Molecule Passivation of Grain Boundaries for Ultra‐Stable Perovskite Solar Cells

Perovskite solar cells have become stars in photovoltaics due to their rapidly increased efficiency. However, their stability is still below par due to moisture permeation from grain boundaries and defects. To conquer both problems at once, a passivation agent 3,4,5,6‐tetrafluorophthalicacid (TFPA) is rationally designed to heal both for not only improved cell efficiency but also better stability. It is found that the TFPA is prone to distribute along grain boundaries and has little influence within the bulk of the perovskite film. In addition, it appears that the TFPA helps to reduce the film roughness, to adjust the energy level, to facilitate hole transporting from perovskite to spiro‐OMeTAD, and to increase the hydrophobicity of the perovskite film, as it is demonstrated by the inhibited nonradiative recombination and prolonged carrier lifetime. Owing to strong interactions between F, ‐COOH, and Pb, the device with TFPA shows outstanding efficiency and stability. A perovskite solar cell with TFPA modification delivers a champion efficiency of 23.70% and a significantly enhanced stability that the device maintains 90% of its initial efficiency after 5200 h, among the best ambient stability. Herein, an effective strategy of grain boundary passivation is provided to improve the stability of perovskite solar cells.