Soft Lattice and Defect Covalency Rationalize Tolerance of β‐CsPbI3 Perovskite Solar Cells to Native Defects

Although all-inorganic metal halide perovskites (MHPs) have shown tremendous improvement, they are still inferior to the hybrid organic-inorganic MHPs in efficiency. Recently, a conceptually new β-CsPbI3 perovskite reached 18.4 % efficiency combined with good thermodynamic stability at ambient conditions. We use ab initio non-adiabatic molecular dynamics to show that native point defects in β-CsPbI3 are generally benign for nonradiative charge recombination, regardless of whether they introduce shallow or deep trap states. These results indicate that MHPs do not follow the simple models used to explain defect-mediated charge recombination in the conventional semiconductors. The strong tolerance is due to the softness of the perovskite lattice, which permits separation of electrons and holes upon defect formation, and only allows carriers to couple to the low-frequency vibrations. Both factors decrease notably the non-adiabatic coupling and slow down the dissipation of energy to heat.