Point defects play a critical role in the structural, physical, and interfacial properties of perovskite oxide superlattices. However, understanding of the fundamental properties of point defects in superlattices, especially their transport properties, is rather limited. Here, we report predictions of the stability and dynamics of oxygen vacancies in $\mathrm{SrTi}{\mathrm{O}}_3\text{/}\mathrm{PbTi}{\mathrm{O}}_3$ oxide superlattices using first-principles calculations in combination with the kinetic Monte Carlo method. By varying the stacking period, i.e., changing of $n$ in $n\mathrm{STO}\text{/}n\mathrm{PTO}$, we discover a crossover from three-dimensional diffusion to primarily two-dimensional planar diffusion. Such planar diffusion may lead to novel designs of ionic conductors. We show that the dominant vacancy position may vary in the superlattices, depending on the superlattice structure and stacking period, contradicting the common assumption that point defects reside at interfaces. Moreover, we predict a significant increase in room-temperature ionic conductivity for 3STO/3PTO relative to the bulk phases. Considering the variety of cations that can be accommodated in perovskite superlattices and the potential mismatch of spin, charge, and orbitals at the interfaces, this paper identifies a pathway to control defect dynamics for technological applications.

• Received 2 December 2017

DOI:https://doi.org/10.1103/PhysRevMaterials.2.035401