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Influence of Fluorine Substitution on the Photovoltaic Performance of Wide Band Gap Polymer Donors for Polymer Solar Cells.

The design and development of wide band gap (WBG) polymer donors are critical for achieving high power conversion efficiencies (PCEs) in polymer solar cells. In this work, four WBG polymer donors, Q4, Q5, Q6, and Q7, with different numbers and positions of fluorine substitution (n = 0, 2, 2, and 4, respectively) were prepared, and the effect of fluorination on their photovoltaic performance was systematically investigated. When blended with a small-molecule electron acceptor MeIC, the devices based on Q4, Q5, Q6, and Q7 showed PCEs of 10.34, 11.06, 5.26, and 0.48%, respectively. When coupled with a low band gap polymer acceptor PYIT to fabricate all-polymer solar cells (all-PSCs), while the other three polymers (Q5-Q7) exhibited much lower PCEs in the range of 0.12-6.71%, the Q4 polymer-based all-PSCs showed the highest PCE of 15.06%, comparable to that of the devices fabricated with the star polymer donor PM6 (PCE = 15.00%). Detailed physicochemical and morphological studies revealed that an over-substitution of F in Q7 results in undesired low-lying HOMO levels and phase separation with the acceptors, thus resulting in its inferior PCEs. Moreover, the less F-substitution and controlling of the positions of F-substitution position in Q4 and Q5 can improve the HOMO energy level matching as well as morphologies between these two polymers with the acceptors, which in turn gives rise to higher performances. Clearly, our results indicate that Q4 is a promising donor candidate for high-performance all-PSCs, and the fine-tuning of both the number and positions of F-substitution in the polymer backbone is essential in developing high-performance WBG polymer donors.