First-Principles Analysis of Radiative Recombination in Lead-Halide Perovskites

Abstract

Slow radiative recombination due to a slightly indirect band gap has been proposed to explain the high efficiency of lead-halide perovskite solar cells. Here, we calculate the radiative recombination rate from first principles for the prototypical lead halide perovskite, MAPbI3 (MA = CH3NH3). Because the structure is dynamic, with the MA molecule rotating even at room temperature, we determine the momentum mismatch between the band edges as a function of the orientation of the MA molecule. Our results demonstrate that the indirect nature of the band gap suppresses the radiative recombination rate by less than a factor of two and that the radiative recombination coefficient is as high as that in traditional direct-gap semiconductors. Our study provides a rigorous assessment of the radiative recombination mechanisms and their relation to the high efficiency of lead-halide perovskite solar cells, and will provide a sound basis for accurate modeling.