Stability and mixing behavior of vanadium-iron oxide monolayers on Pt(111) and Ru(0001) substrates.

Cation mixing is a well-recognized means to obtain oxides of desired functionality with predetermined structure and stoichiometry, which yet has been only little analyzed at the nanoscale. In this context, we present a comparative analysis of the stability and mixing properties of O-poor and O-rich two-dimensional V-Fe oxides grown on Pt(111) and Ru(0001) surfaces, with the aim of gaining an insight into the role of substrate and oxygen conditions on the accessible Fe contents. We find that due to the high oxygen affinity of the Ru substrate, the mixed O-rich layers are highly stable while the stability of O-poor layers is limited to inaccessibly oxygen-poor environments. In contrast, on the Pt surface, O-poor and O-rich layers coexist with, however, a much lower Fe content in the O-rich phase. We show that cationic mixing (formation of mixed V-Fe pairs) is favored in all considered systems. It results from local cation-cation interactions, reinforced by a site effect in O-rich layers on the Ru substrate. In O-rich layers on Pt, Fe-Fe repulsion is so large that it precludes the possibility of substantial Fe content. These findings highlight the subtle interplay between structural effects, oxygen chemical potential, and substrate characteristics (work function and affinity towards oxygen), which governs the mixing of complex 2D oxide phases on metallic substrates.

Single Molecule Vibrational Spectroscopy: CO Bonding to Edge and Terrace Positions on Ag, Au, and Pd Islands on NiAl(110).

The vibrational properties of single CO molecules adsorbed on nanosized Ag, Au, and Pd islands on a NiAl(110) surface were studied with a scanning tunneling microscope. The sensitivity of single molecule vibrational spectroscopy to aspects of the local environment is demonstrated by comparative studies of CO-metal bond vibrations at island terrace and island edge sites. Vibrational spectra of single CO molecules adsorbed on Ag, Au, and Pd island terraces showed peaks at 27, 32, and 44 meV, respectively, which are assigned to the hindered rotational mode. CO molecules on Au and Pd island edges, on the other hand, showed blue-shifted hindered rotational modes at 34 and 46 meV, respectively. On Au islands, CO molecules showed a strong preference for adsorption on edges, while no such preference was observed on Pd.

Diffusion Barriers Block Defect Occupation on Reduced CeO_{2}(111).

Surface defects are believed to govern the adsorption behavior of reducible oxides. We challenge this perception on the basis of a combined scanning-tunneling-microscopy and density-functional-theory study, addressing the Au adsorption on reduced CeO_{2-x}(111). Despite a clear thermodynamic preference for oxygen vacancies, individual Au atoms were found to bind mostly to regular surface sites. Even at an elevated temperature, aggregation at step edges and not decoration of defects turned out to be the main consequence of adatom diffusion. Our findings are explained with the polaronic nature of the Au-ceria system, which imprints a strong diabatic character onto the diffusive motion of adatoms. Diabatic barriers are generally higher than those in the adiabatic regime, especially if the hopping step couples to an electron transfer into the ad-gold. As the population of O vacancies always requires a charge exchange, defect decoration by Au atoms becomes kinetically hindered. Our study demonstrates that polaronic effects determine not only electron transport in reducible oxides but also the adsorption characteristics and therewith the surface chemistry.

A fresh look at an old nano-technology: catalysis.

The development of model catalyst systems for heterogeneous catalysis going beyond the metal single crystal approach, including phenomena involving the limited size of metal nanoparticles supported on oxide surfaces, as well as the electronic interaction through the oxide-metal interface, is exemplified on the basis of two case studies from the laboratory of the authors. In the first case study the reactivity of supported Pd nanoparticles is studied in comparison with Pd single crystals. The influence of carbon contaminants on the hydrogenation reaction of unsaturated hydrocarbons is discussed. Carbon contaminants are identified as a key parameter in those reactions as they control the surface and sub-surface concentration of hydrogen on and in the particles. In the second case study, scanning probe techniques are used to determine electronic and structural properties of supported Au particles as a function of the number of Au atoms in the particle. It is demonstrated how charge transfer between the support and the particle determines the shape of nanoparticles and a concept is developed that uses charge transfer control through dopants in the support to understand and design catalytically active materials.

Quantum well states in two-dimensional gold clusters on MgO thin films.

The electronic structure of ultrasmall Au clusters on thin MgO/Ag(001) films has been analyzed by scanning tunneling spectroscopy and density functional theory. The clusters exhibit two-dimensional quantum well states, whose shapes resemble the eigenstates of a 2D electron gas confined in a parabolic potential. From the symmetry of the highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO) of a particular cluster, its electron filling and charge state is determined. In accordance with a Bader charge analysis, aggregates containing up to 20 atoms accumulate one to four extra electrons due to a charge transfer from the MgO/Ag interface. The HOMO-LUMO gap is found to close for clusters containing between 70 and 100 atoms.

Au dimers on thin MgO(001) films: flat and charged or upright and neutral?

A combination of low temperature scanning tunneling microscopy (STM) and theoretical calculations is used to investigate Au dimers, supported on thin MgO(001) films, whose thickness was chosen such that charge transfer from the Ag substrate to the deposited Au is possible. Au dimers exist not only in an upright geometry--as theoretically predicted to be the most stable configuration--but also as flat lying dimers which populate a manifold of different azimuthal orientations. Apart from the difference in adsorption configurations, these two isomers exhibit rather different electronic structures: while upright dimers are neutral, flat ones are charged.

Counting electrons transferred through a thin alumina film into Au chains.

Low-temperature STM measurements combined with density functional theory calculations are employed to study the adsorption of gold on alumina/NiAl(110). The binding of Au monomers involves breaking of an oxide Al-O bond below the adatom and stabilizing the hence undercoordinated O ion by forming a new bond to an Al atom in the NiAl. The adsorption implies negative charging of the adatom. The linear arrangement of favorable binding sites induces the self-organization of Au atoms into chains. For every ad-chain, the number of transfer electrons from the support is determined by analyzing the node structure of the corresponding highest occupied molecular orbital.

Oxygen-deficient line defects in an ultrathin aluminum oxide film.

A model for the straight antiphase domain boundary of the ultrathin aluminum oxide film on the NiAl(110) substrate is derived from scanning tunneling microscopy measurements and density-functional theory calculations. Although the local bonding environment of the perfect film is maintained, the structure is oxygen deficient and possesses a favorable adsorption site. The domain boundary exhibits a downwards band bending and three characteristic unoccupied electronic states, in excellent agreement with scanning tunneling spectroscopy measurements.

Influence of the metal substrate on the adsorption properties of thin oxide layers: Au atoms on a thin alumina film on NiAl(110).

Thin oxide films grown on metal substrates are widely used in surface science to model bulk oxides, assuming their chemical and electronic properties to be similar. In some cases, however, this might not be justified as the present scanning tunneling microscopy studies demonstrate for Au atoms on a thin alumina film on NiAl(110). Au atoms were evaporated onto the oxide film at a sample temperature of approximately 10 K. At low coverage, this leads to the formation of one-dimensional clusters with unusually large Au-Au distances of 5.6-6.0 A. A direct interaction between the Au atoms can be excluded, and a substrate-mediated mechanism is supposed instead. This assumption is strengthened by the finding that the Au chains exhibit a preferential orientation: They are almost aligned with the [001] direction of the NiAl(110) substrate, clearly indicating that the metal substrate participates in the binding of the Au atoms.

Electronic properties of artificial Au chains with individual Pd impurities.

Artificial Au atomic chains with individual Pd impurities were assembled from single metal atoms with a scanning tunneling microscope on a NiAl(110) surface. Scanning tunneling spectroscopy (STS) revealed an electronic resonance 2.15 eV above the Fermi energy localized within 4 A of single Pd atom impurities and two electronic resonances 2.25 eV and 2.95 eV above the Fermi energy localized within 8 A of Pd dimer impurities. The emergence of these localized resonances was studied by STS at each stage of the atom-by-atom assembly. Additionally, conductance images of the chains revealed delocalized electronic density oscillations in the pure Au segments of the chains.

Realization of a particle-in-a-box: electron in an atomic Pd chain.

Well-defined Pd chains were assembled from single atoms on a NiAl(110) surface with the tip of a scanning tunneling microscope. The electronic properties of the chains were determined by spatially resolved conductance measurements, revealing a series of quantum well states with parabolic dispersion. The particle-in-a-box states in Pd chains show higher onset energy and larger effective mass than those in Au chains investigated before, reflecting the influence of elemental composition on one-dimensional electronic systems. The intrinsic widths and spectral intensities of Pd induced states provide information on lifetime and spatial localization of states in the atomic chain.

Distance dependence of the interaction between single atoms: gold dimers on NiAl(110).

The importance of substrate-mediated adsorbate-adsorbate interactions on electronic states has been demonstrated for Au dimers on NiAl(110) with a scanning tunneling microscope and density functional calculations. An unoccupied resonance observed in single Au atoms splits into a doublet in Au dimers. The energy splitting depends inversely on the distance between the two adatoms, revealing the relative importance of direct and substrate-mediated interactions. Spatially resolved conductance measurements of Au dimers reveal the symmetric and antisymmetric characters of the doublet states.

Localized molecular constraint on electron delocalization in a metallic chain.

An artificial quantum structure consisting of a single CO molecule adsorbed on a Au chain was assembled by manipulating single Au atoms on NiAl(110) at 12 K with a scanning tunneling microscope (STM). The CO disrupts the delocalization of electron density waves in the chain, as it suppresses the coupling between neighboring chain atoms. The possibility to specify the CO position on the chain allows controlled modification of the electronic properties in a quantum system. Inelastic electron tunneling spectroscopy with the STM provides vibrational characterization of the adsorbed CO.

Influence of a heterogeneous Al2O3 surface on the electronic properties of single Pd atoms.

Electronic properties of single Pd atoms, deposited on Al(2)O(3)/NiAl(110), have been characterized by scanning tunneling spectroscopy at 12 K. The spectra reveal distinct conductivity resonances, assigned to discrete electronic levels in the atom. The energy position of the resonances reflects adsorption properties of Pd atoms on different sites of the oxide support. Mapping the spatial extent of conductivity channels in the Pd atoms yields the symmetry of the underlying electronic states. The results demonstrate the effect of a heterogeneous oxide surface on the electronic structure of adsorbed metal atoms.

Atomic structure of antiphase domain boundaries of a thin Al2O3 film on NiAl(110).

Line defects of a thin alumina film on NiAl(110) have been studied on the atomic level with scanning tunneling microscopy at 4 K. While boundaries between two reflection domains do not expose a characteristic structure, antiphase domain boundaries are well ordered. The latter boundaries result from the insertion of a row of O atoms, as atomically resolved images of the topmost oxygen layer show. The insertion occurs only in two of the three characteristic directions of the quasihexagonal O lattice. Depending on the direction, either straight or zigzagged boundaries form. An atomic characterization of line defects on the oxide surface is a first step to correlate their topographic structure and chemical activity.

Electronic density oscillations in gold atomic chains assembled atom by atom.

Linear Au chains two to 20 atoms long were constructed on a NiAl(110) surface via the manipulation of single atoms with a scanning tunneling microscope. Differential conductance (dI/dV) images of these chains reveal one-dimensional electronic density oscillations at energies 1.0 to 2.5 eV above the Fermi energy. The origin of this delocalized electronic structure is traced to the existence of an electronic resonance measured on single, isolated Au atoms. Variations in the wavelength in dI/dV images of an eleven-atom chain taken at different energies revealed an effective electronic mass of 0.4+/-0.1 times the mass of a free-electron.

Development of one-dimensional band structure in artificial gold chains.

The ability of a scanning tunneling microscope to manipulate single atoms is used to build well-defined gold chains on NiAl(110). The electronic properties of the one-dimensional chains are dominated by an unoccupied electron band, gradually developing from a single atomic orbital present in a gold atom. Spatially resolved conductance measurements along a 20-atom chain provide the dispersion relation, effective mass, and density of states of the free electron-like band. These experiments demonstrate a strategy for probing the interrelation between geometric structure, elemental composition, and electronic properties in metallic nanostructures.

Photon emission spectroscopy of individual oxide-supported silver clusters in a scanning tunneling microscope

Photon emission spectra of individual alumina-supported silver clusters have been measured for the first time. The light emission stimulated by electron injection from the tip of a scanning tunneling microscope can be assigned to the (1,0) mode of the Mie-plasmon resonance in small silver particles. As cluster sizes decrease, the resonance position shifts to higher energies and the linewidth increases. In the size range examined (1.5-12 nm), intrinsic size effects are discussed as possible origins for the observed size dependence of the Mie resonance.