Abstract Two polythiophene derivatives using fluorine atoms and hexyl or hexyloxy group as electron-withdrawing and donating substituents have been synthesized. The introduction of fluorine atoms to the polythiophene backbones simultaneously lowers the HOMO and narrows the bandgap, and the stronger electron-donating ability of hexyloxy side chain further reduces the bandgap. As a result, poly [3-hexylthiophene-2, 5-diyl-alt-3, 4- ...