Photoemission studies of adsorbed oxygen and oxide layers

A comprehensive review is given about the enormous versatility of photoelectron spectroscopy to study the especially complex interaction of oxygen with metal surfaces and the nature of the reaction products. The great variety of well definable parameters of a photoemission experiment, e.g. energy, direction of incidence and polarization of the primary photon beam as well as the detection direction of the photocurrent, yields - through the distributions of energy, momentum and spin polarization of the photoelectrons - detailed insight in the kinetic, thermodynamic, electronic and structural aspects of oxygen adsorption on metal surfaces and incipient oxidation. Characteristic electron binding energies, multiplet and satellite structures of both the oxygen and substrate emission allow a distinction between possible states of adsorbed oxygen, i.e. condensed, molecularly and atomically adsorbed, and incorporated oxygen. Even a distinction between octahedral and tetrahedral oxygen coordination of oxide cations may be possible. Analysis of peak intensities (as a measure of coverages and concentrations) as a function of time and temperature provides information about the kinetics and thermodynamics of adsorbed layer and oxide formation. Angular resolved photoemission studies have led to the determination of absolute adsorption site geometries, individual ad-orbital symmetries and two-dimensional band structure formation within the oxygen overlayer. Measurement of the photoelectron spin-polarization offers a method to study surface magnetism, e.g. of ferromagnetic oxides. The determination of local work functions through the photoemission behavior of co-adsorbed rare gas atoms establishes a uniquely important tool to characterize heterogenous surfaces, e.g. oxygenated surfaces with coexisting oxygen states. Numerous different oxygen/metal systems are chosen to demonstrate the state of the art. Results from other surface spectroscopies and theoretical model calculations are, of course, considered and still open problems are named, e.g. the ionicity of the oxygen chemisorption bond. Problems inherent in sputter profiling through surface oxides as observed with photoemission are briefly addressed. This work is rounded by a list of about 600 references in alphabetic order of the reacting metals.