Reaction of atomic oxygen with a Pt(1 1 1) surface chemical and structural determination using XPS, CAICISS and LEED》.pdf

Surface Science 545 (2003) 19–33 /locate/susc Reaction of atomic oxygen with a Pt(111) surface: chemical and structural determination using XPS, CAICISS and LEED C.R. Parkinson *, M. Walker, C.F. McConville * Department of Physics, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, UK Received 23 June 2003; accepted for publication 8 August 2003 Abstract The adsorption of thermally cracked atomic oxygen on the Pt(1 1 1) surface has been investigated using X-ray photoelectron spectroscopy (XPS), co-axial impact collision ion scattering spectroscopy (CAICISS), and low energy electron diffraction (LEED). High concentrations of atomic oxygen (2 · 1015 atoms cm2) can be cleanly adsorbed on the Pt(1 1 1) surface at room temperature by dosing the surface with externally generated atomic oxygen at relatively low exposures (50 L). Two states of oxygen are readily resolved by XPS with O 1s binding energies at 530.8 and 530.2 eV. These states are assigned to chemisorbed oxygen and to an oxidic oxygen state, respectively. XPS spectra of the Pt 4f region confirm the existence of an oxide species with the appearance of a peak at 2.4 eV higher binding energy than the bulk Pt 4f 5=2 peak. Using a combination of angle-resolved XPS, CAICISS, and LEED, evidence is provided to suggest that penetration of oxygen into the surface occurs most likely by an exchange mechanism resulting in the re- construction of the Pt atoms in the first two atomic layers. On annealing the oxygen covered surface at 500 C the oxidic layer is observed to decompose and a p(2 · 2)-O reconstruction is observed. A CAICISS study of this reconstruct