Journal of Alloys and Compounds 279 (1998) 142–152 L

The phase equilibria in the quasi-ternary Cu 2 S–CdS–SnS 2 system

L.V. Piskach, O.V. Parasyuk*, I.D. Olekseyuk
Department of Inorganic and Physical Chemistry, Volyn State University, Voli av. 13, 263009, Lutsk, Ukraine
Received 31 March 1998; received in revised form 20 May 1998

Abstract

The phase equilibria in the quasi-ternary system Cu 2 S–CdS–SnS 2 has been investigated using differential thermal, X-ray phase,
microstructural and energy-dispersive X-ray analyses. The projection of the liquid surface and the isothermal section of the Cu 2 S–CdS–
SnS 2 phase diagram at 770 K over the whole concentration region have been constructed. Two quaternary compounds Cu 2 CdSnS 4 and
Cu 2 CdSn 3 S 8 have been found, which are melting incongruently at 1178 K and 1091 K, respectively.  1998 Elsevier Science S.A. All
rights reserved.

Keywords: Phase diagram; Quaternary compounds; Liquid surface; Isothermal section

1. Introduction with orthorhombic (up to 376.5 K), hexagonal (376.5–708

The quasi-ternary Cu 2 S–CdS–SnS 2 system is very
interesting for the investigation owing to the existence of
compounds, which are known for their semiconductor
properties. Some intermediate phase of this system have
their natural analogies (for instance Cu 2 SnS 3 and
Cu 2 CdSnS 4 ) [1].
The binary compounds Cu 2 S, CdS and SnS 2 melt
congruently and have narrow homogenity regions, which
contain the stoichiometric composition, and can be used as
components of the quasi-ternary Cu 2 S–CdS–SnS 2 system.
The crystallographic data of these compounds are summa-
rised in Table 1. Cu 2 S has three polymorphic modifications
K) and cubic structures (708–1398 K) [2]. The most
typical for CdS is hexagonal wurtzite type structure. This
compound sublimates at 1253 K. Therefore its melting
temperature was determined at high pressure and is equal
1678 K under the pressure of 20 atmospheres [3] and 1643
K under the pressure of argon of 50 atmospheres [4]. The
SnS 2 phase melts at 1143 K [5] and crystallizes with CdI 2
structure type (Table 1).
2. Quasi-binary sections
2.1. Cu2 S–CdS section

Table 1 According to data of Mizetskaya et al. [6] the Cu 2 S–

Crystallographic data of the components and intermediate phases of the
CdS section belongs to the eutectic type (Fig. 1). The
quasi-ternary system Cu 2 S–CdS–SnS 2
eutectic point is at 55 mol % CdS and 1284 K. The
Compound Str. type, Space a, nm b, nm c, nm Ref. solubility on the basis of Cu 2 S is 50 mol % CdS at the
(syngony) group
eutectic temperature. At lower temperatures the solubility
Cu 2 S cubic – 0.5735 – – [2] decreases essentially (40 mol % CdS at 1188 K and 10
CdS ZnS(wurz.) P6 3 mc 0.41348 – 0.67490 [2]
mol % at 828 K). The solubility on the basis of CdS [7] is
SnS 2 CdI 2 P3m1 0.3646 – 0.5879 [5]
Cu 2 SnS 3 cubic – 0.5445 – – [17] 2.7 mol % Cu 2 S at 1273 K and 0.07 mol % at 823 K.
Cu 4 SnS 4 orthorom. – 1.370 0.7750 0.6454 [17]
Cu 2 Sn 4 S 9 cubic F4 1 32 1.040 – – [17] 2.2. CdS–SnS2 section
Cu 2 CdSnS 4 Cu 2 CdFeS 4 I42m 0.5586 – 1.0834 [20]
tetragon. I42m 0.55809 – 1.0826 [18]
The phase equilibria diagram of the CdS–SnS 2 section
has been investigated by Zargarova et al. [8] and by
*Corresponding author. Galliulin et al. [9]. The results of the both papers do not

0925-8388 / 98 / $ – see front matter  1998 Elsevier Science S.A. All rights reserved.
PII: S0925-8388( 98 )00656-2
 L.V. Piskach et al. / Journal of Alloys and Compounds 279 (1998) 142 – 152
Fig. 1. The phase diagram of the quasi-binary system Cu 2 S–CdS [6]: (1)
L, (2) L1b, (3) L1a, (4) 2b, (5) 2a, (6) a1b.
correlate. Ref. [8] reports the existence of three com-
pounds: CdSn 2 S 5 , CdSnS 3 and Cd 2 SnS 4 . The phase
CdSn 2 S 5 melts congruently at 1075 K. The compounds
CdSnS 3 and Cd 2 SnS 4 melt according to peritectic re-
actions L1Cd 2 SnS 4 ⇔CdSnS 3 and L1CdS ⇔ Cd 2 SnS 4 at
960 K and 1060 K, respectively. The possibility of the
existence of the CdSnS 3 phase was mentioned in [10].
According to data Galliutin et al. the diagram CdS–SnS 2
section is of the eutectic type without the formation of the
intermediate phases. The absence of such compounds is
reported in [11] also. In conjunction with such a diver-
gence of the papers [8–11] an additional investigation was
carried out.
2.3. Cu2 S–SnS2 section
The Cu 2 S–SnS 2 section was investigated several times
[12–17]. Wu et al. [15] have found the three compounds
with the composition Cu 4 SnS 4 , Cu 2 SnS 3 and Cu 2 Sn 4 S 9 .
Additionally Khanafer et al. [17] reported the formation of
the fourth phase Cu 4 Sn 3 S 8 . The first three compounds
exist at room temperature. The compound Cu 4 Sn 3 S 8 exists
in the interval of 658–1063 K. The phase Cu 4 SnS 4
decomposes according to the reaction
Cu 4 SnS 4 ⇔Cu 2 SnS 3 1Cu 2 S at 1083 K. The phase
Cu 2 SnS 3 melts congruently at 1123 K and forms eutectic
with Cu 2 S at 1093 K. The Cu 2 Sn 4 S 9 compound de-
composes at 938 K according to the reaction
Cu 2 Sn 4 S 9 ⇔Cu 4 Sn 3 S 8 1SnS 2 . Zotova et al. [12] have
established three phases Cu 2 SnS 3 , Cu 2 Sn 4 S 9 and
Cu 8 SnS 6 . The compound Cu 2 SnS 3 melts congruently at
1173 K. Cu 2 Sn 4 S 9 and Cu 8 SnS 6 are formed according to
peritectoid processes Cu 2 SnS 3 1SnS 2 ⇔Cu 2 Sn 4 S 9 at 938
143
Fig. 2. The phase diagram of the quasi-binary system Cu 2 SnS 3 –CdS [18]:
(1) L, (2) L1b, (3) b, (4) L1g, (5) L1Cu 2 CdSnS 4 , (6) g, (7)
g1Cu 2 CdSnS 4 , (8) Cu 2 CdSnS 4 1b.
K and Cu 2 S1Cu 2 SnS 3 ⇔Cu 8 SnS 6 at 1083 K, respectively.
Crystallographic parameters of the ternary compounds are
shown in Table 1. Some differences in the built diagrams
were a reason of an additionally investigation of the
Cu 2 S–SnS 2 section.
2.4. Cu2 SnS3 –CdS section
The quasi-binary section Cu 2 SnS 3 –CdS was investi-
gated by Olekseyuk and Piskach [18]. There is one
quaternary compound Cu 2 CdSnS 4 in this section, which
melts incongruently at 1178 K (Fig. 2). Cu 2 CdSnS 4 and
Cu 2 SnS 3 form eutectic at 1126 K and 15 mol % CdS. The
solubility on the basis of Cu 2 SnS 3 is 10 mol % CdS at
1126 K and 8 mol % CdS at 820 K. Solid solution on the
basis of CdS contains 6 mol % at 1178 K and solubility
decreases essentially at lower temperatures.
According to data of Moh [19] the quaternary compound
Cu 2 CdSnS 4 melts at 1187 K. Crystallographic parameters
of the structures are shown in Table 1.
3. Experimental procedure
158 alloys were prepared for investigating the quasi-
ternary Cu 2 S–CdS–SnS 2 system. The majority of these
were situated on the ten polythermal sections shown in
Fig. 3. Separate alloys, which do not belong to these
sections, were used for specifying the invariant point
compositions of the continuous solid solutions. The com-
positions of the alloys on the sections are given in mole
percent of that sections components. During the transfer of
the built sections onto the Gibbs triangle a recalculation for
the components of the quasi-ternary system was made.
144 L.V. Piskach et al. / Journal of Alloys and Compounds 279 (1998) 142 – 152

Fig. 4. The state diagram of the quasi-binary system SnS 2 –CdS: (1) L,
(2) L1b, (3) L1d, (4) d, (5) b, (6) d1b.

of the liquid surface and the isothermal section of the

Cu 2 S–CdS–SnS 2 phase diagram at 770 K over the whole
concentration interval.
Fig. 3. The composition of the investigated alloys in the quasi-ternary
system Cu 2 S–CdS–SnS 2 . 4.1. SnS2 –CdS section

The quasi-binary SnS 2 –CdS section is of an eutectic

Alloys for investigation were prepared from pure ele- type (Fig. 4 and Table 2). The eutectic point coordinates
ments (Cu 99.994 wt %, Cd 99.9999 wt %, Sn 99.999 are 22 mol % CdS and 1043 K. The liquid curve of CdS is
wt %, S 99.97 wt %). Sulfur was purified additionally by drawn according to the cooling data. It was impossible to
means of distillation in vacuum. Alloys synthesis was fix the temperature of the liquidus using the curves of
carried out in quartz container vacuumed to 0.1 Pa. heating. Intermediate phases have not been found in this
Preceding synthesis was carried out on an oxygen-gas section.
burner (pressure of sulfur vapours at high temperatures is
so high, that diffusion of oxygen is practically absent 4.2. Cu2 S–SnS2 section
through the walls of the container). The next stage of
synthesis was carried out by means of a single temperature The Cu 2 S–SnS 2 section was investigated in the tem-
method utilizing vibrating mixing. The highest synthesis perature interval of 293–1400 K (Fig. 5 and Table 3). The
temperature was 1420 K (for alloys 50–100 mol % SnS 2 alloys were annealed at 770 K for 100 h and subsequently
temperature was 1220 K). To equilibrate the alloys, they cooled in the interval cooling furnace. Three phases form
were annealed at 770 K for 500 h and subsequently in this system. The compound Cu 2 SnS 3 melts congruently
quenched in cold water. at 1133 K. The phases Cu 4 SnS 4 and Cu 2 Sn 4 S 9 form
The investigations of the alloys were carried out by the according to the peritectoid reactions Cu 2 SnS 3 1
differential thermal, X-ray phase, microstructural and
electron microprobe analyses. The differential thermal Table 2
analysis was carried out by Paulik–Paulik–Erdey system DTA results of SnS 2 –CdS system
derivatograph with Pt / Pt–Rh thermocouple. Al 2 O 3 cal- No Phase composition, mol % Temperature, K
cined at 1270 K was used as standard. We used Cu, Ag, Al,
SnS 2 CdS liquid solid
Zn and Cd for calibration. The heating rate was equal 10
K min 21 . X-ray phase analysis was carried out using the 1 100 0 1143 –
2 95 5 1133 1043
DRON-3M diffractometer with Cu Ka radiation. Micro- 3 90 10 1117 1043
structural electron and energy-dispersive X-ray analyses 4 80 20 – 1042
were carried out by means of the MMU-3 microscope and 5 70 30 1090 a 1039
scanning electron microscope, respectively. 6 66.7 33.3 1100 a 1041
7 65 35 1112 a 1046
8 55 45 1173 a 1051
9 50 50 1203 a 1041
4. Results 10 40 60 1243 a 1036
11 35 65 1273 a 1043
The results of the investigation of the ten polythermal 12 30 70 1263 a 1050
sections and some alloys for refinement of the composition 13 5 95 – 1046
a
of invariant points were used for contracting the projection Cooling data.
 L.V. Piskach et al. / Journal of Alloys and Compounds 279 (1998) 142 – 152 145

Fig. 6. The phase diagram of the polythermal section Cu 4 SnS 4 –CdS: (1)
L, (2) L1b, (3) b, (4) a1b, (5) L1a1b, (6) L1a, (7) L1a1
Cu 2 CdSnS 4 , (8) a1Cu 2 CdSnS 4 , (9) a1Cu 2 CdSnS 4 1b, (10) L1g, (11)
L1g1a, (12) L1a1Cu 4 SnS 4 , (13) Cu 4 SnS 4 1a1Cu 2 CdSnS 4 .

transformation of Cu 2 S. The compound Cu 2 SnS 3 forms

Fig. 5. The phase diagram of the quasi-binary system Cu 2 S–SnS 2 : (1) L, with the components of section two eutectics
(2) L1a, (3) a, (4) L1Cu 2 SnS 3 , (5) a1Cu 2 SnS 3 , (6) a1Cu 4 SnS 4 , (7) L⇔Cu 2 SnS 3 1a and L⇔Cu 2 SnS 3 1d, which melt at 1093
a1a9, (8) a9, (9) a91Cu 4 SnS 4 , (10) a91a0, (11) a0, (12) a91Cu 4 SnS 4 ,
(13) Cu 4 SnS 4 1Cu 2 SnS 3 , (14) L1d, (15) Cu 2 SnS 3 1d, (16) d, (17)
K and 1061 K, respectively.
Cu 2 SnS 3 1Cu 2 Sn 4 S 9 , (18) Cu 2 Sn 4 S 9 1d.
4.3. Cu4 SnS4 –CdS section

a 1 ⇔Cu 4 SnS 4 at 1083 K and Cu 2 SnS 3 1d 2 ⇔Cu 2 Sn 4 S 9 at The Cu 4 SnS 4 –CdS section is polythermal (Fig. 6 and
943 K, respectively. The compound Cu 4 Sn 3 S 8 does not Table 4). It crosses the fields of primary crystallization of
exist, which was confirmed by the following investigation b- (up to point I)3 , a-(between points I and II), and g-solid
of the quasi-ternary system. The processes a⇔a1 solutions 4 (from the point II). The solidus of the section
Cu 4 SnS 4 and a91Cu 4 SnS 4 ⇔a0 take place at 656 K and extends from the two horizontal lines at 1134 K and 1071
381 K, respectively. They are caused by the polymorphic K, which belong to the ternary peritectic processes L1
b⇔a1Cu 2 CdSnS 4 and L1a⇔Cu 2 CdSnS 4 1Cu 4 SnS 4 , re-
Table 3
DTA results of Cu 2 S–SnS 2 system spectively, and the limited b-solid solution and line of
No Phase composition, mol % Temperature, K Table 4
Cu 2 S SnS 2 liquid solid subsolid DTA results of Cu 4 SnS 4 –CdS section

1 100 0 1403 – 698, 376 No Phase composition, mol % Temperature, K

2 95 5 1298 1268 661, 381 Cu 4 SnS 4 CdS liquid subliquid solid
3 90 10 1244 1094 652, 381
4 80 20 1160 1093 1083, 378 1 100 0 – 1092 1083
5 70 30 1096 – 1081 2 95 5 1105 1090, 1083 1072
6 66,7 33,3 – 1092 1083 3 90 10 1100 1088, 1082 1070
7 65 35 1101 – 1084 4 80 20 1148 – 1068
8 55 45 – 1091 1083 5 70 30 1186 1141 1078
9 50 50 1133 – – 6 60 40 1198 1133 1072
10 40 60 1113 1056 939 7 50 50 1238 1200 1134
11 30 70 1085 1065 947 8 40 60 1263 1205 1134
12 25 75 – 1061 945 9 30 70 1288 1198 1147
13 20 80 1060 – 943 10 20 80 – 1189 –
14 15 85 – 1060 939 11 10 90 – 1197 –
15 5 95 1097 1059 – 12 5 95 – 1204 –
16 0 100 1133 – –

1 3
From here on a-solid solution is on the basis of Cu 2 S. From here on b-solid solution is on the basis of CdS.
2 4
From here on d-solid solution is on the basis of SnS 2 . From here on g-solid solution is on the basis of Cu 2 SnS 3 .
146 L.V. Piskach et al. / Journal of Alloys and Compounds 279 (1998) 142 – 152

completion of the secondary crystallization of the binary Table 5

DTA results of A–CdS section
eutectic L⇔a1b (above 1134 K). Another effect at 1083
K belongs to the process L1a1g⇔Cu 4 SnS 4 . The lines No Phase composition, mol % Temperature, K
between the liquidus and solidus correspond to the sec- A CdS liquid solid subsolid
ondary crystallization of the binary eutectics L⇔a1b, 1 100 0 – 1061 945
L⇔a1g and L⇔a1Cu 2 CdSnS 4 . In the subsolidus part of 2 90 10 1073 1058 943
the diagram the section crosses one-phase fields of 3 80 20 1066 1048 939
Cu 4 SnS 4 and b-solid solutions, field a1b and two ternary 4 70 30 1085 1053 950, 941
regions Cu 4 SnS 4 1a1Cu 2 CdSnS 4 and b1a1Cu 2 CdSnS 4 . 5 60 40 1093 1058 953, 938
6 50 50 1143 1091 956
The two ternary regions are separated by the secondary 7 47.36 52.64 1163 1085 936
quasi-binary section a-Cu 2 CdSnS 4 . 8 44.45 55.55 1146 1082 952
9 41.17 58.83 1165 1088 953
10 37.50 62.50 1178 1096 950
4.4. A–CdS section (A525 mol % Cu2 S and 75 mol % 11 33.33 66.67 1173 1093 950
12 28.59 71.41 1183 1093 948
SnS2 ) 13 23.08 76.92 1198 1090 948
14 16.66 83.34 1207 1091 950
In this section a new quaternary phase Cu 2 CdSn 3 S 8 has 15 9.08 90.92 – 1091 950
been found, which melts incongruently according to the
process L1b⇔Cu 2 CdSn 3 S 8 at 1091 K and has a poly-
morphic transformation e⇔e9 at 950 K (Fig. 7 and Table tallizations of L1g and L1e-Cu 2 CdSn 3 S 8 take place. The
5). The composition of the quaternary compound has been liquidus curves cross in point III.
found by using the results of energy-dispersive X-ray
analyses. The structure of the two modifications of 4.5. Cu2 S–B section ( B550 mol % CdS and 50 mol %
Cu 2 CdSn 3 S 8 have not been established. The described SnS2 )
section is not quasi-binary in the part of Cu 2 CdSn 3 S 8 –A
and crosses planes of the invariant processes L⇔g1e- The Cu 2 S–B section crosses the fields of the primary
Cu 2 CdSn 3 S 8 1d (at 1055 K) and g1e9- crystallization of a- and b- solid solutions (Fig. 8 and
Cu 2 CdSn 3 S 8 ⇔Cu 2 CdSnS 4 1m5 (at 940 K). Above the Table 6). The crossing of the liquidus lines corresponds to
solidus the secondary crystallization of the binary eutectics point IV. The solidus of this section consists of three planes
L⇔g1d and L⇔g1e-Cu 2 CdSn 3 S 8 , and primary crys- of the invariant equilibria of L 1b⇔a1Cu 2 CdSnS 4 (at
1134 K), L1b⇔Cu 2 CdSnS 4 1e-Cu 2 CdSn 3 S 8 (at 1078 K)
and L⇔b1d1e-Cu 2 CdSn 3 S 8 (at 1035 K), the composi-
tion limits of b-solid solution (above 1134 K) and the line

Fig. 7. Polythermal section A–CdS (A, 25 mol % Cu 2 S and 75 mol %

SnS 2 ): (1) L, (2) L1b, (3) b, (4) L1g, (5) L1e-Cu 2 CdSn 3 S 8 , (6)
L1g1d, (7) L1g1e-Cu 2 CdSn 3 S 8 , (8) e-Cu 2 CdSn 3 S 8 1b, (9) g1d, (10)
Fig. 8. The phase diagram of the polythermal section Cu 2 S–B (B, 50
g1d1m, (11) d1m, (12) g1d1e-Cu 2 CdSn 3 S 8 , (13) g1d1e9-
mol % CdS and 50 mol % SnS 2 ): (1) L, (2) L1a, (3) a, (4) L1a1b, (5)
Cu 2 CdSn 3 S 8 , (14) g1m1Cu 2 CdSnS 4 , (15) m1Cu 2 CdSnS 4 , (16) m1
L1b, (6) L1b1Cu 2 CdSnS 4 , (7) a1Cu 2 CdSnS 4 , (8) Cu 2 CdSnS 4 1b1e-
Cu 2 CdSnS 4 1e9-Cu 2 CdSn 3 S 8 , (17) e9-Cu 2 CdSn 3 S 8 1b, (18) e9-
Cu 2 CdSn 3 S 8 , (9) L1b1e-Cu 2 CdSn 3 S 8 , (10) L1b1d, (11) b1d, (12)
Cu 2 CdSn 3 S 8 1g1d, (19) e-Cu 2 CdSn 3 S 8 , (20) e9-Cu 2 CdSn 3 S 8 .
e-Cu 2 CdSn 3 S 8 1b1d, (13) Cu 2 CdSnS 4 , (14) Cu 2 CdSnS 4 1b1e9-
Cu 2 CdSn 3 S 8 , (15) e-Cu 2 CdSn 3 S 8 1b, (16) e9-Cu 2 CdSn 3 S 8 1b, (17) e9-
5
From here on m-solid solution is on the basis of Cu 2 Sn 4 S 9 . Cu 2 CdSn 3 S 8 1b1d.
 L.V. Piskach et al. / Journal of Alloys and Compounds 279 (1998) 142 – 152 147

Table 6
DTA results of Cu 2 S–B section
No Phase composition, mol % Temperature, K
Cu 2 S B liquid subliquid solid subsolid
1 100 0 1403 – – –
2 97.44 2.56 1345 – – –
3 94.74 5.24 1316 – – 955
4 91.89 8.11 1281 – – 1037
5 82.35 17.65 1233 – 1131 –
6 75 25 1213 – 1137 –
7 66.70 33.30 1238 1200 1134 –
8 62.07 37.93 1233 1148 – –
9 57.14 42.86 1233 1173 1133 –
10 51.85 48.15 1228 1180 1128 –
11 50 50 1233 – 1078 –
12 46.15 53.85 1218 1148 1073 –
13 40 60 1223 1143 1078 953
14 33.33 66.67 1208 1129 1078 957
15 18.18 81.82 1173 1073 1033 953 Fig. 9. The phase equilibria of the polythermal section C–SnS 2 (C, 50
16 0 100 – – 1041 – mol % Cu 2 S and 50 mol % CdS): (1) L, (2) L1a, (3) L1b, (4) L1a1b,
(5) a1b, (6) L1b1Cu 2 CdSnS 4 , (7) a1b1Cu 2 CdSnS 4 , (8) L1b1e-
Cu 2 CdSn 3 S 8 , (9) L1e-Cu 2 CdSn 3 S 8 , (10) Cu 2 CdSnS 4 1e-Cu 2 CdSn 3 S 8 ,
(11) Cu 2 CdSnS 4 , (12) Cu 2 CdSnS 4 1e9-Cu 2 CdSn 3 S 8 , (13) e-
of completion of the secondary crystallization of the binary Cu 2 CdSn 3 S 8 , (14) e9-Cu 2 CdSn 3 S 8 , (15) e-Cu 2 CdSn 3 S 8 1d, (16) L1d,
eutectic L⇔b1d. The a-solid solution has a maximal (17) d, (18) e9-Cu 2 CdSn 3 S 8 1d.
solubility at 1134 K which decreases essentially at the
lower temperature. The alloys of the region Cu 2 S–
Cu 2 CdSnS 4 annealed at 770 K consist of either one (for crystallization L⇔a1b, horizontal of eutectic process (e 6 )
Cu 2 CdSnS 4 and for alloys from a-solid solution) or two L⇔e-Cu 2 CdSn 3 S 8 1g at 1073 K and horizontals at 1134
phases. The existence of the binary region a1Cu 2 CdSnS 4 K and at 1078 K, which belong to the quadrilaterals of
evidences that the crystallization completes with the peritectical processes L1b⇔a1Cu 2 CdSnS 4 and L1
peritectic process L1b⇔a1Cu 2 CdSnS 4 and the section b⇔Cu 2 CdSnS 4 1e-Cu 2 CdSn 3 S 8 , respectively. The maxi-
Cu 2 S–B in this concentration interval consists of two mum solubility on the basis of SnS 2 of 4 mol % (d-solid
phases. In the part Cu 2 CdSnS 4 –B two three-phase regions solution) occurs at 1073 K. At lower temperatures it
have been found at 770 K: b1Cu 2 CdSnS 4 1e9- decreases essentially (e.g. the alloy with the composition
Cu 2 CdSn 3 S 8 and b1e9-Cu 2 CdSn 3 S 8 1d, which are sepa- 2.66 mol % C and 97.34 mol % SnS 2 consists of two
rated by the two-phase region e9-Cu 2 CdSn 3 S 8 1b. The phases at 770 K). The endothermal effects at 950 K can be
composition of the alloy in the point B corresponds to the interpreted as a polymorphic transformation e-
eutectic crystallization (the primary inclusions belong to
the b-solid solution which are separated by eutectic b1d). Table 7
DTA results of C–SnS 2 section
The secondary crystallization is represent by the crys-
tallization fields of two binary eutectics L⇔a1b and No Phase composition, mol % Temperature, K
L⇔b1d and two binary peritectics L1b⇔Cu 2 CdSnS 4 C SnS 2 liquid subliquid solid subsolid
and L1b⇔e-Cu 2 CdSn 3 S 8 . 1 100 0 – – 1283 –
2 81.82 18.18 1305 1253 1135 –
4.6. C–SnS2 section ( C550 mol % Cu2 S and 50 mol % 3 66.67 33.33 1289 1193 1133 –
CdS) 4 60 40 1265 – 1131 –
5 50 50 1233 – 1178 –
6 48.15 51.85 1228 1178 1073 953
The C–SnS 2 section consists of the stoichiometric 7 42.86 57.14 1223 1170 1078 951
composition of both quaternary phases and crosses the 8 37.93 62.07 1203 1153 1078 946
fields of primary crystallization of a-(up to point V), 9 33.33 66.67 1162 – 1080 949
b-(between points V and VI), g-solid solutions (from point 10 29.04 70.96 1163 – 1078 946
e 6 ) and the field e-Cu 2 CdSn 3 S 8 (between points VI and e 6 ) 11 25 75 1143 – 1091 956
12 17.65 82.35 1108 – 1073 950
(Fig. 9 and Table 7). The secondary crystallization of the 13 14.29 85.71 1081 – – 953
binary eutectic L⇔a1b and of two binary peritectics 14 11.11 88.89 1082 – – 954
L1b⇔Cu 2 CdSnS 4 and L1b⇔e-Cu 2 CdSn 3 S 8 take place 15 8.11 91.89 1093 – 1073 948
below the fields of the primary crystallization. To the 16 5.26 94.74 1113 – 1075 946
complete crystallization of alloys of this section corre- 17 2.56 97.44 1126 – 1095 959
18 0 100 1143 – – –
spond the lines of the completion of the secondary
148 L.V. Piskach et al. / Journal of Alloys and Compounds 279 (1998) 142 – 152

L1Cu 2 CdSnS 4 ⇔e-Cu 2 CdSn 3 S 8 1g at 1068 K, L⇔b1d1

Fig. 10. The phase diagram of the polythermal section Cu 2 SnS 3 –D (D,
33.3 mol % CdS and 66.7 mol % SnS 2 ): (1) L, (2) L1b, (3) L1b1
Cu 2 CdSnS 4 , (4) L1Cu 2 CdSnS 4 , (5) L1g, (6) L1g1Cu 2 CdSnS 4 , (7) g,
(8) L1b1e-Cu 2 CdSn 3 S 8 , (9) L1Cu 2 CdSnS 4 1e-Cu 2 CdSn 3 S 8 , (10) L1
b1d, (11) b1d, (12) g1e-Cu 2 CdSn 3 S 8 , (13) e9-Cu 2 CdSn 3 S 8 , (14)
e-Cu 2 CdSn 3 S 8 1b1d, (15) g1e9-Cu 2 CdSn 3 S 8 , (16) e9-Cu 2 CdSn 3 S 8 ,
(17) b1d1e9-Cu 2 CdSn 3 S 8 , (18) g1m1Cu 2 CdSnS 4 , (19) m1
Cu 2 CdSnS 4 , (20) m1Cu 2 CdSnS 4 1e9-Cu 2 CdSn 3 S 8 , (21) g1m.
Cu 2 CdSn 3 S 8 ⇔e9-Cu 2 CdSn 3 S 8 because the maximum of
this effect has been observed on the thermogram of this
phase.
4.7. Cu2 SnS3 –D section ( D533.3 mol % CdS and 66.7
mol % SnS2 )
The investigation of this section was important for
establishment of the primary crystallization of the
Cu 2 CdSnS 4 phase and the posibillity of the existence of
the compound CdSn 2 S 5 (Fig. 10 and Table 8). The
liquidus of the section consists of three parts: g-solid
solution (up to point VII), Cu 2 CdSnS 4 (between points VII
and VIII) and b-solid solution (from point VIII). The
section crosses three planes of the invariant equilibria:
e-Cu 2 CdSn 3 S 8 at 1035 K and L1b⇔Cu 2 CdSnS 4 1e-
Cu 2 CdSn 3 S 8 at 1078 K. The crystallization of the alloys of
this section is finished at the horizontal lines at 1068 K and
1035 K, the line of the completion of secondary crys-
tallization L⇔d1b and the lines of the limited g-solid
solutions above 1068 K. The secondary crystallization is
represented by the volumes of the crystallization of the
three binary eutectics L⇔g1Cu 2 CdSnS 4 ,
L⇔Cu 2 CdSnS 4 1e-Cu 2 CdSn 3 S 8 and L⇔d1b and the two
binary peritectics L1b⇔Cu 2 CdSnS 4 and L1b⇔e-
Cu 2 CdSn 3 S 8 . In the subsolidus part of the section a
polymorphic transformation e-Cu 2 CdSn 3 S 8 ⇔e9-
Cu 2 CdSn 3 S 8 at 950 K and a solid state peritectoid process
g1e9-Cu 2 CdSn 3 S 8 ⇔Cu 2 CdSnS 4 1m take place.
4.8. Cu2 Sn4 S9 –D section ( D533.3 mol % CdS and 66.7
mol % SnS2 )
The section Cu 2 Sn 4 S 9 –D is polythermal (Fig. 11 and
Table 9). Its liquidus is represented by the lines of the
beginning of primary crystallization of g-solid solution (up
to point IX), e-Cu 2 CdSn 3 S 8 (between points IX and X),
and b-solid solution (up to point X). Below the liquid and
the fields of primary crystallization the diagram consists of
the volumes of the secondary crystallization of four binary
eutectics L⇔g1d, L⇔g1e-Cu 2 CdSn 3 S 8 , L⇔d1e-
Cu 2 CdSn 3 S 8 and L⇔b1d and one binary peritectic L1
d⇔e-Cu 2 CdSn 3 S 8 . Crystallization of most of these alloys
completes with eutectic processes L⇔g1d1e-
Cu 2 CdSn 3 S 8 at 1055 K, L⇔d1e-Cu 2 CdSn 3 S 8 at 1073 K
and L⇔b1d1e9-Cu 2 CdSn 3 S 8 at 1035 K. The alloys in
the small regions near the section components crystallize
two-phase as a results of the completion of the secondary

Table 8
DTA results of Cu 2 SnS 3 –D section
No Phase composition, mol % Temperature, K
Cu 2 SnS 3 D liquid subliquid solid subsolid
1 100 0 1133 – – –
2 95 5 1125 – 1068 940
3 90 10 1123 1106 1068 938
4 80 20 1123 1093 1064 942
5 70 30 1133 1101, 1072 – 938
6 60 40 1145 1088 1068 953, 935
Fig. 11. The phase equilibria of the polythermal section Cu 2 Sn 4 S 9 –D (D,
7 50 50 1143 – 1091 956
33.3 mol % CdS and 66.7 mol % SnS 2 ): (1) L, (2) L1b, (3) L1b1e-
8 40 60 1155 1075 1030 946
Cu 2 CdSn 3 S 8 , (4) L1b1d, (5) b1d, (6) L1e-Cu 2 CdSn 3 S 8 , (7) L1g, (8)
9 30 70 – 1058 1041 948
L1g1d, (9) L1g1e-Cu 2 CdSn 3 S 8 , (10) L1d1e-Cu 2 CdSn 3 S 8 , (11) g1
10 20 80 – – 1033 950
d, (12) g1d1m, (13) g1d1e9-Cu 2 CdSn 3 S 8 , (14) e-Cu 2 CdSn 3 S 8 1d,
11 10 90 – – 1033 952
(15) e9-Cu 2 CdSn 3 S 8 1d, (16) d1m, (17) d1m1e9-Cu 2 CdSn 3 S 8 , (18)
12 5 95 – – 1031 956
e9-Cu 2 CdSn 3 S 8 1b1d, (19) g1d1e-Cu 2 CdSn 3 S 8 , (20) e-Cu 2 CdSn 3 S 8 1
13 0 100 – – 1043 –
b1d.
 L.V. Piskach et al. / Journal of Alloys and Compounds 279 (1998) 142 – 152 149

Table 9 10). Secondary crystallization of three binary eutectics

DTA results of Cu 2 Sn 4 S 9 –D section L⇔d1g, L⇔g1e-Cu 2 CdSn 3 S 8 and L⇔a1b and two
No Phase composition, mol % Temperature, K binary peritectics L1b⇔e-Cu 2 CdSn 3 S 8 and L1
Cu 2 Sn 4 S 9 D liquid subliquid solid subsolid b⇔Cu 2 CdSnS 4 take place below the liquidus. Crystalliza-
tion of the alloys completes by one eutectic process
1 100 0 – – – 943
2 95 5 – – 1056 940 L⇔d1g1e-Cu 2 CdSn 3 S 8 at 1055 K, two binary peritectics
3 90 10 1058 – – 939 L1b⇔e-Cu 2 CdSn 3 S 8 and L1b⇔Cu 2 CdSnS 4 (when the
4 80 20 1068 – 1055 942 rest of b-solid solution is presented) at 1091 K and 1178
5 70 30 1081 1059 – 938 K, respectively, and two ternary peritectic processes L1
6 60 40 1079 – 1055 948
b⇔e-Cu 2 CdSn 3 S 8 1Cu 2 CdSnS 4 at 1078 K and L1
7 50 50 1081 – – 953
8 40 60 1111 1081, 1068 1035 943 b⇔a1Cu 2 CdSnS 4 at 1134 K. On the basis of the
9 30 70 – 1060 1038 948 components of the section insignificant concentration
10 20 80 – 1043 – 950 intervals correspond to the completion of the secondary
11 10 90 – 1040 – 952 crystallization of binary eutectic L⇔d1g and L⇔a1b,
12 5 95 – – 1035 953
which complete the crystallization of alloys of this region.
13 0 100 – – 1043 –
Below the solidus the solid state reaction d1g⇔e-
Cu 2 CdSn 3 S1m at 941 K and polymorphic transformation
crystallization of eutectics L⇔d1g and L⇔b1d. The of Cu 2 CdSn 3 S 8 take place.
horizontal line at 950 K, which corresponds to a poly-
morphic transformation of Cu 2 CdSn 3 S 8 and the invariant 4.10. The projection of liquidus surface and isothermal
planes of the peritectoid process g1d⇔m1e9-Cu 2 CdSn 3 S 8 sections of the quasi-ternary Cu2 C–CdS–SnS2 system at
at 941 K are below the solid. 770 K and at 970 K

4.9. Cu2 Sn4 S9 –F section ( F580 mol % CdS and 20
mol % Cu2 S)
The Cu 2 Sn 4 S 9 –F section is polythermal and crosses the
fields of primary crystallization of g-solid solution (up to
point XI), e-Cu 2 CdSn 3 S 8 (between points XI and XII) and
of b-solid solution (from point XII) (Fig. 12 and Table
Fig. 12. The diagram of the phase equilibria of the polythermal section
Cu 2 Sn 4 S 9 –F (F, 20 mol % Cu 2 S and 80 mol % CdS): (1) L, (2) L1b,
(3) L1a1b, (4) a1b, (5) L1Cu 2 CdSnS 4 1b, (6) L1e-Cu 2 CdSn 3 S 8 ,
(7) L1e-Cu 2 CdSn 3 S 8 1b, (8) L1g, (9) L1g1d, (10) L1g1e-
Cu 2 CdSn 3 S 8 , (11) g1d, (12) g1d1m, (13) g1m, (14) e-Cu 2 CdSn 3 S 8 ,
(15) e9-Cu 2 CdSn 3 S 8 1g1d, (16) e9-Cu 2 CdSn 3 S 8 , (17) m, (18) e9-
Cu 2 CdSn 3 S 8 1m, (19) g1d1e-Cu 2 CdSn 3 S 8 , (20) e-Cu 2 CdSn 3 S 8 1b1
Cu 2 CdSnS 4 , (21) a1b1Cu 2 CdSnS 4 , (22) b1Cu 2 CdSnS 4 1e9-
Cu 2 CdSn 3 S 8 , (23) b1Cu 2 CdSnS 4 .
On the basis of the results of the investigation of the
quasi-binary systems the projection of the liquidus surface
of the quasi-ternary system Cu 2 S–CdS–SnS 2 onto the
Gibb’s triangle has been constructed (Fig. 13). It consists
of seven fields of primary crystallization of the phases: a-,
b-, g-, and d-solid solutions on the basis of the compounds
Cu 2 S, CdS, Cu 2 SnS 3 and SnS 2 , respectively, and phases
e-Cu 2 CdSn 3 S 8 , Cu 2 CdSnS 4 and Cu 4 SnS 4 . They are sepa-
rated by 16 invariant points and 18 monovariant lines.
Their character and temperatures are listed in Table 11.
The quasi-ternary Cu 2 S–CdS–SnS 2 system is separated
into two quasi-ternary subsystems Cu 2 S–Cu 2 SnS 3 –CdS
and CdS–Cu 2 SnS 3 –SnS 2 by the quasi-binary section
Cu 2 SnS 3 –CdS.
In the subsystem Cu 2 S–Cu 2 SnS 3 –CdS four ternary
invariant processes take place: three ternary peritectics U 1 ,
U 2 and P1 , and one ternary eutectic E 1 (the composition of
the invariant points are shown in Table 12). The triangle
a–b–Cu 2 CdSnS 4 of the peritectic quadrilateral a–b-
Cu 2 CdSnS 4 –U 1 contains the three-phase alloys in the
subsolidus part (Fig. 14), which complete their crystalliza-
tion by the process L1b⇔a1Cu 2 CdSnS 4 . This process is
also typical for other alloys of this quadrilateral. There are
enough amounts of L and b on the connection line a-
Cu 2 CdSnS 4 . That is why the alloys of this part are two-
phase. Alloys, which do not crystallize at 1134 K, com-
plete their crystallization by the peritectic process L1a⇔
Cu 4 SnS 4 1Cu 2 CdSnS 4 (U 2 ). A similar behaviour occurs
for this peritectic. Alloys of the triangle a-Cu 4 SnS 4 –
Cu 2 CdSnS 4 crystallize as three-phase, alloys of the con-
necting line Cu 4 SnS 4 –Cu 2 CdSnS 4 crystallize as two-phase
and alloys of the triangle Cu 4 SnS 4 –Cu 2 CdSnS 4 –U 2 crys-
150 L.V. Piskach et al. / Journal of Alloys and Compounds 279 (1998) 142 – 152

Table 10
DTA results of Cu 2 Sn 4 S 9 –F section
No Phase composition, mol % Temperature, K
Cu 2 Sn 4 S 9 F liquid subliquid solid subsolid
1 100 0 1060 – – 943
2 95 5 – – 1056 941
3 90 10 1075 – 1053 941
4 80 20 1129 1088, 1059 – 954, 940
5 75 25 1143 – 1091 956
6 70 30 1162 1091 – 944
7 60 40 1185 1117 1082 947
8 50 50 1208 1129 1078 957
9 40 60 1218 1162 1073 953
10 30 70 1301 1178 1073 –
11 20 80 – – 1141 –
12 10 90 – 1164 1137 –
13 5 95 – 1213 1142 –
14 0 100 – – 1281 –

tallize according to the eutectic process L⇔a1Cu 4 SnS 4 1
Cu 2 CdSnS 4 (E 1 ) after the complete separation of a-phase.
The last process is also typical for other alloys of the
triangle g-Cu 4 SnS 4 –Cu 2 CdSnS 4 (Fig. 14). The peritectic
process L1a1g⇔Cu 4 SnS 4 takes place in point P1 at 1083
k. It is a reason for existence of the field Cu 4 SnS 4 on the
liquidus surface.
Crystallization of alloys of the quasi-ternary subsystem
Cu 2 SnS 3 –CdS–SnS 2 is complicated by the simultaneous
existence of the two quaternary phases. The phase
Cu 2 CdSn 3 S 8 forms according to the peritectic process
L1b⇔e-Cu 2 CdSn 3 S 8 at 1091 K and has an eutectic
reaction L⇔d1e-Cu 2 CdSn 3 S 8 with SnS 2 (d-solid solu-
tion) at 1073 K. That is why alloys, which belong to the
Fig. 13. The projection of the liquid surface of the quasi-ternary system
Cu 2 S–CdS–SnS 2 .
sections CdS–Cu 2 CdSn 3 S 8 and Cu 2 CdSn 3 S 8 –SnS 2 , crys-
tallize as two-phase. For all alloys of the triangle b–d-
Cu 2 CdSn 3 S 8 the eutectic process of crystallization L⇔b1
d1e-Cu 2 CdSn 3 S 8 (E 3 ) is typical. The alloys of the
peritectic quadrilateral b-Cu 2 CdSnS 4 –Cu 2 CdSn 3 S 8 –U 3
crystallize as three-phase according to the process L1
b⇔Cu 2 CdSnS 4 1e-Cu 2 CdSn 3 S 8 in the triangle b-
Cu 2 CdSnS 4 –Cu 2 CdSn 3 S 8 and as two-phase on the line
Cu 2 CdSnS 4 –Cu 2 CdSn 3 S 8 . For other alloys of this quad-
rilateral the process L1Cu 2 CdSnS 4 ⇔e-Cu 2 CdSn 3 S 8 1g
takes place, when the figurative point of liquid comes into
the invariant point U 4 .
In the triangle g-Cu 2 CdSnS 4 –Cu 2 CdSn 3 S 8 the alloys
are three-phase and on the line g–e-Cu 2 CdSn 3 S 8 alloys are
two-phase. The amount of Cu 2 CdSnS 4 in the region g–
U 4 –Cu 2 CdSn 3 S 8 is not enough for complete accomplish-
ment of the peritectic reaction, that is why the crys-
tallization of the alloys is finishing together with other
alloys of triangle g–d–Cu 2 CdSn 3 S 8 by a ternary eutectic
process L⇔g1d1e–Cu 2 CdSn 3 S 8 at 1055 K (E 2 ). The
solubility on the basis of binary Cu 2 S, CdS, SnS 2 and
ternary compounds Cu 2 SnS 3 , Cu 2 Sn 4 S 9 cause the exist-
ence of one-phase alloys in the solid solution regions. The
alloys, which do not belong to the invariant process, are
two-phase and crystallize by binary invariant processes
(Fig. 14).
One should mention the participation of the compound
Cu 2 Sn 4 S 9 in the solid state process, which takes place in
the CdS–Cu 2 SnS 3 –SnS 2 subsystem. The formation of
phase Cu 2 Sn 4 S 9 on the quasi-binary section Cu 2 S–SnS 2
corresponds to the peritectoid process Cu 2 SnS 3 1 SnS 2 ⇔
Cu 2 Sn 4 S 9 at 943 K. As is shown in the isothermal section
at 770 K (Fig. 14), the compound Cu 2 Sn 4 S 9 (m-solid
solution) has the equilibria g–m, d–m and m–e9–
Cu 2 CdSn 3 S 8 . The investigation of some alloys, which
were annealed at 970 K (Fig. 15) [20], show that the
equilibria e-Cu 2 CdSn 3 S 8 –g take place in this part of the
 L.V. Piskach et al. / Journal of Alloys and Compounds 279 (1998) 142 – 152 151

Table 11
Type and temperature of invariant processes in the quasi-ternary Cu 2 S–CdS–SnS 2 system

triangle. That is why we consider that two solid state

processes g1d⇔m1e9-Cu 2 CdSn 3 S 8 and g1e9-
Cu 2 CdSn 3 S 8 ⇔m1Cu 2 CdSnS 4 should take place at lower
temperatures. Deviations of the temperature measurements
(65 K) did not allow to separate the temperatures of these

Table 12
Composition of the ternary invariant points in the quasi-ternary Cu 2 S–
CdS–SnS 2 system
Invariant Composition, mol %
points
Cu 2 S CdS SnS 2
E1 54 8 38
E2 14 5 81
E3 4 17 79
P1 61 7 32
U1 54 14 32
U2 55.5 9.5 35
U3 27 9 64
Fig. 14. The isothermal section of the quasi-ternary system Cu 2 S–CdS–
U4 27 6 67
SnS 2 at 770 K.
152 L.V. Piskach et al. / Journal of Alloys and Compounds 279 (1998) 142 – 152
Fig. 15. The isothermal section of the quasi-ternary system Cu 2 S–CdS–
SnS 2 at 970 K in the region Cu 2 SnS 3 –Cu 2 CdSnS 4 –SnS 2 .
reactions, that is why they are shown schematically at 941
K and 940 K, respectively.
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