Unraveling the Photogenerated Electron Localization on the Defect-Free CH₃NH₃PbI₃(001) Surfaces: Understanding and...

The localization of photogenerated electrons in photovoltaic and photocatalytic materials is crucial for reducing the electron-hole recombination rate. Here, the photogenerated electron localization is systematically investigated on the CH₃NH₃PbI₃ (MAPbI₃) perovskite using first-principles calculations. It is found that under vacuum conditions, the photogenerated electron is delocalized in the MAPbI₃ bulk as well as on the stochiometric MAPbI₃(001) surface with the CH₃NH₃I (MAI) termination, while it is trapped on the defect-free PbI₂-terminated surface. Our ab initio molecular dynamics simulations reveal that the introduction of solutions will prompt the formation of localized electronic states. The photogenerated electron is discovered to be localized on both the MAI- and PbI₂-terminated surfaces in the presence of solutions with different concentrations of HI, from pure water to the saturated solution. We demonstrate that the Pb-I bond weakening or breaking resulting in an unsaturated coordination of a Pb site is the prerequisite to trap the photogenerated electron.