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An average PCE of 4.2% for all‐polymer solar cells from 20 devices with an average JSC of 8.8 mA cm−2 are obtained with a donor‐acceptor pair despite a low LUMO‐LUMO energy offset of less than 0.1 eV. Incorporation of polystyrene side chains into the donor polymer is found to assist in reducing the phase separation domain length scale, and results in more than 20% enhancement of PCE. We observe a...
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