To Fluorinate or Not to Fluorinate in Organic Solar Cells: Achieving a Higher PCE of 15.2% when the Donor Polymer is Halogen-Free

Fluorination of the donor and/or acceptor blocks of photoactive semiconducting polymers is a leading strategy to enhance organic solar cell (OSC) performance. Here, the effects are investigated in OSCs using fluorine-free (TPD-3) and fluorinated (TPD-3F) donor polymers, paired with the nonfullerene acceptor Y6. Interestingly and unexpectedly, fluorination negatively affects performance, and fluorine-free TPD-3:Y6 OSCs exhibit a far higher power conversion efficiency (PCE = 14.5%) than in the fluorine-containing TPD-3F:Y6 blends (PCE = 11.5%). Transmission electron microscopy (TEM) analysis indicates that the TPD-3F:Y6 blends have larger phase domain sizes than TPD-3:Y6, which reduces exciton dissociation efficiency to 81% for TPD-3F:Y6 versus 93% for TPD-3:Y6. Additionally, grazing incidence wide-angle X-ray scattering (GIWAXS) reveals that the TPD-3F:Y6 blends are less textured than those of TPD-3:Y6, while space-charge limited currents reveal lower and unbalanced hole/electron mobility in TPD-3F:Y6 versus TPD-3:Y6 blends. Charge recombination dynamic, transient absorption, and donor-acceptor miscibility assays additionally support this picture. Furthermore, conventional architecture TPD-3:Y6 OSCs deliver a PCE of 15.2%, among the highest to date for halogen-free polymer donor OSCs. Finally, a large-area (20.4 cm(2)) TPD-3:Y6 blend module exhibits an outstanding PCE of 9.31%, one of the highest to date for modules of area >20 cm(2).