Electron Beam Irradiation of Lead Halide Perovskite Solar Cells: Dedoping of Organic Hole Transport Materials despite Hardness of the Perovskite Layer.

Organic-inorganic lead halide perovskite solar cells (PSCs) are highly efficient, flexible, lightweight, and even tolerant to radiation, such as protons, electron beams (EB), and γ-rays, all of which makes them plausible candidates for use in space satellites and spacecrafts. However, the mechanisms of radiation damage of each component of PSC [an organic hole transport material (HTM), a perovskite layer, and an electron transport material (ETM)] are not yet fully understood. Herein, we investigated the EB irradiation effect (100 keV, up to 2.5 × 1015 cm-2) on binary-mixed A site cations and halide perovskite (MA0.13FA0.87PbI2.61Br0.39, MA:methylammonium cation and FA:formaminidium cation), a molecular HTM of doped SpiroOMeTAD, and an inorganic ETM of mesoporous TiO2. Despite the decreased power conversion efficiency of PSCs upon EB exposure, the photoconductivities of the perovskite, HTM, and ETM layers remained intact. In contrast, significant dedoping of HTM was observed, as confirmed by steady-state conductivity, photoabsorption, and X-ray photoelectron spectroscopy measurements. Notably, this damage could be healed by exposure to short-wavelength light, leading to a partial recovery of the PSC efficiency. Our work exemplifies the robustness of perovskite against EB and the degradation mechanism of the overall PSC performance.