Investigation of the CuGaJn, -,Se, Solid SolutionsThe CuTnSe, and CuGaSe, semiconducting compounds refer to the ternary AIBIITCVr type compounds crystallizing in the chalcopyrite structure and are the electron analogues of the AI1BV1 ones. The interest aroused by them is due to the fact that they are promising materials for fabricating light emitting diodes (WAGNER et al.), solar cells based on heterotransitions with the ATIBV1 compounds (SHAY et al. ; ROMEO et al. as well as nonlinear materials (BOYD et al.) Of some interest are the solid solutions based on the CuInSe, and CuGaSe, compounds, making it possible to change smoothly different physical-chemical parameters. Up to now the literature data on the CuGa,Inl-,Se, solid solution properties is scarce (HORIG et al. ; PAORICI et al.). The aim of the present paper is to plot the phase diagram and to study the growth conditions of single crystals as well as their dislocation structure.Copper (99.999%), indium, sulphur, and selenium (99.9999%) were used as starting materials for obtaining the CuGaSe,, CuInSe, ternary compounds and the CuGa,Inl -&e, solid solutions. The synthesis of the above mentioned compounds and solid solutions was carried out in a vertical furnace in doubIe quartz ampoules. The total charge was 10-15 g. The synthesis was made in the following way : the temperature of the furnace was slowly raised up to 650-700 "C and the ampoule was kept a t this temperature for 2 hr, then up to 1050 -1100 "C, with the melt being kept vibrating for 2 -3 hr. Then the melt was quenched up to room temperature. To achieve homogeneity of the obtained ternary CuGaSe,, CuInSe compounds and the CuGa,Inl-,Se, solid solutions the annealing was carried out for 20 d.The composition of the CuGaSe, and CuInSe, ternary compounds and the CuGa,Inl-,Se, solid solutions was tested by chemical analysis. The Cu, Ga, In, and Se elements were determined using the methods given by SRARLO, and ISHCHENKO e t a l . The chemical analysis data given in Table 1 from which it is seen that the experimental data agree with the calculated ones.The homogeneity and structure of the investigated compounds and solid solutions were determined by an X-ray method. X-ray patterns were taken by a URS-50 IM apparatus (copper filtered radiation). The investigations showed that the CuGaSe,, CuInSe, ter nary compounds and their solid solutions crystallize in the chalcopyrite structure (the I42d space group). The lattice periods, calculated according to well resolved doublet lines (424), (2281, (512), and (336) are for CuGaSe, a = 5.616 5 0.002 A; c = 11.016 f 0.005 A and for CuInSe, a = 5.782 f 0.002 A ; c = 11.620 & 0.005 A. The change of the lattice periods a and c obeys Vegard's law.The temperature of phase transformations were determined by the DTA method on an apparatus described by BELEVICH et al. with an accuracy of &2". The DTA measurements
Despite the fact that the ternary compounds AIBmCr and their solid solutions attract great attention due to their possible application in semiconducting devices, up to now there is scarce information about the properties of CuGax19 -xSe2 solid solutions in the literature /1 to 3/. In /2/ the temperature and composition dependences of the band gap (E ) of these solid solutions grown by a modified Bridgman method are investigated in the composition range 0 5 x 0.5, the optical and electrical properties of this system a r e studied at room temperature on specimens of some compositions obtained by a chemical transport method /3/. The results Of /2/ and /3/ on the composition dependence of the band gap essentially differ: in /2/ E changes linearly with composition, and in /3/ this dependence is nonlinear. These investigations were carried out on single crystals grown by a chemical transport method. The specimens were flat mirror-like plates, with surface corresponding to (112). The homcgeneity was tested by an X-ray method.The solid solution composition was determined taking into account the validity of Vegard' s law /1 to 3/, the accuracy of cornposition determination being *l mol%.The transmission spectra in the range from 6000 to 15000 crn" were taken using a SP-700 C spectrophotometer with polarized light. Previously the specimens were polished and lapped from one side to a thickness bf about 100 to 1501.1 m. The absorption coefficient ( OL ) was calculated using the estimated transmission (T) and reflection (R) by the well-known expression which takes into account multiple reflection:1) Podlesnaya 17, 220726 Minsk, USSR.
Thermal properties of a series of ternary compounds of the AIBIrlCgl -type and those of the C U I~S~, S~~(~ -x) solid solutions have been investigated by BODNAR, KOR-XIJN ; MAKOVETSKAYA, BODNAR e t al. ; MAKUVETSKAYA, BUNDAR e t al. (in press). No analogous literature on the CuGa,Inl -,Se, solid solutions is reported so far. The aim of this paper is to study thermal expansion and conductivity of the CuGa,Inl-,Se, solid solutions, where polymorphous transformations occur.The investigations were carried out on the samples obtained by one temperature synthesis with vibration (BODNAR, BOLOGA) or by the method described by BODNAR
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