Critical role of water in defect aggregation and chemical degradation of perovskite solar cells

The chemical stability of methylammonium lead iodide (\ce{MAPbI3}) under humid conditions remains the primary challenge facing halide perovskite solar cells. We investigate defect processes in the water-intercalated iodide perovskite (\ce{MAPbI3}\_\ce{H2O}) and monohydrated phase (\ce{MAPbI3}$\cdot$\ce{H2O}) within a first-principles thermodynamic framework. We consider the formation energies of isolated and aggregated vacancy defects with different charge states under I-rich and I-poor conditions. It is found that a \ce{PbI2} (partial Schottky) vacancy complex can be formed readily, while the \ce{MAI} vacancy complex is difficult to form in the hydrous compounds. Vacancies in the hydrous phases create deep charge transition levels, indicating the degradation of halide perovskite upon exposure to moisture. Electronic structure analysis supports a novel mechanism of water-mediated vacancy-pair formation.