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Titanium nitride (TiN) is widely used in industry as a protective coating due to its hardness and resistance to corrosion and can spontaneously form a thin oxide layer when it is exposed to air, which could modify the properties of the coating. With limited understanding of the TiO-TiN interfacial system at present, this work aims to describe the structural and electronic properties of oxidized TiN based on a density functional theory (DFT) study of the rutile TiO(110)-TiN(100) interface model system, also including Hubbard +U correction on Ti 3d states. The small lattice mismatch gives a good stability to the TiO-TiN interface after depositing the oxide onto TiN through the formation of interfacial Ti-O bonds. Our DFT+U study shows the presence of Ti cations in the TiO region, which are preferentially located next to the interface region as well as the rotation of the rutile TiO octahedra in the interface structure. The DFT+U TiO electronic density of states (EDOS) shows localized Ti defect states forming in the midgap between the top edge of the valence and the bottom of the conduction band. We increase the complexity of our models by the introduction of nonstoichiometric compositions. Although the vacancy formation energies for Ti in TiN (E (Ti) ≥ 4.03 eV) or O in the oxide (E (O) ≥ 3.40 eV) are quite high relative to perfect TiO-TiN, defects are known to form during the oxide growth and can therefore be present after TiO formation. Our results show that a structure with exchanged O and N can lie 0.82 eV higher in energy than the perfect system, suggesting the stability of structures with interdiffused O and N anions at ambient conditions. The presence of N in TiO introduces N 2p states localized between the top edge of the O 2p valence states and the midgap Ti 3d states, thus reducing the band gap in the TiO region for the exchanged O/N interface EDOS. The outcomes of these simulations give us a most comprehensive insight on the atomic level structure and the electronic properties of oxidized TiN surfaces.

Tungsten (W) is an important and versatile transition metal and has a firm place at the heart of many technologies. A popular experimental technique for the characterization of tungsten and tungsten-based compounds is x-ray photoelectron spectroscopy (XPS), which enables the assessment of chemical states and electronic structure through the collection of core level and valence band spectra. However, in the case of tungsten metal, open questions remain regarding the origin, nature, and position of satellite features that are prominent in the photoelectron spectrum. These satellites are a fingerprint of the electronic structure of the material and have not been thoroughly investigated, at times leading to their misinterpretation. The present work combines high-resolution soft and hard x-ray photoelectron spectroscopy (SXPS and HAXPES) with reflected electron energy loss spectroscopy (REELS) and a multitiered ab initio theoretical approach, including density functional theory (DFT) and many-body perturbation theory (G0W0 and GW + C), to disentangle the complex set of experimentally observed satellite features attributed to the generation of plasmons and interband transitions. This combined experiment-theory strategy is able to uncover previously undocumented satellite features, improving our understanding of their direct relationship to tungsten's electronic structure. Furthermore, it lays the groundwork for future studies into tungsten-based mixed-metal systems and holds promise for the reassessment of the photoelectron spectra of other transition and post-transition metals, where similar questions regarding satellite features remain.

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