Alkyl side chain engineering enables high performance as-cast organic solar cells of over 17% efficiency.

Achieving high-performance as-cast OSCs is crucial for industrialization in the future, owing to the advantages of better stability, environmental-friendly, and decreasing production cost. In this regard, we synthesized an A-DA'D-A type acceptor, Y6-eC6-BO, by shortening the straight alkyl side-chains on the thiophene position from C11 to C6 as well as lengthening the branched alkyl side-chains on the pyrrole position of Y6 to achieve a stronger crystallization and better miscibility than Y6. As a result, the corresponding chloroform-processed as-cast PM6: Y6-eC6-BO OSC showed a high PCE of 17.33%, which was one of the highest efficiencies of as-cast OSCs. And the as-cast PM6:Y6-eC6-BO OSCs processed from o-xylene displayed a PCE of 16.38%, as far as we know, this is among the highest efficiencies of non-halogenated-solvent processed as-cast OSCs. These results demonstrated tailoring the alkyl side-chain of NFAs is a feasible and simple approach to achieve high performance as-cast OSCs and provides guideline in molecular design in the future.