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North-Holland
Cointercalation
M. Bianchetti,
in a ternary chalcogenide
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$%
e
3.9,8-s-s
% __
__..____
1% 3.5s-s
_____
Zn,\
-s
39 Ls-s
synthesis
lattice parameters
d (A).
ZnIn$,
lznW&
ZnIn,S.,
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
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,
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.
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
1 A-
119
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.
120
121
(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
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
(A31
122
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).
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-
fHzO+ZnInzS.,-+f02+H++ZnIn&
(I)
(II)
Acknowledgement
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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