Projects per year
Abstract
Point defects in metal oxides such as TiO2 are key to their
applications in numerous technologies. The investigation of thermally induced nonstoichiometry in TiO2 is complicated by the difficulties in preparing and determining a desired degree of nonstoichiometry. We study controlled self-doping of TiO2 by adsorption of 1/8 and 1/16 monolayer Ti at the (110) surface using a combination of experimental and computational approaches to unravel the details of the adsorption process and the oxidation state of Ti. Upon adsorption of Ti, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) show formation of reduced Ti. Comparison of pure density functional theory (DFT) with
experiment shows that pure DFT provides an inconsistent description of the electronic structure. To surmount this difficulty, we apply DFT corrected for on-site Coulomb interaction (DFT+U) to describe reduced Ti ions. The optimal value of U is 3 eV, determined from comparison of
the computed Ti 3d electronic density of states with the UPS data. DFT+U and UPS show the appearance of a Ti 3d adsorbate-induced state at 1.3 eV above the valence band and 1.0 eV below the conduction band. The computations show that the adsorbed Ti atom is oxidized to Ti2+ and a
fivefold coordinated surface Ti atom is reduced to Ti3+, while the remaining electron is distributed among other surface Ti atoms. The UPS data are best fitted with reduced Ti2+ and Ti3+ ions. These results demonstrate that the complexity of doped metal oxides is best understood with a combination of experiment and appropriate computations.
Original language | English |
---|---|
Journal | Physical Review A |
Volume | 77 |
Issue number | 23 |
DOIs | |
Publication status | Published - 2008 |
Keywords
- point defects
- electronic structure
- nonstoichiometry
Fingerprint
Dive into the research topics of 'Electronic structure of point defects in controlled self-doping of the TiO2 (110) surface: Combined photoemission spectroscopy and density functional theory study'. Together they form a unique fingerprint.Projects
- 1 Finished
-
New modelling techniques for reducible transition metal oxides: Titania nanostructures
Mulheran, P. (Principal Investigator)
EPSRC (Engineering and Physical Sciences Research Council)
1/09/07 → 31/12/07
Project: Research