Activated Corrosionand Recovery in Lead Mixed-HalidePerovskites Revealed by Dynamic Near-Ambient Pressure X‑rayPhotoelectron Spectroscopy

Herein, we quantify rates of O₂-photoactivated corrosion and recovery processes within triple cation CsFAMAPb(IBr)₃ perovskite active layers using dynamic near-ambient pressure X-ray photoemission spectroscopy (NAP-XPS). Activated corrosion is described as iodide oxidation and lead reduction, which occurs only in the presence of both O₂ and light through photoinduced electron transfer. We observe electron density reorganization from the Pb–I bonds consistent with ligand exchange, evident from the nonstoichiometric redox change (i.e., <1 e^–). Approximately half of the Pb centers are reduced to weakly coordinated Pb–higher oxidation number than metallic Pb–with a rate coefficient of ∼3 (±0.3) × 10^–4 atomic percent/s. Hole capture by I^– yields I₃^– and is accompanied by increased concentrations of near-surface bromides, hypothesized to be due to anion vacancies and/or oxidation of mobile iodide resulting from ion demixing. Activated corrosion is found to be quasi-reversible; initial perovskite stoichiometry slowly recovers when the O₂/light catalyst is removed, postulated to be due to mobile halide species present within the film below XPS sampling depth. Small deviations in near-surface composition (<2%) of the perovskite are used to connect reaction rates to quantified, near-band edge donor and acceptor defect concentrations, demonstrating two energetically distinct sites are responsible for the redox process. Collectively, environmental flux and rate quantification are deemed critical for the future elucidation of chemical degradation processes in perovskites, where rate-dependent reaction pathways are expected to be very system dependent (environment and material).