Crossover from three-dimensional to two-dimensional geometries of Au nanostructures on thin MgO(001) films: a confirmation of theoretical predictions.

In this Letter, we report a low-temperature scanning tunneling microscopy study aiming to explore the adsorption properties of Au with respect to the thickness of supported MgO films. For different MgO film thicknesses (3 ML and 8 ML), we find significant differences in the distribution of Au adsorption sites and in the Au cluster geometry, in line with recent calculations and electron paramagnetic resonance experiments. On the surface of thick MgO films or unsupported MgO, Au adsorbs on O sites [Phys. Rev. Lett. 96, 146804 (2006)], and the equilibrium cluster geometry is three-dimensional. In contrast, on thin MgO films, the calculations predicted (i) a change of the preferred Au nucleation site [Phys. Rev. Lett. 94, 226104 (2005)] and (ii) a stabilization of two-dimensional Au cluster geometries [Phys. Rev. Lett. 97, 036106 (2006)].

Control of the charge state of metal atoms on thin MgO films.

The arrangement of single gold and palladium atoms deposited on the surface of a 3 monolayer thin film of MgO was investigated using low-temperature scanning tunneling microscopy. While Pd atoms are arranged in a random fashion, Au forms an ordered array on the surface. The long-range ordering as well as the scanning tunneling microscopy appearance of single Au atoms on a 3 monolayer thin MgO film can be explained by partial charge transfer from the substrate to Au atoms as predicted recently by density functional theory calculations [Phys. Rev. Lett. 94, 226104 (2005)10.1103/PhysRevLett.94.226104]. In contrast with that, Au atoms on a thick film were found to be essentially neutral.

Binding of single gold atoms on thin MgO(001) films.

In the present Letter the first electron paramagnetic resonance spectra of single metal atoms on a single crystalline oxide surface are presented. For Au atoms on a MgO(001) film investigated here an analysis of the angular dependent resonance positions and the hyperfine coupling to (17)O shows that the atoms are bound on top of oxygen ions on the terrace of the film. This result is in perfect agreement with scanning tunneling microscopy measurements at 5 K presented here. The measured hyperfine matrix components allow an experimental verification of the theoretically proposed binding mechanism of Au atoms on MgO. In particular, the large reduction of the isotropic hyperfine coupling constant of supported Au as compared to free atoms is not due to a charge transfer at the interface but a hybridization of orbitals and a resulting polarization of the unpaired electron.

Electron paramagnetic resonance and scanning tunneling microscopy investigations on the formation of F(+) and F(0) Color centers on the surface of thin MgO(001) films.

The formation of surface color centers (F(S) centers) by electron bombardment of thin MgO(001) films is investigated using electron paramagnetic resonance and low-temperature scanning tunneling microscopy. At low electron doses both techniques indicate the formation of singly occupied color centers (F(S)(+)), whereas at high electron doses the doubly occupied type (F(S)(0)) is dominant. It is suggested that with increasing electron dose F(S)(+) centers are transformed into F(S)(0). Tunneling spectra of individual F(S)(0) centers reveal a large distribution of energetic positions of occupied and unoccupied states, which is caused by local variations of the coordination number of the defects and explains the broad signals usually detected with integrating spectroscopic techniques.

Identification of color centers on MgO(001) thin films with scanning tunneling microscopy.

Localized electronic defects on the surface of a 4 monolayer (ML) thin MgO(001) film deposited on Ag(001) have been investigated by low-temperature scanning tunneling microscopy and spectroscopy. Depending on the location of the defect, we observe for the first time different defect energy levels in the band gap of MgO. The charge state of defects can be manipulated by interactions with the scanning tunneling microscope tip. Comparison with ground state energy levels of color centers on the MgO surface obtained from embedded cluster calculations corroborates the assignment of the defects to singly and doubly charged color centers.

Self-organization of gold atoms on a polar FeO(111) surface.

The spatial distribution of single Au atoms on a thin FeO film has been investigated by low-temperature scanning tunneling microscopy and spectroscopy. The adatoms preferentially adsorb on distinct sites of the Moiré cell formed by the oxide layer and the Pt(111) support and arrange into a well-ordered hexagonal superlattice with 25 angstroms lattice constant. The self-organization is the consequence of an inhomogeneous surface potential within the FeO Moiré cell and substantial electrostatic repulsion between the adatoms.