Chemical interaction of indium arsenide and gallium antimonide with sulfur

Article abstract of DOI:10.1023/A:1022657020529

The reactions of fine-particle indium arsenide and gallium antimonide with sulfur and the composition of the reaction products obtained from different starting mixtures were studied by differential thermal analysis, x-ray diffraction, chemical analysis, and IR spectroscopy. The reaction between indium arsenide and sulfur begins at lower temperatures in comparison with gallium antimonide, is autocatalyzed, and yields In₂S₃ and As ₂S₃. The reaction between gallium antimonide and sulfur yields Ga₂S₃, Sb₂S₃, and (GaS) ₂. Thermolysis of the resultant sulfide mixtures ensures a more complete separation of the sulfides in the case of indium arsenide.

Full text of DOI:10.1023/A:1022657020529

Inorganic Materials, Vol. 39, No. 3, 2003, pp. 215–219. Translated from Neorganicheskie Materialy, Vol. 39, No. 3, 2003, pp. 276–281.
Original Russian Text Copyright © 2003 by Kompanichenko, Omel’chuk, Kozin.
Chemical Interaction of Indium Arsenide
and Gallium Antimonide with Sulfur
N. M. Kompanichenko, A. A. Omel’chuk, and V. F. Kozin
Vernadsky Institute of General and Inorganic Chemistry, National Academy of Sciences of Ukraine,
pr. Akademika Palladina 32/34, Kiev-142, 03680 Ukraine
e-mail: omelchuk@ionc.kar.net
Received February 7, 2002; in final form, May 23, 2002
Abstract—The reactions of fine-particle indium arsenide and gallium antimonide with sulfur and the compo-
sition of the reaction products obtained from different starting mixtures were studied by differential thermal
analysis, x-ray diffraction, chemical analysis, and IR spectroscopy. The reaction between indium arsenide and
sulfur begins at lower temperatures in comparison with gallium antimonide, is autocatalyzed, and yields In2S3
and As S . The reaction between gallium antimonide and sulfur yields Ga S , Sb S , and (GaS) . Thermolysis
2
3
2
3
2
3
2
of the resultant sulfide mixtures ensures a more complete separation of the sulfides in the case of indium ars-
enide.
INTRODUCTION
tives. There has been less work devoted to the effects of
the oxidation conditions and starting-mixture composi-
tion on the decomposition of fine-particle powders and
the composition of the reaction products.
III–V compounds, in particular InAs and GaSb, are
widely used in semiconductor technology and opto-
electronics [1–3]. The world market for these materials
is increasing every year. In this context, not only
advanced techniques for manufacturing these semicon- of fine-particle indium arsenide and gallium anti-
ductors but also effective, economically viable pro- monide powders with sulfur by differential thermal
The objective of this work was to study the reactions
cesses for InAs and GaSb waste processing are needed
because, in the production of high-tech semiconductor
devices, a large percentage (above 50%) of high-purity
indium- and gallium-containing materials goes to
waste, which may contain as much as 49–78% In or Ga,
whereas their content in natural raw materials does not
exceed tenths of a percent. Therefore, the study of reac-
tions which might underlie novel processes for InAs
and GaSb waste processing is of great practical impor-
tance.
analysis (DTA), x-ray diffraction (XRD), chemical
analysis, and IR spectroscopy.
EXPERIMENTAL
The starting materials used were fine-particle
≤0.5 mm) semiconductor-grade indium arsenide and
(
gallium antimonide and extrapure-grade sulfur. Reac-
tions were run in Stepanov vessels sealed under vac-
uum or open. Vacuum thermolysis was performed in
silica tubes 20–25 cm in length and 0.6–0.7 cm in diam-
eter. DTA curves were recorded using Pt/Pt–Rh ther-
mocouples and KSP-4 and EZ-5 potentiometers or a
PDA-1 XY recorder. As the reference substance, we
used calcined alumina. The composition of reaction
products was determined by chemical analysis, XRD,
and IR spectroscopy using standard techniques. Indium
and gallium were determined by chelatometric titration
with Trilon B or 1-(2-pyridylazo)-2-naphthol after dis-
solving the sample in a mixture of hydrochloric and
nitric acids and precipitating metal hydroxides. Arsenic
was determined by atomic absorption. Sulfur was
InAs and GaSb waste processing via dissolution in
mineral acids and their mixtures with various additives
is accompanied either by the formation of highly toxic
Group V hydrides or by the surface passivation of the
dissolving compound [4–6]. For this reason, this pro-
cess requires a rather long time and is environmentally
hazardous.
III–V compounds are known to react with atmo-
spheric oxygen and sulfur [4, 7–10] to form, for the
most part, oxides or sulfides of the constituent ele-
ments. The reaction products can be used to recover
Group III and V elements from manufacturing waste.
The oxidation mechanisms and kinetics of III–V determined by dissolving the sample in carbon tetra-
compounds have been studied in great detail [4, 7–10], chloride with bromine, followed by barium sulfate pre-
but attention has been paid mainly to the surface oxida- cipitation. Antimony was determined by the permanga-
tion of single crystals and the formation of dielectric nate method. XRD measurements were carried out on a
layers on their surfaces in the presence of various addi- DRON-UM powder diffractometer (CuK radiation).
α
0
020-1685/03/3903-0215$25.00 © 2003 MAIK “Nauka/Interperiodica”

2
16
KOMPANICHENKO et al.
3
80
starting mixtures containing ≤66 mol % S show one
large exotherm (Fig. 1, curve 3).
At 75–85 mol % S, the DTA curve shows two exo-
thermic peaks (Fig. 1, curve 1). To identify these ther-
mal events, we examined the formation of indium sul-
fide, which is the product of the reaction between InAs
and S.
6
25
5
50
In the course of elemental In S synthesis, DTA also
2
3
shows two exothermic events, one of which (360–
4
40°C) is close in position to the lower temperature event
in the reaction of InAs with S (Fig. 1, curves 1–3). The
temperature of the second event (600–625°C) is higher
than that in the reaction of InAs with S (500–550°C),
presumably because the reactions of both In and InAs
with S are accompanied by the formation of lower
indium sulfides (first exothermic event). It is well
known [11] that the reaction between indium and sulfur
4
40
1 112
7
00
1
56
2
3
1
20
4
at 450°C yields In S. In the presence of excess sulfur,
2
In S converts to In S (second exothermic event). The
2
2 3
likely reason for the reduction in the temperature of the
second exothermic event is that several reactions
between arsenic and sulfur occur in parallel. In the
InAs–S system, in addition to the reactions
1
00 200 300 400 500 600 700
t, °C
Fig. 1. DTA curves illustrating reactions in (1) 4 : 1,
2) 3 : 2, and (3) 2 : 1 mixtures of S and InAs; (4) heating
(
curve of reaction products in a 4 : 1 mixture of S and InAs
in air.
2InAs + 4S
InS + 2S
the following reversible reaction is possible:
As S + 2S As S .
In S + As S ,
(1)
(2)
2
2 3
In S ,
2
3
IR spectra were taken on a Specord-80M spectropho-
tometer using the KBr disk method.
(3)
2
3
2 5
RESULTS AND DISCUSSION
Above 500°C, reaction (3) yields As S and sulfur,
2
3
which exhibits a higher reactivity with In S just after
2
The phase compositions of the reaction products
obtained at different starting-mixture compositions are
summarized in the table.
liberation as compared to polymerized sulfur. Thus, the
arsenic sulfides resulting from reactions (1) and (3) act
as a sort of catalyst for the conversion of lower to higher
The reaction between indium arsenide and sulfur indium sulfides, reducing the reaction temperature by
begins in the range 330–400°C. The DTA curves of the 75–100°C.
Phase composition of reaction products according to DTA and XRD results
Thermal events, °C
Final reaction
temperature, °C
Phase composition
of the products
Starting mixture
EXO
ENDO
2
2
3
4
6
S + InAs
S + InAs
S + InAs
S + InAs
S + InAs
330–390
330–390
112, 120
112, 120
480
780
680
750
680
720
730
730
β-In S , InAs
2 3
β-In S , InAs(traces)
2
3
340–380
112, 120
β-In S , γ-In S , InAs(traces)
2
3
2
3
340–380, 500–550
330–380, 500–550
380–440
112, 120
γ-In S , β-In S
2 3 2
3
112, 120
γ-In S , In As S + S
2 3 2 – x x 3
S + GaSb
112, 120, 490, 590, 712
112, 120, 590, 712
112, 120, 712
GaSb, (GaS)2
GaSb, Ga S , (GaS)
2
3
S + GaSb
S + GaSb
380–440
2
3
6
380–440, 560
Ga S , Sb S , (GaS) , S, GaSb
2 3 2 3 2
INORGANIC MATERIALS Vol. 39 No. 3 2003

CHEMICAL INTERACTION OF INDIUM ARSENIDE AND GALLIUM ANTIMONIDE
217
According to XRD results, at S : InAs molar ratios
no greater than 2.0, the reaction products consist
mainly of β-In S and unreacted InAs. At S : InAs =
2
3
3
.0, the reaction yields both β- and γ-In S .
2 3
Solid solutions based on β-In S or InAs were not
2
3
1
detected. The lattice parameters of cubic InAs (a =
6
.0528 Å) and cubic In S (a = 10.74–10.726 Å) were
2
3
2
somewhat smaller than those reported earlier (a =
6
.0584 Å for InAs [1] and a = 10.77 Å for In S [12]).
2
3
Lower indium and arsenic sulfides were missing
3
according to XRD results. As S also could not be
2
3
detected, presumably because this phase was x-ray
amorphous.
4
If the starting mixture contains an excess of sulfur
(
80–86 mol %) relative to the stoichiometry of reaction (2),
γ-In2S3 or a solid solution based on this phase
In2 − xAs S ) is formed [12]. Also possible is the forma-
(
x
3
5
tion of indium sulfoarsenide, (InAs S ) [13]. Since
2
4 2
γ-In S , In As S , and (InAs S ) crystallize in the
2
3
2 – x
x
3
2 4 2
same structure and are close in lattice parameters (a =
3
.80–3.81 Å, c = 9.04–9.09 Å) [12, 13], the reaction
products could not be identified with certainty by XRD.
The lattice parameters of the reaction product in the
mixture with S : InAs = 4.0 were a = 3.78–3.80 Å and
c = 9.039–9.040 Å.
Heating a mixture with S : InAs = 4.0–6.0 from room
2
00
300
400
500
600
700
temperature to 700–750°C at 10–11°C/min ensures a 95–
Wavenumber, cm–1
9
8% conversion.
According to Kamsu Kom [13], indium sulfoars-
Fig. 2. IR absorption spectra of (1) reaction products in a
: 1 mixture of S and InAs, (2)As S , (3) reaction products
4
enides decompose above 300°C, and the resulting
arsenic sulfide sublimes. Our results demonstrate that,
during vacuum thermolysis of the products of InAs sul-
furization, As S sublimation begins at 330°C. Vacuum
2 3
in a 3 : 1 mixture of S and InAs, (4) the above reaction prod-
ucts after heating to 750°C in vacuum, and (5) In S .
2
3
2
3
thermolysis at 580–700°C for 0.5–1.0 h was performed
using 0.2- to 1.5-g samples obtained by reacting indium
arsenide and sulfur. The S : InAs ratio in the reaction
mixture was varied from 4.0 to 6.0. Chemical analysis
peak at 690–700°C in the DTA curve of this process
Fig. 1, curve 4) is attributable to In O formation. Note
(
2
3
that In S and As S oxidation is accompanied by
2
3
2 3
of the thermolysis products showed that, in the temper- vaporization of these compounds [8, 10, 17, 18].
ature range 450–580°C, the degree of As S sublima-
2
3
Thus, after As S sublimation, the product of reac-
2
3
tion was 95–97%. The residual As S content of the
2
3
tion between InAs and S consists almost entirely of
indium sulfide, which can readily be converted into
indium oxide for the preparation of high-purity indium.
thermolysis products obtained at 650–700°C did not
exceed 0.2–0.5 mol %.
The same is evidenced by the IR spectra and XRD
analysis of the products of InAs decomposition before
The reaction between gallium antimonide and sulfur
and after thermolysis. Before heat treatment, the stron- proceeds in a different manner. The initial reaction tem-
gest band in the IR spectrum of the products of the reac- perature (380°C) is somewhat higher than that in the
–1
tion between InAs and S was the one at 310–320 cm , instance of indium arsenide (Fig. 3, curves 1, 2). At
characteristic of arsenic sulfide [14]. After heat treatment, S : GaSb molar ratios from 1 to 3, the DTA curves show
–1
only the band characteristic of In S (325–335 cm ) was only one exothermic event. The main reaction products
2
3
are (GaS) and a small amount of Ga S . At S : GaSb =
present [15] (Fig. 2). The XRD patterns of the heat-
treated samples also showed reflections from In2S3 6.0, the exotherm extends to 560–600°C (Fig. 4, curve 1),
only.
which can be accounted for by the formation of Ga
Sb S , and Sb S . The endotherm due to Sb S melting
2
2 3
S ,
2 3
It is well known [11, 16] that indium sulfide oxi-
2
3
2
5
2 3
(546°C) is missing, which points to the reaction
dizes in air starting at 350–400°C with the formation of
indium sulfate and indium oxide. Above 700°C, the
main oxidation product is In O [11]. The endothermic
Sb S + 2S Sb S .
(4)
2
3
2
3
2 5
INORGANIC MATERIALS Vol. 39 No. 3 2003

2
18
KOMPANICHENKO et al.
4
40
4
60
5
60
6
1
12
1
2
00
4
00
7
12
1
20
1
1
20
6
00
5
90
120
3
80
2
4
90
480
3
1
12
4
40
1
20
7
12
1
00
300
500
700 t, °C
1
00 200 300 400 500 600 700 t, °C
Fig. 4. DTA curves illustrating reactions in a 6 : 1 mixture
of S and GaSb: (1) first, (2) second, and (3) third heating
cycles.
Fig. 3. DTA curves illustrating reactions in (1) 1 : 1 and
2) 3 : 1 mixtures of S and GaSb.
(
Note that, if the amount of sulfur is sufficient for sulfides convert to oxides, which are enriched in Ga
Ga S and Sb S formation (S : GaSb = 3.0–6.0), the (50–53 wt % against 20–25 wt % in the starting sample)
2
3
2 3
reaction products contain (GaS) and unreacted GaSb, owing to Sb O vaporization, as evidenced by chemical
2
2
3
as evidenced by the endotherm at 712°C due to GaSb analysis and IR spectroscopy data (Fig. 5, curve 3). The
melting (Figs. 3, 4). In the case of the mixture with IR spectrum of the resultant material contains bands
S : GaSb = 6.0, this endotherm disappears only upon characteristic of Ga O , Sb O , Sb O , and Sb O [14],
2
3
2
3
2
4
2
5
threefold heating to 800°C, although visual examina-
tion indicates that the reaction products are inhomoge-
neous. According to XRD results, they consist of
Ga S , Sb S , (GaS) , S, and trace levels of GaSb
in agreement with XRD data.
2
3
2
3
2
(
table). The IR spectra (Fig. 5, spectra 1, 2) show
absorption bands characteristic of (GaS) and Ga S
2
2 3
1
–1
420
(290, 315, 350–370, and 420 cm ) and a weak feature
2
90
–1
due to antimony sulfide (400 cm ). Our results coincide
with earlier data [15].
3
15
Thus, our findings demonstrate that, just as GaSb–
Se [19], the GaSb–S system is not pseudobinary.
3
4
70
00
After heating a 2-g reaction mixture from room tem-
perature to 730°C at a rate of 10–11°C/min, the conver-
sion of GaSb to Group III and V sulfides is no greater
than 80–82%. Annealing in a sealed tube at 800°C for
2
3
50
4
20
612
635
3
1
.5 h ensures a conversion of up to 93–95%.
7
50
In contrast to the InAs–S system, vacuum thermoly-
sis of the reaction products in the GaSb–S system at
temperatures below 700–750°C does not ensure com-
plete separation of the sulfides formed. Even after long-
term (3–5 h) heating in vacuum at 750°C, the fraction
of sublimed antimony sulfide does not exceed 5%.
According to Novoselova and Pashinkin [18], Sb2S3
sublimation begins at 650°C; at 750°C, the Sb S vapor
310
700
3
00
400
500
600
700
800
Wavenumber, cm–1
2
3
pressure is as low as 787 Pa. Therefore, a higher tem-
perature is needed to vaporize this compound. In the
course of heating to 700°C in air, antimony and gallium
Fig. 5. IR absorption spectra of reaction products in (1) 3 : 1
and (2) 6 : 1 mixtures of S and GaSb and (3) a 6 : 1 mixture
after air oxidation at 750°C.
INORGANIC MATERIALS Vol. 39 No. 3 2003

CHEMICAL INTERACTION OF INDIUM ARSENIDE AND GALLIUM ANTIMONIDE
219
CONCLUSIONS
vol. 36, no. 2, pp. 153–156 [Inorg. Mater. (Engl.
Transl.), vol. 36, no. 2, pp. 105–107].
We determined the conditions for the reactions of
fine-particle indium arsenide and gallium antimonide
with sulfur and the composition of the reaction products.
6
7
. Sharlton Thomas, L. and Redden Robeunt, F., US Patent
4
094753, 1978.
. Goryunova, N.A., Khimiya almazopodobnykh polupro-
vodnikov (Chemistry of Diamond-like Semiconductors),
Leningrad: Leningr. Gos. Univ., 1963.
The reaction between sulfur and indium arsenide
begins at lower temperatures in comparison with gal-
lium antimonide, is autocatalyzed, and yields In S and
2
3
8. Mittova, I.Ya., Thermal Oxidation of Gallium Arsenide
in Atmospheres with and without Additives, Neorg.
Mater., 1992, vol. 28, no. 5, pp. 917–928.
As S . At 700–750°C and S : InAs molar ratios in the
2
3
range 4.0–6.0, the reaction yield attains 95–98%. Dur-
ing vacuum heat treatment of the sulfurization prod-
ucts, arsenic sulfide sublimes: after vacuum thermoly-
sis at 650–700°C, the As content does not exceed 0.2–
9
. Sysoev, B.I., Bezryadin, N.N., Budanov, A.V., et al.,
Structure of Indium Sulfide Layers on InAs, Neorg.
Mater., 1995, vol. 31, no. 7, pp. 891–895 [Inorg. Mater.
(Engl. Transl.), vol. 31, no. 7, pp. 817–821].
0
.5 mol %. The main thermolysis product is In S .
2 3
1
0. Mittova, I.Ya. and Pukhova, V.V., Thermal Oxidation of
The reaction between GaSb and S (up to 90 at. % in
the starting mixture) yields Ga S , Sb S , and (GaS) .
At 800°C and S : GaSb = 6.0, the conversion of GaSb
to Group III and V sulfides attains 93–95%.
In S /GaAs Structures, Izv. Akad. Nauk SSSR, Neorg.
2
3
2
3
2
3
2
Mater., 1986, vol. 22, no. 6, pp. 885–888.
1
1
1. Yatsenko, S.Ya., Indii. Svoistva i primenenie (Indium:
Properties and Applications), Moscow: Nauka, 1987.
In the case of indium arsenide, the thermolysis of
reaction products ensures a more complete separation
of the sulfides formed.
2. Roland, D. and Nitsche, R., Vapour and Flux Growth of
γ-In S : A New Modification of Indium Sesquisulphide,
2
3
J. Cryst. Growth, 1973, vol. 20, pp. 38–46.
The reactions in question are attractive for InAs and
GaSb waste processing since they do not require much
power or expensive reagents.
1
3. Kamsu Kom, J., Deux nouveaux composés sulfo et
sélénio-arséniques de l’indium: In(AsS ) et In(AsSe ) ,
2
2
2 2
Compt. Rend., 1968, vol. 267, no. 14, pp. 817–819.
The resulting In, Ga, As, and Sb sulfides can be con- 14. Yurchenko, E.N., Kustova, T.N., and Batsanov, S.S.,
verted to oxides and then reduced to elemental form or
can be used in semiconductor technology and optoelec-
tronics.
Kolebatel’nye spektry neorganicheskikh soedinenii
(Vibrational Spectra of Inorganic Compounds), Novosi-
birsk: Nauka, 1981.
1
5. Mushinskii, V.P. and Karaman, M.I., Fotoelektricheskie
i lyuminestsentnye svoistva khal’kogenidov galliya i
indiya (Photoelectric and Luminescent Properties of
Gallium and Indium Chalcogenides), Chisinau: Shti-
intsa, 1975.
REFERENCES
1
2
3
. Glazov, V.M., Chizhevskaya, S.N., and Glagoleva, N.N.,
Zhidkie poluprovodniki (Liquid Semiconductors), Mos-
cow: Nauka, 1967.
1
1
6. Rumyantsev, Yu.V. and Khvorostukhina, N.A., Fiziko-
khimicheskie osnovy pirometallurgii indiya (Physico-
chemical Foundations of Indium Pyrometallurgy), Mos-
cow: Nauka, 1965.
. Nashel’skii, A.Ya., Proizvodstvo poluprovodnikovykh
materialov (Production of Semiconductor Materials),
Moscow: Metallurgiya, 1989.
7. Pashinkin, A.S. and Fedorov, V.A., Physicochemical
Principles of Arsenic Extraction from Sulfide Ores,
Neorg. Mater., 1995, vol. 31, no. 5, pp. 592–603 [Inorg.
Mater. (Engl. Transl.), vol. 31, no. 5, pp. 547–557].
. Arbenina, V.V., Daricheva, O.E., and Pshenichnaya, D.A.,
Luminescent Characteristics of Rare-Earth-Doped GaSb
Epitaxial Layers, Neorg. Mater., 1995, vol. 31, no. 2,
pp. 278–281 [Inorg. Mater. (Engl. Transl.), vol. 31,
no. 2, pp. 260–262].
1
1
8. Novoselova, A.V. and Pashinkin, A.S., Davlenie para
letuchikh khal’kogenidov metallov (Vapor Pressure of
Volatile Metal Chalcogenides), Moscow: Nauka, 1978.
4
5
. Compound Semiconductors, Willardson, R.K. and Goer-
ing, H.L., Eds., New York: Reinhold, 1962. Translated
9. Rustamov, P.G., Alieva, Z.G., Guseinova, M.A., and
Cherstvova, V.B., Phase Relations in the Ternary Semi-
conductor System Ga–Sb–Se, in Nekotorye voprosy
khimii i fiziki poluprovodnikov slozhnogo sostava (Some
Topics in the Chemistry and Physics of Compound
Semiconductors), Uzhgorod, 1970, pp. 205–211.
III
V
under the title Poluprovodnikovye soedineniya A B ,
Moscow: Metallurgiya, 1967.
. Tomashik, Z.F., Danilenko, S.G., Tomashik, V.N., and
Kusyak, N.V., Interaction of InAs and InSb with Aque-
ous Solutions of Nitric Acid, Neorg. Mater., 2000,
INORGANIC MATERIALS Vol. 39 No. 3 2003