Photoinduced electron transfer processes from semiconductor quantum dots (QDs) molecularly bridged to a mesoporous oxide phase are quantitatively surveyed using optical pump-terahertz probe spectroscopy. We control electron transfer rates in donor-bridge-acceptor systems by tuning the electronic coupling strength through the use of n-methylene (SH-[CH2]n-COOH) and n-phenylene (SH-[C6H4](n)-COOH) molecular bridges. Our results show that electron transfer occurs as a nonresonant quantum tunneling process with characteristic decay rates of β(n) = 0.94 ± 0.08 and β(n) = 1.25 per methylene and phenylene group, respectively, in quantitative agreement with reported conductance measurements through single molecules and self-assembled monolayers. For a given QD donor-oxide acceptor separation distance, the aromatic n-phenylene based bridges allow faster electron transfer processes when compared with n-methylene based ones. Implications of these results for QD sensitized solar cell design are discussed.
Exciton quenching dynamics has been systematically studied in pristine P3HT and nano phase separated P3HT/PCBM blend films under various excitation intensities by femtosecond fluorescence up-conversion technique. The behaviors of excitons in the films can be well described by a three-dimensional diffusion model. The small diffusion length and large charge transfer radius indicate that excitons reach the interface most likely by the delocalization of the excitons in P3HT fibrillar at a range of 4.8-9 nm so that the excitons can quickly delocalize in the P3HT domain to reach the interface (instead of by diffusion).
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