Chemically-Localized Resonant Excitons in Silver-Pnictogen Halide Double Perovskites

Abstract

Halide double perovskites with alternating silver and pnictogen cations are an emerging family of photoabsorber materials with robust stability and band gaps in the visible range. However, the nature of optical excitations in these systems is not yet well understood, limiting their utility. Here, we use ab initio many-body perturbation theory within the $GW$ approximation and the Bethe-Salpeter equation approach to calculate the electronic structure and optical excitations of the double perovskite series Cs${}_2$AgBX${}_6$, with B=Bi${}^{3+}$, Sb${}^{3+}$, X = Br${}^{-}$, Cl${}^{-}$. We find that these materials exhibit strongly localized resonant excitons with energies from 170 to 434 meV below the direct band gap. In contrast to lead-based perovskites, the Cs${}_2$AgBX${}_6$ excitons are computed to be non-hydrogenic, with anisotropic effective masses and sensitive to local field effects, a consequence of their chemical heterogeneity. Our calculations demonstrate the limitations of the Wannier-Mott and Elliott models for this class of double perovskites and contribute to a detailed atomistic understanding of their light-matter interactions.

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Cited by in corpus (4)

• Chemical Mapping of Excitons in Halide Double Perovskites
• Fine Structure of Excitons in Vacancy Ordered Halide Double Perovskites
• Direct, indirect, and self-trapped excitons in Cs${}_2$AgBiBr${}_6$
• Electronic structure and optical properties of halide double perovskites from a Wannier-localized optimally-tuned screened range-separated hybrid functional