Determination of the clean 4f peak shape in XPS for plutonium metal

Many of the interesting properties observed with plutonium are ascribed to the influence of 5f electrons, and to the degree of localisation observed within these electrons. Indeed, changes in 5f localisation are sensitively reflected in the final states observed in core-level photoemission measurements. However, when analysing the 4f manifold of elemental plutonium, it is essential to obtain spectra without the influence of oxidation, which can easily be misinterpreted as 5f localisation. The ideal method to extract elemental plutonium 4f spectra is to remove any influence of oxidation from the ‘clean’ plutonium data by careful measurement of the oxygen 1s region, and the subsequent subtraction of the unwanted oxide features. However, in order to achieve this objective it is essential to determine the relative sensitivity factor (RSF) for plutonium 4f and the precise shape of the 4f features from plutonium sesqui-oxide. In this paper, we report an experimental determination of the RSF for the plutonium 4f manifold using experimental data captured from two different Vacuum Generators spectrometers; an ESCALAB Mk II and an ESCALAB 220i.