Insights into the influence of fluorination positions on polymer donor materials on photovoltaic performance

To explore the influence of fluoro substitution position and number on optical, electrochemical and photovoltaic properties, three novel donor-acceptor (D-A) alternative copolymers (PHF, PFH and PFF) were synthesized by Stille polycondensation of 2,3-diphenyl-5,8-di(thiophen-2-yl)quinoxaline (DTQx) acceptor unit and indacenodithiophene (IDT) donor unit. As films, PHF and PFF comprising two fluoro substituents on the lateral phenyl groups displayed a broad absorption ranging from 350 to 700 nm; whereas PFH containing two fluorine atoms on the polymer main chain exhibited a slightly narrower absorption ranging from 350 to 650 nm. In addition, fluoro substitution on the polymer main chain can lower the HOMO level of the resulted polymers. As expected, PFH and PFF possess deeper HOMO energy level than PHF. Polymer solar cells (PSCs) were fabricated with these three polymers as donor materials and PC₇₁BM as acceptor material. PHF based PSCs gave a power conversion efficiency (PCE) of 7.2% with a V_oc of 0.84 V, a J_sc of 12.46 mA/cm² and an FF of 0.69. And PFH based PSCs showed a PCE of 6.19% with a V_oc of 0.93 V, a J_sc of 9.57 mA/cm² and an FF 0.70. However, a PCE of only 2.9% with a V_oc of 0.92 V, a J_sc of 4.61 mA/cm² and an FF of 0.68 was obtained for PFF based PSCs. Transmission electron microscopy (TEM) and resonant soft X-ray scattering (R-SoXS) studies indicated that the introduction of four fluorine atoms at each repeating unit can spoil the morphology of active layer. These results highlight the importance of fluorination position and number to the performance of PSCs.