Dipole Moment Modulation of Terminal Groups Enables Asymmetric Acceptors Featuring Medium Bandgap for Efficient and Stable Ternary Organic Solar Cells

Abstract This study puts forth a novel terminal group design to develop medium‐band gap Y‐series acceptors beyond conventional side‐chain engineering. We focused on the strategical integration of an electron‐donating methoxy group and an electron‐withdrawing halogen atom at benzene‐fused terminal groups. This combination precisely modulated the dipole moment and electron density of terminal groups, effectively attenuating intramolecular charge transfer effect, and widening the band gap of acceptors. The incorporation of these terminal groups yielded two asymmetric acceptors, named BTP‐2FClO and BTP‐2FBrO, both of which exhibited open‐circuit voltage ( V oc ) as high as 0.96 V in binary devices, representing the highest V OC s among the asymmetric Y‐series small molecule acceptors. More importantly, both BTP‐2FClO and BTP‐2FBrO exhibit modest aggregation behaviors and molecular crystallinity, making them suitable as a third component to mitigate excess aggregation of the PM6 : BTP‐eC9 blend and optimize the devices’ morphology. As a result, the optimized BTP‐2FClO‐based ternary organic solar cells (OSCs) achieved a remarkable power conversion efficiency (PCE) of 19.34 %, positioning it among the highest‐performing OSCs. Our study highlights the molecular design importance on manipulating dipole moments and electron density in developing medium‐band gap acceptors, and offers a highly efficient third component for high‐performance ternary OSCs.