The growth of ultrathin zirconia films on Pd3Zr(0001)

J. I. J. Choi, W. Mayr-Schmölzer, F. Mittendorfer, J. Redinger, U. Diebold, M. Schmid

Institut für Angewandte Physik, Technische Universität Wien, 1040 Wien, Austria
Center for Computational Materials Science, Technische Universität Wien, 1040 Wien, Austria

J. Phys.: Condens. Matter 26 (2014) 225003

Despite its importance in many areas of industry, such as catalysis, fuel cell technology and microelectronics, the surface structure and physical properties of ZrO2 are not well understood. Following the successful growth of ultrathin zirconia on Pt3Zr(0001) [Antlanger et al. 2012, Phys. Rev. B 86, 035451], we report on recent progress into ZrO2 thin films, which were prepared by oxidation of a Pd3Zr(0001) crystal. Results from scanning tunneling microscopy (STM), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) as well as density-functional theory (DFT) are presented. Many sputter-annealing cycles are required for preparation of the clean Pd3Zr alloy surface, because oxygen easily dissolves in the bulk. By oxidation and post-annealing, a homogeneous ultrathin ZrO2 film was obtained. This is an O-Zr-O trilayer based on cubic ZrO2(111). Using STM images corrected for distortion and creep of the piezo scanner the in-plane lattice parameter was determined as (351.2 ± 0.4) pm, slightly contracted with respect to the cubic ZrO2 bulk phase. The oxide forms a overlayer that is either incommensurate or has a very large superstructure cell (a = 8.3 nm); nevertheless its rotational orientation is always the same. In contrast to ultrathin zirconia on Pt3Zr(0001), where the uppermost substrate layer is pure (but reconstructed) Pt, STM and XPS suggest a stoichiometric Pd3Zr below the oxide. The oxide film binds to the substrate mainly via bonds between oxygen and the Zr atoms in the substrate. The ultrathin oxide shows large buckling in STM, confirmed by DFT calculations, where the buckling of the Zr layer can exceed 100 pm. Compared to the ZrO2 film on Pt3Zr(0001), the oxide on Pd3Zr(0001) has the advantage that the substrate below does not reconstruct, leading to a homogeneous oxide film.

Corresponding author: Michael Schmid (schmid at iap_tuwien_ac_at).

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