Efficient and stabilized molecular doping of hole-transporting materials driven by a cyclic-anion strategy for...

Bis(trifluoromethane)sulfonimide lithium salt (Li-TFSI) is commonly used as an effective dopant to improve the performance of the hole-transporting material (HTM) in n-i-p perovskite solar cells (PSCs). However, the ultra-hygroscopic and migratory nature of Li-TFSI leads to inferior stability of PSCs. Here, we report on a strategy to regulate the anion unit in Li-TFSI from linear to cyclic, constructing a new dopant, lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (Li-CYCLIC), for the state-of-the-art poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA). Mechanistic and experimental results reveal that the cyclic anion CYCLIC^- exhibits stronger interaction with Li⁺ and PTAA˙⁺ compared with the linear anion TFSI^-, thus significantly restraining the moisture absorption and migration of Li⁺ and improving the thermodynamic stability of PTAA˙⁺CYCLIC^-. With this molecular engineering, the resulting PSCs based on Li-CYCLIC obtained an improved efficiency, along with remarkably enhanced stability, retaining 96% of the initial efficiency after over 1150 hours under continuous 1 sun illumination in an N₂ atmosphere, yielding an extrapolated T ₈₀ of over 12 000 hours. In a broader context, the proposed strategy of linear-to-cyclic doping provides substantial guidance for the subsequent advancement in the development of effective dopants for photoelectric devices.