Heteroatom Engineering of a Dibenzo[g,p]Chrysene‐Based Hole Transporting Material Provides High‐Performance Perovskite Solar Cells

Hole‐transporting materials (HTMs) are indispensable for realizing efficient and stable perovskite solar cells (PSCs). Herein, a novel dibenzo[g,p]chrysene‐based HTM, termed FTPE‐OSMe, is synthesized with peripheral methoxy‐ and methylthio‐groups, which contrasts with most other small molecule HTMs that feature only methoxy‐groups. The presence of methoxy‐ and methylthio‐groups endows FTPE‐OSMe with appropriate energy levels, high‐hole mobility and enhanced interfacial interactions. PSCs employing Li‐TFSI and 4‐tert‐butylpyridine‐doped FTPE‐OSMe demonstrate a remarkable power conversion efficiency (PCE) of 24.94% (certified 24.89%). The larger‐scale PSC (1.0 cm2) and module (29.0 cm2) yield PCEs of 23.57 and 20.22%, respectively. In addition, the dopant‐free FTPE‐OSMe‐based PSCs exhibit a respectable PCE of 22.40% and excellent stability.