Electronic Properties and Bonding in ZrHx Thin Films Investigated by Valence-Band X-ray Photoelectron Spectroscopy

TL;DR

This study investigates the electronic structure and bonding in ZrHx thin films with varying hydrogen content using X-ray photoelectron spectroscopy, revealing phase compositions, charge transfer, and structural stability related to hydrogen incorporation.

Contribution

It provides detailed insights into how hydrogen content affects the electronic structure, phase stability, and bonding in ZrHx thin films, which was not previously characterized in such detail.

Findings

Increased hydrogen reduces 4d valence states near the Fermi level.

ZrHx phases transition from mixed phases to single-phase as x increases.

Charge transfer from Zr to H influences electronic properties and conductivity.

Abstract

The electronic structure and chemical bonding in reactively magnetron sputtered ZrHx (x=0.15, 0.30, 1.16) thin films with oxygen content as low as 0.2 at% are investigated by 4d valence band, shallow 4p core-level and 3d core-level X-ray photoelectron spectroscopy. With increasing hydrogen content, we observe significant reduction of the 4d valence states close to the Fermi level as a result of redistribution of intensity towards the H 1s - Zr 4d hybridization region at about 6 eV below the Fermi level. For low hydrogen content (x=0.15, 0.30), the films consist of a superposition of hexagonal closest packed metal (alpha-phase)and understoichiometric delta-ZrHx (CaF2-type structure) phases, while for x=1.16, the film form single phase ZrHx that largely resembles that of stoichiometric delta-ZrH2 phase. We show that the cubic delta-ZrHx phase is metastable as thin film up to x=1.16 while for higher H-contents, the structure is predicted to be tetragonally distorted. For the investigated ZrH1.16 film, we find chemical shifts of 0.68 and 0.51 eV towards higher binding energies for the Zr 4p3/2 and 3d5/2 peak positions, respectively. Compared to the Zr metal binding energies of 27.26 and 178.87 eV, this signifies a charge-transfer from Zr to H atoms. The change in the electronic structure, spectral line shapes, and chemical shifts as function of hydrogen content is discussed in relation to the charge-transfer from Zr to H that affects the conductivity by charge redistribution in the valence band.