Springs, Colo., 1961 [1962], pp. 233/48, 239).
[8] E. I. Yarembash, E. G. Tyurin, A. A. Reshchikova, et al. (lzv. Akad. Nauk SSSR Neorgan.
Materialy 7 [1971] 761/5; lnorg. Materials [USSR]7 [1971] 661/5).
[9] T. B. Reed, R. E. Fahey, A. J. Strauss (J. Cryst. Growth 15 [1972]174/8).
[10] V. Sh. Zargaryan, N. Kh. Abrikosov (lzv. Akad. Nauk SSSR Neorgan. Materialy 3 [1967]
[11] N. Kh. Abrikosov, K. A. Zinchenko, A. A. Eliseev (lzv. Akad. Nauk SSSR Neorgan.
Materialy 6 [1970]720/5; lnorg. Materials [USSR]6 [1970]634/8).
[12] E. I. Yarembash, E. S. Vigileva, A. A. Eliseev, et al. (lzv. Akad. Nauk SSSR Neorgan.
[14] N. Kh. Abrikosov, L. V. Poretskaya, E. V. Skudnova (Redkozem. Metal. Splavy Soedin.
Mater. 7th Soveshch., Moscow 1972 [1973], pp. 174/5; C.A. 81 [1974] No. 17380).
[16] V. V. Tikhonov, A. V. Golubkov, I. A. Smirnov (Fiz. Tverd. Tela [Leningrad] 8 [1966]3578/82;
Soviet Phys.-Solid State 8 [1966/67] 2860/3).
[17] I. A. Smirnov (Phys. Status Solidi A 14 [1972] 363/404, 372).
[18] E. Sucher, K. Andres, F. J. Di Salvo, et al. (Phys. Rev. [3]11 [1975] 500/13, 504).
Gmel1n Handbook
RE Main Vol. C10
Magnetic Properties 15
[19] A. V. Golubkov, E. D. Devyatkova, V. P. Zhuze, et al. (Fiz. Tverd. Tela [Leningrad]8 [1966]
1761/71; Soviet Phys.-Solid State 8 [1966]1403/10).
[20] V. P. Zhuze, A. V. Golubkov, E. V. Goncharova, V. M. Sergeeva .(Fiz. Tverd. Tela
[Leningrad]6 [1964]257/67; Soviet Phys.-Solid State 6 [1964] 205/12).
280/5; lnorg. Materials [USSR] 3 [1967] 251/5).
Kiev 1968 [1970], pp. 173/80; C.A. 76 [1972] No. 7748).
[24] P. G. Rustamov, E. A. Geidarova (Zh. Neorgan. Khim. 29 [1984] 2982/4; Russ. J. lnorg.
Chem. 29 [1984]1706/7).
[25] M. I. Murguzov, A. P. Gurshumov, Kh. V. Kadyrly, et al. (Zh. Neorgan. Khim. 29 [1984]
2965/7; Russ. J. lnorg. Chem. 29 [1984]1695/7).
[26] F. M. Sadygov, P. G. Rustamov (Zh. Neorgan. Khim. 30 [1985] 1339/41; Russ. J. lnorg.
Chem. 30 [1985] 764/5).
[27] P. G. Rustamov, F. M. Sadygov, Ch. I. Abilov (lzv. Akad. Nauk SSSR Neorgan. Materialy
[28] Z. M. Mukhtarova, T. Kh. Kurbanov, 0. M. Aliev (Zh. Neorgan. Khim. 30 [1985] 1332/4;
Russ. J. lnorg. Chem. 30 [1985] 759/60).
[29] G. M. Kuz'micheva, A. E. Voloshin, A. A. Eliseev (Zh. Neorgan. Khim. 30 [1985] 49/55;
Russ. J. lnorg. Chem. 30 [1985]27/31).
[30] U. Köbler, K. Fischer, K. Bickman, H. Lustfeld (J. Magn. Magn. Mater. 24 [1981] 34/42,
36).
30.1.2.1.5 Magnetic Properties

Most of the monotellurides are paramagnetic and many of them are antiferromagneti-
cally ordered at low temperatures. YbTe is diamagnetic (see p. 279). The following table
summarizes the molar susceptibility Xmol in cm 3 /mol at room temperature, Jlel! in Jls, the
paramagnetic Curie temperature ®P in K for the measured temperature range L\T in K, and
the Neel temperature T N in K for the NaCl type cubic monotellurides:
Xmol · 106 Jlel! ep L\T Ref.
CeTe 2.57 -5 2.05± 0.05 [1]

-4 2.15 [2, 3]
2.49 -8 60 to 400 10 [4]
2.49 -7.5 75 to 500 10 (?) [5 to 7]
PrTe 3.45 -26 50 to 400 [5 to 7]
3.72 -18 77 to 300 [23]
Nd Te 3.54 -14 80 to 300 13 [5 to 7, 21]
4810 3.66 -22 100 to 300 [20]
-21 10.6 [22]
3.2 +10 100 to 530 [26]a)
Sm Te 4292 4.33 -248 193 to 473 [8Jb)
4000 3.07 [10]
7150 (T=O) [9]
Gmelin Handbook
RE Main Vol. C10
16 MTe
Xmol · 106 Jleff 0 p LH TN Ref.
Eu Te - 8 [9]
GdTe 26042 7.63 + 17.8 203 to 473 [8, 27]
-84 ~8o [24]
Tb Te 38800 9.6 + 3 140 to 473 [11]
38760 9.57 + 2.7 213 to 473 [8]
-65 63 [12]
DyTe 45977 10.47 -0.5 173 to 473 [8, 13]
10.4 0 80 to 900 [14]
Ho Te 48780 10.50 + 16 108 to 473 [8, 29]
20 [15]
Er Te 34965 9.30 -12 153 to 473 [8, 16]
35628 9.35 - 9 [17]
Tm Te 25641 7.63 +14 158 to 473 [8]C)
4.96 -0.35 1.3to300 0.21 [9, 12, 19]
a) x-data not corrected for diamagnetism. - b) Magnetic moment varies with the temperature.
- c) Superseded; more recently for XmoL values between (8500 and 11500) x 10- 6 cm 3/mol,
JleH = 4.63 J.! 8 , and 0P = -20 Kare reported; see p. 264.
At elevated temperatures ( ~ 500 to 1300 K) the inverse magnetic susceptibility of Ce Te,

PrTe, and NdTe deviates from linearity. The curves agree well with those calculated by Van
Vleck's method for trivalent cations with a screening constant cr = 36 for Ce3+ and Pr 3 +,
Smolenskii et al. [6], Adamyan et al. [18], for PrTe also Smolensky et al. [5], and cr = 34 for
Nd 3 + [6], Adamyan et al. [20]. Whereas CeTe and NdTe undergo antiferromagnetic transitions
near 10 K, PrTe shows no transition down to 4 K. Calculated parameters for the exchange
interaction for three types of antiferromagnetic order in Ce Te and NdTe are given [5, 6].
A type II antiferromagnetic erdering was stated for CeTe by Ravot et al. [1], for NdTe by
Schobinger-Papamantellos et al. (25], for GdTe by Hulliger, Siegrist [28], and for HoTe and
TbTe by Fischer et al. [15]. For (polycrystalline) NdTe a s.econd-order transition from the
paramagnetic to the antiferromagnetic state of MnO-type (fcc II) was reported in [25]; a first-
order transition to tetragonal symmetry at TN = 10.6 K was found by X-ray studies of single
crystals of NdTe 0 98 ± 0 .02 and a further phase transition between unspecified antiferromagnetic
arrangementswas observed at ~9.6 K (see p. 119 for details), Hulliger et al. [22]. The first-
er second-order character of the transitionwas discussed for nonstoichiometric GdTe [28].
The magnetic moment orientation and the associated lattice distortion may depend on the
stoichiometry of the monotellurides. The magnetic moments in Ce Te, like in CeSe, are oriented
along [111] and parallel to the propagation vector k of the magnetic structure. Two possible
spin arrangements, a single-k structure associated with a rhombohedral distortion and a four-k
structure associated with internal distortions are discussed. But no distortions have been
observed in CeTe, Ott et al. [30]; seealso p. 94, and "Rare Earth Elements" C9, 1986, p. 102.
Gmeltn Handbook
RE Matn Vol C 10
The moment orientation in an inhomogeneaus nonstoichiometric NdTe sample at 4.2 K is

along [111], found by neutron diffraction. There was no clear evidence for a rhombohedraL
distortion, Schobinger-PapamanteLLos et aL. [25]. ln nonstoichiometric GdTe the magnetic
moments point in the [111] direction below TN• associated with a rhombohedraL distortion of
the ceLL. At some Lower temperature, dependent on composition, the spins become oriented
along [110]; i.e., by 35.3° out of the [111] direction. Then the ceLL is monoclinic, HuLLiger,
Siegrist [28]; for details see p. 233. ln TbTe the magnetic moments, dependent on composition,
are oriented either along [111], associated with a rhombohedral distortion of the ceLL (see
p. 242), or they are tilted (for example, 78 °for a sample with the analyzed composition Tb 0 _85Te)
out of the [111] direction Like in HoTe (68°). ln this case no marked deviation from cubic
symmetry was detected, Fischer et al. [15]. For EuTe and TmTe, see the individual sections.
Metamagnetic behavior is observed for CeTe, Ravot et al. [1], and in NdTe two field-
induced magnetic phases were found (see p. 120) [22].
References:
[1] D. Ravot, P. Surlet, J. Rossat-Mignod, J. L. Tholence (J. Phys. [Paris] 41 [1980]1117/20).

[2] F. Hulliger, S. Natterer, H. R. Ott (J. Magn. Magn. Mater. 8 [1978]87/98, 93).
[3] H. R. Ott, F. HuUiger, F. Stucki (Conf. Ser. lnst. Phys. [London] No. 37 [1978] 72/8; C.A. 89
(1978] No. 83867).
[4] G. M. Loginov, A. T. Starovoitov, A. V. Golubkov (Fiz. Tverd. Tela [Leningrad] 11 [1969]
3637/9; Soviet Phys.-Solid State 11 [1969] 3053/4).
[5] G. A. Smolensky [Smolenskii], V. E. Adamyan, G. M. Loginov (J. Appl. Phys. 39 [1968]
786/90).
[6] G. A. Smolenskii, V. P. Zhuze, V. E. Adamyan, G. M. Loginov (Phys. Status Solidi 18 [1966]
873/80).
[7] G. A. Smolenskii, V. E. Adamyan, G. M. Loginov (Phys. Letters 23 [1966] 16/7).
[8] A. landelli (Proc. 1st Conf. Rare Earth Res., Lake Arrowhead, Calif., 1960 [1961], pp. 135/41).
[9] A. Jayaraman (in: K. A. Gschneidner, LeRoy Eyring, Handbock on the Physics and
Chemistry of Rare Earths, Vol. 2, North-Holland, Amsterdam 1979, pp. 575/611, 578).
[10] G. V. Lashkarev, E. I. Yarembash, A. Karabekov, N. P. Giletskii (Phys. Status Solidi S 44
[1971] K41/K44).
[11] G. L. Olcese (Atti Accad. Nazl. Lincei Rend. Classe Sei. Fis. Mat. Nat. (8] 30 (1961]
195/200).
[12) E. Sucher, K. Andres, F. J. Di Salve, et al. (Phys. Rev. (3] S 11 (1975] 500/13, 505).
[13] G. L. Olcese (Atti Accad. NazL. Lincei Rend. Classe Sei. Fis. Mat. Nat. [8] 31 [1961]
256/9).
[14] A. V. Pechennikov, B. A. Kupriyanov, V. I. Chechernikov, et al. (lzv. Akad. Nauk SSSR
Neorgan. Materialy 6 [1970] 1528/9; lnorg. Materials [USSR] 6 (1970] 1346/7).
[15] P. Fischer, P. Schobinger-Papamantellos, E. Kaldis, A. Ernst (J. Phys. C 10 (1977]
3601/11).
[16] G. Sruzzone (Atti Accad. NazL. Lincei Rend. Classe Sei. Fis. Mat. Nat. [8] 31 [1961]
260/4).
[17] J. Hoggins, H. Steinfink (lnorg. Chem. 7 [1968] 826/8).
[18] V. E. Adamyan, N. P. Bodrova, A. V. Golubkov, et al. (lzv. Akad. Nauk Arm. SSR 2 [1967]
126/31; C.A. 67 [1967] No. 95240).
[19] E. Sucher, A. C. Gossard, K. Andres, J. P. Maita, A. S. Cooper (Proc. 8th Rare Earth Res.
Conf., Reno, Nev., 1970, VoL.1, pp. 74/89, 89).
Gmelin Handbook 2
RE Mam Vot. C10
18 MTe
[20] V. E. Adamyan, A. V. Golubkov, G. M. Loginov, V. N. Fedorov (Fiz. Tverd. Tela [Leningrad]

7 [1966]3372/7; Soviet Phys.-Solid State 7 [1966]2715/8).
[21) V. E. Adamyan, G. M. Loginov (lzv. Akad. Nauk Arm. SSR 2 [1967)132/6; C.A. 67 [1967]
No. 95244).
[22) F. Hulliger, M. Landolt, R. Schmelczer, I. Zarbach (Solid State Commun. 17 [1974]
751/4).
[23) E. S. Vigileva, A. V. Pechennikov, V. I. Chechernikov, E. I. Yarembash (lzv. Akad. Nauk
SSSR Neorgan. Materialy 4 [1968]1586/7; lnorg. Materials [USSR]4 [1968]1382/3).
[24] T. R. McGuire, R. J. Gambino, S. J. Pickart, H. A. Alperin (J. Appl. Phys. 40 [1969)
1009/10).
[25] P. Schobinger-Papamantellos, P. Fischer, A. Niggli, E. Kaldis, V. Hildebrandt (J. Phys. C
7 [1974] 2023/38).
[26) A. V. Pechennikov, V. I. Chechernikov, E. I. Yarembash, K. A. Zinchenko (lzv. Akad. Nauk
SSSR Neorgan. Materialy 3 [1967]1086/7; lnorg. Materials [USSR]3 [1967)967/8).
[27] A. landelli (Atti Accad. Nazl. Lincei Rend. Classe Sei. Fis. Mat. Nat. [8)30 [1961]201/7).
[28) F. Hulliger, T. Siegrist (Z. Physik B 35 [1979] 81/90).
[29] G. Bruzzone (Atti Accad. Nazl. Lincei Rend. Classe Sei. Fis. Mat. Nat. [8) 30 [1961)
208/13).
[30] H. R. Ott, J. K. Kjems, F. Hulliger (Phys. Rev. Letters 42 [1979]1378/82).
30.1.2.1.6 Mössbauer Spectra

Isomer shift ö and line width r from the 125Te Mössbauer spectra of MTe with M = La, Pr,
and Nd (35.5 keV y transition, source 12sre03 ):
LaTe PrTe NdTe
ö in mm/s . 0.8 ± 0.2 0.8 ± 0.2 1.0 ± 0.2

r in mm/s. ±
6.5 0.2 6.0 ± 0.2 ±
6.5 0.2
Isomer shift ö and quadrupole Splitting~ increase in the M-Te systems with increasing Te
content above about 50 at% Te, as shown in Flg. 2; also the line width r strongly changes
with the Te concentration. The p electrons of the Te atoms participate in the formation of both
the valence band and the conduction band. The alterations of chemical shift and quadrupole
splitting are explained by stereochemical changes and redistribution of the electron density
of the Te atoms, resulting in changes of the energy band character, Gorbachev et al. [1, 2];
seealso Gorbachev et al. [3], lonov et al. [4], Linskii et al. [5]. Values of ö and r in mm/s for
ScTe, YTe, DyTe, and YbTe with respect to Zn Te from the 12sre Mössbauer spectra at 77 K and
obtained values of the characteristic temperatures SM (for Debye temperatures 9 0 see p. 13):
ScTe YTe DyTe YbTe Zn Te
ö ± 0.2. 0.4 0.5 0 1.3 0

r ± 0.2. 11.4 9.5 6.7 7.5 5.9
eM in K. 110 ± 3 115 ± 5 131 ± 6 147 ±6
The natural line width of ZnTe is 2 r = 5.49 mm/s, Zasimov et al. [6].
Gmelin Handbock
RE Mam Vol. C10
Electrical Properties 19
A--
11----
-
E
E 1.8
.5
<33 1.4 ~
E
1.0 ~
at •t. Te
Fig. 2. Isomer shift o (dashed lines) and quadrupole splitting 6

(solid lines) of phases in the
M-Te systems with M =La, Pr, and Nd.
References:
[1] V. V. Gorbachev, V. A. Linskii, S. P. lonov, et al. (lzv. Akad. Nauk SSSR Neorgan. Materialy
13 [1977] 222/6; lnorg. Materials [USSR]13 [1977]188/91).
[2] V. V. Gorbachev, V. A. Linskii, S. P. lonov, et al. (Proc. 5th Intern. Conf. Mössbauer
Spectrosc., Bratislava 1973 [1975], Vol. 1/3, pp. 522/4; C.A. 87 [1977] No. 209117).
[3] V. V. Gorbachev, V. A. Linskii, S. P. lonov, 0. A. Sadovskaya (Khim. Svyaz Krist. lkh Fiz.
Svoistva 2 [1976] 201/8; C.A. 86 [1977] No. 25033).
[4] S. P. lonov, V. V. Gorbachev, V. A. Linskii, 0. A. Sadovskaya, A. Yu. Aleksandrov (Tezisy
Dokl. 5th Vses. Konf. Khim. Svyazi Poluprovodn. Polumetal., Minsk 1974, p. 108; C.A. 83
[1975] No. 139494).
[5] V. A. Linskii, V. V. Gorbachev, 0. A. Sadovskaya (Strukt. Svoistva Termoelektr. Mater. 1973
56/63; C.A. 81 [1974] No. 143951).
(6] V. S. Zasimov, R. N. Kuz'min, A. I. Firov (Stroenie Svoistva Primen. Metallidov Mater. 2nd
Simp., Moscow 1972 [1974], pp. 93/6; C.A. 82 [1975] No. 148000).
30.1.2.1. 7 Electrlcal Properties
The monotellurides with trivalent rare earth cations have low electrical resistivities; they
show metallic or semimetallic behavior. The monotellurides MTe with the divalent cations
M = Sm, Eu, Tm, and Yb exhibit high resistivities and behave as semiconductors. Pressure-
induced valence changes M2 + -+ M3 + due to 4f electron delocalization have been obtained in
SmTe, TmTe, and YbTe; the electronic collapse results in a decrease of resistivity (see for
example Jayaraman et al. [1], Jayaraman (2] and p. 146 for SmTe, p. 273 for TmTe, and p. 280
for YbTe).
Gmelin Handbock 2'
RE Main Vol C10
20 MTe
Electrical resistivity Q in ~Q · cm at room temperature:
La Te Ce Te Pr Te Nd Te
45.9 154 122 200 300 59.2 135 63.7 40 145

[3] [4] [4] [5, 6] [13] [3] [4] [3] [5, 6] [4]
Sm Te Eu Te GdTe TbTe*l DyTe Ho Te Er Te YbTe
2 X 109 >1012 700 1.5X104 134 119 100 7 X 109

[5, 6] [23] [5, 6] [22] [7] [18] [5, 6] [5, 6]
•I The value Q = 1.5 x 10- 4 Q- 1 · m- 1 presented in [22] is obviously a misprint.
Similar values for NdTe, SmTe, and CeTe as in [5, 6] are reported by Matson et al. [8]. The
electrical properties of single crystals and powders are nearly the same, Reid et al. [6]. The
Q values reported by Brixner [9, 10] for the monotellurides of 13 rare earth elements are in
many cases higher than the data tabulated above by several orders of magnitude. lt was
believed by Zhuze et al. [4] that their own measured values (tabulated for MTe with M = La
to Nd) are a little too high due to M 20 3 or oxide telluride impurities. Between T = 300 to
1300 K these monotellurides show metallic behavior, e.g., Q increases linearly with T; see
figures in the paper [4] for CeTe and PrTe. For curves Q = f(T) for PrTe between 100 and
400 K, see Devyatkova et al. [15], for GdTe between 300 and 1100 K, see Reid et al. [17], and
for YbTe between 300 and 700 K, see Miller et al. [5].
Monotellurides, for example NdTe and SmTe, are suitable as resistance devices with
excellent thermal stability [8]. Sc Te and YTe are suitable as thermoelectric material, Brixner
[11]. According to Hull, Hulliger [19] YTe with a lattice constant a = 6.093 A becomes
superconducting between 2.05 and 1.5 K but Matthias et al. [20] observed no superconductivity
down to 1.02 K for YTe with a = 6.120 A. La Te becomes superconducting at 1.48 K, Sucher et
al. [21]. LuTe shows no transition down to 0.35 K [19]. The Seebeck coefficients S of CeTe
(5 ~V/Kat 300 K) and PrTe (2 ~V/Kat 300 K) decrease linearly with increasing T and become
negative above ca. 600 K and slightly above room temperature, respectively (see figures in
the paper) [4]. However, anS versus T plot for PrTe between 100 K (S ~ 0.5 ~V/K) and 450 K
by the same group of authors shows S as ~ 0 at 300 K and a nonlinear dependence above
~ 310 K, where S changes sign; see Devyatkova et al. [15]. Reported values for S in ~V/Kat
room temperature for Ce Te are + 3, Miller et al. [12], 0 to + 1, Hulliger et al. [13], -1, Tyurin
et al. [14], for NdTe ca. -5, for Gd Te -1 to -2, M illeret al. [12, 16], for HoTe - 5.2, Yarembash
et al. [18], for TbTe 168, Rustamov et al. [22].
References:
[1] A. Jayaraman, P. D. Dernier, L. D. Longinotti (High Temp.-High Pressures 7 [1975]
1/28, 6).
[2] A. Jayaraman (in: K. A. Gschneidner, LeRoy Eyring, Handbook on the Physics and
[3] A. V. Golubkov, T. 8. Zhukova, V. M. Sergeeva (lzv. Akad. Nauk SSSR Neorgan. Materialy
Gmelm Handbook
RE Mam Val. C10
Crystallographic Properlies of M3 Te 4 21
[4] V. P. Zhuze, A. V. Golubkov, E. V. Goncharova, V. M. Sergeeva (Fiz. Tverd. Tela

[Leningrad]6 [1964]257/67; Soviel Phys.-Solid State 6 [1964]205/12).
[5] J. F. Miller, E. J. Reid, L. K. Matson, et al. (AD-607082 [1964]1/79, 31, 34; C.A. 62 [1965]
15562).
[6] F. J. Reid, L. K. Matson, J. F. Miller, R. C. Hirnes (J. Phys. Chem. Solids 25 [1964]
969/76).
[7] N. Kh. Abrikosov, K. A. Zinchenko (Redkozemel. Metally lkh Soedin. Mater. Vses. Simp.,
Kiev 1968 [1970], pp. 173/80; C.A. 76 [1972] No. 7748).
[8] L. K. Matson, F. J. Reid, J. F. Miller (U.S. 3270310 [1964/66]1/6; C.A. 65 [1966]16235).
[9] L. H. Brixner (J. lnorg. Nucl. Chem. 15 [1960]199/201).
[10] L. H. Brixner, E. I. Du Pont de Nemours & Co. (Can. 649834 [1960/62] 1/12, 9; C. 1965
No. 41-2217).
[11] L. H. Brixner, E. I. Du Pont de Nemours & Co. (Can. 649835 [1960/62]; C. 1965 No. 41-
2217).
Springs, Colo., 1961 [1962], pp. 233/48, 247).
[13] F. Hulliger, B. Natterer, H. R. Ott (J. Magn. Magn. Mater. 8 [1978] 87/98).
[14] E. G. Tyurin, E. I. Yarembash, V. I. Chukalin (Elektron. Str. Fiz. Svoistva Tverd. Tela Dokl.
7th Vses. Simp. Fiz. Svoistvam Elektron. Str. Perekhodnykh Metal. lkh Splavov Soedin.,
Kiev 1969 [1972], Vol. 1, pp. 156/61; C.A. 79 [1973] No. 59042).
[15] E. D. Devyatkova, V. P. Zhuze, A. V. Golubkov, et al. (Fiz. Tverd. Tela [Leningrad]6 [1964]
430/5; Soviet Phys. Solid State 6 [1964] 343/6).
[16] J. F. Miller, L. K. Matson, J. S. McNulty, R. C. Hirnes (AD-262215 [1960/61]1/49, A3/A4;
N. S. A. 16 [1962] No. 15260).
[17] F. J. Reid, L. K. Matson, J. F. Miller, R. C. Hirnes (J. Electrochem. Soc. 111 [1964]
943/50).
[19] F. Hull, G. W. Hulliger Jr. (Solid State Commun. 8 [1970]1379/82).
[20] 8. T. Matthias, T. H. Geballe, V. 8. Campton (Rev. Mod. Phys. 35 [1963]1/22, 13).
[21] E. Sucher, K. Andres, F. J. di Salvo, et al. (Phys. Rev. [3] B 11 [1975] 500/13).
[22] P. G. Rustamov, F. M. Sadygov, I. I. Aliev (Zh. Neorgan. Khim. 30 [1985] 263/5; Russ. J.
lnorg. Chem. 30 [1985] 148/50).
[23] W. R. Johanson, D. C. McCollum (Phys. Rev. [3] B 22 [1980] 2435/8).
30.1.2.2 Comparative Data for M 3Te 4 and M'M 2Te 4

30.1.2.2.1 M 3Te 4
Existence and Preparation
The M3Te 4 phases with M = La, Ce, Pr, Nd, Sm, Gd, and Dy were obtained. Nearly all of
them form series of solid solutions with M 2Te 3 (see below). For the existence of Eu 3 Te 4 see
the Eu-Te system, p. 158 and EuTex with x > 1, p. 229. The compounds M 3Te 4 are prepared
fromM+ Te vapor in the samemanneras the M 2Te 3 compounds; for details see p. 31 and,
for example, Miller et al. [1], Mularz, Wolnik [2].
Crystallographic Properlies
Tellurides M 3Te 4 with M = La, Ce, Pr, Nd, and Sm have the cubic Th 3 P4 structure, space
group 143d-T~ (No. 220), Z = 4, analogaus to the sulfides and selenides; see, e.g., Flahaut,
Gmelin Handbook
RE Main Vol. C 10
22
Laruelle (3], and "Rare Earth Elements" C9, 1986, pp.35/6. Computer calculation of cation
vacancies in Nd 3Te 4 and Sm 3Te 4 have been reported by Kutolin et al. [32].
Lattice constants a in A and observed interatomic distances M-Te and Te-Te in A:
La3Te 4 Ce 3Te 4 Pr3Te 4 Nd 3Te 4 Sm 3Te 4 Ref.
a 9.634 9.540 9.487 9.438 9.506 [4, 5]

a 9.624 9.528 9.433 [2]
a 9.566 9.4557 [1' 6]
M-Te. 3.33 3.30 3.28 3.26 3.285 (5]
Te-Te 3.58 3.54 3.52 3.51 3.53 [5]
The lattice constants a = 9.511 ± 0.002 and a = 9.494 A were found for Sm 3Te 4 by Yarembash,
Karabekov [15] and Sugita et al. [33], respectively.
The M-Te distances are greater and the Te-Te distances smaller than the calculated values
for ionic bonding, Lashkarev, Paderno [5], Miller et al. [1, 6]. The covalent bond character is
calculated tobe 47.2% for Ce 3Te 4 and 49.5% for Nd 3Te4 [1, 6]. M 3Te4 with M = La to Nd form
a series of cubic solid solutions with y-M 2Te 3 [3]. ln the case of M = Sm the solid solution
range is said to range only from SmTe1.33 to SmTe1.38 in samples quenched from 1000°C [3,
4]. Gd3Te4 has the orthorhombic Sb 2S3 structure (see under TJ-M 2Te3 , p. 34), Eliseev [34], and
forms solid solutions with TJ-Gd 2Te 3 [1] (see p. 231), whereas Dy3Te 4 has the orthorhombic
Sc2S3 structure (see under 1;-M2Te 3, p.34) and forms solid solutions with 1;-Dy2Te 3 [18]; see
p.243.
Fora comparison of the structure types and lattice constants of M 3Te 4 with those of M 3Se 4
and M 3S4 , see [34].
Density and Microhardness
Measured and calculated density Dexp and Deale in g/cm 3 :
Dexp 6.6 6.7 6.8 7.38 7.28

Deale 6.92 6.91 7.15 7.12 7.31 7.47 7.46 7.42 7.33
Ref. [2] [7] [2] [7] [7] [2] [7] [15,36] [18]
The microhardness of fused polycrystalline M3Te4 samples is 380 kg/mm 2 (3.80 GPa) for M =
La, Ce, Nd [7] and 330 kg/mm 2 forM = Pr [7] and Gd [17].
Gmelin Handbook
RE Main Vol. C10
Thermal Properties 23
Melting Point tm in °C
La3 Te4 Ce3Te4 Pr3Te4 Nd3Te4
tm 1525 1515 ± 25 1645 1700 1650 1680 1660*) ± 15 1465*)

Ref. [8, 9] [10] [8, 9, 11] [8, 9] [8, 9] [1, 12] [13] [14]
Sm 3Te4 Eu 3Te4 Gd3Te4 Dy3Te4
tm . 1680 ±so·> -1500 1255*) -1410 1570

Ref. [15] [16] [17] [1] [18]
•> lncongruent.
lncongruent melting points for La3Te4 (1515°C), Ce3 Te4 (1550°C), Pr 3Te4 (1577°C), and Nd3Te4
(1660°C) are tabulated in Gordienko et al. [37], based on the data assembled by Yarembash,
Eliseev [36].
Heat Capaclty, Entropy, and Debye Temperature

The heat capacity CP at 80 to 400 K was measured for cubic M 3Te4 samples (M = La, Ce,
Pr, Nd) which were prepared by melting the synthesized powders. La3Te4 was single phase ;
the other compounds were contaminated with a second phase. Fig. 3 shows the temperature
dependence of CP and of the Schottky contribution (Cschl· This component is associated with
the transition of the 4f electrons to higher energy Levels which arise from the splitting of the
ground state of the M 3 + ions by the crystal field of the lattice. The Schottky contribution was
obtained as the difference between the total CP values of M3 Te4 and La3Te 4 , which contains
no 4f electrons, assuming an estimated value of the electronic contribution to the heat capac-
ity of - 1 cal · mol- 1 · K - 1 for all compounds and no magnetic contribution . The plot of
Ln (Csch · T2 ) vs. r - 1 for Ce3Te4 and Pr3Te4 arestraight lines, giving a splitting between ground
state and nearest excited Level of 500 ± 40 K for Ce 3Te 4 and 400 ± 30 K for Pr3Te4 . lt follows
from the temperature dependence of Csch for these two compounds that there are some still
higher energy states to which the 4f electrons are able to pass (but see below [21]) . The
12
a) b)
~ SOt----1-------"IV'S~' ~
ö
E ~ 8
~ ~~--~~~~~~--+-~~-W 8
.!: .s 4
J
Q.
u
400 00 400
Temperature in K Temperature in K
Fig. 3. Molar heat capacity CP of M 3Te4 with M =La, Ce, Pr, and Nd (Fig. 3a) and Schottky
contribution Csch of M 3Te4 with M = Ce, Pr, and Nd (Fig. 3b) versus temperature.
Gmelin Handbook
RE Main Vol. C10
24
Temperature in K Tempereture in K
Fig. 4. Molar heat capacity CP of La 3Te 4 and Pr 3Te 4 down to 5 K (Fig . 4a) and Schottky contribu-
tion Csch of Pr3Te4 (Fig. 4b) versus temperature (solid line calculated) .
character and magnitude of the splitting of the 4 1912 term in Nd 3Te 4 is nearly the same as in
Nd2S3 , Tikhonov et al. [20). The heat capacity of La3Te4 and Pr 3Te 4 was also measured from
273 K down to 5 K and the results are shown in Fig. 4a. The samples containing traces of
oxide telluride by synthesis were handled under inert gas to avoid further oxidation . The
electronic component Cet was estimated to be ~ 0.4 cal · mol- 1 · K - 1 at 273 K. The ex-
perimental Schottky contribution Csch for Pr3Te 4 from a comparison with La 3Te4 , shown in
Fig . 4b, agrees satisfactorily with that calculated by the point-ion model with three parameters,
i.e. , when ignoring the effect of the outer shells on the crystal field acting on the 4f Ievels
which , however, might be strong in view of the degree of covalency. Theoretical parameters
and energy Levels for Pr3Te4 obtained in the point-ion model for groups of 61 (a) and 57 (b)
experimental points between 5 and 273 K and 5 and 150 K , respectively, are given below ; x
is the purely theoretical parameter of the coordinate ofTein the Th 3 P4 type structure and ( r")
with n = 2 and 4 are the mean radius steps of the orbit of the 4f electron :
a 0.115 0.0439 0.744 0, 27.5, 88.2 *), 113.5, 332, 338*), 345
b 0.114 0.0440 0.734 0, 28.4, 90.5 *), 113.9, 328, 337 *), 348
•l Doublet.
A study of the entropy change associated with the Schottky effect in Pr3Te4 Leads to th e
conclusion that magnetic ordering does not occur in the temperature range investigated ,
Mitarov et al. [21] . The higher CP values found in the earlier work [20] were evidently due to
a partial oxidation of the tellurides during preparation and measurements [21]. (lt possibly
explains the different course of the Csch versus T curves for Pr3Te4 . )
The Debye temperatures 9 0 = 175 K for La 3Te4 and 9 0 = 125 K for Nd 3Te4 were deter-
mined at 100 K, Ti khonov [35] . Additional values for La 3Te4 are given on p. 74.
Gme!m Hand book
RE Mam Vo! C 10
Values of A. (in W · m- 1 · K- 1) at room temperature:
La3Te4 Ce 3Te 4 Pr3Te4 Nd 3Te 4 Gd 3Te4 Dy 3Te4 Ref.
8.5*) 1.1 8.6 [8, 9, 29]

3.6 2.6 [7]
4.13 [17]
3.1 1.9 3.8 2.2 [2]
•l ln a later work [28] the total thermal conductivity of Ce 3Te 4 was given as A. = 0.85 with the
lattice part Ata1 = 0.80 and the electronic part A.91 = 0.05.
Values for various polycrystalline samples, obtained from melts, at 300 K (A.Lat = A.- A.91):
La3Te4 Nd 3Te4
A. 3.60 2.98 2.68 2.60 4.73

Atat · 1.48 1.65 1.72 1.02 1.88
Ael · 2.12 1.33 0.96 1.59 2.85
Ref. [19] [19] [19] [19] [30]
A pressed powder sample of Nd 3Te 4 had A. = 75 W · m- 1 · K- 1 (= 0.18 cal· cm- 1 · s- 1 · K- 1),

Zinchenko et al. [31].
Magnetic Properlies
Magnetic susceptibility XA in 10- 6 cm 3/g-atom M at room temperature:
Yarembash [8, 9]. The reciprocal magnetic susceptibility for M3Te4 with M = Ce, Pr, Nd
between 80 and 1000 Kin static fields up to 15 kOe is shown in Fig. 5, p. 26. Below 300 K the
Curie-Weiss law is obeyed with SP = -15, +2, and +30 K and lleff = 2.53(2.56), 3.54(3.62),
and 3.44(3.68) lls· respectively (theoretical values for M3+ in brackets). Deviations from this
law above 300 K (equations are given in the paper) can be explained by an increase in the
contribution of the higher Levels of the multiplet state 2 F512 (Ce), 3 H4 (Pr), or 4 1912 (Nd), Loginov,
Sergeeva [22].
The magnetic susceptibility of Sm 3Te4 measured between 1.73 and 300 K is nearly the
same as for Sm 3Se 4 and Sm 3S4 (see "Rare Earth Elements" C7, 1983, Fig.237, p.411). The
magnetization was measured in pulsed fields up to 380 kOe at 1.3 K and in static fields up to
95 kOe at 1.6 and 4.2 K. The magnetization first increases gradually up to 100 kOe and then
increases rather linearly up to 380 kOe (see figurein the paper). Saturation is indicated below
1.6 K, suggesting a kind of antiferromagnetic ordering; SP is -1.5 K. The susceptibility results
are discussed in terms of crystal field splitting. The main effective crystal field is cubic with
r 7 lower. The moment corresponding to the Curie term, obtained by subtracting all the Van
Vleck terms from the high-field magnetization, never shows saturation and is substantially
Gmelin Handbock
RE Main Val. C10
26
"'e
~
§ 800·~----+---~-r-----i
?01
c:
· - <( 4001---+-+--..-:z...-:
~
1200
Temperature in K
Fig. 5. Reciprocal magnetic susceptibility of Ce 3 Te 4 , Pr 3Te 4 , and Nd 3Te 4 versus temperature.
smaller than the saturation value even at 380 kOe. This result is explained by assuming a
field-dependent exchange constant. Such unusual behavior seems to strongly indicate the
existence of some kind of partial quantum tunneling valence fluctuation at Lowest temper-
atures, Sugita et al. [33].
Mössbauer Effect
Values for the chemical shift 8 and the Line width r from the 125Te Mössbauer spectra
(35.5 keV y transition , source 125Te0 3 ) :
8 in mm/s . 0.9 ± 0.2 0.9 ± 0.2 1.10±0.2

r in mm/s. 2.7 ± 0.2 6.6 ± 0.2 7.60 ± 0.2
Gorbachev et al. [26] . The chemical shift and quadrupole splitting ~ of M 3Te 4 (57.2 at% Te)
are compared in Fig . 2, p.19, with those of other compounds in the M-Te systems (M = La ,
Pr, Nd) , Gorbachev et al. [26, 27] .
Electrical Properlies
Mössbauer studies on M 3Te 4 (M = La, Pr, Nd) indicate that 5p electrons of the Te atoms
participate in the formation of both the valence band and the conduction band. The width of
the forbidden zone is ~E = 1.1 (La 3Te4 ), 1.2 (Pr 3Te 4 ), and 1.4 eV (Nd 3 Te 4 ), Gorbachev et al.
[26]. Transport phenomena in M 3Te 4 (M = La, Ce, Pr, Nd) up to 900 K can be interpreted in
that the bottarn of the conduction band is mainly formed from 6s (rather than 5d) states of the
metal, Zhuze et al. [7], without participation of 4f states, Zhuze et al. [19]. The shape of the
Fermi surface is virtually spherical. The Fermi Level Lies several tenths of an electron volt
above the bottarn of the conduction band (0.4 to 0.6 eV is given in the text, but 0.25 to 0.30 eV
in a table) [7]. Peculiarities of the temperature dependence of the thermoelectric power above
900 K might be due to complications of the band structure at high energy Levels or they are
due to the effect of a second phase [19].
Gmelin Handbock
RE Main Vol. C 10
Electrical Properlies 27
The M3Te4 studied (M = La to Nd [7], La to Nd and Dy [2], M = Nd, Gd [1, 24]) are
semiconductors of the n-type as is indicated by the negative sign of the thermoelectric power
[1, 2, 7, 24] and of the Hall coefficient [1, 24], but they are severely-degenerate semiconductors
[7]. For data on Sm3Te4 and Eu3Te4 see pp. 156 and 230, respectively.
The following table is a compilation of room temperature data of the electrical resistivity
Q in t-tfl · cm, the thermoelectric power S in 1-1V/K, the Hall mobility 1-1 in cm 2 · v- 1 · s-1, the
carrier concentration n in cm- 3 , the figure of merit Z = S2 · K · A. - 1 in 10- 4 K-1, and the
effective electron mass m*/m:
Q s ll n z m*/m Ref.
La 3Te 4 340 -30 11.5 1.7 X 1021 1.8 [7]

450 -27 0.51 [2]
910 -30 0.32 [2]
2300 -15 9 X 1020 [26]
Ce 3Te 4 526 -26 4.2 2.8 X 1021 2.1 [7]
1800 -40 0.047 [2]
Pr3Te4 590 -26 6.2 1.7 X 1021 1.6 [7]
2500 -28 1.1 X 1021 [26]
Nd 3Te 4 350 -20 [1, 23 to 25]
450 -23 5.0 2.8 X 1021 2.0 [7]
890 -31 0.29 [2]8)
3200 -36 9.3 x1020 [26]
Gd 3Te4 460 [1, 23 to 25]
850 -20 7.1 1.04 X 1021 [17]
Dy3Te4 3100 -49 0.35 [2]
"Er3Te 4 "b) 280 [1, 23 to 25]
a)Sampie has 91% of theoretical density. - b) Er3Te 4 does not exist in the Er-Te system; see
p.247.
ln Fig. 6, p. 28, is presented the electrical conductivity K and the Seebeck coefficient S of
La3Te4 , Ce 3Te4 , and Pr3Te4 between room temperature and 1800 K. Regarding the high-
temperature behavior of S it was found that the more inclusions the samples contained, the
lower was the temperature at which S began to depart from linearity [19].
A linear rise of Q and ISI with increasing temperature for La3Te4 between 100 and 1400 K
as weil as of ISI for Nd3Te4 between 300 and 1400 K (whole temperature ranges studied) was
found by [7]. Plots of Q vs. 1/T for Nd3Te 4 and Gd 3Te4 between 300 and -1200 K are also
shown in figures in [1, 24].
Values for S, the conductivity K, and figure of merit Z at T = 1200 to 1400 K [7]:
La3Te4 Nd 3Te 4
Tin K . 1200 1300 1400 1200 1300 1400

-S in 1-1V/K 122 132 142 116 126 136
Kin Q- 1 · cm- 1. 960 900 860 800 740 700
Z in 10- 4 K- 1 4.0 4.4 5.0 4.0 4.5 5.0
Gmelin Handbock
RE Main Vol. C10
28
1--'-<:-)~'------"+----+----+-----; 1600 ,
E
u
b:
.!:
~--~~~~~~---~----~ 800 ~
0300 700 1100 1500

Tempereture in K
Fig . 6. Electrical conductivity K and Seebeck coefficient S of La3Te4 , Ce3Te4 , and Pr3Te 4 versus
temperature.
The ratio Jll lld (= 1.7 to 2.7), where lld is the dritt mobility, is larger in the tellurides than
in the sulfides and selenides (7] . For the electrical (especially thermoelectric) properties, see
also the review of Wood [38].
References:
[1] J. F. Miller, F. J. Reid, L. K . Matson, et al. (AD-607082 [1964]1 /79, 6/22, 16, 35, 42 ; CA.
62 [1965]15562).
[2] W . L. Mularz, S. J . Wolnik (Proc. 3rd Conf. Rare Earth Res., Clearwater, Fla. , 1963 (1964],
pp. 473/ 9) .
[3] J . Flahaut, P. Laruelle (Progr. Sei. Techno!. Rare Earths 3 (1968]1 49/208, 169/72).
[4] M.- P. Pardo, J. Flahaut, L. Domange (Campt. Rend . 256 [1963]1793/6).
[5] G. V. Lashkarev, Yu. B . Paderno (lzv. Akad . Nauk SSSR Neorgan. Materialy 1 (1965]
[6] J. F. Miller, L. K. Matson, R. C.Hirnes (Proc. 3rd Conf. Rare Earth Res., Clearwater, Fla.,
1963 [1964], pp. 135/46).
[7] V. P. Zhuze, V. M . Sergeeva, 0 . A . Gotikova (Fiz. Tverd. Tela [Len ing rad] 11 [1969]
2568/76 ; Soviet Phys.-Solid State 11 [1969]2071 /7).
[8] E. I. Yarembash (Colloq. Intern. Centre Natl. Rech. Sei. No. 180 [1969/70] 471/81, 477).
[9] E. I. Yarembash (Therm. Anal. Proc. 2nd Intern. Conf. , Worcester, Mass., 1968 [1969],
Vol.2, pp. 761 /77 , 768 ; CA. 73 [1970] No. 124092).
[10] T . H. Ramsey, H.Steinfink, E. J. Weiss (lnorg . Chem. 4 [1965]1154/7).
[11] V. I. Chukalin , E. I. Yarembash, A. I. Villenskii (lzv. Akad . Nauk SSSR Neorgan. Materialy
3 [1967]1538/ 45 ; lnorg. Materials [USSR] 3 [1967]1341/7).
[12] W. Lin, H. Steinfink, E. J .Weiss (lnorg. Chem . 4 [1965]877/81).
[13] K . A . Znchenko,
i N. P. Luzhnaya, E. I. Yarembash, A. A. Eliseev (lzv. Akad . Nauk SSSR
Neorgan. Materialy 2 [1966]1 747/56 ; lnorg. Materials [USSR]2 [1966]1506/ 14).
[14] N. Kh. Abrikosov, V. Sh. Zargaryan (lzv. Akad . Nauk SSSR Neorgan . Materialy 1 [1965]
1462/7; lnorg. Materials [USSR]1 [1965]1335/ 9).
Gm elon Handbook
RE Matn Val C 10
References 29
[15] E. I. Yarembash, A. Karabekov (Tr. Frunz. Politekhn. lnst. No. 41 [1970] 49/63, 52).
[16] 0. A. Sadovskaya, E. I. Yarembash (lzv. Akad. Nauk SSSR Neorgan. Materialy 6 [1970]
1252/6; lnorg. Materials [USSR]& [1970] 1097/101).
Materialy 6 [1970]720/5; lnorg. Materials [USSR]& [1970]634/8).
[19] V. P. Zhuze, 0. A. Golikova, V. M. Sergeeva, I. M. Rudnik (Fiz. Tverd. Tela [Leningrad]
[20] V. V. Tikhonov, M. V. Romanova, I. A. Smirnov, V. M. Sergeeva (Fiz. Tverd. Tela
[21] R. G. Mitarov, V. V. Tikhonov, L. N. Vasil'ev, et al. (Fiz. Tverd. Tela [Leningrad]17 [1975]
[22] G. M. Loginov, V. M. Sergeeva (Fiz. Tverd. Tela [Leningrad] 12 [1970] 2723/5; Soviet
Phys.-Solid State 12 [1970] 2191/2).
[23] J. F. Miller, L. K. Matson, R. C. Hirnes ·(AD-428091 [1963]14; Proc. 2nd Conf. Rare Earth
Res., Glenwood Springs, Colo., 1961 [1962], pp. 233/48; C.A. 61 [1964]1359).
943/50).
[25] F. J. Reid, L. K. Matson, J. F. Miller, R. C. Hirnes (CONF-68-3 [1963]1/4; N.S.A. 17 [1963]
No. 34469).
[26] V. V. Gorbachev, V. A. Linskii, S. P. lonov, 0. A. Sadovskaya, A. Yu. Aleksandrov (lzv.
Akad. Nauk SSSR Neorgan. Materialy 13 [1977]222/6; lnorg. Materials [USSR]13 [1977]
188/91).
Svoistva 2 [1976]201/8; C.A. 86 [1977] No. 25033).
7th Vses. Simp. Fiz. Svoistvam Elektron. Str. Perekhodnyk Metal. lkh Splavov Soedin.,
Kiev 1969 [1972], Vol. 1, pp. 156/61; C.A. 79 [1973] No. 59042).
[29] E. I. Yarembash, E. S. Vigileva (lzv. Akad. Nauk SSSR Neorgan. Materialy 6 [1970]
1572/8; lnorg. Materials [USSR]& [1970]1388/93).

Neorgan. Materialy 2 [1966]1747/56; lnorg. Materials [USSR]2 [1966]1506/14, 1512).
Chem. 56 [1982]606/8).
[33] M. Sugita, S. Kunii, K. Takegahara, et al. (Cryst. Electr. Field Eff. f-Electron Magn. Proc.
4th Intern. Conf., Wroclaw 1981 [1982], pp. 479/84; C.A. 98 [1983] No. 82452).
[34] A. A. Eliseev (Zh. Neorgan. Khim. 30 [1985] 1111/20; Russ. J. lnorg. Chem. 30 [1985]
627/33).
[35] V. V. Tikhonov (in [7]).
[36] E. I. Yarembash, A. A. Eliseev (Khal'kogenidy Redkozemel'nykh Elementov, Nauka,
Moscow 1975, pp. 1/260, 169/256).
[37] S. P. Gordienko, B. V. Fenochka, G. Sh. Viksman (Termodynamika Soedinenii Lan-
tanoidov, Naukova Dumka, Kiev 1979, pp. 1/373, 18/9).
[38] C. Wood (Energy Convers. Manage. 24 [1984] 331/43).
Gmelin Handbock
RE Main Vol. C10
30
30.1.2.2.2 M'M2Te 4
(M ' =Sm, Eu, Yb; M = a lanthanide other than M' )
The compounds YbEu 2Te4 , YbGd 2Te4 , SmYb2Te4 , and EuYb 2Te4 were prepared from the
elements in vacuum-sealed quartz ampules at 400 °C and then annealed at 800°C, Eliseev et
al. [1]. The compounds EuM 2Te4 with M =La, Ce, Sm, Ho, Er, and Yb were obtained similarly
or by heating EuTe + M 2Te3 in a vacuum. Graytoblack needle-like single crystals with M =
Sm, Gd, Ho, Er, and Yb formed by crystallization from melts of alkali-metal salts, Sadovskaya
et al. [2]. For attempts to prepare other phases, see below.
EuLa2Te4 , EuCe2Te4 [2], YbEu 2Te4 , YbGd 2Te4 , and SmYb 2Te 4 have the orthorhombic Sc2S3
structure, space group Fddd-D~~ (No. 70) [1]. The EuM 2Te4 with M =Sm, Gd, Ho, Er, and Yb
are trigonal, space group P321-D~ (No. 150). This EuEr2Te4 structure type can be derived from
the NaCl type (see the paper). Fig. 7 shows the change of lattice constants along the series.
The absence of breaks in these plots indicates that the M ions are all trivalent [2) . Earlier,
EuYb 2Te4 was found tobe of the orthorhombic Sc2S3 type [1]. Attempts to prepare EuM 2Te 4
and YbM 2Te4 with other rare earth elements M Lead to a mixture of two phases with Sc 2S3 and
NaCl structures for YbM 2Te4 with M = Dy, Er, Lu [1] and (presumably) EuM 2Te 4 with M = Pr,
Nd, and Dy [2) . ln the case of YbLa2Te4 , the formed phases had cubic Th 3 P4 and NaClstructures,
respectively. The paper discusses attempts to predict the structure of AB2X4 compounds with
X= chalcogen from the ionic radii and the electronegativities [1).
7.74 11.91
·~
7.73 .... 11.89
«
.E
c 7.72
~ K 11.87
«
~
u
7.71
~ ~
~
11.85
Sm3·
'j'
Gd:~- ~E~ Vb3"
1.10 1.08 1.04 1.03 101
Fig. 7. Lattice constants of trigonal EuM 2Te 4 versus ionic radius rM3+.
The EuM 2Te4 compounds are p-type semiconductors. Electrical resistivities Q at 77 and
300 Kare: 46.8 and 14.7 n · cm for EuLa 2Te4 ; 93.8 and 11 .8 n · cm for EuSm 2Te4 . Similar values
at room temperature (10 1 n · cm) were also found for EuM 2Te4 with M = Ce, Ho, Er, and Yb.
ln all these compounds Q falls to - 10- 1 n · cm as the temperature is increased to - 800 to
850 °C (for EuYb 2Te4 to - 550 to 570°C). Atthese temperatures the compounds decompose as is
indicated by the sudden Q-rise afterwards (see a figurein paper) and confirmed by differential
Gmelon Handbook
RE M am Val. C 10
31
thermal analyses. The Hall mobilities lie in the range 0.1 to 0.7 cm 2 · v- 1 · s- 1 at 300 K. Values
for the Seebeck coefficient S at 300 K are:
M in EuM 2Te4 La Ce Sm Ho Er Yb
S in J.!VIK . . 220 170 400 440 180 190
Sadovskaya et al. [2)
References:
[1) A. A. Eliseev, G. M. Kuz'micheva, A. K. Belostotskii (Zh. Neorgan. Khim. 25 [1980) 895/9;

Russ. J. lnorg. Chem. 25 [1980] 498/500).
[2) 0. A. Sadovskaya, G. M. Kuz'micheva, V. A. Tolstova, et al. (Zh. Neorgan. Khim. 30 [1985)
2512/6; Russ. J. lnorg. Chem. 30 [1985)1431/4).
30.1.2.3 Comparative Data for M2Te 3
30.1.2.3.1 Preparation
The single suitable method to prepare the rare earth tellurides is the slow reaction of the
elements in sealed evacuated quartz ampules, Flahaut, Laruelle [1). To avoid a violent
reaction, a solid-vapor reaction is used by Miller et al. [2 to 5], Reid et al. [6), Mularz, Wolnik
[7], and Muir [11]. The rare earth metal filings and Te are placed separately in a Vycor tube.
The temperature is slowly increased to 950°C over a period of 24 h and is held at this Level
for an additional 72 h. The granular reaction product is then melted down in an inductively
heated graphite or Ta container under Ar at 1 atm pressure [2, 3). A directional crystallization
of the melts in Ta containers is applied by [4, 5]. The solid-vapor reaction, the melting, and
the crystallization are carried out in the same container by using a cylindrical closed graphite
crucible inside an evacuated quartz tube. The stoichiometric amounts of the components are
slowly heated up to 700°C and held at this temperature until the brown Te vapor disappears.
After the following slow heating of the tubein a horizontal induction furnace above the melting
point of the tellurides the crystallization takes place in a vertical furnace by lowering the tube
at 8 mm/h [7).
Single crystals of M2Te 3 with M = La, Ce, Pr, Nd are prepared from the polycrystalline
material (prepared by melting in graphite crucibles at temperatures up to 1800°C) by a
chemical transport reaction with iodine as the carrier gasinan evacuated quartz ampule with
two temperature zones (900 ->650°C, ratio 12 :M 2Te 3 = 0.09 to 0.37 by weight). While the M2Te 3
crystals form near the M 2Te 3 source at approximately 900°C (it takes two weeks for growth of
large, regular crystals), MTe2 crystals up to 4 x 2 x 1 mm3 appear within 1 to 2 days in the
middle of the ampule at temperatures between 700 and 830°C, Bro [8). The transport reaction
MI + Te 2 -> I + M2Te 3 and MTe2 proceeds via Ml 3 and MI. To prepare LaTe 2 in this way, the
iodine concentration is 5 mg/cm 3 , the temperature gradient 950-> 800°C, and the transport
time 100 h, Luzhnaya et al. [9]. The conditions for preparing Sc 2Te 3 single crystals are:
1050->950°C, 1.15 mg 12 per cm 3 (~0.45 atm), and a transportrate of 7.9 J.LmoVh, Dismukes,
White [10]; for needles of Gd 2Te3 the conditions are: 950->850°C, traces of 12, 144 h; with a
high 12 concentration large platelets of GdTe2 form at this temperature gradient in 260 h [4).
According to Agaev, Sharifov [12] crystals of Gd 2Te3 are obtained in :;;:;: 200 hat a 12 concentration
Gmelin Handbock
RE Main Vol. C10
32
< 12 mg/cm 3 , M = 140°C, and starting with 1 to 1.5 g Gd 2Te 3 . The yield on Gd 2Te 3 crystals
increases from about 35 to 85% with increase of the 12 concentration from 3 to 12 mg/cm 3 . At
> 12 mg/cm 3 polycrystalline products form [12]. The transport occurs at ~1150 K (~877°C).
The calculation of the equilibrium constant of the transport reaction shows that the critical
temperature is ~ 1120 K (change of sign) Agaev, Sharifov [13]. Films of Tm 2Te 3 were prepared
by thermal evaporation of powdered Tm 2Te 3 from W boats in a vacuum chamber at 1300 K
using cold Substrates of glass, NaCl, or celluloid films. The initialamorphaus layers became
polycrystalline after 3 h heating in vacuum at 700 K, Krylov et al. [14].
References:
[1] J. Flahaut, P. Laruelle (Progr. Sei. Technol. Rare Earths 3 [1968]149/208, 149/50).
[2] J. F. Miller, F. J. Reid, R. C. Hirnes (J. Electrochem. Soc. 106 [1959]1043/6).
[3] J. F. Miller, R. C. Hirnes (Proc. 1st Conf. Rare Earth Res., Lake Arrowhead, Calif., 1960
[1961], pp. 232/40).
[4] J. F. Miller, F. J. Reid, L. K. Matson, et al. (AD-607082 [1964]1/79, 6/14; C.A. 62 [1965]
15562).
[5] J. F. Miller, L. K. Matson, R. C. Hirnes (Proc. 2nd Conf. Rare Earth Res. Glenwood Springs,
Colo., 1961 [1962], pp. 233/48, 234/7).
943/50).
[7] W. L. Mularz, S. J. Wolnik (Proc. 3rd Conf. Rare Earth Res., Clearwater, Fla., 1963 [1964],
pp. 473/9).
[8] P. 8ro (J. Electrochem. Soc. 109 [1962]1110).
[9] N. P. Luzhnaya, E. I. Yarembash, Z. S. Medvedeva (Vestn. Akad. Nauk SSSR 1965 No. 10,
pp. 49/54; C.A. 64 [1966]4406).
[10] J. P. Dismukes, J. G. White (lnorg. Chem. 4 [1965] 970/3).
[11] H. M. Muir (AD-277043 [1960/61]1/47, 2/4; N.S.A. 17 [1963] No. 11292).

[12] A. 8. Agaev, K. A. Sharifov (Dokl. Akad. Nauk Azerb. SSR 26 [1970]8/11; C.A. 75 [1971]
No. 11308).
[13] A. 8. Agaev, K. A. Sharifov (Uch. Zap. Azerb. Gos. Univ. Ser. Khim. Nauk 1973 No. 4,
pp. 47/50; C.A. 83 [1975] No. 33710).
[14] V. S. Krylov, S. V. Shchegol'kov, K. A. Agaev, A. E. 8akhyshov (Uch. Zap. Azerb. Gos.
Univ. Ser. Fiz. Mat. Nauk 1975 No. 4, pp. 70/4; C.A. 85 [1976] No. 115262).
30.1.2.3.2 CrystaLLographic Properties. Density
For the crystal field splitting see p. 40.
Polymorphism
The sesquitellurides M 2Te 3 occur in several structure types which are designated with the
Greek letters y, 11. and ~- For the existence of europium telluride Eu 2Te 3 , see p. 158 (Pm 2Te 3
has not been studied). The cubic y form, with the Th 3 P4 structure, is observed for M 2Te 3 with
M = La, Ce, Pr, and Nd. The orthorhombic 11 form, of the U2 S3 structure type, is observed for
M = Nd, Sm, and Gd. To the orthorhombic ~form, with the Sc 2S3 structure, belong the M 2Te 3
with M = Y, Tb to Lu. Only Sc 2Te 3 (see p. 63) occurs in a unique rhombohedral structure,
Flahaut [1, 2], Flahaut, Laruelle [3]. According to Flahaut et al. [12], Yb 2Te 3 does not exist.
Gmelm Handbock
RE Mam Val C 10
Also in Yb-Te phasediagram studies Yb 2Te 3 was not observed (see p. 278), but its existence
is mentioned by others; see p. 287. lt is assumed by Eatough et al. [4] that M2Te 3 with M = Y
and Gd to Lu can also be obtained in the y form by application of high pressure (analogous
to the sulfides), because of the higher density of the cubic forrn (see p. 35). Probably y-Sm 2Te 3
exists above 640°C; see the Sm-Te system, p. 128.
Eliseev, Kuz'micheva [16] compare the unit cells of the M2Te 3 modifications with those of
the cubic MTe compounds (lattice constant a0 ), from which the lattice constants are
approximately a simple multiple of k, with k = (a 0/2) V2-
For comparison of structure types
and lattice constants of M2Te 3 with those of M2S3 and M 2Se 3 , see Eliseev [19]. A computer-
aided prediction of the crystal structure of rare earth element chalcogenides on the basis of
the electronic structure of the components and compound composition is given by Kutolin et
al. [22].
Some of the sesquitellurides form solid solutions with M3Te4 , others possibly with MTe;
see p. 22, p. 9, and in the individual sections.
Structure of the y Form
The cerium group elements La, Ce, Pr, and Nd possess a defective cubic Th 3 P4 structure.
Space group 143d-T~ (No. 220). The body-centered cubic cell contains 16 Te atoms and 102 / 3 M
atoms ( = 4 M813 D 113Te 4 ); i.e. Z = 16/ 3 M 2Te 3 . The 10% M atoms are statistically distributed on
12 equivalent sites and on the average every ninth cation site is vacant. The coordination
number of M is 8. The structure was investigated for the y-M 2S3 ; see "Rare Earth Elements"
C7, 1983, p.84 and Fig.2 in "Rare Earth Elements" C9, 1986, p.36. Lattice constants a in A for
y-M 2Te 3 :
La 2Te 3 Ce 2Te 3 Pr2Te 3 Nd 2Te 3 Ref.
9.627 9.539 9.485 9.438 [5]

9.627 9.539 9.481 [6, 7]
9.618 9.535 9.482 9.435 [8]
9.62 9.55 9.4389 [9, 10]
The lattice constants decrease nearly linearly with decreasing ionic radii from La to Nd.
Extrapolating to Sm gives a = 9.32 A. For quenched Sm Tex samples (from 1 000°C) with X =
1.33 to 1.50 the lattice constant decreases from a = 9.506 A (x = 1.33) to ~ 9.479 ± 0.006 A
(x ~ 1.38 to 1.50), but not to 9.32 A. lt was concluded that stoichiometric cubic Sm 2Te 3 does
not exist in the quenched samples, Pardo et al. [6]. The high value of ~9.48 A observed by
[6] was explained by presence of Sm2+ [19]. For "cubic Sm 2Te 3 " which was contaminated
with a second phase, a = 9.48 A is reported by Miller et al. [9, 10]; seealso Mularz, Wolnik
[8].
Observed interatomic distances in A for y-M 2Te 3 and calculated contribution of covalent
bonding:
La 2Te 3 Ce 2Te 3 Pr2Te 3 Nd 2Te 3 Ref.
M-Te 3.33 3.30 3.266 [9, 10]

3.33 3.30 3.28 [7]
Te-Te . 3.61 3.58 3.539 [9, 10]
3.58 3.54 3.52 [7]
% cov. 46 47 49.5 [9, 10]
Gmelin Handbook 3
RE Main Vol. C 10
34
The M-Te distances are greater and the Te-Te distances are smaller than the calculated values
for ionic bonding according to Lashkarev, Paderno [7], and Miller et al. [9, 10].
Structure of the 11 Form
The structure of the 11-M 2Te 3 with M = Nd, Sm, and Gd is of the orthorhombic U2S3 type,
space group Pbnm-D~~ (No. 62), Z = 4. The M has the coordination number 7, Flahaut et al.
[11]. Other authors propose the Sb 2S3 type, differing in the cation sites; see for example
Eliseev [19], Yarembash, Eliseev [20]. Fora discussion of the two structure types, see [11]
and Flahaut [21]. The 11-phase is also predicted for Pr2Te3 , Flahaut [1, 21], with reference to
[11]. Lattice constants in Afrom Flahaut et al. [11] andin brackets from Yarembash, Karabekov
[23]:
a 12.16 12.06 (12.04) 11.96

b 11.93 11.86 (11.86) 11.75
c 4.37 4.34 (4.34) 4.29
Lattice constants for Nd 2 Te 3 and Gd 2Te 3 are also reported by Flahaut et al. (14], and for Nd 2Te 3
by Lin et al. [15].
Structure of the ~ Form
The structure of ~-M 2Te 3 with M = Y, Tb to Lu is orthorhombic of the Sc 2S3 type with a
cubic subcell. Space group Fddd-D~~ (No. 70); Z = 16 [1, p.11]; cf. "Rare Earth Elements" C9,
1986, pp. 37/8. Lattice constants a' of the strictly cubic subcell and a, b, and c of the
orthorhombic cell from Flahaut et al. [12] in A:
Y2Te 3 Tb 2Te 3 Dy2Te3 Ho2Te3 Er 2Te 3 Tm 2Te 3 Lu 2Te 3
a' 6.114 6.138 6.108 6.086 6.067 6.048 6.011

a 12.228 12.276 12.216 12.172 12.134 12.096 12.022
b 8.645 8.679 8.637 8.606 8.579 8.552 8.499
c 25.935 26.037 25.911 25.818 25.737 25.656 25.497
Values for a', a, b, and c and for the observed and calculated M-Te distances (in A) from
Dismukes, White [13] and for TmTe_ 1.47 from Kaldis et al. [17]:
Y2Te 3 Dy 2 Te 3 Ho 2Te 3 Tm 2Te 3 TmTe_ 1 47
a' 6.112 6.110 6.086 6.042 6.0400(8)

a 12.224 12.220 12.172 12.084 12.060(20)
b 8.642 8.640 8.605 8.543 8.541(5)
c 25.92 25.91 25.81 25.63 25.631 (30)
(M-Te)obs. 3.056 3.055 3.043 3.021
(M-Te)calc 3.045 3.059 3.045 3.020
Gmelin Handbock
RE Main Vol. C10
Density 35
There is good agreement between the observed cation-anion distances and the calculated
values for ionic bond ing (for Te 2 - the radius r = 2.151 A was used) [13]. According to [17] the
real composition of Tm 2Te3 is TmTe 1.47 (see p. 251). For films of Tm 2Te3 the Lattice constants
a = 12.09, b = 8.56, and c = 25.66 Aare reported by Krylov et al. [18].
Denslty
Calculated and observed density Deale and Dexp in g/cm 3 :
y-La 2Te 3 y-Ce2Te 3 y-Pr 2Te 3 y-Nd 2Te3 Ref.
Deale 6.58 6.78 6.91 7.08 [8]

Dexp 6.4 6.6 6.6 6.65 [8]
TJ-Nd 2Te 3 TJ-Sm 2Te 3 TJ-Gd 2Te 3 Ref.
Deale 7.02 7.42 7.66 [11]

Dexp 6.94 7.36 7.42 [11]
Calculated densities for ~-M 2 Te 3 [12]:
M2Te 3 Y2Te 3 Tb 2Te 3 Dy2Te 3 Ho2Te 3 Er2Te 3 Tm 2Te 3 Lu 2Te 3

Deale 5.43 6.72 6.88 7.00 7.07 7.22 7.81
The calculated densities for ~-M 2 Te 3 and for y-M 2Te 3 (including predicted high pressure phases
of the heavier rare earth elements) are shown in Fig. 8 from Eatough et al. [4].
Pm Eu Tb Ho Tm Lu
La Ce Pr Nd Sm Gd Dy Er Vb
s ~~~~~~~~~~~~~
,/
/
/
/
/
-
~E 8 ~--------4---------~------4
u
Cl
-~
-e
cr,·~------~~--------~~----4
1.0 0.9
Fig. 8. Calculated density Deale of y-M 2Te 3 and ~-M 2 Te 3 versus ionic radius rM .
Gmelin Handbock 3"
RE Main Val. C10
36
References:
(1] J. Flahaut (in: K. A. Gsehneidner, LeRoy Eyring, Handbook on the Physies and Chemistry
of Rare Earths, Vol.4, North-Holland, New York 1979, pp. 1/88, 6/12).
[2] J. Flahaut (Les Elements des Terres Rares, Masson, Paris 1969, pp. 126/30).
[3] J. Flahaut, P. Laruelle (Progr. Sei. Teehnol. Rare Earths 3 [1968]149/208, 180/7).
[4] N. L. Eatough, A. W. Webb, H. T. Hall (lnorg. Chem. 8 (1969]2069/71).
[5] M. P. Pardo, J. Flahaut (Bull. Soe. Chim. Franee 1969 6/9).
[6] M. P. Pardo, J. Flahaut, L. Domange (Campt. Rend. 256 [1963]1793/6).
[7] G. V. Lashkarev, Yu. 8. Paderno (lzv. Akad. Nauk SSSR Neorgan. Materialy 1 [1965]
1791/1802; lnorg. Materials [USSR]1 [1965]1620/9, 1625).
[8] W. L. Mularz, S. J. Wolnik (Proe. 3rd Conf. Rare Earth Res., Clearwater, Fla., 1963 [1964],
pp. 473/9).
[9] J. F. Miller, L. K. Matson, R. C. Himes (Proe. 3rd Conf. Rare Earth Res., Clearwater, Fla.,
1963 [1964], pp. 135/46).
(10] J. F. Miller, F. J. Reid, L. K. Matson, et al. (AD-607082 [1964]1/79, 22/3; C.A. [1965]15562).
[11] J. Flahaut, L. Domange, M. Guittard, M. P. Pardo (Bull. Soe. Chim. Franee 1965 326/7).
[12] J. Flahaut, P. Laruelle, M. P. Pardo, M. Guittard (Bull. Soe. Chim. Franee 1965 1399/404).
[13] J. P. Dismukes, J. G. White (lnorg. Chem. 4 [1965] 970/3).
[14] J. Flahaut, L. Domange, M. Guittard, M. P. Pardo, M. Patrie (Campt. Rend. 257 [1963]
1530/3).
[16] A. A. Eliseev, G. M. Kuz'mieheva (Zh. Neorgan. Khim. 24 [1979]3/6; Russ. J. lnorg. Chem.
24 [1979] 1/3; Dokl. Akad. Nauk SSSR 246 [1979] 1162/5; Dokl. Phys. Chem. Proe. Aead.
Sei. USSR 244/249 [1979] 507/9).
[17] E. Kaldis, E. Jilek, H. Spyehiger (J. Less-Common Metals 93 [1983] 399/409, 404).
[18] V. S. Krylov, S. V. Shehegol'kov, K. A. Agaev, A. E. Bakhyshov (Ueh. Zap. Azerb. Gos.
Univ. Ser. Fiz. Mat. Nauk 1975 No.4, pp. 70/4; C.A. 85 [1976] No. 115262).
627/33).
Moseow 1975, pp. 1/260, 198, 204, 216).
[21] J. Flahaut (MTP [Med. Teeh. Publ. Co.] intern. Rev. Sei. lnorg. Chem. Ser. One 10 [1972]
189/241, 201).
[22] S. A. Kutolin, V. I. Kotyukov, S. I. Yakovlev (lzv. Akad. Nauk SSSR Neorgan. Materialy 16
[1980] 997/1000; lnorg. Materials [USSR]16 [1980] 686/8).
[23] E. I. Yarembash, A. Karabekov (Tr. Frunz. Politekhn. lnst. No. 41 [1970] 49/63).
30.1.2.3.3 Thermal Properlies
Melting Points tm in °C
Y2Te 3 La 2Te 3 Ce 2Te 3 Pr 2Te 3
tm . 1525 1450 1465 1485 1595 1560*) 1500*)

Ref. [1, 11, 12] [2, 3] [4] [5] [11] [2, 3] [2, 3]
Gmelm Handbock
RE Mam Vol. C 10
Thermal Properlies 37
Nd 2Te 3 Sm 2Te 3
tm . 1550*) 1620 ~1650 1656 1500 1550±50

Ref. [2, 3] [6] [7] [12] [12] [11]
Gd 2Te 3 Dy 2Te 3 Er2Te 3 Tm 2Te 3
tm . 1505 1510 1460 1650

Ref. [7] [8, 12] [9] [13]
•> lncongruent.
According to Zargaryan, Abrikosov [10] Gd 2Te 3 forms peritectically at 1215°C; see the "Gd-
Te system", p. 231. For melting points estimated from crystal chemical data for the Th 3 P4 type
compounds M2Te 3 with M = La to Sm, see Kuz'micheva et al. (14].
Thermodynamic Data
Estimated values by Mills (15] and some calorimetrically measured values (with asterisk)
for the standard enthalpy of formation LiH2 98 in kcallmol and the absolute entropy S298 in
cal · mol - 1 · K - 1 :
Sc 2Te 3 Y2Te 3 La 2Te 3 Ce 2Te 3 Pr2Te 3 Nd 2Te 3 Pm 2Te 3 Sm 2Te 3
-LiH2gs. 170 190 187.5*) 185, 196.7*) 190 190 190 190
S2gs 43.5 48.0 55.36*) 57.0 63.0 60.56*) 58.0 63.5
Gd 2Te 3 Tb 2Te 3 Dy2Te 3 Ho2Te 3 Er2Te 3 Tm 2Te 3 Lu 2Te 3
-..iH2gs · 190 190 195, 195.7*) 195 195 195 195

S2gs 61.5 63.0 62.0 63.5 62.5 60.5 48.5
The enthalpy of formation was measured for La 2Te 3 by Sharifov et al. [16] (see p. 82), for
Ce 2Te 3 and Dy 2Te 3 by Azizov et al. [17] (see pp. 100 and 244). Values of -..iH 0 (in kcallmol)
determined from emf measurements are: 213.3 for La 2Te 3 at 643 to 755 K, a value from
Literature cited by Vasil'ev, Morozov [18]; 196.3 for Er 2Te 3 at 590 to 710 K, Vasil'ev et al. [19];
186.1 for Lu 2Te 3 at 592 to 738 K [18]. The heat capacitywas measured for La2Te 3 by Nogteva
et al. [20] and for Nd 2Te 3 by Paukov et al. [21] (see pp. 82 and 124) below and at room
temperature. From the measured CP values the heat capacitywas calculated up to 1700 K for
La 2Te 3 and up to 1600 K for Nd 2Te 3 by Mills [15].
lt was shown, that the known S298 data for the cubic compounds La2X3 (with X = Te, Se,
S, 0), Sc 20 3 , and Y20 3 fit the empirical Linear equation S298 = (2.912 x n) -22.43, where n is
the sum of electron shells in cations and anions (e.g. 27 in La 2Te 3 ). Linearrelations were also
Gmelin Handbook
RE Main Vol. C 10
38
obtained at higher temperatures. ln this way the following entropy data were calculated for
(noncubic) Sc 2Te 3 and Y2Te 3 :
Tin K . . . 298 500 1000 1500 2000
Sr (Sc 2Te 3) . 44.5 59.5 81 95 106

Sr (Y2Te3) . 50.4 66 88 102 113.5
Vishnyakov, Suponitskii [22].
Debye temperatures estimated from crystal chemical data for the Th 3P4 type compounds
M 2Te 3 with M = La to Sm are shown in a figurein Kuz'micheva et al. [14].
Values of A. in W · m- 1 · K- 1 near room temperature:
A. . 0.7 1.2 3.8 1.1 0.7 1.9 7.7 1.3 1.13 1.046
Ref. [2, 3] [24, 28] [2, 3] [28] [2, 3] [28] [2, 3] [28] [10] [27]
Tyurin et al. [23] report A. = 0.38 W m- 1 · K- 1 for Ce 2Te 3. The value for Nd 2Te 3 is
A. = 1.45x 10- 3 cal · cm- 1 • s- 1 · K- 1 (= 0.61 W · m- 1 • K- 1) at 300 K. The lattice contri-
bution is the same, Abrikosov, Zargaryan (25]; however, A. = 0.16 cal · cm- 1 · s- 1 · K- 1
( = 67 W · m- 1 · K- 1 ) is given by Zinchenko et al. [26].
References:
[1961], pp. 232/40).
[2] E. I. Yarembash (Therm. Anal. Proc. 2nd Intern. Conf., Worcester, Mass., 1968 [1969].
Vol. 2, pp. 761/77, 769; C.A. 73 [1970] No. 124092).
[3] E. I. Yarembash (Colloq. Intern. Centre Natl. Rech. Sei. No. 180 [1969/70] 471/81, 476,
477).
[4] V. V. Sokolov, L. Kh. Kravchenko, A. A. Kamarzin (lzv. Akad. Nauk SSSR Neorgan.
Materialy 9 [1973]1057/9; lnorg. Materials [USSR]9 [1973] 944/6).
(7] J. F. Miller, F. J. Reid, L. K. Matson, et al. (AD-607082 [1964]1/79, 11, 42; C.A. 62 [1965]
15562).
Materialy 6 [1970] 720/5; lnorg. Materials [USSR] 6 [1970]634/8).
Gmelin Handbook
RE Matn Vol. C 10
[11] E. A. Geidarova, Z. D. Melikova, F. M. Sadygov (lssled. Obl. Neorgan. Fiz. Khim. 1981
131/6; C.A. 98 [1983] No. 186470).
[12] E. A. Geidarova, P. G. Rustamov (Zh. Neorgan. Khim. 30 [1985] 2992/4; Russ. J. lnorg.
Chem. 30 [1985]1705/7).
[13] F. M. Sadygov, Ch. I. Abilov, P. G. Rustamov (Zh. Neorgan. Khim. 30 [1985]3177/9; Russ.
J. lnorg. Chem. 30 [1985]1806/8).
[14] G. M. Kuz'micheva, A. E. Voloshin, A. A. Eliseev (Zh. Neorgan. Khim. 30 [1985] 49/55;
Russ. J. lnorg. Chem. 30 [1985]27/31).
[16] K. A. Sharifov, Z. Sh. Karaev, T. Kh. Azizov (lzv. Akad. Nauk SSSR Neorgan. Materialy 3
[1967] 719/20; lnorg. Materials [USSR]3 [1967] 637/9).
[17] T. Kh. Azizov, A. S. Abbasov, F. M. Mustafaev, I. Ya. Aliev (7th Vses. Konf. Kalorim.
Rasshir. Tezisy Dokl., Moscow 1977, Vol. 1, pp. 30/2; C.A. 91 [1979] No. 217832).
[18] V. P. Vasil'ev, V. V. Morozov (Deposited Doc. VINITI-2249-84 [1984]1/11; C.A. 102 [1985]
No. 138649).
[19] V. P. Vasil'ev, V. I. Goryacheva, Ya. I. Gerasimov, T. S. Lazareva (Vestn. Mosk. Univ.
Khim. 35 No. 4 [1980]339/44; Moscow Univ. Chem. Bult. 35 No. 4 [1980] 36/41).
[20] V. V. Nogteva, I. E. Paukov, E. I. Yarembash (Zh. Fiz. Khim. 43 [1969] 2118/20; Russ. J.
Phys. Chem. 43 [1969]1186/7).
[21] 1. E. Paukov, V. V. Nogteva, E. I. Yarembash (Zh. Fiz. Khim. 42 [1968]998/1000; Russ. J.

Phys. Chem. 42 [1968] 522/3).
[22] A. V. Vishnyakov, Yu. L. Suponitskii (Zh. Fiz. Khim. 59 [1985]1301/3; Russ. J. Phys. Chem.
59 [1985] 767/9).
7th Vses. Simp. Fiz. Svoistvam Elektron. Str. Perekhadnykh Metal. lkh Splavov Soedin.,
Kiev 1969 [1972], Vol. 1, pp. 156/61; C.A. 79 [1973] No. 59042).
[24] A. Aloman (Bul. lnst. Politeh. Gheorghe Gheorghiu Dej. Bucuresti 30 No. 2 [1968] 101/6,
106; C.A. 70 [1969] No. 53450).
Neorgan. Materialy 2 [1966]1747/56; lnorg. Materials [USSR] 2 [1966]1506/14).
Kiev 1968 [1970], pp. 173/80; C.A. 76 [1972] No. 7748).
pp. 473/9).
30.1.2.3.4 Magnetic and Electrical Properlies
The magnetic susceptibility of the orthorhombic M 2Te 3 with M = Dy, Er, and Tm was
measured between 1.3 and 300 K; the Curie-Weiss law is obeyed above ~ 10 K for Tm 2Te 3 ,
above ~20 K for Dy2Te 3 , and above ~so K for Er 2Te 3 . The results are interpreted by means
of the crystal field method since the magnetic properlies are influenced by the crystal electric
field of the 4f electrons. Values of the magnetic quantities (paramagnetic Curie temperature
Gmelin Handbook
RE Main Vol. C 10
40
eP, Neel temperature TN• effective magnetic moment lle«• exchange constants J,lk) and data
of crystal field parameters are as follows:
ep -SK -13 K
TN . 4.1 K < 1.28 K
lleff 10.58 llB 9.50 llB
J1/k 0.082 K
J2/k -0.217 K
A4(r4) 14.12 meV (163.9 K) 13.4 meV (155.4 K)
As(r6) 0.767 meV (8.9 K) 0.904 meV (10.5 K)
r 6 -> r 8 (1l = 2.33 meV (27.0 K) r 7 , r 8 (1)-> r 8 (2l = 4.65 meV (54 K)
r 6 -> r 7 = 13.11 meV (152.2 K) r 7 , r 8 (1l->r 6 = 18.47 meV (214.3 K)
r 6 -> r 8(2l = 23.21 meV (269.3 K) r 7 , r 8 (1l->r 8 (3) = 22.35 meV (259.4 K)
r 6 -> r 8 (3l = 28.73 meV (333.4 K)
Pokrzywnicki [1]. For data on Er 2Te 3 seealso Pokrzywnicki [2]. For Tm 2Te 3 , eP = -6 K, lle« =
±
7.56 lls· and the moment of saturation at 4.2 K is 4.35 0.05 lls· The splitting energy of the
±
Lowest Level r 1 -> r 4 is reported to be 2.35 0.2 meV [1]. For T = 0 K the magnetic
susceptibilities XA(O) = 0.0534 and 0.451 cm 3 /g-atom M for Pr 2Te 3 and Tm 2Te 3 , respectively,
were derived from susceptibility measurements between 1.3 and 400 K by Sucher et al. [23].
Negative paramagnetic Curie temperatures, indicating antiferromagnetic ordering, are

also obtained for Ce 2Te 3 (see p. 100), for Pr 2Te 3 (see p. 105), for Nd 2Te 3 (see p. 125), for Eu 2Te 3
(see p. 230), and for Gd 2Te 3 (see p. 237).
The compounds M 2Te 3 are semiconductors, most of them of the n-type. Nd 2Te 3 and Gd 2Te 3
are obtained as n- or p-type materials depending on their preparation, Miller et al. [7, 15]. Reid
et al. [16, 17]. Gd 2Te 3 with z 59.6 at% Gd could only be obtained as p-type by Zargaryan,
Abrikosov [6]. The following table is a compilation of the electrical resistivity Q (in n · cm),
thermoelectric power S (in jlV/K), Hall mobility ll (in cm 2 · v- 1 · s- 1 ), Hall constant RH (in
cm 3/C), carrier concentration n (in cm- 3 ), and figure of merit Z (in 10- 4 · K- 1) for some
M 2 Te 3 at room temperatu re:
Q s ll RH n z Ref.
Y 2Te 3 . 10 140 -1400 4 X 10 15 [3, 13]
La 2Te 3 1.9x1o- 4 -30 negative ~ 1020 [3, 13]

5.9 X 10- 3 -172 4.5 [11]
6.6 X 10- 3 -130 2.0 [11]
5 90 to 100*) [4, 5]
Ce 2Te 3 0.011 -176 2.6 [11]

14.3 -320 [4, 5, 8]
145 -315 [7, 14 to 16]
Gmelm Handbook
REMam Vol. C 10
Magnetic and Electrical Properlies 41
Q s Ii RH n z Ref.
Pr2Te3 1.5 X 10- 3 -34 0.4 [11)

0.1 to 0.01 -40 to -100 [4, 5]
0.021 -141 -0.18 3.5 X 1019 [9)
Nd2Te3 1.7x1o- 3 -52 0.12 [11)
1.2 X 10- 3 -30 6 -0.008 8 X 1020 [7, 15 to 17]
0.31 +180 5 + 1.15 4.2 X 1018 [7, 15 to 17]
22 -260 negative [7, 15 to 17]
5.55 - 560 1.2 9.3 X 1017 [10)
200 140 *) [4, 5]
Sm 2Te 3 0.85 negative [3]
Gd 2Te3 0.28 +350 6.05 3.54 X 1018 [6)
0.019 +190 18 +0.34 1.9 X 1019 [7, 15 to 17)
0.015 + 160 11 + 0.16 4 X 1019 [7, 15 to 17)
2.0 X 10- 3 - 80 55 -0.11 5.7 X 1019 [7, 15 to 17]
Er2Te 3 1.1 X 10- 3 negative ~ 1019 [3, 13)
•l Sign of S not given.
300
~200
>
::1.
-~
(/)
-100
Temperature in °C
Fig. 9. Absolutevalues for the thermoelectric power I SI of M 2Te 3 with M = La, Sm, Gd , Er, and
Yb versus temperature.
According to Vickery, Mui r [12], the resistivity of M 2Te3 (M = Sm, Gd, Er, and Yb) samples
produced from the melt in Ar atmosphere decreases as the temperature is increased from 30
to ~ 1 000 °C (a figure is given in the paper). The temperature dependence of the thermoelectric
power S of these samples and of La2Te 3 is shown in Fig. 9. There is no discussion about the
sign of S in [12]. The sign is negative for the biphasic samples YTe 1 44 (p. 65) and GdTe 1 .39 (see
a fi gure in the paper) in the studied range 100 to 800 °C, Muir [22); for Dy2Te3 , see p. 245.
Values at room temperature of the width of the forbidden energy zone ~E in eV, the
o, r
chemical shift and the line width in mm/s (from the 125Te Mössbauer spectra) for samples
Gmelm Handbook
RE Mam Vol. C 10
42
characterized by their electrical conductivities K in n- 1 · cm-1, Seebeck coefficient S in

11V/K, and charge carrier concentration n in cm- 3 are as follows:
La 2Te 3 Ce 2Te 3 Pr 2Te 3 Nd 2Te 3 Sm 2Te 3 Ref.
K 5 X 10- 4 ~2 ~0.1 2 4 X 10- 3 [18]

230 0.002 0.0025 [19]
s -20 to -30 -30 to -40 -10 to -20 + 120 to + 140 [18]

-136 -159 -172 [19]
L1E 1.2to1.6 1.3 to 1.7 0.8 to 1.0 [18]
1.20 1.16 1.08 [19]
1.2 [10]
n 4.0 X 1017 4 X 10 17 4.45 X 1017 [19]
8 1.15±0.2 1.23 ± 0.2 1.1 ± 0.2 [19]
r 2.7 ± 0.2 6.5 ± 0.2 7.1 ± 0.2 [19]
The results of the Mössbauer studies of M 2Te 3 are compared with those of other phases in
the M-Te systems (M = La, Pr, Nd) by Gorbachev et al. [19 to 21]; see Fig. 2 on p. 19. The
electrical resistivity of a Tm 2Te 3 film is Q = 104 Q · cm. lt shows semiconducting properties.
From the optical reflection and transmission spectra between about 1.4 and 2.5 11m the energy
gap L1E = 0.5 eV was derived, Krylov et al. [24].
References:
[1] S. Pokrzywnicki (Sei. Papers lnst. lnorg. Chem. Rare Elem. Wroclaw Polytech. lnst. No.
45 [1979]1/69, 45/57; C.A. 92 [1980] No. 87141).
[2] S. Pokrzywnicki (Phys. Status Solidi A 55 [1979] K39/K43).
[1961], pp. 232/40).
(4] E. I. Yarembash (Therm. Anal. Proc. 2nd Intern. Conf., Worcester, Mass., 1968 [1969],
Vol. 2, pp. 761/77, 769; C.A. 73 [1970] No. 124092).
[5] E. I. Yarembash (Colloq. Intern. Centre Natl. Rech. Sei. No. 180 [1969/70] 471/81, 476,
477).
[6] V. Sh. Zargaryan, N. Kh. Abrikosov (lzv. Akad. Nauk SSSR Neorgan. Materialy 3 [1967)
769/76; lnorg. Materials [USSR]3 [1967] 687/94).
[7] J. F. Miller, F. J. Reid, L. K. Matson, et al. (AD-607082 [1964]1/79, 11, 42; C.A. 62 [1965]
15562).
7th Vses. Simp. Fiz. Svoistvam Elektron. Str. Perekhadnykh Metal. lkh Splavov Soedin.,
Kiev 1969 [1972], Vol. 1, pp. 156/61; C.A. 79 [1973] No. 59042).
(9] K. A. Zinchenko, N. P. Luzhnaya, E. I. Yarembash, A. A. Eliseev (lzv. Akad. Nauk SSSR
[10] N. Kh. Abrikosov, V. Sh. Zargaryan (lzv. Akad. Nauk SSSR Neorgan. Materialy 3 [1967)
pp. 473/9).
Gmelm Handbook
RE Ma1n Vol. C10
43
[12] R. C. Vickery, H. M. Muir (Advan. Energy Convers. 1 [1961] 179/86, 184; C.A. 60 [1964]
13973).
[13] J. F. Miller, F. J. Reid, R. C. Hirnes (J. Electrochem. Soc. 106 [1959] 1043/6).
[14] J. F. Miller, L. K. Matson, R. C. Hirnes (Proc. 2nd Conf. Rare Earth Res., GLenwood
Springs, Colo., 1961 [1962], pp. 233/48, 247).
[15] J. F. Miller, F. J. Reid, L. K. Matson, R. C. Hirnes (AD-428091 [1963] 1/65, 14; C.A. 61
[1964] 14012).
943/50).
[17] F. J. Reid, L. K. Matson, J. F. Miller, R. C. Hirnes (CONF-68-3 [1963] 1/4; N.S.A. 17 [1963]
No. 34469).
[18] E. I. Yarembash, E. S. Vigileva, A. A. Eliseev, V. I. Kalitin (lzv. Akad. Nauk SSSR Ser. Fiz.
28 [1964] 1306/9; BuLL. Acad. Sei. USSR Phys. Ser. 28 [1964] 1208/12).
Akad. Nauk SSSR Neorgan. Materialy 13 [1977] 222/6; lnorg. Materials [USSR] 13 [1977]
188/91).
Svoistva 2 [1976] 20118; C.A. 86 [1977] No. 25033).
[21] V. V. Gorbachev, V. A. Linskii, S. P. lonov, 0. A. Sadovskaya, A. Yu. Aleksandrov (Proc.
5th Intern. Conf. Mössbauer Spectrosc., Bratislawa 1973 [1975], VoL. 1/3, pp. 522/4; C.A.
87 [1977] No. 209117).
[22] H. M. Muir (AD-277043 [1960/61]1147, 40/1; N.S.A. 17 [1963] No. 11292).
[23] E. Bucher, K. Andres, F. J. di Salvo, et aL. (Phys. Rev. [3] B 11 [1975] 500/13, 502, 504).
[24] V. S. Krylov, S. V. Shchegol'kov, K. A. Agaev, A. E. Bakhyshov (Uch. Zap. Azerb. Gos.
Univ. Ser. Fiz. Mat. Nauk 1975 No. 4, pp. 70/4; C.A. 85 [1976] No. 115262).
30.1.2.4 Comparative Data for M 4Te7 (= MTe1.r±x)

General
The composition of these poLyteLLurides, usuaLLy formulated as M4Te7 , is variable and may
be described also by M7Te 12 , Eliseev et al. [1]. But more recently the formula M4Te 7 has been
confirmed by X-ray structure analysis on the phase with M = La, Kuznetsov et al. [15]. The
existence of thesetetragonaL phases was established forM = La by [1], Ce by Chukalin et
al. [2], Pr by [1], Nd by [1], Zinchenko et al. [3], and Yarembash et aL. [4], Sm by Yarembash
et aL. [13], Eu (symmetry not known, see p. 229) by Sadovskaya et aL. [14], and Gd by Zargaryan,
Abrikosov [7]. The phase DyTeu5 , with a different tetragonal structure, was originaLLy
considered alsotobe a member of this group, Abrikosov et al. [8]. However, more recentLy,
a chemicaL formula is either avoided for it (see for example, Yarembash, Eliseev [17, p. 222])
or it is classed with the isostructural polyteLLuride MTe2 _x (see p. 49), Eliseev, Grizik [19],
SLovyanskikh et al. [16].
Formation and Preparation

ALL M4Te7 phases form by peritectic reactions at the foLLowing temperatures tp:
tP in °C . . 1350 1470 1340 1280±20 1280 1290 1190

Ref. . . . [17, p. 171] [1] [2] [9] [1] [3] [7]
Gmelin Handbock
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44
The formation temperature of Sm 4Te 7 is not yet known; see p. 128. Eu 4Te 7 is believed to exist
below 520 ± 5°C (see p. 158) [14].
Polycrystalline samples were prepared from the elements by the ampule method (see the
analogaus preparation of M2Te3 , p. 31) and single crystals by the gas transport reaction with
iodine as the carrier gas (see p. 31) starting with polycrystalline M2Te 3 (M = La, Pr, Nd). The
very complex reaction can be approximately depicted by the following schemes:
M2Te 3 + 3 12 :;;:::: 2 Ml 3 + % Te 2
2 Ml 3 + 2 Te 2 :;;:::: 2 MTe2 + 3 12
4 Ml 3 + 7 12 Te 2 :;;:::: M 4Te 7 + 6 12
The temperature gradient in the quartz ampule was 950--> 800°C. Single crystals of MTe2
and M4Te7 with dimensions up to 1 x 1 x 1 mm3 are formed simultaneously in the mixture after
100 to 150 h of continuously conducting the process on the walls of the ampule. The composi-
tion of the selected single crystals was established by chemical analysis, by X-ray diffraction,
and X-ray spectroscopy, Eliseev et al. [1]. For preparation of La 4Te 7 single crystals by this
method, seealso Kuznetsov et al. [15]. The truncated tetragonal pyramids of Pr4Te 7 grown at
950--> 750°C and an iodine concentration of 1 to 2 mg/cm 3 had dimensions up to 1 x 2 x 2 mm 3
after 120 to 150 h, Yarembash, Vigileva [9].
Crystallographic Properties. Density

X-ray single crystal studies on La 4Te 7 show the structure to be tetragonal; the most
probable space group is P4b2-D~d (No. 117), Z = 2, Kuznetsov et al. [15]. This space group
has been accepted also for the compounds with M = Ce. Pr, Nd, and Sm, Yarembash,
Eliseev [17], but not Eu; see p. 229. Originally, the piezoelectric effect was absent and the
centrosymmetric space group P4/mbm-D~h (No. 127) was selected as the most probable,
Eliseev et al. [1]. Lattice constants a and c in A and density D in g/cm3 :
La4Te 7 Ce 4Te 7 Pr4Te 7 Nd 4Te 7 Sm 4Te 7
a. 9.011 8.988 8.858 8.799 9.03

c. 9.172 9.167 9.064 9.001 9.195
Deale 6.46 6.55 6.82 7.01
Dexp 6.40 6.50 6.88 7.08
Ref. [1, 15] [2] [1] [1] [13]
ln a previous work of Eliseev et al. [5] the X-ray powder diagram of polycrystalline La4Te 7
was indexed orthorhombically with a = 4.622, b = 4.497, and c = 9.142 A; slightly deviating
values are found in Eliseev et al. [6].
The M4Te 7 phases have a homogeneity range which has been established as LaTe1.50 to
LaTeu8 (61.2 to 64 at% Te) for the La4Te 7 phase but the lattice constants a and c remain
practically unchanged within the Limits of error ( ± 0.01 Ä) [1]:
LaTe1.50 LaTe1.55 LaTe 1_65 LaTe 1_70 LaTe 1.75 LaTeu 5
at% Te 61.20 62.20 62.30 63.23 63.40 63.60

a in A 9.016 9.022 9.011 9.009 9.005 9.024
c in A 9.170 9.164 9.172 9.172 9.173 9.162
c/a 1.019 1.016 1.017 1.018 1.019 1.015
Gmelm Handbock
RE Mam Vol. C 10
Pr4Te 7 , with a homogeneity range 62.7 to 64.2 at% Te [9], behaves similarly; see Yarembash
et al. [18] .
Since the value of a is approximately twice as large as the lattice period a of the tetragonal
MTe2 _x phases (see p. 48), while the periods c are practically the same, La 4Te 7 is supposed
to be a superstructure of LaTe 2 with Te vacancies. La 4 Te 7 has a five-layer structure similar to
LaTe 2 with layers perpendicular to the c axis . The alternation of layers is -Te(1)-La-Te(2,3,4)-
La-Te(1)-Te(1). Atomic positional parameters (R = 0.108):
atom position X y z
8 La 8(i) 0.4904 0.2490 0.7295

7.95 Te(1) 8(i) 0.4937 0.2528 0.3617
3.06 Te(2) 4(g) 0.2681 0.7681 0
1.69 Te(3) 2(a) 0 0 0
1.55 Te(4) 2(c) 0.5 0 0
Each La atom is surrounded by nine Te atoms with distances between 3.201 and 3.407 A; see
the polyhedron, Fig. 10a. The polyhedra around Te(1) and Te(2) are shown in Fig. 10b and
10c; the coordination numbers are 13 for Te(1) and 12 for Te(2), Te(3), and Te(4). The polyhedra
a)
• La
Q re(l)
Q Te(2)
@Te(3)
a
)_b • Te(4)
Fig. 10. Coordination polyhedra in La4Te 7 around La, Te(1), and Te(2) (Fig. 10a, b, and c,
respectively).
Gmelin Handbook
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46
around Te(3) and Te(4) are similar to that of Te(2), namely, for Te(3): 4 La (3.36 to 3.95 A) +
4 Te(1) (3.95 to 4.00 A) + 4 Te(2) (3.19 A) and for Te(4): 4 La (- 3.35 A) + 4 Te(1) (- 4.03 A)
+ 4 Te(2) (2.96 to 3.42 A), Kuznetsov et al. [15]. Slightly different atomic parameters for La,
Te(1), and Te(2) are given by [17, p. 176].
Additional Physical Properlies

Electrical resistivity Q in n · cm, thermoelectric power S in !J.V/K, carrier concentration n
in cm- 3 and width of the forbidden zone .1E in eV:
La4Te 7 Ce 4Te7 Pr4Te7 Pr4Te 7 Nd 4Te 7 Sm 4Te 7 Eu 4Te 7 Gd 4Te 7
Q 3.12 5 103 0.91 0.067 0.04 5 X 103 0.022

s . +36 -140 +30 +65 -125 +100 + 140
n 6.1x10 16 2.85 X 1017 9.1 X 1020 5.6 X 1019
.1E 0.58 0.53 0.46 0.30 0.5
Ref. [11] [12] [9] [17] [3] [13] [14] [7]
The composition LaTeu has Q = 24.3 n.cm, s

= -100 !J.V/K, Ramsey et al. [10]. The
conductivity changes from impurity to intrinsic conductance at 476 K for Ce4Te 7 and 470 K for
Pr4Te7 , Yarembash, Eliseev [17].
Hall constant RH and carrier concentration n for Nd4Te7 at 298 and 83 Kare IRHI = 0.061
and 0.96 cm 3/C and n = 9.1 x 1020 and 6.7 x 1019 cm- 3 , respectively, Zinchenko et al. [3]. For
La4Te7 with n = 6.1 x 1016 cm- 3 the 125Te Mössbauer spectra (35.5 keV y-transition, source
125Te03 ) give the chemical shifto r
= 1.20 mm/s and line width = 9.0 mm/s, Gorbachev et
al. [11]; cf. p. 18.
References:
[1] A. A. Eliseev, V. G. Kuznetsov, E. I. Yarembash, et al. (lzv. Akad. Nauk SSSR Neorgan.
Materialy 2 [1966] 2241/5; lnorg. Materials [USSR]2 [1966]1934/8).
[4] E. I. Yarembash, A. A. Eliseev, K. A. Zinchenko (lzv. Akad. Nauk SSSR Neorgan. Materialy
1 [1965] 60/7; lnorg. Materials [USSR]1 [1965] 50/6).
[5] A. A. Eliseev, E. I. Yarembash, V. G. Kuznetsov, L. I. Antonova, Z. P. Stoyantsova (lzv.
943/52).
[6] A. A. Eliseev, V. G. Kuznetsov, E. I. Yarembash, L. I. Antonova (Zh. Strukt. Khim. 5 [1964]
640/1; J. Struct. Chem. [USSR] 5 [1964] 592/3).
[10] T. H. Ramsey, H. Steinfink, E. J. Weiss (J. Appl. Phys. 34 [1963] 2917/8).
Gmelm Handbook
RE Main Vol. C10
Preparation of MTe2 _x 47

Akad. Nauk SSSR Neorgan. Materialy 13 [1977] 222/6; lnorg. Materials [USSR]13 [1977]
188/91).
Kiev 1969 [1972], Vol. 1, pp. 156/61; C.A. 79 [1973] No. 59042).
[13] E. I. Yarembash, E. G. Tyurin, A. A. Reshchikova, et al. (lzv. Akad. Nauk SSSR Neorgan.
Materialy 7 [1971] 761/5; lnorg. Materials [USSR] 7 [1971] 661/5).
[14] 0. A. Sadovskaya, E. P. Stepanov, V. V. Khrapov, E. I. Yarembash (lzv. Akad. Nauk SSSR
Neorgan. Materialy 8 [1972]815/20; lnorg. Materials [USSR] 8 [1972] 708/12).
[15] V. G. Kuznetsov, A. A. Eliseev, G. N. Novitskaya (Khim. Svyaz Poluprov. PolurnetaL 1972
119/27; C.A. 79 [1973] No. 10830).
[16] V. K. Slovyanskikh, N. T. Kuznetsov, N. V. Gracheva (Zh. Neorgan. Khim. 30 [1985]
2926/30; Russ. J. lnorg. Chem. 30 [1985]1666/9).
Moscow 1975, pp. 1/260, 169/256).
Neorgan. Materialy 3 [1967] 2184/9; lnorg. Materials [USSR] 3 [1967]1905/9).
[19] A. A. Eliseev, A. A. Grizik (in: V. P. Zhuze, I. A. Smirnov, Redkozemel'nye Poluprovodniki,
Nauka, Leningrad 1977, pp. 146/77, 170).
30.1.2.5 Comparative Data for MTe2 _x (0 ;'i; x ~ 0.3)

General
According to Pardo et al. [1] only the polytellurides MTe2 with M = La and Ce can occur
with the stoichiometric composition; the others, (at least) with M = Pr to Dy, always are Te-
deficient (MTe 2 _x). However, NdTe2 also occurs with stoichiometric composition according to
Zinchenko et al. [17], Lin et al. [18]. For homogeneity ranges, see p. 48, and for the earlier
formulation of the dysprosium phase as Dy4Te 7 , see p. 43. MTe2 _x phases with M = Y, Ho,
Er, Tm, and Lu are only obtained under high pressure. When no analytical composition is
reported in a paper but the formula MTe2 is nevertheless used, the designation "MTe 2 " will
be used with quotation marks in the following.

For the peritectic formation of MTe2 _x with M = La to Dy, see the individual systems.
The tetragonal polytellurides MTe 2 _x with x = 0 to 0.1 forM = La and Ce, with x = 0.1
to 0.2 for Pr, Nd, and Sm, and with x = 0.2 for Gd, Tb, and Dy have been prepared from ihe
element mixtures in evacuated quartz ampules. Annealing for 2 d at 550°C results in complete
reaction, but the blue-black products are poorly crystallized. Annealing for 10 d at 550°C
improves the crystallinity, Pardo et al. [1]; see also Pardo et al. [2]. About the same
compositions with M = La to Sm and Gd have been prepared at 1 000°C in 2 h [1, 2]. By
heating the element mixtures for 48 h at 600°C in evacuated Vycor tubes the isostructural
"MTe 2 " with M = La, Ce, Nd, Sm, Gd, Dy, and Yb have been prepared (no composition
reported). Attempts to prepare ErTe 2 and HoTe2 by the same method produced mixtures of
MTe and MTe3 . lt was predicted that "MTe 2 " with M = Ho, Er, Tm, and Lu cannot be stable.
Due to the small ionic radii of the cations the bond length for Te-Te in the structure becomes
too short, Wang, Steinfink [3].
Gmelin Handbook
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48
Single crystals of "MTe 2 " with M La, Ce, Pr, and Nd have been prepared with the gas
transport reaction with iodine as the carrier gas, Bro [4], Luzhnaya et al. [5], by the same
method described for M 2Te 3 ; see p. 31.
By application of high pressure, tetragonal silvery colared MTe 2 _x with M = Y, Ho, Er,
Tm, and Lu could be obtained. The composition of the phases was MTe" 17 rather than MTe 2 .
Starting with a 1:2 M :Te atomic ratio the final products contained a high amount of MTe 3
i mpurity; thus in most syntheses a 1 : 1. 7 M: Te ratiowas used. A one-hour synthesis of HoTe 2 _ x
at 52 kbar and 1 280°C gave a complete reaction, but the reaction below 1280°C and all
syntheses (mostly 1 h) of MTe 2 _x with M = Y, Er, Tm, and Lu resulted in partial reactions,
with MTe 3 as the major impurity in the final products. ScTe 2 _x could not be obtained with
pressures up to 100 kbar and temperatures up to 1200°C. Minimum pressure p at 700°C and
minimum temperature tat 69 kbar necessary for forming MTe 2 _x are as follows:
M in MTe 2 _x y Ho Er Tm Lu
p in kbar at 700°C 3 3 7 10 26
t in °C at 69 kbar. 425 360 425 425 495
Cannon, Hall [6], Cannon [7]. Pressure-temperature synthesis diagrams for 1: 1.7 M: Te
mixtures are shown in [7, pp. 26/30], and for ErTe 1 7 also in [6].
The polytellurides MTe 2 _x crystallize in the tetragonal Fe 2 As(Cu 2Sb) structure type with
space group P4/nmm-D~h (No. 129), Z = 2; see for example, Domange et al. [8], Eliseev,
Kuznetsov [9], Wang et al. [10], and a review by Flahaut, Laruelle [12].
Lattice constants a and c in A for the MTe 2 _x phases and for values at the upper and lower
boundaries of homogeneity for samples quenched from 550°C:
LaTe 2 LaTe 2 LaTe 2 LaTe 1_9 CeTe 2 CeTe 1_9 PrTe1.9 PrTe 18
a. 4.556(3) 4.507(5) 4.55 4.52 4.49 4.47 4.46 4.44

C. 9.176(5) 9.128(10) 9.17 9.20 9.10 9.11 9.05 9.06
Ref. [9] [10] [1] [1] [1] [1] [1] [1]
NdTe 1.9 NdTe 18 NdTe1.8 SmTe 1_9 SmTe 18 GdTe1.8 TbTe1.8 DyTe 18
a. 4.42 4.40 4.377(5) 4.37 4.35 4.32 4.31 4.29

C. 9.02 9.04 9.060(10) 9.00 9.01 8.98 8.95 8.91
Ref. [1] [1] [10] [1] [1] [1] [1] [1]
For the polytellurides MTe 2 _x with M = La to Sm the results are nearly the same for quenching
from 1 000°C [1]. Other reported homogeneity ranges are: LaTe 2 to LaTe 1_78 , Eliseev et al. [20]
Gmelm Handbock
RE Mam Val. C 10
(see p. 84), PrTe 1.9 to PrTe 1.8 (65.5 to 64.3 at% Te), Yarembash, Vigileva [21], NdTe 2 (black) to
NdTe 1_74 (silver-gray), Lin et al. [18). Further values for lattice constants in A and densities D
in g/cm 3 are tabulated:
PrTe 1_9 PrTe 1_8 NdTe 2 NdTe2 NdTe 1_74 SmTe 1_8 DyTe1.75 DyTe 1_7
a 4.459(2) 4.454(5) 4.405 4.419 4.377 4.337 4.274(2) 4.27

c. 9.072(5) 9.074(5) 9.008 9.021 9.060 8.954 8.917(5) 8.86
Dexp 6.99 6.93 7.15 7.35 7.71
Deale 7.03 6.93 7.53 7.78
Ref. [21, 22) [22) [17] [18) [18) [25] [28) [19)
From lattice constant measurements a homogeneity range GdTe 2 _10 to GdTe 1_77 was concluded
by Niihara et al. [26], but this conclusion does not conform with their reported graphical plots
of a and c which show Linearity only in a small range around the composition GdTe 1_8 . Lattice
constants of the metastable tetragonal high-pressure MTe 2 _x phases with x :::::0.3(?) [6) are:
M in MTe 2 _x . y Ho Er Tm Lu
a in A 4.291(3) 4.264(2) 4.248(2) 4.240(2) 4.222(1)

c in A 8.912(6) 8.872(4) 8.865(5) 8.831(4) 8.807(3)
Plotsofa and c as a function of the ionic radius of M3+ in MTe 2 _x with M = La to Lu, shown
in [6], are based on data from [1, 10, 18) for the compounds with La to Dy. There is a more or
less Linear decrease of a and c on going from La to Lu except for Yb; a = 4.55, c = 9.12 A
for YbTe 2 _x, studied by Wang [27], are read from these plots. However, the parameters a =
4.21, c = 8.82 A for "YbTe 2 " found recently by Slovyanskikh et al. [29) would agree with the
observed trend.
The reported lattice constants a = 9.10, c = 9.30 A for "GdTe 2 " by Miller et al. [15] are
consistent with the tetragonal M 4Te 7 phases; see p. 44.
The structure of the MTe 2 _x phases has been studied by X-ray diffraction on CeTe 2 powder,
Domange et al. [8], on single crystals of LaTe 2 , Eliseev, Kuznetsov [9) (isotropic refinement)
and Wang et al. [10) (anisotropic refinement), and on NdTe 1 8 calculated as NdTe 2 and various
Te-deficient compositions (anisotropic refinement) [10). Atomic positions in the structure of
MTe 2 [9):
2Te(1) in (a) (0, 0, 0); et
2 , 1/ 2 , 0)
2 Te(2) in (c) (0, 1/ 2 , u); Ct 2 , 0, 0)
2M in (c) (0, 1/ 2 , v); Ct 2 , 0, v)
Parameters u and v and interatomic distances in A for the polytellurides of La, Ce, and Nd
are:
LaTe 2 LaTe 2 CeTe 2 NdTe 1.89
u 0.36686 0.362 0.375 0.36783

V 0.72395 0.725 0.740 0.72913
Te(1)-Te(1) 3.187 3.22 3.17
Te(1 )-Te(2) 4.036 4.03 4.09
Te(2)-Te(2) 4.009 4.10 3.91
M-Te 3.260 to 3.381 3.32 to 3.39 3.28 to 3.33
Gmelm Handbook 4
RE Mam Vol. C 10
50 MTe2 _ x
LaTe 2 LaTe 2 CeTe 2 NdTe 1 _89
M-M . 5.183 4.556

R . 0.0776 0.15 0.10 0.0448
Ref. [10] [9] [1, 8, 24] [10]
Distances for Te(1 )-Te(1) deter mined experimentally by Lashkarev, Paderno [11] :
M in " MTe2 " La Ce Pr Nd Sm Gd Dy

Te(1)-Te(1) . 3.22 3.18 3.15 3.13 3.09 3.06 3.03
For comparison , Te-Te= 4.15 Ais calculated from the ion ic radii. Distances for M-Te(1 ) are
given in the paper [11] . The Te(1)-Te(1) distance of 3.03 A in " DyTe 2 " seems tobe the Limiting
distance for form ing a stable compound . For " HoTe2 " and " ErTe 2 " the Te(1)-Te(1) distances
3.015 and 3.005 A have been predicted [3] . The structure has a five-Layer stacking with
alternating Layers perpendicular to c arranged as-Te(1 )-La-Te(2)-Te(2)-La-Te(1 ). Each La atom
is surrounded by 9 Te atoms, Eliseev, Kuznetsov [9], see Fig. 11 a and b from Wang et al. [10] .
The coordination number of Te(1) was said tobe twelve (namely, 4Te(1) + 4 Te(2) + 4 La) ,
that of Te(2) was nine + four (namely, 5La + 4 Te(1) + 4 Te(2)) [9], cf. Eliseev, Grizik [30] .
However, the large distance between Te(1) and Te(2) (see Fig. 11 a) ind icates that very Little
bonding exists between these tellurium layers [10] . Thus, the coordination number for Te(1)
equals eight rather, Flahaut, Laruelle [12] and that of Te(2) may be nine or only five [10], cf.
[12]. The considerably shorter Te(1)-Te(1) distances in the basal plane indicate that these
have considerable metallic-covalent character. Calculations on NdTe2 _x showed that these
are the atoms which can be removed from the structure to produce the Te-deficient
compositions and which influence the electrical properties [10] .
Q)
@Te( I) QTe(2) . La
Fig. 11. Crystal structure of LaTe 2 : unit cell with interatomic distances in A (Fig. 11 a) and
polyhedron around La (Fig. 11 b) .
Gmelm Handbook
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Electrical Properties 51
Mössbauer Spectra and Electrical Properlies

The following are the values for the chemical shift 8 and of the Line width r from the 125Te
Mössbauer spectra (35.5 keV y-transition, source 125Te0 3 ) as weiL as the electrical conductivity
K, the thermoelectric power S, the carrier concentration n, and the width of the forbidden zone
L\E for the ditellurides of La, Pr, Nd, Gorbachev et al. [13]:
"LaTe 2 " "PrTe 2 " "NdTe 2 "
8 in mm/s 1.25 1.30 1.50

r in mm/s . 9.3 9.3 9.80
Kin Q- 1 · cm- 1 14 12 62
S in jlV/K +27 +65 +22.4
n in cm- 3 3 X 10 17 3 X 1017 1.2 X 1018
L\E in eV. 0.08 0.46 0.02
The results of the Mössbauer studies of "MTe 2 " are compared with those of other
compounds in the M-Te systems (M = La, Pr, Nd) by Gorbachev et al. [13, 14]; seealso p. 18.
A much larger L\E value for "NdTe 2 " is given on p. 126. Further data of electrical properties
are: K = 100oQ- 1 ·cm- 1 and S = +21 jlV/K for sintered CeTe 2 . The other ditellurides
MTe2 _x (M = La to Dy except Eu) have similar properties [1]: K = 18.2 Q- 1 • cm- 1 for
polycrystalline, melt-grown "GdTe 2 "; K = 0.56Q- 1 ·cm-1, n = 2.7x10 18 cm- 3 , Hall
coefficient RH = + 2 cm 3 /C, and Hall mobility !l = 1.3 cm 2 · v- 1 · s- 1 for single crystalline
vapor grown "GdTe 2 ", Miller et al. [15,16]. Single crystals of "MTe 2 " with M = La, Pr, and Nd
show a reversal of the sign of the Hall effect below room temperature, Andrellos, Bro [23].
Deviating values for "NdTe 2 ", S = -371-!V/K at 298 K and IRHI = 0.22 and 1.37 cm 3/C at 298
and 83 K, respectively, are reported by Zinchenko et al. [17]. The influence of composition on
the electrical properties has been studied on LaTe 2 _x; see p. 86.
Chemical Reactions
"MTe 2 " with La, Ce, Pr, Nd are said tobe stable in air [4]. However, "LaTe 2 " specimens,
Ramsey et al. [31], and "NdTe 2 " single crystals acquired a Light tarnish in air at room
temperature, Andrellos, Bro [23]. LaTe 2 dissociated to La 2Te 3 at ~935°C [31], but see Fig. 15,
p. 66, for the existence of the intermediate compound La4 Te 7 . Specimens of CeTe 2 under
10- 3 Torr decomposed in 4 h at 700°C into a two-phase mixture of composition CeTe 1_81 ,
whereas after 4 h at 900°C the product was single-phase CeTe 1.46 , Pardo et al. [1]. X-ray
diffraction spectra of HoTe2 _x show no decomposition after 15 d at room temperature, but
complete decomposition after 80 d. When heated under vacuum it remained stable at 260°C
but decomposed at 340°C, Cannon, Hall [6]. The polytellurides MTe 2 _x with M = La to Dy
(except Eu) are decomposed by dilute HCl under vacuum with precipitation of all of the Te [1].
References:
[1] M. P. Pardo, J. Flahaut, L. Domange (Bult. Soc. Chim. France 1964 3267/71).
[2] M. P. Pardo, J. Flahaut, L. Domange (Compt. Rend. 256 [1963] 953/5).
[3] R. Wang, H. Steinfink (lnorg. Chem. 6 [1967] 1685/92).
[4] P. Bro (J. Electrochem. Soc. 109 [1962]1110).
Gmelin Handbook 4.
RE Main Vol. C 10
52
pp. 49/54; C.A. 64 [1966]4406).
[6) J. F. Cannon, H. T. Hall (lnorg. Chem. 9 [1970)1639/43).
[7) J. F. Cannon (Diss. Brigham Young Univ. 1969, pp. 1/54, 18/32; C.A. 73 [1970] No. 41282).
[8) L. Domange, J. Flahaut, M. P. Pardo, A. N. Chirazi, M. Guittard (Compt. Rend. 250 [1960)
857/8).
[9) A. A. Eliseev, V. G. Kuznetsov (lzv. Akad. Nauk SSSR Neorgan. Materialy 1 [1965] 692/7;
lnorg. Materials [USSR]1 [1965] 635/9).
[10) R. Wang, H. Steinfink, W. F. Bradley (lnorg. Chem. 5 [1966]142/5).
[11) G. V. Lashkarev, Yu. B. Paderno (lzv. Akad. Nauk SSSR Neorgan. Materialy 1 [1965]
[12) J. Flahaut, P. Laruelle (Progr. Sei. Techno!. Rare Earths 3 [1968)149/208, 156/9).
[13) V. V. Gorbachev, V. A. Linskii, S. P. lonov, 0. A. Sadovskaya, A. Yu. Aleksandrov (lzv.
Akad. Nauk SSSR Neorgan. Materialy 13 [1977)222/6; lnorg. Materials [USSR]13 [1977)
188/91).
[14) V. V. Gorbachev, V. A. Linskii, S. P. lonov, 0. A. Sadovskaya (Khim. Svyaz Krist. lkh Fiz.
Svoistva 2 [1976]201/8; C.A. 86 [1977] No. 25033).
[15] J. F. Miller, F. J. Reid, L. K. Matson, et al. (AD-607082 [1964] 1/79, 42; C.A. 62 [1965]
15562).
[16] J. F. Miller, F. J. Reid, L. K. Matson, R. C. Hirnes (AD-428091 [1963] 1/65, 14; C.A. 61
[1964)14012).
Neorgan. Materialy 2 [1966]1747/56; lnorg. Materials [USSR] 2 [1966]1506/14, 1509).
[18) W. Lin, H. Steinfink, E. J. Weiss (lnorg. Chem. 4 [1965]877/81).
2926/30; Russ. J. lnorg. Chem. 30 [1985)1666/9).
[20) A. A. Eliseev, E. I. Yarembash, V. G. Kuznetsov, L. I. Antonova, Z. P. Stoyantsova (lzv.
Akad. Nauk SSSR Neorgan. Materialy 1 [1965]1027/38; lnorg. Materials [USSR)1 [1965]
943/52, 949).
1572/8; lnorg. Materials [USSR] 6 [1970)1388/93).
[22) E. I. Yarembash, A. A. Eliseev, E. S. Vigileva, L. I. Antonova (lzv. Akad. Nauk SSSR
Neorgan. Materialy 3 [1967] 2184/9; lnorg. Materials [USSR]3 [1967]1905/9).
[23) J. C. Andrellos, P. Bro (Solid-State Electron. 5 [1962) 414/6).
[24] M. P. Pardo, J. Flahaut (Bult. Soc. Chim. France 1967 3658/64).
[25] E. I. Yarembash, E. G. Tyurin, A. A. Reshchikova, A. Karabekov, N. N. Klinaeva (lzv.
Akad. Nauk SSSR Neorgan. Materialy 7 [1971) 761/5; lnorg. Materials [USSR] 7 [1971]
661/5).
[26] K. Niihara, T. Shishido, S. Yajima (Bult. Chem. Soc. Japan 45 [1972]1239/40).
[27) R. Wang (Diss. Univ. Texas 1967, pp. 1/138; Diss. Abstr. B 27 [1967]4380).
[28) N. Kh. Abrikosov, K. A. Zinchenko, A. A. Eliseev (lzv. Akad. Nauk SSSR Neorgan.
Materialy 6 [1970) 720/5; lnorg. Materials [USSR]6 [1970] 634/8).
[29) V. K. Slovyanskikh, N. T. Kuznetsov, N. V. Gracheva (Zh. Neorgan. Khim. 30 [1985]
1895/6; Russ. J. lnorg. Chem. 30 [1985]1077).
[30] A. A. Eliseev, A. A. Grizik (in V. P. Zhuze, I. A. Smirnov, Redkozemel'nye Poluprovodniki,
Nauka, Leningrad 1977, pp. 146/77, 163).
[31) T. H. Ramsey, H. Steinfink, E. J. Weiss (J. Appl. Phys. 34 [1963] 2917/8).
Gmelm Handbock
RE Mam Vol C 10
Preparation of M2Te5 53
30.1.2.6 Comparative Data for M2Te 5
Existence and Preparation
Polytellurides M2Te 5 have been obtained forM = Y and La to Ho (except Eu; forM = Y
and Ho they were contaminated with other phases) by Pardo, Flahaut [1]. For the existence
of Eu 2Te 5 and Tm 2Te 5 , see pp. 158 and 251. The compounds are stable only in a limited range
of temperature and are prepared from the elements in evacuated ampules within this range
(see below) [1]. Nd 2Te 5 was prepared in this way in quartz tubes by heating below 700°C for
at least two weeks; it is dark golden-colored, Lin et al. [2]. According to [1] the compounds
M2Te 5 are dark brown powders which sometimes contain golden crystalline lamellas. Ce 2Te 5
was described as dark lilac powder with a golden Luster, Chukalin et al. [3], Pr 2Te 5 as golden
plates, Yarembash, Vigileva [4].
Upper and lower temperatures t 1 and t2 (in °C) of the stability range of M2Te 5 according
to [1]:
M in M 2Te 5 y La Ce Pr Nd Sm Gd Tb Dy Ho
t1 ± 5°C 788 811 870 890 903 880 886 870 854 795
t2 ± 50°C >700 650 600 600 450 550 650 >700
Further values for the (peritectic) temperature t 1:
La2Te 5 Ce 2Te 5 Nd 2Te 5 Sm 2Te5 Gd2Te5
t 1 in oc 813 875 910 830 920

Ref. [5] [3] [2, 6] [7] [8]
For t 1, seealso the individual M-Te systems.

A graphic plot of t 1 and t 2 for all M2Te 5 is shown by Pardo, Flahaut [9] and Flahaut, Laruelle
[10].
Crystallographic Propertles. Density

The structure of all M2Te 5 is orthorhombic, pseudotetragonal with space group
Bmmb-D~f, (No. 63), Z = 4 [1] from X-ray diffraction on Nd 2Te 5 single crystals [2]. Lattice
constants a ( = b) and c in A and density D in g/cm 3 (a ± 0.010 A and c ± 0.1 A in [1]):
La2Te5 Ce2Te 5 Ce 2Te 5 Pr2Te 5 Nd 2Te 5 Nd 2Te 5
a. 4.465 4.444 4.42 4.426 4.380 4.409

c. 44.7 44.5 44.35 44.3 44.0 44.1
Deale 6.83 6.94 7.08 7.04 7.29 7.18
Dexp 6.87 6.97 7.10
Ref. [1, 9] [1, 9] [3] [1, 9] [2] [1, 9]
Gmelin Handbock
RE Main Vol. C10
54 M 2Te 5
Sm 2Te 5 Sm 2Te5 Gd 2Te 5 Dy2Te 5 Ho2Te 5 Tm 2Te 5
a. 4.362 4.362 4.336 4.299 4.411 4.44

c. 43.8 43.23 43.6 43.3 45.03 44.97
Deale 7.48 7.72 8.00
Dexp 7.35
Ref. [1' 9] [7] [1, 9] [1' 9] [16] [15]
The X-ray powder pattern ol La2Te 5 was indexed tetragonally with a = 4.397 and c = 25.92 A
by [5]. measured density = 6.20 g/cm 3 .
ln Nd 2Te 5 all atoms occupy the position 4 c (0, 1I 4 , z). Values of z ( ± 0.001):
Te(1) Te(2) Te(3) Te(4) Te(5) Nd(1) Nd(2)

0.040 0.460 0.250 0.826 0.618 0.901 0.691
·<>·
0
• Nd
•
·<>·
o Te 0
td~:
ß 0
·-<>· -cx
•
' ; 0
· 0·
NdTe 2 NdTe3 Nd 2Te 5
Fig. 12. Schematic crystal structure of the polytellurides NdTe2 , NdTe3 , and Nd2Te 5 .
The Nd atoms are coordinated by nine Te atoms. Nd 2Te5 has a layer structure like NdTe2 and
NdTe3 (see the comparison of the schematic structures in Fig. 12 from Pardo, Flahaut [9].
Flahaut, Laruelle [10]; the unit cell for NdTe3 was taken from Norling, Steinfink [14]) . A simple
compact Te layer is present in NdTe2 , a double compact Te layer in NdTe3, and an alternating
arrangement of these two motils in Nd 2Te 5 . There are three sorts of Te atoms in th e latter
structure , designated as a., ß, and y in Fig . 12 (right). The Te atoms y, i.e. Te(1) and Te(2), form
the double layer. They are coordinated by 2 Nd + 4 Te from the same Layer. The Te atoms a.
Gmelon Handbook
RE Main Vol. C10
Crystallographic and Electrical Properlies 55
in z = 1/ 4 and 3 / 4 , i.e. Te(3), form the simple layer and are coordinated by 4 Nd + 4 Te(or.). The
Te atoms ß, i.e. Te(4) and Te(5), situated between the layers, have five Nd as nearest neighbors;
Te atoms at a distance of 4.09 A are not involved in the coordination sphere. lnteratomic
distances in A (±0.04 A) [9, 10]:
Te(or.)-Te(or.) Te(ß)-Te(or.) Te(ß)-Te(ß) Te(y)-Te(y) Te(ß)-Te(y)

3.12 4.01 3.98 3.12 4.09
Nd-Te(ot) Nd-Te(ß) Nd-Te(y) Nd-Nd

3.41 3.21 to 3.31 3.44 5.12
The shortest Te-Te distance between the Te layers in the double layer is 4.16 A [9]. For
computer calculation of anion vacancies in Ho2Te 5 , see Kutolin et al. [17].
Mössbauer Effect. Electrical Properlies
The following table contains the results of the 125fe Mössbauer spectra (35.5 keV y-
transition, source 125fe0 3) and of electrical measurements of M2Te 5 with M = La, Pr, and Nd;
ö = chemical shift in mm/s, r = line width in mm/s, K = electrical conductivity in n- 1 · cm-1,
S = thermoelectric power in llV/K, and n = carrier concentration in cm- 3 :
Ö±0.2 r±o.2 K s n Ref.
La2Te5 . 1.10 9.0 370 + 16 7 X 1017 [11]

Pr2Te 5 . 1.70 10.9 500 + 19.4 5 X 1017 [11]
Nd 2Te 5 . 1.70 10.50 610 +18 8 X 1017 [11]
Nd 2Te 5 . 0.75 -36 2.3 X 1018 [13]
The Mössbauer spectra are compared with those of other compounds in the M-Te systems
(M = La, Pr, Nd) by Gorbachev et al. [11, 12]; see p. 18. The Hall coefficient IRHI = 2.7 cm 3/C
for Nd 2Te5 at 298 K. Zinchenko et al. [13]. The values K = 100 n- 1 • cm- 1 and S = +50 to
60 1-1V/K are reported for Pr2Te 5 [4].
Chemlcal Reactions
The compounds M2Te5 are only stable in a limited range of temperature; see the table on
p. 53. At the peritectic temperatures (t1) they were assumed to decompose according to
M2Te5 ~ 2 MTe2 + Te (M = La to Dy) or M2Te 5 ~ M2Te 3 + 2 Te (M = Ho, Y). On prolonged
heating at ;;::;; t 2, the tellurides M2Te5 disproportionate into MTe2 + MTe3 forM = La to Dy and
into M2Te 3 + MTe3 for M = Y and Ho [1, 10]. However, other studies show the peritectic
reaction to be M2Te5 ~ M3Te 7 + melt for M = La to Sm and a decomposition in the solid
state has not been observed; see the individual M-Te systems.
The darkgolden colared single crystals of Nd 2Te 5 easily tarnish at room temperature in
air and their color turns to gray-black within several hours [2].
Gmelin Handbook
RE Main Vol. C10
56
References:
[1] M. P. Pardo, J. Flahaut (Compt. Rend. C 263 [1966]1058/60).
[5] A. A. Eliseev, E. I. Yarembash, V. G. Kuznetsov, L. I. Antonova, Z. R. Stoyantsova (lzv.
943/52).
661/5).
[9] M. P. Pardo, J. Flahaut (Bult. Soc. Chim. France 1967 3658/64).
[10] J. Flahaut, P. Laruelle (Progr. Sei. Techno!. Rare Earths 3 [1968]149/208, 166/9, 198).
188/91).
Svoistva 2 [1976]201/8; C.A. 86 [1977] No. 25033).
[14] 8. K. Norling, H. Steinfink (lnorg. Chem. 5 [1966]1488/91).
[15] A. A. Eliseev, K. A. Zinchenko, V. M. Zemlyanukhina, Nguyen' Chin'Tam (Zh. Neorgan.
Chem. 56 [1982]606/8).
30.1.2. 7 Comparative Data for M 4Te 11

ln the M-Te phase diagrams with M = La, Ce, Pr, Nd, and Dy (see the individual sections),
shown by Yarembash, Eliseev [1], phases with the approximate composition M4Te 1 ux are
formed at the following peritectic temperatures tP from M 2Te 5 and the melt:
tP in °C. . . . . . 780 830 830 850 855
ln earlier works of these [1] and other authors, before knowledge of the existence of M4Te 11 ,
such high temperatures were regarded as the peritectic temperatures of MTe3 phases (see
p. 59).
Gmelm Handbock
RE Mam Vol C 10
57
From X-ray diffraction on Pr4Te 11 (see p. 114) it was concluded that the M 4Te 11 phases
(M = La to Sm) have orthorhombic symmetry with space group Pmna [1, pp. 191, 241]. But in
the Sm-Te phasediagram the phase Sm 4Te 11 was not observed (see p. 128) and the absence
is explicitly noted in [1, p. 205].
The following table contains the results of the 125Te Mössbauer spectra (35.5 keV
y-transition, source 125Te0 3 ) and of electrical measurements of La 4Te 11 and Nd 4 Te 11
(o = chemical shift in mm/s, r
= Line width in mm/s, K = electrical conductivity inn- 1 · cm-1,
S = thermoelectric power in 11V/K, n = carrier concentration in cm- 3 , and .-1E = width of the
forbidden zone in eV) from Gorbachev et al. [2]:
0 ±0.2 r±o.2 K s n .-1E
1.32 10.8 550 + 15 1.5X10 18 0.06

1.9 11.20 1.7 +51 5.95 X 10 17 0.41
(M = La, Pr, Nd) by Gorbachev et al. [2, 3]; see p. 18.
References:
Moscow 1975, pp. 1/260, 169/256).
188/91 ).
Svoistva 2 [1976] 201/8; C.A. 86 [1977] No. 25033).
30.1.2.8 Comparative Data for MTe 3

The polytellurides MTe3 with M = La, Ce, and Pr were prepared from the reaction of Te
with freshly cleaned rods of the rare earth metals enclosed in a large evacuated Vycor tube.
The reaction was almost complete in 20 hat 700 to 750°C. The MTe3 formed are lustrous Light
pink-brown platelets imperfectly periodic in the direction of the c axis. LaTe 3 and CeTe 3 are
not stable above ~600°C in the absence of excess Te vapor (but see the lower peritectic
temperatures, p. 59). When LaTe 3 and CeTe 3 are exposed to the air at room temperature they
undergo a slow or a rapid decomposition, respectively, to gray products, Carter [1]. WeiL
ordered LaTe 3 was obtained in the form of metallic golden flakes of about 1 mm size and also
as a very fine powder by reaction of the elements in quartz vials above 400°C, Ramsey et al.
[2]. MTe 3 with M = Y and La to Tm except Eu were prepared from the elements in closed
ampules at ~500°C. Attempts to prepare YbTe 3 and LuTe3 at 500°C failed, Pardo et al. [3].
However, on application of pressure, shiny golden colored metastable LuTe 3 formed within 5
to 60 min above ~320°C. The minimum required pressurewas ~ 17 kbar at 700°C and the
minimum required temperature was ~420°C at 69 kbar (for a pressure-temperature synthesis
diagram, see the papers). ScTe 3 could not be obtained with pressures up to 100 kbar and
temperatures up to 1200°C, Cannon, Hall [20], Cannon [21].
Gmelm Handbook
RE Main Val. C10
58

Tritelluride crystals are usually diserdered and easily form twins. This led sometimes to
the beliefthat MTe3 has tetragonal symmetry, space group P42 /n-C~h• Z = 4; see for example,
Eliseev et al. [6] for LaTe 3 ; Yarembash et al. [16] for PrTe 3 ; Zinchenko et al. [11] for NdTe3 ; cf.
Carter [1] for MTe 3 with M = La, Ce, and Pr. However, the symmetry is orthorhombic
pseudotetragonal, space group Bmmb-D~h (No. 63), Z = 4 from X-ray diffraction of an
untwinned NdTe3 crystal, Norling, Steinfink [14]. ln his recent review, Eliseev [25], too, lists
the MTe3 compounds with M = La to Sm, Gd to Ho, and Lu as orthorhombic of the NdTe3
structure. Lattice constants a, b, and c in A (note, a "#- b in case of M = Tm, Lu) and density
D in g/cm 3 :
YTe 3 LaTe 3 LaTe 3 LaTe 3 a) LaTe 2_8a) CeTe 3 CeTe 3 PrTe 3 PrTe2.98a)
a (= b). 4.303 4.422 4.407 4.38 4.405(10) 4.398 4.38 4.376 4.371(5)
c 25.49 26.09 26.14 26.1 25.90(10) 25.99 26.0 25.89 25.57(1)
Deale 6.64 6.80 6.92 6.63 6.91 7.00 7.02 7.10
Dexp 6.65 6.88 6.62 6.87 6.95 6.82 7.06
Ref. [3, 4] [3, 4] [2, 5] [1] [6] [3, 4] [7] [3, 4] [16]
NdTe3 NdTe3 NdTe3 a) SmTe 3 SmTe 3 GdTe3 TbTe 3 DyTe 3 DyTe 28
a (=b). 4.364 4.350 4.347 4.335 4.339 4.326 4.310 4.296 4.28
c 25.80 25.80 25.794 25.65 25.88 25.58 25.52 25.45 25.28
Deale 7.13 7.17 7.35 7.49 7.59 7.71
Dexp 7.12 7.0 6.98
Ref. [3, 4] [9, 14] [11] [3, 4] [13] [3, 4] [3, 4] [3, 4] [26]
HoTe3 HoTe3 bl ErTe3 ErTe3 ErTe3 TmTe 3 TmTe 3 LuTe 3
a 4.290 4.293 4.282 4.285 4.31 4.274 4.267(3) 4.277(1)

b 4.290 4.293 4.282 4.285 4.31 4.274 4.270(6) 4.278(1)
c 25.40 25.40 25.36 25.278 24.45 25.34 25.32(2) 25.137(6)
Deale 7.79 7.83 7.93
Ref. [3, 4] [10] [3, 4] [15] [27] [3, 4] [24] [20]
a) Originally assumed to be tetragonal. - b) a = b = 4.273, c = 24.87 A was reported earlier
by [23].
The structure of MTe 3 , studied on NdTe3 , is closely related tothat of NdTe2 and Nd 2Te 5 ;
see Fig. 12 on p. 54 from Pardo, Flahaut [4], Flahaut, Laruelle [17]. The Nd atoms in these
structures have identical coordination. ln the NdTe3 structure all four crystallographically
independent atoms are in positions 4(c) (0, 1/ 4 , z) with z = 0.8306 for Nd and z = 0.07505 for
Te(1), 0.4294 for Te(2), and 0.7047 for Te(3). There are essentially only two typesofTe and one
type of Nd in the structure. The Te(1) and Te(2) atoms designated as y in Fig. 12 form a double
layer and have identical coordination polyhedra, i.e., irregular prisms. The coordination
polyhedron of Te(3) designated as ß in Fig. 12 is a nearly regular pyramid. lnteratomic
distances in A: Nd-Te(3) = 3.208(4 x) and 3.246(1 x ), Nd-Te(1 ,2) = 3.353(4 x); Te(3)-Te(3) =
3.862(4 x ), Te(3)-Te(1 ,2) = 4.089(4 x); Te(1 ,2)-Te(1 ,2) = 3.076(4 x) and 4.240(4 x ). The nearest
Nd-Nd distance is 4.350 A, Norling, Steinfink [14].
Gmelm Handbock
RE Mam Vol. C 10
Thermal and Electrical Properties 59
Melting Points
The MTe3 phases melt incongruently. ln the case of MTe3 with M = La to Sm, which
decompose according to Yarembash, Eliseev [10] into M4Te 11 + melt, the peritectic decomposi-
tion temperatures tP are considerably lower than the values [3, 4] reported before discovery
of the M4Te 11 phases (see p. 56) existing between M 2Te 5 and melt:
tP in oc 465 779 485 829 455 832 460 834 465 823
Ref. [10] [3, 4] [10] [3, 4] [8, 10] [3, 4] [10] [3, 4] [10, 13] [3, 4]
The other compounds decompose into M 2Te 5 + melt or into M 2Te 3 + melt (M = Er and Tm),
Pardo, Flahaut [4], Flahaut, Laruelle [17]. Values of tP from [3, 4] (and in parentheses from
[12]):
813(835) 870 788 760 678 553
Further values are given in the individual M-Te systems.
Mössbauer Effect. Electrical Properlies

The following table contains the results of the 12Sfe Mössbauer spectra (35.5 keV y-
transition, source 125Te0 3 ) and of electrical measurements of MTe3 with M = La, Pr, and Nd;
ö = chemical shift in mm/s, r = Une width in mm/s, K = electrical conductivity in n- 1 · cm- 1 ,
S = thermoelectric power in jlV/K, and n = carrier concentration in cm- 3 [18]:
Ö±0.2 r±o.2 K s n
LaTe 3 . 1.35 11.6 1000 +12.3

PrTe 3 . 1.60 11.5 3000 + 11.0 7 X 1017
NdTe3 . 1.80 12.50 5300 + 10.3
(M = La, Pr, Nd) by Gorbachev et al. [18, 19] (see p. 18). Values for NdTe3 at 300 K from
Abrikosov, Zargaryan [22]: K = 690 n- 1 cm-1, s = +44j.1V/K. However, NdTe3 with 75.13
0
at% Te had K = 0.1320- 1 · cm-1, S = -31j.1V/K, n = 2.4x 1018 cm- 3, and Hall constant
IRHI = 3.1 cm 3/C at 298 K [11].
References:
[1] F. L. Carter (Met. Soc. Conf. Proc. 15 [1962]245/61; C.A. 59 [1963]14695).
[2] T. H. Ramsey, H. Steinfink, E. J. Weiss (Proc. 3rd Conf. Rare Earth Res., Clearwater, Fla.,
1963 [1964], Vol. 2, pp. 303/14).
[3] M. P. Pardo, 0. Gorochov, J. Flahaut, L. Domange (Compt. Rend. 260 [1965]1666/9).
[4] M. P. Pardo, J. Flahaut (Bull. Soc. Chim. France 1967 3658/64).
[5] T. H. Ramsey, H. Steinfink, E. J. Weiss (lnorg. Chem. 4 [1965] 1154/7; J. Appl. Phys. 36
[1965] 548/53).
Gmelin Handbook
RE Mam Vol. C10
60

943/52).
Moscow 1975, pp. 1/260, 169/256).
661/5).
[14] B. K. Norling, H. Steinfink (lnorg. Chem. 5 [1966]1488/91).
Ser. II Khim. 21 [1980]339/44; Moscow Univ. Chem. Bull. 35 No. 4 [1980]36/41).
[17] J. Flahaut, P. Laruelle (Progr. Sei. Technol. Rare Earths 3 [1968]149/208, 164/8).
188/91).
Svoistva 2 [1976] 201/8, C.A. 86 [1977] No. 25033).
[20] J. F. Cannon, H. T. Hall (lnorg. Chem. 9 [1970] 1639/43).
[21] J. F. Cannon (Diss. Brigham Young Univ. 1969, pp. 1/54, 32; C.A. 73 [1970] No. 41282).
[24] E. Kaldis, E. Jilek, H. Spychiger (J. Less-Common Metals 93 [1983]399/409, 404).
627/33).
[26] V. N. Slovyanskikh, N. T. Kuznetsov, N. V. Gracheva, V. G. Kipiani (Zh. Neorgan. Khim.
30 [1985] 3027/8; Russ. J. lnorg. Chem. 30 [1985]1720/1).
30.1.2.9 Rare Earth Metals in Molten Te
The electrical resistivity of liquid Te containing 0.5, 1.0, and 1.5% Y between the melting
point and ~850°C is somewhat increased compared with that of the pure Te melt (see a figure
in the paper), Ohno [1]. The electrical resistivity Q and the magnetic susceptibility were
measured from the melting temperatures up to about 900°C for Te melts containing one of the
elements La, Ce, Pr, Nd, Sm, Gd, Dy, Er, or Yb insmall amounts (up to 2 to 3 at%). For the
Gmelin Handbock
RE Mam Val. C 10
ScTe 61
melts Q is a little higher than for pure Te and Q decreases smoothly with increasing temperature
as with Te. The additional resistivity L\Q does not vary much from one rare earth to another
(see curves in the paper), except for the Gd melt, which shows a noticeable higher L\Q value.
The increments of the resistivity caused by the rare earth solutes are i nterpreted as a decrease
in the density of states at the Fermi Level. The magnetic susceptibility of the melts (except
with La) is somewhat higher than for pure Te. The additional susceptibilities of Gd, Dy, and
Er solutes are much larger than those of the light rare earths (see curves in the paper). The
temperature independent susceptibilities of light rare earth solutes are considerably larger
than the theoretical values, and the effective magneton numbers are smaller than the theoreti-
cal values. The results suggest that the 4f electrons of light rare earth solutes interact with
the conduction electrons, Kakinuma, Ohno [2].
References:
[1] S. Ohno (J. Phys. Soc. Japan 42 [1977]194/200, 195).

[2] F. Kakinuma, S. Ohno (J. Phys. Soc. Japan 50 [1981]1951/7).
30.1.2.1 0 Data for Individual Tellurides
30.1.2.1 0.1 Scandium Tellurides
Additional data for ScTe and Sc2Te 3 are found in Sections 30.1.2.1 and 30.1.2.3, on pp. 6
and 31, respectively.
30.1.2.10.1.1 ScTe
ScTe can be prepared from the elements in a similar manner as the other rare earth
monotellurides; see p. 6. For example, the compound was obtained by reacting the
components in vacuum-sealed quartz ampules according to the following heating scheme:
20 to 400°C (1 h), 400°C (4 h), 400 to 500°C (6 h), 500 to 1 ooooc (1 h), and 1ooooc (6 h). The
ScTe so-obtained was a crystalline powder, Men'kov et al. [1]. The black ScTe has according
to X-ray powder diffraction studies the hexagonal NiAs-type structure, space group
C6/mmc-D3h (No. 194), Z = 2. Lattice constants in Aare: a = 4.130, c = 6.748, Men'kov et
al. [1]; a = 4.122, c = 6.748, Zhuze et al. [2]. Deviating values reported by Brixner [3, 4] are
a = 6.728, c = 8.360 A. According to the review of Gschneidner [7] it is not clear if ScTe is
polymorphic or if one of the results of [1] or [3, 4] is wrong. The measured density is
Dexp = 5.65 g/cm 3 [1]; the X-ray density Deale = 5.75 g/cm3 [1, 2].
The paramagnetic susceptibility x of ScTe, measured in vacuum or He between 290

x
and 700 K is = 230 x 10- 6 cm 3/mol at 300 K and 1/x increases somewhat with increasing
temperature. x does not change in magnetic fields with an induction of 0.7 to 1.4 T, Adamyan
et al. [5]. The paramagnetic behavior and the metallic conduction are due to the presence of
one delocalized electron per Sc atom. The conduction electron density is ~2 x 1022 cm- 3
[2, 5]. The electrical resistivity Q of single crystals is 1.95 x 10- 4 n · cm at 300 K [2]. A graph
given in the paper shows that Q climbs from ~ 1.9 x 10- 4 at 300 K to ~ 5.7 x 10- 4 n · cm at
Gmelin Handbook
RE Main Vol. C10
62 Scandium Tellurides
1400 K, while the thermoelectric power S declines between 400 and 1100 K from ~ + 8
to ~ -18 J.!VIK, Komarova et al. [6]. The deviating high values Q = 9.55 Q · cm at 298 K
(and 200 Q · cm at 77 K) and S = -255 J.!VIK are reported by [3, 4] for a sample with Dexp =
3.58 g/cm 3 and the lattice constants mentioned above. This product is said to be suitable as
thermoelectric material [4).
The reflection spectrum of Sc Te single crystals in the 0.05 to 21 eV range has been analyzed
by means of the Kramers-Kronig relation. Plots of the reflection R, the real part E' and the
imaginary part E" of the complex dielectric function, the energy loss function E"/[(E') 2 + (E") 2],
and the X-ray photoelectron spectrum (for binding energies down to ~so eV below the Fermi
energy) are shown in the paper as a function of the photon energy. R has a minimum at
1.75 eV and maxima at 2.5, 7.6, 9.5, and 12.3 eV; E" has a deep minimum at 1.8 to 1.9 eV which
separates the low-energy region with "free" electron behavior from the high-energy region
of interband transitions. Maxima of E" are observed at 2.5, 7.5, 9.4, and 11.8 eV. The estimated
optical effective mass is m* = 3.2 m 0 . Screened and unscreened plasmon energies of conduc-
tion electrons are w~ = 1.4 and wP = 2.90 eV. The value E 00 = 4.4 is given for the optical
dielectric constant in the absence of conduction electrons and ' = 2.25 x 10- 15 s for the
relaxation time. The results are interpreted as for ScSe and SeS (see "Rare Earth Elements"
C7, 1983, pp. 134/5 and C9, 1986, p. 66), Zhuze et al. [2].
Crystals of ScTe exhibit significant dissociation when heated above 750 to 800 K [5].
References:
[1) A. A. Men'kov, L. N. Komissarova, Yu. P. Simanov, V. I. Spitsyn (Dokl. Akad. Nauk SSSR
141 [1961]364/7; Proc. Acad. Sei. USSR Chem. Sect. 136/141 [1961)1137/40).
[2) V. P. Zhuze, A. V. Golubkov, M. G. Karin, et al. (Fiz. Tverd. Tela [Leningrad] 24 [1982)
1017/25; Soviet Phys.-Solid State 24 [1982) 577/82).
[3) L. H. Brixner (J. lnorg. Nucl. Chem. 15 [1960]199/201).
[4) L. H. Brixner, E. I. Du Pont de Nemours & Co. (Can. 649835 [1960/62); C. 1965
No. 41-2217).
[5] V. E. Adamyan, A. V. Golubkov, V. P. Zhuze (Fiz. Tverd. Tela [Leningrad] 23 [1981)
1814/5; Soviet Phys.-Solid State 23 [1981)1057/8).
[6) T. I. Komarova, V. M. Sergeeva, A. G. Tutov (Poluch. lssled. Svoistv Soedin. RZM Mater.
1st Nauchn. Semin., Baku 1972 [1975], pp. 43/5; C.A. 83 [1975] No. 186923).
[7) K. A. Gschneidner Jr. (in: C. T. Horovitz, Scandium: lts Occurrence, Chemistry, Physics,
Metallurgy, Biology, and Technology, Academic, London 1975, pp. 1/598, 152/251, 156/7).
30.1.2.1 0.1.2 Sc 2Te 3
Polycrystalline Sc 2Te 3 was prepared by direct reaction of the elements at 1 000°C, using a
small amount of iodine as a mineralizer. Single crystal plates of Sc 2Te 3 were then obtained
by a chemical transport reaction with 12 as the carrier gas (see p. 31 ). The platelets, frequently
twinned, have a bright silvery appearance, but develop a black surface layer after several
days exposure to air, White, Dismukes [1]. A polycrystalline black powder of Sc 2Te 3 forms by
heating the stoichiometric elemental mixture in evacuated sealed quartz ampules for 3 h at
400°C, then slowly within 5 h to 500°C and in 4 hto 1 000°C, Men'kov et al. [2).
Gmel1n Handbock
RE Ma1n Val. C 10
63
According to X-ray single crystal diffraction studies Sc 2Te 3 is rhombohedral, space group
R3m-ogd (No. 166); Z = 4/ 3 in the rhombohedral cell and Z = 4 in the hexagonal cell. The
lattice constants are a = 13.72(2) A, a. = 17°12' ± 2' or ah = 4.109(4), eh = 40.59(5) A,
respectively. Calculated density = 5.29 g/cm 3 . ALL Sc atoms are on octahedral sites. Atom
positions and interatomic distances in A:
atom site position interatomic distances
Te(1) 6c ±(0, 0, 0.1247) Sc(1)-Te(2) = 2.91

Te(2) 6c ± (0, 0, 0.2918) Sc(2)-Te(1) = 2.92
Sc(1) 3a (0, 0, 0) Sc(3)-Te(1) = 2.94
Sc(2) 3b (0, 0, 1/2) Sc(3)-Te(2) = 2.88
Sc(3) 6c Ct 3) ±(0, 0, 0.4150) Sc(2)-Te(3) = 3.45
The Te atomsform a 12-layer stacking sequence containing regions of both cubic and hexag-
onal close packing. The structure may be regarded as being made up of alternate regions of
NaCl and NiAs structure types with the atoms Sc(3) common to both regions being only one-
third occupied [1). For a schematic figure of the structure see the paper [1) and Flahaut,
Laruelle [3]. A nonstoichiometric compound, Sc_ 2_3Te 3 , has the same structure [1). The black
polycrystalline Sc2Te 3 was reported to have the fcc cubic structure of the y' -Al 20 3 type
(defective structure) with a = 5.817 A, Z = 413 , Deale = 5.32, and Dexp = 5.26 g/cm 3 , Men'kov
et al. [2, 4]. For the calculation of the enthalpy of formation and of disproportionation and
reduction reactions using various empirical equations, see Moody, Thomas [5].
References:
[1) J. G. White, J. P. Dismukes (lnorg. Chem. 4 [1965]1760/3).
128 [1959) 92/4; Proc. Acad. Sei. USSR Chem. Sect. 124/129 [1959] 693/5).
[3) J. Flahaut, P. Laruelle (Progr. Sei. Technol. Rare Earths 3 [1968)149/208, 183/4).
141 [1961)364/7; Proc. Acad. Sei. USSR Chem. Sect. 136/141 [1961)1137/40).
[5] G. J. Moody, J. D. R. Thomas (J. Chem. Soc. 1964 1417/22).
30.1.2.10.2 Yttrium Tellurides

Additional data for YTe and Y2Te 3 are found in Sections 30.1.2.1 and 30.1.2.3 on pp. 6 and
31, respectively. Data for YTe 2 _x, Y2Te 5 , and YTe 3 are found in Sections 30.1.2.5, 30.1.2.6,
30.1.2.8 on pp. 47, 53, and 57, respectively.
Y2Te 3 and Phases in the Y2Te 3-YTe System

Y2Te 3 has the orthorhombic 1;-M 2Te 3 structure with a cubic subcell (see p. 34), and generally
a cubic NaCl type structure with a ~6.09 Ais reported forYTe (see p. 8). However, a continuous
series of orthorhombic solid solutions between Y2Te 3 and YTe was assumed by Norman [1).
The samples of the Y2Te 3 - YTe system were prepared by vapor-solid reaction of the
elements (cf. p. 31) in quartz ampules at 900 or 1 000°C for 125 to 150 h followed by heating
at 1200°C for 1 to 2 h and then hot pressing the reaction products at ~ 1 000 to ~ 1200°C and
Gmelin Handbock
RE Main Val. C 10
64 Yttrium Tellurides
E
u
c:
.!:
Q.
Fig . 13.
Electrical resistivity Q of yttrium
tellurides versus temperature.
Temperature in °C
Fig. 14.
Seeback coefficient S of yttrium
tellu rides versus temperature.
-4oo0~~~~~~~L_~~L-~~~
200 400 600 800 1000
Temperature in °C
Gmeh n Handbook
RE Mam Val. C 10
Y2Te 3. The La-Te System 65
pressures from ~48.3 to ~68.9 MPa (7000 to 10000 psi). The lattice constants a = 12.20, b =
8.62, c = 25.84 A (Z = 16), and the calculated density Deale = 5.48 g/cm 3 are reported for
Y2Te 3, a = 12.21, b = 8.63, c = 25.85 A (Z = 12), Deale = 5.69 g/cm 3 for YTe 1.33 , and a =
12.45, b = 8.63, c = 25.62 A (Z = 48), Deale = 6.30 g/cm 3 for YTe [1]. However, Muir [2] found
a sample of the composition YTe 1.44 to be biphasic.
Thermal conductivity 'A in W · m- 1 · K- 1 for samples with compositions YTe and YTe 1.33
between 30 and 300°C (value for 300°C is extrapolated):
YTe 1.57 1.21 0.91 0.72

YTe1.33 1.56 1.28 0.94 0.71
The electrical resistivity Q and the Seebeck coefficient S of samples with compositions YTex
with x = 1.0 to 1.5 as a function of the temperature are shown in Fig. 13 and 14 [1], respectively.
For the two-phase sample YTe 1.44 the values S = 0 at 100°C and S = -300 11V/K at 200°C are
reported. At 400, 600, and 800°C the Seebeck coefficient S ~ -125, -80, and -125 11V/K is
read from a figure in the paper. The electrical resistivity has a maximum of ~0.55 Q · cm at
600°C ( ~0.25 Q · cm at room temperature) (2]. Figure of merit Z = S2 · K · 'A - 1 in K- 1 at 30
and 200°C and the highest value of Z (1]:
highest Z value
YTe1.0. 9 X 10- 6 1 X 10- 5 4 x 10- 5 at 740°C

YTe1.33 4 X 10-S 4 X 10- 7 2 x 10- 6 at 830°C
YTe1.5o 8 X 10-10 2 X 10- 7 1 X 10- 6 at 800°C
References:
[1] L. D. Norman (U.S. Bur. Mines Rept. lnvest. No. 6851 [1966]1/19, 4, 11, 15/9; C.A. 66 [1967]
No. 14966).
[2] H. M. Muir (AD-277043 [1960/61]1/47, 25,41; N.S.A.17 [1963] No. 11292).
30.1.2.10.3 Lanthanum Tellurides
Additional data for LaTe, La 3Te 4 , La2Te 3, La 4Te 7 (= LaTe 1.7 ±x), LaTe 2 _x, La 2Te 5, La 4Te 11 ,
and LaTe 3 are found in Sections 30.1.2.1, 30.1.2.2, 30.1.2.3, 30.1.2.4, 30.1.2.5, 30.1.2.6, 30.1.2.7,
and 30.1.2.8 on pp. 6, 21, 31, 43, 47, 53, 56, and 57, respectively.
30.1.2.10.3.1 The La-Te System
Phase Diagram
The phase diagram in Fig. 15, p. 66, from Yarembash, Eliseev [1] is based on DTA and
X-ray diffraction studies by Yarembash [2] and Eliseev (3]. lt reveals the phase LaTe which
melts congruently at ~ 1750°C and the incongruently melting phases La 3_y Te 4 (y = 0 to 0.33),
Gmelm Handbock 5
RE Main Vol. C 10
66 Lanthanum Tellurides
1600
/
/
/
u I
0 1200
I
-~ I
/
~ /
:I /
/
~ 8850C
g- 800
~ \
I
I
4001::------ - - .i2_Q.O_f - - - '

f-------_11Q_0~- -
at•J. Te
Fig. 15. The La-Te phasediagram [1].
La4Te7 , LaTe 2 , La3Te7 , La 2Te 5 , La4Te 11 , and LaTe 3 with the following homogeneity ranges
(at % Te) and peritectic temperatures tP:
phase La3 _yTe4 La4Te7 LaTe2 La3Te 7 La2Te5
at % Te 57.2 to 60 60.8 to 64 64to 66.67 69.5 to 70.5 ~ 71 to 72
tP in °C (1515±50)*) 1350 ±50 ~ 1300 1060 815
phase La4 Te 11 LaTe 3
at % Te ~ 73 to 74 74.4to?
tP in °C 780 465
•l At y = 0.
The homogeneity range of LaTe does not exceed 0.5 at % Te [1]. Congruent melting points for
La3 Te 4 (1525 °C) and La 2Te 3 (1450 °C) were reported previously by Yarembash [11, 12]. A
preliminary phased iagram constructed by Eliseev et al. [4] from similar studies (DTA only up
to 1200°C) contained all these phases except La 3Te7 and La4 Te 11 (tp = 781 °C was reported
for a phase " LaTe3 _ x" with 71.4 to 75 at % Te) . For earlier studies, seealso Eliseev et al. [5],
Yarembash et al. [6]. According to Pardo, Flahaut [15] La2Te 5 has only a Limited range of
stability between about 811 and 650 °C (see p. 53).
Gmel in Handbook
RE Main VaL C10
The La-Te System 67
at"l. Te
u
0
.S
~
.a 1000
~ 920°C '- ------~9.}~-----
f
~ '\ \
I
4QQOC I 4500C
200o~~--~ID~~--~
4~0~~~~~~~~
~~--1~00
f
La wt"l. Te Te
Fig . 16. The La-Te phasediagram [7].
Melting point measurements in an Ar atmosphere, DTA, X-ray diffraction, and chemical

analyses by Ramsey et al. [7) show the existence of the congruently melting phases LaTe,
La3Te4 , and La2Te3 and the incongruently melting phases LaTe2 and LaTe3 ; see Fig. 16. The
congruent melting points (in °C} are 1720 ± 25 for LaTe, 1515 ± 25 for La3Te4 , and 1485 ± 25
for La2Te3 . Aseries of solid solutions is formed between La3Te4 and La2 Te3 . The phases LaTe2
and LaTe3 melt incongruently at 1450 ± 25°C (at the Lower phase boundary LaTe1.7) and
835 ± 15°C, respectively [7]; the same phase diagram is shown by Haase et al. [8] and
Steinfink, Weiss [9] and a preliminary diagram by Ramsey et al. [10].
The eutectic between La and LaTe is situated at ca. 7 to 9 at % Te and 885°C, and the
eutectic between LaTe3 and Te occurs near the Te side at 445°C [1]. The eutectic points
between La and LaTe and between LaTe 3 and Te Lie near La and Te at ~ 895 and - 400 °C,
respectivety, according to [7].
The polymorphic transformations of La are not greatty influenced by Te. The metat can
take up at most 0.3 to 0.5 at% Te [1].
General Preparation Methods and Properties

Sampies in the La-Te system were at first prepared by reaction of La with Te vapor in
horizontal Vycor tubes, in which La and Te were kept at opposite ends of the tube. The reaction
products were then heated in evacuated silica tubes at 600°C for 3 days with subsequent
heating at various temperatures up to 1 000°C for two weeks and quenching. Sampies with
> ~34 at % La were heated in sealed Ta tubes at approximately 2000°C for severat minutes
before being equilibrated at various temperatures prior to quenching, Ramsey et al. [7]. ln
the studies of Eliseev et al. [4, 5] the samples were prepared from the etements in evacuated
or Ar-filled quartz ampules and homogenized at 600 to 1 000°C for 50 to 100 h.
Single crystals of LaTe and La3Te4 were prepared in sealed Mo or W crucibles by a
modified Bridgman-Stockbarger technique, Bach et al. [13] .
Gmelin Handbock s·
RE Main V ol. C 10
The following colors have been reported for the lanthanum tellurides: La Te, purple-violet
[1], metallic purple [7]; La 3Te4 , black, metallic [7], black [1, 4]; La 2Te 3 , gray-black, dull metallic
[7], black to dark gray [1]; La4Te 7 , black [1, 4]; LaTe 2 , dark violet [1, 4], black, metallic [7];
La 2Te 5 , golden cinnamon brown [1], dark brown [4]; La4Te 11 , golden [1]; LaTe 3, golden metallic
[7], golden to cinnamon brown [1], darkgolden brown [4].
ln the X-ray L111 absorption spectra the position of the principal absorption edge of
lanthanum in several tellurides is displaced relative to that in La 20 3 : by -0.3 eV in LaTe,
-0.5 eV in La 3Te 4 , -0.3 eV in La 2Te 3 , and by -0.6 eV in both LaTe 2 and LaTe 3 . The displace-
ments are somewhat smaller than those found for the sulfides and selenides, Vainshtein et
al. [14].
References:
Moscow 1975, pp. 1/260, 169/82).
[2] E. I. Yarembash (Diss. Moscow 1967 from [1]).
[3] A. A. Eliseev (Diss. Moscow 1965 from [1]).
[5] A. A. Eliseev, E. I. Yarembash, V. G. Kuznetsov, et al. (Zh. Neorgan. Khim. 9 [1964]
876/82; Russ. J. lnorg. Chem. 9 [1964] 482/5).
28 [1964]1306/9; Bull. Acad. Sei. USSR Phys. Ser. 28 [1964]1208/12).
[8] 0. J. Haase, H. Steinfink, E. J. Weiss (Proc. 4th Conf. Rare Earth Res., Phoenix, Ariz. 1964
[1965], pp. 535/44, 536).
[9] H. Steinfink, E. J. Weiss (ANL-6856 [1964]1/53, 19/22; N.S.A. 18 [1964] No. 37115).
1963 [1964], pp. 303/14, 309).
[11] E. I. Yarembash (Therm. Anal. Proc. 2nd Intern. Conf., Worcester, Mass., 1968 [1969],
Vol. 2, pp. 761/77).
[12] E. I. Yarembash (Colloq. Intern. Centre Natl. Rech. Sei. [Paris] No. 180 [1969/70]471/81).
[13] H. Bach, S. Erdt, P. Stauche (J. Cryst. Growth 62 [1983]173/6).
[14] Z. E. Vainshtein, M. N. Bril, I. 8. Staryi, E. I. Yarembash (lzv. Akad. Nauk SSSR Neorgan.
[15] M. P. Pardo, J. Flahaut (Compt. Rend. C 263 [1966]1058/60).
30.1.2.10.3.2 LaTe
Homogeneity Region. Preparation
LaTe is a congruently (at ~ 1750°C) melting purple compound in the La-Te phasediagram
with a homogeneity range $0.5 at% Te (see p. 66). A metal-deficient sample of composition
La0_79Te was assigned as a LaTe phase by Treindl, Wachter [18], and Hauger et al. [25].
For the preparation from the elements see pp. 67 and 6. By heating the hydride telluride
LaHxTe (x ~ 0.9) in Ar atmosphere up to 1200°C LaTe was formed as a dark maroon mass
that turns purple upon powdering. After grinding pellets were fired at 1400°Cfor 15 min under
Ar; they reassumed the dark maroon color, Carter [13]. Single crystals have a metallic purple-
blue appearance, Ramsey et al. [5].
Gmelm Handbock
RE Mam Vol. C10
La Te 69
CryslaLLographic and Mechanical Properlies

LaTe has the cubic NaCL structure, Z = 4. Lattice constant a in A: 6.422(1), Yarembash et
al. [1], Eliseev et al. [2 to 4], 6.436, Ramsey et al. [5]. The assumption of a monoclinic structure
with a = 5.554, b = 7.877, c = 4.103 A, ß = 96° 3' by Brixner [6] was not confirmed by the
authors [1 to 5].
The microhardness Hof {100} faces, the plastic deformation e, and the break point cr were
measured for monocrystalline LaTe tobe H = 110 kg/mm 2 (~107.8x 107 Pa), e ~ 4%, and
cr ~ 18 kg/mm 2 ( ~ 17.6 x 107 Pa), Smirnov et al. [7].
Third-order elastic constants of La Te at 0 K were calculated using the Born-Mayer potential
model. The repulsive interaction was considered up to the second nearest neighbors. The
interionic distance r0 = 3.205 A Leads to the values (in 1011 N/m 2 ~ 1012 dyn/cm 2 ): c~ 11 =
-19.950, c~ 12 = c~ 66 = -1.446, and cb = c~56 = c~ 44 = 0.593. The temperature dependence
for Ca~y is given by Ca~y = c~~Y + aa~y·T, where the aa~y are (in 108 dyn·cm- 2 ·K- 1): a 111 =
7.606, a 112 = 3.048, a 123 = -1.087, a456 = -0.895, a 144 = -0.845, and a 166 = 2.553, Thakur
[8].
Analyses of interionic potentials and cohesive energies and calculation of the bulk modu-
lus K and the pressure derivative dK/dp of some 45 chalcogenides give K = 46.7 GPa
( = 467 kbar) and dK/dp = 3.64 for La Te, Ja in, Shanker [9]. The bulk modulus is
60.6 GPa (606 ± 20 kbar) from length change measurements by Jayaraman et al. [22].
Thermal Properlies
The linear thermal expansion coefficient of LaTe between 20 and 300°C was found to be
(18 ± 3) x 10- 6 K- 1 from the Lattice constants at 20 and 300°C [2].
Selected calorimetrically determined values for the heat capacities CP and Cv of LaTe in
cal· mol- 1 • K-1, from Tikhonov et al. [10], for temperatures T in K:
T 90 120 160 200 240 280 300 320 360 400
cp 9.64 10.62 11.26 11.55 11.77 11.88 11.93 11.97 12.05 12.10
Cv 9.60 10.56 11.17 11.43 11.62 11.70 11.73 11.76 11.81 11.83
The coefficient y for the heat capacity of the electron gas Cet = y · T was determined as
12.5 x 10- 4 and calculated as 3.8 x 10- 4 cal· mol- 1 · K- 2 [10]. Low temperature measurements
givey = 4.65mJ·mol- 1 ·K- 2 (= 11.11x1o- 4 cal·mol- 1 ·K- 2 ), Bucheretal. [11,23].
With the cp values reported by [10] the temperature function cp = 11.50 + 1.47 X 10- 3 . T
was derived for T = 298 to 2 000 K and CP = 11.94 cal· mol- 1 · K- 1 at 298 K. The absolute
entropy S~98 = 21.1 ± 1 cal· mol- 1 · K- 1, the enthalpy increment H~ 98 - Hg = 2.86 ± 0.1
kcal/mol, and the entropy increment S~98 -Sg = 7.77 cal· mol- 1 · K- 1 were obtained.
Calculated values for the enthalpy increment, the entropy increment, and the Gibbs function
in the range T = 298 to 2000 K are given in the paper, Mills [12] and plots of H~- H~ 98 and
S~- S~ 98 vs. T for La Te (LaSe and LaS) between about 300 and 2000 Kare shown in Gordienko,
Fenochka [24].
Sublimation enthalpy ßH~ 98 (sub) = 133.4 ± 1.1 kcaUmol and atomization enthalpy
ßH~ 98 (at) =220.3 ± 2.3 kcal/mol for the reactions LaTe(s)--> LaTe(g) and LaTe(s)--> La(g) +
Te(g); the standard enthalpy of formation of La Te is given with ßH~98 = -66.7 kcal/mol [24].
The Debye temperature 8 0 was determined from Cv at 100 K to be 184 K [10]; 8 0 (0)
175 K [11, 23].
Gmelin Handbook
RE Mam Vol. C 10
60
,..X:
,..C/1
'e 40
':'
ä
..,u 20
I
52
.S
-<
0
100 400
Tempereture in K
Fig. 17. Thermal conductivity 'A of LaTe as a function of temperature (see text).
Flg. 17 shows the total thermal conductivity "-total and its components between 80 and 480 K.
ln calculating the electronic conductivity 'A81 = L · K · T with K = electrical conductivity, the
Lorenz number L was either assumed to be constant (dashed curve and its extension) or
temperature-dependent (L i= const). The respective thermal conductivities of the lattice
'A1at = "-total- A81 are derived by using the two different A81 curves (both give A1at =
0.0126 cal · cm - 1 • s - 1 · K - 1 for 400 K). The thermal resistivity of the lattice 1/'A1at (L i= const)
increases linearly above ~ 380 K. The behavior below that temperature was explained by the
presence of two scattering mechanisms. The cont ribution by phonon-phonon interaction is
1//cp-p = b · T and by phonon-electron interaction 1//cp-e• which is proportional to T - 1·2 . This
exponent lies between the theoretical values 0 and - 2 for temperatures above or ~ 0 0 .
The values 1/ /cp-p = 34.0 and 1//cp-e = 29.8 cal - 1 · cm · s · K were found experimentally at
170 K, i. e., the Debye temperature. 1/'Ap-e = 42 cal- 1 · cm · s · K from experiment and
19 cal - 1 · cm · s · K is calculated at 100 K, Golubkov et al. [15].
Magnetic Susceptibility
The magnetic susceptibility x
of LaTe single crystals between 293 and 800 K reveals a
weak paramagnetism (see curve in the paper) with a temperature-independent part Xoo and
a small temperature-dependent contribution probably due to paramagnetic impurities. The
diamagnetic contribution M ia = -90 x 10- 6 , the susceptibility of the electron gas Xel
97 x 10- 6 , and Xoo = 7 x 10- 6 , all in cm 3/mol, Adamyan et al. [14] .
The electronic structure of LaTe as derived from the reflection spectrum (see p. 72) is
similar tothat of LaS and LaSe, Zhuze et al. [16] ; cf. " Rare Earth Elements" C9, 1986, p.19.
A figure in the paper shows the bottarn of the La(5d) conduction band at ~ 1 eV below the
Fermi energy EF and the Te(5p6 ) valence band to extend from 2.45 to ~ 6.5 eV below EF [16].
The transition 5p6 ----> 5d t 29 as 1.7 eV is derived from the absorption spectrum , Zhuze [28] . For
the structure of the electron energy spectrum of lanthanum chalcogenides studied by group
theory methods, see Andriyashik, Marehenke [19] ; seealso [20, 21] .
LaTe is a superconductor with Tc = 1.48 K, Sucher et al. [11], and has a low electrical
resistivity Q at 300 K (see p. 20) : Q = 64.1 !!il · cm for a nearly stoichiometric single crystal
from melt, Zhuze et al. [16] ; 120 1-lil· cm, Gorbachev et al. [26]. Polycrystalline samples
annealed in a vacuum (1600 to 1800 °C, 10- 5 Torr) have Q = 48.5 IJQ · cm, Golubkov et al. [15],
Gme lon Handbock
RE Main Vol. C 10
LaTe 71
or 45.9 J.i!l · cm, Goncharova [27]. Figures in the papers show Q of the lowest resistive sample
to increase Linearly between 100 and -900 K (1/Q · dQ/dT = 3.1 K- 1) and then to rise more
strongly to -135 J.i!l· cm at 1200 K [27], whereas Q of the slightly higher resistive sample
increases only approximately Linearly in the studied range 80 to 460 K. The residual resistivity
amounts to 12 J.i!l· cm [15]. The resistivity of a sample annealed in Ar (1400°C, 15 min)
increases nonlinearly between 300 and 1350 K, from -70 to 270 J.i!l · cm (values read from a
figure), Carter [13]. Strongly deviating values are Q = 1.5 x 105 !l · cm at 293 K, Eliseev et al.
[4], Yarembash et al. [17] and a fall to 280 n · cm at 443 K [4]. The temperature dependence
of the resistivity of an La0 _79Te single crystal between 4.2 K (Q ~ 40 J.i!l· cm) and 235 K (Q ~
74.3 J.i!l · cm) as measured by Hauger et al. [25] is compared tothat of an La0 _90Se crystal in
"Rare Earth Elements" C9, 1986, Fig. 18, p. 78. Values of the thermoelectric power S (in
J.tV/K) at room temperature are : +1.8 [27], +2.4 [15], -+2 [13], +8.6, Ramsey et al. [5],
-1.3 [26] and (as with Q strongly deviating) S = -40 to -50 [4, 17]. The thermoelectric power
of the vacuum annealed sample (Q300 = 48.5 J.i!l · cm) increases nearly Linearly from ~ + 1.5
to - +3 J.tVIK between 80 and 380 K [15]. More extended measurements on the sample with
Q300 = 45.9 J.i!l · cm show S to increase linearly from - + 0.5 at 140 K to a maximum of - + 2
near 340 K and afterwards to decrease linearly to - - 5 at 850 K ; S changes sign near 525 K
[27]. The thermoelectric power of the Ar annealed sample studied between 300 and - 1350 K
also has a flat maximum (S ~ + 4 between 600 and 700 K); S changes sign near 850 to 900 K,
has a minimum near 1050 K (S ~ -10) and finally approaches very small negative values
(S ~ 0 at 1350 K) [13].
The charge carrier concentration is n = 1.51 x 1022 cm - 3 , Zhuze et al. [16], 1.2 x 1022 cm- 3
[27] at room temperature. The Hall effect gives nH = 2.55 x 1022 cm- 3 and the mobility llH =
8.3 cm 2 · v- 1 · s- 1 [15]. The effective mass of current carriers m*/m 0 = 3.3 was derived from
the heat capacity (y = 12.5 x 10- 4 cal · mol- 1 • K - 2) by use ofthe free-electron model, Tikhonov
et al. [10], whereas m*/m 0 = 6.7 was obtained from the susceptibility of the electron gas,
Adamyan et al. [14]. Analysis of the reflection spectrum of a single crystal gave m*/m 0 = 1.95
and the relaxationtime of conduction electrons 1: = 1.1 x 10- 15 s, Zhuze et al. [16].
Optlcal Properlies
The dispersion curves of the refractive index n and the absorption index k for an LaTe
single crystal are shown in Fig. 18, derived from polarimetric measurements by Zhuze [28] .
The Raman spectrum of LaTe (and GdTe) at 300 K showshigh scattering intensity between
120 and 170 cm- 1 . Two narrow peaks are situated at 126 and 146 cm- 1 (123 and 143 cm- 1 for
GdTe) and a broad peak around 160 cm- 1 . lt was suggested that in LaTe (and GdTe) the
_)..---- ~
2
"'\
_.--><
~
~
0
0.4 0.6 0.8 1.0
). in ~m
Fig. 18. Refractive index n and absorption index k of LaTe in dependence of wave length 'A.
Gmelin Handbook
RE Main Vol. C 10
acoustical and the optical phonon branches are overlapping in frequency with both types of
vibrations contributing to the high one-phonon density of states between 120 and 170 cm-1,
Treindl, Wachter [18].
The absorption spectra of La Te at 293 and 77 K in the range 0.25 to 2.6 11m ( ~ 0.8 to 5 eV)
show a drop ofthe absorption coefficientfrom ~ 15 x 104 cm- 1 to a minimum ( ~ 2.5 x 104 cm- 1)
and a continuous increase to ~ 5 x 104 cm - 1 afterwards. The absorption edge is at 1.7 eV at
room temperature [28]. The reflection spectrum of LaTe single crystals was measured in the
range from 0.05 to 22 eV and analyzed using the Kramers-Kronig relation. A reflection mini-
mum has been observed at 2.0 eV followed by a broad maximum which is attributed to the
onset of p ----> 5d electronic interband transitions. The intersection of the real part of the
complex dielectric function e' with the frequency axis (e' = 0) gives the screened plasmon
energy ro~ = 1.65 eV; the unscreened plasmon energy is roP = 3.25 eV. A broad band of the
imaginary part of the dielectric function e" with a peak at 4.5 eV is due to interband transitions
from the 5p valence band of Te to free Levels in the 5d conduction band of La; the Low-frequency
Limit of the interband transitions is 2.45 eV (e" minimum). The generalform of the spectra e',
e", and the energy Loss function is qualitatively similar for all LaX with X = S, Se, and Te.
The electronic structures derived therefrom are also similar [16]. An earlier investigation of
the reflection spectrum in the range 1.2 to 3 eV, using a polarimetric method, gave the
reflection minimum at 1.9 eV and ro~ = 1.55 eV [28]. The optical permittivity exc = 4.0, when
regarding bound electrons [16], and e"" = 3.0 when not [28].
References:
[1] E. I. Yarembash, E. S. Vigileva, A. A. Eliseev (lzv. Akad. Nauk SSSR Neorgan. Materialy
[2] A. A. Eliseev, V. G. Kuznetsov, E. I. Yarembash (lzv. Akad. Nauk SSSR Neorgan. Materialy
876/82; Russ. J. lnorg. Chem. 9 [1964]482/5).
1963 [1964], pp. 303/14, 308).
[7] B. I. Smirnov, A. V. Ryabov, A. V. Golubkov, et al. (Tugoplavkie Soedin. Redkozem. Metal.
Mater. 3rd Vses. Semin. Novosibirsk 1977 [1979], pp. 201/5; C.A. 93 [1980] No. 159390).
[8] K. P. Thakur (J. Phys. Chem. Solids 41 [1980] 465/72).
[9] V. K. Jain, J. Shanker (Phys. Status Solidi B 106 [1981]287/93).
[10] V. V. Tikhonov, A. V. Golubkov, I. A. Smirnov (Fiz. Tverd. Tela [Leningrad] 8 [1966]
[11] E. Sucher, K. Andres, F. J. di Salvo, et al. (Phys. Rev. [3] B 11 [1975]500/13, 504).
Butterworth, London 1974, pp. 412, 796).
[13] F. L. Carter (Met. Soc. Conf. Proc. 15 [1962]245/61, 255/6; C.A. 59 [1963]14695).
[14] V. E. Adamyan, N. P. Bodrova, E. V. Goncharova, G. M. Loginov (Fiz. Tverd. Tela
[Leningrad]12 [1970] 2770/1; Soviet Phys.-Solid State 12 [1970] 2239/40).
[15] A. V. Golubkov, E. D. Devyatkova, V. P. Zhuze, et al. (Fiz. Tverd. Tela [Leningrad]8 [1966]
Gmelin Handbook
RE Mam Vol C 10
73
[16] V. P. Zhuze, M. G. Karin, D. P. Lukirskii, et al. (Fiz. Tverd. Tela [Leningrad] 22 [1980]
[17] E. I. Yarembash, E. S. Vigileva, A. A. Eliseev, L. I. Antonova (Zh. Neorgan. Khim. 8 [1963]
1542/3; Russ. J. lnorg. Chem. 8 [1963] 804).
[18] A. Treindl, P. Wachter (Phys. Letters A 64 [1977]147/50).
[19] M. V. Andriyashik, V. I. Marchenko (lzv. Akad. Nauk SSSR Neorgan. Materialy 9 [1973]
[20] M. V. Andriyashik, V. I. Marchenko (Elektron. Str. Fiz.-Khim. Svoistva Splavov Soedin.
Osn. Perekhodnykh Metal. Dokl. 8th Simp., Kiev 1974 [1976], pp. 256/60; C.A. 87 [1977]
No. 172996).
[21] V. I. Marchenko, M. V. Andriyashik (Poluch. lssled. Svoistv Soedin. RZM Mater. 1st
Nauchn. Semin., Baku 1972 [1975], pp. 11/8; C.A. 84 [1976] No. 67148).
[22] A. Jayaraman, B. Batlogg, R. G. Maines, H. Bach (Phys. Rev. [3] B 26 [1982] 3347/51).
[23] E. Bucher, A. C. Gossard, K. Andres, J. P. Maita, A. S. Cooper (Proc. 8th Rare Earth Res.
Conf., Reno, Nev., 1970, Vol. 1, pp. 74/89, 89).
[24] S. P. Gordienko, B. V. Fenochka (Splavy Redk. Met. Osobymi Fiz. Svoistvami, Redkozem.
Blagovodn. Met. 1983 119/22; C.A. 99 [1983] No. 182475).
[25] R. Hauger, E. Kaldis, G. von Schulthess, P. Wachter, C. Zürcher (J. Magn. Magn. Mater.
3 [1976]103/8; C.A. 85 [1976] No. 135328).
[27] E. V. Goncharova (Diss. Leningrad 1968 from V. P. Zhuze, E. V. Goncharova in: V. P.
Zhuze, Fizicheskie Svoistva Khal'kogenidov Redkozemel'nykh Elementov, Leningrad
1973, pp. 58/122, 59/67; C.A. 80 [1974] No. 75356).
[28] V. P. Zhuze (in: V. P. Zhuze, Fizicheskie Svoistva Khal'kogenidov Redkozemel'nykh
Elementov, Leningrad 1973, pp. 223/90, 272/7; C.A. 80 [1974] No. 75969).
30.1.2.10.3.3 Solid Solutlons La 3Te 4-La 2Te 3 and TerminaL Compounds

La3Te 4 and La2Te 3 belong to the same phase of variable composition with the cubic Th 3P4
structure. The solid solutions and La2Te 3 contain La vacancies and should be written La3 _yTe4 .
For the preparation from the elements see the La-Te system, p. 67, and p. 31, and for the
crystal structure p. 21.
30.1.2.10.3.3.1 La 3Te4
CrystaLLographic and Mechanical Properties
Lattice constants a in A and calculated and measured density D in g/cm 3 :
a 9.6199(5) 9.621(1) 9.6247(8) •) 9.627 9.628(1) 9.630

Deale 6.85 6.87 6.90
Dexp · 6.68 6.90
Ref .. [1] [2] [21] [3 to 5] [6 to 8] [9, 18]
•) a = 9.5910(6) A at 4.2 K.
A reversible phase transition is assumed from a break in the resistivity at a uniaxial pressure
of ~70 kbar (observed on powder samples), Shelton et al. [15].
Gmelin Handbock
RE Main Vol. C10
2.06
~•
•
2.04
' ·· .......... ••• ••

'· • • Cn- Cu
-
2.02
"'
....E '"'o0
.s 82
00
>
"o~
0
0
0
0'
0
0
80
·c
loc"'
c
0
0
78 0
0
0 100 200 300

Temperature in K
Fig . 19. Temperature dependence of the sound velocity v for c 44 and cw c 12 modes for La 3Te 4 .
The elastic constants in 1012 dyn/cm 2 ( 2o 1011 N/ m 2 ) from so und velocity (v) measurements
are c 44 = 0.213 and (c 11 -cd/2 = 0.279 at 290 K. The temperature dependence of v for c44
and c 11 - c 12 is shown in Fig. 19, Sucher et al. [9] .
Thermal Properlies
Measurement of the heat capacity CP from 5 to 273 K in an adiabatic vacuum calorimeter

gives the following values at T = 273.15 K for CP and the thermodynamic quantities of enthalpy,
entropy, and Gibbs free energy: CP = 42.12cal·mol- 1 ·K - 1, H~ = 8.953kcallmol, S~ =
73.982 cal · mol - 1 • K - 1, and G~ = 11.256 kcal/mol, Tikhonov et al. [1 0]; see also p. 23 for the
temperature dependence of CP. From measurements on La3 Te4 single crystals the followi ng
values for the electronic (y) and lattice (ß) specific heat coefficient were obtained: y =
4.5 mJ · K - 2 · [mol La] - 1, ß = 0.53 mJ · K - 4 · [mol La] - 1 . The jump of CPat the superconducting
transition temperature Tc = 4.0 K (see below) is close to the SCS value (SCS = Sardeen-
Cooper-Schrieffer), Westerholtet al. [20]. y ::::; 4.3 mJ · K - 2 · [mol La] - 1 and the Debye tempera-
ture 8 0 (0) = 162 K, Sucher et al. [18]. 8 0 = 205 K [20] . A plot of 8 0 vs. T is shown in Fig . 22
±
on p. 78 ; 8 0 = 183 2 Kat 77 K, Tikhonov et al. [22].
The total thermal conductivity /.. of cast polycrystalline La3Te4 in dependence of the Iernper-
ature is shown in Fig. 20 and the lattice contribution "-tat = /.. - "-et and thermal resistance
11"-tat is shown in Fig. 21 (Aet = electronic contribution) , Luguev, Smirnov [11]. The valu es
of "-tat and 11"-tat above 800 K were calculated from data given by Zhuze et al. [13] . A curve
/.. = f(T) forT = 100 to 500 K was also shown previously by Smirnov et al. [12] .
Gmehn Handbook
RE Marn Vol. C 10
75
' a r-~--.---r-~--.---r-~--.--.
X:
'"'
'E
~ 6~----1------+------r-~~-r~
...8'g
.!: 41-------t-----~~----t-----......-::....--tBO
.<
Tempereture in K
Fig. 20. Temperature dependence of thermal conductivity A., electrical resistivity Q, and
absolute thermoelectric power ! S Iof La3Te4 . The points represent average values taken from
the literature.
1200
•1nl
0 1131
_Lj/).lat
1000
~V
I
'!" 800
E
~
' ö 600 lF
tL
u
c 3 \ I
400 1:, 'Aiat
--
-~
-< ":":ii 2 ~
200
.. , I
0o 400 800 1IJI
Tin K I
0o 400 800 1200 1600 2000
Temperature in K
Fig. 21. Temperature dependence of the lattice contribution of the thermal conductivity "-tat
and the thermal resistance 11"-tat of La3Te4 .
Electrlcal Properties
La3Te4 is superconducting with Tc = 5.30 K, Sucher et al. [18), Tc = 4.0 K, Westerholtet
al. [20). The critical temperature Tc for two samples (1) and (2) was found tobe 2.45 and 3.75 K,
transition width ~T = 0.1 K. Sampie (1) was prepared by melting and sintering the pressed
body at 1450°C for 1.5 h. Sampie (2) was prepared by melting in a Mo crucible, Zhuze et al.
[14] . Tc = 4.61 K was found for pressed samples fired for 3 h at 1700°C. With application of
hydrostatic pressure p ~ 25 kbar ( ~ 2.5 GPa) Tc decreased linearly at -0.635 ± 0.005 K/GPa,
Shelton et al. [15] . Measurements up to 4.5 GPa (45 kbar) give dTc/dp = - 0.8 K/GPa below
Gmelin Handbook
RE Main Vol. C 10
-2 GPa. At 4 GPa the slope has diminished to dTc/dp = -0.3 K/GPa, Eiling et al. [19]. The
very slight decrease in Tc under a uniaxial pressure (powder samples) up to -5 GPa and an
increase between about 9 and 16.5 GPa reported by [15] was not mentioned Later [16].
According to Matthias et al. [16] Tc is depressed monotonically by both hydrostatic and uniaxial
pressure (no pressure range given). A break in the resistance at -7 GPa indicates the
presence of a phase transition [15].
The electrical resistivity Q for a ceramic sample is 2000 11n ·
cm at room temperature,
Aloman [5] and shows in the Log Q = f(T) plot a small increase above -700 K, Aloman [17].
Between 100 and 500 K an increase from Q ~ 175 to Q ~ 416 11n ·
cm was found by Smirnov
et al. [12]; seealso Fig. 20, p. 75, from Luguev, Smirnov [11] for the range 100 to 900 K. A
decrease of Q between room temperature and 573 K was observed by Ramsey et al. [7]. The
above mentioned samples (1) and (2) have Q ~ 350, 450, and 700 11n ·
cm (sample 1) and
-100, 170, and 350 fl!l· cm (sample 2) at 4, 77, and 300 K (values taken from the curves) [14].
The thermoelectric power S is negative and the absolute value increases slightly with
increasing temperature; see Fig. 20, p. 75 [11]. S = -21flV/K at room temperature [5] and S
~ -75 flV/K at 900 K [17]. A slight increase of ISI between 100 and 500 K was also found by
[12], between room temperature and 573 K by [7]. The ceramic sample with Q = 2000 11n ·
cm
has a carrier concentration of n = 2 x 1e>2° cm- 3 , a carrier mobility of ll = 15 cm 2 • v- 1 · s- 1 ,
and a Hall coefficient of RH = -0.03 cm 3/C [5]. For additional data, see p. 79. For the two
samples (1) and (2) (see above) measurements of Q in perpendicular magnetic fields at 1.4 K
gave values of the critical magnetic field Hc2 = 8 and 12.5 kOe, respectively. The full Meissner-
Ochsenfeld effect was observed at Hc 1 < 20 Oe and < 60 Oe, respectively, for the two samples
in Longitudinal magnetic fields at 1.4 K [14].
References:
943/52).
[3] A. P. Aloman, S. S. Gorelik, V. M. Malovetskaya, V. I. Buzanov (lzv. Vysshikh Uchebn.
Zavedenii Tsvetn. Met. 14 No. 4 [1971]73/7; C.A. 75 [1971] No. 144641).
[4] A. Aloman, S. S. Gorelik, V. M. Malovetkaia (Metalurgia [Bucharest] 20 No. 2 [1968]
72/6; C.A. 69 [1968] No. 90882).
[5] A. Aloman (Bul. lnst. Politeh. Gheorghe Gheorghiu-Dej Bucuresti 30 No. 2 [1968] 101/6;
C.A. 70 [1969] No. 53450).
[8] 0. J. Haase, H. Steinfink, E. J. Weiss (Proc. 4th Conf. Rare Earth Res., Phoenix, Ariz.,
1964 [1965], pp. 535/44; C.A. 65 [1966] No. 14821).
[9] E. Bucher, J. P. Maita, G. W. Hull Jr., et al. (Z. Physik B 25 [1976]41/8).
[10] V. V. Tikhonov, R. G. Mitarov, I. A. Smirnov (Zh. Fiz. Khim. 49 [1975]3008; Russ. J. Phys.
Chem. 49 [1975]1786).
[11] S. M. Luguev, I. A. Smirnov (Fiz. Tverd. Tela [Leningrad]19 [1977]1209/10; Soviet Phys.-
Solid State 19 [1977] 707/8).
[12] I. A. Smirnov, L. S. Parfen'eva, V. Ya. Khusnutdinova, V. M. Sergeeva (Fiz. Tverd. Tela
Gmelln Handbock
RE Mam Vol. C 10
77
[13] V. P. Zhuze, 0. A. Golikova, V. M. Sergeeva, I. M. Rudnik (Fiz. Tverd. Tela [Leningrad]

[14] V. P. Zhuze, S. S. Shalyt, V. A. Noskin, V. M. Sergeeva (Zh. Eksperim. Teor. Fiz. Pis'ma
Redaktsiyu 3 [1966]217/9; C.A. 65 [1966]3145).
[15] R. N. Shelton, A. R. Moodenbaugh, P. D. Dernier, 8. T. Matthias (Mater. Res. Bult. 10
[1975]1111/9).
[16] 8. T. Matthias, P. D. Dernier, R. N. Shelton, A. R. Moodenbaugh (Europhys. Conf. Abstr.
1A [1975]58; C.A. 86 [1977] No. 24971).
[17] A. Aloman (Metalurgia [Bucharest]21 [1969]363/7; C.A. 72 [1970] No. 60484).
[18] E. Sucher, K. Andres, F. J. di Salvo, et al. (Phys. Rev. [3] 8 11 [1975]500/13, 504).
[19] A. Eiling, J. S. Schilling, H. Bach (Phys. Solids High Pressure Proc. Intern. Symp. 1981
385/96; C.A. 96 [1982] No. 134102).
[20] K. Westerholt, F. Timmer, H. Bach (Phys. Rev. [3] B 32 [1985] 2985/92, 2988/9).
[21] P. D. Dernier, E. Sucher, L. D. Longinotti (J. Solid State Chem. 15 [1975]203/7, 206).
[22] V. V. Tikhonov, V. N. Bystrova, R. G. Mitarov, I. A. Smirnov (Fiz. Tverd. Tela [Leningrad]
17 [1975]1225/6; Soviet Phys.-Solid State 17 [1975] 795).
30.1.2.1 0.3.3.2 Solid Salutions La 3Te4-La 2Te 3

Crystallographic Properlies
The cubic solid solutions between La 3Te 4 and La 2Te 3 , formulated as LaTex or La 3 _yTe 4 ,
are prepared from the elements Like other phases in the La-Te system (see p. 67). They have
a defective Th 3 P 4 structure, space group 143d-T~ (No. 220), Eliseev et al. [1]. The concentration
of the cation vacancies in La 3 _yTe4 rises from 0 to 1.5 x 1021 cm- 3 upon transition from La 3 Te4
(y = 0) to La 2Te 3 (y = 0.333), Tikhonov et al. [2].
Lattice constant a and density D in g/cm3 for LaTex phases with various x from Aloman et
al. [3, 4]:
x in LaTex. 1.333 1.375 1.4 1.425 1.455 1.5
a in A. 9.627 9.625 9.623 9.622 9.620 9.618

Deale · 6.87 6.75 6.65 6.62 6.60 6.54
Values from [1]:
x in LaTex. 1.333 1.365 1.399 1.429 1.481
a in A. 9.621(1) 9.619(1) 9.617(1) 9.619(1) 9.619(1)

Deale 6.85 6.61
Dexp · 6.68 6.53
Values from Mitarov et al. [5]:
x in LaTex . . . 1.333 1.370 1.470 1.500

a in A . . . . . 9.623 9.625 9.625 9.623
Plotsofa and D vs. x show a Linear decrease for both with increase of x from 1.333 to 1.5,
Gerasimov et al. [6]. From a = 9.619(1) A at 20°C and a = 9.667(4) A at 300°C for LaTe 1 .423
(= La 2_8Te4 ) the coefficient ofthermal expansion cx = (18 ± 2) x 10- 6 K- 1 was calculated,
Eliseev et al. [7].
Gmelm Handbock
RE Mam Val. C 10
Thermal and ELectricaL Properlies
The heat capacity CP of LaTex (and PrTex) with x = 1.33, 1.37, 1.47 , and 1.50 was measured
between T = 5 and 273 K. Plots of CP vs. T are shown in Fig. 4, p. 24 (see also Fig. 3, p. 23)
for x = 1.33, and for x > 1.33 in the paper. The curves for x = 1.37 and 1.47 lie between those
fo r x = 1.33 and 1.50. For LaTex the heat capacity CP is a sum of lattice and electronic
contributions with Cp(lat) ~ Cp(el) and Cp(el) ~ 0.4 cal · mol - 1 · K - 1 at 273 K. (For PrTex there
is also a contribution due to the Schottky effect, see p. 111) [5] . The Debye temperature for
the four LaTex samples as a function of the temperature is shown in Fig. 22, Tikhonov et al.
[2].
The thermal conductivity J... of LaTex with x = 1.41 (58.5 at % Te) and x = 1.469 (59.5 at % Te)
at 293 K was found tobe 6.8 mW · cm - 1 · K- 1 ( = 1.62 x 10- 3 cal · cm - 1 · s- 1 · K - 1), Kagrama-
nova et al. [8]. According to Aloman et al. [4] (see the table below) J... increases continuously
from 12 mW · cm - 1 · K - 1 for La 2Te 3 (x = 1.5) to 34 mW · cm- 1 · K - 1 for La 3Te 4 (x = 1.33) with
decreasing x in LaTex at room temperature. The lattice contribution Atat of the thermal
conductivity fo r LaTex at 100, 200, and 300 K, shown in Fig. 23, has a minimum at x = 1.36 to 1.38.
This is explained satisfactorily by the competition between the phonon-electron scattering
(occurring in La 3Te 4 because of the high carrier density) and the phonon-defect scattering
(occurring in La2Te 3 because of the high concentration of vacancies) , Luguev et al. [9]. For
250
• 300
0•
•
o•
....
200 X:\500 250
::.:: "'\"' ~----- ••••• ••••••
ooooo • • • • •
ooOOO ::.::
.E t \ : : ldP oooc x: 1.333
000
0
0 0 0 0 0
.E
•·•=1.470
-
0 0
CD 150 "' - 200m
~
X:1.370
............
1
25 50 75 100 125 50
Temperature in K
Fig . 22. Debye temperature vs. temperature for LaTex with x = 1.5, 1.333 (left-hand scale) and
1.470, 1.370 (right-hand scale).
- 6
':.~::
•. 5 1~K ~
_...., 5 -2~K
5
~K
4
111
V 4
_.,., f-r
'eu 4
83 ~ / l.)'- f+-
..j
"
.., 2 V 21...... f<r'"
·~ 2 1
.~ 1.33 1.37 1.41 1.45 1.50 t33 1.37 1.41 1.45 1.50 1.33 1.37 1.41 1.45 1.50
:§
...c x in La Tex x inl.aTex x in La Tex
Fig. 23. Lattice contribution ofthermal conductivity Atat vs. x in LaTex at 100, 200, and 300 K.
Gmelon Handbook
RE Maon Vol C 10
79
curves at 100 and 200 K, see also Fig. 46, p. 112. For values of /...181 for LaTex samples (no
composition reported) at 80 to 300 K, see Smirnov et al. [10]. A figurein the paper [10] shows
the dependence of /...181 on the electrical conductivity K for LaTex samples at 300 K, taken from
the literature; a maximumwas found at K ~ 700 n- 1 · cm - 1.
The thermal conductivity of a hot-pressed LaTex sample with x < 1.45, obtained by melting
LaTe 1.45 in a semiclosed crucible, decreased continuously from - 17 to 13.5 mW · cm - 1 · K - 1
as the temperature was increased from 373 to 1423 K. Estimated /... values (from the measured
electrical resistivity and /...181 = 8 mW · cm- 1 · K- 1 ) for LaTe 1.40 were larger than those for
LaTe 1.45 below 1373 K and both were larger than those for the LaTex sample in the whole
temperature range, Danielson et al. [14].
The following table from [4) contains values for /..., the electrical resistivity Q, the
thermoelectric power S, the Hall coefficient RH, the carrier concentration n, the carrier mobility
J.!, and the figure of merit Z at room temperature for samples homogenized at 1100°C for 10 d:
x in LaTex 1.333 1.375 1.4 1.425 1.455 1.5
/...inW · m- 1 ·K - 1 3.4 3.3 3.2 3.1 2.5 1.2

-S in J.!V/K 17 28 38 52 71 127
Q in Q·cm 2.7 X 10- 3 4 X10- 3 5 X10- 3 7.5 X 10- 3 2.2 X 10- 2 4450
-RH in cm 3 /C 6.25 X 10 - 3 6.9 X 10- 3 7 X10- 3 7.8 X10- 3 1.04 X 10- 2 31.3
n in cm - 3 1 X1021 9 X1020 8.9 X1020 8 X1020 6 X1020 2 X1017
J.!incm 2 ·V - 1 · s - 1 . 2.32 1.73 1.4 1.04 0.47 0.007
Z in K- 1 . 3.7 X 10- l 7.1 X 10- 6 1.1 x 10 - s 1.2 X 10- S 9 X10- 6 2.98 X 10- 10
Upon the transition from La3Te4 (x = 1.333) to La 2Te3 (x = 1.5) the character of the electrical
conductivity abruptly changes from metallic to semiconducting, Gerasimov et al. [11] . The
decrease of the electrical conductivity K with increase of x at 300 K is shown in Fig. 24 from
[9). The conductivity of samples with x = 1.40 to 1.5 increases with increasing temperature
from -160 to 500 K; see Fig. 25, p. 80. For x = 1.33 and 1.35 the conductivity decreases with
increasing temperature (see figurein the paper) . Measurements of S between 100 and 500 K
showhole type conductivity for LaTex with x = 1.40 to 1.50 (nondegenerate semiconductors)
and electronic conductivity for x = 1.35 and 1.33. lt was impossible to calculate quantitatively
S because the value was too small at the temperatures studied, Gerasimov et al. [12] . The
'eu
3
1
- ~~
b 1 \
.E
" -3
'; \
~ -5
- 71.33 1.37 t41 1.45 150

x in LaTex
Fig. 24. Electrical conductivity vs. x in LaTex at 300 K .

Gmelin Handbook
RE Main Vol. C 10
167
'eu
~ -4 r-----~~~~------+------+~
....
.5
g-6 r----+----~~~~---+~
3 -----+4----~~~~~~
-a2~----*
103/T in K-1
Fig. 25. Electrical conductivity of LaTex vs. temperature.
b) LaTex.Y
5 - 250
4 -200
/~Teuo
~\.aTeL45
~
E
u
:.:::
>::L - 150 /
,r;/'
c:3
E c:
.5 2 iii -100
~
Q.
-50
0200 400 600 800 1000 1200

Tempereture in °C Tempereture in°C
Fig . 26. Temperature dependence of electrical resistivity (a) and thermoelectric power (b) for
LaTex samples (see text).
temperature dependence of Q and S above 300 °C (573 K) for three n-type hot-pressed samples
with compositions LaTe 1.40 , LaTe 1 _45 , and LaTex (x < 1.45, obtained by melting LaTe 1 _45 in a
semiclosed crucible) is shown in Fig. 26. Measurements were performed in a vacuum. LaTex
and LaTe 1.40 have Z > 1 x 10- 3 K - 1 and LaTe1.45 has Z > 0.9 x 10- 3 K - 1 at 1273 K; see a
figurein the paper, Danielson et al. [14]. For comparison of the electrical properties of La3 _yTe 4
and La 3 _yS4 at 300, 600, and 900 K, see Gotikova et al. [13] .
References :
[1] A. A. Eliseev, E. I. Yarembash , V. G. Kuznetsov, et al. (lzv. Akad . Nauk SSSR Neorgan.
Gm elin Handbock
RE Main Val. C 10
81
[2] V. V. Tikhonov, V. N. Bystrova, R. G. Mitarov, I. A. Smirnov (Fiz. Tverd. Tela [Leningrad]

17 [1975] 1225/6; Soviet Phys.-Solid State 17 [1975] 795).
Zavedenii Tsvetn. Met. 14 No. 4 [1971] 73/7; C.A. 75 [1971] No. 144641).
72/6; C.A. 69 [1968] No. 90 882).
[5] R. G. Mitarov, V. V. Tikhonov, L. N. Vasilev, et al. (Phys. Status Solidi A 30 [1975] 457/67).
[6] A. F. Gerasimov, N. A. Krushatina, G. I. Bochkina, 0. S. Elizarova (Fiz. Metal. lkh Soedin.
No. 1 [1974] 61/6; C.A. 83 [1975] No. 155866).
[8] R. R. Kagramanova, I. S. Lisker, E. I. Yarembash (Azerb. Khim. Zh. 1967 No. 4, pp. 46/9;
C.A. 68 [1968] No. 90487).
[9] S. M. Luguev, V. S. Oskotskii, L. N. Vasil'ev, et al. (Fiz. Tverd. Tela [Leningrad] 17 [1975]
[10] I. A. Smirnov, L. S. Parfen'eva, V. M. Sergeeva (Fiz. Tverd. Tela [Leningrad] 14 [1972]
[11] A. F. Gerasimov, A. N. Krushatina, V. N. Konev (Tezisy Dokl. 2nd Vses. Konf. Kristallokhim.
lntermetal. Soedin., Lvov 1974, pp. 177/8; C.A. 85 [1976] No. 170289).
[12] A. F. Gerasimov, V. N. Konev, N. A. Krushatina, V. P. Serikova (Fiz. Metal. lkh Soedin.
No. 3 [1975] 61/5; C.A. 86 [1977] No. 99513).
[13] 0. A. Golikova, I. M. Rudnik, V. M. Sergeeva, et al. (Phys. Status Solidi A 37 [1976]
199/203).
[14] L. R. Danielson, V. Raag, C. Wood (Proc. lntersoc. Energy Convers. Eng. Conf. 20 111
[1985] 531/5; C.A. 103 [1985] No. 133214).
30.1.2.1 0.3.3.3 La 2Te 3
La 2Te 3 is the boundary composition of the La3Te 4-La 2Te3 solid solution series; see Fig. 15,
p. 66, and Fig. 16, p. 67.
Preparation
For the preparation from the elements, see also p. 31 and p. 67.
Homogeneaus samples of La2Te 3 can be obtained by heating the stoichiometric elemental

mixture in evacuated or Ar-filled quartz ampules slowly to 1000 to 1100°C and subsequently
holding the temperature at 900 to 1000°C for 40 to 50 h. ln order to avoid the reaction of molten
La with quartz, the initial lanthanum was placed in an alundum crucible, Yarembash et al. [1].
The element mixture was heated in evacuated quartz ampules within 3 weeks from 200 to
950°C and then homogenized by annealing for 5 weeks, Gerasimov et al. [2]. ln order to avoid
an explosive reaction the elements are separately located in an evacuated quartz vessel,
Aloman et al. [3]. By reaction of a mixture of 3 g La20 3 + 4 g Te + 10 g Na2C03 for 1 hat 400°C
gray La 2Te 3 was formed, Montignie [4]. La2Te 3 was prepared by reaction of LaH 3 with Te vapor
(no further information), Yarembash et al. [21]. Single crystals were grown by the vapor
Iransport reaction with iodine as the transporting agent at about 850°C (see p. 31), Murray,
Taylor [5].
Gmelin Handbock 6
RE Main Vol. C10
La2Te3 has the cubic y-M 2Te3 structure (see p. 33), space group 143d-~ (No. 220), Z = 1 %.
Cox et al. [6]. Because of its defective La 3Te 4 structure (every ninth cation site in the cell of
La 2Te 3 is vacant), from the crystal-chemical point of view, the phase La 2Te 3 is not considered
an independent compound, but a subtraction solid solution based on La 3Te 4 , Eliseev et al. [7].
Lattice constant a in A: 9.619 [6 to 10], 9.618 [11]. The calculated and measured density is
DeaLe = Dexp = 6.57 g/cm 3 [8], Dexp = 6.53 g/cm 3 [7, 10]. From X-ray single crystal diffraction
the parameter of the Te atoms situated in 16 (c), x x x, was found to be x = 0.0748. The La
atoms occupy position 12 (a), 3fs 0 1/ 4 ; R = 0.04. ln the La 2Te 3 structure, Lais surrounded by
eightTe atoms at the two different distances 3.244 and 3.418 A (±0.003 A). The Te-Te distances
are 3.66, 4.17, and 4.64 A; the nearest La-La distance is 4.50 A [6].
X-ray diffraction of ceramic La 2Te 3 samples shows no phase transformation between 140
and 300 K, but the temperature function of the Lattice constant a shows a break at 210 K. This
can possibly be explained by ordering of vacancies with decreasing temperature, Zhukova
et al. [12]. From a = 9.619 A at 20°C, 9.639 A at 200°C, and 9.667 A at 300°C the Linear
coefficient of expansion is rJ. = 19 x 10- 6 K- 1 [10].
Thermal Properties
The enthalpy of formation of La 2Te 3 was calorimetrically determined to be -~H~98 =

187.5 ± 6.1 kcal/mol (784.50 ± 25.52 kJ/mol), Sharifov et al. [13]. The heat Capacity CP between
5 and 273 K is shown in a figure in the paper of Mitarov et al. [14]. From CP measurements
between T = 12.8 and 293 K of polycrystalline La2Te 3 in an adiabatic vacuum calorimeter the
following smoothed (selected) values of CP in cal · mol- 1 °K-1, the enthalpy increment
H~-H~ 2 . 8 in caUmol, and the entropy increment S~-S~ 2 . 8 in calo mol- 1 °K- 1 are obtained by
Nogteva et al. [ 15]:
Tin K 1208 20 30 60 90 120 150 180 220 260 298015
cp oo96o 20991 70597 19005 24020 26.72 28033 29.42 29071 30067 31058
H~-H~ 2 . 8 ° 0 13066 65089 48605 1144 1912 2739 3607 4 788 5995 7183
S~-S~ 2 . 8 ° 0 008141 2.868 12011 20.93 28027 34.42 39069 45061 50065 54091
H~ 98 . 15 - Hg = 7187 ± 10 caUmol, standard entropy S~ 98 . 15 = 55036 ± 0°08 calo mol- 1 °K- 1 [15]0
Values at 273o15K for CP = 29092calomoL- 1 oK- 1 and for the absolute values of entropy,
enthalpy, and Gibbs free energy are: S~ 73 . 15 = 510251 calo mol- 1 °K-1, H~73. 15 = 6288 caUmol
and G~73 . 15 = 7711 caUmol, Tikhonov et al. [16]0 The results of the CP measurements between
5 and 273 K agreed with the tabulated values of [15] to within 3 to 5%, but the anomalies in
the CP versus T curve near 200 K found by [15] and [12] were not confirmed by careful
investigation of the temperature dependence of CP in the vicinity of 200 K, Tikhonov et al. [17].
The Debye temperature 9 0 as a function ofT is shown in Figo 22, po 78; 9 0 192 ± 2 K at
77 K [17]0 For the thermal conductivity, see ppo 38 and 780
Electrical Properties
Values of the electrical resistivity Q reported for La2Te 3 at room temperature differ by
several orders of magnitude; see ppo 40 and 790
Gmelon Handbock
RE Maon Vol. C10
83
Additional values of Q and the thermoelectric power S of polycrystalline La2Te 3 at room

temperature are:
Qin Q·cm . 3 X 103 2 X 103 ~2 X 103 4 X 102 62

-S in J.1VIK 20 to 30 20 to 30 ~130 20 to 30 261
Ref. . . . . [10] [19] [20] [21] [11]
According to Ramsey et al. [18] the resistivity decreases as the temperature is increased
from room temperature to 573 K with an activation energy .-\E ~ 0.43 eV at the higher
temperatures. This .-\Eis presumably a measure of surface phenomena activation processes
rather than an indication of intrinsic character. With the assumption of nondegenerated
semiconduction an energy gap of ~0.1 eV can be estimated, which seems more reasonable
than the measured value [18]. A value Q = 12 n · cm at 443 K is reported by [10, 19], but
according to Aloman [20], above room temperature Q is nearly constant up to ~550 K
( ~2000 n· cm) and then decreases to ~ 10 n·cm at 950 K, due to intrinsic conductivity with an
activation energy .-\E = 1.29 eV, Aloman [22]; S is nearly constant up to ~ 550 K (~ -130 J.lV/K
at 300 K) and changes to ~ -90 J.lV/K at 950 K [20]. ln the temperature range between room
temperature and 573°C the measured values for S lie between -200 and a maximum value
of -259 J.1VIK observed at about 373 K, Ramsey et al. [18]. Dependance of Q and S on the
conditions of sample preparation (particle size, pressing pressure, and time of sintering at
1100°C) was studied by Aloman et al. [3] for La2Te3 and Ce 2Te 3 , but detailed data were given
only for Ce 2Te 3 (see p. 100). For the sample with Q = 62 n ·cm and S = -261 J.lV/K (sintered
200 h at 1100°C) the Hall coefficient RH = -12.56 cm 3/C, the carrier concentration n =
5x 1017 cm- 3 , and the carrier mobility J.l = 0.208 cm 2 ·V- 1 ·s-1, Aloman [11].
Chemical Reactions
La2Te 3 is thermally stable up to 1100°C, Aloman et al. [3, 24]. On heating in air La2 0 3 and
Te02 are formed. With H20 at 100°C, and with solutions of H20 2 , KOH (30%), or KCN no
reactions occur, but bromine water and acidic solutions of KMn04 , FeCl3 , HgCl2 , and ammo-
nium molybdate are reduced, as are warmed concentrated HN03 and H2S0 4. With molten
KOH in air La2 0 3 and K2Te04 form [4].
A mixture of 10 ml glacial acetic acid and 1 ml bromine is suitable as an etching solution
for La2Te3 • The etch rate at room temperature is 0.84 g · s- 1 · m- 2 when freshly prepared. The
etch rate increases by addition of C2 H50H; it is 1.63 g · s- 1 • m- 2 with a mixture of 5 ml
CH 3COOH + 5 ml C2H5 0H + 1 ml Br2 . Etching with 10 ml fuming HBr + 30 ml H20 + 1 ml
Br2 the sample initially acquires a high apparent polish, but then twisted Te whiskers grow
profusely and very rapidly from the surface of the sample, Bro [23].
References:
No. 1 [1974] 61/6; C.A. 83 [1975] No. 155866).
[3] A. Aloman, S. S. Gorelik, V. M. Malovetkaia (Rev. Chim. [Bucharest]19 [1968] 268/70;
C.A. 69 [1968] No. 47295).
[4] E. Montignie (Z. Anorg. Allgem. Chem. 362 [1968]329/30).
[5] J. J. Murray, J. B. Taylor (J. Less-Common Metals 21 [1970]159/67).
[6] W. L. Cox, H. Steinfink, W. F. Bradley (lnorg. Chem. 5 [1966] 318/9).
Gmelin Handbock s·
RE Main Vol. C10
[7] A. A. Eliseev, E. I. Yarembash, V. G. Kuznetsov, L. I. Antonova, Z. R. Stoyantsova (lzv.

943/52).
[9] D. J. Haase, H. Steinfink, E. J. Weiss (Proe. 4th Conf. Rare Earth Res., Phoenix, Ariz.,
1964 [1965], pp. 535/44).
876/82; Russ. J. lnorg. Chem. 9 [1964]482/5).
[11] A. Aloman (Bul. lnst. Politeh. Gheorghe Gheorghiu-Dej Bueuresti 30 No. 2 [1968]101/6;
C.A. 70 [1969] No. 53450).
[12] T. 8. Zhukova, R. G. Mitarov, M. V. Romanova, et al. (Dokl. 4th Vses. Sovesheh.
Uporyadoeheniyu At. Ego Vliyaniyu Svoistva Splavov, Tomsk 1972 [1974], Vol. 2, pp.
217/20; C.A. 84 [1976] No. 52324).
[13] K. A. Sharifov, Z. Sh. Karaev, T. Kh. Azizov (lzv. Akad. Nauk SSSR Neorgan. Materialy 3
[1967] 719/20; lnorg. Materials [USSR] 3 [1967] 637/9).
[14] R. G. Mitarov, V. V. Tikhonov, L. N. Vasilev, et al. (Phys. StatusSolidiA 30 [1975]457/67).
[15] V. V. Nogteva, I. E. Paukov, E. I. Yarembash (Zh. Fiz. Khim. 43 [1969]2118/20; Russ. J.
Phys. Chem. 43 [1969]1186/7).
[16] V. V. Tikhonov, R. G. Mitarov, I. A. Smirnov (Zh. Fiz. Khim. 49 [1975]3008; Russ. J. Phys.
Chem. 49 [1975]1786).
[17] V. V. Tikhonov, N. N. Bystrova, R. G. Mitarov, I. A. Smirnov (Fiz. Tverd. Tela [Leningrad]
17 [1975]1225/6; Soviet Phys.-Solid State 17 [1975] 795).
28 [1964]1306/9; Bull. Aead. Sei. USSR Phys. Ser. 28 [1964]1208/12).
[20] A. Aloman (Metalurgia [Bueharest]21 [1969]363/7; C.A. 72 [1970] No. 60484).
[21] E. I. Yarembash, E. S. Vigileva, A. A. Eliseev, L. I. Antonova (Zh. Neorgan. Khim. 8 [1963]
1542/3; Russ. J. lnorg. Chem. 8 [1963] 804).
[22] A. Aloman (Rev. Roumaine Sei. Teeh. Ser. Met. 14 [1969] 39/56, 51; Studii Cereetari Met.
14 [1969]47/63, 59; C.A. 71 [1969] No. 130034, No. 106293).
[23] P. Bro (J. Eleetroehem. Soe. 109 [1962]750).
[24] A. P. Aloman, S. S. Gorelik, V. M. Malovetskaya, V. I. Buzanov (lzv. Vysshikh Uehebn.
Zavedenii Tsvetn. Met. 14 No. 4 [1971]73/7; C.A. 75 [1971] No. 144641).
30.1.2.10.3.4 Lanthanum Polytellurides
30.1.2.10.3.4.1 LaTe 1.7 ±x· LaTe 2 _x

The blaek La 4Te 7 of eomposition LaTe_ 1_6 to LaTe_ 1_78 is observed in the La-Te system
(see p. 65). For its preparation and properties in eomparison to other M4Te 7 eompounds, see
p. 43.
LaTe 2 _x
Homogeneity Range and Preparation
LaTe 2 _x is an ineongruently melting phase (at ~ > 1300°C) in the La-Te system; see p. 65.
lts homogeneity rangewas determined tobe LaTe 2 to LaTe_ 178 by Eliseev et al. [1], LaTe 2
to LaTeu 5 by Gerasimov et al. [2, 3], and LaTe 2 to LaTeu by Ramsey et al. [4, 5]. ln earlier
Gmelm Handbock
RE Mam Vol. C10
works a range of LaTe 2 to LaTe 1_9 was reported by Pardo et al. [6] and LaTe 2 _5 to LaTe1.Bo by
Eliseev et al. [7].
For the preparation of LaTe 2 from the elements see p. 47 and p. 67. To get homogeneous
products the same procedure was used as described for La 2Te 3 (see p. 81), Gerasimov et al.
[2]. The stoichiometric amounts of La and Te were slowly heated in evacuated quartz ampules
to 1 000°C and held at that temperature for 50 to 300 h. At the end of the reaction, dense,
homogeneaus ingots were obtained [4]. Homogeneaus LaTe2 was also obtained by heating
the initial mixture to 800 to 900°C and subsequently holding the temperature at 500 to 600°C
for 24 to 30 h, followed by slow cooling, Yarembash et al. [8]. LaTe 2 was prepared by the
vapor-solid reaction in sealed Vycor tubes at 600°C, Wang et al. [9] and by reaction of Te vapor
with LaH 3 , Yarembash et al. [10]. lt can also be synthesized by distilling Te from La-Te melts
containing more than 75 at% Te [8] (but see the La-Te phase diagram, p. 66).
The formation of single crystals of LaTe2 using the gas transport reaction with iodine as
carrier gas in ampules with a temperature gradient has been described on p. 31 by Bro [11].
The same method was used by Murray, Taylor [12], Luzhnaya et al. [13], and Eliseev et al.
[14, 15]. Starting with polycrystalline LaTe 2 , a temperature gradient 950---. 800°C, an initial
iodine concentration of 5 mg/cm 3 , and a duration of 100 h were employed [15]. Starting with
polycrystalline La 2Te 3 at the same temperature gradient a mixture of LaTe 2 and LaTe1.7 was
obtained (see p. 44) by [14], while [12] reported the formation of La 2Te 3 near 850°C and LaTe 2
at about 700°C in agreement with [11].
Crystallographic Properlies and Density
Single crystal X-ray diffraction shows LaTe 2 to have the tetragonal Fe 2 As (Cu 2Sb) structure,
space group P4/nmm-D~h (No. 129), Z = 2, Eliseev et al. [16, 17], Wang et al. [9].
Lattice constants a and c in A and density 0 in g/cm 3 in LaTe 2 and LaTe 2 _x:
LaTe 2 LaTe 2 LaTe 2 LaTe 2 LaTe 2 LaTe 1 _9 LaTe 1 _9 LaTe1.8
a 4.556 4.53 4.507 4.552 4.558 4.520 4.547 4.534

c 9.176 9.12 9.128 9.178 9.176 9.199 9.169 9.136
Deale · 6.80 6.97 6.88 6.55
Dexp 6.82 6.86 6.82 6.65
Ref. [16, 17] [18] [9] [1] [6] [6] [1] [1]
Note the contrary change observed by [1] and [6] for c in the solid solutions. A shrinkage of
the a axis and an elongation of c [6] as the Te concentration decreases are consistent with
the results from crystal structure refinements (i. e., removal of atoms from the basal plane),
Wang et al. [9], see p. 50. Between 20 and 300°C the lattice constant a increases from 4.552
to 4.589 A and c from 9.178 to 9.226 Afor LaTe 2 , Eliseev et al. [19].
Other Physical Properlies
The linear coefficients of thermal expansion cr(..l.[001]) = (29 ± 6) x 10- 6 K- 1 and

cr(II[001]) = (19 ± 4) x 10- 6 K- 1 for LaTe 2 between 20 and 300°C are derived from lattice
Gmelin Handbook
RE Main Vol. C 10
1.0
OS
'E
u
1::
.
.~
0.1
0.050
4 8 Temperature in OC
1000/T in K" 1
Fig. 27. Electrical conductivity K vs. Fig . 28. Thermoelectric power S
reciprocal temperature of ot LaTe 2 _ x samples
n- and p-type LaTe1.9. vs. temperature.
constants, Eliseev et al. [19]. For single crystalline LaTe 2 at 20°C the magnetic susceptibility
is x9 = -0.03 x 10 - 6 cm 3/g, the electrical resistivity Q = 0.08 Q · cm, and the thermoelectric
power S negative, Eliseev et al. [15], Yarembash et al. [20]; for polycrystalline LaTe 2 Q =
6.6 Q · cm and S = + 15 to + 20 j!V/K at 20°C (Q = 3.3 Q · cm at 170°C) [20] . 1t is possible to
make both p- and n-type materials in the solid solution series LaTe 2 _x depending on the
preparation, Ramsey et al. [18]; seealso Ramsey et al. [4]. lt seems that p-type behavior is
caused by slight oxygen impurities, while the n-type behavior increases with the Te-deficit.
The temperature dependence of the electrical conductivity K for pressed powders of n- and
p-type LaTe 1.9 is shown in Fig. 27 and of S for various LaTe 2 _x samples synthesized under
similar conditions in Fig. 28. The Log K versus 1/T curves for LaTe 2 (T = 300 to 575 K) are
similar for n- and p-type material (with small discontinuities near 500 K) and similar to those
of LaTe 1.9 at the upper temperature range. The unusual exponential behavior of the (metallic)
LaTe 2 and the unrealistic high experimental activation energy (0.34 eV in the upper and
~0 . 6 eV in the Lower temperature range) were explained by surface phenomena due to the
polycrystalline material. Similarly the exponential conductivity of LaTe 1.9 is attributed to
surface phenomena rather than intrinsic character [18]. The electrical resistivity between 530
and 1430 K for hot-pressed p-type LaTe 2.0 and the n-type specimen obtained therefrom after
a 16 h annealing at 1120°C is shown in Fig. 29a; Fig. 29b presents the S behav ior. The p-
type sample was prepared by melting LaTe 2.0 powder and hot pressing the ground material
( ? 1200 °C, 10000 psi , i.e., 69 MPa, 1h) , Danielson et al. [21] (note: LaTe 2 melts incongruently
and Losestellurium at high temperatures; see pp. 66/7).
The color of polycrystalline LaTe 2 is metallic black [4, 5, 18]; single crystals are dark violet
[16, 20] to black [15]. An IR absorption spectrum of LaTe 1 85 showed a broad absorptionband
corresponding to an energy band gap of ~0.09 eV [4]; seealso p. 51 .
Gmelm Handbock
RE Mam Vol. C 10
500 +120
a) b)
+40
E 100 ::.::
~
0: 50 %. 0
E .I;
.I; 1/) -40
Q.
1.1 1.5
1000/T in K1 Tempereture in°C
Fig. 29. Temperature dependence of electrical resistivity (a) and thermoelectric power (b) for
LaTe2 .
References:
[1] A. A. Eliseev, E. I. Yarembash, V. G. Kuznetsov, et al. (lzv. Akad . Nauk SSSR Neorgan.
Materialy 1 [1965]1027/38 ; lnorg. Materials [USSR]1 [1965] 943/52) .
No. 1 [1974]61/6 ; C.A. 83 [1975] No. 155866).
[3] A. F. Gerasimov, A. N. Krushatina, V. N. Konev (Tezisy Dokl. 2nd Vses . Konf. Kristallokhim.
lntermetal. Soedin., Lvov 1974, pp. 177/8; C.A. 85 [1976] No. 170 289) .
[4] T. H.Ramsey, H. Steinfink, E.J. Weiss (J. Appl. Phys. 34 [1963] 2917/8).
[5] T. H. Ramsey, H. Steinfink, E.J. Weiss (lnorg. Chem . 4 [1965]1154/7) .
[6] M. P. Pardo, J. Flahaut, L. Domange (Compt. Rend. 256 [1963] 953/5).
[7] A. A. Eliseev, E. I. Yarembash, V. G. Kuznetsov, et al. (Zh. Neorgan. Khim . 9 [1964]
876/82; Russ. J. lnorg. Chem. 9 [1964]482/5).
1 [1965]167/70; lnorg. Materials [USSR]1 (1965]149/52).
[9] R. Wang, H. Steinfink, W. F. Bradley (lnorg. Chem. 5 [1966]142/5) .
[10] E. I. Yarembash, E. S. Vigileva, A. A. Eliseev, L. I. Antonova (Zh. Neorgan. Khim. 8 (1963]
1542/3; Russ. J. lnorg. Chem. 8 [1963]804).
[11] P. Bro (J. Electrochem. Soc. 109 [1962]1110) .

[12] J. J. Murray, J. B. Taylor (J . Less-Common Metals 21 [1970]159/67) .
pp. 49/54; C.A. 64 [1966] 4406) .
[14] A. A. Eliseev, V. G. Kuznetsov, E. I. Yarembash, et al. (lzv. Akad . Nauk SSSR Neorgan.
Materialy 2 [1966] 2241/5; lnorg. Materials [USSR] 2 [1966]1934/8).
[15] A. A. Eliseev, E. I. Yarembash, E. S. Vigileva (Dokl. Akad . Nauk SSSR 153 [1963] 1333 ;
Dokl. Chem. Proc. Acad. Sei. USSR 148/153 [1963]1 031).
[16] A. A. Eliseev, V. G. Kuznetsov, E. I. Yarembash (Zh. Strukt. Khim. 5 [1964]641/2; J. Struct.
Chem. [USSR] 5 [1964]594) .
[17] A. A. Eliseev, V. G. Kuznetsov (lzv. Akad . Nauk SSSR Neorgan. Materialy 1 [1965] 692/7 ;
lnorg. Materials [USSR]1 [1965] 635/9) .
Gmelin Handbook
RE Main Vol. C 10

28 [1964]1306/9; Bult. Acad. Sei. USSR Phys. Ser. 28 [1964]1208/12).
[21] L. R. Danielson, V. Raag, C. Wood (Proc. lntersoc. Energy Convers. Eng. Conf. 20 111
[1985]531/5; C.A. 103 [1985] No. 133214).
30.1.2.1 0.3.4.2 La 3Te7± x
This polytelluride of unknown structure, Eliseev [1], has a homogeneity range from 69.5
to 70.5 at% Te and melts incongruently at 1 060°C, Yarembash, Eliseev [2]; see p. 66. lts
electrical conductivity K = 100 n- 1 · cm-1, thermoelectric power S = + 19 11V/K, and carrier
concentration n = 6 x 1017 cm- 3 at room temperature. The isomer shift ö = 1.25 ± 0.20 mm/s
and Une width [' = 9.5 ± 0.2 mm/s are derived from the 125Te Mössbauer spectrum (35.5 keV
y transition, source 125Te0 3 ), Gorbachev et al. [3]; seealso Fig. 2 on p. 19.
References:
[1] A. A. Eliseev (Zh. Neorgan. Khim. 30 [1985]1111/20; Russ. J. lnorgan. Chem. 30 [1985]
627/33).
Moscow 1975, pp. 1/260, 169/82).
30.1.2.1 0.3.4.3 La 2Te 5 ± x
The polytelluride La2Te 5 with ~71 to 72 at% Te is an incongruently melting phase (at
~815°C) in the La-Te system; see p. 66. For properties see p. 53.
Emf measurements of the cell LaiKCl-LiCl eutectic + 7% LaCl3 ILa0 286Te 0 .714 at 643
to 703 K give the thermodynamic parameters of formation at 680 K for 1 mol La 0 286Te0 714
as ~Gg80 = -31.20 ± 0.01 kcal/mol, ~H6 80 = -32.30 ± 0.15 kcal/mol, and ~8680 =
-1.62 ± 0.20 cal · mol - 1 · K - 1 . The sample used and identified by X-ray diffraction was pre-
pared in evacuated quartz capsules by slowly (1 K/min) heating the elements to ~650°C,
holding this temperature for 24 h, and homogenizing the ground, pressed material at 410 to
420°C for 300 to 700 h, Somov et al. [1]. A lower Limit of the stability range (650 to 811 °C)
observed by Pardo, Flahaut [2] was thus not confirmed by [1].
References:
[1] A. P. Somov, A. V. Nikol'skaya, Ya. I. Gerasimov (lzv. Akad. NaukSSSR Neorgan. Materialy
[2] M. P. Pardo, J. Flahaut (Campt. Rend. C 263 [1966]1058/60).
Gmelm Handbock
RE Mam Vol C10
30.1.2.1 0.3.4.4 La 4Te 11 ± x
This polytelluride with ~73 to 74 at% Te is an incongruently melting phase (at 780°C) of
the La-Te system according to Yarembash, Eliseev [1] ; see p. 66. For its properties, see p. 56.
There was no ind ication of this phase in X-ray diffraction and emf studies performed on
samples with 72 to 74 at% Te homogen ized at 410 to 420°C for 300 to 700 h, Somov
et al. [2] .
References:
Moscow 1975, pp . 1/260, 169/82).
[2] A. P. Somov, A. V. Nikol'skaya, Ya . I. Gerasimov (lzv. Akad . Nauk SSSR Neorgan. Materialy
30.1.2.10.3.4.5 LaTe 3 _x
The polytelluride LaTe3 is an incongruently melting phase (at 465°C) in the La-Te system
(see p. 66) with a homogeneity range from LaTe 3 to LaTe 290 (74.4 at% Te) according to
Yarembash , Eliseev [9]. The composition LaTe 2 .55 (71 .8 at% Te) was given earlier as the Lower
Limit by Eliseev et al. [1] . For the preparation of polycrystalline specimens from the elements
see pp. 57 and 67. LaTe 3 can also be obtained by distilling Te from melts conta ining more than
75 at% Te, Yarembash et al. [2].
LaTe 3 has orthorhombic pseudotetragonal symmetry; see p. 58 for the structure and
lattice constants . The lattice constants for LaTe 2 .8 are a = 4.402 , c = 25.88 A at 20°C and
Temperature in K
~~~~~~~~__1,s~7--~12r5~~ 30
.....__
:.::
~ 20 /
V
:I.
.S /
,/
lfl
10
'eu
'c.S:
V
E 2
\\
~ V
c:
E /
.S
Q.
1/
O.lo.,..___.J....__-7
4-----'-----:a!:---' 200 ~0 600 800
1000/T in K- 1 Temperature in K
Fig. 30. Electrical conductivity Fig. 31. Thermoelectric power S

vs. reciprocal temperature for and electrical resistivity Q
two high-purity LaTe 3 samples. of LaTe 3 _ x vs . temperature .
Gmelin Handboc k
RE Main Vol. C 10
a = 4.424, c = 25.95 A at 300°C; the linear thermal expansion coefficient a. was calculated
tobe a. (.l[001]) = (18 ± 3) x 10- 6 and a. (11[001]) = (10 ± 3) x 10- 6 K-1, Eliseev et al. [3].
From emf measurements of the cell LaiKCL-LiCL eutectic + 7% LaCL3 1La 1 _xTex at 370 to
430°C and 0.715 ~ x ~ 0.80 the following thermodynamic parameters of formation for
LaTe 3 at 680 K have been calculated for 1 mol La 025Te 0 _75 : L\Gg80 = -27.30 ± 0.01 kcaUmol,
L\Hg 80 = -28.26 ± 0.16 kcaUmol, and L\S~0 = - 1.42 ± 0.22 cal · mol - 1 · K- \ Somov et al. [8].
Some samples of LaTe 3 exhibit an apparent intrinsic conduction (see Fig. 30, p. 89) although
it is difficult to obtain samples with nondegensrate behavior. The thermoelectric power S is
positive; S increases from -25 J.lVIK at 30°C to -80 J.lVIK at 300°C. Most samples of LaTe 3
show metallic behavior, Ramsey et al. [4]. For a Te-deficient phase LaTe 3 _x, prepared by
sintering LaTe 3 pellets under Ar atmosphere at 610°C for 24 h in a sealed Vycor tube, the
electrical resistivity and S are shown in Fig. 31, p. 89, Carter [5].
By heating in vacuum golden brown LaTe 3 gives off Te at >460°C, Eliseev et al. [6]. The
dissociation LaTe 3 --> LaTe 2 was determined by DTA to occur at -450°C, Ramsey et al. [7]
(but see the intermediate phases in Fig. 15, p. 66, found by [9]). When heated in a sealed Ar-
filled ampule to -600°C without excess Te, LaTe 3 Loses Te to a cooler part of the ampule.
When LaTe 3 is exposed to the air, it undergoes a slow decomposition to a gray product [5].
References:
Materialy 1 [1965]1027/38; lnorg. Materials [USSR]1 [1965] 943/52, 951).
[5] F. L. Carter (Met. Soc. Conf. Proc. 15 [1962]245/61, 256/7).
[6] A. A.. Eliseev, E. I. Yarembash, V. G. Kuznetsov, et al. (Zh. Neorgan. Khim. 9 [1964]
876/82; Russ. J. lnorg. Chem. 9 [1964]482/5).
1963 [1964], pp. 303/14, 309).
[8] A. P. Somov, A. V. Nikol'skaya, Ya. I. Gerasimov (lzv. Akad. Nauk SSSR Neorgan. Materialy
Moscow 1975, pp. 1/260, 169/82).
30.1.2.1 0.3.5 (La 0 .8Y 0.2hTe 4
The cubic solid solution (La 0 .8 Y0.2bTe 4 has the Th 3 P4 structure (see p. 21) with the Lattice
constant a = 9.586 A. The coefficient y of the electronic specific heat C(el) = y · T is
2.1 mJ · K- 2 · mol- 1 and the Debye-tamperature 0 0 (0) = 208 K. The critical temperature of
superconductivity is Tc~ 5.3 K for La3Te 4 and < 1.7 K for the solid solution, E. Sucher, K.
Andres, F. J. di Salvo, et al. (Phys. Rev. [3] 8 11 [1975]500/13, 504).
Gmelm Handbock
RE Mam Vol. C 10
The Ce-Te System 91
30.1.2.10.4 Cerium Tellurldes

Additional data for CeTe, Ce3Te4 , Ce2Te 3 , Ce4Te7 ( = CeTe 1_7 ± . ). CeTe2 _ . , Ce2Te 5 , Ce4Te 11,
and CeTe 3 are found in Sections 30.1.2.1, 30.1.2.2, 30.1 .2.3, 30.1.2.4, 30.1.2.5, 30.1.2.6, 30.1.2.7,
and 30.1.2.8 on pp. 6, 21 , 31, 43, 47, 53, 56, and 57, respectively.
30.1.2.10.4.1 The Ce-Te System

Phase Diagram
The phase diagram in Fig. 32 from Yarembash, Eliseev [1] is based on Literature data,
especially on studies from Chukalin [2]. CeTe melts congruently at tm ~ 1750°C (read from
the figure) . The other phases melt incongruently with the following temperatures tP (in °C):
CeTe2 CeTe3
1200 485
The phase diagram constructed earlier by Chukalin et al. [3] based on X-ray phase analysis,
thermal analysis, and melting point determination contained all these phases (except Ce 3Te7
and Ce 4Te 11 ) ; CeTe (tm = 1820°C) has a homogeneity rangenot exceeding 1 at% Te. Ce 3Te4
(assumed to melt congruently at tm = 1645°C) forms a continuous series of solid solutions
with Ce2Te3 [3]; tm = 1645°C for Ce3Te4 and tP = 1560°C for Ce2Te3 were listed by Yarem-
bash [4, 5] . The homogeneity ranges of Ce4Te7 (tp = 1340°C [3] , Tyurin et al. [6]) , CeTe 2
(tp ~ 1250°C [3]), and Ce2Te 5 (tp = 875°C [3]) are 63 to 64.5 at % Te [6]. 66 to 66.67 at % Te,
2000
eer..
/
I ,~l-v T"'
/ \
·- ·· 1550oc
1600 /
/
/
' :.._,r.,,
/
/
..c..r.,2
/ ' 3400C
/
u /
0
.5 1200 /
/
~~Dil:c_
~
I
/
.., ~-~
/
~ /
~ ee,r
e8. Ce2T"s
:I /
/ ~ ~4~~-~
/
/ [;:: 870"C
/::
---
/
E 800 790°C 8300C \
I
~
730°C ~
/.
I
c..r"J-x \I
I 485°C
-4ss<ic
400
%
~
I I ~
20 40 60 80 100
Te
at•J. Te
Fig. 32. The Ce-Te phase diagram.

Gmel in Handbock
RE Main Vol. C 10
92 Cerium Tellurides
and 71 .44 to 73 at% Te , respectively (tp = 825°C for Cele3 ) [3] . For earlier studies in the
range 70 to 100 at% Te, see Chukalin, Yarembash [7]. The homogeneity range of Cele3 is not
reported.
According to Pardo, Flahaut [8] Ce 2Te 5 has only a Limited range of stability between about
870 and 600°C (see p. 53) . The phase diagram reported by Gschneidner, Verkade [9] below
about 70 at % Te is based on the results of [3, 7] and above 70 at % Te on the results of Pardo,
Flahaut [8, 10].
The eutectic with Ce and Gele melts at 790 °C and the degenerate eutectic with Cele3 and
Te at 455°C [1] . The temperatures were 760 and 455 °C, respectively, according to [3]. ln the
diagram shown by [9] the eutectic points are at 760 °C, 3 at % Te, at 435 °C, 99 at % Te, and
further at 1585°C, 55 at% Te (between Gele and Ce 3Te4 ) .
General Preparation Method and Properlies

Homogeneaus samples were prepared by the following method. The mixed element
mixtures were slowly heated in evacuated , vertically arranged quartz capsules ; the exo-
therrnie reaction begins at 360°C. The temperature was held at 350 to 400 °C and then at 800
to 900°C. The reaction time varied from 3 to 5 d. To avoid reaction between Ce and quartz,
the Ce-rich samples were placed in corundum crucibles inside the quartz ampules. To
homogenize the reaction products, they were powdered, pressed to rods (5 x 5 x20 mm 3 ),
and annealed at 800 to 1 000°C for 75 to 100 h, Chukalin et al. [3].
ö
E26
•
äu •
-"
.s 34 •
0~
r
•
<I 42 •
I 0 0.2 0.4 0.6 Q8 1.0
Fig. 33. Heat of formation of cerium telluride phases Ce 1 _xlex.
The heats of formation L1H3oo of cerium telluride phases Ce 1 _ xlex at 300 K, measured
calorimetrically, are shown in Fig. 33, Borzone et al. [11] . Near x = 0.5, L1H300 ~
- 40 kcaUmol, Borzone et al. [12] .
The following colors have been reported for cerium tellurides : Gel e, dark blue ; Ce3Te4 ,
Lightgray ; Ce 2Te3 , gray-black ; Ce4Te7 , black; Cele2 , black-Lilac ; Ce2Te 5 , dark lilac-gold ; Cele 3 ,
brown-gold [3] .
References:
[1] E. I. Yarembash , A . A .Eliseev (Khal'kogenidy Redkozemel 'nykh Elementov, Nauka,
Moscow 1975, pp. 1/260, 182/7).
[2] V. I. Chukalin (Diss. Moscow 1968 from [1]) .
[3] V. I. Chukalin , E. I. Yarembash , A. I. Villenskii (lzv. Akad. Nauk SSSR Neorgan. Materialy
Gmelin Handbock
RE Maon Vol. C 10
CeTe 93
Vol. 2, pp. 761/77, 769; C.A. 73 [1970] No. 124092).
[5] E. I. Yarembash (Colloq. Intern. Centre Natl. Rech. Sei. [Paris] No. 180 [1969/70] 471/81).
7th Vses. Simp. Fiz. Svoistvam Elektron. Str. Perekhodnykh Metal, lkh Splavov Soedin.,
Kiev 1969 [1972], Vol. 1, pp. 156/61; C.A. 79 [1973] No. 59042).
[7] V. I. Chukalin, E. I. Yarembash (lzv. Akad. Nauk SSSR Neorgan. Materialy 3 [1967]
[8] M. P. Pardo, J. Flahaut (Compt. Rend. C 263 [1966] 1058/60).
[9] K. A. Gschneidner Jr., M. E. Verkade (IS-RIC-7, lowa State University 1974, pp. 1/50,
42/3; C.A. 83 [1975] No. 198383).
[10] M. P. Pardo, J. Flahaut (Bult. Soc. Chim. France 1967 3658/64, 3661).
[11] G. Borzone, A. Borsese, R. Ferro (Gazz. Chim. ltal. 113 [1983] 235/8).
[12] G. Borzone, G. Cacciamani, A. Borsese (15th Congr. Naz. Chim. lnorg. [Atti] 1982,
pp. 408/10; C.A. 100 [1984] No. 127523).
30.1.2.10.4.2 CeTe
Preparation and Crystallographic Properlies
Ce Te is a congruently melting phase in the Ce-Te system; see p. 91. For the preparatio.1
from the elements, see pp. 6 and 92. After reaction of the eiementaL mixture in a sealed Mo
crucible under Ar atmosphere, single crystals of 1 x 1 x 3 mm 3 are obtained by sublimation at
the top of the crucible during slow cooling (4 K/h) from a maximal temperature of 2000°C,
Ravot et al. [1], or the single crystals, typically 2 x 2 x 3 mm 3 , are cleaved from the crystaLLized
mass, Leger et al. [20]. Blue or violet-btue single crystals are obtained by slowly cooling the
melts, Hulliger et al. [2]. CeTe has the cubic NaCL structure (see p. 8) with a = 6.361(5) A [1]
and a = 6.3614(6) A [2] for stoichiometric single crystals, a = 6.360(10) A for a powdered
single crystal close to stoichiometry [20], and a = 6.3592(5) A for a Ce-deficient ( < 0.5%) one.
Polycrystalline samples had, for example, a = 6.3495(7) and 6.3606(8) A [2]. Below room
temperature the Lattice constant decreases and has a minimum at about 35 K, Ott et al. [3].
At a pressure of 8 ± 1 GPa at room temperature, the NaCL type structure (a = 6.192 A at
8 GPa) transforms into a CsCL type with a = 3.773(10) A (see p. 10). The Lattice constant
decreases to 3.604(10) A at 23.3 GPa. On release of pressure, the CsCL---+ NaCL Iransformation
takes place around 3 GPa, Leger et al. [20]. The increase of the Ce-Te distance from 3.10 to
3.27 A at the NaCL---+ CsCL phase transition is Larger than expected from the increase of the
coordination number (from 6 to 8). This is possibly due to a decrease of the Ce valence, Leger
et aL. [20, 21] (see in the following).
Cerium Valence
At normal pressure the valence of Ce is v ~ 3 as indicated by the lattice constant and L 111
absorption edge, Leger et al. [20]; see p. 98. Assuming a Linear relationship between valence
and ionic radius, the pressure-volume dependence (see p. 94) may be interpreted by a
continuous increase starting from normaL pressure up to 8 GPa, where the valence ,...., 3.3, and
a discontinuous valence decrease by about 0.3 at the NaCL ---+ CsCL transition, Leger et al.
[20 to 23]; foranother interpretation (Kondo effect), see the following and p. 97.
Gmelin Handbock
RE Main Vol. C10
1.0
0.9
~. I
I
I
.... I
'
......I.....,
0.8 r'-.....
~
!'-....
10 20
p in GPa
Fig. 34. Pressure-volume diagram of CeTe.
Mechanical and Thermal Properties
The compression curve of CeTe at room temperature measured by X-ray diffraction with
an applied pressure up to 25 GPa is shown in Fig. 34. The sharp jump at 8 GPa with a relati ve
volume change of -8.5% indicates the sharp first-order phase transition. Below 8 GPa (for
NaCI type CeTe) th e curve follows the Murnagham state equation with the bulk modulus K =
±
52.8 4 GPa and its first pressure derivative dK/dp = 13.6 2. Above 8 GPa (for CsCI type ±
CeTe) the bulk modulus equals K = 130 ± 10 GPa and dK/dp = -1 .3 ± 0.3. The value K =
52.8 GPa is unexpectedly low and dK/dp = 13.6 unexpectedly high . The results are discussed
assuming a valence change of the Ce ion or a strong enhancement of the Kondo interactions
(see p. 97) und er pressure [20] ; see also [22] and comparison of CeTe with cerium mono-
pnictides in [21, 23].
Analyses of interionic potentials and cohesive energies give K = 47.1 GPa ( = 471 kbar)
and dK/dp = 3.54 for NaCI type CeTe, Jain, Shanker [5]. The compressibility was extrapolated
to 3 x 10- 12 cm 2 /dyn from known data for EuTe and Tm Te (the reciprocal value gives K
33.33 GPa), Ott, Lüthi [6].
Third-order elastic constants of CeTe at 0 K were calculated using the Born-Mayer potential
model. The repulsive interaction was considered up to the second-nearest neighbors. The
inter ionic distance r0 = 3.175 A Ieads to the values (in 1011 N/m2 ~ 1012 dyn/cm 2 ) c~ 1 1 =
-20.203, c~ 12 = c~66 = -1 .509, and c~23 = c~56 = c~44 = 0.616. The temperature dependence
for c,ßr is given by c,ßr = c~ßr + a,ßy · T, where the values for a, ßr are (in 108 dyn · cm - 2 · K - 1)
a 111 = 7.484, a 112 = 3.180, a 123 = -1 .132, a456 = 0.942, a 144 = -0.890, and a 166 = 2.686,
Thakur [4] .
From lattice constant measurements a considerable thermal expansion was deduced

below ~ 35 K [3]. The linear thermal expansion of single crystalline CeTe along [100] below
13 K is shown in Fig. 35a from measurements with a capacitance dilatometer. The weak
anomaly at ~ 2.1 K is due to the antiferromagnetic phase transition ; th e negative thermal
expansion above 3 K can be interpreted as a CEF ( = crystal electric field ) effect with a c ry stal
field splitting M k ;::::: 45 K [2. 6] ; see p. 96. The heat capacity measured around the Neel
Gmel 1n Ha ndbock
RE Maon Val. C 10
CeTe 95
8 • Q
I •
I
!. 1100)
;.:; 4 .
<f'
52 0
\
..... fo••
.!:
.... ...
.. .....
IS
-4
-8 . ...,
40 8
....:. ;.:;
b) ~
;.:; ;:~
.. .
6 "L.. ö
2
..:' .
E
.
0
~
. E •I'
..
E 4 ..:..,
..:..,
. ..
.. .. 4 .!:
l
.!:
-~ \ a.
0. 2 u
u
a.
u
0
3 5 7 9 11 13
Fig. 35. Linear thermal expansion Fig. 36. Molar heat capacity of CeTe
(Fig. 35a) and molar heat capacity below 120 K. 1) experimental values,
(Fig. 35b) of CeTe around 2) lattice contribution,
the Neel temperature. 3) , 4) magnetic contribution (see text).
temperature (TN = 2.1 K) is shown in Fig. 35b. The curve agrees fairly weil with expectations
r
based on assuming a 7 doublet ground state which is split upon magnetic ordering . The
magnetic entropy obtained by integrating Cp/T up to the Neel point is close to Rln2 where R
is the gas constant. lts maximum value at the CP anomaly is appreciably lower than that
calculated in a molecular field approximation. The heat capacity of another (stoichiometric)
single crystal below 120 K is shown in Fig. 36, curve 1. Curve 2 represents the approximated
lattice and free-electron contribution derived from CP measurements on LaTe and LuTe.
Curve 3 is the difference between curves 1 and 2, and represents the magnetic contr ibution.
Curve 4 is the calculated magnetic heat capacity (2].
Magnetic Properties
The magnetic properlies of cerium (and uranium) monochalcogenides and pnictides are
reviewed by Rossat-Mignod et al. [18].
CeTe is paramagnetic above the Neel temperature TN• antiferromagnetically ordered
below TN• and shows field-induced metamagnetic, possibly ferromagnetic, behavior, Loginov
et al. [7]. Susceptibility measurements below room temperature on single crystals confirm
the antiferromagnetic transition [1 , 2]. Reported values for TN are : 2.165 K from neutron
diffraction, Ott et al. (8], Ott, Kjems [9], ~ 2.0 K from both neutron diffraction and susceptibility
[1], 10 K from susceptibility (7], Adamyan, Loginov [10]. TN between 2.1 and 2.2 K and an
exceptional value of < 1.5 K for polycrystalline samples and single crystals from different
batches with no dependence on the lattice constant are reported by [2] ; see also [3] . The
temperature dependence of the sublattice magnetization of CeTe single crystals around T N
by means of neutron diffraction shows the magnetic transition to be continuous [9]. CeTe was
Gmelin Handbook
RE Main Vol. C 10
found to have the same magnetic structure as CeS and CeSe. The compounds are type II
antiferromagnets with the magnetic moments along the [111] direction and parallel to the
propagation vector of the magnetic structure [1, 8, 9]; seealso Hulliger, Ott [11]. The two-
parameter Heisenberg model gives -0.056 K for the effective exchange coupling constants
between nearest neighbors and -0.057 K between next-nearest neighbors in the case of
TN = 2.0 K and a paramagnetic Curie temperature eP = -5.9 K, Ravot et al. [25]. The critical
exponent ß for the magnetization M = C · tP, where t = 1-T/T N• is ß = 0.36 ± 0.04 in the
range 6 x 10- 3 < t < 0.2 with C = (0.45 ± 0.20) !ls [8]. The ordered magnetic moment deduced
from neutron scattering measurements, 0.15 < ll < 0.3 !ls at 0.45 K, is abnormally low
compared to the expected value of -0.7 !ls [1]; 0.3 ± 0.1 !ls at 1.5 K for the ordered moment
was reported by Ott et al. [8]. For a possible explanation in terms of Kondo couplings, see
p. 97.
Magnetization for polycrystalline CeTe (T N = 10 K) was measured in pulsed fields of
intensity up to 250 kOe below TN· CeTe shows antiferromagnetic behavior in fields up to about
20 kOe and is metamagnetic in stronger fields. The induced moment at 100 kOe and 1.3 K is
0.75 !ls per Ce atom. For details, see the paper, Loginov et al. [7]. The metamagnetic transition
in single crystals belowTN = 2 Kin fields H(II[001]) was found at about 18 kOe, associated with
a hysteresis cycle extending between zero and -35 or70 kOe at0.14 and 1.4 K, respectively. lt
seems that the magnetic field induces a transition from the antiferromagnetic state to (prob-
ably) a ferromagnetic state. The magnetization process, with steps on the magnetization
curves, is rather obscure. At 0.14 K the magnetization in 75 kOe fields reaches a value of
0.92 j.t8 /Ce. The magnetization is not saturated up to 80 kOe at 0.14 K and up to 150 kOe at
4.2 K (the respective field Limits studied) [1].
The magnetic form factor was measured on a CeTe single crystal with polarized neutrons
at 1.5 and 12.8 Kin an applied field of 4.65 T ( ~46.5 kOe). The anisotropy of the magnetization
density is important and has the same features as the r 7 ground state but the ground state of
Ce is not pure r 7 and contains a large amount of r 8 admixture, Boucherle et al. [15, 17].
x
The magnetic susceptibility ot a single crystal at H (11[100]) = 160 and 1245 Oe below
TN (2.0 K) exhibited small anomalies associated with the steps in the magnetization curves.
ln the paramagnetic range at H < 4 kOe, x obeyed the Curie-Weisslawin the entire range
measured from 4.2 K to room temperature. The paramagnetic Curie temperature 0P = -5 K
and the effective magnetic moment !len = 2.57 j.t8 , close to the theoretical value of 2.54 !ls for
Ce3+, Ravot et al. [1]. With polycrystalline samples and single crystals (from different batches)
exhibiting small crystal field effects, 0P was between -3 and -5.5 K, and the Curie-Weiss
constant C between 0. 738 and 0. 758 cm 3 · K · mol- 1 with no dependence of eP and C on the
lattice constant, Hulliger et al. [2]. Other polycrystalline samples obeyed the Curie-Weiss law
between -60 and 400 K with 0P = -8 K, Loginov et al. [7], or -7.5 K, Adamyan, Loginov
[10], and !len = 2.49 !ls [7, 10] (which gives C = 0.775 cm 3 · K · mol- 1 [2]).
CrystaL Field Effects and ELectricaL Properlies
The 2 F512 ground state of the 4f 1{Ce 3 +)ion in CeTe is split by the crystal electric field (CEF)
into a r 7 doublet, which is the lowest state, and a r 8 quartet, Ott, Lüthi [6]. For stoichiometric
CeTe the r 7 -r8 CEF splitting Mk was -45 K from heat capacity data, Hulliger et al. [2], and
thermal expansion [6]. Fora Ce-deficient single crystalli/k was -40 K and for polycrystalline
material < 70 K, both from heat capacity data. Susceptibility data give 8/k < 20 K for all these
samples [2]. A similar low value (26 K), which is about ten times smaller than predicted by
the point charge model, has been derived from the electrical resistivity, Escorne et al. [24].
Gmeli n Handbock
RE Main Vol. C10
CeTe 97
450
~
.. • •••
~
/
V
b400
c:
::L
.!;
./
I
a.350
10 20 30 40 50
Tempereture in K
Fig. 37. Electrical resistivity of CeTe as a function of temperature.
The Grüneisen-parameter 'YcEF is -5.8 and the magnetoelastic coupling constants are G11 =
-688 mK and G12 = 0 K, based on ~/k = 45 K [6].
A 1 7 doublet as the Lowest Ce3+ state explains the high-field magnetic properties quite
weiL but not the zero field moment value, Ravot et al. [1]. A possible explanation is to consider
that Ce Te is justat the border Line between a magnetic and a nonmagnetic Kendo state. The
Kendo coupling (d-f mixing) could account for the Low magnetic moment value as well as for
the Large first pressurederivative of the bulk modulus in the NaCL type CeTe and the strongly
reduced value in the CsCL type phase. The Latter effect results from the increased Ce-Te
distance Leading to smaller d-f coupling and to a Kendo reentrant behavior, Leger, Oki [23] ;
see also Leger et al. [20]. The Low ~/k value is attributed to a f-d hybridization [24].
The following data on the electronic structure of CeTe are derived from the reflectivity and
Kerr spectrum. The energy of the 4f1 ----. 4f0 5d transition is 2 eV. When assum ing a high density
of empty d states just above the Fermi Level, the center of the nearly filled p valence band is
situated at ~ 6.0 eV. Valence-to-conduction band (p----> d) transitions start above 2.5 eV, Reim
et al. [26] . For slightly different results obtained from photoemission spectra, see p. 98.
The structure of the electron energy spectrum of CeTe was studied using group-theoretical
methods. lonic bonds predominate. The conduction band corresponds to 16(r15) , 1 8 (115 ),
and 1 8 (r12 ), when the ground term of Ce2+ has J = 9/2, Andriashik, Marehenke [16] .
The electrical resistivity Q of stoichiometric CeTe between T = 4.2 and 50 K is shown in

Fig. 37. An inflexion point of the Q vs. T curve is observed at 8 K . The resistivity increases
from 315 J.tfl· cm at 5 K to 440 J.til· cm at 40 K. Between 40 and 300 K, the resistivity increases
Linearly with temperature. There is no indication of any Kendo effect. The course of the curve
below 30 K is only accomplished by the magnetic contribution to Q which is associated with
the inelastic scattering of the free carriers at the Ce scattering centers. Using a CEF splitting
of 26 K (see p. 96) very good agreement between the theoretical and observed curve is
observed , Escorne et al. [24]. Pressed powders showed a metallic Q = f(T) behavior above
room tempe rature. The S eebeck coefficient ISI had a maximum near 400 K, Tyurin et al. [27] ,
which is in cantrast to the Linear change of ISI up to 1200 K found earlier for polycrystalline
samples (see p. 20) , Zhuze et al. [28] .
Gmelm Handbock
RE Ma m Vol. C 10
Optical Properlies
The near-normal incidence reflectivity spectrum of a cleaved CeTe single crystal in the
range 0.03 to 12 eV at 300 K exhibits a pronounced Drude behavior at low energies. The
coupled plasma frequency amounts to 1.97 eV. A broad maximum centered around 7 eV is
attributed to (p--->d) valence-to-conduction band transitions. The fine structure observed is an
indication of the crystal field splitting of the 5d band and band structure effects. From Kramers-
Kronig transformation, the p--->d joint density of states maximum is centered at 6.3 eV with a
full width at half maximum of -5 eV. There is no structure in the reflectivity spectrum which
may be attributed to an f excitation, Reimet al. [26].
The complex polar Kerr effect for a [100] oriented cleaved single crystal in an applied
magnetic field of 5 T at 2 K, where Ce Te is in an intermediate spin state, was measured at
photon energies in the range 0.5 to 5 eV. The Kerr spectrum exhibits one single sharp structure
at 2.0 eV with a Kerr rotation 8K ~ 3 deg. The feature is attributed to the 4f 1 --->4f 0 5d transition
of Ce3+. The ellipticity for this transition has a slightly different shape. This reflects the fact
that both the diagonal and the off-diagonal conductivity enter into the polar Kerr spectrum
[26].
X-Ray Absorption Spectrum. Photoemission

The X-ray absorption spectrum of the Ce L 111 edge at 300 K shows the standard profile due
to Ce3+ without appearance of Ce4+ in CeTe, Ravot et al. [12].
The resonance-enhanced synchrotron radiation photoemission spectrum of CeTe at
selected photon energies below and at the so-called giant d-f resonance (at about 125 eV)
allows an identification of the Ce f 1 state at (2.5 ± 0.1) eV below the Fermi Level EF, Gudat et
al. [13]. The corresponding peak has a full width at half maximum of -1 eV, Gudat et al. [14].
There is a considerable density of states at EF for Ce Te (in cantrast to CeAs), which is attributed
to both 4f and 5d emission; seefigurein [14]. The 5d electrons contribute in the binding energy
range from EF to -2 to 3 eV, Gudat et al. [19]. The density of states in the region 3 to 6 eV
below EF is made up of the Te-bonding Levels of CeTe [13]. For comparison of the results of
photoelectron spectroscopy of the Ce-pnictides with those of the chalcogenides, see [14, 19].
References:
[1] D. Ravot, P. 8urlet, J. Rossat-Mignod, J. L. Tholence (J. Phys. [Paris]41 [1980]1117/20).
[2] F. Hulliger, 8. Natterer, H. R. Ott (J. Magn. Magn. Mater. 8 [1978] 87/98).
[3] H. R. Ott, F. Hulliger, F. Stucki (Conf. Ser. lnst. Phys. [London] No. 37 [1978]72/8; C.A. 89
[1978] No. 83867).
[4] K. P. Thakur (J. Phys. Chem. Solids 41 [1980] 465/72).
[5] V. K. Jain, J. Shanker (Phys. Status Solidi 8106 [1981]287/93).
[6] H. R. Ott, 8. Lüthi (Z. Physik 8 28 [1977]141/7).
[7] G. M. Loginov, A. T. Starovoitov, A. V. Golubkov (Fiz. Tverd. Tela [Leningrad]11 [1969]
[8] H. R. Ott, J. K. Kjems, F. Hulliger (Phys. Rev. Letters 42 [1979]1378/82).
[9] H. R. Ott, J. K. Kjems (J. Magn. Magn. Mater. 15/18 [1980]401/2).
[10] V. E. Adamyan, G. M. Loginov (Fiz. Tverd. Tela [Leningrad] 8 [1966] 3094/6; Soviet
Phys.-Solid State 8 [1966] 2472/3).
[11] F. Hulliger, H. R. Ott (J. Phys. Colloq. [Paris] 40 [1979] C5-128/C5-129).
[12] D. Ravot, C. Godart, J. C. Achard, P. Lagarde (Valence Fluctuations Solids St. 8arbara
lnst. Theor. Phys. Conf., Santa 8arbara, Calif., 1981, pp. 423/6; C.A. 95 [1981] No. 159004).
Gmelm Handbook
RE Main Vol. C 10
99
[13] W. Gudat, M. Campagna, R. Rosei, et al. (J. Appl. Phys. 52 [1981] 2123/8).
[14] W. Gudat, M. Iwan, R. Pinchaux, F. Hulliger (Valence lnstab. Proc. Intern. Conf., Zürich,
Switz., 1982, pp. 249/57).
[15] J. X. Baucherle (Valence lnstab. Proc. Intern. Conf., Zürich, Switz., 1982, pp. 481/4).
[16] M. V. Andriyashik, V. I. Marchenko (lzv. Vysshikh Uchebn. Zavedenii Fiz. 15 No. 8 [1972]
140/2; Soviet Phys.-J. 15 [1972]1211/3).
[17] J. X. Boucherle, D. Ravot, J. Schweizer (J. Phys. Colloq. [Paris]43 [1982] C7-263/C7-271).
[18] J. Rossat-Mignod, P. Burlet, S. Quezel, et al. (Ann. Chim. [Paris] [15] 7 [1982] 471/87).
[19] W. Gudat, R. Rosei, J. H. Weaver, E. Kaldis, F. Huttiger (Solid State Commun. 41 [1982]
37/42).
[20] J. M. Leger, R. Epain, J. Loriers, et al. (Phys. Rev. [3] 8 28 [1983] 7125/9).
[21] J. M. Leger, K. Oki, D. Ravot, J. Rossat-Mignod, 0. Vogt (J. Magn. Magn. Mater. 47/48
[1985] 277/80).
[22] J. M. Leger (Rev. Phys. Appl. 19 [1984] 815/7).
[23] J. M. Leger, K. Oki (J. Phys. Colloq. [Paris]45 [1984] C8-149/C8-152).
[24] M. Escorne, A. Mauger, D. Ravot, J. C. Achard (J. Phys. Lett. 45 [1984] 75/9).
[25] 0. Ravot, A. Mauger, J. C. Achard, M. Bartholin, J. Rossat-Mignod (Phys. Rev. [3] 8 28
[1983]4558/69).
[26] W. Reim, J. Schoenes, F. Hulliger, 0. Vogt (J. Magn. Magn. Mater. 54157 [1986]1401/2).
Kiev 1969 [1972], Vol. 1, pp. 156/61; C.A. 79 [1973] No. 59042).
[28] V. P. Zhuze, A. V. Golubkov, E. V. Goncharova (Fiz. Tverd. Tela [Leningrad] 6 [1964]
30.1.2.1 0.4.3 Solid Solutions Ce 3Te 4-Ce 2Te 3 and Terminal Compounds
The compounds Ce 3Te 4 and Ce 2Te 3 belang to the same phase of variable composition
Ce 3 _yTe4 with y = 0 to 0.33 (~ CeTex with x = 1.33 to 1.50) and cubic Th 3 P4 structure, see
p. 21. lt is a stable phase in the Ce-Te phase diagram but there are conflicting data with
respect to the melting temperature and behavior upon melting; see p. 91.
Preparation
For the preparation from the elements, see pp. 21, 31, and 92. By dissociation of CeTe 2 in
vacuum between 950 and 1100°C the composition becomes stable near Ce 3Te 4 . An inter-
mediate formation of Ce 2Te3 was not observed, Domange et al. [1].
Crystallographic and Mechanical Properlies

ln the solid solution series Vegard's law is obeyed. Values of the lattice constant a and
density D for Ce Tex with x = 1.33 to 1.50 are:
x in CeTex 1.333 1.375 1.4 1.425 1.455 1.5
a in A .. 9.550 9.547 9.546 9.545 9.544 9.542

D in g/cm 3 7.02 6.97 6.91 6.82 6.79 6.72
Aloman et al. [2, 3]. a = 9.542 A, calculated and measured densities areDeale = 7.16, Dexp =
6.83 g/cm 3 , and the microhardness of a fused polycrystalline sample is H~ = 187.9 kg/mm 2
Gmelm Handbock
RE Main Val. C 10
(~ 1.84 GPa) for x 1.333 and a = 9.530 A, Deate = 6.81, Dexp 6.65 g/cm 3 for x 1.5,
Chukalin et al. [4].
ThermaL Properlies
The enthalpy of formation from the elements has been determined calorimetrically. For
Ce 3Te 4 formulated as Ce 0.43Te 0 57 , ~H300 ~ -40 kcaUmol (see Fig. 33, p. 92), Borzone et al.
[5]. For Ce 2Te 3 , ~H~98 = -196.7 kcaUmol ( ~ -39.34 kcal/mol Ce 0 .40Te 0 _60 ). The Gibbs free
energy and entropy of formation are calculated to be ~G~98 = -181.4 kcaUmol and ~S~98 =
-12.0 cal· mol- 1 · K- 1 . The calculated thermodynamic quantities for the atomization at
298 Kare ~H~1 = 547.7 kcal/mol, ~G~1 = 478.9 kcal/mol, and ~S~1 = 230.9 cal· mol- 1 · K-1,
Azizov et al. [6]; for the calculations the value of Mills [7] for the absolute entropy
S~ 98 =57 cal· mol- 1 · K- 1 was used.
Values of the total thermal conductivity /... of pressed samples at 293 K and the lattice
contribution in brackets, in mW · cm- 1 · K- 1 : /... = 8.5 (8.0) for CeTe 1 _333 , /... = 5.8 (5.4) for
CeTe 1.376 , /... = 3.9 (3.88) for CeTe 1.435 , and A. = 3.8 for CeTe 1.5 . Studies up to 873 K show /... to
increase more rapidly above ~ 700 to 800 K (dependent on Te concentration) than below that
temperature, Tyurin et al. [8].
Ce 2Te 3 at 5 x 10- 6 Torr is thermally stable up to 1100°C, the highest temperature studied
mass spectrometrically, Aloman et al. [9].
Magnetic, ELectricaL, and Other Properties

x
The magnetic susceptibility for Ce 3Te4 and Ce 2Te 3 between 80 and 1000 K is shown in
Fig. 38, p. 102. Values of x for ceramic samples (10 to 12% porosity) of Ce 3Te4 and Ce 2Te 3
are 2150 x 10- 6 and 2130 x 10- 6 cm 3/g-atom Ce, Tyurin et al. [8]. The paramagnetic Curie
temperatu re SP = -12 K, effective magnetic moment 11et1 = 2.32 11s for Ce 3Te 4 and SP =
-11 K, 11etf = 2.34 11s were derived by applying the Curie-Weiss law between 140 and 500 K,
Pechennikov et al. [14]. Values for room temperature of the electrical resistivity Q,
thermoelectric power S, Hall coefficient RH, Hall mobility 11· and carrier concentration n for
polycrystalline CeTex with x = 1.33 to 1.50 homogenized at 1100°C for 10 d:
x in CeTe. 1.333 1.375 1.4 1.425 1.455 1.5
Q in Q·cm 0.001 0.0015 0.002 0.0032 0.015 350

S in 11V/K -27 -39 -47 -60 -79 -143
RH in cm 3/C -0.0016 -0.0018 -0.002 -0.0025 -0.00214 -20.2
11 in cm 2 · v- 1 · s- 1 . 1.56 1.2 1 0.82 0.33 0.04
n in cm- 3 4 X 1021 3.47 X 1021 3.13X10 21 2.54 X 1021 2.37 X 1021 3.1X10 17
Aloman et al. [2]. Values for Q (in Q · cm) and S (in 11V/K) for the ceramic samples (10 to 12%
porosity) are: Q = 0.015, S = -4 for CeTe 1.333 , Q = 0.0175, S = -65 for CeTe 1.376 , Q = 0.526,
S = -282 for CeTe 1435 , and Q = 14.3, S = -320 for CeTe 1 _5 , Tyurin et al. [8]. Dependence of
Q and S on the preparation conditions of pressed Ce 2Te 3 samples yield an optimum value of
the thermoelectric power coefficient, S2 /Q ~ 10- 9 W · cm- 1 · K- 2 , at the following conditions:
particle diameter 0.16 to 0.20 mm, applied pressure 10 t/cm 2 , and sintertime 200 hat 1100°C,
Aloman et al. [9], S2/Q = 4 x 10- 11 for the above mentioned sample (CeTe1.5) homogenized
at 1100°C for 10 d [2].
Gmelin Handbook
RE Mam Vol C 10
101
Plots of Log Q = f(T) show Q of Ce 3Te4 to increase continuously from Q ~ 1 x 10- 3 Q · cm

at 300 K to ~ 7 x 10- 3 Q · cm at 900 K; ISI increases Linearly from ~ 30 to 70 J.1VIK between 300
and 900 K. With Ce2Te 3 , plots of Log Q = f(T) show Q tobe nearly constant ( ~300 Q · cm) at 300
to 500 K, then decreasing to ~3 Q · cm at 900 K, Aloman [10] due to intrinsic semiconductivity;
activation energy is 1.2 eV, Aloman [11]. The thermoelectric power S is ~ -143 to -140 J.lV!K
at 300 to 600 K and ~ -115J.1VIK at 900 K [10]. ln S = f(T) plotsatT = 400 to 1000 K for the
ceramic CeTex samples with x = 1.333, 1.376, 1.435, and 1.50 the curves show extremes. For
the electrical conductivity an activation energy of ßE = 0.046 eV was obtained for Ce 2Te 3 and
a similar value for CeTe 1_435 . The width of the forbidden zone for Ce 2Te 3 was obtained to be
0.57 eV [8]. For comparison of the electrical properties of Ce 3 _yTe 4 and Ce 3 _yS 4 , see Gotikova
et al. [13].
Ce 3Te 4 is gray with metallic Luster. The colors of the powders vary from Light gray for
Ce 3Te4 to gray-black for Ce 2Te 3 ; castings of Ce 2Te 3 are dark blue, Chukalin et al. [4].
The X-ray absorption spectrum of the Ce L 111 edge in Ce3Te 4 at 300 K shows the standard
profile due to Ce3+ without appearance of Ce4+, Ravot et al. [12].
References:
[1] L. Domange, J. Flahaut, M. P. Pardo, et al. (Compt. Rend. 250 [1960]857/8).

72/6; C.A. 69 [1968] No. 90882).
Zavedenii Tsvetn. Met. 14 No. 4 [1971] 73/7; C.A. 75 [1971] No. 144641).
3 [1967]1538/45; lnorg. Materials [USSR] 3 [1967]1341/7).
[5] G. Borzone, A. Borsese, R. Ferro (Gazz. Chim. ltal. 113 [1983] 235/8).
[6] T. Kh. Azizov, A. S. Abbasov, F. M. Mustafaev, I. Ya. Aliev (7th Vses. Konf. Kalorim.
Rasshir, Tezisy Dokl., Moscow 1977, Vol. 1, pp. 30/2; C.A. 91 [1979] No. 217832).
Kiev 1969 [1972], Vol. 1, pp. 156/61; C.A. 79 [1973] No. 59042).
[9] A. Aloman, S. S. Gorelik, V. M. Malovetkaia (Rev. Chim. [Bucharest]19 [1968] 268/70;
C.A. 69 [1968] No. 47295).
[10] A. Aloman (Metalurgia [Bucharest]21 [1969]363/7; C.A. 72 [1970] No. 60484).
[11] A. Aloman (Studii Cercetari Met. 14 [1969] 47/63; Rev. Roumaine Sei. Tech. Ser. Met. 14
[1969]39/56; C.A. 71 [1969] No. 106293, No. 130034).
[12] D. Ravot, C. Godart, J. C. Achard, P. Lagarde (Valence Fluctuations Solids St. Barbara
lnst. Theor. Phys. Conf., Santa Barbara, Calif., 1981, pp. 423/6; C.A. 95 [1981] No. 159004).
[13] 0. A. Golikova, I. M. Rudnik, V. M. Sergeeva, et al. (Phys. Status Solidi A 37 [1976]
199/203).
[14] A. V. Pechennikov, V. I. Chechernikov, M. E. Barykin, et al. (lzv. Akad. Nauk SSSR
Neorgan. Materialy 4 [1968]986/7; lnorg. Materials [USSR]4 [1968] 868/9).
Gmelm Handbook
RE Main Vol. C10
30.1.2.1 0.4.4 Cerium Polytellurides

General Properlies
All the cerium polytellurides are incongruently melting phases in the Ce-Te system; see
p. 91 . The reciprocal magnetic susceptibilities of Ce 4 Te 7 , CeTe 2 , Ce 2Te 5 , and CeTe 3 between
80 and 1000 Kare compared with those of other cerium tellurides in Fig. 38 from Pechennikov
et al. [1] . Similar curves are also given by Yarembash , Eliseev [2] based on studies from
Chukalin [3]. Between 140 and 500 K, 1/x isaLinear function of the temperature [1 , 2] with the
following values for the paramagnetic Curie temperatures 0P and the effective magnetic
moments ~elf [1]:
0P in K -9 2 4 5
~elf in ~B 2.36 2.28 2.27 2.28
The change of sign of 0P at Ce 4Te 7 (CeTex with x ~ 1.75) is confirmed by [3]. Values for ~elf
indicate the existence of Ce 3 + in these tellurides [1 , 3].
Ce 4Te 7
The preparation and properlies are described on pp. 43 and 92. Ce 4Te 7 melts incongruently
x
at 1340°C (see p. 91). The magnetic susceptibility from 80 to 1000 K is shown in Fig . 38. For
ceramic samples (10 to 12% porosity) x
= 2195 x 10 - 6 cm 3/g-atom Ce, Tyurin et al. [4].
According to Yarembash, Eliseev [2], Ce 4Te 7 shows mixed conductivity (K) at room tempera-
ture . The thermoelectric power is negative (K = 0.201 n - 1 · cm - 1 at 20°C and S = -140 ~V/K
for the ceramic samples, Tyurin et al. [4]), whereas the Hall effect gives a hole Goncentration
6 ·105 1--- - - - - + - -
"'e
~ 4 ·10 5 f - - - - - f --++-----,-'--7L.- - t
Cl
.5
0 400 800
Temperature in K
Fig . 38. Reciprocal magnetic susceptibility of cerium tellurides as a function of temperature.

Gmelin Handbook
RE Main Vol. C 10
Cerium Polytellurides 103
nh = 1.88X1017 cm- 3 and hole mobility Jlh = 2.73cm 2 ·V- 1 ·s- 1 at room temperature,
Yarembash, Eliseev [2]. The conductivity K of the ceramic samples was studied between 200
and 666 K. Plots of log K vs. 1/T show an increase of K with .1\E = 0.16 and 0.53 eV below and
above about 300 to 400 K, respectively [4]. lntrinsic conductivity starts at 476 K (.1\E = 0.50 eV)
[2] based on studies from Tyurin [5] and Chukalin [3]. The S vs. (1/T) plot given in the paper
forT = 400 to 666 K shows a minimum in ISI at 400 K [4].
CeTe2 _x
For the preparation from the elements see pp. 47 and 92. The stoichiometric eiemental
mixture was allowed to react at 6oo·oc in evacuated sealed Pyrex tubes to form blue-black
CeTe2 . By reaction of CeCL3 with Te vapor at 800°C in H2 atmosphere in the presence of
graphite CeTe2 is formed along with a Te-rich compound, Domange et al. [6]. CeTe 2 has the
tetragonal Fe2As (Cu 2Sb) structure, space group P4/nmm-D~h (No. 129), Z = 2. lt occurs
usually with a Te deficit; see p. 47. Lattice constants and density for the lilac-black CeTe 2
phase reported by Chukalin et al. [7]: a = 4.56, c = 9.11 A; DeaLe = 6.97, Dexp = 6.90 g/cm 3 .
x
The specific magnetic susceptibility from 80 to 1000 K is shown in Fig. 38. The value = 3070
(presumably in 10- 6 cm 3/g-atom Ce) at 25.6°C is reported by [8]. The electrical resistivity of
CeramiC SampieS (Sintered at 8QQ°C for 30 tO 50 h) iS 1 X 10- 3 Q · Cm and the thermoelectric
power S = +21 JlVIK [8].
Ce 3Te 7 • Ce 2Te5 • Ce4Te 11 • CeTe3

The only data existing for Ce 3Te 7 isthat it melts incongruently at -920°C (see p. 91).
The preparation and properties of the pseudotetragonal Ce 2Te 5 are described on pp. 53
and 92. For the magnetic susceptibility of Ce 2Te 5 and CeTe 3 see Fig. 38. The (presumably)
orthorhombic Ce4Te 11 (see p. 57) melts incongruently at 830°C and the pseudotetragonal CeTe 3
does so at485°C (see p. 91). The preparation and properties ofthis phase have been described
on pp. 57/9. For early data on CeTe 3 , see [9].
References:
[1] A. V. Pechennikov, V. I. Chechernikov, M. E. Barykin, et al. (lzv. Akad. Nauk SSSR Neorgan.
Materialy 4 [1968] 986/7; lnorg. Materials [USSR] 4 [1968] 868/9).
[2) E. I. Yarembash, A. A. Eliseev (Khal'kogenidy Redkozemel'nykh Elementov, Nauka,
Moscow 1975, pp. 1/260, 182/7).
[3] V. I. Chukalin (Diss. Moscow 1968 from [2]).
[4] E. G. Tyurin, E. I. Yarembash, V. I. Chukalin (Elektron Str. Fiz. Svoistva Tverd. Tela Dokl.
Kiev 1969 [1972] Vol. 1, pp. 156/61; C.A. 79 [1973] No. 59042).
[5] E. G. Tyurin (Diss. Moscow 1972 from [2]).
[6] L. Domange, J. Flahaut, M. P. Pardo, A. N. Chirazi, M. Guittard (Compt. Rend. 250 [1960]
857/8).
[8] M. P. Pardo, J. Flahaut, L. Domange (Bult. Soc. Chim. France 1964 3267/71).
[9] Westinghouse Electric Corp. (AD-231565 [1959] 1/78, 24; N.S.A. 14 [1960] No. 19305).
Gmelin Handbock
RE Mam Vol. C10
104 Praseodymium Tellurides
30.1.2.1 0.4.5 Cela 2Te 4-La 2Te 3 Solid Solutions

La 2Te 3 forms cubic solid solutions of the Th 3 P4 structure (see p. 33) with Cela 2Te 4 . The
lattice constants rise linearly going from La 2Te 3 to Cela 2Te 4 . Lattice constants a in A, density
D in g/cm 3 , electrical resistivity Q in Q · cm, thermoelectric power S in 11V/K, Hall coefficient
RH in cm 3 /C, Hall mobility ll in cm 2 · v- 1 · s - 1 , and carrier concentration n in cm - 3 for the cubic
phases:
a D Q -S -RH ll n
La 2Te 3 9.618 6.54 62 261 12.56 0.208 5 X 10 17

Ce 0 _2 La 2Te 3.2 9.619 6.59 2.1 245
Ce 0 _36 La 2Te 3 _36 . 9.621 6.66 0.2 185 0.5*) 2.5 1 X 10 19
Ce 0 _50 La 2Te 3.50 . 9.623 6.72 0.018 112 0.15 8.3 4 X 10 19
Ce 0 .80 La 2Te 3 _8 9.626 6.83 0.0064 42 0.04 6.2 1.5 X 1020
Cela 2Te 4 . 9.628 6.91 0.0042 29
La 3 Te 4 9.627 6.87 0.002 21 0.03 15 2 X 1020
•l Sign not given.
The thermal conductivity /.., for La 2Te 3 and Cela 2Te 4 is 0.012 and 0.030 W · cm- 1 · K- 1 and the
figure of merit Z is 1 x 10- 7 and 7 x 10- 6 K-1, respectively, A. Aloman (Bul. lnst. Politeh.
Gheorghe Gheorghiu-Dej Bucuresti 30 No. 2 [1968]101/6; C.A. 70 [1969] No. 53450).
30.1.2.1 0.5 Praseodymium Tellurides

Additional data for PrTe, Pr 3Te 4 , Pr 2 Te 3 , Pr 4Te 7 , PrTe 2 _x, Pr 2Te 5 , Pr4 Te 11 , and PrTe 3 are
found in Sections 30.1.2.1, 30.1.2.2, 30.1.2.3, 30.1.2.4, 30.1.2.5, 30.1.2.6, 30.1.2.7, and 30.1.2.8,
on pp. 6, 21, 31, 43, 47, 53, 56, and 57, respectively.
30.1.2.1 0.5.1 The Pr-Te System

Phase Diagram
Fig. 39 shows the Pr-Te phase diagram, derived from DTA, X-ray diffraction, and
microstructural or chemical analyses. The praseodymium tellurides were prepared from the
elements in the form of powders and fused in Ta crucibles. Single crystals were grown by
gas-transport reactions and the Bridgman method. PrTe and Pr 3Te 4 melt congruently at
~ 1950 ±50, and 1650 ± 50°C, respectively. The other phases melt incongruently with the
following peritectic temperatures (in °C}:
PrTe 1 _9 PrTe 3
1210±20 455± 5
Most of the phases have variable compositions; their range of homogeneity decreases with
increasing relative Te content. Pr 3Te 4 and Pr 2Te 3 form a continuous series of solid solutions.
The homogeneity ranges of the other compounds are as follows:
compound Pr 4 Te 7 PrTe 19 Pr 3Te 7 PrTe 3

at% Te . . 62.7 to 64.2 64.3 to 65.5 69.5 to 70.5 74 to 74.5
Gmelm Handbook
RE Mam Vol. C10
The Pr-Te System 105
u 1500
0
Pr3T~ 7
.5: - 1280°C
:.rr-P...;:;;:~ 1210 °C
Hü----II-- - =.._-1140°C
0 20 40 60 80 100
Fig . 39. The Pr-Te phase diagram .
The eutectica are at the following temperatures and compositions: 895 ± 5°C, 5 to 7 at% Te
(Pr + PrTe); at 1560 ± 50°C, ~56 at% Te (PrTe + Pr 3Te 4 ); and at 445°C (PrTe 3 + Te),
Yarembash , Vigileva [1] . The Pr-Te phase diagram is also shown by Yarembash [2 , 3]; a
preliminary characterization of the compounds in the Pr-Te system by X-ray diffraction studies
is given by Yarembash et al. [4] .
Magnetic Properties
The temperature dependence of the specific magnetic susceptibility of powdered

praseodymium tellurides between 77 and 300 K follows the Curie-Weiss law over the whole
temperature range as shown in Fig. 40, p. 106. Paramagnetic Curie temperatures E>P in K and
effective magnetic moments lleff in lls :
PrTe PrTe 1 _9
-18 -20 -18 +4 -10

3.72 3.78 3.66 3.53 3.80
The magnetic moments are close to the theoretical value of the Pr3+ ion (3.58). Most of
the compounds order antiferromagnetically at low temperature according to the negative E>P
values, Vigileva et al. (5] .
Gmelin Handbook
RE Main Vol. C10
106 Praseodymium Tellu rides
ME 6 r---r---------~~~~~-7~~2T~3
u
0.
~
Q 4 r-~-,~~~54~~~=--+--~
-~
.....><
o~~,~oo~----~2~o~o------~~
~ o--~
Temperature in K
Fig. 40. Reciprocal magnetic susceptibility of praseodymium tellurides in dependence of

temperature.
At room temperature XA = 5150 x 10- 6 and 5100 x 10- 6 cm 3/g-atom Pr was reported f or
Pr3Te 4 and Pr2Te 3 , respectively, by [1 ] and X A = 5500 x 10- 6 for PrTe 19 by Checherni kov
et al. [6]. Values for X A (0) in cm 3/g-atom Pr for T = 0 K extrapolated from susceptibility
measurements between 1.3 and 400 K by Sucher et al. [7] for ceramic samples :
PrTe PrTe2 PrTe3

0.0374 0.042 0.0230
Additional Physlcal Properlies
The X-ray L 111 absorption spectra were measured on PrTe, Pr 3Te 4 , Pr2Te3 , PrTe 2 , and PrTe3 .
The principal absorption maxi mum of PrTe is displaced by + 0 .4 eV to Longer wavelengths
with reference to PrS 6 ; it shifts to + 0.1 eV for PrTe 3 . From the results it was concluded that
all the tellurides contain trivalent Pr ions, Vainshtein et al. [8] ; the trivalency is also assumed
by [1] . The Te-rich compounds Pr 2Te 3 , Pr4Te7 , and PrTe 1 _9 may be classified as semiconductors.
The tellurides with lower Te-content display metallic or semimetallic properties [1] ; see
also Sucher et al. [7]. The temperature dependence of the electrical conductivity K and the
thermoelectric power S for Pr2Te3 , Pr4 Te 7 , PrTe 19 , and Pr2Te 5 are shown in Fig. 41 [1] . The
colors of the praseodymium tellurides are as follows [7]:
PrTe Pr3Te4 Pr2Te3 PrTe 2 Pr3Te7

deep purple silver-blue silver-gray black-pu rple bright silver
Pr2Te 5 PrTe 3
dark red-gold red-gold
Gm elon Handbook
RE Mam VaL C 10
PrTe 107
320
240
1.6 160
"'0e
b
....
.!:
~
0.8
-
X:
>:I.
.!: 80
1/)
~
0 0
Pr2Te 3
-80
0.6 1.4 2.2 3.0

10001T in K- 1 1000/T in K-1
Fig. 41. Temperature dependence of electrical conductivity log K and thermoelectric power S
for praseodymium tellurides.
References:
[1] E. I. Yarembash , E. S. Vigileva (lzv. Akad. Nauk SSSR Neorgan. Materialy 6 [1970]
Vol. 2, pp. 761/77, 774 ; C.A. 73 [1970] No. 124092).
[3] E. I. Yarembash (Colloq. Intern. Centre Natl. Rech. Sei. No. 180 [1969/70]471/81 , 475).
[4] E. I. Yarembash, A . A. Eliseev, E. S. Vigileva, L. I. Antonova (lzv. Akad. Nauk SSSR
[5] E. S. Vigileva, A. V. Pechennikov, V. I. Chechernikov, E. I. Yarembash (lzv. Akad. Nauk
[6] V. I. Chechernikov, A . V.Pechenn ikov, E. I. Yarembash, E. S. Vigileva (lzv. Akad . Nauk
SSSR Neorgan. Materialy 3 [1967]169/70; lnorg. Materials [USSR] 3 [1 967]138/9).
[7] E. Sucher, K. Andres, F. J. Di Salvo, J . P. Maita, et al. (Phys. Rev. [3] 8 11 [1975] 500/ 13,
502).
[8] E. E. Vainshtein, M. N. Bril, I. 8. Staryi , E. I. Yarembash (lzv. Akad . Nauk SSSR Neorgan.
Materialy 3 [1967]1685/7 ; lnorg. Materials [USSR]3 [1967]1471/3) .
30.1.2.10.5.2 PrTe
PrTe is a congruently melting phase in the Pr-Te system (see Fig. 39, p. 105). For the
preparation from the elements see pp. 6 and 104.
Gmelin Handbook
RE Main Vol. C 10
CrystaLLographic Properties. Crystal Fleld

PrTe has at ambient conditions the cubic NaCL structure. The Lattice constant a in A is
6.320, Sucher et al. [1, p. 502], Turberfield et al. [2], Rettori et al. [3], 6.315(2), Singh et al. [4],
Jayaraman et al. [5], 6.307(1 ), Yarembash et al. [6]. A phase transition to a CsCL-type structure
occurs at a pressure of 9 ± 1 GPa (see p. 10). The Lattice constant of the NaCL phase at the
transition pressure is 6.218(20) A and of the CsCL phase 3.761 (10) A [4, 5] .
lnelastic neutron scattering spectroscopy applied to polycrystalline PrTe (l,n = 4.1 A
corresponding to 4.9 meV) has established that the crystal field Levels can be quantitatively
explai ned by a nearest-neighbor poi nt charge model with an effective charge of - 2. The
crystal field parameters determined are A 4 ( r 4 ) = (9.1 ± 1.3) meV and A6 ( r 6 ) = (0.16 ±
0.19) meV [2]. Somewhat different values are given in Turberfield et al. [7]: A 4 ( r 4 ) =
<
9.4 ± ~:~ meV and A 6 r6 ) = 0.15 ± 8:~3 meV. The values calculated with a point charge model,
8.8 and 0.15 meV, respectively, are reported by (2] and 11.02 and 0.21 meV by Devine [8]. The
transition energies (crystal field Splitting) ~0 = 6.7 ± 0.3 meV ( -77.75 K) for r 4 to r 1 and ~ =
r r
16.3 ± ~6 meV (-187.15 K) for 5 to 4 are reported by [7] and ~0 = 6.567 meV ( ~ 76.2 K) by
[8]. The values ~0 = 79 ± 12 K and 75 ± 5 K are obtained from inelastic neutron scattering
and specific heat measurements at 10 to 30 K, Sucher et al. [9]. For the pressure dependence
of the crystal field parameters, see Devine [8, 10, 16].
Mechanical and Thermal Properlies

The volume change for the NaCL type phase at 9 GPa is ~V!V0 = - 4.5% and for the
NaCL ---> CsCL type transition ~VIV = -11.5% [4, 5]. The bulk modulus K ~ 31 .25 GPa (from
K = 1/K with the given compressibility K = 3.2 x 10- 12 cm 2 /dyn) was deduced from the
measured value for PrSb, Guertin et al. [15].
The Stark contribution to the heat capacity C at Low temperatures (T ~ ~0 ) is shown in
Fig.9, p.114, in "Rare Earth Elements" C9, expressed by the plot ln (Cp,re-CLare) · T 2 vs. 1/T
which is linear only at temperatures above ~ 10 K [9].
The total thermal conductivity "-tot measured on ceramic PrTe samples between 100 and
400 K is shown in Fig. 42. The lattice thermal conductivity "-tat = "-tot - "-et can amount to as
much as -50% of the total. The temperature dependence of the lattice thermal resistivity
11"-tat near above the Debye temperature 0 0 can be reproduced by the relation 1/A.lat =
(a/T) + bT (for phonon-electron and phonon-phonon interactions) with a = 17000 and b =
0.317, Tin K and 1/A.lat in cal- 1 • s · cm · K , Devyatkova et al. [12].
"&,-
/ ~
6/
100 200 300 400 500
Temperature in K
Fig. 42. Total thermal conductivity of PrTe vs. temperature.

Gmel1n Handbook
RE Mam Vol. C 10
PrTe 109
Magnetic and Electrical Properties
PrTe shows paramagneUe behavior below room temperature; see Fig. 40, p. 106 for 77 to
300 K. At <40 K an insignificant deviation from linearity of 1/x = f(T) is observed, Adamyan,
Loginov [13]; seealso Fig. 41, p. 115, in "Rare Earth Elements" C9 from Sucher et al. [9] for
temperatures down to 1.4 K. Paramagnetic Curie temperature E>P = -26 K [13], -18 K,
Vigileva et al. [14], -14 K [9]. Effective magnetic moment lleff in 1-18 : 3.45 [13], 3.72 [14],
3.54 (9]. The measured low-field susceptibility x at 4.2 K is 0.0443 cm 3/mol; the calculated
(from A 4 (r4 ) and A 6 (r6 )) low-temperature zero-field crystal field susceptibility is
0.0410 ± 0.0126 cm 3/mol. The measured susceptibility at 4.2 K decreases slightly under a
pressure up to 6 kbar with (1/x) (dx/dp) :::::: -1 x 10- 3 kbar- 1 , Guertin et al. [15].
The exchange interaction between Pr and Gd in PrTe doped with 1 000 to 6000 ppm Gd has
been studied via the ESR spectrum at 1.4 to 4.2 K, Oavidov et al. [11], Rettori et al. (3]; the
effective g shift of 2.48 ± 0.1 at 1.4 K is interpreted in terms of exchange interaction j (j
-1.63 meV between the spin part of the Gd ions and that of the Pr ion) (3].
The electrical conductivity of ceramic PrTe samples decreases from K :::::: 0.01 at 80 K
to :::::: 0.007 n- 1 • cm- 1 at 400 K and the thermoelectric power from S :::::: + 1 at 80 K to
:::::: -2 1-1V/K at 450 K (all values read from figures in the paper), Oevyatkova et al. [12].
References:
(1] E. Sucher, K. Andres, F. J. Oi Salvo, et al. (Phys. Rev. [3] B 11 (1975] 500/13).
[2] K. C. Turberfield, L. Passell, R. J. Sirgeneau, E. Sucher (Phys. Rev. Letters 25 [1970]
752/5).
(3] C. Rettori, 0. Oavidov, A. Grayevsky, W. M. Walsh (Phys. Rev. [3] S 11 [1975] 4450/4).
(4] A. K. Singh, A. Jayaraman, A. Chatterjee (Solid State Commun. 9 [1971]1459/62).
[5] A. Jayaraman, A. K. Singh, A. Chatterjee (Proc. 9th Rare Earth Res. Conf., Slacksburg,
Va., 1971, Vol. 1, pp. 360/360i).
[7] K. C. Turberfield, L. Passell, R. J. Sirgeneau, E. Sucher (J. Appl. Phys. 42 [1971]
1746/54).
(8] R. A. B. Oevine (Phys. Rev. [3] S 18 [1978] 5877/80).
(9] E. Sucher, A. C. Gossard, K. Andres, J. P. Maita, A. S. Cooper (Proc. 8th Rare Earth Res.
Conf., Reno, Nev., 1970, Vol. 1, pp. 74/89).
[10] R. A. S. Oevine (J. Phys. F 9 [1979] 2107/14).
[11] 0. Oavidov, P. Urban, L. 0. Longinotti (Solid State Commun. 19 [1976] 249/52).

[12] E. 0. Oevyatkova, V. P. Zhuze, A. V. Golubkov, V. M. Sergeeva, I. A. Smirnov (Fiz. Tverd.
Tela [Leningrad] 6 [1964] 430/5; Soviet Phys.-Solid State 6 [1964] 343/6).
[13] V. E. Adamyan, G. M. Loginov (lzv. Akad. Nauk SSSR Neorgan. Materialy 3 [1967]
1688/90; lnorg. Materials [USSR] 3 [1967]1474/6).
[14] E. S. Vigileva, A. V. Pechennikov, V. I. Chechernikov, E. I. Yarembash (lzv. Akad. Nauk
[15] R. P. Guertin, J. E. Crow, L. 0. Longinotti, et al. (Phys. Rev. [3] S 12 [1975]1005/14).
[16] R. A. S. Oevine (Cryst. Electr. Field Struct. Eff. f-Electron Syst. Proc. Intern. Conf.,
Philadelphia 1979 [1980], pp. 165171; C.A. 83 (1975] No. 123873).
Gmelin Handbook
RE Main Vol. C10
30.1.2.10.5.3 Solid Solutions Pr 3Te 4-Pr 2Te 3 and Terminal Compounds

The compounds Pr 3Te 4 and Pr 2Te 3 belang to the same phase of variable composition with
Th 3 P4 structure. The solid solutions and Pr 2Te 3 contain Pr vacancies D and should be written
Pr 3 _ yD yTe 4 with 0 ~ y ~ 1/ 3 ; see for example Mitarov et al. [1], Sucher et al. [2] and p. 33.
CrystaLLographic and Mechanical Properlies

Pr 3Te 4 is a congruently melting compound in the Pr-Te system (see p. 104), forming cubic
solid solutions with the incongruently melting Pr 2Te 3 . The lattice constants a of the cubic
phases scarcely change with the composition:
x in PrTex 1.333 1.370 1.470 1.500

a in A .. 9.485 9.484 9.483 9.483
Mitarov et al. [1]. a = 9.490 A for x = 1.333 ( ~ Pr 3Te 4 ) is reported by Sucher et al. [2 , 3] , and
a = 9.479 A for x = 1.5 ( ~ Pr 2Te 3 ) [2]; a = 9.481 (1) A is reported for Pr 3Te 4 with the measured
density of Dexp = 6.80 g/cm 3 ; a = 9.482 A for Pr 2Te 3 with Dexp = 6.79 g/cm 3 , Yarembash ,
Vigileva [4].
The elastic constants (in 10 11 dyn/cm 2 ~ 10 10 N/m 2) from sound velocity measurements of
Pr 3Te 4 are c 44 = 2.09 and (c 11 -cd/2 = 3.13 at 290 K. The temperature dependence of the
elastic constants is shown in Fig. 43 up to 300 K and in Fig. 44 for the (c 11 - c 12 )/2 mode below
15 K in the presence and absence of a magnetic field [3] . The relative sound velocity change
!w/v0 versus magnetic field (up to 15 kOe) for the c 44 mode in Pr 3Te 4 at 2 K is shown in a figure
in the paper of Wang , Lüthi [5].
3.22
1.~- ~"-·· •••.. 3.2
·.••
Cn-C12
2
I
3.18
3.1
• ....
• ~
3.14 r
z
•
""e • 0 3.10
z ~ -g
"·
S! 2.22 .!:
g
.& "" ... ~
~3.05
ü 2.18
••
I
..
u
tu •
.
2.14 3.00
•
2.10
•
•. 50 kOe
• 2.950
0 100 200 300 5 10 15
Tempereture in K Temperature in K
Fig. 43. Elastic constants c 44 and Fig. 44. Elastic constant (c 11 -c 12 )/2 of Pr 3Te 4
(c 11 -cd/2 of Pr 3Te 4 versus temperature. below 15 Kat various magnetic fields.
Gmeltn Handbook
RE Mam Vol. C 10
111
Thermal Properlies
For melting temperatures see p. 104.
The molar heat capacity CP of Pr3Te4 between 5 and 273 K is shown in Fig. 4, p. 24, and
discussed. ln Fig. 45, the Schottky contribution Csch to Cp for PrTex with x = 1.33, 1.37, 1.47,
and 1.50 is shown, at which Csch is the difference between CP of PrTex and LaTex, assuming
an electronic contribution for all LaTex and PrTex of Cet ~ 0.4 cal· mol- 1 · K- 1 at 273 K. The
experimental values in Fig. 45 are compared with curves calculated by use of a point charge
model or by a Least-squares fit. The Schottky entropy Ssch was obtained by integrating Csch
between 5 and 273 K (for figures see the paper), indicating an increase up to a limiting value
of Ssch = 13.11 cal·mot-LK- 1 for all PrTex samples at high temperatures, close to the
theoretical value of Ssch = 13.03 cal· mol- 1 · K - 1 for 0 to 1 000 K, Mitarov et al. [1] . For the
heat capacity of Pr3Te4 between 1.4 and 30 K, see a figurein the paper of Sucher et al. [2] .
~ PrTeu 1 "'x:
~ 4r.~~~--~-----T~--~ ._
0 0
E E
82~--~--~-=~--~
c:
8
J
-~
%~--~~~--~1~00~~2~00~~
300
Temperoture in K Temperature in K
~ 100 200 300

Tempereture in K Temperature in K
Fig. 45. Schottky contribution to the molar heat capacity for PrTex phases vs. temperature.
Open circles : experimental data; solid line: point charge model; dashed line: direct fitting .
The lattice contribution of the thermal conductivity "-tat for polycrystalline PrTex (and LaTex)
samples at 100 and 200 K, shown in Fig. 46, p. 112, has a minimum at x = 1.35 to 1.36. The
difference ~A. between the thermal conductivity of PrTex and LaTex phases can be ascribed
mainly to the resonance scattering of phonons by the paramagnetic Pr ions and the properties
of this scattering accounted for the dependences of ~A. on the composition and the tempera-
ture, Vasil'ev et al. [6]. This resonance scattering Leadstoa decrease in "-tat· The temperature
dependence of ~A, for PrTe1_44 was obtained from comparison with LaTe1_44 to be ( -~A.l,es
~T - 1, Luguev et al. [7]; for PrTe 1 _33 and PrTe 1 _5 ( - ~A.l,es is proportional T - 0 ·5 and T - 1,
Gmelin Handbook
RE Main Vol. C10
':..:: 6
"!II 200K
"e
V
8
-~
!i
1.33 1.41 ..< 1.3~3:--'---:-1.4!-:1-'---:1c-!l.-:-9---l
x in MTex x in MTex
Fig. 46. Lattice contribution to the thermal conductivity vs. x in PrTex and LaTex phases at 100
and 200 K.
respectively, Luguev et al. [7, 8] . Measurements of "A for PrTe 1 44 and LaTe 1_44 between 80 and
750 K show a negative deviation from the Linearity for the thermal res istance of the crystal
lattice for PrTe 1 _44 above 200 K after correction for (~"-lres (see a figure in the paper) . This is
said to be due to a contribution of a photon component to the total thermal conductivity above
200 K [7] .
Magnetic and Electrical Properlies

Pr3Te 4 is paramagnetic (see p. 25). Pr 2Te 3 is paramagnetic and antiferromagnetic at low
temperatures (see p. 105).
The investigation of the entropy connected with the Schottky effect indicates that between
5 and 273 K magnetic erdering does not take place for PrTex with x = 1.33, 1.37, 1.47, and
1.50, Mitarov et al. [1] . The Pr3Te4 sample used for the elastic measurements does not exhibit
magnetic erdering down to 1 K [3, 5], but the parameters indicate that it is an almest critically
induced ferromagnet [5] . From CP measurements of a silver-blue metallic Pr3Te 4 sample
between 1.4 and 20 K a ferromagnetic Curie temperature Tc ~ 7.8 K was deduced [2].
The character of the electrical properties of cubic PrTex phases gradually changes from
metallic to semiconductive with increasing x. The electrical resistivity and the thermoelectric
power are Q = 10- 2 to 10- 3 Q · cm and S = - (20 to 40) J.lVIK for Pr3Te4 and Q = 10 to
100 Q · cm, S = - (40 to 100) J.lVI K for Pr 2Te3 [4], Yarembash [9, 10] ; Q = 100 Q · cm for PrTe 1_44
was reported by Luguev et al. [7] . The width of the forbidden zone of Pr2Te 3 dete rmined from
th e temperature dependence of the electrical conductivity K is ~E = 0.8 to 0.9 eV, compared
with ~E = 1.3 eV from optical data, Yarembash, Vigileva [4]. For the temperature dependence
of K and S of Pr2Te 3 , see Fig . 41 , p. 107.
References:
[1] R. G. Mitarov, V. V.Tikhonov, L. N. Vasilev, A . V.Golubkov, I. A. Smirnov (Phys . Status
SolidiA 30 [1975] 457/67) .
[2] E. Sucher, K . Andres, F. J . Di Salve, et al. (Phys. Rev. (3] S 11 [1975] 500/ 13, 502) .
[3] E. Sucher, J. P. Maita, G.W. Hull, et al. (Z. Physik S 25 [1976] 41 /8) .
Gmelon Handbook
RE Mam Val C 10
Praseodymium Polytellurides 113
[5] P. S. Wang, 8. Lüthi (Phys. Rev. [3] 8 15 [1977]2718/25).
[6] L. N. Vasil'ev, S. M. Luguev, V. S. Oskotskii, I. A. Smirnov (Fiz. Tverd. Tela [Leningrad]
18 [1976]906/9; Soviet Phys.-Solid State 18 [1976] 524/6).
[7] S. M. Luguev, T. I. Komarova, V. N. 8ystrova, I. A. Smirnov (lzv. Akad. Nauk SSSR
Neorgan. Materialy 14 [1978] 46/9; lnorg. Materials [USSR]14 [1978] 35/8).
[8] S. M. Luguev, V. S. Oskotskii, V. M. Sergeeva, I. A. Smirnov (Fiz. Tverd. Tela [Leningrad]
17 [1975] 2697/701; Soviet Phys.-Solid State 17 [1975]1791/3).
Vol. 2, pp. 761/77, 774; C.A. 73 [1970] No. 124092).
[10] E. I. Yarembash (Colloq. Intern. Centre Natl. Rech. Sei. No. 180 [1969/70] 471/81, 475).
30.1.2.1 0.5.4 Praseodymium Polytellurides
30.1.2.10.5.4.1 PrTe 1 .?±x· PrTe 2 _x
Pr 4Te 7 is an incongruently melting phase in the Pr-Te system; see p. 104. The preparation
and properlies are described on p. 43; for additional magnetic and electrical properlies see
pp. 105/7.
PrTe 1 .9 (= PrTe 2 _x)
The tetragonal PrTe 1_9 is an incongruently melting phase in the Pr-Te system (see p. 104).
The preparation and properlies are described on p. 47 and the magnetic susceptibility of
polycrystalline samples on p. 105. Additional data for PrTe1.9: The magnetic susceptibility x
of single crystals measured between 77 and 300 K is anisotropic and obeys the Curie-Weiss
law, Yarembash, Vigileva [1], Chechernikov et al. [2]. Data for XA• E>P, and lleff from [2]:
XA in cm 3/g-atom E>P in K lleff in lls
single crystals H..Lc . 4800 X 10- 6 - 5 3.32

Hllc. 6000 X 10- 6 +35 3.53
polycrystalli ne 5500 X 10- 6 + 4 3.53
The electrical resistivity Q of single crystals is 0.015 n·

cm at 293 K and 0.008 n·
cm at 371 K.
Hall coefficient RH = 1 cm 3/C at 293 K and thermoelectric power S = 200 to 300 ~-tV/K. For the
temperature dependence of the electrical conductivity and of S (pressed polycrystalline
samples) see Fig. 41, p. 107 [1]. The IR absorption curve of single crystalline PrTe 1 _9 (thickness
up to 0.7 mm), measured in the range A. = 0.67 to 2.5~-tm. shows two distinct edges at 1.288
and 1.02 eV, which can be related to direct and indirect transitions, Zorina, Yarembash [3].
Gmelin Handbook 8
RE Main Vol. C 10
References:
[2] V. I. Chechernikov, A. V. Pechennikov, E. I. Yarembash, E. S. Vigileva (lzv. Akad. Nauk
SSSR Neorgan. Materialy 3 [1967]169/70; lnorg. Materials [USSR] 3 [1967]138/9).
[3] E. L. Zorina, E. I. Yarembash (lzv. Akad. Nauk SSSR Neorgan. Materialy 1 [1965] 446;
lnorg. Materials [USSR]1 [1965]411).
Pr 3Te 7 , Pr 2Te 5 , Pr 4Te 11 , and PrTe 3 are incongruently melting phases in the Pr-Te system;
see p. 104. The properties of Pr 2Te 5 and PrTe 3 are described on p. 53 and p. 57, respectively,
and the magnetic susceptibility of all of the compounds on p. 105.
Pr 3Te 7 . This compound has a region of homogeneity from 69.5 to 70.5 at% Te. lt is assumed
tobe tetragonal, Yarembash, Vigileva [1]. From the 125Te Mössbauer spectrum the chemical
shift 8 = 1.60 ± 0.2 mm/s and the line width r = 10.7 ± 0.2 mm/s were obtained for Pr 3Te 7 ;
electrical conductivity K = 100 n- 1 · cm- \ thermoelectric power S = + 21.5 J..tVIK, width of
the forbidden zone ~E = 0.32 eV, and carrier concentration n = 2.3 x 10 17 cm- 3 , Gorbachev
et al. [2].
Pr2Te 5 . For the temperature dependence of the electrical conductivity and the thermoelec-
trical power of pressed polycrystalline samples, see Fig. 41, p. 107 [1].
Pr4 Te 11 • Single crystals were obtained as brown-gold plates by the Bridgman method
(recrystallization of a melt with 75 at% Te) with a temperature gradient 950---. 750°C and a
rate of passage of the fused zone of 0.75 mm/h (but see the phase diagram, p. 105). The X-ray
diffraction pattern of a powdered Pr4 Te 11 single crystal was identical tothat of a polycrystalline
sample with 73.3 at% Te (theoretical value for Pr 4Te 11 ) [1]. Pr 4Te 11 has orthorhombic symmetry,
space group Pmna-D~h (No. 53), lattice constants a = b = 4.45 A, c = 12.96 A, Yarembash,
Eliseev [3].
PrTe 3 . The formulation as a tritelluride is used throughout the homogeneity range of this
phase (74 to 74.5 at% Te) but does not include stoichiometric PrTe 3 . The electrical conductivity
is of the p-type with K = 10 n- 1 · cm- 1 at 293 K, the thermoelectric power S is 20 to
251-lV/K. ThermalconductivityA, = 1.4W·m- 1 ·K- 1 [1].
References:
[3] E. I. Yarembash, A. A. Eliseev (Khal'kogenidy Redkozemel'nykh Elementov, Nauka, Mos-
cow 1975, pp. 1/260, 191/2).
Gmelin Handbook
RE Main Vol. C 10
The Nd-Te System 115
30.1.2.10.6 Neodymium Tellurides

Additional data for NdTe, Nd3Te4 , Nd2Te3 , Nd4Te7 , NdTe2 _ x, Nd2Te5 , Nd4Te 11 , and NdTe3 are
found in Sections 30.1.2.1, 30.1.2.2, 30.1.2.3, 30.1.2.4, 30.1.2.5, 30.1.2.6, 30.1.2.7, and 30.1.2.8,
on pp. 6, 21, 31, 43, 47, 53, 56, and 57, respectively.
30.1.2.10.6.1 The Nd-Te System

Phase Diagram
The Nd-Te phase diagram from Zinchenko et al. [1] is shown in Fig. 47. Phase diagrams
arealso established by Lin et al. [2], Abrikosov, Zargaryan [3], Yarembash, Eliseev [11], and
for the range ~ 60 at% Te by Yarembash et al. [4]. The following melting points in oc (± 10°C
[2], ± 15 oc [3], ± 5 to 15°C [1], and ±30°C [5]) are reported (i means incongruent):
NdTe Nd3 Te 4 Nd 2Te3 Nd 4Te 7 NdTe2 Nd 2Te5 NdTe3 Ref.
2025 1660i) 1610i) 1290') 1250 ') 910i) 850 i) [1]

2040 1680 1620 1280 1270 910i) 820 i) [2]
2045 1685 1650 [5 to 7]
1755 1465i) 1315i) 1255i) 1120i) 925') 855i) [3]
Later, in the Te-rich region the phases NdTe1.9. Nd3Te 7 , Nd2Te 5 , Nd4Te 11 , and NdTe3 were found
which melt incongruently at 1250, 1020, 919, 850, and 460°C [11]. The eutectic point between
Nd and NdTe is observed at 948 ± 15°C and 10 ± 2 at% Te [1], at 970 ± 15°C and 5 at % Te [3].
2025
1900
u 1500
0
c:
94SOC
at•J. Te
Fig. 47. The Nd-Te phase diagram.
Gmelin Handbook 8'
RE Main Vol. C 10
116 Neodymium Tellurides
Between NdTe3 and Te there is adegenerate eutectic at 455°C [1, 4]. Cubic solid solutions
are formed between Nd 3Te4 and Nd 2Te 3 [1). Miller et al. [5] and tetragonal solid solutions
between Nd 4Te7 and NdTe2 [1, 2). But the phases Nd 4Te 7 (= NdTe 1_7 +xl and NdTe 2 _x have
different crystal structures (see pp. 44 and 48, respectively). -
A possible homogeneity region of Nd 2Te 5 is ;-;;; 1 at% Te. A phase transition at 1000 ± 10°C
of the Nd 3Te 4-Nd 2Te 3 solid solution from the cubic high temperature phase to an orthorhombic
low temperature phase was reported by [2). No thermal effect in the DTA curve of the cubic
phases Nd 3Te 4 and Nd 2Te 3 was observed up to 1600°C [1); but later a phase transition at
1030°C was reported [11).
The methods of investigating the phase diagram were DTA, melting point determination,
X-ray diffraction, microstructure studies, and chemical analyses in [1). and the same without
X-ray studies in [3) or DTA, in [2].
General Preparation Methods

The preparation of phases in the Nd-Te system occurs as usual by slowly heating the
stoichiometric mixture of elements in evacuated silica tubes. Phases with ~60 at% Te were
prepared in this manner in two weeks below 700°C. To prepare phases with < 60 at% Te the
element mixtures were allowed to prereact in silica tubes for ~ 100 h and then sealed in Ta
tubes and heated at ~2000°C for 2 to 5 min. The reaction products can then be equilibrated
in silica tubes. Traces of oxygen contamination could not be ruled out [2). The phases were
synthesized by the ampule methods from the elements followed by diffusion annealing for
70 h between 600 and 1200°C, depending on the composition [1, 4).
To avoid an explosive reaction of the elements the syntheses were carried out in evacuated
double compartment rotated quartz vessels without direct contact of the elements. The hori-
zontal furnace was heated at 200 K/h to 700 to 950°C. The temperature of the vessel containing
Nd was held 100 to 120°C lower than that of the vessel containing Te. The reaction time was
4 to 5 h. The obtained powders were pressed and melted in closed Ta crucibles at 1800 to
2000°C for 1.5 and 2 h [3). The solid-vapor reaction was also used by [5]; see p. 31.
Single crystals (3 x 3 x 2 mm 3) of Nd 3Te4 , Nd 4Te 7 , NdTe2 , and NdTe3 were prepared by the
gas transport reaction starting with powdered Nd 2Te 3 and 12 , Tel 4 , or NH 4CL as transport
agents. The reaction took place in evacuated (10- 4 Torr) quartz ampules (200 mm long, 22 mm
diameter), which were heated in a horizontal furnace with a temperature gradient .M; the
temperature t 1 of the hot zone (Nd 2Te 3 ) was about 900°C, while the temperature t2 of the
crystallization zone was about 800°C for Nd 3Te 4 and 660 to 690°C for the other three
compounds. Dependence of the yield of single crystals on the concentration of transport agent
in 70 h runs, starting with 1 g Nd 2Te 3 (selected values):
.M in oc transport conc. composition of yield in%

agent in mg/cm 3 single crystals
240 Tel 4 2.4 NdTe3 12.4

240 Tel 4 5.2 NdTe3 22.6
240 Tel 4 8.0 NdTe3 25.1
240 Tel 4 10.0 NdTe3 22.5
240 Tel 4 15.2 NdTe3 2.6
240 NH 4 CL 5.2 NdTe3 5.8
220 12 3.2 NdTe 2 2.5
Gmelm Handbook
RE Mam Vol C10
Preparation 117
Min°C transport conc. composition of yield in%

agent in mg/cm 3 single crystals
220 lz 6.2 NdTe2 12.0

220 lz 7.9 NdTe 2 18.2
220 lz 8.8 NdTe2 17.4
215 lz 8.0 NdTe2 + Nd 4Te 7
210 Tel 4 4.7 Nd 4Te 7 6.7
100 Tel 4 3.8 Nd 3Te 4 3.4
The yield of single crystals was better with Tel 4 than TeBr 4 as the transport medium. With
large concentrations of the transport agent (15 to 17 mg/cm 3) films of rose/azure color with
the composition Nd I were formed. Microphotos of the single crystals are shown in the paper,
Zinchenko et al. [9]. Single crystals of NdTe 2 were prepared by this method in 2 to 10 days
with 12 as the transport agent, with t 1 = 900°C and t 2 between 700 and 830°C, Andrellos, Bro
[10].
Color
NdTe Ref.
purple black silver-gray black dark gold gold [2]

blue dark gray Lightgray Light gray gray Lightgold gold [8]
A dark violet color for NdTe is reported by [1].
References:

Springs, Col., 1961 [1962], pp. 233/48, 239; N.S.A. 16 [1962] No. 32068).
[6] J. F. Miller, L. K. Matson, J. S. McNulty, R. C. Hirnes (AD-262215 [1961]1/49, 6; N.S.A. 16
[1962] No. 15260).
15562).
[9] K. A. Zinchenko, E. I. Yarembash, A. A. Eliseev, N. P. Luzhnaya, L. A. Chernyaev (lzv.
23/8).
[10] J. C. Andrellos, P. Bro (Solid-State Electron. 5 [1962] 414/6).

Moscow 1975, pp. 1/260, 194/202).
Gmelin Handbook
RE Mam Vol. C10
30.1.2.10.6.2 NdTe
NdTe is a congruently melting phase in the Nd-Te phase system ; see p. 115. For the
preparation see pp. 6 and 116.
Crystallographic Properties. Crystal Fleld SpLiHing
Nd Te has the cubic NaCl structure (see p. 8) with the lattice constants (in A) a = 6.262(1 ),
Zinchenko et al. [1], a = 6.278, Lin et al. [2], a = 6.2839(5) for stoichiometric single crystals,
and a = 6.268 to 6.284 A for polycrystalline samples, Hulliger et al. [3]. X-ray studies on
(stoichiometric) single crystals NdTe0 _98 ± 0 _02 show that NdTe undergoes a first-order tetragonal
Lattice distortion at the Neel temperature T N = 10.6 K and a second phase transition at ~ 9.6 K
(in zero magnetic field) between two antiferromagnetic phases ; see Fig. 48 [3] . Cubic lattice
constants at 77.3 K (a = 6.245 A) and in the antiferromagnetic region at 4.2 K (a = 6.247 A)
are deduced from neutron diffraction patterns of (nonstoichiometric) NdTe. The sample was
prepared by recrystallization at 1700°C; a blue matrix with black spots was formed and then
powdered, Schobinger-Papamentellos et al. [4]. The results of neutron inelastic scattering for
polycrystalline powdered NdTe at 16 and 78 K can be excellently interpreted in terms of a
nearest-neighbor point charge model. The maxima in the energy spectra at 5.7 ± 0.3 and
± f'h f'h
12.9 0.2 meV are related to the ground state transitions 1~2) ___. 1 6 and 2) ___. 1), respectively.
f'h
The r 6 ___. 1) transition (7 .2 ± 0.5 meV) could not be observed because of its small transition
probability. The overall crystal field splitting factor is W = - 0.22 ± 0.01 meV, Furrer,
Teilenbach [5].
6.28
Q
6.27
"\.,
r-.-
oc{ t..
.!:
u
c·
~
6.26
c ___.;·
6.25
6 10 14
Temperature in K
Fig. 48. Lattice constants of NdTe around the Neel temperature.
The density (in g/cm 3) at room temperature is D exp = 7.40 [1], 7.5 [2] ; Deale = 7.30 [2] . The
microhardness is reported tobe 205 kg/mm 2 ( = 2.01 GPa) , Abrikosov, Zargaryan [11].
Gmelln Handbook
RE Mam Vol. C 10
NdTe 119
fli\1
300
200
..
~ 100
:.:: 10 20 30 40
E 6
u
--
.!:
-<
20
11 2 6 10 20 60 100
Temperature in K
Fig. 49. Thermal resistance 1/A of NdTe versus temperature. The inset shows the positive
deviation near TN due to the magnetic contribution 1/Am.
The heat capacity CP as weiL as the thermal resistance 1/A (obtained by measuring the
thermal conductivity A of a polycrystalline sample between about 2 and 80 K) exhibit a
maximum at 10.2 K (TN); see Fig. 49. The inset in the figure shows the positive deviation near
TN due to the magnetic contribution 1/Am. Within the whole studied temperature range, the
Lorenz number L in the Wiedemann-Franz relationship L = A · Q · r- 1 (A = thermal
conductivity, Q = electrical resistivity) is equal to about twice the Sommerfeld value
(2.45 x 10- 8 V2 · K- 1) . This indicates the significant rote of the phonons in A; magnons may
also beimportantat Low temperatures, Zhuze et al. [6] . CP = 12.0 cal · moL- 1 · K- 1 at 298 K
and CP = 11.56 + 1.46 x 10- 3 T between T = 298 and 2000 K were estimated by analogy with
CP values for other rare earth chalcogenides by Mills [7]; calculated thermodynamic quantities
from these estimated CP values between 298 and 2000 Kare tabulated in [7, p. 806].
Magnetic Properlies
NdTe is paramagnetic and is antiferromagnetically ordered at low temperatures. The Neel

temperature is T N = 10.2 K from measurements of heat capacity, electricaL conductivity, and
thermal conductivity, Zhuze et al. [6], 10.6 K from X-ray studies, Huttiger et al. [3], and
13 K from magnetic susceptibility measurements, Adamyan, Loginov [9]. Further values are
tabulated on p. 15. A second magnetic phase transition between two antiferromagnetic states
at ~ 9.6 K is derived from X-ray studies and susceptibility measurements [3].
The Neel temperature is, according to single crystal studies of [3], associated with the
(first-order) cubic ~ tetragonal transition (see Fig.48). But the tetragonal structure in the
antiferromagnetic state does not agree with the observed magnetic structure of the fcc II type
(MnO type), derived from ne utron scattering studies on powdered samples at 4.2 K (second-
order transition at T N) by Schobinger-Papamantellos et al. [4]. The discrepancy may be
connected with the stoichiometry [3] . The samples of [4], recrystaLLized at 1700°C, contained
Gmel tn Handbock
RE Main Vol. C 10
I
22
"'e 18 V
u
..... /
/
"I
01 /
'1/
"' 14
~
c:
J
~10
6
~
2
0 40 80 120
Temperature in K
Fig. 50. Inverse magnetic susceptibility 1/x of NdTe versus temperature.
black spots in a blue matrix. The magnetic moments at 4.2 K were found to be parallel to the
[111] direction with an ordered moment of 1.1 ~ 8 • but a moment orientation deviating slightly
from the [111] axis is possible [4] .
Susceptibility measurements between about 100 and 530 K showed the Curie-Weiss law
tobe obeyed, Pechennikov et al. [8]. Measurements between 4.2 and 150 K showed deviations
from the Curie-Weiss law below 80 K (see Fig. 50) probably due to crystal field effects. The
susceptibility was independent of the applied external field (6 to 13 kOe) over the whole
temperature range. The paramagnetic Curie temperature eP = - 14 K, and the effective
magnetic moment ~eff = 3.54 ~ 8 were found [9]. Further values of e P and ~eff are tabulated
on p. 15. The inverse magnetic susceptibility in the range from 4.2 to 1300 K is shown in
Fig. 50, p. 131 in "Rare Earth Elements" C9, 1986, from measurements on powdered NdTe
samples by Smolenskii et al. [12]. The magnetization of NdTe single crystals (composition
NdTe0 _98 ±0.02 ) at 1.5 K in the crystallographic [001] direction in pulsed magnetic fields up to
200 kOe (see Fig . 49 in "Rare Earth Elements" C9, 1986, p. 130) shows two field-induced
phase transitions with critical fields on the order of 90 and 150 kOe [3] . Similar measurements
on polycrystalline NdTe showed one (antiferromagnetic-ferromagnetic) transition induced by
a critical field of ~ 90 kOe in studies at both 4.2 and 1.6 K. The maximum of the induced
magnetic moment (1 .3 ~ 8 /Nd3+ ) is smaller than the value for the free Nd3+ ion and Gorresponds
approximately to the ferromagnetic moment of the lowest energy Ievel (r 6 doublet) ,
Starovoitov et al. [10] .
With rising temperature from 300 to 1300 K the electrical resistivity Q of fused polycrystalline
samples increases linearly from ~ 135 to ~ 220 ~Q · cm while the thermoelectric power S
slightly decreases nonlinearly from +2 to about - 5 ~V/K (read from curves in the paper),
Abrikosov, Zargaryan [11] . The temperature function of Q (like CP and A., see p. 119) between
Gmetm Handbook
RE Ma1n Vol. C 10
NdTe 121
1.2
1.0
1. . . . . . .
/
I
I
:.::: I
> 0.2
0.
:::1.
.s:
U"l 0 I
-0.2 \I '-V
~~-~,--~~~~,~0~~~~~~~ V
0 20 40 60 80 100
Temperoture in K Temperature in K
Fig. 51. Electrical resistivity Q of NdTe Fig. 52. Thermoelectric power S of

versus temperature. The inset shows NdTe versus temperature .
the positive deviation ßg near T N·
2 and 400 K shows a slight maximum at 10.2 K (T Nl; see Fig. 51. The thermoelectric power
shows small extreme values in the magnetic ordering region, as shown in Fig. 52 , Zhuze et
al. [6). Resistivities of Q = 30 and 470 l!fl· cm at 143 and 298 K, respectively, are reported by
Matson et al. [13) . The electrical resistivity of phases in the Nd-Te system increases at
298 K from < 10- 4 to ~ 10 n · cm with rising Te content on going from NdTe to NdTe 3 . The
thermoelectric power S = -8 JNIK, the Hall coefficient IRHI = 0.004 cm 3/C, and the carrier
concentration 1.5 x 1021 cm- 3 are reported for a sample with Q = 430 J.!Ü · cm at 298 K [1].
Data on the electrical resistivity and thermoelectric power as functions of temperature and
preparation conditions arealso reported by Miller et al. [14) .
References:
[1) K. A. Zinchenko, N. P. Luzhnaya, E. I. Yarembash, A. A. Eliseev (lzv. Akad . Nauk SSSR

Neorgan. Materialy 2 [1966)1747/56; lnorg . Materials [USSR) 2 [1966]1506/14) .
[2) W. Lin, H. Steinfink, E. J. Weiss (lnorg. Chem. 4 [1965] 877/81) .
[3) F. Hulliger, M. Landolt, R. Schmelczer, I. Zarbach (Solid State Commun . 17 [1974)
751/4) .
[4) P. Schobinger-Papamantellos, P. Fischer, A. Niggli, et al. (J. Phys. C 7 [1974] 2023/38).
[5] A. Furrer, U. Tellenbach (Phys. Status Solidi B 71 [1975] K31/K33) .
[6) V. P. Zhuze, V. I. Novikov, V. M. Sergeeva, S. S. Shalyt (Fiz. Tverd. Tela [Len ingrad)11
[1969) 2192/5; Soviet Phys.-Solid State 11 [1969)1770/2).
[7) K. C. Mills (Thermodynamic Data for lnorganic Sulphides, Selenides, and Tellurides,
Butterworth, London 1974, pp. 1/854, 457) .
[8] A. V.Pechennikov, V. I. Chechernikov, E. I. Yarembash, K. A. Zinchenko (lzv. Akad . Nauk
SSSR Neorgan. Materialy 3 [1967]"1086/7; lnorg. Materials [USSR]3 [1967]967/8).
[9) V. E. Adamyan, G. M. Loginov (Zh . Eksperim. Teor. Fiz. 51 [1966]1044/7; Soviet Phys.-
JETP 24 [1967] 696/8).
[10) A. T.Starovoitov, V. I. Ozhogin, G. M. Loginov (Phys. Letters A 29 [1969] 617/8).
Gmelm Handbook
RE Mam Vol. C 10
[12] G. A. Smolenskii, V. P. Zhuze, E. Adamyan, G. M. Loginov (Phys. Status Solidi 18 [1966]
873/80).
[13] L. K. Matson, F. J. Reid, J. F. Miller, Batelle Memorial Institute (U.S. 3270310 [1964/66]
1/6; C.A. 65 [1966]16235).
[14] J. F. Miller, L. K. Matson, J. S. McNulty, R. C. Hirnes (AD-262215 [1961] 1/49; N.S.A. 16
[1962] No. 15260).
30.1.2.1 0.6.3 Solid Solutions Nd 3Te 4-Nd 2Te 3 and Terminal Compounds
The compounds Nd 3Te 4 and y-Nd 2Te 3 (cubic high-temperature form) belong to the same
phase of variable composition with cubic Th 3 P4 structure. They occur in the Nd-Te phase
diagram; see Fig. 47, p. 115. For the preparation, see p. 116; for the structure see p. 33.
30.1.2.10.6.3.1 Nd 3Te 4 and Nd 3 _yTe 4 (0 ~ y ~ 0.33)

The lattice constant a in A and density D in g/cm 3 for cubic Nd 3Te 4 are as follows:
a in A 9.430 9.434 9.456

Dexp 7.21 7.33
Deale · 7.46 7.41
Ref . . [1 to 3] [4] [5]
Microhardness 300 kg/mm 2 (= 2.94 GPa) of a fused polycrystalline sample at 300 K, Abri-
kosov, Zargaryan [6].
Nd 3Te 4 is paramagnetic with the susceptibility XA = 5600 x 10- 6 cm 3 /g-atom Nd [2, 3]. lt
is an n-type semiconductor. Electrical resistivity Q, thermoelectric power S, carrier mobility
ll. carrier concentration n, and Hall constant IRHI at room temperature for polycrystalline
Nd 3Te 4 samples:
Q in Q·cm S in llV/K ll in cm 2 · v- 1 · K- 1 n in cm- 3 IRHI in cm 3/C Ref.
7.2 X 10- 3 -39 6.4 X 1020 0.097 [1]

1.0 X 10- 2 -40 [2, 3]
2.56 X 10- 4 - 4.85 4.1 6 X 1021 [6]
Values for 83 Kare: n = 9 x 10 19 and IRHI = 0.68 [1].

The change of the electrical conductivity K and thermoelectric power S between about
300 and 1400 K is shown in Fig. 53 from Abrikosov, Zargaryan [6], measured on fused
polycrystalline samples.
Values for K and S of Nd 3 _yTe 4 at 300 K from [6]:
y in Nd 3 _yTe 4 . 0 0.1 0.16 0.19 0.22 0.29 0.33
Kin Q- 1 -cm- 1 . 3900 2300 1980 1300 420 150 0.18

S in llV/K -4.85 -12.5 -16.0 -22.0 -36.0 -62.5 -560
Gmelm Handbock
RE Ma1n Val. C 10
123
600 1000 1400°

Temperature in K
Fig. 53. Electrical conductivity K and thermoelectric power S of Nd 3Te4 versus temperature .
.!:
cn
1000 1400
Fig. 54. Electrical conductivity K (Fig.54a) and thermoelectric power S (Fig.54b) of Nd3 _yTe4
solid solutions versus temperature.
The temperature dependence of K and S for these samples at about 300 to 1400 K is shown
in Fig. 54 a and b from [6] . Values for K , S, and the thermal conductivity A. for Nd2.76 Te 4 at 298
and 1300 K are K = 714 and 133 n- 1 · cm- 1, S = -40 and - 240 jlV/K, and A. = 1.4 and
0.9 W · m - 1 · K - 1 , respectively, Reid et al. [7] , Miller et al. [8]. Data on the electrical conductivity
and thermoelectric power as functions of preparation conditions, composition, and tempera-
ture for polycrystalline samples of the Nd3Te4-Nd2Te3 system arealso reported in the earlier
report of Miller et al. [9] . For comparison of the electrical properlies of Nd 3 _yTe4 and Nd3 _yS4 ,
see Gotikova et al. [10] .
Gmelm Handbock
RE Main Vol. C 10
References:

Vol. 2, pp. 761/77, 768; C.A. 73 [1970] No. 124092).
[3] E. I. Yarembash (Colloq. Intern. Centre Natl. Rech. Sei. No. 180 [1969/70]471/81, 477).
1964 [1965], pp. 535/44, 541; C.A. 65 [1966]14821).
943/50).
15562).
[1962] No. 15260).
[10] 0. A. Golikova, I.M. Rudnik, V. M. Sergeeva, M. M. Kazanin, E. N. Thalenko (Phys. Status
Solidi A 37 [1976] 199/203).
30.1.2.1 0.6.3.2 Nd2Te 3
Nd 2Te 3 is obtained in the cubic y-form (Th 3 P4 type, see p. 33) and in the orthorhombic
TJ-form (U 2S3 or Sb 2S3 type, see p. 34). Lattice constant a in A of the cubic form: 9.421 [1 to 3],
9.424 [4], and 9.427 [5] (see also p. 33). Calculated and measured densities in g/cm 3 of the
cubic form: DeaLe= 7.10 [4], Dexp = 7.10 [1], 7.30 [4]. The cubic form is believed tobe the high-
temperature form which transforms into the orthorhombic form at 1 000°C [4], but according
to [1] annealing of cubic Nd 2Te 3 below 1000°C does not Lead to a phase transition. After
prolonged annealing at 1100°C with subsequent quenching in ice water an orthorhombic
phasewas obtained [1]; seealso p. 116. The microhardness of a fused polycrystalline sample
at 300 K is 240 kg/mm 2 (~2.35 GPa), Abrikosov, Zargaryan [6].
Thermodynamic Properlies
From CP measurements at T = 12 to 300 K of cubic polycrystalline Nd 2Te 3 in an adiabatic

vacuum calorimeter the following smoothed (selected) values of the heat capacity CP in
cal· mol- 1 · K-1, of the enthalpy increment H~-H~ 2 in caUmol and the entropy increment
S~-S~ 2 in cal· mol- 1 · K- 1 are obtained by Paukov et al. [7]:
Tin K 12 20 30 60 90 120 150 180 260 298.15
cp 1.570 4.141 9.128 21.05 26.24 28.28 29.46 30.24 30.98 31.73
H~-H~ 2 0 21.41 86.56 558.1 1282 2104 2971 3868 6301 7498
S~-S~ 2 0 1.310 3.883 14.30 24.01 31.88 38.32 43.77 54.95 59.24
Gmelm Handbook
RE Mam Vol. C 10
125
H~98 . 15 - Hg = 7 507 ± 18 caUmol; standard entropy S~98 . 15 = 60.56 ± 0.18 cal · mol - 1 · K - 1 . The
CP versus T curve shows an abrupt decrease of CP by about 2% at 199 K. The form of this
anomaly suggests that it is associated with a first-order phase transition ; 11H for the transition
is estimated to be 10 ± 2 caUmol. At about 245 K the form of the CP versus T curve changes
appreciably. A positive deviation of CP from the smoothed curve at 26 to 28 K is possibly due
to a magnetic Iransformation [7] . An additional heat capacity component Cf, which is asso-
ciated with the transition of the 4f electrons from the ground state to the first two excited Levels
T1 and T2 , was found for Nd2Te3 in comparison with La2Te3 . The Cf component was calculated
by subtracting from the measured Cp values (Iaken from [6]) the lattice component calculated
from the temperature dependence of the Debye temperature. The basis parameters of the
excited 4f Levels in y-Nd 2Te3 are: T 1 = 76 K, g 1/g 0 = 1; T2 = 300 to 325 K, g 2/g 0 = 2. Plots of
C, from 13 to 120 Kare shown in the paper [8], but see p. 24 (Ref. [21]), where the higher CP
values of Pr3Te4 are attributed to oxygen contamination rather than to the presence of a Cf
component.
Magnetic and ELectricaL Properlies
Measurement of the magnetic susceptibility between about 100 and 530 K shows the Curie-
Weiss Law tobe obeyed with eP = -5 K and lleff = 3.40 lls· Pechennikov et al. [9] . Nd2Te3 is
an n-type semiconductor. On heating, intrinsic conductivity K sets in above 800 K (calculated
width of the forbidden zone 1.12 eV). The conductivity at room temperature is K =
0.18 Q - 1 · cm - 1 according to [6], but see p. 41 for strongly varying values. The temperaturs
dependence of K and of the thermoelectric power S are shown in Fig. 55a and b, measured
on fused polycrystalline samples. S changes from - 560 11V/K at 300 K to -80 11V/K at
850 K [6].
a) b)
-640
"'1\
'Eu
b: ~
>
- 480
....
.S :I.
.s
'
...... 0 -320
(/)
~ -160
r-o...,.
-1 0
Q5 1.5 2.5 400 600 800 1000 1200 1400
103 /T in K-1 Temperature in K
Fig. 55. Electrical conductivity K (Fig. 55a) and thermoelectric power S (Fig. 55b) of y-Nd 2Te 3
versus temperature.
References:
Neorgan. Materialy 2 [1966] 1747/56 ; lnorg. Materials [USSR]2 [1966]1506/14).
Vol. 2, pp. 761/77, 769 ; C.A. 73 [1970] No. 124092).
Gmelin Handbock
RE Main Vol. C 10
[3] E. I. Yarembash (Colloq. Intern. Centre NatL Rech. Sei. No. 180 [1969/70] 471/81 , 477) .
[4] W. Lin, H. Steinfink, E. J. Weiss (lnorg. Chem . 4 [1965]877/81) .
[5] D. J. Haase, H. Steinfink, E. J. Weiss (Proc. 4th Conf. Rare Earth Res., Phoeni x, Ariz. , 1964
[1965]. pp. 535/44, 541; CA 65 [1966]14821) .
280/5; lnorg. Materials [USSR] 3 [1967] 251/5) .
[7] I. E. Paukov, V. V. Nogteva, E. I. Yarembash (Zh. Fiz. Khim. 42 [1968] 998/1000; Russ . J.
Phys. Chem. 42 [1968] 522/3).
[8] V. V. Tikhonov, I. A. Smirnov (Fiz. Tverd . Tela [len ingrad]13 [1971]2749/52 ; Soviet Phys .-
Solid State 13 [1971] 2296/8) .
[9] A. V. Pechennikov, V. I. Chechernikov, E. I. Yarembash, K. A. Zinchenko (lzv. Akad. Nauk
30.1.2.1 0.6.4 Neodymium Polytellurides
Nd4Te 7 , NdTe2 _ x, Nd3Te7 , Nd2Te5, Nd4Te 11 , and NdTe3 occur as incongruently melting
phases in the Nd-Te system. See p. 115 for the phase diagram and the preparation . The
compounds (except Nd3Te7 ) are described in the comparative part. Some additional data
follow. Measurements of the magnetic susceptibility between about 100 and 530 K show the
Curie-Weiss law to be obeyed , Pechennikov et aL [3]. Values for the paramagnetic Curie
temperature E>P and the effective magnetic moment lie« from [3] and for the microhardness
H, the thermal conductivity A., the electrical conductivity K, the thermoelectric power S, and
the width of the forbidden zone ~E measured on fused polycrystalline samples by Abrikosov,
Zargaryan [1] are as follows:
Nd4Te 7 NdTe2 Nd2Te 5 NdTe3 Ref.
E>P in K. -12 -20 -35 -5 [3]

lieft in l!e 3.42 3.40 3.62 3.42 [3]
H in kg/mm 2 (GPa) . 210 (2.06) 180 (1 .76) 140 (1.37) 110 (1.08) [1]
A. in W · m - 1 · K - 1 0.64 0.67 0.75 2.55 [1]
K in Q - 1 · cm - 1 0.64 4.1 100 690 [1]
S in !!V/ K -320 +36.0 +19.4 + 44.0 [1]
~Ein eV 0.38 0.3 0.29 [1]
1.4 1>._, l
~00~-+--~--~-+--~
Nd4Te7
t2
1\
~
'e
' "'
V
b:t
..
-~
~0.8 ~ ...,_
~
01
..2 0.6 "----.
0. 4
t---
1.0 1.5 2.0 2.5 3D 0300 500
1oJ /Tin K-1 Tempereture in K
Fig. 56. Electrical conductivity K and thermoelectric power S of two Nd4Te 7 samples ve rsus
temperature.
Gmelm Handbook
RE Mam VoL C 10
Neodymium Polytellurides 127
2.5
~ 1.6
80 I
I
2.4 l' I f-
~
NdTe 2 NdTe 2 ~
"'"e
\
Nd 2T~
'e
~ 1.2 ~ 2.3
.. I" ' ""'-.:

·; 0.8
~ 0.4
l'a. 20 ' ......._ ..
·; 2.2
~ 2.1
I~
..........
..........
0 0200 400 600 800 1000
1D 1.5 2.0 2.5 10 2•01.0 15 2.0 2.5
1oJ/T in K-1 Temperature in K 103/T in K-1
Fig. 57. Electrical conductivity K of NdTe2 and Nd2Te5 and thermoelectric power S of NdTe2
versus temperature.
Temperature in K
500 250 125 100
" I
I
100
I
~Hin-type
jV
u1o2 10 E
i
~
~
u ~ c:
.~
~
'• .!;;
Q.
a::
101
/ to
1(
2 I 0.2
2 4 6 8 10 12
Fig. 58. Electrical resistivity Q and Hall coefficient RH of NdTe2 versus temperature.
The carrier concentration and mobility for NdTe2 is reported to be 2 x 1020 cm- 3 and
0.13 cm 2 · v- 1 • s-', respectively. The temperature dependence of K and S for Nd4Te7 , NdTe2 ,
and Nd2Te 5 is shown in Fig. 56 and 57. For NdTe3 the temperature dependence of K and S could
not be determined, because of the instability of the material on heating [1]. A reversal of
the Hall coefficient RH of NdTe2 single crystals (containing traces of oxygen) below room
temperature was found by Andrellos, Bro [2] ; see Fig. 58 for the temperature dependence of
Gmelm Handbook
RE Mam Vol. C 10
128 Samarium Tellurides
RH and the electrical resistivity between 83 and 524 K. The compound exhibits n-type conduc-
tion at low temperatures and p-type conduction at elevated temperatures with an apparent
energy gap of 0.48 eV. The net carrier concentration n increased from 4.8 x 1015 at 83 K to
1.4 x 10 16 cm- 3 at 200 K. At temperatures above the Hall reversal n decreased from 5 x 1017
at 300 K to 5.4 x 1015 cm- 3 at 524 K. Corresponding changes were calculated for the Hall
mobility. The temperature of the reversal shifted to a higher temperature value after an
exposure of the crystal to air for 2 weeks at room temperature (see figurein the paper), which
suggested that an oxygen impurity contributed to the reversal [2].
References:
[2] J. C. Andrellos, P. Bro (Solid-State Electron. 5 [1962] 414/6).
[3] A. V. Pechennikov, V. I. Chechernikov, E. I. Yarembash, K. A. Zinchenko (lzv. Akad. Nauk
30.1.2.1 0. 7 Samarium Tellurides

Additional data for Sm Te, Sm 3Te 4 , Sm 2Te 3 , Sm 4Te 7 , SmTe 2 _x, Sm 2Te 5 , and SmTe 3 are found
in Sections 30.1.2.1, 30.1.2.2, 30.1.2.3, 30.1.2.4, 30.1.2.5, 30.1.2.6, and 30.1.2.8, on pp. 6, 21, 31,
43, 47, 53, and 57, respectively.
30.1.2.1 0. 7.1 The Sm-Te System

Phase Diagram
The tentative, incomplete Sm-Te phase diagram is published by Yarembash, Karabekov
[1] (and also by Yarembash, Eliseev [2], Karabekov [3], Sergeeva, Golubkov [4], and
schematically by Eliseev et al. [5]). lt is based on DTA, X-ray diffraction, chemical and
microstructural analyses. The samples were prepared by direct synthesis from the elements
[1, 3]. Eight intermediate phases were found: SmTe, Sm 3Te4 , Sm 2Te 3 , Sm 4Te 7 , SmTe 1.80 _ 1_85 ,
Sm 3Te 7 , Sm 2Te5 , and SmTe 3 [1].
The monotelluride Sm Te melts congruently at 1860 ± 50°C. lncongruent melting was found
for Sm 3Te 4 at 1680 ± 50°C, for Sm 3Te7 at 890°C, Sm 2Te 5 at 830°C, and SmTe 3 at 465°C [1]. A
probable melting point for SmTe 1.8 of ~ 1170°C was reported by Yarembash et al. [6],
Karabekov et al. [7]. The melting point of Sm 2Te3 was not determined for the tentative phase
diagram but assumed as incongruent at 1500 ± 50°C [1] using the reported value 1440 to
1550°C in Miller, Hirnes [8]; 1410 to 1530°C was reported by Miller et al. [9]. Sm 2Te 3 shows a
polymorphic phase transition at 640 ± 5°C from a high temperature form to the orthorhombic
T]-Sm 2Te3 . The eutectic between Sm and SmTe melts at 980°C, that near the Te side at
445°C [1].
The homogeneity range of SmTe extends from 47 to 50 at% Te and that of Sm 3Te 4 from
55.5 to 57.2 at% Te. No solid solutions were found between Sm 3Te 4 (having the cubic Th 3 P4
structure, see p.21) and T]-Sm 2Te3 (having orthorhombic structure, see p.34) [1]. The high tem-
perature form of Sm 2Te3 , not studied by [1], was regarded as cubic y-Sm 2Te 3 (Th 3P4 type) [2].
Gmelm Handbock
RE Mam Vol. C10
The Sm-Te System 129
A small region of solid solutions between Sm 3Te4 and y-Sm 2Te3 in quenched samples was
assumed by Pardo et al. [13] (see p. 22); see also the discussion in [2]. The approximate
homogeneity ranges (in at% Te) of the polytellurides are as follows [1]:
Sm 4Te 7 SmTe1.55 Sm 3Te7 Sm 2Te5 SmTe3

62 to <64 64.3 to 64.9 69.5 to 70.5 71.5 to 72.5 73 to 75
Similar values are reported in [2] from the results of [1, 3]. The Te-deficient ditelluride phase
SmTe 2 _x (having LaTe 2 structure, see p. 48) has as single crystals the composition SmTe 1.85
(64.9 at% Te) [1]. A homogeneity range from SmTe 1.a to SmTe 1.9 was determined by Pardo et
al. [10]; see p. 48.
General Properties
To study the Mössbauer effect in the samples the 35.5 keV y-rays of a 125mTe03 source was
used by Aleksandrov et al. [11]. The source was at room temperature, the absorber at Liquid
nitrogen temperature. Obtained values of the isomer shift ö in mm/s (relative to Te0 3), the
Line width r in mm/s (at half height), and the quadrupole Splitting~ in mm/s (determined from
the broadening of the Lines) for the samples in dependence of their Te content [11]:
at% Te 50 57.2 58.5 61 63.4 69.8 70 72 75 80 85
8±0.2. 0.85 1.05 1.00 1.35 1.20 1.60 1.75 1.55 1.90 1.40 1.50
r± 0.4. 6.00 7.35 7.50 8.45 8.35 9.45 11.0
~±0.4. 0.5 1.85 2.00 2.95 2.90 3.90 4.50 5.50 5.80 4.30 5.20
The same values for ö and ~ arealso reported by Yarembash et al. [6]. Karabekov et al. [7].
From the results the electron structures were discussed [6, 7, 11].
X-ray absorption spectra near the L 111 edge of Sm in samples with 3 to 73.5 at% Te were
tentatively interpreted as indicating a predominant 4F (Sm 3 +) configuration at both 50 and
53 at% Te and essentially 4F (Sm 3 +) in the other samples; see Yarembash, Eliseev [2].
Yarembash et al. [12]. This conflicts with other data on the Sm valence in SmTe (see p. 133).
The following colors have been reported for samarium tellurides: dark gray for SmTe,
black for Sm 3Te4 , dark gray for Sm 4Te 7 , Lightgray for SmTe 1.85 , cinnamon brown for Sm 2Te 5 ,
and cinnamon brown with a golden tint for SmTe 3 [2].
References:
[1] E. I.·Yarembash, A. Karabekov (Tr. Frunz. Politekhn. lnst. No. 41 [1970]49/63).

Moscow 1975, pp. 1/260, 202/8).
[3] A. Karabekov (Diss. Polytech. lnst. Frunze, USSR, 1969 from [2, 4]).
[4] V. M. Sergeeva, A. V. Golubkov (in V. P. Zhuze et al., Fizicheskie Svoistva Khal'kogeni-
dov Redkozemel'nykh Elementov, Nauka, Leningrad 1973, pp. 5/57, 9; C.A. 80 [1974]
No. 75014).
[5] A. A. Eliseev, 0. A. Sadovskaya, G. M. Kuz'micheva (Zh. Vses. Khim. Obshchestva 26
No. 6 [1981]12/21; Mendeleev Chem. J. 26 No. 6 [1981]15/27, 19).
Gmelm Handbock
RE Main Vol. C10
9

661/5).
[7] A. K. Karabekov, E. I. Yarembash, E. G. Tyurin (lzv. Akad. Nauk Kirg. SSR 1973 No. 6,
pp. 68/72; C.A. 80 [1974] No. 75371).
[1961], pp. 232/40, 236).
15562).
[10] M. P. Pardo, J. Flahaut, L. Domange (Bull. Soc. Chim. France 1964 3267/71).
[11] A. Yu. Aleksandrov, S. P. lonov, A. K. Karabekov, E. I. Yarembash (lzv. Akad. Nauk SSSR
[12] E. I. Yarembash, 0. A. Sadovskaya, E. G. Tyurin, A. Karabekov (Khim. Svyaz. Poluprov.
PolurnetaL 1972 263/8; C.A. 79 [1973] No. 36889).
[13] M. P. Pardo, J. Flahaut, L. Domange (Compt. Rend. 256 [1963]1793/6).
30.1.2.10.7.2 SmTe
lntroduction
The most prominent feature of SmTe is its valence instability, which to a different extent
is also characteristic of SmS and SmSe, see "Rare Earth Elements" C7, 1983, pp. 218/317 and
C9, 1986, pp. 137/162. Being divalent in the NaCl type phase at ambient pressure, the Sm
valency increases towards three during a continuous pressure-induced isostructural phase
transition often referred to as a semiconductor-to-metal transition (SMT). The SMT is reflected
in the pressure dependence of many physical properties.
30.1.2.1 0. 7.2.1 Homogeneity Range. Preparation
Apparently there is no extensive knowledge on the phase width of Sm Te. No phase width
is mentioned in an early review by Flahaut, Laruelle [1]. Referring to Yarembash, Karabekov
[2] or Karabekov [3], a homogeneity range of ~ 46 to 50 at% Te in samarium telluride is
mentioned by Yarembash, Eliseev [4] and Eliseev et al. [5], see also p. 128.
SmTe is prepared directly from the elements, landelli [6], landelli, Palenzona [7],
Rooymans [8], Flahaut, Laruelle [1], Yarembash et al. [9], Karabekov et al. [10]. Direct
synthesis from the elements is said to be the only appropriate for the preparation of the rare
earth tellurides by [1]. Sm filings or turnings and Te vapor were prereacted at ~ 450 [7]
to 500°C [1] within evacuated, sealed two-chamber tubes of Vycor or vitreous silica. The
inhomogeneaus material then was equilibrated at 800 to 1 000°C [1], 1000 to 1100°C [6, 7],
1 200°C [8], giving a gray-black powder [6]. SmTe has also been prepared from the ele-
ments at 800°C in evacuated quartz ampules with subsequent heating under 10- 5 Torr
to 1600 to 1700°C in Mo or graphite crucibles to eliminate excess Te, Nagai et al. [11].
Gmelm Handbook
RE Ma1n Vol. C 10
Sm Te 131
Polycrystalline samples with fairly large-sized single crystals have been obtained in a
tantalum tube from melting the reaction product of Sm chipsandTe vapor ( ~ 900°C, 48 h),
Jayaraman et al. [12], similarly described by Birgeneau et al. [13].
For the preparation of SmTe single crystals, metallic Sm and Te were reacted in an
evacuated quartz ampule at 900°C. The reaction product was heated to ~ 2100°C within an
evacuated Ta tube and then cooled down at a rate of ~ 50°C/h, Kurita et al. [14]. Single
crystals with dimensions up to (5 x 4 x 4) mm3 were grown from the melt (overheated to
2090°C) by directional solidification in evacuated and sealed tungsten and molybdenum
crucibles, Batlogg et al. [15]. Mett temperatures up to 2300°C in sealed tungsten crucibles
are used by Mehran et al. [16].
Green thin films of crystalline Sm Te have been prepared by coevaporation of the elements
onto heated substrates (Vycor, Pyrex, or CaF2), Suryanarayanan et al. [17]. Yellow-green
amorphous SmTe films (thickness ~ 0.1 ~tm) have been obtained by thermal evaporation
of monotelluride on glass, vitreous silica, or KBr, Lashkarev, lvanchenko [18], lvanchenko
et al. [19].
SmTe was handlad under an inert atmosphere (dry nitrogen) to avoid reaction with water
vapor. SmTe decomposes slowly in air and is dissolved by acids [6].
Heferences:
[1] J. Flahaut, P. Laruelle (Progr. Sei. Techno!. Rare Earths 3 [1968]149/208, 149/50, 197).
[2] E. I. Yarembash, A. Karabekov (Tr. Frunz. Polytekhn. lnst. No. 41 [1970] 49/63).
[3] A. Karabekov (Diss. Polytech. lnst. Frunze, USSR, 1969 from [5]).
Moscow 1975, pp. 1/260, 202; C.A. 83 [1975] No. 125545).
No. 6 [1981]12/21; Mendeleev Chem. J. 26 No. 6 [1981]15/27, 19).
[6] A. landelli (Z. Anorg. Allgem. Chem. 288 [1956] 81/6).
[7] A. landelli, A. Palenzona (Colloq. Intern. Centre Natl. Rech. Sei. [Paris] No. 157 [1967]
397/405).
[8] C. J. M. Rooymans (Ber. Bunsenges. Physik. Chem. 70 [1966]1036/41).
661/5).
[10] A. K. Karabekov, E. I. Yarembash, E. G. Tyurin (lzv. Akad. Nauk Kirg. SSR 1973, No. 6,
pp. 68/72; C.A. 80 [1974] No. 75371).
[11] S.-1. Nagai, M. Shinmei, T. Yokokawa (J. lnorg. Nucl. Chem. 36 [1974]1904/5).
[12] A. Jayaraman, V. Narayanamurti, E. Bucher, R. G. Maines (Phys. Rev. Letters 25 [1970]
368/70).
[13] R. J. Birgeneau, E. Bucher, L. W. Rupp Jr., W. M. Walsh Jr. (Phys. Rev. [3] B 5 [1972]
3412/8).
[14] A. Kurita, Y. Kaneko, T. Koda (Solid State Commun. 49 [1984] 463/6).
[15] B. Batlogg, E. Kaldis, A. Schlegel, P. Wachter (Phys. Rev. [3] B 14 [1976]5503/14, 5503/4).
[16] F. Mehran, K. W. K. Stevens, R. S. Title, F. Holtzberg (Phys. Rev. Letters 27 [1971]
1368/71).
[17] R. Suryanarayanan, C. Paparoditis, J. Ferre, B. Briat (J. Appl. Phys. 43 [1972]4105/8).
[18] G. V. Lashkarev, L. A. lvanchenko (J. Non-Cryst. Solids 8110 [1972]670/5).
[19] L. A. lvanchenko, G. V. Lashkarev, Yu. B. Paderno, S. V. Drozdova, et al. (Ukr. Fiz. Zh.
16 [1971] 510/2; Ukr. Phys. J. 16 [1971]624/7).
Gmelin Handbook g•
RE Main Vol. C10
30.1.2.1 0. 7 .2.2 Crystallographic Properlies
Phases and Phase Transitions

Solid SmTe has been observed in two different crystal structures, the NaCl type at low
pressure, landelli [1], and the CsCl type at high pressure, Singh et al. [2]. A unit cell
isomorphaus with monoclinic LaTe has also been proposed for a SmTe sample, Brixner [3],
but see p. 8. (The reported unit cell volume with integer number of formula units, however,
implies rather unreasonable density values for Sm 2 + telluride.) ln addition to the structural
change, a pressure-induced semiconductor-to-metal transition (SMT) is observed on electrical
conductivity measurements up to 55 kbar by Jayaraman et al. [4] and by the anomalously
large compressibility between 20 and 60 kbar, Chatterjee et al. [5].
The SMT in SmTe is continuous (in cantrast to SmS) as was shown for example by the
large but gradual change of the specific volume with pressure (investigated up to 150 kbar by
X-ray diffraction) [2], and by the continuous development of a metallic reflectivity (beginning
at ~ 40 kbar, saturation at ~ 100 kbar), Syassen [6]. Previously the pressure dependence of
the lattice parameter (studied up to 70 kbar) had indicated a discontinuous isostructural phase
transition between 30 and 45 kbar, Rooymans [7]. For details see the corresponding sections.
The CsCl type phase is formed above 110 ± 10 kbar and is found to coexist with the NaCl
type at still higher pressures (see Fig. 59 on p. 135). The relative volume change AVIV of the
structural phase transition is -9.1% at 110 ± 10 kbar. At ~ 150 kbar only the X-ray diffraction
lines from the CsCl type are observed [2]. A transition pressure of 130 kbar for the NaCl-CsCl
type transformation was derived from optical studies. The CsCl type is stable up to at least
220 kbar [6].
LaUlee Constants
The NaCl type lattice parameter values a in the Literature range from 6.593A (error
~0.1%), Yarembash et al. [8], seealso [9], to 6.611 A, landelli, Palenzona [10]. The latter
value was obtained after synthesis at 450°C and this changes to 6.601 A after heating to
1100°Cfor 15 h [10]. Additional values are 6.594 A [1], also reported by [11, 12], 6.595 ± 0.002 A
[2, 5, 13]. A thin SmTe film on a substrate (Pyrex, Vycor, or CaF2 ) had a = 6.600 ± 0.004 A,
Suryanarayanan et al. [14]. The lattice parameter changes from a = 6.595 ± 0.002 A at ambient
pressure to a = 5.992 ± 0.02 A at p = 110 ± 10 kbar [2]. A drop from a ~ 6.50 A to ~ 6.25 A
araund 40 kbar can be read from a figurein [7], but see p. 135. The volume decrease is related
to a valence change of Sm in all of the papers. The CsCl type high-pressure phase has a
laHice parameter a = 3.656 ± 0.01 A at 110 ± 10 kbar [2, 5].
For intensities and interplaner spacings of the powder patterns of the NaCl and CsCl type
SmTe, see [1] and [5], respectively.
References:
[1] A. landelli (Z. Anorg. Allgem. Chem. 288 [1956]81/6).

[2] A. K. Singh, A. Jayaraman, A. Chatterjee (Solid State Commun. 9 [1971]1459/62).
[4] A. Jayaraman, V. Narayanamurti, E. Sucher, R. G. Maines (Phys. Rev. Letters 25 [1970]
368/70).
[5] A. Chatterjee, A. K. Singh, A. Jayaraman (Phys. Rev. (3] 8 6 [1972] 2285/91).
[6] K. Syassen (J. Phys. Colloq. [Paris]45 [1984] C8-123/C8-139, C8-134/C8-137).
Gmelln Handbook
RE Mam Vol C10
Sm Te 133
[7] C. J. M. Rooymans (Ser. Sunsenges. Physik. Chem. 70 [1966]1036/41).

661/5).
pp. 68/72; C.A. 80 [1974] No. 75371).
397/405).
1430/3).
[12] S. S. Satsanov, V. P. Sokarev, G. V. Durogova (Zh. Neorgan. Khim. 30 [1985]246/8; Russ.
J. lnorg. Chem. 30 [1985] 138/9).
[13] A. Jayaraman, A. K. Singh, A. Chatterjee (Proc. 9th Conf. Rare Earth Res., Slacksburg,
Virg., 1971, pp. 360/360i).
[14] R. Suryanarayanan, C. Paparoditis, J. Ferre, S. Sriat (J. Appl. Phys. 43 [1972] 4105/8).
30.1.2.10.7.2.3 Valency and Bonding

lntroduction
At atmospheric pressure Sm is divalent in SmTe (Like in SmS and SmSe) apart from small
amounts of Sm3+ impurities, reported in some papers. The Sm valence increases towards 3
during a continuous pressure-induced semiconductor-to-metal transition (SMT). The SMT
implies the delocalization of 4f electrons into the conduction band giving a non-integer
intermediate valence state for the Sm ions, as observed in the other samarium mono-
chalcogenides. Fora survey on theoretical models dealing with this phenomenon, see "Rare
Earth Elements" C7, 1983, pp. 304/16. Additionalinformation on the bonding is related in the
energy band structure; see p. 139.
At Ambient Pressure
The divalency of Sm in SmTe has been established from the magnitude of the lattice
parameter, landelli [1], from the magnetic behavior, landelli [2], Sucher et al. [3], from
photoemission spectra (XPS), Campagna et al. [4], the resistivity which is typical for
semiconductors, Reid et al. [5], and the optical properties, Suryanarayanan et al. [6]. A mean
Sm valency of 2.27 in SmTe is assumed by Lashkarev et al. [7] due to the observed magnetic
susceptibility between 80 and 300 K, while Sucher et al. [3] rate the Sm3+ content as 3% at
most ( ~ mean valency = 2.03) from similar susceptibility data; see p. 137. A kink at about
850°C in the thermal expansion curve of Sm Te has been assigned to a contribution of Sm3+,
Rooymans [8]. A low ionicity in SmTe compared to SmS and SmSe was obtained in band
structure calculations; see p. 139. The calculated charge transfer from Sm to Te is 0.23
electrons, Farberovich [9].
Pressure Dependency of Valency

The initially normal behavior of the compressibility at elevated pressure indicates no
substantial change of the Sm valency below 20 kbar. Above this value up to 60 kbar the
compressibility becomes anomalously high. The extra volume decrease l'lVIV0 of 11% up to
Gmelin Handbook
RE Mam Vol. C10
60 kbar corresponds to a mean Sm valence of 2.66 in the collapsed high-pressure phase (still
NaCl type) if compared to estimates based on ionic radii, Chatterjee et al. [10]. A mean Sm
valence of ~ 2.7 at 100 kbar from lattice parameter scaling is given by Syassen [11]. A
continuous increase of the Sm valence with increasing pressure is also indicated by the
decrease of the electrical resistivity (studied up to 55 kbar), Jayaraman et al. [12]. Also the
continuous evolution of a Drude-like metallic reflectivity with saturation near 100 kbar supports
the occurrence of a major valence change in this pressure range (see p. 152). A possible
decrease of the ·mean Sm valence in the CsCl type phase could be interred from the small
relative volume reduction at the NaCl-CsCl phase transition (9% in SmTe) [11]. The ionicity
in Sm Te is reduced with decreasing lattice parameter ( ~ increasing pressure) beginning with
acharge transfer of 0.23 electrons at a = 6.594 A to 0.17 electrons at a = 6.194 A according
to calculations by Farberovich [9].
References:
[1] A. landelli (Z. Anorg. Allgem. Chem. 288 [1956]81/6).
[2] A. landelli (Proc. 1st Conf. Rare Earth Res., Lake Arrowhead, Calif., 1960 [1961],
pp. 135/41).
[4] M. Campagna, E. Sucher, G. K. Wertheim, L. D. Longinotti (Phys. Rev. Letters 33 [1974]
165/8).
969/76).
[7] G. V. Lashkarev, E. I. Yarembash, A. Karabekov, N. P. Giletskii (Phys. Status Solidi S 44
[1971] K41/K44).
[8] C. J. M. Rooymans (Ser. Sunsenges. Physik. Chem. 70 [1966]1036/41).
[9] 0. V. Farberovich (Fiz. Tverd. Tela [Leningrad]22 [1980]669/79; Soviet Phys.-Solid State
22 [1980] 393/8).
[10] A. Chatterjee, A. K. Singh, A. Jayaraman (Phys. Rev. [3] S 3 [1972]2285/91).
368/70).
30.1.2.10.7.2.4 Mössbauer Spectra

Mössbauer spectra using the 35.5 keV transition of 125Te in SmTe (presumably at 77 K)
showed an isomer shift of 0.85 ± 0.2 mm/s relative to Te0 3 and a quadrupole splitting of
0.5 ± 0.4 mm/s. The values increase with increasing Te content in the series of samarium
tellurides from Sm Te to SmTe 3 , E. I. Yarembash, E. G. Tyurin, A. A. Reshchikova, A. Karabekov,
N. N. Klinaeva (lzv. Akad. Nauk SSSR Neorgan. Materialy 7 [1971] 761/5; lnorg. Materials
[USSR]7 [1971] 661/5). For details see p. 129.
30.1.2.10.7.2.5 Mechanical Properlies
The pycnometric density is 6.51 g/cm 3 , Yarembash, Karabekov [1]. The microhardness is
(320 to 325) · 107 Pa, Aliev et al. [2].
Gmetm Handbook
RE Main Vot. C 10
Sm Te 135
0.00
0.04
0.12
.\
~
\
>
0
::: 0.20
<l
""'- ~ _.
I
t
I
0.28
I
~
50 100 150
p in kbar
Fig. 59. Pressure-volume diagram of SmTe .
The p-V data (Fig. 59) of SmTe from room temperature lattice parameters show a normal
behavior at low pressures, initial compressibility K = 25 x 10- 4 kbar - 1 ( ~ 2.5 x 10- 11 Pa - 1) ,
Chatterjee et al. [3], i. e. , the bulk modulus 1/K = K0 = 400 ±50 kbar ( ~ 40 GPa), Jayaraman
et al. [4) . The anomalously large compression between 20 and 60 kbar gives a volume change
/1V!V0 = -24% at 100 kbar. At 110 ± 10 kbar a second phase with different crystal structure
(CsCl type) is formed with /1V!V = -9.1% at the transformation; see p. 132, (3, 4], Singh et
al. [5] . These p-V data arealso reported and discussed in Jayaraman et al. [7, 8], Jayaraman
[9, 10). A transition pressure of 130 kbar and a relative volume decrease of 9% is mentioned
by Syassen [6) . Earlier data of Rooymans [11) showing a discontinuous isostructurallattice
collapse of Sm Te could not be confirmed. The splitting of the compressibility of the NaCl type
phase into the normal and the extra, electronic part gives l!..V!V0 = -11 ± 1.0% due to the
latter. The transformation of all samarium ions into the trivalent state would yield -16.6%
[3).
A simple model is discussed in which the relative volume at the transition VIV 0 is estimated
from the separation E9 between the 4f states and the conduction band , the pressure coefficient,
and the bulk modulus K0 . For Sm Te, VIV0 = 0.85 at E9 ----> 0 has been calculated [3, 4]. Within
an ionic model of the behavior of SmTe, the valence instability of Sm is introduced by an
anomalous compressibility for the Sm cation, which is assumed tobe identical in all samarium
monochalcogenides. Narayan, Ramaseshan [12] . The elastic properties of samarium mono-
chalcogenides usually are calculated within the framework of the intermediate valency state.
For a survey on theoretical models , see "Rare Earth Elements" C7, 1983, pp. 304/16. p-V
diagrams for SmTe within the Falicov-Kimball model have been derived, Alascio, L6pez [13],
including intraatomic excitonic correlation, Schweitzer [14), and allowing also for hybridization
between localized states and the conduction band , Kanda et al. [15] . Calculations based on
the Anderson model are given by Anderson, Chui [16], within the virtual bound state approach
by Ghatak, Avignon [17], and based on the essentially localized model by Mahanti et al. [18,
19], and similarly by lwamatsu [20] . A one-dimensional periodic Anderson Hamiltonian is also
used by Fuchikami, lshioka [21) (cf. pp. 143/4) to calculate the elastic and other physical
properties of SmTe .
Gmelin Handbook
RE Main Vol. C10
References:
[1] E. I. Yarembash, A. Karabekov (Tr. Frunz. Polytekhn. lnst. No. 41 [1970]49/63, 52).
[2] 0. M. Aliev, 0. A. Alieva, P. G. Rustamov (Zh. Neorgan. Khim. 30 [1985] 2714/7; Russ. J.
lnorg. Chem. 30 [1985]1547/9).
[3] A. Chatterjee, A. K. Singh, A. Jayaraman (Phys. Rev. [3] B 6 [1972] 2285/91).
[4] A. Jayaraman, A. K. Singh, A. Chatterjee, S. Usha-Devi (Phys. Rev. [3] B 9 [1974]
2513/20).
[7] A. Jayaraman, A. K. Singh, A. Chatterjee (Proc. 9th Conf. Rare Earth Res., Blacksburg,
Virg., 1971, Vol. 1, pp. 360/360i).
[8] A. Jayaraman, P. D. Dernier, L. D. Longinotti (High Temp. High Press. 7 [1975]1/28).
[9] A. Jayaraman (in: K. A. Gschneidner Jr., LeRoy Eyring, Handbook on the Physics and
Chemistry of the Rare Earths, Vol. 2, North-Holland, Amsterdam 1979, p. 575/611 ).
[10] A. Jayaraman (Comments Solid State Phys. 7 [1977]135/48).
[12] R. Narayan, S. Ramaseshan (J. Phys. C 14 [1981]211/27).
[13] B. Alascio, A. L6pez (Solid State Commun. 14 [1974] 321/5).
[14] J. W. Schweitzer (Phys. Rev. [3] B 17 [1978] 758/64).
[15] K. Kanda, K. Machida, T. Matsubara (Solid State Commun. 19 [1976]651/4).
[16] P. W. Anderson, S. T. Chui (Phys. Rev. [3] B 9 [1974] 3229/36).
[17] S. K. Ghatak, M. Avignon (Valence lnstab. Relat. Narrow-Band Phenom. Proc. Intern.
Conf., Rochester, N.Y., 1976 [1977], pp. 229/46).
[18] S. D. Mahanti, T. A. Kaplan, M. Barma (J. Appl. Phys. 49 [1978] 2084/9).
[19] S. D. Mahanti, T. A. Kaplan, M. Barma (Phys. Letters A 58 [1976] 43/5).
[20] M. lwamatsu (Phys. Letters A 81 [1981] 515/8).
[21] N. Fuchikami, S. lshioka (J. Phys. C 18 [1985]319/43).
30.1.2.1 0. 7 .2.6 Thermal Properlies
The thermal expansion of SmTe, determined on a small sintered rod between 50 and
1 000°C, is linear with temperature. Above 800°C the expansion coefficient is reduced. Fora
plot of ßUl vs. T, see the paper, Rooymans [1].
SmTe melts at 1860 ± 50°C, Yarembash et al. [2], Yarembash, Karabekov [3], Yarembash,
Eliseev [4]; seealso Aliev et al. [5], between 1910 and 1930°C, Miller et al. (6]. The atomiza-
tion enthalpy of solid SmTe at 0 K is ßH~ = 189 ± 4.3 kcaUmol, derived from mass spectro-
metric studies using Knudsen effusion cells. The Sublimation enthalpy at 0 K is
ßH~ = 125.0 ± 6.5 kcal/mol, Nagai et al. [7]. The thermal conductivity at 300 K is
2.6 x 10- 3 cal· cm- 1 · s- 1 · K-1, Tyurin [8]. The Debye temperature 0 0 = 151 ± 20 K was
derived from X-ray diffraction experiments at room temperature, Subhadra, Sirdeshmukh [9].
References:

[2] E. I. Yarembash, E. G. Tyurin, A. A. Reshchikova, A. Karabekov, N. N. Klinaeva (lzv. Akad.
Nauk SSSR Neorgan. Materialy 7 [1971]761/5; lnorg. Materials [USSR]7 [1971]661/5).
[3] E. I. Yarembash, A. Karabekov (Tr. Frunz. Polytekhn. lnst. No. 41 [1970]49/63, 52).
Gmel1n Handbook
RE Ma1n Vol. C 10
Sm Te 137

Moscow 1975, pp. 1/260, 202; C.A. 83 [1975] No. 125545).
[5] 0 . M. Aliev, 0. A. Alieva, P. G. Rustamov (Zh . Neorgan. Khim . 30 [1985]2714/7; Russ. J.
lnorg. Chem. 30 [1985]1547/9) .
(6] J . F. Miller, F. J. Reid, L. K. Matson, J . W. Moody, R. D. Baxter, R. C. Hirnes (AD-607082
[1964]1/79, 11; C.A. 62 [1965]15562).
(7] S.-1. Nagai, M. Shinmei , T. Yokokawa (J. lnorg . Nucl. Chem. 36 [1974]1904/5) .
[8] E. G. Tyurin (Diss. Moscow 1971 from I. A . Smirnov, Phys. Status Solidi A 14 [1972]
363/404, 392).
[9] K. G. Subhadra, D. B. Sirdeshmukh (Pramana 9 [1977] 223/7).
30.1.2.10.7.2.7 Magnetic Properlies

Semiconducting Sm Te with divalent Sm has a nonmagnetic ground state (F0 ) . Admixtures
of the first excited state (7F1) give rise to Van Vleck paramagnetism.
Magnetic Susceptibility. Dependence on Pressure and Temperature

The molar magnetic susceptibility at room temperature is Xmot (in 10- 3 cm 3/mol) = 4.292,
landelli [1, 2], 4.0, Lashkarev et al. [3], or 3.94, Yarembash et al. [4], Karabekov et al. [5]. The
susceptibility at room temperature shows just a weak (compared to SmSe or SmS) pressure
effect up to 18 kbar with dx/dp = 2.2 x 10- 6 cm 3 · mol - 1 · kbar-1, the x versus p curve flattens
out at ~ 15 kbar, Maple, Wohlleben [6]. Calculations within the molecular field approximation
give dx/dp = (0 ± 3) x 10- 6 cm 3 · mol - 1 · kbar- 1 assuming the distance dependence of the
exchangetobe the sole mechanism contributing to dx/dp, Birgeneau et al. [7]. The tempera-
ture dependence of Xmot at ambient pressure between 1.4 and 400 K is shown in Fig. 60. Below
~ 100 K the susceptibility becomes nearly constant. The low-temperature upturn is ascribed
to Sm3+ ( ~ 3% at most) but may at Least partially arise from Eu 2 + impurities as well, Sucher
et al. [8]. These data appear as consistent with x(T) measurements on powdered samples
between 80 and 300 K giving llett = 2.83 · (Xmot· T) 112 = 3.07 lls at 293 K. The temperature
dependence of lleff for Sm Te and other samarium tellurides is shown in Fig. 71, p. 156,
Lashkarev et al. [3] . Older measurements between 100 and 500 K showed x- 1 proportional
to T above ~ 193 K with a paramagnetic Curie temperature SP = -248 K for T = 193 to
Temperature in K
Fig . 60. Magnetic susceptibility of SmTe versus temperature.

Gmelm Handbook
RE Main Vol. C 10
473 K. Between 193 and 143 K minor antiferromagnetic deviations from the straight Line occur,
landelli [1, 2]. The value eP
= -180 K was derived from measurements between 4.2 and
80 K by Busch et al. [9]. Foraplot of x- 1 versus T between room temperature and 1400 K of
a (possibly decomposing) SmTe sample, see Rooymans [10].
Van Vleck Susceptibility. Exchange Intersetions
A calculated x versus T curve based on Van Vleck behavior and adjusting the spin-orbit
splitting ~ between the 7 F0 and 7 F1 states to the low temperature Limit of Xmol (without consider-
ing exchange effects), reproduced the data of Fig. 60, p. 137, to within 1%. The Van Vleck
susceptibility Xvv = 7.15 x 10- 3 cm 3/mol at 0 K has been obtained also allowing for
diamagnetism and attributing the low temperature rise solely to Sm3+ [8]. A reanalysis of the
x(T) data gave Xvv = 7.00 x 10- 3 cm 3/mol at 4.2 K and a Sm-Sm exchange interaction LZ 1J 1 =
I
+1.6±1 K (~8·Lz 1 J; = 12.8K ~ 1.1 meV) taking the spin-orbit splitting ~ = 415±6K
I
( ~ 35.8 ± 0.5 meV) [5]. The deviation of the observed from the calculated static Van Vleck
susceptibility Xcatc = 7.55 x 10- 3 cm 3/mol at 0 K has been attributed to covalency effects [11].
The exchange parameter 8 ( = 8 LZ;J 1) = 8 cm - 1 ( ~ 11 K ~ 0.95 meV) was derived from
I
optical (Raman and IR) investigations using the Sm2+ free ion value ~ = 293.5 cm- 1
( ~ 422 K ~ 36.4 meV), Nathan et al. [12], and more recently cited as 16 J(O) = 2.0 meV
( ~ 23 K), by Birgeneau, Shapiro [11]. The decrease in the Sm-Sm couplings in SmS, SmSe,
and SmTe is related to the decreasing admixture of the d states due to the increase of the
4f 6-4f 5 5d gap [ 12].
For exchange interactions between impurity ions and Sm 2 +, see pp. 154/5.
References:
[1] A. landelli (Atti Acad. Nazl. Lincei Classe Sei. Fis. Mat. Nat. Rend. [8] 30 [1961] 201/7;
C.A. 56 [1962]1 041).
[2] A. landelli (Proc. 1st Conf. Rare Earth Res., Lake Arrowhead, Calif., 1960 [1961],
pp. 135/41).
[3] G. V. Lashkarev, E. Yarembash, A. Karabekov, N. P. Giletskii (Phys. Status Solidi B 44
[1971] K41/K44).
661/5).
pp. 68/72; C.A. 80 [1974] No. 75371).
[6] M. B. Maple, D. Wohlleben (Phys. Rev. Letters 27 [1971]511/5).
[7] R. J. Birgeneau, E. Sucher, L. W. Rupp Jr., W. M. Walsh Jr. (Phys. Rev. [3] B 5 [1972]
3412/8).
[9] G. Busch, P. Junod, M. Risi, 0. Vogt (Proc. Intern. Conf. Phys. Semicond., Exeter, Engl.,
1962, pp. 727/31).
[11] R. J. Birgeneau, S. M. Shapiro (Valence lnstab. Relat. Narrow-Band Phenom. Proc. Intern.
Conf., Rochester, N.Y., 1976 [1977], pp. 49/60, 53; BNL-22138 [1976] 1/11, 4/5; C.A. 88
[1978] No. 15131).
[12] M. I. Nathan, F. Holtzberg, J. E. Smith Jr., J. 8. Torrance, J. C. Tsang (Phys. Rev. Letters
34 [1975]467/9).
Gmelm Handbook
RE Mam Vol. C10
SmTe 139
30.1.2.1 0.7 .2.8 Electrical Properlies

30.1.2.1 0. 7 .2.8.1 Electronlc Structure
lntroduction
ln principle the energy band structure of SmTe is analogous to those of SmS, EuS, or
SmSe (see "Rare Earth Elements" C7, 1983, pp. 252, 459, and C9, 1986, p. 146, respectively).
The valence band is formed by the tellurium 5p states, and the conduction band is derived
from the 5d and 6s states of samarium. By the octahedral crystal field the 5d states split into
the triply degenerate t 29 (lower) and doubly degenerste e9 states (higher), forming subbands.
At ambient conditions the 41 states are localized or assumed to form a narrow band within
the gap between valence and conduction band. With increasing pressure the conduction band
broadens and the gap E9 to the 41 band closes. Hybridization of 4f with 5d states delocalizes
a previously localized electron giving metallic properlies to the high-pressure SmTe.
Band Structure of Low-Pressure SmTe (NaCLType)

General Features
The band structure of semiconducting SmTe shown in Fig. 61 has been calculated, using
the augmented plane wave (APW) method. The crystal potential Vc,(r) was simulated by muffin
tin potentials and the Xa approximation with a. = 0.67 was used for the exchange contribution
to the crystal potential. The atomic wave functions were derived in the Hartree Fock Slater
approximation. A conliguration 415 ·5 5d 0 ·5 (instead of 416 ) was used for Sm. The energy
eigenvalues were calculated with an accuracy of 0.001 Ry ( ~ 13.6 meV). The band structure
1.0
Fig. 61 . Band structure of semiconducting SmTe (NaCl type).

Gmelin Handbock
RE Main Vol. C 10
calculation shows the broad valence band (width 9.69 eV) to be composed of a fairly strongly
localized s-like subband (width 0.79 eV) derived from the Te 5s states at the bottarn and of a
p-like subband (width 1.89 eV) from the Te 5p states at the top. The conduction band minimum
is at the X point (representation X3 ) and is derived from d states. The f-band is obtained within
the forbidden zone between the conduction and the valence band rather close to the Latter.
Some energy parameters (E0 ) are given in the table on p. 141, Farberovich [1]. Recently
similar band structure calculations were carried out by Caldas et al. [21], using the X"
approximation with cx = 0.71; for a figure see the paper (double group notation, considering
spin orbit coupling). Below the valence band mainly s-type states were found from the Sm
and Te atoms. Next there are the p states from Te as weiL as from Sm atoms going into the
Low-Lying valence bands, starting at r 7 - and rsat the center of the Brillouin zone. The
conduction bands are primarily composed of hybridized 5d-6s states of Sm. The Lowest Lying
conduction band is d-Like, occurring at X7+. Also p-f admixtures and s-like states were found
in the conduction band. The top of the f-band occurs at the zone center at rsat 0.30 Ryd
[21].
Similar results regarding the sequence and the character of the bands were obtained
within a tight binding model and from optical data which showed the 4f states in the Sm2+-
monochalcogenides to be between the top of the valence band (Te 5p) and the bottarn of the
5d (t29 ) conduction band at an energy about 1.5 eV higher than in the Eu 2 + chalcogenides,
Batlogg et al. [2] (see Fig. 58, p. 147 in "Rare Earth Elements" C9, 1986). Also the reflectivity
and electroreflectivity spectra (see p. 151) were explained by a band structure comprising a
p-like upper edge of the valence band and a d-Like bottarn of the conduction band, Kurita et
al. [3]. Differently, a spherically symmetric bottarn of the conduction band (due tos character)
was assumed in the interpretation of piezoresistance and piezo-Hall effect measurements in
Sm monochalcogenides, Vinogradov et al. [4]. An earlier and probably outdated band structure
calculation along the r-X, r-L, and r-K directions (for the diagrams see the paper) had shown
the f-states below the valence band, Davis [5].
Gap Energies
The gap between the valence band and the f band (0.30 eV) is smaller compared to SmS
and SmSe Leading to a stronger interaction between states of appropriate symmetry (r15 );
therefore the f band is broadened and a considerable amount of p character is admixed [1].
Photoemission spectra (XPS) show the valence band maximum between 3 and 4 eV below
the Fermi Level EF (see p. 153), Campagna et al. [6].
The energy gap E9 between the f- and the conduction band (indirect gap r, 5 (f)-X 3 =
0.52 eV) is comparable tothat of SmSe [1]. The value is consistent with the energies observed
for the absorption edge: 0.62 ± 0.02 eV, Jayaraman et al. [7], 0.70 ± 0.03 eV, lvanchenko et
al. [8] (see p. 149). Later 0.70 eV for the 41 to conduction band edge separation was reported
also by Jayaraman et al., see for example [9, 10]. E9 = 0.60 eV [7] and 0.76 eV, Zhuze et al.
[11], was derived from the pressure and the temperature dependence, respectively, of the
electrical resistivity; seealso p. 145 for E9 values of Yarembash et al. [12]. E9 = 0.63 eV was
inferred from a model for SmTe based on the anomalaus compressibility curve of the Sm2+
ion (see p. 135), Narayan, Ramaseshan [13]. The band structure calculations of Caldas et al.
x
[21] gave a direct gap of 1.0 eV between 7 - and X7+ and a value 0.67 eV for the indirect gap
between X7+ and rs-, in good agreement with the experimental values for E9 .
The f-d band gap at the X point X5(f)-X3 = 1.09 eV [1]. The p-d band gap (indirect, edge-
to-edge) was calculated as 1.89 eV [1]. The observed minimum direct valence-to-conduction
band gap at the X point and the next at the r point ( ~ 3 and ~ 4.4 eV, respectively, see pp. 150/1),
Kurita et al. [3], are in qualitative agreement with the APW calculation (1.088 and 3.597 eV,
Gmelon Handbook
RE Maon Vol. C10
Sm Te 141
respectively) by [1], whereas no indication was found in the experiments [3) for a predicted
[1) third conduction band minimum at the K point connected with a direct gap with a magnitude
comparable tothat at the r point [3). A peak-to-peak separation p-5d(t29 ) = 4.6 eV was given
by Batlogg et al. [2). The p-d band gap = 2.3 eV in amorphaus SmTe was deduced from the
optical transmissionofthin films, Lashkarev, lvanchenko [14), lvanchenko et al. [8], Lashkarev
et al. [15] (see p. 151).
The crystal field splitting t29 -e 9 of the 5d band, 10 Dq = 1.6 eV [2], Suryanarayanan et al.
(16], was obtained from optical density and reflectivity measurements (see p. 151). An earlier
(possibly erroneous [16)) interpretation of the optical absorption spectrum resulted in 10 Dq =
0.62 eV [17) . For the energies of the 4f 5 5d 1 derived multiplet states, see p. 151.
Pressure Dependence of the NaCL Type Electronic Structure
The pressure-induced change of the electronic structure at the continuous semiconductor-

to-metal transition (SMT) of SmTe has been calculated with the APW method (see p. 139)
using decreasing lattice constants for increasing pressure. (The change from a = 6.594 to
6.194 Ais equivalent to a volume reduction VIV0 = 0.83.) As the lattice parameter decreases,
one finds a reduced ionicity associated with an increase of the metallic component of the Sm-
Te band. The change of the energies of the various Levels with the lattice parameter (see
Fig. 62) follows the relation E; = E0 + V (a 0 - a,) with the following coefficients (a 0 = 6.594Ä):
state
E0 in eV 1.972 2.258 2.312 2.761 3.332 3.849 5.569 6.406 6.453

V in eV/Ä 4.1 ~8 ~9 ~7 ~8 1.9 2.8 5.8 3.6
The differing dependences on the lattice parameter give a closing (at a rate of 2.9 eV/Ä)
r
of the indirect gap ( ~ E9 ) between the 15 (f) and the X3 states [1). Simple closing of the
valence-to-conduction band gap had been said to cause the pressure-induced semiconductor
to metal transition in the (presumably outdated) band structure calculation of Davis [5]. The
calculated volume reduction VIV0 = 0.92 ( ~ a = 6.415 Ä) at E9 = 0 [1) has tobe compared
with the experimental VIV 0 = 0.85 ( ~ a = 6.246 Ä) at E9 = 0, Jayaraman et al. [9).
o.?sr-r----,---.,..--.,..----,-----,
06.594 6~94 6394 6.294 6.194 6.094

a in A
Fig. 62. Energy shifts of the electronic states in semiconducting Sm Te (NaCL type) with change
of the lattice constant a.
Gmelm Handbook
RE Mam Vol. C 10
The lattice parameter dependence of the gap dE9 /da has been transformed to the pressure
dependence dE9 /dp = - 15.9 meV/kbar [1) using the experimental initial bulk modulus K0 =
400 kbar C~ 40 GPa) from [18]. dE9 /dp = - 11 .9 meV/ kbar was obtained from the resistivity
vs . pressure curve of Jayaraman et al. [7) . The deformation potential is given as l: =
[dE 9 /dp] · K0 = - 4.7 eV, Jayaraman et al. [9] . From their model, Narayan, Ramaseshan [1 3)
calculate dEgfdp = -6.6 meV/ kbar (compare p . 135).
The direct f-d gap (X3 -X5) becomes zero (onset of hybridization ) at a = 6.205 A. Th is
X5-X3 band crossing occurs at a larger relative change of the lattice parameter in SmTe
compared to SmSe and SmS due to the stronger p-f band interaction and the f band broadening .
This is thought to favor a transition into another crystal structure at high pressure with a b road
hybridized f-d band [1) (see below). For the pressure dependence of the energy Ievels from
optical spectra, Vedam, Kirk [19), Syassen [20], see p. 152.
Band Structure of High-Pressure SmTe (CsCL Type)

lt was interred that the p-d band gap becomes d irect at the NaCl-CsCl type transition from
a discontinuous red shift of the reflectivity edge at the transition. CsCl type Sm Te is expected
tobe close to a valence-to-conduction band overlap at 150 kbar from comparison with proper-
lies of high-pressure CsCl type SrTe, Syassen [20] . The band structure for SmTe in the CsCl
structure type with lattice parameter a = 3.656 A is shown in Fig. 63, calculated with the APW
method (see p. 139). The main differences from the band structure of NaCl type SmTe are the
broaden ing of the s a nd p subbands of the valence band (by 2.80 and 4.26 eV, respectively)
and the mixing of almost all the d states with the f band . The minimum of the f-d band lies at
r
the and X points. SmTe in the CsCl type modification is expected to be more metallic th an
the NaCl type high-pressure phase, Farberovich [1).
1.0
Q8
0.6
~
.5:
-•l'~
-0.7 R A r ll X
Fig . 63. Band structure of high-pressure SmTe (CsCl type) .

Gmelon Handbook
RE Mam Vol. C 10
Sm Te 143
References:
[1] 0. V. Farberovich (Fiz. Tverd. Tela [Leningrad]22 [1980]669/79; Soviet Phys.-Solid State
22 [1980] 393/8).
[2] S. Satlogg, E. Kaldis, A. Schlegel, P. Wachter (Phys. Rev. [3] S 14 [1976] 5503/14).
[3] A. Kurita, Y. Kaneko, T. Koda (Solid State Commun. 49 [1984] 463/6).
[4] A. A. Vinogradov, S. I. Grebinskii, V. V. Kaminskii, N. N. Stepanov, et al. (Fiz. Tverd. Tela
[Leningrad] 26 [1984] 402/8; Soviet Phys.-Solid State 26 [1984] 240/3).
[5] H. L. Davis (Proc. 9th Rare Earth Res. Conf., Slacksburg, Va., 1971, Vol. 1, pp. 3/14).
165/8).
368/70).
[8] L. A. lvanchenko, G. V. Lashkarev, Yu. S. Paderno, S. V. Drozdova, V. A. Obolonchik, et
al. (Ukr. Fiz. Zh. 16 [1971]510/2; Ukr. Phys. J. 16 [1971]624/7).
[9] A. Jayaraman, A. K. Singh, A. Chatterjee, S. Usha Devi (Phys. Rev. [3] S 9 [1974]
2513/20).
[10] A. Jayaraman (Proc. 11th Rare Earth Res. Conf., Traverse City, Mich., 1974, Vol. 2,
pp. 830/9, 839).
[11] V. P. Zhuze, A. V. Golubkov, E. V. Goncharova, V. M. Sergeeva (Fiz. Svoistva Poluprov.

A-111 S-V A-111 S-VI Mater. Vses. Konf., Saku 1965 [1967], pp. 326/30; C.A. 70 [1969]
No. 42126).
661/5).
[13] R. Narayan, S. Ramaseshan (J. Phys. C 14 [1981]211/27).
[14] G. V. Lashkarev, L. A. lvanchenko (J. Non-Cryst. Solids 8/10 [1972] 670/5).
[15] G. V. Lashkarev, L. A. lvanchenko, Yu. S. Paderno, S. V. Drozdova, V. A. Obolonchik
(Redkozemel. Metal. Splavy Soedin. Mater. 7th Soveshch., Moscow 1972 [1973], pp.
303/4; C.A. 81 [1974] No. 18806).
[16] R. Suryanarayanan, C. Paparoditis, J. Ferre, S. Sriat (J. Appl. Phys. 43 [1972]4105/8).
[18] A. Chatterjee, A. K. Singh, A. Jayaraman (Phys. Rev. [3] S 6 [1972]2285/91).
[19] K. Vedam, J. L. Kirk (Proc. 11th Rare Earth Res. Conf., Traverse City, Mich., 1974, Vol. 2,
pp. 840/4).
[21] A. Caldas, C. A. Taft, H. N. Nazareno (J. Phys. C 19 [1986]3615/8).
30.1.2.1 0. 7 .2.8.2 Theoretical Models on the Valence lnstability
Surveys of the models used to describe the valence instability in Sm chalcogenides are
given in "Rare Earth Elements" C7, 1983, pp. 304/16, or for example by Suryanarayanan [1].
Most of the theoretical models are able to describe the continuous or discontinuous
semiconductor-to-metal transition (SMT). Within an extended Falicov-Kimball model including
hybridization, Kanda et al. [2] calculated the electron occupation number at T = 0 K of the
Gmelin Handbook
RE Main Vol. C10
conduction band as a function of the Localized Level. The SMT becomes continuous when the
mixing interaction is Large. The transition type is also influenced by the attraction between
the conduction electrons and the Localized holes [2]. Essentially the same model was dis-
cussed earlier by Gon<;:alves da Silva, Falicov [3] and Avignon, Ghatak [4]. Comments on
these papers are given in [2]. For an extended Falicov-Kimball model, seealso Alascio, L6pez
[5]. The Falicov-Kimball model without hybridization has also been extended to include
intraatomic excitonic correlation, Schweitzer [6]; seealso [7, 8]. The indirect exchange interac-
tion between f- and conduction electrons was introduced into the Ramirez-Falicov-Kimball
model with hybridization. lt was found to influence the order of the SMT, Porras-Montenegro
[9]. ln a recent paper of Hammoud et al. [22] the f-d hybridization is treated in a variational
method to describe the Local mixed valence state in the semiconducting phase.
Within the Anderson model, Anderson, Chui [10] treat Sm2+ and Sm3+ ions as impurities
of highly different size in an anharmonically elastic medium. The type of the SMT, first-
order or gradual, is determined from the sign (negative, attractive or positive, repulsive,
respectively) of the dominant term beyond the Linear one [10].
The number of holes nh in the f band has been calculated by Ghatak, Avignon [11], using
the Anderson model with hybridization in the virtual bound state approach with a Linear
relation between the variation in the Lattice parameter reflecting the volume and the average
valence. The plots of 1/nh versus pressure are similar to the observed resistivity versus
pressure curves [11]. The essentially Localized model (ELM) is based on the Localized picture
(two electron excitations at two neighboring sites) and incorporates the Lattice energy and the
descent of the conduction band with pressure, Mahanti et al. [12, 13]. The variational wave
function of the ELM has been used for the periodic Anderson type model Hamiltonian,
lwamatsu [14]. A variational ground state of samarium monochalcogenides has been investi-
gated using a one-dimensional periodic Anderson Hamiltonian. The f orbitals on one site
were taken to be mixed with d orbitals on neighboring sites rather than on the same site,
Fuchikami, lshioka [20]. ln an excitonic model related to ELM, the order of the SMT is
determined by the gap size, the exciton coupling with the Lattice, and the dipole-dipole
interaction between f-d excitons, which itself is reduced at increased Lattice parameter in the
Sm monochalcogenide series, Druzhinin [15]. The model for the pressure-induced SMT at
T = 0 of Barabanov, Tsvelik [16] includes Coulomb repulsion of 4f electrons at a single site
and hybridization of the 4f electrons with the electrons of the s-type conduction band. lt uses
a modified Anderson Hamiltonian. ln this model, the observed gap follows directly from the
hybridization. The order of the SMT is determined by the hybridization constant, the s-f
repulsion parameter, and the width of the conduction band [16]. The interaction between the
Sm valence fluctuation and Lattice vibrations was studied by Kuroda, Bennemann [17]. A
simple ionic modelwas proposed for MX with M = Sm, Eu, Yb, and X = S, Se, Te by Dagys,
Anisimov [18], based on the complete transfer of the 6s 2 electrons of the Lanthanide ion to the
chalcogenide. The authors postulate a spherical symmetry component of the Hartree-Fock
potential for the inner electrons of M which is approximately the same as for a free neutral
atom; see also Anisimov, Dagys [19]. The ionic model of Narayan, Ramaseshan [21] was
mentioned already on p. 135.
References:
[1] R. Suryanarayanan (Phys. Status Solidi B 85 [1978] 9/43).

[2] K. Kanda, K. Machida, T. Matsubara (Solid State Commun. 19 [1976] 651/4).
[3] C. E. T. Gon<;:alves da Silva, L. M. Falicov (Solid State Commun. 17 [1975]1521/4).
Gmeltn Handbook
RE Ma1n Val. C 10
Sm Te 145
[4] M. Avignon, S. K. Ghatak {Solid State Commun. 16 [1975]1243/6).

[5] B. Alascio, A. L6pez {Solid State Commun. 14 [1974] 32115).
[6] J. W. Schweitzer {Phys. Rev. [3] 8 17 [1978] 758/64).
[7] J. W. Schweitzer {Collect. Eff. Condens. Media 14th Winter School Theor. Phys., Karpacz,
Pol., 1977 [1978], Vol. 2, pp. 31/70).
[8] J. W. Schweitzer {J. Appl. Phys. 49 [1978]2090/2).
[9] N. Porras-Montenegro {Phys. Letters A 97 [1983] 202/6).
[10] P. W. Anderson, S. T. Chui {Phys. Rev. [3] 8 9 [1974] 3229/36).
[11] S. K. Ghatak, M. Avignon {Valence lnstab. Relat. Narrow-Band Phenom. Proc. Intern.
Conf., Rochester, N.Y., 1976 [1977], pp. 229/46).
[12] S. D. Mahanti, T. A. Kaplan, M. Barma {Phys. Letters A 58 [1976]43/5).
[13] S. D. Mahanti, T. A. Kaplan, M. Barma {J. Appl. Phys. 49 [1978] 2084/9).
[14] M. lwamatsu {Phys. Letters A 81 [1981] 515/8).
[15] A. A. Druzhinin {Pis'ma Zh. Eksperim. Teor. Fiz. 32 [1980] 596/9; JETP Letters 32 [1980]
582/5).
[16] A. F. Barabanov, A. M. Tsvelik {Zh. Eksperim. Teor. Fiz. 76 [1979] 558/65; Soviet Phys.-
JETP 49 [1979] 281/4).
[17] Y. Kuroda, K. H. Bennemann {Phys. Rev. [3] B 23 [1981]4114/21).
[18] R. S. Dagys, F. G. Anisimov {Fiz. Tverd. Tela [Leningrad]26 [1984]899/901; Soviet Phys.-
Solid State 26 [1984] 547/8).
[19] F. G. Anisimov, R. S. Dagys {Lietuvos Fiz. Rinkinys 25 [1985] 14/21; C.A. 102 [1985]
No. 22624).
[20] N. Fuchikami, S. lshioka {J. Phys. C 18 [1985] 319/43).
[21] R. Narayan, S. Ramaseshan {J. Phys. C 14 (1981]211127).

[22] Y. Hammoud, J. C. Parlebas, F. Gautier {J. Phys. C 18 [1985] 6603/14).
30.1.2.1 0.7 .2.8.3 Electrical Conductivity

At Ambient Pressure
At ambient conditions stoichiometric SmTe is a p-type semiconductor as shown by
thermoelectric, Yarembash et al. [1], Karabekov et al. [2], Vinogradov et al. [3], and
magnetoelectric measurements [3]; see p. 147. The type of conductivity is influenced by the
actual sample composition [1, 2] and also n-type conductivity at room temperature has been
observed, Zhuze et al. [4].
Room temperature conductivities K ~ 3 X 10- 4 n- 1 • cm- 1 { ~ Q ~ 3.3 X 103 n. cm)
for pressed sintered samples of Sm Te [1, 2], Q = 2 x 103 n · cm for Sm Te cast ingots, Reid
et al. [5], consistent with results of Zhuze et al. [4], and for single crystalline samples
Q ~ 103 Q · Cm, Jayaraman et al. (6], K = 2.1 X 10- 4 Q- 1 · Cm- 1 {~ Q = 4.8 X 103 Q · Cm) (3].
The resistivity of Sm Te films on CaF2 or glass substrates is about 103 n · cm, Suryanarayanan
et al. [7].
The temperature dependence of the conductivity K and the thermoelectric power S is

shown in Fig. 64a, b, p. 146, for powdered SmTe. The K versus 1/T plot is explained by two
ranges of different behavior showing that SmTe is not a simple semiconductor: between
room temperature and 570 K with an activation energy EA = 0.38 eV assuming K =
K 0 exp {- EA/kT), and from 570 to 1 000 K with EA = 0.73 eV assuming K = K 0 exp {- EA/2 kT).
The carrier concentration is supposed to change only slightly in the temperature range
studied. Above 570 K samarium is supposed to be present completely as Sm3+ [1, 2]. Earlier
Gmelin Handbock 10
RE Main Vol. C10
Tempereture in K
1000 500 333 285
10
a)
1 \.....
Temperoture in K
~ 1000 500 333 285
"'
b: 10-
.!: 50 - b)
,--A
3 >~
10
~
"b. .!: -10
.."
1Ö
111
-50 V
Q5 1.5 2.5 3.5
2 3 3.5
1000/T in K- 1 1000/T in K- 1
Fig . 64. Electrical conductivity K (Fig . 64a) and thermoelectric power S (Fig . 64b) of powdered
Sm Te .
a log K versus 1/T plot was given by Zhuze et al. [4] for two SmTe samples in the same
temperature range w ith EA = 0.76 eV below ~ 600 K. A carrier activation energy of ~ 0.35 eV
(temperature range not given) is reported by [6]. Strongly differing values of Q measured on
bulk SmTe samples between 296 and 862 K with pressure contacts are reported by Miller et
al. [8].
Pressure Dependence
The pressure dependence of Q at room temperature (see Fig. 65) and the temperature
dependence of Q at different pressures are compared with optical data. A proposed model
shows the 4f Level 0.62 ± 0.02 eV and a trap Level 0.38 ± 0.02 eV below the conduction band.
05 '\
',\
\
'
"'u~
E
u
C:
.!:
a.
0
'~
"
1ö'
0"3 ~
~
0-f.
0 20 40 60
pinkbar
Fig. 65. Electrical resistivity Q of SmTe at room temperature versus pressure.

Gmetm Handbook
RE Main Vot. C 10
Sm Te 147
The gap closes with increasing pressure. This behavior shows the Fermi Level EF to be
essentially locked to the 4f Level, Jayaraman et al. [6]. The high-pressure resistivity (50 to
60 kbar) of SmTe is (3 to 4) x 10- 4 Q · cm, Jayaraman et al. [6, 9]. The temperature coefficient
of the resistivity is negative at low pressure but becomes positive at the highest pressure [6].
For the pressure dependence of the activation energy or the energy gap, see p. 141. The
pressure coefficients for hydrostatic pressure below and above 20 kbar are d Ln Q/dp = -0.10
and -0.46 kbar-1, respectively, yielding -2.6 and -11.9 meV/kbar, Jayaraman et al. [6].
The piezoresistance 1tQ = 1/Q · OQ/op was determined for uniaxial pressure along [100] as
n'j 1 = 0.23 x 10- 4 and for hydrostatic pressure as n~ = 0.69 x 10- 4 cm 2 /kp (,~2.34 x 10- 10 and
7.04 x 10- 10 m 2 /N, respectively) [3]; seealso Kaminskii, Smirnov [10].
References:
661/5).
pp. 68/72; C.A. 80 [1974] No. 75371).
[Leningrad] 26 [1984]402/8; Soviet Phys.-Solid State 26 [1984] 240/3).
[4] V. P. Zhuze, A. V. Golubkov, E. V. Goncharova, V. M. Sergeeva (Fiz. Svoistva Poluprov.
A-111 S-V A-111 S-VI Mater. Vses. Konf., Saku 1965 [1967], pp. 326/30; C.A. 70 [1969]
No. 42126).
969/76).
368/70).
[8] J. F. Miller, L. K. Matson, J. S. McNulty, R. C. Hirnes (AD-262215 [1961] 1/49, 34; N.S.A.
16 [1962] No. 15260).
1430/3).
[10] V. V. Kaminskii, I. A. Smirnov (Prib. Sist. Upr. 8 [1985] 22/4; C.A. 103 [1985] No. 170580).
30.1.2.10.7.2.8.4 Magnetoelectric and Thermoelectric Properlies

Measurements of the Hall effect at room temperature indicated positive charge carriers
(in contrast to results on SmS and SmSe and the alloy systems SmS-SmSe, SmS-SmTe) with
a concentration n = 1.2 x 10 16 cm -a and a Hall mobility 1.1 = 0.1 cm 2 · v- 1 · s- 1, Vinogradov et
al. [1].
The thermoelectric power is S = + 26 ~.tV/K at 293 K; it does not change very much
between 293 and 1000 K, yet becomes negative above 570 K. A plot of S versus 1/T for a
powder sample is shown in Fig. 64b [2, 3]. No change of the positive sign of S is reported by
Miller et al. [4] for temperatures up to 862 K:
Tin K . . . . 319 333 485 557 599 862

S in ~.tV/K . . 480 109 120 31 63 17
Gmelin Handbook 10"
RE Main Vol. C10
References:
[Leningrad] 26 [1984]402/8; Soviet Phys.-Solid State 26 [1984] 240/3).
pp. 68/72; C.A. 80 [1974] No. 75371).
[4] J. F. Miller, L. K. Matson, J. S. McNulty, R. C. Hirnes (AD-262215 [1961]1/49, 34; N.S.A. 16
[1962] No. 15260).
30.1.2.10.7.2.9 Optical and Dielectric Properlies
SmTe is gray-black at ambient pressure, landelli [1]. Thin films are described as green in
transmission, Suryanarayanan et al. [2], or yellow-green, Lashkarev, lvanchenko [3].
The following section contains data on electronic spectra restricted to the description of
the solid state properties of SmTe. A more comprehensive treatise on the electronic spectra
of rare earth ions in host crystals will be given in another volume of the Gmelin Handbook.
General
The bands in the optical spectra of semiconducting SmTe in the range from about 0.5 to
6 eV (Labelled by E1 to Es for increasing photon energy) usually have been assigned to
transitions from the 7 F0 (4f 6 ) ground state of Sm 2 + to (4fs5d 1)-derived states analogous to the
spectra of SmS and SmSe (assignment of E4 and Es interchanged relative to SmS). The 5d
states are split by the octahedral crystal field into Lower Lying t 29 and higher e9 states, separated
by 10 Dq. The Coulomb interaction of the 4f electrons partially Lowers the degeneracy of
the 4fs5d 1 configuration giving the sextets 6 H, 6 F, and 6 P, the Latter two being expected,
respectively, at - 1 and -3.25 eV from 6 H, see for example Holtzberg, Torrance [4],
Suryanarayanan et al. [2, 5], Batlogget al. [6], "Rare Earth Elements" C7, 1983, pp. 292/6 and
C9, 1986, pp. 155/9. Recently the bands at hv > 2.5 eV have been proposed to be related
to valence-to-conduction band transitions from comparisons with spectra of alkaline earth
chalcogenides, Kurita et al. [7], Syassen [8]; see p. 151. The bands E1 and E2 had been initially
assigned to transitions to the 5d(t29 ) and 5d(e 9 ) crystal field states of the conduction band,
Sucher et al. [9]. The current assignment is as follows (considering discussion from [2, 5 to
7]):
E1 : 4f 6 (F0 )--> 4fs( 6 HJ)5d(t29 )

E2 : 4f 6 eF 0)--> 4fs( 6 FJ)5d(t29 )
E3 : 4f 6 ( 7 F0 )--> 4fs( 6 HJ)5d(e 9 ) or excitonic p-d transition
E4 : 4f 6 eF0 )--> 4fs( 6 FJ)5d(e 9 ) or excitonic p-d transition
Es: 4f6 eF 0)--> 4fs( 6 PJ)5d(t29 ) or excitonic p-s transition
E6 : excitonic p-s transition
The fine structure of the 4fs multiplets is not experimentally observed in absorption spectra,
presumably due to a d-electron spin-orbit coupling (splitting the t 29 Level) comparable to the
multiplet splitting [4].
Gmelln Handbook
RE Mam Vol C10
Sm Te 149
Raman Spectra
Raman scattering experiments on freshly cleaved SmTe single crystals in agreement with
infrared transmission experiments at temperatures between 6 and 300 K showed a strong
temperature-dependent peak just below 300 cm-1, which is assigned to the J = 0 to J = 1
transition of the 7 FJ ground state multiplet Levels of Sm2+. Many additional transitions in the
spectra with energies up to 2500 cm- 1 are believed to correspond mainly to transitions to
J = 2, 3, and 4 multiplet lines. The temperature dependence of the J = 0 to J = 1 transition
( ~ 285 cm- 1 at 6 K, ~ 290 cm- 1 at 300 K) is well described by the random phase approxima-
tion. A good fit to the experimental data is obtained using the free ion value (293.5 cm- 1) for
the spin-orbit splitting in Sm 2 +, Nathan et al. [1 0]. The values given compare to ~ 250 cm - 1
derived from magnetic circular dichroism [2]; see p. 152. Below 250 cm- 1 strong phonon
absorption limited the Raman studies [10].
Absorption and Reflection Spectra
Ranges and Methods
Data on the ranges of the spectra and the conditions of investigations are compiled in the
following table. Abbreviations: abs = absorption, refl = reflection, cryst = single crystal,
am = amorphous, fi = film on supporting substrate, rt = room temperature.
rangein eV Tin K conditions Ref.
~ 0.083 to 0.7 300 abs, cryst Jayaraman et al. [11]

0.4 to 2.4 295 (5.2?) abs, fi Sucher et al. [9]
~ 0.5 to 1.8 300 refl, powder lvanchenko et al. [12]
~ 0.5 to 2.5 300 abs, fi, am lvanchenko et al. [12]
0.18 to 4.3 300 abs, fi, am Lashkarev, lvanchenko [3]
~ 0.5 to 6 10 to rt abs, fi Suryanarayanan et al. [2, 5]
0.4 to 2.8 (?) 300 abs, fi, cryst Holtzberg, Torrance [4]
~ 0.5 to 2.5 rt ( ?) abs, fi Vedam, Kirk [13]
0.03 to 12 300 refl, cryst Batlogg et al. [6]
~ 2.5 to 5.5 2 refl, cryst (100) Kurita et al. [7]
77 refl, cryst, a.c. el. field Kurita et al. [7]
~ 0.5 to 3.3 rt (?) refl, pressures up to Syassen [8]
220 kbar
Bands below 0.8 eV and Absorption Edge
Weak absorption maxima of a thin single crystal at 0.22 eV ( ~ 5.6 Jlm) and 0.38 eV
( ~ ~ 3 Jlm) remained unassigned or were attributed to a trap Level, respectively. The absorp-
tion edge has been recognized at 0.62 ± 0.02 eV. At wavelengths shorter than 1.9 Jlm
( ~ > 0.65 eV) the sample was opaque, Jayaraman et al. [11]. This energy value for the
absorption edge was confirmed by reflectivity measurements of Batlogget al. [6]. lt was given
as 0.70 ± 0.03 eV by lvanchenko et al. [12].
Gmelm Handbook
RE Matn Vol. C10
A weak absorption band has been observed at - 0.5 eV, Sucher et al. [9], and also at
- 0.73 eV ( ~ A. = 1.7 J.lm), Vedam , Kirk [13], on samples prepared by the authors of [9] . lt
was tentatively attributed to an impurity Level or the absorption edge [9, 13]. While
Suryanarayanan et al. [2] could not decide on the existence of such a band from their data,
no absorption peak in this rangewas found, bothonthin film and single crystalline samples
by Holtzberg, Torrance (4] .
Bands between - 0.8 and 12 eV
The assignments of the observed bands E1 to E6 are given on p. 148. The room temperature
absorption of various Sm Te films on Pyrex is shown in Fig. 66. Spectra at temperatures as low
as 10 K are almost identical to the room temperature spectra in the range 1.8 to 6 eV (2].
.,
,_
Z'2
"iii
~
"Q
ß
;3-,
%~~~L-~~2~~~3L_~
Photon energy in eV
Fig. 66. Absorption spectra of various SmTe films at room temperature.
3 Es
y
.l!!
·c:
e,
I IV
::J
...>.2 I - - E3 r-
g
...
:ö A if"-/
<( ,/""'J ..........,
3.5 4.5 5.5

Photon energy in eV
Fig. 67. Reflection spectrum of a SmTe single crystal at 2 K.

Gmelon Handbook
RE Mam Vol. C 10
Sm Te 151
A Kramers-Kronig analysis of the reflectivity of polished and annealed Sm Te single crystals

(for the figure see the paper) has been made; for results see also below. The calculated
absorption coefficient (see the figure in the paper) follows the Urbach rule in the vicinity of
the absorption edge, Batlogg et al. [6]. The reflectivity maximum at E3 has been related to a
valence-to-conduction band transition at the zone center rather than to a 4f6-4f 55d transition,
Syassen [8]. This explanation is similar to that given for the structures in the reflectivity (at
2 K) of in situ cleaved SmTe single crystals, Fig. 67, which have been identified as Wannier
type band edge excitons formed between the d-like conduction band state Xt and p-like
valence band states X7 and Xa (upper) at the X point (E 3 and E4, respectively) and between
the s-like conduction band state rt and the p-like valence band states rs
and rsat the r
point (E 5 and E6 , respectively). This assignment is consistent with electroreflectance spectra
at 77 K, where the sample is in an a. c. electric field (1 kHz, 48 kV/cm) along [010]; see the
paper for a figure, Kurita et al. [7].
Positions of the Bands E1 to Es (in eV)
Tin K E1 E2 E3 E4 Es Ref.
rt 1.20±0.03 2.00±0.03 2.8 to 3.05 1l 3.6 4.4 Suryanarayanan et al. [2]

300 1.20±0.02 2.05±0.02 2.8 3.5 Holtzberg, Torrance [4]
rt (?) 1.22 2.14 Vedam, Kirk [13]
~1.1 -1.9 -2.9 -3.6 Batlogg et al. [6] 2l
2 -3.0 -3.6 -4.4 Ku rita et al. [7] 3l
1l Depending on film thickness. - 2l Read from a figurein the paper. - 3l Read from Fig. 67,
rt = room temperature.
Substantially different IR bands are reported by Lashkarev, lvanchenko [3], and by

lvanchenko et al. [12]. The absorption spectrum between 0.18 and 4.3 eV of a thin film of
amorphaus SmTe (for the figure see the paper) shows maxima at 0.8, 1.5, 1.8, 2.2 eV, and a
sharp increase of the absorption coefficient at higher energies, which has been related to the
gap E9 = 2.3 eV between the valence and conduction bands. The first two maxima were
assigned to transitions from the 4f 6 Level to the 5d(t29 ) subband, the other two to the 5d(e9)
subband [3]; seealso [12].
The assignments of the bands E1 to Es to f-> d derived transitions implies values for the
6 H, 6 Fmultiplet splitting of 0.85 eV, Holtzberg, Torrance [4], - 0.8 eV, Suryanarayanan et al.
[2, 5], -0.9 eV, Vedam, Kirk [13], and the crystal field splitting 10 Dq ~ 1.6 eV [2, 5]. Both
quantities are consistent with the analysis of the dielectric function [6] and the photoelectron
spectra, Campagna et al. [15]. The excitation energies in Sm chalcogenides are about 1.5 eV
Lower than those in Eu chalcogenides. This energy difference corresponds to the difference
in the third ionization potantials of Eu and Sm [6]. For calculated excitation spectra in samarium
monochalcogenides, see Sargautis, Dagys [14].
Dielectric Properlies
The real and imaginary parts of the dielectric function, e' and ~:", respectively (see Fig. 68,
p. 152), have been derived from the reflection spectrum by a Kramers-Kronig analysis.
The 4fs multiplet states 6 HJ, 6 FJ, and 6 PJ appear twice due to the crystal field splitting
(10 Dq = 1.6 eV) of the d states, Batlogget al. [6].
Gmelon Handbook
RE Maon Vol. C10
152 Samarium Tellu ri des
8
stil I
1
6 \
·w
\/y
}-..,
I 6 6p -
I
w 4
--
____p[f \'', ',,
2 I
- ----
'I I
E "-.
I II I I
I
2 4 6 8 10 12
Photon energy in eV
Fig . 68. Real (E' ) and imaginary (E") parts of the complex dielectric function for Sm Te.
Pressure Dependence of the Optical Spectra

The pressure dependence of the optical spectra has been investigated between /... = 2.2
and 0.5 J.lm (0.56 to 2.5 eV) up to 7 kbar on thin films of crystalline SmTe on a KBr substrate .
The transitions E1 and E2 (see p. 148) shift with a rate of -8 and - 16 meV/kbar. The direc-
tion of the shifts confirms the assignments of both transitions to the same (5d(t29 )) subband ,
Vedam, Kirk [13]. The reflection spectra for pressures up to 220 kbar are shown in Fig. 69. The
negative pressure coefficients of the transition energ ies in the semiconducting phase (a) and
the gradual change to metallic reflectivity (b) are clearly seen . The shift of the reflectivity
edge by about 0.7 eV towards lower energy at pressures above ~ 130 kbar (c) is related to
the NaCL-CsCl type phase transition , Syassen [8] .
c)
60 1- 1""-
220<· . ·."'\
"7
\
~4~--~~--~---r.~~
.f \
Ir \ ,
2 V.
""' .... _ 1\..---- :;.;;
2 3
Photon energy in eV Photon energy in ev Photon energy in ev
Fig. 6!? I 1eflection spectra of SmTe at pressures up to 220 kbar. a) Sem iconducting phase;
b) inte rmediate valent phase with NaCL structure ; c) region of NaCL-CsCl type transition.
Magnetic Clrcular Dichrolsm (MCD)

MCD experiments on SmTe films on CaF2 substrates in th e energy range 2.5 to 4 eV at
temperatures of 58, 100, and 300 K and a magnetic field H = 35 kOe show the spectra strongly
tempe rature dependent, especially in the 2.7 to 3.1 eV region ; for a figure see the paper. The
transitions arise from a ground state with at least two close lying Levels sepa rated by ~
- 250 c m - 1 . This agrees with th e assignment of 7 F0 and 7 F1 as the ground state multi plet of
Sm in SmTe, Suryanarayanan et al. [2, 5]. For other values of this energy parameter, see
pp. 138 and 149, respectively.
Gmelm Handbock
RE M a 1n Val. C 10
SmTe 153
References:
[1] A. landelli (Z. Anorg. Allgem . Chem. 288 [1956] 81/6) .

[2] R. Suryanarayanan, C. Paparoditis, J. Fern~. B. Briat (J. Appl. Phys. 43 [1972] 4105/8).
[3] G. V. Lashkarev, L. A. lvanchenko (J. Non-Cryst. Solids 8/10 [1972] 670/5).
[4] F. Holtzberg, J. B. Torrance (AlP [Am. lnst. Phys.] Conf. Proc. No. 5 [1972] 860/4) .
[5] R. Suryanarayanan, C. Paparoditis, J. Fern~ (Conf. Digest. lnst. Phys. [London] No. 3
[1971] 210/4).
[6] B. Satlogg, E. Kaldis, A. Schlegel, P. Wachter (Phys. Rev. [3] S 14 [1976] 5503/14) .
[7] A. Kurita, Y. Kaneko, T. Koda (Solid State Commun. 49 [1984] 463/6) .
[10] M. I. Nathan, F. Holtzberg, J. E. Smith Jr., J . B.Torrance, J. C. Tsang (Phys. Rev. Letters
34 [1975]467/9).

368/70).
[12] L. A. lvanchenko, G. V. Lashkarev, Yu. B. Paderno, S. V. Drozdova, V. A. Obolonchik, et
al. (Ukr. Fiz. Zh. 16 [1971]510/2; Ukr. Phys. J. 16 [1971]624/7) .
[13] K. Vedam, J. L. Kirk (Proc. 11th Rare Earth Res. Conf., Traverse City, Mich., 1974, Vol. 2,
pp. 840/4).
[14] A. Sargautis, R. Dagys (Lietuvos Fiz. Rinkinys 24 [1984]29/33 ; C.A. 101 [1984] No. 218723) .
165/8).
30.1.2.10.7.2.10 Photoemission and X-Ray Absorption Spectra
The X-ray photoemission spectrum (XPS) of SmTe for binding energies down to E8
~ - 10 eV below the Fermi Level (see Fig. 70) shows the 4f5 multiplet (6 H, 6 F, 6 P) which is the
final state spectrum of Sm2+ . Additional intensity is attributed to the valence band density of
states which has its maximum between - 3 and -4 eV. The intensity near -8 eV is attributed
to an energy Loss, Campagna et al. [1, 2]. X-ray absorption spectra near the L 111 edge of various
compositions (including 1: 1) in the Sm-Te system are reported to show the change of the 4f
electron number; for plots of the spectra, see the paper, Slokhin [3] .
61-- t- - + -- -
-4 -2
Es in eV
Fig. 70. X-ray photoemission spectrum (EF = 0) of SmTe.
Gmelm Handbook
RE Main Vol. C 10
References:
[1) M. Campagna, E. Sucher, G. K. Wertheim, L. D. Longinotti (Phys. Rev. Letters 33 [1974)

165/8).
[2) M. Campagna, G. K. Wertheim, E. Sucher (Struct. Bonding [Berlin] 30 [1976] 99/140,
121/124).
[3) S. M. Blokhin from E. I. Yarembash, A. A. Eliseev (Khal'kogenidy Redkozemel'nykh
Elementov, Nauka, Moscow 1975, pp. 1/260, 208; C.A. 83 [1975] No. 125545).
30.1.2.10.7.3 ESR Spectra of SmTe Doped with Eu and Gd
Experimental Data
SmTe crystals (prepared from the elements as described on p. 131) were found to contain
as impurities: ~ 30 ppm Eu and also Mn, Mehran et al. [1, 2], 10 to 20 ppm of Eu2+ and
somewhat less Mn 2 +, Birgeneau et al. [3]. Gd 3 + impurities (nominal 0.01 and 0.1 %) were
introduced intentionally by dilution of a master alloy containing 1 at% of Gd [3).
Electron paramagnetic resonance measurements were performed at X-band frequencies

at 4.2 and 77 K with the magnetic fields varied in the (100) and (110) planes of the crystals [1)
and at 12, 17, and 34 GHz at 1.4 and 4.2 K with the magnetic field rotated in the (110) plane
[3].
Eu 2 + Doping
The measurements yielded slightly increased g values: 2.016 ± 0.001 at 4.2 K,

2.019 ± 0.002 at 77 K [1], and 2.020 ± 0.003 at 1.4 and 4.2 K [3] compared to the usual 1.99.
The shift in the g value is less than in the analogaus selenide and sulfide systems. This is
attributed to the different size of the Eu2+ -Sm2+ exchange interaction [1, 3). A total exchange
parameter is given as I ( ~ 12 J 1 + 6 J2 ) ~ 1.2 x 10- 4 eV [2) and ~z,J; = -1.3 ± 0.3 K
i
( ~ ( -1.1 ± 0.3) x 1o- 4 eV) [3), assuming a Linear dependence of the absolute value of the
g-shift from the total exchange parameter with 8/1:!. as proportionality factor. The spin-orbit
splitting of the Sm2+ ions 1:!. = 38 meV, derived from the susceptibility data of Sucher et al.
[4], has been used. The sign of the g-shift indicates ferromagnetic interaction [1). For the
exchange integrals of impurity ions in Sm chalcogenides, see Fig. 204, p. 384 in "Rare Earth
Elements" C7, 1983. The fine structure constant is given as b4 = 6 ± 2 G [1) and lb4 1 =
(10±1)X10- 4 cm- 1 (~11G) [3], and the hyperfine structure parameter A C51 Eu) as
30.7 ± 0.3 G [1) and (28.6 ± 0.5) x 10- 4 cm- 1 (~30.6 G) [3), and A C53 Eu) = 13.8 ± 0.3 G [1).
The fine structures are quite broad, presumably due to residual strains of lower than cubic
symmetry [3].
Gd 3 + Doping
SmTe doped with Gd 3 + yields spectra where no hyperfine interaction could be identified
but the fine structure pattern of a spin S = 7 / 2 in cubic symmetry could be resolved, though
in many cases with considerable additional structure. As in the Eu 2 + case the g value is
Gmelin Handbook
RE Mam Vol C10
155
increased but Less than in SmSe or SmS host crystals: g = 2.10 ± 0.01. The g-shift of Gd3+ is
roughly twice as Large as with Eu2+, which is thought to be due to the Gd 3 + -Sm 2 + exchange
involving the extra electron of Gd 3 +. This extra electron is thought to be Localized near Gd in
a cubically symmetric orbital. This picture is consistent both with the observed independence
at Low temperatures of the Gd3 + g shifts and (roughly) of the electrical resistivity from the
Gd 3 + concentration. The total exchange parameter ~z;Jj = -5.4 ± 1.1 K. The fourth order
I
crystal field parameter lb 4 l = (37 ± 2) x 10- 4 cm- 1 (~40 G) is markedly increased relative to
other studied chalcogenides, Birgeneau et al. [3]. For analogaus investigations on the Mn
impurities, see the papers [1, 3].
References:
[1] F. Mehran, K. W. H. Stevens, R. S. Title, F. Holtzberg (Phys. Rev. Letters 27 [1971]

1368/71).
[2] F. Mehran, K. W. H. Stevens, R. S. Title, F. Holtzberg (AlP [Am. lnst. Phys.] Conf. Proc.
No. 5 [1972] 865/8).
[3] R. J. Birgeneau, E. Bucher, L. W. Rupp Jr., W. M. Walsh Jr. (Phys. Rev. [3] B 5 [1972]
3412/8).
[4] E. Bucher, V. Narayanamurti, A. Jayaraman (J. Appl. Phys. 42 [1971]1741/5).
30.1.2.10.7.4 The SmTe-NdTe System
A continuous series of solid solutions is formed in the SmTe-NdTe system, as shown by

X-ray studies on samples synthesized under high dynamic pressure (explosion-induced). The
Lattice parameters of the intermediate compositions are close to (yet slightly Larger than) the
values extrapolated from Vegard's Law; see the paper for a plot of the Lattice parameters vs.
the composition, S. S. Batsanov, V. P. Bokarev, G. V. Durogova (Zh. Neorgan. Khim. 30 [1985]
24618; Russ. J. lnorg. Chem. 30 [1985]138/9).
For their existence in the Sm-Te system and Mössbauer spectroscopy see pp. 128/9, for
the crystallographic properties pp. 21 and 32.
Valency
Magnetic susceptibility data at room temperature Lead to an effective valence of samarium

of 2.67 for SmTe 1_23 ( ~ Te deficient Sm 3Te4) and 2.93 for Sm 2Te 3 according to Lashkarev et al.
[1]. However, for Sm 2Te3 (Tl-form) a content of -30% Sm2+ and 70% Sm3+ is given by
Yarembash et al. [2], Karabekov et al. [3], and Karabekov [4]. Lattice constant data as a
function of the M3+ radius (M = La to Sm) also indicate the presence of Sm 2 + and Sm3+
in Sm 3Te4 and y-Sm 2Te 3 , Eliseev [5]; for "cubic y-Sm 2Te 3 " the value a ~9.48 A from Pardo
et al. [6] was used (but see p. 128 for the existence of y-Sm 2Te 3). Fora possible partial quan-
tum tunneling valence fluctuation in Sm 3Te 4 at -1.3 K, derived from magnetization studies,
see pp. 25/6.
Gmelin Handbook
RE Mam Vol. C10
The magnetic susceptibility of powdered samples of SmTe 1 23 and Sm 2Te 3 was measured
between 80 and 300 K by Lashkarev et al. [1). The obtained temperature dependence of the
effective magnetic moments Jle1t of these and other samarium tellurides is shown in Fig. 71 ,
compared with the theoretical values for Sm 2 + , Sm3+, and (2 Sm3+ + Sm 2 + ). The atom
susceptibility of SmTe 123 is XA = 2380 x 10- 6 cm 3/g-atom and Jleft = 2.37 Jls at 293 K [1). The
same XA value is reported by Yarembash et al. [2) and Karabekov et al. [3) for Sm 3Te4 without
mention of a Te deficiency. The paramagnetic Curie temperature eP = -1.5 K is reported
for Sm 3Te4 ; see p. 25. The sesquitelluride Sm 2Te3 has XA = 1310 x 10- 6 cm 3/g-atom and Jle11 =
1.75 Jls at 293 K [1). According to Pechennikov et al. [7] the specific magnetic susceptibility
between 77 and 900 K obeys a Curie-Weiss Law below 300 K with 0P = -354 K and Jleft =
2.56 Jls·
Temperaturein K
Fig . 71 . Temperature dependence of the effective magnetic moments Jle1t of samarium

tellurides. Curves 1, 2, and 3 are calculated assuming Sm 2 + , Sm 3 + , and (2 Sm3+ + Sm 2 + ),
respectively.
Sm 3Te 4 and Sm 2Te3 exhibit semiconducting properties. Curves for the electrical
conductivity K and thermoelectric power S of pressed sintered samples between 250 and
-1000 Kare given in the papers. Sm 3Te4 has K = 0.01 n - 1 · cm- 1 and S = -100 JlV/K at
293 K. The activation energy 11E = 0.25 eV derived below -500 K is ascribed to the Sm 2 + --.
Sm3+ excitation process. S changes sign at 770 K [2, 3] . According to Karabekov [4], S changes
sign at 520 K and falls to almost zero at 900 K. For Sm 2Te 3 at 293 K, K = 3 x 10- 3 n- 1 · cm - 1
(read from a curve; 3 x 1o- 6 Q - 1 ·cm - 1 was erroneously tabulated) and S = + 350J.!VI K ;
11E = 0.68 eV near room temperature [2) . For a discussion, see Yarembash, Eliseev [8].
The thermoelectric power is almost constant between 293 and - 500 K [2) . Almost the
same data for Sm 2Te 3 were given by Karabekov et al. [3] ; however, thei r plots of Log K
and S versus temperature are obviously erroneous. K = 1.18Q- 1 · cm - 1 at 300K and
1.96 X 10- 6 n - 1 . cm - 1 at 90 K, Miller et al. [9] .
Gmelln Handbook
RE Main Vol. C 10
Samarium Polytellurides 157
References:
[1] G. V. Lashkarev, E. I. Yarembash, A. Karabekov, N. P. Giletskii (Phys. Status Solidi B 44

[1971] K41/K44).
Nauk SSSR Neorgan. Materialy 7 [1971] 761/5; lnorg. Materials [USSR]7 [1971] 661/5).
pp. 68/72; C.A. 80 [1974] No. 75371).
[4] A. Karabekov (Diss. Polytech. lnst. Frunze, USSR, 1969 from [8]).
627/33, 628).
[6] M.-P. Pardo, J. Flahaut, L. Domange (Compt. Rend. 256 [1963]1793/6).
[7] A. V. Pechennikov, V. I. Chechernikov, M. E. Barykin, E. I. Yarembash (lzv. Akad. Nauk
SSSR Neorgan. Materialy 4 [1968] 771/2; lnorg. Materials [USSR] 4 [1968] 674/5).
Moscow 1975, pp. 1/260, 202/8).
[9] J. F. Miller, J. W. Moody, L. K. Matson, R. C. Hirnes (AD-246851 [1960]1/20, 17).
30.1.2.1 0. 7.6 Samarium Polytellurides
For the existence of Sm 4Te7 , SmTe 2 _x, Sm 3Te7 , Sm 2Te 5, and SmTe3 and of the Mössbauer
spectra see the Sm-Te system, p. 128, and for other properties the comparative sections,
pp. 43/60.
The magnetic susceptibility of powdered samples was measured between 80 and 300 K
by Lashkarev et al. [1], and the obtained temperature dependence of the effective magnetic
moments lleff is shown in Fig. 71, compared with the theoretical values for Sm2+, Sm 3 +, and
(2 Sm3+ + Sm 2 +). Values for lleff (in llsl and the atomic susceptibility 'XA (in 10- 6 cm 3/g-atom)
at 293 K as well as for the effective valency of smn+ in the compounds [1]:
SmTe 1.8
lleff 1.75 1.56 1.46 1.46

XA. 1300 1040 940 900
n . 2.93 3.00 3.02 3.03
Values of 'XA are also given by Yarembash et al. [2], Karabekov et al. [3]. The temperature
dependence of the reciprocal specific magnetic susceptibility of SmTe 2 measured between
77 and 900 K is shown in a figure in the paper of Pechennikov et al. [4].
The polytellurides have metallic or semimetallic properties. Values at 293 K for JC in
n- 1 · cm- 1 and the thermoelectric power S in 11V/K:
SmTe 1.8
1C 25 200 250 500

s +100 + 18 + 10 +10
Curves for Log K and S between 250 and 1173 Kare given in the papers for Sm 2Te 5 . Whereas
Log K is almost constant up to -900 K, S increases Linearly with 1/T up to -700 K and rises
more rapidly above that temperature [2, 3].
Gmelon Handbook
RE Main Vol. C10
158 Europium Tellurides
References:
[1] G. V. Lashkarev, E. I. Yarembash, A. Karabekov, N. P. Giletskii (Phys. Status Solidi B 44

[1971] K41/K44).
pp. 68/72; C.A. 80 [1974] No. 75371).
SSSR Neorgan. Materialy 4 [1968] 771/2; lnorg. Materials [USSR] 4 [1968] 674/5).
30.1.2.1 0.8 Europium Tellurides
Additional data for EuTe and Eu 3Te 4 are found in Sections 30.1.2.1 and 30.1.2.2, on pp. 6
and 21, respectively.
30.1.2.10.8.1 The Eu-Te System
Phase Diagram Studies
There are conflicting results regarding the number and kind of existing compounds in the
Eu-Te system studied by Sadovskaya [1], Sadovskaya, Yarembash [2], Sadovskaya et al. [3],
and Eliseev, Sadovskaya [4] and reviewed by Yarembash, Eliseev [5] and Eliseev et al. [6].
ln [2] by means of DTA and X-ray diffraction studies, a tentative phasediagram was constructed
and the four compounds EuTe, Eu 3Te 4 , Eu 4Te 7 , and Eu 3Te 7 were assumed to exist (the Last two
of variable composition and melting incongruently at 520 and 430°C, respectively). Two
eutectics, at 780 ± 5°C (near the Eu side) and at 410 ± 5°C (near the Te side) were found.
Cubic solid solutions with the NaCL structure (based on EuTe) exist for samples with 50 to
57 at% Te when annealed between 600 and 900°C, but on slow cooling from 900°C the solid
solutions probably transform to Eu 3Te 4 which is not cubic (see p. 229). ln the following paper
[3] based on DTA and X-ray and chemical analyses, Eu 2Te 3 was reported to exist in addition
to the four initial phases. Melting or decomposition temperatures in °C from [3] (and from the
Eu-Te phasediagram shown in [5]):
Eu Te
(1 525 ± 20) a) 1460 ± 20 (520 ± 5)b) (430 ± 5) b)

a) Higher melting points were found by other authors; see p. 177. - b) The phasesexist below
that temperature.
ln the next paper [4] (with reference to [1]) the existence of six compounds, EuTe, Eu 3Te 4 ,
Eu 4Te 7 , EuTe 2 , Eu 3Te 7 , and Eu 2Te 5 , but not Eu 2Te 3 , was reported and later, in the review [6]
(with reference to [2] !), the existence of the four phases Eu Te, Eu 3Te 4 , Eu 2Te 5 , and EuTe 3 was
reported.
Gmel1n Handbock
RE Ma1n Val C 10
The Eu-Te System. EuTe 159
Cubic solid solutions based on EuTe were observed in samples with 50 to 60 at% Te,
when annealed at 600°C, but they decomposed when annealed at 400 to 450°C [4]. The
decomposition of these cubic solid solutions (ct) below 550°C Leads to the ß-phase with
54 to 59 at% Te interpreted as "Kurnakov phase" based on Eu 3Te 4 (~ EuTe 1.33 ±x with
0.11 ~X~ 0.2) [5, 6].
According to Ravot et al. [7] the range of cubic solid solutions extends from 48.9 to 58.5
at% Te(~ Eu/Te= 1.05 to 0.71) in polycrystalline material quenched from 2000°C. The EuTe
single crystals obtained from initial charges with 46.7 to 55.6 at% Te (~ Eu/Te = 1.14 to
0.80) by slow cooling (4 K/h) from 2000°C were all cubic and had compositions between
EuTe 0 .980 and Eu 0 _986Te deduced from their density [7].
General Preparation Methods
The europium tellurides with ~50 at% Te were prepared by slowly heating the eiemental
mixtures in stages in evacuated quartz ampules up to 600°C. The reaction begins at 390 ± 5°C
(see p. 160). To prepare samples with <50 at% Te double quartz ampules with Ti or Zr getters
between the ampule walls and corundum crucibles inside the inner ampule were used to
avoid reaction between Eu and quartz. The reaction products were then homogenized by
annealing at 600 or 900°C [2]. Sampies with 33.3 to 91.4 at% Te were prepared in evacuated
L-shaped quartz ampules without contact of the components by solid-vapor reaction and
annealing of the reaction products at 450, 600, and 900°C [4].
References:
[1] 0. A. Sadovskaya (Diss. Moscow 1970 from [4] and [5]).

Moscow 1975, pp. 1/260, 208/15).
No. 6 [1981]12/21; Mendeleev Chem. J. 26 No. 6 [1981]15/27).
[7] D. Ravot, J. C. Achard, 0. Gorochov, et al. (J. Phys. Colloq. [Paris] 41 [1980] C5-357/
C5-359).
30.1.2.10.8.2 EuTe
The compound is a congruently melting phase of the Eu-Te system. lt formsTe-rich solid
solutions at high temperatures; see pp. 158/9. This section describes data for EuTe which was
prepared with the intention of studying the monotelluride. The solid solutions EuTex with x > 1
are described on p. 229.
Gmelm Handbook
RE Main Vol. C10
30.1.2.1 0.8.2.1 Formation and Preparation

Polycrystalline Samples
All manipulations should be made under inert gas atmosphere due to the air sensitivity
of both Eu metaland EuTe, Katdis [1].
According to visual Observations the reaction Eu + 1/2 Te 2 ....... EuTe in evacuated and
sealed quartz ampules starts at 600 to 730°C; a DTA peak at 556°C (heating rate 1 K/min) was
attributed to the beginning reaction. The reaction is not complete after several days at 880°C
as judged from the Te vapor still present. Higher temperatures should not be used because
of the reaction with silica. The synthesis from the elements can also be made in Mo crucibles,
Katdis [2]; see also [1]. The reported start of reaction at 390 ± 5°C refers presumably to
elemental mixtures containing Te in Large excess; see Sadovskaya, Yarembash [3]. Chunks
of Eu were heated below 600°C and reacted with Te vapor from a Te reservoir Located
separately in the horizontal fused quartz tube at a position of Lower temperature in order to
prevent too rapid reaction. After the reaction was essentially complete, in one or two days,
the temperature was raised to 900°C for 16 h. This material still showed no evidence of a
reaction with the quartz, Reed, Fahey [4].
Eu Te powder obtained from the elements at 950°C was purified by double distillation under
vacuum, Johanson, McCollum [5]. ALLthese materials can be used as a starting material for
single crystal growth. The yellow-red samples prepared from the elements in a 10 d reaction
between room temperature and 900°C and those samples pressed afterwards and annealed at
2000°C under controlled Te vapor pressure had nearly stoichiometric composition (electrical
resistivities Q :::o 107 Q · cm), Busch et al. [6]. Similar samples were obtained by gradually
heating the elements in a sealed evacuated quartz tube from 200 to 1 000°C in 14 d and
maintaining at 1 000°C for 5 d. After pressing, the material was annealed for 5 hat 1700°C in
Ta crucibles under vacuum, Hidaka [7]. Direct synthesis from the elements in stoichiometric
ratio or with excess Te at ~2200°C in sealed Mo crucibles is described by Köbler, Fischer
[8].
The compound was prepared from EuH 2 and Te in flowing H2 at 600 to 850°C. Dark brownish
red EuTe formed when a mixture of freshly prepared EuO and a threefold excess of Te was
allowed to react in flowing H2 for 12 h at 600°C and for 2 h at 900°C; any excess Te was
removed in a Mo crucible at 1450°C in a high vacuum, Petzet [9]. The compound was also
obtained from Eu 20 3 in a gas mixture of H2 and tellurium at ~ 1 000°C with subsequent
annealing at 1600 to 1700°C in Moor C crucibles under 10-s Torr, Nagai et al. [10].
EuTe had at first been obtained by reaction of EuCl 2 and excess Te in streaming H2 while
the temperature was raised within 6 h to 600°C. Excess Te was removed by heating to 820°C
in the H2 stream, Klemm, Senff [11]. The same reaction with EuCL2 , and also with EuS0 4 as
starting material, has been conducted by McGuire et al. [12] and at 800°C with EuC 2 0 4 · H2 0
or Eu 2 (C 20 4 b · n H2 0 by Pink [13]. Excess Te was removed at above 1 000°C [12] or at 900°C
[13].
Single Crystal Growth

W crucibles should be used for crystal growth. Crystals grown in Mo crucibles were
sometimes contaminated with the crucible material, Johanson, McCollum [5], Katdis [14].
Other contaminations, observed mass spectrometrically, in single crystals grown from the
melt, by Sublimation, and by chemical transport were compared by [14].
Single crystals grown from EuTe melts [14] or melts containing EuTe and an added excess
of Eu metal are generally nonstoichiometric and opaque. EuTe melts in sealed W crucibles
Gmelm Handbock
RE Ma1n Val. C 10
Eu Te 161
were cooled from 2500°C, Reed, Fahey [4] or 2400°C at 5 K/h. Crystals were made nearly
stoichiometric by annealing in Ar for 24 h at 1500°C, Shapira et al. [15] or by additional
annealing in a vacuum for 24 h at 1000°C [5]. Growth by the Bridgman method in C crucibles
was mentioned by Sera et al. [16]. Single crystals have been obtained in sealed W crucibles
from melts of EuTe with an added 20 wt% excess of Eu metal on cooling in a temperature
gradient, from 2300 to 1200°C at a rate of 10 K/h and then at 20 K/h down to room temperature
[4]. Samples grown from a melt of EuTe with added 10% excess Eu metal on cooling from
2400°C at 5 K/h were annealed for 60 h at 1500°C in Ar [15]. The single crystals obtained in
Mo crucibles from melts with a Eu:Te ratio between 0.8 and 1.14, with cooling from 2000°C
at 4 K/h, had compositions between Eu 0 _986Te and EuTe0 _980 (~ Eu 1.02Te), deduced from their
densities, Ravot et al. [17].
Sublimation of EuTe powder at 2000-> 1857°C in Mo containers, evacuated and sealed
under 10- 6 Torr, gave dark red, slightly transparent single crystals (up to 5 x 4 x 2 mm 3 ) at the
Lid of the container, growth rate 14.7 mg/h. They contained microscopic dark inclusions, Katdis
[1]; seealso Katdis [14], McMasters et al. [18]. The stoichiometry and transparency of samples
obtained at """'1900°C could be improved by a thermal after-treatment. The optimal conditions
are temperatures between 1100 and 1150°C with a gradient of 30 K over the crucible Length,
sealed evacuated Mo containers, and 2 to 14 d reaction time, Busch et al. [19]. Sublimation
in a temperature gradient at 2120 to 1960 K (1847 to 1687°C) and 2320 to 2070 K within Mo
ampules sealed under vacuum ("""' 10- 3 Pa, ~ 7.5 · 10- 6 Torr) gave coarse grained products
with large monocrystals, up to 8 mm in one direction (Q ~ 8.5 ·107 Q · cm). The Mo content
was below 10- 4 wt%. Experimentally observed mass transport rates, 115.4 and 323.2 mg/h
at2070-> 1960 and 2320-> 2070 K, respectively, were compatible with a diffusion mechanism
associated with dissociative Sublimation. The limiting step of the process at 2120 to 1960 K
is the diffusion of molecular tellurium and at higher temperatures the diffusion of Eu, Vel'mizov
et al. [20]. Sublimation of EuTe under vacuum within a current-heated, loosely sealed Ta foil
gave single crystals with dimensions up to 2 x 3 x 2 mm 3 , Nakai et al. [21].
Wine red transparent stoichiometric single crystals have been grown by iodine transport.
lodine was added to the elements and prereacted in a silica ampule. Crystal growth (up
to 9 x 8 x 3 mm 3) took place in a vacuum sealed Mo crucible at 1722 -> 1627°C, [1 2] =
1.35 mg/cm3 , growth rate 18.6 mg/h [1]. Growth at lower temperatures gave crystals
contaminated with Mo [14]. Transparent crystals with dimensions up to 10 x 6 x 6 mm 3 have
also been obtained from EuTe powder and Eul 2 at 1868 to 1845°C, Katdis [2] or 1895-> 1868°C
at a growth rate of 2 x 10- 7 cm/s. The calculated iodine pressure was 1.3 atm at 1900°C
assuming complete dissociation [14]. Mass spectrometric analysis yielded a content of
290 ppm (atomic) iodine as the main impurity, other anionic contaminants below 5 ppm atomic;
neither Mo nor Si were detected. Bromine (EuBr2) as transport agent at 2015 to 1975°C gave
slower growth rates and smaller final dimensions [2]. Due to the sizable partial pressure of
EuTe at the temperatures used by Katdis [1, 2] crystal growth through condensation from the
vapor phase seems to be more likely than chemical transport, Vel'mizov et al. [22]. The
transport experiments of these authors made with iodine in the temperature range between
1170 and 1470 K (~ """'900 to 1200°C) showed EuTe tobe transported from both higher and
lower temperatures into an intermediate region. Crystals up to 2 mm in diameter were
obtained at a growth rate of 20 mg/h. The starting EuTe powder had been spread uniformly
over the length of an evacuated quartz capsule which was placed into the temperature
gradient. The observed crystallization temperature was said to agree to within 5% of the
value ("""' 1400 K) calculated from thermodynamic data; for further details see the paper [22].
Other temperatures reported for the chemical transport by iodine are T = 1750°C, Oliveira
et al. [23] and 1 050-> 1 000°Cfor 120 h, [1 2] = 5 mg/cm3 , giving ruby red crystals, Sadovskaya,
Yarembash [3].
Gmelin Handbock 11
RE Main Vol. C10
Preparation of Films
Thin films of EuTe have been prepared under vacuum (10- 5 Torr) by coevaporation of the
elements onto heated Substrates (350 < T < 500°C) of fused silica, Vycor, or freshly cleaved
(100) NaCL. The preferred orientation of the thin films is [200], Suryanarayanan, Paparoditis
[24]. Films were also deposited on (111) CaF 2 , by the same method, Ferre et al. [25]. Epitaxial
growth of EuTe was observed on vapor deposition onto cleaved plates of LiF or NaCl held at
400°C, lkezawa, Suzuki [26].
Thin films are also obtained by electron gun evaporation of small EuTe single crystals in
a vacuum of 5 x 10- 8 Torr and condensation onto fused silica substrates held at 500°C. Due
to the short evaporation time by this method contaminants of the films originate mainly from
the starting crystals; those contaminants introduced du ring evaporation are estimated to be
less than 100 ppm. The films are polycrystalline with a weak preference for the [100] direction,
Schoenes [27]; seealso Schoenes [28].
References:
[1] E. Kaldis (J. Cryst. Growth 3/4 [1968]146/9).

[2] E. Kaldis (J. Cryst. Growth 9 [1971] 281/94).
[4] T. B. Reed, R. E. Fahey (J. Cryst. Growth 8 [1971] 337/40).
1962, pp. 727/31; C.A. 60 [1964] 2423).
[7] Y. Hidaka (J. Sei. Hiroshima Univ. A II 35 [1971]93/110; C.A. 77 [1972] No. 94651).
[8] U. Köbler, K. J. Fischer (Z. Physik B 20 [1975] 391/7).
[9] T. Petzel (High Temp. Sei. 6 [1974] 246/53).
[10] S.-1. Nagai, M. Shinmei, T. Yokokawa (J. lnorg. Nucl. Chem. 36 [1974]1904/5).
[11] W. Klemm, H. Senff (Z. Anorg. Allgem. Chem. 241 [1939]259/63).

[12] T. R. McGuire, B. E. Argyle, M. W. Shafer, J. S. Smart (J. Appl. Phys. 34 [1963]1345/6).
[13] H. Pink (Z. Anorg. Allgem. Chem. 364 [1969]248/52).
York, 1974, pp. 49/191,99/108, 164/5).
[15] Y. Shapira, S. Foner, N. F. Oliveira Jr., T. B. Reed (Phys. Rev. [3] B 5 [1972] 2647/57).
[16] M. Sera, A. Takase, M. Kawakami, T. Suzuki, T. Kasuya (J. Phys. Colloq. [Paris]41 [1980]
C5-97/C5-99).
[17] D. Ravot, J. C. Achard, 0. Gorochov, M. Escorne, A. Mauger (J. Phys. Colloq. [Paris] 41
[1980] C5-357/C5-359).
[18] 0. D. McMasters, K. A. Gschneidner Jr., E. Kaldis, G. Sampietro (J. Chem. Thermodyn.
6 [1974]845/57).
[19] G. Busch, R. Verreault, 0. Vogt (Solid State Commun. 8 [1970] 617/20).
[20] S. I. Vel'mizov, V. K. Gartman, L. A. Klinkova (lzv. Akad. Nauk SSSR Neorgan. Materialy
[21] J. Nakai, S. Kunii, E. Hirahara (J. Phys. Soc. Japan 34 [1973] 917/24).
Gmelm Handbook
RE Mam Vol C 10
Eu Te 163
[23] N. F. Oliveira Jr., S. Foner, Y. Shapira, T. B. Reed (Phys. Rev. [3] B 5 [1972] 2634/46).
[24] R. Suryanarayanan, C. Paparoditis (Colloq. Intern. Centre Natl. Rech. Sei. [Paris] No. 180
[1969/70]149/55).
[25] J. Ferre, M. Billarden, J. Badoz, R. Suryanarayanan, C. Paparoditis (J. Phys. Colloq.
[Paris]32 [1971] C1-930/C1-931).
[26] M. lkezawa, T. Suzuki (J. Phys. Soc. Japan 35 [1973]1556).
[27] J. Schoenes (Z. Physik B 20 [1975] 345/68, 349/50).
[28] J. Schoenes (J. Magn. Magn. Mater. 11 [1979]102/8).
30.1.2.1 0.8.2.2 Crystallographic Properties
Crystal Structure. Polymorphism
EuTe crystallizes in the cubic NaCL structure at low pressure, Klemm, Senff [1] and the
cubic CsCL structure at high pressure, Singh et al. [2]. The relative volume change ll.VIV of
the structural transition at 110 ± 10 kbar is -13.2% (see p. 10). Both phases coexist up to
140 kbar, Chatterjee et al. [3].
Lattice parameters (in Ä) of NaCL type single crystals at room temperature are: a = 6.597,
Levy [4], 6.5984 ± 0.0001 (powdered single crystals, Debye Scharrer method), McMasters et
al. [5], 6.586 for vapor-grown crystals, Vel'mizov et al. [6], 6.601 for a crystal grown by chemical
transport, Vel'mizov et al. [7]. The following values were read from a figurein the paper: 6.591
and 6.586 (presumably) for melt-grown crystals, 6.590 and 6.591 for crystals grown by chemical
transport with iodine and bromine, respectively, and 6.584 to 6.587, (presumably) for vapor-
grown crystals with up to 1% excess Eu or Te, Katdis [8]. Single crystals of presumed
composition Eu 0 .986Te to EuTe 0 .960 , grown from melts of initial mole ratios Eu :Te = 0.8 to 1.14,
all had a = 6.60 A, Ravot et al. [9]. Lattice parameters for polycrystalline samples prepared
from the elements are: 6.590 ± 0.005, Sadovskaya, Yarembash [10]. 6.591 ± 0.001, Chatterjee
et al. [3], 6.598, Busch et al. [11], 6.60, Hidaka [12], 6.603 ± 0.001, Enz et al. [13]. ~6.55 and
6.58 from a figure in Rooymans [14]. Lattice constants for samples annealed at 400 to 450°C
(a = 6.603 ± 0.001) or at 600°C (a = 6.594 ± 0.002), Eliseev, Sadovskaya [15] are compared
with those of Te-rich samples on p. 229.
Preparations starting from Eu2+ compounds gave a = 6.585 A (from EuCL2), Klemm, Senff
[1], 6.70 A (from EuC 20 4 · H20), and as low as 6.47 A (from Eu 2 (C 2 0 4 b · aq), Pink [16].
Epitactically grown thin films show 6.600 ± 0.003 Aand 6.610 ± 0.003 Aat substrate temper-
atures of 400 and 500°C, respectively, du ring growth, Suryanarayanan, Paparoditis [17].
The lattice parameter of a single crystal was found to decrease from 6.597 A at 295 K to
6.576 A at 4.2 K. There was no anomaly at TN observed within the error Limits (~a/a =
1 x 10- 4), Levy [4]; see Fig. 72, p. 164. ln contrast a relative change of 4 x 10- 4 at TN from a
~ 6.575 A forT between 10 and 77 K to a ~ 6.572 A below T N (values read from a figure) had
previously been observed in studies between 2 and 77 K. There was also no obvious trigonal
distortion at T N• Rodbellet al. [18]. A neutron diffraction study yielded a = 6.56 A at 4.2 K, Will
et al. [19].
The lattice parameter at room temperature changes linearly and without hysteresis with
hydrostatic pressure (studied up to 4 kbar), Levy, Wachter [20]. A normal decrease of a in
Gmelon Handbock
RE Main Vol. C10
,,.
~
.f
0
Temperature in K
Fig. 72. Lattice constant a for an EuTe single crystal versus temperature from Levy (4] . Full
circles are values from Rodbellet al. (18].
±
the NaCl phase (cf. "Compressibility", p. 175) from the initial a = 6.591 0.002 A to a =
6.212 ± 0.02 A at ~ 100 or 110 kbar and a discontinuous change at this transition pressure to
a = 3.755 ± 0.01 A in the CsCL type structure was observed by Singh et al. [2]; see also
Jayaraman et al. [21] . For somewhat deviating values, see p. 10. There seems tobe no valence
change from Eu 2 + towards Eu3+ , either from these studies or from qualitative reflectivity
observations up to 300 kbar. From the pressure coefficient of the energy gap such a valence
change may occur at V!V0 = 0.58 for the NaCl type structure, which is outside of its stability
range [21]; seealso Jayaraman [22] and p. 175. An anomalous decrease of the lattice parame-
ter from a ~ 6.53 A at 25 kbar to a ~ 6.25 A at 40 kbar was observed earlier in studies up to
70 kbar and was attributed to a Eu 2 +-> Eu 3 + transition , Rooymans [14]. This behavior could
not be confirmed [2, 3] . (a = 6.22 A [14] or 6.16 A, Eliseev [23] is predicted for hypothetical
Eu 111Te.)
Surface Structure
Fourfold symmetry was found in the low-energy electron diffraction (LEED) patterns of the
in situ cleaved (100) surface of vapor-grown (nonstoichiometric) EuTe (electrical resistivity of
5 n · cm). The LEED pattern was independent of the cleaving and recording temperature
between 10 and 300 K and was rather stable (at Least one day). lt disappeared due to
adsorption of carbon compounds rather than by oxygen adsorption. The diffraction pattern
could not be recovered by ion etching and annealing , Grazhulis et al. [24].
Additional Data
The energy of formation of surface vacancies was estimated based on the surface energy
per single surface atom derived from Literature data for the specific surface energy. The
following values are obtained :
Gm elon Handbook
RE Maon Vol C 10
Eu Te 165
surface, hkl 111 110 100
specific surface energy crhkL in erg/cm 2 695 565 402

surface energy per surface atom YhkL in eV 0.81 0.54 0.27
formation energy of a surface vacancy 11HhkL in eV 0 0.54 1.08
Sergeeva [25].
References:
[1] W. Klemm, H. Senff (Z. Anorg. Allgem. Chem. 241 [1939]259/63).

[3] A. Chatterjee, A. K. Singh, A. Jayaraman (Phys. Rev. [3] B 6 [1972]2285/91).
[4] F. Levy (Physik Kondensierten Materie 10 [1969] 71/84, 75/8).
[5] 0. D. McMasters, K. A. Gschneidner Jr., E. Kaldis, G. Sampietro (J. Chem. Thermodyn.
6 [1974] 845/57).
York 1974, pp. 49/191, 106).
[1980] C5-357/C5-359).
1962, pp. 727/31).
[12] Y. Hidaka (J. Sei. Hiroshima Univ. A II 35 [1971]93/110, 101).
[13] U. Enz, J. F. Fast, S. van Houten, J. Smit (Philips Res. Rept. 17 [1962]451/63, 453).
[16] H. Pink (Z. Anorg. Allgem. Chem. 364 [1969] 248/52).
[1969/70]149/55).
[18] D. S. Rodbell, L. M. Osika, P. E. Lawrence (J. Appl. Phys. 36 [1965] 666/7).
[19] G. Will, S. J. Pickart, H. A. Alperin, R. Nathans (J. Phys. Chem. Solids 24 [1963]1679/81).
[20] F. Levy, P. Wachter (Solid State Commun. 8 [1970]183/5).
[21] A. Jayaraman, A. K. Singh, A. Chatterjee, S. Usha Devi (Phys. Rev. [3] 8 9 [1974]
2513/20).
[22] A. Jayaraman (in: K. A. Gschneidner Jr., LeRoy Eyring, Handbook on the Physics and
945/8).
[24] V. Grazhulis, A. M. lonov, V. P. Kuleshov (Poverkhnost 1985 No. 2, pp. 94/8; C.A. 102
[1985] No. 120346).
[25] L. A. Sergeeva (Kristallografiya 27 [1982] 592/6; Soviet Phys.-Cryst. 27 [1982] 358/60).
Gmelm Handbook
RE Mam Vol. C 10
30.1.2.10.8.2.3 lonicity. Bonding
For additional data, see " Rare Earth Elements " C7, 1983, pp. 425/6 and C9, 1986,
pp. 186/7.
The ionicity i ::::; 22% is attributed to EuTe by Gerth et al. [1) , Schwob [2), Wachter [3) based
on the definition by Sanderson [4) . There is a linear relationship between the thus defined
ionicities and the observed isomer shifts for the Eu monochalcogenides [1) . The Pauling
ionicity ip ::::; 25% is used by Zinn [5]; cf. Pauling [6] . An ionicity value iph = 18.5% has been
obtained within the modified Philips-Van Vlechten model. in this model a valence state o f 4
is assigned to Eu 2 + in EuTe by contribution of two 6s electrons and two 5d electrons. Within
the model of Tubbs the ionicity is given as i = 21 % (for details see the paper) , Singh , Gupta
[7]. The linear correlation of the iph for the Eu monochalcogenides [7] is not as good as that
for the "Sanderson ionicity" reported by [1).
References:
[1) G. Gerth , P. Kienle, K. Luchner (Phys. Letters A 27 [1968) 557/8) .

[2) P. Schwob (Physik Kondensierten Materie 10 [1969]186/218, 188).
[3) P. Wachter (CRC Crit. Rev. Solid State Sei. 3 [1972)189/241 , 202) .
[4] T. Sanderson (Chemical Periodicity, 2nd Ed ., Reinhold , New York 1961 , pp. 16/36, 29).
[5) W. Zinn (J . Phys. Colloq. [Paris] 32 [1971] C1-724/C1-730).
[6) L. Pauling (The Nature of the Chemical Bond , 3rd Ed ., Cornell Univ. Press, lthaka, N. Y.,
1960, pp. 93, 98) .
[7] 0 . P. Singh, V. P. Gupta (Phys. Status Solidi B 129 [1985] K 153/K 156).
30.1.2.10.8.2.4 LaHice Vibrations
Using on overlap shell model (9 parameters) the phonon dispersion curves w ere cal-
culated and are shown in Fig. 73. The c alculated one-phonon density of states (temperature
weighted) has the strongest maxima at ~ 100 and ~ 50 cm - 1 ; see the paper for a figure ,
Zeyher, Kress [1] .
3
N
:I:
1-
'e...
,!; 2 .f
;:. I>
50
0
X IOW L
Fig . 73. Calculated phonon dispersion for EuTe.

Gmelm Handbook
RE Main Vol. C 10
Eu Te 167
The bands centered at 112 cm- 1 in the Raman spectra of EuTe at zero magnetic field both
above and below T N have been assigned to scattering mainly from LO(L) phonons, which
become Raman allowed in Eu monochalcogenides, Grünberget al. [2], Güntherodt et al. [3, 4],
Schmutzet al. [5]; seealso p. 210. The band at 145 cm-1, which increases in intensity with
increasing magnetic fields up to saturation for 8 ~ 8c" corresponds to scattering from LO(r)
phonans [4, 5], Güntherodt [6]. 8y a single oscillator fit the oscillator wave numbers row =
141.5 ± 2 cm- 1 and ffiro = 102.3 ± 2 cm- 1 were deduced from the room temperature re-
flectivity, Holah et al. [7], Pidgeon et al. [8]. The fit is thought nottobe very accurate, Güntherodt
[9, pp. 52, 58].
Phonon dispersion curves along the r-L direction [10] and along the r-L, r-K, r-x,
and (0.6, q, 0) directions (q = 0 to 0.6) [11] have been calculated semiempirically on the basis
of a 9-parameter breathing shell model. The derived phonon density of states shows a strong
double peak just below 100 cm-1, Ousaka et al. [10, 11]. A single absorptionofthin film EuTe
(T = 2 K) at 111.7 cm- 1 was attributed to the TO phonon at the r point, which is the only IR
active mode, lkezawa, Suzuki [12].
References:
[1] R. Zeyher, W. Kress (Phys. Rev. [3] 8 20 [1979]2850/63).

[2] P. Grünberg, G. Güntherodt, A. Frey, W. Kress (Physica 8 + C 89 [1977] 225/8).
[3] G. Güntherodt, R. Merlin, P. Grünberg (Phys. Rev. [3] 8 20 [1979] 2834/49).
[4] G. Güntherodt, R. Merlin, G. Abstreiter (J. Magn. Magn. Mater. 15/18 [1980] 821/2).
[5] L. E. Schmutz, G. Dresselhaus, M. S. Dresselhaus (J. Magn. Magn. Mater. 11 [1979]
412/5).
[6] G. Güntherodt (J. Magn. Magn. Mater. 11 [1979] 394/402).
[7] G. D. Holah, J. S. Webb, R. 8. Dennis, C. R. Pidgeon (Solid State Commun. 13 (1973]
209/13).
[8] C. R. Pidgeon, G. D. Holah, R. 8. Dennis, J. S. Webb (Proc. 11th Intern. Conf. Phys.
Semicond., Warsaw 1972, Vol. 2, pp. 1280/6).
[9] G. Güntherodt (Phys. Condens. Matter 18 [1974] 37/78).
[10] Y. Ousaka, 0. Sakai, M. Tachiki (Solid State Commun. 23 [1977] 589/92).
[11] Y. Ousaka, 0. Sakai, M. Tachiki (J. Phys. Soc. Japan 48 [1980]1269/78).
[12] M. lkezawa, T. Suzuki (J. Phys. Soc. Japan 35 [1973]1556).
30.1.2.1 0.8.2.5 Mössbauer Effect

Isomer shifts and line widths are given in mm/s. For hyperfine fields derived from Möss-
bauer spectra, see p. 171.
151 Eu Spectra
lf not otherwise stated, the isomer shift 8 for the 21.7 keV y transition of 151 Eu in EuTe was
measured relative to Eu 20 3 with the source, 151 Sm in Sm 20 3 , and the absorber held at the
same temperature. Values for 8 at room temperature are: -12.87 ± 0.09, Gerth et al. [2],
-12.5 ± 0.3 relative to EuF3 (source 151 Sm in SmF3 ), 8rix et al. [3] (cf. Hüfner et al. [1]),
-12.71 ± 0.10 at 80 K, Steichele [4]. ln the antiferromagnetic state at4.2 K, 8 = -12.85 ± 0.10,
Saueret al. [5], -12.4 ± 0.1 (presumably at 4.2 K), Shenoy et al. [6], -12.67(1). Application
Gmelin Handbock
RE Main Vol. C 10
of hydrostatic pressure (studied up to 60 kbar) causes 8 to become less negative at a rate

aolap = 14.8x1o- 3 mm·s- 1 ·kbar-1, Klein et al. [7,8]; the corresponding volume co-
efficient is ao/atnV = -5.8±0.1 mm/s, Klein et al. [9]. 8 = -12.7 in the paramagnetic
phase with ferromagnetically aligned spins (4.2 K, 12.0 T). The shift derivative a/5/ap =
(11 ± 2) x 10- 3 mm · s - 1 · kbar- 1 ( ~ a/5/aln V = -4.4 mm/s) was derived from studies up to
18.6 kbar, Zaker [10], Zaker et al. [11]. Fora discussion of the lattice parameter dependence
of the isomer shift using hydrostatic pressure or anion Substitution (Eu monochalcogenide
series), see "Rare Earth Elements" C7, 1983, pp. 426/7 and the papers [10], Saueret al.
[12, 13]. The pressure-induced increase of the electron density at the Eu nuclei originates
from an increased intraatomic 4f-5d exchange interaction, at Least at Low pressures
(~ 18.6 kbar) [10], rather than from a compression of the closed inner shells as proposed by
[8]; see "Rare Earth Elements" C9, 1986, p. 189.
119Sn Spectra in Sn-Doped EuTe

119Sn Mössbauer spectra (23.8 keV y transition) of Sn-doped EuTe (approximately
Eu 0 _99 Sn 001 Te) give /5 = 3.91 ± 0.01 relative to Ba 119mSn03 weiL below TN, Bykovetz [14]. 8 =
3.86(2) at 4.2 K (source Ca 119msn03 ), decreasing with increasing hydrostatic pressure to
3.80(5) at 54 kbar; aö/atn V = +0.08(7) mm/s is given. For the configuration Sn(5s 2 5px), the
effect of the shielding of the 5p electrons seems to dominate slightly over that of the compres-
sion of the 5s shell, thus Leading to a decrease of the electron density at the Sn nuclei, Abd
Elmeguid [15]. The pressure dependence of 8 at 1.5 K given in the paper [15] appears tobe
in conflict with ao/ap = + 0.001 (1) mm · s- 1 · kbar- 1 reported by Abd Elmeguid, Kaindl [16] (a
value of -0.001(1), however, is consistent).
125Te Spectra
Mössbauer spectra of the 35.5 keV y transition of 125Te in EuTe give 8 = 1.15 ± 0.20 at
300 K with the source, 125Te in ß-Te0 3 , at 80 K. /5 = 1.1 ± 0.1 and 1.05 ± 0.10 at 80 and 4.2 K
for source and absorber at the same temperature, Sadovskaya et al. [17]. Fora comparison
with other europium tellurides, see p. 229.
Results on line widths are contradictory. Using a C25 Sb)Cu source, Sauer, Zinn [18] ob-
served r = 6.05 ± 0.10 at 78 K and r = 6.18 ± 0.10 in the type II antiferromagnetic state at
4.2 K on (presumably insulating) powdered single crystals. These nearly identical values
correspond to a line broadening of about 17% relative to the naturalline width of 5.2 mm/s.
The line broadening below T N, observed by other authors (see below), was not confirmed.
Application of an external magnetic field of 6.11 T at the absorber increases r in the now
canted spin phase at 4.2 K by 18%. The spectra have been fitted using a superposition of
single Lorentzian lines with equalline width and the intensity ratio 3:0: 1 [18]. Polycrystalline
samples (electrical resistivity Q = 1.3 x 103 n · cm) had r = 7.4 ± 0.1, 7.6 ± 0.1, and 12.1 ± 0.1
at 300, 80, and 4.2 K, respectively, when the source, 125Te in ß-Te0 3 , was held at 80, 80, and
4.2 K, respectively, Sadovskaya et al. [17]. A strong line broadening between 80 K (r = 7.5)
and 4.2 K (r = 11.2) was also observed by Blum, Franke! [19] on more conducting powdered
crystals (Q ~ 10- 2 n. cm).
References:
[1] S. Hüfner, P. Kienle, D. Quitmann, P. Brix (Z. Physik 187 [1965]67/84, 71).
[2] G. Gerth, P. Kienle, K. Luchner (Phys. Letters A 27 [1968] 557/8).
[3] P. Brix, S. Hüfner, P. Kienle, D. Quitmann (Phys. Letters 13 [1964]140/2).
Gmelln Handbock
RE Ma1n Vol. C 10
Eu Te 169
[4] E. Steichele (Z. Physik 201 [1967] 331/49, 339).

[5] C. Sauer, U. Köbler, W. Zinn, G. M. Kalvius (J. Phys. Colloq. [Paris] 35 [1974] C6-269/
C6-274).
[6] G. K. Shenoy, F. Holtzberg, G. M. Kalvius, B. D. Dunlap from G. J. Ehnholm, T. E. Katila,
0. V. Lounasmaa, et al. (Z. Physik 235 [1970]289/307, 301).
[7] U. F. Klein, J. Moser, G. Wortmann, G. M. Kalvius (Physica B + C 86/88 [1977]118/20).
[8] U. F. Klein, G. Wortmann, G. M. Kalvius (J. Magn. Magn. Mater. 3 [1976] 50/4).
[9] U. F. Klein, G. Wortmann, G. M. Kalvius (Europhys. Conf. Abstr. 1A [1975] 43/4; C.A. 85
[1976] No. 185905).
[10] A. M. Zaker (JUEL-1817 [1982]1/80, 42/9; C.A. 98 [1983] No. 99900).
[11] A. M. Zaker, C. Sauer, W. Zinn (J. Magn. Magn. Mater. 27 [1982]337/42).
[12] C. Sauer, A. M. Zaker, W. Zinn (J. Magn. Magn. Mater. 38 [1983]225/34).
[13] C. Sauer, A. M. Zaker, W. Zinn (in: P. Gütlich, G. M. Kalvius, Trends Mössbauer
Spectroscopy, Gutenberg University, Mainz, FRG, 1983, pp. 147/57; C.A. 102 [1985]
No. 16215).
[14] N. Bykovetz (Diss. Univ. Pennsylvania 1976, pp. 1/270, 135; Diss. Abstr. Intern. B 37 [1976]
1759).
[15] M. Abd Elmeguid (INIS-mf-5123 [1979]1/87, 44/51; C.A. 92 [1980] No. 13291).
[16] M. Abd Elmeguid, G. Kaindl (J. Phys. Colloq. [Paris] 40 [1979] C2-310/C2-312).
[17] 0. A. Sadovskaya, E. A. Stepanov, V. V. Khrapov, E. I. Yarembash (lzv. Akad. Nauk SSSR
[18] C. Sauer, W. Zinn (J. Magn. Magn. Mater. 3 [1976]46/9).
[19] N. A. Blum, R. B. Franke! (AlP [Am. lnst. Phys.] Conf. Proc. No. 29 [1976] 416/7).
30.1.2.10.8.2.6 Nuclear Magnetic Resonance (NMR)

Resonance Frequencies
Hyperfine fields derived from NMR are given on p. 171.
Weak resonances at 115.1 and 98.0 MHz in the spin echo NMR of polycrystalline EuTe at
1.4 K were tentatively assigned to the 125-fe and 123Te resonances, respectively. The origin of
other weak lines at 103.8, 81.5, and 79.8 MHz is not known. The intense 151 Eu resonance was
observed with the frequency v(1.4 K) = 264.7 MHz in a conducting sample (Q ~ 10- 2 Q · cm),
Raj et al. [1], and near 248 MHz at 4.2 Kin a polycrystalline sample using a continuous wave
method. Extrapolation to 0 K gave v(O K) = 267.7 MHz for the unpulled frequency (see below),
Hihara et al. [2].
The intense 153 Eu NMR was observed near 110 MHz at 4.2 K using a continuous wave
method [2]. ln weak magnetic fields (0 to 0.5 T [3]) the frequencies, Une widths, and intensities
are extremely dependent on the applied magnetic field by coupling with the antiferromagnetic
resonance modes (frequency pulling effect) [2], Schwarz et al. [3, 4]. ln contrast, the spin
echo NMR frequency and Une width of both a stoichiometric sample (Q ~ 106 Q · cm) and a
conducting one (Q ~ 10- 2 Q · cm) were found independent of the magnetic field (0.004 to 2 T),
whereas the echo amplitude has a maximum at about 0.1 T which approximately agrees with
the spin flop field 8 1 (see p. 182). ln the stoichiometric sample, the 153 Eu spin echo was
observed only in applied fields greater than 0.04 T, with v(1.4 K) = 117.9 ± 0.1 MHz and a
half width of 0.3 ± 0.1 MHz, compared to v(1.4 K) = 118.3 ± 0.2 MHz and a half width of
0.7 ± 0.2 MHz in the conducting sample at 0.004 T. Extrapolations from measurements be-
tween 1.2 and 4.2 K assuming a T2 dependence give for this sample in the type II anti-
Gmeltn Handbook
RE Matn Vol. C10
120P====J===t=====t==t=J 26
~t'f:.;:.~::--
. ~-I:.,, . .)=OK ~
. i.a;:j ... ·:·. ~,
·......../·...., ··:·~-'
115 2.6-1 ., __ .• . >. 25
161 · · ·,·. . - · :>~

~ . . . . r. · · . . . _ -...:-~\
3.8..:. ·.. '·. ·. ~
.!: 4.2 .. _ ... :
;:. 110P.........._._..P.~-+----...,-.-+-~--H
·,.
p ;"..
·....
. . ~
23
105~--+----+----1\~·--H
·,r
.,
: 0
0~~2~~4~~6~~e 22
8 0 in T
Fig. 74. 153Eu NMR frequency v of Eu Te and effective magnetic field IBe11 I versus external field
8 8 at various temperatures. The dashed curve is the extrapolation forT= 0 K, Schwarz et al.
[3]. The circles represent 151 Eu Mössbauer-effect measurements on EuTe powder at 4.2 K by
Hihara, Kojima [6].
ferromagnetic state v(OK) = 119.42±0.18MHz and v(OK) = 119.00±0.20MHz for the

stoichiometric one [1). The latter value agrees with the unpulled frequency v(O K) =
119.03 MHzforasingle crystal (see Fig. 74) [3, 4]; v(O K) = 118.7 MHzfora polycrystalline
sample studied between 1.4 and 4.2 K [2).
Fig. 74 shows the unpulled 153 Eu NMR frequency (and the derived effective magnetic field)
as a function of the external field at several temperatures. Those measurements below 2 K
in fields up to 7.9 T (see figures in the papers) were used for a precise determination of the
critical field, where the canted spin structure transforms into a ferromagnetically aligned one.
The straight line in Fig. 74, with slope y/2rc = 4.626 MHz/T, represents the behavior that would
appear in a state of ferromagnetic saturation [3), Lütgemeier, Schwarz [5).
Relaxation Times
8oth the spin-lattice and the spin-spin relaxation times T1 and T2 of 153Eu are found tobe
rather short in EuTe single crystal spheres. At 1.2 K, T1 decreases with the external field from
10 ms at 0.5 T to 50 IJ.S near the critical field Bcr· T2 is even shorter and decreases at increasing
temperature and at the approach to Bcr from larger or lower fields. A figurein the paper shows
T2 at 1.2 and 2.1 K for external fields of 7.1 to 7.85 T; at 1.2 K, T2 = 51J.S bothat 7.5 and 7.85 T,
Schwarz et al. [3).
The effective spin-spin relaxation time T2 ~ 21J.S in an insulating polycrystalline sample
in a field of 0.045 Tat 1.4 K was derived from the echo decay which is exponential at all fields.
Gmelin Handbook
RE Matn Vol. C10
Eu Te 171
T2 increases rapidly with the external magnetic field. The echo decay in a conducting sample
is nonexponential yet can be decomposed into two exponential components with relaxation
times of 6 ± 2 and 18 ± 3 JlS independently of the magnetic field. The spin echo in the
conducting sample can be excited in weaker fields and at Lower powers compared to the
stoichiometric sample, Raj et al. [1]. For spin-spin relaxation times from ESR, see p. 194.
References:
[1] K. Raj, J. I. Budnik, T. J. Burch (AlP [Am. lnst. Phys.] Conf. Proc. No. 24 [1974]44/6).
[2] T. Hihara, T. Komaru, Y. Koi (Ferrites Proc. Intern. Conf., Kyoto 1970 [1971], pp. 623/5).
[3] B. R. I. Schwarz, H. Lütgemeier, W. Zinn (J. Magn. Magn. Mater. 45 [1984] 369/76).
[4] B. R. I. Schwarz (JUEL-1929 [1984]1/77; C.A. 101 [1984] No. 221 066).
[5] H. Lütgemeier, B. R. I. Schwarz (Magn. Resonance Relat. Phenomena Proc. 22nd Congr.
AMPERE, Zürich 1984, pp. 297/8; C.A. 102 [1985] No. 104900).
[6] T. Hihara, Kojima (from [3]).
30.1.2.10.8.2.7 Hyperfine Fields

Atthe Eu 2 + Nuclei
General
For more general remarks on hyperfine fields in the Eu monochalcogenides, see for
example Zinn [1] and "Rare Earth Elements" C9, 1986, p. 194. The total magnetic hyperfine
fields Bh1 in the magnetically ordered state of EuTe are derived from the Local effective fields
Bell (obtained from NMR or Mössbauer experiments) after considering the applied field Ba
and the dipolar field Bdip• Bh1 = Be11 - Bdip- Ba. ln type II antiferromagnetic Eu Te (T N ~ 9.6 K)
at Ba = 0, Bd;p consists of the sum of the point dipole contributions from all Eu atoms
(7 Jls) around the site considered, Bykovetz [2], Zinn [1]. Bdip = 0.33 T, Bykovetz [3], is used
generally; cf. p. 186. At ferromagnetic spin alignment (Ba > Bcro see p. 183), Bdip consists of
the Lorentz and the demagnetization fields which cancel each other in the case of a spherical,
homogeneously polarized sample [1].
Values of Be11 and Bh1 at Ambient Pressure

ln the Antiferromagnetic Phase. Experimental values for Be11 and Bh1 in antiferromagnetic
EuTe at Ba = 0, T--+ 0 K (if not otherwise stated), derived from 153 Eu NMR studies are: Be11 =
-25.73(10) T, Schwarz et al. [4], Schwarz [5, p. 56], see Fig. 74; Be11 = -25.72(4) T (from
frequencies at Ba = 0.45 T by Raj et al. [6]) and Be11 = -25.7 T (from frequencies by Hihara
et al. [7]) were calculated by [5, p. 56]; Be11 = -25.5 T and Bh1 = -25.9 T, Kojima et al. [8]
with reference to [7]. 151 Eu Mössbauer studies Lead to Bell = -25.6 ± 0.3 Tat 1.49 K for a
nearly stoichiometric sample and Be11 ~ -23 T (read trom a figure) at 4.2 K for an 12-doped
sample grown by iodine transport, Sauer et al. [9]; Bh1 = - 26.0(3) T (presumably at 0 K) for
the formerwas Listed by Sauer, Zinn [10], Lütgemeier et al. [11], Saueret al. [12]. Early values
are IB811I = 24.5(2) T, Shenoy et al. [13], and 25.5 T, Wickman, Cohen [14].
As EuTe is subject to zero-point spin-fluctuations the measured B811 values in the anti-
ferromagnetic state are reduced. The values B~11 corresponding to the full sublattice magneti-
zation M0 = 7 Jls per Eu ion are B~ = B911 (1 + e(O)) at Ba = 0, T = 0 K, where the zero-point
spin-reduction e(O) = 2.3%. ln the antiferromagnetic canted phase of EuTe (0 <Ba< Bcro see
Gmelin Handbook
RE Main Vol. C10
p. 183), I B~11 1 decreases with increasing external field. At Ba = Bcr ( = 7.33 Tat 0 K), IB~11 1 =
1Be11 1of the now paramagnetic phase with ferromagnetic spin alignment (s = 0), Schwarz et
al. [4]. The effective field at this phase transition is Be11 = -24.43(10)T, derived from 153 Eu
NMR by extrapolationtoT = 0 K [4, 5].
ln the High Field Paramagnetic Phase. The total magnetic hyperfine field at ferromagnetic
alignment is Bht = -32.14(10) T, from 153 Eu-NMR by extrapolationtoT = 0, Schwarz et al.
[4]. Schwarz [5]. Values for Bht derived from 151 Eu Mössbauer studies at 4.2 Kare -31.5(2) T,
Saueret al. [12], and -31.4 T, Lütgemeier et al. [11]. both for extrapolation to zero field.
Earlier a value of -30.6 ± 0.5 T was given by Saueret al. [9, 10] presumably due to a different
treatment of the dipolar field. Bht = -31.25(8) T for Ba = 12 Tat 4.2 K, Zaker et al. [15, 16].
Pressure Dependence ol Be11 and Bht
Based on 151 Eu Mössbauer studies, the effective field Be11 at the Eu nuclei in the anti-
ferromagnetic phase at 4.2 K changes from -23.8 T at 0 kbar to -24.1 T at 57 kbar;
oBe11/op = -0.005 T/kbar. Studies at 4.2 and 2 K give oBe11/oln V = -2(1) T for T-> 0 K,
Klein et al. [17]; a value of 0 ± 0.4 T at 4.2 K was reported earlier by Klein et al. [18].
ln the ferromagnetically aligned state (4.2 K, Ba = 12 T), oBh 1/op = -0.026(4) T/kbar or
oBh1/oa = + 47.3 T/nm from similar studies up to 18.6 kbar, Zaker et al. [15]; see also Sauer
et al. [12].
Transferred Hyperfine Fields
The spin-state-dependent transferred hyperfine field Btht is obtained from the total
hyperfine fields Bht by subtraction of the intrinsic hyperfine field B,ht· The latter is due to the
core s electron polarization caused by the 4f moment. B;ht = -28.3(1) T, derived from ESR
measurements on Eu-doped SrTe by Kojima et al. [8], is used also for pure EuTe. The so-
obtained transferred hyperfine fields derived from NMR and Mössbauer experiments can be
reasonably explained with only nearest-neighbor Eu2+ spin contributions (B 1) and next-
nearest-neighbor Eu2+ spin contributions (B 2 ). At type II antiferromagnetic spin order, Btht =
-6 B 2 and at ferromagnetic spin alignment, B1ht = 12 B1 + 6 B 2 , Bykovetz [2], Zinn [1]; see
also "Rare Earth Elements" C9, 1986, p. 194.
B 1 = -0.18(2) T and B2 = -0.27(2) T have been derived from 153Eu NMR, allowing for a
zero-point spin-deviation s = 2.3%. Neglecting s, the data yield B 1 = -0.13 T and B2 =
-0.37 T, Schwarz et al. [4, 5], compared with B 1 = -0.06 T and B2 = -0.38 T, from 151 Eu
Mössbauer spectroscopy, Sauer et al. [12]. Lütgemeier et al. [11], and 12 B1 = -0.6 T
(~ B 1 = -0.05 T) and 6 B2 = -2.4 T (~ B 2 = -0.4 T) estimated from data for Eu 1 _xGdxTe
[8]. For other superseded values, see [1].
The volume coefficients in terms of lattice constant (oB 1/oa)r = 4.7 T/nm and (oB 2/oa)r =
-1.5 T/nm were derived by Zaker et al. [15, 16] from own Mössbauer studies for the ferro-
magnetically aligned state and those from Klein et al. [17] for the antiferromagnetic state. lt
was assumed that B;ht is pressure invariant. This assumption seems justified from the
hyperfine field determinations in the EuxSr 1 _xS system [12]. The volume coefficients agree in
sign with the general behavior of B 1 and B2 vs. interatomic distance along the Eu mono-
Gmelm Handbock
RE Mam Vol. C 10
Eu Te 173
chalcogenide series as given by Lütgemeier et al. [11]; see Zaker et al. [15, 16]. For a
discussion of the B1 and B2 in the Eu monochalcogenides and their relation to the exchange
integrals J 1 , J 2 , see "Rare Earth Elements" C9, 1986, pp. 196/7 and the papers [15, 16, 19].
At the Sn2+ Nuclel in Sn-Doped EuTe
119Sn Mössbauer studies (23.8 keV y transition) on type II antiferromagnetic Eu 099 Sn 001 Te
reveal an effective field Be11 = + 4.35 T forT-+ 0 K (via T2 ) and a transferred hyperfine field
B1h1 ( = Be11 - Bdip) ~ + 4.0 T (read from a figure). The latter is due to only the next-nearest
Eu neighbors, Bykovetz [2] . Similar studies at 4.2 and 1.5 K as a function of pressure (0 to
54 kbar) give Be11 = + 4.21 (7) T for T --. 0 K (via T2) and B1h1 = + 3.88(9) T, both at ambient
pressure (p = 0 kbar) . The fields increase with increasing p (decreasing lattice constant) to
Be11 = +5.51(11) T and Btht = + 5.16(11) T, respectively, at 54 kbar. This corresponds to
aB,h1tatn V = -17(2) T, compared to the "chemical" aBtht/atn V = -3.6 T from the volume
decrease upon going from EuTe to EuSe, Abd Elmeguid , Kaindl [20]. The same pressure
coefficients, but Befl = + 4.11(7) T and B1ht = + 3.78(9) T for 0 Kat p = 0, were given by Abd
Elmeguid [21 , p. 44/7] .
At the Te 2 - Nuclei
The problern of the possible existence of a hyperfine field Bh1 at the Te nuclei in the type II
antiferromagnetic phase in zero external field is not settled . The 125Te Mössbauer spectra at
4.2 K (Ba = 0) taken by Sauer, Zinn [22] revealed Bht = 0 in agreement with the expected
cancellation of the transferred hyperfine fields from nearest or next-nearest Eu neighbors at
the Te site. ln contrast, other authors studying conducting samples (Q ~ 10- 2 Q · cm) observed
strongly broadened lines at 4.2 K (Ba = 0), from which they estimated IBhtl = 7.3 T, Blum ,
Franke! [23] or IBhtl = 4.9 T, Sadovskaya et al. [24] . A tentative assignment of NMR spin
echoes toTe resonances gave IBhtl ~ 8.6 Tat 1.4 Kin both a conducting and a nonconducting
sample, Raj et al. [6] .
Fig. 75 from [22] shows the dependence of the effective magnetic fi eld Be11 at the Te
nuclei on the external magnetic field at 4.2 K. At Ba = 12.4 T the hyperfine field of the now
ferromagnetically aligned paramagnetic phase of EuTe and the external field cancel each
40
20
1-
.5 0
"t
CD
-20
8 0 inT
Fig. 75. Effective magnetic field Be11 at the 125Te nuclei in EuTe as a function of the external
field Ba·
Gmelm Handbock
RE M ain Vol. C 10
other, Bh, = -12.4 ± 0.5 Tor -2.06 T per nearest Eu neighbor [22]. An initially slow increase
of IBhtl with Ba is described in [23] with \Bhtl = 7.3, 7.8, 8.1, and 11.3T at Ba= 0, 5.0, 6.5,
and 7.0 T, respectively; the rapid rise occurs near the transition from the canted to the
ferromagnetically aligned state at Ba ~ 6.6 T [23].
References:
[1] W. Zinn (J. Magn. Magn. Mater. 3 [1976]23/36).

[2] N. Bykovetz (Solid State Commun. 18 [1976]143/8).
[3] N. Bykovetz (Diss. Univ. Pennsylvania 1976, pp. 1/270; Diss. Abstr. Intern. B 37 [1976]
1759; C.A. 86 [1977] No. 11327).
[4] B. R. I. Schwarz, H. Lütgemeier, W. Zinn (J. Magn. Magn. Mater. 45 [1984]369/76).
[6] K. Raj, J. I. Budnik, T. J. Burch (AlP [Am. lnst. Phys.] Conf. Proc. No. 24 [1974] 44/6).
[7] T. Hihara, T. Komaru, Y. Koi (Ferrites Proc. Intern. Conf., Kyoto 1970 [1971], pp. 623/5;
C.A. 76 [1972] No. 92047).
[8] K. Kojima, T. Komaru, T. Hihara, Y. Koi (J. Phys. Soc. Japan 40 [1976]1570/4).
C6-274).
[10] C. Sauer, W. Zinn (Physica B + C 86/88 [1977]1031/2).
[11] H. Lütgemeier, C. Sauer, W. Zinn (Mater. Res. Soc. Symp. Proc. 3 [1981]467/72).
[12] C. Sauer, A. M. Zaker, W. Zinn (J. Magn. Magn. Mater. 38 [1983] 225/34).
[13] G. K. Shenoy, F. Holtzberg, G. M. Kalvius, B. D. Dunlap from G. J. Ehnholm, T. E. Katila,
0. V. Lounasmaa, et al. (Z. Physik 235 [1970]289/307, 301).
[14] H. H. Wickman, R. L. Cohen from A. A. Gomes, R. Moreira Xavier, J. Danon (Chem. Phys.
Letters 4 [1969] 230/40).
[15] A. M. Zaker, C. Sauer, W. Zinn (J. Magn. Magn. Mater. 27 [1982]337/42).
[16] A. M. Zaker (JUEL-1817 [1982]1/80, 42/60; C.A. 98 [1983] No. 99900).
[18] U. F. Klein, G. Wortmann, G. M. Kalvius (Europhys. Conf. Abstr. 1A [1975] 43/4; C.A. 85
[1976] No. 185905).
[19] C. Sauer, A. M. Zaker, W. Zinn (J. Magn. Magn. Mater. 31/34 [1983]423/4).
[20] M. Abd Elmeguid, G. Kaindl (J. Phys. Colloq. [Paris]40 [1979] C2-310/C2-312).
[21] M. Abd Elmeguid (INIS-mf-5123 [1979]1/87, 44/51; C.A. 92 [1980] No. 13291).
[22] C. Sauer, W. Zinn (J. Magn. Magn. Mater. 3 [1976]46/9).
[23] N. A. Blum, R. B. Frankel (AlP [Am. lnst. Phys.] Conf. Proc. No. 29 [1976]416/7).
30.1 .2.10.8.2.8 Mechanical Properlies
Density in g/cm 3
The pycnometric density Dexp = 6.40 is given for a EuTe sample with Deale = 6.50, from
the lattice parameter a = 6.590 A, Sadovskaya et al. [1]. Deale = 6.45 from a = 6.598 A,
Wachter [2]. Dexp = 6.47 is attributed to stoichiometric EuTe whereas densities as low as 6.41
and 6.40 of the nonstoichiometric samples obtained from melts with Eu :Te ratios of 0.8 or 1.14
Gmelin Handbook
RE Mam Vol. C10
Eu Te 175
are explained by Eu and Te deficits (corresponding to Eu 0 .986Te and EuTe0 _980 , respectively),
Ravot et al. [3]. The density DeaLe = 6.55 at 77 K was calculated by Shapira, Reed [4] from the
lattice parameter a = 6.57 A at this temperature, Rodbellet al. [5].
The molar volume VmoL = 43.3 cm 3 , Jayaraman et al. [6].
Compressibility. Elastlc Constants
EuTe exhibitsanormal compression curve up to about 110 ± 10 kbar, where it transforms

from the NaCL to the CsCL type; see a figurein "Rare Earth Elements" C7, 1983, p. 432, for all
Eu monochalcogenides. The relative volume VIV0 (V0 = volume at ambient pressure) in Eu Te
decreases in the NaCL phase to ~0.84, at the transition to ~0.74, and only slightly in the CsCL
type phase (studied up to ~ 140 kbar), Jayaraman et al. [6], Chatterjee et al. [7]. The relative
volume change of the transition is llVIV = -11.6%, Singh et al. [8], Jayaraman et al. [9], cf.
p. 10. A different behavior is described by Rooymans [10] who found an anomalously large
compressibility between ~25 and 40 kbar; see p. 164.
The initial bulk modulus K0 = 400 ±50 kbar (:= 40 GPa) is obtained from the data of [6].
A compressibility K = 2.5X10- 3 kbar- 1 (:= 2.5x10- 11 Pa-1; K0 = 40±3GPa) is derived
from the linear change of the Lattice constant of a single crystal up to 4 kbar, in good agreement
with K = 2.3 x 10- 3 kbar- 1 estimated from IR data, Levy, Wachter [11]. The bulk modulus
of EuTe fits reasonably weiL into the linear relation that exists between Ln K and Ln VmoL
(VmoL = molar volume) of divalent rare earth monochalcogenides and some alkaline earth
chalcogenides, i.e., an Anderson-Nafe plot [6, 11].
The adiabatic compressibility at 77.6 K of n-type EuTe K 8 = (2.8 ± 0.4) x 10- 11 Pa- 1
(:= K8 = 357 kbar), is calculated from the elastic constants, Shapira, Reed [4, 12].
K ~ 1.2 x 10- 3 kbar- 1 at 0 K is estimated from compressibility measurements between 200
and 280 K, giving K values from 3.0 x 10- 3 to 3.6 x 10- 3 kbar- 1 ; see the figure in the paper,
Hidaka [13]. K = 1.3 x 10- 3 kbar- 1 at 4.2 K was estimated by Abd Elmeguid, Kaindl [14] from
the room temperature value (from [11]) and the temperature dependence of K observed for
EuS.
The elastic constants (in 1011 dyn/cm 2 = 1010 Pa) c 11 = 9.36 ± 0.4, c 44 = 1.63 ± 0.07, and
c 12 = 0.67 ± 0.6 for 77.6 K were obtained from the sound velocities [4, 12].
Sound Propagation
The sound velocities in km/s at 77.6 K are 3.78 and 3.19 for longitudinal modes with
propagation vector q I [100] and [110], respectively, 1.58 for shear modes, both with q I [100],
displacement vector ~in the (100) plane and q I [110], ~II [001], and 2.58 for the shear mode
with q I [110] and ~II [110], Shapira, Reed [4, 12]. Similar values of sound velocities were
observed in the paramagnetic spin aligned phase at 4.2 Kin magnetic fields B > Ber (Ber =
critical field, see p. 183) [4].
The attenuation of these five waves using frequencies from 10 to 50 MHzwas determined
for a melt-grown, conducting EuTe single crystal at 1.4 ~ T ~ 14 K and in magnetic fields up
to 10 T. At B = 0, the attenuation for shear waves with q I [100] increased abruptly as the
sample entered the antiferromagnetic phase at TN = 9.6 K. Detailed studies below 4.2 K
Gmelin Handbock
RE Main Vol. C10
showed a rather complex magnetic field dependence. Fields on the order of 0.01 T, which
increase the magnetization of the sample rapidly, also increase the attenuation of some
modes, whereas the attenuation of other modes decreases; see figures in paper. The first
category includes the shear modes with Ci I [100], (in (100) and with Ci I [110], (II [001], and
the Longitudinalmode with q, (II [110]. High field experiments with H Ii [100] for these modes
show that at 8 ~ 0.3 T the attenuation is higher in the canted phase (8 <Be,) than in the
paramagnetic phase (8 >Be,), that it decreases monotonically with increasing 8 up to a peak
and an abrupt drop at Bcro and that it is field invariant in the paramagnetic phase. (The peaks
observed at constant temperatures ~ 4.2 K and those observed at constant 8 for T > 4.2 K
were used for a determination of Bcr for 0 K, see p. 196.) High-field experiments at 4.2 K with
H along [110] showed that for these three modes the attenuation in the canted phase (at Least
for 8 ~ 1.5 T where echoes could be seen) first decreases with increasing 8 and Later becomes
nearly field independent. This occurs for two of these modes at 8 ( ~ 3.5 T) < Bcro whereas for
the third mode, the attenuation has a small peak at Bcr [4]. Fora preliminary report on shear
waves propagating along the [100] direction, see Shapira, Reed [15]. ln the second category
including the Longitudinal mode with q, (II [100] and the shear mode with q I [011], (II [011],
the attenuation does not show any Large effects at higher fields after the initial drop and does
not show any Large effect at Bcr for either H I [100] or H I [110], see [4].
The experimental results are not well understood. Perhaps the coupling of phonans to
Low-frequency spin waves plays a role. A mechanism involving the interaction of ultrasonic
waves with antiferromagnetic domains (see p. 182) can only partially explain the observations.
The peaks at Be, observed for some modes may be related to critical fluctuations in the spin
system or to an abrupt Lattice distortion. For more details on both the experimental results
and the models, see the paper [4].
References:

Neorgan. Materialy 8 [1972] 815/20; lnorg. Materials [USSR] 8 [1972] 708/12).
[2] P. Wachter (in: K. A. Gschneidner Jr., LeRoy Eyring, Handbook on the Physics and
[ 1980] C5-357 /C5-359).
[4] Y. Shapira, T. 8. Reed (Phys. Rev. [3] 8 5 [1972] 2657/67).
[6] A. Jayaraman, A. K. Singh, A. Chatterjee, S. Usha Devi (Phys. Rev. [3] 8 9 [1974]
2513/20).
[7] A. Chatterjee, A. K. Singh, A. Jayaraman (Phys. Rev. [3] 8 6 [1972]2285/91).
[9] A. Jayaraman, P. D. Dernier, L. D. Longinotti (High Temp.-High Pressures 7 [1975].
1/28, 6).
[11] F. Levy, P. Wachter (Solid State Commun. 8 [1970]183/5).

[12] Y. Shapira, T. 8. Reed (AlP [Am. lnst. Phys.] Conf. Proc. No. 5 [1972] Pt. 2, 837/9).
[14] M. Abd Elmeguid, G. Kaindl (J. Phys. Colloq. [Paris] 40 [1979] C2-310/C2-312).
[15] Y. Shapira, T. 8. Reed (Phys. Letters A 31 [1970] 381/2).
Gmelm Handbook
RE Mam Val. C10
Eu Te 177
30.1.2.1 0.8.2.9 Thermal Properties
Thermal Expansion
The change in the Lattice parameter near room temperature (see p. 163) corresponds to
the Linear thermal expansion coefficient r:x. = 13.6 x 10- 6 K- 1 in a single crystal, Levy [1].
Melting Point
The melting point of EuTe is tm = 2183 ± 2°C ( ~ Tm= 2456 ± 2 K), determined by thermal
analyses in sealed Mo crucibles. A maximum supercooling of 70°C was observed, Reed et al.
(2]. Earlier EuTe was supposed to melt between 2320 and 2450°C, Reed, Fahey (3] or around
2300°C, Katdis (4] from crystal growth studies; tm > 2000°C, Methfessel et al. [5]. ln marked
contrast a melting point of 1525°C for EuTe was assumed in the construction of the Eu-Te
system (see p. 158), Sadovskaya, Yarembash [6].
Vaporization. Sublimation
EuTe vaporizes congruently according to X-ray studies by Petzet [7] and X-ray and chemical
analysis by Nagai et al. [8]. lt sublimes mainly according to EuTe(s) ---> Eu(g) + r:x.Te(g) +
0.5(1- r:x.) Te 2 (g) with r:t = 0.996 to 0.980 at temperatures between 1800 and 2300 K. A figure
in the paper shows that the vapor pressure PKn under equilibrium (Knudsen regime) decreases
from ~10Torr at 2273K to ~0.3Torr at 1873K and that at free vaporization (Langmuir
regime), the vapor pressure PL decreases from ~0.03 Torr at 1873 K to ~ 3 x 10-s Torr at
1473 K. The evaporation coefficient r:x. = PLIPKn is 0.1 and 0.2 at 1473 and 2 273 K, respectively.
This order of magnitude indicates that the evaporation and probably also the condensation
are activated processes even though they take place at such high temperatures, Kaidis [9].
Partial pressures of the gas phase components were calculated using thermodynamic
data from the Literature (however, the values reported in the paper for the equilibrium constant
KP, for Pre,• Pre• PEu• and their sum ~p at 2070, 2200, and 2320 K are in part inconsistent),
Vel'mizov et al. [10]. From Knudsen effusion experiments at 1717 to 1887 K and from the
thermodynamic data it was concluded that Eu and Te are the principal vapor species in that
temperature range and that Less than 1 and 0.2% of the vapor is present as EuTe and
Te 2 , respectively. Neglecting the presence of Te 2 , weight Loss studies yield the temperature
dependence of KP of the atomization EuTe(s)---> Eu(g) + Te(g) as
log KP = - (39160 ± 594) · T- 1 + (12.26 ± 0.33) (Kp in atm 2 ).
The equilibrium pressure of the Sublimation EuTe(s)---> EuTe(g) follows
Log PEuTe = - (26288 ± 305). T- 1 + (7.60 ± 0.17) (p in atm)

Petzet [7].
Gmeltn Handbook 12
RE Ma1n Vol. C10
Second- and third-Law enthalpies and entropies of sublimation and atomization for 1803
and 298 K derived from weight Loss studies [7] and for 0 K from mass spectrometric studies
[8], using Knudsen effusion cells, are (ßH in kcal/mol, ßS in cal · mol - 1 · K- 1):
Tin K. 1803 298 298 0

treatment 2nd Law 3rd Law 3rd Law
ßHsub · 120.3 ± 1.4 126.6 ± 2.0 126.4 ± 3.8 126.8 ± 6.5

ßSsub 34.8 ± 0.8 42.8 ± 1.6 42.3
ßHat 179.2 ± 2.7 184.5 ± 3.2 183.6 ± 3.0 185.9 ± 4.3
ßSat 56.1 ± 1.5 62.1 ± 2.1 61.6
ßH~ 1 (298) = 182 kcal/mol and 196 kcal/mol for atomization under equilibrium and free atomiza-
tion, respectively, Kaldis [9], cf. McMasters et al. [11].
Thermodynamic Data of Formation
The enthalpy, entropy, and Gibbs free energy of formation of EuTe from the elements
under standard conditions ßHf(298) = -93.2 ± 0.8 kcal/mol (~ -389.9 kJ/mol), ßSf(298) =
-3.26 ± 1.2 cal· mol- 1 · K-1, and ßGf(298) = -92.2 ± 1.2 kcaUmol were calculated from
calorimetric data and from Literature data of EuTe (from [9]), McMasters et al. [11], cf. [12].
ßHf(298) = -96.6 ± 5.4 kcaUmol was derived from the heats of formation of the gaseous
elements (taken from Literature), Petzel [7]. The values ßHf = -265.0 and -224.0 kJ/mol for
the formation from elements in the solid state and in the Liquid state, respectively, were
estimated by Sheinfel'd [13] from melting point data.
Selected values for ßHfand ßGfas a function of temperature up to 1700 K for the elements
in their normal reference state (Eu is solid up to 1 090 K and Liquid between 1 090 and 1700 K;
Te is solid up to 723 K, Liquid between 723 and 1262 K, and gaseous above 1262 K) are in
kcal/mol; error Limits ±2.0 kcaUmol [11]:
Tin K 400 723 723 900 1090 1090 1262 1262 1500 1700
93.2 93.8 98.0 98.8 99.7 101.9 102.6 114.9 114.7 114.4
91.8 90.6 88.9 86.7 84.2 78.5 73.7
For the formation according to Eu(s) + 1/ 2 Te 2 (g)--> EuTe(s), ßHf(298) -113.3 kcaUmol
[11].
Heat Capacity and Additional Thermodynamic Functions
At Low Temperatures
The heat capacity of pressedEuTe powder determined calorimetrically between 1.3 and
20 K (see a figurein the paper) exhibited a relatively broad peak with CP ~ 18 J · mol- 1 · K- 1
at 9.64 ± 0.06 K attributed to the Neel temperature, Busch et al. [14]. Fig. 76 shows the
measured heat capacity forapure (high resistivity) single crystal grown in a tungsten crucible
and annealed for 24 h at 1500 and 1 000 K in Ar and in a vacuum, respectively, Johanson [15].
This sample has CP > 40 J · mol- 1 · K- 1 at 9.816 K. The analysis of the data near TN by
Gmelin Handbook
RE Mam Vol. C 10
Eu Te 179
40
~
~ I
...., 20
.5 I
V ----
Q.
u
\...
/ 4 8 12 16 20
Temperature in K
Fig. 76. Molar heat capacity CP of a EuTe single crystal versus temperature .
cp = (A' /a.) ·It ,-o

+ E. t + B below TN• with A: replaced by A above TN• where t = (T- TN)/ TN•
suggested that the peak is rounded at Jtl < 0.005. A weighted Least-squares fit to the data
outside this region up to Jtl = 0.06 yielded the following parameters : a. = 0.08 ± 0.06, AlP.: =
0.75 ± 0.15, E = 7 ± 10, B = -30(errorlimits + 30, - 50) , TN = 9.816 ± 0.005K ; rootmean
square deviation : 0.0044. The use of a different expression for Cp did not give a more satisfying
result. The obtained exponent a. agrees with the renormalization-g roup prediction f or a
second-order transition of a system having n = 2. Since EuTe under zero stress has n = 8,
a uniaxial thermal contraction is supposed to be present. A weakly Mo-contaminated sample
(grown in a Mo crucible) had a Lower peak height and a Neel temperature about 10 to 15 mK
higher than the sample described above, Johanson, McCollum [16) ; seealso [15] .
The magnetic entropy of the pure crystal was 17.0 J · mol - 1 · K - 1, tobe compared to the
expected value of Rln (2S + 1) = 17.3 J · mol- 1 · K- 1 for Eu 2 + with spin S = 7/2 [ 15, 16). A
magnetic entropy of 16.9 J · mol- 1 · K- 1 was determined from CP measurements between 0.5
and 20 K, Passenheim , McCollum [17); seealso Passenheim [18] . The sample had an oxygen
content of 0.327 ± 0.010% by weight. Other samples with higher oxygen content had Lower
entropies [18]. The value 12 J · mol- 1 · K - 1 was found for the pressed powder sample [14].
At Room Temperature and Above
Enthalpies were measured from 424 to 1728 K in a copper block drop calorimeter and
found to vary nearly Linearly with the temperature. Above 800 K this is described by
H~ -H~98 _ 1 5 = -3462.841 + 11 .3421 T + 1.0778 x 10- 3 T2 (cal/ mol)
McMasters et al. [11 , 12). Heat capacities derived at the Lower temperatures were adjusted
to give a CP vs. T curve paralleltothat for EuS, for which more accurate Low tempe rature data
were available. From this adjusted CP curve revised values of the enthalpy increments were
derived. The standard entropy was estimated from S~98 ( EuTe) = Sm (EuS)- S~98 (S) + S~98 (Te)
Gmelin Handbock 12.
RE Main Vol. C 10
with values of S~ 98 for the chalcogens taken from Wagman et al. [19]. Selected values for
H~- H~ 98 in caUmol and for CP, S~, and (G~- H~ 98 )/T in cal · mol - 1 · K - 1 are [11]:
T 298.15 500 700 900 1100 1300 1500 1700
cp 12.47 12.79 12.98 13.28 13.71 14.14 14.57 15.00

H~- H~sa 0 2559 5136 7618 10318 13103 15975 18934
s~ . 27.17 33.73 38.07 41.36 44.07 46.39 48.45 50.30
- ( G~- H~ 98 )/T 27.17 28.61 30.73 32.90 34.69 36.31 37.80 39.16
Debye Temperstures
The Debye temperature 8 0 = 189 K was derived from Ultrasound velocities at 77 K,

Shapira, Reed [20]; 8 0 = 150 ± 10 K, Passenheim, McCollum [17] and 8 0 = 140 K, Busch et
al. [14] were calculated from specific heat measurements. A value of 8 0 = 400 K was said
tobe consistent with the observed lattice constant variation below room temperature, Rodbell
et al. [21]. 8 0 = 199 K was derived from compressibility data above 200 K by Hidaka [22].
The thermal conductivity /... of a sintered hot-pressed Eu Te sample was measured between
4 and 25 K and can be described by a T 2 dependence; approximate values from a figure are
0.1, 0.9, and 3.4 W · m - 1 · K - 1 at 4, 10, and 25 K, respectively. The sample had a density of
5.09 g/cm 3 , which is 79% of the expected value for bulk EuTe, Seward, Taylor [23].
References:
[1] F. Levy (Physik Kondensierten Materie 10 [1969] 71/84, 78).

[2] T. B. Reed, R. E. Fahey, A. J. Strauss (J. Cryst. Growth 15 [1972]174/8).
[3] T. B. Reed, R. E. Fahey (J. Cryst. Growth 8 [1971]337/40).
[4] E. Kaldis (J. Cryst. Growth 9 [1971]281/94, 284).
[5] S. Methfessel, 0. E. Eastman, F. Holtzberg, et al. (Colloq. Intern. Centre Natl. Rech. Sei.
[Paris] No. 180 [1969/70]565/77, 574; C.A. 78 [1973] No. 77147).
[7] T. Petzel (High Temp. Sei. 6 [1974) 246/53).
[8) S.-1. Nagai, M. Shinmei, T. Yokokawa (J. lnorg. Nucl. Chem. 36 [1974]1904/5).
York, 1974, pp. 49/191, 142/4).
[10) S. I. Vel'mizov, V. K. Gartman, L. A. Klinkova (lzv. Akad. Nauk SSSR Neorgan. Materialy
19 [1983] 31/5; lnorg. Materials [USSR)19 [1983] 25/9).
[11) 0. 0. McMasters, K. A. Gschneidner Jr., E. Kaldis, G. Sampietro (J. Chem. Thermodyn.

6 [1974) 845/57).
Gmelm Handbook
RE Mam Vol. C 10
Eu Te 181
[12] 0. D. McMasters, K. A. Gschneidner Jr., E. Kaldis, G. Sampietro (Proc. 10th Rare Earth
Res. Conf., Carefree, Ariz., 1973, Pt. 2, pp. 970/5).
[13] V. L. Sheinfel'd (lzv. Akad. Nauk SSSR Neorgan. Materialy 18 [1982] 2059/60; lnorg.
Materials [USSR]18 [1982]1785/7).
[14] G. Busch, P. Junod, R. G. Morris, J. Muheim, W. Stutius (Phys. Letters 11 [1964] 9/10).
[15] W. R. Johanson (Diss. Univ. California, Riverside 1978, pp. 1/136; Diss. Abstr. Intern. B
39 [1978/9] 5439/40).
[17] B. C. Passenheim, D. C. McCollum (Bull. Am. Phys. Soc. [2]13 [1968]1645).
[18] B. C. Passenheim (Diss. Univ. California, Riverside 1969, pp. 1/156, 69; Diss. Abstr. Intern.
B 30 [1969] 2374).
[19] D. D. Wagman, W. H. Evans, V. B. Parker, I. Halow, et al. (NBS-TN-270-3 [1968] 1/264;
C.A. 69 [1968] No. 30787).
[20] Y. Shapira, T. B. Reed (Phys. Rev. [3] B 5 [1972] 2657/67).
[21] D. S. Rodbell, L. M. Osika, P. E. Lawrence (J. Appl. Phys. 36 [1965]666/7).

[23] W. D. Seward, D. J. Taylor (J. Am. Ceram. Soc. 56 [1973] 599).
30.1.2.1 0.8.2.1 0 Magnetic Properlies
For the description of doped or nonstoichiometric EuTe samples, see p. 196.
30.1.2.1 0.8.2.1 0.1 lntroduction and General
Antiferromagnetic ordering in EuTe was first interred from the negative paramagnetic
Curie temperature, McGuire et al. [1, 2] and from further magnetization, Busch et al. [3], and
susceptibility vs. temperature curves, van Houten [4], Enz et al. [5] with a Neel temperature
TN ~ 8 to 11 K. The type II antiferromagnetic order (MnO type) was indicated by neutron
diffraction, Will et al. [6, 7]; seealso Will [8].
EuTe is regarded as a nearly ideal model substance of a Haissenberg antiferromagnet,

Methfessel, Mattis [9]. Usually the observed magnetic behavior is described by two
parameters, J 1 and J 2 , which within the molecular field approximation represent the exchange
interaction of a Eu 2 + ion with its 12 nearest neighbors (nn) and with the 6 next-nearest
neighbors (nnn), respectively. lnteractions with more distant cations are neglected.
Mössbauer [10] or neutron scattering experiments [11] on Eu monochalcogenides, however,
indicate that this restriction is a simplification giving only effective exchange integrals, J 1 and
J2 , within a two-parameter model, Zinn [12].
References:
[1] T. R. McGuire, B. E. Argyle, M. W. Shafer, J. S. Smart (Appl. Phys. Letters 1 [1962]17/8).

1962, pp. 727/31; C.A. 60 [1964] 2423).
Gmelin Handbock
RE Mam Vol. C10
[4] S. van Houten (Phys. Letters 2 [1962] 215/6).

[5] U. Enz, J. F. Fast, S. van Houten, J. Smit (Philips Res. Rept. 17 [1962] 451/63).
[7] G. Will, S. J. Pickart, H. A. Alperin, R. Nathans (CONF-20-17 [1962]1/25; N.S.A. 17 [1963]
No. 30967; Bull. Am. Phys. Soc. [2] 8 [1963]213).
[8] G. Will (Angew. Chem. 81 [1969]984/95; Angew. Chem. Intern. Ed. Engl. 8 [1969]950/61).
[9] S. Methfessel, D. C. Mattis (in: S. Flügge, Encyclopedia of Physics, Vol. 18, Pt. 1, Springer,
Berlin 1968, pp. 389/562, 504/12, 507).
[10] C. Sauer, W. Zinn (Physica B + C 86/88 [1977]1031/2).
[11] H. G. Bohn, W. Zinn, B. Dorner, A. Kollmar (J. Appl. Phys. 52 [1981]2228/30).

[12] W. Zinn (J. Magn. Magn. Mater. 3 [1976] 23/36, 24, 26).
30.1.2.10.8.2.10.2 Magnetic Structure. Magnetic Phase Diagram
A neutron powder diffraction study (A. = 1.055 A) showed antiferromagnetic order of type II
Like MnO where the Eu spins of a single (111) plane are parallel to each other and the plane.
The spins of neighboring planesareanti parallel, Will et al. [1, 2]. The theoretically predicted
Lattice contraction or distortion at TN is still controversial, Rodbellet al. [3], Uwy [4], Vitins,
Wachter [5]; see also p. 163.
The variation of the intensity of the magnetic reflections from (111) planes is not described
by a Brillouin temperature dependence. The discrepancy is related to biquadratic exchange
in addition to the usual bilinear term, Will et al. [1]. EuTe showseasy plane behavior ([111]
the hard axis) as determined by antiferromagnetic resonance (AFMR) measurements, which
also showed a weak anisotropy within the {111} easy planes, which makes (112) the easy
axes at zero field, Battles, Everett [6]; the equivalent [112] direction is given by Nakai et al.
[7]. For the anisotropy energies and the anisotropy fields, see p. 186. The symmetry reduction
du ring the magnetic ordering Leads to the formation ofT domains (in correspondence to the
four different planes { 111} in the paramagnetic phase) in each of which there are up to three
S domains with the spins along (112), [6, 8]. Macroscopic crystals therefore show a nearly
isotropic behavior in magnetization and NMR experiments, Schwarz et al. [9], Schwarz [10].
The domain structure is not noticeably influenced by cooling through T N in magnetic fields up
to 24 kOe, yet cooling through TN with application of a uniaxial stress along [111] is expected
to produce single domain samples, Streit, Everett [11]. The four T domains are expected to
show birefringence, which makes the domain structure directly visible on pure and iodine-
doped EuTe single crystals in a polarizing microscope. The domain pattern in the pure sample
is practically unaltered by a magnetic field of 3 kOe parallel to the transmitted beam, whereas
the domain pattern vanishes in the doped sample and the transmitted Light becomes strongly
depolarized. The difference is attributed to the presence of ferromagnetic spin clusters in the
doped sample, Vitins, Wachter [5].
The magnetic phasediagram is given in Fig. 77, Schwarz [10]. A magnetic field parallel to
(112) Leaves the spin structure unchanged unless it exceeds a certain value, the spin flop
±
field B1 = 0.077 0.02 T ~ (2 Ba· BE)% with Ba the in-plane anisotropy field and BE the
intersublattice exchange field of the molecular field approximation (MFA) [6]. At B1 the spin
vectors flop to a position perpendicular to the applied fieldas expected within the Neel theory
of antiferromagnets, Oliveira et al. [8], cf. [6, 7]. Magnetic fields perpendicular to the spin
direction (112) turn the spins of both sublattices towards the direction of the applied field.
Gmelm Handbock
RE Mam Vol C10
EuTe 183
poramagnetic
rJl
8
~
6 ~
"""
.....
.5 ~
\.
ID 4 ~;f 1\.
canted spin
2
\
AF n
---r--~-- - - - ---
2 4 6 8
Tempereture in K
Fig . 77. Magnetic phase diagram of EuTe (field is valid for spherical samples) . The fu llline
represents data from [8], the points correspond to [10] .
7.5 .-------,...---...-------,-----.
'1.33
.....
.5
af ·
6·0o
! ,---:!:-
s ----+-,o:-----f.,s=-----'
T2 in K2
Fig . 78. Critical field Bcr of EuTe vs. T2 from NMR (full c ircles), r.f. susceptibility (open circles) ,
magnetization (squares) , and relaxation time T 2 (vertical bars). The dashed line is from [8],
the dash-dotted line is from [11].
The canting angle 0 in the canted-spin structure depends on th e field strength, sin 0 =
B/ Bcro B; = internal field. At a critical field Bcr there is a second-order phase transition to
the paramagnetic phase with induced ferromagnetic spin orde r. Within MFA thi s critical field
is twice the exchange field , Bcr ~ 2 BE [8, 9]. Extrapolations to T = 0 K assuming a T 2 tem-
perature dependence give Bcr = 7.33(3) T from NMR experiments (Fig. 78) , Schwarz et al. [9] .
Gmel m Handbook
RE Main Vol. C 10
Bc,(O) = 7.22 ± 0.1 T from differential susceptibility measurements and extrapolationtoT = 0

from Bc,(T) = Bc,(O) · (1 - cxt'''), t = T/T N• Oliveira et al. [8]. Bc,(O) = 7.25 ± 0.1 T from the
Faraday rotation experiments (no power of the temperature dependence specified), Schoenes,
Wachter [12]; Bcr = 7.5 ± 0.2 Tat 1.5 K from magnetoreflectance measurements, Pidgeon et
al. [13]. A value of 7.30 T for the exchange field BE (apparently twice the exchange field BE of
MFA) has been compared to Bcr and the good agreementwas said to be partially fortuitous,
Streit, Everett [11]. For Bc,(T) data of conducting samples from Shapira, Reed [14], see p. 196.
A small deviation from the T''' Law appeared below 2 K [8]. By also considering Long range
dipolar interactions within spin wave theory, Figueiredo, Salinas [15] showed a Linear
dependence of Bcr on T2 in the Low-temperature Limit and obtained a very good agreement
between their theory and the experiment [15].
Specific heat measurements gave TN = 9.64 ± 0.06 K, Busch et al. [16, 17], and the
maximum in d:xtdT(T) gave 9.58 ± 0.10 K, Schwob, Vogt [18], Schwob [19], or 9.6 ± 0.1 K,
Oliveira et al. [8, 20], confirmed by Nakai, Hirahara [21], Vitins, Wachter [5, 22], Schwarz et
al. [9]. ln antiferromagnetic resonance conditions, T N = 9.6 ± 0.2 Kat 9.20 GHz and a magnetic
field of ~2 to 3 kOe and T N = 9.35 ± 0.10 Kat 33.99 GHz and ~ 11 kOe were found [21]. TN =
9.6 K or values only insignificantly different therefrom are also reported for doped samples
(showing n-type conductivity), Shapira et al. [14, 23, 24]. A value TN= 10 to 11 K is reported
for a high-resistivity sample of attributed composition EuTe0 .980 (from the observed effective
magnetic moment, 7.89 l!s, see p. 196) by Ravot et al. [25]. Other reported values are T N =
9.81 ± 0.05 K, Passenheim, McCollum [26], 9.81 ± 0.01 K, Johanson, McCollum [27] from
specific heat measurements, TN = 8.7 K from magnetization measurements, Hidaka et al. [28]
(see also [29]), TN = 7.8 K from neutron diffraction, Will et al. [1, 2], and TN ~ 8 K, Busch et al.
[30]. Other, mostly earlier values forT N ranging from ~6 K [31, 32] to ~ 11 K [33 to 35] possibly
suffered from problems with sample quality and calibration of thermometers, Wachter [36,
p. 514].
Theoretical estimates of the Neel temperature based on a Green's function method

(random phase approximation) gave TN = 9.76 ± 0.41 K, using exchange integrals J 1 and J 2
from fits of the experimental specific heat curve, Masset [37]. These calculations have been
criticized as giving TN too high and TN = 8.56 K is given for the identical model, Swendsen
(38]. The more advanced "Modified Gallen Decoupling" method yields TN= 9.59 K, Swendsen
[39] using the J1 and J 2 values of [37]. Attempts to calculate TN by a Pade approximant analysis
gave TN ~ 2 to 3 K, Trowbridge et al. [40].
The Neel temperature has a small positive pressure coefficient; dT N/dp = 0.015(7) K/kbar
was derived from Mössbauer spectroscopy at pressures up to 60 kbar, Klein et al. [41]. Earlier
susceptibility measurements at pressures Less than 7 kbar yielded 0.1 K/kbar, Hidaka et al.
[28, 29] and pressure invariance ofT N• Schwob, Vogt [18].
The magnetic Grüneisen's constant YM = -d Ln T N/d Ln V= + 0.6(3) was derived by [41]

from the pressure coefficient ofT N and the observed bulk modulus (K 0 = 400 kbar, Chatterjee
et al. [42]), consistent with the range given by Schwob [19].
References:
[1] G. Will, S. J. Pickart, H. A. Alperin, R. Nathans (J. Phys. Chem. Solids 24 (1963]1679/81).
[2] G. Will, S. J. Pickart, H. A. Alperin, R. Nathans (CONF-20-17 [1962]1/25; N.S.A. 17 [1963]
No. 33967; Bult. Am. Phys. Soc. [2]8 [1963]213).
Gmelm Handbock
RE Mam Vol. C10
Eu Te 185

[4] F. LEwy (Physik Kondensierten Materie 10 [1969/70] 71/84).
[5] J. Vitins, P. Wachter (Phys. Rev. [3] B 12 [1975] 3829/39, 3833/4).
[6] J. W. Battles, G. E. Everett (Phys. Rev. [3] B 1 [1970] 3021/9).
[10] B. R. Schwarz (JUEL-1929 [1984]1/77; C.A.101 [1984] No. 221066).
[11] P. K. Streit, G. E. Everett (Phys. Rev. [3] B 21 [1980]169/82).

[12] J. Schoenes, P. Wachter (Physica B + C 89 [1977]155/8).
[13] C. R. Pidgeon, J. Feinleib, T. B. Reed (Solid State Commun. 8 [1970]1711/4).
[14] Y. Shapira, T. B. Reed (Phys. Rev. [3] B 5 [1972] 2657/67).
[15] W. Figueiredo, S. R. Salinas (Phys. Letters A 83 [1981] 231/2).
[16] G. Busch, P. Junod, R. G. Morris, J. Muheim, W. Stutius (Phys. Letters 11 [1964] 9/10).
[17] G. Busch, P. Junod, R. G. Morris, J. Muheim (Helv. Phys. Acta 37 [1964]637).
[18] P. Schwob, 0. Vogt (J. Appl. Phys. 40 [1969]1328/9).
[19] P. Schwob (Physik Kondensierten Materie 10 [1969/70]186/218, 200, 214).
[20] N. F. Oliveira Jr., S. Foner, Y. Shapira, T. B. Reed (J. Appl. Phys. 42 [1971]1783/4).
[21] J. Nakai, E. Hirahara (Solid State Commun. 11 [1972] 267/70).

[22] J. Vitins, P. Wachter (Tr. Mezhdunar. Konf. Magn., Moscow 1973 [1974], Vol. 1, Pt. 2,
pp. 140/5; C.A. 85 [1976] No. 55593).
[23] Y. Shapira, S. Foner, N. F. Oliveira Jr., T. B. Reed (Phys. Rev. [3] B 5 [1972]2647/57).
[24] Y. Shapira, T. B. Reed (Phys. Letters A 31 [1970]381/2).
[1980] C5-357/C5-359).
[26] B. C. Passenheim, D. C. McCollum (Bull. Am. Phys. Soc. [2]13 [1968]1645).
[28] Y. Hidaka, H. Fujii, T. Okamoto, E. Tatsumoto (J. Phys. Soc. Japan 29 [1970]515).
[29] Y. Hidaka (J. Sei. Hiroshima Univ. A 1135 [1971]93/110; C.A. 77 [1972] No. 94651).
1962, pp. 727/31; C.A. 60 [1964]2423).

[33] U. Enz, J. F. Fast, S. van Houten, J. Smit (Philips Res. Rept. 17 [1962]451/63).
[34] G. Busch, P. Junod, P. Schwob, 0. Vogt, F. Huttiger (Phys. Letters 9 [1964]7/8).
[35] G. Busch, P. Junod, 0. Vogt (Colloq. Intern. Centre Natl. Rech. Sei. [Paris] No. 157 [1967]
325/36).
[36] P. Wachter (in: K. A. Gschneidner Jr., LeRoy Eyring, Handbook on Physics and Chemistry
of Rare Earths, Vol. 2, North-Holland, Amsterdam 1979, pp. 507/74).
[37] F. Masset (Phys. Rev. [3] B 3 [1971]2364/5).
[38] R. H. Swendsen (J. Phys. C 6 [1973] 3763/73).
[39] R. H. Swendsen (Phys. Rev. [3] B 13 [1976] 3912/5).
[40] B. Trowbridge, P. C. Y. Chen, J. D. Patterson (Proc. South Dakota Acad. Sei. 47 [1968]
235/40; C.A. 71 [1969] No. 106925).
[41] U. F. Klein, J. Maser, G. Wortmann, G. M. Kalvius (Physica B + C 86/88 [1977]118/20).

[42] A. Chatterjee, A. K. Singh, A. Jayaraman (Phys. Rev. [3] B 6 [1972] 2285/91).
Gmelin Handbook
RE Main Vol. C10
30.1.2.1 0.8.2.1 0.3 Anisotropies
The phenomenological anisotropy energies (which relate the magnetic and the crys-
tallographic lattice) in antiferromagnetic EuTe have been evaluated from antiferromag-
netic resonance (AFMR) measurements, Battles, Everett [1], Nakai et al. [2], Streit, Everett
[3]. The dipolar or out-of-plane anisotropy field, which forces the spins to parallel the (111)
easy planes, was obtained as BA= 0.40 ± 0.04 T from 24 GHz AFMR at 1.17 K [1]. This value
has been confirmed by AFMR between 35.2 and 44.7 GHz and 1.8 K, probably with different
definitions, Borovik-Romanov et al. [4]. This field is equivalent to the anisotropy energy K1 =
4/ 3 BA· M = 0.24 x 106 W · s · m- 3 witn M = sublattice magnetization [1]. The value
K1 =
(0.197 ± 0.026) x 106 W · s · m- 3 (9.2 GHz AFMR at 1.7 K) [2] corresponds to the anisotropy
constant 0 1 = 0.13 K, Maekawa [5] using a relationship of Masset, Callaway [6] who
themselves give 0 1 = -0.13 K; see below. These experimental values are compared with
0.294 x 106 W · s · m- 3 at 0 K [2] from the theory of Keffer, O'Sullivan [7] and with a similar
value calculated by [1] referring to Kaplan [8]. (The anisotropy energy K of Kaplans paper
[8], used by Battles [1, 9], is 1/ 4 of K1 as defined by [7].) A differently defined out-of-plane
anisotropy energy Kd = (0.0817 ± 0.0015) x 106 W · s · m- 3 has been derived from high-
frequency AFMR experiments. The value is said to be 10% greater than the classically
calculated value (K~h = 0.0732 x 106 W · s · m- 3 ) [3] also referring to [8]. 0 1 = -0.13 K was
calculated together with the exchange integrals by fitting the experimental specific heat curve
within spin wave theory. lt is related by k 6 · 0 1 = -3 K1/(2 NS2) (with N = concentration of Eu
ions) to the definitions of [7], Masset, Callaway [6]. Very similar values are calculated by
Stevens using pseudo-boson operators [10]. K 1 = 0.350 x 106 W · s · m- 3 , equivalent to 0.147 K,
is reported by Zinn [11] (from Literature data ?) ; the transformation factor used here (1/(12 · N))
is ~% of that of [6]. The anisotropy field BA consists mainly of the dipolar field B~,P =
0.3260(10) T, which was calculated as the sum of the field contributions of all Eu spins within
a radius of 15 times the lattice parameter (~56 x 103 Eu atoms), Schwarz [12, p. 9], Schwarz
et al. [13]. The value is consistent with Bd,p = 0.33 T given by Bykovetz [14]. The evaluation
for 140 Eu neighbors yields Bdip = 0.334 Tat 0 K, Figueiredo, Salinas [15]; 0.23 T is estimated
by Busch et al. [16], and Bd,p = 0.38 T by Kojima et al. [17].
The spin alignment along (112) is described by an in-plane anisotropy energy or by the
equivalent field Ba= (8 ± 4) x 10- 4 T ( ~ K2 = 1/ 9 M ·Ba = 40 W · s · m- 3 ) at 24 GHz and 1.17 K
[1], Ba~ (6±2)X10- 4 T (~(K 2 +K 3 /9) = 28±13W·s·m- 3 ) at 9.2GHz and 2K, and
Ba~ (37 ± 7) x 10- 4 Tat 33.99 GHz and 4.2 K (for a plot of the temperature dependence, see
the paper), Nakai et al. [2]. Earlier, Ba= (3.8 ± 1.2) x 10- 4 Tat 9 GHz and 2 K was given [18].
0 2 (= -(9 K2 -K 3)/(k 6 NS2)) = -1.0x 10- 4 K has been obtained by the application of spin
wave theory on the specific heat [6], similarly by [10]. K2 = 7.5 x 103 W · s · m- 3 ~ 31.4 x 10- 4 K
is reported by [11] (from Literature data?).
References:
[1] J. W. Battles, G. E. Everett (Phys. Rev. [3] B 1 [1970]3021/9).
[2] J. Nakai, S. Kunii, E. Hirahara (J. Phys. Soc. Japan 34 [1973]917/24).
[4] A. S. Borovik-Romanov, S. 0. Oemokritov, N. M. Kreines, V. I. Kudinov (Zh. Eksperim.
Teor. Fiz. 88 [1985]1348/58; Soviet Phys.-JETP 61 [1985]801/7).
[5] S. Maekawa (J. Phys. Soc. Japan 34 [1973]1477/85).
[6] F. Masset, J. Callaway (Phys. Rev. [3] B 2 [1970] 3657/9).
[7] F. Keffer, W. O'Sullivan (Phys. Rev. [2]108 [1957] 637/44).
Gmelm Handbock
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Eu Te 187
[8] J. I. Kaplan (J. Chem. Phys. 22 [1954] 1709/12).

[9] J. W. Battles (AD-703622 [1970]1/94; C.A. 73 [1970] No. 103622).
[10] A. Stevens (J. Phys. C 5 [1972]1859/75, 1873).
[11] W. Zinn (J. Magn. Magn. Mater. 3 [1976]23/36).
[13] B. R. I. Schwarz, H. Lütgemeier, W. Zinn (J. Magn. Magn. Mater. 45 [1984]369/76).
[14] N. Bykovetz (Diss. Univ. Pennsylvania 1976, pp. 1/270, 159; Diss. Abstr. Intern. B 37 [1976]
1759).
[15] W. Figueiredo, S. R. Salinas (Phys. Letters A 83 [1981]231/2).
[16] G. Busch, B. Natterer, H. R. Neukomm (Phys. Letters 23 [1966]190/1 ).
[17] K. Kojima, T. Komaru, T. Hihara, Y. Koi (J. Phys. Soc. Japan 40 [1976]1570/4).
[18] J. Nakai, S. Kunii, E. Hirahara (Solid State Commun. 9 [1971] 713/6).
30.1.2.1 0.8.2.1 0.4 Exchange Field, Exchange Interaction Parameters

Experimental Results
The exchange field BE= A.Mu = 3.7 ± 0.3 T was calculated by Battles, Everett [1], from the
sublattice magnetization Mu = 451 x 10- 4 T [1], Nakai et al. [2], and the molecular field constant
A. (also referred to as A-2, Streit, Everett [3], Schwarz [4]), which is directly related to the sum
of the exchange integrals J; [1, 2]. BE~ 3.6 T is derived within the molecular field approxima-
tion from the transition field to the paramagnetic phase at T = 0, Oliveira et al. [5], 3.6 ± 0.05 T,
Schoenes, Wachter [6].
The following values are reported for the individual exchange interaction parameters:
J1/k 8 in K -J 2/k 8 in K derived from Ref.
0.09 0.21 magnetization meas. at T > T N; Be., E>P [7]

0.10 ±0.03 0.215 ± 0.03 BCP E>p [5]
0.07 ±0.02 0.21 ±0.02 low-temperature cp from [9, 10] [8]
0.07 ±0.02 0.215 ± 0.005 as before, refined treatment [11]
0.02 ±0.02 0.12 ±0.02 low-temperature CP, T <% TN [10]
0.117 0.250 random phase approx.; TN• ep [12]
0.025 ± 0.025 0.12 ± 0.01 mean field approx. (MFA), TN• E>P [13]
0.03 0.17 MFA, TN, E>P [14, 15]
0.02 0.14 MFA, TN, E>p [16]
0.06 + 0.02 0.20 ±0.05 weighted average of Literature data [17]
-0.058 Bloembergen-Rowland exchange [18]
0.0389 Eu-Te-Eu configuration [19]
0.0555 as before plus remaining crystal [19]
0.12 0.16 (see text, p. 188) [20]
The J 1 and J2 values of [8] and [5] are consistent with T N= 9.6 K according to the "Modified
Callen Decoupling" method, Swendsen [12, 21].
Pressure coefficients 1/J1. aJ/ap = -280 X 10- 6 bar- 1 and 1/J2. aJ2/ap = 13 X
10- 6 bar- 1 were calculated within MFA from the pressure coefficients up to 5 kbar of E>P
and TN by Hidaka et al. [16, 22]. The corresponding volume coefficients are alnJ 1/alnV =
Gmelin Handbook
RE Main Vol. C10
34.2 x 10- 3 and oln J2/0ln V= -1 x 10- 3 [16]. The behavior of J2 is consistent with the stability
of the magnetic structure of EuTe at pressures up to 57 kbar, Klein et al. [23, 24].
Theoretical Work on Exchange Interaction

Various mechanisms for the exchange have been proposed. From the generat trends in
EuX, X= 0, S, Se, Te, it was interred that the ferromagnetic exchange integral J 1 decreases
strongly with increasing lattice parameter a from X= 0 to Te, while J2 is weakly anti-
ferromagneUe and less dependent on a [14, 25]. The simplest models are based on a direct
exchange between nearest neighbors (nn) and 180° indirect exchange (Kramers-Anderson
mechanism) via the anion between next-nearest neighbors (nnn), Methfessel [26], Methfessel,
Mattis [27]. Will et al. [13], in analogy to the situation in transition metal oxides. But because
the direct exchange interaction between nearest Eu neighbors (J 1) by the direct4f-4f interaction
is regarded as too small, an indirect ferromagneUe exchange mechanism based on the ideas
of Goodenough [28] was proposed; cf. Wachter [29]. Smit [30]. lt implies the activation of a 4f
electron into an empty 5d(t29 ) state on a nn Eu atom plus an intra-atomic f-d exchange and is
said to give results reasonably consistent with the experiment, Wachter [29, p. 541]. Using a
similar model Kasuya [31] emphasizes that the activated state has the same (odd) parity as
the f electrons to be transferred; see also [32]. The indirect exchange interaction between
one spin and the spin polarization of its neighbor ( = the Bloembergen-Rowland mechanism
[28, 33]) is said to be of no importance in EuTe, de Graaf, Xavier [34], Xavier [35]. The
Bloembergen-Rowland exchange was treated (apparently using an unusual sign convention)
within a multielectron theory, Kazakov [18]. Another polarization exchange mechanism for
the nn exchange with excitation of an anion electron into the conduction band is proposed by
Berdyshev, Letfulov [36]. A direct exchange mechanism by a simultaneaus two-electron-
excitation to 4f65d 1 states on two nearest Eu atomswas considered by Karpenko [37]. Also
the possibility of indirect 90° superexchange was studied by Ter Maten, Jansen [38]. while
Kocharyan, Ovnanyan [20] treated the nn exchange within a band structural model; see below.
The exchange interaction between next-nearest Eu neighbors usually takes place via 180°
superexchange. But because the overlap between 4f and anion p states is too small, the
transfer of the p electrons into Eu 5d states and intra-atomic d-f exchange have been proposed
as the main contribution to J2 , Kasuya [31]. Wachter [29, p. 540]. The actual Superexchange
integral J2 for the Eu-Te-Eu configuration has been calculated by the configuration interaction
method within a many-electron model with and without allowing for the influence of the
remaining crystal. lt was found that the p electron transfer from the anion to empty d states
of the cation gives the largest contributions to J2 . The difference between the calculated and
the experimental values is attributed to the fact that these represent effective exchange
integrals, Falkovskaya, Sapozhnikov [19].
A model involving up to three anions in the superexchange mechanism and using "effective
electrons" consistently accounted for the magnetic properties of the Eu monochalcogenides.
Yet the applied orbital parameters of the "effective electrons" are not consistent with other,
more generat features, which makes the model unsatisfactory, Ter Maten, Jansen [38]. The
exchange parameters were calculated from band structure data allowing for hybridization of
f electron states with valence and conduction band states, intra-atomic exchange, and Cou-
lomb repulsion, Kocharyan, Ovnanyan [20].
The change of the magnetic properties within the series of the Eu monochalcogenides
was related to the isomer shifts in Mössbauer spectra and was discussed in terms of covalency
effects that determine the relative importance of the various exchange mechanisms, Danon,
de Graaf [39].
Gmelm Handbock
RE Mam Vol. C10
Eu Te 189
The discussions of the behavior of the exchange interaction and the hyperfine fields in
EuTe on distance variation [17, 24, 40] is briefly referenced in "Rare Earth Elements" C9,
1986, pp. 197.
References:

[4] B. R. I. Schwarz (JUEL-1929 [1984]1/77; C.A.101 [1984] No. 221066).
[8] F. Masset, J. Callaway (Phys. Rev. [3] B 2 [1970]3657/9).
[9] B. C. Passenheim (Diss. Univ. California 1969, pp. 1/156; Diss. Abstr. Intern. B 30 [1969]
2374).
[10] B. C. Passenheim, D. C. McCollum (Bult. Am. Phys. Soc. [2]13 [1968]1645).
[11] F. Masset (Phys. Rev. [3] B 3 [1971]2364/5).

[15] G. Busch, P. Junod, P. Schwob, 0. Vogt, F. Huttiger (Phys. Letters 9 [1964]7/8).
[16] Y. Hidaka (J. Sei. Hiroshima Univ. A 1135 [1971]93/110).
(17] W. Zinn (J. Magn. Magn. Mater. 3 [1976] 23/36).
(18] A. A. Kazakov (Fiz. Tverd. Tela [Leningrad]12 [1970]2021/6; Soviet Phys.-Solid State 12
[1970] 1605/9).
[19] L. D. Falkovskaya, V. A. Sapozhnikov (J. Magn. Magn. Mater. 8 [1978]313/7).
[20] A. N. Kocharyan, P. S. Ovnanyan (Zh. Eksperim. Teor. Fiz. 74 [1978]620/8; Soviet Phys.-
JETP 47 [1978] 326/30).
[21] R. H. Swendsen (Phys. Rev. [3] B 13 [1976] 3912/5).

[22] Y. Hidaka, H. Fujii, T. Okamoto, E. Tatsumoto (J. Phys. Soc. Japan 29 [1970]515).
(24] U. F. Klein, G. Wortmann, G. M. Kalvius (J. Magn. Magn. Mater. 3 [1976] 50/4).
[25] T. R. McGuire, M. W. Shafer (J. Appl. Phys. 35 [1964] 984/8).
[26] S. Methfessel (Z. Angew. Physik 18 [1965]414/32).
[27] S. Methfessel, D. C. Mattis (in: S. Flügge, Encyclopedia of Physics, Vol. 18, Pt. 1, Springer,
Berlin 1968, pp. 389/562, 504/12).
[28] J. B. Goodenough (Magnetism and the Chemical Bond, Wiley, New York 1963, pp. 165/8).
Chemistry of Rare Earths, Vol. 2, North-Holland, Amsterdam 1979, pp. 507/74).
[30] J. Smit (J. Appl. Phys. 37 [1966]1455/6).
[31] T. Kasuya (IBM J. Res. Develop. 14 [1970] 214/23).

[32] T. Kasuya, A. Yanase (Rev. Mod. Phys. 40 [1968] 684/96).
[33] P. W. Anderson (Phys. Rev. [2]115 [1959]2/13).
[34] A. M. de Graaf, R. M. Xavier (Phys. Letters 18 [1965]225/6).
[35] R. M. Xavier (Phys. Letters A 25 [1967] 244/5).
Gmelin Handbook
RE Main Vol. C 10
[36] A. A. Berdyshev, B. M. Letfulov (Fiz. Tverd. Tela [Leningrad]11 [1969] 2759/63; Soviet
Phys.-Solid State 11 [1969] 2234/7).
[37] B. V. Karpenko (J. Magn. Magn. Mater. 1 [1976]231/40).
[38] G. Ter Maten, L. Jansen (Physica B + C 95 [1978]11/22).
[39] J. Danon, A. M. de Graaf (J. Phys. Chem. Solids 27 [1966]1953/5).
[40] C. Sauer, A. M. Zaker, W. Zinn (J. Magn. Magn. Mater. 38 [1983] 225/34).
30.1.2.1 0.8.2.1 0.5 Magnetization and Low-Temperature Susceptibility
The magnetization M of Eule below T N• measured on powders, was found to increase

Linearly with the applied fields, measured up to 32 kOe, Enz et al. [1], at H ~55 kOe, Holtzberg
et al. [2], on single crystals with H along [100] at 2 < H < 20 kOe, Oliveira et al. [3] (see also
[4, 5]), and in the LimitofT-> 0 [6]. ln an external magnetic field the magnetization vectors of
the two sublattices are turned into the field direction by a canting angle 0, sin 0 = B/Bcr with
the internal field B, being the difference between the external field and the demagnetization
field and Bcr the critical field at the phase transition to the paramagnetic phase, Schwarz et
al. [7]. At higher fields the increase of M is steeper than at Low fields. in disagreement with
the molecular field approximation (MFA) [3, 8, 9] by, for example, a factor of 1.22 at 2.1 K. The
increase is attributed to the zero point spin reduction, which means a field dependence of the
sublattice magnetization [8]. A deviation up to +8% from MFA was observed at 2 Kin fields
up to ~8 T [7].
Saturation of the magnetization is reached at 75 kOe, measured at 2.1 K in fields up to

200 kOe [8, 9], from measurements up to 120 kOe [6], and at 80 kOe at 1.5 K, Henry [10, 11].
See p. 182 for details on the transition between the canted and the ordered paramagnetic
high field phase.
The saturation magnetization at 1.5 K, studied up to 150 kOe, was found as

132 ± 3 emu · g- 1 equivalent to 6.6 l!s per Eu ion (previously reported higher values [4, 5]
were due to a small systematic error), Oliveira et al. [3]. A saturation magnetization of
99.1 %, with a reproducibility of 0.008 of the theoretical value (see below), was evaluated by
extrapolation of the experimental saturation magnetization to H-> oo, Köbler, Fischer [12].
Extrapolations toT= 0 give 6.9 and 6.1 lls/Eu, Busch et al. [6, 13]. On the other hand, Henry
[11] reports ~ 3.5 !!s/Eu at 4.2 K and 80 kOe. Taking the full value of 7 fl 8 /Eu gives a theoretical
saturation magnetization cr0 = 139 emu · g-1, Enz etal. [1], equivalenttothe magnetic polariza-
tion 4 n M0 = 1.1360 T, Köbler, Fischer [12] or 1.15 ± 0.02 T allowing for an estimated 0.5%
shrinkage in the Lattice parameter at 0 K, Zinn [14]. The sublattice magnetization Mu(O) is
assumed independent of the external field in the MFA with Mu(O) = g ·11 8 · S · N/2 = 0.0451 T
(where N = number of Eu atoms in 1 cm 3 , S = 7/2, g = 2.00), Battles, Everett [15], Nakai et al.
[16], Schwarz et al. [7].
At Low temperature Mu was found to be field dependent with the zero point spin reduction
e = 2.3% being the dominant term of the deviation from simple theory, but a field dependence
of the spin wave energies in the canted spin phase can also be considered. Neglecting the
zero pointspin reduction, e = 0, would Leadtorelative sublattice magnetizations (MJMu(O)) > 1
on extrapolation of the experimental data toT= 0. Fig. 79 shows the behavior of the sublattice
magnetization at nonzero field and various temperatures derived from magnetization and
NMR measurements [7]; for details see Schwarz [17], Lütgemeier, Schwarz [18]. This ex-
Gmelm Handbook
RE Mam Vol. C10
Eu Te 191
Fig. 79. Field dependence of the sublattice magnetization Mu/Mu(O). The points in the para-
magnetic phase are taken from Bell• the dash-dotted lines represent spin wave calculations.
perimental value is consistent with the theoretical result 1:: = 2.6% . The effect is designated
as a quantum defect, Swendsen [19] .
At the lowest temperature, below ~ 2 K, the differential susceptibility dcr/dH for

single crystals of EuTe at H = 0 is close to 2/3 Xmax· The maximal value Xmax =
1.6 x 10- 3 emu · g- 1 · oe - 1 is reached near the Neel point and corresponds to the
temperature-independent X1. in the MFA. ln magnetic fields at 4.25 K, dcr/dH at first increases,
then goes through a broad maximum, and reaches a constant value at 2 to 20 kOe, which is
equal to X max (within experimental error). The broad maximum is observed between 1.2 and
7 K at 1.1 kOe. Above ~ 7 K it is not clearly observed. lt is attributed to the spin flop. At
higher fields dcr/dH exhibits a A.-shaped maximum at Bcro the canted-to-paramagnetic phase
transition, and drops to a very low value in the magnetically saturated region [3]. ln fields
x
lower than 4 kOe is reduced compared to the expected x.~. . which is reached in higher fields,
x
McGuire, Shafer [20] . For plots of vs. Taraund TN, also at elevated pressures ::; 4.3 kbar,
see Hidaka [21] , Schwob, Vogt [22], Schwob [23].
References:
[1] U. Enz, J. F. Fast, S. van Houten, J.Smit (Philips Res. Rept. 17 [1962]451/63).
[2] F. Holtzberg, T. R.McGuire, S. Methfessel (J . Appl. Phys. 37 [1966] 976/80).
[3] N. F. Oliveira Jr., S. Foner, Y. Shapira, T. B. Reed (Phys. Rev. [3] B 5 [1972]2634/46) .
[4] N. F. Oliveira Jr. , S. Foner, Y. Shapira (Phys. Letters A 33 [1970]153/4).
[5] N. F. Oliveira Jr. , S. Foner, Y. Shapira (J. Appl. Phys. 42 [1971]1783/4).
Gmelin Handbock
RE Mam Vol. C 10
[6] G. Busch, P. Junod, P. Schwob, 0. Vogt, F. Hulliger (Phys. Letters 9 [1964] 7/8).
[8] I. S. Jacobs, S. D. Silverstein (Phys. Rev. Letters 13 [1964]272/4).
[9] I. S. Jacobs, S. D. Silverstein (in: C. D. Graham Jr., J. J. Becker, I. S. Jacobs, AFML-65-
253 [1965]1/64, 35/9; C.A. 65 [1966]17873).
[10] W. E. Henry (Proc. 4th Conf. Rare Earth Res. Phoenix, Ariz., 1964 [1965], pp. 27/54, 51).
[11] W. E. Henry (Bull. Am. Phys. Soc. [2]9 [1964]114).

[12] U. Köbler, K. J. Fischer (Z. Physik B 20 [1975]391/7).
325/36; C.A. 68 [1968] No. 7294).
[14] W. Zinn (J. Magn. Magn. Mater. 3 [1976] 23/36).
[16] J. Nakai, S. Kunii, E. Hirahara (J. Phys. Soc. Japan 34 [1973]917/24).
[18] H. Lütgemeier, B. R. I. Schwarz (22nd Congr. AMPERE Magn. Resonance Relat. Phe-
nomena Proc., Zürich, Switz., 1984, pp. 297/8; C.A. 102 [1985] No. 104900).
[20] T. R. McGuire, M. W. Shafer (J. Appl. Phys. 35 [1964]984/8).

[22] P. Schwob, 0. Vogt (J. Appl. Phys. 40 [1969]1328/9).
[23] P. Schwob (Physik Kondensierten Materie 10 [1969/70]186/218, 201).
30.1.2.1 0.8.2.1 0.6 ParamagneUe Susceptibility

The susceptibility of EuTe in the paramagnetic phase obeys the Curie-Weiss law above
11 K, Enz et al. [1], between 40 and 290 K, Busch et al. [2], above 100 K, Oliveira et al. [3],
between 80 and 800 K, Butusov et al. [4], between 20 and 200 K, Köbler, Fischer [5], and
between 100 and 300 K, Ravot et al. [6]. The room temperature susceptibility Xmot =
23.3 x 10- 3 cm 3/mol [4].
The Literature values for the effective paramagnetic moment lleff or the Curie-Weiss
constant C and the paramagnetic Curie temperature E>P apparently strongly depend on the
sample quality, on the measured temperature range, and on the corrections applied. The
Curie-Weiss constant C = 0.1904 K was derived with a reproducibility of ±0.8% and E>P =
-3.8 K from susceptibility data at H = 10 kOe in the range 2 TN < T < 20 TN after allowing for
the diamagnetism of the ionic cores. The value is larger by a factor of 1.045 than the theoretical
value 0.1822K (~C 9 =0.0282K·cm 3 ·g- 1 ) taking g=2.00 and S=7/2. This increase has
been assigned to a spin quantum number S enhanced by contributions from 5d and 6s states
that are partly filled by covalency effects rather than to orbital contributions. Without aUowing
for the core diamagnetism the Curie-Weiss constants obtained are too low by about 5%,
Köbler, Fischer [5]. C9 = 0.0278 ± 0.0003 K · cm 3 • g- 1 from susceptibility data between about
100 and 273 K on a single crystal with H = 2, 13, and 17 kOe along [100], Oliveira et al. [3];
lleff in lls = 7.6 [1], 7.91 [7], ~ 7.8 [8], 7.65 [9], 7.4 [10], or 7.30 [4]. Magnetic moments roughly
identical to the free ion value of Eu2+ (7.94) are reported by Ravot et al. [6]; see also p. 196.
The data of McGuire et al. [11, 12] show a considerable scatter.
x
The paramagnetic Curie temperature E>P is given as -3.8 K from corrected data at about
20 to 100 K, Köbler, Fischer [5], -1 ± 2 K from uncorrected x between ~ 100 and 273 K,
Gmelm Handbock
RE Mam Vol. C10
Eule 193
Oliveira et al. [3], and -2.8(1.0) K, Schwarz et al. [13]. A weighted average value of Literature
data 8P = -4 ± 2 K is given by Zinn [14]. Other Literature data (in K) range from 8P = -7.5,
Enz et al. [1], to -7, Busch et al. [15], Hidaka [16], -6, Busch et al. [7], -5, Butusov et al.
[4], van Houten [10], -5 ± 4, McGuire et al. [17], and -4, McGuire et al. [11].
lhe ratio R between the Curie-Weiss constant and the saturation magnetization is indepen-
dent of the number of Eu 2 + cations per unit volume, assuming g and J are the same in the
paramagnetic and the ferromagnetically ordered state. R = 3 k 8 · C/(M 0 · J..ls) = g (J + 1) =
9.50 ± 0.08 has been evaluated. For selected "good" Eule samples the scatter is limited to
within ±0.5%. lhe quantity is thought to be an intrinsic property of Eule and the other
Eu monochalcogenides. lhe deviations from the expected value R' = 9.0 for g = 2 and
S ( = J) = 712 in the series of the Eu monochalcogenides have been tentatively related
to the hyperfine fields at the 151 Eu nuclei in the ferromagnetically ordered phase, giving a
linear relationship, Köbler, Fischer [5].
References:
(2] G. Busch, P. Junod, M. Risi, 0. Vogt (Proc. Intern. Conf. Phys. Semicond. Exeter, Engl.,
1962, pp. 727/31; C.A. 60 [1964] 2423).
[3] N. F. Oliveira Jr., S. Foner, Y. Shapira, l. B. Reed (Phys. Rev. [3] B 5 [1972]2634/46).
(4] 0. B. Butusov, V. I. Chechernikov, A. V. Pechennikov, E. I. Yarembash, et al. (lzv. Akad.
Nauk SSSR Neorgan. Materialy 9 [1973] 1339/41; lnorg. Materials [USSR] 9 [1973]
1190/1 ).
[5] U. Köbler, K. J. Fischer (Z. Physik B 20 [1975] 391/7).
[6] 0. Ravot, J. C. Achard, 0. Gorochov, M. Escorne, A. Mauger (J. Phys. Colloq. [Paris] 41
[1980] C5-357/C5-359).
(7] G. Busch, P. Junod, 0. Vogt (Colloq. Intern. Centre Natl. Rech. Sei. [Paris] No. 157 [1967]
325/36; C.A. 68 [1968] No. 7294).
[8] W. Klemm, H. Senff (Z. Anorg. Allgem. Chem. 241 [1939] 259/63).
[9] E. Kaldis (J. Cryst. Growth 3/4 [1968]146/9).
[10] S. van Houten (Phys. Letters 2 [1962]215/6).
[11] l. R. McGuire, B. E. Argyle, M. W. Shafer, J. S. Smart (J. Appl. Phys. 34 [1963]1345/6).
[12] l. R. McGuire, M. W. Shafer (J. Appl. Phys. 35 [1964]984/8).
[14] W. Zinn (J. Magn. Magn. Mater. 3 [1976] 23/36).
[15] G. Busch, P. Junod, P. Schwob, 0. Vogt, F. Hulliger (Phys. Letters 9 [1964] 7/8).
[16] Y. Hidaka (J. Sei. Hiroshima Univ. A II 35 [1971]93/110).
[17] l. R. McGuire, B. E. Argyle, M. W. Shafer, J. S. Smart (Appl. Phys. Letters 1 [1962]17/8).
30.1.2.1 0.8.2.1 0. 7 Magnetic Resonances
Antiferromagnetic Resonance
AFMR was studied on Eulesingle crystal spheres, Streit, Everett [1], Battles, Everett [2],
Battles [3, 4], Everett, Streit [5], and on single crystalline discs cut parallel to (111 ), (110), or
(100), Nakai et al. [6], or on single crystalline grains with faces {100}, Nakai et al. [7]. ln all
of the studies the applied magnetic field exceeded the spin flop field; Eule was thus in the
spin flopped state.
Gmelm Handbook 13
RE Mam Vol. C 10
Up to four branches of the resonance signal are observed, depending on the crystal
orientation relative to the field, which is due to the formationofT domains. A detailed treatment
of the multi-domain and anisotropy behavior of type II antiferromagnets in AFMR is given in
[1]; see also the other papers for the resonance equations and plots of the observed and
calculated resonance fields vs. the rotation angle or vs. the applied field [2, 6, 8]. Also the
AFMR Line width is orientation dependent [6]. The AFMR behavior of EuTe at ro/2rc = 35.2,
39.7, 42.6, and 44.7 GHz, T = 1.8 K was studied by means of the Brillouin scattering by the
spin waves under resonance conditions yielding consistent results, Borovik-Romanov et al.
[8, 9]; see also Demokritov et al. [10].
The low-frequency AFMR branches were measured between 1.5 and 4.2 K at 9 to 34 GHz
and analyzed for the out-of-plane and the in-plane anisotropy fields; see p. 186. The angular
dependence of the resonance field on rotation around [111] with Hin the easy plane (111)
showed a Superposition of a two- and a sixfold periodicity, which is due to the S domains
caused by thein-plane anisotropy [2, 6]. The intensity ratios of the six- and twofold components
vary from sample to sample. The latter can be enhanced by cooling in a magnetic field H =
20 kOe along a direction <112) [7]. The zero field resonance frequencies of the low and the
high frequency branch are ro.;- = 2 GHz and rot = 68 GHz, respectively, calculated from the
anisotropy fields [2].
The high frequency branch was analyzed for the experimental zero field resonance
frequency, the exchange field, and the out-of-plane anisotropy field [1, 5]. Plots of the high
frequency resonance vs. the magnetic field yield the experimental zero field resonance
frequency rot at the actual temperature, 1.26 K ~ T ~ 6 K. Plots of the resulting rot vs. T312
show a Linear relationship at T ~ 3 K, giving 80.87 ± 0.2 GHz at 0 K (rot vs. T2 for T ~ 6 K
extrapolates to 80.65 ± 0.2 GHz at 0 K). Applying the demagnetization correction for spherical
samples gives 78.91 ± 0.2 GHz at 0 K (T312 extrapolation) [1].
A field of 7.67 T, termed exchange field, has been derived from the slopes of (ro+) 2 vs. the
square of the applied magnetic field at the experimental temperatures and extrapolation to
T = 0 K, assuming a T312 dependence. Consideration of the demagnetization factor yields
7.30 T. This field is compared to the transition field Bcr at the canted to the high field
paramagneUe phase transition and apparently corresponds to twice the exchange field BE of
the molecular field approximation (MFA) [1].
AFMR of a thin crystalline Eu Te film ( -13 x 13 x 0.001 mm 3) is generally comparable to
those of bulk samples but with increased Line widths and larger errors in the resonance fields.
Sometimes only resonance signals of less than 4 of the T domains were observed. The
direction of the moment is expected tobe determined mainly by the anisotropy energy rather
than by the much smaller electrostatic energy of the surface, Nakai et al. [6].
Electron Paramagnetic Resonance

ESR-measurements at room temperature and 9.38 GHz on polycrystalline EuTe show an
exchange-narrowed absorption Line of Lorentzian type; g = 2.01 ± 0.01 is calculated. The Line
width is .'\H = 650 ±50 Oe, in reasonable agreement with the theoretical 940 Oe. Therefrom
it is concluded that exchange narrowing plays the determining role. Since no radical changes
in the Line width between 100 and 300 K occur it is concluded that the spin-spin relaxation
time T2 =(0.9±0.1)x1Q- 10 s is much shorter than the spin-lattice relaxationtime and
determines the Line width, Busch et al. [11]. lf the resonance frequency and the reciprocal
correlation time of the local dipolar fields ,- 1 = 74 GHzare of the same order of magnitude
the exchange-narrowed ESR Line width is expected and found to become frequency dependent:
Gmelm Handbook
RE Mam Vol. C 10
Eu Te 195
~H = 600 ± 20 and 450 ± 20 Oe at 9.400 and 70.55 GHz at room temperature, Sperlich, Jansen
[12]. For the free spin wave spectra of EuTe with k along [111] calculated at various strengths
of the external field, see Maekawa [13].
Temperature Dependence of the Magnetic Resonances
Measurements between 1.48 and 300 Kat 9.2 and 33.99 GHz with H along [110] or [112]
on an EuTe single crystal disc (II to (111)) showed that the resonance field shift from the
diphenylpicrylhydrazyl (DPPH)-line to smaller fields has a large dip at TN• Nakai, Hirahara
[14]. The temperature dependence of the resonance field below TN has been derived from
spin wave theory and was found to depend mainly on the second-order effect of a three-
magnon process, as the temperature dependence of the canting angle and the first-order
effect of four-magnon processes nearly cancel each other. The results are in reasonable
agreement with the experiment after adjusting to the observed field shift at the lowest ex-
perimental temperature (see the paper for a figure), Maekawa [13].
Measurements at 24 GHz and H ~ 8.5 kOe along [112] of an Eu Te single crystal sphere
showed the line widths to rise from 150 Oe at 0.1 TN to a sharp maximum of 2.700 kOe
slightly above T N and then to decrease to 1.000 kOe at 2.0 TN• Battles, Everett [15] (see also
[4, pp. 59/63], [3, pp. 84/92]). A maximum of the AFMR or ESR line width at TN is also described
by [6] from measurements between 1.48 and 300 K [14]. Additional measurements of the
AFMR line widths for an EuTe sphere between 1.25 and 4.20 K with H along [112] or [110]
show the field shift at 9.2 GHz to increase almost exponentially with the temperature, while
at 22.12 and 33.99 GHz the increase is linear in Twith 138 Oe· K- 1 and 47 Oe· K-1, respective-
ly. The line width was found to be composed mainly of two parts, one dependent and one
independent of temperature. The latter has been related to the presence of lattice defects and
the multi-domain state of the sample. The temperature dependent part is essentially explained
by the three-magnon process. On comparison of the calculated line widths with the ex-
perimental ones a systematic deviation occurred at all of the three frequencies, which
tentatively has been attributed to the spin-phonon interaction and the four-magnon process,
Kunii et al. [16].
References:

[2] J. W. Battles, G. E. Everett (Phys. Rev. [3] B 1 [1970] 3021/9).
[3] J. W. Battles (Diss. University California, Riverside, 1969, pp. 1/125; Diss. Abstr. Intern.
B 31 [1970] 347).
[4] J. W. Battles (AD-703622 [1970]1/94; C.A. 73 [1970] No. 103612).
[5] G. E. Everett, P. Streit (Proc. Intern. Conf. Magnetism, Moscow 1973 [1974]. Vol. 4,
pp. 136/40).
[7] J. Nakai, S. Kunii, E. Hirahara (Solid State Commun. 9 [1971] 713/6).
[8] A. S. Borovik-Romanov, S. 0. Demokritov, N. M. Kreines, V. I. Kudinov (Zh. Eksperim.
Teor. Fiz. 88 [1985]1348/58; Soviet Phys.-JETP 61 [1985] 801/7).
[9] A. S. Borovik-Romanov, S. 0. Demokritov, N. M. Kreines, V. I. Kudinov (J. Magn. Magn.
Mater. 54/57 [1986]1181/2).
[10] S. 0. Demokritov, N. M. Kreines, V. I. Kudinov (Pis'ma Zh. Eksperim. Teor. Fiz. 41 [1985]
38/40; JETP Letters 41 [1985]46/9).
Gmelm Handbock 13"
RE Mam Vol. C10
[11] G. Busch, B. Natterer, H. R. Neukomm (Phys. Letters 23 [1966]190/1).

[12] G. Sperlich, K. Jansen (Solid State Commun. 15 [1974]1105/9).
[13] S. Maekawa (J. Phys. Soc. Japan 34 [1973]1477/85).
[14] J. Nakai, E. Hirahara (Solid State Commun. 11 [1972] 267/70).
[15] J. W. Battles, G. E. Everett (J. Appl. Phys. 40 [1969]1240).
[16] S. Kunii, S. Maekawa, E. Hirahara (J. Phys. Soc. Japan 37 [1974] 57/62).
30.1.2.1 0.8.2.1 0.8 Magnetic Properlies of Doped or Nonstoichiometric Eu Te Samples
The presence of excess charge carriers in doped or nonstoichiometric EuTe samples (see
p. 200) is also seen in the magnetic properties. The zero field differential susceptibility at
T ~ 2 T N is increased compared to normal high-resistivity Eu Te and a second peak appears
well below T N at ~ 2.7 and 3.9 K for two samples with a conduction electron concentration
n ~ 1019 cm~ 3 , Oliveira et al. [1]. Extrapolated to H = 0, the low field magnetization curves
derived from the interband Faraday rotation indicate a nonzero magnetic moment of 1.2
and 0.4 l!s/Eu for samples with n = 6 x 10 19 and 4 x 1018 cm~ 3 , respectively, at room temper-
ature, Vitins, Wachter [2]; see also [3, 4]. Other values are 7 emu/g ( ~ 0.35 l!siEu) [1] and
0.0051! 8 /Eu at n = 1.65 x 1018 cm~ 3 , Sera et al. [5]. The internal transition field 8 0 , for the
canted-to-paramagnetic phase transition has been deduced more accurately from measure-
ments of the ultrasonic attenuation (see p. 175) than from dcr/dH measurements, because the
A. anomaly in the latter curve is apparently suppressed by the charge carriers, Oliveira et al.
[1, p. 2643]. With RI [100] the values 8 0 ,(0) = 7.33 and 7.44 T have been obtained for a melt-
and a solution-grown sample, respectively, on extrapolating to zero temperature, by 8 0 ,(T) =
8 0 ,(0) · (1- cxt'12 ). With RI [110] they are 8 0 ,(0) = 7.40 and 7.52 T for two samples cut from a
melt-grown single crystal. The coefficient cx of the temperature dependence is slightly in-
creased relativetothat for a nonconducting sample, which is attributed to the charge carriers.
The accuracy of the internal fields given is estimated as better than 3%, Shapira, Reed [6];
see also [7].
The saturation magnetic moment at 1.5 K was 138 ± 3 emu/g, equivalent to 6.91!8 /Eu [1].
A lower (by 0.1 K) Neel temperature in an iodine-doped sample on direct comparison with a
pure sample was observed by Vitins, Wachter [2]. Contrary to this invariance of TN toward
increasing carrier concentration n the paramagnetic Curie temperature is considerably in-
creased: 0P = + 4 ± 1 K, Oliveira et al. [1], + 9 K, Saueret al. [8], between -4.5 and + 9 K,
Köbler, Fischer [9], and + 12 and + 14 K, Vitins, Wachter [2].
Effective magnetic moments of 8.09, 7.75, 8.14, 7.93, and 7.89 l!s in single crystalline
samples with assigned (see p. 161) Eu/Te ratios 0.986, 0.997, 1, 1.017, and 1.020, respectively,
were derived from the Curie-Weiss behavior of the susceptibility between 100 and 300 K, in
fields up to 4 kOe. The sample EuTe 0 .980 ( ~ Eu 1 .020Te, !!elf= 7.89 l!s) showed a paramagnetic
Curie temperature 0P = -6 K, Ravot et al. [10]. A single crystalline n-type conducting EuTe
sample with n ~ 8 x 1018 cm~ 3 and resistivity Q ~ 1.8 x 10~ 2 n· cm at room temperature
showed at 4.5 K at first a rapidly rising magnetization in small magnetic fields (H < 2 kOe)
followed by a linear increase up to 50 kOe, Stankiewicz et al. [11].
Gmelm Handbock
RE Ma1n Val. C 10
Eu Te 197
Interpretation
The spontaneaus magnetization (and other, mainly optical properties, see p. 225) of the
dopedEuTe samples indicates the existence of ferromagnetic spin clusters at low temperature
extending over as many as 2000 or 500 Eu atoms in the higher or less doped sample,
respectively, Vitins, Wachter [2]; see also Vitins, Wachter [3, 4, 12]. Different impurity states
are postulated by Sera et al. [5]: in most of the impurity states each electron sits only on six
sites, probably six nearest-neighbor sites of a Te vacancy; in addition there are other, in the
studied case less than 10%, shallow localized, yet extended donor impurities [5].
More recently the spontaneaus magnetic moments have been explained within the bound
magnetic polaron model. The self-trapped magnetic polaron, "ferron", possibly similar to the
ferromagnetic spin clusters, probably does not exist in all the samples studied so far, Mauger,
Mills [13], Umehara [14]; see p. 201. The calculation for a sample with n = 4 ·10 18 cm- 3 and
an activation energy of the carriers of EA = 0.022 eV (these values are typical for the less
doped sample from [2]) shows that each bound magnetic polaren contributes 545 J..ls to the
anomalaus magnetization. This is equivalent to the contribution from the moment of roughly
75 Eu spins. The core of the polaren, where the magnetization is saturated, contains about
20 spins. So ~ 70% of the magnetic moment associated with the bound magnetic polaren
comes from the halo around the core. ln all, this gives an additional moment of 0.36 J..ls per
unit cell, which is in good accord with the experimental data (0.4 J..Ls/Eu ion [2]) [13]. The
induced ferromagnetic moment ~ 7 emu/g for the conducting sample of [1] is in good agree-
ment with a bound magnetic polaren with a radius of between 1.5 and 2 times the lattice
parameter. The low moment of 0.005 J..L 8 /Eu in the sample studied by [5] indicates that no
bound magnetic polaron is present [14]. The general behavior of their low resistivity sample
is qualitatively described by the de Gennes model, Oliveira et al. [1].
References:
[1] N. F. Oliveira Jr., S. Foner, Y. Shapira, T. 8. Reed (Phys. Rev. [3] 8 5 [1972] 2634/46).
[2] J. Vitins, P. Wachter (Phys. Rev. [3] 8 12 [1975]3829/39).
[3] J. Vitins, P. Wachter (Solid State Commun. 13 [1973]1273/7).
pp. 140/5; C.A. 85 [1976] No. 55593).
C5-97 /C5-99).
[6] Y. Shapira, T. 8. Reed (Phys. Rev. [3] 8 5 [1972] 2657/67).
[7] Y. Shapira, T. 8. Reed (Phys. Letters A 31 [1970] 381/2).
C6-274).
[9] U. Köbler, K. J. Fischer (Z. Physik 8 20 [1975] 391/7).
[1980] C5-357/C5-359).
[11] J. Stankiewicz, S. von Molnar, F. Holtzberg (J. Magn. Magn. Mater. 54/57 [1986]1217/8).
[12] J. Vitins, P. Wachter (Solid State Commun. 17 [1975] 911/4).
[13] A. Mauger, D. L. Mills (Phys. Rev. [3] 8 31 [1985] 8024/33).
[14] M. Umehara (J. Phys. Soc. Japan 50 [1981]1082/90).
Gmelin Handbook
RE Ma1n Vol. C10
30.1.2.1 0.8.2.11 Electrical Properties
30.1.2.1 0.8.2.11.1 Electronic Structure
The seven electrons of the half-filled 4f shell form an 8S712 ground state. The generat
characteristics of the eLectronic structure of the Eu monochaLcogenides have aLready been
discussed in "Rare Earth Elements" C7, 1983, pp. 459/67. ln the case of EuTe, data on the
electronic structure have mainLy been derived from the opticaL properties, e.g., by Methfessel
et al. [1], Güntherodt et al. [2], Güntherodt [3], Schoenes [4], Dimmock et al. [5].
Photoemission (UPS) studies Lead to the energy distribution curves shown in Fig. 80. They
give the position of core Levels, an Auger band, and the range near the Fermi energy EF,
Gudat et al. [6]. The valence band is formed from 5p (Te) states. A maximum at 3.5 eV beLow
EF in the UPS is attributed to these states, Munz [7]. The highest occupied 4f states are just
above the vaLence band and overlap somewhat with it. This overlap is indicated in the Faraday
rotation, Schoenes [4], and the photoemission spectra. The intensity near 2 eV beLow EF in
these spectra is attributed to the Eu 4f Levels [6] (see Fig. 80) or to unresolved 4f and valence
band states [7], Sato et al. [8]; see p. 227.
Eu4f
Eu5p
Te
I 1
I .,....--l-..
5s 5p
-40 VB
E8 in eV
Fig. 80. Photoemission spectra (UPS) of EuTe.
The vaLence-to-conduction band gap at 300 K is given as 2.15 eV by Campagna, Siegmann

[9], Campagna et al. [10]. The gap between the 4f states and the conduction band E9 ~ 2.0 eV
has been derived by opticaL measurements; see p. 215. Different energy values have been
calcuLated from the temperature dependence of the eLectrical conductivity: 1.1 eV [11], 1.28 eV
[12], 1.33 eV [13]. The pressure dependence of the optical gap energy oE9 Jap = -12 meV/kbar
was obtained from transmission experiments under hydrostatic pressure of ~ 1 kbar, Wachter
Gmelm Handbock
RE Ma1n Vol. C 10
Eu Te 199
[14]. The same sign of the pressure coefficient, which agrees with the band picture (see below),
is also implied from the pressure dependence of the activated conduction by Rooymans [15].
ln contrast a positive pressure coefficient has been derived from resistivity measurements
up to 5.2 kbar, in conformance with the concept of the "magnetic exciton" (see below), Hidaka
(12]. A pressure dependence of the 4f-5d energy gap oE 9/op = -8.0 meV/kbar was calculated
within a simple model based mainly on cohesive energy and enthalpy arguments, Johansson
[16]. For the blue shift of the edge observed on cooling and its magnetic field induced red
shift, see p. 215.
The conduction band is derived from the cationic Sd and 6s states. The former are split by
the crystal field, yielding the Lower Lying t29 and the higher e9 subband; 10 Dq = 1.5 eV [2, 17]
or 1.6 eV (5]. The optical spectra are generally assigned to transitions into an excited state
derived from d states. The reported energy Level schemes (band picture) show the bottom of
the 6s band higher than that of the 5d(t29 ) subband. The Latter has a width of 0.6 eV at 300 K,
Güntherodt et al. [2]; for additional data, see p. 219. ln the concept of the "magnetic exciton"
the 6s band is assumed to form the bottom of the conduction band; see "Rare Earth Elements"
C7, 1983, pp. 464/5.
ln the antiferromagnetic phase the 5d(t29 ) band is split at the new zone boundaries into
two unpolarized subbands. This was interred from the Faraday rotation experiments,
Schoenes [18]; for additional data, see p. 224. A two-subband structure of the conduction band
was also obtained in a theoretical study of the electronic quasi-particle spectrum, within
the s-f model using only intraatomic s-f interaction. The splitting persists above the Neel
temperature, von der Linden, Nolting [19]. ln this model [19] and in the s-f model with S =
712, used by Matlak et al. [20]. the bottom of the conduction band is practically independent
of temperature in antiferromagnetic EuTe; see also p. 215. ln the ferromagnetically aligned
paramagnetic phase the conduction band is also split into two subbands. However, they are
spin-polarized and the splitting extends over the whole 8rillouin zone [18]; seealso p. 224.
A simple ionic model is proposed for MX with M = Sm, Eu, Yb and X = S, Se, Te by
Dagys, Anisimov [21] based on the complete transfer of the 6s 2 electrons of the Lanthanide
ion to the chalcogenide. The authors postulate a spherical symmetry component of the
Hartree-Fock potential for the inner electrons of M, which is approximately the same as for a
free neutral atom.
References:
[1] S. Methfessel, F. Holtzberg, T. 8. McGuire (IEEE Trans. Magn. 2 [1966] 305/6).

(2] G. Güntherodt, P. Wachter, D. M. lmboden (Physik Kondensierten Materie 12 [1970/71]
292/310).
[3] G. Güntherodt (Phys. Condens. Matter 18 [1974]37/78).
(4] J. Schoenes (Z. Physik 8 20 [1975] 345/68).
(5] J. 0. Dimmock, J. Hanus, J. Feinleib (J. Appl. Phys. 41 [1970]1088/9).
[6] W. Gudat, S. F. Alvarado, M. Campagna, Y. Petroff (J. Phys. Colloq. [Paris] 41 [1980]
C5-1/C5-7).
[7] P. Munz (Helv. Phys. Acta 49 [1976] 281/309).
[8] S. Sato, M. Watanabe, T. Sagawa, S. Kono, S. Suzuki, et al. (Vac. Ultraviolet Radiat. Phys.
Proc. 4th Intern. Conf., Hamburg, FRG, 1974, pp. 499/502).
[9] M. Campagna, H. C. Siegmann (Physik Kondensierten Materie 15 [1973]247/83).
[10] M. Campagna, D. T. Pierce, H. C. Siegmann (Amorphous Liq. Semicond. Proc. 5th Intern.
Conf., Garmisch-Partenkirchen, FRG, 1973 [1974], Vol. 2, pp. 1379/84).
Gmelin Handbock
RE Main Vol. C10
325/36; C.A. 68 [1968] No. 7294).
[12] Y. Hidaka (J. Sei. Hiroshima Univ. A II 35 [1971]93/110).
[13] 0. B. Butusov, V. I. Chechernikov, A. V. Pechennikov, E. I. Yarembash, 0. A. Sadovskaya,
E. G. Tyurin (lzv. Akad. Nauk SSSR Neorgan. Materialy 9 [1973]1339/41; lnorg. Materials
[USSR]9 [1973]1190/1).
[14] P. Wachter (Solid State Commun. 7 [1969] 693/6).
[16] B. Johansson (Phys. Rev. [3] B 12 [1975] 3253/7).
Chemistry of Rare Earths, Vol. 2, North-Holland, Amsterdam 1979, pp. 507/74, 535/7).
[19] W. von der Linden, W. Nolting (Z. Physik B 48 [1982]191/9).
[20] M. Matlak, A. Ramakanth, K. Skrobis (Z. Physik B 48 [1982]227/31).
[21] R. S. Dagys, F. G. Anisimov (Fiz. Tverd. Tela [Leningrad]26 [1984]899/901; Soviet Phys.-
Solid State 26 [1984] 547/8).
30.1.2.1 0.8.2.11.2 Conduction Mechanism
Conduction Type
Both n- and p-type conduction were observed in Eule, Busch et al. [1], Sera et al. [2]. A
p-type conduction is possible in EuTe in the presence of acceptor Levels (e.g. EuH) just above
the filled 4f states and due to the overlap of the 4f states with the 5p valence band, Güntherodt
et al. [3]; p-type conductivity is also predicted at excitation energies Larger than the energy
gap, Cho [4]. A high-resistivity sample (Q = 1.4 x 103 n · cm) showed p-type conduction with
an activation energy ~E = 0.4 eV assigned to the impurity Level and ~E = 1.33 eV at high
temperatures, Yarembash, Eliseev [5], compared to the optical gap of ~ 2 eV (see p. 214). An
"insulating" sample with carrier concentration n ~ 5 x 1017 cm- 3 (showing a reststrahlen peak
in the infrared), Holah et al. [6], and Low-resistivity samples (Q ~ 0.1 Q · cm) with n >
1.65 x 1018 cm- 3 have n-type conductivity, Shapira et al. [7], Sera et al. [2], Stankiewicz et al.
[8]. A sample with n ~ 1 x 1019 cm- 3 had a conduction band density-of-states mass of m* =
0.2 me and 11 = 50 cm 2 · v- 1 · s - 1 , derived from the plasma reflectivity edge at 300 K [6].
The source of the free charge carriers is unknown; possible sources are deviations from
stoichiometry, impurities, or vacancies [7]. Weakly and more heavily iodine-doped,
nondegenerate Eule samples, with n = 4 x 10 18 and 6 x 10 19 cm- 3 , d.c. mobilities 11 = 66 and
11 cm 2 ·V- 1 ·s- 1 and effective mass m* = 0.23m 0 and 0.43m 0 from optical data, exhibit
activation energies in the carrier concentration of ~E(n) = 20 meV at > 70 K. This indicates
that the free carriers measured by the optical absorption and Faraday rotation in the far-
infrared are activated from shallow donors, Vitins, Wachter [9].
Below room temperature conduction in pure EuTe is proposed to occur by hopping with
an activation of mobility decreasing from ~E(J.l) = 33 meV near 100 K to 0.29 meV below the
Neel temperature, Wachter, Weber [10]. The slightly iodine-doped EuTe sample showed a
similar activation energy in the hopping mobility above 70 K: ~E(!l) = 30 meV. As ~E(J.l) >
~E(n), hopping does not occur between impurity states [9]. This behavior, derived from
photoconductivity studies. was interpreted in termsofasmall (self-trapped) magnetic polaron
in the case of pure Eule [10] (but see p. 201) and abound magnetic polaron in the case of the
Lightly doped EuTe [9].
Gmeltn Handbook
RE Main Vol. C10
Eu Te 201
An n-typecrystal with n = 1.65 x 1018 cm- 3 , Jl = 29 cm 2 · v- 1 · s- 1 showed activated conduc-

tion below room temperature and a maximum in the Hall etfect near 80 K. This behavior was
tentatively interpreted in a three-band model with a transient delocalized band with a small
mobility (Jl = 0.25 cm 2 · v- 1 · s- 1) compared to Jl = 29 and 2 cm 2 · v- 1 · s- 1 in the conduction
and impurity bands, respectively. A figure in the paper shows the temperature dependence
of carrier concentration in these bands between 300 and 40 K. The unusual behavior of this
sample at lower temperatures, involving a nonactivated conduction below 13 K, an increase
of the resistivity in elevated magnetic fields followed by a drop near the critical field Bcro and
no detectable Hall valtage below 20 K for ~ 9.0 T, led to an interpretation in terms of different
kinds of shallow impurity states (Te vacancies and other donor impurities) and their extended
localization in a kind of amorphaus magnetic Wigner crystal, Sera et al. [2].
Degenerate n-type EuTe (n = (5.6 to 13) x 1018 cm- 3 at 77 K) appears to showband conduc-
tion below room temperature, with electron mobilities of 33 to 58 cm 2 • v- 1 · s- 1 (error Limit
~ 30%) at 300 K. The small resistivity decrease with decreasing temperature is presumably
caused by scattering of electrons by phonons, Shapira et al. [7]. Welt below the Neel tempera-
ture (TN ~ 9.6 K) the activated transport in the canted spin phase of such a crystal (n ~
8 x 1018 cm- 3 at 300 K) exhibits a weaker temperature dependence than required in a variable
range hopping law, Stankiewicz et al. [8]. The origin of positive magnetoresistance at 77 K in
low magnetic fields is not clear. lts decrease in high fields may be caused by the same
effect that dominates the magnetoresistance at lower temperature. Hall effect measurements
(reliable results only for fields > 2.0 T) show that the large negative magnetoresistance
observed at 14.5 K and also at 4.2 and 1.6 K in the canted spin phase is mainly due to an
increased mobility of the eh arge carriersandnot to an increase in their concentration, Shapira
et al. [7]. Nevertheless, there is a clear change in the carrier concentration (Hall constant) at
the magnetic field-induced insulator-metal transition. The properlies are tentatively in-
terpreted in terms of the bound magnetic polaren model, yet the donor electron is localized
not only by (random) Coulomb potantials but also by the ferromagneUe polarization of the
neighboring Eu spins of the antiferromagnetic sublattice. The magnetic field finally causes
the mobility edge (Ec) to be tuned through the Fermi energy (EF), with EF- Ec > 0 in the
metallic regime [8]. Similarly, Shapira et al. [7] tentatively discuss their results in terms of
self-trapped electrons, a polaren model resembling the "ferron"; but see below.
Bound Magnetic Polaron, Self-Trapped Magnetic Polaron (Ferron),

and "Electron CrystaLLization"
For a survey on polaren models, see, for example, "Rare Earth Elements" C 9, 1986,
pp. 231/4.
Various polaren models have been discussed to describe the electric, magnetic, and
magneto-optical properties of doped or conducting samples of EuTe. The bound magnetic
polaren has been shown to account for the Large spontaneaus magnetic moments observed
in nondegenerate iodine-doped EuTe (see p. 197), Mauger, Mills [11], Umehara [12]. The self-
trapped magnetic polaren, the ferron, is expected to be formed (if it is stable) only in the high
purity crystals containing no defects, otherwise the electron becomes trapped araund defects,
Umehara [12]. Theoretical studies of the possible stability of the ferron in EuTe differ in the
parameters thought appropriate to describe EuTe. With a conduction electron-local moment
(d-f) exchange energy of 0.27 eV (derived from the splitting of the Faraday rotation) and a
conduction band width of 2.5 eV, the variational calculation by [11] suggested that the ferron
Gmelin Handbock
RE Main Vol. C10
state is not stable at T = 0 in low magnetic fields and, moreover, that the ferrons could not
explain, for example, the spontaneaus magnetizationobserved by Vitins, Wachter [9] in doped
Eu Te [11]. Earlier Umehara [12], using a tight binding model at H = 0 and considering electron-
=
phonon interaction, also found no stability of the self-trapped magnetic polaron at a conduction
band width of 2 eV ( m* = 0.5 m8 ) and a d-f exchange energy of 0.35 or an s-f exchange
energy of 0.1 eV (corresponding to d or s character, respectively, of the lower conduction
band edge). A stable self-trapped magnetic polaron is obtained for a d-f exchange energy of
0.35 eV, small band widths of 1.5 and 1.0 eV, and one set (E 00 = 4.18, a0 = 8.23) of the
experimental dielectric constants [12]. (These values for the d-f exchange energy and the
band widths are estimated as unrealistic for Eule by Mauger, Mills [11].) However, if the
magnetic polaron is stable in Eule, it becomes a large one and in this case the mobility is
not of the hopping type [12], in cantrast to the proposal of Wachter, Weber [10]. For calculations
based on a conduction band width of SeV, see Lakhno, Nagaev [13].
The possibility of "electron crystallization", which means a strongly inhomogeneaus state
of electrons in an antiferromagnetic semiconductor, was studied for degenerate Eule, with a
carrier concentration n = 1.4 x 1019 cm- 3 at T and H = 0, by a density functional method.
With the large d-f exchange energy (0.35 eV) and a similar small conduction band width
(described by m* = 1 m8 ) as used earlier, the electron crystallization associated with a dense
magnetic polaron state becomes stable at T ~ 1.4 TN· lt is a stable regular arrangement and
consists at T and H = 0 of an inner region with a high electron density associated with
ferromagnetic order (dense magnetic polaron state). Outside this region the electron density
is extremely low and the spin order is antiferromagnetic; the figurein the paper indicates for
this "electron unit cell" a parameter of ~50 A under these conditions. Electron crystallization
associated with a dense magnetic polaron state is able to explain the nonmetal behavior at
low temperatures and the magnetic field-induced nonmetal-metal transition (as observed by
[7]). Preliminary studies of electron crystallization associated with an amorphaus Wigner
crystal yield a Large unit cell of about 200 A for n = 0.5 x 1017 cm- 3 even in the absence of a
d-f exchange, Umehara [14].
References:

CS-97/CS-99).
[3] G. Güntherodt, P. Wachter, D. M. lmboden (Physik Kondensierten Materie 12 [1970/71]
292/310, 302).
[4] S. J. Cho (Phys. Rev. [3] 8 1 [1970] 4589/603, 4596).
Moscow 1975, pp. 1/260, 211).
[6] G. D. Holah, J. S. Webb, R. 8. Dennis, C. R. Pidgeon (Solid State Commun. 13 [1973]
209/13).
[7] Y. Shapira, S. Foner, N. F. Oliveira Jr., T. B. Reed (Phys. Rev. [3] 8 5 [1972]2647/57).
[8] J. Stankiewicz. S. von Molnar, F. Holtzberg (J. Magn. Magn. Mater. 54/57 [1986]1217/8).
[9] J. Vitins, P. Wachter (Phys. Rev. [3] 8 12 [1975]3829/39).
[10] P. Wachter, P. Weber (Solid State Commun. 8 [1970]1133/7).
[11] A. Mauger, D. L. Mills (Phys. Rev. [3] 8 31 [1985]8024/33).
[12] M. Umehara (J. Phys. Soc. Japan 50 [1981]1082/90).
[13] V. D. Lakhno, E. L. Nagaev (Fiz. Tverd. Tela [Leningrad]18 [1976] 3429/32; Soviet Phys.-
Solid State 18 [1976]1995/7).
[14] M. Umehara (J. Magn. Magn. Mater. 52 [1985]406/8).
Gmelln Handbook
RE Main Vol. C10
Eule 203
30.1.2.1 0.8.2.11.3 Electrical Conductivity
Pure stoichiometric Eule is a semiconductor with values of the d.c. electrical resistivity
Qd.c. (in n ·cm) at room temperature as follows: 8.5 x 107 for a single crystal grown from the
vapor phase, Vel'mizov et al. [1], > 106 for a melt-grown crystal with after-heat treatment,
Johanson, McCollum [2] and one grown by iodine transport, Oliveira et al. [3], and Q ~ 107
for pressed powder samples, Enz et al. [4], van Houten [5], Busch et al. [6]. Nonstoichiometric
(or contaminated) samples have lower resistivities: Qd.c. ~ 103 (from Eule melt), Singh et al.
[7]; Q = 1.4 x 103 (~ conductivity K = 7 x 10- 4 n- 1 -cm- 1) for a sample (from the elements)
described as p-type conducting, Butusov et al. [8]. Resistivities from ~ 0.1 to 0.004 n · cm
were found for the n-type conducting crystals grown from a Eule melt in a carbon crucible,
Sera et al. [9], and from (Eule + 10% Eu metal) melts, Shapira et al. [10], respectively.
lhe temperature dependence of Q for the high-resistivity samples is typical for

semiconductors [6, 11, 12]. Above room temperature, the increase in K (decrease in Q) is
characterized by an activation energy L\E of 1.1 eV for a stoichiometric sintered sample
studied between 300 and 1200 K [11]; L\E = 1.28 eV for a pressed sintered sample in the
range ~ 330 to 400 K [12]. However, L\E = 1.33 eV for the p-type sample (measured between
300 and 1000 K) [8], presumably weiL above room temperature, and L\E 1 = 0.4 eV for the
activation energy of the impurity Level (presumably near room temperature), Yarembash,
Eliseev [13].
Below room temperature the d.c. resistivity of samples with carrier concentrations
n(77 K) = (5.6 to 13) x 1018 cm- 3 first decreases, then reaches a shallow minimum well above
the Neel temperature (l N ~ 9.7 K), and finally increases rapidly at l ~ 2l N• with a small
structure at l N (see a figure in the paper). Values of Qd.c. at 300, 77, and 4.2 Kare 0.012, 0.008,
and 0.7 n · cm, respectively, for a crystal grown from a Eule melt, and 0.004, 0.003, and
0.25 n · cm or 0.024, 0.021, and 7 n ·cm for two pieces cut from one single crystal grown from
a (Eule + 10% Eu) melt. Below 4.2 K (studied down to 1.6 K), the increase of Q is proportional
to eMT with L\ ~ 11 to 14 K (~ 0.9 to 1.2 meV), Shapira et al. [10]. lhe increase of the a.c.
resistivity Qa.c. from ~ 10 n · cm at 4.2 K to ~ 106 n ·cm at 1 K, observed in a similar single
crystal (Qd.c. ~ 0.018 n ·cm and n ~ 8 x 1018 cm- 3 , both at 300 K), corresponds to L\E ~
1.4 meV, Stankiewicz et al. [14]. A totally different Qd.c. vs. 1/l behavior of some of their
samples is reported by Sera et al. [9]. lhe resistivity of a single crystal (grown in a carbon
crucible) with Qd.c. ~ 0.1 n · cm and n = 1.65 x 1018 cm- 3 at 300 K increases continuously to
~ 17 n · cm at 13 K (see the log Qd.c. vs. 1/l plot in the paper) with L\E = 20 meV ( ~ 230 K) at
~ 100 K and of L\E = 7.4 meV (~ 86 K) at ~ 40 K. lt is nearly constant below 13 K; L\E = 0 at
1.37 K, the lowest temperature studied [9]. An increase of Qd.c. below 300 K seems also to
have been observed by Ravot et al. [15], who give L\E = 200 meV for the range 160 to 300 K
for a single crystal of presumed composition Eule 0 _980 (~ Eu 1.02le).
A negative pressure coefficient of the electrical resistivity was measured up to ~50 kbar
on a sample which showed an anomalaus lattice constant vs. pressure behavior (see p. 164).
lhe resistance dropped steeply by one order of magnitude on increasing the pressure to
12 kbar and by an additional two orders of magnitude between 12 and ~50 kbar. Release of
pressure was associated with strong hysteresis, Rooymans [16]. However, an increased
resistance at 2.6 and 5.2 kbar with respect to ambient pressure was observed on another
sample between ~ 330 and 400 K, indicating a positive pressure coetficient of the activation
energy of ~ 90 meV/kbar (read from a figure), which is equivalent to atnl\E/atnV = -63,
Hidaka [12]; seealso p. 199.
Gmelin Handbock
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References:
[3] N. F. Oliveira Jr., S. Foner, Y. Shapira, T. B. Reed (Phys. Rev. [3] B 5 [1972] 2634/46,
2637).
[4] U. Enz, J. F. Fast, S. van Houten, J. Smit (Philips Res. Rept. 17 [1962] 451/63, 453).
1962, pp. 727/31).
[USSR] 9 [1973]1190/1).
C5-97/C5-99).
325/36; C.A. 68 [1968] No. 7294).
Moscow 1975, pp. 1/260, 211).
[1980] C5-357/C5-359).
30.1.2.1 0.8.2.11.4 Magnetoresistance

The magnetic field dependence of the electrical resistance of relatively highly conductive
n-type EuTe single crystals, with carrier concentrations n from (5.6 to 13) x 1018 cm- 3 at 77 K,
was studied between 300 and 1.6 K for applied fields Ba up to 10 T. Results obtained with
transverse magnetic fields (I 11 [100], B II [010]) were close to those obtained with longitudinal
magnetic fields (1, B II [100]). No field dependence to within 2% accuracy was found at room
temperature. At 77 K a positive magnetoresistance was observed, which had a maximum
(increase by 10%) at Ba = 3.0 or 4.0 T (sample dependent); Q(10.0 T) ~ Q(O). At 14.5 K, the
resistivity was nearly field independent up to 0.1 T, then decreased steeply to ~ 75% of the
zero field value at 2.0 T, and was ~ 30% at 10.0 T. Below the Neel temperature (T N ~ 9.7 K),
the transition from the canted to the spin aligned paramagnetic phase (see p. 183) is marked
by discontinuities in ÜQ/oT and ÜQ/oB, which were used to determine the temperature
dependence of the critical field Bcr· Studies at ~ 4.2 K showed a strong negative
magnetoresistance at all fields. At 4.2 K, Q(B)/Q(O) of a sample with Q(300 K) = 0.010 Q · cm
and n(77 K) = 13 x 1018 cm- 3 decreased strongly with increasing internal field B, in the
antiferromagnetic type II phase, to ~ 0.1 at B, = 0.1 T, and less strongly in the canted
phase, to ~ 0.08 at Bcr ~ 6.1 T; Q(B)/Q(O) was almost field independent in the spin aligned
paramagnetic phase, at B > Bcr· This behavior was observed for I I [100], B II [100] or [010].
Other samples behaved qualitatively the same, also with I II [110], B I [110], [110], or [001].
As the temperature is decreased (exponential increase of the zero field resistivity), the
Gmelin Handbock
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Eu Te 205
negative magnetoresistance at 0.1 T increased to g(0.1 T)/g(O) ~ 10- 3 at 1.7 K. The resistivity
at B ~ Ber was nearly temperature independent. The high-field saturation value of Q is
approximately equal to the value obtained by extrapolating the high-temperature part of the
zero field Q vs. T curve to Low temperatures, Shapira et al. [1]. Some of these results were
also reported in Shapira et al. [2]. A strong negative magnetoresistance was also observed
by Stankiewicz et al. [3], who studied the a.c. resistivity of a similar n-type sample (Qd.e. ~
1.8 x 10- 2 Q · cm and n ~ 8 x 1018 cm-· 3 at 300 K) between 4.2 to 0.32 Kin applied fields up to
9.5 T. The sample is an insulator in zero magnetic field, whereas the Longitudinal
magnetoresistance indicates a clearly nonactivated, metallic behavior in high fields. The field
Be(=l= Be,) at the metal-insulator transition is estimated as 6.5 ± 1.0 T. ln fields Ba ~ Be the
temperature dependence of the electrical conductivity Log K is more closely proportional to
(1/T) 112 than to (1/T) 114 ; i.e., a variable range hopping Law is not valid. ln magnetic fields close
toBe an even weaker dependence on 1/T is observed [3].
A completely different behavior of the magnetoresistance is reported for a sample with
n(300 K) = 1.65 x 10 18 cm- 3 , which was studied between 1.37 and 5.2 Kin applied fields up
to 9.0 T. The ~g/g(O) vs. Ba curves (see figure in the paper for five temperatures) all show a
decrease to a small minimum of about - 1% at ~ 0.5 T. The magnetoresistance is positive
at Ba ~ 1.5 T. The resistivity increase is almostLinear at 1.37 K up to 9.0 T (~g/g(O) ~ 9%)
with no discontinuity at Ber = 7.3 T. For higher temperatures a fairly Large drop of the resistivity
begins to appear at high fields just below Ber with the offset (from Be,) becoming Larger with
increasing temperature, Sera et al. [4].
References:
[1] Y. Shapira, S. Foner, N. F. Oliveira Jr., T. B. Reed (Phys. Rev. [3]5 [1972] 2647/57).
[2] Y. Shapira, S. Foner, N. F. Oliveira Jr. (Phys. Letters A 32 [1970] 323/4).
C5-97/C5-99).
30.1.2.10.8.2.11.5 Hall Effect

The Hall voltage of n-type EuTe samples with resistivities from 0.010 to 0.024 Q · cm was
Linear with the applied magnetic field Ba at 300 and at 77 K. Hall coefficients (in cm 3/C,
uncertainty 2%) RH(300) = - 0.53 and RH(77) = -0.52 were obtained for a melt-grown
single crystal and values from -0.53 to - 1.16 and from -0.49 to - 1.12 at 300 and 77 K,
respectively, for various pieces of a crystal grown in the presence of excess Eu metal. Slight
deviations from proportionality between the Hall voltage and the magnetic field were found
at 14.5 K. The slow decrease of IRH(14.5) I observed at increasing applied field is small
compared to the decrease of the resistivity of the sample under the same condition:
RH(0.85 T) = 1.2 RH(10.2 T). The anomalaus term in the Hall voltage was shown tobe very
small compared to the normal term in the high-field paramagnetic phase at 1.6 K. The data
for Ba > 9.0 T could weiL be described by the normal Hall coefficient RH = -0.48 cm 3/C
alone, a value that is very close to RH = - 0.49 cm 3/C of the same sample at 77 K in
zero magnetic field. lt was therefore assumed that the anomalaus Hall coefficient could be
neglected at all temperatures below T N and magnetic fields. The measurements at 4.2 and1.6 K
then showed nearly field independent Hall coefficients in the high-field phase (B; ~ 6.0 and
> 7.0 T, respectively) and slightly more negative values at Lower fields down to ~ 2.0 T (no
Gmelm Handbock
RE Main Vol. C10
accurate measurements were possible at lower fields), Shapira et al. [1]; studies at 4.2 K,
also Shapira et al. [2]. ln a similar n-type sample (Q ~ 0.018 Q · cm at 300 K) the normalized
transverse a.c. resistivity Qx/Ba at 0.35 K, shown to be proportional to the normal Hall
coefficent RH, decreases from ~ 1.45 cm 3 /C at 6.0 T to a saturation value of ~ 0.85 cm 3 /C for
~ 8.0 T, which is equal to RH at 300 K. Note the change of RH at the metal-insulator transition
occurring at ~ 6.5 ± 1.0 T, Stankiewicz et al. [3].
Quite different results for the Hall coefficient are reported by Sera et al. [4] for a slightly
more resistive n-type sample (Q ~ 0.1 Q · cm at 300 K) having RH ~ - 4.5 cm 3/C at 300 K.
Below room temperature, where the logQ vs. 1/T curve rises continuously, the log IRHI vs.
1/T curve has a maximum (RH ~ -20 cm 3/C) at ~ 80 K; RH ~ -2 cm 3/C at 35 K (all values
read from a figure in the paper). Below 20 K no Hall valtage could be detected in fields up to
9.0 T. Note the nearly temperature independent resistivity of the sample below 13 K in zero
field, indicating zero activation energy [4]. For the models proposed see p. 201.
References:
[2] Y. Shapira, S. Foner, N. F. Oliveira Jr. (Phys. Letters A 33 [1970] 323/4).
C5-97/C5-99).
30.1.2.1 0.8.2.11.6 Thermoelectric Properlies

The thermoelectric power S = + 296 j.lV/K at room temperature, Butusov et al. [1],
decreasing to S = + 125 j.lV/K at 1000 K, was measured for a EuTe sample with electrical
resistivity Q(300 K) = 1.4 x 103 Q · cm, indicating p-type conductivity in the whole temperature
range, Yarembash, Eliseev [2]. A strongly negative thermoelectric power was observed in
a Eu-rich sample showing low, yet increasing absorption below the absorption edge (cx ~
20 cm- 1 at 211m, read from a figure); see p. 214. Other impure or nonstoichiometric samples
showing still higher absorption had less negative and finally a positive thermoelectric power,
Busch et al. [3].
References:

[USSR]9 [1973]1190/1).
Moscow 1975, pp. 1/260, 211).
30.1.2.1 0.8.2.11.7 Photoelectric Effects

The spectral photosensitivity (photocurrent/light intensity), studied on an undoped EuTe
single crystal, exhibits a maximum at the short wavelength side of the absorption edge. The
Gmel1n Handbock
RE Main Vol. C 10
Eu Te 207
energetic position of this maximum is only weakly temperature dependent in the range
between 50 and 300 K. Below 50 K (studied down to 4.2 K), practically no temperature
dependence can be measured. Above the Neel temperature (TN = 9.6 K) the temperature
dependence of the photosensitivity S excited in the maximum agrees with that of the other Eu
monochalcogenides in that it exhibits a maximum near 100 K. Above this temperature the
photosensitivity is governed by Lifetime effects and below ~ 100 K it reflects the decrease in
the mobility of the charge carriers. S drops by ~ 5 orders of magnitude between 100 K and
TN and on further cooling below the magnetic ordering temperature the photosensitivity
continues to decrease in cantrast to the behavior of the other Eu monochalcogenides. A plot
of Log S vs. 1/T below 100 K shows sections with nearly straight Lines, the slopes of which
correspond to activation energies L'.E between 33 and 24 meV at T ~ 25 K, to L'.E = 3.7 meV
between 25 K and TN• and L'.E = 0.29 meV below TN· A magnetic field of B = 1.09 T slightly
enhanced the photosensitivity between T = 4.2 and ~50 K (negative magnetoresistance).
The results are discussed in terms of small magnetic polarans that become self-trapped at
decreasing temperature and remain Localized also below TN· The photoconduction is of the
hopping type, Wachter, Weber [1]; seealso the review by Wachter [2], but see p. 202.
ln contrast, the photosensitivity of an iodine-doped, nondegenerate sample increased
below 55 K (upper Limit of measurement) to a broad maximum near 15 K, foUowed by a sharp
minimum at T N• and S was almost constant between ~ 7 and 4 K. A magnetic field of 1.75 T
decreased S above ~ 17 K (positive magnetoresistance) and increased S at Lower tem-
peratures (negative magnetoresistance). The behavior at T ~ TN was explained by the
presence of ferromagnetic clusters, whereas at TN critical scattering may occur, Vitins,
Wachter [3].
References:
[1] P. Wachter, P. Weber (Solid State Commun. 8 [1970]1133/7).
[2] P. Wacher (Grit. Rev. Solid State Sei. 3 [1972]189/241, 227/31).
[3] J. Vitins, P. Wachter (Phys. Rev. [3] B 12 [1975]3829/39).
30.1.2.10.8.2.12 Optical Properties
30.1.2.1 0.8.2.12.1 Color
lnsulating stoichiometric crystals of EuTe are wine red, Katdis [1], ruby red, Sadovskaya,
Yarembash [2], or deep red by transmission, Jayaraman [3], and show transmission in the
red recognizable to the naked eye, Busch, Wachter [4]. ln reflection the crystals are dark
green, Reed, Fahey [5]. Unlike the pure stoichiometric samples the Low-resistivity, melt-grown
single crystals areopaque in the red, Shapira et al. [6]. The deep red color of single crystals
darkens under pressure, Jayaraman [3]. EuTe powders are dark brown [2], or yellow-red,
Busch et al. [7], or metallic black (sample obtained from the reaction of EuCL2 and excess Te),
Klemm, Senff [8].
References:
[1] E. Katdis (J. Cryst. Growth 3/4 [1968]146/9).
Gmelin Handbook
RE Main Vol. C 10
[3] A. Jayaraman (Proc. 11th Rare Earth Res. Conf., Traverse City, Mich., 1974, Vol.2,
pp. 830/9).
[4] G. Busch, P. Wachter (Physik Kondensierten Materie 5 [1966]232/42, 240).
[5] T. B. Reed, R. E. Fahey (J. Cryst. Growth 8 [1971]337/40).
[6] Y. Shapira, S. Foner, N. F. Oliveira Jr., T. B. Reed (Phys. Rev. [3] B 5 [1972]2647/57, 2648).
1962, pp. 727/31; C.A. 60 [1964]2423).
[8] W. Klemm, H. Senff (Z. Anorg. Allgem. Chem. 241 [1939] 259/63).
30.1.2.1 0.8.2.12.2 Ra man Spectra
lntroduction
The Raman scattering (RS) of Eule has been studied both experimentally and theoretical-
ly together with the other Eu monochalcogenides. Thus, moregenerat data and those concern-
ing the paramagnetic and ferromagnetically aligned states have already been described in
"Rare Earth Elements" C 7, 1983, pp. 477/81, and C 9, 1986, pp. 246/51 and will not be
repeated here. First-order Raman scattering was expected to be symmetry forbidden in Eu
monochalcogenides. lt was nevertheless observed due to the symmetry breaking effects of
spin disorder in the paramagnetic phase. ln EuTe especially the effect of type II anti-
ferromagneUe order on RS was of interest. Raman spectra of EuTe are thus reported mainly
for three different types of spin order: the paramagnetic phase (T > TN), the type II anti-
ferromagnetic phase (T < T N), and the ferromagnetically aligned paramagnetic phase (T < T N•
Ba> Be., Ba perpendicular to the incident Light; Bcr = transition field of the canted to parallel
spin order). The RS shows a strong resonance enhancement effect both above and below T N:
the scattering stimulated by Light of or above the frequency of the absorption edge of EuTe
(see pp. 214/5; resonant case, f... ~ 514.5 nm, hv ~ 2.4 eV in the following) is generally more
intense than that from Light of lower frequency (nonresonant case, f... = 647.1 nm, hv = 1.92 eV,
for example). The scattering experiments have been made in the back scattering configuration
on (100) surfaces if not otherwise stated in the following. By means of polarization analysis
it was possible to discern between different contributing components of the Raman tensor.
Thus, parallel electric field vectors, E, of the incident Light i and the scattered Light s, E, I Es,
also referred to as diagonal configuration or z(xx)z, are characteristic for components (r{ +
4r;t) and a 90° rotation, E, ..L Es, referred to as off-diagonal configuration or z(xy)z, indicates
contributions from components (rii; + r;'i;). The assignments of the Raman bands to the lattice
modes will be given in the course of their description. A short comment on the theoretical
modelswill be given on p. 212.
Paramagnetic Range (T > T N)

Nooresonant Conditions
Raman spectra of Eu Te at 300 K (f... = 647.1 nm) show a rich structure due to second-order
Raman scattering with a cut-off near twice the zone center LO phonon frequency. The spectra
for two scattering configurations are included in Fig. 81. At 20 K two additional peaks at
178 and 189 cm- 1 appear, which are most Likely due to second-order RS with resonance
enhancement of unknown origin, Güntherodt et al. [1]; seealso [2, pp. 2842/3].
The room temperature spectra have been compared to the temperature-weighted two-
phonon density of states (see the figure in the paper). The overall agreement in the mutual
Gmelon Handbook
RE Maon Vol. C 10
Eu Te 209
m i
2K~l
s.sr I -
2K_).-..I\..
Fig. 81. Raman spectra of EuTe for nonresonant excitation as a function of temperature and
applied magnetic field H II [100) . Bottom scale shows zone center phonon frequencies at
300 K; solid line: rt + 4r;t, broken line: rts + r;5
peak positions indicates that the lattice frequencies are correctly described by the model
applied. Yet a quantitative explanation needs a more detailed calculation which takes into
account the proper q dependent matrix elements for second-order RS, Zeyher, Kress [3] ; see
also p. 212 and below.
Resonant Conditions
Raman scattering (A. = 514.5 or 488.0 nm, for example) on paramagnetic EuTe was first
described as a single weak line at ~ 120 cm - 1, Ray et al. [4, 5], which spans from ~ com to
cow, e.g. from ~ 110 to 145 cm - 1, Tsang et al. [6). Later measurements gave a well-resolved
broad peak (300 K, A. = 514.5 nm) at co0 ~ 113 cm - 1, Merlin et al. [7] (see also Grünberg et
al. [8) and [3, p. 2862)) with a Line width of 22 cm - 1, Güntherodt et al. [2, p. 2836) . A broad
peak with FWHM ( = full width half maximum) ~ 35 cm - 1 ranging from ~ 90 to 145 cm- 1 is
reported for 40 > T > T N• A. = 476.5 nm by Schmutzet al. [9) and a line width of ~ 50 cm- 1
at A. = 441 .6 nm also by Vitins [10), Vitins, Wachter [11]. The intensity shows only a small
dependence on the temperature between TN and 300 K; see the figurein the papers [10, 11] .
The plot of the scattering intensity at 300 K vs. the excitation energy ( ~ 2.3 to 2.7 eV) shows
a maximum slightly above 2.5 eV ; see the plot in the paper [10) . The broad Raman line was
described as nonpolarized [9], which is consistent with the spectra shown by Merlin et al. [7)
and for two different scattering configurations by Zeyher, Kress [3] .
The first-order nature of the scattering, which arises predominantly from LO(L) phonons,
was deduced also from the anion mass dependence of the fundamental mode co0 , for all EuX
(X = 0, S, Se, and Te) , Grünberg et al. [8); see also [2, pp. 2836, 2843) . A model of spin
disorder has been proposed to explain the violation of the usual selection rules from the
crystal symmetry [6). The large line width is attributed to sampling from the entire LO phonon
branch, Safran et al. [12, 13); seealso [14, pp. 2754/5]. The observed spectra from resonant
Gmelin Handbook 14
RE Main Vol. C 10
excitation agree reasonably with the calculated one-phonon spin-disorder-induced Raman

scattering intensity, Zeyher, Kress [3]. ln cantrast to EuS and EuSe, calculations for Eule at
T = 0.9 to 2.5 TN show the dominating contributions from the LO phonon but sizable
contributions also from the TO, LA, and TA phonons, Ousaka et al. [15]. See also p. 212.
Antiferromagnetic Range (T < T N• Ha = 0)
Nonresonant Conditions
Aside from the peaks already present in the paramagnetic phase and partly persisting in
the antiferromagnetically ordered state of Eule, the nonresonant Raman scattering at A. =
647.1 nm ~ 1.92 eV and T = 2 K shows a new narrow peak at 113 cm- 1 (see Fig. 81, p. 209,
for two scattering configurations), Güntherodt et al. [1, 16, 17]. This band was not observed
previously by Güntherodt [18], possibly due to unintentional sample heating, Güntherodt [19].
This scattering intensity is attributed to elastic spin-inelastic LO(L) phonon scattering also
referred to as magnetic "Bragg" scattering, Güntherodt et al. [1], [2, pp. 2847/8], Güntherodt
[19], Ousaka et al. [20]. The larger magnetic unit cell results in zone folding into a smaller
Brillouin zone, giving rise to additional zone center modes, some of which are Raman active,
Dresselhaus [21, p. 326], [1, 16]. The observation of this line also for the diagonal configuration
(E, II Es) is in cantrast to earlier predictions from Ousaka et al. [22]. lt is explained by the
Iransformation properlies of the Raman tensor in the point group D3d of the magnetic cell (1].
Resonant Condilions
At excitation with A. = 514.5 nm ~ 2.4 eV at T = 2 K the Raman spectra show a broad

peakaraund ro0 = 113 ± 1 cm- 1 with no line shift and an increased intensity compared to
the paramagnetic phase, but no sharpening, Merlin et al. [7], Güntherodt et al. [2, pp. 2839/40],
Güntherodt [19]. Contrary to EuO and EuS an increased intensity rather than a quenching
below TN at A. = 441.6 nm is also reported by Vitins, Wachter [11, 23], Vitins [10, pp. 227/8].
The reliability of the temperature data in these papers has been questioned [9]. A sharp peak
at w0 = 112 cm- 1 at 1.8 Kupon excitation with A. = 476.5 nm and a significant quenching of
the broad Line contribution was found. ln addition a second sharp Line at 145 cm- 1 is described
with a second harmonic at 290 cm- 1 . The line is attributed to LO(r) phonans [9, 24]. Polariza-
tion analysis of the line at 113 cm- 1 shows the contribution of the q- + 4r;t components to
belarger than that of the ri5 + r;ts components [2, p. 2840] and [19, p. 400]. ln contrast, only
E; .l Es polarization (equivalent to the latter) was found. The polarization of the line at 145 cm - 1
and its higher harmonic is E, II Es [9, 24]. As in the nonresonant case the Line at 113 cm- 1 is
attributed to magnetic "Bragg" scattering of the LO(L) phonon (1, 2, 9, 16, 21]. ln an earlier
paper the Line had been assigned to the LA(L) phonon, Merlin et al. [7]. The LO(L) phonon
frequency has been calculated as 111 cm-1, Ousaka et al. [15, 22] and similarly by Zeyher,
Kress (3]. The nearly [2, p. 2847] unshifted line position of the line at 113 cm- 1 relative to the
paramagnetic state is due to the small antiferromagnetic magnon frequency [7, 19]. The
absence of the very sharp peak at the 113 cm- 1 line is attributed to a strong resonance
enhancement effect [2, 19, 25]. A maximum of the scattering intensity at hv ~ 2.5 eV was
found in a plot of the intensity at 4.2 K vs. the excitation energy ~ 2.3 to 2.7 eV; see the plot
in the paper, Viiins [10]. Raman spectra at T < TN have been calculated by Ousaka et al.
[15] and later also taking the excitation energy dependence of the scattering intensity into
consideration [20, 26].
Raman scattering experiments on n-type conducting Eule at 2 K showed symmetry-
forbidden narrow scattered lines with a half width of ~ 8 cm- 1 . The Raman shift increases
Gmelin Handbock
RE Main Val. C10
Eu Te 211
I&ILO(I")
12 T
9T
.l!!
·;::
~
~ 7T
2
:ä... ST
<(
4T
OT
TO(r) LO(r)
0 100 200 300

v in cm-1
Fig. 82. Raman spectra (unpolarized) of EuTe for resonant excitation as a function of applied
magnetic field B II [001].
from ~ 100 to 120 cm - 1 with the wavelength of the exciting Laser Light of 514.5 nm ~ 2.4 eV
to 476.5 nm ~ 2.6 eV, respectively. This dependence is attributed to phonons with a Large
wave vector q that may be due to surface effects, Holah et al. [27]; see also the preliminary
report [28]. The Raman spectrum of a doped EuTe sample excited by ').. = 441.6 nm shows
(as does that of pure EuTe) marked differences compared to the scattering of EuS and EuSe.
The Line width is Larger (~50 cm - 1), the shape is symmetrical, the intensity is only weakly
dependent on the temperature and on magnetic fields Less than 10 kOe, and it is not quenched
below TN, Vitins, Wachter [11].
Raman SesHering in Applied Magnetic Fields

ln nonresonant conditions the LO(L) phonon scattering, ~113 cm - 1, of EuTe at 2 K is
quenched at 6.5 T, at the phase transition. indicating an actual sample temperature of 3.5 K
(see Fig . 81, p. 209) according to the magnetic phase diagram; see p. 183. The decrease of
the intensity is nearly Linear in 8 2 . The observed field dependence was compared to calculated
curves derived within renormalization group theory [16, 19].
The field dependence up to 12 T of the Raman scattering at resonant excitation is shown
in Fig. 82 for 'A = 514.5 nm and 2 K .The intensity around m0 shows a weak maximum at B =
7 T. For B > 7 T the intensity decreases slightly but still persists because of one-phonon one-
magnon scattering. Simultaneously a strong Line develops at 145 cm - 1 tagether with one
harmonic [16, 19]. This scattering is explained as "forbidden" LO(f) phonon scattering which
originates from small but finite wave vector effects in the Raman tensor, due to the Fröhlich
electron phonon interaction [1] ; see also [19], [21 p. 319] . This "ferro" Line at 145 cm - 1 and
its harmonic at 290 cm - 1 were observed with 'A = 501 .7 nm and 1.8 K also by Schmutzet al.
[9]; for Low applied magnetic fields, H < 10.5 kOe, the Raman intensities at 113 and 145 cm- 1
are only weakly dependent on the Laser excitation energy [24] . The intensity of the LO(r)
scattering increases strongly by a factor of 102 to 103 with the magnetic field at ~ 2 K and 'A =
514.5 nm, studied up to ~ 120 kOe. The increase is most steeply around the critical field Bcr
Gme1in Handbock 14.
RE Main Vol. C10
(see p. 183) and saturates around 12 T; see the figurein the papers [9, 24, 29]. A theoretical
study of the integrated Raman intensity near the canted-to-paramagnetic phase boundary
gave maximum intensity both for E; I Es and E, .l Es at Be,; see the paper for a plot of the field
dependence of the intensity normalized to Bcr forT = 0.7 TN· This result was obtained by the
renormalization group method and also by the random phase approximation. The possibility
to derive the critical exponents from Raman scattering experiments is discussed, Safran et
al. [13]; see also Safran et al. [30]. The intensity of the LO(f') scattering is also strongly
dependent on the excitation energy hv with a maximum near 2.42 eV, the energy of the peak
E1' in the magneto reflectance. The "ferro" line is strongly polarized with maximum intensity
at E, I Es and E, .l Ha (implying E, .l M, M = magnetization) [9, 24, 29].
The increase of the temperature from below to above T N at fields above Bcr decreases the
intensity, which disappears at about 30 K. The occurrence of the "ferro" line also at T > T N is
attributed to short range ferromagnetic spin alignment [24].
Theoretical Models
Usual first-order Raman scattering is nominally symmetry-forbidden in NaCl type Eu

monochalcogenides. First-order scattering is nevertheless observed in the paramagnetic
state. This one-phonon scattering is due to the spin disorder mechanism proposed by Tsang
et al. [6]; see also Grünberg et al. [8], Merlin et al. [31]. Earlier or alternatively proposed
scattering mechanisms based on extrinsic properties (local modes, defects), Ray et al. (4] or
on "hot luminescence" (cf. p. 282), Vitins [10], Vitins, Wachter [11, 23] (see also Wachter [32]),
have been ruled out; see for example Silberstein et al. [33], Merlin et al. [31], Güntherodt et
al. [2], Zeyher, Kress [3]. Microscopic theories have been developed to describe the scattering
process, Safran et al. [13, 14], Merlin et al. [7, 31], Sakai, Tachiki [34], and have been extended
to include the various types of spin order, Ousaka et al. [15, 20, 22, 26], Safran et al. [13],
Merlin et al. [7].
Most of the available data can be qualitatively understood by considering the one-phonon
one-spin polarizability; see for example Safran et al. [12 to 14]. Merlin et al. (7, 31]. Ousaka
et al. [15, 22]. This gives rise to the spin disorder-induced scattering in the paramagnetic case
and to scattering by folded phonons in the magnetically ordered (nonferromagnetic) phases.
At resonant excitation the observed scattering is derived from the one-phonon two-spin
polarizability [2, 19, 25].
The model of Safran et al. [14] results in a symmetric Raman tensor. This is said to disagree
with the model of Sakai, Tachiki [34] and experimental, Güntherodt et al. [2], and theoretical
results, Zeyher, Kress [3], which show a dominant contribution from the 1{5 Raman tensor
component (see also [25]) according to which the model of Ousaka et al. [20] does not explain
the observed polarization property of the LO(L) phonon scattering near 113 cm- 1 and the
magnetic field dependence of the scattering intensity. The model of Zeyher, Kress [3] had
been regarded as consistent with calculations by Ousaka et al. [15]. The contribution of s-d
(or s-f) interaction on the resonant Raman scattering in EuTe by a two-magnon process at
T ~ T N has been studied by Coutinho, Coutinho-Filho [35]. A semi-localized magnetic exciton
modelwas proposed which considers some of the differences between the "normal" and the
"magnetic" (Fröhlich) LO(f') scattering, Abiko [36].
References:
[1] G. Güntherodt, R. Merlin, G. Abstreiter (J. Magn. Magn. Mater. 15/18 [1980]821/2).
[2] G. Güntherodt, R. Merlin, P. Grünberg (Phys. Rev. [3] B 20 [1979] 2834/49).
Gmelm Handbock
RE Main Vol. C10
Eule 213
[3] R. Zeyher, W. Kress (Phys. Rev. [3] 8 20 [1979] 2850/63).

[4] R. K. Ray, J. C. Tsang, M. S. Dresselhaus, R. L. Aggarwal, T. 8. Reed (Phys. Letters A
37 [1971]129/31).
[5] R. K. Ray, J. C. Tsang, M. S. Dresselhaus, R. L. Aggarwal, T. 8. Reed (Proc. Nucl. Phys.
Solid State Phys. Symp. C 16 [1972] 251/4; C.A. 78 [1973] No. 153386).
[6] J. C. Tsang, M. S. Dresselhaus, R. L. Aggarwal, T. 8. Reed (Phys. Rev. [3] 8 9 [1974]
984/96).
[7] R. Merlin, R. Zeyher, G. Güntherodt (lnst. Phys. Conf. Ser. No. 43 [1978/79] 145/8; C.A.
90 [1979] No. 159548).
[8] P. Grünberg, G. Güntherodt, A. Frey, W. Kress (Physica 8 + C 89 [1977] 225/8).
[9] L. E. Schmutz, G. Dresselhaus, M. S. Dresselhaus (J. Magn. Magn. Mater. 11 [1979]
412/5).
[10] J. Vitins (J. Magn. Magn. Mater. 5 [1977] 212/33).
[12] S. A. Safran, G. Dresselhaus, R. P. Silberstein, 8. Lax (J. Magn. Magn. Mater. 11 [1979]
403/7).
[13] S. A. Safran, G. Dresselhaus, 8. Lax (J. Appl. Phys. 49 [1978] 2180/2).
[14] S. A. Safran, G. Dresselhaus, 8. Lax (Phys. Rev. [3] 8 16 [1977] 2749/63).
[16] G. Güntherodt, G. Abstreiter, W. 8auhofer, G. 8enedek, E. Anastassakis (J. Magn. Magn.
Mater. 15/18 [1980] 777/8).
[17] G. Güntherodt, R. Merlin, W. 8auhofer, G. Abstreiter (J. Magn. Magn. Mater. 13 [1979]
187/8).
[18] G. Güntherodt (Proc. 13th Intern. Conf. Phys. Semicond. Tipografia Marves, Rome 1976,
pp. 291/300).
[19] G. Güntherodt (J. Magn. Magn. Mater. 11 [1979]394/402).
[21] G. Dresselhaus (NATO Advan. Study lnst. Ser. 8 60 [1980]315/35).
[22] Y. Ousaka, 0. Sakai, M. Tachiki (Solid State Commun. 23 [1977] 589/92).
[23] J. Vitins, P. Wachter (Physica 8 + C 86/88 [1977] 213/7).
[24] R. P. Silberstein, L. E. Schmutz, V. J. Tekippe, M. S. Dresselhaus, R. L. Aggarwal (Solid
State Commun. 18 [1976]1173/7).
[25] G. Güntherodt, R. Zeyher (Top. Appl. Phys. 54 [1984]203/42).
[26] Y. Ousaka, 0. Sakai, M. Tachiki (J. Magn. Magn. Mater. 31/34 [1983] 583/4).
[27] G. D. Holah, J. S. Webb, R. 8. Dennis, C. R. Pidgeon (Solid State Commun. 13 [1973]
209/13).
[28] C. R. Pidgeon, G. D. Holah, R. 8. Dennis, J. S. Webb (Proc. 11th Intern. Conf. Phys.
Semicond., Warsaw 1972, pp. 1280/6; C.A. 81 [1974] No. 179396).
[29] V. J. Tekippe, R. P. Silberstein, L. E. Schmutz, M. S. Dresselhaus, R. L. Aggarwal (Proc.
3rd Intern. Conf. Light Scattering Solids, Campinas, 8raz., 1975 [1976], pp. 362/6; C.A.
85 [1976] No. 151290).
[30] S. A. Safran, R. P. Silberstein, G. Dresselhaus, 8. Lax (Solid State Commun. 29 [1979]
339/43).
[31] R. Merlin, R. Zeyher, G. Güntherodt (Phys. Rev. Letters 39 [1977]1215/8).
[33] R. P. Silberstein, V. J. Tekippe, M. S. Dresselhaus (Phys. Rev. [3] 8 16 [1977] 2728/48).
[34] 0. Sakai, M. Tachiki (J. Phys. Chem. Solids 39 [1978]265/83).
[35] S. Coutinho, M. D. Coutinho-Filho (Physica 8 + C 86/88 [1977]987/8).
[36] S. Abiko (Z. Physik 8 39 [1980] 53/63).
Gmelin Handbook
RE Main Vol. C10
30.1.2.10.8.2.12.3 Additional Light ScaHering Studies
Light scattering experiments on EuTe crystals in which antiferromagnetic resonance,

AFMR, was excited simultaneously showed inelastically scattered satellite Lines under reso-
nance conditions which were shifted by the frequency of the microwave field (direct scattering
geometry with incident (A. = 632.8 nm) and scattered Light perpendicular to a cleaved (100)
face, H(::;i; 65 kOe) 11 [100] and [010], ro = 35.2 to 44.7 GHz, T = 1.8 K). The effect is attributed
to inelastic Light scattering by spin waves. A new inelastic Light scattering mechanism is
proposed, involving s-f exchange; for details see the papers, Borovik-Romanov et al. [1, 2],
Oemokritov et al. [3]. ln a more recent paper a single-magnon inelastic scattering at 2 K by
thermal magnons betonging to both branches of the excitation spectrum is reported,
Demokritov et al. [4].
References:
[1] A. S. Borovik-Romanov, S. 0. Demokritov, N. M. Kreines, V. I. Kudinov (Zh. Eksperim.

Teor. Fiz. 88 [1985]1348/58; Soviet Phys. JETP 61 [1985] 801/7).
[2] A. S. Borovik-Romanov, S. 0. Demokritov, N. M. Kreines, V. I. Kudinov (J. Magn. Magn.
Mater. 54/57 [1986]1181/2).
38/40; JETP Letters 41 [1985]46/9).
312/4; JETP Letters 43 [1986]403/6).
30.1.2.1 0.8.2.12.4 Absorption. Reflection
Below E9
The infrared reflectivity between A. = 250 and 311m (40 and 3300 cm- 1) of an insulating
EuTe sample with acharge carrier density n ~ 5 x 1017 cm- 3 at 300 K showed a raststrahlen
peak; see Fig. 83. A "Least-squares fit" of the single oscillator model (broken Line in Fig. 83)
yielded the phonon frequencies (see p. 166) and the dielectric constants (see p. 221), Holah
et al. [1], Pidgeon et al. [2]. Reflectivity measurements between A. = 4 and 1.5 11m ( ~ 0.31 and
0.83 eV) at T = 4.2 to 300 K were reported to show only a very weak temperature independent
structure at A. = 3.5 11m(~ 2900 cm- 1 , 0.35 eV), Ravot et al. [3]. The strong effects of magnetic
fields on the reflectivity spectrum near 4 K between 10 and 400 cm- 1 can not be explained by
a simple model, Faymonville et al. [4]. A high transparency (absorption coefficients a. below
10 cm-1, which generally decreased with increasing A.) for wavelengths shorter than 2.5 11m
down to the absorption edge at - 0.62 11m is characteristic for pure EuTe samples. The higher
absorption coefficient of other EuTe samples, which increases roughly in proportion to 1..2 , is
attributed to free charge carriers due to nonstoichiometries, Busch et al. [5]; seealso Verreault
[6], Kaldis [7], [8, p. 105]. The optical density determined by Iransmission for hv = 0.5 to
2.5 eV of an EuTe film on quartz (thickness 520 nm) was found to show several small nearly
equidistant maxima which were attributed to interference effects from multiple reflection,
Schoenes [9, p. 352].
Absorption Edge E9
At Ambient Pressure
The absorption edge corresponds to the onset of the 4f(8 S712 ) -+ 4f6 eFJ)5d(t29 ) transition
and is equivalent to the energy gap E9 between the f-states and the conduction band. The
Gmelin Handbook
RE Mam Vol. C10
Eule 215
>.
~ 0.4 t---t----:;;~t------\t---+---i
~
Fig. 83. Experimental (full line) and calculated (broken line) reflectivity of Eule at 300 K vs.
wave number.
value E9 = 2.0 eV from measurements on bulk Eule was first reported by Holtzberg et al.
[10], Methfessel et al. [11], from thin single crystals, Wachter [12). lhis value is generally
accepted; see for example [13, 14].
lhe value hv = 2.05 ± 0.1 eV, the energy at which the curve of the absorption coefficient
a vs. hv starts to deviate from the exponentiallaw, is taken as E9 by Schoenes [9, pp. 352/3] .
lhe values of Busch et al. [15, 16] are superseded [12]. E9 = 2.25 to 2.29 eV was proposed
from thin film absorption spectra, Suryanarayanan , Paparoditis [17). A gap E9 = 1.959 eV is
reported by Reed, Fahey [18) referring to Oliver [19) . An Urbach gap parameter E9 = 2.062
± 0.005 eV at zero field and at 1.7 K is derived from the magnetic field dependence of the
optical absorption, Schmutz et al. [20]; see below.
Dependence of E9 on Temperature, Pressure, and Magnetic Field
lhe absorption edge of Eule measured on single crystals shows the usual blue shift on
cooling within the paramagnetic range, due to electron-phonon interaction. lhe latter becomes
frozen in below about 30 K. An additional blue shift of about 0.03 eV is found on cooling from
~ 25 to 5 K with a remarkable kink at l N· lhe kink is tentatively related to a spontaneaus
exchange striction ; seealso p. 163. By this observation previous reports [21, 22) stating no
appreciable shift around l N are superseded. lhe model of Rys et al. [23) agrees reasonably
with the observed blue shift, Wachter, Weber [24) . A blue shift of the edge of ~ 0.057 eV
between l N and 0 K is obtained within the s-f model for a hypothetic two-sublattice anti-
ferromagnetic model structure using parameters suitable for Eule. lhe real type ll anti-
ferromagnetic structure shows practically no temperature dependence, Matlak et al. [25]. Also
the many-body approach yields a temperature independent edge position . From the Zener
model a red shift is predicted. After allowing for the paramagnetic preshift a small blue shift
results. For detailsseevon der Linden , Nolting [26] .
lhe pressure dependence of the absorption edge at room temperature was derived from
the shift of the transmission curves of polished single crystals in silicon oil. Using hydrostatic
pressures of ~ 1 kbar the curves shift linearly to lower energy at a rate of -12meV/kbar,
Wachter [27] . lhe exponential energy dependence of the absorption coefficient near the
absorption edge was shown to follow the Urbach rule (A. = 590 to 630 nm, hv = 2.10 to
1.968 eV). lhe dependence lrom the magnetic field (H I [100], incident beam II [001), trans-
mission geometry, polarization : E II Ft or E .l H) of the absorption coefficient at 1.7 K could
be fit for the studied range, 0 < H < 9.5 l , by considering a field dependence of the parameters
of the Urbach rule (edge sharpness, gap parameter) . lhe gap parameter E9 decreases with
Gmelin Handbook
RE Main Vol. C 10
2 .oe .-----.,-----..--~---.
E.I.H
1.96
0~~2~.5~~S~ 0--~7~.5~-,~QO
Applied field in T
Fig. 84. Urbach gap parameter E9 for a Eulesingle crystal at 1.7 K versus applied field.
increasing applied field (H < 7 T); see Fig. 84. The red shift saturates at H ~ 7 T. The gap
parameter shows different field dependences : proportional to H at E II A and proportional t o
H2 at E j_ H, giving a splitti ng of ~ 44 ± 4 meV at saturation. The behavior is related to the
magnetic phasediagram of Eule. lt is said to suggest an excitonic interpretation of the excited
state electronic structure, Schmutzet al. [20); seealso Dresselhaus [14]. The optical density
near E9 of Eule films ( ~ 200 nm thickness) at applied magnetic field parallel to the incident
light, T = 2.7 K ,seems to indicate a slight blue shift of E9 at moderate fields ( < 20 kOe) and
a significant red shift for fields up to 100 kOe. The effect saturates between 80 and 90 kOe ;
see Fig. 85. The analysis gives a total averaged magnetic red shift of 0.11 ± 0.005 eV between
zero field and saturation. The disagreement at moderate fields with the results of [24] (see
below) is attributed to different data correction, the actual onset of the red shift is regarded
undecided, Schoenes [28]. The total red shift in the Eu monochalcogenides is inversely
proportional to the gap size [28] . For the simple explanation of the red shift see p. 224. Asmall
red shift of E9 compared to zero field had been observed at H = 16.9 kOe. in this field the
temperature dependence of E9 no Iongershows a kink at T N• Wachter, Weber [24] ; cf. [29].
Absorption and Reflection Above E9
The absorption coefficient r:t of Eule single crystals at 300 K between ~ 2 and 5.5 eV has
been derived from reflectivity measurements. lt shows two main maxima at E1 ~ 2.6 eV,
absorption coefficient r:t ~ 2.3 x 105 cm - 1 and E2 ~ 4 eV, r:t ~ 5.3 x 105 cm - 1 (read from a
figure) , Güntherodt et al. [30], Güntherodt [31 , p. 49], Busch et al. [32], Wachter [29, p. 202];
see Fig . 263 in "Rare Earth Elements" C 7, 1983, p.484. These results a re consistent w ith
spectra obtained on thin film samples at room temperature (A = 800 to 200 nm) , E1 at ~ 470 nm
( ::= 2.6 eV) and E2 at 300 nm ( ::= 4.1 eV), Holtzberg et al. [10], Methfessel et al. [11], Wachter
[29, p. 201], E1 = 2.64 eV with r:t = 1.82 x 105 cm- 1 (studied range from 2 to 6 eV), Schoenes
(9, p. 353],and measured at 7 K between 2.2 and 4.8 eV giving r:t ~ 2 and 5.5 in 105 cm - 1 at
E1 and E2 , respectively, Busch et al. [33] . The energy of E1 ~ 2.45 eV and another absorption
maximum at ~ 3.3 eV for thin film absorption spectra at room temperature and hv = 2 to
3.5 eV is reported by Suryanarayanan, Papa roditis [17] . Eule shows a higher absorption and
a smaller difference E2 - E1 compared to the other Eu monochalcogenides (31] .
The reflection spectrum of Eul e , shown in Fig. 86 for photon energies between 2 and 11 eV
at normal incidence on a polished single crystal surface at 300 K, has pronounced maxima
around E 1 and E2 (doublet) , a weaker one between 5 and 6 eV, and a very weak one at 7.5 eV
Gm eh n Handbook
RE Main Vol. C10
Eu Te 217
Fig . 85.
Absorption spectrum of a EuTe
film at magnetic fields
OL-~~--~--~~--~--~~--~ from 0 to 100 kOe and T = 2.6 K.
2.0 2.5 10
Photon energ y in eV
28
II
(\
'\ \""
24
20
1\
;!!-
V
.!:
~
:2: 16
~
~ 12 \
8
\ .........
\.__ Fig. 86.
Reflection spectrum of EuTe at 300 K.
3 6 9 12
Photon energy in eV
[31] . This is in agreement with the nearly normal reflectivity between 0 and 12 eV on cleaved
(100) faces of melt-grown single crystals at 300 K (E 1 = 2.37 eV, E2 (doublet) = 3.43 and
3.83 eV, small yet pronounced peak around 7.5 eV; see the figurein the paper), Pidgeon et
aL [34]. Other previously measured reflectivity spectra deviate to a minor (Güntherodt et aL
[30]) or larger extent, showing reflectivity maxima at 2.12, 3.1 (shoulder) , 3.26, 3.47, 4.67, and
4.92 eV, Güntherodt, Wachter [35] . The discussion of absorption and reflection spectra by
Wachter [21] refers to the latter (possibly superseded) spectrum . The reflectivity peak at E,
shifts slightly with decreasing temperature [36] and splits to a doublet and finally to a triplet
below T N on cooling to 1.5 K [34]. The split below T N is smaller than for the other europium
chalcogenides, Schoenes [9, p. 355]. The dependence of the absorption spectrum near E1 of
a EuTe film on magnetic fields up to 100 kOe at 2.6 K is shown in Fig . 85, Schoenes [28].
Gmel1n Handbook
RE Main VoL C 10
The reflectivity at 1.5 K araund E1 for right and left circularly polarized light, crR and crL,
was measured at nearly normal incidence on cleaved (100) faces of melt-grown single crystals
with H .l (100) in the Faraday configuration up to 97.4 kOe. The structure changes significantly
with increasing magnetic field, reaching Saturation at H ~ 80 kOe. The polarization-indepen-
dent triplet structure at zero field broadens up to 40 kOe. Near 60 kOe it changes to a
polarization-dependent sharp triplet, the lowest energy peak of which has pure crR polariza-
tion, while the highest is pure crL. The central peak has a greater crR component; see the
figure in the paper. Parallel to the change in shape there is also a shift in the energy position
of the structure giving the central peak at 2.2 eV at ferromagnetic spin order in the highest
magnetic field. The splitting into crR and crL components and shifts in energy are also found
for E2 [34, 37].
Modulated Reflection and Transmission

Fora short description of the modulation techniques see "Rare Earth Elements" C 9, 1986,
p. 256. The thermally modulated reflection (temperature modulation of 0.01 to 0.1 Kat 10Hz)
on single crystalline samples at 9 K and for photon energies between 2 and 5 eV shows two
groups of signals. The fairly broad signal below 3 eV corresponds to the 4f--> 5d(t 29 ) transition
and can be accounted for by the magnetic exciton model. The signal in the range between
3.4 and 4 eV is believed to be due to Wannier type excitons associated with the direct band
edge 1 10-1 15 v; a further signal in this rangeisnot interpreted, Mitani, Koda [41]. The doublet
structure is weak in the paramagnetic state of EuTe (for example at 17.3 K), it becomes
strenger and slightly shifts to higher energies on cooling to 4.2 K, i.e., below T N· ln the
antiferromagnetic state no splitting of the doublet due to spin polarization is observed in
cantrast to the ferromagnetic EuO and EuS, Mitani, Koda [42].
The thermoreflection (10Hz) and thermotransmission (20Hz) spectra recorded at 5 K on
0.5 1-1m Eu Te film on Pyrex by Paparoditis et al. [43] appear rather different from those referred
to above. 8oth the relative transmission and reflectivity changes, ~T/T and ~R/R, respectively,
show a large effect below 2 eV. The dominant signal at 1.86 eV in the ~R/R curve has a red
shift and increasing intensity upon decreasing temperature (studied in the range 5 to 21 K).
The intensity decreases in an external magnetic field at H = 3 kOe and T = 8.5 K. The smaller
maxima at 2.06 and 2.45 eV coalesce at 2.25 eV both on heating to 21 K and on applying an
external magnetic field [43].
ln polarization-modulated reflection spectra in an external magnetic field the difference
is measured between the reflectivity for periodically changed right ( +) and left (-) ci rcularly
polarized light. This ~R is correlated to the reflectivity for unpolarized light giving the relative
~R/R = (R_- R+)/R. The polarization modulated reflectivity ~R/R from hv = 2 to 2.6 eV
for EuTe at 1.5 Kin magnetic fields H = 59 to 97.4 kOe is shown in a figure in the paper.
The effect saturates at H > 84 kOe. After correction for the internal demagnetization field,
8 0 , = 7.5 ± 0.2 T is obtained for the transition field from the canted to the ferromagnetically
aligned spin structure, Pidgeon et al. [44].
Interpretation
The structures at E1 and E2 in the absorption and the reflection spectra are attributed to
transitions from localized 4f( 8S712 ) into 4f6 ( 7 FJ)5d(t 29 ) and 4f6 (FJ)5d(e 9 ) states, respectively;
see for instance [31].
A contribution from valence-to-conduction band transitions to the intensity observed at E2
is supposed from comparison with SrTe spectra, Dimmock [36]. Energy Level schemes derived
Gmelm Handbook
RE Mam Vol. C10
Eu Te 219
from the optical properties of EuTe and the other Eu monochalcogenides are developed by
Methfessel et al. [11]. Dimmock et al. [38], Busch et al. [32) and arealso reproduced in [29 to
31]. Batlogget al. [39); seealso Wachter (13). The assignments given imply a crystal field
splitting of the d-states 10 Dq = 1.5 eV (30, 32]. cf. [31]. The values 10 Dq = 10000 cm- 1
( ~ 1.24 eV) [11]. 1.3 eV ( = E2 - E1 ) [36]. and 1.6 eV [38] arealso reported. A width of the 5d(t 29 )
subband of 0.6 eV is obtained after allowing for the width (0.6 eV) of the 7 FJ (J = 0, 1 to 6) (30,
32). The splitting of the reflectance peaks below TN is discussed in terms of superlattice
splitting of the bands at the new zone boundary. The splitting into different spectra for crR and
crL in external magnetic fields is related to exchange splitting of the d-states and to different
transition probabilities for crR and crL for the various J values of the 7FJ final state. The behavior
of E2 is obviously more complex than that of E1 [34, 36]; see also [30]. The optical spectra of
the Eu monochalcogenides have also been discussed in terms of the magnetic exciton model
of Kasuya [40); see for example "Rare Earth Elements" C 7, 1983, p. 486.
References:
[1) G. D. Holah, J. S. Webb, R. B. Dennis, C. R. Pidgeon (Solid State Commun. 13 [1973)

209/13).
[2) C. R. Pidgeon, G. D. Holah, R. B. Dennis, J. S. Webb (Proc. 1Hh Intern. Conf. Phys.
Semicond., Warsaw 1972, pp. 1280/6; C.A. 81 [1974] No. 179396).
[3) D. Ravot, J. C. Achard, 0. Gorochov, M. Escorne, A. Mauger (J. Phys. Colloq. [Paris] 41
[1980) C5-357 /C5-359).
[4) R. Faymonville, P. Grosse, M. Salem, J. Heleskivi, M. Mäenpää (Verhandl. Deut. Physik.
Ges. 13 [1978]155/6).
[5] G. Busch, R. Verreault, 0. Vogt (Solid State Commun. 8 [1970]617/20).
[6] R. Verreault (Solid State Commun. 7 [1969)1653/6).
[7] E. Katdis (J. Cryst. Growth 3/4 [1968] 146/9).
[8] E. Katdis (in: C. H. L. Goodman, Crystal Growth, Theory and Techniques, Plenum, New
York 1974, pp. 49/191).
[9] J. Schoenes (Z. Physik B 20 [1975] 345/68).
[10) F. Holtzberg, T. R. McGuire, S. Methfessel (J. Appl. Phys. 37 [1966] 976/8).
[11) S. Methfessel, F. Holtzberg, T. B. McGuire (IEEE Trans. Magn. 2 [1966] 305/6).
[12) P. Wachter (Helv. Phys. Acta 41 [1968]1249/55).
(13) P. Wachter (in: K. A. Gschneidner Jr., LeRoy Eyring, Handbook on the Physics and
[14) G. Dresselhaus (NATO Advan. Study lnst. Ser. B 60 [1980] 315/35).
1962, pp. 727/31; C.A. 60 [1964) 2423).
[16] G. Busch, P. Junod, P. Wachter (Phys. Letters 12 [1964]11/2).
(17] R. Suryanarayanan, C. Paparoditis (Colloq. Intern. Centre Natl. Rech. Sei. [Paris] No. 180
[1969/70]149/55).
[18] T. B. Reed, R. E. Fahey (J. Cryst. Growth 8 [1971] 337/40).
[19) M. R. Oliver (Diss. MIT Electr. Eng. Dept., Cambridge, Mass., 1970).
[20) L. E. Schmutz, G. Dresselhaus, M. S. Dresselhaus (Solid State Commun. 28 [1978)
597/600).
[21] P. Wachter (Physik Kondensierten Materie 8 [1968/69]80/6).
[22) G. Busch, P. Wachter( Physik Kondensierten Materie 5 [1966] 232/42).
[23) F. Rys, J. S. Hetman, W. Baltensperger (Physik Kondensierten Materie 6 [1967]105/25).
(24) P. Wachter, P. Weber (Solid State Commun. 8 [1970]1133/7).
Gmelin Handbook
RE Main Vol. C 10
[25] M. Matlak, A. Ramakanth, K. Skrobis (Z. Physik B 48 [1982]227/31).

[26] W. von der Linden, W. Nolting (Z. Physik B 48 [1982]191/9).
[27] P. Wachter (Solid State Gommun. 7 [1969] 693/6).
[29] P. Wachter (GRG Grit. Rev. Solid State Sei. 3 [1972]189/241).
[30] G. Güntherodt, P. Wachter, 0. M. lmboden (Physik Kondensierten Materie 12 [1970/71]
292/310).
[31] G. Güntherodt (Phys. Gondens. Matter 18 [1974]37/78).
[32] G. Busch, G. Güntherodt, P. Wachter (J. Phys. Golloq. [Paris] 32 [1971] G1-928/G1-929).
[33] G. Busch, J. Schoenes, P. Wachter (Gzech. J. Phys. B 21 [1971] 570/3).
[34] G. R. Pidgeon, J. Feinleib, W. J. Scouler, J. 0. Dimmock, T. B. Reed (IBM J. Res. Develop.
14 [1970]309/11).
[35] G. Güntherodt, P. Wachter (Phys. Letters A 29 [1969]660/1).
[36] J. 0. Dimmock (IBM J. Res. Develop. 14 [1970] 301/8).
[37] J. Feinleib, G. R. Pidgeon (Phys. Rev. Letters 23 [1969]1391/4).
[38] J. 0. Dimmock, J. Hanus, J. Feinleib (J. Appl. Phys. 41 [1970]1088/9).
[39] B. Batlogg, E. Kaldis, A. Schlegel, P. Wachter (Phys. Rev. [3] B 14 [1976] 5503/14).
[40] T. Kasuya (GRG Grit. Rev. Solid State Sei. 3 [1972]131/64).
[41] T. Mitani, T. Koda (Proc. 12th Intern. Gonf. Phys. Semicond., Stuttgart, FRG, 1974,
pp. 889/93; G.A. 83 [1975] No. 18364).
[42] T. Mitani, T. Koda (Physica B + G 86/88 [1977]127/8).
[43] G. Paparoditis, J. G. Gillon, N. Defranould, J. Richard (J. Phys. Golloq. [Paris] 41 [1980]
G5-101/G5-104).
[44] G. R. Pidgeon, J. Feinleib, T. B. Reed (Solid State Gommun. 8 [1970]1711/4).
30.1.2.1 0.8.2.12.5 Optical and Dielectric Constants
Refractive Index
The refractive index n of EuTe at 300 K was determined by the prism method to ± 0.006.
lt increases from n = 2.44 at 2.5 Jlm (0.5 eV) to n = 2.8 at 0.6 J.tm (2.1 eV); values read from
a figurein the paper. The etassie dispersion relation is valid, Wachter [1].
The refractive index decreases with increasing sample purity from n between 2.761 and
2.684 ( ± 0.005) for crystals from Sublimation to n = 2.654 ± 0.005 both at /.. = 0.635 Jlm
( ~ 1.95 eV) for a crystal grown by chemical transport. A value n = 2.65 is proposed as
characteristic for pure EuTe. The sensitivity of the refractive index and the absorption
coefficient near the absorption edge to impurities is attributed to donor Levels within the gap,
the concentration of which increases with increasing impurities, Verreault [2]. Polarization-
dependent reflectivity data for 300 K yielded the refractive index (accuracy better than 0.5%)
by means of the Fresnel equations as shown in Fig. 87 for energies from below E9 to nearly
6 eV. The obtained value, n = 2.71, at the absorption edge is close to the directly measured
values, n = 2.74 [1] and 2.65 [2], Güntherodt et al. [3, pp. 294/5). The refractive index n =
2.76 ± 0.08 at 2 eV was determined by interference on a thin EuTe film, Schoenes [4, p. 352].
The refractive index of a thin EuTe film between hv = 0.4 to 2.25 eV shows good overall
agreement with the curve of Wachter [1] after calibration of the values at hv = 2 eV,
Suryanarayanan, Paparoditis [5]. The refractive index in the wavelength range 0.6 to 2.5 Jlm
does not change on cooling through T N• Wachter [6].
Gmelm Handbock
RE Mam Val C10
Eule 221
2.6
~
c:
~
><
Cll
:g 2.2
.~
ü
2
't 1.8
a::
\ \_
1.4 ~
t5 25 3.5 4.5 5.5
Photon energy in eV
Fig. 87. Refractive index of Eule versus photon energy.
Dielectric Constants
The static and optical dielectric constants for pure crystals, derived from reflectivity
measurements, are e0 = 6.9, and E00 = 5.75, Güntherodt [7, p. 45] or e0 = 8.23 and E00 = 4.18
(single oscillator fit of IR reflectivity), Holah et al. [8), Pidgeon et al. [9]. These values are
not considered reliable since they do not follow the trends in the Eu monochalcogenides
[7, pp. 52 and 58]. e0 = 10.7 (reflectivity in the reststrahlen range), Faymonville et al. [101 .
e0 = 11 .2, estimated from the reststrahlen band of EuO, and E 00 = 5.92, from the refractive
index extrapolation, Wachter [1).
The real and the imaginary parts of the complex dielectric function (see " Rare Earth
Elements" C 7, 1983, p. 489 and the figurein the paper, respectively) have been derived from
room temperature reflectivity data and those of [8) from nearly zero frequency to hv = 12 eV
by means of a Kramers-Kronig (K-K) analysis. e' has a minimum of 0.2 at 7.6 eV, which ,
however, does not indicate a plasma resonance. The K-K result for the imaginary part e" is
in good agreement with that derived from the polarized light method at ~ 2 to 6 eV, yet
showing higher absolute values towards 6 eV. The main contributions to e" are confined to a
narrower energy range in Eule than in the other Eu monochalcogenides. The effective static
dielectric constant e'(O)eff• derived from e", shows Saturation as the high-energy Limit of the
integration reaches the upper energy Limit of the experiments. The effective electron number
neff (from the sum rule) for Eule shows an unexpected behavior above ~ 6.5 eV, increasing
much less than the curve of EuSe and reaching only neff = 4.1 at 11.2 eV. This is related to the
missing oscillator strengthin the experimental reflectivity between ~ 7 to 9.5 eV (compared to
spectra of Pidgeon et al. [11)). The maximum in the energy loss function. indicating the plasma
resonance frequency, is at 10.15 eV compared to lirop = 10.8 eV calculated from the sum rule
assuming 6 valence electrons per unit cell, Güntherodt [7, pp. 45/54, 57/60] .
The imaginary part K~y of the complex conductivity tensor has been evaluated forthin films
between hv = 2 and 5.5 eV fo r T = 5 and 15 K from Faraday rotation experiments at H =
11.5 kOe and absorption data plus additional data above 6 eV from Güntherodt [7) ; see the
figure in the paper. This plot resembles the plot of the circular dichroism (for a figure see the
paper) also showing the complementary temperature dependence of the various extreme
values (at 2.4 to 3 eV). As shown in detail in the paper for EuS the main contributions to
K~y arise from 4f~--> 5d 1 intra-cation and p6 (anion)--> 5d 1 " (Eu 2 + ) transitions, Schoenes [4,
pp. 364/5] .
Gmelm Handbook
RE Main Vol. C 10
References:
[1] P. Wachter (Physik Kondensierten Materie 8 [1968/69] 80/6).

[2] R. Verreault (Solid State Commun. 7 [1969]1653/6).
[3] G. Güntherodt, P. Wachter, D. M. lmboden (Physik Kondensierten Materie 12 [1970/71]
292/310).
[1969/70]149/55).
[7] G. Güntherodt (Phys. Condens. Matter 18 [1974]37/78).
[8] G. D. Holah, J. S. Webb, R. B. Dennis, C. R. Pidgeon (Solid State Commun. 13 [1973]
209/13).
[9] C. R. Pidgeon, G. D. Holah, R. B. Dennis, J. S. Webb (Proc. 11th Conf. Phys. Semicond.,
Warsaw 1972, pp. 1280/6; C.A. 81 [1974] No. 179396).
[10] R. Faymonville, P. Grosse, M. Salem, J. Heleskivi, M. Mäenpää (Verhandl. Deut. Physik.
Ges. 13 [1978]155/6 and from [12]).
[11] C. R. Pidgeon, J. Feinleib, W. J. Scouler, J. 0. Dimmock, T. B. Reed (IBM J. Res. Develop.

14 [1970]309/11).
[12] R. Zeyher, W. Kress (Phys. Rev. [3] B 20 [1979]2850/63, 2857).
30.1.2.1 0.8.2.12.6 Faraday Effect

For generat remarks on the effect see "Rare Earth Elements" C 7, 1983, p. 491.
The Faraday rotation E>F is given in angular degrees per cm and the Verdet constant V in
min · oe- 1 · cm- 1 ; E>F = V· L· H, where L = optical pathlength in the sample, H = magnetic
field strength.
The difference nR- nL in the refractive indices for the two directions of circularly polarized
Light was determined on a polished single crystal and is approximately - 0.0007 at room
temperature and about - 0.01 just below T N in a magnetic field of 30 kOe, A. = 632.8 nm. The
Faraday rotationangle E>F at 300 K is proportional to the field strength, giving a Verdet constant
V = - 3.79 ± 0.04, Verreault [1]. A different behavior is observed at Low temperatures,
T < T N; see below.
The Faraday rotation spectra of Eule depend on the magnetic phase (canted or
paramagnetic), Schoenes [2]. The Faraday rotation was determined on slightly textured thin
films on quartz or KBr with the magnetic field parallel to the incident beam. A spectrum is
shown in Fig. 88 for the photon energy range hv = 2 to 6 eV at H = 11.5 kOe and temperatures
above and below T N• Schoenes [3, p. 360].
Similar spectra recorded at slightly different experimental conditions (T = 4.5 and 7 K,
H = 2.2 to 6.7 kOe, hv = 2.2 to 4.3 eV) had previously been published by Busch et al. [4, 5].
Consistent results aside from a maximum at ~ 2.75 eV below TN have also been obtained by
the dynamic method with an alternating magnetic field at 1000Hz and H = 100 to 200 Oe;
Gmelln Handbock
REMamVol C10
Eule 223
.,.. !
I v'K
II l~
i I I
. ,_~9K
I I
I
'
jl
V
~ I I I
I I I
I I I
.~ -1
'"\;"\ ( ,,
I
-2 ~ \I
.,
11
2D 2.5 lO 3.5 4D 4.5 5.0 ss

Photon energy in eV
Fig . 88. Dispersion of the Faraday rotation of Eule at 5, 9, and 15 K in an applied magnetic
field of 11 .5 kOe.
Photon energy in eV
Fig. 89. Faraday rotation of Eule for various temperatures and magnetic fields of 20 and
100 kOe.
see the paper for the spectra for photon energies between ~ 1.8 and 3 eV and temperatures
l = 5, 9.5, and 300 K, Schoenes [3, pp. 356/8]. lhe Faraday rotation spectra of Eule in the
paramagnetic state at 15 K resemble those of EuSe and EuS but show smaller ( ~ 1/6) rotation
angles. The large negative rotation at ~ 3.3 eV (comparable to the positive maxima, not
observed fo r EuS, EuSe) is attributed to a certain overlap of 5p(le2 -) and 4f(Eu 2 + ) initial
states. The maximum in eF in the paramagnetic phase (l = 15 K) is approximately 2 X 105 at
11.5 kOe [3, p. 360] . The value is confirmed by Demokritov et al. [13, 14] . ln strong magnetic
fields , at H = 10 l ~ 100 kOe, e F up to ~ 13 x 105 and 22 x 105 at 33 and 2.6 K, respectively,
are observed, Schoenes, Wachter [2, 6, 7]; seealso below.
ln the spectral range of the firstabsorptionband the Faraday rotation is strongly dependent
on the temperature and the applied magnetic field ; see Flg. 89. Three different components
Gmelin Handbook
RE Mam Vol. C 10
224 Europium lellurides
are recognized at P1 ~ 2.25, P2 ~ 2.5, and P3 ~ 2.8 eV [2]. ln the canted antiferromagnetic
phase eF at P2 remains a maximum as in the paramagnetic phase and a new maximum at P3
evolves, which had been just a shoulder (Fig. 88 on p. 223) [3, p. 360] or a small relative
maximum (see Fig. 89 on p. 223) [2, 6, 7]. lhe same effects had previously been observed by
Busch et al. [4, 5]. Also below lN at l = 5 K the Faraday rotation at 2.45 and 2.7 eV is
proportional to the strength of moderate magnetic fields up to 12 kOe, but with two different
slopes below and above (slightly steeper) about 6 and 5 kOe, respectively. lhis is attributed
to the phase transition at the spin flop field B1 = 0.4 l [3, p. 361].
However, a systematic study of the effect of temperature variation through l Nand of fields
up to 100 kOe showed the Faraday rotation at 2.75 eV (P 3) to be apparently not correlated to
the sample magnetization (see the figures in the paper) in contrast to the behavior of the peak
at 2.45 eV (P2). For B < 8 l, E>F(P3 ) increases with decreasing temperature down to at Least
2.5 K. At B = 8 l the behavior changes and at B = 10 l, E>F(P3 ) displays a maximum at ~ 8 K
[7]. At 2.5 K the sum of Faraday rotation angles at P1, P2, and P3 was shown tobe proportional
to the applied field up to Large field strengths before saturation occurs (see the figure in the
paper) [6]. By this complementary behavior the assumption was confirmed that all three peaks
are due to basically the same transition [6, 7].
Interpretation
lhe main maxima (or groups of extreme values) in eF at ~ 2.5 and ~ 4 eV are generally
attributed to transitions 4f--> 5d(t29 ), Schoenes [2, 3], Schoenes, Wachter [6, 7], Busch et al.
scheme proposed for the Eu monochalcogenides in general: 3.3 to 4 eV =

[4, 5] and 4f--> 5d(e 9 ), respectively. Further assignments are derived from an energy Level
(Eu),
5p(anion)--> 5d(t29 )
are tentative. lhe
(Eu). Beyond 5 eV the assignments, for example 5p(le) --+ 5d(e 9 )
various components in the 4f--> 5d(t29 ) transition are attributed to transitions from the 85 712
ground state to excited multiplet states with J = 5/2, 7/2, and 9/2. ln particular, the shoulder
at ~ 2.8 eV in the dynamic Faraday rotation spectrum at 300 K is assigned to a spin flip
transition to an S = 5/2 final state that arises from an intra-atomic f-d spin-spin interaction
[3, pp. 356/8, 363].
lhe temperature and magnetic field dependence of the Faraday rotation in the range 2 to
3 eV is related to the magnetic phase diagram of Eule. ln a simple band model the decrease
and the increase of eF below l N at ~ 2.45 (P 2) and ~ 2.75 eV (P3) are explained by a splitting
into two nonpolarized subbands of the d-type conduction band due to Brillouin zone folding
in the Larger magnetic unit cell of the type 11-antiferromagnetic state. lhis gives rise to two
discrete transitions. ln high magnetic fields, i.e., i~ the ferromagnetically aligned phase, the
magnetic and the chemical unit cells become identical again. Yet due to the induced spin
order the spin up and spindown wave function are split by the exchange interaction. Neglecting
spin-flip transitions only transitions into the Lower (spin up) subband occur. From the peak
positions in the various magnetic phases the exchange energy of 0.11 eV and the subband
width of 0.2 eV are interred in the antiferromagnetic phase. lhis simple modelalso accounts
for the red shift of the energy gap E9 by 110 meV in magnetic fields for magnetic saturation,
Schoenes [2]. lhe same model in Less detailed form had already been used earlier by
Schoenes, Wachter [6, 7, 8], Schoenes [3], Busch et al. [4, 5].
Faraday Rotation in Doped EuTe
lhe Faraday rotation of iodine-doped Eule single crystals in the range 2.5 to 0.6jlm
(=4000 to 17000 cm -1, 0.50 to 2 eV) consists of three components: the interband FR, the FR
Gmelm Handbock
RE Mam Val. C 10
Eule 225
due to charge carriers, and the wavelength-independent Faraday rotation (in pure samples
only the first has been observed). The Faraday rotation with wavelengths larger than that of
the band gap is largely due to the tail of the dispersion curve resulting from a 4f-> 4f65d
transition anQ,is accurately described by the same law in both pure and doped Eule samples.
The interband Faraday rotation is directly proportional to the sample magnetization as verified
by comparison with magnetic measurements. The Faraday rotation from the charge carriers
is much smaller than that from interband transitions. The wavelength-independent part was
determined with an accuracy of ~ 10% by extrapolation towards zero frequency of the total
Faraday rotation and after allowing for the effects of the charge carriers. A study of the
temperature dependence (increase of E>F on cooling, saturation at about 2TN• further increase
up to 3600 deg/cm below TN) and the field dependence (behavior similar to magnetization but
no direct correspondence) indicated the presence of ferromagnetic spin clusters with an
estimated size (for two doped samples) of 500 or 2000 Eu atoms. The anomalously large
wavelength-independent Faraday rotation is proposed to be due to resonance of the large
ferromagnetic spin clusters in the exchange field of the magnetic sublattice. For further details
and figures see the papers, Vitins, Wachter [9, 10]; seealso [11] and Wachter [12, pp. 527/9].
References:
[1] R. Verreault (Z. Krist. 136 [1972] 350/86, 383/6).

[4] G. Busch, J. Schoenes, P. Wachter (Solid State Commun. 8 [1970]1841/4).
[5] G. Busch, J. Schoenes, P. Wachter (Czech. J. Phys. 21 [1971] 570/3).
[6] J. Schoenes, P. Wachter (Physica B + C 86/88 [1977]125/6).
[8] J. Schoenes, P. Wachter (IEEE Trans. Magn. 12 [1976] 81/5).
[9] J. Vitins, P. Wachter (Phys. Rev. [3] B 12 [1975]3829/39).
pp. 140/5; C.A. 85 [1976] No. 55593).
38/40; JETP Letters 41 [1985]46/9).
312/4; JETP Letters 43 [1986] 403/6).
30.1.2.10.8.2.12.7 Magnetic Circular Dichroism (MCD). Magnetic Linear Dichroism (MLD)
The magnetic circular dichroism is the difference in the optical density (or absorption) for
right (cr+) and left (cr~) circularly polarized light, ~Dc = D.,. - D.,_ (Faraday arrangement:
magnetic field H parallel to light propagation and perpendicular to the film under study).
Absolute values of the effect, D, are derived from Faraday rotation by a Kramers-Kronig
relation. lnflections in the dichroism correspond to extrema in the Faraday rotation and vice
versa. Thus, spectra aretobe interpreted analogously to the Faraday effect; see p. 224.
The magnetic linear dichroism is the difference in the optical density for linearly polarized
light beams paralleland perpendicular to H: ~0 1 = D 11 - D1..
Gmelin Handbock 15
RE Main Val. C10
Spectra between hv = 2 and 4 eV of ~Dc and ~DL of an EuTe film deposited on Vycor for
temperatures above and below T N and magnetic fields of 0.067 T for MCD or 0.62 and 0.85 T
for MLD are shown in a figure in the paper, Ferre [1]. Consistent results have been obtained
from films on (111) faces of CaF 2 crystals in magnetic fields H = 0.01 to 0.50 T, hv = 2 to
4.4 eV, and T = 5.9, 13.4, and 22 K, Ferre et al. [2] (see also Briat et al. [3]), and from Kramers-
Kronig transformation of the Faraday rotation data at H = 1.15 T, hv = 2 to 5.5 eV, and T =
5, 9, and 15 K, Schoenes [4, p. 364], and at H = 2.0 T, T = 3.7 and 27 K, Schoenes [5]. On
cooling below T N the spectrum changes remarkably, resembling the magnetic phase depend-
ent Faraday rotation. A detailed analysis of the MCD spectra (method of moments) allowed
discussion of the spectra in terms of both macroscopic and microscopic properties and a
comparison of various models; for further details see [1]. The assignments given agree with
respect to the transitions from the 4f ground state to 4F5d(t29 and e9 ) excited states at
~ 2 to 3 and above 3.5 eV, respectively [4, pp. 363/4], [1, 2]. The two extreme values at 2.3
and 2.6 eV are interpreted as transitions to the J = 512 and 9/2 states, respectively, of the
4f65d(t29 )( 8 PJ) final state multiplet [1, 2]. The 2.3 eV peak contains also contributions from the
J = 712 final state [1].
Different assignments are proposed for the (spin order dependent) structure araund
~ 2.8 eV, which is attributed to the conduction band splitting due to Brillouin zone folding
in the antiferromagnetic state [5] (see also p. 224) or to a spin-forbidden transition
4f---> 4f6 5d(t29 )( 6P) with spin flip from total spin S = 712 toS = 5/2 [1]. This latter assignment
has also been discussed within a localized model by Schoenes [4, p. 358]. Transitions between
3.5 and 4 eV attributed in the Faraday rotation spectra to 5p(Te)---> 5d(t29 )(Eu) by Schoenes
[4] are assigned to 4f---> 4F5d(e 9 ) by [1].
The spectrum of the magnetic linear dichroism has been explained consistently with the
magnetic circular dichroism spectrum [1].
References:
[1] J. Ferre (J. Phys. [Paris]35 [1974]781/801, 792/801).
[2] J. Ferre, M. Billardon, J. Badoz, R. Suryanarayanan, C. Paparoditis (J. Phys. Colloq.
[Paris] 32 [1971] C1-930/C1-931 ).
[3] B. Briat, M. Billardon, R. Suryanarayanan, C. Paparoditis (Phys. Status Solidi 35 [1969]
983/6).
30.1.2.1 0.8.2.12.8 Luminescence
The Luminescence spectrum of Eu Teexcited by an 15 kV, 5 x 10- 6 A electron beam displays
a strong, broad maximum at 1.48 and 1.44 eV at sample temperatures of 12 and 77 K, respec-
tively. Maxima weaker by one to three orders of magnitude and narrower are found in the
range 1.8 to 2.4 eV at 12 and 77 K and at 3.36 eV at 12 K, Tsu, Esaki [1]. The strong maximum
has been observed independently of the exciting energy at ~ 1.35 and ~ 1.32 eV at 4.3 and
10 K, respectively, by photoluminescence excited by hv = 2 to 2.4 eV from both powders and
single crystals, Busch et al. [2]. Measurements at ~ 1.5 to 4 eV also show a narrow Lu-
minescence maximumatabout 2 eV and a sharp one at about 3.4 eV with excitation in single
crystals at 6 K by an electron beam, a mercury Lamp, or a He-Cd Laser. A figure is given in
Gmelm Handbook
RE Mam Vol. C10
Eule 227
the paper. lhe intensity ratio of the weak Luminescence maxima depends on the excitation
Level, Hulin et al. [3]. lhe relative quantum yield of the photoluminescence has a maximum
at an exciting photon energy hv ::::; 2.14 and 2.12 eV at 4.3 and 10 K, respectively; it drops to
zero for hv < 2 eV or to nearly zero for hv > 2.3 eV. On temperature variation the emission
becomes detectable below 150 K and increases to a constant relative quantum yield between
~60 K and 15 K. Below about 50 K the Luminescence band shifts slightly towards shorter
wavelengths. Cooling below l N further enhances the relative quantum yield by a factor of
~ 1.7 between 10 and 4.3 Kat a simultaneously increased blue shift of the Luminescence. A
magnetic field of 1.1 l quenches the intensity by a factor of ~ 0.9 and produces a slight red
shift both above (10 K) and below (4.3 K) l N• Busch et al. [2, 4], Streit [5].
Interpretation
lhe most intense Luminescence band (below 1.5 eV) has been attributed to an interband
transition 4f6(FJ)5d(t29 )--> 4f( 8S712 ) [1, 2, 4]. lentatively a line at 2.65 eV was ascribed to this
transition, du ring the interpretation of experiments between 1.5 and 4 eV, Hulin et al. [3]. lhe
weak lines between 1.53 and 2.68 eV are attributed to intraband transitions between 4f6
configurations (FJ - 5DJ) and the line at ~ 3.4 eV is related to a 8S712 - 6PJ transition with
J = 3/2 [1], J = 712, 512, 3/2 [3]. lhe kinetics of the Luminescence is discussed in [3].
lhe dependence of the Luminescence properties on magnetic ordering is interpreted in the
Localized magnetic polaron model, Busch et al. [2]; see also [4, 5].
Additional magnetic exchange, introduced by doping of Eule, Leads to mixed ferro- and
antiferromagnetic Luminescence behavior. Luminescence from ferromagnetic clusters (see
p. 197) is quenched below ~ 30 K, whereas below l N the Long-range antiferromagnetic order
outside the clusters gives an increase in the Luminescence. ln a magnetic field of 0.95 l the
Luminescence is enhanced between ~ 70 K and l N· For more heavily doped samples the
Luminescence is heavily quenched, Vitins, Wachter [6].
References:
[1] R. lsu, L. Esaki (Proc. 10th Intern. Conf. Phys. Semicond., Cambridge, Mass., 1970,
pp. 282/5; C.A. 75 [1971] No. 92664).
[2] G. Busch, P. Streit, P. Wachter (Solid State Commun. 8 [1970]1759/63).
[3] D. Hulin, J. Hanus, C. Benoit a La Guillaume, l. B. Reed (Solid State Commun. 8 [1970]
1525/8).
[4] G. Busch, P. Streit, P. Wachter (J. Phys. Colloq. [Paris]32 [1971] C1-926/C1-927).
[5] P. Streit (Physik Kondensierten Materie 15 [1972/73]284/326, 302/324).
[6] J. Vitins, P. Wachter (Phys. Rev. [3] B 12 [1975] 3829/39).
30.1.2.1 0.8.2.13 Photoemission. Electron Energy Loss Spectra

lhe photoelectric threshold energy <I> ( = energy difference between the highest occupied
Level and the vacuum Level) depends on the structural order. ln the antiferromagnetic state
at 4.2 K, <I> = 4.8 ± 0.1 eV for a polycrystalline film obtained by evaporation onto a substrate
held at 400 K and <I> = 4.2 ± 0.1 eV for a disordered metastable film from evaporation onto
a 4.2 K substrate, Campagna, Siegmann [1].
lhe spin polarization P = (Nj - Nl)/(Nj + N!) of the photoelectrons emitted from these
films at 4.2 K increases linearly with increasing applied magnetic field (B .l film surface); see
a figure in the paper for B ~ 4.5 l. For photoelectrons from states near the photothreshold
Gmelm Handbook 15"
RE Mam Vol. C 10
(produced with hv ~ 4.95 eV by a fittered Hg-Xe Lamp), P ~ 22% in the polycrystalline film
at 4.5 T, whereas the slope of the curve for the metastable film is reduced by a factor of 0.35.
This indicates the creation of new, in part unpolarized, states in the forbidden zone upon
disordering. For photoelectrons produced with the unfiltered Hg-Xe Lamp (i.e., including hv ~
5 eV), P ~ 10% at H = 4.5 T in both films. This decrease in P is caused by an increased
emission from the valence band [1); seealso Campagna et al. [2), for the polycrystalline film,
also Busch et al. [3). A maximum polarization Pmax = 0.31 is expected for polycrystalline
EuTe in the ferromagnetically aligned paramagnetic state [3).
Fig. 80, p. 198, shows the energy distribution curve of photoelectrons excited by synchrotron
radiation (UPS) of energies hv = 135 to 139 eV for insulating EuTe in the binding energy range
down to -45 eV, Gudat et al. [4). The curves down to Es = -5.5 eV from UPS studies on a
freshly cleaved single crystal showed only one peak for hv = 7.8 eV and three peaks for hv =
9.7 eV. The broad peak with a maximum at- -2.5 eV, attributed to unresolved 4f plus valence
band states, was independent of exciting photon energy. A shoulder (for hv = 8.4 eV) and
finally a small peak (for hv = 9.2 and 9.7 eV), which developed on the Low energy side of the
broad peak and seemed to shift with increasing hv to Es ~ -3.5 eV, were attributed to valence
band states. The origin of a weak maximum at ~ 5 eV below EF, observed for hv = 9.7 eV,
was not clear, Munz [6). The UPS studies with hv = 40 and 61 eV for vapor-deposited samples
(copper substrate at 200°C) for Es down to -15 eV was similar, showing only one peak at Low
binding energies (at- -1.8 eV) and a broad peak near -5 eV (not assigned). The origins of
an additional broad peak in the range Es = -8 to -11 eV and a peak at - -13 eV for hv =
40 eV were also not clear. The broad one did not appear for hv = 61 eV and the one at
- -13 eV was not studied at this photon energy, Sato et al. [5]. Studies in the range hv = 50
to 150 eV (see a figure in the paper) show that the photo cross section of the Te 4d Levels
decreases monotonically above -75 eV, whereas the 4f photoemission intensity strongly
increases at hv = 137.5 eV. A maximum in the relative intensities of the Eu 4f and the Te 4d
photoemission is reached at hv -141 eV and a further increase occurs at hv > 145 eV. This
behavior is explained as a resonance effect due to transitions hv + 4d 104f --+ 4d 94f8 --+
4d 104f6 + e~~b• where e~~b indicates the electron emitted through the so-called super-Coster-
Kronig recombination mechanism of the excited state 4d 94fB. The Eu 5p emission resonates
paralleltothat of Eu 4f [4].
Electron energy Loss spectra (ELS) of the cleaved (100) surface of a conducting EuTe single
crystal (Q = 5 n · cm) have been obtained with an incident electron energy of 800 eV. They
show weak structures below 7 eV (see a figure in the paper, up to 24 eV), assigned to 4f-to-
conduction band transitions, to 4f ionization Losses, and to interband transitions, and a
relatively strong maximum at 7.8 eV and a strong maximum at 10.6 eV, attributed to the
excitation of the surface plasmon and the bulk plasmon, respectively. A purely ionic model
gives a bulk plasmon energy of 10.8 eV (see p. 221). The so-called giant resonance, cor-
responding to the 4d 104f - 4d 9 4f8 transition, was observed at 143 eV in all the Eu mono-
chalcogenides, shifted by 2.4 eV from the Eu 20 3 value. The giant resonance confirms the
divalent state of Eu also at the surface of the monochalcogenides, Grazhulis et al. [7).
The Auger spectrum for the (100) surface of this crystal, excited by 3 keV electrons, is
shown in the paper up to 990 eV. Shifts of the spectrum up to 20 eV have been observed due
to charging of the sample, Grazhulis et al. [8).
References:
[1) M. Campagna, H. C. Siegmann (Physik Kondensierten Materie 15 [1972/73) 247/83,

271/3).
Gmelm Handbock
RE Mam Vol. C10
EuTex with x > 1 229
[2] M. Campagna, D. T. Pierce, H. C. Siegmann (Amorphous Liq. Semicond. Proc. 5th Intern.
Conf., Garmisch-Partenkirchen, FRG, 1973 [1974], Vol. 2, pp. 1379/84; C.A. 82 [1975] No.
179415).
[3] G. Busch, M. Campagna, H. C. Siegmann (AlP [Am. lnst. Phys.] Conf. Proc. No. 5 [1972]
575/90, 579/82).
[4] W. Gudat, S. F. Alvarado, M. Campagna, Y. Petroff (J. Phys. Colloq. [Paris] 41 [1980]
C5-1/C5-7).
[5] S. Sato, M. Watanabe, T. Sagawa, S. Kono, S. Suzuki, et al. (Vac. Ultravialet Radiat. Phys.
Proc. 4th Intern. Conf., Harnburg 1974, pp. 499/502).
[6] P. Munz (Helv. Phys. Acta 49 [1976] 281/309, 292/8).
[7] V. Grazhulis, A. M. lonov, V. F. Kuleshov, A. V. Pokrovskii (Poverkhnost 1985 No. 11,
pp. 21/5; C.A. 103 [1985] No. 221100).
[8] V. Grazhulis, A. M. lonov, V. F. Kuleshov (Poverkhnost 1985 No. 2, pp. 94/8; C.A. 102 [1985]
No. 120346).
30.1.2.1 0.8.3 Compounds EuTex with x> 1
For the existence and the preparation of cubic solid solutions based on EuTe and of the
compounds Eu 3Te4 , Eu 2Te 3, Eu 4Te 7, EuTe 2 (?), Eu 3Te 7 , and Eu 2Te5 (?), see the Eu-Te system,
p. 158.
Crystallographlc Propertles. Density
The solid solutions based on EuTe have the cubic NaCl structure at high temperatures.
Lattice constants a for phases annealed at 600°C (compositions refer to the initial charge):
at% Te 50 55.6 57.2 60.0

a in A. 6.594(2) 6.603(2) 6.605(1) 6.600(1)
The X-ray powder diagrams of phases annealed at 400 to 450°C display a series of superlattice
lines with respect to the NaCl structure, the number of which increases over the range 50 to
57.2 at% Te and decreases again for specimens with ~59 at% Te. For the NaCl sublattice
a = 6.603 A at 50 to 57.2 at% Te and a = 6.593 A at 59 to 61 at% Te were found. The
superlattice lines for phases with 59 to 61 at% Te could not be assigned to the Sc2S3 struc-
ture (~-M 2Te3 type), Eliseev, Sadovskaya [3]. Previously, the structure of Eu 3Te4 was assumed
to be orthorhombic, Sadovskaya, Yarembash [1], or tetragonal with a = b = 12.8 and
c = 6.40 A. For Eu 2Te3 a = 6.56 A was reported, Sadovskaya et al. [2]. The diffraction patterns
of the polytellurides Eu 4Te 7 , EuTe2 , Eu 3Te7 , and Eu 2Te 5 are unlike those of the other rare earth
polytellurides. Their schematic diagrams tagether with those of Eu 3Te4 and EuTe are shown
in the paper [3]. Measured densities in g/cm 3 : 6.45 for Eu 3Te4 , 6.71 for Eu 4Te 7 , and 6.93 for
Eu 3Te7 [2].
Mössbauer Spectra. X-Ray L111 Absorption Spectra

Results of Mössbauer spectroscopy with a 35.5 keV 125Te03 source at varying temperatures
T of absorber (Ta) and source (T9 ) for the isomer shift ö (relative to Te03) and line width r:
Ta in K T9 in K ö in mm/s r in mm/s effect in%
Eu 3Te4 4.2 4.2 1.3 ± 0.1 13.2 ± 0.1 12.8

80 80 1.03 ± 0.1 12.7 ± 0.1 2.3
300 4.2 1.75 ± 0.3 10.2 ± 0.1 0.53
Gmelm Handbock
RE Main Vol. ClO
Ta in K T5 in K 8 in mm/s r in mm/s effect in%
4.2 4.2 1.3 ± 0.1 12.5 ± 0.1 11.4

80 80 1.6 ± 0.1 16.5 ± 0.1 4.2
300 80 0.7 ±0.3 13.0 ± 0.1 0.5
4.2 4.2 1.4 ± 0.1 13.7±0.1 14.0
80 80 1.55 ± 0.1 14.1 ± 0.1 5.9
The increase of 8 with increasing Te content of the compounds, compared to Eu Te (see p. 168),
may indicate an increase of the covalent component of the chemical bond. A marked change
of 8 in Eu 3Te 4 and Eu 4Te 7 at 78 to 293 K may be due to a polymorphic transition. The magnetic
field at the 125Te nuclei of Eu 3Te 4 , Eu 4Te 7 , and Eu 3Te 7 is estimated tobe 47 to 73 kOe [2]; see
also Yarembash et al. [7]. For Eu 2Te 3 using the 21.7 keV y-transition in 151 Eu the isomer shift
at room temperature was found to be - 0.14 ± 0.08 mm/s relative to Eu 20 3 (for Eu 20 3 , 8 =
+ 0.22 mm/s and for EuF3 , 8 = - 0.59 mm/s), Gerth et al. [4]; in an earlier paper 8 =
+ (1.0 ± 0.5) mm/s relative to EuF3 was reported, Hüfner et al. [5]. These isomer shifts in
Eu 2Te 3 indicate the presence of mainly trivalent europium in this compound [4], whereas the
magnetic moments of Eu 3Te 4 , Eu 2Te 3 , Eu 4Te 7 , and Eu 3Te 7 (see below) and the Large negative
shift of the absorption maximum (of 8 to 9 eV) in the X-ray Eu L 111 absorption spectra of Eu 3Te 4 ,
Eu 4Te 7 , and Eu 3Te 7 with respect to Eu 20 3 (see a figure in [7]) indicate that the europium is
essentially divalent, Yarembash, Eliseev [6].
Measurements of the magnetic susceptibility of Eu 3Te 4 , Eu 4 Te 7 , and Eu 3Te 7 between about

80 and 800 K show the Curie-Weiss Law tobe obeyed. The following table contains values for
the atom susceptibility XA in 10- 2 cm 3/g-atom, the paramagnetic Curie temperature eP in K,
the effective magnetic moment llett in lls· the electrical conductivity Kin Q- 1 · cm- 1 , the width
of the forbidden zone ßE 0 in eV, and the thermoelectric power S in ~-tV/K (with respect to Pt
at 293 K) [2] :
XA ep llett K ßE 0 s
Eu 3Te 4 2.28 - 8 7.10 0.30 1.10 + 240
Eu 2Te 3 2.30 -10 7.25
Eu 4Te 7 2.30 -17 7.30 2 X 10- 4 0.30 + 30
Eu 3Te 7 2.26 -20 7.15 0.18 0.36 + 390
The results of measurements of K and S at diff€rent temperatures indicate the semiconductive
character of the conductivity of Eu tellurides [2]. The same ßE 0 values are reported in the
review of Yarembash, Eliseev [6]. However, the above-mentioned values for K and S in the
case of Eu 3Te 4 refer to 750 K and K = 38 Q- 1 · cm-1, S = + 140 ~-tV/K at 1000 K; activation
energy of the impurity Level ßE 1 = 0.46 eV. With Eu 4Te 7 , the above-mentioned K and S values
refer to 293 K and K = 3 x 10- 3 Q- 1 · cm-1, S = + 5~-tV/K at 625 K; ßE 1 = 0.09 eV. The small
values of S are probably connected with the oxidation of the sample during measurement [6].
Color
According to Sadovskaya et al. [2], Eu 3Te 4 is dark brown, Eu 2Te 3 gray, Eu 4Te 7 dark gray,
and Eu 3Te 7 is black.
Gmelm Handbook
RE Main Vol. C10
The Gd-Te System 231
References:
[1) 0 . A. Sadovskaya, E. I. Yarembash (lzv. Akad . Nauk SSSR Neorgan. Materialy 6 [1970)
[2) 0. A. Sadovskaya, E. P. Stepanov, V. V. Khrapov, E. I. Yarembash (lzv. Akad. Nauk SSSR
Neorgan. Materialy 8 [1972) 815/20; lnorg. Materials [USSR)8 [1972) 708/12).
1394/8; lnorg. Materials [USSR)13 [1977]1127/30).
[4] G. Gerth, P. Kienle, K. Luchner (Phys. Letters A 27 [1968) 557/8).
[5) S. Hüfner, P. Kienle, D. Quitmann, P. Brix (Z. Physik 187 [1965]67/84, 71).
Moscow 1975, pp. 1/260, 208/15).
[7] E. I. Yarembash, 0. A. Sadovskaya, E. G. Tyurin, A. Karabekov (Khim. Svyaz Poluprovodn.
PolurnetaL 1972 263/8; C.A. 79 [1973) No. 36889) .
30.1.2.1 0.9 Gadolinium Tellurides

Additional data for GdTe, Gd3Te4 , Gd 2Te 3 , Gd 4Te7 , GdTe 2 _ x, Gd 2Te5 , and GdTe3 are found
in Sections 30.1.2.1, 30.1.2.2, 30.1.2.3, 30.1.2.4, 30.1.2.5, 30.1.2.6, and 30.1 .2.8, on pp. 6, 21 , 31 ,
43, 47, 53, and 57, respectively.
30.1.2.10.9.1 The Gd-Te System

Phase Diagram
Fig. 90 shows the phasediagram derived from the results of DTA, X-ray diffraction, micro-
structure studies, and chemical analysis by Zargaryan, Abrikosov [1) . From the seven
wt•f. Te
10 30 50 70
u
0
.~
0 20 40 60 80 100
Gd at•f. Te Te
Fig. 90. The Gd-Te phase diagram.
Gmelin Handbook
RE Main Vol. C 10
232 Gadolinium Tellurides
compounds obtained only the blue GdTe melts congruently, at 1825 ± 15°C. Melting point in
oc of the other incongruently melting compounds [1]:
GdTe 2 GdTe 3
1000 835
The homogeneity range of GdTe 2 is said to extend from GdTe 1 _77 to GdTe 2 . 10 according to X-ray
studies of Niihara et al. [2] (but the conclusions drawn by [2] do not correspond to their
experimental curves, see Fig. 97, p. 241). Gd 3Te 4 and Gd 2Te 3 form solid solutions. The eutectic
between Gd and GdTe at ~3 at% Te melts at 1290°C; the degenerate eutectic between GdTe 3
and Te melts at 450°C [1]. Melting points of ~ 1410°C for Gd 3Te 4 (incongruent) and 1505°C for
Gd 2Te 3 were reported by Miller et al. [3], who also reported the existence of a compound with
the composition GdTe 4 ; seealso Miller et al. [4]. A schematic phasediagram of [4, 7] shows
the existence of at Least four phases: GdTe (melting congruently at 1870°C), Gd 3Te 4-Gd 2Te 3
solid solutions, GdTe 2 , and GdTe 4 .
General Preparation Methods and Properlies
The preparation of the samples from the elements is the same as described for the Nd-Te
system (see p. 116 [3]) [1]; seealso p. 31. Gd 2Te 3 was prepared from the elements in evacu-
ated double-compartment rotated quartz ampules without direct contact of the starting
components. The temperature at the Gd side was 100 to 150°C Lower than that of the Te side
[2]. Vapor-solid reactions were usually used by [4] as weiL as crystallization from melts or
directional crystallization in tantalum tubes (for experimental details, see the paper). Gd 2Te 3
single crystals were obtained by Agaev, Sharifov [5] by a chemical transport reaction with
iodine as carrier gas (see p. 31). The crystals so-obtained decompose when kept in air for
Ionger than 24 h. The disintegration of GdTe single crystals in air within a few days was
observed by Hulliger, Siegrist [6].
Sampies with Lower concentrations of tellurium reveal n-type conductivity and with higher
Te content p-type; the boundary between n- and p-type is assumed to be around the Gd 2Te 3
composition (Gd 2Te 3 could be obtained in both types) [4]. The temperature dependence of the
electrical conductivity and the thermoelectric power measured by [1] between 300 and 1300 K
shows that the electrical properties of the tellurides with increasing Te content change from
those of pure metals to those for semiconductors. The following colors were reported by [1]:
GdTe Gd 2Te 3 Gd 4Te 7 GdTe 2 Gd 2Te 5 GdTe3

blue Lightgray Lightgray gray Lightgold golden
GdTe 2 is a dark violet powder according to Niihara et al. [2].
References:
Gmelm Handbook
RE Main Val. C 10
GdTe 233
[2] K. Niihara, T. Shishido, S. Yajima (Bult. Chem. Soc. Japan 45 [1972]1239/40).

[3] J. F. Miller, F. J. Reid, L. K. Matson, et al. (AD-607082 [1964]1/79, 16; C.A. 62 [1965]15562).
[4] J. F. Miller, L. K. Matson, J. S. McNulty, R. C. Hirnes (AD-262215 [1960/61]1/49, 3/5, 7/10;
N.S.A. 16 [1962] No. 15260).
[5] A. B. Agaev, K. A. Sharifov (Dokl. Akad. Nauk Azerb. SSR 26 [1970] 8/11; C.A. 75 [1971]
No. 11308).
[6] F. Hulliger, T. Siegrist (Z. Physik B 35 [1979] 81/90).
[7] J. F. Miller, L. K. Matson, R. C. Hirnes (Proc. 2nd Rare Earth Res. Conf., Glenwood Springs,
Colo., 1961 [1962] pp. 233/48; N.S.A. 16 [1962] No. 32068).
30.1.2.1 0.9.2 GdTe
GdTe is a congruently melting phase in the Gd-Te phase diagram, see p. 231.
Blue single crystals of GdTe (containing about 5% of a second phase) are grown by high
temperature vapor growth (see p. 7) with a temperature gradient 1943 to 1890°C and an
average linear growth rate of 2.1 x 10- 6 cm/s, Beckenbaugh et al. [1]. For the preparation,
see also pp. 6 and 232.
GdTe has the cubic NaCL structure with Lattice constants between 6.139 and 6.1238 A (see
p. 9). The lattice constants of the nonstoichiometric samples Gd 0.97Te, Gd 0_99Te, and GdTe0.98
at 22°C are 6.1587(5), 6.1651(6), and 6.1556(6) A, respectively; their colors are dark blue,
violet-btue (containing oxygen), and blue. GdTe shows structural distortions below the Neel
temperature TN• where type II antiferromagnetic ordering occurs. The structural distortions
were studied by low temperature X-ray diffraction and measurement of the magnetic
susceptibility on nonstoichiometric GdTe samples. At least two antiferromagnetic phases with
different spin orientations and structures are observed existing below TN and T1, respectively
(for TN and T1 see the table on p. 234). The phase existing between TN and T1 has a
rhombohedrally distorted NaCL structure with ß = 90° - .1ß and with the magnetic moments
parallel to the wave vector k with k = [ 1/ 2 , 1/ 2 , 1/ 2]. The phase existing below T1 is monoclinic
with a ~ b ~ c, ß = 90° + .1ß, and a spin orientation along [110], Hulliger, Siegrist [2]. The
structure distortions arealso discussed by Hulliger, Stucki [3].
The microhardness of the fused polycrystalline sample is 290 kg/mm ( ~ 2.84 GPa). The
total thermal conductivity at room temperature (in 10- 3 cal· cm- 1 • s- 1 • K- 1) is A. = 12.4
with the electronic (A.81 ) and lattice (A.~a1) contributions 11.2 and 1.2, respectively, Zargaryan,
Abrikosov [4]. The thermodynamic data of formation were derived from emf measurements
at 320 to 460 K as well as 650 to 720 K and are as follows: .1G~98 = -72.6 ± 1.0, .1H~8 =
-76.2±3.6kcaUmol, .1S~98 = -8.5±1.2cal·mol- 1 ·K- 1. The absolute entropy is S~8 =
19.1 ± 1.2 cal· mol- 1 · K-1, Guseinov et al. [5]. The values .1H = -300.2 and -251.0 kJ/mol
(71.8 and 60.0 kcaUmol) for the formation from the elements in the solid and liquid state,
respectively, were estimated from melting point data by Sheinfel'd [11].
Gmelm Handbook
RE Main Vol. C10
234 Gadolinium Tellu rides
Data regarding the etfective magnetic moments lleff in lls and the paramagnetic Curie
temperature 8P, the magnetic ordering temperatures TN• T 1 (see p. 233), and the exchange
parameters J 1 and J2 (next and next-nearest neighbors), all in K, for the nonstoichiometric
samples according to (2]:
lleff -ep TN T1 J1 J2
Gd 097Te . 8.15 89 68.5 56.5 -0.16 - 1.06

Gd 099Te *l 7.94 42 82 43.5 + 0.32 - 1.31
GdTe0 98 . (7.54) 13 86 (66?) + 0.64 - 1.51
•l Oxygen-containing phase.
8P = - 90 K for Gd Te is reported by Holtzberg et al. [6] .
GdTe showsmetallic conductivity ; see p. 19. The electrical conductivity K = 6450 n - 1· cm - 1

and the thermoelectric power S = - 2.0 j.!V/K for a fused polycrystalline sam ple are reported
by Zargaryan, Abrikosov [4] . The values K = 1639Q- 1 ·cm - 1 at 111 K and 1429Q- 1 ·cm - 1
at 300 K, S = -2j.!V/K at 327 K were determined on a cast ingot ; foranother sample K =
4348 Q - 1 · cm- 1 is reported, Miller et al. (7]. Below room temperature thetemperature function
of the electrical resistivity Q exhibits a peak at T Nfor stoichiometric GdTe. The temperatu re
dependence of Q for anion- and cation-deficient GdTe single crystals, shown in Fig. 91 , is
similar to the better investigated GdSe, Hauger et al. [8] . Above room temperature the
resistivity of a fused polycrystalline sample increases from Q ~ 150 llQ · cm at 300 K
to ~ 300 jill · cm at 1300 K and the th ermoelectric power from S ~ - 3 toS ~ - 22 j.!V/ K (all
read from a figure in the paper) [1].
90
80 / V
k-:::
~ GdT•1- x
70
/
E
~
/
<5. 60
.5
Q.
--
50
~;:::·
40
50 100 150 200

T4mlperoture in K
Fig. 91 . Electrical resistivity Q of GdTe1 _ x and Gd 1 _yTe vs. temperature.

Gmelin Handbook
RE Main Vol. C 10
GdTe 235
By X-ray photoemission spectroscopy (XPS) and measurement of the electron energy Loss
spectrum (ELS) on vacuum-cleaved single crystal surfaces, the 4f electron Coulomb repulsion
energy U in GdTe (and GdSb or EuO) was measured. The derived value of Uc = 11.6 eV is a
Lower Limit of U, Dietz, Campagna [9]. For a comparison of the Pauling values for the single
band electronegativity differences with values obtained from mass spectrometry with a spark
ion source, see Muheim [10].
Optical and Dielectrical Properlies
The reflection spectrum measured from 0.03 to 12 eV at 300 K with perpendicular Light
incident on monocrystalline GdTe shows high reflectivity of R ~ 100% at very Low photon
energies (---+ 0 eV). There are minima of Rat 2.0 and 8 eV and maxima at 2.9 and around 10 eV.
Optical constants were calculated using the Kramers-Kronig relationship. The maximum of the
imaginary part of the dielectric constant &" is located at 2.9 eV and &00 = 3.9 eV. The energy
Loss function r."/[(&') 2 + (&") 2] for photon energies between 1 and 12 eV is shown in a figure in
the paper. Collective electron Vibrations (plasmons) are coupled with interband transitions. The
coupled and unperturbed plasmon frequencies were found to be 1.25 and 3.1 eV, respectively.
The interband transition goes from the anion p-valence into a 5d-conduction band. The number
of the free carriers and their effective mass m*/m 0 were determined from the optical spectra
to be 1.74 x 1022 cm- 3 and 2.5, respectively [1].
For the Raman spectrum, see p. 71.
References:
[1] W. Beckenbaugh, J. Evers, G. Güntherodt, E. Kaldis, P. Wachter (J. Phys. Chem. Solids 36
[1975] 239/48).
[2] F. Hulliger, T. Siegrist (Z. Physik B 35 [1979] 81/90).
[3] F. Hulliger, F. Stucki (Conf. Ser. lnst. Phys. [London] No. 37 [1978] 92/5; C.A. 89 [1978]
No. 83213).
[5] A. G. Guseinov, A. S. Abbasov, A. A. Kuliev, T. Kh. Azizov (Dokl. Akad. Nauk Azerb. SSR
40 No. 5 [1984]31/3; C.A. 102 [1985] No. 12991).
[6] F. Holtzberg, T. R. McGuire, S. Methfessel (J. Appl. Phys. 37 [1966]976/8).
[7] J. F. Miller, L. K. Matson, J. S. McNulty, R. C. Hirnes (AD-262215 [1961]1/49, A-3; N.S.A. 16
[1962] No. 15260).
[8] R. Hauger, E. Kaldis, G. von Schulthess, P. Wachter, C. Zürcher (J. Magn. Magn. Mater. 3
[1976]103/8).
[9] R. E. Dietz, M. Campagna (Rare Earths Mod. Sei. Technol. 1 [1977/78]475/80; C.A. 91 [1979]
No. 217169).
[10] J. T. Muheim (Proc. 10th Rare Earth Res. Conf., Carefree, Ariz., 1973, Vol. 1, pp. 208/17;
C.A. 85 [1976] No. 55409).
[11] V. L. Sheinfel'd (lzv. Akad. Nauk SSSR Neorgan. Materialy 18 [1982] 2059/60; lnorg.
Materials [USSR]18 [1982]1785/7).
Gmelin Handbook
RE Mam Vol. C10
30.1.2.10.9.3 The GdTe-EuTe System
GdTe (with Gd3+) and EuTe (with Eu 2 + ) form a continuous series of solid solutions with
the NaCl structure. While both antiferromagnetic compounds have negative paramagnetic
Curie temperatures with E>P = -90 K for GdTe and -10 K for EuTe the solid solutions
GdxEu1_xTe exhibit a maximum of E>P = + 28 K at x = 0.2; see Fig. 92. The variation of E>P
with x is analogous to the GdSe-EuSe and GdS-EuS systems and is attributed to the Ruderman-
Kittel-Yosida type interaction via the conduction electron donated by Gd3 +. The magnetic
moments at 4.2 K as a function of magnetic field strength H are given in Fig. 93. The magneti-
zation at x = 0 and x = 0.05 increases linearly with H, a characteristic of antiferromagnetic
order. For x = 0.20 magnetic saturation is found only in fields above 45 kOe, which may be
due to either spin canting or a more complex magnetic structure involving ferromagnetic
clusters. ln contrast to the sulfide and selenide systems, no true ferromagnetic order occurs
in GdxEu 1 _ xTe at 4.2 K for any composition. From the temperature dependence of the low-
field moments Curie temperatures Tc are estimated as shown in Fig . 92, Holtzberg et al. [1) .
The effect of inter-valley transitions on the indirect exchange interaction in the magnetic
semiconductor GdxEu 1 _ Je is discussed by Cullen et al. [2].
theory
40
6p
.......
20 "..
0
-f Tc
""\
\
0
~ 801---+-r-~~+-
~
.!; -20 1\
\
~
c
Q.
·;_ 60 1---htl'---+---v-~-1---t----l
<D -40
-60 1\
-80 \ \
0 Q2 Q4 0.6 Q8 1.0 20 30 40 50 60
EuTe GdTe
x in GdxEu1. xTe H in kOe
Fig. 92. Paramagnetic (8p) and estimated Fig. 93. Field dependence of magnetic
ferromagnetic Curie temperatures (Tc) moments at 4.2 K for GdxEu 1 _ xTe
for GdxEu 1 _ Je in dependence of x. with various values of x
(numbers at the curves).
Rectifying p-n junctions are obtained by diffusing Pb or Sn in ferromagnetic semiconductors

and also in Gd 0 _15 Eu0 _85Te using GdTe as an ohrnie contact, Holtzberg, von Molnar [3), Holtzberg
[4).
Relerences:
[1) F. Holtzberg, T. R. McGuire, S. Methfessel (J. Appl. Phys. 37 [1966) 976/8).

[2) J. R. Cullen , E. Gallen, A . H. Luther (J. Appl. Phys. 39 [1968]1105/6).
Gmelm Handbook
RE Mam Vol. C 10
237
[3] F. Holtzberg, S. von Molnar, Intern. Business Mach. Corp. (Ger. Offen. 1963707 [1969/70];
U.S. 3544865 [1968/70]; C.A. 75 [1971] No. 12351,74 [1971] No. 36232).
[4] F. Holtzberg, Intern. Business Mach. Corp. (U.S. 3574675 [1968/71]; C.A. 74 [1971]
No. 148175).
30.1.2.10.9.4 Solid Solutions Gd3Te 4-Gd 2Te3 and Terminal Compounds
For the preparation see pp. 31 and 232, respectively.

Gd 2Te 3 has the orthorhombic structure of the Tt-M 2Te 3 type (see p. 34) with a = 11.98,
b = 11.75, and c = 4.29 A, Agaev, Sharifov [1]. The lattice constants a = 12.01, b = 11.83,
and c = 4.28 A (a and c interchanged in the original paper) for the whole Gd 3Te 4-Gd 2Te3
solid solution region are reported by Miller et al. [2].
The following thermodynamic data of formation and the absolute entropy were derived from
emf measurements at 320 to 460 K as well as 650 to 720 K for Gd 3Te4 by Guseinov et al. [3] and
from measurements at 320 to 430 K for Gd 2Te 3 by Azizov et al. [4]:
-dG~ 98 -dH~ -dS~ 98 s~

in kcaVmol in cal· mol- 1 • K- 1
231.0 ± 3.3 242.2 ± 11.2 34.2 ± 2.6 60.4± 2.6

156.8 ± 2.3 164.6 ± 7.4 23.6 ± 1.4 43.5 ± 1.4
An earlier calorimetric determination gave dH~98 = -221.4 ± 5.3 kcaVmol for Gd 2Te3 , Agaev,
Sharifov [5]; seealso [6]. S~8 = 60.7 cal· mol- 1 · K- 1 and CP = 31.8 cal· mol- 1 • K- 1 is re-
ported by [6].
The magnetic susceptibility of Gd 3Te4 and Gd 2Te3 between 77 and 600 K obeys the Curie-
Weiss law; the paramagnetic Curie temperatures eP are -12 and -14 K and the effective
magnetic moments llefl = 7.86 and 7.90 11 8 , respectively. For 1/x vs. T curves, see the paper,
Pechennikov et al. [7]. eP = -15 K for Gd 2Te 3 was reported by Busch et al. [8].
The following physical properties at 300 K for fused polycrystalline samples in the
solid Solution region are tabulated below: the microhardness H is in kg/mm 2 , the total ther-
mal conductivity /.. with the electronic (/..9 L) and the lattice contribution (/..~a1 ) in
10- 3 cal· cm- 1 · s- 1 • K-t, the electrical conductivity Kin n- 1 • cm-t, the width of the forbidden
zone dE in eV, the absolute thermoelectric power S in JlV/K, the carrier concentration n in
cm- 3 , and mobility 11 in cm 2 ·V- 1 ·s- 1 [11]:
K s 'A "-el Atat dE 11 n H
Gd 3Te4 . 1180 20.0 9.88 2.21 7.67 7.1 1.04 X 1021 330
Gd 2_96Te 4 635 29.0
Gd 2_9Te 4 530 37.0 8 0.93 7.07 6.72 ~5 X 1020 320
Gd 2.84Te 4 350 55.0
Gd2.78Te4 95 -120 6.3 0.15 6.15
Gd2.7Te4 37.2 +125 0.74
Gd 2_69Te4 30.2 +140 3.2 0.03 3.17 0.74 6 ~3 X 1019
Gd 2_68Te4 25.1 +155 0.74
Gd 2Te3 . 3.55 +350 2.7 2.7 0.74 6.05 3.54 X 1018 260
Gmelin Handbock
RE Main Val. C10
b)
-200
-160
o-
V
..."._
::0:: ~43 _
> -120 /
:..0.,
~ ~ ~~
:L
.E ./
~ ob
~ - 80
"'
-40 ~~
d"
Oix; 400 600 800 1000 1200 1400

Tempereture in K Tempereture in K
Fig. 94. Temperature dependence of the electrical conductivity K (a) and the thermoelectric
power S (b) for 1) Gd 2 96Te4 , 2) Gd 2 _90Te4 , 3) Gd 2 _84Te4 , and 4) Gd 278 Te4 .
According to figures in the paper the electrical resistivity of Gd3Te4 increases smoothly from
Q ~ 100 llQ · cm at 300 K to ~ 350 flil· cm at 1 350 K and the thermoelectric power from S ~ -20
to ~ - 80 f.!V/K. The conductivity versus temperature plot for Gd 2Te 3 is typical fo r impurity
semiconductors ; Q decreases smoothly up to ~ 400 K and remains nearly constant up to ~ 800 K
(weak increase) . Above ~ 800 K the resistivity drops sharply (the slope yields the width of the
forbidden zone of 0.74 eV). The data agree quite well w ith the results of Miller [9, 10] for p-type
Gd 2Te3 . The thermoelectric power decreases from S = 350 f.!V/ K at room temperature to
~250 f.!V/ K at 800 K and decreases quickly to -50 f.!V/ K at ~ 1000 K, changing sign at 880 K.
Fig. 94 a) and b) shows the electrical conductivity K and S for Gd 2 _96Te4 , Gd 2 _90Te4 , Gd 2 _84Te4 , and
Gd 278Te4 . The figures in the paper for the solid solutions Gd2.7Te4 , Gd 2 _69Te4 , and Gd 268Te4 show
pronounced maxima for Q and S araund 800 K, Zargaryan , Abrikosov [11]. The Hall coefficient
RH of p-type Gd 2Te3 ( ~ 4 cm3/C at room temperature) decreases with increasing temperature
but does not change sign up to 1223 K; figures in the paper show Q versus 1/T plots for p- and
n-type Gd 2Te3 and R H versu s 1/T for p-type Gd 2Te3 [9] . For Q and S between 100 and 800°C fo r
a sample GdTe 1 39 , which consists of two or three phases, see figures in Muir [12]. For the
temperature dependence of Q and S measured on various samples of the Gd 3Te4-Gd 2Te 3
system, seealso [2, 10].
Relerences :
[1] A. 8. Agaev, K. A. Sharifov (Dokl. Akad . Nauk Azerb. SSR 26 [1970] 8/ 11 ; C.A. 75 [1971]
No. 11308).
[2] J. F. Miller, F. J. Reid, L. K. Matson, et al. (AD-607082 [1964] 1/79, 35/43 ; C.A. 62 [1965]
No. 15562).
[3] A. G. Guseinov, A .S. Abbasov, A. A . Kuliev, T. Kh. Azizov (Dokl. Akad. Nauk Azerb. SSR
40 (1984]31/3 ; C.A. 102 [1985] No. 12991).
[4] T. Kh. Azizov, A . 8 . Agaev, A. S. Abbasov, A. G.Guseinov (Dokl. Akad. Nauk Azerb. SSR
36 [1980]37/9 ; C.A. 93 [1980] No. 226628).
[5] A . 8 . Agaev, K. A. Sharifov (Uch. Zap. Azerb. Gos. Univ. Ser. Khim . Nauk 1972 No. 3,
pp. 72/4 ; C.A. 79 [1973] No. 97662) .
Gmelm Handbook
RE Mam Vol. C10
The Gd-Nd-Te System 239
[6] A. 8. Agaev, K. A. Sharifov (Uch. Zap. Azerb. Gos. Univ. Ser. Khim. Nauk 1973 No. 4,
pp. 47/50; C.A. 83 [1975) No. 33710).
SSSR Neorgan. Materialy 4 [1968]771/2; lnorg. Materials [USSR) 4 [1968]674/5).
[8] G. Busch, P. Junod, M. Risi , 0. Vogt (Proc. Intern. Conf. Phys. Semicond., Exeter, Engl.,
1962, pp. 727/31).
[9] J. F. Miller, F. J. Reid, R. C. Hirnes (J. Electrochem. Soc. 106 [1959]1043/6).
[1962] No. 15260).
[12] H. M. Muir (AD-277043 [1961]1/47, 24, 40; N.S.A. 17 [1963] No. 11292).
30.1.2.10.9.5 Gd2Te3 -Nd2Te3 and Gd 2Te3-Nd3Te 4 Systems

The cross sections Gd 2Te3-Nd 2Te3 and Gd 2Te3-Nd 3Te4 in the Gd-Nd-Te system have been
studied regarding formation of solid solutions and physical properties of the alloys. The alloys
were prepared from shavings of the rare earth metals and Te in evacuated double wall quartz
ampules with Ti as getter between their walls. The alloys were melted in closed Ta crucibles.
Fig. 95. Fig. 96.
200
3
80
-40
2 1020
'e -160
b:
~
...
.!: 1019 'g
~ .f
"
~
c
"
0
-1
1.2 .,:E
0.8 ~
.!:
-< 0
!:--'----7:::----L~'=-...:::10.4 -< ~-'----:4'!-=o----1.----=8~0__,
o
~Te4 mo1 "I.G~Te3
Change of thermoelectric power S, electrical conductivity K, charge carrier concentration n,
total (A.), and lattice thermal conductivity (A.181) with the composition of alloys in the systems
Nd 2Te3-Gd 2Te3 (Fig. 95) and Nd3Te4-Gd 2Te3 (Fig. 96).
Gmetin Handbook
RE Main Vot. C 10
The isothermal cross section at 1 000°C is shown in the paper. Between Nd2Te 3 and Gd 2Te 3
there exist Te-deficient solid solutions based on Nd 2Te 3 with the cubic Th 3 P4 structure in the
range 0 to 55 mol% Gd 2Te 3 and solid solutions based on Gd 2Te 3 (orthorhombic T]-M 2Te 3 , see
p. 34) between 88 and 100 mol% Gd 2Te3 . Between Nd3Te 4 and Gd 2Te 3 the solid solutions
based on cubic Nd 3Te4 extend to ~63 mol% Gd 2Te 3 and those based on Gd 2Te 3 extend from
~80 to 100 mol% Gd 2Te3 . The microhardness of the cubic solid solutions based on Nd 2Te 3
increases with rising Gd 2Te 3 content while the microhardness of the Nd 3Te4 -based cubic solid
solutions decreases with rising Gd 2Te3 content (see figurein the paper). Fig. 95 and 96, p. 239,
show the change of the thermal (A.) and electrical (K) conductivity, the thermoelectric power
S, and the charge carrier concentration n with the composition of the alloys at room tempera-
ture. Alloys in the Nd2Te 3-Gd 2Te 3 system are semiconductors of either n-type for Nd 2Te 3-based
cubic solid solutions or p-type for Gd 2Te 3-based solid solutions. The broad maxima in the
isotherms of A., K, and n (see Fig. 95) for the cubic solid solutions indicate maxima in the
deviations from stoichiometry. For the alloys in the Nd 3Te4-Gd 2Te 3 system (see Fig. 96), n, K,
and A. decrease sharply with increasing Gd 2Te 3 content of the cubic solid solutions based on
n-type Nd 3Te4 , L. V. Poretskaya, N. Kh. Abrikosov (lzv. Akad. Nauk SSSR Neorgan. Materialy
13 [1977]1215/20; lnorg. Materials [USSR]13 [1977] 984/8).
30.1.2.1 0.9.6 Gadolinium Polytellurides
The Gd-Te phase diagram shows the existence of the polytellurides Gd 4Te 7 , GdTe 2 _x,
Gd 2Te 5 , and GdTe3 ; see p. 231. For their preparation, see p. 232.
The compound GdTe4 is said tobe obtained by dissolving 10 wt% Gd in tellurium at 800°C,
then cooling the melt slowly. The ductile Leaflets were mechanically separated from the Te
matrix, Miller et al. [1, p. 7]. The compound is rhombohedral with a = 13.0 A, cx = 25.5°, Miller
et al. [2, p. 16]. However, the existence is not mentioned by other authors.
From emf measurements between 320 and 430 K the thermodynamic quantities of formation
as well as the absolute entropy have been calculated for some gadolinium tellurides:
- ~G~8 - ~H~ 98 -~S~ 98 S~ 98

in kcallmol in cal· mol- 1 · K- 1
Gd 4Te 7 . 313.6 ±4.8 328.1 ± 14.0 48.5 ±2 97.6 ± 2.0

GdTe 2 . 77.0 ± 2.1 80.8 ± 3.8 12.8 ± 0.7 26.7 ± 0.7
Gd 2Te 5 . 157.9 ± 2.1 165.1 ± 7.6 23.9 ± 1.8 66.9 ± 1.8
GdTe3 . 79.5 ± 1 83.0 ± 4.1 11.6±0.7 39.8 ± 0.7
Azizov et al. [3]. GTe 2 is tetragonal; the Lattice constants for the stoichiometric composition
are a = 4.317, c = 8.951 A. From the change of the Lattice constants as a function of the Te: Gd
ratio in the samples (see Fig. 97) a homogeneity range from GdTe 1 _77 to GdTe 2 .10 is derived.
(But the Te: M ratio in all other studied ditellurides always is ~ 2; see p. 47.) The densities for
GdTe 1.77 , GdTe2 .0 , and "GdTe2 .1 " are Dexp = 7.2, 8.1, and 7.8 g/cm 3 , respectively (read from a
figure in the paper), Niihara et al. [4]. The value Dexp = 6.8 g/cm 3 for GdTe2 reported by
[1, p. 5] is evidently too Low compared with values for the other rare earth ditellurides.
The magnetic susceptibility of GdTe 2 between 77 and 600 K follows the Curie-Weiss Law with
E>P = -10 K; the effective magnetic moment is lleff = 7.04118 , Pechennikov et al. [5]. The follow-
ing physical properties at 300 K for fused polycrystalline samples are tabulated below:
microhardness H is in kg/mm 2 , the total thermal conductivity A. with the electronic (A.etl
Gmelon Handbock
RE Maon Vol. C10
Gadolinium Polytellurides 241
o<(
o<(
4.310f-=F=\::---t--l--f--P='--H 8.955 -~
-~
a u
4.300
1.7 1.9 2.1 2.3
Te :Gdratio
Fig. 97. Lattice constants of phases around the Gdle2 composition.
and the Lattice contribution (Atatl in 10- 3 cal · cm- 1 · s- 1 · K-1, electrical conductivity K in
Q - 1 · cm - 1, width of the forbidden zone ilE in eV, absolute thermoelectric power S in J.lV/K,
carrier concentration n in cm- 3 , and the carrier mobility 11 in cm 2 · v- 1 · s- 1 .
K s I. Ael Atat ilE ll n H
Gd 4Te7 . 44.7 + 140 3.1 3.1 0.5 ~5 ~5.6 · 1019 190

Gdle2 5.3 + 45 4.2 4.2 0.4 165
Gd 2Te5 . 195 + 8.5 4.4 0.2 4.2 155
Gdle3 430 + 11.4 4.7 0.75 3.95 130
The log K versus 1/T curves in the paper show for Gd4Te7 a smooth decrease from Log K
(Kin Q - 1 -cm - 1) ~ 1.6 at room temperature to 1.1 around 850 K and then a Linear increase to
1.6 at ~ 1300 K (the slope yields the width of the forbidden zone ilE). For Gdle2 Log K increases
from ~ 0.7 at room temperature to ~1 . 0 around 850 K and then with a steeper slope to ~ 1 . 5
at ~ 1000 K. The thermoelectric power of Gd 4Te7 reaches a maximum of S ~ 200 11V/K around
700 K and then drops rapidly to ~ - 25 J.lV/K at 1000 K changing sign at ~ 900 K. The
thermoelectric power of Gdle2 decreases from 45J.lV/K at room temperature to ~ 20 J.lV/K at
1000 K, Zargaryan, Abrikosov [6] .
References:
[1] J. F. Miller, L. K. Matson, J. S. McNulty, R. C. Hirnes (AD-262215 [1961]1/49; N.S.A. 16 [1962]

No. 15260).
[2] J . F.Miller, F.J. Reid, L. K. Matson, et al. (AD-607082 [1964]1/79; C.A. 62 [1965] No. 15562).
[3] T. Kh. Azizov, A. 8. Agaev, A. S. Abbasov, A. G. Guseinov (Dokl. Akad. Nauk Azerb. SSSR
36 [1980]37/9 ; C.A. 93 [1980] No. 226628).
[4] K. Niihara, T. Shishido, S. Yajima (Bull. Chem. Soc. Japan 45 (1972]1239/40).
[5] A. V.Pechennikov, V.I. Chechernikov, M.E. Barykin, E. I. Yarembash (lzv. Akad. Nauk SSSR
Neorgan. Materialy 4 [1968] 771/2 ; lnorg. Materials [USSR]4 [1968]674/5).
769/76 ; lnorg. Materials [USSR] 3 [1967] 687/94) .
Gmelin Handbook 16
RE Main Vol. C 10
242 Terbium Tellurides
30.1.2.10.10 Terbium Tellurides
Additional data for Tb Te are found in Section 30.1.2.1 on p. 6.
Data forTb 2Te 3 , TbTe2 _x, Tb2Te5 , and TbTe 3 arefound in Sections 30.1.2.3, 30.1.2.5, 30.1.2.6,
and 30.1.2.8, on pp. 31, 47, 53, and 57, respectively.
Tb Te
For the preparation of the cubic TbTe with NaCl structure see p. 6; for the lattice constants
see p. 9.
The appearance is described as deep purple metallic by Sucher et al. [1] and graymetallic
by Olcese [2]. Tb Te films obtained by simultaneously evaporating Tb and Te at a pressure of
- 10- 6 Torr on NaCl Substrates kept at 100°C have a primitive cubic cell with a = 3.1465(5) A
(powder diffraction), Chander et al. [3]. The lattice constant of the fcc cell is a = 6.102 A
[1, 2], a = 6.1150(6) A, Hulliger, Stucki [4], a = 6.137(4) A for TbTe 1 _019 prepared by the
chemical transport reaction with iodine as carrier gas, Khan, Garcia [5]. From the lattice
constants above 70 K the thermal expansion coefficient r:1. = 10 x 10- 6 K- 1 is obtained [4].
TbTe is paramagneUe (see p. 16) and shows fcc type II antiferromagnetic order below the
Neel temperature T N• Fischer et al. [6]. Selow T N (51 K) the lattice is trigonally distorted with
a = 6.1004(6) A, ß = 89.807(11) 0 at 6.2 K from X-ray studies on powdered single crystals. A
figurein the paper shows a smooth increase of ßto 90°C at T N [4]. From neutron diffraction of
polycrystalline nonstoichiometric cation-deficient Tb Te samples at 4 K the magnetic moment
orientation with respect to the [111] axis varies for different samples [6]. The phase transition
at T N for Tb Te as well as for TbSe, TbS, and TbSi appears to be of second order [4].
References:
[1] E. Sucher, K. Andres, F. J. di Salvo, et al. (Phys. Rev. [3] S 11 [1975] 500/13).
[2] G. L. Olcese (Atti Accad. Nazl. Lincei Rend. Classe Sei. Fis. Mat. Nat. [8] 30 [1961]
195/200).
[3] R. Chander, R. Kumar, S. S. Sharma (Phys. StatusSolidiA 17 [1973] K157/K160).
[4] F. Hulliger, F. Stucki (Z. Physik S 31 [1978] 391/3).
[5] A. Khan, C. Garcia (Proc. 12th Rare Earth Res. Conf., Vail, Colo. 1976, Vol. 2, pp. 953/60;
C.A. 85 [1976] No. 134614).
[6] P. Fischer, P. Schobinger-Papamantellos, E. Kaldis, A. Ernst (J. Phys. C 10 [1977]
3601/11).
30.1.2.10.11 Dysprosium Tellurides
Additional data for DyTe, Dy3Te 4 , Dy 2Te 3 , and Dy4Te 7 are found in Sections 30.1.2.1, 30.1.2.2,
30.1.2.3, and 30.1.2.4 on pp. 6, 21, 31, and 43, respectively.
Data for DyTe 2 _x, Dy2Te 5 , and DyTe 3 are found in Sections 30.1.2.5, 30.1.2.6, and 30.1.2.8
on pp. 47, 53. and 57, respectively. The compounds Dy2Te 5 and DyTe3 are regarded as Dy4Te 9
and Dy4Te 11 , respectively, in the Dy-Te system, see p. 243.
Gmelin Handbock
RE Maon Vol. C10
The Dy-Te System 243
at•f. Te
Fig. 98. The Dy-Te phase diagram.
Phase Diagram of the Dy-Te System
From the results of thermal, microstructural, X-ray, and chemical analyses the Dy-Te phase
diagram, Fig. 98, was constructed . The observed compounds with their melting points in oc
(* incongruent) are:
DyTe
1850
The eutectic between Dy and DyTe melts at 1385°C, that between DyTe and Dy3Te4 at
1540°C, and the degenerate eutectic between Dy4Te 11 and Te melts at 455°C. Dy3Te 4 and
Dy2Te 3 form a continuous series of solid solutions, Abrikosov et al. [1], Abrikosov, Zinchenko
[2]. The Te-rich phase has the NdTe3 structure (see p. 58) but its composition lies between the
Iimits 73.0 and 73.7 at% Te (Dy4Te 11 has 73.33 at% Te), Slovyanskikh et al. [3].
Compounds of the Dy-Te System

To prepare dysprosium tellurides the finely crushed mixtures of Te and Dy were heated
in evacuated quartz ampules at 100 to 150 K/h to 800 to 1100°C,depending on the composition,
and kept at this temperature for 20 to 25 h. The pressed reaction products were then annealed
for 200 hat the synthesis temperatures. They were melted by induction heating in Ta crucibles
and equilibria were reached by annealing 30 to 40°C below the melting points [1, 2],
Pechennikov et al. [4]. To prepare homogeneous samples in the concentration range 0 to
50 at% Te, the element mixture was heated inductively in a vitreous carbon crucible, 60 mm
in height, 10 mm in diameter; the Lower zone with the initial mixturewas kept at 360 to 400°C
and the upper zonewas 500 to 550°C. After heating for 30 min both temperatures were raised
until the sample fused , but the temperature gradient between the zones was retained at 100
Gmelin Handbock 16'
RE Main Vol. C 10
244 Dysprosium Tellurides
to 150°C. The total synthesis time was 1 h [1]. Single crystals of Dy3Te 4, DyTeu Dy 4Te 9 , and
Dy 4Te 11 were obtained by chemical transport reactions with iodine as the carrier gas and
Dy 2Te 3 as the starting material; the temperature zone varied in the range 900 to 700°C, Eliseev
et al. [5] (photomicrographs of the single crystals are shown in the paper). The preparation
of cation-deficient DyTe crystals by the gas transport reaction is reported by Khan, Manzi [6];
see p. 7. For the preparation of dysprosium tellurides a mixture of the elements (Te: Dy ratio
> 3) was heated at 1300 K for 5 h in an evacuated quartz ampule. The reaction product was
then heated at fixed temperatures and part of the Te sublimed into the cold part of the ampule
( ~ 300 K). Depending upon the fixed sublimation temperature the following tellurides were
obtained in the residues: DyTe 28 at 680 K (25 h); Dy 2Te 5 at 770 K (10 h); DyTe 17 at 830 K (7 h);
Dy 2Te 3 at 940 to 1180 K (5 to 3 h), Slovyanskikh et al. [3].
Cryslallographic Properlies
The solid solutions between Dy3Te 4 and Dy 2Te 3 have the orthorhombic Sc 2 S3 structure (see
t;-M 2Te 3, p. 34) with the lattice constants a = 12.32(3), b = 8.57(1), c = 26.17(5) A for Dy3Te 4
and a = 12.20(3), b = 8.645, and c = 25.85(5) A for Dy 2Te 3. The phase Dy4Te 9 was indexed
on the basis of the orthorhombic M2Te 5 structure (see p. 53) with a = b = 4.301(1), c =
43.2(1) A. The phase Dy 4Te 11 was indexed on the basis of the orthorhombic MTe 3 structure
(see p. 58) with a = b = 4.298(3), c = 25.42(1) A [1, 2]. Very similar or identical lattice
constants for the phases Dy 2Te 3, Dy 2Te 5 (Dy4Te 9), and DyTe 2.8 (Dy4Te 11 ) are reported by
Slovyanskikh et al. [3].
For the structure of the tetragonal Dy4Te 7 ( ~ DyTe 2 _x) see p. 49, of the cubic DyTe p. 6.
The lattice constant of the metallic gray DyTe is reported as a = 6.079 A by Olcese [7], and
of dark green DyTe 1.031 as 6.105 A by [6].
Values for the calculated and measured density D in g/cm 3 from [1, 2] and for the thermal
conductivity A, in 10- 3 cal · cm- 1· s- 1 · K- 1 from [2]:
DyTe Dy3Te 4 Dy 2Te 3 Dy4Te 7 Dy4Te 9 Dy4Te11
Deale 7.33 6.84 7.78 8.04 7.76

Dexp 7.93 7.28 6.80 7.71 7.95 7.61
A. 17 4.5 2.5 2.75 3.15 3.35
The standard enthalpy of formation for solid Dy 2Te 3 was calorimetrically determined to be
11H398 = - 195.7 ± 7.2 kcal/mol. The Gibbs free energy and the entropy of formation were
calculated as 11G398 = - 192.2 kcal/mol and 11S398 = - 9.3 cal · mol - 1· K - 1. The
corresponding thermodynamic data of atomization at 298 K are 11H~1 = 477.1 kcal/mol,
11G~ 1 = 407.6 kcal/mol, and 11S~ 1 = 233.8 cal · mol - 1 · K - 1. The absolute entropy value
S3 98 = 62 cal · mol - 1 · K- \ reported by Mills (see p. 37), was used for the calculations, Azizov
et al. [8].
Magnetic and Eleclrical Properlies
The magnetic susceptibility of dysprosium tellurides measured between 80 and 900 K in

a magnetic field of ~ 10 kOe obeys the Curie-Weiss law; for a 1/x versus T plot see the paper.
The paramagnetic Curietemperatureis 0 K for DyTe, Dy3Te4 , and Dy 2Te 3, - 10 K for Dy 4Te 7 ,
Gmelm Handbook
RE Mam Vol. C10
Magnetic and Electrical Properlies 245
- 15 K for Dy 4Te 9, and - 25 K for Dy4Te 11 . For all the compounds Jleff is between 10.3 and
10.7 Jls, i.e., close tothat of the Dy3+ ion in the ground state (10.65 Jlsl [4].
Electrical conductivity K, thermoelectric power S, the width of the forbidden zone ~E. the
carrier concentration n, and the mobility Jl for pressed polycrystalline dysprosium telluride
phases at room temperature [2]:
Kin Q - 1· cm- 1 S in J.!VIK ~Ein eV n in cm - 3 Jl in cm 2 · v- 1 · K- 1
DyTe 7440 3
Dy3Te 4 965 8
DyTe1 .36 776 12
DyTe 1.40 18.4 + 73 0.6
DyTe 1.45 5.7 + 140 0.6 4.8 X 1019 2.4
Dy 2Te 3 2.46 +260 0.69 5.7 X 1018 4.2
Dy 4Te 7 34.5 + 120 0.35 5.5 X 10 19 4.6
Dy 4Te 9 235 + 16.7
Dy 4Te 11 530 + 9.3
The temperature dependence of K and S was measured on the samples mentioned above
between 300 and 1300 K ; for figures see the paper. They show for DyTe a linear change of K
to ~ 4 700 Q- 1· cm - 1 and of S to ~ - 12 J.!VIK at 1300 K. ln the Dy3Te 4-Dy 2Te 3 solid solution
region DyTe 1_33 and DyTe 1_36 show a nonlinear but smooth decrease of K and increase of ISI
(above ~ 1000 K the conductivity of DyTe 136 is nearly constant). The log K versus 1/T curves
show a weak decrease of K up to ~ 1 000 K for DyTe 1_40 and a weak increase for DyTe 1.4s·
Above ~ 1 000 K a steep linear increase with the same slope for both samples is observed.
(From the slope ~E is derived.) The curvature for DyTe 1_5 is similar to that of DyTe 1.45 (with
lower values of K) as well as for Dy 4Te 7 (but with higher K values). The thermoelectric power
of DyTe 1.40 , DyTe 1.45 , and DyTe 1_5 does not change substantially up to about 910 to 940 K, where
Schanges sign to negative values. A weak decrease of ISI is shown for Dy4Te 7 up to ~ 870 K
and a change of sign at this temperature. The data indicate metallic conductivity for the Te-
poorer tellurides up to the solid solution DyTe 1_36 and semiconducting properties for the Te-
richer samples DyTe 1_40 to Dy4Te 7 , with positive charge carriers at lower temperatures and
intrinsic conductivity at higher temperatures [2]. The electrical conductivity of a cast Dy 2Te 3
6.132
/
-r: t==f2
< T
........ I
.S ..... "
! ....
/I
0 6.116 ......
......
f-""
6.100
0 20 40 60 80 100
mot"lo Tb Te
Fig. 99. Lattice constant a in dependence of compos ition in the DyTe-TbTe system.
Gmelon Handbook
RE Main Vol. C 10
246 Dysprosium Tellurides. Holmium Tellurides
sample is 33 n- 1 • cm- 1 at 100°C and does not change up to 800°C. The thermoelectric power
is + 44, + 33, + 3, -1, and - 5J.LV/K at 100, 200, 400, 600, and 800°C, respectively (data for
phases in the Dy2Te 3- Dy2Se3 system see p. 352), Muir et al. [9].
The DyTe-TbTe System
To prepare samples in the DyTe-TbTe system the chemical transport reaction with iodine
as the carrier gas was used: iodine concentration 7.0 mg/cm 3 , temperature gradient 940 -->
880°C (see p. 7). There is only a limited solid solubility between DyTe and TbTe according to
the lattice constants; see Fig. 99, p. 245. Crystals of DyxTb 1 _xTe are grayish green, unstable
in air, and decompose to give a strongly toxic product, Khan, Garcia [10].
References:
[1) N. Kh. Abrikosov, K. A. Zinchenko, A. A. Eliseev (lzv. Akad. Nauk SSSR Neorgan.
Materialy 6 [1970] 720/5; lnorg. Materials [USSR]6 [1970]634/8).
[2) N. Kh. Abrikosov, K. A. Zinchenko (Redkozem. Metally lkh. Soedin. Mater. Vses. Simp.,
Kiev 1968 [1970), pp. 173/80; C.A. 76 [1972) No. 7748).
2926/30; Russ. J. lnorg. Chem. 30 [1985]1666/9).
[4) A. V. Pechennikov, 8. A. Kupriyanov, V. I. Chechernikov, N. Kh. Abrikosov, K. A. Zinchenko
(lzv. Akad. Nauk SSSR Neorgan. Materialy 6 [1970] 1528/9; lnorg. Materials [USSR] 6
[1970]1346/7).
[5] A. A. Eliseev, K. A. Zinchenko, N. Kh. Abrikosov (Zh. Neorgan. Khim. 22 [1977) 238/40;
Russ. J. lnorg. Chem. 22 [1977]131/2).
[6] A. Khan, L. Manzi (Proc. 5th Conf. Chem. Vap. Deposition Intern. Conf., Slough, Engl.,
1975, pp. 317/30).
[7) G. L. Olcese (Atti Accad. Nazl. Lincei Rend. Classe Sei. Fis. Mat. Nat. [8) 31 [1961)
256/9).
[8) T. Kh. Azizov, A. S. Abbasov, F. M. Mustafaev, I. Ya. Aliev (7th Vses. Konf. Kalorim.
Rasshir. Tezisy Dokl., Moscow, 1977, Vol. 1, pp. 30/2; C.A. 91 [1979] No. 217832).
[9] H. M. Muir (AD-277043 [1961)1/47, 26/8; N.S.A.17 [1963) No. 11292).
[10) A. Khan, C. Garcia (Proc. 12th Rare Earth Res. Conf., Vail, Colo., [1976), Vol. 2,
pp. 953/60).
30.1.2.1 0.12 Holmium TeLLurides
Additional data for HoTe, Ho2Te5 , and HoTe3 are found in Sections 30.1.2.1, 30.1.2.6, and
30.1.2.8, on pp. 6, 53, and 57, respectively. Data for Ho2Te 3 are found in Section 30.1.2.3, on
p. 31.
From the results of DTA, X-ray diffraction, and microstructural studies the Ho-Te phase
diagram, shown in Fig. 100, was constructed. The three compounds HoTe, Ho2Te 5 , and HoTe 3
were observed (the existence of Ho2Te3 is not mentioned). HoTe melts congruently at
1370 ± 25°C; its homogeneity range extends from 50 to 55± 1 at% Te. The dark brown Ho2Te 5
forms peritectically at 800°C and the golden colored HoTe3 forms peritectically at 780°C. HoTe 3
may be better formulated as HoTe3 _x· The eutectic between Ho and HoTe at ~ 23 at% Te
melts at 1110°C, the degenerate eutectic between HoTe3 and Te at 455°C. The alloys were
Gmelm Handbook
RE Mam Vol. C10
Holmium TeUurides. The Er-Te System 247
1400 \ 1370°C
'' \
\
\ /
1200 \ /
V
___ .1.i'o-5'.!1!P~C- 0
0
0
.!:
~ 1000
'\\
..
:::J
2
Q. \
-~
.....~ · 800 780"C ;
\
I
600
400o~~~~2o~~~~~~~_u~s~o--~~~o
·
Ho at"lo Te
Fig . 100. The Ho-Te phase diagram.
prepared as usual, from the elements in evacuated quartz ampules. The samples were fused
in Ta crucibles, Yarembash et al. [1].
ln the range 50 to 55 at% Te the lattice constant of cubic HoTe changes from a = 6.090 to
6.085 A, the electricalconductivitytrom 8388to 2220 n- 1 · cm- 1 , and the thermoelectric power
from - 5.2 to - 52 ~V/K [1]. Neutron scattering studies in the antiferromagnetic range (see
p. 16) at 4 K gave an ordered magnetic moment of 7.6 ~ 6 for HoTe, much lower than the free
ion value, Fischer et al. [2].
References:
Materialy 10 [1974]1409/13 ; lnorg. Materials [USSR]10 [1974]1212/5).
[2] P. Fischer, P. Schobinger-Papamantellos, E. Kaldis, A. Ernst (J . Phys . C 10 [1977]
3601/11, 3610) .
30.1.2.10.13 Erbium TeLLurides

Additional data for ErTe, Er 2Te 3 , ErTe 2 _ ., and ErTe3 , are found in Sections 30 .1.2.1, 30.1 .2.3,
30.1 .2.5, and 30.1.2.8 on pp. 6, 31 , 47, and 57, respectively.
Phase Diagram of the Er-Te System

From the results of thermal, X-ray, microstructural, and chemical analyses the phase
diagram, Fig. 101, p. 248, was constructed . Three compounds have been observed : the con-
gruently melting ErTe ( ~ 1490°C}, the congruently melting Er 2Te 3 ( ~ 1190°C}, and the incon-
Gmelm Handbook
RE Mam Vol. C 10
248 Erbium TeUurides
~1490°C
I
l;'
.s
~ 1000
~
~
8.
~ 500
~~--~2~0--~40~~~6~0~~8~0---1~00
at •1. Te
Fig. 101. The Er-Te phase diagram.
gruently melting ErTe 2 (at 680°C). The eutectic between Er and ErTe melts at 1270 °C, that
between ErTe and Er2Te3 at 1090°C, and that near the Te side at 445 °C, Abrikosov et al. [1] .
Similar phasediagram studies by Haase et al. [2], Haase [3] showdifferent results; between
ErTe and Er2Te 3 solid solutions were observed whose melting points continuously change
from 1525°C (ErTe) to 1460°C (Er2Te3) and whose colors change from metallic black (ErTe) to
slightly blue (at ~ 57.2 at% Te) to slightly greenish (at 60 at % Te). The third compound is the
golden colared ErTe 3 , incongruently melting at 575 °C. The eutectic between Er and ErTe at
13 at% Te melts at 1270°C [2, 3]. Similar results but small deviations in the measured melting
points were reported earlier, Haase et al. [4], Steinfink, Weiss [5]. Studies of the Er-Te system
in the range 60 to 100 at % Te by emf and X-ray diffraction measurements show the existence
of the two compounds Er2Te3 and ErTe3 _ x with x = 0.15, Vasil'ev et al. [6].
Compounds of the Er-Te System
Preparation
The samples were prepared in evacuated quartz ampules in the presence of a Ta wire as
a getter. They were melted in inductively heated Ta crucibles in a vacuum and homogenized
by annealing at 600 or 1 000 °C, depending on the composition [1] . Si milar preparation by [2] .
The samples were prepared in two steps by [6]. Er chips and Te powder were slowly heated
to about 430°C while shaking the ampule. The reaction products were pressed to tablets and
annealed for 2 to 4 weeks at 450 or 550 °C [6] . Light gray ErTe1.034 was obtained by Khan ,
Manzi [7] by gas transport reaction with iodine as the Iransport agent, see p. 7. Films of Er2Te 3
were prepared by thermally evaporating powders of stoichiometric composition in a vacuum .
and depositing them on a degassed mica substrate at ~ 100°C, Vasil'kovskii et al. [8] .
ErTe has the cubic NaCl structure (see p. 8) with the lattice constant a = 6.02 A and Er2Te 3
has the orthorhombic Sc2S3 structure (see p. 34) with a cubic subcell of a = 6.05 A [1];
Gmelm Handbock
RE M am Vol. C10
Physical Properties 249
a = 6.065(5) A for ErTe 1034 is given by [7]. The orthorhombic lattice constants for Er2Te 3 are
a = 12.13, b = 8.58, and c = 25.70 A [6]. Lattice constants in A and measured densities Dexp
in g/cm 3 for the solid solutions Er Tex with x = 1 to 1.50, reported by [2, 3]:
ErTe ErTe 1_08 ErTe 1_17 ErTe1.222 ErTe1.326 ErTe 1_50
a. 12.020 11.996 11.972 12.048 12.124 12.096

b. 8.499 8.482 8.465 8.519 8.573 8.553
c. 25.497 25.446 25.395 25.557 25.719 25.659
Dexp 8.6 8.1 7.7 7.6 7.3 7.1
Between the orthorhombic lattice constants and a0 of the cubic subcell exist the relationships
a = 2 a0, b = a0 y2,
and c = a0 ·3y2. Between 50 and 54 at% Te a0 decreases linearly;
there is a jump to higher values around 55 at% Te and a decrease between about 56 and
60 at% Te [2, 3]. For the structure of the orthorhombic ErTe3, see p. 58 and for a high-
pressure phase ErTe 2_x, see p. 49.
Thermodynamic Data
From emf measurements of the Er-Te system in the range 60 to 100 at% Te with a liquid
electrolyte of alkali chlorides and ErCL3 the following thermodynamic data of formation were
obtained for Er 2Te 3 and ErTe 2_85 (g-atom is related to Er xTe 1_x) [6]:
-L1G!in kcal/g-atom -L1H!in kcal/g-atom -L1S!in cal· g-atom- 1· K- 1
36.71 ± 0.05 (650 K) 39.3 ± 0.8 (590 to 710 K) 4.0 ± 1.3 (590 to 710 K)
24.42 ± 0.03 (650 K) 24.3 ± 0.3 (580 to 720 K) 0.2 ± 0.8 (580 to 720 K)
Similar values were reported by Goryacheva et al. [9]. For estimated values of L1H! at
298 K for Er 2Te 3, see p. 37.
x
Measurements of the magnetic susceptibility between 1.7 K and room temperature for
erbium telluride phases show the Curie-Weiss law tobe obeyed. Values for x9 in 10- 6 cm 3/g
at 24°C, for the paramagnetic Curie temperature eP in K, and the effective magnetic moment
lleff in lls:
Er Te ErTeus ErTe 1_20 ErTe1.30 ErTe 1_33 ErTe 1_5 ErTe3
Xg . 120.85 116.48 118.39 106.06 102.84 103.73 66.02

ep -9 -6 -8 -2 0 -3 -3
lleff 9.35 9.39 9.45 9.24 9.18 9.50 9.35
Hoggins, Steinfink [10]. Magnetic susceptibility measurements on Er 2Te 3 between 1.3 and
300 K show the Curie-Weiss law tobe obeyed above 50 K with a paramagnetic Curie tempera-
ture eP = -13 K. The effective magnetic moment lleff = 9.5Jls is close to the free Er3+ ion
value of 9.58 lls· The extrapolated value for the low temperature range gives eP = -1 K. No
magnetic transition was observed over the entire temperature range. The results are in-
terpreted in terms of crystal field splitting and exchange interactions, Pokrzywnicki [11].
Gmelm Handbook
RE Mam Vol. C10
250 Erbium Tellurides
c;
.!:
Q.
1011---J..- + - - - + - - - l
6.1·10 21 excess Er
Erle
1000/T in K-1
Fig. 102. Electrical resistivity for three compositions of the suggested ErTe-Er 2Te 3 solid
solutions (see text).
The electrical resistivity of the suggested solid solutions ErTex with x = 1 to 1.5 between
170 and 850 K is shown in Fig. 102. The slope for the intrinsic region is 0.45 eV. Measurements
of the thermoelectric power S between room temperature and about 600 K show Er 2Te 3 to be
a p-type semiconductor with S changing from ~ 90 to 70 11V/K with increasing temperature.
ErTe 1_33 and ErTe exhibit n-type conductivity. S changes for ErTe 1 _33 from ~ -15 to -27 11V/K
with increasing temperature while S is nearly unchanged ~ - 1 11V/K for ErTe. (For ErTe 3
S ::::; + 5!1V/K in this temperature range.) ln the intrinsic region the concentration of Er atoms
in the solid solution series is directly related to the number of carriers present. ln the extrinsic
region the Er atoms act as impurity donors as their concentration increases going from the
p-type ErTe 1 _5 to the n-type Er Te; for carrier concentration versus 1/T plots see the paper,
Haase, Steinfink [12], see also [3]. Studies of the electrical conductivity K, S, the carrier
concentration n, and mobility 11 of Er 2Te 3 films show the films to be p-type conductors in a
nearly degenerate state. The measured values are: K = 0.5 to 35 n - 1 · cm - 1, n = (0.8 to
26) x 10 18 cm- 3 , 11 = 5 to 72 cm 2 · V - 1 · s - 1 . The values change very little after an neali ng the
films [8]. ErTex, with x smaller than but very close to 1.5 (prepared from the elements in carbon
crucibles in a C0 2 atmosphere) is suitable as an n-type thermoelectric Leg in thermoelectric
generators with , for example, Q ::::; 1.1 mn · cm, S = - 119 11V/K at 200°C and S = - 200 11V/K at
700°C, Hampl [13] .
ErTe-TbTe and ErTe-DyTe Systems

ErTe forms a continuous series of cubic solid solutions with TbTe and DyTe . The
mixed crystals were prepared in the same manner as the components (see p. 6) by the
Gmelm Handbook
RE Mam Vol. C10
The Tm-Te System 251
gas transport reaction with iodine as the carrier gas; the temperature gradients are
930-+890°C and 960-+930°C, the iodine concentration 9.3 and 8.0 mg/mL, respectively. The
lattice constants show positive deviations from Vegard's law. Crystals of (Er, Tb)Te are dark
green and (Er, Dy)Te grayish green. The crystals have an octahedral habit, are unstable in
air, and decompose to products which are strongly toxic, Khan, Garcia [14].
References:
[1] N. Kh. Abrikosov, L V. Poretskaya, E. V. Skudnova (Redkozem. MetaL Splavy Soedin.
Mater. 7th Soveshch., Moscow 1972 [1973], pp. 174/5; CA 81 [1974] No. 17380).
[3] D. J. Haase (Diss. Univ. Texas 1965, pp. 1/112, 13/9, 41/62).
1964 [1965], pp. 535/44; CA 65 [1966] No. 14821).
[5] H. Steinfink, E. J. Weiss (ANL-6856 [1964]19/22; N.S.A. 18 [1964] No. 37115).
Ser. II Khim. 21 [1980]339/44; Moscow Univ. Chem. Bult. 35 No. 4 [1980] 36/41).
[7] A. Khan, L Manzi (Proc. Conf. Chem. Vapor Deposition 5th Intern. Conf., Slough, EngL,
1975, pp. 317/30; CA 84 [1976] No. 52193).
[8] A. A. Vasil'kovskii, E. T. Sharnopol'skaya, N. Yu. Shitsevalova, S. V. Shchegol'kov
(lzv. Akad. Nauk SSSR Neorgan. Materialy 13 [1977] 730/1; lnorg. Materials [USSR]13
[1977] 595/6).
[9] V. I. Goryacheva, V. P. Vasilev, Ya. I. Gerasimov (Tezisy DokL 2nd Vses. Konf. Fiz. Khim.
Redkozem. Poluprovodn., Leningrad 1979, pp. 96/7; CA 93 [1980] No. 121255).
[10] J. Hoggins, H. Steinfink (lnorg. Chem. 7 [1968] 826/8).
[11] S. Pokrzywnicki (Phys. StatusSolidiA 55 [1979] K39/K43).
[12] D. J. Haase, H. Steinfink (J. AppL Phys. 37 [1966] 2246/8).
[13] E. F. Hampl, Minnesota Mining Manuf. Co. (U.S. 4061505 [1973/77]; CA 88 [1978]
No. 201961).
[14] A. Khan, C. Garcia (Proc. 12th Rare Earth Res. Conf., Vail, Colo., 1976, VoL 2,
PP- 953/60).
30.1.2.10.14 Thulium Tellurides

Additional data for Tm Te, Tm 2Te3 , and TmTe 3 are found in Sections 30.1.2.1, 30.1.2.3, and
30.1.2.8, on pp. 6, 31, and 57, respectively.
Data for the high-pressure phase TmTe 2 _x are found in Section 30.1.2.5 on p. 49.
30.1.2.10.14.1 Studies ln the Tm-Te System

The Tm-Te phasediagram is not known. X-ray diffraction studies of phases in the Tm-Te
system have been reported by Eliseev et aL [1], landelli, Palenzona [2], and Katdis et aL [3],
but the results are not in accord with each other. From studies in the concentration range 50
to 75 at% Te the existence of cubic Tm Te (NaCL structure, a = 6.361 A), of possibly a
continuous series of solid solutions between cubic Tm Te and Tm 2Te 3 (having an orthorhombic
Sc2S3 structure, see p. 34), and of Tm 2Te5 (orthorhombic with a = b = 4.44, c = 44.97 A, see
p. 54) was reported by [1]. For the proposed solid solutions TmTex 1 < x~ 1.5 (not stated by
Gmelon Handbook
RE Main Vol. C10
252 Thulium Tellurides
[2, 3]) with the orthorhombic superstructure (the cubic subcell of the ordered defect NaCl
structure has a :::::: 6.06 A for x = 1.33 to 1.5 from a figure) the lattice constants are a = 12.730
(this tabulated value probably is a misprint; from the figure in the paper a = 12.130 is
obtained), b = 8.561, c = 25.770 A for x = 1.33 and a = 12.050, b = 8.537, c = 25.640 A for
x = 1.5. The studied samples were prepared from the elements as usual (prereaction at low
temperatures with subsequent melting; see, e.g., the Dy-Te system, p. 243) or by reaction of
the components in sealed quartz ampules at 500 to 550°C and homogenization annealing at
600 to 650°C for 120 h [1]. The compound Tm 2Te 5 was not obtained by [3], but the copper-
colored polytelluride TmTe 3 (incongruently melting at 553°C, see p. 59) is present (besides
the green-blue phase Tm Te~ 1 _d in cooled samples, prepared at 800°C from a Tm-Te mixture
with atomic ratio 1:3. The orthorhombic TmTe 3 (a = 4.267(3), b = 4.270(6), c = 25.32(2) A)
was formed when a Tm-Te mixture with atomic ratio 1:10 was melted in a vertical silica
ampule equipped with a thin capillary for seed selection and cooled slowly at ~ 3 K/h in a
temperature gradient of ~ 70°C. The best results were achieved with T:::::: 550°C [3].
The existence of a continuous series of solid solutions between TmTe and Tm 2Te 3 (pro-
posed by [1]) was not observed by [2] and [3]. According to [2]. who studied compositions
around TmTe, the reaction between fine Tm turnings and Te to form TmTe is incomplete
between 500 and 1 000°C. So the samples were also annealed for 2 to 4 h at 1400°C after
prereaction at low temperatures. By heating Tm-Te mixtures with Tm/Te = 0.9, 1.0, and 1.1
for 15 or 30 hat 520°C at first a cubic phase with a = 6.044 Aand high magnetic susceptibility
(showing a high content of Tm3+) was formed. in the mixtures with Tm/Te = 0.9 and 1.0 a
second phase with a :::::: 6.365 Awas obtained after 120 h heating at 520°C. The phase with the
high lattice constant and low magnetic susceptibility (showing a high content of Tm 2 +) re-
placed the other cubic phase after heating for 24 h at 1 000°C (initial Tm/Te = 0.9). Samples
prepared at 1400°C show the existence of three phases: a cubic phase in Tm-rich samples
with a = 6.364 at TmTe096 (sample with lowest susceptibility attributed to Tm 11 Te and probably
free Tm), a rhombohedral phase at TmTe 1. 11 to TmTeu 5 • and a cubic phase with a = 6.044 A
at TmTe1.25 (attributed to a Tm-deficient lattice with predominantly Tm3+. but see below [3]).
The structure of the rhombohedral phase (a = 6.145 A, a = 89.1 °) results from a small
contraction of the diagonal of the Na Cl cell. From the magnetic susceptibility it was concluded
that Tm has a mixed valency in the rhombohedral phase [2]. Furthermore in Tm-deficient
phases TmTe, with 1 < x < 1.1 cubic solid solutions containing Tm 2 + and Tm3+ (with a =
6.338 A at x = 1.01 and a = 6.294 A at x = 1.04) were assumed by [2]. for Tm 0 _94Te
( = TmTe 1.064 ) with a = 6.308 A by Ott, Hulliger [4]. and for Tm 0 _92Te ( = TmTe 1_087 ) with
a = 6.33 Aby Kaindl et al. [5]. They derived the existence of Tm3+ in the phases from magnetic
[2, 4] and X-ray absorption measurements [5].
According to [3] single phase stoichiometric cubic Tm 11 Te (accuracy of the chemical

analysis 0.25 wt%). which has a lattice constant of a = 6.36 A, cannot be prepared from an
equiatomic element mixture at 500 to 800°C. lt forms as Single crystals from a slowly cooled
melt (1925 °C) with the stoichiometric composition (and also from melts with excess Tm); but
in quenched samples. prepared at 600 or 800°C, only the strongly Tm-deficient orthorhombic
phase TmTe., 1_47 with the Sc 2S3 superstructure of the NaCl lattice (cubic subcell a ::::::6.039 A)
was obtained. The results suggest that a monotelluride with Tm3+ and a low cubic lattice
constant (a :::::: 6.04 A) does not exist (as opposed to earlier suggestion by landelli [7]). The
phase TmTe"01 _47 (or Tm 068 Te, respectively) with Tm3+ can be obtained as single crystals by
slowly cooling a melt with the composition Tm 2Te 3 at ~ 2000°C. The phases Tm 11 Te and
TmTe 1.47 do not show appreciable solid solubility ranges and probably have integral valences.
Extended cubic Tm~1 Tmj 1~xTe solid solutions, which would allow an intermediate valence
state, do not exist. The transition from Tm 11 Te to Tm 111 Te 1.47 takes place via a miscibility
Gmelm Handbock
RE Main Vol. C 10
Tm Te 253
gap and a phase with a slightly rhombohedrally deformed NaCL structure, observed in the
composition range between TmTe 1_09 and TmTe1.2 5 besides the NaCL-type TmTe (which is
present as a single phase only at TmTex with x < 1.09). The pure rhombohedral phasewas
present only at a Tm: Te atomic ratio of 1 : 1.25. Single crystals of this phase, with a =
8.620(1) Aand c = 10.812(2) Afor the hexagonal cell and a = 6.147 Aand a: = 89.055° for the
rhombohedral cell, can be grown from the melt at T ~ 1920°C [3].
Tm Te is very sensitive to 0 2 . On the preparation in evacuated containers sometimes traces

of Tm 20 2Te were formed (see p. 288) [3]. The formation of a Tm 20 2Te surface layer after
exposure to 0.5 x 10- 6 Torr· s 0 2 of a freshly cleaved Tm Te (100) face is assumed by Kaindl
et al. [8]. According to Sucher et al. [6] the light green semiconducting Tm 2Te 3 and the golden
red TmTe 3 are very unstable in air.
References:
[1] A. A. Eliseev, K. A. Zinchenko, V. M. Zemlyanukhina, Nguyen'Chin'Tam (Zh. Neorgan.

[2] A. landelli, A. Palenzona (Colt. Intern. Centre Natl. Rech. Sei. [Paris] No. 157 [1967]
397/405; C.A. 68 [1968] No. 63803).
[4] H. R. Ott, F. Huttiger (Z. Physik B 49 [1983]323/30).
[5] G. Kaindl, W. 0. Brewer, G. Kalkowski, F. Holtzberg (Phys. Rev. Letters 51 [1983] 2056/9).
[6] E. Bucher, K. Andres, F. J. di Salvo, et al. (Phys. Rev. [3] 811 [1975]500/13, 504).
[7] A. landelli (Atti Acad. Nazl. Lincei Classe Sei. Fis. Mat. Nat. Rend. [8]30 [1961]201/7; C.A
56 [1962] 1041 ).
[8] G. Kaindl, C. Laubschat, B. Reiht, R. A. Pollak, et al. (Phys. Rev. [3] B 26 [1982]1713/27,
1718).
30.1.2.10.14.2 TmTe
30.1.2.10.14.2.1 lntroduction
No intermediate valence state is proposed for TmTe at ambient pressure, in cantrast to

TmSe.
From the studies in the Tm-Te system (see p. 251) by Katdis et al. [1] and landelli,
Palenzona [2] it was concluded that cubic NaCL type stoichiometric TmTe (a ~ 6.36 Ä) is a
compound with divalent Tm and that a stoichiometric cubic TmTe phase with trivalent Tm
and Tm~1 Tmj 1~xTe solid solutions do not exist at atmospheric pressure. No appreciable
homogeneity range on the Tm side was found in melt-grown TmTe crystals by [1]. On the Te-
rich side the limiting composition is approximately ;S TmTe 1.09 [1]. From the lower lattice
constants (a between ~ 6.29 and 6.338 Ä) and the higher magnetic susceptibility in this range
(compared with stoichiometric TmTe) it was concluded that Tm-deficient solid solutions with
both Tm 2 + and Tm3+ exist (see p. 257) [2], Ott, Hulliger [3]. As melt-grown TmTe crystals
showed a variation in the lattice constants and deviations from stoichiometry, even when
prepared from stoichiometric mixtures, it was believed by [3] that all samples regarded as
Tm 11 Te in the Literature are in fact Tm-deficient solid solutions [3]. Although this assumption
Gmelin Handbook
RE Mam Vol. C10
was not stated by [1] (see also valence studies, p. 257), it is always appropriate to mention
the Lattice constants of the studied samples. Under pressure the valence of the Tm in TmTe
increases continuously (to ~ 2.7 at 40 kbar) and the lattice constant decreases without change
of the lattice structure (a = 5.94 A at 40 kbar), Jayaraman et al. [4], Chatterjee et al. [5]. At
~ 150 kbar a structural changewas observed; see p. 256.
References:
[1] E. Kaldis, E. Jilek, H. Spychiger (J. Less-Common Metals 93 [1983]399/409).

397/405; C.A. 68 [1968] No. 63803).
[3] H. R. Ott, F. Hulliger (Z. Physik S 49 [1983] 323/30).
[4] A. Jayaraman, E. Sucher, D. S. McWhan (Proc. 9th Rare Earth Res. Conf., Slacksburg,
Va., 1971, pp. 333/44).
[5] A. Chatterjee, A. K. Singh, A. Jayaraman (Phys. Rev. [3] S 6 [1972] 2285/91).
30.1.2.1 0.14.2.2 Preparation
For the preparation see also p. 6.
Tm Te was generally prepared from the elements in equimolar ratio. To prevent contamina-
tion by 0 2 or moisture all manipulations and reactions should be performed under inert gas
or in vacuum. ln a first step Tm turnings or chips were allowed to react with Te vapor in
evacuated silica tubes between 500 and 800°C; see, e.g., Ott, Hulliger [1], Katdis et al. [2].
The reaction at ~ 800°C [2], 900°C, Jayaraman et al. [3], or 1 000°C, landelli, Palenzona [4],
was not complete; quenched samples from 800°C contained the green-blue product TmTe_ 1_47
(with a = 6.04 A for the NaCL sublattice) [2], (see p. 252). Annealing a prereacted sample at
1400°C (2 to 4 h in Pythagoras crucibles in closed iron bombs) gives a product "TmTe 0 _96 "
with a = 6.364 A (see p. 252) [4]. ln most cases the prereacted material was melted in sealed
evacuated crucibles of W [2, 5, 6] or Ta [1, 3], Köbler et al. [7], Sucher et al. [8] (melting
point of TmTe: 1870 ± 5°C [7]). Changas in the starting composition caused by incongruent
evaporation were avoided by putting the charge in the colder part of the crucible (1925°C)
and keeping the Lid temperature at 1955°C to suppress Te sublimation. The crucible was kept
at this temperature for 18 h and was then slowly cooled at a rate of 5 K/h. Large single
crystals (up to 5 mm) were cleaved from the solidified ingot. The crystals had stoichiometric
composition (the accuracy of the chemical Tm analysiswas 0.25 wt%) and a = 6.365 A [2].
The crystals obtained by Sarraclough [6] had a = 6.359 A; those obtained by Suryanarayanan
et al. [5] had a = 6.340(1) A and the composition TmTe from electron probe microanalysis
(accuracy 2%). Melt-grown crystals annealed for several weeks at 450°C had a = 6.34 A [3].
Crystals obtained by [1] had the composition Tm 0 _94Te (~ TmTe 1064) with a = 6.308(2) A
(electron probe microanalysis); the preparation of stoichiometric Tm Te did not succeed, and
sometimes traces of thulium oxide or oxide telluride were observed [1, 9].
Thin films (thickness ~ 0.5 Jlm) ofTmTe were prepared in evacuated (5 x 10- 6 Torr) Contain-
ers by electron beam heating of TmTe (pellets sintered at 1650°C} and condensation on a
silica or CaF 2 substrate at about 350°C. The dark gray to black films had lattice constants
between 6.30 and 6.335 A. ln one case a blue film with two cubic phases, a = 6.29 and 6.10 A,
was obtained, Suryanarayanan et al. [5].
Gmeltn Handbook
RE Mam Vol. C 10
Tm Te 255
References:
[1] H. R. Ott, F. Hulliger (Z. Physik S 49 [1983]323/30).

[3] A. Jayaraman, E. Sucher, D. S. McWhan (Proc. 9th Rare Earth Res. Conf., Slacksburg,
Va., 1971, pp. 333/44).
397/405; C.A. 68 [1968] No. 63803).
[5] R. Suryanarayanan, G. Güntherodt, J. L. Freeouf, F. Holtzberg (Phys. Rev. [3] S 12 [1975]
4215/22).
[6] K. G. Sarraclough (J. Cryst. Growth 41 [1977] 321/4).
[7] U. Köbler, K. Fischer, K. Sickmann, H. Lustfeld (J. Magn. Magn. Mater. 24 [1981] 34/42).
[8] E. Sucher, K. Andres, F. J. di Salvo, J. P. Maita, A. C. Gossard, A. S. Cooper, G. W. Hull
(Phys. Rev. [3] S 11 [1975] 500/13).
[9] F. Hulliger (private communication to the Gmelin-lnstitut 1984).
30.1.2.1 0.14.2.3 Crystallographic Properties
At Atmospheric Pressure
Tm Te has the cubic NaCL structure (see p. 8), landelli, Palenzona [1]. Sroadened high angle
X-ray reflections have been observed in stoichiometric TmTe samples nearly independent of
annealing time or cooling rate. This was attributed to sizable lattice defects or a suppressed
phase transition. The amount of lattice defects (Schottky pairs) has been deduced from the
measured and the X-ray density (see p. 259). The calculated Schottky pair concentrations
ranged from 0.28 to 0.84% and 1.1 to 1.3% in slowly cooled and rapidly quenched samples,
respectively. These concentrations are regarded as too low to explain the unusual line
width in the X-ray diffraction pattern, Katdis et al. [2]. Lattice parameters of single- and
polycrystalline cubic TmTe samples which had been analyzed for their composition (see
p. 254 for the accuracy of analyses) are as follows:
ratio Tm:Te 1.00 1.00 1.00 1.00 0.94 0.92
a in A 6.3668 ) 6.355b) 6.359(2) 6.353 6.340(1) 6.308(2) 6.33

Ref .. [2] [2] [3] [4] [5] [6] [7]
a) Slowly cooled. - b) Quenched.
The lattice parameter was found to increase from "'6.351 to greater than 6.361 A along
the axis of a Tm Te ingot grown by directional freezing, Köbler et al. [8]. Du ring crystal growth
the melt is supposed to segregate the denser material, which is richer in Tm3+, at the bottom
of the crucible [8].
Additional lattice parameters of other nominally stoichiometric TmTe samples are as

follows, in A: 6.364 [1], 6.364 to 6.342 Sucher et al. [9], 6.361(2) Eliseev et al. [10], 6.360(2)
TripleU et al. [11], 6.359 Mörke, Wachter [12], 6.354(2) Usha-Devi, Singh [13], 6.35 Lassailly et
al. [14], 6.346 Sucher et al. [16], 6.34 Jayaraman et al. [15], 6.337(1) Chatterjee et al. [17],
6.32(2) Clayman et al. [18].
Gmelm Handbock
RE Main Val. C10
Estimated lattice parameters for stoichiometric Tm 11 Te at room temperature are a = 6.38 A,

Ott, Hulliger [6], 6.39 A, Campagna et al. [19], and 6.361 A, Kaldis et al. [20].
At low temperature (0.070 K) a = 6.292 A was determined from neutron diffraction,
Lassailly et al. [14]. For additional data on the symmetry at the Tm 2 + site at low temperatures.
see p. 262. For the lattice constants of films see p. 254.
At High Pressure
With increase in pressure the 4f 13 shell of Tm in Tm 11 Te is destabilized, driving it into an

intermediate-valence configuration. The cubic lattice constant decreases without change of
the NaCl type crystal structure and the valence increases continuously without reaching a
valence of 3 at the applied pressures of 1 to 40 kbar [15]. This partial electronic collapse was
indicated by the pressure dependence of the electrical resistivity, Jayaraman et al. [15], of
the magnetic susceptibility, Wohlleben et al. [21], and of the compressibility, Chatterjee et al.
[17]. The lattice constant decreased from 6.34 A at ambient pressure to 5.94 A at 30 kbar [15].
The Tm valence was assumed to increase up to ~ 2.7 in the pressure range 1 to 40 kbar [17]
and up to 2.12 at 29 kbar [21]. A change of the crystallographic structure type was observed
at about 150 kbar [17]. The volume change at the transformation is 11V = - 3.8%. The high
pressure (at ~ 15 GPa) X-ray powder pattern (estimated intensities) was explained reasonably
well by the hexagonal (anti-)NiAs structure type (space group P6 3 /mmc-D~h; No. 194), Z = 2
with Tm in the special position 2c, ± (1/3, 2/3, 1/4) and Te in the special position 2a, (0,0,0;
0,0, 1/2). The lattice parameters are a = 4.07 ± 0.04 and c = 6.84 ± 0.07 A at 15 GPa
( ~ 150 kbar). Tm is coordinated to six Te at 2.91 A forming a trigonal prism; Te is surrounded
by six Tm at the apices of an octahedron (same distance as before) plus 2 Te at 3.42 A
(~ ± c/2). lt seems possible that Tm Te at > 15 GPa is transformed into the CsCl type structure
in conformity with, e.g., SmTe or EuTe, Usha-Devi, Singh [13].
References:
397/405).
[3] K. G. Barraclough (J. Cryst. Growth 41 [1977] 321/4).
[4] B. Batlogg, E. Kaldis, A. Schlegel, P. Wachter (Phys. Letters A 56 [1976]122/4).
[5] R. Suryanarayanan, G. Güntherodt, J. L. Freeouf, F. Holtzberg (Phys. Rev. [3] B 12 [1975]
4215/22).
[6] H. R. Ott, F. Hulliger (Z. Physik B 49 [1983] 323/30).
[7] G. Kaindl, W. D. Brewer, G. Kalkowski, F. Holtzberg (Phys. Rev. Letters 51 [1983]
2056/9).
[8] U. Köbler, K. Fischer, K. Bickmann, H. Lustfeld (J. Magn. Magn. Mater. 24 [1981]34/42).
[10] A. A. Eliseev, K. A. Zinchenko, V. M. Zemlyanukhina, Nguen'Chin'Tam (Zh. Neorgan.
[11] B. B. Triplett, Y. Mahmud, N. S. Dixon, S. S. Hanna, F. Holtzberg (Phys. Letters A 67 [1978]
151/4).
[12] I. Mörke, P. Wachter (Solid State Commun. 48 [1983]441/3).
[13] S. Usha-Devi, A. K. Singh (Solid State Commun. 52 [1984] 303/5).
[14] Y. Lassailly, C. Vettier, F. Holtzberg, A. Benoit, J. Flouquet (Solid State Commun. 52 [1984]
717/9).
Gmelm Handbook
RE Main Val. C 10
Tm Te 257
[15] A. Jayaraman, E. Bucher, D. B. McWhan (Proc. 8th Rare Earth Res. Conf., Reno, Nev.,
1970, Vol. 1, pp. 333/44).
[16] E. Bucher. A. C. Gossard, K. Andres, J. P. Maita, A. S. Cooper (Proc. 8th Rare Earth Res.
Conf., Rano, Nev., 1970, Vol. 1, pp. 74/89).
[18] B. P. Clayman, R. W. Ward, J. P. Tidman (Phys. Rev. [3] B 16 [1977]3734/41).
[19] M. Campagna, E. Bucher, G. K. Wertheim, L. D. Longinotti (Proc. 11th Rare Earth Res.
Conf., Traverse City, Mich., 1974, pp. 53/62).
[20] E. Kaldis, B. Fritzler, W. Peteler (Z. Naturforsch. 34a [1979] 55/67).
[21] D. Wohlleben, J. G. Huber, M. B. Maple (AlP [Am. lnst. Phys.] Conf. Proc. No. 5 [1972]
1478/82).
30.1.2.10.14.2.4 Valence
For additional data on the pressure or volume dependence of the Tm valence, see p. 259.
Several physical measurements were carried out on the cubic NaCl-type TmTe phase to
find out whether Tm is solely divalent, of intermediate (noninteger) valence, or of (in-
homogeneously) mixed valence. Most of the results show that in nominally stoichiometric
Tm Te crystals (lattice constants a ~ 6.34 A) Tm is exclusively divalent at normal pressure
(see in the following) but of intermediate valence at high pressure (see p. 256). To avoid
surtace contamination (oxidation to Tm 3 +), which would falsify the results, the studied Tm Te
crystals were handledunder absolute exclusion of air. The crystals were polished in gettered
Ar, Batlogget al. [1] or cleaved in ultrahigh vacuum at -1o- 10 Torr, Kaindl et al. [2 to 4], at
2 x 10- 8 Torr, Suryanarayanan et al. [5], and at 5 x 10- 9 Torr, Campagna et al. [6]. From the
reflectivity (at 300 K) of a stoichiometric, crystallographically perfect single crystal (a =
6.353 A) it was stated that Tm in TmTe is divalent and that ICF (interconfiguration fluctuation)
is not present [1]. Essentially divalent Tm in a single crystal (a = 6.340(1) A) was also found
by reflectance and UV photoemission spectra (UPS). A small amount of Tm3+ found in
the UPS spectra (increasing with increasing time after cleavage) was attributed to surface
contamination effects [5]. Divalent Tm in TmTe crystals (a = 6.43 A) was found by
photoelectron spectroscopy on a (100) surface [2, 3]; presence of small amounts of Tm3+ was
probably due to surtace oxidation [3]. X-ray photoemission spectra of TmTe crystals (a =
6.35 A) in vacuum (better than 10- 9 Torr; duration of the run 6 to 8 h) showed simultaneous
appearance of Tm3+ and Tm2+ in the final state spectra and were explained by spontaneous
ICF [6], but according to [5] the presence of Tm3+ was due to surface oxidation, overlooked
by [6]. Integer valent Tm2+ was also found by measuring of ESR spectra of Gd-doped TmTe
(1 to 3% Gd) at various temperatures, Huang, Sugawara [7].
ln cubic NaCl-type TmTe with lower lattice constants the presence of Tm3+ contributions
was found by measurements of the magnetic susceptibility by Jayaraman et al. [8], Sucher
et al. [9], landelli, Palenzona [10], and Ott, Hulliger [11] and from the X-ray absorption spectrum
measured on a vacuum-cleaved crystal with analytical composition Tm 0.92Te (a = 6.33 A).
From the relative intensities of the resonance Lines a content of 21.3% Tm3+ was derived,
Kaindl et al. [4]. From the magnetic measurements the following contents of Tm3+ were
calculated: 17.5% for a Tm 0.94Te crystal (a = 6.308(2) A) [11]; 12% for polycrystalline Tm Te
(annealed several weeks at 450°C after melting) with a = 6.34 A [8, 9]; 3% Tm was calculated
by [11] from the magnetic moment measured by [10] on a polycrystalline sample, sintered at
1400°C, with a = 6.364 A. lt should be mentioned that the content of Tm3+ in a TmTe crystal
slightly increased with powdering as shown by magnetic measurements (see p. 262).
Gmelm Handbock 17
RE Mam Vol. C 10
The valence of Tm-deficient samples was calculated by [11] from the lattice constants (or
compositions) with the assumption that solid solutions Tm 1 _xDxTe between Tm 11 Te and
Tmb11 Te 3 ( = Tm 213 D 113Te) exist (but see p. 252) with a linear decrease of the lattice constants
from a = 6.38 A (expected for stoichiometric TmTe at x = 0) to 6.045 (at x = 1/3, cubic
sublattice of Tm 2Te 3). With this assumption a Tm3+ content of 18 and 11% was calculated for
the above-mentioned samples with a = 6.308 and 6.34 A, respectively [11]. Sut according to
this assumption all prepared nominally stoichiometric TmTe samples with lattice constants
of at most 6.366 A (see p. 255) would contain some Tm3+ (e.g., 5% Tm3+ was calculated from
the lattice constant in the sample with a = 6.364 A [11]). With the assumption that the sample
with the high lattice constant (a = 6.364 Ä) contains only Tm 2 +, a content of 7% Tm3+ was
calculated from the lattice constant of the studied sample with a = 6.34 A [9].
References:
[1] S. Satlogg, E. Kaldis, A. Schlegel, P. Wachter (Phys. Letters A 56 [1976]122/4).

[2] G. Kaindl, C. Laubschat, S. Reiht, R. A. Pollak, N. Märtenson, F. Holtzberg, D. E. Eastman
(Phys. Rev. [3] S 26 [1982]1713/27, 1723).
[3] G. Kaindl, C. Laubschat, S. Reiht, R. A. Pollak, N. Märtenson, F. Holtzberg, D. E. Eastman
(Valence lnstab. Proc. Intern. Conf., Zürich 1982, pp. 281/5).
[4] G. Kaindl, W. D. Srewer, G. Kalkowski, F. Holtzberg (Phys. Rev. Letters 51 [1983]
2056/9).
4215/22).
[6] M. Campagna, E. Sucher, G. K. Wertheim, D. N. E. Suchanan, L. D. Longinotti (Phys. Rev.
Letters 32 [1974] 885/9).
[7] C. Y. Huang, K. Sugawara (J. Low Temp. Phys. 28 [1977]229/39, 236).
[8] A. Jayaraman, E. Sucher, D. S. McWhan (Proc. 8th Rare Earth Res. Conf., Reno, Nev.,
1970, pp. 333/44).
(Phys. Rev. [3] S 11 [1975] 500/13).
397/405).
[11] H. R. Ott, F. Huttiger (Z. Physik S 49 [1983] 323/30).
30.1.2.10.14.2.5 LaHice Vibrations
The wave numbers oo,-0 = 125 and (I)LO = 140 cm- 1 for the transversal and longitudinal
optical phonons have been derived from a simple oscillator fit of the Low-temperature far-
infrared reflectivity, ffiro = 115 ± 2 and ffiLO = 146 ± 2 cm- 1 from the observed inflection
points, Wardet al. [1], Clayman et al. [2]; see p. 275.
References:
[1] R. W. Ward, S. P. Clayman, T. M. Rice (Solid State Commun. 17 [1975]1297/300).

[2] S. P. Clayman, R. W. Ward, J. P. Tidman (Phys. Rev. [3] S 16 [1977]3734/41).
Gmelin Handbock
RE Ma1n Vol. C10
TmTe 259
30.1.2.10.14.2.6 Mechanical Properlies

Density
Measured densities Dexp and X-ray densities Deale (in g/cm3 ) derived from polycrystalline
samples by landelli, Palenzona [1) and from annealed or quenched stoichiometric si ngle
crystals by Katdis et al. [2) :
composition TmTe0 .96 TmTe 1.04 TmTe 1.00 TmTe 1.00 TmTe1.00*l
Dexp · 7.69 7.64 7.645 7.603 7.624

Deale· 7.64 7.74 7.656 7.634 7.674
Ref . . [1) [1) [2) [2) [2)
•l Quenched sample.
For additional density data seealso [2, 3). Deale = 9.4 g/cm3 follows from the Lattice parameter
a = 5.94 A at 30 kbar for a TmTe sample with a = 6.34 A at normal pressure, Jayaraman et
al. [4) .
Pressure-Volume Relationship. Elastic Constants

The relative volume change !1VIV0 shown in Fig.103 was derived from the pressure
dependence of the Lattice constants of a Tm Te sample with a = 6.337 A. The compressibility
is unusually high between about 18 and 30 kbar, Chatterjee et al. [5]. At 30 kbar !1VIV0 is about
three times as large as expected from the behavior of SmTe or EuTe. This is attributed to a
valence transition, Jayaraman et al. [4); see also p. 256. The initial compressibility is K =
2.2 x 10- 6 bar- 1 (1/K = bulk modulus K0 = 46.0 ± 5 GPa), Chatterjee et al. [5), Jayaraman
et al. [6, 7) . K0 = 45 ± 10 GPa was obtained with theoretical calculations by Monnier et al.
[8) (cf. p. 268). K0 and the molar volume V mol at ambient pressurefit in a Linearrelation between
Ln K0 and Ln Vmol for divalent rare earth monochalcogenides [6). Fig. 104, p. 260, shows the
temperature dependence of the elastic constants of TmTe (sample with a = 6.346 A). The
behavior was interpreted by crystal electric field (CEF) effects assuming a CEF Level scheme
(see p. 262) r 8-r7 (10 K)-r6 (16 K) of the Tm 2 + ground state, Ott et al. [9), Lüthi [10]. At 300 K
the elastic constants, in 1010 N/m2 , are c44 = 1.86, (c 11 - c 12)/2 = 4.8, K0 = (c11 + 2cd/3 =
3.8 ( = 38 GPa) [9), implying c 11 = 10.2, c 12 = 0.6.
-0.081--\-- -t-- - - + - - ---l

~
~
- 0.16 1---~---+-----l
-o.24o!:------::so;o-------:=----,,;:~.so
p in kbor
Fig. 103. Pressure-volume diagram of Tm Te.

Gmelin Handbook 17 "
RE Main Vol. C 10
..
c
...
·;. 4.81-----+- - - - + - - -----i
u
100 200 300

Tempereture in K
Fig. 104. Elastic constants of Tm Te versus temperature. Full circles : observed data, solid lines:
calculated fit based on the CEF Level scheme 1 8-17 (10 K)-16 (16 K), broken lines: background.
References :
397/405).
[2] E. Kaldis, E. Jilek, H. Spychiger (J. Less-Common Metals 93 (1983] 399/409).
[3] E. Kaldis, 8. Fritzler (J. Phys. Colloq. [Paris]41 [1980] C5-135/C5-142) .
[4] A. Jayaraman, E. Sucher, D. B. McWhan (Proc. 8th Rare Earth Res. Conf., Reno, Nev.,
1970, Vol.1, pp. 333/44).
[6] A. Jayaraman, A. K. Singh , A. Chatterjee, S. Usha Devi (Phys. Rev. [3] B 9 [1974]
2513/20).
[7] A. Jayaraman, P. D. Dernier, L. D. Longinotti (High Temp.-High Pressures 7 [1975]
1/28, 2).
[8] R. Monnier, H. J. F. Jansen, A.J. Freeman (J. Less-Common Metals 111 [1985]203/6).
[9] H. R. Ott, 8. Lüthi , P. S. Wang (Valence lnstab. Relat. Narrow Band Phenom. Proc. Intern.
Conf., Rochester, N.Y., 1976 [1977] pp. 289/302).
[10] B. Lüthi (AlP [Am. lnst. Phys.] Conf. Proc. No. 34 [1976]7/11).
30.1.2.10.14.2.7 Thermal Properlies

For the melting point see p. 13.
Thermal Expansion
The linear thermal expansion coefficient along [100] between 2 and 16 K of a TmTe single
crystal with a = 6.346 A is shown in Fig. 105, Ott et al. [1] and for Tm 0 .94Te (a = 6.308 A)
between 0.1 and 1.3 Kin Fig.106, Ott, Hulliger [2] . The solid line in Fig. 105 isafit based on
Gmeton Handbook
RE Maon Vot. C 10
TmTe 261
Fig. 105. Fig. 106.
3 4r-- o - - - , - - - , - - , ---TO--II
I .·...:.:'
I
2 3
I
~2
::.:::
.
""·...
1
__.__ / .!:
.
IS
0
_ ;../ ··:
• ••••• t-.
4 8 12 16 00~~--~--~~~~--~~
04 0.8 1.2
Linear thermal expansion coefficient r:x of TmTe versus temperature determined on a

single crystal with a = 6.346 A along [100] (Fig. 105) and on Tm 094Te with a = 6.308 A
(Fig. 106).
the CEF Level scheme used for the interpretation of the elastic constants ; see p. 262. The Low
temperature part shows good agreement between experiment and calculations using the
Grüneisen parameters y(17) = 1.26 and y(f'6) = - 1.52. Above 8 K additional thermal ex-
pansion due to Lattice contributions becomes important with the T5 term ~ 2 x 10- 12 K- 6 [1].
Heat Capacity
The temperature dependence of the molar heat capacity between 1.5 and 13 K is shown
in Fig. 107, Sucher et al. [3, 4] . The anomaly at ~ 6 K could be interpreted fairly well with the
CEF Level sequence 1 8 -17-16 (see p. 262) [1].
The Debye temperature 8 0 = 193 K was calculated by Gopikrishna et al. [5] using the
elastic constants from Ott et al. [1]; cf. p. 259. An approximatety Linear retation between 8 0
and the inverse of the Lattice parameter is discussed for rare earth monochalcogenides [5];
seealso p. 13.
ll ;t~- ~§f
0 4 8
Temperature in K
12
I
Fig. 107. Molar heat capacity of TmTe versus temperature.
Gmelm Handbo ck
RE Main Vol. C10
References:
[1] H. R. Ott, 8. Lüthi, P. S. Wang (Valence lnstab. Relat. Narrow Band Phenom. Proc. Intern.
Conf., Rochester, N.Y., 1976 [1977], pp. 289/302; C.A. 89 [1978] No. 98063).
[2] H. R. Ott, F. Huttiger (Z. Physik 8 49 [1983]323/40, 327/8).
(Phys. Rev. [3] 8 11 [1975] 500/13, 505).
(5] N. Gopikrishna, G. K. Subhadra, D. 8. Sirdeshmukh (Indian J. Pure Appl. Phys. 22 [1984]
618/9).
30.1.2.10.14.2.8 Mössbauer Spectra, Magnetic Hyperfine Field, and Crystal Field
The 169Tm Mössbauer spectra (8.4 keV transition) were studied at 0.057, 0.127, and 3 K on
powdered TmTe single crystals (a = 6.360(2) Ä). The source was 169 Er in an alloy of 10 wt%
168 Er in AL The spectra below the magnetic ordering temperature (T N ~ 0.3 K for this sample)
are composed of a magnetic six-line hyperfine pattern (3/2-> 1/2 spin transition in 169 Tm) and
a nonmagnetic doublet of about 23% of the total spectral weight. The doublet is regarded
as a contaminant, supposedly Tm3+. Du ring powdering the molar Curie constant, in
cm 3 • K · mol- 1 , was shifted from 2.79 to 3.05, compared with 2.57 and 7.17 for pure Tm 2 + and
Tm3+, respectively. At 3.0 K the spectrum shows a doublet. Magnetic hyperfine parameters
attributed to Tm 2 + are as follows: AE 101 = 57.2(6) cm/s, hyperfine field B;nt = 345 T (compared
to 423 T for free Tm 2 +), and the quadrupole interaction Ql = e2 qQ/4Ey (where Ey = 8.401 eV) =
6.91(8) cm/s (8.43 cm/s for free Tm 2 +). The quadrupole interactionwas derived by assuming
a constant Ql = 7.84 cm/s for Tm3+. The comparatively large value of the ratio Ql: Ql(free
ion) below TN and the asymmetric doublet of the spectrum at 3 K indicates noncubic site
symmetry of Tm 2 + in Tm Te. in Fig. 108 the temperature dependence of Ql for Tm2+ is plotted.
The solid line was fitted using a lattice contribution Qltatt = 0.72 cm/s and the standard cubic
CEF Hamiltonian modified by an additional axially symmetric interaction, Triplett et al. [1];
see also [2].
The 2 F712 ground state of Tm 2 + in TmTe is split by a crystal electric field (CEF) of Oh
symmetry into f 6 , f 7 , and f 8 , of which f 7 was assumed tobe the lowest state, Suryanarayanan
et al. [3]. However, Ott et al. [4] proposed the Level sequence f 8-f7 (10 K)-f6 (16 K) to explain
the observed temperature variation of the elastic constants, the linear thermal expansion
coefficient, and the heat capacity. lt is consistent with the rather large 8 6 term of the CEF
·potential [4], and it also agrees with the low temperature, low-field susceptibility of Tm 0 .94Te.
The noncubic site symmetry observed by [1] could be explained by the presence of ~ 6%
Tm 3 + (~ Tm 098Te), Ott, Hulliger (5]. This Level sequence agrees with neutron scattering
studies at 10 K, by Furrer et al. [6], and with neutron scattering studies down to 0.07 K. The
r 7 ground state seems tobe ruled out, Lassailly et al. [7]. The behavior of this Level scheme
in a magnetic field parallel to one of the main axes has been calculated by Thalmeier, Fulde
[8]; for a figure see the paper. A previously published scheme f 6-f7 (10 K)-f8 (17 K), Lüthi
[9], is superseded; also, Tm3+ -based Level schemes cannot explain the low-temperature
anomalies of TmTe [4]. Neutron scattering studies on polycrystalline TmTe samples at 10 K
showed, besides an intense elastic peak, two well-defined inelastic lines at 8.6 and 17.3 meV
(the intensities decrease with raising temperature), attributed to the fa -> r7 and fa -> r6
transitions, Furrer et al. [6], which were not observed in the neutron inelastic spectra of Tm Te
Gmelm Handbock
RE Main Vot. C 10
TmTe 263
a~--.----.---.----.---~
0 20
Temperature in K
Fig. 108. Quadrupole interaction Ql for Tm 2 + in powdered TmTe versus temperature. The
inset shows a possible CEF Level diagram (but see text).
single crystals between 1.3 and 50 Kin the range 2.5 to 7 THz (:: 10 to 29 meV), i.e., there is
no indication of crystal field excitations, Lassailly et al. [7]. The total crystal field splitting
of 17.3 meV (200 K) is also inconsistent with magnetic susceptibility data for Tm0 .94Te [5].
The following crystal field parameters were derived from the inelastic lines (at 8.6 and
17.3 meV): total CEF splitting factor W = - 0.59 ± 0.02 meV, the ratio between the fourth-
and sixth-order term of the CEF Hamiltonian x = - 0.28 ± 0.03, 8 4 = (28 ± 4) x 10- 4 meV,
8 6 = (-337±26)x10- 6 meV, A4 a5 = (-7.4±1.1)X104 meV·A, and A6 a7 =
(- 1.72 ± 0.13) x 10- 6 meV · A [6]. The Mössbauer spectra were interpreted for noncubic
(tetragonal) Tm 2 + symmetry with the parameters 8 2 = - 0.216 K and 8 4 = - 0.01 K, using
the Level scheme r 6-r 8 (9.68 K)-r7 (10.94 K) derived from the cubic r 6-r 8 (7.6 K)-r7 (12 K) by
the additional axially symmetric interaction [1].
References:
[1] B. B. Triplett, Y. Mahmud, N. S. Dixon, S. S. Hanna, F. Holtzberg (Phys. Letters A 67 [1978]

151/4).
[2] B. B. Triplett, N.S. Dixon , Y. Mahmud, S. S. Hanna (AlP [Am. lnst. Phys.] Conf. Proc. No.
38 [1977]118/29) .
[3] R. Suryanarayanan , G. Güntherodt, J . L. Freeouf, F.Holtzberg (Phys. Rev. [3] B 12 [1975]
4215/22).
[4] H. R. Ott, B. Lüthi , P. S. Wang (Valence lnstab. Relat. Narrow Band Phenom . Proc. Intern.
Conf., Rochester, N. Y. , 1976 [1977], pp. 289/302).
[5] H. R. Ott, F. Hulliger (Z. Physik B 49 [1983] 323/30).
[6] A. Furrer, W. Bührer, P. Wachter (Valence lnstab. Proc. Intern. Conf., Zürich 1982,
pp. 319/23).
[7] Y. Lassailly, C.Vettier, F.Holtzberg, A. Benoit, J. Flouquet (Solid State Commun. 52 [1984]
717/9).
[8] P. Thalmeier, P.Fulde (Z. Physik B 29 [1978]299/305).
[9] B. Lüthi (AlP [Am. lnst. Phys.] Conf. Proc. No. 34 [1976] 7/12).
Gmelin Handbook
RE Mam Vol. C 10
30.1.2.1 0.14.2.9 Magnetic Properties

General
The magnetic properties of nearly stoichiometric Tm Te samples are determined by divalent
Tm. Some differing results in the following section may be due to differences in the composi-
tion. With decreasing Tm content, i.e., decreasing Lattice constants, an increasing fraction
changes to trivalent Tm; see for example Ott, Hulliger [1], and pp. 257/8.
Magnetic Ordering
TmTe is paramagnetic at room temperature and orders as a type II antiferromagnet at
rather Low temperature, as shown by neutron scattering experiments at 70 mK. No other
magnetic scattering, in particular ferromagnetic, was observed. A single q structure was
proposed with an even domain distribution. The refinement of the magnetic reflection showed
the Fourier component of the magnetic moment mii to be in the (111) plane but its orientation
in this plane could not be determined. The magnetic moment lmiil extrapolated to zero
temperature is 2.3 ± 0.1 Jls, consistent with the CEF Level scheme f 8-f 7 (10 K)-f 6 (16 K),
Lassailly et al. [2]; see p. 262. Earlier measurements of susceptibility and thermal expansion
could be interpreted also by an antiferromagnetic order of type I, Ott, Hulliger [1]. "Tm 111 Te"
shows no sign of magnetic ordering down to 0.02 K, interred from susceptibility measurements
on samples with Lattice constants of Tm 11 Te and Tm 111 Te (?) by Sucher et al. [3].
Values for the Neel temperature, in K, of several samples additionally characterized by
their Lattice parameter (in parenthesis) are: 0.21(6.346 A), from susceptibility measurements,
Sucher et al. [4], 0.235(6.308 A), from measurements of some magnetic properties and the
thermal expansion of Tm 0 _94Te, Ott, Hulliger [1], ~ 0.3(6.360 A), from Mössbauer spectra,
Triplett et al. [5], and 0.43(6.35 A), from neutron scattering, Lassailly et al. [2]. The dis-
crepancies in the T N values may be due to possible impurities, disorder, or compositional
inhomogeneities [2].
Susceptibility and Magnetization at Ambient Pressure

Molar magnetic susceptibilities Xmol (in 10- 3 cm 3/mol) of 8.5, 10.5, and 11.6 at room
temperature were measured on polycrystalline samples with the nominal compositions
Tm 1 _04Te, Tm 0 _99 Te, and Tm 096Te (a = 6.346, 6.338, and 6.289 A, respectively), prepared at
1400°C. Additional values of Xmol for samples with a variety of compositions and differing
preparation temperatures are given in the paper. For the sample Tm 1 _04Te with the Lowest Xmol
value, measurements between -50 and + 200°C gave an effective moment of 1-leff = 4.63 1-ls
and a Curie temperature of E>P = - 20 K for Tm Te assuming a mixture of 1 Tm Te + 0.04 Tm
metal, landelli, Palenzona [6]. Fig. 109 shows the temperature dependence of the inverse
magnetic susceptibility, measured on Tm 094Te (a = 6.308 Ä) by Ott, Hulliger [1], and on
nominally stoichiometric TmTe (a = 6.346 A) by Sucher et al. [4, 7]. For comparison a
theoretical curve is shown, assuming all the Tm ions to be divalent in stoichiometric TmTe
and neglecting any crystal field or exchange effects. A calculated curve based on the total
crystal field splitting of 200 K (see pp. 262/3) is not consistent with the experimental data [1].
Fora 1/x versus T curve seealso Köbler et al. [8]. WeiL above TN the temperature dependence
of Xmol follows the Curie-Weiss Law with: E>P = - 0.35 K, Jleff = 4.96 Jls per Tm (77 to 300 K),
Sucher et al. [4]; E>P = 0 K [7]; E>P = -5 K, Jleff = 5.22 Jls per Tm (1.5? to 300 K) for Tm 0 _94Te
[1]; E>P = - 2 K (read from a figurein the paper), Jleff = 4.64 Jls per Tm (50 to 300 K) determined
on a sample from a single crystal with Lattice constants changing from ~6.35 to 6.36 A along
Gmelm Handbook
RE Ma1n Vol. C10
Tm Te 265
12o.---- -r-----,-- .----,------r--,

---- calculated
- - eocp. Bucher et al. !4,71
• • • •• e~ Ott. Huttiger [ 11
:::J
f 80~-------+---------~~~~~
~
.5
~
~ 40 f-----~7-r''----f-----l
100 200
Tempereture in K
Fig. 109. Temperature dependence of the inverse magnetic susceptibility of Tm 0.94Te [1] and
of nominally stoichiometric TmTe [4, 7]. The theoretical curve is calculated assuming
stoichiometric Tm Te and divalent Tm (see text) .
1.0
0.8
.
/
:::J
E
L
~ 0.6
ö
E
.!: 0.4
V
.. /
~
V
0.2
0.5 1.0 1.5

Temperature in K
Fig. 110. Temperature dependence of the inverse magnetic susceptibility of Tm 0 .94Te near T N·
The solid line is calculated as explained in the text.
the long axis [8]; ep = - 1.76 K, fleH = 4.89 fls per Tm (5 to 200 K) and E>p = - 1.31 K, fleH =
4.80 fls per Tm (5 to 9.5 K) both from a TmTe sample with a = 6.35 A, Lassailly et al. [2] . The
experimental fleH values are all near to the theoretical value of ~ 4.54 fls for divalent Tm
(theoretical value for Tm3+ is 7.56 fls); see for example [2, 8] . The values E>P = 14 K and
fleH = 7.63 fls per Tm (see p. 16) for a sample with a = 6.049 A (attributed to TmTe, but cf.
pp. 252/3) of landelli [9] seems to be superseded. The zero-field susceptibility for Tm 094Te
below 1 K is shown in Fig. 110 from [1]. Between T N and 1 K the susceptibility could be
calculated (solid line in Fig . 110) assuming 82.5% Tm 2 + with the 4f ground state split by CEF
effects into r 8 (O)-r7 (10 K)-r6 (16 K) and 17.5% Tm3+ (described by fleH (Tm 3 + ) adjusted to
0.83fltreeion (Tm3+)), and E>P = -0.05 K (this Tm 2 + :Tm3+ ratio would correspond to Tm 0 .92Te) .
GmeL1n Handbock
RE Ma1n Vol. C10
...
... . • · ts•K
2
... ...
0
. .
0
. ..
0
0
•lOK
.
.. .. .
0
• " 20K
0
1(u§K
.!. ..
0
0 • •
0 •
n~·
0 40 80
H in kOe
Fig. 111 . Magnetization along [100] of a Tm 0 _94Te single crystal at various temperatures as a
function of the magnetic field H.
Fig. 111 shows the magnetization Mofa Tm 0 _94Te single crystal along [100] at 0.29 to 20 K
as a function of the magnetic field up to H = 100 kOe ; forM versus H curves of polycrystalline
Tm 0 _94Te samples at 0.115 to 0.692 K up to ~ 1.8 kOe, see the paper [1] . Magnetization curves
for 0.47 to 4.22 K up to 8 kOe are given by Wohlleben et al. [10] . The magnetization of TmTe
measured at 1.4 K in fields up to ~ 100 kOe was found to follow a 8rillouin function with a
saturation moment of ~ 2 !ls and a Van Vleck contribution of the same order of magnitude,
Chouteau et al. [ 11].
Pressure Dependence of Susceptibility and Magnetization
The susceptibility of Tm Te was measured between 0.47 K and room temperature at pres-
x
sures up to 50 kbar. At room temperature increases between 18 and 29 kbar (in a field of
8 kOe from ~ 3.6 x 10-5 to ~ 4. 3 x 10- 5 cm 3/g, read from a figure in the paper) while at Low
temperatures it increases between 29 and 39 kbar and flattens out again above this range.
Fig. 112 shows the pressure dependence of the magnetic moment at 4.25 to 15 K indicating
three different electronic phases, Labeted A, 8, and C. The low- and high-pressure phases
differ in the temperature dependence of the magnetic moments, as shown in a figure in
the paper for H = 7.83 kOe. The absolute magnitude of the (negative) paramagnetic Curie
temperature E>P of the Low-pressure phase increases according to jE>(H)I = (0.3 + 0.25 H) K
with H in kOe. At room temperature, phase A extends up to the pressure (18 kbar) at which
the lattice parameter begins to drop abnormally fast (see p. 259) and the electrical resistivity
starts to saturate after its initial drop (see p. 273) . This indicates that the Tm valence change
starts around 18 kbar. The increase in magnetic moment (at 8 kOe) in 8 or C never reaches
th e value expected for free trivalent Tm. Themagnetization is rather t emperature and pressu re
independent in the C phase between about 39 and 49.5 kbar and at temperatures between
0.39 and 4.2 K . The magnetization versus H curves Look rather ferromagnetic although they
Gmelln Handbook
RE Mam Vol. C 10
TmTe 267
A B c
%~~5~~~20~~~~~~~~40~-L~~
pinkbar
Fig. 112. Magnetic moment of TmTe at 7.83 kOe and various temperatures as a function of
pressure.
do not saturate in higher fields (measured up to 8 kOe). The magnetization curves of TmTe
below 4.2 K in this pressure range and also between 29 and 39 kbar resemble very closely
those of TmSe at 1.4 K and atmospheric pressure, Wohlleben et al. [10].
Magnetostriction and Thermal Expansion in Magnetic Fields

Fig. 113a shows the magnetostriction E(H) of a TmTe sample (a = 6.346 A) along [100] at
H = 12 kOe below 20 K [12]. The integrated relative length change E(T) of Tm 0 .94Te at H = 0
and H = 1.8 kOe is plotted in Fig. 113 b. The sign of the length change is reversed by the
magnetic field and the magnetostriction coefficient changes its sign at about 0.7 K [1]. The
magnetoelastic coupling constants g~ = 0.81 mK and g§ = 24.5 mK have been deduced
from the temperature dependence of the elastic constants (see pp. 259/60). The values for
911 = - 18.6 mK and 912 = 0.28 mK have been derived from the linear thermal expan-
sion coefficient, Ott et al. [12]; seealso Lüthi [13] .
4 a) 2 b)
3
•
• w
•
12 1 r------r~--~r-----~
•.
• •
• • •
5 10 15 20
Fig. 113. Tamperature dependence of the magnetostriction E(H) of TmTe along [100] in a
parallel field of H = 12 kOe (Fig . 113a) and integrated relative length change of Tm 0 .94Te at
H = 0 and 1.8 kOe (Fig. 113b).
Gmelin Handbook
RE Main Vol. C 10
References:
[1] H. R. Ott, F. Hulliger {Z. Physik 8 49 [1983] 323/30).
[2] Y. Lassailly, C. Vettier, F. Holtzberg, A. Benoit, J. Flouquet {Solid State Commun. 52 [1984]
717/9).
[3] E. Sucher, V. Narayanamurti, A. Jayaraman {J. Appl. Phys. 42 [1971]1741/5).
[4] E. Sucher, A. C. Gossard, K. Andres, J. P. Maita, A. S. Cooper {Proc. 8th Rare Earth Res
[5] B. B. Triplett, Y. Mahmud, N. S. Dixon, S. S. Hanna, F. Holtzberg {Phys. Letters A 67 (1978]
151/4).
[6] A. landelli, A. Palenzona {Colloq. Intern. Centre Natl. Rech. Sei. [Paris] No. 157 [1967]
397/405; C.A. 68 [1968] No. 63803).
{Phys. Rev. [3] B 11 [1975]500/13).
[8] U. Köbler, K. Fischer, K. Bickmann, H. Lustfeld {J. Magn. Magn. Mater. 24 [1981]34/42).
[9] A. landelli {Atti Accad. Nazl. Lincei Classe Sei. Fis. Mat. Nat. Rend. [8]37 [1964]160/4).
[10] D. Wohlleben, J. G. Huber, M. B. Maple {AlP [Am. lnst. Phys.] Conf. Proc. No. 5 [1972]
1478/82).
[11] G. Chouteau, F. Holtzberg, J. M. Mignot, 0. Peiia, R. Tournier {Valence lnstab. Relat.
Narrow Band Phenom. Proc. Intern. Conf., Rochester, N. Y., 1976 [1977], pp. 483/6).
[12] H. R. Ott, 8. Lüthi, P. S. Wang {Valence lnstab. Relat. Narrow Band Phenom. Proc. Intern.
Conf., Rochester, N. Y., 1976 [1977], pp. 289/302; C.A. 89 [1978] No. 98063).
[13] 8. Lüthi {AlP [Am. lnst. Phys.] Conf. Proc. No. 34 [1976]7/11).
30.1.2.1 0.14.2.1 0 Electrical Properlies

TmTe is a semiconductor which shows a pressure-induced transition into the metallic
state.
30.1.2.1 0.14.2.1 0.1 Electronic Structure

General Features
A schematic energy Level diagram {Fig.114) is proposed by Suryanarayanan et al. (1],
based on the ideas on Eule of Methfessel; see "Rare Earth Elements" C7, 1983, pp. 459/60,
and spectroscopic studies. The valence band is assumed to be formed from the 5p states of
Te with a width of ~ 6 eV and its upper edge about 1.7 eV below the Fermi Level, the conduction
band is constructed from 5d and 6s states of Tm, and the strongly Localized 4f states form a
narrow impurity band between the valence and the conduction band. The 2F712 ground state
of Tm 2 + is split by the crystal electric field {CEF) into r 6 , r 7 , and r 8 states {see p. 262) and
the conduction band 5d states into the Lower Lying t 29 and the e 9 states, Suryanarayanan et
al. [1]. The ground state energy of TmTe was derived as a function of volume by total energy
Local density calculations. The total energy versus volume plot {for a figure see the paper)
shows a minimum near the volume of the Tm-deficient rhombohedral phase; see p. 252. The
calculated bulk modulus for TmTe agrees fairly weiL with experimental data but the Lattice
constants differ strongly, Monnier et al. [2].
The Te 4d Levels have binding energies E8 ~ -41 eV with a spin orbit Splitting of 1.47 ±
0.02 eV according to UPS; see Fig. 115 on p. 270, Kaindl et al. [3, 4]. The valence band density
Gmelm Handbook
RE Mam Vol. C10
TmTe 269
Fig. 114. Schematic energy Level diagram for Tm 11Te.
of states shows 3 maxima at E8 = 3.6, 5.2, and 7.3 eV with edges at 4.3, 5.7, and 7.9 eV (all
± 0.2 eV) below EFand is thus comparable to that of many tellurides. From optical absorption
spectra the splitting of the t29 and e9 subbands has been determined as 10 Dq ~ 1.1 eV,
Suryanarayanan et al. [1].
Gap E9 Between 41 States and Conduction Band
The band gap E9 between the 41 states and the conduction band has been determined by
various methods. From the pressure dependence ol the electrical resistivity, E9 has been
estimated to be 210 meV, Jayaraman et al. [5], Sucher et al. [6], 220 meV, Sucher et al. [7] ,
280 meV, Boppart et al. [8]. Pressure-valurne data gave 200 meV [5, 6]; seealso [9) . E9 =
220 meV was derived lrom the absorption edge [6] , and E9 = 200 meV lrom the tem-
perature dependence ol the electrical resistivity Q above room temperature [7]. The
value 320 ± 40 meV is estimated lrom the room temperature resistivities ol TmTe and
TmTe0 17Se0 .83 (cl. p. 346) by Batlogg [10] , Batlogget al. [11, 12]. E9 = 350 meVwas estimated
lrom absorption data [1]. See also p. 273 lor activation energies ol the electrical conductivity.
The pressure dependence ol E9 has been determined lrom resistivity vs. pressure curves,
giving dEgfdp = - 10.0 meV/kbar below - 20 kbar; see p. 273, Sucher et al. [6]. A pressure
coefficient ol - 10 to- 13 meV/kbar at pressures up to 10 kbar is reported lor semiconducting
TmTexSe 1 _x phases (including x = 1), Batlogg, Wachter [12]. This corresponds to the delorma-
tion potential [dEgfdp] · K0 = -4.5 eV, Jayaraman et al. [9]. The gap closing is explained by
the CEF Splitting ol the 5d conduction band , which increases with increasing pressure. The
5d(t29 ) subband is thus lowered and the gap is gradually closed, Boppart et al. [8]; see also
Jayaraman et al. [5, 9]. Thus, TmTe is expected to become a metal at ~ 35 kbar, Batlogg ,
Wachter [12], or at 25 kbar, Boppart et al. [8], as the gap between the 41 states and the valence
band vanishes. This behavior represents a continuous pressure-induced semiconductor-to-
metal transition [5, 7, 8, 12].
Gmelin Handbock
RE Main Vol. C 10
111 15
'i§ 0.6
:::J
10
~
g
:a 0.2
.!i
-12 -8 -4
E8 ineV
Fig. 115. Photoemission spectra in the valence band region measured on freshly cleaved
(100) faces of TmTe excited by hv =50 and 110 eV, and by hv = 70 eV after exposure to
0.5 x 10- 6 Torr · s of 0 2 . Theinsetshows the Te 4d spectrum excited by hv = 80 eV. The bar
diagrams represent the final4f multiplets from the bulk (solid bars) and from the surface layer
(dotted bars). The solid lines represent the results of Least-squares fits and the dashed lines
give the integral background plus the contributions from the Te valence band.
Photoemission Spectra
Photoemission spectra induced by synchrotron radiation (UPS) were measured on freshly

cleaved (100) faces of divalent TmTe at 50 to 110 eV and on surfaces exposed to
0.5 x 10- 6 Torr· s o f 0 2 with 70 and 110 eV photons. Fig. 115 shows the valence band spectra
at 50 and 110 eV of the clean and at 70 eV of the exposed surface as well as the Te 4d spectrum
of a freshly cleaved surface. The spectra of the freshly cleaved surface are characterized by
only weak 4f11 final state multiplet lines (Tm3+ ), probably due to contaminations. The
complicated structure of the 4f 12 features (Tm 2 + ) indicates the presence of a 4f12 multiplet
shifted by surface effects. The energies of the 4f 12 (Tm 2 +) and 4f11 (Tm 3 + ) final state multiplets
used for the fits are derived from opticalliterature data (for Tm3+ ) and estimated (from Er3 + ),
respectively, Kaindl et al. [3]; see also [4] . The UPS measured earlier by Suryanarayanan et
al. [1] with 10 to 90 eV showed the existence of small amounts of Tm3+ with a Tm 3 + :Tm2 +
ratio < 0.06 on freshly cleaved (100) surfaces, which increase with the time (indicating a
surface oxidation). The assumption of an intermediate valence state by Campagna et al. [13,
14] ; seealso [15] , to explain this XPS could not be confirmed [1 , 3] . The Coulomb correlation
Gmelm Handbook
RE Main Vol. C 10
Tm Te 271
energy separating the 4f 11 and 4f 12 final states is estimated tobe 7.4 eV [13]. The position of
the 4f 12 multiplet reported by [1] is confirmed. The binding energy of the bulk 4f 12 multiplet
energy closest to EF is E6 = - 0.65 eV, confirming Tm Te tobe an integer valent semiconductor.
The binding energy of the uppermost 4f 11 multiplet line is at -7.2 eV. The high Tm3+ :Tm 2 +
ratio of 0.65 observed by [14] is probably due to surface contamination by oxygen (possibly
by Tm 20 2Te) as demonstrated by the spectrum after oxygen exposure; see Fig. 115 (3]. The
XPS of [14] have been simulated with fractional parentage coefficients (FCPs) by Wertheim
[16].
The UPS, presumably of the purest samples, can be resolved into the emission from the
bulk and the emission from the surface layers shifted by the surface core-level shift ~~ = 0.41
± 0.05 eV towards higher binding energies (mean values from spectra at photon energies
50 ;::;; hv ;::;; 110 eV), Fig. 115 [3]. The shift ~~in TmTe is mainly due to differences in the
Madelung energy of surface and bulk. Neglecting the electronic contribution, ~~ = 0.45 eV
has been calculated within a semiempirical model using a surface coordination number of 5,
the NaCL Madelung factors for (100) surface and bulk material, and the measured TmTe bulk
modulus for both surface and bulk, Srocksch et al. [17, 18]. The intensity ratio of the integrated
4f 12 surface to 4f 12 bulk multiplet intensities decreases with increasing photon energies. From
the relative intensities the mean electron-free-path l is derived. Similar as for TmS and TmSe
l increases from 5.8(8) to 9.4(12) A when hv is increased from 50 to 110 eV, respectively. ln
contrast to TmSe no surface-induced core-level shift for the 4d Level of Te could be resolved
[3].
References:

4215/22).
[2] R. Monnier, H. J. F. Jansen, A. J. Freeman (J. Less-Common Metals 111 [1985] 203/6).
[3] G. Kaindl, C. Laubschat, S. Reihl, R. A. Pollak, N. Märtensson, F. Holtzberg, D. E. Eastman
(Phys. Rev. [3] S 26 [1982]1713/27).
[4] G. Kaindl, C. Laubschat, S. Reiht, R. A. Pollak, et al. (Valence lnstab. Proc. Intern. Conf.,
Zürich 1982, pp. 281/5).
[5] A. Jayaraman, E. Sucher, D. S. McWhan (Proc. 8th Rare Earth Res. Conf., Reno, Nev.,
1970, Vol. 1, pp. 333/44).
(Phys. Rev. [3] S 11 [1975]500/13).
[8] H. Soppart, E. Kaldis, P. Wachter (Helv. Phys. Acta 55 [1982] 538/40).
[9] A. Jayaraman, P. D. Dernier, L. D. Longinotti (High Temp.-High Pressures 7 [1975]1/28,
6/7).
[10] S. Satlogg (Phys. Rev. [3] S 23 [1981]650/63, 651/3).
[11] S. Satlogg, E. Kaldis, P. Wachter (J. Phys. Colloq. (Paris]40 [1979] C5-370/C5-371).
[12] S. Satlogg, P. Wachter (J. Phys. Colloq. [Paris]41 (1980] C5-50/C5-63).
[13] M. Campagna, E. Sucher, G. K. Wertheim, D. N. E. Suchanan, L. D. Longinotti (Phys. Rev.
Letters 32 [1974] 885/9).
[14] M. Campagna, E. Sucher, G. K. Wertheim, L. D. Longinotti (Proc. 11th Rare Earth Res.
Conf., Traverse City, Mich., 1974, pp. 53/62).
[15] M. Campagna, G. K. Wertheim, E. Sucher (AlP [Am. lnst. Phys.] Conf. Proc. No. 24 [1975]
22/6).
Gmelin Handbook
RE Main Vol. C10
[16] G. K. Wertheim (Chem. Phys. Letters 72 [1980]518/21).

[17] H. J. Brocksch, D. Tomanek, K. H. Bennemann (Phys. Rev. [3] 8 27 [1983] 7313/7).
[18] H. J. Brocksch, 0. Tomanek, K. H. Bennemann (Valence lnstab. Proc. Intern. Conf., Zürich
1982, pp. 291/4) .
30.1.2.1 0.14.2.1 0.2 Electrical Conductivity
At Ambient Pressure
The electrical resistivity of TmTe is sample dependent. The following room temperature
resistivities are reported for single crystals (samples characterized by the Lattice constants) :
a in A. 6.308 6.29 6.32 6.34 6.351 6.359 6.361 6.364
Q in Q·cm . 0.77 2.3 0.10 0.5 to 1 18 2 ± 0.4 46 10 to 50

Ref. . [1]*l [2] [2] [3] [4] [6] [4] [5]
•l Analytical composition Tm0 _94Te.
A smooth increase of both the resistivity and the Lattice parameter along the ingot axis in a
single crystal sample grown by directional freezing was observed by Köbler et al. [4].
Fig. 116 shows the temperature dependence of the d.c. resistivity normalized to Q at 300 K
for the samples with a = 6.29 and 6.32 A (see above) from Clayman et al. [2] (see also Ward
et al. [7, 8]) compared with the results for a sample w ith a = 6.364 A Üboo = 59.7 Q · cm) from
Sucher et al. [5]. The activation energies EA = 300, 160, and 30 meV were obtained for the
high-temperature region of these samples with a = 6.364, 6.29, and 6.32 A, respectively,
assuming Q proportional to exp (EA/2kT) for intrinsic semiconductors [2]. At Lower temperatures
Ln Q is notaLinear function of 1/T [2, 5] . The expression for intrinsic semiconductors is omitted
l 05
1.!
·\
...4 1 I
V I
I
o1 03 ~~-32A
I
\
- oz
[2]
0
M I \6364A lSJ
a.
....
I
I \'
a.
l
I \
\ \ .\
\
0
0
•\..__.::
\~
\
100
',
'--t::-Ä
200 300
'\
"
Temperature in K
Fig . 116. Electrical resistivity normalized to Q at 300 K versus temperature for three TmTe
samples, characterized by the Lattice constants from Clayman et al. [2) and Sucher et al. [5].
Gm elln Handbook
RE Ma m Vol. C 10
Tm Te 273
' '··. ..
3.2
E
~ -
3
~ 3.0
.
~ ...
·- .. .
E
V
Q.
c: 2 2.80 Q4 QS \2 -
.~
a. ....... ..
• • •• • • • Tempereture in K
1 . ..
100 200 300
Temperature in K
Fig. 117. Electrical resistivity Q of Tm 094Te between 0.025 and 300 K. The inset shows the
temperature range below 1 K with expanded scale.
by Sucher et al. [5] and for Tm(Te, Se) (see p. 343) by Satlogg [9], because of the apparent
pinning of the Fermi Level EF by trap Levels in semiconducting chalcogenides. Using Q oc
exp(EA/kT), EA = 200 meV is obtained by Sucher et al. [5]; seealso p. 269. ln contrast to this
Large variation of Q with temperature, Ott, Hulliger [1] observe in Tm 0_94Te only a moderate
increase from 0.77 n. cm at room temperature to 3.2 n. cm at the magnetic ordering tempera-
ture (0.235 K) with almost no further changedown to ~ 20 mK, Fig. 117. The differences in the
behavior of the various samples have tentatively been attributed to differing Low concentra-
tions of ionized impurities [2]. lmpurities, nonstoichiometry, and the possibility of noninteger
valency are discussed by Sucher et al. (5]. However, noninteger valency of Tm in TmTe has
been shown tobe improbable; see p. 257.
Pressure Dependence
The electrical resistivity ( ~ 0.75 n · cm at ambient pressure) decreases Linearlyon a Loga-
rithmic scale with increasing pressure up to ~ 20 kbar; at 35 kbar saturation is reached at
Q ~ 25 x 10- 5 n · cm; for a figure see the paper, Jayaraman et al. [3]. Above 10 kbar Satlogg,
Wachter [10] state a reduced (by a factor of 2 at ~ 20 kbar) d(Log Q)/dp. See p. 269 for the
derived pressure coefficients of the energy gap parameter.
References:
[1] H. R. Ott, F. Hulliger (Z. Physik S 49 [1983] 323/30) .
[2] S. P. Clayman, R. W.Ward, J . P.Tidman (Phys. Rev. [3] S 16 [1977]3734/41) .
[3] A. Jayaraman, E. Sucher, D. S. McWhan (Proc. 8th Rare Earth Res. Conf., Reno , Nev.,
1970, Vol.1, pp. 333/44) .
[4] U. Köbler, K. Fischer, K. Sickmann, H. Lustfeld (J. Magn. Magn. Mater. 24 [1981] 34/42) .
[5] E. Sucher, K. Andres, F. J. di Salvo, J. P. Maita, A . C. Gossard, A . S. Cooper, G. W. Hull
(Phys. Rev. [3] S 11 [1975] 500/13) .
[6] K. G. Sarraclough (J. Cryst. Growth 41 [1977] 321/4).
Gmelm Handbook 18
RE Main Vol. C 10
[7] R. W. Ward, 8. P. Clayman, T. M. Rice (Solid State Commun. 17 [1975]1297/300).

[8] R. W. Ward, 8. P. Clayman, T. M. Rice (Proc. 14th Intern. Conf. Low Temp. Phys., Otanimi,
Finland, 1975, Vol. 3, pp. 480/3; C.A. 85 [1976] No. 54172).
[9] 8. 8atlogg (Phys. Rev. [3] 8 23 [1981] 650/63, 651/3).
[10] 8. 8atlogg, P. Wachter (J. Phys. Colloq. [Paris]41 [1980] C5-59/C5-63).
30.1.2.1 0.14.2.11 Optical Properties
Color
For ambient condition the following colors of the various TmTe samples are reported:
black [1], shiny black [2], gray-black [3], gray [4], silvery [5], bluish gray [6], and silver-blue
[7, 8]. Thin films Look black, gray, or blue in reflection, and in transmission they appear
greenish yellow, orange-brown, or red, respectively [1]. Oxidized films are bluish in reflec-
tion [1].
Raman Spectrum
The spectrum at 10 K induced by < 10 mW Laser power shows a nonassigned peak at
~ 160 cm- 1 (read from a figure in the paper). A stronger peak at 126 cm- 1 obtained with
~ 20 mW Laser power is attributed to Te clusters or Te0 2 at the sample surface, Mörke,
Wachter [9].
Reflection and Absorption Spectra

General
While the far infrared reflectivity has been related to the lattice Vibrations, the absorption
and reflection spectra in the range 0.2 eV ~ hv ~ 2.5 eV are usually assigned to transitions
from the 4f13 eF712 ) ground state of divalent Tm to 4f125d-derived excited states, according to
the energy Level scheme shown in Fig. 114, p. 269. The region beyond 2.5 eV contains valence-
to-conduction band transitions and transitions of the type 4f13-4f12(3H6)6s. The 5d band is split
by the crystal field into the lower lying t29 and the e9 subbands.
The main bands below ~ 2.5 eV are assigned as follows:
E1: 4t 13 eF712 ) ..... 4t 12 eH 6 )5d(~9 )
E2: 4f13eFm) ..... 4f 12 eH4)5d(~9 )
E3: 4f 13 eF712 ) ..... 4t12 eH 6)5d(e 9)
E4: 4f 13 (2F712 ) -+ 4f12 eF 4)6d(t29)
E5 : 4f13 eF712 ) ..... 4f12 eH 4)5d(e 9)
Additional tentative assignments are implicitly given in Fig. 114, p. 269, Suryanarayanan et
al. [1]. The onset of valence-to-conduction band transitions is observed near 3 eV, 8atlogg et
al. [10].
Bands Below 0.5 eV

The farinfrared reflectivity of TmTe single crystals measured between 5 and 300 cm- 1 at
temperatures between 1.3 and 300 K is rather low and slightly sample-dependent, Clayman
et al. [3], Ward et al. [11]. Aside from a temperature-invariant strong reststrahlen peak at
~ 120 cm- 1 two new features at ~ 173 and ~ 209 cm- 1 appear in the spectrum as the sample
Gmelin Handbock
RE Main Vol. C10
Tm Te 275
~
c
~ 10~--~----~~~----~--~
-300K
- ·-20K
----511-
2 4
Photon energy in eV Photon energy in eV
Fig. 118. Reflectance R of air-cleaved Fig. 119. Optical density of TmTe films
(dotted Line and dashed Line) at 5, 20, and 300 K versus photon
and vacuum-cleaved (solid Line) energy characterized by the lattice
Tm Te single crystals at 293 K constants : 1) a = 6.30 ± 0.005 A;
versus photon energy. 2) a = 6.31 ± 0.005 A;
3) a = 6.335 ± 0.004 A.
with a = 6.29 A, is heated from 1.3 to 2.5 K ;both persist to room temperature . The spectrum
at 4.2 K of a sample with a = 6.32 A is qualitatively similar but with an additional peak at
238 cm - 1 . The temperature dependence, however, of the reflectivity of this sample is different;
the structure between 160 and 260 cm - 1 does not change on cooling to 1.3 K, but changes
significantly on heating to room temperature. The extra features were tentatively attributed
to interconfiguration fluctuations or nonstoichiometry [3]. For the interpretation of these results
in terms of lattice vibrations, see p. 258. The reflectivity measurements between 0.03 and
12 eV by Batlogg et al. [10] on a polished single crystal (a = 6.353 A, stoichiometric within
0.5%) confirm the results of Ward et al. [11] for both the structure and magnitude of the
reflectivity in the overlapping range ( ~ 240 to 300 cm- 1) [10].
Bands Between 0.5 and 20 eV
The reflectance at room temperature has been measured between 0.05 and 20eV on air-
cleaved and vacuum-cleaved single crystals with a = 6.340 A; see Flg. 118. The absorption
spectra of Tm Te films (quartz or CaF 2 substrates, thickness 450 to 500 nm) with a = 6.30, 6.31,
and 6.335 A in the range 0.20 to 4.5 eV is shown in Fig. 119. The following maxima in eV,
± 0.03 eV, were observed (F = film, cryst. = single crystal):
sample a in A Tin K E1 E2 E3 E4 Es
F 6.335 300 0.75 1.37 1.80

F 6.335 5 0.70 1.40 1.75 2.25 2.45
F 6.30 300 0.73 1.79
F 6.30 20 0.66 1.40 1.67 2.19 2.38
cryst. 6.31 300 0.70 1.30 1.75 2.22 2.48
The crystal field splitting 10 Dq :::; 1.1 eV is obtained from these energies [1] .
Gmelin Handbock 18"
RE Main Vol. C 10
The absorption coefficientofthe (nearly) stoichiometricfilm at E1 = 0.7 eV is ~ 2 x 104 cm- 1

neglecting reflection loss. The absorption coefficient increases below ~ 200 K and a sizable
red-shift can also be recognized. The absorption coefficient for the single crystal (for a figure
see the paper) has been calculated by the Kramers-Kronig relation from the reflectivity, shown
in Fig. 118, p. 275, Suryanarayanan et al. [1]. A similar reflection spectrum is given by Batlogg
et al. [10] measured at 300 K between hv = 0.03 and 12 eV on a sample with a = 6.353 A
(stoichiometric within 0.5%, prepared and handled und er complete exclusion of oxygen); for
a figure see the paper [10]. No structure indicating Tm3+ ions is observed in the spectra of
the vacuum-cleaved crystals. The exposure to air increases the reflectivity below about hv =
6 eV and decreases it at higher photon energies; the peaks at 2.5, 6, and 8 eV disappear,
while the peak at ~ 3.3 eV is enhanced. For hv < 7 eV the main effect of exposure to air
seems tobe a slight shift of the absorption to lower energies [1].
MagnetoopticaL Properlies
A theory of magnetoelastic coupling is applied to Tm Te, including only strain contributions

to the first-order magnetoelastic interaction. The resulting Faraday rotation and Cotton-Mouton
phase shift ö at T = 5 K as a function of the magnetic field are shown in a figure in the paper.
At higher temperatures the Faraday rotation angle will decrease rapidly, Thalmeier, Fulde
[12].
References:
[1] R. Suryanarayanan, G. Güntherodt, J. L. Freeouf, F. Holtzberg (Phys. Rev. [3] 8 12 [1975]
4215/22).
[2] E. Kaldis, 8. Fritzler (J. Phys. Colloq. [Paris]41 [1980] C5-135/C5-142).
[3] 8. P. Clayman, R. W. Ward, J. P. Tidman (Phys. Rev. [3] 816 [1977]3734/41).
[4] E. Kaldis, 8. Fritzler, E. Jilek, A. Wisard (J. Phys. Colloq. [Paris] 40 [1979] C5-366/
C5-369).
Conf., Reno, Nev., 1970, pp. 74/89).
[6] H. R. Ott, F. Hulliger (Z. Physik 8 49 [1983] 323/30).
(Phys. Rev. [3] B 11 [1975] 500/13).
[8] K. G. Barraclough (J. Cryst. Growth 41 [1977] 321/4).
[10] 8. Batlogg, E. Kaldis, A. Schlegel, P. Wachter (Phys. Letters A 56 [1976]122/4).
[11] R. W. Ward, 8. P. Clayman, T. M. Rice (Solid State Commun. 17 [1975]1297/300; Proc.
14th Intern. Conf. Low Temp. Phys., Otanimi, Finland, 1975, Vol. 3, pp. 480/3).
[12] P. Thalmeier, P. Fulde (Z. Physik 8 29 [1978]299/305).
30.1.2.10.14.3 TmTe-MTe Systems (M = Y, La, Gd)

The TmTe-YTe System
Semiconducting TmTe and metallic YTe form a complete series of solid solutions with
cubic NaCl structure, as shown by measurements of the lattice constants and the electrical
resistivity. The samples were prepared by reaction of the elements at 800°C for 4 h in Ar
Gmelm Handbook
RE Mam Vol C 10
TmTe-MTe Systems 277
6A a) b)
o<
s
6.3
6.2
""' ~ ' E
V
c: 10 -2\'-..
--
d '-...... .!:
6.1
~ a.
,-,I
I'--
10
rE
Q2 Q4 Q6 0.8 1.0 Q2 OA Q6 0.8 1.0
x in Tm,..l"Te
Fig. 120. Lattice constant a (Fig. 120a) and electrical resistivity Q at room temperature
(Fig. 120b) of Tm 1 _xYxTe mixed crystals as a function of x.
atmosphere in a sealed tungsten crucible. The reaction products were then heated (above
their melting points) to 2000°C and cooled down after ~ 30 min to ~ 1600°C at a rate of 10 K/h,
then at 30 K/h to 1 000°C; at this temperature the furnace was switched off. The crystals thus
formed (up to 8 mm long) cleaved along { 100} faces. Analytical compositions agree within
± 1% with the initial composition. The surfaces of the TmTe-rich samples were silver-blue
and those of the YTe-rich samples red-purple in dry air. The color of Tm 1 _ xYxTe mixed crystals
with x > 0.3 turned to a matt gray in ambient air. The YTe-rich mixed crystals contained small
amounts of needle-like impurities, as shown by metallographic examination of polished single
crystal surfaces. The lattice constants decrease smoothly from a = 6.359 A for Tm Te to 6.097 A
for YTe; see Fig.120a. The electrical d.c. resistivity of Tm 1 _xYxTe mixed crystals decreases
by two orders of magnitude between x = 0 and 0.1, as shown in Fig. 120b, Barraclough [1] .
Metallic behavior for Tm 0 _6Y0 .4Te is indicated by the positive temperature coefficient of the
electrical resistivity between ~ 5 and 20 K, measured at 9.2 GHz by a microwave method (for
a figure see the paper), Huang, Sugawara [2].
(Tm, M)Te Mixed Crystals (M = La, Gd)

The electrical resistivity has been measured on cubic mixed crystals (Tm 0 _6Y0 _4S),
Tm 0 _1 La 0 _9Te and Tm 0 _97Gd 0 _03Te between ~ 5 and 20 K at 9.2 GHz in the microwave range.
lncrease of the resistivity with rising temperature shows the metallic behavior of the samples.
ln cantrast to the corresponding sulfides the curves show no peaks , Huang, Sugawara [2].
The temperature dependence of the Gd3+ ESR spectrum was studied with 9.2 GHz on a
powdered Tm 0 _99 Gd 0m Te sample. Contrarily to Tm 0 _99 Gd 0mSe the width of the Lorentzian-
shaped line decreases drastically from 5 to 40 K. This unexpected temperature dependence
is explained by the presence of the extra electron from Gd3+, localized around Gd but
delocalized at higher temperatures . This extra electron directly influences the exchange
interaction between Gd3+ and its surrounding Tm 2 + , Huang, Sugawara [3].
References:
[1] K. G. Barraclough (J. Cryst. Growth 41 [1977]321/4).
[2] C. Y. Huang, K. Sugawara (J . Phys . Soc. Japan 41 [1976]1803/4) .
[3] C. Y. Huang, K. Sugawara (J. Low Temp . Phys. 28 [1977] 229/39, 233/6) .
Gmelm Handbook
RE Mam Vol. C 10
278 Ytterbium Tellurides
30.1.2.1 0.15 Ytterbium Tellurides

Additional data for YbTe and data on YbTe 2 _x are found in Sections 30.1.2.1 and 30.1.2.5,
on pp. 6 and 47, respectively.
30.1.2.10.15.1 The Vb-Te System

Studies of the Yb-Te phasediagram by thermal, microstructural, and X-ray analyses show
that only one phase, YbTe, exists. (For the possible existence of Yb 2Te 3 and YbTe 2 see p. 287.)
lt melts congruently at 1730 ± 10°C and forms degenerate eutectics with Yb and Te at 820
and 455°C, respectively. Alloys in the part of the system between Yb and YbTe were heated
at 800°C for 200 h, those between YbTe and Te for the same period at 425°C, Abrikosov et al.
[1]. Estimated melting temperature for YbTe: 1720 to 1760°C, Miller, Hirnes [2]. Other results
are obtained by Kaldis, Peteier [3] from DTA measurements of samples sealed in small
tungsten crucibles; YbTe melts at 2200 ± 10°C and exhibits a homogeneity range which
increases at high temperatures (above about 1800°C). Anomalies at 1750 and 960°C
(possibly phase transitions) have not yet been clarified. The preliminary phase diagram is
shown in the paper [3]. A melting point of 2260 K (1987°C) for YbTe was found by Mukhtarova
et al. [4].
References:
[1] N. Kh. Abrikosov, K. A. Zinchenko, A. A. Eliseev (lzv. Akad. Nauk SSSR Neorgan. Materialy
6 [1970]1172; lnorg. Materials [USSR]6 [1970]1021/2).
[1961], pp. 232/40, 236).
[3] E. Kaldis, W. Peteier (J. Cryst. Growth 52 [1981]125/30).
[4] Z. M. Mukhtarova, T. Kh. Kurbanov, 0. M. Aliev (Zh. Neorgan. Khim. 30 [1985] 1332/4;
Russ. J. lnorg. Chem. 30 [1985] 759/60).
30.1.2.10.15.2 YbTe
Preparation
For the preparation of YbTe seealso pp. 6 and 286. Thin films were prepared by coevapora-
tion of Yb and Te under vacuum on heated substrates of Pyrex, glass, or freshly cleaved CaF 2
or NaCL, Suryanarayanan et al. [1 to 3]. For the evaporation of Yb and Te, Knudsen type
crucibles made of Ta or graphite are used. The substrates were held at a constant temperature
between 400 and 500°C. The films on CaF 2 show epitaxy, Paparoditis, Suryanarayanan [4].
The YbTe films Look purple [1, 4] or pale blue in transmission [2]. Thermalevaporation of
YbTe in vacuum and substrates of glass, quartz, or KBr are used by Lashkarev et al. [5] to
prepare films of 0.3 to 0.12 11m thickness.
Crystallographic and Mechanical Properties

YbTe has the cubic Na CL structure. Lattice constants a in A (see also p. 9): 6.366, Abrikosov
et al. [6]; 6.361, Chatterjee et al. [7], Jayaraman et al. [8]; 6.359(2), Francillon et al. [9];
6.350(3) A for a thin film of YbTe on Na CL substrate [3]; 6.360(3) for a film on CaF2 substrate
[2].
Gmelm Handbook
RE Mam Vol. C 10
YbTe 279
- 0.400~-.I...----:-~-.1...-----=~-...L...-----:~____J
100 200 300
pinkbar
Fig. 121. Pressure-volume diagram of YbTe.
According to Kaldis, Peteier [10] YbTe exhibits a homogeneity range around 50 at % Te

with lattice constants varying from 6.357 A for YbTe equilibrated with Yb to 6.351 A for a Te-
rich sample [10]. A homogeneity range up to 52 at % Te is reported by Abrikosov et al. [21].
The lattice constant of YbTe at about 180 kbar (after electronic collapse) is 5.73 A [8]. The
molar volume of YbTe is 38.75 cm 3 , Jayaraman et al. [1 2].
The pressure-volume relationship (see Fig. 121) has been derived from high-pressure
X-ray diffraction data up to 300 kbar. The anomaly in the 150 to 200 kbar region (volume
change - 8% ) is attributed to a continuous Yb2 + -+ Yb3 + valence change (4f-5d electronic
collapse), but the NaCl-type structure remains unchanged in the entire pressure range,
Chatterjee et al. [7, 11]; see also Jayaraman et al. [8, 12, 13], Singh et al. [14] . The initial
compressibility estimated from the low-pressure range is 2 x 10- 3 kbar - 1. By comparison of
the high-pressure compressibilities with the data calculated from the ionic radii an intermedi-
ate valence of 2.8 is obtained for Yb [7]. Forareview of the pressure-induced valence transition
in rare earth monochalcogenides see Jayaraman et al. [15], Jayaraman [16, 17]. The calculated
bulk modulus for YbTe is 46 ± 5 GPa ( ~ 460 ± 50 kbar) [12] , [15, p. 2]. From the pressure
dependence of the lowest-lying 4f-5d absorption band in YbTe films (see p. 281) the gap
collapse is predicted at pressures on the order of 175 kbar, Narayanamurti et al. [18] .
YbTe (with a = 6.361 Ä) is diamagnetic. For YbTe prepared at relatively low temperatures
x
(14 hat 550°C; a = 6.366 Ä) the magnetic susceptibility = 290 x 10- 6 cm 3/mol was found ,
landelli, Palenzona [19]; x = 448 x 10- 6 cm 3/mol was reported by Bruzzone et al. [20]. The
diamagnetism of YbTe was derived from magneto-optical measurements on thin films (see
p. 283) [2, 4].
YbTe is a semiconductor with p-type conductivity. The temperature dependence of the

electrical conductivity K and the thermoelectric power S between 300 and 1300 K for
stoichiometric YbTe and cation deficient Yb 1 _xTe ( 51.5 at % Te) is shown in Fig.122, p. 280,
from Abrikosov et al. [21]. The curve K = f(T) for YbTe is also shown by [6]; the activation
energy is obtained as 0.95 eV [6, 8]. Values for the electrical resistivity Q and thermoelectric
Gmelin Handbook
RE Maon Vol. C 10
Temperature in K
Temperature in K
400 333 1000 667 500 500 333
1000 667 500
10 Q)_ 800 b) 40
I
~~ YbT•
'eu :.::600
~~
~~ ~~ >::1.400 ~ -;,.-- 0 ...... I
'c: .....::!..,b·-.T• - 1
/-
1()"1 -"
v.,..;.-
""'
.f; ~
.... _ I ~
.~
"' 10-2 ~ 200
3 Yb~· / 2.5 3.0 3S

0
1.0 1.5 2.0 2.5 3.0 35 1.0 1.5 2.0
1000/Tin K-1 1000/T in K-1
Fig. 122. T<c:-.-.perature dependence of the electrical conductivity K (Fig. 122a) and
thermoelectric power S (Fig. 122b) of YbTe and an Yb-deficient sample (see text).
power S at room temperature : Q = 350 Q · cm, S = + 580 J.lV/K [6]; Q = 340 Q · cm, Miller,
Hirnes [22]; Q ~ 104 Q · cm, Francillon et al. [9]; Q = 980 Q · cm , S = + 820 !!V/K, Hall
coefficient RH = + 2600 cm 3/C, Hall mobility I! ~ 1 cm 2 · v- 1 · s - ', carrier concentration
n = 2.5 x 1016 cm - 3 , Miller et al. [23].
Below room temperature (T = 300 to 77 K) the electrical resistivity was measured at
atmospheric pressure (p 0) and up to 16 kbar pressure, and the relation Log R/R 0 is plotted vs.
1/T and pressure p, where R0 is the resistivity at 296 K and ambient pressure. With decreasing
temperature the resistivity increases sharply. The curve Log R/R 0 vs. 1/T is Linear between
300 and ~ 140 K; the activation energy EA = 0.46 eV. With increasing pressure Log R/ R0
decreases by a factor of 2 between 1 and 16 kbar; EA decreases linearly from 0.43 eV at 4 kbar
to 0.33 eV at 12 kbar. The low activation energy can probably be assigned to the Iransport of
holes in the valence band [9] . For the photoconductivity, see p. 281 .
Electronic Structure and Optical Properlies

General
An energy band structure scheme of YbTe does not exist, but the schemes proposed for
other rare earth monochalcogenides with the NaCL structure Like SmS or EuS (see " Rare Earth
Elements" C7, 1983, pp. 252 and 459, respectively) are often used. Accordingly, the valence
band is derived predominantly from the 5p states of Te and the conduction band from the 5d
and 6s states of Yb. The cubic crystal field splits the 5d states into lower 129 (triplet) and higher
e 9 (double!) states. The spin-orbit splitting of these 5d states results in 2F712 and 2F512 . The 41
states are within the forbidden zone. The bands in the optical spectra are usually assigned
to transitions from the 4f 14 ('S0 ) ground state of Yb2 + to the 5d states. The character of the
conduction band minimum is not yet clear. Usually the energy gap E9 is attributed to 4f-5d
transitions (see for example Suryanarayanan et al. [1, 2], Chatterjee et al. [11]) but according
to Francillon et al. [9] the conduction band minimum is formed by 6s states. For schematic
energy band diagrams see [9], Güntherodt [25], Lashkarev et al. [26], Abrikosov et al. [21 ] .
For calculations of the energies of Low-Lying 4f-5d excitations of Yb monochalcogenides by
use of the Ligand field theory or by a one-electron band approximation see Anisimov et al.
[27] . A simple ionic model for the electronic structure of MX with M = Sm , Eu, Yb and X =
S, Se, Te with a spherical symmetry component of the Hartree-Fock potential is proposed by
Gmelm Handbook
RE Maon Vol. C 10
YbTe 281
Dagys, Anisimov [28]. For comparison of the Pauling values for the single bond electro-
negativity differences with values obtained from mass spectrometry with a spark ion source
see Muheim [29].
Measurement of the photoconductivity of YbTe single crystal films indicate that the optical
transition 4f14 --+ 4f135d(t29 ) responsible for the long wavelength absorption peak at ,...., 2.05 eV
results in a conductive process. The photoconductive onset occurs at ,...., 1.7 eV and the
activation energy is 1.85 eV from the wavelength at half-maximum photoresponse. The re-
sponse time is ,...., 700 J.I.S. The photoresponse is linear up to light intensities of 10 mW/cm 2,
Hurych et al. [30]. lt is believed by Chatterjee et al. [11] that the low energy gap of 0.46 eV
below the conduction band, derived from resistivity measurements by [9], is associated with
an impurity rather than with the 4f Level. An energy gap of E9 ~ 2 eV is in accordance with
optical measurements [2, 11] (see below). E9 = 1.8 eV is reported by Güntherodt [25].
Reflection and Absorption Spectra
The optical absorption (and magnetic circular dichroism, see p. 282) of a YbTe film was
measured at 10 and 300 K between 1.85 and 6 eV. At 300 Kinaddition to absorption bands
centered around 2 and 3 eV shoulders or steps on a continuously rising background up to
6 eV are observed. The spectrum at 10 K is better resolved with the following locations of the
bandEn with increasing photon energy in eV:
E, E3 Es Es Ea
1.97; 2.09 3.28; 3.38 4.08 4.24 4.73
By considering Literature values from free ion spectra for the crystal field splitting 10 Dq
(t29 -e 9) and the Spin Orbit Splitting eF 512-2F712 ) the bands are assigned as follows:
E1 4f14CS0 ) --+ 4f13 eF712) 5d(~ 9 )

E2 4f14CS0 ) --+ 4f13 eF712 ) 5d(e 9)
E3 4f14 CSo) --+ 4f13 eFst2l 5d(~ 9 )
Es 4f14CS0 ) --+ 4f13 eF512 ) 5d(e 9)
Transition E1 corresponds to the energy gap E9. The best fit between the observed data and
the theoretical predictions is obtained for 10 Dq ~ 1 eV. lf all the terms in the Hamiltonian
(see the paper) are considered, 18 transitions are allowed. The absorption edge around
4eV is likely to be associated with transitions between the conduction and valence bands,
Suryanarayanan et al. [2]; for the spectrum seealso the earlier papers of Suryanarayanan et
al. [1, 3], Paparoditis, Suryanarayanan [4]. The absorption edge at ,...., 2 eV, assigned to the
energy gap, is also observed in the absorption spectrum of a YbTe film on CaF 2 substrate by
Wong, Wood [24]. Absorption bands at 1.24 eV (1 1.1.m) and 2 eV (0.6 J.l.m) were found between
0.4 and 1.4 1.1.m for polycrystalline YbTe at 77 K. They are assigned to 4f --+ 5d transitions [9].
Absorption bands at 1.1, 1.45, 2.25, and 2.9 eV and a band at 0.95 eV in the diffuse reflection
spectrum of YbTe films were reported by Abrikosov et al. [21], Lashkarev et al. [26]. The band
at 1.1 eV is assigned to a transition from the p valence band to a 4f13 state of Yb3+ (due to
deviations from stoichiometry). The bands at 2.25 and 2.9 eV are assigned to transitions from
the 4f14 Level to the 5d(t29 ) and 5d(e 9) states, respectively. The origin of the band at 1.45 eV is
not yet clear [21, 26]. The spin-orbit Splittings .1(t29) = 0.7 eV and L\(e 9) = 1.2 eV are derived
from these spectra by Lashkarev et al. [5]. The absorption coefficient cx ofthin films of YbTe
(and YbS, YbSe) on NaCL substrates in the region of the absorption band due to the lowest
Gmelon Handbook
RE Maon Vol. C10
Photon energy in fN
121.24 155 2.06
e
..g
7 8~-----#~-+~~~~-1
u
.!:
08 0.6 04
X in 1-1m
Fig. 123. Absorption coefficient a. for films of YbS, YbSe, and YbTe near the absorption edge.
4f-+ 5d transition (at ~ 2 eV) is shown in Fig. 123. The absorption edge at a. ~ 5 x 104 cm- 1
is shifted towards smaller values with increasing pressure (up to 6 kbar) by - 11 .2 meV/kbar
( ~ 1.9 eV at atmospheric pressure), Narayanamurti et al. [18].
Raman Spectra and Photoluminescence
First-order Raman spectra should be symmetry-forbidden because of the cubic NaCL

structure , but inelastic multiphonon scattering is observed at low temperatures and an excita-
tion energy larger than the energy gap. A figure in the paper shows the spectrum of YbTe
(single crystal) at 4.2 K for the range from ~ 250 to 700 cm- 1 excited by Laser light with /... =
633.9 nm ( ~ 1.96 eV). The scattering intensity decreases strongly with increasing temperature
as for the other chalcogenides of Yb (and Eu) and depends strongly on the excitation energy;
for a figure see the paper. The first multiphonon line is attributed to the zone-center LO phonon
mode (ro(LO) = 141 cm - 1). The zone center scattering occurs only at the bottom of the
conduction band (slightly higher energy than the absorption edge at ~ 1.8 eV). Between - 2.3
and 2.8 eV a broad-line scattering is observed, resulting from zone-boundary phonons (first
line at m0 = 128 cm - 1) . The scattering due to zone center phonon modes is polarized parallel
to the incident polarization and the broad line scattering perpendicular. The latter is practically
temperature independent between 4.2 and 300 K. The data suggest that the multiphonon lines
result from recombination during time-resolved relaxation of the excited hot electron. The
scattering is therefore interpreted as a two-step process of absorption followed by emission
(hot luminescence) as for YbSe (see " Rare Earth Elements" C9, 1986, pp . 404/5). The
photoluminescence exhibits a maximum in the quantum yield at excitation energies slightly
above the energy gap. A figure in the paper shows the spectra for excitation energies of
1.97 and 2.02 eV (maximum emission at ~ 1.6 eV), Vitins [31, 32]; see also Vitins, Wachter
[33, 34] .
Additional Optical Properlies
Fig. 124 shows the refractive index of a YbTe film at room temperature, derived from
Iransmission and reflection spectra up to 3.5 eV; a curve for the absorption coefficient is given
in the paper, Suryanarayanan, Paparoditis [3]. The magnetic circular dichroism (MCD) was
Gme!in Handbook
RE Mam Val C 10
YbTe 283
l5 ~\
;\ ) \
c 3.0
2.5
- V \~
;r
2.0
0.5 1.0 1.5 2.0 2.5 3.0
Photon energy in eV
Fig . 124. Refractive index n of a YbTe film at room temperature as a function of the photon
energy.
measured at 10 and 300 K on a YbTe film (CaF 2 substrate) between 1.85 and 3 eV in a magnetic
field of 37.5 kOe; for a figure see the paper. The diamagnetism of YbTe could be identified
and the spectroscopic splitting factor of the lowest excited state could be estimated (cf. p.281 ),
Suryanarayanan et al. [2] .
The X-ray photoemission spectrum of the 4f and valence band region of YbTe is shown in
a figure down to ~ - 8 eV, referred to the Fermi energy in Campagna et al. [35]. The relative
intensities of the 4f 7/2 and 5/2 multiplets at ~ - 0.5 and ~ -2 eV (read from the figure) are
equal to within 5% of the theoretical value; the peak near -4 eV due to valence band states
is visible only after tenfold magnification.
Chemical Reactions
YbTe is unstable in moist air according to Senff, Klemm [36], Wong, Wood [24], but
stoichiometric YbTe films are assumed tobe quite stable in air [2] . On heating in vacuum YbTe
evaporates incongruently. The high temperature evaporation of YbTe has been investigated by
thermogravimetry and mass spectrometry at 1 000 to 1900°C, the surface morphology du ring
evaporation was studied by scanning electron microscopy, and the composition by chemical
and X-ray analyses. The results of weight-loss measurements of YbTe as a function of tem-
perature under conditions of free (Langmuir) evaporation (1 000 to 1400°C) and equilibrium (Knud-
sen) evaporation (1300 to 1900°C) are shown in Fig. 125, p. 284. ln the figure log(m/t ·1/AW) · T 112
vs . 1/T is plotted, where m/t is the weight loss per unit of time, W the clausing factor of the
orifice area A, and T the absolute temperature. The curve for the equilibrium evaporation
shows a break at T ~ 1750°C; above this temperature the evaporationrate increases strongly.
The free evaporation rate is 30 times smaller than that of the equilibrium evaporation. The
morphological studies reveal the formation of !arge agglomerates (diameter ~ 5 J.lm) of a Yb-
rich phase on the surface, which hinder the evaporation. The segregation at the surface
diminishes strongly if an oil-free vacuum of ~ 10- 8 Torr is used instead of an oil pump
vacuum of 10- 6 Torr. Evaporation of stoichiometric single crystals at 10- 4 Torr results in an
appreciable decrease (of a few percent) of the Yb content in the bulk of the crystals, Kaldis,
Peteier [10, 37, 38].
Gmelin Handbook
RE Ma1n Vol. C 10
- 2 0.0005 0.0006 0.0007

1/T in K- 1
Fig. 125. Weight Loss of YbTe as a function of temperature under equilibrium (Knudsen) and
free evaporation (Langmuir) conditions (see text).
References:
[1] R. Suryanarayanan, C. Paparoditis, J. Ferre, B. Briat (Solid State Commun. 8 [1970]

1853/5).
[2] R. Suryanarayanan, J. Ferre, B. Briat (Phys. Rev. [3] B 9 [1974] 554/7).
[3] R. Suryanarayanan, C. Paparoditis (Colloq. Intern. Centre Natl. Rech . Sei. [Paris] No. 180
[1969/70]149/55).
[4] C. Paparoditis, R. Suryanarayanan (J. Cryst. Growth 13/14 [1972]389/92).
[5] G. V. Lashkarev, L. A. lvanchenko, Yu. B. Paderno, S. V. Drozdova, V. A. Obolonchik
(Redkozem. Metal. Splavi Soedin. Mater. 7th Soveshch., Moscow 1972 [1973], pp. 303/4 ;
C.A. 81 [1974] No. 18806).
[6] N. Kh . Abrikosov, K. A. Zinchenko, A. A. Eliseev (lzv. Akad. Nauk SSSR Neorgan.
Materialy 6 [1970]1172/3; lnorg. Materials [USSR]6 [1970]1021 /2).
[7] A. Chatterjee, A. K. Singh, A. Jayaraman (Phys. Rev. [3] B 6 [1972]2285/91) .
[8] A. Jayaraman, A. K. Singh, A. Chatterjee (Proc. 9th Rare Earth Conf. , Blacksburg, Virginia,
1971, Vol. 1, pp. 360/360i).
[9] M. Francillon, D. Jerome, J. C. Achard, G. Malfait (J. Phys. [Paris] 31 [1970] 709/ 14).
[10] E. Kaldis, W. Peteier (J. Cryst. Growth 52 [1981]125/30) .
[11] A. Chatterjee, A. K. Singh, A. Jayaraman, E. Sucher (Phys. Rev. Letters 27 [1971]
1571/3).
[12] A. Jayaraman, A. K. Singh , A. Chatterjee, S. Usha Devi (Phys. Rev. [3] B 9 [1974]
2513/20) .
[13] A. Jayaraman (Indian J. Pure Appl. Phys. 9 [1971]983/5) .
[14] A. K. Singh, A. Jayaraman, A. Chatterjee (Solid State Commun. 9 [1971]1459/62) .
[15] A. Jayaraman, P. D. Dernier, L. D. Longinotti (High Temp.-High Pressures 7 [1975]1/28).
[16] A. Jayaraman (in: K. A. Gschneidner Jr., LeRoy Eyring, Handbock on the Physics and
Chemistry of Rare Earths, Vol. 2, North-Holland, Amsterdam 1979, pp. 575/611) .
Gmelon Handbook
RE Matn Vol. C 10
YbTe-MTe Systems 285
[17] A. Jayaraman (Comments Solid State Phys. S 7 [1977]135/48).

[18] V. Narayanamurti, A. Jayaraman, E. Sucher (Phys. Rev. [3] B 9 [1974] 2521/3).
397/405; C.A. 68 [1968] No. 63803).
[20] G. Bruzzone, A. F. Ruggiero, G. L. Olcese (Atti Accad. Nazl. Lincei Rend. Classe Sei. Fis.
Mat. Nat. [8] 36 [1964] 66/9).
[21] N. Kh. Abrikosov, S. V. Drozdova, K. A. Zinchenko, etal. (Khim. Svyaz Poluprov. Polurnetal
1972 269/76; C.A. 79 [1973] No. 109669).
[1961], pp. 232/40).
Springs, Colo., 1961 [1962], pp. 233/48; N.S.A. 16 [1962] No. 32068).
[24] C. C. Wong, C. Wood (Phys. Letters A 34 [1971]125/6).
[25] G. Güntherodt (Advan. Solid State Phys. 16 [1976]95/116, 97).
[26] G. V. Lashkarev, L. A. lvanchenko, Yu. S. Paderno (Phys. Status Solidi S 49 [1972]
K61/K65).
[27] F. G. Anisimov, R. Dagys, A. Sargautis (Lietuvos Fiz. Rinkinys 19 [1979] 337/44; Soviet
Phys.-Collection 19 No. 3 [1979]22/8; Intern. J. Quantum. Chem. 24 [1983]429/33).
[28] R. S. Dagys, F. G. Anisimov (Fiz. Tverd. Tela [Leningrad] 26 [1984]899/901; Soviet Phys.-
Solid State 26 [1984]547/8).
[29] J. T. Muheim (Proc. 10th Rare Earth Res. Conf., Carefree, Ariz., 1973, Vol. 1, pp. 208/17,
212; C.A. 85 [1976] No. 55409).
[30] Z. Hurych, C. C. Wong, C. Wood (Phys. Letters A 34 [1971]291/2).
[31] J. Vitins (ETH-5846 [1976]1/85; C.A. 88 [1978] No. 128422).

[32] J. Vitins (J. Magn. Magn. Mater. 5 [1977]212/33).
[33] J. Vitins, P. Wachter (Physica B + C 86/88 [1977]213/7).
[34] J. Vitins, P. Wachter (AlP [Am. lnst. Phys.] Conf. Proc. No. 29 [1976] 662/3; C.A. 85 [1976]
No. 53918).
[35] M. Campagna, G. K. Wertheim, E. Sucher (Struct. Bonding [Serlin] 30 [1976] 99/140,
104/9).
[36] H. Senff, W. Klemm (Z. Anorg. Allgem. Chem. 242 [1939] 92/6).
[37] E. Kaldis, W. Peteier (Therm. Anal. Proc. 6th Intern. Conf. Therm. Anal., Bayreuth, Ger.,
1980, pp. 67/73; C.A. 93 [1980] No. 245736).
[38] E. Kaldis, W. Peteier (lzv. Khim. [Sofia]11 [1978]431/58; C.A. 93 [1980] No. 58548).
30.1.2.10.15.3 YbTe-MTe Systems
Metallographie and X-ray studies indicate a continuous series of solid solutions with cubic
NaCl structure between YbTe and Eule and with a linear change of the lattice constants from
6.36 A for YbTe to 6.60 A for Eule.
Measurements of the magnetic susceptibility between 4.2 and 300 K show that the Curie-
Weiss law is obeyed between 100 and 300 K for alt compositions; an antiferromagnetic
ordering is observed only for YbxEu 1 _xTe with x < 0.7 (YbTe is diamagnetic). Values for the
Gmelin Handbock
RE Mam Vol. C10
Neel temperature TN• the paramagnetic Curie temperature ep. and the effective magnetic
moment lle11 :
x in YbxEu 1 _xTe. 0 0.2 0.35 0.36 0.50 0.80

TN in K. 10 to 11 9 7 to 8 6 to 7 4 to 5 <2
®PinK 6 4 -1 -1 +2
llen in lls 7.89 8.13 8.37 8.17 8.29
All samples have a high electrical resistivity ( ~ 105 n · cm). For the sample with x = 0.5 a
carrier concentration of 6 x 1012 cm- 3 is deduced from Hall measurements and a Hall mobility
of 15 cm 2 · v- 1 · s- 1 is obtained from resistivity measurements according to the Van der Pauw
method. The activation energy of the electrical conductivity below room temperature is highest
for solid solutions with x = 0.5 (EA = 0.38 eV), and is 0.2 eV for x = 0 (EuTe) as well as for
x > 0.8. All solid solutions have p-type conductivity; only Eu Te is n-type. The reflection spectra
between 4.2 and 300 K for wavelengths between 1.5 and 4 IJ.m show a very small temperature-
independent structure at 3.51J.m for YbxEu 1 _xTe with x = 0.5 and 0.35 in agreement with the
activation energy (0.35 to 0.38 eV) obtained from the electrical measurements, Ravot et al.
[1]. The X-ray L 111 spectra at 300 K showed no change of the divalent state by addition of Yb
up to x ~ 0.8, Ravot et al. [2]. For theoretical considerations of the properties of mixed systems
containing a ferromagnet (europium chalcogenide) and a diamagnet (ytterbium chalcogenide)
with respect to the ratio J 2/J 1 of the first and second neighbor exchange parameters see
Nowick [3].
For the preparation of solid solutions the desired mixtures of YbTe and Tm Te were heated
in a Ta crucible and homogenized for 2 h at 1000 to 1200°C. The initial monotellurides were
made in a two-section rotating furnace in sealed evacuated quartz ampules at 500°C for 24
to 28 h followed by annealing at 700 to 800°C for 200 h. X-ray powder diffraction shows the
formation of a continuous series of cubic solid solutions with statistical distribution of Yb and
Tm on the cation sites of the NaCl lattice. The lattice constants, which exhibit a positive
deviation from Vegard's law, are as follows:
x in Ybx Tm 1 _x Te 0 0.10 0.20 0.30 0.40 0.50 0.70 0.90 1.0

a in A . . . . . 6.134 6.196 6.174 6.169 6.278 6.272 6.344 6.350 6.366
For additional lattice constants see the paper, Eliseev et al. [4].
References:
[1980] C5-357/C5-359).
[2] D. Ravot, C. Godart, J. C. Achard, P. Lagarde (Valence Fluctuations Solids St. Barbara
lnst. Theor. Phys. Conf., Santa Barbara, Calif., 1981, pp. 423/6).
[3] I. Nowick (Phys. Letters A 29 [1969]718/9).
[4] A. A. Eliseev, F. Rukk, N. Kh. Abrikosov, K. A. Zinchenko, V. M. Zemlyanukhina (Zh.
Neorgan. Khim. 22 [1977]1124/5; Russ. J. lnorg. Chem. 22 [1977]616).
Gmelm Handbock
RE Mam Vol. C10
Yb2Te3 . YbTe2 . The LuTe-TmTe System 287
30.1.2.10.15.4 Yb2Te3 (?). YbTe 2 (?)

During the attempt to prepare Yb0 _5U05Te2 by reaction of the elements at 1570 K in
graphitized quartz ampules, followed by annealing at 1100 K for 400 h, the compound Yb 2Te3
is formed (besides Yb0_5 U0_5Te3 and small amounts of UTe2 and YbTe2 (see p. 47)) . Yb2Te3
crystallizes in the orthorhombic Sc2S3 structure with a = 12.70, b = 8.98, c = 26.93 A,
Slovyanskikh et al. [1]. A thin film of Yb2Te3, prepared like Er2Te3 films (see p. 248), is a
p-type semiconductor. The electrical conductivity is 1.0 to 6.9 n- 1 · cm-1, the charge
carrier concentration (2 to 17) x 1018 cm - 3 , the mobility 0.9 to 4.0 cm 2 · v- 1 · s -1, and the
thermal activation energy 100 to 200 meV. The values change very little alter annealing the
film, Vasil'kovskii et al. [2]. Yb2Te3 doped with Cu is a p-n junction Laser with emission at
9000 A at excitation current 8000 A/cm 2 , Vickery [3]. YbTe2 is probably tetragonal (see p. 49).
Relerences:
[1) V. K. Slovyanskikh, N. T. Kuznetsov, N. V. Gracheva (Zh. Neorgan. Khim. 30 [1985)

1895/6; Russ. J. lnorg. Chem. 30 [1985]1077) .
[2) A. A. Vasil'kovskii, E. T. Sharnopol'skaya, N. Yu . Shitsevalova, S. V. Shchegol'kov (lzv.
595/6).
[3] R. C. Vickery, Semi-Elements lnc. (U.S. 3340108 (1963/67]; C.A. 68 [1968] No. 74014).
30.1.2.1 0.16 Lutetium Tellurides

Data for Lu Te, Lu 2Te3 , LuTe2 _x, and LuTe3 are found in Sections 30.1 .2.1, 30.1.2.3, 30.1.2.5,
and 30.1.2.8, on pp. 6, 31, 47, and 57, respectively.
The LuTe-Tm Te System
LuTe and TmTe form a continuous series of solid solutions with cubic NaCL structure and
a color ranging from metallic blue (rich in Lu) to metallic green (rich in Tm). The crystal
6.045
6.035
~/
/
/-
/
oc(
.!: 6.025
~
0 l-/
I
1/
//
6.015
Fig. 126.
0.2 0.4 0.6 Q8 1.0
Lattice constant a of Lu 1 _ xTmxTe
mixed crystals versus composition.
Gmelin Handbock
RE Main Vol. C 10
288 Hydride Tellurides. Oxide Tellurides
growth of the mixed crystals with octahedral habit is possible by the iodine transport method
(see p. 7) at temperatures of about 950 --+ 900°C by carefully manipulating the growth
conditions. The crystals varied in sizes from 0.5 to 3 mm. They are relatively stable in air. The
lattice constants (see Fig.126, p. 287) exhibitapositive deviation from Vegard's rule. A. Khan,
C. Vallaneilla (Proc. 5th Conf. Chem. Vap. Deposition Intern. Conf., Slough, Engl., 1975,
pp. 331/43).
30.2 Hydride TeLLurides MH.Te (M = La, Ce, and Pr)

Mixed hydride tellurides with M = La, Ce, and Pr were prepared by cautious heating of
MH 3 and Te mixtures. Composition, preparation temperature t, and lattice constants a and c
of the tetragonal cell are as follows:
composition t in oc a in A c in A
LaH 0 _91 Te 280 4.50 9.15
CeH 1.4 1Te 250 to 300 4.45 9.10
PrH 1_39Te 260 4.42 9.05
Heating LaH 0 _91 Te to 1200°C under Ar yields LaTe, F. C. Carter (Met. Soc. Conf. Proc. 15 [1962]
245/61, 254/5).
30.3 Oxide TeLLurides
Unlike the other rare earth oxide chalcogenides, for tellurium only the type M2 0 2Te is
known.
General References:
A. A. Eliseev, A. A. Grizik, in: V. P. Zhuze, I. A. Smirnov, Redkozemel'nye Poluprovodniki,
Nauka, Leningrad 1977, pp. 178/201; C.A. 89 [1978] No. 68658.
J. Flahaut, Chimie Cristalline des Combinaisons Ternaires Soufrees, Seleniees et Tellurees
Formees par les Elements des Terres Rares, Progr. Sei. Technol. Rare Earths 3 [1968]
209/83, 267/70.
V. A. Obolonchik, G. V. Lashkarev, Selenidy i Telluridy Redkozemel'niykh Metallov i
Aktinoidov, Dumka, Kiev 1966, pp. 1/162.
30.3.1 Comparative Data for M 20 2Te
30.3.1.1 Formation. Preparation
Like the other rare earth oxide chalcogenides M 20 2Te may be prepared by the following
methods:
1) H2Te(gas) + M20 3 ---+ M 20 2Te. (Usually H2-Te mixtures were used because H2Te is very
unstable, giving poor results.)
2) M20 3 + M2Te 3 ---+ M20 2Te in vacuum or inert atmosphere at 1200 to 1800°C.
Gmelm Handbook
RE Mam Vol. C10
289
3) M20 3 + Te---> M20 2Te at high temperature (poor yields).

4) Reduction of tellurates.
See for example the review of Eliseev, Grizik [1].
For the preparation according to the first method Te vapor was swept by a H2 gas stream
over M20 3 for 4 to 12 hat 500 to 960°C. The reaction M20 3 (s) + H2(g) + Te(g)---> M20 2Te(s)
+ H20(g) took place for M = La, Ce, Pr, Nd, Sm, Eu, Gd, and Dy; however, Ho and the other
heavier rare earth elements react only partially or not at all even on prolonged heating up to
1500°C. M20 3 and elementalTe were placed in separate quartz or alundum boats in a quartz
tube, Kent, Eick [2 to 4]. The green Y20 2Te is prepared by heating Y20 3 and Te in an evacuated
and sealed tube for 24 hat 1300°C [3]. Synthesis at 1000 to 1100°C in a stream of H2 was also
performed by Obolonchik et al. [5], who placed a mixture of M20 3 (M = La, Pr, Nd, Sm, Gd,
Dy) and Te powder in a 1:5 ratio in a graphite boat and additional Te in aseparate boat in a
quartz reactor tube. Du ring the process the Te vapor pressure was ~50 Torr, and the H2 flow
5 to 6 Llh. With alundum or porcelain boats instead of graphite boats nonstoichiometric
compounds resulted [5]. Without H2 the process in vacuum at 1000°C is very slow, Pardo et
al. [6]; seealso Dudnik et al. [7]. Heating in vacuum at 1300 to 1400°C is proposed by [4] for
M = Y, Tb, and the heavier rare earth elements. Stoichiometric portions of M 2Te 3 and M20 3
(M = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er) were pressed and heated to 1200°C in sealed
Si0 2 tubes in vacuum [6]. For the preparation of M20 2Te with M = Y, Ho, Er, Tm, Yb, and Lu
according to 2 M20 3 + 3 Te + 2M---> 3 M20 2Te the mixed reactants were placed in evacuated
Si0 2 ampules, sealed, and heated progressively: 3d at 500°C, 2 dat 800°C, and 1 dat 1000°C,
Pardo, Flahaut [8]. M20 2Te is formed when M2Te0 5 (M = Pr, Nd, Sm, Gd) is heated to 950°C
in H2 [4].
References:
[1] A. A. Eliseev, A. A. Grizik (in: V. P. Zhuze, I. A. Smirnov, Redkozemel'nye Poluprovodniki,

Nauka, Leningrad 1977, pp. 178/201, 180; C.A. 89 [1978] No. 68658).
[2] R. A. Kent, H. A. Eick (lnorg. Chem. 1 [1962] 956/8).
[3] R. A. Kent, H. A. Eick (TID-14090 [1962]1/54, 34/9; N.S.A. 16 [1962] No. 93).
[4] R. A. Kent, H. A. Eick (TID-15386 [1962]1/6; N.S.A. 16 [1962] No. 14695).
[5] V. A. Obolonchik, G. V. Lashkarev, V. G. Dem'yanchuk (lzv. Akad. Nauk SSSR Neorgan.
[6] M.-P. Pardo, J. Flahaut, L. Domange (Compt. Rend. 255 [1962] 937/9).
[7] E. M. Dudnik, G. V. Lashkarev, Yu. 8. Paderno, V. A. Obolonchik (lzv. Akad. Nauk SSSR
[8] M.-P. Pardo, J. Flahaut (Compt. Rend. C 265 [1967]1254/6).
30.3.1.2 Properlies
M20 2Te with M = La to Dy and possibly Ho are isomorphous body-centered tetragonal in

contrast to the M20 2S or M20 2Se, which are (for steric reasons) trigonal; see "Rare Earth
Elements" C9, 1986, p. 415, C7, 1983, p. 564. From powder X-ray diffraction studies on Nd 2 0 2Te
the space group 14/mmm-Dlf, (No. 139) with Z = 2 is derived by Raccah et al. [1]; see p. 296.
Gmelm Handbock 19
RE Main Vol. C10
290 Oxide Tellurides
Lattice parameters in A, measured and calculated density, Dexp and Deale in g/cm 3 , are as
follows:
M2 0 2Te a c cla Dexp Deale Ref.
La 20 2Te 4.12 13.10 3.179 6.36 6.54 [2]

4.12 13.09 6.47 [3]
Ce 20 2Te 4.09 12.92 3.159 6.64 6.76 [2]
4.09 12.91 6.54 [3]
Pr20 2Te 4.06 12.83 3.160 6.74 6.94 [2]
4.06 12.83 6.83 [3]
Nd 20 2Te 4.03 12.77 3.168 7.18 [2]
4.04 12.78 6.98 [3]
Sm 20 2Te 4.00 12.61 3.152 7.58 [2]
4.00 12.60 7.6 [3]
Eu 20 2Te 3.98 12.57 3.158 7.74 [2]
Gd 20 2Te 3.96 12.54 3.166 8.00 [2]
3.96 12.54 [3]
Dy 20 2Te 3.92 12.38 3.158 8.46 [2]
3.92 12.38 8.28 [3]
Ho20 2Te 3.92 12.38 3.158 [7]
The lattice parameters decrease linearly from La to Dy, and c/a is nearly constant,
~3.16 ± 0.01. Debye-Scherrer diagrams have been given, Pardo et al. [2]. Similar lattice
constants for M20 2Te with M = Pr, Nd, and Sm are reported by Dudnik et al. [5], Lashkarev
et al. [11], and for La 20 2Te, assuming the space group 14/m-C~h (No. 87) by Ballestracci [6].
A smaller tetragonal cell with Z = 1, a = 4.108 to 3.916, c = 8.687 to 8.260 A and Dexp = 4.96
to 6.36 forM = La to Dy including V is proposed by Kent, Eick [4]. According to [1] the density
measurements of [4] were performed on compacted cylindrical samples containing voids, so
Dis too low and Leads to incorrect lattice constants. According to X-ray powder data of La 20 2Te
(see p. 295) the structure consists of M20 2 and Te layers perpendicular to the c-axis. The M 20 2
layers consist of M tetrahedra which share four edges with other tetrahedra, Ballestracci [6].
M20 2Te with M = V, Ho, Er, Tm, Vb, and Lu are orthorhombic with Z = 8 and the following
lattice parameters in A and densities Deale and Dexp in g/cm 3 :
M. V Ho Er Tm Vb Lu
a ± 0.03 7.72 7.74 7.65 7.62 7.58 7.56

b ± 0.02 4.09 4.08 4.05 4.04 4.01 4.01
c ± 0.08 25.73 25.86 25.59 25.45 25.36 25.22
Deale 5.52 8.00 8.28 8.56 8.71 8.83
Dexp · 5.39 7.96
Ho20 2Te may also be tetragonallikethe lighter M20 2Te when prepared at :;=:;800°C. At~ 1 ooooc
it is orthorhombic. There is not enough room in the M2 0 2 planes for the large Te atoms from
Ho towards the heavier rare earth elements, so no dense tetragonal lattice may be built up,
Pardo, Flahaut [7]. The M-Te bond seems tobe weakened against the M-0 [3].
Gmelm Handbook
RE Mam Vol. C10
291
For generat crystal chemical considerations on compounds of the Mn YnXm type (for
example rare earth oxide chalcogenides) with Nd 2 0 2Te or other structures, see Kuz'micheva
et al. [14].
Thermal Properties
Coefficient of thermal expansion a measured on pressed specimens with 25 to 40%

porosity that were annealed in evacuated quartz ampules (10- 4 Torr) at 1050 to 1150°C from
room temperature to 500°C, calculated melting point T m• calculated molar specific heat CP,
and calculated Debye temperature 8 0 :
M 2 0 2Te Pr 2 0 2Te Nd 2 0 2Te Sm 2 0 2Te
a in 10- 6 K- 1 9.95 9.95 10.4 12.1 12.1 12.5 13.1 13.1 13.5
Tm in K 2000 2642 2543 1690 2230 2167 1580 2080 2004
CP in cal·mol- 1 ·K- 1 31.18 31.46 42.02
8 0 in K 351 365 358 322 334 328 358 372 367
Ref .. [3] [5] [11] [3] [5] [11] [3] [5] [11]
Similar a values were reported earlier by [8]. The increase of a on going from Pr to Sm may
be due to increasing anharmonicity of the crystal Lattice vibrations owing to increasing
difference in the components' atomic mass. The marked increase from Pr to Nd is evi-
dently due to substoichiometric Te content in Nd 20 2Te (3]. The standard entropy S~98
(in cal·mot-1.K- 1 ) of Sc2 0 2Te, Y2 0 2Te, and La2 0 2Te is estimated tobe 27.1, 32.9, and
38.7, respectively, Vishnyakov, Suponitskii [15].
Magnetic and Electrical Properties
M 2 0 2Te with M = La, Ce, Pr, Nd, and Sm are paramagnets (for M = La this is due to
x
admixtures of other M not specified), which obey the Curie Law = C/T from 300 to 500 K. The
following table gives the results of measurements and calculations of the atomic susceptibility
XA · 106 cm 3/g-atom, Curie constant CA in cm 3 · K · g-atom- 1 at Tx, effective magnetic moment
lleff at T max of the M ions and theoretical lleff (theor) bothin lls:
M 2 0 2 Te XA Tx in K CA Tmax in K lleff lleff (theor) Ref.
La 2 0 2Te 46.26 298 0.0135 594 0.329 0 [3, 9]

Ce 2 0 2Te 1986 292 0.664 408 2.31 2.56 (3]
1980 298 0.664 408 2.31 [9]
Pr 2 0 2Te 7248 288 2.27 381 4.27 3.62 [3]
7120 298 2.27 381 4.20 [9]
Nd 2 0 2Te 5162 298 1.82 473 3.82 3.68 [3, 9]
Sm 2 0 2Te 1351 287 0.534 451 1.9 1.9 [3]
1310 298 0.534 451 1.9 [9]
Gmelin Handbook 19.
RE Main Vol. C10
1000r-----.-----,-----,-----.------.----. 200 200

...E ...E ..,E
.!:!
iu 750 ~----~----~----~~~--~----~----~
....u 150 ~
ct 0'
E .9
~ 0
'6I ö
100E
~5oo r-----~~~~~~~~-----r~~~~----i
g
Q
.E .E
<( <( .E
....>< ><
;::: ö
- 25or-----r-----r-----~==~~--~-----1 50 E
....
><
0
--- 100 200 300 400 500 6000 0
Temperature in K
Fig . 127. Magnetic susceptibility of oxide tellurides versus temperature.
Magnetic measurements from 88 to 500 K (see Fig. 127) are better interpreted by a Curi e-
Weiss law XA = CA/(T- 0p) . For Pr20 2Te, ep = - 146 Kat 180 to 380 K; at 100 to 140 K the
Curie constant CA = 1.57cm3 · K·g-atom- 1 and llett = 3.5411 8 at 138K are obtained. For
Ndp2Te, CA = 1.61 cm 3 · K · g-atom - 1, 0P = - 38 Kat 88 to 190 K, llett = 3.593!18 at 188 K,
and 0P = -146 K above 290 K. For Sm 20 2Te, 0 P = +415 K (sign?) at 88 to 450 K. Further
results are given in the table above. La20 2Te, which is diamagnetic, is contaminated with
0.3% paramagnetic rare earth elements. lts temperature-independent susceptibility from 80
to 200 K is connected with impurities having an even number of f electrons and the substanti al
asymmetry of the strong crystalline field. The difference between llett and its theoretical value
for Ce20 2Te is explained with the deviation from the Curie-Weiss Law. From the values of llett•
which are close to the theoretical moments for the trivalent ions, it is concluded that the
interatomic bonds have a significant ionic component, Lashkarev, Savitskii [9] .
Pr20 2Te, Nd20 2Te, and Sm 20 2Te are assumed to be semiconductors with electrical re-
sistivities Q (in 106 Q · cm) of approximately 4, 30, and 3, respectively, measured on poly-
crystalline specimens, Lashkarev, Paderno [8] ; values between 106 and 107 Q · cm for these
compounds are reported by Obolonch ik et al. [3] .
Optical Properlies
The colors of M20 2Te with M = La to Dy range from chartreuse (Light green) to dark green,
except forM = Ce, which is darkred [4]. M20 2Te with M = Y, Ho to Lu are black [7].
The following colors are reported:
La2 0 2Te dark green [2] ; dirty green [3]

Ce20 2Te brown-violet [2]; violet [3] ; darkred [4]
Pr2 0 2Te Light green [2, 3]
Nd 2 0 2Te dark green [2, 3]
Gmel m Handbook
RE Mam Vol. C 10
293
Sm 20 2Te dark green [2]; dirty green [3]

Eu 20 2Te brown [2]
Gd 20 2Te bister (nut brown) [2]; Lightgreen [3]
Dy2 0 2Te dark brown [2]; dark chestnut [3]
The IR absorption spectra of pressed powder samples on KBr were studied in the range
from 40 to 5000 cm- 1 (250 to 2 Jlm), and the following Iransmissionminima were observed at
the wave numbers v (±3 cm- 1):
La 20 2Te 83 118 337 515

Pr 20 2Te 83 124 350 530
Nd 20 2Te 82 125 360 535
Sm 20 2Te 82 127 358 535
Gd 20 2Te 82 128 385 540
Tb 20 2Te 82 130 394 545
Dy 20 2Te 78 131 388 545
The most intense absorption bands between 337 and 394 cm- 1 are assigned to M-Te
vibrations, and the bands between 515 and 545 cm- 1 may be due to M-0 vibrations. The
spectra for La 20 2Te and Pr 20 2Te are presented in the paper, Voloshina et al. [16].
ln the reflection spectra from 200 to 1200 nm at 293 K of freshly polished samples of
densely pressed powders there are weak maxima at 300 to 450 nm and stronger maxima at
700 to 840 nm:
Pr20 2Te 300 440 740 840

Nd 2 0 2Te 300 440 680 840
Sm 2 0 2Te 300 420 680 840
Zalevskii et al. [10]. The reflection spectra of Pr20 2Te and Nd 20 2Te in the region 4000 to
30000 cm- 1 (2500 to 333 nm) at liquid nitrogen temperature have a very fine pronounced
structure, comparable with the corresponding oxide chlorides, Jrz~rgensen et al. [13].
Chemical Reactions
M20 2Te (M = Y, Ho to Lu) change very easily in air [7]. When Pr2 0 2Te, Nd 20 2Te, Sm 2 0 2Te,
and Gd 20 2Te are heated to constant weight in air at 450°C, Pr2Te0 5 (tan), Nd 2Te0 5 (blue),
Sm 2Te0 5 (cream), and Gd2Te05 (white) are formed. These compounds are stable up to 600°C;
on further heating to 750 to 800°C they oxidize to give M2Te0 6 of colors similar to M2Te0 5 but
with different X-ray diffraction patterns. Eu 20 2Te is continuously oxidized to gray Eu 2Te0 6 .
Above 800°C the oxides are obtained [4]. According to [3], M20 2Te with M = La, Pr, Nd, and
Sm on heating in air up to 1 000°C do not show significant weight changes due to formation
of a fine proteelive film of M20 3 on the surface. Only Ce 20 2Te is decomposed to Ce0 2 .
M20 2Te (M = La to Dy) are insoluble in water and dilute alkali but dissolve in acids with
evolution of H2Te, Eick et al. [12]. M20 2Te (M = La, Pr, Nd, Sm, Gd, Dy) dissolve completely
in concentrated HN03 with formation of M(N03h and H2Te04 . Ce 20 2Te does not dissolve
completely due to the presence of poorly soluble Ce0 2 . Concentrated HCL, KOH, and NaOH
do not dissolve these compounds completely [3]; seealso [2]. M20 2Te with M = Y, Ho to Lu
are insoluble in minerat acids [7].
Gmelon Handbook
RE Main Vol. C10
References:
[1] P. M. Raccah, J. M. Longo, H. A. Eick (lnorg. Chem. 6 [1967]1471/3).

[2] M.-P. Pardo, J. Flahaut, L. Domange (Compt. Rend. 255 [1962]937/9).
[3] V. A. Obolonchik, G. V. Lashkarev, V. G. Dem'yanchuk (lzv. Akad. Nauk SSSR Neorgan.
Materialy 2 [1966]100/4; lnorg. Materials [USSR] 2 [1966] 84/7).
[4] R. A. Kent, H. A. Eick (lnorg. Chem. 1 [1962] 956/8; TID-14090 [1962] 1/54, 34/9; N.S.A.
16 [1962] No. 93; TID-15386 [1962]1/6; N.S.A. 16 [1962] No. 14695).
[5] E. M. Dudnik, Yu. 8. Paderno, V. A. Obolonchik (lzv. Akad. Nauk SSSR Neorgan. Materialy
[6] R. 8allestracci (Compt. Rend. 8 264 [1967]1736/8).
[7] M.-P. Pardo, J. Flahaut (Compt. Rend. C 265 [1967] 1254/6).
[8] G. V. Lashkarev, Yu. 8. Paderno (lzv. Akad. Nauk SSSR Neorgan. Materialy 1 [1965]
[9] G. V. Lashkarev, A. V. Savitskii (Fiz. Tverd. Tela [leningrad]9 [1967]1883/6; Soviet Phys.-
Solid State 9 [1967] 1485/7).
[10] 8. K. Zalevskii, G. V. Lashkarev, V. V. Sobolev, N. N. Syrbu (Khim. Svyaz Poluprov. Tverd.
Telakh 1966 251/60; C.A. 66 [1967] No. 120421).
[11] G. V. Lashkarev, E. M. Dudnik, Yu. 8. Paderno (Khim. Svyaz Poluprov. Tverd.Telakh 1966
291/8; C.A. 66 [1967] No. 98742).
[12] H. A. Eick, G. L. Galloway, R. Kent, etal. (TID-6920 [1961]1/8, 3; N.S.A.15 [1961] No. 9431).
[13] C. K. Jengensen, R. Pappalardo, J. Flahaut (J. Chim. Phys. 62 [1965] 444/8).
[14] G. M. Kuz'micheva, I. V. Perelkin, A. A. Eliseev (Zh. Neorgan. Khim. 29 [1984] 2690/2;
Russ. J. lnorg. Chem. 29 [1984]1541/2).
[15] A. V. Vishnyakov, Yu. L. Suponitskii (Zh. Fiz. Khim. 59 [1985]1301/3; Russ. J. Phys. Chem.
59 [1985]767/9).
[16] A. L. Voloshina, L. A. lvanchenko, V. A. Obolonchik, V. A. Serdyuk (Poroshkovaya Met.
1984 No. 2, pp. 90/1; Soviet Powder Met. Metal Ceram. 23 [1984]166/7).
30.3.2 Lanthanum Oxide TeLLurides
Additional data for La 2 0 2Te are found in Section 30.3.1 on p. 288.
X-ray powder studies in the La 2Te 3-La 20 3 system showed the existence of homogeneaus
solid solutions LaTe 1 _s~xOx up to x ~ 0.005. The samples were prepared with the ampule
synthesis. The solid solutions did not have the cubic La 2Te 3 structure (see p. 33), but have the
tetragonal LaTe 2 structure of the Fe 2As type (see p. 48). The lattice constants of the samples
with x = 0.002, 0.003, and 0.005 are: a = 4.47, 4.495, and 4.51 A; c = 9.36, 9.24, and 9.10 A
(read from figures in the paper). The experimental densities are 6.46, 6.42, and 6.37 g/cm 3 ,
respectively. The change of the electrical conductivity of pressed powder samples with
temperature (between 100 and 500 K) and with x (shown in a figurein the paper) is similar as
in the LaTe 15 ~,Sex system (cf. Fig. 149, p. 351), Gerasimov et al. [1].
A compound of the composition La 2 0Te 2 with apparently variable composition is said to

form by partial oxidation during synthesis of lanthanum tellurides. X-ray studies indicate a
tetragonal structure with a = 8.21, c = 4.37 A, Yarembash et al. [2]. (The composition is
possibly a typographical error in the paper; in the Literature only compounds of the type
M 20 2Te are mentioned.)
Gmelm Handbook
RE Main Vol. C10
295
La2 0 2Te is tetragonal with a = 4.113, c = 13.08 A, as shown by X-ray powder pattern.
Assuming the space group 14/m-C~h (No. 87), the following atomic positions were obtained
with R = 0.06 (0, 0, 0; %, %, Y., plus):
La(4e) 0, 0, z; 0, 0, z with z = 0.346

0(4d) 0, %, y..; Y,, 0, y..
Te(2a) 0, 0,0
The compound is isomorphous with the other oxide tellurides M2 0 2Te with M = Ce to Dy. The
structure is characterized by La 20 2 and Te layers perpendicular to the c-axis, Ballestracci [3].
The space group 14/mmm-Dl~ (No. 139) is usually given for these compounds; see p. 289.
References:
[1] A. F. Gerasimov, V. N. Konev, N. A. Krushatina, G. I. Bochkina (Fiz. Metal. lkh Soedin.

No. 4 [1976]19/26; C.A. 88 [1978] No. 201583).
[3] R. Ballestracci (Compt. Rend. 8 264 [1967] 1736/8).
Additional data are found in Section 30.3.1 on p. 288.
A porcelain boat with Te and an alundum boat with a mixture of Ce0 2 and a fivefold excess
in weight of Te were placed in a porcelain tube. The part with the Te was heated to 650 to
700°C and the vaporized Te passed over the Ce0 2-Te mixture with a stream of dried H2 . Then
it is heated to 1 000°C for 5 h and cooled in the H2 stream. A powder diagram of the brown-
violet product with interplanar spacings and intensities is given in the paper. The measured
density is D~ = 6.74 g/cm 3 . Ce 20 2Te is insoluble in acids, even when heated, and attacked
only slowly by boiling aqua regia. NaOH and KOH solutions do not attack it, but molten KOH
reacts quickly forming K2Te and Ce0 2 . Ce 20 2Te ignites when reacted with dry Cl2 at 150°C
according to Ce 20 2Te + 3 Cl2 --+ 2 CeOCl + TeCl4 ; with dry Br 2 a mixture of Ce8r3 and CeOBr
is formed. ln the presence of H2 0 at room temperature Br 2 attacks Ce 2 0 2Te rapidly with
formation of Ce0 2 and even more quickly when HCl is added. ln boiling H20, Ce(Te0 3 ) 2 and
Ce0 2 are slowly obtained. H2 does not reduce it below 1 000°C. With Al at higher temperature
partial attack and formation of Ce-Al alloy is observed. ln air Ce 20 2Te is oxidized by heating
to maximal 928°C with 100 K/h according to 2 Ce 20 2Te + 5 0 2 --+ Ce(Te04 b + 3Ce0 2 ; but
already at 550°C Ce(Te0 4 b dissociates and Te0 2 vaporizes, Domange et al. [1]; this behavior
is not unusual, since Ce commonly exhibits an oxidation state of four, Kent, Eick [2].
References:
[1] L. Domange, J. Flahaut, Abbas Naderi Chirazi (Bull. Soc. Chim. France 1959 150/2).
[2] R. A. Kent, H. A. Eick (lnorg. Chem. 1 [1962] 956/8).
Gmelin Handbook
RE Main Vol. C10
The tetragonal compound was prepared by placing Nd 20 3 and Te chips in separate quartz
boats in an open-ended Vycor tube (1 .5 mol excess of Te). The temperature was increased
slowly to about 700°C and maintained there for ~5 h while H2 was swept through the tube,
thereby transporting the Te over Nd 20 3 , Pilato [1, p. 54]. Sintering at 1 000°C is proposed by
Lashkarev et al. [2] .
The lattice constants are 4.04 and 12.78 A, corresponding with Literature data [2]. The
crystal structure of the olive green compound has been determined and refined to R = 0.034
with isotropic temperature factors from powder X-ray diffraction and intensity data; see
Fig. 128. lnterplanar spacings and intensities are given in the paper. Nd 2 0 2Te is body-centered
tetragonal with a = 4.032 ± 0.002, c = 12.80 ± 0.001 A, Z = 2, Deale = 7 .15, Dexp = 7.2 ± 0.1
g/cm 3 . Space group 14/mmm-DK Nd is located in 4(e) ± (0 0 z), z = 0.341, 0 in 4(d) (0 Y, %;
Y, 0 %), Te in 2(a) (0 0 0) . Nd exhibits ninefold coordination . There are Te and Nd 2 0 2 layers
±
perpendicular to the c-axis. The bond lengths are : Nd-0 = 4 x 2.328 0.010 A, Nd-Te =
4 x 3.503 ± 0.010, and 1 x 4.365 ± 0.016 A, Nd-Nd = 4 x 3.682 ± 0.010, 4 x 4.032 ± 0.002, and
1 x 4.070 ± 0.030 A, 0-0 = 4 x 2.851 ± 0.001 and 4 x 4.032 ± 0.002 A, Te-Te = 4 x 4.032 ±
0.002 A, and Te-0 = 8 x 3.782 ± 0.003 A, Raccah et al. [3].
Nd •
0 @
Te Q
Fig. 128. Crystal structure of Nd 2 0 2Te.
X-ray powder diffraction analyses of the residue after evaporation showed that Nd 2 0 2Te
vaporized incongruently to Nd 2 0 3 . Mass spectrometric analysis of the effusing vapor indicated
that the vaporizing species are Nd(g), NdO(g), Te(g), and at higher temperature also O(g).
The ratio of partial pressures of NdO(g) and Nd(g) changes from < 1 to > 1 at ~ 2150 K. These
observations are explained by several simultaneaus equilibria occurring in the vaporization
of Nd 2 0 2Te:
1) Nd 20 2Te(s)--->% Nd 20 3 (s) +% Nd(g) + Te(g)

2) Nd 20 2Te(s) + O(g)---> Nd 20 3 (s) + Te(g)
3) Nd 20 3 (s)---> 2 NdO(g) + O(g)
4) Ndp 2Te(s)---> 2 NdO(g) + Te(g)
Gmelm Handbook
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At Low temperature reaction 1) is postulated to predominate, 2) is a side reaction, and 3) and

4) become favorable at higher temperature. This temperature dependence is consistent
with calculated equilibrium constants K for the reactions in which the free energy function
(ßG-ßH~ 98 )/T and standard enthalpy of formation ßH~ 98 (f) of Nd 20 2Te(s) were estimated.
(G 0 -H~ 98 )/T is -68.64, -72.40, and -75.27 cal · mol- 1 · K- 1 at 1800,2000, and 2200 K, respec-
tively, from Literature data on Nd 20 3 (s), Te(g), and O(g); ßH~98 (f) = -419.1 cal/mol. Data for
reactions 1) to 4) are summarized in the following table:
- (ßG- ßH~98 (f) )/T -ßHm(t)/T Log K

in cal·mol- 1 ·K- 1 in cal· mol- 1 · K- 1
reaction: 1) 2) 3) 4) 1) 2) 3) 4) 1) 2) 3) 4)
1800 K 56.24 20.40 116.6 137 127 -14.6 233 219 -15.5 7.65 -25.4 -17.9
2000 K 55.90 20.48 115.3 136 114 -13.1 210 197 -12.7 7.33 -20.7 -13.3
2200 K 55.71 20.52 114.3 135 104 -11.9 191 179 -10.6 7.08 -16.8 - 9.6
Reaction 1) increases in this temperature range by a factor of ~ 105 , the side reaction 2) stays
nearly constant, and reactions 3) and 4) increase by a factor of 108 ·6 and 108·3 . The partial
pressures of reaction 3) at 2215 Kare Low but detectable, PNdO and p0 being 4.951 x 10- 6 and
0.7900 x 10- 6 atm. At 2300 K p0 is 1.35 x 10- 6 atm [1].
The magnetic susceptibility was measured from 290 K to nearly 0 K. The 1/x versus T plot
is a straight Line with C = 1.63 cm 3 · K · g-atom - 1 and lleff = 3.62 ± 0.01 J.Ls (theoretical value
for Nd 3 +: 3.62 J.Ls) [3].
References:
[1] P. A. Pilato (Diss. Michigan State Univ. 1968, pp. 1/162; Diss. Abstr. 8 29 [1968]524/5).
[2] G. V. Lashkarev, E. M. Dudnik, Yu. 8. Paderno (Khim. Svyaz Poluprov. Tverd. Telakh 1966
291/8; C.A. 66 [1967] No. 98742).
[3] P. M. Raccah, J. M. Longo, H. A. Eick (lnorg. Chem. 6 [1967]1471/3).
30.3.5 Eu 20 2Te
The gray compound was prepared by the reaction of Eu 2 0 3 or Eu shavings with Te powder
for 6 hat 600°C in a sealed but not evacuated capsule, Sadovskaya et al. [1]. When Eu 20 2Te
was prepared Like the other M20 2Te (see p. 289), Eule was formed in addition and became
the predominant species at higher reaction temperatures, Kent, Eick [2]. Eu 2 0 2Te is tetragonal,
space group 14/m-C~h (No. 87), with a = 3.93, c = 12.52 A; c/a = 3.19, density D = 7.7 g/cm 3 .
lt is paramagnetic [1].
References:
[1] 0. A. Sadovskaya, E. I. Yarembash, A. A. Eliseev (lzv. Akad. Nauk SSSR Neorgan. Materialy
[2] R. A. Kent, H. A. Eick (lnorg. Chem. 1 [1962]956/8; TID-14090 [1962]1/54, 34/9; N.S.A. 16
[1962] No. 93).
Gmelon Handbook
RE Main Vol. C10
298 Oxide Tellurides. Tellurates
30.3.6 Dy2 0 2Te

The Mössbauer spectrum of powdered 161 Dy 2 0 2Te at 1.6 K with 161 Tb in 160GdF3 as the
source shows Superposition of magnetic and quadrupole interactions with g0 J.lnHett =
845(5) MHz and e2 qQ = 10.7(2) cm/s. The experimental and calculated electric field gradient
at the Dy nucleus is eVzz = 6.2 x 10- 6 or 6.78 x 10- 6 erg/cm 2 , respectively. The magnetic
moment is J.l = 10.1(2) J.ls from the Mössbauer spectrum and 10.0(5) J.ls from neutron diffrac-
tion. The Neel temperature is T N = 10.2 K. The Dy3+ spin makes an angle of 90° with the
c axis, J. Chappert, Y. Abbas, J. Rossat-Mignod (Physica B + C 86/88 [1977]102/4).
30.3.7 Ho2 0 2Te. Er 2 0 2Te

Ho2 0 2Te is the only compound from the M2 0 2Te series that is found tobe tetragonal Like
those with M = La to Dy when prepared at ~ 800°C and orthorhombic Like those with M =
Y, Er to Lu when prepared at ~ 1 000°C; for details of preparation, see p. 289. The Lattice
constants are a = 3.92, c = 12.38 A. c/a = 3.158 for the tetragonal form and a = 7.74 ± 0.03,
b = 4.08 ± 0.02, c = 25.86 ± 0.08 A for the orthorhombic form (a 0 ~ 2a1, b0 ~ a1, C0 ~ 2c1).
The transformation of the tetragonal into the orthorhombic modification is very slow. lt is
complete in 1 h at 1200°C and is probably monotropic. The inverse reaction does not occur
in 7 d at 750°C. The orthorhombic form has a 7.25% greater volume than the tetragonal form.
ln the !arger cells from Ho onward the Large Te atoms are better placed than in the tetragonal
Layer structure. Calculated and measured densities of the orthorhombic Ho2 0 2Te are 8.00 and
7.96 g/cm 3 .
Black Er 2 0 2Te powder was prepared corresponding to M2 0 2Te with M = Y, Ho to Lu; see
p. 289. Very fine monocrystalline Lamellas, which are colorless and transparent, can be
obtained on heating the powder for 10 h at 800°C in the presence of a Large excess of KBr as
a flux.
Reference:
M.-P. Pardo, J. Flahaut (Compt. Rend. C 265 [1967]1254/6).
30.4 Tellurates
30.4.1 TeLLurates(IV)
30.4.1.1 General
Systematic investigations of the M20 3-Te0 2 systems throughout the whole concentration
region do not exist up to now and the reported compositions of some compounds are still
under discussion. Tellurates(IV) of the type M2Te0 5 ( = M2 0 3 · Te0 2 ) form according to Kent,
Eick [1] by oxidation of the oxide tellurides M2 0 2Te, but Redman et al. [2] claim the composition
M4Te 30 12 ( = 2 M2 0 3 · 3 Te0 2 ) for samples obtained by solid state reaction of M2 0 3 and Te0 2 .
For these phases M: Te ratios between 3:2 and 11:10 and the content of some Tev 1 are reported
by Trömel et al. [5]. No conflicting data exist on the tellurates(IV) of the type M 2 (Te0 3 )s
Gmelin Handbock
RE Ma1n Val. C 10
Tellurates(IV) 299
( = M20 3 • 3 Te0 2) obtained by solid state reaction [2], or by dehydration of M2 (Te0 3 b · n H20
(see for example Voloshina et al. [3, 4]) and on M2Te 40 11 ( = M20 3 · 4 Te0 2 ), prepared by solid
state reaction [2]. Anti-glass phases M2Te 60 15 to M4Te 70 20 are obtained by quenching from
the melt [5].
Tellurates(IV) with tetravalent Lanthanides are only known for Ce (see the phase diagram
Ce0 2-Te0 2 , Bart et al. [6]) but many questions on composition and properties arestill open.
Lanthanide tellurates may be used in electronic technology as Lasermaterialsand as pigments
for staining ceramies; see for example [3, 4]. Silica-supported phases of the (Ce, Te)0 2 system
may act as catalysts, for example in the ammoxidation of propylene, Bart, Giordano [7].
References:
[1] R. A. Kent, H. A. Eick (lnorg. Chem. 1 [1962]956/8).
[2] M. J. Redman, W. P. Binnie, J. R. Carter (J. Less-Common Metals 16 [1968]407/13).
[3] A. L. Voloshina, L. A. lvanchenko, V. A. Obolonchik, E. S. Lugovskaya (Poroshkovaya Met.
1982 No. 9, pp. 53/7; Soviet Powder Met. Metal Ceram. 21 [1982]728/31).
[4] A. L. Voloshina, V. A. Obolonchik (Ukr. Khim. Zh. 48 [1982]1028/9; Soviet Progr. Chem. 48
No. 10 [1982], pp. 21/3).
[5] M. Trämel, W. Hützler, E. Münch (J. Less-Common Metals 110 [1985]421/4).
[6] J. C. J. Bart, N. Giordano, C. Gianoglio (Z. Anorg. Allgem. Chem. 481 [1981]153/67, 165).
[7] J. C. J. Bart, N. Giordano (J. Catal. 75 [1982]134/9).
30.4.1.2 M 20 3-Te0 2 Systems
The Y2 0 3-Te0 2 System

The system was studied in the concentration range 80 to 100 mol% Te0 2 by DTA and
X-ray phase analyses. Mixtures of the components were annealed at 700 ± 5°C in Ar for
300 h. A eutectic is established at 720°C and 1.5 mol% Y20 3 . The solubility of V20 3 in molten
Te0 2 reaches ~ 10 mol% at 1 000°C. A thermal effect at 860°C is not interpreted. The forma-
tion of Y2Te 4 0 11 is suggested, Safonov et al. [1].
The La 2 0 3(La 2(S0 4h)-Te0 2 System

Glass formation is observed in the range from 95.5 to 90.5 mol% Te0 2, lmaoka [2], Vogel
et al. [3]. Glasses obtained by melting at 800 to 1100°C in Au or Pt crucibles and cooling
down with 8 to 10 K/s in the transformation region have a density of D = 5.662 and
5. 707 g/cm 3 at 96.0 and 90.1 mol% Te0 2 , respectively; the refractive index is n 0 = 2.2056 and
2.1596 and the Abbe number v 0 = 16.4 and 17.6 at these compositions [3]. ln the same way
glasses with compositions from 96 to 99.3 mol% Te0 2 were obtained in the La 2 (S04 lJ-Te0 2
system. For the Limiting compositions the density is D = 5.476 and 5.591 g/cm 3 , the refractive
index n 0 = 2.0531 and 2.1619, and the Abbe number v 0 = 20.8 and 17.7, respectively, Vogel
et al. [4].
The Sm 2 0 3- Te0 2 System

An optical recording material (Sm 20 3 ) 1 _x(Te0 2)x with x = 0.75 to 0.82 was obtained from
weighed and mixed Sm 20 3 and Te0 2 powders by melting in a Pt crucible for 5 to 10 min. After
Gmelm Handbock
RE Mam Vol. C10
300 Tellurates
cooling the material was pulverized and evaporated in a Cu crucible on a glass plate at
6 x 10- 6 Torr. The material has improved sensitivity to Laser Light and produces readily
detectable optical changes upon recording. For x = 0.8, recording using a 15 mW semicon-
ductor Laser with 'A = 820 nm decreased the Light transmittance from 50 to 25%, Seiko Denshi
Kogyo K. K. [5].
The system was investigated in the Goncentration range of 80 to 100 mol% Te0 2 by DTA
and X-ray phase analyses. Mixtures of the compounds were annealed at 700 ± 5°C in Ar for
300 h. A eutectic is observed at 720°C and 2.5 mol% Er 20 3 , along with the formation of
Er 2Te 4 0 11 , which melts at 1260 ± 50°C. The solubility of Er 20 3 in molten Te0 2 increases from
3.5 to 5.0 and 7.5 mol% at 800, 900, and 1 000°C, Safonov et al. [1).
References:
[1) V. V. Safonov, E. G. Yarotskaya, R. K. lvnitskaya (Zh. Neorgan. Khim. 25 [1980) 865/6;

Russ. J. lnorg. Chem. 25 [1980]482/3).
[2) M. lmaoka (Advances in Glass Technology, Part 1, Plenum, New York 1962, pp. 149/64,
152).
[3] W. Vogel, H. Bürger, F. Folger, R. Oehrling, G. Winterstein, H.-G. Ratzenberger, C. Ludwig
(Silikattechnik 25 [1974] 206/7).
[4) W. Vogel, H. Bürger, G. Zerge, B. Müller, et al. (Silikattechnik 25 [1974] 207/8).
[5) Seiko Denshi Kogyo K. K. (Japan Kokai Tokkyo Koho 84-74549 [1984) from C.A. 102 [1985]
No. 103684).
When the oxide tellurides M 2 0 2Te with M = Pr, Nd, Sm, Gd are heated to 450 to 480°C in
air the tellurates(IV) Pr 2Te0 5 (tan), Nd 2Te0 5 (blue), Sm 2Te0 5 (cream), and Gd 2Te0 5 (white) are
formed, Kent, Eick [1, 2). The formation in 5 h at 300°C is reported by Kent, Eick [3). The
tellurates(IV) are stable up to 600°C; on further heating in air M 2Te0 6 is formed at 750 to 800°C
with the same colors as for M 2Te0 5 but with different X-ray diffraction pattern [1, 2). At 950°C
the oxides are obtained [2, 3]; see also [1). On heating M 2Te0 5 to 950°C in H2 the oxide
tellurides, M 20 2Te, are formed again [1 to 3]. The existence of M 2Te0 5 could not be confirmed;
alter firing pressed mixtures of M 20 3 and Te0 2 the samples always contained excess M 20 3
as indicated by X-ray diffraction, Redman et al. [4).
References:
[1) R. A. Kent, H. A. Eick (lnorg. Chem. 1 [1962) 956/8).

[2) R. A. Kent, H. A. Eick (TID-15386 [1962)1/6; N.S.A. 16 [1962) No. 14695).
[3) R. A. Kent, H. A. Eick (TID-14090 [1962)1/54, 34/9; N.S.A. 16 [1962) No. 93).
[4) M. J. Redman, W. P. Binnie, J. R. Carter (J. Less-Common Metals 16 [1968]407/13).
Gmel1n Handbook
RE Mam Vol. C 10
Tellurates(IV) 301
30.4.1.4 M 4 Te 3 0 12 ( = 2 M 20 3 · 3 Te0 2). Anti-Glass Phases with Similar Compositions

For tellurium-rich anti-glass phases, see p. 309.
The compounds may be prepared by solid state reaction from pressed mixtures of M 20 3
and Te0 2 , for instance at 800°C forM = Dy. The powder diagram of Dy4Te 30 12 can be indexed
as cubic with a = 10.95 A and Z = 3; d values are given in the paper. On heating to 850°C
other lines appeared in the powder pattern, showing that the existence of the cubic phase is
very temperature-dependent. Other M 4Te 30 12 , and most markedly for M = Gd and Er, also
contain lines that can be indexed on the cubic system, but its stability range seems to be very
limited. lt appears that excess M 20 3 stabilizes the cubic phase, Redman et al. [1). According
to Trömel et al. [2) samples obtained from M 20 3 or Pr 60 11 and Tb 40 7 and Te0 2 powder mixtures
±
in 2 h at 800 20°C under N2 are nonstoichiometric anti-glass phases (metastable non-
stoichiometric crystalline compounds with undefined short-range order) with M: Te ratios
between about 3:2 and 11:10 which contain some Tev 1• They are cubic face-centered with the
following lattice constants a in A:
M M:Te a M M:Te a
y 1.2 to 1.3 5.464 Tb 1.3 to 1.4 5.485

La 1.6 to 1.9 5.739 Dy 1.3 to 1.4 5.463
Pr ~1.7*) 5.640*) Ho 1.2 to 1.4 5.454
Nd 1.6 to 1.7 5.610 Er 1.2 to 1.3 5.435
Sm 1.5 to 1.7 5.553 Tm ~1.2 5.415
Eu 1.4 to 1.5 5.537 Yb ~1.2 5.401
Gd 1.3 to 1.5 5.508 Lu ~ 1.1 5.390
•l No pure cubic phase obtained.
The larger cell proposed by [1) is not necessary when statistical distribution of heavy
atoms occurs. The Tev 1 content may be due to disproportionation of Te 1v on reacting excess
M 20 3 with Te0 2 . The phases appear to be stable upon prolonged heating ( ~ 16 h) at 800°C
but decompose irreversibly above 850°C [2).
References:
[1) M. J. Redman, W. P. Binnie, J. R. Carter (J. Less-Common Metals 16 [1968]407/13).
[2) M. Trömel, W. Hützler, E. Münch (J. Less-Common Metals 110 [1985] 421/4).
30.4.1.5 M 2(Te0 3h ( = M 20 3 · 3 Te0 2 )
Additional data for the preparation and for chemical reactions are found in Section 30.4.1.6,
p. 304.

For the preparation of M2 (Te0 3b with M = La to Lu (but not Pm), M(N03 b is dissolved in
hot H20 and treated with a 10% excess of a hot aqueous solution of Na2Te0 3. Soon alter
mixing the solutions a gelatinous precipitate forms. lt is decanted, filtered, washed a few
times with H2 0, and dried at 105°C. X-ray investigations show that the compounds are
Gmelm Handbook
RE Main Vol. C10
302 Tellurates
amorphaus even after heating at 1 000 to 1 050°C, Dobrowolski [1]. The tellurates(IV) were
obtained also by precipitation from M(N03b and K2Te0 3 solutions. On Ii ring the gelatinous
precipitates at 800°C in N2 the X-ray powder patterns are identical with those of the products
of solid state reaction of M 20 3 and Te0 2 . Compounds of Y and M other than Ce, Pr, Pm, and
Tb were prepared by pressing pellets from weighed mixtures of M 20 3 and Te0 2 , wrapping the
pellets in Pt foil (which successfully prevented volatilization of Te0 2 ), and Ii ring in N2 for 8 to
10 h at 800°C for M = La and Nd and at 900°C for the others. The firing was followed by
regrinding, repelleting, and refiring, Redman et al. [2]. M 2 (Te0 3 b with M = Y, La to Lu (but
not Ce, Pm) were obtained by dehydration of the hydrates at 550 to 800°C, Voloshina et al.
[3]; see also [4]. The dehydration process was studied by IR spectroscopy on the sample
of La 2 (Te0 3b · 6 H2 0 (cf. p. 306). Amorphaus tellurates(IV) were obtained alter heating all
M 2 (Te0 3b · n H20 at 150 to 400°C to a constant weight. Those maintained at 500 to 580°C have
the C'l-modification and those above 600°C the ß-modification, Voloshina et al. [5]. According
to Maier et al. [6] anhydrous amorphaus Pr 2 (Te0 3 b forms on heating the hydrate to 150°C. lt
starts to crystallize at ~ 500°C and Te 1v is slightly oxidized to Tev 1 at 570°C.
Physical Properlies
The compounds fall into three structural groups: 1) La, Nd; 2) Y, Sm, Eu, Gd, Dy, Ho, Er;
3) Tm, Yb, Lu. Representative interplanar spacings of La 2 (Te0 3b, Dy 2 (Te0 3 b and Lu 2 (Te0 3 b
are given in the paper. The compounds melt above 950°C. The accurate melting points could
not be determined on account of oxidation and volatilization of Te0 2 , Redman et al. [2].
Specimens annealed at 550 to 600°C have cubic symmetry; above 700°C tellurates(IV) with
crystal structures of other symmetry were obtained, Voloshina et al. [3]. IR spectra of high-
temperature ß-M 2 (Te0 3 b support the existence of the three structural groups with different
Teo~- symmetries, Voloshina et al. [5]. Pr 2(Te0 3b obtained by heating the hydrate melts at
960 to 980°C (the small amounts of Tev 1 formed by oxidation at ~570°C are reduced to Te 1v
again). The formation enthalpy of amorphaus and crystalline Pr 2(Te0 3 b is obtained from the
solution enthalpy = -47.39 ± 0.22 and -36.80 ± 0.12 kcal/mol in 10% HCl (dilution 1 :8000)
or in 20% HCl (dilution 1 :7128), respectively, bothat 25°C, and from Literature data. ~H~98 =
-722.83 ± 2.0 kcal/mol for 2 Pr(s) + 3 Te(s) + 9 / 2 0 2 (gas) ---> Pr 2 (Te0 3 b (amorphous) and
~H~ 98 = -738.34 ± 1.9 kcal/mol for 2 Pr(s) + 3 Te(s) + %0 2 (gas)---> Pr 2 (Te0 3 b (crystalline).
The difference between the two values, -15.51 kcal/mol, is the enthalpy of crystallization,
Maier et al. [6].
The diffuse reflection spectra of M 2 (Te0 3b indicate semiconducting properties with a
smaller width of the forbidden zone ~Ethan the hydrates by about 0.2 to 0.6 eV. The following
values were obtained for La 2 (Te0 3b by Voloshina et al. [3, 7] and Pr 2 (Te0 3b to Lu 2 (Te0 3b by
Voloshina et al. [3]:
M2 (Te0 3 b La 2 (Te0 3 b Pr 2 (Te0 3b Nd 2 (Te0 3b Sm 2 (Te0 3b Eu 2 (Te0 3b

~Ein eV. 4.0 4.14 4.10 4.3 4.0
M 2 (Te0 3 b Gd 2 (Te0 3 b Tb 2 (Te0 3b Dy 2 (Te0 3b Ho 2(Te0 3 b Er 2 (Te0 3b

~Ein eV. 4.05 4.0 3.93 4.15 3.8
M 2 (Te0 3b Tm 2 (Te0 3b Yb 2 (Te0 3b Lu 2 (Te0 3b

~Ein eV. 3.8 3.8 3.92
Only for Sm 2 (Te0 3b and its hydrate the same width is found, possibly due to intra-atomic
absorption caused by f-f transitions of electrons. For other M (except La and Lu) this effect is
less marked. Apparently interband transitions predominate. The hypothesis is put torward
Gmeltn Handbock
RE Matn Val. C 10
Tellurates(IV) 303
2.5
2.0
... 1.5
c
1.0
0.5
0
500 700 900 1100
v in cm-1
Fig. 129. Refractive index n and absorption index k of a.-La2(Te03)s versus wave number.
that the conduction band is formed by 6s and 5d states. The reduction of the energy gap
between the bottom of the conduction band and the top of the valence band on transition from
amorphaus to crystallized products could be attributed to an energetic separation of 6s and
5d states in an increasing crystal field, Voloshina et al. [3].
The following colors were observed :
La2 (Te03 )s white [1] Tb2 (Te0 3 }s cream-white [1], white [3]
Ce2 (Te03 )s white [1] Dy2 (Te03)s white [1 , 3]
Pr2(Te03 )s green-yellow [1), Lightgreen [3] Ho2(Te03 )s cream-white [1], Light cream [3]
Nd2 (Te03 ) 3 rose-violet [1], light violet [3] Er2(Te0 3 )s pale rose [1], pink [3]
Sm 2 (Te0 3 )s cream-yellow [1), pale yellow [3] Tm 2 (Te0 3)s cream-white [1] , white [3]
Eu 2(Te03)s white [1 , 3] Yb2 (Te03 )s white [1 , 3]
Gd 2(Te03)s cream-white [1], white [3] Lu 2 (Te03b white [1 , 3]
The cubic a.-La2 (Te03 )s has the refractive index n = 1.98. The ß-modification obtained at
~ 700°C consists of Long prismatic transparent grains with high birefringence, direct extinc-
tion, and positive elongation, na = 2.04, n1 = 2.05, Voloshina et al. [3, 7] . Refractive index n
and absorption index k of a.-La2 (Te03 )s (dehydrated at 660°C) in the farinfrared region between
-400 and 1000 cm - 1 are shown in Fig.129, derived by a Kramers-Kronig analysis from the
reflection spectrum in the range of 0.2 to 25 11m and the Iransmission spectrum of the same
powder in the region of 40 to 400 cm - 1 . Real (e') and imaginary (e") parts of the complex
dielectric function are shown in Fig. 130, p. 304. Reflection maxima were observed at 422 ± 3
and 675 ± 2 cm- 1 and minima at 470 ± 10 and 815 ± 10 cm- 1 . Longitudinal optical phonans
are at vw ( ± 10 cm - 1) = 437 and 735, and a transversal phonon at vro = 550 ± 10 cm - 1 . The
dielectric constant for high and low frequency is e00 = 5.0 ± 0.1 and eo = 18.0 ± 0.1, respective-
ly. Slightly higher values for a.-La2(Te03 )s obtained by heating the hydrate at 550°C are
given in the paper, Voloshina et al. [7] . An IR band at 705 cm - 1 remains unchanged in
La2(Te03 )s · n H20 (cf. p. 306) and a.-La2 (Te03 )s ; bands in the region of 400 to 500 cm - 1 are
assigned to M-0 Vibrations. The IR spectra of ß-M2 (Te03 )s are more complex as shown for
M = La, Sm, and Yb in a figure in the paper, with characteristic differences for the three
structural groups, mentioned on p. 302. The differences indicate different symmetries of the
Teo~ - structural group, Voloshina et al. [5] .
Gmelin Handbook
RE Maon Vol. C10
304 Tellurates
8 f\ 1
---
E"
6
1
·w 4
·..; 2 /' \ \
0 7 \ II''7-
-2
I
(
V
500 700 900 1100
Fig . 130. Real (c') and imaginary (c" ) parts of the complex dielectric function of IX-La 2 (Te0 3 lJ
versus wave number.
References:
[1] J . Dobrowolski (Roczniki Chem. 40 [1966]1169/72; C.A. 66 [1967] No. 61343).
[2] M. J. Redman, W. P. Binnie, J. R. Carter (J. Less-Common Metals 16 [1968]407/13) .
[3] A. L. Voloshina, L. A. lvanchenko, V. A. Obolonchik, E. S. Lugovskaya (Poroshkovaya Met.
1982 No. 9, pp. 53/7; Soviel Powder Met. Meta! Ceram . 21 [1982]728/31).
[4] A. L. Voloshina, V. A .Obolonchik (Ukr. Khim. Zh . 48 [1982]1028/9; Soviel Progr. Chem . 48
No. 10 [1982] 21/3).
[5) A. L. Voloshina, L. A. lvanchenko, V. A. Obolonchik, V. A. Serdyuk (Ukr. Khim . Zh. 50 [1984)
383/6; Soviel Progr. Chem. 50 No. 4 [1984]51 /3).
[6] A. I. Maier, T. A. Soldatova, M. Kh. Karapet'yants (Tr. Mosk. Khim. Tekhnol. lnst. No. 62
[1969]43/6 ; C.A. 74 [1971] No. 131284).
(7] A. L. Voloshina, L. A. lvanchenko, V. A . Obolonchik, N. G. Khotynenko (Zh . Prikl. Spektrosk.
40 [1984] 975/8; J . Appl. Spectrosc. [USSR]40 [1984] 693/5) .
30.4.1.6 M 2(Te0 3h · n H20

Hydrated tellurates(IV) M 2 (Te0 3b · n H20 may be precipitated from aqueous solutions, as
shown by investigations of the systems M(N03lJ-Na 2Te0 3-H20 with M = La to Lu (except
Ce, Pm) using potentiometric and conductometric titration or measurements of residual
concentration, pH , and electrical conductivity. The precipitates were washed with water and
dried in air at 20 to 25°C. The M 2 (Te03b · n H2 0 samples thus obtained were X-ray amorphaus
with n ~ 4 to 6, Voloshina et al. (1 , 2]. Conductometric studies at 25 ± 0.5°C show that
La2 (Te0 3 b is quantitatively precipitated by titration of La(N03 b with Na2Te03 in 15 to 20%
ethanol and Nd2 (Te03 b by titration of Nd(N03b in 20 to 25% ethanol (content of H20 is not
reported), Prasad , Pathak [3). Analogaus investigations indicate the quantitative precipitation
of Ce 2 (Te03 b with K2Te03 at 30 ± 0.5 °C in 30% ethanol, Prasad, Kumar [4], and of Pr 2 (Te0 3b
with Na2Te0 3 at 25 ± 0.5°C in 10% ethanol, Prasad , Pathak [5]. Pr2 (Te03b (no H20 content
reported) was obtained also by mixing of 6% boiled aqueous solutions of PrCL3 and 10%
excess of Na2Te0 3 . lt was filtered, washed with H2 0 , and dried in air to constant weight, Maier
et al. (6). Eu 2 (Te0 3b · 2 H20 is precipitated from a saturated EuCL3 solution by Na 2Te03 . Th e
product is washed and dried at 105°C, Kravchenko et al. [7]. M 2 (Te03 b · n H20 samples dried
Gmelm Handbook
RE M a1n Vol. C 10
Tellurates(IV) 305
at 150°C have n ;::: 3, Voloshina et al. [8]. Heating of La2(Te03h · 6 H20 to constant weight
results in n = 3, 1.6, 0.45, and 0 for annealing temperatures of 150, 200, 400, and 550°C,
Voloshina et al. [2, 9].
Physical Properlies
The hydrated tellurates(IV) M2 (Te0 3h · n H2 0 are X-ray amorphaus and have refractive
indices n ~ 1.6780 [2] or ~ 1.780 [9] . The colors of the hydrated tellurates(IV) are the same
as those of the anhydrous compounds (see p. 303) [2). The diffuse reflection spectra of
M2 (Te03 lJ · n H20 powders indicate semiconducting properties with the following values for
the width of the forbidden zone dE ( ±0.05 eV):
M2 (Te03 h · n HP dE M2 (Te03 lJ · n H20 dE
La2 (Te0 3b · 6 H20 4.37 Dy2 (Te03b · 5.1 H20 4.35

Pr2 (Te0 3b · 5.8 H2 0 4.34 Ho2 (Te03 b · 5.3 H20 4.3
Nd 2 (Te0 3b · 5.3 H20 4.35 Er2 (Te03 b · 5.0 H20 4.2
Sm 2 (Te0 3 b · 4.8 H20 4.3 Tm 2 (Te03b · 4.8 H2 0 4.4
Eu 2 (Te03 b · 3.8 H20 4.2 Yb2 (Te03b · 5.4 H20 4.4
Gd 2 (Te0 3 b · 4.9 H20 4.3 Lu 2 (Te03 lJ · 4.9 H20 4.4
Tb 2(Te03 b · 4.6 H20 4.2
For La2 (Te03 b · n H20 with n = 3, 1.6, and 0.45, obtained by annealing at 150, 200, and
400 °C widths of dE = 4.34, 4.35, and 4.23 eV, respectively, were determined. Reflection and
absorption spectra for the region from ~2.8 to ~4.5 eV of La2(Te0 3b · 6 H20 with and without
heat treatment up to 900°C and reflection spectra for M2 (Te0 3b · n H20 with M = Dy and Lu
with and without heat treatment up to 550°C are presented in the paper, Voloshina et al. [2);
seealso [9). Refractive index n and absorption index k of La2 (Te03 b · n H20 annealed at 150°C
(n ;::: 3) in the farinfrared region between ~ 400 and 1200 cm - 1 are shown in Fig. 131 , derived
by a Kramers-Kronig analysis from the reflection spectrum in the range of 0.2 to 25 11m and
the transmission spectrum of the same powder in the region of 40 to 400 cm - 1 . The reflection
spectra of all X-ray amorphaus La2(Te03 b · n H20 specimens (annealing temperatures be-
tween 20 and 400°C) were qualitatively close to each other. The following optical data were
Fig.131. Refractive index n and absorption index k of La2 (Te03h · n H20 annealed at 150°C
(n ;::: 3) versus wave number.
Gme!m Handbook 20
RE Mam Vol. C 10
306 Tellurates
derived with La 2 (Te0 3 h · n H2 0 annealed at 150°C, i. e., n ~ 3, or annealed at 400°C, i. e.,

n ~ 0.45 (values in parenthesis): reflection maxima at 400 ± 7 and 680 ± 10 cm- 1 (420 ± 5
and 690±15cm- 1); reflection minima at 495±10 and 850±20cm- 1 (515±15 and
840 ± 10 cm- 1); Longitudinal optical phonans at 425 ± 10 and 800 ± 10 cm- 1 (427 ± 10 and
725 ± 10 cm- 1); transversal optical phonans at 570 ± 10 cm- 1 (545 ± 10 cm- 1). Dielectric
constants for high and Low frequencies (±0.1) are EX; = 5.1 (5.0) and Eo = 13.2 (19.8),
Voloshina et al. [9]. The IR transmission spectra of M2 (Te0 3h · n H20 (with M = La to Lu)
annealed at 150°C (i. e., n ~ 3) show absorption maxima at the following wave numbers v:
M2 (Te0 3 h · n H2 0 v in cm- 1
La 2 (Te0 3 h · n H2 0 412 705 1395 1490 1650 3440
Pr 2 (Te0 3 h · n H2 0 413 700 1390 1498 1655 3470
Nd 2(Te0 3 h · n H2 0 405 700 1390 1500 1650 3360
Sm 2 (Te0 3 h · n H2 0 412 700 1395 1500 1650 3430
Eu 2 (Te0 3 h · n H2 0 412 700 1395 1500 1640 3435
Gd 2 (Te0 3 h · n H2 0 407 700 1390 1515 1650 3460
Tb 2 (Te0 3 h · n H2 0 410 700 1394 1515 1640 3360
Dy 2 (Te0 3 h · n H2 0 413 700 1395 1520 1660 3400
Ho 2 (Te0 3 h · n H2 0 415 700 1393 1520 1645 3400
Er 2 (Te0 3 h · n H2 0 420 715 1390 1520 1640 3370
Tm 2 (Te0 3 h · n H2 0 415 705 1390 1520 1640 3350
Yb 2 (Te0 3 h · n H2 0 415 710 1395 1535 1640 3370
Lu 2 (Te0 3 h · n H2 0 410 710 1390 1540 1640 3370
The bands between 405 and 420 cm- 1 are attributed to M-0 vibrations and those between 700
and 715 cm- 1 are assigned to antisymmetrical stretching vibrations of the Teo~- anion. The
bands at ~ 1390, ~ 1500, and ~ 1640 cm- 1 correspond to the water deformation vibrations
8(H 20) and those at ~3400 cm- 1 to the water Stretching vibrations v(H 2 0). Spectra in the
range 40 to 5000 cm- 1 for La 2 (Te0 3 h · n H2 0 annealed at 150, 400, and 580°C are presented
in the paper. The water in M2 (Te0 3h · n H2 0 is crystallization water, Voloshina et al. [8].
Chemical Reactions
On heating La 2(Te0 3h · 6 HP to constant weight at 150, 200, 400, or 500°C the tellurates(IV)
La 2 (Te0 3 h · n H2 0 with n = 3, 1.6, 0.45, and 0, respectively, were formed, Voloshina et al.
[2, 9]. ALL studied tellurates(IV) M 2 (Te0 3h · n H20 maintained at temperatures of 150 to 400°C
are X-ray amorphaus; those maintained at 500 to 580°C have the ct-M 2 (Te0 3h structure,
Voloshina et al. [8]. Freshly precipitated cerium(lll) tellurate(IV) is oxidized immediately under
ambient conditions to cerium(IV) tellurate(IV) and then to cerium(IV) tellurate(VI), Dobrowolski
[10]; see below. On heating Pr 2 (Te0 3h (H 20 content not reported) at a heating rate of
10 K/min the compound is dehydrated at 150°C to form amorphaus Pr 2 (Te0 3 h, which begins
to crystallize at 500°C. Exotherrnie effects at 570 and 640°C correspond toslight (insignificant)
oxidation and subsequent crystallization. At 960 to 980°C melting and reduction from Tev 1 to
Te 1v are observed. The products were identified by X-ray and chemical analyses, Maier et al.
[6]. At the melting points ( > 950°C) the compounds oxidize and Te0 2 volatilizes and no crucible
material, including Pt, could be found in the melts at these temperatures, Redman et al. [11].
Eu 2 (Te0 3 h · 2 H2 0 is reduced by H2 at 400°C, forming Eu Te with an admixture of oxide telluride,
as shown by DTA and X-ray analysis. Pure EuTe is obtained by reacting a Eu 2 (Te0 3 h · 2 H20
+ Te mixture in a 1:1 ratio for 2 h at 500°C and eliminating the excess Te by briet annealing
in H2 at 850°C, Kravchenko et al. [7].
Gmelm Handbook
RE Main Vol. C 10
Tellurates(IV) 307
ALL M2(Te0 3 )s (water content not reported) are very sparingly soluble in H20, the solution
being slightly alkaline. They are resistant against oxidation, except Ce 2(Te0 3b, which oxidizes
rapidly to Light green Ce(Te0 3b and then to brown Ce(Te0 4b. The tellurates M 2(Te0 3 )s are
soluble in HCL, H2S0 4 , and HN03 . The solution in concentrated HCL takes on a yellow color
characteristic of H2TeCL6 . The H2S0 4 solution is cherry red from TeS0 3 • The compounds are
insoluble in solutions of Na2Te0 3 in excess andin organic solvents, Dobrowolski [10]. Similar
properties are reported by Voloshina, Obolonchik [1]. The tellurates(IV) are easily soluble in
hydrochloriG and nitric acids and do not dissolve in alkalis, alcohol, ether, and acetone [1].
References:
[1] A. L. Voloshina, V. A. Obolonchik (Ukr. Khim. Zh. 48 [1982]1028/9; Soviet Progr. Chem.
48 No. 10 [1982] 21/3).
[2] A. L. Voloshina, L. A. lvanchenko, V. A. Obolonchik, E. S. Lugovskaya (Poroshkovaya
Met. 1982 No. 9, pp. 53/7; Soviet Powder Met. Metal Ceram. 21 [1982]728/31).
[3] S. Prasad, K. C. Pathak (J. Electroanal. Chem. 12 [1966]360/2).
[4] S. Prasad, S. Kumar (J. Proc. lnst. Chem. [lndia]35 [1963] 4/9).
[5] S. Prasad, K. C. Pathak (J. Indian Chem. Soc. 43 [1966]176/8).
[6] A. I. Maier, T. A. Soldatova, M. Kh. Karapet'yants (Tr. Mosk. Khim. Tekhnol. lnst. No. 62
[1969]43/6; C.A. 74 [1971] No. 131284).
[7] L. Kh. Kravchenko, V. V. Sokolov, T. E. Sokolova, Yu. A. Stonoga (lzv. Akad. Nauk SSSR
[8] A. L. Voloshina, L. A. lvanchenko, V. A. Obolonchik, V. A. Serdyuk (Ukr. Khim. Zh. 50
[1984]383/6; Soviet Progr. Chem. 50 No. 4 [1984]51/3).
[9] A. L. Voloshina, L. A. lvanchenko, V. A. Obolonchik, N. G. Khotynenko (Zh. Prikl. Spek-
trosk. 40 [1984] 975/8; J. Appl. Spectrosc. [USSR]40 [1984]693/5).
[10] J. Dobrowolski (Roczniki Chem. 40 [1966]1169/72; C.A. 66 [1967] No. 61343).
30.4.1.7 M 2Te 4 0 11 (= M20 3 ·4 Te0 2)

The compounds were prepared, Like M 2 (Te0 3 )s, by solid state reaction between M 20 3 (M
not Ce, Pr, Pm, Tb) and Te0 2 at 850°C. Single crystals of M 2Te4 0 11 were obtained by air-
cooling melts with the composition 85 mol% Te0 2 and 15 mol% M20 3 contained in tightly
covered Pt crucibles. Melt temperatures of 850 to 1 000°C (the high er temperatures for the
heavier M) and cooling rates of 2 to 20 K/h were employed. The slow cooling rates did not
result in Larger crystals. The crystals were mechanically separated. Some Larger crystals may
be obtained by employing a selecting technique, Redman et al. [1].
Ce 2Te 4 0 11 , Pr2Te 40 11 , and Tb 2Te 40 11 , are also obtained by solid state reaction between
Ce 20 3 , Pr6 0 11 , or Tb 40 7 and Te0 2 in vacuum for Ce andin air for Pr and Tb. The mixtures with
ratios of 1:2, 1:2.1, and 1:2.1 were ground in an agar mortar and heated stepwise with
quenching and regrinding between the steps. Ce was heated to 773 and 973 K, Pr to 923, 973,
and 993 K, and Tb to 923, 973, and 1043 K, Parada et al. [5]. ln the systems M(N03 )s-Na 2Te0 3 -
H20 no M2Te 40 11 is observed, Voloshina, Obolonchik [2]. DTA and X-ray studies of the M 20 3 -
Te02 systems with M = Y or Er indicate the existence of M2Te 4 0 11 (cf. p. 299), Safonov et al.
[3]. For the preparation of La 2Te 4 0 11 the pelletized mixture of 0.651 g La 20 3 and 1.276 g Te0 2
was wrapped in a Pt foil and fired in an N2 atmosphere at 800°C for 8 to 10 h, Kennecott
Gmelln Handbook 20'
RE Mam Val. C 10
308 Tellurates
Copper Corp., Redman [4]. With the object of evaluating M 2Te 40 11 as a possible Laser host
material an attempt was made to pull Nd-doped La 2Te 40 11 crystals from a melt with 14.6 mol%
La2 0 3 , 0.90 mol% Nd2 0 3 , and 84.5 mol% Te0 2 . The resulting crystals contained poly-
crystalline inclusions but good monocrystalline portions could be cut from them. Their La: Nd
ratio was 12:1, slightly more than in the melt, Redman et al. [1]. La 1_51 Nd 0 .49Te 40 11 was
prepared by carefully cooling a mixture of 3.909 g La20 3 , 1.0 g Nd 20 3 , and 13.56 g Te0 2 ,
previously heated to 900°C, Kennecott Copper Corp., Redman [4].
Physical Properties
The platelets of Nd 2Te4 0 11 with extended basal pinacoidal faces were suitable for single
crystal X-ray analyses. The crystals belong to the monoclinic system with the space group
C2/c-C~h (No. 15) or Ce-Ci (No. 9). Pyroelectric tests did not indicate the absence of a center
of symmetry. The measured density of 6.3 g/cm 3 allows Z = 4, the cell dimensions are a =
12.63, b = 5.21, c = 16.28 A; ß = 106.1° (error 0.25%). ALL examined tellurates(IV) gave
similar powder patterns, showing that they form an isomorphaus series [1]. The Lattice
constants (error 0.07% [1]), cell volumes V, and X-ray densities D are given in the following
table:
M2Te4 0 11 a in A bin A c in A ß V in A3 D in g/cm 3 Ref.
Y2Te 40 11 12.37 5.100 15.99 106.12° 968.8 5.92 [1]

La 2Te4 0 11 12.80 5.278 16.42 105.92° 1066.5 6.01 [1]
Ce 2Te 40 11 12.734(4) 5.247(1) 16.403(8) 106.00(4)0 1 053.6(5) 6.09 [5]
Pr2Te 40 11 12.685(5) 5.230(2) 16.329(9) 105.95(5)D 1 041.6(6) 6.17 [5]
Nd 2Te 4 0 11 12.60 5.216 16.27 106.00° 1028.4 6.30 [1]
Sm 2Te 40 11 12.56 5.174 16.19 106.00° 1011.2 6.48 [1]
Eu 2Te 4 0 11 12.50 5.163 16.14 106.02° 1001.2 6.57 [1]
Gd 2Te4 0 11 12.46 5.142 16.09 106.08° 991.1 6.71 [1]
Tb 2Te 40 11 12.458(7) 5.129(2) 16.08(1) 106.02(7)0 987.6(8) 6.75 [5]
Dy2Te 40 11 12.40 5.120 16.04 106.08° 978.7 6.86 [1]
Ho2Te4 0 11 12.37 5.105 16.00 106.12° 971.0 6.95 [1]
Er2Te 40 11 12.35 5.089 15.97 106.14° 964.4 7.03 [1]
Tm 2Te 40 11 12.29 5.073 15.94 106.10° 955.2 7.12 [1]
Yb 2Te 40 11 12.26 5.069 15.92 106.15° 950.6 7.21 [1]
Lu 2Te4 0 11 12.26 5.058 15.90 106.18° 946.6 7.27 [1]
The calculated densities are consistent with the range of measured densities. lnterplanar
spacings d, relative intensities I, and Miller indices of La 2Te40 11 and Lu 2Te4 0 11 are given [1];
for main d and I values of Y2Te 40 11 and Er 2Te4 0 11 , see Safonov et al. [3]. lnterplanar spacings
and intensities for Ce 2Te 40 11 , Pr2Te 40 11 , and Tb 2Te4 0 11 are tabulated in [5]. The melting point
of Er 2Te4 0 11 is 1260 ± 50°C [3].
Ce2 Te 40 11 , Pr2Te4 0 11 , and Tb2 Te4 0 11 are paramagnetic. The molar susceptibility Xmot obeys
a Curie-Weiss Law between 77 and 300 K. The paramagnetic Curie temperatures E>P, 1/Xmot•
and magnetic moments 11 are as follows:
M 1/XmoL in moUcm 3 -E>P in K 11 in 11s 11(theor)
Ce 1.393 T + 90.2 64.8 2.407(7) 2.56

Pr 0.672 T + 20.3 30.2 3.46(1) 3.62
Tb 0.086 T + 0.24 2.8 9.72(4) 9.72
Gmelm Handbock
RE Mam Vol. C10
Tellurates(IV) 309
Therefrom an oxidation state of 3 is confirmed. The IR spectra of yellow Ce 2Te 40 11 , green

Pr2Te 40 11 , and white Tb2Te 40 11 on KBr discs between 250 and 800 cm- 1 show 11 bands which
shift to higher frequencies with increasing atomic weight due to lattice Vibrations; for instance,
the strong band that occu rs at 400 cm - 1 for Ce is observed at 404 cm - 1 for Pr and at 427 cm - 1
for Tb [5].
Transmission spectra were obtained for single crystalline La 2Te40 11 and Nd 2Te4 0 11 . For
La2Te 4 0 11 the short wave absorption edge occurs at 0.3251-lm. The material is then transparent
out to 61-1m where a sharp cutoft occurs. Nd 2Te40 11 shows the characteristic absorptions of
the Nd 3 + ion with a short wave absorption edge at 0.34 11m and transparency to 6 11m. Dielectric
constant E, dissipation factor tan ö of Nd 3 + -doped La2Te 40 11 , and electrical resistivity Q in
Q · cm (all for 1 kHz) are summarized in the following table:
t in °C. 25 80 100
E .. 14.399 14.566 14.692

tan ö 0.00049 0.0004 0.00041
Q .. 4.01 X 1011 3.24 X 1011 1.26 X 1011
The results are typical for good insulators. The fluorescence at 1.061-lm excited by a Xe flash
Lamp was detected. The decay time from the slope of the decay curve is 721-ls. This Low value
rules out the usefulness of this material as a Laser host, Redman et al. [1], as proposed by
[4], according to whom it may also be used as pigment in ceramic glasses, paints, and dyes.
References:

[2] A. L. Voloshina, V. A. Obolonchik (Ukr. Khim. Zh. 48 [1982]1028/9; Soviet Progr. Chem. 48
No. 10 [1982] 21/3).
[3] V. V. Safonov, E. G. Yarotskaya, R. 8. lvnitskaya (Zh. Neorgan. Khim. 25 [1980] 865/6;
Russ. J. lnorg. Chem. 25 [1980] 482/3).
[4] Kennecott Copper Corp., M. J. Redman (U.S. 5723600 [1971/73]; C.A. 79 [1974] No. 33227).
[5] C. Parada, J. A. Alonso, I. Rasines (lnorg. Chim. Acta 111 [1986]197/9).
As with the Sr and Pb tellurates(IV) there exist anti-glass phases among the lanthanide
tellurates(IV). These metastable nonstoichiometric crystalline compounds are formed from
Te0 2 and oxides with ionic radii suitable for stabilizing the fluoritetype structure. The samples
were prepared from powder mixtures of Te0 2 and M20 3 (or Ce0 2 , Pr60 11 , and Tb 40 7) by
quenching the homogeneous melt to room temperature forM = Y, La to Ho or to the tempera-
ture of Liquid N2 forM = Er to Lu. M-richer phases with M: Te = 3:2 to 11:10 form on heating
Gmelm Handbock
RE Mam Vol. C 10
310 Tellurates
the powders 2 h at 800°C under N2; see p. 301. The lattice constants a of the cubic CaF 2 phases
of the approximate formulas are as follows:
compound a in A compound a in A
Y2Tes01s 5.586 Tb 2Te 60 15 5.600

La 2Te 60 15 5.695 Dy2Tes01s 5.587
CeTe6013. 80 5.675 Ho2Te 50 13 5.575
Pr2Te 60 15 5.668 Er2Te 50 13 5.567
Nd 2Te 60 15 5.655 Tm 2Te 50 13 5.551
Sm 2Te 60 15 5.638 Yb 2Te40 11 5.537
Eu 2Te 60 15 5.617 Lu 4Te 70 20 5.49
Gd 2Te6 0 15 5.611
The metal positions in the CaF2 structure are occupied statistically by M and Te and the
population of the anion sites is incomplete. At 500 to 600°C the phases decompose, forming
stable crystalline compounds, Trömel et al. [1]; seealso [2]. (Composition CeTe 60 13_8 from a
private communication to the Gmelin-lnstitut.)
References:
[1] M. Trömel, W. Hützler, E. Münch (J. Less-Common Metals 110 [1985]421/4).
[2] M. Trömel, H.-G. Burckhardt, H. Heydarian, F. W. Hützler, E. Münch (Acta Cryst. A 40 [1984]
Suppl., p. C216).
30.4.2 Compounds in the Cerium(lll, IV)-Tellurium(IV, VI)·O(-H 20) System

Because of the complex redox equilibria these compounds are treated together. For
cerium(lll)tellurates(IV) and cerium(IV)tellurates(VI) see pp. 301/10 and 317, respectively.
The Ce0 2- Te0 2 System

The phase equilibria in the Ce0 2-Te0 2 system were studied by DTA, TGA, X-ray diffraction,
and XPS. A phasediagram was established in the temperature range -650 to 1100°C and is
given in Fig. 132. lt shows the existence of Ce(Te0 3b, congruently melting at 805°C, and two
eutectics, Ce0 2 + Ce(Te0 3b at 51 mol% Te0 2 and 794°C and Ce(Te0 3b + Te0 2 at 91 mol%
Te0 2 and 689°C. At lower temperatures the phase relations are very complex due to Ce and
Te being in two valence states each. At temperatures as low as 450°C in airsolid solutions
(Ce, Te)0 2 exist. After a redox process leading to Ce 2(Te04 b (500 to 600°C} a reverse redox
reaction at higher temperatures ( >550°C) forms Ce(Te03b, which is also obtained from
(Ce, Te)0 2 in N2 at 600°C, Bart et al. [1].
A compound of the composition CeTe30 8 ( = Ce02 · 3 Te0 2) was previously claimed by
Bayer [2], but according to Sotto, Baran [3] only Ce(Te0 3b ( = Ce0 2 · 2 Te0 2) exists in the
system Ce0 2-Te0 2 at 600°C in air. Sorrell [4] also stated the stability of Te 1v in CeTe 30 8,
TiTe 30 8, and ZrTe30 8 is unusual in view of the widely reported stability of Tev1• A
cerium(IV)tellurate(IV) with a Ce: Te ratio of 1 : 1 is reported by Nabi, Rao [5] but without any
confirmation in the literature.
Gmelm Handbook
RE Mam Vol. C10
The Cerium(lll, IV)-Tellurium(IV, Vl)-0 System 311
1100
I
I
I
1000 I
u I
0 I
·=
~ 900
I
I
I
~ I
2
&.
E
{!!
800 . 794°C
I
,~~~
805°C
?;
700 0
~
689°C
~
20 40 60 80 100
mot•f. Te0 2
Fig. 132. Phase diagram of the Ce02-Te02 system.
Sampies over the whole composition range were prepared by adding Ce(N0 3lJ · 6 H20 to
a hot acidic aqueous solution of H6Te06 . The solutions were evaporated to dryness under
continuous stirring and left overnight at 110°C. Subsequently, the samples were calcined in
air up to 600 °C in 50 K intervals for 8 h , Bart et al. [1), Bart, Giordano [6].
(Ce, Te)0 2 Solid Solutions
When dri ed Ce(N03!J · 6 H20 + H6Te06 mixtures are calcined at about 450 to 500°C the
X-ray spectra show the presence of yellow fluoritetype a.- and ß-(Ce, Te)02 solid solutions up
to a limiting value at ~ 80 mol % Te0 2 and lattice constants a = 5.411 A at 0 and 5.666(3) A
at 80 mol% Te0 2 . lnterplanar spacings and relative intensities of the powder pattern and the
IR spectrum at 400 to 1000 cm - 1 for 60 mol % Te02 and a = 5.551 A are given. The more
highly erdered ß may possibly arise from erdering upon cooling the more diserdered a..
Alternatively, ß might represent a stoichiometrically fairly weiL defined composition. When
heated in air, (Ce,Te)02 with tetravalent Ce and Te forms Ce2 (Te04!J at 500 to 550°C with Ce 111
and Tev1. On heating in an inert atmosphere Ce(Te0 3) 2 is obtained at ~ 650 °C, Bart et al. [1].
According to Bart, Giordano [6] the binary oxide system consists of a single nonstoichiometric
fluorite type a.-(Ce, Te)02 phase up to 80 mol % Te0 2 and a Te-saturated solid solution
ß-(Ce, Te)02 together with a.-Te0 2 at > 80 mol % Te02 in the case of the Si02-supported
Ce-Te-0 system. The variation of the lattice constant with the Te02 concentration is shown in
Fig. 133, p. 312, [6] .
Cerium(IV)Tellurates(IV)
Cerium(IV)tellurate(IV) with a 1 1: Ce : Te ratio was prepared as a cation exchanger by

mixing solutions of ammonium cerium(IV) sulfate and tellurous acid at pH ~ 1 (adjusted
Gmel1n Handbook
RE Mam Vol. C10
312 Tellurates
I
I"
I
80
N
0
~
~0 40
E
5.5 5.6 5.7

a in A
Fig. 133. Lattice constants of solid solutions in the Ce0 2-Te02 system.
with H2S04 or HN03 ). The Ce1v concentration was varied between 0.02 and 0.05 M and the
concentration of the tellurous acid between 0.02 and 0.10 M. The precipitates were allowed
to settle for 24 h, washed with water, filtered, and dried at 40°C (not higher). A sample obtained
at pH = 7 showed no ion exchange properties . An IR band with maximum at 1050 cm - 1 is
attributed to Ce-0 vibrations ; a sharp peak at 1620 cm- 1 and a broad band in the region
3000 to 3600 cm - 1 are assigned to vibrations of external H2 0 and to interstitial H2 0 molecules,
respectively. The compound is quite stable in H20, HCOOH, CH3COOH, and fairly stable in
low concentrations of HCl and HN03 . The solubility S is as follows :
solvent 2M HN03 0.1 M HCl 1 M HCl 1M HCOOH

S in mg/L 196 62 154 80
solvent 0.1 M CH 3 COOH 0.1 M citric acid 0.1 M oxalic acid

S in mg/L 54 42 88
Data on the ion exchange of alkali metaland alkaline-earth metal ions are given in the paper,
Nabi, Rao [5] .
Ce(Te03h ( = Ce0 2 · 2 Te02 )

The compound, melting congruently at 805 °C, exists in the system Te02-Ce0 2 ; see p. 310.
lt is obtained by reaction of Ce(N03 )s · 6 H20 with hot aqueous solution of H6Te0 6 and is
reported to be orange-yellow. lt is also obtained by heating Ce2 (Te04 b in air at > 550 °C or
(Ce, Te)02 solid solutions in inert atmosphere at ~ 650°C (1]. The Lightgreen compound formed
rapidly by oxidation of Ce 2 (Te0 3 )s at the precipitation from aqueous solutions (cf. p. 306) . The
fo rmed Ce(Te03 h was then oxid ized to brown Ce(Te04 h, Dobrowolski [7]. Ce(Te0 3 h was also
formed by the reaction of Ce 20 2Te with boiling water, Domange et al. [8]. Ce(Te03 h was
prepared by solid state reaction of Te0 2 and Ce02 in the molar ratio 2: 1. The finely powdered
constituents were heated 48 hat 600°C in a Pt crucible in air and thoroughly ground in between
a few times. Ce(Te0 3h has a cubic CaF 2-type superstructure with a = 21 .261(8) A, Z = 64 ;
the calculated and measured (at 25°C} densities are 5.43 or 5.3 g/cm 3 , respectively. lnterplanar
spacings and relative intensities of the X-ray powder diagram are given , Sotto, Baran [3];
see also [1] . The space group was not identified but it is of Lower symmetry than that of
Gmelon Handbook
RE Ma m Vol. C 10
The Cerium(lll, IV)-Tellurium(IV, Vl)-0 System 313
CaF2 (Fm3m-O~) and TiTe 30 8 (la3-Th). The lower symmetry is also shown by the splitting of IR
bands. The following maxima of KBr pellets are given: 260 (w), 301 (m), 329 (st), 365 (m), 390
(sh), 405 (sh), 488 (st), 612 (m), 635 (v st), ~670 (sh), 716 (m), and 753 (m) cm- 1 ; assignment
would be questionable [3]. An IR and aRaman spectrum are given in [1].
CeTe 30 8(?) ( = Ce02 · 3Te0 2 )

The crystalline compound is prepared by intimately mixing finely powdered Te0 2 and
Ce0 2 in a 3: 1 molar ratio and heating from 600 to 700°C (preferable at 650°C) for 20 h in air.
lnterplanar spacings and intensities of the powder pattern are given in a table. The structural
similarities with ZrTe 30 8 and TiTe30 8 are discussed. CeTe 30 8 has an intense yellow color and
may be employed in coloring ceramics, enamals, and so on. lt is stable up to ~ 750°C. At
higher temperatures Te begins to volatilize as Te0 3 . The compound is insoluble in H20 and
dilute HCl and soluble in strongly alkaline solutions, Bayer [2], Owens-lllinois Glass Co.,
Bayer [9]. According to the studies of [1] the preparations of [2, 9] contain a.-Te0 2 and Ce(Te0 3 b,
and the d spacings conform to those of Ce(Te0 3b.
Cerium(III)Tellurates(VI)
Ce 2(Te0 4h (Hydrate?)
A white gelatinous precipitate forms in aqueous solution according to the reaction:
3 Na2Te04 + 2 Ce(N0 3)s ---> 6 NaN03 + Ce 2 (Te0 4)s. lt is easily soluble in acids, Montignie
[10].
Ce 20 3 • 2 Te0 3 • 10 H20
To a solution of 2 g H6Te06 in 50 ml H20 a solution of Ce(N0 3)s in 0.5 N HN03 (with
0.0157 g/ml Ce) was added followed by a solution of 0.5 N KOH until pH 5 is reached. The
white amorphous precipitate was thoroughly washed with H20 and dried in air at 50°C.
The structure may be CeOH[Te0 2 (0H) 4]· 2.5 H20. The IR spectrum was recorded at 600 to
1800 cm- 1 in KBr tablets and is virtually identical with that of Ce0 2 • Te0 3 • 4.5 H20. The
thermal decomposition was studied by TG, DTG, and DTA up to ~900°C; figures are given in
the paper. Dehydration takes place up to 500°C. At 508°C TeVI is reduced to Te 1V by removal
of oxygen. The presence of Te 1v at lower temperature is due to the reaction Tev1 + 2 Ce 111 --->
Te 1v + 2 Ce 1v. Exoeffects at 537 and 553 °C, not clearly distinguished, are due to rapid formation
of a crystalline phase and the oxidation of Te 1v to Tev1 by atmospheric oxygen, respectively.
Above 690°C Ce02 appears and is the only productat 820°C. Ce20 3 · 2 Te0 3 · 10 H20 is readily
soluble in acids, Gusel'nikov et al. [11].
References:
[1] J. C. J. Bart, N. Giordano, C. Gianoglio (Z. Anorg. Allgem. Chem. 481 [1981]153/67).
[2] G. Bayer (Ber. Deut. Keram. Ges. 39 [1962] 535/54, 543).
[3] I. L. Botto, E. J. Baran (Z. Anorg. Allgem. Chem. 484 [1982] 215/20).
[4] C. A. Sorrell (J. Am. Ceram. Soc. 51 [1968] 674/7).
[5] Syed Ashfaq Nabi, Rifaqat Khan Rao (J. Indian Chem. Soc. 58 [1981]1030/2).
[6] J. C. J. Bart, N. Giordano (J. Catal. 75 [1982]134/9).
Gmelm Handbook
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314 Tellurates
[7] J. Dobrowolski (Roczniki Chem. 40 [1966]1169/72).

[8] L. Domange, J. Flahaut, Abbas Naderi Chirazi (Bult. Soc. Chim. France 1959 150/2).
[9] Owens-lllinois Glass Co., G. Bayer (U.S. 3053617 [1960/62], U.S. 3053619 [1961/62]; C.A.
58 [1963] 276).
[10] E. Montignie (Bull. Soc. Chim. France [5] 2 [1935]864/6).
[11] V. S. Gusel'nikov, V. M. Zaitsev, A. B. Kolyadin, V. Va. Mishin, V. A. Serova (lzv. Akad.
Nauk SSSR Neorgan. Materialy 8 [1972]122/6; lnorg. Materials [USSR]S [1972]105/8).
30.4.3 Tellurates(VI)
For cerium(lll)tellurates(VI) see Section 30.4.2, p. 310.
30.4.3.1 M6 Te0 12 (= 3 M20 3 ·Te03 )

The compounds were prepared by firing a mixture of Te0 2 and M20 3 (M = Sc, V, La, Nd,
Sm, Gd, Dy, Er, and Lu) in 0 2 first at 900°C and then at 1100°C. The X-ray powder diagrams
of the tellurates with M = Sc, V, and Gd to Lu show them to be rhombohedrallike V6 U0 12 .
Forthelarger M a face-centered cubic fluorite structure is found with a = 5.47 and 5.40 A for
M = Nd or Sm. For M = La a cubic pyrochlore structure with a = 11.12 A is observed. The
(hexagonal) lattice constants of the rhombohedral tellurates are as follows:
M .. Sc V Gd Dy Er Lu
a in A 9.20 9.75 9.89 9.75 9.69 9.59

c in A 8.72 9.29 9.42 9.33 9.25 9.12
Reference:
G. Blasse (J. lnorg. Nucl. Chem. 31 [1969] 3335/6).
30.4.3.2 M2Te0 6 ( = M20 3 · Te0 3)

Tellurates(VI) M2Te0 6 with M = Pr, Nd, Sm, Eu, or Gd form by oxidation of M20 2Te at 750
to 800°C via the tellurates(IV) M2Te0 5 (except M = Eu) as intermediates, Kent, Eick [1]. Well-
crystallized tellurates with M = Sc to Lu, but not Ce and Pm, were synthesized by thoroughly
mixing equimolar quantities of M20 3 and H6Te06 and heating them in a quartz crucible for 4 h
successively at 800, 900, and 1 000°C in 0 2 . The samples were ground in an agate mortar after
each heating step. To prevent oxidation of Pr and Tb to the tetravalent state these components
were preheated in air in an open crucible at 500°C to decompose H6Te0 6 , Natansohn [2].
Lu 2Te0 6 was obtained by reacting the oxides at 800°C, Malone et al. [3].
Properties
The well-defined, sharp X-ray powder diagrams were indexed on the basis of a hexagonal
unit cell. The isomorphous tellurates with M = V to Tm contain 8 molecules. Those with M =
Sc and Lu arealso isomorphous and contain three molecules; in Vb 2Te0 6 both structure types
Gmelm Handbook
RE Mam Vol. C10
Tellurates(VI) 315
occur. lnterplanar spacings and relative intensities for M 2Te0 6 with M = Sc, Y, La, Eu, Er,
and Lu are given in the paper. The Lattice constants, a and c in A, and the calculated and
measured densities, Deale and Dexp in g/cm 3 , are as follows:
M 2Te0 6 a c Deale Dexp
Sc 2Te0 6 8.74 4.80 4.92 4.90

Y2Te0 6 10.46 9.95 5.67 5.60
La 2Te0 6 10.96 10.35 6.22 6.10
Pr 2Te0 6 10.79 10.24 6.50
Nd 2Te0 6 10.77 10.18 6.65 6.72
Sm 2Te0 6 10.64 10.10 7.03 7.04
Eu 2Te0 6 10.63 10.06 7.12 7.11
Gd 2Te0 6 10.60 10.05 7.27 7.17
Tb 2Te0 6 10.54 10.02 7.46 7.50
Dy 2Te0 6 10.50 9.98 7.65 7.75
Ho2Te0 6 10.45 9.94 7.80 7.90
Er 2Te0 6 10.42 9.90 7.96 7.84
Tm 2Te0 6 10.39 9.85 8.10 7.91
Lu 2Te0 6 8.94 5.08 8.12 8.19
The Lattice constants vary Linearly with the M3+ ionic radii within the series (M = Y to Tm);
a figure is given [2]. Of the possible space groups P6 3-Cg, P6 3/m-qh, or P6 322-Dg the first one
is favored from spectroscopic investigations on Y2Te0 6 , Blasse, Kamphorst [4]. The X-ray
powder pattern of Lu 2Te0 6 and the Lattice constants reported by [2] were confirmed. The
cation distribution giving the best agreement with the observed intensities was an idealized
Na2SiF 6 structure (R = 0.09); for calculated and observed d-values, see the paper. The Lu and
Te atoms are octahedrally coordinated to a distorted close-packed array of 0 with distortions
Lengthening the Lu-0 distances and shortening the Te-0 bond Lengths, Malone et al. (3]. The
following colors were observed by Kent, Eick [1]:
M 2Te0 6 Gd 2Te0 6
color white
The white crystals of M 2Te0 6 (M = Y, La, Gd, and Lu), activated by Eu, Dy, Ho, Er, show
significant Luminescence under UV or cathode ray excitation, Natansohn [5]. The IR and
Raman spectra of Y2Te0 6 were studied and the following bands of the tellurate(VI) ion
observed (in cm- 1 ):
Raman 440 510 520 580 615 635 670 705 750
IR . . . 430 470 525 550 585 600 670 710 750
The Last two correspond to v 1 and v3 , respectively, the others to v2 . From the spectra it is
concluded that Te is surrounded octahedrally by 0 and the space group must be P6 3-Cg. lt is
assumed that the symmetry of the Te site is trigonal, i.e., 2a or 2 bin P6 3 , Blasse, Kamphorst
[4].
When M 2Te0 6 with M = Pr, Nd, Sm, Eu, Gd are heated in air to 800°C the oxidesform [1].
Gmelm Handbook
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316 Tellurates
References:
[1] R. A. Kent, H. A. Eick (lnorg. Chem. 1 [1962]956/8; TID-15386 [1962]1/6; N.S.A. 16 [1962]
No. 14695).
[2] S. Natansohn (J. lnorg. Nucl. Chem. 30 [1968] 741/5).
[3] J. A. Malone Jr., J. F. Dorrian, 0. Muller, R. E. Newnham (J. Am. Ceram. Soc. 52 [1969]
570).
[4] G. Blasse, J. G. Kamphorst (Z. Naturforsch. 29b [1974]153/5).
[5] S. Natansohn (J. Electrochem. Soc. 116 [1969]1250/4).
For the preparation of La 2 (Te0 4 )s the solution of LaCL3 and H6Te0 6 (La:Te = 2:3) was
adjusted to pH 4.5 by aqueous NH 3 . The white flocculent precipitate was filtered, washed, and
dried in vacuum at 50°C. The compound was X-ray amorphous, Gonzalez, Oe Carvalho [1].
ln this way all M 2 (Te0 4 )s with M = Y to Lu, but not Ce, Pm were prepared in amorphaus form
by addition of NH 4 0H to an aqueous solution of MCL3 and H6Te0 6 (M: Te = 2:3 or 1: 3). NH 4 0H
can not be replaced by NaOH or KOH due to the Low solubility of Na2Te0 4 and K2Te0 4 and the
possible formation of double tellurates. At higher pH the yield would certainly be better, but
possibly hydroxide tellurates form. Double decomposition of solutions of K2Te0 4 and MCL3 at
pH < 4 was unsuccessful as was the reaction of an aqueous suspension of M 2 (C0 3)s with a
solution of H2Te0 4 , Gonzalez, De Carvalho [2].
Estimated values for the enthalpy of formation ~H:
M in M 2 (Te0 4 )s . Sc y La Ce Pr Nd Sm Eu
-~H in kcal/mol 802.5 814.5 837.9 835.4 834.9 828.9 825.9 823.9
M in M2 (Te0 4 )s . Gd Tb Dy Ho Er Tm Yb Lu
-~H in kcal/mol 822.6 819.0 814.8 805.3 802.7 801.9 801.7 799.4
The values have been derived from empirical relations of Literature data for the enthalpies of
formation of rare earth chlorides, series of some sulfates, selenates, and tellurates, as weiL
as from ionic radii, Amosov, Plyushchev [3].
The thermogram of La 2 (Te0 4 )s shows evidence of isothermal weight Loss at 350 to 400 and
750 to 820°C. Above 850°C a sharp decrease in weight is observed. The cation exchange
properties of La 2 (Te0 4 )s and NaCL solution are studied; a figure of the exchange capacity
versus pH is given. The functional group must be HTe04 obtained by the hydrolysis according
to La3+ + OH- ~ LaOH 2 +, Teo~- + H+ ~ HTe04. Above pH = 8 the formation of poly-
nuclear species, [Te(OH) 6 b0H- and [Te(OH) 6 b(OH)~-, predominates, Gonzalez, Oe Carvalho
[1]. The thermal decomposition of M 2 (Te0 4 )s with M = Y to Lu (but not Ce, Pm) was studied
by DTA, TG, and DTG at heating rates of 0.5 to 25 K/min. The thermograms exhibit a similar
shape, with two well-defined plateaus at 300 to 450°C and 700 to 850°C. A third plateau, not
weiL defined in some thermograms, is observed in the range of 520 to 600°C. Above 800 to
850°C a net weight Loss is noticed up to 1 000°C, the maximum temperature reached in the
experiments. La 2 (Te0 4 )s, Gd 2 (Te0 4 b, and Yb 2 (Te04 )s were taken as representatives of three
Gmel1n Handbook
RE Ma1n Vol. C 10
Tellurates(VI) 317
groups and the formal composition of their decomposition products is as follows (from the
weight-loss curves):
M2(Te0 4 b . La 2(Te04 b Gd 2(Te04 b Yb 2(Te04 b
heated up to 400°C La 2Te 2_60 9_6 Gd2 Te2.s010.2 Yb 2Te2.70 11 _7

heated up to 750°C La2 Te2.60a.9 Gd2Te2.s09.3 Yb 2Te2.70 10_3
heated up to 1 000°C La 2Te 2_60 8 .4 Gd2Te2.sOa.9 Yb 2Te2.70 9_8
Ouring the process M is also increasingly volatilized with increasing temperature and atomic
number, the ratio M :Te remaining constant at ~ 2:2.6 in the residue and the volatile products.
Te is partly reduced; for instance for M = La it was found that after heating to 1 000°C ~ 70%
of the Te is present as Te 1v. Only products heated at 750 and 1 000°C exhibit a crystalline
pattern, the others being amorphaus (line diagrams for M = La are given in the paper). The
transition of amorphaus to crystalline products may occur at about 600°C as shown by an
endothermic peak for M = Gd. ALL the tellurates are rather insoluble in H20. The following
table shows the solubility S in g/L at 25°C:
M in M2(Te0 4 b y La Pr Nd Sm Eu Gd
S X 106 . . . . 60 20 28 64 6 64 58
M in M2(Te04 b Tb Oy Ho Er Tm Yb Lu
SX 106 . . . . 20 36 42 274 78 20 184
These low values suggest the possibility of using the tellurates(VI) as quantitative precipitating
agents of lanthanides [2].
References:
[1] C. G. Gonzalez, R. A. Guedes Oe Carvalho (J. Chromatog. 136 [1977]176/7).

[2] C. G. Gonzalez, R. A. Guedes Oe Carvalho (Thermochim. Acta 24 [1978]165/75).
[3] V. M. Amosov, V. E. Plyushchev (lzv. Vysshikh Uchebn. Zavedenii Khim. Khim. Tekhnol.
11 [1968]1128/34, 1131; C.A. 70 [1969] No. 61888).
30.4.3.4 Cerium(IV)TeLLurates(VI)
The compound forms according to 2 K2Te04 + Ce(S0 4b---+ 2 K2S04 + Ce(Te0 4 ) 2 in very
basic solutions with a great excess of K2Te0 4 , Montignie [1]. lntermediary formation occurs
on heating Ce 20 2Te in air to 928°C with 100 K/h. However, at 550°C the tellurate starts to
dissociate and Te0 2 vaporizes, Oomange et al. [2]. Ouring preparation of Ce 2(Te0 3b (see
p. 312) this compound is rapidly oxidized to Lightgreen Ce(Te0 3b and then to brown Ce(Te0 4 b
in the air, Oobrowolski [3]; see also Montignie [4]. The compound is soluble in weak acids
and is easily reduced in acidic media to Ce3+ by H20 2 and in neutral media a red-brown ceric
hydroxide is formed. On heating the oxides are obtained [1].
Gmelin Handbook
RE Main Vol. C10
318 Tellurates. Telluride Halides
To a solution of 2.9 g H2Te0 4 in 25 ml H20 a solution of KOH (0.0175 g/L) was added. The
solution thus obtained and 100 ml of a solution of Ce(S0 4) 2 in 1 M H2S0 4 containing 0.0143 g/L
Ce were heated to ~ 70°C and poured tagether with thorough stirring. The solution pH was
then brought to 8 to 9 by adding a KOH solution. The yellow precipitate was carefully washed
with H20 and dried in air at 50°C. The structure may be Ce(OHb · [Te0 2 (0H) 4 ] · 1.5 H20. The
IR spectrum at 600 to 1800 cm- 1 in KBr tablets shows broad bands characteristic of amorphaus
substances; for a figure see the paper. The band at 650 cm- 1 is due to valence vibrations of
Te-0 bonds, the broad band centered at 1100 cm- 1 is due to deformation vibrations of Te-OH
bonds, and the band at 1660 cm- 1 to deformation vibrations of crystallization water. The
thermal stability was studied by TG, DTG, and DTA in air up to ~900°C at a heating rate of
10 K/min (figures are given). Dehydration takes place over a wide range of temperatures up
to 500°C (endothermic effect at 140°C). At 510°C Tev 1 is partially reduced to Te 1v but at 540°C
Te 1v is vigorously oxidized by atmospheric oxygen. At 625°C the compound melts to a yellow-
green melt. lncrease in temperature to 800 to 950°C Leads to complete decomposition in
several hours, and the only end product is Ce0 2 , Gusel'nikov et al. [5].
The yellowish basic precipitate forms according to 2 K2Te0 4 + Ce(S0 4 ) 2 + 2 H20--> 2 K 2S0 4
+ H2Te0 4 + Ce0 2 · Te0 3 · H20 in strongly acidic solutions (with an excess of Ce(S0 4 b). lt is
soluble in weak acidsandinsoluble in concentrated CH 3 COOH and KOH, Montignie [1].
References:
[1] E. Montignie (Bull. Soc. Chim. France [5]6 [1939]672/6).

[2] L. Domange, J. Flahaut, Abbas Naderi Chirazi (Bull. Soc. Chim. France 1959 150/2).
[3] J. Dobrowolski (Roczniki Chem. 40 [1966]1169/72; C.A. 66 [1967] No. 61343).
[4] E. Montignie (Bull. Soc. Chim. France [5] 7 [1940] 681/5).
[5] V. S. Gusel'nikov, V. M. Zaitsev, A. 8. Kolyadin, V. Ya. Mishin, V. A. Serova (lzv. Akad.
Nauk SSSR Neorgan. Materialy 8 [1972]122/6; lnorg. Materials [USSR] 8 [1972]105/8).
30.5 Telluride Halides. Tellurate Halides
The following section deals with rare earth compounds and systems containing tellurium
and halogens or tellurium, halogens, and oxygen; i. e., telluride halides, tellurate(IV) halides,
tellurate(VI) halides as well as the corresponding basic compounds.
Compounds Containing Fluorine
NdTeF
NdTeF was synthesized by reaction of stoichiometric amounts of NdF3 and Nd 2Te 3 in a Pt

crucible in an evacuated Si0 2 ampule in 18 h at 600°C and analyzed by X-ray diffraction
studies. Due to the thermal instability of the compound it always contained slight amounts of
Gmelm Handbook
RE Ma1n Vol. C 10
Tellurate Fluorides 319
NdF3 . lnterplanar spacings and relative intensities of the powder diagram are given. The
compound is tetragonal, PbFCl type, Z = 2; with a = 4.487, c = 7.345 A, c/a = 1.637.
Calculated and measured densities are 6.53 and 6.60 g/cm3 . Calculated interatomic distances
are Nd-F = 2.70, Nd-Te = 3.35 and 3.27 A. Comparison is made with Nd-F in NdOF, NdSF,
and NdSeF and this shows that the Nd-F distance increases with decrease of electronegativity
of the chalcogen and with increase of ionic character. The force constants K = 89 and
129 N/m are calculated for Nd-Te and Nd-F from the atomic distances and electronegativ-
ities. Valence vibrations are calculated at 149 and 360 cm- 1 for Nd-Te and Nd-F; the latter
is experimentally confirmed. The IR spectrum of Csl pressings from 250 to 800 cm- 1 is pre-
sented in the paper, Filatkina et al. [1].
Te0 2 and NdOF mixtures were annealed in Ar at 900°C in sealed Pt ampules and sub-
sequently cooled in air to give cubic Nd 1 _.Tex01+xF 1 _x solidsolutions with 0.05 ~ x ~ 0.70.
The solid solutions show no ordering of any kindas shown by the absence of superstructure
lines on the powder diagram and by the degenerate character of the IR spectra, and also by
Mössbauer investigations. The mixed crystals are stable in air. On heating they begin to
oxidize at 600°C to form Nd4Te07F4. According to TG studies the OXidationtoTeVI is complete
at 750°C. The change of oxidation state is clearly revealed in the Mössbauer spectrum; on 125Te
and with 125Sb/Cu source the isomer shift is ö = -1.4 ± 0.1 mm/s at liquid N2 temperature. The
strong quadrupole interactions caused by 5 s electrons of Te 1v disappear, Falikman et al. [2].
By heating the solid solutions with M = La, Pr, Nd, and Sm at 650°C in dry air or in an 0 2
atmosphere, compounds of the type M4Te07F4 as well as Nd 2Te0 5F2 and NdTe20 7F were
obtained. Heating to 900°C gave the original solid solutions, Falikman, Spiridonov [3].
On heating solid solutions of Nd 1 _.Te.o1+.F 1 _x (see above), Nd 4Te0 7F4 forms at 600 to
750°C. lt is stoichiometric in nature and specimens differing by 1 mol% are two-phase
mixtures. The change in the valence state of Te is clearly revealed in the Mössbauer spectra.
Analogous compounds with M = La, Pr, and Sm may be isolated. According to X-ray powder
pattern (a table is given) the compound is primitive cubic with a = 9.510 and 9.416 ± 0.002 A
for M = Nd and Sm, respectively. The calculated density for Nd 4Te0 7F4 is 6.87 g/cm3 . The most
probable space groups are P2 13-T4 or P4232-02 , Falikman et al. [2]. The lattice constants a =
9.63 and 9.55 A for La 4Te0 7F4 and Pr4Te0 7F4, respectively, are given by Falikman, Spiridonov
[3]. The comparison of the IR spectra of Nd4Te0 7F4 and Ba2NiTe06 indicates the existence of
isolated Te06 octahedra; for a figure see the paper. The Mössbauer spectrum of 125Te in
e
Nd 4Te07F4 25Sb/Cu source, liquid N2 temperature) shows a negative chemical shift of
1.4 ± 0.1 mm/s in good agreement with Literature data on Tev 1• The changed electron density
on the Te nuclei is evidence of the 5 s electrons of Te forming chemical bonds. Nd 4Te0 7F4 is
stable in air up to 900°C. Above 900°C the original solid solutions form [2]; the original solid
solutions were also obtained on heating M4Te0 7F4 with M = La, Pr, Sm above 900°C [3].
The compounds were obtained on heating the cubic solid solutions Nd 1 _.Te.o1+xF 1 _x
(see above) at 650°C in dry air or in 0 2 atmosphere. Heating above 900°C gave the original
Gmelm Handbock
RE Main Vol. C10
320 Tellurate Halides
solid solutions. Nd 2Te05 F2 may be hexagonal. NdTe20 7 F is monoclinic, with the space group
Bb-C~ (No. 9) or 82/b-C~h (No. 15); the Lattice constants (in A) are a = 12.653(4), b = 16.304(4),
c = 5.219(1), and y = 106.05(5)0 . The structure data indicate the existence of Te0 6 octahedra,
Falikman, Spiridonov [3].
Compounds Containing Chlorine
The NdCL3- TeCL4 System
The phase equilibria in the system NdCL3-TeCL4 were studied by DTA and X-ray phase
analysis. No compounds are formed. The system is of the eutectic type with the eutectic at
224 oc and ~ 0.1 mol% NdCL3 , Safonov et al. [4].
Compounds M2 (TeCLsh · 24 H20 with M = Y, La, Ce were prepared by adding TeCL4 to a

solution of MCL3 in dilute HCL or by mixing solutions of Te0 2 in concentrated HCL and MCL3 in
H20. The solutions are concentrated on a water bath and dried in vacuum over H2S0 4 . The
densities of the very hygroscopic yellow crystalline compounds Y2 (TeCL6h · 24 H20,
La2 (TeCLsh · 24 H20, and Ce 2 (TeCLsh · 24 H20 are 2.209, 2.354, and 2.375 g/cm 3 , respectively.
The corresponding melting points are 47.5, 59.7, and 74.2°C, respectively. ln air HCL is evolved.
On standing in a desiccator over H2 S04 or P2 0 5 the compounds become opaque, Lose HCL and
H20, and decompose partly. On heating they melt to a yellow liquid and then decompose into
oxides and chlorides. ln H20 they decompose hydrolytically. They are soluble in methanol,
ethanol, and glycerine and insoluble in benzene and toluene, Angosa y Catalina [5].
MCL 3-Te0 2 Systems
The YCL3-Te0 2 System. The phasediagram of the system is of the eutectic type, as shown
by DTA and X-ray diffraction studies. The eutectic formed by YCL3 and Te02 is at 45 mol%
Te0 2 and 475°C. Endetherrnie effects were observed in the range from 10 to 35 mol% Te0 2
at 385 to 395°C, the nature of which was not established, Safonov et al. [6].
The LaCL3-Te0 2 System. Glass formation is observed in the range from 96.2 to 92.2 mol%
Te0 2 . The glasses were obtained by melting the components at 800 to 1100°C in Au or Pt
crucibles and cooling down in the Iransformation region with 8 to 10 K/s. At these end
compositions the densities of the glasses are 5.382 and 5.289 g/cm 3 , the refractive indices
n0 = 2.1361 and 2.0651, and the Abbe numbers v 0 = 18.0 and 20.5, respectively, Vogel
et al. [7].
The NdCL3-Te0 2 System. Fig. 134 shows the phasediagram of the system, derived from DTA
and X-ray diffraction studies. The compound 2 NdCL3 · Te0 2 melts congruently at 720°C; the
X-ray diffraction patterns of this phase are given in the paper. The eutectics Lie at 685°C,
15 mol% Te0 2 and 595°C, ~55 mol% Te0 2 . Transparent pale Lilac glasses are formed in the
range from 79 to 92.5 mol% Te0 2 , Safonov et al. [6].
Gmelm Handbock
RE Mam Vol. C10
Tellurate Bromides 321
soor--.---.--~--~--~
754°C
!!::3
0.... 0
N
GI ~
a. ·..,
E 400 ü
{!t
"
z
N
2000 20 100
mot•t. Te02
Fig. 134. Phase diagram of the NdCL3-Te02 system.
Compounds Containing Bromine
The hygroscopic ruby red bromotellurates with M = Y, La, Ce, Pr, Gd, and Er are prepared
by dissolving Te in a solution of HBr and Br2 and adding a solution of M, M20 3 , or Ce02 in
HBr with an excess of Br2 . The crystals form on Goncentrating on a water bath. They are
washed and dried in dry air at -10°C. Pycnometrically measured density and melting
point t,:
M . . y La Ce Pr Gd Er
D in g/m3 2860 2.910 2.920 2.922 2.925 2.942

t, in °C. . 217.8 188.9 191 .4 195 225 248.9
On standing in vacuum over H2S04 or P20 5 the compounds become opaque and Lose HBr with
partial decomposition to the bromides. They are decomposed by heat into the oxides and
bromides, hydrolyzed by water, soluble in methyl, ethyl, and amylalcohol, and insoluble in
benzene, toluene, and xylene, Alpanseque Frias (8].
The LaBr3-Te0 2 System
Glass formation is observed in the range from 98.0 to 97.1 mol % Te0 2. The glasses were
obtained Like the LaCL3-Te02 glasses (see p. 320) . At theseend compositions the densities of
the glasses are 5.537 and 5.632 g/cm 3 , the refractive indices n0 = 2.1589 and 2.0720, and the
Abbe numbers v 0 = 17.1 and 20.7, Vogel et al. (7] .
GmeL1n Handbook 21
RE Ma1n Vol. C 10
322 Sulfide Tellurides
The YbTe-1 2 System
The chemical transfer processes in the YbTe-1 2 system were studied. ln cantrast to
YbSe-1 2 no Yb 2Te3 is found but only Ybl 2 and Tel 2, Obolonchik et al. [9].
References:
[1] V. S. Filatkina, G. N. Kustova, S. S. Batsanov (lzv. Akad. Nauk SSSR Ser. Khim. 1972
2171/4; Bult. Acad. Sei. USSR Div. Ghem. Sei 1972 2107/10).
[2] V. R. Falikman, P. B. Fabrichnyi, F. M. Spiridonov, V. I. Spitsyn (Dokl. Akad. Nauk SSSR
230 [1976]1360/2; Dokl. Ghem. Proc. Acad. Sei. USSR 226/31 [1976]657/8).
[3] V. R. Falikman, F. M. Spiridonov (5th Vses. Sim. Khim. Neorgan. Ftoridov, Dnjepropetrovsk
1978, p. 278; G.A. 89 [1978] No. 224375).
[4] V. V. Safonov, E. A. Fedorov, V. G. Lebedev (Zh. Neorgan. Khim. 23 [1978]1981/2; Russ.
J. lnorg. Ghem. 23 [1978]1088/9).
[5] A. Angosa y Gatalina (Acta Salmanticensia Giene. [2]3 No. 1 [1961]77/103, 88/94).
[6] V. V. Safonov, N. I. Tishchenko, I. A. Kazakova (Zh. Neorgan. Khim. 29 [1984]2163/4; Russ.
J. lnorg. Ghem. 29 [1984]1236/7).
[7] W. Vogel, H. Bürger, G. Zerge, B. Müller, et al. (Silikattechnik 25 [1974]207/8).
[8] B. Alpanseque Frias (Acta Salmanticensia Giene. [2]3 No. 1 [1961]31/51, 34/41).
[9] V. A. Obolonchik, L. M. Kulikov, A. A. Yanaki (Khim. Fiz. Khal'kogenidov 1977 25/8; G.A.
88 [1978] No. 126978).
30.6 Sulfide Tellurides
The SmTe-SmS System
An SmTe 0 _05 S0 _95 single crystal with cubic NaGt structure was obtained by oriented
crystallization. Hall effect and thermoelectric power measurements indicate p-type
conductivity with K = 11.2 Q- 1 · cm- 1 at room temperature and ambient pressure. The Hall
mobility is ~H = 22 cm 2 · v- 1 · s- 1 and the carrier concentration nH = 3.2 x 10 18 cm- 3 . The
piezoresistance coefficient for uniaxial pressure in the [100] direction is 1t~ 1 = 1/Q x OQ/op
= 1.58 x 10- 4 and for hydrostatic pressure n~ = 4.66 x 10- 4 cm 2/kg ( ~ 1.6 x 10- 9 and
4.7 x 10- 9 m2 /N). The piezo-Hall coefficient for uniaxial pressure is n~1 = 1/R x oR/op =
1.48 x 10- 4 cm 2 /kg ( ~ 1.51 x 10- 9 m2 /N) and the uniaxial pressure coefficient for ~H is
(0.10 ± 0.04) x 10- 4 cm 2 /kg ( ~ 1.0 x 10- 10 m2 /N). The Ln QIQ 0 and Ln R/R 0 versus p plots for
uniaxial pressures studied up to 300 kg/cm 2 and for hydrostatic pressure studied up to 6 kbar
arelinear as shown in a figurein the paper. A spherically symmetric bottarn of the conduction
band (due tos character) is assumed as for SmTe (see p. 140), Vinogradov et al. [1].
The pressure p1, at the pressure-induced semiconductor-to-metal phase transition (SMT)

and the density n of the charge carriers of a compositionally unspecified Sm(Te, S) mixed
crystal fit a simple relationship which is valid for SmS-based solid solutions with n in the
range 1018 to 1019 cm- 3 ; for a figure see the paper, Stepanov, Kaminskii [2]. The pressure
dependence of the Hall mobility ~H of the charge carriers was studied on a compositionally
unspecified SmTexS 1 _x sample with n = 5x 1018 cm- 3 . A maximum in ~H (~ 1.7 times the
zero pressure value) is observed (see the figure in the paper) at ~ 0.7 to 0.8 GPa, which is
slightly lower than the pressure p1, at the SMT. This behavior, which is similar tothat of other
Gmelm Handbook
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323
SmS-based solid solutions, Leadstoamodel in which centers of the metallic phase nucleate
even at 0.1 to 0.2 GPa below the SMT pressure. This Leads to "mismatch dislocations" in the
Lattice, which cause additional scattering of the charge carriers, Kaminskii et al. [3].
M 2Te 3-M 2S 3 Systems
Solid solutions M 2Te 3 _xsx with M = Er, Tm, Lu were prepared by heating mixtures of
M2Te 3 and M2S3 in evacuated quartz ampules at 900, 1200, or 1300°C with subsequent
quenching in H2 0. Depending on the heating temperature the range of homogeneity extends
from x = 0 to nearly 2 at 1 000°C for the gray-black phases with metallic Luster. From X-ray
powder diffraction the structure is shown to be of the orthorhombic Sc 2 S3 type, space group
Fddd-D~~ (No. 70), Z = 16 (see p. 34), Ghemard [4], Ghemard et al. [5]; see also Flahaut [6].
Homogeneous solid solutions in the LaTe 1_5 -xSx system were obtained up to x ~ 0.1, as
shown by X-ray powder analysis of samples prepared with the ampule synthesis. The solid
solutions did not have the cubic La 2Te 3 structure, but have the tetragonal LaTe 2 structure of
the Fe 2 As type (see p. 48). The Lattice constants of the samples with x = 0.01, 0.05, and 0.1
are: a = 4.51, 4.53, and 4.58; c = 9.22, 9.19, and 9.00 A, respectively (read from figures in
the paper). The experimental densities are 6.36, 5.97, and 5.67 A, respectively. The course of
the electrical conductivity of pressed powder samples with temperature (between 100 and
500 K) and with x (shown in a figure in the paper) is similar tothat in the LaTe 1 _5 -xSex system
(cf. Fig. 149, p. 351), Gerasimov et al. [7].
M 2Te1+xS 2 Phases (M = Y, Tb, Dy, Ho, Er, Tm) with 0 ~ x < 0.50
Preparation and Polymorphism
These phases were prepared by addition of Te to the monosulfides or to a mixture of M2Te 3
and M2S3 according to M2Te 3 + 2 M2S3 + 3x Te--> 3 M2Te1+xS 2 . The pressed mixtures were
heated for several days at 450°C and 2d at 750°C. The color of the products is orange-brown
and becomes darker with increasing Te content. For Dy 2Te1+xS 2 , e.g., a value of x = 0.15 was
obtained [4]. ForM = Ho and Er the value of x can reach higher values, Ghemard et al. [8].
Starting with powdered Ho2TeS2 and an excess of Te crystals of Ho2Te 1_34S2 were grown within
3 weeks in an evacuated quartz ampule with temperature gradient. The hot part is ~ 850°C,
the temperature of crystal deposition is 80°C Lower. The crystals are dark and orange-brown
in transmission, elongated with approximately the form of parallelepipeds. Cleavage faces
are (001), (010), and (100) of the orthorhombic phase. The phases M2 Te 1 +xS2 exhibit a disorder-
order transition at about 450°C from an orthorhombic form to a monoclinic Low-temperature
form, GMmard et al. [9].
Orthorhombic Phases
From X-ray diffraction studies of monocrystalline Tb 2TeS2 and Dy2Teu 5S2 [4] and
Ho2Te 1_34 S2 [9] the space group of the orthorhombic phase is lmmm-0~~ (No. 71 ), Z = 2. Lattice
constants in A and density D in g/cm 3 for M2TeS 2 from [8] with the setting of a, b, and c
according to [4, 6, 9]:
a b c Deale Dexp
Y2TeS 2 4.17 5.33 13.43 4.11 4.18

Tb 2TeS 2 4.18 5.32 13.68 5.57
Dy2TeS 2 4.16 5.31 13.57 5.72 5.82
Gmeltn Handbook 21"
REMatn Vol. C 10
324 Sulfide Tellurides
a b c Deale Dexp
Ho2TeS 2 . 4.14 5.33 13.42 5.85

Er 2TeS2 4.12 5.31 13.34 5.98
Tm 2TeS2 . 4.10 5.26 13.28 6.15
With increasing x in M 2Te1+xS 2 the lattice constant a remains constant, while b and c show
the following changes:
a = 4.16, b = 5.29, c = 13.65 A for Dy 2Te1.05S2 [8]
a = 4.16, b = 5.22, c = 13.72 A for Dy2Teu 5S2 [4]
a = 4.158(3), b = 5.199(3), c = 13.657(5) for Ho2Te 1.34S2 [9]
Positional parameters for Ho2Te 1.34S2 (R = 0.061) [9]:
atom position multiplicity X y z
Ho 4j 1.0 0.50 0.00 0.1608(2)

s 4i 1.0 0.00 0.00 0.2868(3)
Te(1) 2a 0.21 0.00 0.00 0.00
Te(2) 4g 0.46 0.00 0.2664(5) 0.00
Previously reported parameters for Tb2TeS 2 and Dy2Teu 5S2 are: z(Tb) = 0.16, z(S) = 0.286,
and y(Te) = 0.264 in Tb 2TeS 2 and z(Dy) = 0.160, z(S) = 0.287, and y(Te) = 0.263 in Dy 2Teu 5S2
[4]. For data on Tb 2TeS2 seealso Flahaut et al. [10]. The disordered orthorhombic M 2Te1+xS 2
exhibits a sheet structure containing (M 4S) tetrahedra connected by edges, alternating with
planar layers of disordered Te atoms. The Te atoms occupy the sites 2a and 4g statistically
at a degree of 24 and 38%, respectively, in Tb2TeS2 (R = 0.11) and 21 (42?) and 46% in
Ho2Te 1.34S2 [9].
Monoclinic Phases
ln the monoclinic superstructure, forming below 450°C, the Te layers are ordered with
82/m symmetry; however, some sites remain partially vacant. The S atoms conserve mmm
symmetry, but the metal atoms are slightly displaced from their substructure positions,
Ghemard et al. [11]. The space group of the monoclinic ordered phases is 82/m (C2/m)-C~h
(No. 12), Z = 4 [4, 9]. The relations of the lattice constants a, b, and c to those of the subcell
are a = b = (a~ + b~) 112 and c = c0 ; cell volume V = 2V0 . The values for Ho2Te 1.34S2 are a =
b = 6.658, c = 13.657 A, y = 102°43' [11], for Dy 2Teu 5S2 a = b = 6.67 A, c = 13.72 A and
y = 102°50' [4], and for Er2Te 1_3S2 , a = b = 6.62 A (c is not reported), y = 103° [11]. Atomic
positional parameters x, y, and z for Dy2Teu 5S2 [4] and Ho2Te 1_34S2 (R = 0.037) [11]:
Dy2Teu 5S2 Ho2Te 1_34 S2

X y z X y z
M (8j) 0.254 0.254 0.160 0.2596(1) 0.2557(1) 0.1606(1)

S(1) (4h) 0 1/2 0.213 •) 1/2 1/2 0.2824(8) •)
S(2) (4g) 0 0 0.287 0 0 0.2879(7)
Te(1) (2a) 0 0 0 0 0 0
Te(2) (4i) 0.631 0.369 0 0.6330(3) 0.3663(3) 0
*) Related by (1/2 + x, y, 1/2- z).

Gmelm Handbock
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325
Ho
Fig. 135. Coordination of Ho atoms around Te(1) and Te(2) in the monoclinic structure of
HoTe 1.34S2 .
e Ho
os
Qre
Fig. 136. Projection of the monoclinic structure of HoTe 134Se 2 on (001) . The displacement of
the Ho atoms related to the substructure is indicated by the arrows.
lnteratomic distances in A in the monoclinic superstructure of Ho 2Te 1.34 S2 are: Ho-S(1) =

2.613 and 2.734; Ho-S(2) = 2.675 and 2.759 ; Te(2)-Te(2) = 2.774; Ho-Te(1) = 3.066; Ho-Te(2) =
3.275 and 3.296. The Ho atoms are coordinated by seven atoms : two S(1), two S(2), one Te(1),
and two Te(2). The S-atoms are Located at the centers of Ho tetrahedra. The Te(2) atoms at
4(i) form pairs with a distance of 2.77 A, typical for covalent bonds. They have four nearest
Ho neighbors; see Fig.135 (left). The Te(1) atoms are coplanar surrounded by four Ho atoms;
see Fig. 135 (right). A projection of the superstructure on (001) is shown in Fig. 136. The
ordering of the Te atoms occurs in such a way that each Te plane can be oriented in two
different ways, forming twinning domains with space group 82/m or A2/m. These domains
are directly observed by imaging high resolution electronic microscopy and are about 100 A
wide [11] .
Chemical Reactions
The phases M 2Te1+xS 2 aresensitive to the atmospheric humidity. They melt incongruently,
but are thermally stable up to nearly 1200°C [9) . On heating M 2Te1+xS 2 with M = Er, Tm, Lu
at 1200°C the gray-black phases M 2Te 3 _xSx appear [4).
References:
[1) A. A . Vinogradov, S. I. Grebinskii, V. V. Kaminskii, N. N. Stepanov, V. M. Sergeeva, I. A.

Smirnov (Fiz. Tverd. Tela [Leningrad)26 [1984)402/8; Soviet Phys .-Solid State 26 [1984)
240/3).
Gmelm Handbook
RE Mam Vol. C 10
326 Selenide Tellurides
[2] N. N. Stepanov, V. V. Kaminskii (Fiz. Tverd. Tela [Leningrad] 26 [1984] 2551/3; Soviet
Phys.-Solid State 26 [1984]1548/50).
[3] V. V. Kaminskii, N. N. Stepanov, L. N. Vasil'ev, Yu. N. Kharchenko, I. A. Smirnov (Fiz.
Tverd. Tela [Leningrad]27 [1985] 77/82; Soviet Phys.-Solid State 27 [1985]44/7).
[4] G. Ghemard (Bult. Soc. Chim. France 1976 1007112).
[5] G. Ghemard, C. Souleau, J. Flahaut (Compt. Rend. C 274 [1972]1817/20).
[6] J. Flahaut (in: K. A. Gschneidner Jr., LeRoy Eyring, Handbock on the Physics and
Chemistry of Rare Earths, Vol. 4, North-Holland, New York 1979, pp. 1/88, 71/8).
[7] A. F. Gerasimov, V. N. Konev, N. A. Krushatina, G. I. Bochkina (Fiz. Metal. lkh Soedin
No. 4 [1976]19/26; C.A. 88 [1978] No. 201583).
[8] G. Ghemard, C. Souleau, J. Etienne (Compt. Rend. C 272 [1971] 468/70).
[9] G. Ghemard, J. Etienne, J. Flahaut (J. Solid State Chem. 45 [1982]140/5).
[10] J. Flahaut, P. Laruelle, C. Dagron, et al. (Proc. 11th Rare Earth Res. Conf., Traverse City,
Mich., 1974, pp. 947/53; C.A. 83 [1975] No. 106267).
[11] G. Ghemard, J. Etienne, G. Schiffmacher, J. Flahaut (J. Solid State Chem. 45 [1982]
146/53).
30.7 Selenide Tellurides
30.7.1 MTe-MSe Systems
30.7.1.1 CeTe 05Se0 .5

The orange-red crystals obtained from the melts have the cubic NaCl structure with a =
6.1785(7) A at 295 K. Susceptibility measurements below 300 K show paramagnetic behavior
with E>P = - 1 K and C = 0.73 cm 3 • K · mol- 1• Crystals become antiferromagnetic at
TN < 1.8 K. The Seebeck coefficient isS = + (2 to 3) 11V/K near 300 K, F. Hulliger, B. Natterer,
H. R. Ott (J. Magn. Magn. Mater. 8 [1978]87/98, 93).
30.7.1.2 The EuTe-EuSe System

EuTe and EuSe form a continuous series of solid solutions EuTexSe 1 _x with the cubic NaCl
structure, McGuire etal. [1]. Polycrystalline samples of EuTexSe 1 _x with x ~ 0.1 were prepared
from appropriate mixtures of EuSe andEuTe, which were pressed into a pellet, sealed into a
Ta crucible, and heated to 1700°C for 10 h, Hihara et al. [2], Kojima et al. [3].
The lattice parameter obeys Vegard's law (a = 6.195 A at x = 0, a = 6.60 A at x = 1) [1].
lt changes linearly with x from a = 6.195 A at x = 0 to 6.227 A at x = 0.1 [2].
Nuclear Magnetic Resonance (NMR)
Resonance Frequencies
Polycrystalline EuTexSe 1 _x with x ~ 0.1 has been studied by both continuous wave and
pulsed 153 Eu-NMR methods between 1.7 and 4.2 K, Hihara et al. [2, 4], Kojima et al. [3]. ln
polycrystalline EuSe ( ~ x = 0), two 153Eu NMR frequencies are found at 1.7 K. The one at
Gmelin Handbook
RE Main Vol. C10
lhe Eule-EuSe System 327
118 MHz is assigned to nuclei in the S planes of the ferrimagnetic NNS structure (denoted by
NN§.) and also to nuclei in the N and S planes of the antiferromagnetic type II structure (NSNS).
lhe other one at 129 MHz is attributed to the N planes of the NNS phase (denoted by NNS).
ln EulexSe 1 _x with x ~ 0.1 only the low frequency Line is observed, indicating the presence
of only the NSNS phase at 1.7 K. For x = 0.01, this Line disappeared at 2.8 K and for x =
0.03, 0.06, and 0.1, it became weak above 3.2 K and could not be detected above ~ 3.6 K.
Extrapolating from the 153 Eu NMR frequencies of the three samples with x = 0.01, 0.03, and
0.06 gives v = 121.8 ± 0.2 MHz at l = 0, assuming a l 2 dependence [2].
ln Eule0 _01 Se 0_99 the frequency of the NSNS Line at 1.7 K is lower by 0.7 MHz than for the
NN§. Line in EuSe. On increasing the temperature two new Lines, attributed to NN§. and NNS
occur at 2.3 K. lhe NSNS and NNS phases coexist between 2.3 and 2.8 K. lhe NMR Lines from
the NNS phase, with the same frequencies as in EuSe, are Observable up to 4.2 K, although
weak above 3.5 K. A resonance attributable to the antiferromagnetic NNSS phase (observed
in EuSe) was not detected even at 4.2 K [2]. At 1.7 K the intensity of the NSNS Line of
Eule 0.o1Se0 _99 increases thirtyfold or more in an applied field of 0.05 l. lt decreases at higher
fields and disappears at ~ 0.2 l. At the sametime the Lines of the NNS structure appear at
0.04 land attain maximum intensity at ~ 0.2 l, which indicates that the NNS phase is induced
by a small magnetic field. ln Eule 0_1Se 0 _9 only the signal of the NSNS phase was observed up
to 0.8 l with a maximum at 0.1 l. lhe field-induced enhancement of the intensity is related
to the spin flop transitions in the easy plane of the type II antiferromagnetic structure of
Eule [2].
Transferred Hyperfine Fietds
From the observed effective field 8 911 = - 26.26 ± 0.04 l in the type II antiferromagnetic
(NSNS) phase the transferred hyperfine field from six next-nearest-neighbor Eu ions, B1h1 =
-6 8 2 = 2.5 ± 0.2 l, is derived after allowing for the intrinsic hyperfine field B;h1 =
- 29.2 ± 0.1 l (in the paper, erroneously, - 29.6 l) and the dipotar field Bdip = + 0.4 l. lhis
value for 8 2 , which is comparable to 6 8 2 = - 2.4 ± 0.3 l in the NSNS phase of Eule, indicates
a weak dependence of 8 2 on the lattice parameter. lhe difference between the rather constant
value of 8 2 and the more lattice parameter dependent next-nearest-neighbor exchange param-
eter J2 is discussed in terms of different mechanisms for the two interactions [2]; see also
"Rare Earth Elements" C 9, 1986, p. 197.
Magnetic Properties
EulexSe 1 _x is paramagnetic above the magnetic ordering temperature of ~ 4.6 K. ln view

of NMR and a.c. susceptibility data, the studied polycrystalline samples with 0 < x ~ 0.1 form
=
magnetically ordered phases similar to those of EuSe ( x = 0), i.e., they all consist of
ferromagnetic (111) planes with their magnetization pointing either north (N) or south (S) and
the structures are described by following the [111] axis (see "Rare Earth Elements" C 9, 1986,
pp. 205/10). Samples with x = 0 and 0.01 are at first antiferromagnetic NNSS below ~ 4.6 K,
then become ferrimagnetic NNS, and finally antiferromagnetic type II, NSNS. Samples around
the composition Eule 0 .03Se 0_97 are ferrimagnetic NNS below ~ 4.6 K, in view of a.c.
susceptibility data, and become antiferromagnetic NSNS at still lower temperatures. However,
samples with x ~ 0.06 form only the NSNS phase below the Neel temperature l N (studied
until 1.7 K). l N ( ~ 4.6 K for x = 0.06) increases slightly with increasing x. lhe magnetic phase
diagram (plot of l versus x) given in the paper shows the temperature of the NSNS-NNS
Gmelin Handbook
RE Main Vol. C10
transition to shift from 1.8 Kat x = 0 to ~ 4.6 Kat x ~ 0.04 and that of the NNS-NNSS transition
to shift from 2.8 Kat x = 0 to ~ 4.6 Kat x ~ 0.02, Kojima et al. [3]. A field-induced NSNS-NNS
transition is observed in EuTe0 .o1Se0_99 at 1.7 K and ~ 0.04 T, whereas EuTe 0.1Se 0 9 appears to
remain antiferromagnetic (studied up to 0.8 T), Hihara et al. [2]. The compounds with x = 0.1
and 0.2 exhibit an almost Linear relation between the magnetization and the applied field at
4.2 K, measured for fields up to 2T [1].
Plots of the a.c. susceptibility Xa.c. versus temperature in the range from ~ 2 to 5 K
show, with decreasing temperature, for x = 0 (~Eu Se) a sudden drop at TN• followed by a
temperature-independent Xa c. (NNSS phase), then a rise of Xa.c. near 3 K to a broad peak (NNS
phase), and again a drop near 2 K (NSNS phase). For x = 0.01, the drop of Xa.c. at T N is
immediately followed by a broad peak (maximum at ~ 4 K) characteristic for a relatively Large
stability range of the NNS phase and Xa.c. becomes temperature-independent below ~2.8 K.
For a sample with x = 0.03 the behavior of Xa.c. is quite different, in that it increases to a
maximum at the magnetic erdering temperature (NNS phase) and falls off gradually after-
wards, becoming temperature-independent below ~ 3.7 K. Sampies with x = 0.06 and 0.1
show only the drop at T N; Xa.c. is nearly temperature-independent below ~4.6 K in the form er
sample and below ~ 4.8 K in the LaUer one (all values read from the figures in the papers)
[2, 3].
The paramagneUe Curie temperatures for EuTe.Se 1_x with x = 0.1 and 0.2 are E>P = + 3
and + 2 K, respectively, derived from susceptibility measurements up to 300 K. The values
thus markedly deviate from the "Vegard" Line between EuSe (E>p = + 9 K) and Eule (E>p =
-6 K), McGuire et al. [1]. A Larger value, E>P = + 7 K was derived for EuTe0 1Se0_9 (compared
to E>P = + 8.5 K for EuSe) from studies between 77 and 300 K by [2]. (Note the positive values
of E>P although these samples order antiferromagnetically.)
References:
[1] T. R. McGuire, M. W. Shafer, W. Palmer (Proc. Intern. Conf. Magnetism, Nottingham 1964
[1965], pp. 474/7; N.S.A. 19 [1965] No. 38068).
[2] T. Hihara, K. Kojima, T. Kamigaichi (J. Phys. Soc. Japan 50 [1981]1499/504).
[3] K. Kojima, T. Hihara, T. Kamigaichi (Ferrites Proc. 3rd ICF, Kyoto 1980 [1982]. pp. 918/21;
C.A. 97 [1982] No. 192038).
[4] T. Hihara, K. Kojima, T. lmai, H. Fujii, T. Kamigaichi (J. Magn. Magn. Mater. 15/18 [1980]
665/6).
30.7.1.3 The TmTe-TmSe System
30.7.1.3.1 General
The solid solutions TmTe.Se 1 _x have attracted special interest, because it seemed pos-
sible to change the Tm valence from purely trivalent (Tm-deficient Tm.Se) through the inter-
mediate valence state (stoichiometric TmSe) to divalent (TmTe). The decrease of the mean
valence is connected with the transition from metallic to semiconducting character. Originally
an almost continuous series of solid solutions was suggested, but more recent studies indicate
the existence of a miscibility gap (see p. 329). Fora recent review on the TmTe.Se 1 _x system,
Gmelm Handbock
RE Mam Vol. C10
see for example Boppart [1]; for TmSe and TmxSe see "Rare Earth Elements" C 9, 1986,
p. 318.
A miscibility gap at 0.18 ~ x ~ 0.38 is derived from lattice constant measurements by

Kaldis et al. [2], Kaldis, Fritzler [3]. For x ~ 0.4 the samples are semiconducting and for
~ 0.18 metallic, Boppart [1]. Observed solid solutions in the approximate range from 0.18 to
0.38 are metastable, as shown by prolonged annealing of TmTe 0 .23Se 0 .77 crystals at 1500°C,
resulting in mixed crystals with the compositions TmTe 0 .18Se 0 .82 and TmTe 0 .38Se 0 .62 [3].
Samples with a composition within the gap have been obtained, e.g., with x = 0.3, 0.33, Köbler
et al. [4], x = 0.30, Treindl, Wachter [5], and x = 0.33, Haen, Lapierre [6]. Unlike the others,
samples with a composition within the gap yield only small single crystals, due to severe
segregation, which also becomes obvious from the color changes [3, 4]. Samples at x = 0.33
are either clearly metallic or clearly semiconducting. Specimens from the middle part of a
TmTe 0 .33Se 0 .67 ingotseparate during powdering into two phases with lattice parameters a =
5.83 and 6.05 A. The discontinuous change of properties is discussed in terms of a lattice
parameter gap rather than of a miscibility gap, Köbler et al. [4]. Gradients in the Se/Te ratio
parallel to temperature gradients are observed [7].
Precipitates of one and two other phases with compositions similar to the crystal matrix
were found in TmTe 0 . 18Se 0 .82 and TmTe 0 .77 Se 0 .23 , respectively, in scanning electron microscope
micrographs of cleaved crystals, Kaldis, Fritzler [3]. The samples (0 ~ x ~ 1) studied by
Batlogg [8] did not show any obvious second phase under the optical microscope. Samples
on the Te-rich side of the gap are black to gray semiconductors [3, 7, 9] with Tm valencies
close to two [2, 4, 8] while on the Se-rich side they are copper-colored, metallic, and have an
intermediate valent Tm [4, 8]. There is some disagreement about the range of the chemical
composition at the semiconductor-to-metal transition (SMT). lt is given as 0.2 < x < 0.5 [10],
0.2 ~ x < 0.3 [6], and x = 0.33 [4]. Samples with x as large as 0.5 were observed to transform
irreversibly into the metallic state during powdering in the mortar (indicated also by a color
change) [7].
References:
[1] H. Boppart (J. Magn. Magn. Mater. 47/48 [1985] 436/42).

[2] E. Kaldis, B. Fritzler, H. Spychiger, E. Jilek (Valence lnstab. Proc. Intern. Conf., Zürich,
Switz., 1982, pp. 131/9).
[3] E. Kaldis, B. Fritzler (J. Phys. Colloq. [Paris]41 [1980] C5-135/C5-142).
[4] U. Köbler, K. Fischer, K. Bickmann, H. Lustfeld (J. Magn. Magn. Mater. 24 [1981] 34/42).
[5] A. Treindl, P. Wachter (Solid State Commun. 36 [1980] 901/5).
[6] P. Haen, F. Lapierre (Valence Fluctuations Solids St. Barbara lnst. Theor. Phys. Conf.,
Santa Barbara, Calif., 1981, pp. 313/6).
[8] B. Batlogg (Phys. Rev. [3] B 23 [1981] 650/63).
[9] E. Kaldis, B. Fritzler, E. Jilek, A. Wisard (J. Phys. Colloq. [Paris]40 [1979] C5-366/C5-369).
[10] B. Batlogg, P. Wachter (J. Phys. Colloq. [Paris]41 [1980] C5-59/C5-63).
30.7 .1.3.2 Preparation
Generally the samples were prepared by methods comparable to TmSe (see "Rare Earth
Elements" C 9, 1986, pp. 318/9) or TmTe (see p. 254). The handling of starting materials and
Gmelin Handbook
RE Main Vol. C 10
reaction products should be performed with exclusion (Less than 1 ppm) of 0 2 or H2 0. Tm and
the chalcogen were prereacted (below 800°C [1]) in vitreous silica ampules and then heated
to above the melting point in evacuated W crucibles sealed by electron beam welding, Kaldis,
Fritzler [2]; seealso Katdis et al. [1]. Single crystals were grown by solidification of the melt
from about 2100°C at a cooling rate of 30 K/h. The top of the crucible was kept at a higher
temperature (~T ~50 K) in order to prevent solidification from the gas phase [2]. Large single
crystals have also been obtained by directional freezing, Köbler et al. [3]. Compositions have
been established by complexometric titration for Tm, accuracy ± 0.2%, and by gravimetry
for Se and Te, accuracy ± 0.4%, Kaldis, Fritzler [2]. Thin films were obtained by coevaporation
of the elements on glass, Suryanarayanan [4].
References:

[2] E. Kaldis, B. Fritzler (J. Phys. Colloq. [Paris]41 [1980] CS-135/CS-142).
[4] R. Suryanarayanan (Valence lnstab. Relat. Narrow Band Phenom. Proc. Intern. Conf.,
Rochester, N.Y., 1976 [1977], pp. 541/3).
30.7 .1.3.3 Crystallographic Properlies
The TmTexSe 1 _x solid solutions crystallize in the cubic NaCL structure with apparently
random distribution of Te and Se on the anion sites. The dependence of the lattice parameter
a on the composition x is shown in Fig. 137 from Katdis et al. [1], Kaldis, Fritzler [2, 4], a
similar plot is given in [3]. Selected values of Lattice parameters of semiconducting and
metallic samples are compiled in the following table.
Semiconducting solid solutions:
x in TmTexSe 1 _x 0.95 0.91 0.84 0.77 0.72 0.68 0.55 0.51 0.41 0.4 0.33
a in A 6.3211 6.3063 6.2749 6.245 6.2262 6.21 6.14 6.0724 6.024 6.061 6.05
Ref. . [4] [4] [4] [5] [4] [6] [6] [4] [4] [7] [3]
Metallic solid solutions:
x in TmTexSe 1 _x 0.33 0.30 0.18 0.17 0.17 0.15 0.13 0.11 0.09 0.07 0.05
a in A. 5.83 5.8499 5.8611 5.86 5.783 5.785 5.7086 5.740(5) 5.6745 5.663 5.6817
Ref. . . [3] [8] [4] [5] [9] [10] [4] [11] [8] [4] [4]
The Lattice parameters given by [ 4] and [8] were derived (with a precision better than ± 0.001 A
[12]) from diffraction patterns of small single crystals obtained in a Gandolfi camera. Additional
values are a = 6.223 A for TmTe 0.70Se 029 , a = 6.063 A for TmTe 0.33Se 0 _70 (X-ray powder
method, compositions from analysis), Haen, Lapierre [11], a = 6.15 A for a TmTe 0_70 Se 0_30
film, Suryanarayanan [13], and a = 5.731 A at 4.2 K for TmTe 0 16Se0 _84 , Fischer et al. [9].
Gmelon Handbook
RE Maon Vol. C10
6.3
6.2
6.1
20 40 60 80 100
mol•t. Tmlt
Fig. 137. Lattice constants of TmTe-TmSe solid solutions versus composition, measured on
cleaved single crystals with a Gandolfi camera and with a Debye-Scherrer camera by Katdis
et al. [1] compared with the (presumably) X-ray powder data of Köbler et al. [3] . The isovalent
Vegard-Law Lines indicate the change of the Tm-valence. The Lattice constants of Tm 11 Se and
Tm 111 Te are estimated .
in cantrast to powder patterns obtained from small single crystals of TmTexSe 1 _x by a

Gandolfi camera, the Lines in normal powder patterns of the same charge are sometimes
unusually diffuse. This could indicate induced phase transition during powdering , Kaldis,
Fritzler [4]. Decreases in Lattice parameters by up to 2.7% are reported between single
crystals and powdered material for compositions 0.18 ~ x ~ 0.51, Katdis et al. (4, 12, 14].
The apparent irreversibility of the phase transition has been related to surface effects (12].
The following concentrations of Schottky pairs have been derived from the densities
presented on p. 334 [4] .
x in TmTexSe 1 _ x . . 0.84 0.72 0.51 0.40 0.05 0.00

pairsin10 22 mol- 1 . 0.8±1.1 2.0±0.3 0.9±0.3 4.0±0.1 1.9±0.1 3.0±0.1 1.4±0.1
References:
[1] E. Kaldis, B. Fritzler, H. Spychiger, E. Jilek (Valence lnstab. Proc . Intern. Conf. , Zürich,
Switz., 1982, pp. 131/9).
[2] E. Kaldis, B. Fritzler (Zh. Vses. Khim. Obshchestva 26 No. 6 [1981] 54/64; Mendeleev
Chem. J. 26 No. 6 (1981]78/91).
(3] U. Köbler, K. Fischer, K. Bickmann , H. Lustfeld (J. Magn. Magn. Mater. 24 [1981] 34/42).
[4] E. Kaldis, B. Fritzler (J. Phys. Colloq. [Paris] 41 [1980] C5-135/C5-142) .
Gmelin Handbook
RE Main Vol. C 10

[6] H. Boppart (J. Magn. Magn. Mater. 47/48 [1985]436/42).
[7] I. Mörke, P. Wachter (Solid State Commun. 48 [1983] 441/3).
[9] P. Fischer, W. Hälg, P. Schobinger-Papamantellos, H. Boppart, E. Kaldis, P. Wachter
(Valence lnstab. Proc. Intern. Conf., Zürich, Switz., 1982, pp. 551/4).
[10] E. Holland-Moritz (J. Magn. Magn. Mater. 38 [1983] 253/63).
[13] R. Suryanarayanan (Valence lnstab. Relat. Narrow Band Phenom. Proc. Intern. Conf.
Rochester, N.Y., 1976 [1977], pp. 541/3).
[14] E. Kaldis, B. Fritzler, E. Jilek, A. Wisard (J. Phys. Colloq. [Paris]40 [1979] C5-366/C5-369).
30.7.1.3.4 Valency
General
lt is usually accepted that solid solutions TmTexSe 1 _x with x < 0.18 aremetallic with Tm
in the intermediate valence state as in stoichiometric TmSe and that samples between x =
0.4 and 1 are semiconductors with divalent Tm. The two regions are separated by the
miscibility gap; see p. 329. Usually the valence is derived from the lattice parameters, Köbler
et al. [1], Kaldis et al. [2], Boppart, Wachter [3], from magnetic properties [1, 3], or from
electrical properties [4] as well as from photoemission and X-ray absorption spectra. The
reliability of the methods is discussed, for example, by [1], Boppart [5], Wertheim et al. [6],
Neumann et al. [7]. The correlation between v values from the lattice parameters and the
effective magnetic moments, for example, is shown in a figure in [1]. A similar correlation
has been made by Boppart, Wachter [3, 8], who emphasize the marked deviation from the
Linearrelation between valencies from the two different methods. According to their magnetic
measurements the Tm ions are essentially divalent in the semiconducting state, even though
crystal lattice related properties already indicate sizable f-d mixing; seealso Boppart [5]. The
valence shift at the SMT is far more pronounced in the valencies from the lattice parameters,
~ = 0.65, compared to those from the magnetic moments, ~ ~ 0.26, Köbler et al. [1]. Fora
possible nonlinearity between the valence and the lattice parameter, seeNeumannet al. [7].
Results and Interpretation
The following valencies v of TmTexSe 1 _x have been derived from magnetic studies
(v (magn)) or from the lattice constants (v (lattice)):
x in TmTexSe 1 _x. ~0.5 0.33 0.33 0.17 0.11 0 0
v (lattice) 2 ~2 2.10 2.75 2.5 ~2.8 ~2.75 2.83

v (magn) 2.15 ~2 2.15 2.40 2.5 2.55 ~2.5 2.62
Ref. [1] [4] [1] [1] [4] [9] [9] [1]
Gmelm Handbock
RE Mam Val. C 10
Additional values v(lattice) are 2.35 at x = 0.4 [10], 2.55(5) at x = 0.30, 2.75(5) at x = 0.17,
and 2.95(5) at x = 0.09 [11]. v = 2.49 was obtained for TmTe 0_15Se 0 _85 from the magnetic cross
section in neutron scattering experiments [12]. For valence assignments, see also Fig. 137,
p. 331. The assigned valence of 2.5 for TmTe0 _17Se 0 _83 by [4] is questioned by Haen, Lapierre
[9] as not being obvious from the data given.
The differing results from the various methods are attributed to the differing influence of
the conduction electrons on the various properties, e.g., Lattice parameter and magnetic
moment [1]. Based on the band structure model for TmSe of Jansen et al. [13] (see "Rare
Earth Elements" C 9, 1986, p. 360) the differing results are discussed, emphasizing the
important rote of the f-d and f-p hybridization. lt is concluded that Mv edge X-ray absorption
spectroscopy (XAS) with the excited electron in a Localized 4f state is less sensitive to
hybridization effects than L111 -XAS, Brewer et al. [14]. The predictions of the Falicov model
(see for example Ramirez, Falicov [15]) for the Tm valence disagree with the results from the
magnetic moments [1].
Semiconductor-Metal Transition (Valence Transition)
The TmTexSe 1 _x solid solutions show a compositionally-induced semiconductor-metal

transition at the miscibility gap. The Tm cations in the semiconducting solid solutions are
concluded to be divalent from the absorption spectra, Suryanarayanan [17], and from both
optical and magnetic data, Batlogg [4]; seealso Boppart, Wachter [3]. Intermediate valency
for the Tm cations may be interred from the valence numbers > 2, irrespective of their origin
(see for example [1]), and from all the Lattice related properties, Boppart [5], Boppart, Wachter
(3]; see also (10, 18, 19]. The semiconducting solid solutions can be transformed into the
metallic state by application of pressure. The results are discussed in terms of the pressure-
induced 4f-5d hybridization in the recent review of Boppart (5]; see also Boppart et al. (16].
The application of external pressure Leads at first to increased f-d mixing and then to a
pressure-induced semiconductor-to-metal transition (SMT) [3, 5, 16], as monitored for example
by the elastic, magnetic, and electrical properties. Measurements of the effective magnetic
moment of TmTe 0 _68 Se0 _32 under pressure, however, are interpreted to unambiguously show
a divalent state of Tm up to the SMT [3]. The SMT at 300 K is continuous for x ~ 0.55 and
discontinuous for x = 0.40 to 0.45 [5, 16]. The room temperature transition pressures p1, are:
x in TmTexSe 1 _x . 0.83 0.68 0.55 0.4
p1, in kbar. 25 20 14 15.4 12 3 to 5

Ref. [16] [19] [5] [18] [5, 20] [5, 16, 21]
At 4 K, p1, of TmTe 04 Se 0 _6 is 7 kbar [21].
The metallic solid solutions are clearly intermediate valent compounds with a degeneracy
of the bottom of the conduction band with the 4f states at the Fermi Level EF [22]. The double
exchange mechanism is thought to play a major role in these metallic alloys, Batlogg [4],
Köbler et al. (1], following a model of Varma [23]. The validity of this model, however, for
metallic TmTexSe 1 _x is still regarded as unproven, Haen, Lapierre [9].
At the semiconductor-to-metal transition a positive isomer shift of 0.05 ± 0.03 mm/s has
been measured in Te Mössbauer spectra (no further data given) although the shift is much
smaller than the Te Line. Such an effect is expected for itinerant conduction electrons [1].
Gmelln Handbook
RE Mam Vol. C10
References:
[1] U. Köbler, K. Fischer, K. Bickmann, H. Lustfeld (J. Magn. Magn. Mater. 24 [1981]34/42).
[2] E. Kaldis, B. Fritzler, H. Spychiger, E. Jilek (Valence lnstab. Proc. Intern. Conf., Zürich,
Switz., 1982, pp. 131/9).
[3] H. Boppart, P. Wachter (Phys. Rev. Letters 53 [1984]1759/62).
[4] B. Batlogg (Phys. Rev. [3] B 23 [1981]650/63).
[5] H. Boppart (J. Magn. Magn. Mater. 47/48 [1985]436/42).
[6] G. K. Wertheim, W. Eib, E. Kaldis, M. Campagna (Phys. Rev. [3] B 22 [1980] 6240/6).
[7] G. Neumann, R. Pott, J. Röhler, W. Schlabnitz, D. Wohlleben, H. Zahel (Valence lnstab.
Proc. Intern. Conf., Zürich, Switz., 1982, pp. 87/91).
[8] H. Boppart, P. Wachter (NATO Advan. Study lnst. B No. 117 [1984]229/35; C.A. 102 [1985]
No. 177791).
[10] I. Märke, P. Wachter (Solid State Commun. 48 [1983]441/3).
[11] A. Treindl, P. Wachter (Solid State Commun. 36 [1980]901/5).
[13] H. J. F. Jansen, A. J. Freeman, R. Monnier (Phys. Rev. [3] B 31 [1985]4092/5).
[14] W. D. Brewer, G. Kalkowski, G. Kaindl, F. Holtzberg (Phys. Rev. [3] B 32 [1985] 3676/86,
3684).
[15] R. Ramirez, L. M. Falicov (Phys. Rev. [3] B 3 [1970] 2425/30).
[16] H. Boppart, E. Kaldis, P. Wachter (Helv. Phys. Acta 55 [1982] 538/40).
Rochester, N.Y., 1976 [1977], pp. 541/3).
[18] H. Boppart, W. Rehwald, E. Kaldis, P. Wachter (Valence lnstab. Proc. Intern. Conf., Zürich,
Switz., 1982, pp. 81/5).
[19] H. Boppart, P. Wachter, B. Batlogg, R. G. Maines (Solid State Commun. 38 [1981]75/7).
[20] P. Wachter (J. Magn. Magn. Mater. 31/34 [1983] 439/42, 442).
[21) B. Batlogg, H. Boppart, E. Kaldis, D. B. McWhan, P. Wachter (Valence lnstab. Proc. Intern.
Conf., Zürich, Switz., 1982, pp. 523/6).
[23] C. M. Varma (Solid State Commun. 30 [1979]537/9).
30.7 .1.3.5 Mechanical Properties

Density
The measured densities Dexp (buoyancy method on single crystals, error ~ ± 0.04 except
for x = 1 with ± 0.14) and the X-ray densities DeaLe of TmlexSe 1 _x alloys are as follows:
x in TmlexSe 1 _x. 0.95 0.84 0.77 0.72 0.51 0.40 0.18 0.10 0.05 0.0
Dexp in g/cm 3 .. 7.58 7.50 7.68 7.55 7.48 8.58 8.62 8.74
Deale in g/cm 3 . . 7.68 7.73 7.76 7.76 7.79 8.09 8.10 8.47 9.25 9.07 8.95
For additional values see the paper. The differences between the measured and calculated
densities are discussed in terms of lattice defects and internal lattice pressure, which are
induced by the difference of the ionic radii of Te2 - and Se 2 -, Kaldis, Fritzler [1]; see also
Gmelin Handbook
RE Main Vol. C 10
~ 2r:==--'r--!-'~--l---+---i
(.!)
.!:
Q.
V/Vo
Fig. 138. Pressure-volume diagram for solid solutions TmTexSe 1 _ x at 300 K, normalized to V0
of TmTe0 .83Se 0 .17 .
Katdis et al. [2] . Under pressure the X-ray density of TmTe0 .68Se0 .32 was found to be 7.800,
8.159, and 8.430 g/cm 3 at zero, 1.26, and 1.54 GPa, respectively [3); seealso [4].
Pressure-Volume Data
The p-V behavior of semiconducting samples was studied at hydrostatic pressure below
~ 3.5 GPa ( ~ 35 kbar); see Fig. 138 from Boppart [5], which includes earlier data for x = 0.83
from Boppart et al. [6], x = 0.68 from Boppart et al. [3, 4], Boppart, Wachter [7, 8] . The
decreased slope of the curves at VIV0 = 0.90 to 0.95 indicates the semiconductor-to-metal
transition (continuous for x ~ 0.50 and discontinuous for x = 0.40 to 0.45) [5) with a volume
change !l.VIV = - 5.5% at ~ 4 kbar for x = 0.40, Batlogget al. [9) .
The isothermal bulk moduli K were derived from the p-V curves and the adiabatic K from
elastic constants (for x = 0.68) . The typical behavior is shown in Fig. 139 for x = 0.68 from
[5, 7]; analogaus plots for x = 0.83 are reproduced in [6, 10]. Already the initial values of
0 2 3
p in GPa
Fig. 139. Pressure dependence of the isothermal bulk modulus K (solid Line) of TmTe0 .68 Se0 .32
trom p-V data and adiabatic K (dashed Line), calculated from the elastic constants, at 300 K.
Gmelm Handbock
RE Mam Vol. C 10
336 Selenide TeUurides
Gr---r---~--,----r---n
o
2 02 Q4 0.6 OB 10
pinGPa
Fig. 140. Pressure dependence of the isothermal compressibility K of TmTe 0 17Se0 _83 and TmSe
at 300 K.
the bulk moduli are reduced against values typical for divalent compounds. With increas-
ing pressure the bulk modulus decreases giving a minimum (i.e., a maximum of the
compressibility K = 1/K) at the semiconductor-metal transition. Beyond the minimum the bulk
moduli return to roughly their initial value [5, 6). The initial (isothermal) compressibilities K
(in 10- 11 Pa - 1 ) of semiconducting mixed crystals are as follows (in parenthesis Kin GPa):
x in TmTe.Se 1 _ x . 1.0 0.83 0.77 0.68 0.68 0.55 0.40
K (K) 2.2(45) 2.4(42) 2.3(43) 3.0(33) 2.7(37 ± 1) 3.3(30) 4.5(22)

Ref. . [5, 11) [6,11,12) [12) [5, 11) [3) [5, 11) [5, 11)
The initial (adiabatic) bulk modulus, i.e., K = (c11 + 2cd/3, of TmTe0 _68Se0 _32 is 35 GPa [3) .
The maximum compressibility of TmTe. Se 1 _ x with x = 0.83, 0.68, and 0.55 at the transition
pressures (in GPa) 1.9, 1.4, and 1.2 is K (in 10- 11 Pa- 1) = 9, 17, and 35, respectively (i.e. ,
minimum of K = 11, 6, and 3 GPa) [5, 11), cf. [13). The initial compressibilities fit well into
Anderson-Nafe plots of other semiconducting, isostructural rare earth compounds [6, 12),
which relate the relative volume and the compressibility by apower law K ~ vg [16] .
For metallic TmTe0 17Se 083 the compressibility is ~ 5 Iimes higher than the value expected
for an integer valent compound . The pressure dependence up to 10 kbar is shown in Fig. 140,
Batlogg [12) .
Fig. 141 shows the pressure dependence of the elastic constants c 11 , c 12 , and c 44 for
semiconducting TmTe0 _68Se0 32 , derived from measurements of the longitudinal and the Irans-
versesound velocities in the [100) and the [110) direction of a single crystal at 20 MHz under
hydrostatic pressures up to 1.7 GPa by the pulse echo overlap method . The constant c 12
becomes negative above 0.6 GPa, which is far below the transition pressure to the metallic
state, ~ 1.5 GPa. Numerical values (in GPa) for ambient pressure, 1.26, and 1.54 GPa, respec-
tively, are c 11 = 97.40, 87.80, and 85.90, c 12 = 3.67, - 22.2, and - 33.8, c44 = 21.8, 22.2, and
22.45, which give the anisotropy factors 2c44/(c 11 - c 12 ) = 0.43, 0.40, and 0.37. The experimental
data indicate that the softening of the longitudinal acoustic phonons and the bulk modulus is
mainly caused by the negative sign of c 12 . A discussion in terms of the " breathing shell model"
(see for example " Rare Earth Elements" C 7 , 1983, p. 351) favors the assumption of the
appearance of the intermediate valence state even in the semiconducting phase [3) ; seealso
[4, 14).
Gmehn Handbock
RE M ai n Vol. C 10
The Tm Te-Tm Se System 337
100 -- ~ r-...
"
~
~ 0
\_ e. -10
\~
1\
(!)
.5:
80 !::!
u
\
-20
e.
(!) c..
.5: 23
... L.o
-3
u" 21 \;
0 05 1D 1.5 0 05 1.0 1.5
pin GPa p in GPa
Fig. 141 . Pressure dependence of the elastic constants c 11 , c44 , and c 12 of TmTe0 .68Se 0.32 .
The relative volume VIV0 in the metallic high-pressure phase (verified for x = 0.83 in [6]
and 0.68 in (7]) is higher than the value estimated for trivalent Tm ions by the Birch-Murnaghan
equation [5, 6], thus making obvious the intermediate valence state of Tm in the high-pressure
phase [6]. A mean-field type of behavior of the valence transition under pressure is suggested
from the generat appearance of the p-V properties of semiconducting TmTexSe 1 _x compounds.
The critical exponents o
= 2.72 below and o
= 3.1 for p above the critical pressure were
obtained for TmTe0.45Se0 .55 by the relation p-pc = IV - Vcls · sgn (V - Vc). These values are
o
close to = 3 predicted by the mean-field-theory [5, 11].
References:
[1] E. Kaldis, B. Fritzler (J. Phys. Colloq . [Paris]41 [1980] C5-135/C5-142) .

[2] E. Kaldis, 8 . Fritzler, W. Peteier (Z. Naturforsch. 34a [1979] 55/67, 62).
[3] H. 8oppart, W. Rehwald, E. Kaldis, P. Wachter (Valence lnstab. Proc. Intern. Conf. , Zürich ,
Switz. , 1982, pp. 81/5) .
[4] H. 8oppart, W. Rehwald, E. Kaldis, P. Wachter (Physica B + C 117/118 [1983]573/5).
[6] H. Boppart, P. Wachter, B. 8atlogg, R. G. Maines (Solid State Commun . 38 [1981]75/7).
[7] H. Boppart, P. Wachter (Phys. Rev. Letters 53 [1984]1759/62) .
[8) H. 8oppart, P. Wachter (Mater. Res. Soc. Symp. Proc. 22 Pt. 1 [1984]273/6).
[9] 8. 8atlogg, H. 8oppart, E. Kaldis, D. 8. McWhan, P. Wachter (Valence lnstab. Proc. Intern.
Conf., Zür ich, Switz., 1982, pp. 523/6).
[10) H. 8oppart, P. Wachter (Ann. Chim. [Paris] [15]7 [1982) 83/91).
[11] H. Boppart, P. Wachter (Mater. Res. Soc. Symp. Proc. 22 Pt. 1 [1984]341/4).
[12] B. Batlogg (Phys. Rev. [3] B 23 [1981]650/63).
[13] H. 8oppart, E. Kaldis, P. Wachter (Helv. Phys. Acta 55 [1982] 538/40).
[14] H. 8oppart, E.Kaldis, P. Wachter, W.Rehwald (Helv. Phys. Acta 55 [1982] 537/8) .
Gmelm Handbook 22
RE Main Vol. C 10
30.7 .1.3.6 Thermal Properlies

A thermal expansion coefficient rx = 20 x 10- 6 K- 1 is given for "metallic" TmTe 0 _33Se 0 67
measured at70 K, Köbleretal. [1] andrx = -13x 10- 6 K- 1 at3.8 KforTmTe 0 _17Se 0 _83 , Batlogg
et al. [2].
Preliminary DTA studies on TmTexSe 1 _x alloys show a smooth decrease of the melting
points from ~ 2000 to ~ 1800°C when x is increased from ~ 0.2 to ~ 0.6; at 0.6 < x < ~ 0.8
the melting point does not change significantly. Thermal effects, possibly indicating a phase
transition, appear at about 300 K below the melting points of the respective sample; for a
figure see the paper, Kaldis, Fritzler [3].
References:
[2] 8. Batlogg, H. R. Ott, P. Wachter (Phys. Rev. Letters 42 [1979] 278/81).
[3] E. Kaldis, 8. Fritzler (J. Phys. Colloq. [Paris]41 [1980] C5-135/C5-142).
30.7 .1.3. 7 Magnetic Properlies

lnlroduclion
8oth semiconducting and metallic TmTexSe 1 _x samples are magnetically ordered at
sufficiently low temperatures. The magnetic structure is antiferromagnetic for the former,
TN = 0.2 K and 0.3 Kat x = 0.68 and 0.40, respectively, Boppart, Ott [1], and ferromagnetic
for the latter, for example, Tc between 2 and 4 K, Boppart [2]. At ~50 K [3, 4], well above the
ordering temperatures, a Curie-Weiss behavior is observed for all compositions with the
effective magnetic moments lleff and the paramagnetic Curie temperatures 0P as follows;
included in this table arealso results from Köbler et al. [3] for two samples both of nominal
composition TmTe 0_33Se 0 _67 yet with different lattice parameters (6.05 Aand 5.83 A, respective-
ly), which apparently correspond to the two boundaries of the miscibility gap:
0.68 0.55 0.5 0.40 0.33 0.33 0.17 0.15 0.11 0.09 0
llel! in !ls · 4.73 4.61 4.51 4.74 4.56 4.98 5.77 5.87 6.42) 5.85 6.39
-eP in K 1.5 2 2 0±0.5 2 ~ 6 1) ~ 15 1) 17 19.2 3) 30 15 29
Ref . . . . [2] [2] [2] [5] [2] [3] [3] [5] [6] [4] [5] [5]
1l Values read from a figure. - 2l From the Curie constant Cm = 5.1 cm 3 · K · mol- 1. - 3l E>P
given by [6] was calculated from the Line width in quasi-elastic neutron scattering.
The free ion values for Tm 2 + and Tm3+ are 4.54 and 7.56J.L 8 ; see for example [3].
Semiconducting TmTexSe 1 _ x
The effective magnetic moments lleff of semiconducting samples, from susceptibility mea-
surements up to T = 500 K, are independent of x and very close to the free ion value for
Tm2+, except lleff of TmTe. Also no influence of x on the paramagnetic Curie temperature 0P
is found, Boppart, Wachter [7]; see also [2]. However, an increase of !lall with increasing Se
content and an increase of the absolute value of E>P were found from measurements between
~ 10 and 200 K. The Curie-Weiss behavior is observed above ~50 K, Köbler et al. [3].
Gmelm Handbock
RE Mam Vol. C10
---
3
f.---
/"
1/
20 40 60 80 100
H in kOe
Fig. 142. Magnetization of semiconducting TmTe 0 .5Se 0 .5 at 4.2 K as a function of the magnetic
field strength H.
Deviations from the Curie-Weiss behavior below ~ 80 K of a sample with x = 0.5 were
attributed to crystal electric field effects, Batlogg [5]; cf. [8].
Susceptibilities under pressure have been measured for TmTe 0 .68 Se 0 .32 up to 1.71 GPa
(see the figure in the paper), Boppart, Wachter [7], Wachter [9] and for TmTe 04 Se 0 6 up to
1.23 GPa, Batlogget al. [10]; seealso [11]. The susceptibilities between ~ 80 to 300 Kat x =
0.68 follow the Curie-Weiss Law at all pressures. The obtained effective magnetic moments
remain constant and close to the free ion value of Tm 2 + at pressures below ~ 1.4 GPa and
increase gradually at higher pressure, up to lleff ~ 4.73 lls at 1.71 GPa (value read from a
figure) . This is interpreted to indicate divalent Tm in the semiconducting phase below the
pressure at the semiconducting-metallic transition (SMT) ( ~ 1.4 to 1.5 GPa) and intermediate
valent Tm in the metallic phase [7]. The a.c. susceptibilities of TmTe 0 ße 0 6 were measured
at T between ~ 2 and 8 K and p between 0.71 and 1.23 GPa (see a figure in the paper)
[10]. Below 0.68 GPa the susceptibility is very Low and slightly increases on decreasing
temperature, indicating an ordering point weiL below 1.6 K, the Lowest temperature of this
experiment. Above 0.7 GPa the x(T) curves are completely different, showing a maximum at
5.6 K up to p = 0.76 GPa. At still higher pressures the peak shifts to Lower temperatures
reaching 3.25 Kat p = 1.23 GPa. ln the range between 0.7 and 0.86 GPa the shape of the
x(T) curve resembles those observed at ambient pressure in ferromagnetic (and metallic)
TmTexSe 1 _x alloys. The change in the X(T) shape above 0.8 GPa Leads to speculations that
there might be a sequence with pressure from weakly magnetic ground states at Low pressures
(ordering temperature < 1 K) to ferromagnetic and to antiferromagnetic ground states in
TmTe 0ße 0 .6 [10, 11].
The magnetization of TmTe 05 Se 05 measured at 4.2 K in fields up to 100 kOe (Fig. 142) is
far below the expected values from the Brillouin function, thus showing that this compound
is notasimple paramagnet [5].
Metallic TmTexSe 1 _x
Magnetic Structure
ln cantrast to the antiferromagnetic ground state (type I) in TmSe ( ~ x = 0) the

Te-containing metallic samples (0 < x < 0.33) are ferromagnetic, Boppart [2].
Ferromagnetic spinorderwas interred from the Observation of magnetic Bragg reflections
and Large magnetic moments in neutron diffraction experiments at 1.5 K for TmTexSe 1 _x, a
powder sample with x = 0.16 and a single crystal with x = 0.17 (compositions estimated from
Gmelin Handbock 22"
RE Main Vol. C 10
Jr----,.-----.-----.- ----.-----,
Hin kOe
Fig. 143. Magnetization of metallic TmTexSe 1 _x solid solutions with x = 0, 0.09, and 0.17 at
1.8 K as a function of the magnetic field strength H. The insets show the temperature
dependence of the magnetization for H = 0.1 to 3.8 kOe.
the lattice parameters) . The halfwidth of the magnetic Bragg reflection indexedas 111 depends
only weakly on the temperature below the Curie temperature, thus establishing the magnetic
ordertobe of long range. Tc > 4.2 K was attributed to a polycrystalline sample with x ~ 0.21.
No antiferromagnetic reflections could be detected in any of the measured samples even at
the lowest temperatures used, but small peaks due to weak antiferromagnetic short range
correlation might still be hidden in the background , Fischer et al. [12) .
Low•Temperature Magnetization. Magnetic Moments
The following spontaneaus magnetic moments Jls and ordering temperatures Tc have been
obtained from magnetization and neutron scattering (indicated by *) experiments (the Curie
temperatures Tc given by [13) are derived from the maxima of dx/dT curves in various fields
extrapolated to H = 0; in centrast to other samples, the TmTe 0 _11 Se0 _89 crystals studied by [4)
do not exhibit ferromagnetic order):
x in TmTexSe 1 _ x 0.21 0.17 0.17 0.16 0.11 0.09
Jls in JlsiTm 1.2(1)* 0.5(1) 0.6(3)* 0.8 1.6(1)* 0.05 0.3

Tc,TN in K ~ 4.2* 3.4(1)* 3.7±0.1 3.7(1)* 1.9 2.8 ±0.1
Ref.. [12) [12) [12) [13), cf. [5) [12] [4) [13)
The magnetization at 1.8 K for x = 0.17 and 0.09 increases with increasing field yet is not
saturated even above ~ 80 kOe ; see Flg. 143. The value of 2.5 Jls for x = 0.17 in a field of
80 kOe is far below the free ion values of Tm2+ or Tm3+ ions [5, 13, 14]. The magnetization
measurements in a field of 2 kOe between 2 and 10 K for samples with x = 0.3 and 0.15 show
the magnetic transition temperature only as an obtuse kink in the magnetization . A real
ferromagnetic order was not obvious. Yet the type of order appears to change from anti-
ferromagnetic to metamagnetic with an increasing ferromagnetic component with increasing
Te content towards the SMT at x = 0.33, Köbler et al. [3).
Gmetm Handbook
RE Main Vot. C 10
The exchange parameters J 1, J 2 within the mean field approximation could be derived
consistently only from the Low temperature data of the samples with x = 0.17 and 0.09 [5].
Estimates confine J 1/k 8 to positive values for both compositions and J 2/k 8 ~ 0.45 and ~ 0.35 K
for x = 0.17 and 0.09, respectively [13). The magnetic behavior of TmTe 0_17Se0 .83 , as observed
by [14], is discussed as consistent with the properties of TmSe extrapolated to negative
pressure (i.e. expanded Lattice), Guertin, Foner [15).
A rather Linear correlation was shown to exist for the metallic samples and the metallic
high-pressure phase of TmTe 0.4Se0.6 between the observed magnetic ordering temperature
and the Tm valence v from the effective magnetic moments, !!elf• or the molar Curie constants,
Cm (Tc ~ 2 K at v = 2.5, Tc ~ 5.5 K at v = 2.1 from a figure in the paper), Boppart [2]. The
analogaus relation based on Lattice parameter derived valence numbers, Boppart et al. [11],
is Less Linear.
Susceptibilities
The susceptibility of the TmTe.Se 1 _x samples, measured between 1.5 and 300 K, obeys
the Curie-Weiss Law above ~ 40 K in the samples with x = 0, 0.09, and 0.17. The increase of
the effective magnetic moments !!elf with decreasing Te content in the metallic samples
indicates an increasing intermediate valence number, Batlogg [5), similarly stated by Köbler
et al. [3]. The change of 0p from -29 K for TmSe to - 15 and - 17 K for two Te-containing
samples is said to indicate an enhanced ferromagnetic exchange interaction [5). The analysis
of eP for its contributions is regarded as too complex [3]. ln contrast to the data of [3] and [5)
the temperature dependence of the a.c. susceptibility (98 Hz) of TmTe0 . 11 Se 0.89 measured for
two single crystal samples between 1.2 and 4.2 K shows a well-defined peak at 1.9 K and
decreasing x at Lower temperature; thus, no ferromagnetic order is exhibited. These
differences may possibly be related toslight yet important variations of the metallurgical state
of the samples, Haen, Lapierre [4]. A maximum in the initial x(T) curve was also observed for
TmTe 0.17Se0 _83 . lt was related to domain effects or nonnegligible antiferromagnetic interactions
due to canting of the predominantly ferromagnetic structure, Fischer et al. [12).
lnelastic and Quasi-Elastic Lines in Magnetic Neutron ScaHering
ln neutron scattering experiments (time offlight spectrometer, various incident energies,

e.g., 3.5 meV) on TmTe 0_15Se0 _85 with Lattice parameter a = 5.785 A a quasi-elastic Line is
observed, comparable to the behavior of TmSe. Above ~ 100 K the Line width increases only
slightly with temperature (at 300 K f/2 = 5.6 ± 0.7 meV). Below this temperature it decreases
drastically, f/2 ~ 0.7 x k8 · T, k8 = Boltzmann constant, and remains below the corresponding
thermal energy; see Fig. 174 in "Rare Earth Elements" C9, 1986, p. 349. An inelastic Line is
observed (at an incident beam energy of 12 meV) between 5 and 30 K. The excitation energy
L\ increases with decreasing temperature from 5.4 meV at 30 K to 7.8 ± 0.5 meV at 5 K; the
Line width f/2 = 1.8 ± 0.5 meV at 5 K. By comparison with other intermediate valent Tm
compounds (both concentrated and dilute) it becomes obvious that the excitation energy, the
width and intensity of the inelastic Line, and the room temperature Line width of the quasi-
elastic Line decrease with increasing Lattice parameter (i.e. volume per Tm), Holland-Moritz
[6). The experimental results are said [6) to confirm models which treat valence fluctuations
of Tm as a single ion effect, for example, Mazzaferro et al. [16). Within these models the
magnetic relaxation time r M corresponds to the experimental width r/2 of the quasi-elastic
Line at high temperatures. A hybridization energy W0 = 4.547 meV and further a paramagnetic
Gmelm Handbock
RE Mam Vol. C 10
Curie temperature ®P = - 19.2 K has been calculated [6] from the experimental quasi-elastic
line width using a Tm valence of 2.49 and r M (in 21t W0) = 0.196, cf. [17].
Theoretical Models
The occurrence of ferro- and antiferromagnetism in intermediate valent Tm compounds

has been treated in a periodic lattice model by Alascio et al. [18]; see also "Rare Earth
Elements" C9, 1986, pp. 349, 364/5. For ferro (FM)-antiferromagnetic (AFM) phase diagrams
as a function of the electron number per site and the energy position of the locallevel, see
the paper. According to this model stoichiometric TmTexSe 1 _x samples with x > 0.2 are
semiconductors with an antiferromagnetic ground state. Nonstoichiometry and small magnetic
fields destabilize the AFM ground state with respect to an FM state. Stoichiometric TmTexSe 1 _x
samples, with x ;;:; 0.2, are expected tobe antiferromagnetic semiconductors. ln this regime
the AFM ground state is less sensitive towards nonstoichiometry [18]. The magnetic properties
of the metallic samples are estimated to be in best agreement with a double exchange
mechanism as the dominant magnetic coupling between intermediate valent ions, Batlogg
[5].
References:
[1) H. Boppart, H. R. Ott (from [2)).

[2) H. Boppart (J. Magn. Magn. Mater. 47/48 [1985] 436/42).
[3) U. Köbler, K. Fischer, K. Bickmann, H. Lustfeld (J. Magn. Magn. Mater. 24 [1981) 34/42).
[4) P. Haen, F. Lapierre (Valence Fluct. Solids St. Barbara lnst. Theor. Phys. Conf., Santa
Barbara, Calif., 1981, pp. 313/6).
[5) B. Batlogg (Phys. Rev. [3) B 23 [1981]650/63).
[7) H. Boppart, P. Wachter (NATO Advan. Study lnst. Ser. 8 No. 117 [1984) 229/35; C.A. 102
[1985] No. 177791).
[8] B. Batlogg, E. Kaldis, P. Wachter (J. Phys. Colloq. [Paris]40 [1979] C5-370/C5-371).
[9] P. Wachter (Proc. Intern. Conf. Rare Earth Develop. Appl., Beijing, Peop. Rep. China,
1985, Vol. 2, pp. 952/9).
[10) 8. Batlogg, H. Boppart, E. Kaldis, D. 8. McWhan, P. Wachter (Valence lnstab. Proc. Intern.
Conf., Zürich, Switz., 1982, pp. 523/6).
[11] H. Boppart, E. Kaldis, P. Wachter, B. Batlogg, D. 8. McWhan (Helv. Phys. Acta 55 [1982)
545/6).
[12) P. Fischer, W. Hälg, P. Schobinger-Papamantellos, H. Boppart, E. Kaldis, P. Wachter
(Valence lnstab. Proc. Intern. Conf., Zürich, Switz., 1982, pp. 551/4).
[13) B. Batlogg (J. Magn. Magn. Mater. 15/18 [1980]939/41).
[14] 8. Batlogg, H. R. Ott, P. Wachter (Phys. Rev. Letters 42 [1979) 278/81).
[15] R. P. Guertin, S. Foner (Phys. Rev. [3) B 20 [1979]3926/8).
[16] J. Mazzaferro, C. A. Balseiro, 8. Alascio (Phys. Rev. Letters 47 [1981)274/7).
[17) Y. Kuramoto, E. Müller-Hartmann (Valence Fluct. Solids St. Barbara lnst. Theor. Phys.
Conf., Santa Barbara, Calif., 1981, pp. 139/46).
[18] 8. Alascio, A. A. Aligia, J. Mazzaferro, C. A. Balseiro (Valence lnstab. Proc. Intern. Conf.,
Zürich, Switz., 1982, pp. 493/6).
Gmel1n Handbook
RE Ma1n Vol. C10
30.7 .1.3.8 ELectricaL Properlies
30.7.1.3.8.1 Electronic Structure
General
Solid solutions TmTe.Se 1 _x with x ~ 0.40 are semiconductors and with ~ 0.18 are metallic.
The semiconductor-metal transition (SMT) can also be induced by pressure. The electronic
structure of the solid solutions can be described by the models used for Tm Te (see pp. 268/
9) or TmSe (see "Rare Earth Elements" C9, 1986, pp. 359/66). The 4f states are treated as a
narrow impurity band below the conduction band and the energy gap E9 between the 4 f states
and the conduction band decreases with decreasing Te content. The miscibility gap between
about x = 0.18 and 0.40 is in the region where E9 is expected to approach zero. The
composition-induced SMT is discontinuous; see for example Boppart [1], Köbler et al. [2].
The Fermi Level EF is apparently pinned to the 4 f states. This was interred from the temperature
dependence of the resistivity by analogy to Sm and Eu monochalcogenides, Batlogg [3].
The mechanism leading to the observed SMT as afunction of composition or of pressure

is understood as mainly due to the lattice parameter dependence of the crystal field split of
the 5d states. On substituting Te by Se or on application of pressure the mean cation-anion
distances decrease, which is monitared by the lattice parameter. By the increasing crystal
electric field the split of the 5d band into 5d(t29 ) and 5d(e9 ) subbands becomes more pro-
nounced, leading to a Lowered 5d(~9 ) subband at the cost of the energy gap E9 ; see, for
example, Batlogg [3].
The reduction of the energy gap Leads to strong f-d mixing even in the semiconducting
state, causing a generat softening of the crystal. This is shown by the compressibilities
and the elastic constants; see for example [1, 4] or p. 336. This valence instability in the
semiconducting state is not observed in the magnetic properties. This discrepancy is dis-
cussed in terms of electron lattice interactions. Changas of screening effects for the outer
electrons are due to the changing f and ds orbital overlap with pressure. ln contrast, the
localized 4f states, already with 5d admixture, retain their original quantum numbers up to
the SMT [1].
Energy Gap E9
The energy gap E9 and the pressure coefficients dEgfdp for the semiconducting samples
were derived from the dependence of the resistivity on temperature, Batlogg, Wachter [5),
Batlogg [3], or on pressure, Boppart, Wachter [6], Boppart [1), Boppart et al. [7]. The following
values are reported for E9 (in meV) and dE9 /dp (in meV/GPa) at lower pressures (in parenthesis
at higher pressures):
x in TmTe.Se 1 _. 0.83 0.83 0.77 0.68 0.55 0.5 0.50 0.40
Eg . . . 210 250 240 170 110 180 100 40

- dE9 /dp 140(98) 125 110 130(110) 126(99) 100 67
Ref .. [6, 7] [3] [3] [1, 6] [1, 6] [3] [8] [1, 6)
Gmelin Handbook
RE Main Vol. C 10
The E9 values given by [3] are rough estimates ( ~ ± 30 meV) from the resistivities of the
ambient and the high-presssure metallic phase. Accuracy of the pressure coefficients is
± 10 meV/GPa [3]. dE9 /dp = - 122 meV/GPa for TmTe068Se 032 was derived from the variation
of the Hall effect under pressure [9]. The deformation potentials L = (dE 9 /dp) · K0 (with K0 =
bulk modulus) are, in eV, 5.2 ± 0.5, 4.8 ± 0.6, and 4.5 ± 0.5 for x = 0.83, 0.77, and 0.5,
respectively, [3]. A kind of warped bottarn of the conduction band was interred from the
reduced closing rate of the gap at elevated pressure ( > 1 GPa) for x = 0.83. This might be
due to different surroundings of Tm sites [3].
ln metallic TmTe 0 _18Se 082 the presence of a small hybridization gap (below ~ 5 to 10 meV;
see the figure in the paper) in the paramagnetic state close to Tc was interred from point
contact spectroscopy at 4K. A maximum in N(E) at the Fermi Level EF (but no gap) was found
below Tc in the ferromagnetically ordered phase at 1.8 K, Frankowski, Wachter [10, 11],
Wachter [12]; see p. 347.
Charge Carrier Properlies
The conductivity is mainly determined by the thermal activation of electrons from the
Localized 4f13 Level into the 4f 12 (5d6s) 1 bandlike states. The charge carrier concentration n =
2 x 10 18 cm- 3 in TmTe 0 _68 Se 0 _32 at ambient pressure is derived from the Hall effect assuming
a one-band model. The electron concentration increases exponentially with increasing pres-
sure. Deviations occur only at 0.1 to 0.2 GPa below the transition to the metallic state (p 1, =
1.4 GPa) where n ?- 1021 cm- 3 ; for a figure see the paper [1, 9, 13]. The mobility llH increases
from ~ 6 cm 2 · v- 1 · s- 1 at ambient pressure to ~ 10 cm 2 • v- 1 · s- 1 at the SMT, Boppart,
Wachter [9]; seealso [1].
References:

[3] B. Batlogg (Phys. Rev. [3] B 23 [1981] 650/63, 651/4).
[4] H. Boppart, W. Rehwald, E. Kaldis, P. Wachter (Valence lnstab. Proc. Intern. Conf., Zürich,
Switz., 1982, pp. 81/5).
[6] H. Boppart, P. Wachter (Mater. Res. Soc. Symp. Proc. 22 Pt. 1 [1984] 341/4).
[8] H. Boppart, A. Treindl, P. Wachter (Valence Fluctuations Solids St. Barbara lnst. Theor.
Phys. Conf., Santa Barbara, Calif., 1981, pp. 103/11, 109).
[10] I. Frankowski, P. Wachter (Valence lnstab. Proc. Intern. Conf., Zürich, Switz., 1982,
pp. 309/12).
[11] I. Frankowski, P. Wachter (J. Appl. Phys. 53 [1982]7887/9).

[12] P. Wachter (J. Magn. Magn. Mater. 31/34 [1983]439/42).
[13] H. Boppart, P. Wachter (Mater. Res. Soc. Symp. Proc. 22 Pt. 1 [1984] 273/6).
Gmelm Handbook
RE Mam Vol. C 10
30.7 .1.3.8.2 Electrical Conductivity
General
A survey on the room temperature resistivities Q as a function of the Lattice parameter of
TmTe.Se 1 _ x reflects the discontinuous nature of the composition-induced semiconductor-
metal transition (SMT), Köbler et al. [1]; see the figurein the paper.
Semiconducting Solid Solutions

Numerical values for room temperature resistivities Q at ambient pressure are (in Q · cm) :
1.5, 0.28, 0.032, and 0.0018 for TmTe.Se 1 _x with x = 0.83, 0.68, 0.55, and 0.4, respectively,
Boppart, Wachter [2], Boppart [3]. For the samples with x = 0.55 and 0.4 the values are
considerably Lower (by a factor of ~ 30) than the values measured earlier by Köbler et al. [1],
which themselves are reasonably consistent with the results, Q from 50 to 0.25 Q · cm for x =
1 to 0.5, of Batlogg [4].
The curves of Logg vs. 1/T are slightly curved Lines as shown in Fig.144 for TmTe 0 _83 Se 0 _17
and TmTe 0 _5Se 0 _5 , which appear to indicate a kind of "extrinsic" origin of the charge carriers
thermally activated into the conduction band [4] ; see p. 343 for the derived activation energy
attributed to E9 .
The variation of the electrical resistivity Q with pressure at room temperature is shown in
Fig.145, p. 346, for four compositions [3, 5] . The pressure coefficients of Q below 1.0 GPa are
d log g/dp = 0.21, 0.18, and 0.16 kbar- 1 for x = 0.83, 0.77, and 0.5, respectively, from studies
under hydrostatic pressure up to 2.0 GPa, Batlogg [4]; previously, 0.17 kbar- 1 for TmTe 0.5Se 0 .5
had been given (6]. Above 1.0 GPa the resistivity changes with only 2/3 of its rate at lower
T~mperoture in K
100 50 33
E
u
ö:~o21--_ _,_-+----t-:",,
.:
Q.
10 f -l -- - t --710 ~
~ u0.83 •
c:·
.5
Q.l
2 3
1~~~----~----~~----~~
0 10 20 30
1/T in 10 3 K-1
Fig . 144. Temperature dependence of the electrical resistivity Q of semiconducting solid

solutions TmTe.Se 1 _x with x = 0.5 and 0.83.
Gmetin Handbook
RE Main Vol. C10
104~--~----=----~-'
0 2 3
p in GPa
Fig. 145. Pressure dependence of the electrical resistivity Q of semiconducting solid solutions
TmTexSe 1 _ x with x = 0.40 to 0.83 at room temperature.
pressure [4, 7). or 1/2 at 2.0 GPa [8]. On releasing the pressure the crystal fragments of the
TmTe0 _5Se0 _5 crystal attained the ambient pressure resistivity again [4]. The conductivity above
the SMT is nearly independent of pressure, for transition pressures see p. 333 [2, 3, 7]. The
change of Q of the Te-richer samples at the SMT in TmTexSe 1 _ x is continuous and the change
of the samples with x = 0.40 to 0.45 is discontinuous at pressures between 0.3 and 0.5 GPa.
The resistivity of TmTe 04Se 0 6 changes from ~ 1 000 to ~ 300 J.lf! · cm at the SMT. On releasing
pressure hysteresis is observed [3]. The values of Q in the high-pressure phase range from
320 to 400 J.lf! · cm independent of the composition, 0.40 ~ x ~ 0.83 [2].
Metallic Solid Solutions
Typical room temperature resistivities Q ( in Jl!l · cm) of metallic TmTexSe 1 _ x samples

(x ~ 0.18) are 100 to 200, Batlogget al. (6]. 200 to 250, Batlogg (4]. and ~ 400 (9]. in agreement
with the data of Köbler et al. [1] with Q ;::; 400 for x ~ 0.3, from a figure in the paper of [1] .
Fig. 146 shows the temperature dependence of Q below room temperature for a sample with
x = 0.11 from Haen, Lapierre [10]. in comparison with the curve for a sample with x = 0.09
from Batlogg et al. [11] . A maximum of Q is observed at about 5 and 3.5 K for x = 0.17 and
0.09 (read from a figure), Batlogg [4]. cf. [6, 11] or at 2.2 K for x = 0.11 [1 0] . The change of Q
for x = 0.11 between 15 and 35 K is described by dg/dln T = 125 Jl!l · cm [10]. while adeviation
from the Logarithmic dependence between 4 and 40 K for x = 0.17 and 0.09 is observed by
[4]. This behavior is not well reproduced by the f-d electron-hole pair theory of Chui [12] and
the double exchange model is preferred [4]. The Q(T) behavior was related to Kondo-like
scattering effects by [1 0].
Gmelm Handbock
RE Main Vol. C 10
E
u
~~~-------r--~---+---H
.5
Q.
Temperature in K
Fig. 146. Temperature dependence of the electrical resistivity Q of metallic solid solutions
TmTe.Se 1 _x for x = 0.11 from Haen, Lapierre [10) and for x = 0.09 from Batlogg et al. [11).
The resistivity Q decreases in magnetic fields both parallel [4) and perpendicular [10) to I.
For example, the transverse magnetoresistance Q(H1_) of TmTe 0 .11 Se0 _89 at 1.4 K reaches at
105 kOe the zero-field value at room temperature, QRr• and at 4.2 K the value at Q(H1_) reaches
QRr at 130 kOe. For H ~ 20 kOe the magnetoresistance is proportional to the square of the
magnetization M; for 20 < H ~ 90 kOe it is proportional to M and varies Less rapidly at higher
fields [10]. The decrease of Q(H 11) at T just above Tc is proportional to the square of the applied
field, studied up to 1.8 Ton TmTe 0 _17Se 0 _83 and TmTe 0 _09 Se0 _91 at 2.0 to 9.0 K; for a figure see
the paper. A linear relation between Q and the magnetic susceptibility x is observed at
temperatures between 30 and 300 K, Batlogg [4); see the figurein the paper.
Point Contact Spectroscopy (PCS)
TmTe 0 _18Se 0 _82 has been studied by point contact spectroscopy. The dependence of the
dynamic resistance on U, dU/di(U), is related to the density of states N(E) near the Fermi Level
EF. At 4.2 K (above the magnetic ordering temperature Tc :::o 3 K) dU/dl has a maximum at
zero bias. ln the ordered state (1 .8 K) a relative minimum is observed comparable to that of
(metamagnetic) TmSe in high magnetic fields ( > 1.5 T) [13]. This supports the nonexistence
of a hybridization gap in TmTe 0 _18Se 0 .82 in the ferromagneUe state (at 1.8 K) and the existence
of a small gap in the paramagnetic state [13, 14]. (For further details and references on PCS,
see [13).)
References:
[1) U. Köbler, K. Fischer, K. Bickmann, H. Lustfeld (J . Magn. Magn. Mater. 24 [1981) 34/42) .
[2) H. Boppart, P. Wachter (Mater. Res . Soc. Symp. Proc . 22 Pt. 1 [1984)341/4; C.A. 101 [1984)
No. 121 064).
[3] H. Boppart (J . Magn. Magn. Mater. 47/48 [1985]436/42).
[4) 8. Batlogg (Phys. Rev. [3) B 23 [1981) 650/63) .
Gmelin Handbook
RE Mam Vol. C 10
[5] H. Boppart, E. Kaldis, P. Wachter (Helv. Phys. Acta 55 [1982] 538/40).

[6] 8. Batlogg, E. Kaldis, P. Wachter (J. Phys. Colloq. [Paris]40 [1979] C5-370/C5-371).
[10] P. Haen, F. Lapierre (Valence Fluct. Solids St. Barbara lnst. Theor. Phys. Conf., Santa
Barbara, Calif., 1981, pp. 313/6).
[11] 8. Batlogg, H. R. Ott, P. Wachter (Phys. Rev. Letters 42 [1979] 278/81 ).

[12] S. T. Chui (Phys. Rev. [3] B 13 [1976]2066/71).
[13] I. Frankowski, P. Wachter (J. Appl. Phys. 53 [1982] 7887/9).
[14] I. Frankowski, P. Wachter (Valence lnstab. Proc. Intern. Conf., Zürich, Switz., 1982,
pp. 309/12).
30.7 .1.3.9 Optical Properlies
Color
The colors of TmTexSe 1 _x samples change as follows: shiny black at x = 1, black at

x = 0.72, dark blue-black at x = 0.40, copperred at x = 0.18 and 0.13, copper violetat
x = 0.1 0, red-violet at x = 0.07, and copper at x ~ 0.05, Kaldis, Fritzler [1].
Raman Spectra
For precautions necessary in generating Raman spectra of these compounds, see p. 274.
Raman spectra have been measured for both semiconducting and metallic TmTexSe 1 _x
samples at 10 K by Mörke, Wachter [2]; see a figure in the paper. Previous measurements on
cleaved or polished TmTe 0 _30Se 0 _70 or metallic samples (x = 0.17, 0.09) at temperatures from
2 to 300 K and magnetic fields up to 1.2 T showed no influence of the magnetic field and no
unusual temperature-dependent phenomena, Treindl, Wachter [3]. The spectra of the two
semiconducting mixed crystals (x = 0.68 and 0.40) show an extra peak at ~ 60 cm-1, just as
in the intermediate valent metallic TmTexSe 1 _x samples. This peak is absent in the integer
valent Tm Te and Tm 0 _87 Se with di- and trivalent Tm, respectively. The extra peak is related to
a renormalization of the LA(i,;~~) mode, where the LA mode is Lowered below the TA branch
in the middle of the Brillouin zone at A. This renormalization is a consequence of the breathing
type deformation of the rare earth ions due to strong f-d mixing, even in the semiconducting
solid solutions (with divalent Tm, see pp. 332/3) [2, 3]. The existence of the peak near 60 cm 1
in the spectra of samples with x = 0.09, 0.17, and 0.30 was also reported in the previous
papers of Boppart et al. [4, 5]. The breathing-shell model is discussed in analogy to (Sm,Y)S
mixed crystals (see "Rare Earth Elements" C7, 1983, pp. 350/2); seealso Güntherodt et al.
[6]. A peak in the Raman spectrum of metallic TmTe 0 15Se 085 at 123 cm- 1 is assigned to the
gap mode which in TmSe appears at 145 cm- 1 (see "Rare Earth Elements" C9, 1986, pp. 329/
30) and is discussed in terms of a "bound fluctuon" mode, StüBer et al. [7]. The transversal
acoustic (TA) and the Longitudinal acoustic (LA) phonans are recognized at 70 and 100 cm- 1
[3]. The acoustic modes are presumed tobe nearly unaffected by anion Substitution [2]. The
Raman intensities from about 135 to 240 cm- 1 were assigned to optical phonons, but it was
not possible to distinguish between transversal and Longitudinal modes. The distinct peak at
Gmel1n Handbock
RE Ma1n Val. C 10
349
180 cm- 1 in cleaved TmTe 0 _09Se 0 _91 is shifted to 160 cm- 1 in TmTe 0 _3 Se 0 _7 , which could be
compared with the softening of the LO mode in Tm.Se with increasing Tm valence [3].
Absorption and Reflection Spectra
Optical spectra at 300 K in the region 0.03 to 0.5 eV confirm the semiconducting character
of the TmTe.Se 1 _x compounds with 0.5 ;;;; x ;;;; 0.83. The Te-richest sample shows a relative
maximum in reflectivity (R = 24%) at 0.4 to 0.5 eV, due to the onset of interband absorption,
and a very slow decrease towards lower photon energies. ln samples with 0.5 ;;;; x ;;;; 0.8 the
electrons thermally activated at room temperature form a conduction band plasma with a
plasmon energy of several tenths of an eV. The optical spectra confirm the narrowing of the
energy gap with decreasing Te content, Batlogg [8]; seealso [9]. The spectrum of TmTe 0 _7 Se 0 _3
(a = 6.15 A) at 10 K is nearly unchanged compared to the optical density of TmTe, indicating
the presence of divalent Tm. The spectrum of a metallic film with x = 0.2 to 0.4 (lattice
parameter a = 5.88 A) is considerably different from that of a semiconducting sample and
can be interpreted by the appearance of the intermediate valence state; for figures of the
spectra see the paper, Suryanarayanan [10].
References:
[1] E. Kaldis, B. Fritzler (J. Phys. Colloq. [Paris]41 [1980] C5-135/C5-142).

[4] H. Boppart, A. Treindl, P. Wachter (Valence Fluctuations Solids St. Barbara lnst. Theor.
Phys. Conf., Santa Barbara, Calif., 1981, pp. 103/11).
[5] H. Boppart, A. Treindl, P. Wachter (J. Appl. Phys. 52 [1981]2140/2).
[6] G. Güntherodt, A. Jayaraman, H. Bilz, W. Kress (Valence Fluctuations Solids St. Barbara
lnst. Theor. Phys. Conf., Santa Barbara, Calif., 1981, 121/8, 126/7).
[7] N. StüBer, G. Güntherodt, A. Jayaraman, K. Fischer, F. Holtzberg (Valence lnstab. Proc.
Intern. Conf., Zürich, Switz., 1982, pp. 69/75).
Rochester, N.Y., 1976 [1977], pp. 541/3).
La 3Te 0.4Se3 _6 single crystals were prepared in sealed Mo or W crucibles by a modified

Bridgman-Stockbarger technique, Bach et al. [1].
The cubic solid solutions LaTe.Se 1_33 _x with 0 ;;;; x ;;;; 1.33 were synthesized from the
elements in evacuated quartz ampules and then pressed and sintered at 900°C for 7 d in
ampules at 10- 5 to 10- 6 Torr. The lattice constants of these phases, which have the Th 3 P4
structure (see p. 21), increase with a slight negative deviation from Vegard's law from x = 0
to x = 1.33; for a figure see the paper. The densities increase linearly. The electrical
conductivity K and the thermoelectric power ISI at 300 K exhibit a minimum and a maximum,
Gmelin Handbock
RE Main Val. C 10
'E
u :.:::
'c:.t= >::::1.
.!:
Vl
"' I
.s"' - ~-.L_----l-:----'---:::"=----'---:'-=---'
Fig. 147. Electrical conductivity K (Fig. 147a) and thermoelectric power S (Fig. 147b) of the
solid solutions LaTexSe 1 _33 _x at 300 K versus composition .
respectively, at x = 0.6 to 0.7; see Fig. 147a, b. The sign of S is negative. The temperature
functions of K and S between about 150 and 500 K are typical for strongly degenerate
semiconductors or metals; for figures see the paper, Antropov et al. [2] .
References:
[1] H. Bach, S. Erdt, P. Stauche (J. Cryst. Growth 62 [1983]173/6).

[2] V. M. Antropov, A . F. Gerasimov, N. A. Krushatina, V. P. Serikova (Deposited Doc. VINITI-
2947-78 [1978]1/7; C.A. 91 [1979] No. 220846).
30.7.3 M 2Te3-M 2Se3 Systems
Sc2Te0 _33Se2 .67

The mixed crystals Sc2Te0 _33Se2 _67 have been prepared in the samemanneras Sc2 Te 3 (see
p. 62) by a chemical Iransport reaction with iodine as the carrier gas at the following conditions:
1 000---> 950 °C, 0.86 mg 12/cm 3 ( ~ 0.35 atm), transport rate of 6.3 11mol/h. The structure is the
same as the ~-form of M2Te3 (see p. 34), i.e., of the orthorhombic Sc2S3 type. Lattice constants
for the orthorhombic cell in Aare a = 10.915, b = 7.729, c = 23.12, and for the pseudocubic
subcell a ' = 5.458 A, Dismukes, White [1] .
The La 2Te3-La 2Se 3 System

The cubic solid solutions La2 (Te,Seb were synthesized from the elements in evacuated
2-section rotating quartz ampules in two steps : for 4 to 5 h at 600 °C (the chalcogen section
~ 500°C) and then for 6 hat 1050 to 1100°C. The inner walls of the rare earth compartment
of the ampule were pregraphitized to prevent reaction with the quartz. The results of X-ray
powder data and visual polythermal studies indicate a continuous series of solid solutions. A
minimum of the liquidus curve was found at 50 mol% La2Te 3 ; see Fig. 148. The decrease in
the lattice constants with composition exhibits a slight positive deviation from Vegard 's law
going from La 2Te3 (a = 9.617 ±
0.003 A) to La2Se 3 (a = 9.036 ±
0.002 A). Lattice c onstants
for La 2 (Te,Seb in A :
mol% La2Te3 90 80 67 60 50 40 33 20 10
a in A 9.565 9.514 9.432 9.414 9.343 9.296 9.237 9.161 9.088
Gmelin Handbock
RE Mam Vol. C 10
351
~
.!:
~ 1500i -------r--~--v--;
e8.
~
~ 1300~-----P~----~-;
0 20 80 100
mol"lol~Se3
Fig. 148. Phase diagram of the La 2Te 3-La 2Se 3 system .
Temperoture in K
333 250 200
,.
~-?~~~~~~~~
-92~----~3~---+----~5
103/T in K- 1
Fig . 149. Electrical conductivity K of the solid solutions LaTe 1_5 -xSex with x = 0 to 0.6 versus
inverse temperature.
Sokolov et al. [2]. According to Gerasimov et al. [3 to 5] only a Limited solid solubility exists
because of the big difference in the ionic radii of Te and Se. X-ray powder studies and density
measurements show that the homogeneity ranges of solid solutions LaTe 1 _5 -xSex based on
LaTe 1 _5 extend from x = 0 to 0.6 and based on LaSe 1 _5 from x = 1.5 to 1.0. The samples were
obtained by sintering at 950°C for 6 weeks [4]. The experimental densities are as follows:
x in LaTe 1_5 -xSex 0.1 0.2 0.3 0.4 0.5

D in g/cm 3 . . . 5.88 6.01 6.13 6.16 6.18
Possible reasons for the increase of D with increasing La 2Se 3 content are discussed in the
paper. The electrical conductivity of the pressed sintered samples (7 d at 900°C), measured
between about 200 and 500 K, decreases with decrease of temperature and increase of the
Se content as shown in Fig. 149, Gerasimov et al. [5].
Gmelin Handbook
RE Mam Vol. C 10
352 Selenide Tellurides. Alkali Rare Earth Tellurates
Phases in the Dy2Te3-Dy2Se 3 System

Electrical resistivity Q in Q · cm and thermoelectric power S in J.LV/K between 100 and 800°C
for phases in the Dy2Te3-Dy2Se3 system with 0, 50, 75, and 100 mol% Dy2Se 3 :
t in °C Dy 2Te 3 50 mol% Dy2Se3 75 mol% Dy2Se 3 Dy2Se 3

Q s Q s Q s Q s
100 0.03 +44 0.06 + 17 0.02 - 24 25 +2
200 0.03 +33 0.06 + 10 0.02 - 38 19 0
400 0.02 + 3 0.07 + 9 0.01 -106 3.60 -2
600 0.03 1 0.04 -15 0.01 88 1.50 -62
800 0.03 5 0.03 -39 0.01 - 98 1.50 -169
The phases were prepared using the standard vapor-solid reaction and melting in vacuum
(see, e.g., p. 31), Muir [6].
References:
[1] J. P. Dismukes, J. G. White (lnorg. Chem. 4 [1965]970/3).

[2] V. V. Sokolov, L. Kh. Kravchenko, A. A. Kamarzin (lzv. Akad. Nauk SSSR Neorgan.
[3] A. F. Gerasimov, A. N. Krushatina, V. N. Konev (Tezisy Dokl. 2nd Vses. Konf. Kristallokhim.
lntermetal. Soedin., Lvov 1974, pp. 177/8; C.A. 85 [1976] No. 170289).
[4] A. F. Gerasimov, N. A. Krushatina (lzv. Akad. Nauk SSSR Neorgan. Materialy 11 [1975]
[5] A. F. Gerasimov, V. N. Konev, N. A. Krushatina, G. I. Bochkina (Fiz. Metal. lkh Soedin.
No. 4 [1976]19/26; C.A. 88 [1978] No. 201583).
[6] H. M. Muir (AD-277043 [1961]1/47, 26/8; N.S.A. 17 [1963] No. 11292).
30.8 Alkali Rare Earth Tellurates
30.8.1 Alkali Rare Earth Tellurates (IV)
Data on stoichiometric rare earth tellurates(IV) are not known. A summary on lu-
minescence and prediction of radiative transition probabilities of M3 + (M = Pr, Nd, Sm, Eu,
Tb, Dy, Ho, Er, Tm) in compositionally unspecified tellurate(IV) glasses (which presumably
contain alkali) is given by Reisfeld [1]. For spectroscopic studies on Nd-doped glasses with
79 to 89 mol% Te02 , 10 to 20 mol% A 20 (A = Li, Na, K, Rb, Cs), and 1 mol% Nd 20 3 (for
instance on 79% Te0 2 + 20% K20 with density D = 4.59 g/cm 3 or on 79% Te0 2 + 20% Li 20
with refractive index n 0 ~ 2.01 and Abbe number v = 20.5) see Weber et al. [2]. Further
references can be found in [1] and [2].
References:
[1] R. Reisfeld (J. Less-Common Metals 112 [1985]9/18).

[2] M. J. Weber, J. D. Myers, D. H. Blackburn (J. Appl. Phys. 52 [1981]2944/9).
Gmelin Handbock
RE Mam Vol. C10
353
30.8.2 Alkali Rare Earth TeLLurates(VI)
Data on alkali rare earth tellurates(VI) are Limited; most papers deal with the Lithium
compounds of the type Li 3M3Te 20 12 . Thesetellurates have the cubic garnet structure with the
space group la3d-0~ 0 .
Preparation
Tellurate(VI) garnets Li 3M3Te 20 12 with M = Y, Pr to Lu, but not Pm, were prepared by
heating M20 3, Te0 2 , and Li 2C0 3 in stoichiometric amounts slowly to 700°C to oxidize Te0 2 and
regrinding and refiring at 850°C for 10 h in porcelain crucibles, Kasper [1]. Stepwise heating
(30 min at 500, 600, and 700°C, respectively, followed by two to four periods of 8 hat 850°C) in
a corundum crucible in air is used by Köngeter, Kemmler-Sack [2] for M-activated Li 3Gd 3Te 2 0 12
samples with M = Pr to Tm (not Pm). For Pr and Tb the initial oxides were Pr4 0 7 and Tb 40 7 .
Properlies
The cubic lattice constants from powder diffraction diagrams and colors are as follows:
Li 3M 3Te 20 12 a in A color Li 3M 3Te 20 12 a in A color
Li 3Y3Te 2 0 12 12.265 white Li 3Dy3Te 20 12 12.306 pale yellow

Li 3Pr 3Te 20 12 12.607 green Li 3Ho3Te 20 12 12.270 pale orange
Li 3Nd 3Te 20 12 12.555 Light blue Li 3Er3Tep 12 12.236 rose
Li 3Sm 3Te 20 12 12.463 pale yellow Li 3Tm 3Te 20 12 12.203 white
Li 3Eu 3Te 20 12 12.426 Light brown Li 3Yb 3Te 20 12 12.172 white
Li 3Gd 3Te 20 12 12.390 white Li 3Lu 3Te 20 12 12.148 white
Li 3Tb 3Te 20 12 12.346 pale yellow
Comparison is made with other garnets. The garnets contain isolated Te0 6 units, Kasper [1].
For the mixed crystal Li 3Gd 2 _5 Eu 0 _5Te 20 12 the lattice constant is a = 12.39 A, the densities are
Dexp = 6.44(5) and Deale = 6.55 g/cm 3 [2]. The lattice constant a = 12.24 A for Li 3Y3Te 20 12 is
reported by Krol, Blasse [5]. The site symmetry of Te is S6 and there are eight Te6+ ions in
the primitive cell. The cation distribution is most probably {Y 3}[Te 2](Li 3)0 12 in view of the
preference of Te6+ for hexacoordination in oxides. Assuming Te0 6 groups bound together by
y3+ and u+ ions, two v 1 and four v2 vibrations are expected in the Raman spectrum and three
v3 in the IR. Experimentally found: v1 at 730 and 750 cm-1, v 2 at 515, 530, 600, and 650 cm-1,
v 5 at 432 and 467 cm- 1 in the Raman spectrum; v 3 at 590,630,665, and 710 cm-1, v 4 at ~ 420,
465, and 490 cm- 1 in the IR. The difference between prediction and experiment may be due
to a deviation from the ideal cation distribution [5].
The IR and Raman spectra of garnets with M = Y, Nd, Gd, Er, and Yb were measured and
the vibrational properties of the Te06 polyhedron are discussed by Sotto et al. [3]. The
photoluminescence and the energy transfer in M3+ -activated Li 3Gd 3Te 20 12 garnet were stud-
Gmelin Handbook 23
RE Main Vol. C10
354 Alkali Rare Earth Tellurates
ied. The luminescence colors and the most intense 4f-4f transitions are given in the following
table [2]:
M3+ luminescence 4 f ---> 4 f-transition

color emission excitation
Pr pale pink 3po --> 3H4 3H4 --> 3p2

Sm orange 4G512 --> sH712 sH512 --> 4l1312· 6 P3,2
Eu red 5Do --> 7F2 7Fo --> 5Ls
Tb green 504 --> 7F5 7Fs --> 5Gs. 5L1o• 5G5
Dy yellow-green 4F912 --> 5 H1312 6 H1512 --> Bp7/2
Ho green 5S2,5F4 --> 518 518 --> 3Ka.5Gs
Er green 4S3/2 --> 4115/2 4115/2 --> 4G1112
Tm blue 1G4 --> 3Hs 3Hs --> 102
For similar studies on Eu3+- and/or Tb 3+-doped Li 3Gd 3Te 20 12 , see Köngeter, Kemmler-
Sack [4].
The scheelitetype single crystals were grown by the flux method in Pt crucibles by cooling
from the annealing temperature at 1.2 K/h. The yellow-green compound is tetragonal with
a = 5.204, c = 11.442 A, cell volume V = 309.372 A3, Schieber [6].
The yellow-green single crystals were grown similarly to LiDy(Te0 4h; see above. The
compound is tetragonal, a = 5.251, c = 11.595 A; V = 319.811 A3 [6].
References:
[1] H. M. Kasper (lnorg. Chem. 8 [1969]1000/2).

[2] B. Köngeter, S. Kemmler-Sack (Z. Naturforsch. 39a [1984]490/4).
[3] I. L. Botto, E. J. Baran, L. L. Fournier (Anales Asoc. Quim. Arg. 70 [1982] 479/90; C.A. 97
[1982] No. 171557).
[4] 8. Köngeter, S. Kemmler-Sack (Mater. Chem. Phys. 11 [1984]495/9).
[5] D. Krol, G. Blasse (J. lnorg. Nucl. Chem. 37 [1975]1328).
[6] M. M. Schieber (lnorg. Chem. 4 [1965] 762/3).
Gmelon Handbook
RE Maon Vol. C10
Polonides 355
31 Rare Earth Elements and Polonium
31.1 Polonides
31.1.1 Gaseous Molecules
For diatornie MPo molecules, where M =La to Lu, Fenochka and Gordienko [1] have
estimated dissociation energies from a model of electron distribution in diatornie rare earth
chalcogenide molecules. For rare earth selenides and tellurides, the same model gave
dissociation energies which were higher than the experimental values throughout by up to
30 kcaVmol; cf. p. 2 and "Rare Earth Elements" C9, 1986, p. 4. The interatomic distances Sc-
Po, Y-Po, and La-Po are 2.62, 2.72, and 2.77 A, respectively; they were obtained with an
empirical relation for diatornie molecules by Spiridonov, Tatevskii [2].
References:
[1] 8. V. Fenochka, S. P. Gordienko (Konfigurats. Predstavleniya Elektron. Str. Fiz.

Materialoved. Mater. 2nd Nauchn. Semin. Konfigurats. Modeli Kondens. Sostoyaniya
Veshchestva, Lvov 1976 [1977], pp. 67/70; C.A. 88 [1978] No. 177425).
[2] V. P. Spiridonov, V. M. Tatevskii (Zh. Fiz. Khim. 36 [1962]2024/9; Russ. J. Phys. Chem. 36
[1962]1086/9).
31.1.2 Solid Polonides
General Reference:
F. A. Shunk, Constitution of Binary Alloys, Second Supplement, McGraw-Hill, New York

1969.
31.1.2.1 General
The first attempts to prepare rare earth sesquipolonides M2Po3 by reaction of 210Po with
rare earth sponges or powders around 1 000°C and < 10- 3 Torr resulted in the formation of
nonstoichiometric compounds with M: Po ratios between 1 :0.3 and 1:1, usually around 1:0.75.
A sesquipolonide was obtained only for M = Gd, which melts at 1635°C and shows red
fluorescence. The nonstoichiometry could be caused by oxidation, Kershner, Steinmeyer [1];
seealso Grove et al. [2, 3], Hertz [4]. According to Bagnall [5] the rare earth polonides have
the greatest thermal stability of any polonium compound.
More recently yttrium polonides with Y: Po ratios from 1 :0.68 to 1 :1.53 were obtained by
reacting at 700 to 950°C for 1 to 20 h. followed by final heating at 1000°C. The thermal stability
did not depend on the composition of the sample. The Liberation of Po starts at > 1 ooooc in
a vacuum of 1 Pa and between 400 and 430°C in a C02 atmosphere of 20.4 kPa. The Po vapor
pressure on heating a sample of the composition YPo1.44 from 445 to 660°C in C02 follows the
equation (p in Pa) log p = (9.34 ± 0.24) - (5380 ± 300)/T; this gives the reaction enthalpy
AH, = 103 ± 6 kJ/mol. On cooling from 695 to 420°C, the vapor pressure follows the equation
Gmelm Handbook 23"
RE Mam Vol. C10
log p = (9.48 ± 0.34) - (5180 ± 440)/T with ilH, = 99 ± 8 kJ/mol. The reaction enthalpies
are comparable with the enthalpy of the vaporization of eiemental polonium in vacuum. The
reaction mechanism with C0 2 is discussed, Abakumov et al. [6].
References:
[1] C. J. Kershner, R. H. Steinmeyer (MLM-1163 [1963] F1/F6).

[2] G. R. Grove, L. V. Jones, J. F. Eichelberger (MLM-1140 [1962] 1/26; N.S.A. 17 [1963]
No. 10239).
[3] G. R. Grove, L. V. Jones, J. F. Eichelberger (MLM-1139 [1962] 1/27, 9; N.S.A. 17 [1963]
No. 7662).
[4] M. R. Hertz (U.S. 3154501 [1963/64]; N.S.A. 18 [1964] No. 44008).
[5] K. W. Bagnall (The Chemistry of Selenium, Tellurium, and Polonium, Elsevier, Amsterdam
1966, p. 47).
[6] A. S. Abakumov, A. D. Khoklov, N. F. Reznikova (Radiokhimiya 28 [1986] 7/11; C.A. 104
[1986] No. 198858).
31.1.2.2 MPo
For convenience, all these compounds are designated by the formula MPo without
allowance for the actual composition.
The procedure of preparation in a solid-vapor reaction resembles that used for the
selenides and tellurides but the amount of material that could be synthesized was limited to
approximately 20 mg (because of the Limitation on the quantity of 210 Po that could be safely
handled) and the procedure was carried out inside a glove box. The use of hydrogen-activated
rare earth metals reduced the reaction temperature by about 300 K below that required for
bulk rare earths. Forthis purpese the hydrides were decomposed and the rare earth metals
were obtained as finely divided powders for the higher melting M or as a sponge for the lower
melting M, like Ce and Pr. Because of the volatility of Sm, Eu, and Yb their powdered hydrides
were used directly. The weighed metals were loaded into a Ta crucible and sealed in a quartz
ampule with a breakoft tip. This ampule was sealed into a three-chambered quartz reaction
tube. The whole quartz apparatus and the crucible were cleaned with concentrated HN03 ,
rinsed with distilled H20, and dried and degassed at 1 000°C under vacuum prior to use. ln
one of the chambers platinum gauzes containing an excess of 210 Po were placed and sealed
after evacuating to 10- 4 Torr. From there the Po was distilled into the supply chamber at
700°C and this was separated from the depleted chamber. After the breakoft tip was crushed
on the rare earth-containing tube, the reaction tube was placed in the furnace and the
temperature was increased slowly. Reaction temperature t and reaction time are as follows:
MPo . YPo La Po Ce Po Pr Po Nd Po PmPo*l SmPo Eu Po
t in °C 1000 600 600 600 600 850 600 800

time in min 120 120 120 60 60 120 45
Gmelm Handbook
RE Mam Vol. C 10
Polonides 357
MPo Gd Po Tb Po DyPo Ho Po Er Po Tm Po VbPo Lu Po
t in °C 600 700 800 700 700 800 800 1000

time in min 60 58 60 45 65 50 60 120
•J Given in [12].
Excess unreacted Po was driven into the supply chamber at 1 000°C. The physical properties
must be measured immediately after the synthesis because they change due to the 0.5%
decay of 210 Po per d with the growth of 206 Pb in the products, Kershner et al. [1, 2].
ScPo was obtained by heating pulverized Sc and Po in an evacuated two-section quartz
ampule at 400 to 700°C for 1 to 4 h, Prokin et al. [5]. VPo was prepared by reaction of 210 Po
vapor and V metal in an evacuated Ta ampule at 850°C in 5 h (but see p. 356), Abakumov,
Ershova [7]. A maximal twofold excess of Po and a quartz ampule were used at 750 to 800°C.
The opposite end of the capsule was heated only to 700°C to prevent condensation of Po in
the zone containing the sample. The reaction time of 4 to 6 h was governed largely by the
rate at which Po was brought into contact with V, Prokin et al. [8]. The reaction mechanism
of Po with V in the vacuum thermal method was studied metallographically by Abakumov
et al. [9].
PrPo was obtained by reacting the elements in vacuum at 400°C (but see p. 356); Gd Po
was similarly obtained at 500°C with completion at 500 to 600°C, Ershova et al. [10].

ScPo is hexagonal according to X-ray diffraction data and crystallizes in the NiAs structure
with a = 4.206 ± 0.003, c = 6.92 ± 0.01 A; c/a = 1.64, the calculated density is 7.94 g/cm 3,
Prokin et al. [5].
The other known rare earth monopolonides crystallize in the cubic NaCl structure, as
shown for MPo with M = V by Prokin et al. [8], M =Pm by Kershner, DeSando [11], and M =
Sm, Eu, Tb, Dy, Ho, Tm, Vb, and Lu by Kershner et al. [1]. The lattice constants a, calculated
densities Deale• and the M-0 distances are as follows:
MPo. VPo Pm Po Sm Po Eu Po Tb Po DyPo Ho Po Tm Po VbPo Lu Po
a in A 6.251 6.360 6.724 6.720 6.254 6.214 6.200 6.256 6.542 6.159
Deale in g/cm3 . 8.12 9.61 7.87 7.92 10.01 10.31 10.45 10.28 9.08 10.94
M-O in A. 3.16 3.36 3.36 3.13 3.11 3.10 3.13 3.27 3.08
Ref .. [8] [11] [1] [ 1] [1] [1] [1] [1] [1] [1]
For the other monopolonides X-ray data are not available. The lattice constants of M = Sm,
Eu, and Vb, which appear to exhibit the divalent state, are higher than those of trivalent M; a
figure is given in comparison with the corresponding tellurides. Therefrom a deviation of
TmPo is shown that is explained with a mixed valence state [1]. But Ott, Hulliger [3] suggest
that the sample of [1] had the composition Tm 0_7 Po, rather than an intermediate valence of
Tm close to 3, based on the assumption that the lattice constants are 6.55, 6.18, and 6.22 A
for Tm 11 Po, Tm 111 Po, and Tm 213 D 113Po, respectively.
The mechanical strength of VPo is low. The microhardness of a VPo layer on unreacted V
is 84 kg/mm 2 ( ~ 0.82 GPa). lt is brittle and is readily converted into a black powder under
mechanical influence [9].
Gmelm Handbock
RE Ma1n Val. C10
Melting Point. Vaporization

No dissociation was observed on heating PrPo up to 1 050°C or Gd Po up to ~ 1 000°C,
Ershova et al. [10]. APo dissociation pressure greater than 10- 3 Torr was detected at 1 ooooc
for Y, Sm, Eu, Tb, Ho, Er, and Yb, Kershner et al. [1, 2].
The rare earth monopolonides melt incongruently (with rapid Loss of Po above the melting
point) at the following temperatures tm in oc (±50) [1, 2]:
MPo. YPo La Po Ce Po Pr Po Nd Po PmPo*l Sm Po Eu Po

tm . . 1700 1457 1430 1253 1423 1292 1474 1488
MPo. Gd Po Tb Po DyPo Ho Po Er Po Tm Po YbPo Lu Po

tm . . 1675 2000 2048 1760 2081 2200 2212 1898
•) From [11].
The equilibrium dissociation pressure of Po above YPo was determined by the Knud-
sen effusion method at 1300 to 1600°C and is represented by the following equation:
Log p(Po) = (6.40 ± 0.13) - (15600 ± 190)/T with T in K and p in Torr. The calculated en-
thalpy of the process is 71.4 kcaVmol, Abakumov et al. [7]. The monopolonides MPo with
M = La, Nd, Gd, and Dy vaporize incongruently and decompose to the elements at the
appearance temperature of Po at 1300, 850, 1100, and 1 040°C, respectively. The predominant
process for the incongruent vaporization is MPo(s) -> MPo 1 _x(s) + x Po(gas). The following
gaseous species were detected when the polonides were heated slowly in a Knudsen effusion
cell at the temperature t in oc (± 20):
MPo. La Po Nd Po Gd Po DyPo
1300 1360 1535 850 1100 1440 1040

species Po+ Lao+ La+ Po+, Po{ Po+ Gd+ Po+,oy+
Small amounts of 206 Pb + and 206PbPo + were observed at ~ 800°C due to the IX-decay of 210 Po.
LaPo contained some 0 2 contamination as evidenced by the Lao+ species. From the Po{
species in NdPo it is concluded that Po was present in a slight excess over the stoichiometric
amount, Steiger, Miles [4]. The vapor pressure p of Po over ScPo, DyPo, and HoPo was
determined by the Knudsen effusion method as follows ( ± ~ 20%):
MPo . Sc Po DyPo Ho Po
t in oc 1200 1250 1300 1400 1600 1300 1350

p in mTorr 64 100 3.8 12 120 0.95 3.6
Simultaneausevaporation of the rare earth elementswas ascertained. A general relation of

p(Po) above MPo with the vapor pressure of M is discussed. ScPo may possibly evaporate
in molecular form, Abakumov, Ershova [6].
The temperature dependence of the Po vapor pressure is given by Log p(Pa) = A- 8/T
with the following coefficients and heat of dissociation .-lH in kJ/mol (at t 1 , t 2 in °C}:
Gmelon Handbock
RE Maon Vol. C10
Polonides 359
MPo Sc Po YPo DyPo Ho Po
A 6.83 8.52 ± 0.13 8.90 17.88

8 8895 15600 ± 190 14509 29543
t 1 to t 2 1200 to 1250 1300 to 1600 1300 to 1600 1300 to 1350
L\H . . 166 298 277 565
The great differences in L\H indicate different vaporization processes, Abakumov [12].
Chemical Reactions
When YPo was immersed in distilled water with pH 6.5 at room temperature, initially a
vigorous gas evolution was observed, and the sample broke down into small pieces. Sub-
sequently there was a slow Liberation of small gas bubbles. After some time small visible
particles remained at the bottom of the container. Probably as a result of hydrolysis ~ 35%
of the Po passes into the water in the form of Suspensions of various sizes and colloidal
particles, Abakumov et al. [13]. The pyrochemical reaction of YPo with Tal 5 or NH 4 1 yields
Pol 4 according to tensimetric investigations. The reaction starts at 230 to 240°C or 370 to
380°C, respectively. Pol 4 passes into the vapor phase in the form of Pol 2 + 12 , Abakumov,
Malyshev [14].
The black finely divided MPo (M = Y to Lu) powders are easily oxidized in air due to the
great surface area and by self-heating of the radioactive 210Po. The thermal stabilities (and
melting points) are lower than for the corresponding selenides and tellurides and are in
keeping with the expected decrease in ionic character of chalcogen-rare earth bonding for
the heaviest members of the group, Kershner et al. [1, 2].
References:
[1] C. J. Kershner, R. J. DeSando, R. F. Heidelberg, R. H. Steinmeyer (J. lnorg. Nucl. Chem.

28 [1966]1581/8).
[2] C. J. Kershner, R. F. Heidelberg, R. H. Steinmeyer (4th Rare Earth Res. Conf., Phoenix,
Ariz., 1964; CONF-405-33 [1964]1/12; N.S.A. 18 [1964] No. 24127).
[3] H. R. Ott, F. Hulliger (Z. Physik 8 49 [1983] 323/30, 330).
[4] R. P. Steiger, C. J. Miles (J. lnorg. Nucl. Chem. 32 [1970] 3469/70).
[5] E. S. Prokin, Z. V. Ershova, E. E. Ermolaev (Radiokhimiya 19 [1977] 845/6; Soviet
Radiochem. 19 [1977] 706/7).
[6] A. S. Abakumov, Z. V. Ershova (Radiokhimiya 18 [1976] 383/6; Soviet Radiochem. 18
[1976] 338/41).
[7] A. S. Abakumov, Z. V. Ershova (Radiokhimiya 17 [1975] 178/82; Soviet Radiochem. 17
[1975]179/82).
[8] E. S. Prokin, Z. V. Ershova, N. T. Chebotarev, E. E. Ermolaev (lzv. Akad. Nauk SSSR
[9] A. S. Abakumov, Z. V. Ershova, V. S. Zverev (Radiokhimiya 17 [1975] 106/10; Soviet
Radiochem. 17 [1975]107/10).
[10] Z. V. Ershova, A. S. Abakumov, M. L. Malyshev (Radiokhimiya 15 [1973] 688/93; Soviet
Radiochem. 15 [1973] 694/8).
Gmelm Handbock
RE Main Vol. C10
[11] C. J. Kershner, R. J. DeSando (J. lnorg. Nucl. Chem. 32 [1970]2911/8).

[12] A. S. Abakumov (Usp. Khim. 51 [1982]1091/102; Russ. Chem. Rev. 51 [1982]622/9).
[13] A. S. Abakumov, V. S. Zverev, T. N. Anania, A. D. Khoklov (Radiokhimiya 19 [1977]
838/44; Soviet Radiochem. 19 [1977] 700/5).
[14] A. S. Abakumov, M. L. Malyshev (Radiokhimiya 25 [1983] 221/5; Soviet Radiochem. 25
[1983] 208/11).
31.2 Polonates
For the preparation of polonates ampules with 0.1 mg Y20 3 , Pr20 3, or Dy20 3 and 0.42, 0.37,
or 0.38 mg Po0 2 in opposite ends were sealed at an 0 2 pressure of 153 Torr to prevent the
dissociation of Po0 2 . ln the working temperature interval 700 to 1 000°C the pressure was
raised to 490 to 650 Torr. At 710 to 720°C, yellowish Y20 2 Po0 3, brownish Pr 20 2Po0 3, and
grayish Dy2Po 20 7 begin to form. The reaction duration was 15 to 17 h, followed by an additional
15 to 17 h exposure after completion of the reaction. Dy2Po20 7 dissociates at 820°C to form
the oxide pyropolonate, Abakumov, Reznikova [1]. ln the same way La 20 2Po03 and Gd 2Po20 7
were prepared at 850 to 950°C in -so h, Abakumov et al. [2).
At 820 to 1 010°C the vapor pressure p in Pa of Po02 over La20 2Po03 in 0 2 atmosphere
(ampules sealed under 20.4 kPa) is given by log p = (14.42 ± 0.67) - (14840 ± 730)/T. The
heat of reaction for the process is 284 ± 14 kJ/mol. ln vacuum, dissociation with formation
of metallic Po is observed by tensimetric studies. The Po0 2 pressure at 820 to 1 030°C over
Gd 2 Po20 7 in an oxygen atmosphere corresponds to log p = (13.88 ± 0.80) - (14470 ± 460)/T.
The heat of reaction for the process is 277 ± 9 kJ/mol. Intermediate formation of oxide
pyropolonate is not observed [2). The thermal decomposition of Dy 2Po20 7 in 0 2 atmosphere
follows the scheme:
Y20 2Po03 and Pr20 2Po03 form M20 3 at 960 and 940°C. The decomposition of Y20 2Po03 and
Dy2Po20 7 in vacuum proved to be the same as in 0 2 . Polypolonates M20 3 • 4 Po02 seem to
be extremely thermally unstable (if they exist at all) as shown by a modified method of
preparation [1).
References:
[1] A. S. Abakumov, N. F. Reznikova (Radiokhimiya 18 [1976] 378/82; Soviet Radiochem. 18

[1976] 334/8).
[2] A. S. Abakumov, A. D. Khokhlov, N. F. Reznikova (Zh. Neorgan. Khim. 26 [1981] 2005/10;
Russ. J. lnorg. Chem. 26 [1981] 1082/5).
Gmelm Handbook
RE Mam VoL C 10
:OGl
m3
;:::!2.
0>5
5::1:
~~
:-a.
(')g Table of Conversion Factors
~o
0,..
Following the notation in Landolt-Börnstein [7], values that have been fixed by convention are indicated by a bold-face last digit.
The conversion factor between calorie and Joule that is given here is based on the thermochemical calorie, calthch• and is defined as
4.1840 J/cal. However, for the conversion of the "Internationale Tafelkalorie", cal1T, into Joule, the factor 4.1868 J/cal is to be used
[1, p. 147]. For the conversion factor for the British thermal unit, the Steam Table Btu, BTUsT• is used [1, p. 95).
Force N dyn kp ~
C"
(j)
1 N (Newton) 1 105 0.1019716 s.

()
1 dyn 10-5 1 1.019716 x1o-s 0
9.80665 9.80665 X 1Q5 1 ::I
1 kp
~
ül
ö'
::I
~
Pressure Pa bar kp/m 2 at atm Torr lb/in 2 s
ül
1 Pa (Pascal) =1 N/m2 1 10-5 1.019716 x1o- 1 1.019716 x 10-5 0.986923 x1o-s 0.750062 x1o- 2 145.0378 x1o-s
1 bar= 106 dyn/cm 2 105 1 10.19716x103 1.019716 0.986923 750.062 14.50378
1 kp/m 2 =1 mm H20 9.80665 o.9B0665 x 1o-4 1 10-4 0.967841 x10- 4 0.735559 x1o-t 1.422335 x1o- 3
1 at = 1 kp/cm 2 0.980665 X 1Q5 0.980665 104 1 0.967841 735.559 14.22335
1 atm = 760 Torr 1.01325 x105 1.01325 1.033227 X 104 1.033227 1 760 14.69595
1 Torr=1 mm Hg 133.3224 1.333224x1o-3 13.59510 1.359510x10-3 1.315789x1o-3 1 19.33678 X 10-3
11b/in2 =1 psi 6.89476 x103 68.94 76 x 1o- 3 703.069 70.3069 x 1o-3 68.0460 x 1o-3 51.7149 1
~
.....
I
~
Work, Energy, Heat J kWh kcal Btu MeV
1J (Joule)=1Ws= 1 2.778 x1o- 7 2.39006 x 1o- 4 9.4781 x10- 4 6.242x10 12

1Nm=107 erg
1 kWh 3.6x106 1 860.4 3412.14 2.247 x10 19
1 kcal 4184.0 1.1622 X 10-3 1 3.96566 2.6117 X 1016
1 Btu 1055.06 2.93071 x 1o- 4 0.25164 1 6.5858 x10 15
(British thermal unit)
1 MeV 1.602X10- 13 4.450 x 1o- 20 3.8289 x 1o- 17 1.51840 x 1o- 16 1
-t
1 eV ~ 23.0578 kcaUmol = 96.473 kJ/mol I»
C"
iD
2.
0
Power kW PS kp m/s kcal/s 0
:::l
<
CD
1 kW=10 10 erg/s 1 1.35962 101.972 0.239006 iil
1 PS 0.73550 1 75 0.17579 er
:::l
1 kp m/s 9.80665x1o- 3 0.01333 1 2.34384 x 1o- 3
426.650 1 ~
1 kcal/s 4.1840 5.6886 0
ö
iil
References:
[1] A. Sacklowski, Die neuen 51-Einheiten, Goldmann, München 1979. (Conversion tables in an appendix.)
[2] International Union of Pure and Applied Chemistry, Manual of Symbolsand Terminology for Physicochemical Quantities and Units,
Pergamon, London 1979; Pure Appl. Chem. 51 [1979] 1/41.
[3] The International System of Units (51), National Bureau of Standards Spec. Publ. 330 [1972].
[4) H. Ebert, Physikalisches Taschenbuch, 5th Ed., Vieweg, Wiesbaden 1976.
[5] Kraftwerk Union Information, Technical and Economic Data on Power Engineering, Mülheim/Ruhr 1978.
:ll
m [6] E. Padelt, H. Laporte, Einheiten und Größenarten der Naturwissenschaften, 3rd Ed., VEB Fachbuchverlag, Leipzig 1976.
.,:;s: [7] Landolt-Börnstein, 6th Ed., Vol. II, Pt. 1, 1971, pp. 1/14 .
[8]150 Standards Handbock 2, Units of Measurement, 2nd Ed., Geneva 1982.
~
C'l
0
Key to the Gmelin System
of Elements and Compounds
System Symbol Element ! System Symbol Element

Number 1 Number
1 Noble Gases 37 ln lnd1um
f
2 H Hydrogen 38 Tl Thallium
3 0 Oxygen 39 Sc, Y Rare Earth
4 N Nitrogen La-Lu Elements
5 F Fluorine 40 Ac Actm1um
6 Cl Chlorine 41 Ti T1tan1um
CrCI 2 42 Zr Z1rcomum
7 Br Bromme
43 Hf Hafnium
8 I lod1ne
44 Th Thorium
At Astatme
45 Ge Germanium
9 s Sulfur
IZnCr0 4 46 Sn Tm
10 Se Selen1um
47 Pb Lead
11 Te Tellunum
48 V Vanad1um
12 Po Polon1um
49 Nb Niobium
13 B Boron
50 Ta Tantalum
14 c Carbon
51 Pa Protactmium
15 Si S1licon
16 p Phosphorus r 1
52 Cr Chromium
17 As Arsemc
53 Mo Molybdenum
18 Sb Ant1mony
19 Bi B1smuth
54 w Tungsten
20 Li Lithium
55 u Uramum
56 Mn Manganese
21 Na Sod1um
57 Ni N1ckel
22 K Potass1um
58 Co Cobalt
23 NH 4 Ammonium
59 Fe lron
24 Rb Rub1d1um
Caes1um
60 Cu Copper
25 Cs
61 Ag Silver
Fr Franc1um
Beryllium
62 Au Gold
26 Be
Zn~ 27 Mg Magnes1um
63 Ru Ruthemum
Calc1um
64 Rh Rhodium
28 Ca
Stront1um
65 Pd Palladium
29 Sr
66 Os Osm1um
30 Ba Barium
Radium
67 Ir Iridium
31 Ra
68 Pt Platmum
32 Zn Zinc 69 Tc Technet1um'
33 Cd Cadm1um 70 Re Rhen1um
l
34 Hg Mercury 71 Np, Pu ... Transuran1um
35 Al Alumm1um Elements
36 Ga Gall1um
r
Material presented under each Gmelin System Number mcludes a/1 mformatton concernmg the element(sj
ltsted for that number plus the compounds wtth elements of lower System Number
Forexample. zinc (System Number 32) as weil as a/1 zinc compounds wtth elements numbered from 1 to 31
are classtfted under number 32
1 A Gmehn volume t1tled "Masunum" was pubhshed w1th th1s System Number m 1941
A Periodic Table of the Elements with the Gmelin System Numbers is given on the Inside
Front Cover

1986 Book ScYLa-LuRareEarthElements

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Pariodic Table of the Elements with the Gmelin System Numbers

I*** Actini des 90 44 91 51 93 71 94 71 95 71 96 71 97 71 99 71 100 71 102 71 103 71

Gmelin Handbuch der Anorganischen Chemie

Achte, völlig neu bearbeitete Auflage

Prepared Gmelin-lnstitut für Anorganische Chemie

Director: Ekkehard Fluck

Founded by Leopold Gmelin

Springer-Verlag Berlin Heidelberg GmbH 1987

DIRECTOR DEPUTY DIRECTOR

CORRESPONDENT MEMBERS OF THE SCIENTIFIC STAFF Dr. H. C. Andersen, Dr. J. R. Clark,

CORRESPONDENT MEMBERS OF THE INSTITUTE Prof. Dr. Hans Bock

STAFF GMELIN ONLINE DATA SYSTEM

Dr. L. Kießling - Dr. R. Froböse, Dr. B. Roth

* Completely or o partly in English

Compounds with Te, Po

With 149 illustrations

AUTHORS lngeborg Hinz, Peter Kuhn, Ursula Vetter, Eberhard Warkentin

EDITORS Hartmut Bergmann, Hiltrud Hein, lngeborg Hinz, Ursula Vetter

CHIEF EDITOR Hartmut Bergmann

Springer-Verlag Berlin Heidelberg GmbH 1987

Library of Congress CataLog Card Number: Agr 25-1383

ISBN 978-3-662-06368-2 ISBN 978-3-662-06366-8 (eBook)

© by Springer-Verlag Berlin Heidelberg 1986

Frankfurt am Main Hartmut Bergmann

30 Rare Earth Elements and Tellurium .

30.1.1 Gaseous Molecules 2

30.1.2 Solid Tellurides . . 6

30.2 Hydride Tellurides MHx Te 288

30.3 Oxide Tellurides . . . . . 288

30.3.1 Comparative Data for M 2 0 2 Te 288

30.3.2 Lanthan um Oxide Tellurides. 294

30.4 Tellurates 298

30.4.2 Compounds in the Cerium(lll, IV)-Tellurium(IV, VI)-O(-H 20) System 310

30.4.3 Tellurates(VI) 314

30.5 Telluride Halides. Tellurate Halides . 318

Compounds Containing Fluorine 318

Compounds Containing Bromine 321

30.6 Sulfide Tellurides 322

30.7 Selenide Tellurides 326

30.7.2 The La 3Te4 -La 3 Se4 System 349

30.8 Alkali Rare Earth Tellurates . . 352

31 Rare Earth Elements and Polonium . 355

31.1 Polonides . . . . . . 355

31.2 Polonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360

Table of Conversion Factors . . . . . . . . . . . . . . . . . . . . . . . . . . 361

A. A. Eliseev, The Crystal-Chemical Characteristics of Chalcogenides of Lanthanides with

30.1.1 Gaseous Molecules

lnternuclear Distances r. Vibrational Frequencies OJ

r in A. 2.44 2.47 2.62 2.49 2.51 2.57 2.51 2.78

r in A. 2.55 2.51 2.51 2.51 2.51 2.51 2.94 2.49

M equilibrium Tin K method og Ref.

Sc ScTe(g) + M'(g) ~ Sc(g) + M'Te(g)a) 70.4± 1.5 [2]

molecule ScTe YTe LaTe CeTe PrTe NdTe

molecule Pm Te Sm Te Eu Te GdTe Tb Te DyTe HoTe

LlHf2ss [7] 65 ± 16 34.8 33.8 65.7 56.6 54.0 63.7

molecule ErTe Tm Te YbTe Lu Te

LlHf2ss [7] 58.4 75.5

For gaseaus EuTe, Schumm et al. [9] give LlHf0 = 41 kcaUmol.

M Tin K H~-Hg s~ -(G~-Hg)/T Ref.

Sc 298 2.305 61.4 53.67 [3, 7] a)

y 298 2.334 63.23 55.40 [3, 7]a)

Table 30.1.1/2 (continued)

M Tin K H~-Hg s~ -(G~-Hg)/T Ref.

tm 1525 1515 ± 25 1645 1700 1650 1680 1660) ± 15 1465)