Herein, we report a detailed study on the optoelectronic properties, photovoltaic performance, structural conformation, morphology variation, charge carrier mobility, and recombination dynamics in bulk heterojunction solar cells comprising a series of donor-acceptor conjugated polymers as electron donors based on benzodithiophene (BDT) and 5,8-bis(5-bromothiophen-2-yl)-6,7-difluoro-2,3-bis(3-(octyloxy)phenyl)quinoxaline as a function of the BDT's thienyl substitution (alkyl (WF3), alkylthio (WF3S), and fluoro (WF3F)). The synergistic positive effects of the fluorine substituents on the minimization of the bimolecular recombination losses, the reduction of the series resistances (), the increment of the shunt resistances (), the suppression of the trap-assisted recombination losses, the balanced charge transport, the finer nanoscale morphology, and the deeper highest occupied molecular orbital () are manifested versus the alkyl and alkylthio substituents. According to these findings, the WF3F:[6,6]-phenyl-C-butyric acid methyl ester (PCBM)-based organic photovoltaic device is a rare example that features a high power conversion efficiency (PCE) of 17.34% under 500 lx indoor light-emitting diode light source with a high open-circuit voltage () of 0.69 V, due to the suppression of the voltage losses, and a PCE of 9.44% at 1 sun (100 mW/cm) conditions, simultaneously.
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