Abstract Developing high‐performance and stable Sn‐based perovskite solar cells (PSCs) is difficult due to the inherent tendency of Sn 2+ oxidation and, the huge energy mismatch between perovskite and Phenyl‐C61‐butyric acid methyl ester (PCBM), a frequently employed electron transport layer (ETL). This study demonstrates that perovskite surface defects can be passivated and PCBM's electrical properties improved by doping n‐type polymer N2200 into PCBM. The doping of PCBM with N2200 results in enhanced band alignment and improved electrical properties of PCBM. The presence of electron‐donating atoms such as S, and O in N2200, effectively coordinates with free Sn 2+ to prevent further oxidation. The doping of PCBM with N2200 offers a reduced conduction band offset (from 0.38 to 0.21 eV) at the interface between the ETL and perovskite. As a result, the N2200 doped PCBM‐based PSCs show an enhanced open circuit voltage of 0.79 V with impressive power conversion efficiency (PCE) of 12.98% (certified PCE 11.95%). Significantly, the N2200 doped PCBM‐based PSCs exhibited exceptional stability and retained above 90% of their initial PCE when subjected to continuous illumination at maximum power point tracking for 1000 h under one sun.

Minimization of Energy Level Mismatch of PCBM and Surface Passivation for Highly Stable Sn‐Based Perovskite Solar Cells by Doping n‐Type Polymer