Anomalous Temperature-Dependent Charge Recombination in CH3NH3PbI3 Perovskite: Key Roles of Charge Localization and Thermal Effect

Optimizing metal halide perovskite solar cells necessitates understanding of nonradiative electron-hole recombination because it comprises a dominant route for charge and energy losses. In principle, the electron-hole recombination rate increases as temperature grows due to enhanced electron-phonon coupling. Experiments defy this expectation in MAPbI3 (MA = CH3NH3+). By performing nonadiabatic (NA) molecular dynamics analyses combined with time-domain density functional theory simulations, we demonstrate that nonradiative electron-hole recombination in MAPbI3 at high temperature occurs more slowly than that at low temperature. First and most important, increasing temperature enhances thermal disorder and leads to significant distortion of the inorganic Pb-I framework, giving rise to electron and hole wave functions locating spatial separation and reducing NA coupling by a factor of 28% in comparison with low temperature. Second, rising temperature enhances the thermal fluctuations of both the inorganic and organic components that accelerate decoherence process by a factor of 12%. Both factors, particularly the small NA coupling, contribute to suppressing electron-hole recombination at high temperature. The simulations show excellent agreement with experiments and emphasize how the charge localization driven by thermal effects impacts electron-hole recombination in perovskites and advances our understanding of the unusual charge dynamics.