Chemical Mapping of Excitons in Halide Double Perovskites.

Biega, Raisa-Ioana; Chen, Yinan; Filip, Marina R; Leppert, Linn · Nano Lett · 2023

basic_science · Level V

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Abstract

Halide double perovskites comprise an emerging class of semiconductors with tremendous chemical and electronic diversity. While their band structure features can be understood from frontier-orbital models, chemical intuition for optical excitations remains incomplete. Here, we use ab initio many-body perturbation theory within the <i>GW</i> and the Bethe-Salpeter equation approach to calculate excited-state properties of a representative range of Cs<sub>2</sub>BB'Cl<sub>6</sub> double perovskites. Our calculations reveal that double perovskites with different combinations of B and B' cations display a broad variety of electronic band structures 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 them 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 computationally inexpensive density functional theory calculations.