Oxidation state depth profiling by self-consistent fitting of all emission peaks in the X-ray photoelectron spectrum of SnTe

X-ray photoelectron spectroscopy (XPS) is among the most widely used methods for surface characterization. Currently, the analysis of XPS data is almost exclusively based on the main emission peak of a given element and the rest of the spectrum is discarded. This makes quantitative chemical state analyses by peak fitting prone to substantial error, especially in light of incomplete and flawed reference literature. However, most elements give rise to multiple emission peaks in the X-ray energy range, which are virtually never analyzed. For samples with an inhomogeneous depth distribution of chemical states, these peaks show different but interdependent ratios of signal components, as they correspond to different information depths. In this work, we show that self-consistent fitting of all emission peaks lends additional reliability to the depth profiling of chemical states by angular-resolved (AR-)XPS. We demonstrate this using a natively oxidized thin film of the topological crystalline insulator tin telluride (SnTe). This approach is not only complementary to existing depth profiling methods, but may also pave the way towards complete modelling of the XPS spectrum, facilitating a more comprehensive and holistic understanding of the surface chemistry of solids.