† Corresponding author. E-mail:
‡ Corresponding author. E-mail:
Project supported by the National Natural Science Foundation of China (Grant Nos. 61574080, 11404162, 61505085, and 61264008) and the Natural Science Foundation of Jiangsu Province, China (Grant No. BK20130549).
Oxygen vacancies (OVs) play a critical role in the physical properties and applications of titanium dioxide nanostructures, which are widely used in electrochemistry and photo catalysis nowadays. In this work, OVs were artificially introduced in the surface of a pure TiO2 single crystal by pulsed laser irradiation. Raman spectra showed that the intensity of Eg mode was enhanced. Theoretical calculations disclose that this was caused by the strong coupling effect between the phonon vibration and plasmon induced by the OVs-related surface deformation, and good agreement was achieved between the experiments and theory.
Metal oxides have played important roles in scientific research and industrial production, because of their potential use in optical devices, catalysts, batteries, gas-sensors, and biosensors.[1–5] Among the different metal oxides, titanium dioxide (TiO2) has attracted much attention due to its interesting applications such as water splitting, photo catalysis and gas sensing.[6–10] In various technological applications, nanosized materials have yielded excellent performance because of their small dimensions, i.e., the large surface-to-volume ratio. Nanoscale titanium dioxide such as nanotubes (NTs), nanocrystals (NCs), nanodisks, and nanowires have been fabricated and their optical and electronic characteristics and potential applications have been extensively studied.[11–14] Among these, many novel physical characteristics are simply ascribed to its oxygen vacancies, but cannot be confirmed with evidence.[15–18] Because the nanostructure is very complex, its intrinsic physical mechanism about OVs is still not clarified. Therefore, how to directly characterize and analyze the existing states of OV has become a crucial problem.
In order to clearly investigate the phonon characteristics of metal oxide nanomaterials with different OV types, we introduced OVs in the surface of a pure TiO2 single crystal artificially by pulsed laser irradiation. Spectral analysis and theoretical calculations showed that strong coupling effect existed between the phonon relating to surface OVs and the plasmon induced by the surface deformation potential. This effect caused the intensity of Raman active mode Eg to increase while A1g mode decreased. This work improves our understanding of the OVs properties in TiO2 and is beneficial to further applications.
A 248-mm laser beam with a 1-Hz repetition rate was selected to irradiate the TiO2 single crystal (named sample A) via a 90° prism. The laser beam was a Gauss distribution of linear polarized light with the power of 451 mJ/pulse and the irradiation time was 5 s. A 20-times microscope objective was added to converge the laser to TiO2 single crystal and also to enhance the laser intensity. After irradiation, the sample A was annealed in O2 at 1000 °C for 5 h to prepare sample C. The Raman spectra of irradiated crystal (sample A), non-irradiated crystal (sample B), and the annealed crystal (sample C) were acquired on a T64000 triple Raman system at backscattering geometries using the 514.5-nm line of an Ar–ion laser as the excitation source. The diameter and power of the beam spot were 3 mm and 4.6 mW, respectively. The resolution of the spectrometer is 0.5 cm−1. X-ray photoelectron spectroscopy (XPS) was performed on the PHI 5000 Versa Probe.
Figure
![]() | Fig. 1. (a) XPS spectra from samples A and B, and (b) larger image of the Ti 2p3/2 spectra, (c) PL spectra from samples A and B, (d) EPR spectra of sample A. The unit 1 Gs = 10−4 T. |
To clarify the existence of OVs, PL spectra were acquired from the two samples and shown in Fig.
![]() | Fig. 2. (a) Raman spectra of samples A and B at room temperature and Raman spectra of annealed sample A, (b) temperature-dependent Raman spectra of sample A. |
Density functional theory (DFT) calculations were conducted to theoretically confirm the anomalous behavior of Raman spectra. The optimized primitive TiO2 with a = 4.59 Å, b = 2.96 Å lattice constant was shown in Figs.
Our calculations were performed under the framework of DFT as implemented in the CASTEP package. Electron–ion interactions were described by the projector augmented plane wave method, and the wave function was expanded in a plane wave basis set with an energy cutoff of 500 eV. The k points in the Brillouin zone were sampled on a 5 × 5 × 8 mesh. The norm-conserving pseudo-potential method was chosen together with the gradient correction and the Perdew–Burke–Ernzerhof potential function.[26] Finally, the optimized geometrical structure was employed for construction and the diagonalized Hessian matrix:
![](cpb_25_12_127103/cpb161739ieqn1.gif)
In Fig.
![]() | Fig. 4. (a) The Raman spectra of TiO2 surface calculated by DFT, (b) the Raman spectra of TiO2 surface calculated by phonon–plasmon coupling mechanism. |
By considering the deformation potential in the surface layer caused by the phonon–plasmon coupling mechanism, the Raman spectrum could be calculated by[28]
![](cpb_25_12_127103/cpb161739ieqn2.gif)
In conclusion, we have revealed that when OVs are introduced in the surface of TiO2, the phonon vibration of OVs and the plasmon induced by the surface deformation potential must be considered together. This leads to the large enhancement of the Eg mode intensity.
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