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However, the PCEs afforded by currently reported low\u2010cost electron acceptors remain substantially limited. Herein, we report the regulation of molecular crystallization and film formation kinetics of the low\u2010cost electron acceptors with A\u2013DA'D\u2013A\u2010type pentacyclic fused\u2010ring structures and achieved an impressive PCE of 18.04% and a tiptop figure\u2010of\u2010merit (FOM) of 0.363, representing the best\u2010known values for OSCs. Single crystal X\u2010ray diffraction studies indicate that the long and flexible side chain on the central core could hinder the unfavorable dimer formation of electron acceptors and lead to three\u2010dimensional network packing, which is critical for exciton diffusion and charge transport. Moreover, the in situ optical spectroscopy revealed that the side chain elongation of the electron acceptor could slow the film formation kinetics of the small molecular acceptor while accelerating those of the polymer donor, which is conducive to forming bi\u2010continuous interpenetrating fibril networks with better intermixing. This work demonstrates that low\u2010cost, simple\u2010structured fused\u2010ring electron acceptors hold a bright future in the OSC commercialization.<\/jats:p>","DOI":"10.1002\/anie.202517485","type":"journal-article","created":{"date-parts":[[2025,10,3]],"date-time":"2025-10-03T10:47:43Z","timestamp":1759488463000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Low\u2010Cost Fused\u2010Ring Electron Acceptors for Efficient Organic Solar Cells by Fine\u2010Tuning Molecular Crystallization and Film Formation Kinetics"],"prefix":"10.1002","volume":"64","author":[{"given":"Wenkui","family":"Wei","sequence":"first","affiliation":[{"name":"Institute of Polymer Optoelectronic Materials and Devices Guangdong Basic Research Center of Excellence for Energy &amp; Information Polymer Materials State Key Laboratory of Luminescent Materials and Devices South China University of Technology  Guangzhou 510640 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiyue","family":"Yuan","sequence":"additional","affiliation":[{"name":"Institute of Polymer Optoelectronic Materials and Devices Guangdong Basic Research Center of Excellence for Energy &amp; 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