The power conversion efficiency (PCE) of tin perovskite solar cells is impeded by the extremely poor resistance to oxidation and high density of intrinsic Sn vacancies. Herein, we grow a 2D-quasi-2D-3D Sn perovskite film using removable pseudohalogen NH4SCN as a structure regulator. This hierarchy structure remarkably enhances air stability resulting from the parallel growth of 2D PEA2SnI4 as the surface layer. We then explore the hierarchy structure perovskite films in planar structural solar cells, which generate a PCE up to 9.41%. The device retains 90% of its initial performance for almost 600 hr. Our results suggest that adding removable NH4SCN in a perovskite precursor can significantly improve the stability and photovoltaic performance of Sn perovskite. This finding provides a powerful strategy to manipulate the structure of low-dimensional perovskite in order to enhance the performance of perovskite solar cells.
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