Ab initio description of oxygen vacancies in epitaxially strained [Formula: see text] at finite temperatures

Epitaxially grown [Formula: see text] (STO) thin films are material enablers for a number of critical energy-conversion and information-storage technologies like electrochemical electrode coatings, solid oxide fuel cells and random access memories. Oxygen vacancies ([Formula: see text]), on the other hand, are key defects to understand and tailor many of the unique functionalities realized in oxide perovskite thin films. Here, we present a comprehensive and technically sound ab initio description of [Formula: see text] in epitaxially strained (001) STO thin films. The novelty of our first-principles study lies in the incorporation of lattice thermal excitations on the formation energy and diffusion properties of [Formula: see text] over wide epitaxial strain conditions ([Formula: see text]%). We found that thermal lattice excitations are necessary to obtain a satisfactory agreement between first-principles calculations and the available experimental data for the formation energy of [Formula: see text]. Furthermore, it is shown that thermal lattice excitations noticeably affect the energy barriers for oxygen ion diffusion, which strongly depend on [Formula: see text] and are significantly reduced (increased) under tensile (compressive) strain. The present work demonstrates that for a realistic theoretical description of oxygen vacancies in STO thin films is necessary to consider lattice thermal excitations, thus going beyond standard zero-temperature ab initio approaches.