Core hole and surface excitation correction parameter for XPS peak intensities

Abstract

In XPS analysis, surface excitations and excitations originating from the static core hole created during the photoexcitation process are usually neglected. However, both effects significantly reduce the measured peak intensity. In this paper we have calculated these effects. Instead of considering the two effects separately, we introduce a new parameter, namely the Correction Parameter for XPS (or CP XPS ) defined as the change in probability for emission of a photoelectron caused by the presence of the surface and the core hole in comparison with the situation where the core hole is neglected and the electron travels the same distance in an infinite medium. The CP XPS calculations are performed within the dielectric response theory by means of the QUEELS-XPS software determining the energy-differential inelastic electron scattering cross-sections for X-ray photoelectron spectroscopy (XPS) including surface and core hole effects. This study has been carried out for electron energies between 300 eV and 3400 eV, for angles to the surface normal between 0° and 60° and for various materials, especially metals, semiconductors and oxides. For geometries and energies normally used in XPS, i.e. for emission angle ≤ 60° and photoelectron energy ≤ 1500 eV, we find that CP XPS values are significantly larger for oxides, (0.55 ≲ CP XPS ≲ 0.75) than for metals and semiconductors (0.45 ≲ CP XPS ≲ 0. 6). We show that this behavior is due to the difference in the wave vector dispersion of the energy loss function. This dispersion has been determined from analysis of REELS and is found to be free electron like ( α ≅ 1) for metals but is substantially smaller ( α ≈ 0.02–0.05) for materials with a wide band gap. As a result, the group velocity of the valence electrons is very small for oxides with a large band gap. This leads to a reduction in the screening of the core-hole potential before the photoelectron has left the region of interaction and thereby to an increase in the intrinsic excitations caused by the core hole.