Suppressed nonradiative electron–hole recombination in bismuth halide perovskite Cs3Bi2Cl9: Time domain ab initio analysis

Time-domain density functional theory, coupled with non-adiabatic molecular dynamics simulations, was employed to explore the defect characteristics and the associated nonradiative recombination processes in the bismuth halide perovskite Cs3Bi2Cl9. Our findings indicate that Cs3Bi2Cl9 inherently exhibits p-type semiconductor behavior, with vacancies at the Cs and Bi sites acting as predominant shallow acceptor defects. Although Cl vacancy and interstitial Cl defects introduce trap states within the bandgap of Cs3Bi2Cl9, the by-defect electron–hole (e-h) recombination is substantially impeded, which is attributed to the remarkable local structural deformations associated with the BiCl63− octahedral compression around the defects, which further results in decoupling between the defect state and the band edge state. As a result, the enhanced delocalization of defect states leads to a notably small wave function overlap between defect states and band edge states, as well as weak nonadiabatic couplings dominated by low-frequency phonons. Our study offers crucial insights into the mechanism of defect-mediated e-h recombination in bismuth-based perovskites and provides guidelines for designing efficient optoelectronic devices based on these materials.