Ligand engineering is an effective method to reduce defects in perovskite solar cells (PSCs) and to enhance efficiency. Likewise, enhancing device stability through ligand engineering is currently emerging as a key focus to suppress the bidirectional migration of halides and silver ions, which otherwise can cause irreversible chemical corrosion to the electrode and perovskite layer. Here, triphenylphosphine oxide (TPPO) is demonstrated to improve the long-term operational stability of PSCs when introduced at the interface between the perovskite and the electron transport layer (ETL). TPPO effectively eliminates uncoordinated Pb2+ and thus reduces surface defects. Accordingly, the target solar cell yields a hero power conversion efficiency (PCE) of 26.01% and a maximum open-circuit voltage (VOC) of 1.23 V, representing the minimum voltage deficit (0.32 V) reported for methylammonium-free (MA-free) PSCs. Moreover, long-term operational analysis reveals that the bidirectional migration of halides and silver ions is significantly suppressed, resulting in enhanced device stability. TPPO-modified PSCs retain 90% of the initial PCE after 1200 hours of operation in maximum power point tracking. Ligand engineering with TPPO marks a significant advancement in enhancing the stability of PSCs and is fully compatible to upscaling scenarios.
