Multi‐Functional Interface Passivation via Guanidinium Iodide Enables Efficient Perovskite Solar Cells

Perovskite solar cells have become a leading contender in next‐generation photovoltaic technologies due to their high efficiency and low‐cost potential. Managing the deep defects present effectively in the crystal lattice and at the interfaces is essential for enhancing the performance and longevity of perovskite solar cells. Here, perovskite's crystallization modulation and interfacial defect passivation are achieved by developing a guanidinium iodide (GAI)‐based surface passivation strategy. The integration of GAI passivates the grain boundaries, leading to a perovskite thin film with a smoother and more uniform grain distribution, facilitating charge carrier transport. Notably, the ammonium group, unsaturated nitrogen atoms, and iodide ions in GAI can collectively repair the surface defects of perovskite through various pathways, effectively suppressing non‐radiative recombination, thereby enhancing the photovoltaic performance of the device. Ultimately, the champion device treated with GAI achieves a power conversion efficiency (PCE) of 23.02% and demonstrates similar ambient stability under unencapsulated conditions. These findings underscore the effectiveness of GAI passivation as a strategy to balance the improvement of the performance and stability of perovskite solar cells. A multi‐functional perovskite interface passivation strategy based on guanidinium iodide is proposed. The guanidinium iodide, with its ammonium group, unsaturated nitrogen atoms, and iodide ions, synergistically repairs the perovskite interface defects through various pathways, passivates the grain boundaries, effectively suppresses non‐radiative recombination, and significantly improves the photovoltaic performance of the device.