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J Phys Chem B. 2005 Sep 1;109(34):16406-14.

Lithium ion effect on electron injection from a photoexcited coumarin derivative into a TiO2 nanocrystalline film investigated by visible-to-IR ultrafast spectroscopy.

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  • 1National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.


The dynamics of ultrafast electron injection from a coumarin derivative (NKX-2311), which is an efficient photosensitizer for dye-sensitized solar cells, into the conduction band of TiO(2) nanocrystalline films have been investigated by means of femtosecond transient absorption spectroscopy in a wide wavelength range from 600 nm to 10 mum. In the absence of Li(+) ions, electron injection into the TiO(2) conduction band occurred in about 300 fs. In the presence of Li(+) ions, however, electron injection occurred within approximately 100 fs, and the oxidized dye generated was found to interact with nearby Li(+) ions. Possible positions of Li(+) ion attachment to the dye molecule were examined by means of semiempirical molecular orbital calculations. The electron injection efficiency was found to increase by a factor of 1.37 in the presence of Li(+) ions. The effects of Li(+) ions on the energy of the TiO(2) conduction band and the electronic interaction between the dye molecule and Li(+) ions are discussed, and the major cause for the acceleration of electron injection was suggested to be a conduction-band shift of TiO(2).

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