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 similar to 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 MAPbI(3), 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.
Infrared Dielectric Screening Determines the Low Exciton Binding Energy of Metal-Halide Perovskites
Mosconi, Edoardo;De Angelis, Filippo
2018
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 similar to 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 MAPbI(3), 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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
