COMPARATIVE 2ND-HARMONIC GENERATION AND X-RAY PHOTOELECTRON-SPECTROSCOPY STUDIES OF THE UV CREATION AND O-2 HEALING OF TI3+ DEFECTS ON (110)RUTILE TIO2 SURFACES

Citation
An. Shultz et al., COMPARATIVE 2ND-HARMONIC GENERATION AND X-RAY PHOTOELECTRON-SPECTROSCOPY STUDIES OF THE UV CREATION AND O-2 HEALING OF TI3+ DEFECTS ON (110)RUTILE TIO2 SURFACES, Surface science, 339(1-2), 1995, pp. 114-124
Citations number
28
Categorie Soggetti
Chemistry Physical
Journal title
ISSN journal
00396028
Volume
339
Issue
1-2
Year of publication
1995
Pages
114 - 124
Database
ISI
SICI code
0039-6028(1995)339:1-2<114:C2GAXP>2.0.ZU;2-V
Abstract
SHG studies on polished and etched (110) rutile TiO2 single-crystal su rfaces suggest that above band gap, low-energy (4.7 eV) ultraviolet ph otons create stable Ti3+ surface defects in UHV. Such defects can be h ealed by subsequently exposing the surface to O-2 gas. These results a re similar to recently reported measurements on polished and etched (0 01) rutile single-crystal surfaces. Observations on the (001) surfaces were interpreted as the photodesorption and re-adsorption of molecula r oxygen bound loosely to Ti3+ defects on the surface as a Ti4+:O-2(-) complex. For the current (110) study, XPS was used to confirm the def ect type and to quantify the density of Ti3+ defects created. Defects on the surfaces studied using XPS were generated using photons of even lower energy (3.4 eV), indicating that the oxygen species removed was very loosely bound. The same defect creation and healing processes we re also observed on a nearly defect-free thermally annealed single-cry stal surface using XPS. Whether bridging oxygen ions on the (110) surf ace or O-2(-) tons are the photo-labile species has yet to be determin ed. Transient photodesorption of O-2 at high oxygen pressure also was observed using SHG. SHG has proven to be a sensitive probe of surface defects, consistent with XPS results, under conditions ranging from UH V to atmospheric.