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

TL;DR

This study uses advanced computational methods to reveal that silver-pnictogen halide double perovskites host strongly localized, non-hydrogenic resonant excitons with unique properties, enhancing understanding of their optical behavior.

Contribution

It provides the first detailed ab initio analysis of optical excitations in Cs₂AgBX₆ double perovskites, highlighting their localized excitons and limitations of traditional models.

Findings

Exhibit strongly localized resonant excitons below the band gap

Excitons are non-hydrogenic with anisotropic effective masses

Local field effects significantly influence exciton properties

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.