Abstract: | We successfully designed and synthesized two BDT‐BT‐T (BDT=benzo[1,2‐b:4,5‐b']dithiophene, BT‐T=4,7‐dithien‐2‐yl‐2,1,3‐benzothiadiazole) based polymers as the electron donor for application in all‐polymer solar cells (all‐PSCs). By adopting N2200 as the electron acceptor, we systematically investigated the impact of fluorination on the charge transfer, transport, blend morphology and photovoltaic properties of the relevant all‐PSCs. A best power conversion efficiency (PCE) of 3.4% was obtained for fluorinated PT‐BT2F/N2200 (BT2F=difluorobenzo[c][1,2,5]thiadiazole) all‐PSCs in comparison with that of 2.7% in non‐fluorinated PT‐BT/N2200 (BT=benzothiadiazole) based device. Herein, all‐polymers blends adopting either non‐fluorinated PT‐BT or fluorinated PT‐BT2F exhibit similar morphology features. In depth optical spectrum measurements demonstrate that molecular fluorination can further enhance charge transfer between donor and acceptor polymer. Moreover, all‐polymer blends exhibit improved hole mobilities and more balanced carriers transport when adopting fluorinated donor polymer PT‐BT2F. Therefore, although the PCE is relatively low, our findings may become important in understanding how subtle changes in molecular structure impact relevant optoelectronic properties and further improve the performance of all‐PSCSs. |