Understanding the mechanisms driving
the early stages of oxidation
of metallic surfaces is of fundamental importance in fields such as
nanocatalysis, electrochemistry, and nanoelectronics. In this work,
the early stages of oxidation of ultrathin Co films deposited on the
Fe(001)-p(1 × 1)O surface have been investigated
by means of Auger electron spectroscopy, scanning tunneling microscopy,
and scanning tunneling spectroscopy. The oxidation is initiated by
homogeneous oxide nucleation over the atomically flat Co terraces,
inducing the development of a smooth oxide wetting layer when the
islands coalesce. Atomically resolved images reveal that the oxide
wetting layer is highly defective, possibly due to the presence of
oxygen vacancies. Constant current scanning tunneling microscopy images
acquired in different tunneling conditions, as well as scanning tunneling
spectroscopy, reveal the distinct electronic properties of the oxide
nuclei with respect to the chemisorbed phase. The fundamental band
gap develops since the early stages of oxide nucleation. Moreover,
spectroscopic curves acquired in the near-field-emission regime reveal
a significant lowering of the sample work function induced by the
oxide development. Our results represent a remarkable case in which
metal oxidation can be studied at the atomic-scale level.