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Progress in Solid State Chemistry 29 (2001) 170

www.elsevier.nl/locate/pssc

Synthesis of perovskite-related layered


AnBnO3n+2 = ABOX type niobates and titanates
and study of their structural, electric and
magnetic properties
F. Lichtenberg*, A. Herrnberger, K. Wiedenmann, J. Mannhart
University of Augsburg, Institute of Physics, Center for Electronic Correlations and Magnetism,
Experimentalphysik VI, D-86135 Augsburg, Germany

Abstract

ABOX niobates and titanates belonging to the homologous series AnBnO3n+2 are a special
group of perovskite-related layered materials. These oxides comprise the highest-Tc ferroelectr-
ics such as CaNbO3.50 and LaTiO3.50, as well as thermodynamically stable bulk compounds
involving well-ordered stacking sequences of layers with different thickness such as SrNbO3.45.
An extensive overview on many ABOX compositions of the AnBnO3n+2 family and its properties
is presented. The crystal structure type is given by n and can be tuned by adjusting the oxygen
content X. The charge carrier concentration of the electrical conducting oxides can be varied
by appropriate substitutions at the A or B site. To investigate the properties of these systems,
more than 150 different compositions were prepared. Most of them were grown by floating
zone melting, of which many were fabricated as single crystals with precise control of the
oxygen content X. For these crystalline compounds, the synthesis, structural, electric and mag-
netic features are discussed. Attempts to prepare series members beyond the known structure
types n=4, 4.33, 4.5, 5 and 6 were not successful. For some of the known structures types n,
however, pronounced non-stoichiometric homogeneity ranges with respect to the oxygen con-
tent X and cation ratio A/B were found. Thus, these systems offer many possibilities to vary
the compositional, structural, chemical and physical properties. Further, measurements of the
resistivity as a function of temperature T are reported for crystals of the n=4 type
Sr0.8La0.2NbO3.50, n=4.5 type Sr0.96Ba0.04NbO3.45 and n=5 types Sr1YLaYNbO3.41 (Y=0, 0.035,
0.1), Sr0.95NbO3.37, CaNbO3.41 and LaTiO3.41. These measurements, which were performed in
the temperature range 4 KT290 K and along the a-, b- and c-axis, revealed a highly
anisotropic conductivity and intricate behavior. In parts of the temperature range, these
materials are quasi-1D metals which display temperature-driven metal-semiconductor tran-
sitions at lower temperatures. The niobates and titanates investigated represent a new group

* Corresponding author.
E-mail address: Frank.Lichtenberg@Physik.Uni-Augsburg.de (F. Lichtenberg).

0079-6786/01/$ - see front matter 2001 Published by Elsevier Science Ltd.


PII: S 0 0 7 9 - 6 7 8 6 ( 0 1 ) 0 0 0 0 2 - 4
2 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

of quasi-1D metals which are in compositional, structural and electronical proximity to non-
conducting layered (anti)ferroelectrics. Furthermore, measurements of the magnetic suscepti-
bility as a function of temperature are reported for many compounds. As a typical property
at elevated temperatures, it was observed that the magnetic susceptibility rises with increasing
temperature. 2001 Published by Elsevier Science Ltd.

Keywords: Niobates; Titanates; Oxygen content; Crystal growth; Floating zone melting; Layered struc-
tures; Mixed valence; Electrical conductors; Quasi-1D metals

1. Introduction and overview

Perovskites and materials with perovskite-related structures display a very broad


range of structural, chemical and physical properties. The properties of the perovsk-
ite-related title compounds of the AnBnO3n+2 type and their crystal structures are not
well known, however. To introduce these materials in this work, first a more familiar
and structurally somewhat simpler example will be briefly described, the so-called
RuddlesdenPopper phases Am+1BmO3m+1. Fig. 1 sketches the crystal structures of the
members of this perovskite-related layered homologous series Am+1BmO3m+1, estab-
lished by Ruddlesden and Popper in the Sr-Ti-O system [1,2]. The thickness of the
layers rises with m, for m= the three-dimensional perovskite structure ABO3 is
realized. The m=1 member is also known as the K2NiF4 crystal structure type. Fig.
1 shows compositional examples from the Sr-Ti-O, (La,Ba)-Cu-O and Sr-Ru-O sys-
tems. Due to their physical properties two of them are especially remarkable. The
first is the m=1 cuprate (La,Ba)2CuO4, for which Bednorz and Muller discovered
high-Tc superconductivity with Tc30 K [3]. It represents the parent compound of
the high-Tc superconductors. The second noteworthy system, the m=1 ruthenate
Sr2RuO4, is remarkable for several reasons. Single crystals fabricated by Lichtenberg
et al. revealed a highly metallic conductivity along its layers and it was demonstrated
that Sr2RuO4 was the first metallic substrate for the epitaxial growth of high-Tc thin
films [4]. On the same crystals Maeno et al. found superconductivity with Tc=0.93
K [5]. Crystals grown with a small concentration of impurities showed a Tc of 1.3
K [6]. Sr2RuO4 is the only Cu-free superconductor known, that has the same crystal
structure like (La,Ba)2CuO4. Furthermore, it is argued that Sr2RuO4 is an unconven-
tional p-wave spin-triplet superconductor, see e.g. ref. [7]. Therefore, this compound
is a subject of intensive research.
Figs. 24 display the idealized (i.e. non-distorted) perovskite-related layered crys-
tal structures of the members of the title series AnBnO3n+2. A comparison between
the series AnBnO3n+2 and the RuddlesdenPopper phases Am+1BmO3m+1 is given in
Table 1. The RuddlesdenPopper phases Am+1BmO3m+1 are known for many B cations,
whereas the AnBnO3n+2 type oxides exist only for B=Ti, Nb or Ta (see Table 1).
More specific compositions will be given later. Both series share a layered structure,
in which the layers are n or m octahedra thick. For n=m= the three-dimensional
perovskite structure ABO3 is realized. However, both systems differ in the arrange-
ment of the corner-shared BO6 octahedra within the layers, as well as in the cation
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 3

Fig. 1. Sketch of the crystal structure of the m=1, 2, 3 and members of the perovskite-related layered
homologous series Am+1BmO3m+1 projected along the a- (or b-) axis. Circles represent the A cations. The
layers are formed by corner-shared BO6 octahedra within the ab-plane. The layers are m octahedra thick,
thus the thickness of the layers rises with increasing m. For m= the three-dimensional perovskite structure
ABO3 is realized. Light and heavy drawing of the BO6 octahedra as well as filled and open circles indicate
a height difference perpendicular to the drawing plane. Compositional examples are taken from the sys-
tems Sr-Ti-O, (La,Ba)-Cu-O and Sr-Ru-O.

ratio A/B. With respect to the a- and b-axis, the Am+1BmO3m+1 members are structur-
ally (almost) isotropic, whereas the AnBnO3n+2 type compounds show a pronounced
crystallographic anisotropy. In Figs. 24 only the idealized, i.e. non-distorted,
AnBnO3n+2 type structures are sketched. The BO6 octahedra are usually strongly dis-
4 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 2. Sketch of the idealized (i.e. non-distorted) crystal structure of the n=2, 3, 4 and 4.33 members
of the perovskite-related layered homologous series AnBnO3n+2 projected along the a-axis. The stoichio-
metries are also given as ABOX with its corresponding ideal oxygen content X=3+2/n. Circles represent
the A cations. Within the layers the corner-shared BO6 octahedra extend zig-zag-like along the b-axis and
chain-like along the a-axis (see also Fig. 4). The layers are n octahedra thick, thus the thickness of the
layers rises with increasing n. The n=4.333 member represents the well-ordered stacking sequence n=5,
4, 4, 5, 4, 4,... Light and heavy drawing of the BO6 octahedra indicates a height difference perpendicular
to the drawing plane of about 2 A, the half of the octahedron body diagonal and B-O bond length.
Filled and open circles indicate A cations also differing in height by this distance perpendicular to the
drawing plane.
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 5

Fig. 3. Sketch of the idealized (i.e. non-distorted) crystal structure of the n=4.5, 5, 6 and members
of the perovskite-related layered homologous series AnBnO3n+2 projected along the a-axis. The stoichio-
metries are also given as ABOX with its corresponding ideal oxygen content X=3+2/n. Circles represent
the A cations. Within the layers the corner-shared BO6 octahedra extend zig-zag-like along the b-axis and
chain-like along the a-axis (see also Fig. 4). The layers are n octahedra thick, thus the thickness of the
layers rises with increasing n. For n= the three-dimensional perovskite structure ABO3 is realized. The
n=4.5 member represents the well-ordered stacking sequence n=5, 4, 5, 4,... Light and heavy drawing of
the BO6 octahedra indicates a height difference perpendicular to the drawing plane of about 2 A, the half
of the octahedron body diagonal and B-O bond length. Filled and open circles indicate A cations also
differing in height by this distance perpendicular to the drawing plane.

torted. This structural feature will be discussed later in more detail regarding the
electric properties and results from band structure calculations.
The lattice constants of the idealized (i.e. non-distorted) AnBnO3n+2 type com-
pounds are derived from a cubic perovskite with unit cell length a0:
6 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 4. Sketch of the idealized (i.e. non-distorted) crystal structure of the n=5 member of the perovskite-
related layered homologous series AnBnO3n+2 projected along the a- and b-axis. In contrast to Figs. 2 and
3 the projection along the b-axis clearly shows the chain-like array of the corner-shared BO6 octahedra
along the a-axis using the n=5 member as a representative example. The circles represent the A cations.
Light and heavy drawing of the BO6 octahedra as well as filled and open circles indicate a height difference
perpendicular to the drawing plane.
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 7

Table 1
Comparison between the perovskite-related layered homologous series Am+1BmO3m+1 and AnBnO3n+2

Am+1 Bm O3m+1 (Ruddlesden An Bn O3n+2


Popper phases)

integer index m or n number of BO6 octahedra within a layer along the c-axis
layer thickness rises with increasing m or n

cation ratio A/B 1 for m =1


=1 for m=

crystal structure type for m=n= three-dimensional perovskite structure ABO3

series members for which bulk m= n=


compounds are known
n=6
n=5
n=4.5
n=4.333
n=4
m=3
m=2 (n=2)
m=1
(n=2 members are known at
fluorides but not for oxides)

B cations for which compounds Al Ti V Cr Mn Fe Co Ni Cu Ti Nb Ta (for n=2


with m, n are known Ga Zr Mo Ru Rh Sn Ir Pb U fluorides:Mg Mn Fe Co Ni Zn)

symmetry for m, n tetragonal or orthorhombic orthorhombic or monoclinic

a a0
b a02
c 2s na02
where s2.3 A is the distance between neighbouring layers [8]. Compared to these
cell parameters the real materials often display a doubled a-axis and/or a half or
doubled c-axis. In the following the compositions of the AnBnO3n+2 type oxides are
expressed as ABOX, thus normalized to one B cation, whereby the corresponding
ideal oxygen content X of a structure type n is given by X=3+2/n.
The existence of phases of the AnBnO3n+2 type was established by Carpy et al. in
1972 in the Na-Ca-Nb-O and Ca-La-Ti-O systems [9]. Later, related and more
detailed studies were published by Galy and Carpy in 1974 [8]. In the following
years Nanot et al. performed comprehensive crystallographic studies on these and
other quaternary niobates and titanates, of which examples are given in references
[1014].
8 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Before 1991, only fully oxidized AnBnO3n+2=ABOX type titanates and niobates were
prepared and studied, i.e. electrical insulators involving exclusively Ti4+ (3d0) and/or
Nb5+ (4d0). To the best of our knowledge, the only exception was a crystallographic
study on CaNbOX (3.4X3.5) by Hervieu et al. in 1977 [15]. This CaNbOX system
involves a mixed valence Nb4+/Nb5+ for X3.5 and therefore a high electrical con-
ductivity can be expected. The physical properties were not investigated, however.
Among the fully oxidized insulating titanates and niobates there are compounds with
remarkable structural and physical properties. An interesting structural phenomenon
was already been shown in Figs. 2 and 3, namely the structure types n=4.333 and
n=4.5, which involve well-ordered stacking sequences of layers with different thick-
ness. Examples are La0.923Ca0.077TiO3.462 (n=4.333) [10] and CaNb0.889Ti0.111O3.444
(n=4.5) [11]. Some fully oxidized n=4 type compounds such as CaNbO3.50, SrNbO3.50
and LaTiO3.50 display extraordinary dielectric properties. They are ferroelectric up
to extremly high temperatures, as shown by Nanamatsu et al. in 1974 and 1975 [16
18]. Their ferroelectric transition temperatures Tc lie in the range of 1615 K to 1850
K. No other ferroelectric materials with such high Tc are known. Fig. 5 shows the
temperature dependence of the dielectric permittivity of SrNbO3.50 along the a-,
b- and c-axis. Below its ferroelectric transition temperature Tc=1615 K, several
dielectric and structural (also incommensurate) phase transitions occur [19].
Since 1991 electrically conducting ABOX titanates and niobates of the AnBnO3n+2
type were synthesized and investigated with respect to their physical and structural
properties [2037], initiated by Lichtenberg et al. in the LaTiOX, SrNbOX and
CaNbOX systems [2022]. In the case of LaTiOX the oxygen content X was systemati-
cally varied between the two known end members LaTiO3.0 and LaTiO3.5 [21].
LaTiO3 (Ti3+, 3d1) has a three-dimensional orthorhombically distorted perovskite
structure of the n= type, whereas LaTiO3.5 (Ti4+, 3d0) is a ferroelectric insulator
with a layered n=4 type structure. A summary of this study is shown in Fig. 6, which
reveals a surprising richness and complexity of structural and physical phenomena
in the LaTiOX system. Recently, Becker studied in great detail the structural mech-
anisms of oxidation and reduction in the LaTiOX system [30]. For crystals of
LaTiO3.42 (n=5) and SrNbO3.45 (n=4.5), semiconducting resistivity behavior along
and perpendicular to the layers was reported in the temperature range between T=4
K and T=300 K [22]. However, within the layers the resistivity was measured along
only one direction which was arbitrarily selected and not specified. The electrical
conducting titanates and niobates were crystallographically explored by Williams et
al. using high-resolution transmission electron microscopy [2124]. An example is
shown in Fig. 7, namely the well-ordered stacking sequence n=4, 5, 4, 5, in the
n=4.5 type compound SrNbO3.45 (see also Fig. 3, where the n=4.5 type is sketched).
This well-ordered stacking sequence was found to be a bulk property. The thermo-
dynamic stability of the n=4.5 type phases is remarkable.
Among the electrical conductors there is up to now only one compound for which
the atomic coordinates are precisely known. It is SrNbO3.4 (n=5) on which Schmalle
et al. and Abrahams et al. carried out detailed crystallographic studies by means of
single crystal x-ray diffraction [29].
A further step concerning the study of physical properties on these layered electri-
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 9

Fig. 5. Log-linear plot of the dielectric permittivity versus temperature of ferroelectric SrNbO3.50 along
the a-, b- and c-axis measured at 1 MHz. The dielectric anomaly at 1342C represents the ferroelectric
transition temperature Tc. A second dielectric anomaly or transition occurs at 156C. After Nanamatsu
et al. [17]. Note that in ref. [17] the longest axis is defined as the b-axis. The labels a, b and c shown
in this figure correspond to the definition used in this work where c represents the longest axis.

cal conductors was recently carried out by exploring the electronic properties of some
niobate crystals such as SrNbO3.45 (n =4.5), SrNbO3.4 (n =5) and Sr0.9La0.1NbO3.4 (n
=5) [22]. The electronic structure of SrNbO3.45 was investigated by Lu et al. using
angle-resolved photoemission (ARPES) [28]. The electronic structure of SrNbO3.45,
SrNbO3.4 and Sr0.9La0.1NbO3.4 along the a- and b-axis was comprehensively explored
by Kuntscher et al. using x-ray absorption (NEXAFS), ARPES and optical spec-
troscopy [3134]. LDA band structural calculations by means of the pseudopotential
and LMTO method were performed on SrNbO3.4 by Bohnen [31] and Winter [35],
respectively, using the atomic coordinates determined by Schmalle et al. and Abrah-
ams et al. [29]. The most surprising results obtained by ARPES on SrNbO3.45 at
T=150 K, SrNbO3.4 at T=75 K and Sr0.9La0.1NbO3.4 at T=75 K and 100 K were strong
indications of the presence of a quasi-1D metallic behavior, because discernible elec-
tronic dispersion of one of two bands near the Fermi energy EF and its apparent
crossing of EF was observed only along the a-axis but not along the b-axis [31,32,34].
10 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 6. Phase diagram of the LaTiOX system. Informations about the crystal structure at room temperature
are given at the top of the diagram. The index n indicates the structure type of the series LanTinO3n+2.
After Lichtenberg et al. [21] and modified at X3.41 according to results from this work (see Fig. 24).

These results were corroborated by optical spectroscopy experiments and band struc-
ture calculations [3135]. The outcomes of the following very recent experiments
will be mentioned later: High-resolution ARPES by Kuntscher et al. on SrNbO3.4 at
low temperatures [32,33], dielectric response along the c-axis on Sr0.8La0.2NbO3.5
(n=4), SrNbO3.45 and SrNbO3.4 by Bobnar et al. [36] as well as nuclear magnetic
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 11

Fig. 7. Transmission electron microscopy lattice image from the electrical conducting n=4.5 type com-
pound SrNbO3.45. It reveals the well-ordered stacking sequence n=4, 5, 4, 5,... (see also Fig. 3 where this
sequence is sketched). The dark spots represent the A cations. The electron diffraction pattern (inset)
confirms the perfection of ordering. After Lichtenberg et al. [22] and Williams et al. [24].

resonance (NMR) and electron paramagnetic resonance (EPR) by Weber et al. on


SrNbO3.4 at low temperatures [37].
This work mainly reports on the materials synthesis of AnBnO3n+2=ABOX type niob-
ates and titanates including crystal growth by floating zone melting and structural,
electric and magnetic features. To start, a comprehensive overview on many ABOX
compositions with a AnBnO3n+2 type structure and their properties is presented in
Tables 218, which lists literature data and results obtained in this work. Tables 2
15 are classified according to the structure type n. Specified are the composition,
electron configuration N of the B cation based on charge neutrality, lattice constants
with z as number of formula units ABOX per unit cell, references, special properties
and remarks. Almost all materials from this work which are presented in Tables 415,
17 and 18 were prepared by floating zone melting. If samples were not synthesized in
12

Table 2
Overview on n =2 type compounds which are only known for fluorides. Lattice constants are given as rounded numbers

Composition ABOx N Lattice constants References Special properties,


remarks

V (A3) a(A) b (A) c (A) b () z

Ba Mn F4 3d5 381 4.22 5.98 15.10 90 4 [38]


Ba Fe F4 3d6 367 4.24 5.83 14.84 90 4 [38]
Ba Co F4 3d7 360 4.21 5.85 14.63 90 4 [38] ferroelectric
Ba Ni F4 3d8 348 4.15 5.80 14.46 90 4 [38] ferroelectric
Ba Zn F4 3d0 358 4.21 5.84 14.56 90 4 [38] ferroelectric
Ba Mg F4 348 4.13 5.81 14.51 90 4 [38] ferroelectric
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170
Table 3
Overview on n =4 type tantalates. Lattice constants are given as rounded numbers. The reference 301304 is related to the ICDD (former JCPDS) data base

Composition ABOX N Lattice constants References Special properties,


remarks
V (A3) a(A) b (A) c (A) b () z

Sr Ta O3.50 5d0 609 3.94 5.69 13.602=27.19 90 8 301304, [17] ferroelectric, TC=166 K
[17]

Sr1-W CaW Ta O3.50 5d0 [17] 0W0.8, ferroelectric


properties of this solid
solution studied on
polycrystalline samples

Sr0.9 Na0.05 Nd0.05 Ta 5d0 558 3.86 5.49 13.192=26.38 90 8 [39] ferroelectric, TC=363 K
O3.50

Sr Ta0.88 Nb0.12 O3.50 5d0 611 3.96 5.69 13.562=27.11 90 8 [40] ferroelectric, TC=675 K
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170
13
Table 4 14
Overview on n=4 type niobates (part 1). Lattice constants are given as rounded numbers. References such as 281246 are related to the ICDD (former
JCPDS) data base

Composition ABOx N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

Sr Nb O3.50 4d0 604 3.96 5.70 13.392=26.78 90 8 281246, [17] ferroelectric, TC=1615 K
604 3.96 5.71 13.382=26.76 90 8 this work [17], several ferroelectric
[19,4143] and structural (also
incommensurate) phase
transitions below 1615 K
[19,41,42]
preparation of thin films
[43]
Sr0.8 La0.2 Nb O3.50 4d0.2 598 3.99 5.65 13.282=26.56 90 8 this work for 90 KT150 K
[24,32,34,36] quasi-1D metal along a-
axis according to
resistivity measurements
(this work); electron
diffraction displays
doubled a-axis,
photoemission at T=75 K
shows along a-axis weak
and along b-axis no
electronic dispersion
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

[32,34]; along the c-axis:


dielectric measurements
indicate charge transport
by hopping of localized
charge carriers [36]

(continued on next page)


Table 4
Continued

Composition ABOx N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

Sr0.9 Ba0.1 Nb O3.50 4d0 606 3.96 5.71 13.392=26.78 90 8 this work

Sr0.85 Ba0.1 La0.05 Nb 4d0.03 605 3.97 5.70 13.362=26.72 90 8 this work
O3.51

Sr0.7 Ba0.1 La0.2 Nb 4d0.2 601 4.00 5.67 13.282=26.56 90 8 this work electron diffraction
O3.50 [32,34] displays doubled a-axis,
photoemission at T=75 K
shows no electronic

dispersion along a- and b-
axis [32,34]
Sr0.6 Ca0.2 La0.2 Nb 4d0.2 591 3.96 5.63 13.252=26.51 90 8

O3.50

Sr0.5 Ca0.5 Nb O3.50 4d0 583 3.90 5.62 13.312=26.61 90 8 47492


F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170
15
Table 5 16
Overview on n=4 type niobates (part 2). Lattice constants are given as rounded numbers. References such as 23122 are related to the ICDD (former JCPDS)
data base

Composition ABOX N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

Ca Nb O3.50 4d0 559 3.85 5.49 13.232=26.46 90 8 23122 ferroelectric,TC1850

558 3.84 5.49 13.232=26.45 90 8 this work K=melting point [16],

558 3.85 5.49 13.222=26.43 90 8 [39] probably a phase


560 3.85 x 2=7.70 5.50 13.36 98.4 8 18301 transition into an
564 3.86 x 2=7.72 5.51 13.40 98.2 8 [16,44] incommensurate structure
at T=750 K [44]
Ca0.8 La0.2 Nb O3.51 4d0.18 563 3.90 5.50 13.132=26.25 90 8 this work

Sr0.8 La0.2 Nb O3.60 4d0 602 3.96 5.69 13.342=26.69 90 8 this work significantly
overstoichiometric with
respect to the oxygen
content x
Sr0.86 La0.14 Nb 4d0 601 3.96 5.69 13.352=26.71 90 8 this work


O3.57
Sr0.75 La0.25 Nb 4d0.11 599 3.98 5.66 13.302=26.59 90 8 this work
O3.57
Sr0.65 Ba0.1 La0.25 4d0.11 602 3.99 5.68 13.302=26.60 90 8 this work
Nb O3.57
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Ca0.86 La0.14 Nb 4d0 561 3.88 5.50 13.152=26.30 90 8 this work


O3.57

(continued on next page)


Table 5
Continued

Composition ABOX N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

Sr0.85 La0.1 Nb O3.50 4d0 603 3.96 5.70 13.362=26.72 90 8 this work significantly
understoichiometric with
respect to the A site
(cation ratio A / B =0.95)

Sr0.85 La0.1 Nb O3.45 4d0.1 601 3.97 5.68 13.332=26.67 90 8 this work significantly
understoichiometric with
respect to the A site
(cation ratio A / B =0.95)
and with respect to the
oxygen content x

Sr1-W CaW Nb O3.50 4d0 [17] 0W1

Sr1-Y PbY Nb O3.50 4d0 [17] 0Y0.4, ferroelectric


properties of these solid
solutions studied on
polycrystalline samples
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Sr1-Z BaZ Nb O3.50 4d0 [17]


0Z0.6
17
Table 6 18
Overview on n=4 type titanates. Lattice constants are given as rounded numbers. References such as 28517 are related to the ICDD (former JCPDS) data base

Composition ABOX N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

La Ti O3.50 3d0 558 3.912=7.82 5.55 13.01 98.6 8 28517, [18] ferroelectric, TC=1770 K
[18], several structural
557 3.902=7.81 5.55 13.00 98.6 8 this work (also incommensurate)
phase transitions below
5582=1115 3.912=7.81 5.55 12.872=25.75 90 16 [45,46] 1770 K [47,48],
[4749] structural study on thin
films [49]

La Ti0.9 Zr0.1 O3.50 3d0 562 3.912=7.82 5.56 13.05 98.5 8 this work

La Ti0.8 Nb0.2 O3.51 3d0.18 560 3.912=7.83 5.55 13.02 98.3 8 this work in contrast to this work,
ref. [26] says that no
substitution of Ti by Nb
could be achieved

La0.67 Ce0.33 Ti 3d0 554 3.892=7.79 5.53 13.00 98.6 8 this work see text for peculiarities
O3.50 of Ce oxides

Ce Ti O3.50 3d0 548 3.882=7.75 5.50 12.98 98.6 8 47667 prepared at 1400C under
Argon using the mixture
CeO2 + 0.25 TiN + 0.75
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

TiO2

(continued on next page)


Table 6
Continued

Composition ABOX N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

Pr Ti O3.50 3d0 546 3.862=7.71 5.50 13.02 98.5 8 35267 unstable in air (35267),
prepared by
5472=1093 3.872=7.73 5.49 12.882=25.76 90 16 35224 coprecipitation [46,50]
[46,50] ferroelectric, TC 1770 K
[51]

Nd Ti O3.50 3d0 540 3.842=7.68 5.46 13.00 98.6 8 33942, [51]

La0.5 Pr0.5 Ti O3.50 3d0 5462=1092 3.872=7.74 5.51 12.812=25.61 90 16 [46] prepared by
coprecipitation
La0.5 Nd0.5 Ti O3.50 3d0 5442=1089 3.862=7.72 5.51 12.802=25.60 90 16

La0.5 Sm0.5 Ti O3.50 3d0 5402=1081 3.852=7.70 5.47 12.832=25.66 90 16


La0.5 Eu0.5 Ti O3.50 3d0 5382=1076 3.842=7.67 5.46 12.852=25.70 90 16
Pr0.5 Nd0.5 Ti O3.50 3d0 5362=1072 3.842=7.67 5.45 12.832=25.65 90 16
Pr0.5 Sm0.5 Ti O3.50 3d0 5342=1069 3.822=7.63 5.44 12.882=25.75 90 16
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Pr0.5 Eu0.5 Ti O3.50 3d0 5332=1066 3.822=7.64 5.44 12.832=25.65 90 16


Nd0.5 Sm0.5 Ti O3.50 3d0 5292=1057 3.812=7.62 5.42 12.802=25.60 90 16
Nd0.5 Eu0.5 Ti O3.50 3d0 5282=1056 3.802=7.60 5.42 12.822=25.63 90 16
19
Table 7 20
Overview on miscellaneous n=4 type compounds. Lattice constants are given as rounded numbers. The reference 35225 is related to the ICDD (former
JCPDS) data base

Composition ABOX N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

Sr1-W CaW Ta1-W d0 [17] 0W1, ferroelectric


properties of these solid
NbW O3.50
solutions studied on
polycrystalline samples
Sr Ta1-W NbW O3.50 d0 [17]
Sr1-W LaW Ta1-W d0 [18]
TiW O3.50
Sr0.5 La0.5 Ta0.5 d0 5802=1159 3.942=7.88 5.60 13.142=26.27 90 16 35225 prepared by
Ti0.5 O3.50 [50] coprecipitation
Sr0.5 Nd0.5 Ta0.5 d0 5722=1144 3.912=7.81 5.57 13.152=26,30 90 16 [50]
Ti0.5 O3.50
Sr0.5 Pr0.5 Ta0.5 Ti0.5 d0 5712=1142 3.912=7.81 5.57 13.122=26.24 90 16 [50] these compositions are
O3.50 individual compounds and
no solid solutions [50]
Sr0.5 La0.5 Nb0.5 d0 5822=1164 3.942=7.88 5.63 13.122=26.24 90 16 [50]

Ti0.5 O3.50
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Sr0.5 Pr0.5 Nb0.5 d0 5762=1151 3.922=7.83 5.60 13.132=26.25 90 16 [50]


Ti0.5 O3.50
Ca0.5 La0.5 Nb0.5 d0 5612=1121 3.892=7.78 5.54 13.012=26.02 90 16
Ti0.5 O3.50 5592=1118 3.892=7.78 5.54 12.982=25.97 90 16
[50]

this work
Table 8
Overview on n=4.33 type titanates. Lattice constants are given as rounded numbers

Composition ABOX N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

La Ti O3.47 3d0.06 3.92=7.8 5.5 85 [24]

Ce Ti O3.47 3d0.06 3499 3.882=7.76 5.50 82.7 97.6 50 this work see text for peculiarities
of Ce oxides
Nd Ti O3.47 3d0.06 [26,27]

La0.92 Ca0.08 Ti 3d0 3571 3.902=7.80 5.53 83.6 98 50 [10]

O3.46 3551 3.922=7.84 5.52 82.8 97.7 50 this work


F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170
21
22

Table 9
Overview on n=4.5 type titanates. Lattice constants are given as rounded numbers. The reference 27-1058 is related to the ICDD (former JCPDS) data base

Composition N Lattice constants References Special properties,


ABOX remarks

V (A3) a (A) b (A) c (A) b () z

La0.89 Sr0.11 Ti O3.44 3d0 12322=2464 3.912=7.81 5.53 57.0 90 36 [52]

La0.89 Ca0.11 Ti 3d0 12342=2468 3.902=7.81 5.54 57.6 97.8 36 271058,


O3.44 [11]

12392=2478 3.902=7.81 5.54 57.8 97.8 36 [30]

Nd0.89 Ca0.11 Ti 3d0 11962=2392 3.842=7.68 5.46 57.5 97.7 36 [11]


O3.44

La Ti O3.44 3d0.12 12382=2477 3.902=7.81 5.54 57.8 98.0 36 [30]

La0.98 Sr0.02 Ti O3.45 3d0.08 12332=2465 3.952=7.91 5.52 56.9 97.5 36 this work

La Ti0.95 Nb0.05 3d0.17 12232=2446 3.952=7.90 5.49 56.9 97.5 36 this work
O3.44
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170
Table 10
Overview on n=4.5 type niobates. Lattice constants are given as rounded numbers. The reference 271412 is related to the ICDD (former JCPDS) data base

Composition ABOX N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

Sr Nb O3.45 4d0.1 13302=2660 3.952=7.90 5.68 59.3 90 36 this work quasi-1D metal along a-
59 90 [24] axis according to
[22,28,31] photoemission at T=150 K
[32,34,36] and optical spectroscopy
[28,31,32,34],
along the c-axis:
according to dielectric
measurements phase
transition at T=290 K,
relatively high values of
the high frequency
dielectric permittivity and
charge transport by
hopping of localized
charge carriers [36]

Sr0.96 Ba0.04 Nb O3.45 4d0.1 13302=2661 3.942=7.88 5.68 59.4 90 36 this work for 120 KT240 K
quasi-1D metal along a-
axis according to
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

resistivity measurements
Sr0.96 Ba0.04 Nb0.95 4d0.12 13322=2665 3.962=7.92 5.70 59.1 90 36 this work
Ta0.05 O3.44

(continued on next page)


23
24

Table 10
Continued

Composition ABOX N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

Sr0.96 Ba0.04 Nb0.9 Ta0.1 4d0.11 13342=2667 3.962=7.92 5.70 59.0 90 36 this work
O3.45

Ca Nb O3.44 4d0.12 1242 3.85 5.49 58.8 90 18 [15] crystallographic study by


electron microscopy and
diffraction
Ca Nb O3.45 4d0.1 1244 3.86 5.51 58.4 90 18 this work

Ca0.95 La0.05 Nb O3.46 4d0.13 12422=2484 3.872=7.74 5.51 58.4 90 36 this work

Ca0.89 Na0.11 Nb O3.44 4d0 1245 3.85 5.50 58.9 90 18 271412, [12]

Ca Nb0.89 Ti0.11 O3.44 d0 12392=2478 3.842=7.68 5.48 59.4 97.4 36 [11]


F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170
Table 11
Overview on n=5 type Ca-based niobates. Lattice constants are given as rounded numbers. The reference 271411 is related to the ICDD (former JCPDS)
data base

Composition ABOX N Lattice constants References Special properties, remarks

V (A3) a (A) b (A) c (A) b () z

Ca Nb O3.4 4d0.2 674 3.86 5.47 15.962=31.92 90 10 [15] crystallographic study by


electron microscopy and
diffraction

Ca Nb O3.39 4d0.22 683 3.88 5.49 16.022=32.04 90 10 this work polycrystalline sample, not
prepared by floating zone
melting

Ca Nb O3.41 4d0.18 682 3.88 5.49 16.012=32.03 90 10 this work for 185 KT290 K quasi-1D
metal along a-axis according to
resistivity measurements

Ca0.95 Nb O3.36 4d0.18 680 3.87 5.50 16.112=32.23 96.7 10 this work significantly understoichiometric
with respect to the A site (cation
ratio A / B =0.95) and with
respect to the oxygen content x
Ca0.9 Sr0.1 Nb O3.41 4d0.18 687 3.89 5.51 16.032=32.06 90 10 this work
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Ca0.93 La0.07 Nb O3.41 4d0.25 683 3.89 5.50 15.962=31.91 90 10 this work

Ca0.8 Na0.2 Nb O3.40 4d0 680 3.85 5.50 16.072=32.14 90 10 271411, [12]
25
Table 12 26
Overview on n=5 type Sr-based niobates. Lattice constants are given as rounded numbers

Composition ABOX N Lattice constants References Special properties, remarks

V (A3) a (A) b (A) c (A) b () z

Sr Nb O3.41 4d0.18 734 3.99 5.67 16.232=32.45 90 10 this work for 60 KT130 K quasi-1D
736 4.00 5.67 16.232=32.46 90 10 [29] metal along a-axis according to
[22,3133] resistivity measurements (this
[3437] work),

quasi-1D metal along a-axis


according to photoemission at
T=75 K, optical spectroscopy
and band structure calculations
[3135],
along the a-axis at low
temperatures T50 K:
semiconducting state with very
small energy gap of few meV
according to resistivity
measurements (this work),
photoemission [32,33], optical
spectroscopy [33] and nuclear
magnetic resonance (NMR) [37],
NMR hints to a charge density
wave [37]
along the c-axis: according to
dielectric measurements phase
transition at T=300 K, relatively
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

high values of the high


frequency dielectric permittivity
and charge transport by hopping
of localized charge carriers [36]

(continued on next page)


Table 12
Continued

Composition ABOX N Lattice constants References Special properties, remarks

V (A3) a (A) b (A) c (A) b () z

Sr0.965 La0.035 Nb O3.41 4d0.22 732 3.99 5.67 16.192=32.37 90 10 this work for 105 KT290 K quasi-1D
metal along a-axis according to
resistivity measurements
Sr0.93 La0.07 Nb O3.41 4d0.25 732 4.00 5.66 16.162=32.32 90 10 this work

Sr0.9 La0.1 Nb O3.41 4d0.28 731 4.00 5.66 16.132=32.27 90 10 this work for 80 KT290 K quasi-1D
metal along a-axis according to
resistivity measurements

Sr0.9 La0.1 Nb O3.39 4d0.32 [22,31,32] quasi-1D metal along a-axis


according to photoemission at
T=75 K and T=100 K [31,32]

Sr0.95 Nb O3.37 4d0.16 732 3.98 5.67 16.222=32.44 90 10 this work for 60 KT160 K quasi-1D
metal along a-axis according to
resistivity measurements

significantly understoichiometric
with respect to the A site (cation
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

ratio A / B=0.95) and with


respect to the oxygen content x

Sr0.93 Nb O3.36 4d0.14 733 3.98 5.67 16.242=32.47 90 10 this work significantly understoichiometric
with respect to the A site (cation
ratio A / B=0.93) and with
27

respect to the oxygen content x


Table 13 28
Overview on n=5 type titanates. Lattice constants are given as rounded numbers. The reference 271059 is related to the ICDD (former JCPDS) data base

Composition ABOX N Lattice constants References Special properties, remarks

V (A3) a (A) b (A) c (A) b () z

La Ti O3.40 3d0.2 6792=1358 3.932=7.86 5.53 15.752=31.5 97.2 20 [21,22]


0.18
La Ti O3.41 3d 6792=1357 3.932=7.86 5.53 15.742=31.48 97.1 20 this work for 60 KT205 K
[22] quasi-1D metal along a-
axis according to
resistivity measurements
(this work)
La Ti O3.42 3d0.16 6782=1357 3.932=7.86 5.53 15.732=31.47 97.1 20 [2123]
6782=1357 3.932=7.86 5.53 15.732=31.46 97.1 20 [30]

La0.5 Ce0.5 Ti OX ? 6762=1353 3.932=7.85 5.52 15.722=31.44 97.0 20 this work see text for peculiarities of
Ce oxides,

the presence of a n=5 type


structure suggests an
oxygen content of x=3.4
Nd Ti O3.4 3d0.2 673 3.92=7.8 5.5 15.80 96.5 10 [25]
La0.8 Sr0.2 Ti O3.40 3d0 6752=1350 3.912=7.81 5.53 15.762=31.51 97.1 20 [52]
Nd0.8 Sr0.2 Ti O3.40 3d0 [53]
La0.8 Ca0.2 Ti O3.40 3d0 6732=1346 3.892=7.78 5.52 15.782=31.56 97.1 20 27-1059,
[11]
6732=1346 3.892=7.78 5.52 15.782=31.57 97.0 20 [30]
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

0.17
La0.89 Ca0.11 Ti 3d 6692=1337 3.922=7.84 5.52 15.552=31.09 96.1 20 this work significantly
O3.36 understoichiometric with
respect to the oxygen
content x
Nd0.8 Ca0.2 Ti O3.40 3d0 6522=1304 3.842=7.68 5.44 15.732=31.45 97.0 20 [11]
Table 14
Overview on miscellaneous n=5 type compounds. Lattice constants are given as rounded number

Composition ABOX N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

Sr0.5 Ca0.5 Nb O3.41 4d0.18 711 3.94 5.60 16.122=32.23 90 10 this work
0.12
Sr Nb0.9 Ti0.1 O3.39 4d 729 3.97 5.65 16.222=32.44 90 10 this work
0
Sr Nb0.8 Ti0.2 O3.40 d 720 3.95 5.59 16.32=32.6 90 10 [54] antiferroelectric, TC860
this work K [54],
[55] preparation by floating
zone melting was
practically impossible
because the feed material
showed an extremely
strong tendency to grow
out of the molten zone
(this work)

Ca Nb0.8 Ti0.2 O3.40 d0 6762=1353 3.842=7.69 5.48 16.172=32.33 96.8 20 [11]


La Ti1-Y NbY O3.4 from [26] 0Y0.1, in-plane
3d0.2 to resistivity measurements
3d0.3 (direction not specified)
revealed thermally
activated behavior,
activation energy rises
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

with increasing Nb
content Y from 9 to 51
meV
La Ti0.9 Zr0.1 O3.42 3d0.17 6872=1373 3.942=7.88 5.55 15.812=31.62 97.1 20 this work
29
Table 15 30
Overview on n=6 type compounds. Lattice constants are given as rounded numbers. References such as 271057 are related to the ICDD (former JCPDS)
data base

Composition ABOX N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

La0.67 Sr0.33 Ti O3.33 3d0 7942=1588 3.892=7.79 5.54 18.422=36.84 90 24 this work

La0.73 Sr0.27 Ti O3.36 3d0 7982=1596 3.912=7.83 5.52 18.572=37.14 95.8 24 this work significantly
overstoichiometric with
respect to the oxygen
content x
La0.67 Ca0.33 Ti 3d0 7902=1580 3.892=7.78 5.52 18.402=36.80 90 24 271057 also incommensurate
O3.33 7892=1578 3.892=7.77 5.52 18.402=36.80 90 24 [30] modulated phases

7812=1563 3.872=7.74 5.50 18.342=36.67 90 24 this work prepared and


[11,13,14, crystallographically
56,57]

investigated [13,14,56]
Nd0.67 Ca0.33 Ti 3d0 7632=1526 3.832=7.66 5.44 18.322=36.64 90 24 [11,13,56] most probably
O3.33 764 3.832=7.66 5.44 18.42 95.7 12 [57] ferroelectric because of

Ca Nb0.67 Ti0.33 d0 789 3.842=7.67 5.46 18.91 95.8 12 [11,13] non-centrosymmetric


O3.33


space group and results
from second harmonic
generation experiments,
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

however dielectric
measurements are not
presented [13,57]

(continued on next page)


Table 15
Continued

Composition ABOX N Lattice constants References Special properties,


remarks

V (A3) a (A) b (A) c (A) b () z

Sr Nb0.67 Ti0.33 d0 854 3.93 5.66 19.22=38.4 90 12 [55,58] ferroelectric, TC =900 K


O3.33 [58]

Ca Nb0.8 Ti0.2 O3.33 4d0.14 7922=1583 3.862=7.72 5.47 18.742=37.48 90 24 this work

Ca0.67 Na0.33 Nb 4d0 800 3.86 5.50 18.862=37.71 90 12 27-1413,


O3.33 [12]
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170
31
Table 16 32
Overview on compounds whose atomic coordinates are precisely known from single crystal x-ray diffraction studies. If the temperature T is not specified
the data refer to room temperature

Composition ABOX N Structure Crystal symmetry Lattice constants References Special properties, remarks
type

a (A) b (A) c (A) b ()

Sr Ta O3.50 5d0 n=4 orthorhombic 3.937 5.692 27.20 90 [59] results for T=123 K are given in ref.
[40]
Sr Nb0.12 Ta0.88 O3.50 d0 n=4 orthorhombic 3.961 5.687 27.11 90 [40] results for T=573 K, 773 K and
1073 K are also presented
Sr Nb O3.50 4d0 n=4 orthorhombic 3.933 5.683 26.73 90 [60]
0
Ca Nb O3.50 4d n=4 orthorhombic 7.692 5.501 26.46 90 [61]
monoclinic 7.697 5.502 13.39 98.3 [62]
La Ti O3.50 3d0 n=4 monoclinic 7.800 5.546 13.01 98.6 [63]
monoclinic 7.812 5.544 13.01 98.7 [64]
orthorhombic 3.954 5.607 25.95 90 [65] T=1053 K
orthorhombic 7.810 5.547 25.75 90 [45]
Nd Ti O3.50 3d0 n=4 monoclinic 7.677 5.465 26.01 98.4 [66]
0.2
Sr Nb O3.41 4d n=5 orthorhombic 3.995 5.674 32.46 90 [29] the atomic coordinates were used
for band structure calculations
which indicated a quasi-1D metallic
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

system along the a-axis [31,32,35]


Nd0.67 Ca0.33 Ti O3.33 3d0 n=6 orthorhombic 7.664 5.436 36.64 90 [67]
Table 17
Results of studies aimed at the preparation of compounds with n4, 5n6 and oxygen overstoichiometry by floating zone melting. Structural investigations
were done by powder x-ray diffraction (XRD)
Composition ABOX N Structure type Reference Special properties, remarks

Aim Actual result found by


XRD

La Ti0.67 Nb0.33 O3.67 d0 n=3 (x=3.667) multiphase [24] incongruent melting; transmission electron
microscopy revealed minority phases with
disordered as well as ordered intergrowth of
n=3 and n=4 type layers
Sr0.67 La0.33 Nb O3.67 4d0 n=3 (x=3.667) multiphase this work incongruent melting
0
Ca0.67 La0.33 Nb O3.67 4d n=3 (x=3.667) multiphase this work incongruent melting
Ba0.67 La0.33 Nb O3.67 4d0 n=3 (x=3.667) multiphase this work incongruent melting
Ca0.8 La0.2 Nb O3.60 4d0 n=4 beyond x=3.57 multiphase this work main phase is of n=4 type
La Ti0.86 Nb0.14 O3.57 d0 n=3.5 (x=3.571) multiphase this work incongruent melting
Sr0.8 La0.2 Nb O3.60 4d0 n=4 beyond x=3.57 n=4 this work significantly overstoichiometric with
respect to the oxygen content x (the
Sr0.86 La0.14 Nb O3.57 4d0 n=3.5 (x=3.571) n=4 this work ideal x of the n=4 type is x=3.50),
see also Table 5
0.11
4d n=3.5 (x=3.571) n=4 this work
Sr0.75 La0.25 Nb O3.57

Sr0.65 Ba0.1 La0.25 Nb O3.57 4d0.11 n=3.5 (x=3.571) n=4 this work
0
Ca0.86 La0.14 Nb O3.57 4d n=3.5 (x=3.571) n=4 this work

La0.89 Ca0.11 Ti O3.36 3d0.17 n=5.5 (x=3.364) n=5 this work significantly understoichiometric with respect
to the oxygen content x (the ideal x of the n=5
type is x=3.40), see also Table 13
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

La0.73 Sr0.27 Ti O3.36 3d0 n=5.5 (x=3.364) n=6 this work significantly overstoichiometric with respect to
the oxygen content x (the ideal x of the n=6
type is x=3.33), see also Table 15
Ca Nb0.73 Ti0.27 O3.36 d0 n=5.5 (x=3.364) multiphase this work main phase is of n=6 type
33
Table 18 34
Results of studies aimed at the preparation of compounds with understoichiometry at the A site by floating zone melting. Structural investigations were done
by powder x-ray diffraction (XRD). The number 45295 refers to Sr0.6NbO3 in the ICDD (former JCPDS) data base. Also mentioned are n= types which
are known as polycrystalline materials
Composition AYBOX Y N Structure type References Special properties, remarks
found by XRD

Sr0.85 La0.1 Nb O3.50 0.95 4d0 n=4 this work


Sr0.85 La0.1 Nb O3.45 0.95 4d0.1 n=4 this work significantly understoichiometric also with respect to
x (the ideal x of the n=4 type is x=3.50)
Ca0.95 Nb O3.36 0.95 4d0.18 n=5 this work significantly understoichiometric also with respect to
x (the ideal x of the n=5 type is x=3.40)
Sr0.95 Nb O3.37 0.95 4d0.16 n=5 this work significantly understoichiometric also with respect to
x (the ideal x of the n=5 type is x=3.40),
for 60 KT160 K quasi-1D metal along a-axis
according to resistivity measurements
Sr0.93 Nb O3.36 0.93 4d0.14 n=5 this work significantly understoichiometric also with respect to
x (the ideal x of the n=5 type is x=3.40),
thermogravimetry hints to the presence of a second
phase in small amounts (see text) Y=0.93 could be
the stability limit
La0.933 Ti O3.40 0.933 3d0 multiphase this work change of solidified composition during floating
zone melting: at first LaTiO3.50 did grow, but later a
multiphase composition did appear
Sr0.7 La0.2 Nb O3.50 0.90 4d0 multiphase this work main phase is SrNbO3.50
0.16
Sr0.7 La0.2 Nb O3.42 0.90 4d multiphase this work 2 phases: n=4 type (main phase) + Sr0.6NbO3 (45
295)
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Sr0.9 Nb O3.40 0.90 4d0 multiphase this work change of solidified composition during floating
zone melting: at first SrNbO3.50 did grow, but later a
multiphase composition did appear
SrY Nb O3 0.750.95 4d0.5 - 4d0.9 n= [68]
LaY Ti O3 0.671.00 3d0 - 3d1 n= [6971]
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 35

this way, it is explicitly mentioned. Table 16 shows an overview about compounds


whose atomic coordinates are precisely known from single crystal x-ray diffrac-
tion studies.

2. Experimental

2.1. Sample preparation

Starting materials were CaCO3 (99.9%, MaTeck), SrCO3 (99+ %, MaTeck),


BaCO3 (99.8% Alfa), La2O3 (99.99%, MaTeck), CeO2 (99.99%, Alfa), TiO2 (99.9%,
Alfa), ZrO2 (99.98%, Alfa), Nb2O5 (99.9%, MaTeck), Ta2O5 (99.99%, MaTeck), Nb
powder (99.9%, MaTeck) and TiO (99.9%, MaTeck). The powders were weighed
with an accuracy of 0.3 mg and mixed in an agate mortar. Special care was taken
to prepare nearly moisture-free powders. The carbonates were heated for several
hours in vacuum at 110C and subsequently stored in a dry atmosphere. The oxides
(apart from TiO) were heated at higher temperatures (7001100C) in air, then kept
in a dry ambience, too. Thermogravimetry (NETZSCH TG 209) was used in order
to check the oxygen content of the Nb powder and of the TiO. Small amounts of
powders were oxidized in air at temperatures up to 1000C. Assuming that the uptake
of oxygen leads to 100% Nb and 100% Ti, the actual compositions of the powders
were found to be NbO0.02 and TiO1.03. These formulas were used for stoichio-
metric calculations.
The synthesis of electrical conducting ABOX type niobates and titanates, i.e.
reduced mixed-valence compositions, involved the following steps.

1. Preparation of a nearly carbonate-free fully oxidized Ti4+ or Nb5+ composition


AB1VOY-W. This was done by using a mixture of oxides and carbonates of total
composition AB1VOY-W(CO2)Z with 0Z1 which was heated in air for at least
6 h at temperatures of typically 1250C. The carbonate loss was traced by weigh-
ing the powder mixture before and after this process.
2. The nearly carbonate-free and fully oxidized composition AB1VOY-W was mixed
with a reduced powder BVOW, resulting in a composition ABOY according to the
following equation
AB1VOYW BVOW ABOY (powder, total amount about 6 g) (1)
The oxygen content Y of the powder (1) was checked thermogravimetrically by
oxidizing a small amount at temperatures up to 1000C in air. Fig. 8 displays the
measured thermogravimetric behavior using an example from the SrNbOX system.
The difference between the thermogravimetrically determined oxygen content, YM,
and the theoretical value based on the corresponding stoichiometric calculation,
YC, was typically found to be |YMYC|0.005.
3. The powder mixture (1) was pressed into two rectangular rods and then heated
at temperatures in the range of 12001400C under argon (purity 5.0) in a molyb-
denum furnace (GERO HTK8MO) for at least 6 h. Fig. 9 shows the sintered rods
36 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 8. Thermogravimetric behavior of the oxidation of reduced ABOX compositions by means of an


example from the SrNbOX system. The specimen were heated in air with a rate of 10C/min from room
temperature to 1000C. Shown is the relative specimen mass, (m+m)/m, as function of temperature T.
The saturation at higher temperatures indicates the presence of fully oxidized compositions involving
Nb5+ . The total mass increase was used to calculate the oxygen content X of the specimen. For this a
constant cation ratio A/B=Sr/Nb=1 was assumed. Numbers of X are given with three digits behind the
comma to display the tendency. The materials were prepared to grow crystals of n=5 type SrNbO3.4,
which has a homogeneity range from SrNbO3.40 to SrNbO3.42. The resulting niobate had the compo-
sition SrNbO3.41.

as obtained after this heating process. In most cases this heat treatment resulted
in a small oxidation of the pressed powder mixture (1), however for some titanates
a decrease of the oxygen content was observed. The small change of the oxygen
content is described by the following equation
ABOY O ABOY (polycrystalline sintered rods) (2)
The causes of a small oxidation 0 are probably small concentrations of moist-
ure, carbonates and/or hydroxides in the powder mixture (1), but may also be
associated with the degree of the purity of the inert gas atmosphere in the furnace.
A small piece of the rods (2) was used to check the oxygen content Y+ by
thermogravimetric oxidation at temperatures up to 1000C in air. Fig. 8 displays
the measured thermogravimetric behavior using an example from the SrNbOX
system. In most cases, the amount of absorbed oxygen was found to be 0.02.
4. The sintered rods (see Fig. 9) were subjected to a floating zone melting process
under argon (purity 5.0) whereby the long rod acted as feed material and the small
rod as seed part. An optically heated floating zone melting furnace (GERO) was
used. The zone speed and the rotation frequency of the seed part were chosen
within the range 515 mm/h and 1015 rpm, respectively. By this, single crystals
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 37

Fig. 9. Photograph of two sintered rectangular rods after heating at high temperatures under argon. The
length of the long rod is 8 cm.

can be grown if the compositions melt congruently or almost congruently. The


as-prepared samples have a cylindrical shape. Fig. 10 displays a part of such a
cylinder with composition SrNbO3.41. Because of the layered structure the cylin-
drical samples can easily be cleaved. By crushing the sample in an agate mortar,
single crystalline platelets can be obtained as shown in Fig. 10. Also the as-grown
samples were inspected with respect to a change d of the oxygen content according
to the equation
ABOY Od ABOX with X Y d (asgrown samples) (3)
Small pieces of the as-grown samples (3) were used to check the oxygen content
38 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 10. (a) Photograph of a 15 mm long cylindrical part of as-grown crystalline SrNbO3.41. Its layered
structure is revealed by shining faces which easily cleave. (b) Photograph of a plate-like single crystal
obtained by crushing the cylindrical sample.

X=Y++ by thermogravimetric oxidation at temperatures up to 1000C in air.


Fig. 8 displays the measured thermogravimetric behavior using an example from
the SrNbOX system. For samples which melt (almost) congruently and/or which
are compositionally more or less homogeneous, the extent of this small change
was typically found to be 00.01.

A few reduced samples were also prepared by using the following approach. Rods
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 39

were pressed from powders with a fully oxidized composition ABOF and heated in
air at temperatures of 12001400C. The sintered, fully oxidized rods were then
subjected to a floating zone melting process under a reducing atmosphere consisting
of 98% argon (purity 5.0) and 2% hydrogen (purity 5.0). If the materials are reduced
under these conditions, the resulting as-grown samples have a composition ABOFE
with E0. The oxygen content X=FE was determined thermogravimetrically by
oxidizing small pieces from the samples at temperatures up to 1000C in air. Com-
pared to the steps 14 described above, this way of preparation is relatively simple.
However, for a given composition of A and B the final oxygen content X=FE is
fixed and cannot be varied systematically. Fully oxidized samples were grown in a
similar manner, the only difference being that the atmosphere during the floating
zone melting consisted of artificial air.
In the course of previous [21,22] and this work, the accuracy of the thermogravi-
metrically measured oxygen content X of samples with reduced composition was
found to be about 0.3% (i.e. two digits behind the comma). In addition a relative
check was done by comparing the compositional status (1), (2) and (3) of the sample,
as described above in the steps 14 and shown in Fig. 8 using an example from the
SrNbOX system.

2.2. Structural, magnetic and electric measurements

Bulk structural analysis of powdered samples was performed by powder x-ray


diffraction (XRD) with Cu Ka radiation using a PHILIPS XPert diffractometer.
Lattice constant refinement of peaks located in the diffraction angle range
4260 was done with the PHILIPS software XPert Plus. Laue diffraction was
used to check the quality and orientation of selected (single) crystalline platelets,
which were considered as candidates for resistivity measurements.
Magnetic measurements were taken on a SQUID magnetometer (QUANTUM
DESIGN MPMS-5S) in a temperature range 2 KT390 K and in small magnetic
fields H, i.e. 50 GH1000 G. For these experiments, pieces of the samples with
relatively large size or mass were selected, typical masses were in the range 300
1000 mg.
Resistivity measurements between room temperature and T=4 K were done on rec-
tangular plate-like crystals obtained by crushing the melt-grown samples. Frequently
the as-crushed crystals were additionally cleaved and/or cut by means of a razor blade
to obtain a rectangular shape with appropriate size. In a few cases the crystals were
cut with a wire saw. Laue diffraction was used to check the quality and orientation of
the (single) crystalline platelets. Typically, the platelets were 0.20.8 mm thick and 2
4 mm long and wide. The resistivity r was measured in a four-point configuration
along the a-, b- and c-axis in a way as shown in Fig. 11. The voltage contacts along
the c-axis, i.e. perpendicular to the layers, and the current contacts along the a-, b- and
c-axis were made by gold wires which were attached to the sample with silver paint.
The voltage contacts along the a- and b-axis, i.e. along the layers, were made on the
crystal surface by ultrasonically bonded aluminum wires.
40 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 11. Sketch of the arrangement of electrical contacts for resistivity measurements in a four-point
configuration on a rectangular plate-like crystal along the a-, b- and c-axis. V and I denote voltage and
current contacts, respectively.

3. Results and discussion

More than 100 compositionally different samples were prepared by floating zone
melting. Additionally, more than 50 exclusively polycrystalline specimen were syn-
thesized by heating pressed powder mixtures at high temperatures according to the
steps 13 as described in the experimental section. Apart from a few exceptions, the
following sections focus on compounds grown by floating zone melting.

3.1. Sample growth by floating zone melting and structural features

Those compounds or crystals which were identified by powder x-ray diffraction


as single phase are presented in Tables 415 together with materials reported in
literature. Although every composition shows its own characteristic properties, the
crystals share the following common features. In most cases, the layers grow parallel
to the cylinder axis. In some cases, however, they grow with an inclination relative
to the cylinder axis, but never perpendicular to it. This behavior may be explained
by the crystal growth rates, which probably differ strongly along and perpendicular
to the layers. Furthermore, it was often observed that crystals of reduced composition
preserve their shape when they are fully oxidized during thermogravimetry at high
temperatures in air (note that in many cases this oxidation results in a change of the
structure type n). This observation is in accordance with the results of a detailed
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 41

study of the structural mechanisms of oxidation and reduction in the LaTiOX system,
which was recently performed by Becker [30]. For layered LaTiOX compounds, it
was revealed that the oxidation proceeds in a topotactic manner [30].

3.1.1. Compositions based on SrNbOX


Most of the following refers to several of the compounds presented in Tables 4,
10, 12 and 14.
All n=4 and n=5 type plate-like crystals which were subjected to Laue diffraction
were found to be oriented with the a-axis parallel to the cylinder axis of the as-
grown sample.
Fig. 12 shows the powder x-ray diffraction pattern of several n=4, 4.5 and 5 type
(Sr,La)NbOX niobates. From the position of the (0 0 L) peak at small diffraction
angles the structure type n can be inferred.
The n=4 type niobates Sr1YLaYNbO3.5 remain single phase at least up to Y=0.2.
For Y=0.25, the powder x-ray diffraction pattern shows additional peaks which do
not belong to the n=4 type structure. This statement about the homogeneity range
refers to samples prepared by floating zone melting.
According to the refinement of powder x-ray diffraction data, the n=4.5 type
materials show a doubled a-axis, i.e. a 7.9 A, whereas the n=4 and n=5 types
display a simple a-axis of a 3.95 A. The latter is in contrast to the results from
low energy electron diffraction (LEED), which revealed weak superstructure reflec-

Fig. 12. Square root-linear plot of powder x-ray diffraction pattern of some (Sr,La)NbOX compounds.
For clarity only selected peaks are indexed, namely those with the highest intensity and those in the range
of small diffraction angles 42q7. The position of the latter indicates the structure type n. Note the
diffraction pattern of Sr0.8La0.2NbO3.60, one of several examples of n=4 type phases which are significantly
overstoichiometric with respect to the oxygen content X (see Section 3.1.4 and Table 17).
42 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

tions and therefore a doubled a-axis [31,32]. Even for SrNbO3.41, LEED as well as
neutron scattering experiments indicated a doubled a-axis [32], whereas a simple a-
axis was inferred from single crystal x-ray diffraction studies [29]. This discrepancy
suggests that these materials contain some sophisticated structural details which are
possibly difficult to verify. Maybe these details depend also on the preparation pro-
cess. Subtle crystallographic features like phase transitions and incommensurate
phases are already known for fully oxidized compounds, e.g. for SrNbO3.50 [19,41].
Dielectric measurements by Bobnar et al. along the c-axis on the electrical conductors
SrNbO3.45 (n=4.5) and SrNbO3.41 (n=5) revealed a phase transition for both niobates
at T300 K [36]. Due to its relatively low resistivity, however, it was impossible
to conclude whether these are polar or structural phase transitions [36].
Laue diffraction performed on many different plate-like crystals of the n=4.5 type
SrNbO3.45 always displayed an unclear orientation of the a- and b-axis. In contrast
to that, plate-like crystals with clear orientation could readily be found from the
corresponding Ba-containing compound Sr0.96Ba0.04NbO3.45. Therefore attempts to
measure the resistivity along the a-, b- and c-axis were done on Sr0.96Ba0.04NbO3.45.
Note that for both niobates the conditions during floating zone melting were the
same (argon atmosphere, zone speed 15 mm/h).
The n=5 type compositions Sr1YLaYNbO3.4 (0Y0.1) grown by floating zone
melting under argon atmosphere with a zone speed of 15 mm/h revealed a tendency
to form a second phase with a flashy purple-like color. Depending on the La content
Y, the second phase appears in the whole as-grown sample or only within the first
few grown millimeter. Perhaps this second phase is the Sr-deficient cubic perovskite
compound SrWNbO3 because for W 0.8 a purple color was reported [68]. By using
lower zone speeds and an atmosphere containing 98% argon and 2% hydrogen the
formation of the second phase was completely suppressed, or its formation was
restricted to the first 1 or 2 mm of the as-grown sample.
For the fully oxidized n=5 type material SrNb0.8Ti0.2O3.4, the presence of antiferro-
electricity with Tc860 K was reported by Isupov et al. [54]. Attempts to grow
crystals of this composition turned out to be practically impossible because the feed
material showed an extremely strong tendency to grow out of the molten zone. A
similar composition, the electrical conducting compound SrNb0.9Ti0.1O3.4, displayed
the same tendency but in a less pronounced manner and it was possible to grow
small amounts of SrNb0.9Ti0.1O3.4.
The Sr-based niobates SrNbOX are those with the largest unit cell volume V com-
pared to CaNbOX and LaTiOX. Regarding the same structure type n, CaNbOX and
LaTiOX have approximately the same unit cell volume V. Fig. 13 displays the evol-
ution of the lattice constants a, b, c and V of n=5 type Sr1YCaYNbO3.41 as a function
of the Ca content Y (see also Tables 11, 12 and 14). One may expect that the lattice
constants and the unit cell volume also influence the physical properties. For
example, the resistivity and its temperature dependence of the both n=5 type niobates
SrNbO3.41 (Y=0) and CaNbO3.41 (Y=1) are quite different as shown in Figs. 19 and 23.
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 43

Fig. 13. Lattice constants a, b, c and the corresponding unit cell volume V of orthorhombic n=5 type
Sr1YCaYNbO3.41 as function of the Ca content Y.

3.1.2. Compositions based on CaNbOX


Attempts to prepare single phase n=4.333 type compositions (ideal oxygen content
X=3.462), which are known for titanates, were unsuccessful. Examples are the follow-
ing. CaNbO3.47 displays a powder x-ray diffraction (XRD) pattern, which suggests the
concurrent presence of n=4.333 and n=4.5 type phases. Ca0.95La0.05NbO3.46 (see Table
10) was identified as a single phase n=4.5 type compound by means of XRD.
The following refers to several of the compounds presented in Tables 5, 10, 11,
14 and 15.
In contrast to the SrNbOX based compositions, all plate-like crystals which were
44 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 14. Powder x-ray diffraction pattern of some compounds related to (La,Ce)TiOX and CaNbOX. It
shows the position of the (0 0 L) peak in the range of small diffraction angles 42q7 for different
structure types n. The indexing of the peaks is focussed on the small-angle peaks whose (H K L) are
given in large numbers, the other peaks are indexed with numbers of smaller size. The c-axes of the
compounds are provided in relationship to L of (0 0 L).

subjected to Laue diffraction revealed an inclination of the a-axis with respect to


the cylinder axis of the as-grown sample.
The n=4 type niobates Ca1YLaYNbO3.5 remain single phase at least up to Y=0.2.
For Y=0.25, the powder x-ray diffraction pattern displays additional peaks which do
not belong to the n=4 type structure. This statement about the homogeneity range
refers to samples prepared by floating zone melting. For the composition with Y=0.2,
the following phenomenon was observed during the floating zone melting process.
As the crystallized material passed slowly through the temperature gradient, large
cracks arose. These cracks seemed to work through from the inner to the outer part
of the sample resulting in large cavities and poor quality of the grown crystals.
Maybe a phase transition at high temperatures was responsible for this phenomenon.
However, a similar behavior was not observed for any other compositions shown in
Tables 415, even for compounds where structural phase transitions at high tempera-
tures are known, like for LaTiO3.50.
In a previous work, the composition CaNbO3.35 was grown by floating zone melt-
ing [22]. Structural investigation by transmission electron microscopy (TEM) indi-
cated a n=5 type structure with monoclinic symmetry and doubled a-axis, i.e.
a23.9 A =7.8 A [22]. The n=5 type homogeneity range of CaNbOX was suggested
to be 3.35X3.42, whereas the corresponding ranges for SrNbOX and LaTiOX were
established as 3.40X3.42 for samples synthesized by floating zone melting
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 45

Fig. 15. Thermogravimetric (TG) behavior of the oxidation of reduced (La,Ce)-based titanates. The
specimen were heated in air with a rate of 10C/min from room temperature to 1000C. Shown is the
relative specimen mass, (m+m)/m, as function of temperature T. The saturation at higher temperatures
indicates the presence of fully oxidized compositions involving Ti4+ and Ce4+. The total mass increase
was used to calculate the oxygen content X of the specimen. For this a constant cation ratio
A/B=(La,Ce)/Ti=1 was assumed. Consistent interpretation of the TG and powder x-ray diffraction data
were obtained for CeTiO3.47 and LaTiO3.41. For Ce0.5La0.5TiOX, however, the oxygen content results in
X=3.55 (3.30) assuming a Ce oxidation state of Ce4+ (Ce3+) in the range where the saturation takes place.
This is in contrast to its n=5 type structure which has an ideal oxygen content of X=3.40 (see text for a
discussion of this discrepancy).

[21,22]. During this work, several polycrystalline and melt-grown CaNbOX samples
with 3.33X3.39 were prepared in order to investigate the n=5 type homogeneity
range in more detail. The polycrystalline specimen were synthesized by heating
pressed powder mixtures according to the steps 13 as described in Section 2.1.
Structural analysis by powder x-ray diffraction (XRD) indicated the presence of
orthorhombic n=5 type structures with simple a-axis (a =3.88 A). For X=3.39 a single
phase n=5 type compound was observed. For X3.38 additional peaks appeared,
which could be assigned to the perovskite CaNbO3. With decreasing oxygen content
X the intensity of the CaNbO3 peaks increased, but the peak positions and lattice
constants of the n=5 type phase did not show any significant change. These results
on polycrystalline samples with orthorhombic symmetry and simple a-axis suggest
a lower bound of X=3.39 for the n=5 type homogeneity range. Also the melt-grown
samples showed indications for a multiphase composition for X3.39, but this was
not so clearly visible in the XRD pattern as for the polycrystalline specimen. Thermo-
gravimetric analysis and magnetic measurements, however, revealed an inhomogen-
ous distribution of the oxygen content X over the sample and the presence of Nb.
Therefore a lower bound of X=3.39 or X=3.40 for the n=5 type homogeneity range
is also suggested for the melt-grown samples. This is in contrast to the melt-grown
sample with X=3.35 from the previous work mentioned, where the structural examin-
ation by TEM indicated a monoclinic symmetry and a doubled a-axis. Most probably
the TEM results were not representative for the bulk properties regarding the lower
bound of the n=5 type homogeneity range.
46 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 16. Sketch of non-stoichiometric homogeneity ranges with respect to the oxygen content X of
AnBnO3n+2=ABOX type niobates and titanates as suggested from structural analysis by powder x-ray diffraction.

3.1.3. Compositions based on (La,Ce)TiOX


The following refers to several of the compounds presented in Tables 6, 8, 9, 13
and 15.
Plate-like crystals of n=5 type LaTiO3.4 subjected to Laue diffraction did not reveal
a clear tendency regarding the orientation of the a-axis. Some samples showed an
a-axis parallel to the cylinder axis of the as-grown sample, whereas some other
platelets displayed an a-axis inclined to that axis.
The majority of the titanates crystallize in a monoclinic form, in contrast to the
niobates which are orthorhombic in the most cases.
Fig. 14 shows the powder x-ray diffraction pattern of n=4, 4.33, 4.5 and 5 type
titanates and n=6 type CaNb0.8Ti0.2O3.33 in the range of small diffraction angles. The
position of the (0 0 L) peak indicates the structure type n.
It was possible to prepare the n=4 type compound LaTi0.8Nb0.2O3.51, whereas in
ref. [26] it is said that a substitution of Ti by Nb in LaTiO3.5 could not be achieved.
Titanates involving Ce display some peculiarities, because Ce may appear in the
two different oxidation states Ce3+ and Ce4+. In most ternary or higher oxides Ce3+
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 47

Fig. 17. Log-linear plot of the resistivity r versus temperature T of n=4 type Sr0.8La0.2NbO3.50 along the
a-, b- and c-axis. The activation energies in meV indicate that parts of r(T) can be fitted to a thermally
activated behavior rexp(/T), the corresponding temperature ranges are also provided.

is preferred, whereas for synthesis purposes CeO2 (Ce4+) is the most common starting
material. For the preparation of polycrystalline n=4 type CeTiO3.5 involving Ce3+ and
Ti4+, a heat treatment at 1400C under argon using a mixture of CeO2, TiN and TiO2
was reported (see Table 6). During this work, Ce containing titanates were synthesized
by floating zone melting using air as oxidizing atmosphere, or 98% argon +2% hydro-
gen as reducing ambience. Only rods with fully oxidized compositions involving TiO2
(Ti4+) and CeO2 (Ce4+) were used. The oxidation state of Ce in the samples grown
in this way was suggested to be Ce3+, as indicated by the crystal structure type and/or
by the oxygen content X. Thus Ce4+ (CeO2) converts to Ce3+ even under an oxidizing
atmosphere like air, if the compositions are molten at high temperatures. The n =4
type compound La0.67Ce0.33TiO3.50 involving Ce3+ and Ti4+, for example, was obtained
in this way (see Table 6). Under reducing ambience a single phase n=4.33 type
material, CeTiO3.47, involving Ce3+ and mixed-valence Ti could be grown. Only a
few n=4.33 type bulk compounds are known, all of them being titanates (see Table
8). Also a sample with composition Ce0.5La0.5TiOX was obtained under the reducing
48 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 18. Log-linear plot of the resistivity r versus temperature T of n=4.5 type Sr0.96Ba0.04NbO3.45 along
the a-, b- and c-axis. The activation energies in meV indicate that parts of r(T) can be fitted to a
thermally activated behavior rexp(/T), the corresponding temperature ranges are also provided. The
linear-linear type inset displays the presence of metallic behavior (i.e. dr/dT0) along the a-axis which
is not so clearly visible at the log-linear scale.

atmosphere. Powder x-ray diffraction clearly revealed a single phase n=5 type titanate.
However, there was no straightforward way to determine its oxygen content X by
thermogravimetric analysis for this composition. Fig. 15 shows the thermogravimetric
behavior of the oxidation of Ce0.5La0.5TiOX in comparison to CeTiO3.47 and LaTiO3.41.
It was assumed that Ce reaches an oxidation state of Ce4+ at high temperatures where
the saturation appears. For CeTiO3.47 and LaTiO3.41 this leads to a consistent interpret-
ation of the results of powder x-ray diffraction and thermogravimetric analysis. For
Ce0.5La0.5TiOX, however, the oxygen content results in X=3.55 (3.30) assuming a Ce
oxidation state of Ce4+ (Ce3+) in the range where the saturation is reached. This is
in contrast to its n=5 type structure with an ideal oxygen content of X=3.40. Concern-
ing this, the following interpretations are conceivable:
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 49

1. The n=5 type sample Ce0.5La0.5TiOX contains Ce3+, but its thermogravimetric oxi-
dation up to 1000C was not sufficient to reach the highest Ce valence of Ce4+.
A separate themogravimetric experiment up to temperatures of 1200C, however,
revelead a decreasing specimen mass above 1000C. This suggests that the highest
possible oxidation was already reached around 1000C. Therefore this interpret-
ation seems to be unlikely.
2. The n=5 type sample Ce0.5La0.5TiOX contains Ce3+ but its thermogravimetric oxi-
dation up to temperatures of 1000C results in a composition involving mixed
valence Ce. A formal oxidation state of about Ce3.5+ in the oxidized sample leads
to an oxygen content of X3.4 which is in agreement with the n=5 type structure.
This seems to be the most likely interpretation.
3. The n=5 type sample Ce0.5La0.5TiOX contains Ce in a mixed valence state
Ce3+/Ce4+ and the thermogravimetric oxidation leads to a composition in which
all Ce cations are in the Ce4+ state. In this case, the gain of the specimen mass
due to the oxidation is smaller compared to the assumption that the sample
Ce0.5La0.5TiOX includes only Ce3+. This interpretation agrees qualitatively with
the thermogravimetric results. On the other hand, the temperature dependence of
the magnetic susceptibility c of Ce0.5La0.5TiOX is similar to other titanates involv-
ing Ce3+ and the magnitude of c lies between that of compounds with 100% Ce3+
and 33% Ce3+ at the A site (see Fig. 33). This might indicate the exclusive pres-
ence of Ce3+ in Ce0.5La0.5TiOX, which supports interpretation 2. Note that c of
the Ce containing titanates (see Fig. 33) is governed by the large paramagnetic
contribution of Ce3+, otherwise the magnitude of c would be much smaller.

Further studies are necessary to clarify this subject.

3.1.4. Attempts to prepare series members with n4, 5n6 and non-
stoichiometric materials
ABOX bulk compounds of the AnBnO3n+2 type are known for n=4, 4.33, 4.5, 5 and
6 (see also Tables 115). In a previous work a hypothetical n=3 type composition
LaTi0.67Nb0.33O3.67 was prepared by floating zone melting [24]. It melted incongru-
ently and was multiphase. Nevertheless, transmission electron microscopy revealed
a minority phase which showed disorded and ordered intergrowths of n=3 and n=4
type layers [24].
Table 17 shows the results of several attempts to synthesize n=3, 3.5 and 5.5 type
compounds by floating zone melting. All of the hypothetical n=3 type compositions
ABO3.67 melted incongruently and were found to be multiphase. The floating zone
melting of compositions with a hypothetical n=3.5 type structure (X=3.57) and with
even higher oxygen content (X=3.60), however, resulted in samples which were often
identified as single phase n =4 type compounds by powder x-ray diffraction. Fig.
12 displays the example Sr0.8La0.2NbO3.60 in comparison to niobates having an ideal
oxygen content of X=3.50. These observations suggest a large overstoichiometric
homogeneity range for some n=4 type phases with respect to the oxygen content X.
It seems to resemble to the n= type LaTiOX with a three-dimensional perovskite
structure. Its homogeneity range was found to be extraordinarily large, namely
50 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 19. Log-linear plot of the resistivity r versus temperature T of n=5 type SrNbO3.41 along the a-,
b- and c-axis. The activation energies in meV indicate that parts of r(T) can be fitted to a thermally
activated behavior rexp(/T), the corresponding temperature ranges are also provided.

3.00X3.20 as displayed in Fig. 6 whereby the unit cell volume V diminishes with
increasing oxygen content X [21]:
n type LaTiOX V 250 A3 for X 3.00 (ideal oxygen content)
V 243 A3 for X 3.20 (maximum overstoichiometry)

This volume change hints to a structural implementation of the overstoichiometry


by cation deficiency, which can be expressed by normalizing the formula LaTiOX
with 3.00X3.20 to its ideal oxygen content X=3.00, i.e. LaYTiYO3 with
1Y0.94. This has to be compared with the n=4 type niobates. For Sr0.8La0.2NbOX
with X=3.50 and X=3.60 the unit cell volume V is directly available (see Tables 4
and 5). The value for X=3.57 can be also obtained from Table 5 by using the average
V of the adjacent compositions Sr0.75La0.25NbO3.57 (V=599 A3) and Sr0.86La0.14NbO3.57
(V=601 A3), thus
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 51

n 4 type Sr0.8La0.2NbOX V 598 A3 for X 3.50 (ideal oxygen content)


V 600 A3 for X 3.57 (overstoichiometric)
V 602 A3 for X 3.60 (overstoichiometric)

Compared to LaTiOX the relative volume change is smaller and of opposite direc-
tion, i.e. the lattice expands upon oxidation. This suggests that the excess oxygen is
located at interstitial sites or is intercalated between the layers. In the case of
(Ca,La)NbOX there are indications for a smaller homogeneity range, because a sam-
ple with X=3.57 was identified as single phase, whereas a composition with X=3.60
consists of two phases (see Table 17). The Ca-based niobates possess smaller unit
cell volumes than their Sr-based counterparts. Therefore the Ca-based materials could
have less capacities to incorporate the excess oxygen.
Also the n=5 type phases SrNbOX, LaTiOX and CaNbOX have an overstoichiometric
homogeneity range, even though its extent 3.40X3.42 is smaller than that of the
n=4 and n= types just mentioned [21,22]. The reason for that is certainly the follow-
ing. The oxidation of a n=5 type compound (ideal X=3.40) leads quickly to a formation
of a n=4.5 type phase (ideal X=3.44) because the difference between these both oxygen
contents X is relatively small. Therefore it is impossible for n=5 type structures to
have a large overstoichiometric homogeneity range. The oxidation of a n=4 type com-
pound (ideal X=3.50), however, may take place within the same structure type up to
an unknown limit because there were no indications for a formation of a n=3.5 type
phase (ideal X=3.57) found. Therefore the n=4 type phases may have a larger oversto-
ichiometric homogeneity range compared to its n=5 type counterparts.
For the hypothetical n=5.5 type composition La0.73Sr0.27TiO3.36 powder x-ray dif-
fraction indicates a n=6 type structure (see Table 17). The ideal oxygen content of
the n=6 type structure is X=3.33. Therefore the existence of n=6 type phases having
a significant overstoichiometry with respect to its ideal oxygen content is suggested.
For the hypothetical n=5.5 type composition La0.89Ca0.11TiO3.36 powder x-ray dif-
fraction indicates a n=5 type structure (see Table 17). The ideal oxygen content of
the n=5 type structure is X=3.40. Thus the existence of n=5 type phases having a
significant understoichiometry with respect to its ideal oxygen content is suggested.
As yet, non-stoichiometric compositions with respect to the oxygen content X were
discussed. Materials which are non-stoichiometric with respect to the A site are known
for n= types, namely SrYNbO3 with 0.75Y0.95 [68] and LaYTiO3 with 0.67Y1
[6971]. That raises the question if also n types with a cation deficiency at the A
site exist. Several of such AYBOX compositions with Y1 were synthesized during this
work. The results are summarized in Table 18. Indeed, several single phase compounds
with a cation deficiency at the A site were obtained. Note that some of these single
phase oxides are simultaneously understoichiometric with respect to the oxygen content
X (see Table 18). That hints to the existence of many materials with a great variety
of non-stoichiometric composition. Sr0.93NbO3.36 was identified as a single phase n=5
type niobate by powder x-ray diffraction, however the results of thermogravimetric
oxidation hint to a presence of a second phase in small amounts. The thermogravi-
metric curves show a weak increase in the region of saturation, which indicates that
52 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

small partitions of the samples were not completely oxidized (the specimen were
heated in air with a rate of 10C/min up to a temperature of 1000C). This is in
accordance with the observation that small partitions of the oxidized specimen display
a black color. Therefore it seems that among the prepared AYBOX compositions Y0.93
is the smallest value which ensures a single phase material.
All these results show that the synthesis of bulk compounds having a structure
beyond the known types n=4, 4.33, 4.5, 5 and 6 seems to be difficult. However, for
the known structure types n a further possibility to modify its composition was found,
namely the creation of a distinct non-stoichiometry with respect to its ideal oxygen
content X =3+2/n and ideal cation ratio A/B=1. In Fig. 16 an overview of suggested
non-stoichiometric homogeneity ranges is sketched.

3.2. Electric properties

Already in a previous work resistivity measurements performed on LaTiO3.42,


SrNbO3.45 and CaNbO3.35 crystals were reported [22]. A semiconducting behavior
along and perpendicular to the layers was found, but the direction of the current
along the layers was arbitrarily selected and not specified [22]. In that previous work,
the electrical contacts were prepared using indium or gold-beryllium wires and silver
paint [22]. In the present study the same kind of electrical contacts were used for
the first attempts of measuring the resistivity along the a- and b-axis. However, only
semiconducting behavior and no anisotropy with respect to the a- and b-axis was
observed. This outcome stood in contrast to the results from photoemission, optical
spectroscopy and band structure calculations, which revealed a behavior differing
strongly between the a- and b-axis, as already mentioned above [3134]. Therefore,
the voltage contacts were improved in two ways. First, the wires were attached with
a conductive silver epoxy kit instead of with silver paint. Second, aluminum wires
were bonded ultrasonically. Resistivity measurements using the first technique indeed
revealed a clear anisotropy with respect to the a- and b-axis and even indications
for a metallic behavior along the a-axis. However, these contacts were difficult to
prepare and showed a poor quality concerning scattering and reproducibility of the
measured data. The second method turned out to be the best, and was therefore used
for all measurements. Depending on the composition of the crystals (see Figs. 17
24), the upper bounds of the contact resistance of the voltage contacts were found
to be in the range from 5 to 250 . The contact resistances were obtained from
resistance measurements in a two-point configuration.
Resistivity measurements were performed on rectangular plate-like crystals of 8
different compounds: Sr0.8La0.2NbO3.50 (n=4), Sr0.96Ba0.04NbO3.45 (n=4.5), SrNbO3.41
(n=5), Sr0.965La0.035NbO3.41 (n=5), Sr0.9La0.1NbO3.41 (n=5), Sr0.95NbO3.37 (n=5),
CaNbO3.41 (n=5) and LaTiO3.41 (n=5). Figs. 1724 show the measured resistivity r
as function of temperature T between T=300 K and T=4 K along the a-, b- and c-
axis. Obviously, these oxides are highly anisotropic conductors. Along the b- and
c-axis they behave like semiconductors. Along the a-axis the temperature dependence
of the resistivity is quite complicated. In parts of the temperature range the com-
pounds investigated are quasi-1D metals, whereas at lower temperatures a metal-
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 53

Fig. 20. Log-linear plot of the resistivity r versus temperature T of n=5 type Sr0.965La0.035NbO3.41 along
the a-, b- and c-axis. The activation energies in meV indicate that parts of r(T) can be fitted to a
thermally activated behavior rexp(/T), the corresponding temperature ranges are also provided.

semiconductor transition appears. SrNbO3.41 deviates somewhat from this picture


because a weak metallic temperature dependence of the resistivity is also observed
along the b-axis (see Fig. 19). Angle-resolved photoemission at T=75 K and optical
spectroscopy at T=5, 50, 100, 150, 200, 250 and 300 K on SrNbO3.41 by Kuntscher
et al., however, revealed quasi-1D metallic features along the a-axis and semiconduc-
tor-like properties along the b-axis [3234].
Figs. 1724 display that the temperature of the metal-semiconductor transition
ranges from 50 K for SrNbO3.41, Sr0.95NbO3.37 and LaTiO3.41 to 180 K for
CaNbO3.41. An increasing La content in the n=5 type niobates (Sr,La)NbO3.41 leads
to a decreasing resistivity r (see Figs. 1921) and for Sr0.9La0.1NbO3.41 the metal-
semiconductor transition is almost completely suppressed (see Fig. 21). Among the 8
different compounds on which resistivity measurements were carried out, CaNbO3.41
displays a decreasing resistivity below T17 K along the a-axis and below T11
K along the b- and c-axis (see Fig. 23). As can be seen in Fig. 27, the magnetic
susceptibility of CaNbO3.41 does not show any evidence for anomalous properties in
54 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 21. Log-linear plot of the resistivity r versus temperature T of n=5 type Sr0.9La0.1NbO3.41 along the
a-, b- and c-axis. The activation energies in meV indicate that parts of r(T) can be fitted to a thermally
activated behavior rexp(/T), the corresponding temperature ranges are also provided.

this temperature range. This strange resistivity behavior is at least partly in agreement
with results from a previous work on CaNbO3.35, for which a saturation of the resis-
tivity along the layers was found at low temperatures [22].
The semiconducting behavior of the resistivity r along the a-, b- and c-axis was
inspected if it can be fitted to a thermally activated behavior rexp(/T). In parts
of the temperature range a good fit was found. The corresponding activation energies
are often very small, especially for temperatures below that of the metal-semicond-
uctor transition, and vary from 0.5 to 58 meV as shown in Figs. 1724. In these
figures, the activation energies are provided with the corresponding temperature
range for which the fit r exp(/T) was used.
A small activation energy or energy gap along the a-axis at temperatures below
that of the metal-semiconductor transition was not only observed in resistivity
measurements. This was shown for SrNbO3.41 which is presently the most intensively
studied AnBnO3n+2 type compound. High-resolution angle-resolved photoemission
along the a-axis at T=25 K and optical spectroscopy between T=5 K and T=300 K
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 55

Fig. 22. Log-linear plot of the resistivity r versus temperature T of significantly non-stoichiometric n=5
type Sr0.95NbO3.37 along the a-, b- and c-axis. The activation energies in meV indicate that parts of
r(T) can be fitted to a thermally activated behavior rexp(/T), the corresponding temperature ranges
are also provided.

with polarization of the incident light along the a- and b-axis by Kuntscher et al.
revealed a small energy gap of 58 meV [33]. This is similar to a=3.3 meV
obtained from the resistivity raexp(a/T) in the tempearture range 20 KT40 K
(see Fig. 19). In the same temperature range, nuclear magnetic resonance (NMR)
measurements by Weber et al. also indicated an activated behavior of the spin-lattice
relaxation rate with an energy gap of 6.5 meV [37].
During this work the semiconducting resistivity behavior along the a-, b- and c-
axis was exclusively considered with respect to a thermal activation rexp(/T).
However, dielectric measurements along the c-axis on Sr0.8La0.2NbO3.50, SrNbO3.45
and SrNbO3.41 by Bobnar et al. [36] as well as NMR and electron paramagnetic
resonance (EPR) experiments on SrNbO3.41 by Weber et al. [37] point to a further
process of charge transport. Among other things, the dielectric measurements on
Sr0.8La0.2NbO3.50 and SrNbO3.41 indicate that the resistivity rc along the c-axis
behaves rather like rcexp[(T0/T)1/2] than rcexp(/T), at least for temperatures
56 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 23. Log-linear plot of the resistivity r versus temperature T of n=5 type CaNbO3.41 along the a-,
b- and c-axis. The activation energies in meV indicate that parts of r(T) can be fitted to a thermally
activated behavior rexp(/T), the corresponding temperature ranges are also provided. The linear-linear
type inset displays the presence of metallic behavior (i.e. dr/dT0) along the a-axis which is not so
clearly visible at the log-linear scale.

T100 K [36]. For T20 K the NMR spin-lattice relaxation rate and EPR line width
of SrNbO3.41 displays the same temperature dependence (for T20 K the NMR spin-
lattice relaxation rate shows an activated behavior as already mentioned above) [37].
The results of the dielectric measurements along the c-axis and the NMR and EPR
experiments suggest a charge transport by hopping of localized charge carriers like
small polarons, at least at low temperatures [36,37].
The most striking electronic property of the materials investigated is the presence of
a quasi-1D metallic conductivity along the a-axis (see Figs. 1724). This is in accordance
with the results from angle-resolved photoemission (ARPES) along the a- and b-axis
by Kuntscher et al. on SrNbO3.45 at T=150 K, SrNbO3.41 at T=75 K, Sr0.9La0.1NbO3.39
at T=75 K and 100 K [31,32,34]. It is furthermore in agreement with the outcomes of
optical spectroscopy with polarization of the incident light along the a- and b-axis by
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 57

Fig. 24. Log-linear plot of the resistivity r versus temperature T of monoclinic n=5 type LaTiO3.41 along
the a- and b- axis as well as perpendicular to the layers. The activation energies in meV indicate that
parts of r(T) can be fitted to a thermally activated behavior rexp(/T), the corresponding temperature
ranges are also provided.

Kuntscher et al. on SrNbO3.41 at T=5, 50, 100, 150, 200, 250 and 300 K [33]. Also
band structure calculations on SrNbO3.4 revealed significant electronic dispersion near
the Fermi energy only along the a-axis but not along the b-axis [31,32,35]. ARPES on
Sr0.8La0.2NbO3.50 at T=75 K revealed only a weak electronic dispersion along the a-axis
[32,34]. This is in qualitative agreement with the resistivity behavior of Sr0.8La0.2NbO3.50
which shows only a weak metallic character along the a-axis (see Fig. 17).
Is is known that quasi-1D metals are inclined to structural instabilities (Peierls
transition, charge density wave) or electronic instabilities. At these transitions an
energy gap arises and the electronic state changes from metallic to semiconducting,
which resembles the temperature-driven metal-semiconductor transitions along the
a-axis shown in Figs. 1724. Among the materials on which resistivity measurements
were carried out (see Figs. 1724) there are some compounds like SrNbO3.41 where
the metal-semiconductor transition takes place at very low temperatures (T50 K)
58 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 25. Distortions of the BO6 octahedra of n=4, 5 and 6 type compounds whose atomic coordinates are
known. The distortion is defined as [(largestsmallest) B-O distance]/[average B-O distance]. The percentage
values of these distortions are shown as bold numbers. They were calculated from the atomic coordinates
at room temperature presented in the references of Table 16. The numbers of different B-O bond lengths
are given in parenthesis. The layers consisting of corner-shared BO6 octahedra are sketched at the left side.
The simple sketch of the BO6 octahedra does not reveal any distortion and for clarity the A cations are
omitted. A bold number in a line displays the distortion of the octahedra located in the same line. Bold
numbers which are presented in two columns indicate different distortions for adjacent octahedra along the
a-axis. This Figure clearly reveals that octahedra located at the boundary of the layers possess larger distor-
tions compared to those residing inside. Note that for the n=4 type SrTaO3.50 the distortions refer to the
paraelectric phase, whereas all other n=4 type compounds are ferroelectrics at room temperature.

and the energy gap in the semiconduting state is very small (a few meV), compared
to most of the other known quasi-1D metals. The intriguing electronic features of
Sr-based niobates are discussed in detail by Kuntscher et al. [3134]. NMR experi-
ments on SrNbO3.41 by Weber et al. at low temperatures hint to the presence of a
charge density wave [37]. The present results from the investigations of the electronic
and magnetic properties call for further studies, especially for the clarification of the
nature of the metal-semiconductor transitions.
A further remarkable feature of the layered AnBnO3n+2=ABOX type niobates and
titanates is the structural, compositional and electronical proximity between quasi-1D
metals and non-conducting (anti)ferroelectric series members. Some of these layered
(anti)ferroelectrics can be directly transformed into quasi-1D metals by creating
charge carriers using appropriate substitutions at the A or B site. The most obvious
examples are (see Tables 4, 12 and 14 and Figs. 5, 17, 1921):
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 59

Fig. 26. Molar magnetic susceptibility c in low fields (H1000 G) versus temperature T of several
SrNbOX type compounds. The layers of the crystalline samples were aligned parallel to the magnetic field.

layered n=4 type:


high-Tc ferroelectric insulator SrNbO3.5 (4d0) weakly metallic quasi-1D-like
conductor Sr0.8La0.2NbO3.5 (4d0.2)
layered n=5 type:
antiferroelectric insulator SrNb0.8Ti0.2O3.4 (4d0) quasi-1D metal
(Sr,La)NbO3.4 (4d0.24d0.3)

Usually (anti)ferroelectrics display a high dielectric permittivity or polarizability.


An example can be found in Fig. 5 where the dielectric permittivity of ferroelectric
SrNbO3.50 along the a-, b- and c-axis is shown over a large temperature range. As
already mentioned, these (anti)ferroelectrics are structurally, compositionally and
electronically in proximity to the quasi-1D metals. Therefore, the structurally and
electronically low-dimensional AnBnO3n+2=ABOX type materials could allow the
possibility to create systems with an intrinsic coexistence of high dielectric polariz-
ability and metallic conductivity. Such systems were considered as candidates for
60 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

excitonic superconductivity [72]. An experimental hint for the realization of a simul-


taneous existence of metallic conductivity and high polarizability can be found in
SrNbO3.41. Dielectric measurements along the c-axis by Bobnar et al. revealed the
high-frequency dielectric permittivity c in the temperature range 2 KT70 K
and relatively large values of c 100 were found [36]. In a part of this temperature
range, namely 60 KT70 K, a metallic resistivity behavior was measured along
the a-axis (see Fig. 19). For temperatures T70 K it was impossible to determine
c because of a high inductance contribution in the circuit [36]. However, it may
be expected that the relatively large c persists also at higher temperatures where
the resistivity along the a-axis is metallic up to T=130 K (see Fig. 19).
Band structure calculations by Bohnen [31] as well as by Winter [35] on the n=5
type niobate SrNbO3.4 suggested that the quasi-1D metallic features are related to the
subtleties of the distortions of the NbO6 octahedra [31,32,35]. Some of these calcu-
lations were done on the real structure involving the distorted octahedra and on a
hypothetical structure in which the distortions had been removed artificially [31,32].
Two results of these calculations are especially remarkable. First, the density of elec-
tronic states at the Fermi energy is mainly given by those Nb atoms belonging to the
less distorted octahedra located in the middle of the layers [31,32,35]. Second, the
distortion-free system is more of a quasi-2D type, indicating a close connection
between the quasi-1D behavior and the characteristic distortions of the NbO6 octahedra
[31,32]. This outcome calls for a detailed inspection of the BO6 octahedra distortions
in several AnBnO3n+2=ABOX type materials. Such an inspection requires the atomic
positions and B-O bond lengths to be known exactly. This is the case for the com-
pounds shown in Table 16. The corresponding atomic coordinates and B-O bond
lengths can be found in the references given in Table 16. These data and the definition

BO6 octahedra distortion = [(largest - smallest) B-O distance]/[average B-O distance]

were used to establish Fig. 25 which displays the distortions in several niobates and
titanates. For the limited number of compounds listed, Fig. 25 reveals that the BO6
octahedra in the middle of the layers are less distorted than those located at the
boundary. Furthermore, it is conspicuous that the n=5 and n=6 type materials display
a relative large variation of the distortion along the c-axis compared to their n=4
type counterparts (the only exception is SrTaO3.50 which is paraelectric, whereas all
other n=4 types are ferroelectrics at room temperature). Especially for the n=5 type
SrNbO3.41 the distortion gradient is very large involving nearly non-distorted NbO6
octahedra in the middle of the layers (see Fig. 25).
Figs. 17 and 19 present the resistivity r(T) of the n=4 type Sr0.8La0.2NbO3.50 and
n=5 type SrNbO3.41, respectively. Both of these niobates have a formal electron con-
figuration of 4d0.2 per Nb. Therefore these compounds may be used to compare the
electric properties between the structure types n=4 and n=5. Figs. 17 and 19 reveal
that the n=5 type niobate shows a larger anisotropy with respect to the a- and b-
axis, a lower resistivity and a more pronounced metallic character in the resistivity
behavior than its n=4 type counterpart. Maybe these differences are related to the
characteristic distortions of the NbO6 octahedra. The n=5 type niobate involves a
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 61

relatively strong distortion gradient with nearly non-distorted NbO6 octahedra in


the middle of the layers (see Fig. 25). Assuming that the NbO6 octahedra distortions
of the insulating SrNbO3.50 (see Fig. 25) are also representative for the electrical
conductor Sr0.8La0.2NbO3.50 , then the n=4 type niobate involves a relatively small
distortion gradient with relatively large distortions (see Fig. 25).

3.3. Magnetic properties

Figs. 2632 show the molar magnetic susceptibility c of many compounds in low
magnetic fields (50 GH1000 G) as a function of temperature T. The layers of
the crystalline samples were aligned parallel to the magnetic field. Some attempts
were performed to measure the susceptibility for different orientations of the layers
relative to the magnetic field. No significant influence of the orientation with respect
to the temperature dependence was observed. Therefore it seems that the orientation
does not play a crucial role.
As expected, the insulating ferroelectrics SrNbO3.50, CaNbO3.50 and LaTiO3.50

Fig. 27. Molar magnetic susceptibility c in low fields (H1000 G) versus temperature T of several
CaNbOX type compounds. The layers of the crystalline samples were aligned parallel to the magnetic field.
62 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 28. Molar magnetic susceptibility c in low fields (H1000 G) versus temperature T of several
LaTiOX type compounds. The layers of the crystalline samples were aligned parallel to the magnetic field.

exhibit a nearly temperature-independent diamagnetism of the ionic cores (see Figs.


2628). The increase of c(T) at low temperatures is indicative for a Curie- or Curie-
Weiss-like behavior of impurities and/or defects. For the niobates this effect is small
compared to LaTiO3.50, which shows a relatively strong increase. The latter could
result from the use of TiO2 (La2O3) as starting material which may have contained
small concentrations of strongly paramagnetic impurities like Fe3+ (rare earths like
Ce3+, Pr3+ and Nd3+).
Compared to the ferroelectric insulators, the electrical conducting niobates and
titanates exhibit a distinct temperature dependence in c(T). As expected, the suscepti-
bility rises with an increase of the formal charge carrier concentration obtained from
charge neutrality (see Figs. 2632), especially for compounds with the same structure
type and similar composition like the n=5 type Sr-based niobates shown in Fig. 32.
The titanates with their 3d electrons have a higher magnetic susceptibility than the
niobates, for which the charge carriers are given by 4d electrons. This is in accord-
ance with the fact that 3d electrons display stronger electronic correlations than the
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 63

Fig. 29. Molar magnetic susceptibility c in low fields (H1000 G) versus temperature T of miscel-
laneous materials. Note that La0.89Ca0.11TiO3.36 and Sr0.75La0.25NbO3.57 are significantly non-stoichiometric
compounds. The layers of the crystalline samples were aligned parallel to the magnetic field.

spatially more extended 4d electrons. The enhanced correlations result in a higher


magnetic susceptibility.
A characteristic property of the majority of the electrical conducting niobates and
titanates is the presence of a minimum in c(T) (see Figs. 2632). The increase of
c(T) at low temperatures is indicative for a Curie- or Curie-Weiss-like behavior of
impurities, defects and/or paramagnetic moments located at regular lattice sites like
Ti3+ and Nb4+ which result from the mixed-valence composition of the compounds.
The latter possibility was ruled out for SrNbO3.41, because a Curie-like behavior
belonging to Nb4+ was not observed in electron paramagnetic resonance (EPR)
experiments by Weber et al. [37]. This could imply, for example, a dimerization into
pairs of Nb4+ with opposite spin or that every Nb4+ has transferred its 4d electron
into bands leaving all Nb in a Nb5+ state. Some of the starting materials, Nb2O5 and
SrCO3, were investigated by EPR and traces of Fe3+ and Mn2+ impurities were
detected [37]. Note that the valence and therefore the magnetic moment of the
impurities may change during the preparation process. For most of the compounds
64 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 30. Molar magnetic susceptibility c in low fields (H1000 G) versus temperature T of n=4 type
niobates. Note that Sr0.85La0.1NbO3.45 and Sr0.65Ba0.1La0.25NbO3.57 are significantly non-stoichiometric
compounds. The layers of the crystalline samples were aligned parallel to the magnetic field.

shown in Figs. 2632 it seems likely that the low-temperature behavior of c(T) is
not related to the intrinsic features of the samples, but is due to impurities or defects.
The special case of electrical conducting materials which do not display a minimum
in c(T) will be briefly discussed later.
In a simple approach the following contributions to the magnetic susceptibility
c(T) may be assumed:

1. temperature independent diamagnetism of the ionic cores


2. Curie- or Curie-Weiss-like behavior c1/(T) from defects, impurities and/or para-
magnetic moments loacted at regular lattice sites c diminishes with increasing T
3. (nearly temperature independent) paramagnetism of itinerant electrons in the con-
duction band
4. thermal activation of electrons into the conduction band, i.e. cexp(/T) c
rises with increasing T
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 65

Fig. 31. Molar magnetic susceptibility c in low fields (H1000 G) versus temperature T of n=4.5 type
niobates. The layers of the crystalline samples were aligned parallel to the magnetic field.

A combination of (2) and (4) can lead to a minimum in c(T). For the n=5 type
SrNbO3.41 this simple model is discussed by Weber et al. in comparison to the
BonnerFisher model for the magnetic susceptibility of a quasi-1D spin-chain,
including its extension for delocalized electrons [37]. For temperatures T above 100
K a well description of the magnetic susceptibility c(T) of SrNbO3.41 in terms of a
quasi-1D spin chain was found [37]. This suggests that the enlargement of c(T) with
increasing T, which is observed in many compounds at elevated temperatures (see
Figs. 2632), is related to their quasi-1D electronic features.
In contrast to the majority of the conducting AnBnO3n+2=ABOX type materials
investigated, there are also compounds for which c(T) diminishes with increasing T
in the whole temperature range (see Figs. 28, 29, 31 and 33). Fig. 33 displays the
inverse of c(T) of some of these compounds with a relatively large magnitude of
c(T), like Ce-containing titanates and oxides involving the concurrent presence of
Ti and Nb at the B site. Also in parts of the high-temperature range a linear Curie-
or CurieWeiss-like behavior is observed. This indicates the presence of localized
paramagnetic moments like Nb4+, Ti3+ or Ce3+ at high temperatures (see Fig. 33)
66 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

Fig. 32. Molar magnetic susceptibility c in low fields (H1000 G) versus temperature T of n=5 type
niobates. Note that Sr0.95NbO3.37 is a significantly non-stoichiometric compound. The layers of the crystal-
line samples were aligned parallel to the magnetic field.

which suggests the two following possibilities. First, the quasi-1D metallic features
coexist with the presence of localized paramagnetic moments which dominate the
magnitude and temperature behavior of c(T). Second, the quasi-1D metallic conduc-
tivity is totally lost and all charge carriers are either localized or occupy a completely
filled band. For the ABOX compounds with B=(Ti,Nb) the second possibility could
result from a statistical distribution of Ti and Nb at the electronically active B sites,
which may lead to a disordered-induced localization of the charge carriers. Further
studies are required to clarify this subject.

3.4. Special features referring to Tables 115

It can be inferred from Tables 215 that ferroelectricity and/or non-centrosym-


metric space groups occur only for series members having an even number, i.e. for
the n=2 type fluorides, the n=4 and n=6 type oxides. The presence of antiferroelectr-
icity was reported only for a member having an uneven number, namely for the n=5
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 67

Fig. 33. Inverse molar magnetic susceptibility c in low fields (H1000 G) versus temperature T of
miscellaneous compounds. To fit into this scale, the inverse susceptibilities of CaNb0.8Ti0.2O3.33 and
LaTi0.8Nb0.2O3.51 were multiplied with a factor of 0.07 and 0.3, respectively. The calculated molar suscepti-
bility of La0.5Ce0.5TiOX refers to X=3.40. The layers of the crystalline samples were aligned parallel to
the magnetic field. In parts of the temperature range a linear Curie- or CurieWeiss-like behavior appears,
which suggests the presence of localized paramagnetic moments like Ti3+, Nb4+ or Ce3+.

type compound SrNb0.8Ti0.2O3.40 (see Table 14). This different dielectric behavior
of the even and uneven series members seems to be a general feature. It calls for
more dielectric investigations on fully oxidized materials of the uneven n=5 type.
In this context, the question is raised for the dielectric properties of the fully oxidized
non-integer n=4.33 and n=4.5 type compounds. To the best of our knowledge they
are so far not known.
It is conspicuous that bulk compounds of the n=6 type are only known for quatern-
ary oxides (see Table 15), whereas bulk materials of the n=2, 4, 4.33, 4.5 and 5 type
occur also in ternary systems (see Tables 213).
Looking at Table 1 it is remarkable that bulk compounds of the RuddlesdenPopper
series Am+1BmO3m+1 are known up to m=3, whereas its AnBnO3n+2 type counterpart
begins its existence just at the next higher integer n=4 (m or n is the number of BO6
octahedra within a layer along the c-axis). Both series differ in the arrangement of the
corner-shared BO6 octahedra within the layers. Possibly, the particular arrangement in
compounds of the AnBnO3n+2 type allows the stability of thicker layers.

4. Summary and conclusion

In the work presented, perovskite-related layered AnBnO3n+2=ABOX type niobates


and titanates, in particular electrical conducting compounds, have been investigated.
It was known that these materials involve the following structural features:
68 F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170

the framework of the layers consists of distorted corner-shared BO6 octahedra


along the c-axis the layers are n BO6 octahedra thick
along the a-axis the BO6 octahedra are connected like a chain
there are non-integer n=4.5 and 4.33 type phases which represent thermodyn-
amically stable bulk compounds in which a well-ordered stacking sequence of
layers with different thickness is realized
the structure type n can be tuned by adjusting the oxygen content X

During this work more than 150 different compositions were prepared, many of
them as single crystals and with tight control of the oxygen content X. Hereby it
was found that single phase materials with many substitutions at the A and/or B site
are possible. Attempts to synthesize compounds with a structure type n beyond the
known types n=4, 4.33, 4.5, 5 and 6 were unsuccessful. For some of the known
structure types n, however, distinct non-stoichiometric homogeneity ranges with
respect to the oxygen content X and cation ratio A/B were found. Therefore, many
possibilities exist to vary the structural, physical and chemical properties in these
materials. In the course of this study, mixed-valence electrical conductors with a
formal charge carrier concentration of 0.3 electrons per B cation were prepared.
Resistivity measurements on single crystals of 8 different compositions along the a-,
b- and c-axis between T=300 K and T=4 K revealed

a highly anisotropic resistivity


a semiconductor-like temperature dependence of the resistivity along the b- and c-axis
a complex behavior of the resistivity along the a-axis involving quasi-1D metallic
conductivity and, at lower temperature, a metal-semiconductor transition
the temperature TMS at which the metal-semiconductor transition appears was
found to be in range from TMS50 K to TMS180 K
in parts of the temperature range the semiconductor-like resistivity seems to show
a thermally activated behavior, whereby the corresponding activation energies are
often very small, especially in the semiconducting state for TTMS, and vary from
0.5 to 58 meV

These compounds represent a new group of quasi-1D metals which offer many
possibilities to vary the structural, compositional and electronic properties. The com-
plex electronic features of these materials call for further studies, e.g. the clarification
of the origin and nature of the metal-semiconductor transition along the a-axis.
Of particular interest is the structural, compositional and electronical proximity
between the quasi-1D metals and (anti)ferroelectric compounds. Therefore, these
structurally and electronically low-dimensional oxides may have the potential to cre-
ate systems in which an intrinsic coexistence of high dielectric polarizability and
metallic conductivity can be realized.
F. Lichtenberg et al. / Progress in Solid State Chemistry 29 (2001) 170 69

Acknowledgements

We thank R. Schulz, C. Schneider, G. Hammerl, B. Goetz and S. Weigel for their


help, A. Reller and O. Becker for many interesting discussions and C. A. Kuntscher
for critically reading the manuscript. Furthermore we acknowledge fruitful collabor-
ations with C. A. Kuntscher, S. Schuppler, D.-H. Lu, B. Gorshunov, M. Dressel, H.
Schmalle, J. Hanss, N. Buttgen, H.-A. Krug von Nidda, J. Hemberger, V. Bobnar,
J.-E. Weber, C. Kegler and A. Loidl. This work was supported by the BMBF (project
number 13N6918/1).

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