Limits on the Fill Factor in Organic Photovoltaics: Distinguishing Nongeminate and Geminate Recombination Mechanisms

In this Letter, we present transient optoelectronic experimental studies of the recombination processes limiting the fill factor (FF) in three conjugated polymer fullerene systems, poly(3-hexylthiophene) (P3HT) and two lower-band-gap polymers that exhibit lower FFs poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole) (PCPDTBT) and poly(2,7-(9,9-dioctylfluorene)-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)) (APFO-3). Using transient absorption spectroscopy, charge extraction, and transient photovoltage experiments, we show that the lower FF observed for the PCPDTBT-based device results from enhanced nongeminate recombination even at short circuit, In contrast, we show that for APFO-3 devices, the FF is primarily limited by a voltage-dependent free charge generation, which we assign to a geminate recombination process.