No abstract

Through an interplay between scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we show that bridging oxygen vacancies are the active nucleation sites for Au clusters on the rutile TiO 2 110 surface. We find that a direct correlation exists between a decrease in density of vacancies and the amount of Au deposited. From the DFT calculations we find that the oxygen vacancy is indeed the strongest Au binding site. We show both experimentally and theoretically that a single oxygen vacancy can bind 3 Au atoms on average. In view of the presented results, a new growth model for the TiO 2 110 system involving vacancy-cluster complex diffusion is presented.

Defects such as oxygen vacancies play a crucial role in the surface properties of transition metal oxides. By means of time-resolved, high-resolution scanning tunneling microscopy, we unraveled an adsorbate-mediated diffusion mechanism of oxygen vacancies on rutile TiO2(110). Adsorbed oxygen molecules mediate vacancy diffusion through the loss of an oxygen atom to a vacancy and the sequential capture of an oxygen atom from a neighboring bridging oxygen row, leading to an anisotropic oxygen vacancy diffusion pathway perpendicular to the bridging oxygen rows.

Diffusion of oxygen molecules on transition metal oxide surfaces plays a vital role for the understanding of catalysis and photocatalysis on these materials. By means of time-resolved scanning tunneling microscopy, we provide evidence for a charge transfer-induced diffusion mechanism for O2 molecules adsorbed on a rutile TiO2(110) surface. The O2 hopping rate depended on the number of surface donors (oxygen vacancies), which determines the density of conduction band electrons. These results may have implications for the understanding of oxidation processes on metal oxides in general.

We have investigated methods for cleaning dc-etched polycrystalline tungsten tips for scanning tunnelling microscopy (STM). The cleaning methods include Ar-ion sputtering, heating, chemical treatments and Ne-ion self-sputtering. We correlate transmission electron microscopy images of the tip, field-emission data from the tip and images of a clean Cu(111) surface to find an optimum procedure for STM imaging. Clean and sharp tips are made by sputtering, combined with careful heating by electron bombardment. We found that optimum sputtering was obtained either by use of a 4 keV Ar-ion gun for a few seconds or by self-sputtering with Ne ions for a few seconds or until decapitation occurs.