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­Chemical Bonding in Epitaxial ZrB2 Studied by X-ray Spectroscopy
Linköpings universitet, Institutionen för fysik, kemi och biologi, Tunnfilmsfysik. Linköpings universitet, Tekniska fakulteten.ORCID-id: 0000-0002-0317-0190
Linköpings universitet, Institutionen för fysik, kemi och biologi, Tunnfilmsfysik. Linköpings universitet, Tekniska fakulteten.
Linköpings universitet, Institutionen för fysik, kemi och biologi, Tunnfilmsfysik. Linköpings universitet, Tekniska fakulteten.ORCID-id: 0000-0002-4898-5115
Linköpings universitet, Institutionen för fysik, kemi och biologi, Tunnfilmsfysik. Linköpings universitet, Tekniska fakulteten.ORCID-id: 0000-0002-2837-3656
Vise andre og tillknytning
2018 (engelsk)Inngår i: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, Vol. 649, s. 89-96Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

The chemical bonding in an epitaxial ZrB2 film is investigated by Zr K-edge (1s) X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies and compared to the ZrB2 compound target from which the film was synthesized as well as a bulk α-Zr reference. Quantitative analysis of X-ray Photoelectron Spectroscopy spectra reveals at the surface: ~5% O in the epitaxial ZrB2 film, ~19% O in the ZrB2 compound target and ~22% O in the bulk α-Zr reference after completed sputter cleaning. For the ZrB2 compound target, X-ray diffraction (XRD) shows weak but visible   11, 111, and 220 peaks from monoclinic ZrO2 together with peaks from ZrB2 and where the intensity distribution for the ZrB2 peaks show a randomly oriented target material.  For the bulk α-Zr reference no peaks from any crystalline oxide were visible in the diffractogram recorded from the 0001-oriented metal. The Zr K-edge absorption from the two ZrB2 samples demonstrate more pronounced oscillations for the epitaxial ZrB2 film than in the bulk ZrB2 attributed to the high atomic ordering within the columns of the film. The XANES exhibits no pre-peak due to lack of p-d hybridization in ZrB2, but with a chemical shift towards higher energy of 4 eV in the film and 6 eV for the bulk compared to α-Zr (17.993 keV) from the charge-transfer from Zr to B. The 2 eV larger shift in bulk ZrB2 material suggests higher oxygen content than in the epitaxial film, which is supported by XPS. In EXAFS, the modelled cell-edge in ZrB2 is slightly smaller in the thin film (a=3.165 Å, c=3.520 Å) in comparison to the bulk target material (a=3.175 Å, c=3.540 Å) while in hexagonal closest-packed metal (α-phase, a=3.254 Å, c=5.147 Å). The modelled coordination numbers show that the EXAFS spectra of the epitaxial ZrB2 film is highly anisotropic with strong in-plane contribution, while the bulk target material is more isotropic. The Zr-B distance in the film of 2.539 Å is in agreement with the calculated value from XRD data of 2.542 Å. This is slightly shorter compared to that in the ZrB2 compound target 2.599 Å, supporting the XANES results of a higher atomic order within the columns of the film compared to bulk ZrB2.

sted, utgiver, år, opplag, sider
Elsevier, 2018. Vol. 649, s. 89-96
Emneord [en]
Zirconium boride, thin films, bond distances, chemical bonding, X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction
HSV kategori
Identifikatorer
URN: urn:nbn:se:liu:diva-144578DOI: 10.1016/j.tsf.2018.01.021ISI: 000427524100015Arkivnummer: 1801.08663OAI: oai:DiVA.org:liu-144578DiVA, id: diva2:1178147
Merknad

Funding agencies: Swedish Energy Research [43606-1]; Swedish Foundation for Strategic Research (SSF) through the synergy grant FUNCASE [RMA11-0029]; Carl Trygger Foundation [CTS16:303, CTS14:310]; Swedish Research Council (VR) [621-2010 3921]; Knut and Alice Wallenberg Fou

Tilgjengelig fra: 2018-01-29 Laget: 2018-01-29 Sist oppdatert: 2018-04-12bibliografisk kontrollert

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Fulltekst tilgjengelig fra 2020-03-06 14:13
Tilgjengelig fra 2020-03-06 14:13

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