Unravelling the effects of oxidation state of interstitial iodine and oxygen passivation on charge trapping and recombination in CH(3)NH(3)PbI(3) perovskite: a time-domain ab initio study

Understanding nonradiative charge recombination mechanisms is a prerequisite for advancing perovskite solar cells. By performing time-domain density functional theory combined with nonadiabatic (NA) molecular dynamics simulations, we show that electron–hole recombination in perovskites strongly depends on the oxidation state of interstitial iodine and oxygen passivation. The simulations demonstrate that electron–hole recombination in CH(3)NH(3)PbI(3) occurs within several nanoseconds, agreeing well with experiment. The negative interstitial iodine delays charge recombination by a factor of 1.3. The deceleration is attributed to the fact that interstitial iodine anion forms a chemical bond with its nearest lead atoms, eliminates the trap state, and decreases the NA electron–phonon coupling. The positive interstitial iodine attracts its neighbouring lattice iodine anions, resulting in the formation of an I-trimer and producing an electron trap. Electron trapping proceeds on a very fast timescale, tens of picoseconds, and captures the majority of free electrons available to directly recombine with free holes while inhibiting the recombination of free electrons and holes, delaying the recombination by a factor of 1.5. However, the positive interstitial iodine easily converts to a neutral iodine defect by capturing an electron, giving rise to a singly occupied state above the valence band maximum and acting as a hole trap. The photoexcitation valence band hole becomes trapped by the hole trap state very rapidly, followed by acceleration of recombination with the conduction band free electron by a factor of 1.6. Surprisingly, molecular oxygen interacting with interstitial iodine anion forms a stable IO(3)(–1) species, which inhibits ion migration, stabilizes perovskites, and suppresses the electron–hole recombination by a factor of 2.7. Our simulations reveal the microscopic effects of the oxidation state of interstitial iodine defects and oxygen passivation in perovskites, suggesting an effective way to improve perovskite photovoltaic and optoelectronic devices.