High Open Circuit Voltage Over 1 V Achieved in Tin‐Based Perovskite Solar Cells with a 2D/3D Vertical Heterojunction

2D–3D mixed tin halide perovskites are outstanding candidate materials for lead‐free perovskite solar cells (PSCs) due to their improved stability and decreased trap density in comparison with their pure 3D counterparts. However, the mixture of multiple phases may lead to poor charge transfer across the films and limit the device efficiency. Here, a stacked quasi‐2D (down)–3D (top) double‐layered structure in perovskite films prepared via vacuum treatment is demonstrated, which can result in a planar bilayer heterojunction. In addition, it is found that the introduction of guanidinium thiocyanate (GuaSCN) additive can improve the crystallinity and carrier mobility in the 2D perovskite layer and passivate defects in the whole film, leading to a long carrier lifetime (>140 ns) in photoluminescence measurements. As a result, the PSCs show a high open circuit voltage (V(OC)) up to 1.01 V with a voltage loss of only 0.39 V, which represents the record values ever reported for tin‐based PSCs. The champion device exhibits a power conversion efficiency (PCE) of 13.79% with decent stability, retaining 90% of the initial PCE for 1200 h storage in N(2)‐filled glovebox.