Dual‐Doping Strategy of Metal Chlorides in Ambient Air with High Humidity for Achieving Highly Air‐Stable All‐Inorganic Perovskite Solar Cells

It is fundamentally challenging to achieve stable and efficient all‐inorganic perovskite solar cells (PSCs) in ambient air conditions for low‐cost commercial manufacturing, as the crystallinity, surface morphology, and optical activity of all‐inorganic perovskites exhibit high sensitivity to environmental factors such as moisture and illumination. Herein, a dual‐doping strategy is presented to prepare high‐quality dual‐doping CsPbI 2 Br films under ambient air with relative humidity of 70% (70% RH) by introducing CaCl 2 and InCl 3 additives into precursor solution. The results from the experiments and calculations reveal that the CaCl 2 additive can isolate moisture by forming hydrates at the surface and grain boundary of perovskites. Meanwhile, the addition of InCl 3 can significantly improve the optoelectronic properties via the heterovalent substitution of Pb 2+ by a small amount of In 3+ . Moreover, the phase segregation can be significantly suppressed in the dual‐doping CsPbI 2 Br films owing to decreasing the electron–phonon coupling strength and increasing the activation energy of ion migration. The unencapsulated dual‐doping CsPbI 2 Br PSC with the power conversion efficiency (PCE) of 15.51% (70% RH) demonstrates high humidity storage and long‐term optical stability, remaining 90% of the original PCE after aging 2400 h under ambient air (50% RH) and 1500 h under continuous illumination, respectively.