Nanoscale oxidation of Cu100: oxide morphology and surface reactivity

Surface oxidation of Cu(100) in O(2) has been investigated in situ by x-ray photoelectron spectroscopy, x-ray induced Auger electron spectroscopy (XAES), and scanning tunneling microscopy (STM) as a function of surface temperature (T(S)=303-423 K) and O(2) pressure (p(O(2) )=3.7 x 10(-2)-213 mbars). Morphology of the oxide on the surface and in the near surface layers is characterized by utilizing STM and the inelastic electron background of the XAES O KLL signal. Analysis of the peak shape of the XAES Cu LMM facilitates the quantification of Cu, Cu(2)O, and CuO surface concentrations. The authors conclude that the surface oxidation of Cu(100) proceeds in three distinct steps: (1) Dissociative adsorption of O(2) and the onset of Cu-(2 square root 2 x square root 2)R45 degrees -O (theta(O)=0.5 ML) surface reconstruction, (2) initial formation of Cu(2)O and the appearance of 1.8 A high elongated islands that also adopt the Cu-(2 square root 2 x square root 2)R45 degrees -O structure, and (3) formation of highly corrugated Cu-O islands which together with the surface reconstruction strongly enhance the reactivity of the surface towards further oxide formation. Both Cu(2)O and CuO formations are enhanced by increased surface temperature, but no pressure dependence can be seen.