Xanthene dye molecules form a chelate complex with the titanium species on the titania surface in dye−titania systems. The complex formation causes a fast electron injection into the titania conduction band. In this study, simple spectroscopic and photocurrent measurements of the xanthene dye-doped titania gels prepared by the sol−gel method were conducted in order to clarify the influence of a steam treatment on the dye−titania interaction and electron transfer. The photocurrent quantum efficiency of the fluorescein-doped electrode was remarkably increased by the steam treatment compared to that of the untreated electrode consisting of an amorphous titania gel. The photocurrent action spectrum was red-shifted, and the short circuit photocurrent and open circuit voltage values increased with the steam treatment time. The steam treatment promoted the dye−titania complex formation, a negative shift in the conduction band potential of the titania, and the electron injection from the dye to the titania.
Influences of the titania nanostructure and dye dispersion in a dye-doped titania electrode on its photoelectric conversion property were investigated by simple spectroscopic and electric measurements.The dye-doped nanocrystalline titania electrodes were prepared on the glass plates coated with ITO and normal crystalline titania films by the following two procedures: (1) the dye-doped titania gel films were prepared from a titanium alkoxide solution containing the dye and then steam-treated, and (2) the titanium alkoxide sol containing the dye was refluxed and then spread onto the plates. The photocurrent quantum efficiency remarkably increased by the steam treatment and the reflux compared to that of the untreated dye-doped electrode consisting of amorphous titania gel. The efficiency in the former was higher than that in the latter. The growth and crystallization of the titania particles and the decrease in the defect density by these treatments improved the electric conductivity. The steam treatment was the more prominent method because it enhanced the electric conductivity of the titania depending on its nanostructure and the dye-titania interaction depending on the dye dispersion. These factors appear to play important roles in transport in the electron through the electrode.
The time-resolved fluorescence and photoelectrochemical properties of dyesensitized solar cells using crystalline titania electrodes coated with N3 dye-dispersing amorphous titania gel were investigated to clarify the influence of the dye−titania interaction and electron transfer on their photoelectric conversion performance. The photocurrent quantum efficiency of the electrodes was remarkably increased by a steam treatment due to the crystallization and densification of the amorphous titania layer compared to that of the untreated electrode. The electron injection from the dye to the crystalline titania foundation via the steam-treated titania dispersing the dye was confirmed to be more efficient than that in the conventional electrodes. The dye-dispersing titania layer prevented interaction between the dye molecules and back electron transfer from the titania to the electrolyte. The charge separation and photoelectric conversion performance of the dye-sensitized solar cells were improved by forming the specific dye-dispersing titania layer.
Amorphous dye-containing titania gel films were prepared on ITO electrodes coated with a crystalline titania foundation from titanium alkoxide sols containing a dye at room temperature. Photoinduced electron transport in the amorphous titania gel film was investigated by spectroscopic and photovoltaic measurements. Influences of the structure and morphology of the multilayered film on the photoelectron transport and electrically conductive properties were discussed. The photocurrent was observed from only the layer contacting the crystalline titania foundation. The electron transport from the amorphous upper layers was limited. Steam treatment of the electrodes improved the electron transport due to crystallization of the amorphous titania to anatase accompanied by enhancement of its electrical conductivity. The efficiency of the dye-sensitized electron transport in the steam-treated titania film was close to that of the anatase film prepared by heating at 773 K.The dye-containing titania layers functioned as efficient sensitizers.
Transient absorption spectroscopy is generally used to study the photoinduced electron transfer process in the dye–titania systems. Time-resolved fluorescence spectroscopy is more sensitive than transient absorption spectroscopy. Fluorescein-dispersing titania gel films were prepared by a sol–gel process and steam treatment using a titanium alkoxide solution containing fluorescein. The photoinduced electron transfer process in the films was investigated by steady state and time-resolved fluorescence measurements. The fluorescence quenching efficiency increased with an increase in the steam treatment time due to the dye–titania complex formation. The titanium species were coordinated to the carboxylate of the fluorescein species during the steam treatment based on an FTIR analysis. The dye–titania complex formation played an important role in the electron injection from the dye to the titania conduction band.
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