Rudi Agus Setiawan

Photoinduced electron transport in dye-containing titania gel films

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.

Titanium complex formation of organic ligands in titania gels.

Thin films of organic ligand-dispersing titania gels were prepared from titanium alkoxide sols containing ligand molecules by steam treatment without heating. The formation of the ligand-titanium complex and the photoinduced electron transfer process in the systems were investigated by photoelectrochemical measurements. The complex was formed between the 8-hydroxyquinoline (HQ) and titanium species, such as the titanium ion, on the titania nanoparticle surface through the oxygen and nitrogen atoms of the quinolate. A photocurrent was observed in the electrodes containing the complex due to the electron injection from the LUMO of the complex into the titania conduction band. A bidentate ligand, 2,3-dihydroxynaphthalene (DHN), formed the complex on the titania surface through dehydration between its two hydroxyl groups of DHN and two TiOH groups of the titania. The electron injection from the HOMO of DHN to the titania conduction band was observed during light irradiation. This direct electron injection was more effective than the two-step electron injection.

Influence of dye dispersion on photoelectric conversion properties of dye-containing titania electrodes

Dye-dispersing titania electrodes were prepared from the dye-containing titanium alkoxide sols by a room temperature sol–gel process and steam treatment at 110 °C. The spectroscopic and photoelectric conversion properties of the electrodes were investigated in order to clarify the influences of the dye dispersion and the co-dispersion of the two dyes on the electron transfer process. The fluorescein and eosin Y molecules were dispersed into the titania as their monomers. The shapes of the photocurrent action spectra of the fluorescein and/or eosin Y-dispersing titania electrodes corresponded well to those of their absorption spectra because the excited electrons in the dyes were directly injected into the titania conduction band without any interaction between the dye molecules, such as energy transfer. This result indicated that the dye molecules were separately encapsulated in the pores between the titania nanoparticles and tightly adsorbed or bonded to the titania particle surface. The internal quantum efficiency of the photoelectric conversion was higher than that of the conventional dye-adsorbing titania electrodes in which the dye molecules were easily aggregated and thus deactivated by the energy transfer. The co-dispersion of the two dyes on the titania surface allowed effective extension of the visible light region for the photoelectric conversion.

Influence of Dye Content on the Conduction Band Edge of Titania in the Steam‐treated Dye‐dispersing Titania Electrodes

The titania and dye‐dispersing titania electrodes were prepared by a nitric acid‐catalyzed sol‐gel process. The dye‐dispersing titania contains the dye molecules dispersed on the surface of the individual nanosized titania particles. The photo‐cyclic voltammetry (Photo‐CV) and photoelectric measurements of the dye‐dispersing titania electrodes were conducted to clarify the factors changing the conduction band edge of the titania and the open‐circuit voltage (Voc) of the electrodes. The remaining nitrate ions caused a negative shift of conduction band edge of the titania of the dye‐dispersing titania. The conduction band edge of the titania was shifted in a negative direction in the electrode containing a greater amount of the dye. These results are due to the adsorption of nitrate ions and the dye‐titania complex formation on the titania particle surface. The effect of the dye‐titania complex formation on the shift in the titania conduction band edge was greater than that of the adsorption of nitrate ions due to strong interaction between the dye and titania through the carboxylate and quinone‐like groups of the dye. The shift in the titania conduction band edge corresponded to the change in the Voc value.

Influences of Acid on Molecular Forms of Fluorescein and Photoinduced Electron Transfer in Fluorescein‐Dispersing Sol–Gel Titania Films

Fluorescein‐dispersing titania gel films were prepared by the acid‐catalyzed sol–gel reaction using a titanium alkoxide solution containing fluorescein. The molecular forms of fluorescein in the films, depending on its acid–base equilibria, and the complex formation and photoinduced electron transfer process between the dye and titania surface were investigated by fluorescence and photoelectric measurements. The titanium species were coordinated to the carboxylate and phenolate‐like groups of the fluorescein species. The quantum efficiencies of the fluorescence quenching and photoelectric conversion were higher upon excitation of the dianion species interacting with the titania, i.e. the dye–titania complex. This result indicated that the dianion form was the most favorable for formation of the dye–titania complex exhibiting the highest electron transfer efficiency. Using nitric acid as the catalyst, the titania surface bonded to the fluorescein instead of the adsorbed nitrate ion during the steam treatment. The dye–titania complex formation played an important role in the electron injection from the dye to the titania conduction band.