An Integrated Deposition and Passivation Strategy for Controlled Crystallization of 2D/3D Halide Perovskite Films

This work introduces a simplified deposition procedure for multidimensional (2D/3D) perovskite thin films, integrating a phenethylammonium chloride (PEACl)‐treatment into the antisolvent step when forming the 3D perovskite. This simultaneous deposition and passivation strategy reduces the number of synthesis steps while simultaneously stabilizing the halide perovskite film and improving the photovoltaic performance of resulting solar cell devices to 20.8%. Using a combination of multimodal in situ and additional ex situ characterizations, it is demonstrated that the introduction of PEACl during the perovskite film formation slows down the crystal growth process, which leads to a larger average grain size and narrower grain size distribution, thus reducing carrier recombination at grain boundaries and improving the device's performance and stability. The data suggests that during annealing of the wet film, the PEACl diffuses to the surface of the film, forming hydrophobic (quasi‐)2D structures that protect the bulk of the perovskite film from humidity‐induced degradation. A facile method for depositing multidimensional perovskite thin films is presented, incorporating phenethylammonium chloride (PEACl) treatment into the antisolvent step for 3D perovskite formation. Using multimodal in situ characterization, it is shown that PEACl slows crystal growth, resulting in reduced grain boundary recombination and improved device efficiency. PEACl also forms hydrophobic 2D structures, protecting the film from humidity‐induced degradation.