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In this work, two newly designed wide\u2010bandgap polymer donors, BDT\u2010TS\u20106 and BDT\u2010TS\u201020, were developed by incorporating a diester\u2010functionalized terephthalate unit into a common BDTT\u2010based conjugated backbone and introducing linear C6 or branched C20 ester substituents on the terephthalate\u2010derived units. The short linear C6 and bulky long\u2010branched C20 side chains were selected to provide contrasting steric and molecular packing environments while maintaining solution processability. Accordingly, the two polymer guest donors exhibited distinct aggregation behavior, relative miscibility with the PM6:Y6 host components, and molecular ordering. Both BDT\u2010TS guest donors showed complementary absorption and well\u2010aligned energy levels with the PM6:Y6 host system, supporting extended light harvesting and charge generation in the ternary blends. Notably, BDT\u2010TS\u20106 exhibited more favorable relative miscibility and more ordered molecular packing, whereas BDT\u2010TS\u201020 showed stronger aggregation and predominantly amorphous character. The optimized PM6:BDT\u2010TS\u20106:Y6 and PM6:BDT\u2010TS\u201020:Y6 ternary OSCs achieved PCEs of 17.55% and 16.92%, respectively, outperforming the PM6:Y6 binary OSC (15.92%). Overall, this work demonstrates that side\u2010chain length, branching, and steric bulk collectively regulate aggregation, miscibility, molecular ordering, and the resulting photovoltaic performance of ternary OSCs.<\/jats:p>","DOI":"10.1002\/smll.75603","type":"journal-article","created":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T07:31:23Z","timestamp":1788420683000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Controlling Molecular Packing via Side\u2010Chain Engineering of BDTT\u2010Based Guest Donors for High\u2010Performance Ternary Organic Solar Cells"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0001-6553-9766","authenticated-orcid":false,"given":"Mihyun","family":"Kim","sequence":"first","affiliation":[{"name":"Department of Materials Engineering and Convergence Technology Gyeongsang National University (GNU)  Jinju Republic of 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