Oxygen adsorption on nickel surfaces: Detection of different species by x-ray photoelectron spectroscopy

Interaction of oxygen with evaporated nickel films has been studied by X-ray photoelectron spectroscopy, XPS, over the temperature range 77–500 K and pressure range 10^?9?10^?4 torr. Three oxygen species have been positively identified from O(1s) binding energy shifts (I, II and III with BE's 529.5, 531.4 and 533.2 eV). A fourth state at ca. 534.8 eV may also exist. The relative proportions of each species present depends on the temperature of the substrate. Type I is tentatively considered to represent oxygen atoms in an oxide-like electronic environment, type II is assigned as chemisorbed oxygen atoms, although the possibility of assignment at high oxygen coverages to a defect Ni₂ O₃ structure is admitted. Type III is only formed in sub-monolayer quantities on interaction at 77 K; converting irreversibly to II on warming to 300 K. I and II are always formed together between 300 and 500 K. The authors believe this implies some incorporation of oxygen atoms from the start of adsorption, which in turn has important implications for recent LEED studies.