Microscopic Mechanism of Water-Assisted Diffusional Phase Transitions in Inorganic Metal Halide Perovskites

The stability of perovskite materials is profoundly influenced by the presence of moisture in the surrounding environment. While it is well-established that water triggers and accelerates the black-yellow phase transition, leading to the degradation of the photovoltaic properties of perovskites, the underlying microscopic mechanism remains elusive. In this study, we employ classical molecular dynamics simulations to examine the role of water molecules in the yellow-black phase transition in a typical inorganic metal halide perovskite, CsPbI3. We have demonstrated, through interfacial energy calculations and classical nucleation theory, that the phase transition necessitates a crystal-amorphous-crystal two-step pathway, rather than the conventional crystal-crystal mechanism. Simulations for CsPbI3 nanowires show that water molecules in the air can enter the amorphous interface between the black and yellow regions. The phase transition rate markedly increases with the influx of interfacial water molecules, which enhance ion diffusivity by reducing the diffusion barrier, thereby expediting the yellow-black phase transition in CsPbI3. We propose a general mechanism through which solvent molecules can greatly facilitate phase transitions that otherwise have prohibitively high transition energies.