0000000000276762
AUTHOR
Hélène Magnan
Defects at the TiO2(100) surface probed by resonant photoelectron diffraction.
We report photoelectron diffraction (PED) experiments of weakly sub-stoichiometric TiO 2 (100) rutile surfaces. Apart from standard core-level PED from the Ti-2p3/2 line, we have studied valence band PED from the defect induced Ti-3d states in the insulating band gap. For maximum yield, the latter were resonantly excited at the Ti-2p absorption edge. The PED patterns have been analyzed within the forward scattering approximation as well as by comparison with simulated PED patterns obtained in multiple scattering calculations. The analysis shows that the defect induced Ti-3d charge is mainly located on the second layer Ti atoms. © 2007 Elsevier B.V. All rights reserved.
Defect States at theTiO2(110)Surface Probed by Resonant Photoelectron Diffraction
The charge distribution of the defect states at the reduced ${\mathrm{TiO}}_{2}(110)$ surface is studied via a new method, the resonant photoelectron diffraction. The diffraction pattern from the defect state, excited at the $\mathrm{Ti}\mathrm{\text{\ensuremath{-}}}2p\mathrm{\text{\ensuremath{-}}}3d$ resonance, is analyzed in the forward scattering approach and on the basis of multiple scattering calculations. The defect charge is found to be shared by several surface and subsurface Ti sites with the dominant contribution on a specific subsurface site in agreement with density functional theory calculations.
Interpretation of absorption edges by resonant electronic spectroscopy: experiment and theory
Abstract Resonant electronic spectroscopy consists in measuring a non-radiative decay process (Auger or autoionization process) excited with photon energies around an absorption edge. The resonant spectra carry information both on the nature of the electronic transitions near the absorption edge by scanning the very first empty orbitals above the Fermi level (through the absorption process), and, on the other hand, on the atomic electronic configuration through the lineshape of the observed decay process. In this paper, after a quick review of the pioneering works in this field, we show that resonant measurements and their theoretical modeling can be used to precisely interpret complex abso…
Intra-atomic versus interatomic process in resonant Auger spectra at the TiL23edges in rutile
The two components of the Ti ${L}_{23}{M}_{23}V$ Auger transition recorded on a stoichiometric rutile crystal are identified as ${L}_{2}{M}_{23}V$ and ${L}_{3}{M}_{23}V$ contributions. This assignment is evidenced by concordant data relative to resonances of the LMV decay at the Ti ${L}_{23}$ thresholds and to Auger emission recorded in coincidence with the ${2}_{1/2}$ and ${2}_{3/2}$ photoemission at a photon energy far above the Ti ${L}_{23}$ edges. The ${L}_{3}{M}_{23}V$ transition is shown to follow either the direct photoexcitation of a ${2}_{3/2}$ electron or the fast Coster-Kronig decay of a ${2}_{1/2}$ photohole. Although specific LMV contributions related to valence orbitals are id…
Stoichiometry-related Auger lineshapes in titanium oxides: Influence of valence-band profile and of Coster-Kronig processes
International audience; The ability to determine the nature and the occurrence of defects is a central need of ceramic surface chemistry. In titanium oxides, the Ti-LMV Auger decays line shape is very sensitive to the titanium degree of oxidation, and has long been empirically used as a qualitative probe of the stoichiometry. In the present work, resonant Auger and resonant valence-band measurements at the Ti-L2,3 edges in TiO2, TiO2–x and metallic titanium provide a clear evidence that the evolutions of the Ti-LMV Auger line shape are due to drastic changes in the valence-band profile and in the probability of L2L3V Coster-Kronig decay processes when a fraction of titanium ions is reduced.…
Hard X-ray resonant electronic spectroscopy in transition metal oxides
K-edge X-ray absorption and 2p-XPS spectra of 3d-element oxides present spectral features which cannot be explained within a simple one-electron model. These features reveal the fine electronic structure of transition metal (TM) oxides valence states resulting from hybridized TM-3d and O-2p states, and the correlations between these valence electrons. In this paper, we show how resonant electronic spectroscopy (resonant Auger or resonant photoelectron spectroscopy) around the TM K-edge can be used to interpret the structures of the threshold and, with the help of theoretical calculation, to determine the electronic configuration of the excited ion. Quadrupolar transitions towards localized …
QUADRUPOLAR CHARACTER OF THE Ti K-EDGE PREPEAKS IN TiO2 BY RESONANT AUGER
Resonant spectroscopies offer a new opportunity to get more insight into excited electronic states by studying line shapes and intensities of decay processes. For photon excitations in the pre-K-edge region, the Ti KL 2,3 L 2,3 Auger spectra in TiO 2 show additional peaks when an electron is promoted in localized d-like states via a quadrupolar transition. This resonant process is used to unravel the respective contributions of quadrupolar and dipolar transitions to the absorption edge prepeaks.
A surface EXAFS study of thin nickel deposits on (110) TiO2 surfaces
Abstract The first stages of nickel deposition on a clean (110) TiO 2 surface were studied using surface extended X-ray absorption fine structure (EXAFS). Experiments were performed on two kinds of nickel deposits, one of 0.8 equivalent monolayers and another of 1.6 equivalent monolayers. Depositions were performed on well characterized TiO 2 (110)-p(1 × 1) surfaces. The correlation of Auger experiments with EXAFS results showed that no islands were present on the surface; only two-dimensional growth of nickel was observed. Moreover, it was shown, in the case of the thinner deposit, that a model with nickel atoms forming chains in the channels determined by oxygen atoms on the surface is co…