Differential charging in X-ray photoelectron spectroscopy: a nuisance or a useful tool?

We apply a negative bias to the sample while recording an XPS spectrum to enhance differential (positive) charging. The enhanced differential charging is due to the repulsion of stray electrons from the sample, which normally cause partial neutralization of the poorly conducting samples or regions accumulating positive charging, as a consequence of the photoelectron emission. This enhanced differential charging (obtained by negative biasing) is shown to have the ability to separate otherwise overlapping peaks of PDMS layer from that of the SiO(2)/Si substrate. Each layer experiences different charging that can be used to derive information related to dielectric properties of the layers, proximity of the atoms within composite multilayers, or both. Hence, differential charging in XPS, which is usually considered as a nuisance, is turned into a useful tool for extracting additional information from nanometer-size surface structures.