Modulating Crystal Packing, Film Morphology, and Photovoltaic Performance of Selenophene-Containing Acceptors through a Combination of Skeleton Isomeric and Regioisomeric Strategies

Here, we report a series of acceptor–donor–acceptor (A–D–A) architecture isomeric acceptors (SeCT-IC, CSeT-IC, and CTSe-IC), which have an identical electron-deficient terminal A-group and three different central D-cores with the selenophene at the innermost, relatively outer, and outermost positions of the central core, respectively. From CSeT-IC to the atom regioisomer of CTSe-IC and to the conjugated skeleton isomer of SeCT-IC, the optical band gap of neat films continuously reduced and highest occupied molecular orbitals (HOMO) gradually upshifted with changing the selenophene from relatively outer position to the outermost position and to the innermost position of the central core. More importantly, the single-crystal structure and the GIWAXS measurements revealed that CTSe-IC presents the closest π–π stacking distance, the largest CCL, and the best molecular order and crystallinity, which led to the highest electron mobility in neat films. Furthermore, the J71:CTSe-IC blend film presents a more ordered film morphology with more proper phase separation domain size, more dominant face-on orientation, and relatively higher and more balanced electron–hole mobilities in comparison with that of J71:SeCT-IC and J71:CSeT-IC. Consequently, the J71:CTSe-IC-based organic solar cell gave a superior power conversion efficiency (PCE) of 11.59%, which was obviously higher than those for J71:SeCT-IC (10.89%) and J71:CSeT-IC (8.52%). Our results demonstrate that the acceptor with selenophene in the outermost position led to significantly enhance the PCE. More importantly, rational modulation of the central fused core in combination with the conjugated skeleton isomeric method and the atom regioisomeric method provides an effective way to understand the structure–crystallinity–photovoltaic property relationship of selenophene-based regioisomers.