摘要： We synthesized a donor polymer of bis(2-ethylhexyl)thiophene-substituted benzodithiophene (BDT-Th) and 1,3-bis(2-ethylhexyl)-5,7-di(thiophene-2-yl)benzo[1,2-c:4,5-c′]dithiophene-4,8-dione, for which the BDT-Th unit includes chlorine and sulfur-bridged 2-ethylhexyl in the thiophene side group. When compared with PBDB-TF, which includes fluorine and 2-ethylhexyl in BDT-Th, PBDB-TSCl shows more efficient exciton dissociation and charge-generation, which is probably because large dipole moment changes from ground to excited states lead to reduced exciton binding energy. Consequently, despite small donor-acceptor interface in the bulk-heterojunction (BHJ) film, PBDB-TSCl achieves higher photovoltaic performance than PBDB-TF under various light intensities; PBDB-TSCl achieved higher efficiency of 13.13% than 12.12% of PBDB-TF under 1 sun illumination. Moreover, PBDB-TSCl showed the highest efficiency of 21.53% with fill factor (FF) of 76.29% under a 500 lux fluorescence lamp, whereas PBDB-TF has lower efficiency of 15.57% with FF of 65.25%. Furthermore, the PBDB-TSCl device shows improved thermal stability due to more stabilized morphology of its BHJ film.