Electronic structure of Ta2O5 polymorphs: Variation trend of band gap and the role of oxygen vacancies

We provide a systematic study on the electronic structure of a series of Ta2O5 polymorphs using standard density functional theory (DFT) calculations as well as the more accurate many-body perturbation theory within the GW approximation. For the defect-free polymorphs, the variation trend of band gap can be microscopically related to the strength of orbital hybridization, and to the macroscopic bulk formation energy. The presence of oxygen vacancies is found to have profound effects on the electronic properties near the Fermi level, notably the reduction of band gap and gap closure (insulator-to-metal transition). Furthermore, depending on the vacancy sites, the band gap of some defective system may be enlarged with comparison to its defect-free counterpart. Such an anomalous behavior originates from the unexpected formation of Ta-Ta bonds.