Electron and Hole Trap Distribution and Transport in Titanium Dioxide Nanotubes
Mercado, Candy Cadang
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Titanium dioxide functions as an electron transport medium in dye sensitized solar cells. Nanotubular anatase titanium dioxide is expected to be a better photoanode because of the direct path of the electrons from injection to the working electrode due to the ordered nanotube walls. However, the performance of titanium dioxide nanotube-based solar cells lags behind the nanoparticulate-based. In this work, the crystallographic and defect properties of titanium dioxide nanotubes are examined with spectroscopic and materials characterization techniques in order to understand its electrical properties. Defects in the crystal structure lead to trap states within the bandgap which either assist or hinder electron collection. Shallow traps, those within the range of kT from the conduction band help in increasing the density of states thus increasing conduction. Deep traps capture the electrons and increase the probability of recombination with the oxidized form of the electrolyte. To probe these intra-band states, intra-band photoluminescence spectroscopy was used.Nanotube photoluminescence consists of three types of emission at approximate peak positions of 425 nm (2.9 eV), 550 nm (2.2 eV), and 650 nm (1.9 eV), which are attributed to recombination of the following nature: exciton, mobile electrons to trapped holes, and mobile holes to trapped electrons, respectively. These defects are similar to that found in nanoparticulate anatase. Although the nature of the defects is the same, the emission intensity in nanotubes is lower than nanoparticles. However, comparison with single nanotube photoluminescence revealed that quenching in "bulk" array is caused by significant charge transport in the lateral direction (between neighboring nanotubes).The orientation of the nanotube wall length is parallel (with slight angular deviations) to the c-axis direction of the unit cell as shown by electron backscatter diffraction. This leads to exposed planes of (100), (110), and (101). Single nanotube photoluminescence in epi-illumination showed that the walls are uniform with respect to defect densities. However, a focused laser beam gave satellite emissions from the ends of a nanotube that show recombination of mobile electrons with trapped holes giving a visual indication of electron transport in the nanostructure.