Abstract
Nanomaterials based on transition-metal oxides (TMOs) that contain late 3d transition metals (e.g., Mn, Fe, Co, Ni) have diverse properties and functionality that are related to the oxidation state of constituent transition-metal (TM) cations. X-ray photoelectron spectroscopy (XPS) of TM 2p orbitals has been widely used to quantify the TM oxidation state of TMOs. However, 2p XPS spectra of late 3d TM cations usually have complicated shapes due to the charge transfer between the TM cation and oxygen ligands (anions), which makes the analysis highly nontrivial. In this article, we will examine the validity of commonly used analysis methods based on either peak fitting or the shift of binding energy (BE). The different origins of the BE shift in XPS spectra will be discussed. We will then introduce a model to reproduce the complex shapes of TM 2p spectra, based on fundamental parameters that describe the TMO electronic structure.
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