Unidirectional Sidechain Engineering to Construct Dual‐Asymmetric Acceptors for 19.23 % Efficiency Organic Solar Cells with Low Energy Loss and Efficient Charge Transfer

Abstract Achieving both high open‐circuit voltage ( V oc ) and short‐circuit current density ( J sc ) to boost power‐conversion efficiency (PCE) is a major challenge for organic solar cells (OSCs), wherein high energy loss ( E loss ) and inefficient charge transfer usually take place. Here, three new Y‐series acceptors of mono‐asymmetric asy‐YC11 and dual‐asymmetric bi‐asy‐YC9 and bi‐asy‐YC12 are developed. They share the same asymmetric D 1 AD 2 (D 1 =thieno[3,2‐ b ]thiophene and D 2 =selenopheno[3,2‐ b ]thiophene) fused‐core but have different unidirectional sidechain on D 1 side, allowing fine‐tuned molecular properties, such as intermolecular interaction, packing pattern, and crystallinity. Among the binary blends, the PM6 : bi‐asy‐YC12 one has better morphology with appropriate phase separation and higher order packing than the PM6 : asy‐YC9 and PM6 : bi‐asy‐YC11 ones. Therefore, the PM6 : bi‐asy‐YC12‐based OSCs offer a higher PCE of 17.16 % with both high V oc and J sc , due to the reduced E loss and efficient charge transfer properties. Inspired by the high V oc and strong NIR‐absorption, bi‐asy‐YC12 is introduced into efficient binary PM6 : L8‐BO to construct ternary OSCs. Thanks to the broadened absorption, optimized morphology, and furtherly minimized E loss , the PM6 : L8‐BO : bi‐asy‐YC12‐based OSCs achieve a champion PCE of 19.23 %, which is one of the highest efficiencies among these annealing‐free devices. Our developed unidirectional sidechain engineering for constructing bi‐asymmetric Y‐series acceptors provides an approach to boost PCE of OSCs.