Stability of Tin- versus Lead-Halide Perovskites: Ab Initio Molecular Dynamics Simulations of Perovskite/Water Interfaces

Tin-halide perovskites (THPs) have emerged as promising lead-free perovskites for photovoltaics and photocatalysis applications but still fall short in terms of stability and efficiency with respect to their lead-based counterpart. A detailed understanding of the degradation mechanism of THPs in a water environment is missing. This Letter presents ab initio molecular dynamics (AIMD) simulations to unravel atomistic details of THP/water interfaces comparing methylammonium tin iodide, MASnI₃, with the lead-based MAPbI₃. Our results reveal facile solvation of surface tin-iodine bonds in MASnI₃, while MAPbI₃ remains more robust to degradation despite a larger amount of adsorbed water molecules. Additional AIMD simulations on dimethylammonium tin bromide, DMASnBr₃, investigate the origins of their unprecedented water stability. Our results indicate the presence of amorphous surface layers of hydrated zero-dimensional SnBr₃ complexes which may protect the inner structure from degradation and explain their success as photocatalysts. We believe that the atomistic details of the mechanisms affecting THP (in-)stability may inspire new strategies to stabilize THPs.