Symmetry Breaking at MAPbI3 Perovskite Grain Boundaries Suppresses Charge Recombination: Time-Domain ab Initio Analysis

The influence of grain boundaries (GBs) on charge carrier lifetimes in methylammonium lead triiodide perovskite (MAPbI(3)) remains unclear. Some experiments suggest that GBs promote rapid nonradiative decay and deteriorate device performance, while other measurements indicate that charge recombination happens primarily in non-GB regions and that GBs facilitate charge separation and collection. By combining time-domain density functional theory and nonadiabatic (NA) molecular dynamics, we demonstrate that charge separation and localization happening at MAPbI(3) GBs due to symmetry breaking suppresses charge recombination. Even though GBs lower the MAPbI(3) bandgap and charge localization enhances interactions with phonons, electron-hole separation decreases the NA coupling, and the excited state lifetime remains virtually unchanged compared to the pristine perovskite. Our study rationalizes how GBs can have a positive influence on perovskite optoelectronic properties and advances fundamental understanding of charge carrier dynamics in these fascinating materials.