Defect Tolerance in Methylammonium Lead Triiodide Perovskite

TLDR

Photovoltaic perovskite semiconductors attract interest because primary defect levels are predicted to lie outside the bandgap. The study experimentally verifies that CH₃NH₃PbI₃ exhibits this defect‑tolerant property, aligning with theoretical predictions. X‑ray photoemission spectroscopy was used to induce and monitor dynamic chemical and electronic changes in the perovskite. Experimental data demonstrate that MAPbI₃ maintains its electronic structure under X‑ray exposure, tolerating compensating defect pairs across a broad I/Pb range, with valence‑band shifts occurring only when the halide–lead ratio drops below 2.5, confirming the predicted defect‑tolerant behavior.

Abstract

Photovoltaic applications of perovskite semiconductor material systems have generated considerable interest in part because of predictions that primary defect energy levels reside outside the bandgap. We present experimental evidence that this enabling material property is present in the halide-lead perovskite, CH3NH3PbI3 (MAPbI3), consistent with theoretical predictions. By performing X-ray photoemission spectroscopy, we induce and track dynamic chemical and electronic transformations in the perovskite. These data show compositional changes that begin immediately with exposure to X-ray irradiation, whereas the predominant electronic structure of the thin film on compact TiO2 appears tolerant to the formation of compensating defect pairs of VI and VMA and for a large range of I/Pb ratios. Changing film composition is correlated with a shift of the valence-band maximum only as the halide–lead ratio drops below 2.5. This delay is attributed to the invariance of MAPbI3 electronic structure to distributed defects that can significantly transform the electronic density of states only when in high concentrations.