Direct, indirect, and self-trapped excitons in Cs${}_2$AgBiBr${}_6$

Abstract

Cs${}_2$AgBiBr${}_6$ exhibits promising photovoltaic and light-emitting properties, making it a candidate for next-generation solar cells and LED technologies. Additionally, it serves as a model system within the family of halide double perovskites, offering insights into the broader class of materials. Here, we study various possible excited states of this material to understand its absorption and emission properties. We use Time-Dependent Density Functional Theory (TD-DFT) coupled with non-empirical hybrid functionals, specifically PBE0($\alpha$) and dielectric-dependent hybrids (DDH) to explore direct, indirect, and self-trapped excitons in this material. Based on comparison with experiment, we show that these methods can give excellent prediction of the absorption spectrum and that the fundamental band gap has been underestimated in previous computational studies. We connect the experimental photoluminescence signals at 1.9-2.0 eV to the emission from self-trapped excitons and electron polarons. Finally, we reveal a complex landscape with energetically competing direct, indirect, and self-trapped excitons in the material.

References in corpus (9)

• Koopmans' condition for density-functional theory
• GW quasiparticle band gap of the hybrid organic-inorganic perovskite CH${}_3$NH${}_3$PbI${}_3$: Effect of spin-orbit interaction, semicore electrons, and self-consistency
• Chemically-Localized Resonant Excitons in Silver-Pnictogen Halide Double Perovskites
• Accurate and efficient band-gap predictions for metal halide perovskites at finite temperature
• Excitonic polarons and self-trapped excitons from first-principles exciton-phonon couplings
• Quantifying Dynamic Tilting in Halide Perovskites: Chemical Trends and Local Correlations
• Theory of excitonic polarons: From models to first-principles calculations
• Self-Trapped Excitons in Metal-Halide Perovskites Investigated by Time-Dependent Density Functional Theory
• Topological polarons in halide perovskites