Plasma-Assisted N-Doped TiO2 Nanotube Array as an Active UV–vis Photoanode

Abstract

This work shows the possibility of using plasma nitriding under ultra-high-vacuum conditions to introduce nitrogen into a titanium dioxide structure in the form of nanotubes with a diameter of about 110 nm. Nanotubes were produced by the anodic oxidation of Ti foil in a solution based on glycerine and water with the addition of ammonium fluoride at a voltage of 25 V. Based on experimental evidence obtained by X-ray photoelectron spectroscopy (XPS, in situ), it has been shown that alternating nitriding and annealing processes at 450 °C leads to formation of Ti-N-O, Ti-N, and Ti-O-N chemical bonds in the TiO2 crystal structure (anatase). The observed changes were identified as interstitial or substitutional admixtures or variations of these. The spectrophotometric and spectrophotoelectrochemical tests performed showed that the photoactivity of the photoanodes doped with nitrogen and annealed at 450 °C in the UV–vis range was significantly greater than that of the photoanodes without nitrogen. The highest maximum photocurrent density, of about 30.0 μA·cm–2 at a wavelength of λ = 350 nm, was obtained for the double-nitrided and once-annealed sample, where nitrogen was mainly incorporated in the interstitial positions in the TiO2 lattice. For the materials not nitrided as well as annealed only at 450 °C and pristine, the worse photoresponse was received at the levels of ∼16 and ∼0.2 μA·cm–2, respectively. The thermo-chemical treatment applied also effectively extended the operational range of the photoanodes toward visible light, where a wide maximum of light absorption was observed from ∼400 to ∼700 nm, with a maximum wavelength of 550 nm and an estimated bandgap energy of 2.5 eV. Our investigations confirmed that photoelectrochemical (PEC) performance for TiO2 NT-based photoanodes was achieved by the optimum annealing condition and concentration of nitrogen, where the narrowed bandgap was observed by generating a new N 2p energy level above the O 2p valence band. The following research techniques were used to identify the changes taking place in the materials produced: XPS spectroscopy, UV–vis spectroscopy, PEC measurements, X-ray diffraction structural measurements, and scanning electron microscopic observations.