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Nonetheless, the impact of the alkyl spacer length of SAMs remains inadequately understood. To improve the knowledge, four dichloride\u2010substituted carbazole\u2010based SAMs (from 2Cl\u20102PACz to 2Cl\u20105PACz) with spacer lengths of 2\u20135 carbon atoms is developed. Single crystal analyses reveal that SAMs with shorter spacers exhibit stronger intermolecular interactions and denser packing. The molecular conformation of SAMs significantly impacts their molecular footprint and coverage on ITO. These factors result in the highest coverage of 2Cl\u20102PACz and the lowest coverage for 2Cl\u20103PACz on ITO. OSCs based on PM6:L8\u2010BO with 2Cl\u20102PACz as HTL achieved high efficiencies of 18.95% and 18.62% with and without methanol rinsing of the ITO\/SAMs anodes, corresponding to monolayer and multilayer structures, respectively. In contrast, OSCs utilizing the other SAMs showed decreased efficiencies as spacer length increased. The superior performance of 2Cl\u20102PACz can be attributed to its shorter spacer, which reduces series resistance, hole tunneling distance, and barrier. This work provides valuable insights into the design of SAMs for high\u2010performance OSCs.<\/jats:p>","DOI":"10.1002\/advs.202410277","type":"journal-article","created":{"date-parts":[[2024,12,4]],"date-time":"2024-12-04T08:50:30Z","timestamp":1733302230000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":35,"title":["Effects of Alkyl Spacer Length in Carbazole\u2010Based Self\u2010Assembled Monolayer Materials on Molecular Conformation and Organic Solar Cell Performance"],"prefix":"10.1002","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1788-9454","authenticated-orcid":false,"given":"Qiaonan","family":"Chen","sequence":"first","affiliation":[{"name":"Department of Chemistry and Chemical Engineering Chalmers University of Technology  G\u00f6teborg SE\u2010412 96 Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6223-6751","authenticated-orcid":false,"given":"Kangbo","family":"Sun","sequence":"additional","affiliation":[{"name":"College of New Materials and New Energies Shenzhen Technology University  Shenzhen 518118 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Leandro R.","family":"Franco","sequence":"additional","affiliation":[{"name":"Department of Engineering and Physics Karlstad University  Karlstad 65188 Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9868-3721","authenticated-orcid":false,"given":"Jingnan","family":"Wu","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Engineering Chalmers University of Technology  G\u00f6teborg SE\u2010412 96 Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6420-2141","authenticated-orcid":false,"given":"Lars","family":"\u00d6hrstr\u00f6m","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Engineering Chalmers University of Technology  G\u00f6teborg SE\u2010412 96 Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3190-2774","authenticated-orcid":false,"given":"Xianjie","family":"Liu","sequence":"additional","affiliation":[{"name":"Department of Science and Technology Laboratory of Organic Electronics (LOE) Link\u00f6ping University  Norrk\u00f6ping 60174 Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7018-4595","authenticated-orcid":false,"given":"Maureen","family":"Gumbo","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Engineering Chalmers University of Technology  G\u00f6teborg SE\u2010412 96 Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mailde S.","family":"Oz\u00f3rio","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Copenhagen  Universitetsparken 5 Copenhagen DK\u20102100 Denmark"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"C. 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