Glycol Monomethyl Ether‐Substituted Carbazolyl Hole‐Transporting Material for Stable Inverted Perovskite Solar Cells with Efficiency of 25.52%

Organic self‐assembled molecules (OSAMs) based hole transporting materials play a pivotal role in achieving highly efficient and stable inverted perovskite solar cells (IPSCs). However, the reported carbazol‐based OSAMs have serious drawbacks, such as poor solubility in alcohol solution, worse matched energy arrangement with perovskite, and limited molecular species, which greatly limit the device performance. To address above problems, a novel OSAM 4‐(3,6‐glycol monomethyl ether‐9H‐carbazol‐9‐yl) butyl]phosphonic acid (GM‐4PACz) was synthesized as hole‐transporting material by introducing glycol monomethyl ether (GM) side chains at carbazolyl unit. GM groups enhance the surface energy of Indium Tin Oxide (ITO)/SAM substrate to facilitate the nucleation and growth of up perovskite film, suppress cation defects, release the residual stress at SAM/perovskite interface, and evaluate energy level for matching with perovskite. Consequently, the GM‐4PACz based IPSC achieves a champion PCE of 25.52%, a respectable open‐circuit voltage (VOC) of 1.21 V, a high stability, possessing 93.29% and 91.75% of their initial efficiency after aging in air for 2000 h or tracking at maximum power point for 1000 h, respectively.