Symmetrically Fluorinated Benzo[1,2‑b:4,5‑b′]dithiophene-Cored Donor for High-Performance All-Small-Molecule Organic Solar Cells with Improved Active Layer Morphology and Crystallinity

Side-chain engineering is an efficient molecular design strategy for morphology optimization and performance improvement of organic solar cells (OSCs). Herein, a novel small-molecule donor C-2F, which owns a benzo­[1,2-b:4,5-b′]­dithiophene (BDT) central unit with a symmetrically difluorinated benzene ring as a conjugated side chain, has been synthesized. The conjugated side chain possesses both the symmetry and halogenation effect in novel small molecular donor material. The photovoltaic devices were fabricated with N3 as an acceptor. C-2F:N3 based devices achieved an outstanding power conversion efficiency of 14.64% with a J_sc of 24.87 mA/cm², a V_oc of 0.85 V, and an FF of 69.33%. Then, we investigated the basic material properties, photovoltaic mechanism, and active layer morphology, and the results show that this molecular design strategy of the symmetrically difluorinated moiety as the conjugated side chain provides an effective method for fine-tuning the molecular stacking pattern and active layer phase separation morphology, to improve the all-small-molecule (ASM) OSCs’ performances.