TY - JOUR A1 - Gehrig, Dominik W. A1 - Roland, Steffen A1 - Howard, Ian A. A1 - Kamm, Valentin A1 - Mangold, Hannah A1 - Neher, Dieter A1 - Laquai, Frederic T1 - Efficiency-limiting processes in low-bandgap polymer:Perylene diimide photovoltaic blends JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - The charge generation and recombination processes following photo-excitation of a low-bandgap polymer:perylene diimide photovoltaic blend are investigated by transient absorption pump-probe spectroscopy covering a dynamic range from femto-to microseconds to get insight into the efficiency-limiting photophysical processes. The several tens of picoseconds, and its efficiency is only half of that in a polymer:fullerene photoinduced electron transfer from the polymer to the perylene acceptor takes up to blend. This reduces the short-circuit current. Time-delayed collection field experiments reveal that the subsequent charge separation is strongly field-dependent, limiting the fill factor and lowering the short-circuit current in polymer:PDI devices. Upon excitation of the acceptor in the low-bandgap polymer blend, the PDI exciton undergoes charge transfer on a time scale of several tens of picoseconds. However, a significant fraction of the charges generated at the interface are quickly lost because of fast geminate recombination. This reduces the short-circuit current even further, leading to a scenario in which only around 2596 of the initial photoexcitations generate free charges that can potentially contribute to the photocurrent. In summary, the key photophysical limitations of perylene diimide as an acceptor in low-bandgap polymer blends appear at the interface between the materials, with the kinetics of both charge generation and separation inhibited as compared to that of fullerenes. Y1 - 2014 U6 - https://doi.org/10.1021/jp503366m SN - 1932-7447 VL - 118 IS - 35 SP - 20077 EP - 20085 PB - American Chemical Society CY - Washington ER -