Energy Level Tuning of Poly(phenylene‐alt‐dithienobenzothiadiazole)s for Low Photon Energy Loss Solar Cells

Six poly(phenylene‐alt‐dithienobenzothiadiazole)‐based polymers have been synthesized for application in polymer–fullerene solar cells. Hydrogen, fluorine, or nitrile substitution on benzo­thiadiazole and alkoxy or ester substitution on the phenylene moiety are investigated to reduce the energy loss per converted photon. Power conversion efficiencies (PCEs) up to 6.6% have been obtained. The best performance is found for the polymer–fullerene combination with distinct phase separation and crystalline domains. This improves the maximum external quantum efficiency for charge formation and collection to 66%. The resulting higher photocurrent compensates for the relatively large energy loss per photon (E (loss) = 0.97 eV) in achieving a high PCE. By contrast, the poly­mer that provides a reduced energy loss (E (loss) = 0.49 eV) gives a lower photocurrent and a reduced PCE of 1.8% because the external quantum efficiency of 17% is limited by a suboptimal morphology and a reduced driving force for charge transfer. [Image: see text]