Chemical Mapping of Excitons in Halide Double Perovskites

Abstract

Halide double perovskites are an emerging class of semiconductors with tremendous chemical and electronic diversity. While their bandstructure features can be understood from frontier-orbital models, chemical intuition for optical excitations remains incomplete. Here, we use \textit{ab initio} many-body perturbation theory within the $GW$ and the Bethe-Salpeter Equation approach to calculate excited-state properties of a representative range of Cs$_2$BB$'$Cl$_6$ double perovskites. Our calculations reveal that double perovskites with different combinations of B and B$'$ cations display a broad variety of electronic bandstructures and dielectric properties, and form excitons with binding energies ranging over several orders of magnitude. We correlate these properties with the orbital-induced anisotropy of charge-carrier effective masses and the long-range behavior of the dielectric function, by comparing with the canonical conditions of the Wannier-Mott model. Furthermore, we derive chemically intuitive rules for predicting the nature of excitons in halide double perovskites using electronic structure information obtained from computationally inexpensive DFT calculations.