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In this regard, design of new NFAs capable of achieving optimal aggregation in large\u2010area organic photovoltaic modules has not been realized. Here, an NFA named BTA\u2010HD\u2010Rh is synthesized with longer (hexyl\u2010decyl) side chains that exhibit good solubility and optimal aggregation. Interestingly, integrating a minute amount of new NFA (BTA\u2010HD\u2010Rh) into the PM6:L8\u2010BO system enables the improved solubility in halogen\u2010free solvents (<jats:italic>o<\/jats:italic>\u2010xylene:carbon disulfide (<jats:italic>O<\/jats:italic>\u2010XY:CS<jats:sub>2<\/jats:sub>)) with controlled aggregation is found. Then solar sub\u2010modules are fabricated at ambient condition (temperature at 25\u00a0\u00b1\u00a03 \u00b0C and humidity: 30\u201345%). Ultimately, the champion 55 cm<jats:sup>2<\/jats:sup> sub\u2010modules achieve exciting efficiency of &gt;16% in <jats:italic>O<\/jats:italic>\u2010XY:CS<jats:sub>2<\/jats:sub> solvents, which is the highest PCE reported for sub\u2010modules. Notably, the highest efficiency of BTA\u2010HD\u2010Rh doped PM6:L8\u2010BO is very well correlated with high miscibility with low Flory\u2010Huggins parameter (0.372), well\u2010defined nanoscale morphology, and high charge transport. This study demonstrates that a careful choice of side chain engineering for an NFA offers fascinating features that control the overall aggregation of active layer, which results in superior sub\u2010module performance with environmental\u2010friendly solvents.<\/jats:p>","DOI":"10.1002\/advs.202404997","type":"journal-article","created":{"date-parts":[[2024,6,18]],"date-time":"2024-06-18T14:18:07Z","timestamp":1718720287000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Accomplishing High\u2010Performance Organic Solar Sub\u2010Modules (\u224855 cm<sup>2<\/sup>) with &gt;16% Efficiency by Controlling the Aggregation of an Engineered Non\u2010Fullerene Acceptor"],"prefix":"10.1002","volume":"11","author":[{"given":"Thavamani","family":"Gokulnath","sequence":"first","affiliation":[{"name":"Department of Chemistry Education Graduate Department of Chemical Materials Institute for Plastic Information and Energy 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