Journal article

Photoinduced ultrafast dynamics of the triphenylamine-based organic sensitizer D35 on TiO2, ZrO2 and in acetonitrile

The relaxation dynamics of the dye D35 was characterized by transient absorption spectroscopy in acetonitrile and on TiO2 and ZrO2 thin films. In acetonitrile, upon photoexcitation of the dye via the S0 → S1 transition, ultrafast solvation dynamics with subpicosecond time consts. is obsd. Subsequent decay of the S1 excited state absorption (ESA) band with a 7.1 ps time const. is tentatively assigned to structural relaxation in the excited state, and a spectral decay with 203 ps time const. results from internal conversion (IC) back to S0. On TiO2, fast (< 90 fs) electron injection from the S1 state of D35 into the TiO2 conduction band is obsd., followed by a biphasic dynamics arising from changes in a transient Stark field at the interface, with time consts. of 0.8 and 12 ps, resulting in a characteristic blue-shift of the S0 → S1 absorption band. Several processes can contribute to this spectral shift: (i) photoexcitation induces immediate formation of D35√+ radical cations, which initially form electron-cation complexes, (ii) dissocn. of these complexes generates mobile electrons, and when they start diffusing in the mesoporous TiO2, the local electrostatic field may change, (iii) this may trigger the reorientation of D35 mols. in the changing elec. field. A slower spectral decay on a nanosecond timescale is interpreted as a redn. of the local Stark field, as mobile electrons move deeper into TiO2 and are progressively screened. Multiexponential electron-cation recombination occurs on much longer timescales, with time consts. of 30 μs, 170 μs, and 1.4 ms. For D35 adsorbed on ZrO2, there is no clear evidence for a transient Stark shift, which suggests that initially formed cation-electron (trap state) complexes do not dissoc. to form mobile conduction band electrons. Multiexponential decay with time consts. of 4, 35, and 550 ps is assigned to recombination between cations and trapped electrons, and also to a fraction of D35 mols. in S1 which decay by IC to S0. Differential steady-state absorption spectra of D35√+ in acetonitrile and dichloromethane provide access to the complete D0 → D1 band. The absorption spectra of D35 and D35√+ are well described by TDDFT calcns. employing the MPW1K functional.


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