Anion Doping Delays Nonradiative Electron–Hole Recombination in Cs-Based All-Inorganic Perovskites: Time Domain ab Initio Analysis

Using time-domain density functional theory combined with nonadiabatic (NA) molecular dynamics, we demonstrate that composition engineering of the X-site anions has a strong influence on the nonradiative electron-hole recombination and thermodynamic stability of cesium-based all-inorganic perovskites. Partial substitution of iodine(I) with bromine (Br) and acetate (Ac) anions reduces the NA electron-vibrational coupling by minimizing the overlap between the electron and hole wave functions and suppressing atomic fluctuations. The doping also widens the energy gap to further reduce the NA coupling and to enhance the open-circuit voltage of perovskite solar cells. These factors increase the charge carrier lifetime by an order of magnitude and improve structural stability in the series CsPbI_1.88BrAc_0.12 > CsPbI₂Br > CsPbI₃. The fundamental atomistic insights into the influence of anion doping on the photophysical properties of the all-inorganic lead halide perovskites guide the design of efficient optoelectronic materials.