Effects of Alkaline Earth Metal Additives on Methylammonium‐Free Lead Halide Perovskite Thin Films and Solar Cells

Organic–inorganic lead halide perovskite solar cells are regarded as one of the most promising technologies for the next generation of photovoltaics due to their high power conversion efficiency (PCE) and simple solution manufacturing. Among the different compositions, the formamidinium lead iodide (FAPbI 3 ) photoactive phase has a bandgap of 1.4 eV, which enables the corresponding higher PCEs according to the Shockley–Queisser limit. However, the photoactive crystal phase of FAPbI 3 is not stable at room temperature. The most high‐performing compositions to date have reduced this problem by incorporating the methylammonium (MA) cation into the FAPbI 3 composition, although MA has poor stability at high temperatures and in humid environments, which can limit the lifetime of FA x MA 1− x PbI 3 films. Cs x FA 1− x PbI 3 perovskites are also explored, but despite better stability they still lag in performance. Herein, the additive engineering of MA‐free organic−inorganic lead halide perovskites using divalent cations Sr 2+ and Ca 2+ to enhance the performances of Cs x FA 1− x PbI 3 perovskite compositions is explored. It is revealed that the addition of up to 0.5% of Sr 2+ and Ca 2+ leads to improvements in morphology and reduction in microstrain. The structural improvements observed correlate with improved solar cell performances at low additive concentrations.