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Phase equilibria in the systems AgGaS2–SnS2, AgGaSe2–SnSe2
Journal of Alloys and Compounds 433 (2007) 171–174
Phase equilibria in the systems AgGaS2–SnS2, AgGaSe2–SnSe2 M.V. Shevchuk ∗ , I.D. Olekseyuk Department of General and Inorganic Chemistry, Volyn State University, 13 Voli Ave, Lutsk 43009, Ukraine Received 21 February 2006; received in revised form 16 June 2006; accepted 19 June 2006 Available online 28 July 2006
Abstract The AgGaS2 –SnS2 , AgGaSe2 –SnSe2 sections of the ternary reciprocal system AgGaS2 + SnSe2 ⇔ AgGaSe2 + SnS2 were studied by the physicochemical analysis methods. It was established that these sections are quasi-binary, type V of Roozeboom classification. Wide solid solution ranges of AgGaS2 and AgGaSe2 were discovered as well as practically the absence of solid solubility based on SnS2 and SnSe2 . The change of the lattice parameters of solid solutions was determined. The existence of the AgGaSnSe4 compound is not confirmed. © 2006 Elsevier B.V. All rights reserved. Keywords: Quasi-binary section; Solid solutions; Crystal structure; Phase diagram; Synthesis
1. Introduction The study of the AgGaS2 –SnS2 , AgGaSe2 –SnSe2 sections is a part of the systematic investigation of the reciprocal system AgGaS2 + SnSe2 ⇔ AgGaSe2 + SnS2 . The compounds of the AI BIII XVI 2 formula are widely used in non-linear optics [1,2]. To increase the transparency region and the double refraction angle, an investigation of the solid solubility of the compounds I III VI CIV XVI 2 in A B X2 is promising [3,4]. The existence of the phases AgGaGeS4 and AgGaGe3 Se8 in the systems AgGaS2 –GeS2 and AgGaSe2 –GeSe2 , respectively, is known as well as significant solid solubility ranges of the ternary compounds AgGaS2 and AgGaSe2 [5,6]. The crystal structure of the compound AgGaSnSe4 was determined in ref. [7]; it crystallizes in the tetragonal symmetry, space group (S.G.) I4d2; a = 0.5853 nm, c = 1.0820 nm. There is, in the literature, no information on the phase equilibria in the systems AgGaS2 –SnS2 and AgGaSe2 –SnSe2 , therefore, the investigation of these phase equilibria is of current interest. According to refs. [8,9], AgGaS2 and AgGaSe2 melt congruently at 1268 and 1124 K, respectively. Silver thiogallate crystallizes in the tetragonal symmetry, S.G. I4d2; a = 0.57572 nm, c = 1.03036 nm [10]. Silver selenogallate crystallizes in the tetragonal symmetry, S.G. I4d2; a = 0.5992 nm, c = 1.0880 nm ∗
Corresponding author. Tel.: +380 3322 68130; fax: +380 3322 41007. E-mail address: [email protected] (M.V. Shevchuk).
0925-8388/$ – see front matter © 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2006.06.067
[11]. According to refs. [12,13], SnS2 and SnSe2 melt congruently at 1143 and 898 K, respectively. Tin diselenide crystal¯ lizes in the monoclinic symmetry, S.G. P 3m1; a = 0.3811 nm, c = 0.6137 nm [14]. Tin disulfide crystallizes in the monoclinic ¯ symmetry, S.G. P 3m1; a = 0.3646 nm, c = 0.5879 nm [12]. 2. Experimental The synthesis of the alloys of the AgGaS2 –SnS2 and AgGaSe2 –SnSe2 sections was performed by the two-temperature method from the elementary components of high purity (Ag 99.997 wt.%, Ga 99.997 wt.%, Sn 99.999 wt.%, Se 99.997 wt.%, S 99.9997 wt.%) in quartz ampoules evacuated to 0.1 Pa using vibrational mixing. The maximum synthesis temperature was 1370 K. The alloys near the AgGaS2 and AgGaSe2 composition increase in volume during cooling [15], therefore, quartz ampoule-in-ampoule containers were used to avoid oxidation upon the cracking of ampoules. The homogenization of the alloys was attained by annealing at 720 K during 480 h followed by quenching into cold water. The alloys were investigated by differential thermal, X-ray phase and microstructure analysis. Differential thermal analysis utilized a VDTA-8M3 thermograph calibrated by the melting points of the following reference substances: In, Sn, Zn, Al, NaCl, Ge, Ag, Cu, Fe. The tungsten powder was selected as a standard. The studied samples were heated at a 10 K/min rate. Temperature was controlled by the W–Re 0.05/W–Re 0.2 thermocouple. X-ray phase analysis used a DRON 4-13 diffractometer, Cu K␣ radiation. Microstructure analysis, employed to verify the XRD data as having better precision (1 mol.% versus 3 mol.%), used a Leica VMHT Auto microhardness meter.
3. Results and discussion The phase diagram of the AgGaS2 –SnS2 system is presented in Fig. 1. It is quasi-binary belonging to type V of
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M.V. Shevchuk, I.D. Olekseyuk / Journal of Alloys and Compounds 433 (2007) 171–174 Table 1 The results of differential thermal analysis of the alloys of the AgGaS2 –SnS2 system No.
Fig. 1. The phase diagram of the system AgGaS2 –SnS2 .
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Phase composition (mol.%)
Temperature (K)
AgGaS2
SnS2
Tliquidus
Ts1
Ts2
100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
1271 1247 1233 1221 1208 1178 1164 1145 1115 1095 1062 1013 995 1012 – 1043 1063 1075 1090 1110 1143
– 1184 1133 1064 1002 996 993 993 996 993 993 996 995 992 993 993 994 993 992 993 –
– – – 798 – – – – – – – – – – – – – – – – –
Table 2 The results of differential thermal analysis of the alloys of the AgGaSe2 –SnSe2 system No.
Fig. 2. The change of the lattice parameters of the solid solution range of AgGaS2 .
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28
Phase composition (mol.%)
Temperature (K)
AgGaSe2
SnSe2
Tliquidus
Ts
100 95 90 85 80 75 70 65 60 55 50 49 47 45 40 35 30 28 26 25 24 22 20 15 10 5 3 0
0 5 10 15 20 25 30 35 40 45 50 51 53 55 60 65 70 72 74 75 76 78 80 85 90 95 97 100
1124 1104 1084 1066 1050 1035 1020 1006 987 963 942 936 929 924 901 871 856 – 859 – 866 870 874 877 889 892 893 898
– 1026 982 928 904 871 844 844 843 843 844 844 841 844 844 847 841 841 842 842 839 840 844 842 845 850 849 –
M.V. Shevchuk, I.D. Olekseyuk / Journal of Alloys and Compounds 433 (2007) 171–174
173
Roozeboom classification. The results of differential thermal analysis are given in Table 1. The system liquidus consists of two parts: the primary crystallization of ␣-solid solution range of AgGaS2 and of SnS2 . The wide solid solution range of AgGaS2 extends at the eutectic temperature to 21 mol.% SnS2
and narrows to 13 mol.% SnS2 at 720 K. The lattice parameters change from a = 0.5759 nm, c = 1.0306 nm for AgGaS2 to a = 0.5751 nm, c = 1.0286 nm for the boundary composition of the solid solution at 720 K (Fig. 2). The solid solubility based on SnS2 is virtually nil, as witnessed by the invariability of the reflection angles of the diffraction patterns of the samples in the two-phase regions. The microstructure analysis supports the XRD data on the phase composition. The eutectic point coordinates are 59 mol.% SnS2 and 994 K. The phase diagram of the AgGaSe2 –SnSe2 system is shown in Fig. 3. It belongs to Roozeboom type V as well. The results of differential thermal analysis are listed in Table 2. The system liquidus consists of two parts: the primary crystallization of ␣solid solution range of AgGaSe2 and of SnSe2 . The wide solid solution range of AgGaSe2 extends at the eutectic temperature to 29 mol.% SnSe2 which narrows to 26 mol.% SnSe2 at 720 K. The lattice parameters within the solid solution range change from a = 0.5992 nm, c = 1.0880 nm for AgGaSe2 to a = 0.5922 nm, c = 1.080 nm for the boundary solid solution (Fig. 4). The solid solubility based on SnSe2 is practically absent. The eutectic point coordinates are 71 mol.% SnSe2 , 843 K. Based on the analysis of the DTA data, the diffraction patterns of the investigated alloys (Fig. 5), the change of the lattice parameters of
Fig. 4. The change of the lattice parameters of the solid solution range of AgGaSe2 .
Fig. 5. Diffraction patterns of the alloys of the system AgGaSe2 –SnSe2 .
Fig. 3. The phase diagram of the system AgGaSe2 –SnSe2 .
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M.V. Shevchuk, I.D. Olekseyuk / Journal of Alloys and Compounds 433 (2007) 171–174
the solid solution range of AgGaSe2 and the microstructure studies, the existence of the compound AgGaSnSe4 could not confirmed. The solid solution ranges of the initial compounds AgGaS2 (Se2 ) are promising new materials for optoelectronics. References [1] D.T. Huseinov, N.E. Hasanov, A.G. Kyazym-Zade, R.K. Nani, Phys. Technol. Semicond. 15 (1981) 1811–1814. [2] V.V. Badikov, I.E. Matveev, S.M. Pshenichnikov, Kristalografia 26 (1981) 537. [3] O.H. Hydhes, J.C. Wooley, S.A. Lopez-Rivere, B.R. Pamplin, Solid State Commun. 35 (1980) 573. [4] B.R. Pamplin, T. Ohachi, S. Maeda, Inst. Phys. Conf. Ser. 35 (1977) 35–42. [5] I.D. Olekseyuk, G.P. Gorgut, M.V. Shevchuk, Polish J. Chem. 76 (2002) 915–919.
[6] I.D. Olekseyuk, A.V. Gulyak, L.V. Sysa, G.P. Gorgut, A.F. Lomzin, J. Alloys Compd. 241 (1996) 187–190. [7] E.R. de Gil, C.D. Gomez, A.V. Rivera, A. Lopez-Rivera, Prog. Cryst. Growth Charact. 10 (1985) 217–223. [8] S.N. Nenasheva, E.F. Sinyakova, Izv. Acad. Nauk USSR Neorgan. Mater. 19 (1983) 1622. [9] J.C. Mikkelsen, Mater. Res. Bull. 12 (1977) 497–502. [10] V.B. Lazarev, Z.Z. Kish, E.Yu. Peresh, E.E. Semrad, Complex Chalcogenides in AI–BIII–CVI Systems, Metallurgiya, Moscow, 1993, p. 240 (in Russian). [11] L.S. Palatnik, E.K. Belova, Neorgan. Mater. 3 (1967) 967–973. [12] M.I. Karakhanova, A.S. Pashinkin, A.V. Novoselova, Izv. Acad. Nauk USSR Neorgan. Mater. 2 (1966) 991–996. [13] A.Z. Hajiyeva, P.G. Rustamov, B.N. Mardakhayev, Azeri Khim. Zh. 4 (1973) 138–141. [14] N.K. Abrikosov, L.E. Shelimova, Semiconductor Chalcogenides and Their Alloys, Nauka, Moscow, 1975. [15] O.E. Andreyeva, N.S. Orlova, I.V. Bondar, Mater. Electron. 3 (1999) 66–70.
Phase equilibria in the systems AgGaS2–SnS2, AgGaSe2–SnSe2 M.V. Shevchuk ∗ , I.D. Olekseyuk Department of General and Inorganic Chemistry, Volyn State University, 13 Voli Ave, Lutsk 43009, Ukraine Received 21 February 2006; received in revised form 16 June 2006; accepted 19 June 2006 Available online 28 July 2006
Abstract The AgGaS2 –SnS2 , AgGaSe2 –SnSe2 sections of the ternary reciprocal system AgGaS2 + SnSe2 ⇔ AgGaSe2 + SnS2 were studied by the physicochemical analysis methods. It was established that these sections are quasi-binary, type V of Roozeboom classification. Wide solid solution ranges of AgGaS2 and AgGaSe2 were discovered as well as practically the absence of solid solubility based on SnS2 and SnSe2 . The change of the lattice parameters of solid solutions was determined. The existence of the AgGaSnSe4 compound is not confirmed. © 2006 Elsevier B.V. All rights reserved. Keywords: Quasi-binary section; Solid solutions; Crystal structure; Phase diagram; Synthesis
1. Introduction The study of the AgGaS2 –SnS2 , AgGaSe2 –SnSe2 sections is a part of the systematic investigation of the reciprocal system AgGaS2 + SnSe2 ⇔ AgGaSe2 + SnS2 . The compounds of the AI BIII XVI 2 formula are widely used in non-linear optics [1,2]. To increase the transparency region and the double refraction angle, an investigation of the solid solubility of the compounds I III VI CIV XVI 2 in A B X2 is promising [3,4]. The existence of the phases AgGaGeS4 and AgGaGe3 Se8 in the systems AgGaS2 –GeS2 and AgGaSe2 –GeSe2 , respectively, is known as well as significant solid solubility ranges of the ternary compounds AgGaS2 and AgGaSe2 [5,6]. The crystal structure of the compound AgGaSnSe4 was determined in ref. [7]; it crystallizes in the tetragonal symmetry, space group (S.G.) I4d2; a = 0.5853 nm, c = 1.0820 nm. There is, in the literature, no information on the phase equilibria in the systems AgGaS2 –SnS2 and AgGaSe2 –SnSe2 , therefore, the investigation of these phase equilibria is of current interest. According to refs. [8,9], AgGaS2 and AgGaSe2 melt congruently at 1268 and 1124 K, respectively. Silver thiogallate crystallizes in the tetragonal symmetry, S.G. I4d2; a = 0.57572 nm, c = 1.03036 nm [10]. Silver selenogallate crystallizes in the tetragonal symmetry, S.G. I4d2; a = 0.5992 nm, c = 1.0880 nm ∗
Corresponding author. Tel.: +380 3322 68130; fax: +380 3322 41007. E-mail address: [email protected] (M.V. Shevchuk).
0925-8388/$ – see front matter © 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2006.06.067
[11]. According to refs. [12,13], SnS2 and SnSe2 melt congruently at 1143 and 898 K, respectively. Tin diselenide crystal¯ lizes in the monoclinic symmetry, S.G. P 3m1; a = 0.3811 nm, c = 0.6137 nm [14]. Tin disulfide crystallizes in the monoclinic ¯ symmetry, S.G. P 3m1; a = 0.3646 nm, c = 0.5879 nm [12]. 2. Experimental The synthesis of the alloys of the AgGaS2 –SnS2 and AgGaSe2 –SnSe2 sections was performed by the two-temperature method from the elementary components of high purity (Ag 99.997 wt.%, Ga 99.997 wt.%, Sn 99.999 wt.%, Se 99.997 wt.%, S 99.9997 wt.%) in quartz ampoules evacuated to 0.1 Pa using vibrational mixing. The maximum synthesis temperature was 1370 K. The alloys near the AgGaS2 and AgGaSe2 composition increase in volume during cooling [15], therefore, quartz ampoule-in-ampoule containers were used to avoid oxidation upon the cracking of ampoules. The homogenization of the alloys was attained by annealing at 720 K during 480 h followed by quenching into cold water. The alloys were investigated by differential thermal, X-ray phase and microstructure analysis. Differential thermal analysis utilized a VDTA-8M3 thermograph calibrated by the melting points of the following reference substances: In, Sn, Zn, Al, NaCl, Ge, Ag, Cu, Fe. The tungsten powder was selected as a standard. The studied samples were heated at a 10 K/min rate. Temperature was controlled by the W–Re 0.05/W–Re 0.2 thermocouple. X-ray phase analysis used a DRON 4-13 diffractometer, Cu K␣ radiation. Microstructure analysis, employed to verify the XRD data as having better precision (1 mol.% versus 3 mol.%), used a Leica VMHT Auto microhardness meter.
3. Results and discussion The phase diagram of the AgGaS2 –SnS2 system is presented in Fig. 1. It is quasi-binary belonging to type V of
172
M.V. Shevchuk, I.D. Olekseyuk / Journal of Alloys and Compounds 433 (2007) 171–174 Table 1 The results of differential thermal analysis of the alloys of the AgGaS2 –SnS2 system No.
Fig. 1. The phase diagram of the system AgGaS2 –SnS2 .
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Phase composition (mol.%)
Temperature (K)
AgGaS2
SnS2
Tliquidus
Ts1
Ts2
100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
1271 1247 1233 1221 1208 1178 1164 1145 1115 1095 1062 1013 995 1012 – 1043 1063 1075 1090 1110 1143
– 1184 1133 1064 1002 996 993 993 996 993 993 996 995 992 993 993 994 993 992 993 –
– – – 798 – – – – – – – – – – – – – – – – –
Table 2 The results of differential thermal analysis of the alloys of the AgGaSe2 –SnSe2 system No.
Fig. 2. The change of the lattice parameters of the solid solution range of AgGaS2 .
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28
Phase composition (mol.%)
Temperature (K)
AgGaSe2
SnSe2
Tliquidus
Ts
100 95 90 85 80 75 70 65 60 55 50 49 47 45 40 35 30 28 26 25 24 22 20 15 10 5 3 0
0 5 10 15 20 25 30 35 40 45 50 51 53 55 60 65 70 72 74 75 76 78 80 85 90 95 97 100
1124 1104 1084 1066 1050 1035 1020 1006 987 963 942 936 929 924 901 871 856 – 859 – 866 870 874 877 889 892 893 898
– 1026 982 928 904 871 844 844 843 843 844 844 841 844 844 847 841 841 842 842 839 840 844 842 845 850 849 –
M.V. Shevchuk, I.D. Olekseyuk / Journal of Alloys and Compounds 433 (2007) 171–174
173
Roozeboom classification. The results of differential thermal analysis are given in Table 1. The system liquidus consists of two parts: the primary crystallization of ␣-solid solution range of AgGaS2 and of SnS2 . The wide solid solution range of AgGaS2 extends at the eutectic temperature to 21 mol.% SnS2
and narrows to 13 mol.% SnS2 at 720 K. The lattice parameters change from a = 0.5759 nm, c = 1.0306 nm for AgGaS2 to a = 0.5751 nm, c = 1.0286 nm for the boundary composition of the solid solution at 720 K (Fig. 2). The solid solubility based on SnS2 is virtually nil, as witnessed by the invariability of the reflection angles of the diffraction patterns of the samples in the two-phase regions. The microstructure analysis supports the XRD data on the phase composition. The eutectic point coordinates are 59 mol.% SnS2 and 994 K. The phase diagram of the AgGaSe2 –SnSe2 system is shown in Fig. 3. It belongs to Roozeboom type V as well. The results of differential thermal analysis are listed in Table 2. The system liquidus consists of two parts: the primary crystallization of ␣solid solution range of AgGaSe2 and of SnSe2 . The wide solid solution range of AgGaSe2 extends at the eutectic temperature to 29 mol.% SnSe2 which narrows to 26 mol.% SnSe2 at 720 K. The lattice parameters within the solid solution range change from a = 0.5992 nm, c = 1.0880 nm for AgGaSe2 to a = 0.5922 nm, c = 1.080 nm for the boundary solid solution (Fig. 4). The solid solubility based on SnSe2 is practically absent. The eutectic point coordinates are 71 mol.% SnSe2 , 843 K. Based on the analysis of the DTA data, the diffraction patterns of the investigated alloys (Fig. 5), the change of the lattice parameters of
Fig. 4. The change of the lattice parameters of the solid solution range of AgGaSe2 .
Fig. 5. Diffraction patterns of the alloys of the system AgGaSe2 –SnSe2 .
Fig. 3. The phase diagram of the system AgGaSe2 –SnSe2 .
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M.V. Shevchuk, I.D. Olekseyuk / Journal of Alloys and Compounds 433 (2007) 171–174
the solid solution range of AgGaSe2 and the microstructure studies, the existence of the compound AgGaSnSe4 could not confirmed. The solid solution ranges of the initial compounds AgGaS2 (Se2 ) are promising new materials for optoelectronics. References [1] D.T. Huseinov, N.E. Hasanov, A.G. Kyazym-Zade, R.K. Nani, Phys. Technol. Semicond. 15 (1981) 1811–1814. [2] V.V. Badikov, I.E. Matveev, S.M. Pshenichnikov, Kristalografia 26 (1981) 537. [3] O.H. Hydhes, J.C. Wooley, S.A. Lopez-Rivere, B.R. Pamplin, Solid State Commun. 35 (1980) 573. [4] B.R. Pamplin, T. Ohachi, S. Maeda, Inst. Phys. Conf. Ser. 35 (1977) 35–42. [5] I.D. Olekseyuk, G.P. Gorgut, M.V. Shevchuk, Polish J. Chem. 76 (2002) 915–919.
[6] I.D. Olekseyuk, A.V. Gulyak, L.V. Sysa, G.P. Gorgut, A.F. Lomzin, J. Alloys Compd. 241 (1996) 187–190. [7] E.R. de Gil, C.D. Gomez, A.V. Rivera, A. Lopez-Rivera, Prog. Cryst. Growth Charact. 10 (1985) 217–223. [8] S.N. Nenasheva, E.F. Sinyakova, Izv. Acad. Nauk USSR Neorgan. Mater. 19 (1983) 1622. [9] J.C. Mikkelsen, Mater. Res. Bull. 12 (1977) 497–502. [10] V.B. Lazarev, Z.Z. Kish, E.Yu. Peresh, E.E. Semrad, Complex Chalcogenides in AI–BIII–CVI Systems, Metallurgiya, Moscow, 1993, p. 240 (in Russian). [11] L.S. Palatnik, E.K. Belova, Neorgan. Mater. 3 (1967) 967–973. [12] M.I. Karakhanova, A.S. Pashinkin, A.V. Novoselova, Izv. Acad. Nauk USSR Neorgan. Mater. 2 (1966) 991–996. [13] A.Z. Hajiyeva, P.G. Rustamov, B.N. Mardakhayev, Azeri Khim. Zh. 4 (1973) 138–141. [14] N.K. Abrikosov, L.E. Shelimova, Semiconductor Chalcogenides and Their Alloys, Nauka, Moscow, 1975. [15] O.E. Andreyeva, N.S. Orlova, I.V. Bondar, Mater. Electron. 3 (1999) 66–70.