Photogeneration and Recombination in P3HT/PCBM Solar Cells Probed by Time-Delayed Collection Field Experiments

Time-delayed collection field (TDCF) experiments are performed on bulk heterojunction solar cells comprised of a blend of poly(3-hexylthiophene) and 6,6-phenyl C71 butyric acid methyl ester. TDCF is analogous to a pump−probe experiment using optical excitation and an electrical probe with a resolution of <100 ns. The number of free charge carriers extracted after a short delay is found to be independent of the electric field during illumination. Also, experiments performed with a variable delay between the optical excitation and the electrical probe do not reveal any evidence for the generation of charge via field-assisted dissociation of bound long-lived polaron pairs. Photocurrent transients are well fitted by computational drift diffusion simulations with only direct generation of free charge carriers. With increasing delay times between pump and probe, two loss mechanisms are identified; first, charge-carriers are swept out of the device by the internal electric field, and second, bimolecular recombination of the remaining carriers takes place with a reduced recombination coefficient.