A Versatile Ionic Liquid Additive for Perovskite Solar Cells: Surface Modification, Hole Transport Layer Doping, and Green Solvent Processing

Abstract Hole‐transport layers (HTL) in perovskite solar cells (PSCs) with an n‐i‐p structure are commonly doped by bis(trifluoromethane)sulfonimide (TFSI) salts to enhance hole conduction. While lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) dopant is a widely used and effective dopant, it has significant limitations, including the need for additional solvents and additives, environmental sensitivity, unintended oxidation, and dopant migration, which can lead to lower stability of PSCs. A novel ionic liquid, 1‐(2‐methoxyethyl)‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (MMPyTFSI), is explored as an alternative dopant for 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamino)‐9,9′‐spirobifluorene (spiro‐OMeTAD). MMPy ions act as a surface passivator, reducing defects on the perovskite surface, while TFSI ions facilitate p‐type doping. MMPyTFSI functions as an efficient dopant, maintaining excellent performance even when tetrahydrofuran (THF) is utilized as a solvent in place of chlorobenzene (CB), while significantly reducing the environmental impact of the process. The optimized PSC achieves a power conversion efficiency (PCE) of 23.10% and demonstrates enhanced long‐term stability in all aging tests for over 1000 h in a humid atmosphere, at high temperature, and under simulated sunlight illumination. These results demonstrate that MMPyTFSI is an effective and environmentally friendly dopant for producing stable and efficient PSCs.