0000000000465045
AUTHOR
Jacques Jupille
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.
Intrinsic Nature of the Excess Electron Distribution at theTiO2(110)Surface
The gap state that appears upon reduction of TiO2 plays a key role in many of titania's interesting properties but its origin and spatial localization have remained unclear. In the present work, the TiO2(110) surface is reduced in a chemically controlled way by sodium adsorption. By means of resonant photoelectron diffraction, excess electrons are shown to be distributed mainly on subsurface Ti sites strikingly similar to the defective TiO2(110) surface, while any significant contribution from interstitial Ti ions is discarded. In agreement with first principles calculations, these findings demonstrate that the distribution of the band gap charge is an intrinsic property of TiO2(110), indep…
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.…
The defined adsorption site of sodium on the TiO2(110)–(1×1) surface
The adsorption site of sodium on the TiO2(1 1 0)–(1 × 1) surface was studied by extended X-ray absorption fine structure. For coverage ranging between 0.25 and 0.5 ML, we find that sodium is on an ‘in-between' site where it is bound to two bridging oxygen atoms at 2.25 Å and one in-plane oxygen atom at 2.40 Å, in full agreement with DFT calculations. At higher coverage the site becomes an hollow site where the sodium atom is equidistant to the three oxygen atoms at 2.30 Å, while metallic sodium clusters are also formed at the surface.
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 …
Excess Electrons at Oxide Surfaces
Excess electrons profoundly affect the properties of oxide surfaces. The present review deals with excess charges on rutile and anatase. These much studied titania polymorphs open with strong prospects regarding (photo)catalysis and dye-sensitized solar cells. In the complex landscape of the mechanisms of electron trapping and electron transfer toward adsorbates, excess electrons open with flexible model systems which are the focus of an extensive research effort.
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.