Substitutional alkaline earth metals delay nonradiative charge recombination in CH3NH3PbI3 perovskite: A time-domain study.

Experiments reported that alkaline earth metal dopants greatly prolong carrier lifetime and improve the performance of perovskite solar cells. Using state-of-the-art ab initio time-domain nonadiabatic molecular dynamics (NAMD), we demonstrate that incorporation of alkaline earth metals, such as Sr and Ba, into MAPbI3 (MA = CH3NH3 +) lattice at the lead site is energetically favorable due to the largely negative formation energies about -7 eV. The replacement widens the bandgap and increases the open-circuit voltage by creating no trap states. More importantly, the substitution reduces the mixing of electron and hole wave functions by pushing the hole charge density away from the dopant together with no contribution of Sr and Ba to the conduction band edge state, thus decreasing the NA coupling. The high frequency phonons generated by enhanced atomic motions and symmetry breaking accelerate phonon-induced loss of coherence. The synergy of the three factors reduces the nonradiative recombination time by a factor of about 2 in the Sr- and Ba-doped systems with respect to pristine MAPbI3, which occurs over 1 ns and agrees well with the experiment. The study highlights the importance of various factors affecting charge carrier lifetime, establishes the mechanism of reduction of nonradiative electron-hole recombination in perovskites upon alkaline earth metal doping, and provides meaningful insights into the design of high performance of perovskite solar cells and optoelectronics.