Enhanced absorption of TiO₂ nanotubes by N-doping and CdS quantum dots sensitization: insight into the structure

Anodization of titanium film sputtered on fluorine doped tin oxide (FTO) glass was performed to obtain highly ordered ∼2 μm long and ∼60 nm wide TiO₂ nanotubes. The titania films were annealed in ammonia atmosphere to enable the doping with N. The annealing did not affect the nanotubular morphology and the porosity remained open which is a very important requirement for further deposition of CdS quantum dots. The analysis done by transmission electron microscopy (TEM) has shown that the N-doped nanotubes have a smaller interplanar distance as compared to the undoped ones, whose interplanar distance corresponded to anatase phase. This difference was attributed to the N doping and the Sn migration from the substrate, as demonstrated by energy dispersive spectroscopy (EDS) combined with electron energy loss spectroscopy (EELS). The near edge X-ray absorption fine structure (NEXAFS) analysis clearly demonstrated that also the doped TiO₂ film has anatase phase. Regarding the chemical composition of the studied samples, the X-ray photoelectron spectroscopy (XPS) and synchrotron radiation photoelectron spectroscopy (SRPES) analyses have shown that N is incorporated both interstitially and substitutionally in the TiO₂ lattice, with a decreased contribution of the interstitial after ionic sputtering. The shift of the valence band maximum (VBM) position for the doped TiO₂ vs. the undoped TiO₂ proved the narrowing of the band gap. The CdS/TiO₂ films show bigger VBM shifting that can be attributed to CdS deposit. Comparing the absorption spectra of the bare undoped and doped TiO₂ samples, it was noticed that the doping causes a red shift from 397 to 465 nm. Furthermore, the CdS deposition additionally enhances the absorption in the visible range (575 nm for undoped TiO₂/CdS and 560 nm for doped TiO₂/CdS films).