Influence of Methylammonium Chloride on Wide‐Bandgap Halide Perovskites Films for Solar Cells

Abstract Wide‐bandgap perovskites are of paramount importance as the photoactive layer of the top cell in high‐efficiency tandem solar cells. Comparably high Br contents are required to widen the perovskite bandgap. However, the increase in Br content causes heterogeneous halide distribution and photoinstability. Here, the positive effect of the additive methylammonium chloride (MACl) on the optical and electronic properties of Br‐rich perovskite, deposited using N‐methyl‐2‐pyrrolidone (NMP) as co‐solvent and the gas quenching method, is investigated. Simultaneous in situ grazing‐incidence wide‐angle X‐ray scattering and photoluminescence spectroscopy are used to track the evolution of the structural and optoelectronic properties of the perovskites with different amounts of Br and MACl during the spin‐coating and thermal annealing steps. The formation mechanism is elucidated in the presence of MACl. It is observed that chloride ions inhibit the intermediate phases, favoring the formation of a perovskite phase with higher crystallinity. Nano X‐ray fluorescence mapping recognizes Br‐richer and poorer nanometric domains, whose average sizes reduce for samples with MACl. In conclusion, it is demonstrated that adding MACl affects the formation of wide‐bandgap perovskites via destabilization of the intermediate phases and acts on the homogenization of the halide distribution, leading to improved solar cell performances.