Jan Höcker

Growth mode and oxidation state analysis of individual cerium oxide islands on Ru(0001)

The growth of cerium oxide on Ru(0001) by reactive molecular beam epitaxy has been investigated using low-energy electron microscopy (LEEM) and diffraction as well as local valence band photoemission. The oxide islands are found to adopt a carpet-like growth mode, which depending on the local substrate morphology and misorientation leads to deviations from the otherwise almost perfect equilateral shape at a growth temperature of 850 °C. Furthermore, although even at this high growth temperature the micron-sized CeO₂(111) islands are found to exhibit different lattice registries with respect to the hexagonal substrate, the combination of dark-field LEEM and local intensity-voltage analysis reveals that the oxidation state of the islands is homogeneous down to the 10 nm scale.

Ultrathin, epitaxial cerium dioxide on silicon

It is shown that ultrathin, highly ordered, continuous films of cerium dioxide may be prepared on silicon following substrate prepassivation using an atomic layer of chlorine. The as-deposited, few-nanometer-thin Ce2O3 film may very effectively be converted at room temperature to almost fully oxidized CeO2 by simple exposure to air, as demonstrated by hard X-ray photoemission spectroscopy and X-ray diffraction. This post-oxidation process essentially results in a negligible loss in film crystallinity and interface abruptness.

Surface resonances in electron reflection from overlayers

Electron scattering by oxygen monolayers on the Ru(0u20090u20090u20091) surface is studied both experimentally and theoretically. Sharp transmission resonances at low energies are revealed and established to originate from critical points of a special kind in the complex band structure of the substrate. Electron reflection from the clean and oxidized Ru(0u20090u20090u20091) is measured for kinetic energies up to 40 eV at normal incidence for oxygen coverages of 1/4, 1/2, 3/4, and one monolayer. The reflection spectra R(E) are analyzed using a Bloch-waves based ab initio scattering theory. In addition to the substrate-induced resonances the reconstructed (2 × 1) and (2 × 2) surfaces show surface resonances due to pre-emergent secondary diffraction beams. The R(E) spectra are shown to give unambiguous evidence of the hcp stacking of the oxygen layer.

Nanoscale analysis of the oxidation state and surface termination of praseodymium oxide ultrathin films on ruthenium(0001)

The complex structure and morphology of ultrathin praseodymia films deposited on a ruthenium(0001) single crystal substrate by reactive molecular beam epitaxy is analyzed by intensity-voltage low-energy electron microscopy in combination with theoretical calculations within an ab initio scattering theory. A rich coexistence of various nanoscale crystalline surface structures is identified for the as-grown samples, notably comprising two distinct oxygen-terminated hexagonal Pr2O3(0001) surface phases as well as a cubic Pr2O3(111) and a fluorite PrO2(111) surface component. Furthermore, scattering theory reveals a striking similarity between the electron reflectivity spectra of praseodymia and ceria due to very efficient screening of the nuclear charge by the extra 4f electron in the former case.

Exploiting micro-scale structural and chemical observations in real time for understanding chemical conversion: LEEM/PEEM studies over CeO x –Cu(111)

Proper consideration of length-scales is critical for elucidating active sites/phases in heterogeneous catalysis, revealing chemical function of surfaces and identifying fundamental steps of chemical reactions. Using the example of ceria thin films deposited on the Cu(111) surface, we demonstrate the benefits of multi length-scale experimental framework for understanding chemical conversion. Specifically, exploiting the tunable sampling and spatial resolution of photoemission electron microscopy, we reveal crystal defect mediated structures of inhomogeneous copper-ceria mixed phase that grow during preparation of ceria/Cu(111) model systems. The density of the microsized structures is such that they are relevant to the chemistry, but unlikely to be found during investigation at the nanoscale or with atomic level investigations. Our findings highlight the importance of accessing micro-scale when considering chemical pathways over heteroepitaxially grown model systems.