Extending Carrier Lifetimes in Lead Halide Perovskites with Alkali Metals by Passivating and Eliminating Halide Interstitial Defects

Defects, such as halide interstitials, act as charge recombination centers, induce degradation of halide perovskites, and create major obstacles to applications of these materials. Alkali metal dopants greatly improve perovskite performance. Using ab initio nonadiabatic molecular dynamics, it is demonstrated that alkalis bring favorable effects. The formation energy of halide interstitials increases by up to a factor of four in the presence of alkali dopants, and therefore, defect concentration decreases. When defects are present, alkali metals strongly bind to them. Halide interstitials introduce mid‐gap states that rapidly trap charge carriers. Alkalis eliminate the trap states, helping to maintain high current density. Further to charge trapping, the interstitials accelerate charge recombination. By passivating the interstitials, alkalis make carrier lifetimes up to seven times longer than in defect‐free perovskites and up to thirty times longer than in defective perovskites. Alkalis passivate iodine interstitial defects in lead perovskites, eliminate the mid‐gap states, and suppress the nonradiative recombination. Theoretical guidelines are developed for defect inactivation in perovskite solar cells and other devices.