The surface morphology of CeO(2)(111) single crystals and silicon supported ceria films is investigated by non-contact atomic force microscopy (NC-AFM) and Kelvin probe force microscopy (KPFM) for various annealing conditions. Annealing bulk samples at 1100 K results in small terraces with rounded ledges and steps with predominantly one O-Ce-O triple layer height while annealing at 1200 K produces well-ordered straight step edges in a hexagonal motif and step bunching. The morphology and topographic details of films are similar, however, films are destroyed upon heating them above 1100 K. KPFM images exhibit uniform terraces on a single crystal surface when the crystal is slowly cooled down, whereas rapid cooling results in a significant inhomogeneity of the surface potential. For films exhibiting large terraces, significant inhomogeneity in the KPFM signal is found even for best possible preparation conditions. Applying X-ray photoelectron spectroscopy (XPS), we find a significant contamination of the bulk ceria sample with fluorine while a possible fluorine contamination of the ceria film is below the XPS detection threshold. Time-of-flight secondary ion mass spectroscopy (TOF-SIMS) reveals an accumulation of fluorine within the first 5 nm below the surface of the bulk sample and a small concentration throughout the crystal.

The cross-linked (1 × 2) reconstruction of TiO(2)(110) is a frequently observed phase reflecting the surface structure of titania in a significantly reduced state. Here we resolve the atomic scale structure of the cross-linked (1 × 2) phase with dynamic scanning force microscopy operated in the non-contact mode (NC-AFM). From an analysis of the atomic-scale contrast patterns of the titanium and oxygen sub-structures obtained by imaging the surface with AFM tips having different tip apex termination, we infer the hitherto most accurate model of the atomic structure of the cross-linked (1 × 2) phase. Our findings suggest that the reconstruction is based on added rows in [001] direction built up of Ti(3)O(6) units with an uninterrupted central string of oxygen atoms accompanied by a regular sequence of cross-links consisting of linear triples of additional oxygen atoms in between the rows. The new insight obtained from NC-AFM solves previous controversy about the cross-linked TiO(2)(110) surface structure, since previously proposed models based on cross-links with a lower O content do not appear to be consistent with the atom-resolved data presented here. Instead, our measurements strongly support the Ti(3)O(6) motif to be the structural base of the cross-linked (1 × 2) reconstruction of TiO(2)(110).

Impact of near-surface native point defects, chemical reactions, and surface morphology on ZnO interfaces

We present a versatile system for the preparation of oxide crystal surfaces in the ultra-high vacuum (UHV) at temperatures up to 1300 K. Thermal treatment is accomplished by direct current heating of a tantalum foil in contact with the oxide sample. The sample temperature is measured by a thermocouple at a position close to the crystal and its reading is calibrated against the surface temperature determined by a second thermocouple temporarily attached to the surface. The design of the sample holder is based on a transferable plate originally developed for a commercial UHV scanning probe microscope. The system is, however, also suitable for the use with electron spectroscopy or electron diffraction based surface analytical techniques. We present results for the high-temperature preparation of CeO(2)(111) surfaces with atomically flat terraces exhibiting perfect atomic order and cleanliness as revealed by non-contact atomic force microscopy (NC-AFM) imaging. NC-AFM imaging is, furthermore, used to demonstrate the temperature-controlled aggregation of gold atoms on the CeO(2)(111) surface and their evaporation at high temperatures.

No abstract