Suppressing Polaronic Defect–Photocarrier Interaction in Halide Perovskites by Pre-distorting Its Lattice

Abstract

In halide perovskites, photocarriers can have strong polaronic interactions with point defects. For iodide-deficient MAPbI₃, we found that the Fermi level can shift significantly by 0.6–0.7 eV upon light illumination. This energy level shift is accompanied by the formation of deep electron traps. These experimental observations are consistent with the formation of a Pb–Pb dimer when photoexcited electrons are trapped at an iodide vacancy. Interestingly, we found that this polaronic interaction is suppressed when a portion of MA⁺ cations is replaced by smaller Cs⁺ ions. Density functional theory calculations reveal that Cs-doping can reduce the distance between two Pb atoms across an iodide vacancy, even without electron trapping. The predistortion of the lattice induced by cation replacement resembles the Pb–Pb dimer formed by electron trapping at the defect site, which explains the suppression of light-induced effects observed in the experiment. Our finding unveils a counterintuitive strategy to enhance the photostability of halide perovskites by preintroducing distortions into its lattice.