Sulfonated Dopant‐Free Hole‐Transport Material Promotes Interfacial Charge Transfer Dynamics for Highly Stable Perovskite Solar Cells

Abstract The integration of a functional group into dopant‐free hole‐transport materials (HTMs) to modify the perovskite|HTM interface has become a promising strategy for high‐performance and stable perovskite solar cells (PSCs). In this work, a sulfonated phenothiazine‐based HTM is reported, namely TAS, which consists of a butterfly structure with a readily synthesized N ,​ N ‐​bis[4‐​(methylthio)​phenyl]​aniline side functional group. The interaction between TAS and perovskite via Pb–S bond induces a dipole moment that deepens the valence band of perovskite and thereby leads to enhanced open‐circuit voltage in corresponding n‐i‐p PSCs. More importantly, the functionalization of perovskite surface via Pb–S bond promotes the hole extraction reaction while suppressing the interfacial non‐radiative recombination, contributing to a 20–50% performance improvement compared to less‐ (4‐​(methylthio)​‐​ N ‐​[4‐​(methylthio)​phenyl]​aniline, DAS) or non‐interacting ( N , N ‐bis(4‐methoxyphenyl)aniline, TAO) counterparts. Consequently, TAS‐based PSCs exhibit superior device stability with a high PCE retention (>90% of the initial value) after 125 days of storage in the air.