Polaron Self-Trapping Rates from First Principles

Mark E. Turiansky; Joel B. Varley; Audrius Alkauskas; Chris G. Van de Walle

paper

Polaron Self-Trapping Rates from First Principles

arXiv:2609.03336

Abstract

Polaron formation, also known as self-trapping, is a process akin to nonradiative carrier capture at point defects or impurities. In this work, we develop the formalism to determine how long it takes to form a small hole or electron polaron from first principles. We employ an accurate, fully first-principles approach based on a Koopmans compliant hybrid functional. The self-trapping rate is the product of two components: the nonradiative capture coefficient, which we evaluate using a one-dimensional approximation, and the maximum density of polaron sites, whose physics we elucidate based on finite-size interactions present in supercells. We apply our methodology to several technologically relevant materials known to host hole polarons, Ga $_{2}$ O $_{3}$ , Al $_{2}$ O $_{3}$ , BeO, KBr, MgO, NaCl, SiO $_{2}$ , SnO $_{2}$ , TiO $_{2}$ , and ZnO, and to an electron polaron in rutile TiO $_{2}$ . We also study an emerging semiconductor, rutile GeO $_{2}$ , where we find that polaron formation could hamper $p$ -type conductivity. The calculated self-trapping lifetimes span 7 orders of magnitude, from $1 0^{- 1}$ to $1 0^{6}$ ~ps, in agreement with experiments where available, and providing detailed insight into the dynamics of carrier localization and relaxation in solids.