Stable Surface Contact with Tailored Alkylamine Pyridine Derivatives for High‐Performance Inverted Perovskite Solar Cells

Abstract Formamidinium‐cesium lead triiodide (FA 1‐x Cs x PbI 3 ) perovskite holds great promise for perovskite solar cells (PSCs) with both high efficiency and stability. However, the defective perovskite surfaces induced by defects and residual tensile strain largely limit the photovoltaic performance of the corresponding devices. Here, the passivation capability of alkylamine‐modified pyridine derivatives for the surface defects of FA 1‐x Cs x PbI 3 perovskite is systematically studied. Among the studied surface passivators, 3‐(2‐aminoethyl)pyridine (3‐PyEA) with the suitable size is demonstrated to be the most effective in reducing surface iodine impurities and defects (V I and I 2 ) through its strong coordination with N pyridine . Additionally, the tail amino group (─NH 2 ) from 3‐PyEA can react with FA + cations to reduce the surface roughness of perovskite films, and the reaction products can also passivate FA vacancies (V FA ), and further strengthen their binding interaction to perovskite surfaces. These merits lead to suppressed nonradiative recombination loss, the release of residual tensile stress for the perovskite films, and a favorable energy‐level alignment at the perovskite/[6,6]‐phenyl‐C 61 ‐butyric acid methyl ester interface. Consequently, the resulting inverted FA 1‐x Cs x PbI 3 PSCs obtain an impressive power conversion efficiency (PCE) of 25.65% (certified 25.45%, certified steady‐state efficiency 25.06%), along with retaining 96.5% of the initial PCE after 1800 h of 1‐sun operation at 55 °C in air.