The side-chain structures of conjugated molecules are well recognized to sensitively influence the crystallinity, morphology and thus carrier transport properties of organic semiconductors. Here, by varying the alkyl side-chain length in the polymer acceptors, the effect of side-chain engineering on the photovoltaic performance is systematically studied in all-polymer solar cells. Clear trends of first an increase and then a decrease in the Jsc and FF values are observed as the branched alkyl groups are extended from 4 to 8 carbons. Correspondingly, the maximum average PCE (ca. 7.40%) is attained with an acceptor bearing a branched side-chain length of seven carbon atoms.
