Chemical Bonding in Epitaxial ZrB2 Studied by X-ray Spectroscopy

TL;DR

This study uses X-ray spectroscopy to analyze the chemical bonding and structural properties of epitaxial ZrB2 films, revealing differences in oxygen content and atomic ordering compared to bulk ZrB2 and α-Zr.

Contribution

It provides detailed spectroscopic and structural insights into epitaxial ZrB2 films, highlighting differences from bulk materials and the effects of oxygen incorporation.

Findings

Epitaxial ZrB2 film shows higher atomic ordering than bulk.

Oxygen content is lower in the epitaxial film compared to bulk ZrB2.

Structural parameters differ slightly between film and bulk ZrB2.

Abstract

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 {\alpha}-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 {\alpha}-Zr reference after completed sputter cleaning. For the ZrB2 compound target, X-ray diffraction (XRD) shows weak but visible -111, 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 {\alpha}-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 {\alpha}-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 {\AA}, c=3.520 {\AA}) in comparison to the bulk target material (a=3.175 {\AA}, c=3.540 {\AA}) while in hexagonal closest-packed metal ({\alpha}-phase, a=3.254 {\AA}, c=5.147 {\AA}).