Ferroelectric Polarization Suppresses Nonradiative Electron-Hole Recombination in CH3NH3PbI3 Perovskites: A Time-Domain ab Initio Study

The ordered alignment of polar organic cations in hybrid organic-inorganic perovskites causes a ferroelectric phase, which is believed to be benign for photovoltaic devices. Using a combination of time-domain density functional theory and nonadiabatic molecular dynamics, we study the influence of the interactions of polar MA (CH3NH3+) cations and between their inorganic counterparts on the nonradiative electron-hole recombination in the room-temperature ferroelectric MAPbI(3) perovskite. We show that ferroelectric alignment of the polar C-N bonds favors charge separation and reduces nonadiabatic coupling. Symmetry breaking enhances low-frequency collective motions and introduces additional high-frequency vibrations, thus accelerating quantum decoherence. Both factors contribute to suppressing the nonradiative electron-hole recombination, extending the charge carrier lifetimes to several nanoseconds and showing a factor of 3 increase compared to the pristine system. Consequently, ferroelectric engineering provides an excellent route to improve hybrid perovskite device performance as a result of long-range charge separation and slow charge recombination.