The inverted inorganic CsPbI3 perovskite solar cells (PSCs) are prospective candidates for next-generation photovoltaics owing to inherent robust thermal/photo-stability and compatibility for tandems. However, the performance and stability of the inverted CsPbI3 PSCs fall behind the n-i-p counterparts due to poor energetic alignment and abundant interfacial defect states. Here, an inorganic 0D Cs4PbBr6 with a good lattice strain arrangement is implemented as the surface anchoring capping layer on CsPbI3. The Cs4PbBr6 perovskite induces enhanced electron-selective junction and thus facilitates efficient charge extraction and effectively inhibits non-radiative recombination. Consequently, the CsPbI3 PSCs with Cs4PbBr6 demonstrate the highest power conversion efficiency (PCE) of CsPbI3-based inverted PSCs, reaching 21.03% PCE from a unit cell and 17.39% PCE from a module with a 64 cm2 aperture area. Furthermore, the resulting devices retain 92.48% after 1000h under simultaneous 1-sun and damp heat (85°C / 85% relative humidity) environment.
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