Solid State Ionics 50 ( 1992) 115-l 23

North-Holland

Cointercalation
M. Bianchetti,

in a ternary chalcogenide

G. Herren , G. Lascalea and N.E. WalsSe de Reca

Program of Research in Solid State Physics, CONICET-CITEFA.

Zufriategui 4380, (1603) Villa Martelli, Buenos Aires, Argentina

Received 10 July 199 1; accepted for publication 9 August 199 1

The chalcogenide ZnInrS~ was obtained by transport in vapor phase employing iodine as transporting agent under the usual
conditions reported in technical literature and for the first time under anhidre conditions: [ZnIn,S,].+ Both layered compounds
were characterized by X-ray diffraction, scanning electron microscopy and Edax microprobe. Characteristic results of both compounds in dry air environment were compared with those obtained in humid air and in mixtures (of gaseous iodine+ humid air).
All experiments proved that gaseous iodine does not react with ZnIn,S, or [ZnIn,S,]A but, a possible intercalation process takes
place when the compounds are exposed to a mixture of (iodine+humid air). Evidences are shown to put aside an absorption
process. Refined parameters of the compounds obtained under usual and anhidre conditions as well as those of the intercalated
compounds were determined by X-ray diffractometry and Debye-Scherrer methods enabling the determination of the volume of
their primitive cells: V, ~443.21 A, V,=467.97 A3and V,=495.70 A.A new stable compound: I,(HzO),ZnIn,S,
(with x=0.55
at.% I2 and mz0.41 at.% HzO) was found at room temperature. Iodine deintercalation from the chalcogenide was performed by
heating and halogenide reintercalation was produced through a new exposure to humid iodine atmosphere. A possible mechanism
of cointercalation is discussed assuming the formation of a polar complex compound (I,H,O) + (ZnIn&) -, which stability could
be due to its ionicity. Electrical conductivity (a) was measured by different techniques. For the first time the effect of humid air
on the reported ZnIn#, was evaluated and data were discussed in comparison with other from literature . Low CJ
values of both
compounds in dry atmosphere [a= 1O- * S (cm)- ] increased to _ cr= 1O- S (cm)- in humid air and even more when compounds were exposed to a mixture of (gaseous iodine+ humid air). Results are discussed.

1. Introduction
The semiconductor chalcogenide ZnIn2$ with a
minimal band gap of 2.86 eV [ 1 ] exhibits a hexagonal cell with lattice parameters a=3.85,, 8, and
~=36.6~ A to 37.06 A [ 2-4 ] with N=3. It crystallizes with a layered structure and belongs to the spatial group R3m-C3,5 [2]. Its density of 4.83 g cm-3
[ 21 enabled to determine that the unit cell was built
up of three primitive cells, each one exhibiting the
following sequence: sulphur layers alternating with
zinc atoms occupying tetrahedral sites (Zn,), indium in octahedral (In,,) and in tetrahedral places
(Int). Otherwise, between the primitive cells there
are two sucessive sulphur layers with van der Waals
forces linking the identical slabs together, suggesting
a weak bonding and the cleaving of crystals parallel
Fundacidn Bunge & Born.
2 Author to whom all correspondence should be addressed.
Elsevier Science Publishers B.V.

to the basal plane. Fig. 1 shows a possible arrangement of octahedral and tetrahedral spaces with cations inside. In order to study the compound reaction
with gaseous iodine, previous experiments of characterization of the chalcogenide were rigorously
performed.
In the last few years ZnIn2S4 has been given much
attention both, from experimental and theoretical
points of view. In spite of that, the results of many
experiments show a considerable disagreement (for
example dc resistivity values) [5-l 11. This may be
due to the fact that data of experiments conditions
(surrounding atmosphere, humidity, light effect or
electrodes reaction with the compound) are not
specified.
The aim of this work was to grow the ternary chalcogenide ZnIn2S., by transport in vapor phase under
anhidre conditions and to compare its characterization results with those of the compound, which was
obtained by the same technique under the usual con-

116

_I!%
I ________
M. Bianchetti et al. / Cointercalation in a ternary chalcogenide

e_

___-

---_--

, *-\,

o-

.___-___---1Zf-y S-2.4
___

__-._--- f

__________

._______
._ __.__---I

7
Q

8,

_____
f s-s-3.7$%

2.2. Characterization of compounds

e
3.9,8-s-s
% __
__..____

1% 3.5s-s
_____
Zn,\

-s

39 Ls-s

Fig. 1. Sequence of sulphur atoms stacking is numbered from 1

to 4. The unit cell is indicated by I. On the upper part the average
diameter of octahedral and tetrahedral sites are reported (Zn,: 0,
In,:0 and In,-,:O). On the lower part the average distance between sulphur layers are shown.

ditions reported by literature. The humidity effect

on the reaction of both compounds with gaseous iodine was evaluated. Structural and electrical changes
of compounds, which were exposed to different environmental media have been reported and clear evidences of a high chemical reactivity of compounds
with the humidity of the surrounding atmosphere (at
room temperature) are given.

2. Materials and methods

2.1. ZnIn_& and [ZnZn$&

In& and ZnS, cooled in liquid nitrogen and closed

in the dry-box while connected to a vacuum
line(10-6/10-7
Hg mm) [17]. Growth was performed in the same temperature gradient as reported
in literature [ 2,3]. Ampoules were open in the dry
box separating crystals in hermetically closed containers to be analyzed with X-ray diffraction (XRD)
or with the electron microprobe (EMP).

synthesis

Transport in vapor phase from a stoichiometric

mixture of It& and ZnS [ 2,3] in a temperature gradient from 1000 to 700C was performed employing
iodine as the transporting agent.
Several researchers found retained iodine in the
ZnIn& crystals [ 12- 15 1. We detected in our crystals [ lo] an iodine concentration of 10 to 100 ppm
employing spark source mass spectroscopy.
The chalcogenide was also obtained by vapor phase
transport (with Iz) under anhidre conditions
( [ ZnIn2Sb]A) working in a dry-box with controlled
humidity (c 1W). The ampoules were tilled with

2.2.1. X-ray diiaction

Powder patterns were obtained with a microfocus

Rigaku-Denki generator and diffractometry was
performed in a Philips Electronic Inc. equipment. In
both experiments, the Cu Ka, Ni filtered radiation
was employed. A&O3 powder was used as reference
material.
The lattice parameters d(A) of both compounds
were determined by both techniques and data are reported in table 1. Data corresponding to ZnIn,S, are
in agreement with those of the stoichiometric compound which is stable at ambient atmosphere and
room temperature as reported in JCPDS Card Ner.
24-1449 [ 181 in which experiment conditions are
not specified. Data corresponding to [ZnIn&]A
agree neither with ZnIn&, data nor with those belonging to the other ternary chalcogenides reported
by JCPDS Cards.
2.2.2. Scanning electron microscopy (SEM)
SEM micrographs were obtained with a 505 Philips microscope in the secondary electron mode. Fig.
2a (M= 370 x ) shows as grown ZnIr& crystals and
fig. 2b (M= 13000x ) a detail of the layered
structure.
Direct observation of [ZnIn,S,]A did not reveal
differences in colour or aspect when compared with
ZnIr&, crystals. SEM observations revealed that
both kinds of crystals were similar in size and aspect.
Fig. 2c shows the layered structure of [ZnIn$S,]A
(M= 13000x).
In order to perform the electrical conductivity (a)
measurements, crystals were pressed in cylindric pellets. SEM observations enabled to conclude that in
pressed specimens the crystals were ordered with
their basal plane (00.1) normal to the compression
axis. In SEM experiments the acelerating voltage of

M. Bianchetti et al. / Cointercalation in a ternary chalcogenide

Table 1
Comparative

lattice parameters

d (A).

ZnIn$,

lznW&

ZnIn,S.,

JCPDS Nbr. 24-l 449

Debye-Scherrer

Debye-Scherrer

Difractom.

d(A)

III0

hkl

12.2

30

4.10
3.34
3.286
3.148
3.049
2.827
2.709
2.484
2.467
2.371
2.168
2.072
2.053
1.932
1.904
1.821
1.765
1.749

100
50
30
80
20
10
80
20
20
10
80
30
40
70
10
80
30
40

(this work)

IAIWLZnIn&

d(A)

III0

d(A)

III0

d(A)

003

3.860

12.2

vw

12.2

009
101
012
104
015
107
018
IO&l
oou
OlU
lOl_3
0114
002
110
lo&
OlZ
0021
119

3.172
2.804
2.580
2.398
2.154
2.045
1.930
1.759
1.727
1.407
1.2998
1.1144

w
w
w
w
m
m
m
m
m
w
vw
w

a) Difficult to be measured;

117

b, (003) peak disappeared.

4.09
3.36
3.11
2.712
2.160
2.062
1.920
1.811
1.750

s
m
m
w
w
w
m
m
m

4.08
3.32
3.229
3.135
2.704
2.460
2.263
2.164
2.116
2.066
2.052
1.982
1.928
1.857
1.819
1.757
1.754
1,746

s= strong, m =medium,

electron beam was kept at 25 kV to avoid damage of

specimens.

2.2.3. Edax Microprobe (EMP)

The quantitative analysis (QUANT program) with
the EMP confirmed that both compounds had the
same composition ZnIn& within the EMP error. Fig.
3a shows a concentration curve (CPS versus E) of
ZnIn& where CPS is the number of counts per second of the X-ray radiation emitted by the specimen
and E are the energy values of the X-ray characteristic peaks of the analyzed elements. Analogous concentration curves were obtained for [ ZnIn,S,] A because this analysis cannot discriminate a possible
water content of the chalcogenide.
The above-described techniques were carried out
on coarse crystals ( N 0.3 to 0.5 cm diameter) and on
pressed polycrystalline specimens.

Debye-Scherrer
III0

d(A)

8)

s
m
w
m
w
w
w
w
w
w
m
w
w
vw
w
m
w
w

4.05
2.030
1.842
0.742
1.368
1.305
1.236

w= weak,

VW =

III0

Difractom.

d(A)

III0

b)
S

s
m
m
m
m
m

3.39
3.162
3.103
3.076
3.006
2.847
2.794
2.769
2.605
2.520
2.187
2.079
1.863
1.720

m
w
vw
w
w
WV
vw
vw
vw
vw
w
w
vw

very weak.

2.2.4. Electrical dc conductivity

The electrical conductivity Q (S cm- ) was evaluated through the resistance R (L2) measurements.
Specimens were obtained as follows:
(a) On a substrate of alumina (electronic purity)
two Ag.Pd contacts were cut by photolitography, two
platinum electrodes were evaporated on them and a
thin deposit of ZnIn&, in an ethanol paste was
printed (by serigraphic method) and dried between
electrodes. The whole circuit was tailored with a
computer (Smart-work program).
(b) Cylindrical pressed (1000 to 1625 kg. cme2)
polycrystalline specimens of ( 1.28 f 0.02) cm of diameter and (0.076 + 0.010) cm thick were employed. Attempts were made to perform measurements on single crystals but, in spite of being coarse,
crystals were thin and fragile to set good contacts.
In order to measure the electrical resistance (R)
the following techniques were used:
( 1) R was calculated from the difference of electrical potential (AV) between a standard resistance

118

M. Bianchetti et al. / Cointercalation in a ternary chalcogenide

(5 x 10 Q) and the specimen as measured with a

power source (HP 62 12 A) employing a value of 100
V.
(2 ) R was measured employing a high impedance
electrometer (6 16 Keithley ).
(3) R was evaluated with a HP 4329 A high
impedance resistance meter.
ZnIn& specimens were characterized by the above
described techniques, before and after being exposed
to the effect of different atmospheres.
2.3. Controlled atmosphere cell
Specimens were introduced in a glass hermetically
sealed cell (fig. 4) able to be employed with dried or
humid air atmosphere and with the possibility of
adding iodine vapor. The cell enabled to introduce
a thermal sensor (25 Fluke digital thermometer)
and
electrical leads and it was thermostated
in a 4KR
Lauda thermostat. In order to avoid light effect on
measurements
the cell was conveniently
protected.

3. Results and discussion

3.1. Identification of compounds
Table 1 reports the X-ray diffraction values of lattice parameters
(A) measured by Debye-Scherrer
and diffractometry
methods and intensities
ratio
(Z/Z,) as evaluated on pure ZnIn,S, and [ZnIn&]A
crystals at ambient atmosphere in this work.
3.2. Polycrystalline specimens in dry air
3.2. I. dc resistivity measurements
The dark dc resistivity p of ZnIn,S, in dry air atmosphere (employing silica gel as drying agent) was
measured giving a value of lOI S2 cm at (20 + 1) C
in agreement with the p value corresponding
to
[ZnIn2&

Ftg. 2. SEM mlcrographs ot chalcogemde crystals: (a) as grown

ZnIn&
(M=370x ); (b) lamellar structure of ZnIn&
(M= 13000x ); (c) lamellar structure of [ZnIn2S,]A
(M= 13000x).

1 A-

In order to evaluate the gaseous iodine effect on

both compounds,
an open little container with iodine crystals was introduced into the glass cell during
times ranging from 24 to 48 h. The other parameters
were kept constant and a drying agent (silica gel)
was employed to avoid humidity effect.
ZnIn,S, and [ZnIn,S,],
crystals did not change

119

M. Bianchetti et al. / Cointercalation in a ternary chalcogenide

In

Zn

0
.r
s

Fig. 3. Edax concentration curves CPS versus E (all the specimens belonging to the same batch): (a) ZnInxS, specimen exposed to the
air surrounding or environmental atmosphere; (b) ZnIn& specimen exposed to (iodine + dry air) 48 h with drying agent. T= (2 1k 1) C;
(c) ZnIt& specimen exposed to (iodine+air) 48 h without drying agent. T= (2Ok 1) C; (d) ZnIn& specimen exposed to (iodine+humidair)
48 h. T= (20f I)C, (e) I,,5,ZnIn&, afterbeing heated 18 min at - 180C; (f ) the same specimen of 3e after being
exposed 15 min to (iodine+air) without dryingagent at T= (20+ 1)C.

their original yellow colour. The resistivity values for

these specimens showed no significant differences in
comparison with those measured without gaseous iodine in dry air atmosphere at the same temperature.
3.2.2. SEM and EMP experiments
ZnIn,S, and [ ZnIn,S,]
specimens (previously
exposed to gaseous iodine in dry air atmosphere)
were observed by SEM exhibiting no changes in
comparison with those of the compounds without
exposure to iodine. A tipical EMP concentration
curve (CPS versus E) is shown in fig. 3b. Considering that EMP information is sampled from a depth
of several micrometers and in order to prove that it
was not an absorption process, crystals were broken
and immediately analyzed on their inner part to assure a real bulk analysis.
A

3.3. Specimens in humid air atmosphere

3.3.1. dc resistivity measurement

Sets of ZnIn& and [ZnIn,S,]A specimens were

exposed to (iodine+air) without drying agent during 48 h at (25+ 1)C.
Another sets of specimens were exposed to humid
air atmosphere, water vapor pressure of (2493 + 133 )
Pa at (2 1 f 1) C and dark dc resistivity was evaluated. If gaseous iodine was employed at the same
conditions, the resistivity decreased and it was stabilized after 40 min. In both cases, yellow crystals
turned to dark orange colour. Single crystals were
then broken and the reddish colour was not restricted to the surface or to a thin zone underneath
but it was homogeneously extended all over the crystal bulk. The resulting resistivity was of 10 f2 cm in

120

M. Bianchettiet al. / Cointercalationin a ternarychalcogenide

dine+ humid air). The curve 3d is CPS of ZnIn&

after this treatment for 48 h. In spite of observing in
both types of specimens that sharp edges of layers
became slightly rounded and that surfaces looked
rougher in comparison with as-grown crystals, we
could not assign these facts to a chemical etching by
HI (generated by I* reaction with humid
atmosphere ) :
(i) Fig. 5a (M=37x)
and 5b (M=13000X)
correspond to the same zone of fig. 2a and 2b after
exposition of ZnIn& crystals to (iodine (g ) + humid
air) and corrosion pitting is not observed;
(ii) wetting of specimen surface during the experiments was not observed;

Fig. 4. Glass cell to measure the electrical resistance; leads of the

digital thermometer pass through A and leads of specimen through
B.

humid atmosphere and of 1O6Q cm when iodine was

added to humid air. In both cases, it was not possible
to separate the contribution due to the resistivity of
specimen bulk from that of the humidity film lying
on surfaces which were exposed to the atmosphere.
3.3.2. SEM and EMP experiments
Sets of the above described specimens (see section
3.3.1. ) were observed by SEM, finding no significant
structural changes in case of ZnIn&, and
[ ZnIn& IA exposed to (iodine + air) without drying
agent but the CPS =f( E) revealed the iodine presence. Fig. 3c is a typical curve for ZnIn&. EMP
quantitative analysis after a little iodine loss, probably due to desorption, revealed a new compound,
with the composition Io.55ZnIn&. If the experiment
was repeated with [ ZnIn&] A the same final result
was reached after six- or seven-times longer periods
of exposure to (iodine+air), without drying agent.
The next set of experiments considered the exposure of specimens to a mixture of (gaseous io-

Fig. 5. SEM micrographs of ZnIn& crystals after being exposed

to (iodine+humid
air) during 48 h. T=(Zl+l)C:
(a)
(M=370x) and (b) (M=13OOOX).

121

M. Bianchettiet al. / Cointercalationin a ternarychalcogenide

(iii) a simple experiment was performed to produce corrosion: few drops of diluted iodine solution
in destilled water were sprayed on crystal surface.
Specimens were left for 24 h in open glass cell at
and 6b
(21 &l)C.
Fig. 6a (M= 1440x)
(M= 1440x ) show crystals before and after this
treatment and corrosion effects can be easily observed in fig. 6b.
Fig. 3e shows the CPS=j(E) curve for the same
specimen of fig. 3d after heating it for 18 min at
u 180 C. Iodine could not be detected by EMP. The
resulting ZnIn& was exposed to (gaseous iodine+air) without drying agent for 15 min and an
iodine concentration fo 1.27 wt% was evaluated (fig.
3f). Assuming that EMP was informing of surfaceconcentration, the experiment was repeated after exposition specimens for 70 min at (iodine (g) +air)
and performing the analysis on broken single crystals.
3.3.3. X-ray diflraction
Diffi-actometry and Debye-Scherrer methods were
employed to analyze ZnIn,S, and [ZnIn&],
after
their exposure to (gaseous iodine+air) without a
drying agent for different periods. Final values of refined lattice parameters [ 19,201 of both types of
specimens were coincidental within the determination error and they are reported in table 1. In both
cases, the peak corresponding to the family of planes
with d= 12.2 A was not observed by diffractometry.
In table 2, the obtained refined parameters of pure
[ ZnInzS,], (a,, cl ) and ZnIn& (az, c2) and those
of both intercalated materials (as, c3) are reported.
The volumes of the primitive cells ( V,, V, and V3)
are also given. In the initial lamellar compound inTable 2
Refined parameters

Fig. 6. (a) SEM micrograph of ZnIn,S, crystal with sprayed drops

of iodine solution in distilled water (M= 1440x ); (b) SEM micrograph of the same specimen as (a) after an exposure of 24 h
at (21 k 1) C to air surrounding atmosphere. Corrosion is
observed.

(A) and unit cell volume (A).

(A)

Compound

Refined parameters

pure [ZnIn,S,IA

a, = 3.8 1, + 0.008
c, = 36.48 f 0.02
c,=c,/N=12.16
(N=3)

V, =443.26

pure ZnInsS,

az=3.84,k0.008
c,=36.63&0.02
c,=c,/N= 12.21 (N=3)

V,=461.97

a3=3.933f0.008
c,=37.58f0.04
c3=c2/N= 12.52 (N=3)

V,=495.?0

Unit cell vohtme

(A31

M. Bianchetti et al. / Cointercaiation in a ternary chalcogenide

122

tercalation produces an expansion of primitive cell

fundamentally along c-axis. V, differs from V, in a
10.57% and from V2in 5.59% justifying the swelling
produced by intercalation.
3.3.4. Relative conductivity data (a&j
The variation of the relative conductivity (o/a,,)
versus time (minutes) and taking as reference the
conductivity a0 value of ZnInzS, after exposing it to
an atmosphere of (gaseous iodine+ humid air) is
shown in fig. 7. The following, different working
conditions were taken into account to evaluate the

I
*

Lil

I
0

t (min)

50

100

150

I
XXI

Fig. 7. Relative conductivity (a/~) variation versus time (minutes), measurements are refered to, which is the conductivity of
ZnIn& in (iodine+humid air): (--)
ZnIn& in dry air;
( - - - ) ZnIn& in (iodine+dry air); ( + + + ) ZnIn,S, in
humid air; (0) ZnIn& in (iodine+humid air); (...) substrate
and leads in humid air; (*) substrate and leads in (iodine
(g)+humidair).

relative conductivity of the compounds: exposition

to dry air; (iodine (g ) + dry air), humid air and (iodine (g) + humid air). Besides, substrate and leads
contributions after exposure to humid air and to
(iodine (g) + humid air) were also considered,

4. Conclusions
For the first time the chalcogenide [ZnIn&], was
grown (by iodine transport in vapor phase) and
identified under anhydrous conditions and the structural and electrical characterization data were compared with those of ZnIn$, grown by the same technique under the usual conditions reported in
literature [ 2,3 1. Lattice parameters of [ ZnIn,S,] A
do not coincide with those of ZnIn& (or with those
belonging to the other ternary chalcogenides reported by JCPDS Cards). Refined lattice parameters of both compounds enable to determine a volume expansion of the ZnIn& primitive cell of 5.57%
in comparison with that of [ZnIn&],,
supporting
the assumption that the first compound had already
incorporated water. Size, colour and aspect of
[ ZnIn,S,], and ZnIn& single crystals were quite
similar and the same composition was found for both
compounds as determined within the EMP limitation. Broken single crystals were analyzed with EPA
to avoid determination of surface composition. Several facts suggest that the reaction of [ ZnIn&], and
ZnIn& with the mixture (gaseous iodine+humid
air) may be considered an intercalation process:
(i) both compounds are semiconductors with layered structure;
(ii) lattice parameters variation was observed by
X-ray diffraction and a volume expansion of primitive cells was found;
(iii) changes of composition within the limitations of EMP were determined;
(iv) a homogeneous change of colour from yellow
to dark orange was observed in the bulk of freshly
broken single crystals;
(v) a variation of conductivity was measured;
(vi) the reversibility of iodine reaction was suggested by EMP analysis after heating treatments and
new exposures of specimens to (iodine (g ) + humid
air).
Iodine can be intercalated in the van der Waals va-

M. Bianchettiet al. / Cointercalationin a ternarychalcogenide

cancy of the chalcogenide. Weak S-S bondings would

require an intercalation activation energy relatively
low and the process could occur easily with intercalate nucleophiles agents. Schijlhorn [ 2 1 ] showed
that nucleophiles like OH- or RSOz could be intercalated in binary chalcogenides even at room temperature. To our knowledge the iodine intercalation
was not yet investigated in ternary chalcogenides.
Experiments of structural and electrical characterization of both compounds showed that iodine does
not intercalate directly. Then the formula of the new
could
be better
expressed
by
compound
I0.ss( HzO),,,,ZnInzS, than by 10.,,ZnIn& Iodine
intercalation seems to be induced by the previous
water reaction with the chalcogenide. It was alreadyshown that water traces may considerably alter the
stability, structure and properties of intercalated
compounds and processes of cointercalation as well
as redox reaction between guest and host species are
possible [ 22,23 1.
A possible mechanism includes previous redox reactions of the 02/Hz0 and ZnIn2S4/ZnIn& couples:
jHzO-+tOz+H++e-,
ZnIn$,+e--,ZnIn&

fHzO+ZnInzS.,-+f02+H++ZnIn&

(I)

and, subsequently, an ( Iz + HzO) solvation reaction:

12+Hz0+H++I,(H,0)+

(II)

yielding (I) and (II) a polar compound

(I,H,O) + (ZnI$, ) - whose stability can be related
to its ionicity. Acrivos et al. [ 241 employing the absolute reaction rate theory explained the intercalation of molecular gaseous species (like NH3 and
H2H4) in TaS*, suggesting also the formation of molecular complexes [ 25,261.

Acknowledgement

We are indebted to CONICET (National Council

for Scientific and Technological Research) for the
Grant No. 3-9135-01-85 given to one of us

123

(N.E. Walsoe de Reca) and to Dr. R. Brec of the Laboratoire de Chimie des Solides, IPCM, Universite
de Nantes for his valuable discussion of the manuscript. Thanks are given to Dra. P. Perazzo and to
Miss G. Padula for their assistance in X-ray diffractometry and in the photographic laboratory.
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