Oxidation state and interfacial effects on oxygen vacancies in tantalum pentoxide

First-principles density-functional theory calculations are used to study the atomistic structure, structural energetics, and electron density near the O monovacancy (VOn; n = 0,1+,2+) in both bulk, amorphous tantalum pentoxide (a-Ta2O5), and also at vacuum and metallic Ta interfaces. We calculate multivariate vacancy formation energies to evaluate stability as a function of oxidation state, distance from interface plane, and Fermi energy. VOn of all oxidation states preferentially segregates at both Ta and vacuum interfaces, where the metallic interface exhibits global formation energy minima. In a-Ta2O5, VO0 is characterized by structural contraction and electron density localization, while VO2+ promotes structural expansion and is depleted of electron density. In contrast, interfacial VO0 and VO2+ show nearly indistinguishable ionic and electronic signatures indicative of a reduced VO center. Interfacial VO2+ extracts electron density from metallic Ta, indicating that VO2+ is spontaneously reduced at the expense of the metal. This oxidation/reduction behavior suggests careful selection and processing of both oxide layer and metal electrodes for engineering memristor device operation.