Influence of TiO2 nanotube morphology and TiCl4 treatment on the charge transfer in dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) were fabricated using TiO2 nanoparticles (NPs), TiO2 nanotube arrays (NTAs), and surface-modified NTAs with a TiCl4 treatment. The photovoltaic efficiencies of the DSSCs using TiO2 NP, NTA, and TiCl4-treated NTA electrodes are 4.25, 4.74, and 7.47 %, respectively. The highest performance was observed with a TiCl4-treated TiO2 NTA photoanode, although in the case of the latter two electrodes, the amounts of N719 dye adsorbed were similar and 68 % of that of the NP electrode. Electrochemical impedance measurements show that the overall resistance, including the charge–transfer resistance, was smaller with NTA morphologies than with NP morphologies. We suggest that a different electron transfer mechanism along the one-dimensional nanostructure of the TiO2 NTAs contributes to the smaller charge–transfer resistance, resulting in a higher short circuit current (Jsc), even at lower dye adsorption. Furthermore, the TiCl4-treated NTAs showed even smaller charge–transfer resistance, resulting in the highest Jsc value, because the downward shift in the conduction band edge improves the electron injection efficiency from the excited dye into the TiCl4-treated TiO2 electrodes.