The interface modification between perovskite and electron transport layer (ETL) plays a crucial role in achieving high performance inverted perovskite photovoltaics (i‐PPVs). Herein, non‐fullerene acceptors (NFAs), known as Y6‐BO and Y7‐BO, were utilized to modify the perovskite/ETL interface in i‐PPVs. Non‐polar solvent‐soluble NFAs can effectively passivate surface defects without structural damage of the underlying perovskite films. Additionally, the improved PCBM ETL induced by NFAs modification significantly accelerates the electrons extraction. As a result, both Y6‐BO and Y7‐BO exhibit more effective interface modification effects compared to traditional PI molecules. The power conversion efficiency (PCE) of the inverted perovskite solar cell (i‐PSC) modified with Y7‐BO reaches 25.82%. Moreover, the adoption of non‐polar solvents and the superior semiconductor properties of Y7‐BO molecules also enable perovskite solar modules (i‐PSM) with effective areas of 50 cm2, 400 cm2, and 1160 cm2 to achieve record efficiencies of 23.05%, 22.32%, and 21.1% (certified PCE), respectively, making them the best PCE reported in the literature. Importantly, enhanced interface mechanical strength between the perovskite and PCBM layer results in significantly improved environmental and operational stability of the cells. The cells modified with Y7‐BO maintained 94.4% of the initial efficiency after 1522 hours of maximum power point aging.
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