Formamidinium and Cesium Hybridization for Photo‐ and Moisture‐Stable Perovskite Solar Cell

Although power conversion efficiency (PCE) of state‐of‐the‐art perovskite solar cells has already exceeded 20%, photo‐ and/or moisture instability of organolead halide perovskite have prevented further commercialization. In particular, the underlying weak interaction of organic cations with surrounding iodides due to eight equivalent orientations of the organic cation along the body diagonals in unit cell and chemically non‐inertness of organic cation result in photo‐ and moisture instability of organometal halide perovskite. Here, a perovskite light absorber incorporating organic–inorganic hybrid cation in the A‐site of 3D APbI 3 structure with enhanced photo‐ and moisture stability is reported. A partial substitution of Cs + for HC(NH 2 ) 2 + in HC(NH 2 ) 2 PbI 3 perovskite is found to substantially improve photo‐ and moisture stability along with photovoltaic performance. When 10% of HC(NH 2 ) 2 + is replaced by Cs + , photo‐ and moisture stability of perovskite film are significantly improved, which is attributed to the enhanced interaction between HC(NH 2 ) 2 + and iodide due to contraction of cubo‐octahedral volume. Moreover, trap density is reduced by one order of magnitude upon incorporation of Cs + , which is responsible for the increased open‐circuit voltage and fill factor, eventually leading to enhancement of average PCE from 14.9% to 16.5%.