Scalable Route toward Superior Photoresponse of UV-Laser-Treated TiO₂ Nanotubes

Titanium dioxide nanotubes gain considerable attention as a photoactive material due to chemical stability, photocorrosion resistance, or low-cost manufacturing method. This work presents scalable pulsed laser modification of TiO₂ nanotubes resulting in enhanced photoactivity in a system equipped with a motorized table, which allows for modifications of both precisely selected and any-large sample area. Images obtained from scanning electron microscopy along with Raman and UV-vis spectra of laser-treated samples in a good agreement indicate the presence of additional laser-induced shallow states within band gap via degradation of crystalline structure. However, X-ray photoelectron spectroscopy spectra revealed no change of chemical nature of the modified sample surface. Photoelectrochemical measurements demonstrate superior photoresponse of laser-treated samples up to 1.45-fold for an energy beam fluence of 40 mJ/cm² compared to that of calcined one. According to the obtained results, optimal processing parameters were captured. Mott-Schottky analysis obtained from impedance measurements indicates an enormous (over an order of magnitude) increase of donor density along with a +0.74 V positive shift of flat band potential. Such changes in electronic structure are most likely responsible for enhanced photoactivity. Thus, the elaborated method of laser nanostructuring can be successfully employed to the large-scale modification of titania nanotubes resulting in their superior photoactivity. According to that, the results of our work provide a contribution to wider applications of materials based on titania nanotubes.