Tin‐based perovskite (Sn‐PS) is one of the most promising candidates in lead‐free perovskite solar cells (PSCs), but its poor stability and low power conversion efficiency (PCE) have been the main bottleneck towards further development. Here, to develop a stable and efficient Sn‐based PSC, nitrogen‐doped graphene oxide (NxGO) has been, for the first time, incorporated in active, hole‐transport and interfacial layers. The inclusion of NxGO slowed the crystallization of Sn‐PS and suppressed the Sn2+/Sn4+ oxidation, resulting in pinhole‐free dense films having large grains, reduction of recombination loss, well‐matched energy levels, and thereby significantly improving the device performance. Compared to the pristine Sn‐PS cells, the champion devices with NxGO‐based composites in active, hole‐transport, and interfacial layers showed dramatic enhancement of photovoltaic parameters (i.e., open‐circuit voltage = 0.961 V, photocurrent = 21.21 mA cm−2, fill factor = 65.05% and PCE = 13.26%). Furthermore, the NxGO‐based cells without encapsulation showed remarkable improvement of long‐term stability with sustaining 91% of the initial PCE over 60 d, photostability, and reproducibility.
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