LAUSR

Here, we systematically study the effect of fluorination on the performance of all-polymer solar cells by employing a naphthalene diimide (NDI)-based polymer acceptor with thiophene-flanked phenyl co-monomer. Fluorination of the phenyl co-monomer with either two or four fluorine units is used to create a series of acceptor polymers with either no fluorination (PNDITPhT), bifluorination (PNDITF2T), or tetrafluorination (PNDITF4T). In blends with the donor polymer PTB7-Th, fluorination results in an increase in power conversion efficiency from 3.1 to 4.6% despite a decrease in open-circuit voltage from 0.86 V (unfluorinated) to 0.78 V (tetrafluorinated). Countering this decrease in open-circuit voltage is an increase in short-circuit current from 7.7 to 11.7 mA/cm2 as well as an increase in fill factor from 0.45 to 0.53. The origin of the improvement in performance with fluorination is explored using a combination of morphological, photophysical, and charge-transport studies. Interestingly, fluorination is found not to affect the ultrafast charge-generation kinetics, but instead is found to improve charge-collection yield subsequent to charge generation, linked to improved electron mobility and improved phase separation. Fluorination also leads to improved light absorption, with the blue-shifted absorption profile of the fluorinated polymers complementing the absorption profile of the low-band gap PTB7-Th.