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Here, we report three new benzo[\n                    <jats:italic>a<\/jats:italic>\n                    ]phenazine\u2010core small\u2010molecule acceptors, namely NA5, NA6, and NA7, and systematically evaluate their photovoltaic properties in\n                    <jats:italic>o<\/jats:italic>\n                    \u2010xylene\u2010processed binary and ternary OSCs. Halogenation significantly strengthens intermolecular interactions, improves charge carrier mobility, and facilitates exciton dissociation, leading to a remarkable increase in binary device efficiencies from \u223c2% (NA5) to over 17% (NA6, NA7). However, halogenation also increases charge\u2010transfer state character, which can induce higher nonradiative recombination and energy loss. Despite this drawback, the enhanced driving force for charge separation and improved morphological order enabled by halogenation outweigh the negative effects on energy loss. Notably, incorporation of NA7 into the PM6:BTP\u2010eC9 ternary system optimizes blend morphology, suppresses nonradiative recombination, and thus achieves a record power conversion efficiency of 20.14% (certified 19.93%)\u2014the highest reported for OSCs processed with hydrocarbon solvents. These findings highlight the dual role of halogenation in modulating both beneficial and detrimental aspects of device energetics, providing new insights into molecular design strategies for high\u2010performance, environmental\u2010friendly OSCs.\n                  <\/jats:p>","DOI":"10.1002\/anie.202512237","type":"journal-article","created":{"date-parts":[[2025,9,1]],"date-time":"2025-09-01T11:47:07Z","timestamp":1756727227000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":22,"title":["Halogenation\u2010Engineered Acceptor Enables 20.14% Efficiency in Hydrocarbon\u2010Solvent Processed OSCs: From Binary Trade\u2010Offs to Ternary Synergy in Exciton and Energy Loss Management"],"prefix":"10.1002","volume":"64","author":[{"given":"Jun","family":"Zhang","sequence":"first","affiliation":[{"name":"Guangdong Provincial Key Laboratory of New Energy Materials Service Safety Shenzhen Key Laboratory of New Information Display and Storage Materials College of Materials Science and Engineering Shenzhen University  Shenzhen 518060 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Weifei","family":"Wei","sequence":"additional","affiliation":[{"name":"Guangdong Provincial Key Laboratory of New Energy Materials Service Safety Shenzhen Key Laboratory of New Information Display and Storage Materials College of Materials Science and Engineering Shenzhen University  Shenzhen 518060 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhenghui","family":"Luo","sequence":"additional","affiliation":[{"name":"Guangdong Provincial Key Laboratory of New Energy Materials Service Safety Shenzhen Key Laboratory of New Information Display and Storage Materials College of Materials Science and Engineering Shenzhen University  Shenzhen 518060 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