A Thienothiophene‐Based Cation Treatment Allows Semitransparent Perovskite Solar Cells with Improved Efficiency and Stability

Perovskite surface treatment with additives has been reported to improve charge extraction, stability, and/or surface passivation. In this study, treatment of a 3D perovskite ((FAPbI3)1−x(MAPbBr3)x) layer with a thienothiophene‐based organic cation (TTMAI), synthesized in this work, is investigated. Detailed analyses reveal that a 2D (n = 1) or quasi‐2D layer does not form on the PbI2‐rich surface 3D perovskite. TTMAI‐treated 3D perovskite solar cells (PSCs) fabricated in this study show improved fill factors, providing an increase in their power conversion efficiencies (PCEs) from 17% to over 20%. It is demonstrated that the enhancement is due to better hole extraction by drift‐diffusion simulations. Furthermore, thanks to the hydrophobic nature of the TTMAI, PSC maintains 82% of its initial PCE under 15% humidity for over 380 h (the reference retains 38%). Additionally, semitransparent cells are demonstrated reaching 17.9% PCE with treated 3D perovskite, which is one of the highest reported efficiencies for double cationic 3D perovskites. Moreover, the semitransparent 3D PSC (TTMAI‐treated) maintains 87% of its initial efficiency for six weeks (>1000 h) when kept in the dark at room temperature. These results clearly show that this study fills a critical void in perovskite research where highly efficient and stable semitransparent perovskite solar cells are scarce. Perovskite solar cells (PSCs) are fabricated using a novel organic cation (TTMAI) treatment on a 3D perovskite, which enables higher power conversion efficiency (PCE) and improves stability. The PCE enhancement is explained by the drift‐diffusion modeling. In addition, TTMAI‐treated 3D perovskite‐based semitransparent PSCs are also realized, and a notable increase in PCE and stability is obtained.