Synergistically manipulating the shape of alkyl-chain and asymmetric side groups of non-fullerene acceptors enables organic solar cells to reach 18.5% efficiency

Side-chain modification and asymmetric design for non-fullerene acceptors (NFAs) have been proven to be effective methods for harvesting high-performance organic solar cells (OSCs). Combining the two molecular design strategies, we adopted phenyl chain and alkyl chains with different shapes to develop two novel asymmetric NFAs, named BTP-P2EH-C11 and BTP-P2EH-C2C4. Compared with BTP-P2EH-C2C4 attached 2-ethylhexyl side chain, BTP-P2EH-C11 with linear alkyl side chain have slightly red-shifted absorption and intensive absorption strength. Moreover, the PM6:BTP-P2EH-C11 blend film presents higher and more balanced charge mobilities, reducing charge recombination, tighter intermolecular packing and more favorable fibrous network morphology with appropriate phase separation than PM6:BTP-P2EH-C2C4, which lead to significantly enhanced short-circuit current density (JSC) of PM6:BTP-P2EH-C11-based devices. Thus, the OSCs based on PM6:BTP-P2EH-C11 achieve a superior power conversion efficiency (PCE) of 18.50% with a good trade-off among open-circuit voltage (VOC) of 0.876 V, JSC of 26.85 mA cm−2 and fill factor (FF) of 78.65%, while PM6:BTP-P2EH-C2C4-based device exhibits a lower PCE of 17.49%. Our investigation elucidates that the combination of finely optimizing the shape of alkyl-chain and asymmetric side groups of NFAs could pave a promising avenue toward morphology optimization and performance promotion of OSCs.