Abstract
Abstract X-ray photoelectron (XPS), emission (XES), and absorption (XAS) spectroscopy methods have been used to study the electronic structure of cubic TaCx and hexagonal Ta2Cy (y=2x) carbides, and also rhombohedral ζ-Ta4C3 and ϵ-Ta3C2 phases. The XPS core-level binding energies (BEs) and valence-band structures for TaCx over the range 0.36≤x≤0.98 have been determined. It was established that Ef was generally lowered by the introduction of C-vacancies in cubic tantalum carbides. The results of the XPS and XES studies indicate that the layered subcarbides ζ-Ta4C3 and ϵ-Ta3C2 are individual phases and are by no means a simple mixture of the cubic TaCx and hexagonal Ta2Cy carbides. In the layered subcarbides ζ-Ta4C3 and ϵ-Ta3C2 the formation of new (shortened) M–M bonds between the tantalum atoms neighbouring the {111} plane of the carbon sublattice, where the C-vacancies concentrate, results in the appearance of an additional peak (EBE≈2 eV below Ef) in the XPS valence-band spectra. In the row TaCx→ζ-Ta4C3→ϵ-Ta3C2→Ta2Cy the XPS Ta 4f and C 2s core-level BEs and main peaks of the XPS valence-band spectra shifted toward the Fermi level by about 0.5 eV, while the C 1s BEs remained constant (within the experimental error) for all studied subcarbides. In this row some shifts of the main maxima of the XES Ta 5d-like and C 2p-like bands toward Ef are observed. In all tantalum carbides the charge transfers from Ta atoms to C atoms.
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More From: Journal of Electron Spectroscopy and Related Phenomena
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