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Structure engineering of SAMs has proven to be an effective approach to enhance device performance. In this work, a novel SAM featuring extended conjugation is designed and synthesized, designated E\u2010CbzBT. Compared with CbzBT, E\u2010CbzBT exhibits enhanced asymmetric and noncoplanar screw\u2010shaped configuration, leading to uniform and tight packing on ITO. The uniform packing of E\u2010CbzBT increases the wettability of the perovskite precursor solution on the substrate, thereby facilitating perovskite crystallinity and suppressing interfacial trap density more effectively than CbzBT. Accordingly, inverted PSCs employing E\u2010CbzBT reach a champion power conversion efficiency of 25.15%, surpassing 24.06% for CbzBT\u2010based devices. Importantly, the E\u2010CbzBT\u2010based PSCs demonstrate superior ambient and thermal stability. The extending conjugation approach in SAMs represents a promising avenue for further advancements in perovskite solar cell technology.<\/jats:p>","DOI":"10.1002\/smll.202500296","type":"journal-article","created":{"date-parts":[[2025,3,23]],"date-time":"2025-03-23T13:23:32Z","timestamp":1742736212000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":19,"title":["A Novel Self\u2010Assembled Hole\u2010Transporting Monolayer with Extending Conjugation for Inverted Perovskite Solar Cells"],"prefix":"10.1002","volume":"21","author":[{"given":"Qian","family":"Wang","sequence":"first","affiliation":[{"name":"Institute for Advanced Materials and Technology University of Science and Technology Beijing  Beijing 100083 P. R. 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