Abstract
Stable and metastable phase equilibria in the binary system GeSe2-Se have been investigated by means of optical and electron microscopy, electron probe microanalysis (EPMA), x-ray diffraction (XRD), thermal analysis, and adiabatic calorimetry. A revised equilibrium phase diagram is presented. A not previously observed λ-type phase transition was observed near ∼420 K (147 °C) for GeSe2. The intermediate phase, φ, which earlier had been considered as metastable, is shown to be stable through extensive annealing experiments and by adiabatic calorimetry. The φ phase, with composition near Ge3Se7, melts incongruently at 658±5 K (385±5 °C) to GeSe2 and a liquid with 85±2 at.% Se. The liquidus of GeSe2 and φ was determined by EPMA of annealed-and-quenched samples. Both a stable (φ-Se-liquid) and a metastable (GeSe2-Se-liquid) eutectic point were observed. The stable one was observed at 480±2 K (207±2 °C) and 92.5±1.0 at.% Se, whereas the temperature of the metastable eutectic (GeSe2-Se-liquid) was observed to be ∼10 K lower. Metastable phase equilibria, obtained on thermal evolution of glasses with different compositions, are described and discussed.
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References
S.A. Dembovskii, G.Z. Vinogradova, and A.S. Pashinkin, Crystallization of Glasses of the Ge-Se System, Russ. J. Inorganic Chem., Vol 10, 1965, p 903
F. Grønvold, Adiabatic Calorimeter for the Investigation of Reactive Substances in the Range from 25 to 775 °C. Heat Capacity of α-aluminium Oxide, Acta Chem. Scand., Vol 21, 1967, p 1695
V.V. Tarasov, V.M. Zhdanov, and A.K. Mal’tsev, Low-Temperature Heat Capacity, Enthalpy, and Entropy of Germanium Disulphide and Germanium Diselenide, Russ. J. Phys. Chem., Vol 42, 1968, p 685
G.Z. Vinogradova, S.A. Dembovskii, and N.B. Sivkova, Refining the Equilibrium Diagram of the Ge-Se System in the GeSe-GeSe2 Region, Russ. J. Inorganic Chem., Vol 13, 1968, p 1051
F. Grønvold, Heat Capacities and Thermodynamic Properties of Hexagonal and Liquid Selenium in the Range 298 to 1000 K. Enthlapy and Temperature of Fusion, J. Chem. Thermodyn., Vol 5, 1973, p 525
S.S. Chang and A.B. Bestul, Heat Capacities of Selenium Crystal (Trigonal), Glass, and Liquid from 5 to 360 K, J. Chem. Thermodyn., Vol 6, 1974, p 325
R. Azoulay, H. Thibierge, and A. Brenac, Devitrification Characteristics of Ge x Se1−x Glasses, J. Non-Cryst. Solids, Vol 18, 1975, p 33
P.J. Burgeat, G. Le Roux, and A. Brenac, Sur une Nouvelle Forme Cristalline de GeSe2, J. Appl. Crystallogr., Vol 8, 1975, p 325 (in French)
G. Dittmar and H. Schäfer, Die kristallstruktur von Germaniumdiselenid, Acta Crystallogr., Vol B32, 1976, p 2726 (in German)
M.I. Karakhanova, L.P. Sokolova, A.V. Novoselova, and A.S. Pashinkin, Investigation of the System Ge-S-Se over the Cross Section GeS2-GeSe2, Inorganic Chem., Vol 12, 1976, p 1219; TR Izv. Akad. Nauk. SSSR Neorg. Mater., Vol 12, 1976, p 1484 (in Russian)
R.J. Nemanich, S.A. Solin, and G. Lucovsky, First Evidence for Vibrational Excitations of Large Atomic Clusters in Amorphous Semiconductors, Solid State Commun., Vol 21, 1977, p 273
A.F. Novozhilov and V.P. Zlomanov, Determination of the Heats of Phase Transition in GeSe, GeSe2, GeS and GeS2 by Thermography, Inorganic Mater., Vol 13, 1977, p 438; TR: Izv. Akad. Nauk. SSSR, Neorg. Mater., Vol 13, 1977, p 532 (in Russian)
M. Esquerre, J.C. Carballes, J.P. Audiere, and C. Mazieres, Crystallization of Amorphous (Bulk and Thin Films) Ge x Se1−x (0<x<0.20) Alloys, J. Mater. Sci., Vol 13, 1978, p 1217
L. Baldé, B. Legendre, and P. Khodadad, The Ternary System Germanium-Tin-Selenium, J. Chem. Res., 1979, p 162
H. Ipser, M. Gambino, and W. Schuster, The Germanium-Selenium Phase Diagram, Monatsh. Chem., Vol 113, 1982, p 389
V.M. Glazov, L.M. Pavlova, and D.S. Gaev, The Thermal Stability of the Selenides of the Elements of Groups IV and V of the Periodic System, from Data on the Curvature of the Liquidus at the Melting Point, Russ. J. Inorganic Chem., Vol 29, 1984, p 620
L. Ferrari, W.A. Phillips, and G. Russo, Heat Capacity at the Glass Transition, Europhys. Lett., Vol. 3, 1987, p 611
A.B. Gokhale and R. Abbaschian, The Ge-Se (Germanium-Selenium) System, Bull. Alloy Phase Diagrams, Vol 11 (No. 3), 1990, p 257
H. Preston-Thomas, The International Temperature Scale of 1990 (ITS-90), Metrologia, Vol 27, 1990, p 3
X. Torrelles, S. Bordas, M.T. Clavaguera-Mora, and N. Clavaguera, Neutron Diffraction Study of Structural Changes Induced by Heat Treatment in Ge-Se Glasses, Trends in Non-Crystalline Solids, Proc. Third International Workshop on Non-Crystalline Solids, 1991, p 201
J. Zarzycki, Glasses and the Vitreous State, Cambridge University Press, Cambridge, United Kingdom, 1991
S. Stølen and F. Grønvold, Adiabatic High-Temperature Calorimetry for the Investigation of Slow Exothermal Phase Transformations, High Temp.—High Press., Vol 25, 1993, p 161
P.A.G. O’Hare, A. Zywocinski, and L.A. Curtiss, Thermodynamics of (Germanium + Selenium): A Review and Critical Assessment, J. Chem. Thermodyn., Vol 28, 1996, p 459
S. Stølen, R. Glöckner, and F. Grønvold, Heat Capacity of the Standard Reference Material Synthetic Sapphire, α-Al2O3, at Temperatures from 298.15 to 1000 K by Adiabatic Calorimetry. Improved Precision and Accuracy through Improved Instrumentation and Computer Control, J. Chem. Thermodyn., Vol 28, 1996, p 1263–1281
Y. Wang, M. Nakamura, O. Matsuda, K. Inoue, and K. Murase, Temperature Dependence of Raman Spectra in Amorphous, Crystalline and Liquid GeSe2, J. Non-Cryst. Solids, Vol 198–200, 1996, p 753
A. Grzechnik, personal communication, 1998
E. Gulbrandsen, H.B. Johnsen, M. Endregaard, T. Grande, and S. Stølen, Short-Range Order in Se-Rich Ge-Se Glasses—An EXAFS Study, to be published
S. Stølen and F. Grønvold, Critical Assessment of the Enthalpy of Fusion of Metals Used as Enthalpy Standards at Moderate to High Temperatures, Thermochim. Acta, in press
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Stølen, S., Johnsen, H.B., Bøe, C.S. et al. Stable and metastable phase equilibria in the GeSe2-Se system. JPE 20, 17–28 (1999). https://doi.org/10.1361/105497199770335901
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DOI: https://doi.org/10.1361/105497199770335901