High-quality phase-pure formamidinium lead triiodide (FAPbI₃) perovskite film needs to be fabricated under strict control of the surrounding atmosphere, which becomes more rigorous when large-area FAPbI₃ film is involved, leading to high-performance FAPbI₃ perovskite solar cells and modules predominantly carried out in an inert gas-filled atmosphere. In this work, we propose a scalable printing strategy for the large-area high-quality phase-pure FAPbI₃ film under a high-humidity atmosphere (up to 75% ± 5% relative humidity) by regulating the perovskite precursor ink with a functional perfluoroalkylsulfonyl quaternary ammonium iodide. This approach decreases the energy barriers of cubic phase formation and heterogeneous nucleation, thereby regulating the FAPbI₃ crystallization. The printed photovoltaic small-area cells and large-area modules achieved remarkable power conversion efficiencies of 24.37% and 22.00%, respectively. Specifically, the unencapsulated device exhibits superior operational stability with T₉₀ > 1,060 h, ambient stability with T₉₀ > 2,020 h, and thermal stability with T₉₀ > 2,350 h.

高质量的相纯甲脒三碘化铅（FAPbI ₃ ）钙钛矿薄膜需要在严格控制周围气氛的情况下制备，当大面积FAPbI ₃ 薄膜时，这一点变得更加严格参与其中，导致高性能 FAPbI ₃ 钙钛矿太阳能电池和模块主要在惰性气体填充的气氛中进行。在这项工作中，我们提出了一种在高湿度气氛（高达 75% ± 5% 相对湿度）下大面积高质量相纯 FAPbI ₃ 薄膜的可扩展打印策略，通过调节具有功能性全氟烷基磺酰基碘化季铵的钙钛矿前体墨水。这种方法降低了立方相形成和异质成核的能垒，从而调节FAPbI ₃ 结晶。印刷的光伏小面积电池和大面积组件分别实现了24.37%和22.00%的惊人功率转换效率。具体来说，未封装的器件表现出优异的操作稳定性，T ₉₀ > 1,060 小时，环境稳定性 T ₉₀ > 2,020 小时，以及热稳定性 T ₉₀ > 2,350 小时。