摘要： A bithiophene donor unit, 3-alkoxy-3’-alkyl-bithiophene (TRTOR), was copolymerized with difluorobenzochalcogenadiazole (ffBZ) containing different heteroatoms on their diazole structure to afford a series of PffBZ copolymers (where Z = X, T, Se) with narrow optical bandgaps in the range of 1.34-1.47 eV. The effects of ffBZ heteroatoms (O, S, and Se) on the optical properties, electrochemical characteristics and film morphologies of polymers as well as device performance were fully investigated. The results revealed that the highest occupied molecular orbitals (HOMOs) of polymers are gradually elevated accompanied by increased material solubility in common organic solvents as the size of heteroatoms increases. The PffBZ copolymers exhibit substantial hole mobility of 0.08-1.6 cm2 V-1 s-1 in organic thin-film transistors (OTFTs). The PffBX, PffBT, and PffBSe-based polymers exhibit maximum power conversion efficiencies (PCEs) of 5.47%, 10.12%, and 3.65%, respectively in polymer solar cells (PSCs). For PffBZ copolymers, the alkyl chain exerts a great influence on the morphology of the polymer:PC71BM blend films and hence affect PCEs in PSCs. It was found that the performing of polymers branching on the 2nd position for alkyl chain and the 3rd position for alkoxy chain were the best among PffBT and PffBSe-based polymers, and it is different from the tetrathiophene-based benchmark polymer branching on the 2nd position of the alkyl chain. X-ray diffraction revealed that all PffBZ-based polymers has obvious a face-on dominated orientation, and that chalcogen atom and branched position on alkoxy chain have a great influence on the morphologies of neat and blend films. The above results indicated that the branching positions and chalcogen atoms should be carefully optimized to maximize performance.