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Thermodynamics of Al(1-x)Ga(x)N solid solution: Inclination for phase separation and ordering

Jacob, KT and Rajitha, G and Rannesh, L and Fukuyama, H and Waseda, Y (2012) Thermodynamics of Al(1-x)Ga(x)N solid solution: Inclination for phase separation and ordering. In: Acta Materialia, 60 (1). pp. 59-66.

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Official URL: http://dx.doi.org/10.1016/j.actamat.2011.09.005

Abstract

Although Al(1-x)Ga(x)N semiconductors are used in lighting, displays and high-power amplifiers, there is no experimental thermodynamic information on nitride solid solutions. Thermodynamic data are useful for assessing the intrinsic stability of the solid solution with respect to phase separation and extrinsic stability in relation to other phases such as metallic contacts. The activity of GaN in Al(1-x)Ga(x)N solid solution is determined at 1100 K using a solid-state electrochemical cell: Ga + Al(1-x)Ga(x)N/Fe, Ca(3)N(2)//CaF(2)//Ca(3)N(2), N(2) (0.1 MPa), Fe. The solid-state cell is based on single crystal CaF(2) as the electrolyte and Ca(3)N(2) as the auxiliary electrode to convert the nitrogen chemical potential established by the equilibrium between Ga and Al(1-x)Ga(x)N solid solution into an equivalent fluorine potential. Excess Gibbs free energy of mixing of the solid solution is computed from the results. Results suggest an unusual mixing behavior: a mild tendency for ordering at three discrete compositions (x = 0.25, 0.5 and 0.75) superimposed on predominantly positive deviation from ideality. The lattice parameters exhibit slight deviation from Vegard's law, with the a-parameter showing positive and the c-parameter negative deviation. Although the solid solution is stable in the full range of compositions at growth temperatures, thermodynamic instability is indicated at temperatures below 410 K in the composition range 0.26 <= x <= 0.5. At 355 K, two biphasic regions appear, with terminal solid solutions stable only for 0 <= x <= 0.26 and 0.66 <= x <= 1. The range of terminal solid solubility reduces with decreasing temperature. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to Elsevier Science.
Keywords: Thermodynamics;Gibbs energy;Chemical potential;Enthalpy; Solid solution
Department/Centre: Division of Mechanical Sciences > Materials Engineering (formerly Metallurgy)
Date Deposited: 03 Jan 2012 12:03
Last Modified: 03 Jan 2012 12:03
URI: http://eprints.iisc.ernet.in/id/eprint/42956

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