Ab initio Phase Diagram of Ta2O5

Abstract

Tantalum pentoxide (Ta2O5) is a polymorphic wide-bandgap semiconductor with outstanding dielectric properties and widespread use in optical and electronic technologies. Its rich structural diversity, arising from multiple polymorphs accessible under different synthesis conditions, has made Ta2O5 a long-standing subject of interest. However, a unified understanding of the thermodynamic stability and phase transitions of its polymorphs across pressure-temperature (P-T) space has remained elusive. Here, using first-principles calculations, we map the thermodynamic landscape of Ta2O5 and establish a comprehensive P-T phase diagram together with a phase-stability hierarchy. We find that Gamma-Ta2O5 and B-Ta2O5 dominate the phase diagram over a broad range of P-T conditions: Gamma-Ta2O5 is stabilized at low pressures, while B-Ta2O5 becomes thermodynamically favored at higher pressures up to ~ 60 GPa, beyond which Y-Ta2O5 emerges as the most stable phase. Crucially, the zero-point energy (ZPE), one aspect of nuclear quantum effects (NQEs), plays a significant role in determining relative phase stability, contributing substantially to the Gibbs free energy and altering phase boundaries. A re-entrant phase transition between Gamma and B-Ta2O5 is predicted near ~ 2 GPa, revealing unexpected complexity in the phase behavior of this oxide. More generally, we identify a characteristic temperature (T_0), at which zero-point and thermal phonon contributions to the free energy become comparable, and show that T_0 is approximately one-third of the Debye temperature. This relationship provides a simple, physically transparent criterion for assessing the importance of NQEs in phase stability, with implications extending beyond Ta2O5 to a broad class of complex oxides.