L P Marushko, Y E Romanyuk, L V Piskac - The reciprocal system cugas2cuinse2cugase2cuins2 - страница 1
Chemistry of Metals and Alloys
Chem. Met. Alloys 3 (2010) 18-23 Ivan Franko National University of Lviv www. chemetal-j ournal.org
The reciprocal system CuGaS2+CuInSe2±+CuGaSe2+CuInS2
L.P. MARUSHKO1*, Y.E. ROMANYUK2, L.V. PISKACH1, O.V. PARASYUK1, I.D. OLEKSEYUK1, S.V. VOLKOV3, V.I. PEKHNYO3
1 Department of Inorganic and Physical Chemistry, Lesya Ukrainka Volyn National University,
Voli Ave 13, 43025 Lutsk, Ukraine
2 EMPA, Swiss Federal Laboratories for Materials Science and Technology,
Uberlandstrasse 129, CH 8600 Dubendorf, Switzerland
3 V.I. Vernadskii Institute of General and Inorganic Chemistry of the Ukrainian National Academy of Sciences,
Acad. Palladina Ave 32/34, 03680 Kyiv-142, Ukraine * Corresponding author. Tel./fax: +380-3322-41007; e-mail: email@example.com
Received February 18, 2010; accepted June 29, 2010; available on-line November 5, 2010
Phase equilibria in the reciprocal system CuGaS2+CuInSe2^CuGaSe2+CuInS2 were investigated by differential thermal and X-ray phase analyses. The isothermal section of the system at 870 K was constructed. The region of existence of the a-solid solution range of the system components with chalcopyrite structure was determined. The vertical sections CuGaS2-CuGaSe2 and CuGaS2-CuInSe2 were constructed from DTA data.
Phase diagram / Isothermal section / Solid solution Introduction
The finite quantity of fossil resources accelerates the development of renewable energy sources, of which solar energy is a promising front-runner. Increase of the efficiency and reduction of the cost of solar cells are researched both by trying to improve the production technology for cells based on already known materials and by searching for new materials. Alternatives to classic silicon in solar cells are CuInSe2 (CIS) and its solid solutions. Among the primary challenges in the search for new materials the optimization of the composition of the solid solutions CuInSxSe2_x, CuInxGa1_xSe2 (CIGS), CuInxGa1-xSySe2_y (CIGSSE) is attracting most interest [1-8].
The working element of CIS-based solar cells is the CIS/CdS heterojunction where p-type CIS is the absorption layer and n-type CdS is the buffer layer. The study of systems that combine the heterojunction components has interesting practical applications.
We have earlier investigated the ternary reciprocal systems CuInS2+2CdSe ±+ CuInSe2+2CdS , CuGaS2+2CdSe±+CuGaSe2+2CdS  and the ternary systems CuGaS2_CuInS2_2CdS , CuGaSe2_ CuInSe2_2CdSe , which are the bounding sides of the quaternary reciprocal system
CuIn, CuGa,Cd || S,Se (Fig. 1) that covers all variants of solid solutions of the ternary phases and the cadmium chalcogenides CdS and CdSe.
The CuInS2+2CdSe±+CuInSe2+2CdS system features the existence of a y-phase, which is a solid solution range of HT-modifications of CuInS2 and CuInSe2 with the sphalerite structure that is stabilized at the annealing temperatures (620 K and 870 K) by cadmium chalcogenides . Physical properties of y-solid solutions were studied on single crystals grown by the horizontal Bridgman method . The crystals were photosensitive, primarily of p-type, with a carrier concentration of 1015-1016 cm_3 and mobility 18 cm/(V-s); their bandgap energy ranges from 1.05 to 1.43 eV, thus suitable for the use in photovoltaic cells.
Fig. 1 Quaternary reciprocal system CuIn, CuGa,Cd || S,Se and the position of the reciprocal system
Minor y-solid solution ranges have been found in the CuGaS2+2CdSe±+CuGaSe2+2CdS system centered at the quaternary compound CuCd2GaSe4  and in the CuInS2_CuGaS2_2CdS system .
The CuGaSe2_CuInSe2_2CdSe system exhibits a large range of y-solid solutions based on the stabilized HT-CuInSe2 and the CuCd2GaSe4 phases. Using the horizontal Bridgman method, 11 single crystals were grown from the y-solid solution range along the 'CuCd2InSe4'_CuCd2GaSe4 section .
The object of this paper is the reciprocal system CuGaS2+CuInSe2±+CuGaSe2+CuInS2, which is also one of the bounding sides of the quaternary reciprocal system CuIn, CuGa,Cd || S,Se.
Literature data on the quasi-binary systems
The CuGaS2-CuGaSe2 system
The CuGaS2_CuGaSe2 system was studied in . The CuGaS2 thermogram features one effect at 1515 K, which corresponds to the melting point of the compound; the CuGaSe2 thermogram shows two effects at 1320 and 1345 K. Two similar effects are observed for solid solutions near CuGaSe2. The authors describe the thermal effect of CuGaSe2 at 1320 K as an order-disorder polymorphous transition (cation-cation disordering) and ascribe the investigated phase diagram to Type I of Roozeboom's classification. The ternary compounds and their solid solutions crystallize in the chalcopyrite structure.
The CuInS2-CuInSe2 system
The CuInS2_CuInSe2 phase diagram was investigated in [9,15,16]. Two continuous solid solution series were found in the system, as well as a limited solid solution range of HT(2)-CuInS2, which undergoes a metatectic decomposition (P—L+y) at 1315 K. The coordinates of the invariant point are 31 mol.% CuInSe2 and 1315 K.
The CuGaS2-CuInS2 system
The CuGaS2_CuInS2 phase diagram was investigated in [17,18]. Our report  established that the CuGaS2_CuInS2 diagram is of peritectic type with two peritectic points: 45 mol.% CuGaS2, 1426 K and 68 mol.% CuGaS2, 1451 K. The system features a continuous a-solid solution series and two limited P-and y-solid solution ranges, based on the HT(1) and HT(2) modifications of CuInS2, respectively.
The CuGaSe2-CuInSe2 system
The CuGaSe2_CuInSe2 system was investigated in [12,22]. The phase diagram  was ascribed to Type I of Roozeboom's classification. The thermograms of the ternary compounds feature two thermal effects, at 1318 and 1361 K for CuGaSe2, and at 1083 and 1259 K for CuInSe2. The phase transitions at 1318 and 1083 K were interpreted as cation-cation disordering. Similar phase transitions characterize the solid solution CuGaxIn1_xSe2 in the entire concentration range. However, the phase diagram is inconsistent with the fact that CuGaSe2 forms in the Cu2Se_Ga2Se3 system by a peritectic reaction [19-21]. This was the reason for the re-investigation of the system. Our diagram  agrees well with the version in  at low temperatures, but features additional fields at near-liquidus temperatures in the CuGaSe2-rich region, which are caused by the incongruent formation of copper selenogallate.
Single crystals of the solid solution CuGaxIn1_xSe2 obtained in  had the chalcopyrite structure and p-type conductivity.
A total of 90 alloys were synthesized for the investigation of the phase equilibria in the reciprocal system CuGaS2+CuInSe2±+CuGaSe2+CuInS2; their compositions are presented in Fig. 2. The alloys were synthesized from the elements (Cu, Ga, In, S, Se) with a content of the main element of at least 99.99 wt.%. The calculated amounts were placed into quartz ampoules that were evacuated to the residual pressure 10_2 Pa and soldered. The synthesis was performed in two stages. At the first stage the ampoules with the batches were heated in the flame of an oxygen-gas burner with visual control of the process (to complete bonding of sulfur). At the second stage the ampoules were heated in a single-zone shaft-type furnace at the rate of 50 K/h to a maximum synthesis temperature of 1470 K. After 2-3 h exposure the ampoules were
slowly cooled at the rate of 10 K/h to 870 K. The
samples were annealed at this temperature for 1500 h, followed by quenching into cold water. This process resulted in compact dark-grey polycrystalline ingots.
CuGaSc,, mol. % ->•
CuGaS2 20 40 60 80 CuGaSe2
CuInS2 «о 60 40 20 CuInSe,
<- CuInS,, mol. %
Fig. 2 Chemical composition of the alloys and the isothermal section of the reciprocal system CuGaS2+CuInSe2±+CuGaSe2+CuInS2 at 870 K.
Fig. 3 Vertical section CuGaS2_CuGaSe2: 1 _ L; 2 _ L+a; 3 _ L+y'; 4 _ L+a+y'; 5 _ a+y'; 6 _ a.
Fig. 4 Variation of the unit cell parameters of the alloys of the CuGaS2_CuGaSe2 section at 870 K.
The obtained alloys were investigated by differential thermal analysis (Paulik-Paulik-Erdey derivatograph, Pt/Pt-Rh thermocouple) and XRD (DRON 4-13 diffractometer, CuKa radiation). The lattice parameters were computed using the PDWin-2 software package.
Results and discussion
The isothermal section of the reciprocal system CuGaS2+CuInSe2SCuGaSe2+CuInS2 at 870 K
The isothermal section of the reciprocal system CuGaS2+CuInSe2±+ CuGaSe2+CuInS2 at 870 K, constructed from the results of the X-ray phase analysis of the alloys, is presented in Fig. 2. At this temperature the system exists as an a-solid solution of CuGaS2, CuGaSe2, HT-CuInS2 and HT-CuInSe2 with the chalcopyrite structure that occupies the entire concentration square.
The vertical section CuGaS2-CuGaSe2
The CuGaS2_CuGaSe2 system is one of the sides of the reciprocal system. The phase diagram is non-quasi-binary above the solidus due to the incongruent melting of the CuGaSe2 compound. The vertical section is presented in Fig. 3. The liquidus consists of two lines that belong to the fields of primary crystallization of y'-phase, which participates in the peritectic process of formation of CuGaSe2 (the homogeneity region of the y'-phase is localized in the Cu2Se_Ga2Se3 section) and of the a-phase, which is the solid solution of CuGaSe2 and CuGaS2. The fields of primary crystallization are separated by the three-phase field L+a+y'. XRD data show that all alloys annealed at 870 K are single-phase and crystallize in the tetragonal chalcopyrite structure (Fig. 4), which agrees well with the results of .
The CuGaS2-CuInSe2, CuGaSe2-CuInS2 sections
The vertical section CuGaS2_CuInSe2 (Fig. 5) is a diagonal section of the phase diagram of the reciprocal system CuGaS2+CuInSe2±+ CuGaSe2+CuInS2. The section liquidus consists of the curves of primary crystallization of the a- and y-solid solutions. The section is non-quasi-binary below the liquidus (it crosses the monovariant line that separates the fields of primary crystallization of the a- and y-solid solutions). y-solid solutions of HT-CuInSe2 exist only at high temperatures and decompose upon cooling. The thermograms of selected alloys are presented in Fig. 6.
Fig. 5 Vertical section CuGaS2_CuInSe2:
1 _ L; 2 _ L+a; 3 _ L+a+y; 4 _ L+y; 5 _ y;
6 _ a+y; 7 _ a.з
800 1000 1200 1400
Fig. 6 Thermograms of alloys at the CuGaS2_ CuInSe2 section (mol.% CuInSe2): 1 _ 25; 2 _ 50; 3 _ 70.
All alloys of the CuGaS2_CuInSe2 section are single-phase at the annealing temperature and crystallize in the chalcopyrite structure of the a-solid solutions (Fig. 7). The change of the unit cell parameters with composition follows Vegard's rule (Fig. 8).
The other diagonal of the phase diagram of the reciprocal system CuGaS2+CuInSe2^CuGaSe2+CuInS2 is the CuGaSe2_ CuInS2 section. All alloys of this section are also single-phase (Figs. 9,10).
The 'CuGaSL5Se0.5'-'CuInSL5Se0.5', 'CuGaSSe'-'CuInSSe' and 'CuGaSa5SeL5'-'CuInSa5SeL5' sections
According to XRD data, all the alloys from the 'CuGaS15Se05'_'CuInS15Se05', 'CuGaSSe'_ 'CuInSSe' and 'CuGaS0.5Se1.5'_'CuInS0.5Se1.5' sections are single-phase. The change of the unit cell parameters along these sections is plotted in
Fig. 7 Diffraction patterns of alloys of the CuGaS2_CuInSe2 section (mol.% CuInSe2): 1 _ 0; 2 _ 20; 3 _ 50; 4 _ 80; 5 _ 100.
Fig. 9 Diffraction patterns of alloys of the
CuGaSe2_CuInS2 section (mol.% CuInS2):
1 _ 0; 2 _ 20; 3 _ 50; 4 _ 80; 5 _ 100.
Fig. 8 Variation of the unit cell parameters of the alloys of the CuGaS2_CuInSe2 section at 870 K.
Fig. 10 Variation of the unit cell parameters of the alloys of the CuGaSe2_CuInS2 section at
Fig. 11 Variation of the unit cell parameters of the alloys of the 'CuGaS15Se05'_ 'CuInS15Se05' section at 870 K.
Fig. 12 Variation of the unit cell parameters of the alloys of the 'CuGaSSe'_'CuInSSe' section
at 870 K.
Fig. 13 Variation of the unit cell parameters of the alloys of the 'CuGaS05Se15'_ 'CuInS05Se15' section at 870 K.
The reciprocal system CuGaS2+CuInSe2±+ CuGaSe2+CuInS2 was investigated by DTA and XRD methods. At 870 K the system is a continuous solid
solution series of its components with the chalcopyrite structure. The vertical sections CuGaS2_CuGaSe2 and CuGaS2_CuInSe2 were constructed. As CuInSe2-based solid solutions are widely used in solar cells, a thorough study of the physical properties of the solid solutions that exist in the reciprocal system CuGaS2+CuInSe2±+CuGaSe2+CuInS2 is necessary.
A. Goetzberger, C. Hebling, H.-W. Schock, Mater. Sci. Eng. 40 (2003) 1. R.W. Miles, K.M. Hynes, I. Forbes, Prog. Cryst. Growth Charact. Mater. 51 (2005) 1. K. Ramanathan, F.S. Hasoon, S. Smith, D.L. Young, M.A. Contreras, P.K. Johnson, A.O. Pudov, J.R. Sites, J. Phys. Chem. Solids 64 (2003)1495.
R.W. Miles, K.T. Ramakrishna Reddy, I. Forbes, J. Cryst. Growth 198_199 (1999) 316. T. Walter, A. Content, K.O. Velthaus, H.W. Schock, Sol. Energy Mater. Sol. Cells 26 (1992) 357.
J. Djordjevic, C. Pietzker, R. Scheer, J. Phys.
Chem. Solids 64 (2003) 1843.
V. Probst, J. Palm, S. Visbeck, T. Niesen, R. Tolle, A. Lerchenberger, M. Wendl, H. Vogt, H. Calwer, W. Stetter, F. Karg, Sol. Energy
Mater. Sol. Cells 90 (2006) 3115.
Th. Glatzel, H. Steigert, S. Sadewasser, R. Klenk, M. Ch. Lux-Steiner, Thin Solid Films 480-481 (2005) 177.
O.V. Parasyuk, I.D. Olekseyuk, V.I. Zaremba, O.A. Dzham, Z.V. Lavrynyuk, L.V. Piskach, O.G. Yanko, S.V. Volkov, V.I. Pekhnyo, J. Solid State Chem. 179 (2006) 2998. L.V. Piskach, Z.V. Lavrynyuk, O.V. Parasyuk, O.F. Zmiy, Е.М. Kadykalo, V.I. Pekhnyo, S.V. Volkov, Nauk. Visn. Volyn. Nats. Univ. 16 (2008) 47.
 L.P. Marushko, L.V. Piskach, Y.E. Romanyuk,
O.V. Parasyuk, I.D. Olekseyuk, S.V. Volkov,
V.I. Pekhnyo, J. Alloys Compd. 492 (2010)
 L.P. Marushko, Y.E. Romanyuk, L.V. Piskach, O.V. Parasyuk, I.D. Olekseyuk, S.V. Volkov, V.I. Pekhnyo, J. Alloys Compd. 505 (2010) 101.
 Y.E. Romanyuk, K.M. Yu, W. Walukiewicz,
Z.V. Lavrynyuk, V.I. Pekhnyo, O.V. Parasyuk,
Sol. Energy Mater. Sol. Cells 92 (2008) 1495.
 I.V. Bodnar, A.P. Bologa, Neorg. Mater. 18
 E.N. Kholina, V.B. Ufimtsev, A.S. Timoshyn,
Neorg. Mater. 15 (1979) 1918.  I.V. Bodnar, A.P. Bologa, B.V. Korzun, Krist. Tech. 15 (1980) 1285.
L.P. Marushko et al., The reciprocal system CuGaS2+CuInSe2^CuGaSe2+CuInS2
 I.V. Bodnar, Neorg. Mater. 17 (1981) 583.  J.C. Mikkelsen, J. Electron. Mater. 10 (1981)  L.P. Marushko, L.V. Piskach, O.V. Parasyuk, 541.
V.I. Pekhnyo, Nauk. Visn. Volyn. Nats. Univ. 13  I.V. Bodnar, A.P. Bologa, Cryst. Res. Technol.
(2007) 3. 17 (1982) 339.
 L.S. Palatnik, Ye.K. Belova, Neorg. Mater. 3  K. Yoshino, H. Yokoyama, K. Meada, T. Ikari,
(1967) 967. J. Cryst. Growth 211 (2000) 476.
 L.S. Palatnik, Ye.K. Belova, Neorg. Mater. 3 (1967) 2194.
Chem. Met. Alloys 3 (2010)