Suppressing Ion Migration by Synergistic Engineering of Anion and Cation toward High‐Performance Inverted Perovskite Solar Cells and Modules

Abstract Ion migration‐induced intrinsic instability and large‐area fabrication pose a tough challenge for the commercial deployment of perovskite photovoltaics. Herein, an interface heterojunction and metal electrode stabilization strategy is developed by suppressing ion migration via managing lead‐based imperfections. After screening a series of cations and nonhalide anions, the ideal organic salt molecule dimethylammonium trifluoroacetate (DMATFA) consisting of dimethylammonium (DMA⁺) cation and trifluoroacetate (TFA⁻) anion is selected to manipulate the surface of perovskite films. DMA⁺ enables the conversion of active excess and/or unreacted PbI₂ into stable new phase DMAPbI₃, inhibiting photodecomposition of PbI₂ and ion migration. Meanwhile, TFA⁻ can suppress iodide ion migration through passivating undercoordinated Pb²⁺ and/or iodide vacancies. DMA⁺ and TFA⁻ synergistically stabilize the heterojunction interface and silver electrode. The DMATFA‐treated inverted perovskite solar cells and modules achieve a maximum efficiency of 25.03% (certified 24.65%, 0.1 cm²) and 20.58% (63.74 cm²), respectively, which is the record efficiency ever reported for the devices based on vacuum flash evaporation technology. The DMATFA modification results in outstanding operational stability, as evidenced by maintaining 91% of its original efficiency after 1520 h of maximum power point continuous tracking.