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Cu–In–S
Copper – Indium – Sulphur
Vasyl Tomashik
Introduction
The investigation of the Cu-In-S ternary system is related mainly to the studies of the CuInS2 ternary
compound which has semiconductor properties and a big practical importance (Table 1). The compound
CuIn3S5 [1972Gan, 1974Gus] is probably metastable because it does not appear in subsequent Cu2S-In2S3
diagrams. The melting point of CuInS2 equals 1090°C [1988Aks, 1980Bin, 1983Bod, 1984Bod, 1985Mec,
1991Fea], 1080 " 10°C [1990Rig], 1089 " 2°C [1981Kue, 1984Kue], 1093 " 3°C [1998Fie] and 1101°C
[1991Mat]. The melting point from [1982Thi, 1983Thi] for CuInS2 (1115°C) is substantially above the
literature values.
The melting point of the CuIn5S8 compound is 1085°C [1980Bin] (1090°C [1998Aba]).
[1998Aba] indicated the existence of one more compound, Cu3In5S9, which melts congruently at 1085°C.
According to the data of [1971Nan] the thioindate Cu3In2S6 could be obtained by precipitation in the system
CuCl2-Li3InS3-H2O using the corresponding concentrations and ratio of initial components. The CuIn11S17
compound was prepared by the reaction of alloys of the Cu and In with sulphur vapor [1977Oha].
Binary Systems
Binary systems Cu-S and In-S are accepted from [Mas2], Cu-In is from [2000Goe], it is based mainly on
[1972Jai].
Solid Phases
Crystallographic data of all unary, binary and ternary phases are listed in Table 2.
The region of the solid solutions formation around In2S3 has been investigated using X-Ray diffraction, by
[1992Py] which showed that this compound may include copper as well under the form of Cu2+ than under
the form of Cu+. Cu+ ions are found preferentially on the tetrahedral sites of the spinell-type In2S3 whereas
Cu2+ ions may be found on both sites, tetrahedral and octahedral. Cu3In4S9 compound belongs to the
CuS-In2S3 system [1998Aba].
The chalcopyrite structure of CuInS2 transforms into sphalerite (a cation-cation disordering) at 975°C
[1983Bod, 1984Bod, 1985Mec, 1991Fea] (971°C [1987Sun], 980°C [1980Bin, 1988Aks, 1998Fie],
989-995°C [1991Mat]). A cation-anion disordering or transformation into würtzite structure takes place at
1040°C [1984Bod, 1985Mec] (1035°C [1987Sun], 1045°C [1980Bin, 1988Aks], 1047°C [1991Fea,
1991Mat, 1998Fie]). The quenched samples fail to reveal any indication of crystal structure other than that
of chalcopyrite type [1987Sun].
The CuInS2 compound is slightly non-stoichiometric [1973Abr]. It was shown that the chalcopyrite
structure for the Cu-In-S system exists not only in the exact composition CuInS2 [1980Hwa]. CuInS2 was
found in nature as the mineral roquesite [1969Sut, 1973Igl]. This compound forms a sphalerite-type
structure at high pressure and high temperature [1969Ran] and this structure is characterized by a
considerable degree of disorder. The results of [1991Met] gave no indication of a tetragonal distortion of
the CuInS2 unit cell.
A CuAu-ordering was found in CuInS2 epilayers grown by molecular beam epitaxy and it was shown that
In rich condition favours the formation of such phase [1998Su].
It was shown that sulfospinel CuIn5S8 undergoes an order-disorder transformation [1980Man]. Two
different long range order superstructure were found: one is cubic and a second one is tetragonal. Electron
diffraction reveals the existence of a high-temperature disordered modification having the normal spinel
structure.
The single crystals Cu1.75In0.05S (the solid solution based on Cu2S along the Cu2S-“In2S5” section) were
obtained at the slow cooling of the melts after a long annealing at 300°C [1987Ism]. At 95°C the
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orthorhombic structure transforms in fcc phase and at 167°C a monoclinic modification turns into fcc phase.
At the crystallization from the melt two fcc phases are formed in the case of Cu1.75In0.05S composition.
There is a rigid constraint between the orthorhombic, monoclinic and fcc phases [1987Ism]: (fcc)1 +
orthorhombic + (fcc)2 + monoclinic (95°C) º (fcc)1 + (fcc)2 + monoclinic (167°C) º (fcc)1 + (fcc)2. The
analogous results were obtained by investigation of the Cu1.85In0.05S composition (the solid solution based
on Cu2S along the Cu2S-In2S3 section) in [2003Dzh].
Quasibinary Systems
The data of [1980Bin, 1987Sun], accepted by [1990Rig], suggest that DTA and XRD methods may not be
suitable techniques for the determination of the phase relationships in the Cu2S-In2S3 system. Actually, they
present a diagram which, in its CuInS2-In2S3 part, contradicts severely the later investigations of [1998Aba]
by not taking into account the formation of the new compound Cu3In5S9, which melts congruently at
1085°C and exhibits a phase transition at 800°C. It is necessary to note that Cu2S, In2S3 and their mixed
sulfides are characterized by their close melting temperatures which complicate the investigations of the
Cu2S-In2S3 quasibinary system.
[1961Fla, 1980Bin] consider that a solid solution exists between CuIn5S8 and In2S3, both compounds
having a spinel-type structure. This point of view is not shared by [1998Aba]. The solubility of In2S3 in
Cu2S at room temperature does not exceed 3 mol% [1980Mam]. Fig. 1 presents a tentative diagram of the
Cu2S-In2S3 quasibinary section. For the Cu2S-CuInS2 part it is based on [1980Bin, 1987Sun] for the
CuInS2-In2S3 part on [1998Aba]. However, severe modifications have been applied for the sake of
thermodynamic coherency. Also, the transformation temperatures of J1, J4 and J6 given by [1998Aba] have
been modified to match the currently accepted temperatures given in Table 2 and, respectively the
temperatures of the invariant reactions had to be shifted up. The whole diagram, shown in dashed lines in
Fig. 1, is considered as tentative only.
Invariant Equilibria
Known invariant equilibria in the Cu-In-S system are shown in Table 3. The invariant reactions E1, E2 and
e5 are given after [1991Fea, 1992Fea]. Compositions and temperatures for other reactions are not greported
here as they are not accepted from the original publications [1980Bin, 1987Sun,1998Aba] and taken here
as tentative only.
Liquidus, Solidus and Solvus Surfaces
The partial liquidus projection has been constructed by [1992Fea]. Fig. 2 shows the partial liquidus
projection after modifications have been made to bring it to agreement with the quasibinary section
Cu2S-In2S3 and with the accepted binary diagrams. Also the shapes of the monovariant lines were changed
to eliminate the violation of the Schreinmaker rule originating form the diagram in [1992Fea]. [1992Fea]
suggests that J1 takes part in the reaction E2, however, this is improbable according to the quasibinary
section Cu2S-CuInS2, Fig. 1. The crystallization field labeled J? in the diagram represents actually the
crystallization field of one of the three phases J1, J4 or J6. The border line between these crystallization
fields have not been determined. The solubility of CuInS2 in CuxIn1–x-melts (x = 0 - 0.2) was determined in
[1998Hac] and it was shown that the solubility decreases with increasing Cu content in the melt. Fig. 3
depicts an enlarged part of the liquidus surface near the In corner with some liquidus lines taken from
[1998Hac] after some modifications made to bring it to agreement with the accepted edge binary diagrams.
Isothermal Sections
The relevant two-phase equilibria in the Cu-In-S ternary system at 450°C are shown in Fig. 4 [1994Mig].
CuInS2 is shown to equilibrate with nearly all of the compounds at room temperature (Fig. 5) [1991Met,
1991Mig, 1992Bru]. Fig. 6 shows the area of predominance of all phases with respect to the partial pressures
of S and In [1994Mig]. The areas are separated from each other by the respective two-phase equilibria
shown in Fig. 4. It is necessary to note that Figs. 4 and 5 must be regarded as tentative.
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Cu–In–S
It was revealed that coexisting phases within the triangle Cu-CuInS2-Cu2S are CuInS2, Cu2S and Cu2In, so
no equilibrium exists between CuInS2 and Cu [1983Bin]. According to the data of [1983Thi] CuInS2, Cu2S
and CuIn coexists at 740°C. [1988Bru] showed that CuInS2 and InS could coexist in thermal equilibrium.
Temperature – Composition Sections
The In-CuInS2 (Fig. 7) and Cu-CuInS2 (Fig. 8) polythermal sections reveal a region of liquid immiscibility
indicating the extension of the two-liquid region from Cu-S binary system [1991Fea, 1992Fea]. CuS-InS
section is shown in Fig. 9 [1998Fie]: InS rich mixtures are composed of CuInS2, CuIn5S8, InS and In and
CuInS2 and CuS coexist in InS-poor mixtures.
Thermodynamics
Some thermodynamic properties of the phases formed in the Cu-In-S ternary system are given in Tables 4
and 5.
CuInS2 decomposes under steady-state conditions according to the reaction 2CuInS2(s) º Cu2S(s) + In2S(g)
+ S2(g) [1983Wie]. During the initial transient period of the CuInS2 vaporization the ion intensities of In2S+
and S2+ change and assume steady-state values after some time. In2S(g) is the most abundant species in the
vapor phase above this compound. It was established that in the case of this compound a particularly large
inharmonicity effects on the heat capacity were observed [1987Neu].
The solution enthalpy of CuInS2 dissolution in the CuxIn1–x-melts (x = 0 - 0.2) could be estimated at a value
of 800 " 20 J@mol–1 in the temperature range from 500 to 600°C and does not depend on the composition
of the solvent [1998Hac].
Notes on Materials Properties and Applications
The CuInS2 compound in the view of single crystals and films is an effective material for high-efficiency
and radiation-hard solar cell applications [1980Bin, 1988Bru, 1991Met, 1991Mig, 1992Bru, 1992Fea,
1994Mig, 1996Bod, 2000Bod, 2001Xia, 2002Laz]. It is also a candidate for the cathode material of
photochemical devices to its high performance and high output stability [2001Xia] and for preparing of
thermoelectric materials [1990Rig]. This compound has nonlinear optical properties [1980Bin].
The structural and electronic properties of CuInS2 determined and the elastic constants were derived from
stress-stress relationships by [2002Laz].
The grain size of deposited films of CuInS2 on glass substrates was smaller than 10 nm [1980Hwa]. The
as-deposited films are p-type with resistivities in the range 0.1-10 S@cm. The post-deposition heat
treatments were found to increase both the resistivity and the grain size of the thin films.
The spray pyrolysis conditions required to prepare single-phase CuInS2 films of good optical property were
optimized by [1985Tiw]. The as-deposited films had a sphalerite structure which transformed to the
chalcopyrite structure on annealing at 400°C. The resistivity of both as deposited and annealed single-phase
films changed from about 103 S@m to about 0.1 S@m with increasing Cu/In ratio in the spray solution. An
optical gap of about 1.38 eV was measured for both sphalerite and the chalcopyrite structures [1985Tiw].
The photocurrent spectra of the CuIn5S8 crystals reveal an energy band gap of 1.31 eV at room temperature
[2001Qas].
A rapid and convenient polyol method has been proposed in [2003She] to synthesize foam-like CuInS2
nanocrystal line with extended, sponge-like, porous structure by refluxing CuCl2@2H2O, InCl3@4H2O and
thiourea in ethylene glycol at 195°C. The magnetic stirring during the reaction and the ratio of reagents are
critical in the formation of the final products.
Well-defined ternary CuInS2 nanorods 20-25 nm in diameter and 400-450 nm length were synthesized by
the reaction of CuCl2, In, CS2 and NaOH at temperature as low as 180°C for 15 h when water was used as
solvent [2001Xia].
The temperature dependence of the linear coefficient of thermal expansion of CuIn5S8 is represented by the
following equations [1982Kis]: "T (°C–1) = 11.231@10–6 + 2.169@10–9T + 3.441@10–12T2 (28-685°C).
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The thermal expansion coefficient of the CuInS2 compound is equal 8.2@10–6 K–1 [1983Bod]. The linear
thermal expansion coefficient "a and "c of the lattice parameter a and c respectively are anisotropic
("a > "c) [1985Kis, 2000Bod] and their temperature dependences can be expressed as "a(T) = 9.312@10–6
+ 2.556@10–9T + 2.085@10–12T2K–1 (28-685°C) and "c(T) = 9.070@10–6TK–1 [1985Kis]. The
room-temperature value of the thermal expansion coefficient for CuIn5S8 is 11.1@10–6K–1, its temperature
dependence could be express by the equation "(T) = 7.69@10–6 + 1.41@10–8T + 1.24@10–12T2K–1 (80 - 650 K)
and temperature dependence of the " parameter is "T = 1074.1 + 7.8@10–3T + 6.3@10–6T2 + 2.15@10–9T3 pm
(80-650 K) [1997Orl].
Miscellaneous
A study of the co-precipitation of In with CuS by physicochemical analysis has shown that the process
results from formation of the compound CuInS2 [1964Rud]. This compound can be also obtained by a
hydrothermal method [1966Cam] and by a mechanical alloying method using a high-energy planetary ball
mill [1997Oht] and its single crystals could be grown by the chemical transport reactions [1973Bra,
1974Gus, 1979Pao, 1984Bod, 1988Aks]. The single crystals of CuIn5S8 could be also prepared by the
chemical transport reactions [1981Bod] or using vertical Bridgman-Stockbarger technique [1997Orl,
1998Orl] or by a travelling solvent method [2000Bod].
Single-phase films of CuInS2 exhibiting the sphalerite structure could be obtained by sulphurization of
Cu1.0In1.0 layers in an H2S flow for temperatures higher than 250°C and for temperatures higher than 375°C
in the presence of liquid S [1982Bin]. Double layers consisting of Cu covered with In could be converted
into single-phase CuInS2 at t > 325°C in the presence of liquid sulphur. The influence of deviations from
the ideal composition (Cu/In ratio) is reflected in the occurrence of particles of a second phase on the film
surface.
The supercooling of CuInS2 could reach 38°C [1990Rig].
A calculated Debye temperature for CuInS2 is equal 264 K [1976Osh] and its measured value is 273 - 277 K
[1977Bac, 1983Bod].
The enthalpy of vacancies formation in CuInS2 was calculated by [1988Kul] and its value is within the
interval from ~ 1.8 to ~ 2.5 eV.
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Aksenov, I.A., Makovetskaya, L.A, Popelnyuk, G.P, Shilovich, I.P, “Phase Diagram of
CuAlxIn1–xS2 Solid Solutions”, Phys. Status Solidi, A, A105(2), K97-K102 (1988)
(Experimental, Crys. Structure, 7)
MSIT®
306
[1988Bru]
[1988Kul]
[1990Rig]
[1991Ben]
[1991Fea]
[1991Mat]
[1991Met]
[1991Mig]
[1992Bru]
[1992Die]
[1992Fea]
[1992Py]
[1994Mig]
[1994Sub]
[1996Bod]
[1997Oht]
[1997Orl]
[1998Aba]
MSIT®
Cu–In–S
Bruessler, M., Metzner, H., Husemann, K.-D., Lewerenz, H.J., “Phase Identification in the
Cu-In-S System by (-( Perturbed Angular Correlations”, Phys. Rev. B, Cond. Matter,
38(13), 9268-9271 (1988) (Experimental, Phase Relations, 14)
Kulish, U.M., “Enthalpy of Vacancy Formation in AIBIIICVI2 Semiconductor Copper
Compounds”, Inorg. Mater. (Engl. Trans.), 24(4), 470-472 (1988), translated from Izv.
Akad. Nauk SSSR, Neorg. Mater., 24(4), 567-569 (1988) (Calculation, Thermodyn., 9)
Rigan, M.Yu., Tkachenko, V.I., Stasyuk, N.P., Novikova, L.G., “The Cu2S-In2S3 System
and Some Properties of CuInS2”, Vysokochist. Veshchestva, (3), 152-157 (1990)
(Experimental, Phase Diagram, Crys. Structure, 15)
Bente, K., Doering, T., “Solid Solution, Phase Transition, and Single Crystal Synthesis in
the System ZnS-CuInS2”, Chem. Erde, 51(4), 291-295 (1991) (Experimental, Crys.
Structure, 5)
Fearheiley, M.L., Dietz, N., Birkholz, M., Hoepfner, C., “Phase Relations in the System
In-CuInS2”, J. Electron. Mater., 20(2), 175-177 (1991) (Experimental, Phase Diagram, 17)
Matsushita, H., Endo, S., Irie, T., “Thermodynamic Properties of I-III-VI2-Group
Chalcopyrite Semiconductors”, Jpn. J. Appl. Phys., 30(6), 1181-1185 (1991)
(Experimental, Thermodyn., 9)
Metzner, H. Bruessler, M., Husemann, K.D., Lewerenz, H.J., “Characterization of Phases
and the Determination of Phase Relations in the Cu-In-S System by (-( Perturbed Angular
Correlations”, Phys. Rev. B, Cond. Matter, 44(21), 11614-11623 (1991) (Experimental,
Phase Relations, 39)
Migge, H., “Thermochemistry in the System Cu-In-S at 298 K”, J. Mater. Res., 6(11),
2381-2386 (1991) (Calculation, Phase Diagram, 31)
Bruessler, M., Metzner, H., Husemann, K.D., Lewerenz, H.J., “Characterization of CuInS2
by Perturbed Angular Correlations of ( Rays”, Non-Stoichiometry in Semicond., Proc.
Symp. Int. Conf. Adv. Mater., A3, 59-61 (1992) (Experimental, Phase Relations, 4)
Dietz, N., Fearheiley, M.L., Schroetter, S., Lewerenz, H.J., “Structural and Defect
Characterization of CuInS2 Single Crystals Grown under Elevated Pressures”, Mater. Sci.
Eng. B., 14(1), 101-109 (1992) (Experimental, Electronic Structure, Optical Prop., 60)
Fearheiley, M.L. Dietz, N., Lewerenz, H.J., “Phase Relations in the Cu-In-S System and
Growth of Large CuInS2 Single Crystals”, J. Electrochem. Soc., 139(2), 512-517 (1992)
(Experimental, Phase Diagram, Crys. Structure, Optical Prop., 35)
Py, F., Olivier-Fourcade, J., Jumas, J.-C., “Characterization of a Solid Solution Range with
Spinel Structure in the System In2S3-Cu2S-CuS” (in French), J. Solid State Chem., 99,
319-328 (1992) (Experimental, Crys. Structure, Phase Diagram, 23)
Migge, H., Grzanna, J., “Thermochemistry in the System Cu-In-S at 723 K”, J. Mater. Res.,
9(1), 125-131 (1994) (Calculation, Phase Diagram, Thermodyn., 34)
Subramanian, P.R., “Cu (Copper)”, in “Phase Diagrams of Binary Copper Alloys”,
Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E., (Eds.), ASM International, Materials
Park, OH, 1-3 (1994) (Crys. Structure, Thermodyn., Review, 16)
Bodnar, I.V., “Growth and Properties of CuAlxIn1–xS2 Single Crystals”, Inorg. Mater.
(Engl. Trans.), 32(9), 936-939 (1996) (Experimental, Crys. Structure, 11)
Ohtani, T., Maruyama K., Ohshima, K., “Synthesis of Copper, Silver, and Samarium
Chalcogenides by Mechanical Alloying”, Mater. Res. Bull., 32(3), 343-350 (1997)
(Experimental, Crys. Structure, 30)
Orlova, N.S., Bodnar I.V., Kudritskaya, E.A., “Structure and Physicochemical Properties of
CuIn5S8”, Inorg. Mater. (Engl. Trans.), 33(8), 784-786 (1997), translated from Izv. Akad.
Nauk SSSR, Neorg. Mater., 33(8), 932-934 (1997) (Experimental, Crys. Structure, Phys.
Prop., 6)
Abasova, A.Z., Gasanova, L.G., Kyazym-zade, A.G., “Cu3In5S9 Single Crystals Growth
and the Investigation of their Photoelectric Properties”, Inst. Phys. Conf. Ser., Ternary and
Landolt-Börnstein
New Series IV/11C1
Cu–In–S
[1998Fie]
[1998Hac]
[1998Orl]
[1998Su]
[2000Bod]
[2000Goe]
[2001Hae]
[2001Qas]
[2001Xia]
[2002Laz]
[2003Dzh]
[2003She]
307
Multinary Compounds. Section A. Cryst. Growth and Characterization, (152), 87-90 (1998)
(Experimental, Crys. Structure, Electr. Prop., Phase Diagram, 1)
Fiechter, S., Diesner, K., Tomm, Y., “Phase Behaviour and Homogeneity Ranges of
Chalcopyrite-Type Compound Semiconductors”, Inst. Phys. Conf. Ser., Ternary and
Multinary Compounds. Section A. Cryst. Growth and Characterization, 152, 27-30 (1998)
(Experimental, Phase Diagram, 9)
Hack, Ch., Wolf, D., Mueller, G., “Liquid Phase Homoepitaxy of CuInS2”, Inst. Phys. Conf.
Ser., Ternary and Multinary Compounds. Section B. Thin Film Growth and
Characterization, 152, 285-288 (1998) (Experimental, Phase Relations, Morphology, 7)
Orlova, N.S., Bodnar, I.V., Kudritskaya, E.A., “Structural and Physical-Chemical
Properties of the Ternary Compounds CuIn5S8 and AgIn5S8”, Inst. Phys. Conf. Ser.,
Ternary and Multinary Compounds. Section A. Cryst. Growth and Characterization, 152,
147-150 (1998) (Experimental, Crys. Structure, Electr. Prop., Electronic Structure, 10)
Su, D.S., Neumann, W., Hunger, R., Giersig, M., Lux-Steiner, M.Ch., Lewerenz, H.J.,
“Non-Chalcopyrite Ordering in CuInS2 Epilayers on Si(111)”, Inst. Phys. Conf. Ser.,
Ternary and Multinary Compounds. Section B. Thin Film Growth and Characterization,
152, 229-232 (1998) (Experimental, Crys. Structure, 3)
Bodnar, I.V., “Growth and Properties of CuInS2 Single Crystals”, Inorg. Mater. (Engl.
Transl.), 36(2), 108-110 (2000), translated from Izv. Akad. Nauk SSSR, Neorg. Mater.,
36(2), 157-159 (2000) (Experimental, Crys. Structure, Electr. Prop., 15)
Goedecke, T., Haalboom, T., Ernst, F., “Phase Equilibria of Cu-In-Se. II. The
In-I2Se3-Cu2Se-Cu Subsystem”, Z. Metallkd., 91(8), 635-650 (2000) (Experimental, Phase
Relations, 13)n
Haeuseler, H., Elitok, E., Memo, A., Osnowsky, A., “Materials with Layered Structures XI:
X-Ray Powder Diffraction Investigations in the Systems CuIn5S8-CuIn5Se8 and
AgIn5S8-AgIn5Se8”, Mater. Res. Bull., 36, 737-745 (2001) (Experimental, Crys.
Structure, 18)
Qasrawi, A.F., Gasanly, N.M., “Crystal Data, Photoconductivity and Carrier Scattering
Mechanisms in CuIn5S8 Single Crystals”, Cryst. Res. Technol., 36(12), 1399-1410 (2001)
(Experimental, Crys. Structure, Phys. Prop., 18)
Xiao, J., Xie, Y., Tang, R., Qian, Y., “Synthesis and Characterization of Ternary CuInS2
Nanorods via a Hydrothermal Route”, J. Solid State Chem., 161, 179-183 (2001)
(Experimental, Crys. Structure, 29)
Lazewski, J., Jochym, P.T., Parlinski, K., “Band Structure, Born Effective Charges and
Lattice Dynamics of CuInS2 from Ab Initio Calculations”, J. Chem. Phys., 117(6),
2726-2731 (2002) (Calculation, Phys. Prop., 34)
Dzhafarov, K.M., “Polymorphic Transformations of Cu1.90–xMxS (M = Fe, In, x = 0, 0.05)”,
Inorg. Mater. (Engl. Trans.), 39(5), 444-448 (2003), translated from Izv. Akad. Nauk SSSR,
Neorg. Mater., 39(5), 538-542 (2003) (Experimental, Crys. Structure, 10)
Shen, G., Chen, D., Tang, K., Fang, Z., Sheng, J., Qian, Y., “Polyol-Mediated Synthesis of
Porous Nanocrystalline CuInS2 Foam”, J. Cryst. Growth, 254(1-2), 75-79 (2003)
(Experimental, Morphology, Optical Prop., 18)
Table 1: Investigations of the Cu-In-S Phase Relations, Structures and Thermodynamics
Reference
Method/Experimental Technique
Temperature/Composition/Phase Range Studied
[1953Hah]
XRD
CuInS2
[1961Fla]
XRD
CuIn5S8
[1964Rud]
XRD
CuInS2
Landolt-Börnstein
New Series IV/11C1
MSIT®
Cu–In–S
308
Reference
Method/Experimental Technique
Temperature/Composition/Phase Range Studied
[1966Cam] XRD
CuInS2
[1969Ran]
XRD
CuInS2
[1971Nan]
Method of solubility, measuring of
electroconductivity and pH
CuCl2-Li3InS3-H2O, Cu3In2S6
[1971Rob]
XRD
CuIn5S8
[1972Gan]
XRD, DTA
melting temperature / CuIn3S5
[1973Abr]
XRD
CuInS2
[1973Bra]
XRD
CuInS2
[1974Gus]
XRD, MSA, microhardness testing
melting temperature / CuIn3S5
[1977Bac]
Pulse calorimeter and semi-adiabatic 40-300 K / CuInS2
techniques
[1977Oha]
XRD
CuIn11S17
[1979Pao]
XRD
CuIn5S8
[1980Bin]
DTA, XRD
Cu2S-In2S3
[1980Gas]
XRD
CuIn5S8
[1980Hwa] XRD, TEM, SEM, Rutherford
backscattering, atomic absorption
analysis
CuInS2
[1980Mam] DTA, XRD
Cu2S-In2S3
[1980Man]
Electron microscopy and electron
diffraction
CuIn5S8
[1981Bod]
XRD
CuIn5S8
[1981Kue]
DTA
melting temperature / CuInS2
[1982Kis]
XRD
28-685°C / CuIn5S8
[1982Thi]
DTA
Cu0.5In0.5-S
[1983Bin]
XRD
Cu44In16S40
[1983Bod]
DTA
melting temperature / CuInS2
[1983Wie]
XRD, Knudsen cell mass
spectrometric techniques
629-837°C / CuInS2
[1984Bod]
DTA, XRD
melting temperature / CuInS2
[1984Kue]
Quantitative DTA
melting temperature / CuInS2
[1985Kis]
XRD
CuInS2
[1985Mec]
Quantitative DTA, XRD
melting temperature / CuInS2
[1987Ism]
DTA, XRD
Cu1.75In0.05S (35Cu2S.“In2S5”)
[1987Neu]
Heat flow calorimeter
27-227°C / CuInS2
[1987Sun]
DTA, XRD
Cu2S-In2S3
MSIT®
Landolt-Börnstein
New Series IV/11C1
Cu–In–S
309
Reference
Method/Experimental Technique
Temperature/Composition/Phase Range Studied
[1988Aks]
XRD, DTA
CuInS2
[1988Bru]
Perturbed angular correlations of rays Cu-In-S
[1990Rig]
DTA, XRD, MSA, microhardness
testing
Cu2S-In2S3
[1991Ben]
XRD
CuInS2
[1991Fea]
DTA, XRD
CuInS2-In
[1991Mat]
DTA
CuInS2
[1991Met]
Perturbed angular correlations of rays 25°C / Cu-In-S
[1991Mig]
Thermochemical analysis
[1992Bru]
Perturbed angular correlations of rays 25°C / Cu-In-S
[1992Die]
XRD, Electron microscope analysis
CuInS2
[1992Fea]
DTA, XRD
Cu-CuInS2
[1992Py]
XRD
Cu2S-CuS-In2S3
[1996Bod]
XRD
CuInS2
[1997Oht]
XRD
CuInS2
[1997Orl,
1998Orl]
XRD
80-650 K / CuIn5S8
[1998Fie]
DTA
CuS-InS
[1998Aba]
DTA, XRD
CuInS2-In2S3
[1998Hac]
SEM, electron back-scattering
diffraction, dispersive spectroscopy
500-600°C / Cu-In-S
[1998Su]
TEM, HREM
CuInS2
[2000Bod]
XRD
CuInS2
[2001Hae]
XRD
CuIn5S8
[2001Qas]
XRD
CuIn5S8
[2001Xia]
XRD, TEM, electron diffraction,
X-ray photoelectron spectroscopy,
UV-VIS absorption techniques
CuInS2
[2003Dzh]
DTA, XRD
Cu1.85In0.05S (37Cu2S@In2S3)
Landolt-Börnstein
New Series IV/11C1
25°C / Cu-In-S
MSIT®
Cu–In–S
310
Table 2: Crystallographic Data of Solid Phases
Phase/
Temperature Range
(°C)
Pearson Symbol/
Space Group/
Prototype
Lattice Parameters Comments/References
(pm)
(Cu)
< 1084.62
cF4
Fm3m
Cu
a = 361.46
at 25°C [Mas2]
melting point [1994Sub]
(In)
< 156.634
tI2
I4/mmm
In
a = 325.3
c = 494.7
at 25°C [Mas2]
($S)
115.22 - 95.5
mP64
P21/c
$S
a = 1102
b = 1096
c = 1090
$ = 96.7°
[Mas2]
("S)
< 95.5
oF128
Fddd
"S
a = 1046.4
b = 1286.60
c = 2448.60
at 25°C [Mas2]
", Cu4In
710 - 574
cI2
Im3m
W
a = 301.40
a = 304.61
20.50 at.% In at 625°C [1994Sub]
18.64 at.% In at 672°C [1941And]
$, Cu7In3
< 631
aP40
P1
Cu7In3
a = 1007.1
b = 913.1
c = 672.6
" = 90.2°
$ = 82.84°
( = 106.82°
30.0 at.% In [1980Vro]
a = 1000
b = 910
c = 672
" = 89.9°
$ = 82.6°
( = 106.9°
29.6 at.% In [1994Sub]
(, Cu9In4
684 - 631
cP52
P43m
InMn3 or Al4Cu9
a = 925.03
29.6 at.% In at 650°C [1951Rey]
*1, Cu2In
667 - 440
hP6
P63/mmc
Ni2In
a = 412.0
c = 526.3
[V-C2]
*2, Cu7In4(h2)
480 - 350
oP55
?
a = 2137.5
b = 740.5
c = 521.8
[1972Jai] superstructure of the Ni2In
type
*3, Cu7In4(h1)
450 - 298
oP88
?
a = 3419.4
b = 739.5
c = 526.2
[1972Jai] superstructure of the Ni2In
type
MSIT®
Landolt-Börnstein
New Series IV/11C1
Cu–In–S
311
Phase/
Temperature Range
(°C)
Pearson Symbol/
Space Group/
Prototype
Lattice Parameters Comments/References
(pm)
*4, Cu7In4(r)
< 389
-
-
[1972Jai]
*5, Cu15In8
< 350
-
-
[1972Jai]
CuS
< 507
hP12
P63/mmc
CuS
a = 379.4 " 0.8
c = 1633.2 " 0.1
covellite, [Mas2, 1994Sub]
*Cu2S
1130-72
cF12
Fm3m
CaF2
a = 556.7
digenite
at 80°C [Mas2, 1994Sub]
(Cu2S
< 93
oP80?
Pmnm
or
P21/nm
a = 269.5 " 0.5
b = 157.1 " 0.3
c = 135.6 " 0.3
djurleite [Mas2, 1994Sub]
$Cu2S
435-93
hP6
P63/mmc
Ni2In
a = 395
c = 675
$-chalcocite
at 125°C [Mas2, 1994Sub]
"Cu2S
< 103.5
mP44?
P21c
-
a = 1524.6 " 0.4
b = 1188.4 " 0.2
c = 1349.4 " 0.3
$ =116.35°
"-chalcocite [Mas2, 1994Sub]
"Cu7S4
< 75
oP44?
Pnma
-
a = 789 " 1.6
b = 784 " 1.6
c = 1101 " 2.2
anilite [Mas2, 1994Sub]
$InS
683 - 659
-
-
[Mas2]
"InS
< 659
oP8
Pnnm
InS
a = 444.7 " 0.1
b = 1064.8 " 0.2
c = 394.4 " 0.1
[Mas2, V-C2]
(In2S3
1090 - 750
hP7
P3m1
(In2S3
a = 380.6 " 0.1
c = 904.4 " 0.3
[Mas2, V-C2]
$In2S3
< 852
cF56
Fd3m
Al2MgO4
a = 1077.4 " 0.2
[Mas2, V-C2]
"In2S3
< 414
tI80
I41/amd
"In2S3
a = 761.8 " 0.1
c = 323.3 " 1
at 30°C [Mas2, V-C2]
In6S7
< 780
mP26
P21/m
In6S7
a = 909.0 " 0.5
b = 388.7 " 0.1
c = 1770.5 " 0.4
$ = 108.20
[Mas2, V-C2]
Landolt-Börnstein
New Series IV/11C1
MSIT®
Cu–In–S
312
Phase/
Temperature Range
(°C)
Pearson Symbol/
Space Group/
Prototype
Lattice Parameters Comments/References
(pm)
* J1, (CuInS2
1090 - 1045
ZnS (würtzite)
-
[1984Bod] Cation-anion disordered
chalcopyrite
* J2, $CuInS2
1045 - 975
cF8
F43m
ZnS (sphalerite)
-
[1984Bod] Cation-cation disordered
chalcopyrite
* J3, "CuInS2
< 975
tI16
I42d
CuFeS2
[2001Xia]
a = 551.4
c = 1113.9
a = 552.28 " 0.01 at 27°C [1985Kis]
c = 1113.21 " 0.02
a = 556.01 " 0.01 at 685°C [1985Kis]
c = 1119.84 " 0.02
c**
ZnS
a = 551
at 50 kbar and 400°C [1969Ran]
* J4, Cu3In5S9
< 1085
m*17
a = 660
b =691
c = 812
$ = 89°
[1998Aba]
* J5, CuIn3S5
< 1090
hP*
a = 1563
c = 1895
[1974Gus] probably CuFeS2 prototype
* J6, CuIn5S8
< 1085
cF56
Fd3m
Al2MgO4
a = 1068.94 " 0.01
a = 1069.22 " 0.02
a = 1069.99
a = 1071.61
a = 1073.25
a = 1074.71
a = 1076.54
a = 1078.08
[2001Hae]
at 28°C [1982Kis]
at 116°C [1982Kis]
at 234°C [1982Kis]
at 346°C [1982Kis]
at 442°C [1982Kis]
at 566°C [1982Kis]
at 685°C [1982Kis]
t**
I41/amd
a = 1060
c = 3180
Ordered spinel [1980Man]
Table 3: Invariant Equilibria
Reaction
T (°C)
Type
Phase
Composition* (at.%)
Cu
In
S
L º J1 + J4
?
e1
-
-
-
-
L º J6 + (In2S3
?
e2
-
-
-
-
L º J4 + J6
?
e3
-
-
-
-
L º Cu2S + J1
?
e4
-
MSIT®
Landolt-Börnstein
New Series IV/11C1
Cu–In–S
Reaction
T (°C)
Type
313
Phase
Composition* (at.%)
Cu
In
S
L 1 º L 2 + J1
/800
e5(max)
L1
L2
J1
38.66
65.8
25.0
27.86
34.2
25.0
33.48
~0.0
50.0
L´ º L´´ + Cu2S + J1
~800
E1
L´
L´
Cu2S
J1
53.1
71.44
66.7
25.0
13.3
28.44
0.0
25.0
33.6
0.12
33.3
50.0
L´ º L´´ + J? + InS
633
E2
L´
L´´
InS
3.1
5.0
0
60.5
91.2
50
36.4
3.8
50
* compositions are given tentatively as read from the diagram in [1992Fea]
Table 4: Thermodynamic Data of Reaction or Transformation
Reaction or Transformation Temperature
(°C)
Quantity, per mol of atoms
(kJ, mol, K)
Comments
CuInS2 º L
1089 " 2
H = 11.2 " 1.7
[1981Kue, 1984Kue]
1090
H = 16.7
[1985Mec]
1101
H = 16.53
[1991Mat]
1090
H = 10
[1980Bin]
CuInS2(h2) º CuInS2(h1)
CuInS2(h1) º CuInS2(r)
1047
989-995
H = 0.55
H = 4.16
[1991Mat]
CuInS2(h2) º CuInS2(h1)
CuInS2(h1) º CuInS2(r)
1045
980
H=2
H=4
[1980Bin]
CuIn5S8 º L
1085
H = 10
[1980Bin]
Table 5: Thermodynamic Properties of Single Phases
Phase
Temperature Range Property, per mol of atoms
(°C)
(J, mol, K)
Comments
CuInS2
25
S0 = 33.89-34.31
H0298-H00 = 4895
[1977Bac]
H0 = –81925
[1983Neu]
0
CuIn5S8
H = –55425 " 3250
[1983Wie]
27-227
cp = 23.675 – 1.3405@105 T–2 + 0.6985@10–2T
[1987Neu]
25
G = –78750 " 13500
[1991Mig]
25
G = –88430 " 930
[1991Mig]
Landolt-Börnstein
New Series IV/11C1
MSIT®
Cu–In–S
314
Fig. 1: Cu-In-S.
Tentative phase
diagram of the
Cu2S - In2S3
quasibinary system
L
1090
1085
Temperature, °C
τ 1 e1
1045
1085
τ4
e2
e3
τ6
τ2
1000
In2S3
e4
975
Cu2S
930
τ3
10
Cu 66.70
0.00
In
S 33.30
20
30
Cu 0.00
In 40.00
S 60.00
In, at.%
S
Data / Grid: at.%
Fig. 2: Cu-In-S.
Partial liquidus
projection
Axes: at.%
20
80
40
τ 4 e3
e
60
γ In2S3
p β In2S3
60
p
p
900
800
e4
40
e'
E'2
e'5
E'1
In6S7
β InS
p αInS
700
τ?
e'
e2
0
100
τ1 1
δCu2S
τ6
L1+L2
80
20
900
1100°C
e''
e
Cu
MSIT®
1000
(Cu) δCu S
2
700°C
800 E''1
20 p e
E''2
e''5
p 40
60
80 Cu In p
11 9
e''
αInS
e
e (In)
In
Landolt-Börnstein
New Series IV/11C1
Cu–In–S
315
5.0 Cu
0.00
In 95.00
S
5.00
Fig. 3: Cu-In-S.
Liquidus lines in the
enlarged In corner
4.0
S, at.%
3.0
600°C
2.0
550°C
1.0
520°C
Cu 30.00
In 60.00
S
0.00
70
80
In
90
In, at.%
S
Fig. 4: Cu-In-S.
Tentative isothermal
section at 450°C
Data / Grid: at.%
S
Axes: at.%
20
80
αIn2S3
40
τ3
τ4
τ6
60
In6S7
CuS
αInS
60
40
δCu2S
80
Cu
Landolt-Börnstein
New Series IV/11C1
(Cu)
20
20
δ1
40
60
80
L
In
MSIT®
Cu–In–S
316
S
Fig. 5: Cu-In-S.
Tentative isothermal
section at room
temperature
Data / Grid: at.%
S
Axes: at.%
20
80
αIn2S3
40
τ3
τ6
τ4
60
In6S7
CuS
αInS
αCu7S460
40
γ Cu2S
αCu2S
80
Cu
Fig. 6: Cu-In-S.
Tentative
predominance area
diagram at 450°C
20
20
(Cu)
β δ5
40
60
δ4
80
(In)
0
βIn2S3
In6S7
=0
log p In2S
αInS
-5
“In6S7”
Sliq
log pIn, Pa
In
= -10
log p In2S
Cu15In8
Inliq
Cu7In3
-10
log p In2S
= -20
log p In2S
= -30
τ6,CuIn5S8
-15
δCu2S
nS 2
CuI
τ 3,α
Cu
-20
CuS
-10
-12
-14
-16
-18
log ps, Pa
MSIT®
Landolt-Börnstein
New Series IV/11C1
Cu–In–S
Fig. 7: Cu-In-S.
Vertical section
CuInS2 - In
317
τ1+L
Temperature, °C
1000
τ2+L
τ3+L2
L2
750
L1+L2
τ3+L1+L2
L1
500
τ3+L1+α InS
250
τ3+(In)+α InS
0
Cu 50.00
In 25.00
S 25.00
Fig. 8: Cu-In-S.
Vertical section
Cu - CuInS2
40
60
80
In
In, at.%
L2+τ1
L2+τ2
L1+L2+δ Cu2S
1000
Temperature, °C
L1+L2
L2+τ3
750
L1+L2+τ3
L1+τ3+δ Cu2S
500
250
0
Cu
10
20
30
S, at.%
Landolt-Börnstein
New Series IV/11C1
40
Cu 25.00
In 25.00
S 50.00
MSIT®
Cu–In–S
318
Fig. 9: Cu-In-S.
Vertical section
CuS - InS
L+τ1
L+τ1
1000
τ1
L+τ2
L
L+τ2
τ2
Temperature, °C
L+τ3
L+τ3
τ3
750
L'+In6S7+τ3
L''+δ Cu2S+τ3
L'+α InS+τ3
L'+β InS+τ3
500
L'+α InS+τ3
CuS+τ3
250
α InS+τ3
Cu 50.00
0.00
In
S 50.00
MSIT®
10
20
30
In, at.%
40
Cu 0.00
In 50.00
S 50.00
Landolt-Börnstein
New Series IV/11C1