Oxygen Point Defect Chemistry in Ruddlesden-Popper Oxides (La${}_{1-x}$Sr${}_x$)${}_2$MO${}_{4\pm \delta }$ (M = Co, Ni, Cu)

Abstract

Stability of oxygen point defects in Ruddlesden-Popper oxides (La${}_{1-x}$Sr${}_x$)${}_2$MO${}_{4\pm \delta }$ (M = Co, Ni, Cu) is studied with density functional theory calculations to determine their stable sites, charge states, and energetics as functions of Sr content ($x$), transition metal (M) and defect concentration (δ). We demonstrate that the dominant O point defects can change between oxide interstitials, peroxide interstitials, and vacancies. Generally, increasing $x$ and atomic number of M stabilizes peroxide over oxide interstitials, as well as vacancies over both peroxide and oxide interstitials; increasing δ destabilizes both oxide interstitials and vacancies, but affects little peroxide interstitials. We also demonstrate that the O 2$p$-band center is a powerful descriptor for these materials and correlates linearly with the formation energy of all the defects. The trends of formation energy versus $x$, M and δ and the correlation with O 2$p$-band center are explained in terms of oxidation chemistry and electronic structure.

Manuscript has 3 figures and 17 pages; Supporting Information has 4 figures, 4 tables and 19 pages