Pathways of Water-Induced Lead-Halide Perovskite Surface Degradation: Insights from In Situ Atomic-Scale Analysis

While organic–inorganic hybrid perovskites are emerging as promising materials for next-generation photovoltaic applications, the origins and pathways of perovskite instability remain speculative. In particular, the degradation of perovskite surfaces by ambient water is a crucial subject for determining the long-term viability of perovskite-based solar cells. Here, we conducted surface characterization and atomic-scale analysis of the reaction mechanisms for methylammonium lead bromide (MA(CH₃NH₃)PbBr₃) single crystals using ambient-pressure atomic force microscopy (AP-AFM) and near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) in environments ranging from ultrahigh vacuum to 0.01 mbar of water vapor. MAPbBr₃ single crystals, grown by a solution process, were mechanically cleaved under UHV conditions to obtain an atomically clean surface. Consecutive topography and friction force measurements in low-pressure water (p_water ≈ 10^–5 mbar) revealed the formation of degraded patches, one atomic layer deep, gradually increasing their coverage until the surface was entirely covered at a water exposure of 4.7 × 10⁴ langmuir (L). At the perimeters of these degraded patches, a higher friction coefficient was observed, along with an interstitial step height, which we attribute to a structure equivalent to that of the MA–Br terminated surface. Combined with NAP-XPS analysis, our results demonstrate that water vapor induces the dissociation of surface methylammonium ligands, eventually resulting in the depletion of the surface MA and the full coverage of hydrocarbon species after exposure to 0.01 mbar of water vapor.