Preparation of Nitrogen-Substituted TiO2 Thin Film Photocatalysts by the Radio Frequency Magnetron Sputtering Deposition Method and Their Photocatalytic Reactivity under Visible Light Irradiation†
journal contributionposted on 21.12.2006, 00:00 authored by Masaaki Kitano, Keisho Funatsu, Masaya Matsuoka, Michio Ueshima, Masakazu Anpo
Nitrogen-substituted TiO2 (N−TiO2) thin film photocatalysts have been prepared by a radio frequency magnetron sputtering (RF-MS) deposition method using a N2/Ar mixture sputtering gas. The effect of the concentration of substituted nitrogen on the characteristics of the N−TiO2 thin films was investigated by UV−vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM) analyses. The absorption band of the N−TiO2 thin film was found to shift smoothly to visible light regions up to 550 nm, its extent depending on the concentration of nitrogen substituted within the TiO2 lattice in a range of 2.0−16.5%. The N−TiO2 thin film photocatalyst with a nitrogen concentration of 6.0% exhibited the highest reactivity for the photocatalytic oxidation of 2-propanol diluted in water even under visible (λ ≥ 450 nm) or solar light irradiation. Moreover, N−TiO2 thin film photocatalysts prepared on conducting glass electrodes showed anodic photocurrents attributed to the photooxidation of water under visible light, its extent depending on wavelengths up to 550 nm. The absorbed photon to current conversion efficiencies reached 25.2% and 22.4% under UV (λ = 360 nm) and visible light (λ = 420 nm), respectively. UV−vis and photoelectrochemical investigations also confirmed that these thin films remain thermodynamically and mechanically stable even under heat treatment at 673 K. In addition, XPS and XRD studies revealed that a significantly high substitution of the lattice O atoms of the TiO2 with the N atoms plays a crucial role in the band gap narrowing of the TiO2 thin films, enabling them to absorb and operate under visible light irradiation as a highly reactive, effective photocatalyst.