Unveiling the Valence State of Interstitial Bromine on Charge Carrier Lifetime in CH3NH3PbBr3 by Quantum Dynamics Simulation

Interstitial halogens are detrimental to the optoelectronic properties of metal halide perovskites. Using nonadiabatic (NA) molecular dynamics, we demonstrate that the valence state of interstitial bromine strongly changes the carrier lifetimes of MAPbBr3 (MA = CH3NH3 +). Both neutral and negatively charged interstitial bromine create no midgap states, and they decrease the bandgap, weaken the NA coupling, and accelerate decoherence in a different extent with respect to pristine MAPbBr3, making free charge recombination either slow down about a 3-fold or remain largely unchanged. In contrast, a positively charged interstitial bromine forms a Br trimer and introduces a deep electron trap state, causing a 1.4-fold increase of charge recombination followed by a rapid electron trapping or across the bandgap because of an enhanced NA coupling. The simulations uncover the influence of different charged interstitial bromine defects on MAPbBr3 carrier lifetimes and provide rational guidelines for optimizing perovskite solar cells.