Engineering Carrier Dynamics in Halide Perovskites by Dynamical Lattice Distortion

Abstract The electronic structure of halide perovskites is central to their carrier dynamics, enabling the excellent optoelectronic performance. However, the experimentally resolved transient absorption spectra exhibit large discrepancies from the commonly computed electronic structure by density functional theory. Using pseudocubic CsPbI 3 as a prototype example, here, it is unveiled with both ab initio molecular dynamics simulations and transmission electron microscopy that there exists pronounced dynamical lattice distortion in the form of disordered instantaneous octahedral tilting. Rigorous first‐principles calculations reveal that the lattice distortion substantially alters the electronic band structure through renormalizing the band dispersions and the interband transition energies. Most notably, the electron and hole effective masses increase by 65% and 88%, respectively; the transition energy between the two highest valence bands decreases by about one half, agreeing remarkably well with supercontinuum transient‐absorption measurements. This study further demonstrates how the resulting electronic structure modulates various aspects of the carrier dynamics such as carrier transport, hot‐carrier relaxation, Auger recombination, and carrier multiplication in halide perovskites. The insights provide a pathway to engineer carrier transport and relaxation via lattice distortion, enabling the promise to achieve ultrahigh‐efficiency photovoltaic devices.