Superior End-Group Stacking Promotes Simultaneous Multiple Charge-Transfer Mechanisms in Organic Solar Cells with an All-Fused-Ring Nonfullerene Acceptor

The all-fused-ring acceptor (AFRA) is a success for nonfullerene materials and has attracted considerable attention as its high optical and chemical stability expected to reduce energy loss, and power conversion efficiency (PCE) approaching 15% in constructed all-small-molecule organic solar cells (OSCs). Herein, the intrinsic role of the structure of AFRA F13 and the reason for its high PCE were revealed by comparison with those of typical fused acceptors IDT-IC and Y6 . An increased degree of conjugation in F13 leads to broader and red-shifted absorption peaks, facilitating enhancement of the short-circuit current. Multiple charge-transfer mechanisms are mainly attributed to the higher Frenkel exciton (FE) state due to the multiple transition ways for acceptors in the C1–CN:F13 system. The increased number of atoms contributing to the charge-transfer (CT) state facilitated the existence of more superior stacking patterns with easy formation of CT and FE/CT states and a high charge separation rate. It was found using the AFRA is an effective strategy to enhance end-group stacking, enhancing the borrowing of oscillator strength to promote multiple CT mechanisms in the complexes, explaining the high performance of this OSC device. This work is promising to guide designing an efficient AFRA in the future.