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

The influence of grain boundaries (GBs) on charge carrier lifetimes in methylammonium lead triiodide perovskite (MAPbI₃) 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 MAPbI₃ GBs due to symmetry breaking suppresses charge recombination. Even though GBs lower the MAPbI₃ 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.