Structures and energetics of Ga₂O₃polymorphs

Abstract

First-principles calculations are made for five Ga2O3 polymorphs. The structure of ε-Ga2O3 with the space group Pna 21 (No. 33, orthorhombic), which is sometimes called κ-Ga2O3 in the literature, is consistent with experimental reports. The structure of γ-Ga2O3 is optimized within 14 inequivalent configurations of defective spinel structures. Phonon dispersion curves of four polymorphs are obtained. The volume expansivity, bulk modulus, and specific heat at constant volume are computed as a function of temperature within the quasi-harmonic approximation. The Helmholtz free energies of the polymorphs are thus compared. The expansivity shows a relationship of β<ε<α<δ, while β<ε<δ<α for the bulk modulus. The formation free energies have the tendency β<ε<α<δ<γ at low temperatures. With the increase of temperature, the difference in free energy between the β-phase and the ε-phase becomes smaller. Eventually the ε phase becomes more stable at above 1600 K.