Nuclear Quantum Effects Accelerate Charge Recombination but Boost the Stability of Inorganic Perovskites in Mild Humidity.

ABSTRACT

Experiments have demonstrated that mild humidity can enhance the stability of the CsPbBr3 perovskite, though the underlying mechanism remains unclear. Utilizing ab initio molecular dynamics, ring polymer molecular dynamics, and non-adiabatic molecular dynamics, our study reveals that nuclear quantum effects (NQEs) play a crucial role in stabilizing the lattice rigidity of the perovskite while simultaneously shortening the charge carrier lifetime. NQEs reduce the extent of geometric disorder and the number of atomic fluctuations, diminish the extent of hole localization, and thereby improve the electron-hole overlap and non-adiabatic coupling. Concurrently, these effects significantly suppress phonon modes and slow decoherence. As a result, these factors collectively accelerate charge recombination by a factor of 1.42 compared to that in scenarios excluding NQEs. The resulting sub-10 ns recombination time scales align remarkably well with experimental findings. This research offers novel insight into how moisture resistance impacts the stability and charge carrier lifetime in all-inorganic perovskites.