Infrared Dielectric Screening Determines the Low Exciton Binding Energy of Metal-Halide Perovskites

Abstract

The performance of lead-halide perovskites in optoelectronic devices is due to a unique combination of factors, including highly efficient generation, transport, and collection of photogenerated charge carriers. The mechanism behind efficient charge generation in lead-halide perovskites is still largely unknown. Here, we investigate the factors that influence the exciton binding energy (E_b) in a series of metal-halide perovskites using accurate first-principles calculations based on solution of the Bethe-Salpeter equation, coupled to ab initio molecular dynamics simulations. We find that E_b is strongly modulated by screening from low-energy phonons, which account for a factor ∼2 E_b reduction, while dynamic disorder and rotational motion of the organic cations play a minor role. We calculate E_b = 15 meV for MAPbI₃, in excellent agreement with recent experimental estimates. We then explore how different material combinations (e.g., replacing Pb → Pb:Sn→ Sn; and MA → FA → Cs) may lead to different E_b values and highlight the mechanisms underlying E_b tuning.