A study of local density of states of atom clusters on the W(110) surface

The kinetic energy distributions of field desorbed He ions from tungsten clusters of one to five atoms on a W(110) surface are measured using a high resolution pulsed-laser time-of-flight atom probe. The He field ion energy distribution from the single W adatom shows an extra peak-like feature centered at 2.7 eV above the Fermi level. It has a full width at half maximum (fwhm) of 2.3 eV. The data from two tungsten adatoms separated by two lattice constants have nearly the same feature with the extra peak located at 2.5 eV above the Fermi level. These peaks arise from resonance tunneling with the adatom local density of states (LDOS). The He ion energy distribution of a tungsten dimer has an extra peak centered at 1.5 eV above the Fermi level. The fwhm is about 4 eV. The spectra from four and five tungsten adatom clusters show only one peak each, similar to that from a flat plane.     

Diffusion of hydrogen into the (110) plane of a tungsten field emitter at low temperatures

Experiments taking advantage of the very small dissociative sticking coefficient of H₂ on the (110) plane of a tungsten field emitter show that diffusion into, rather than on the plane limits entry of H into the plane at low temperatures, i.e. diffusion on the plane is much faster than entry into the plane. The barrier to entry of H is nearly independent of temperature from 130 to 27 K and is independent of applied field. Over the limited range experimentally accessible tunneling diffusion on the (110) plane is independent of field emission current.     

Bonding of gold nanoclusters to oxygen vacancies on rutile TiO2(110)

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 TiO2(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 TiO2(110) system involving vacancy-cluster complex diffusion is presented.     

The work function of perfect W(110) planes: Fowler-Nordheim studies

Fowler-Nordheim measurements have been carried out on tungsten specimens field evaporated at low temperature in an endeavor to resolve conflicting values of the work function for the W(110) plane. Interpretation of such measurements has in the past been difficult, because of unknown contributions from plane edges and patch fields. These contributions have been isolated by taking advantage of the unusually low reactivity of W(110) toward molecular hydrogen. Observations on perfect W(110) planes yield a work function of 5.47 eV.     

Diffusion of nickel on the (110) region of a tungsten field emitter

The diffusion of nickel atoms on the (110) plane of a thermally cleaned tungsten crystal has been investigated by a field emission technique. The measurements were carried out for low nickel coverage and substrate temperatures T390 K when the nickel atoms escape from the (110) plane to its surroundings. the value of the activation energy obtained, Q=0.96 eV, is discussed taking into account the conditions under which diffusion occurs.     

Work function in field emission — the (110) plane of tungsten

Field emission for the (110) plane of field evaporated and thermally annealed tungsten has been restudied with particular reference to the significance of interpretation of the work function. It is concluded that the results obtained in field emission are consistent with results from non-field emission methods where the important variable of the local field is adequately considered. Possible contribution of other factors to measurement of the clean surface work function is also discussed.     

Measurement of the dipole moments of single 5-d transition metal adatoms on the tungsten (110) plane

The surface-induced dipole moments of single 5-d transition metal atoms adsorbed on the W(110) plane have been experimentally determined from field emission work function changes. The resulting values are found to be small (less than 0.5 Debye) and exhibit a monotonically decreasing behavior across the series from Ta to Pt. This same type of d-electron dependence is also found for the relative sizes of the field emission current jumps associated with adsorption of the various atoms on the W(110) plane. The data are interpreted using the concept of charge transfer, and a qualitative discussion of the adatom polarizabilities and desorption fields in relation to this model is given.     

Study of C60/Au(110)-p(6x5) reconstruction from In-plane X-Ray diffraction data

Fullerene molecules absorbed on the highly anisotropic Au(110)-p(1x2) surface induce an ordered p(6x5) superstructure that has been solved by applying the 2D "direct methods" difference sum function to the surface x-ray diffraction data set. We found that the C (60)-gold interface is structurally much more complex than the one previously suggested by scanning tunneling microscopy data [J. K. Gimzewski, S. Modesti, and R. R. Schlittler, Phys. Rev. Lett. 72, 1036 (1994)]. Indeed a large fraction of Au surface atoms are displaced from their original positions producing microscopic pits that may accommodate the fullerene molecules.     

The epitaxy of gold on (110) tungsten studied by leed

Growth of gold condensed on the (110) plane of tungsten has been studied using LEED and AES. Three ordered surface structures were observed when condensation takes place at or above 700 K, and no detectable order is seen below this temperature. Structure 1 is developed as the coverage approaches one monolayer and has gold atoms held in the W(110) array with a resultant 2% reduction in gold atom diameter. The second gold layer adopts the Au(111) structure with $\text{Au}\text{[1}\text{2}\text{1]}$ rotated by 2.5° from $\text{W}\text{[1}\text{1}\text{0]}$ and the first gold layer may also be constrained to adopt this structure. Deposition of more gold produces three dimensional crystallites with Au(111)∥W(110) which are double-positioned with their 121 directions parallel to the 121 directions of tungsten. Addition of half a monolayer of oxygen before condensation, completely prevents formation of structures 1 and 2. Instead, at coverages of 3 or more monolayers, three dimensional crystallites develop with Au(111) ∥ W(110) and $\text{Au}\text{[1}\text{2}\text{1] ∥}\text{W}\text{[1}\text{1}\text{0]}$. This behaviour is compared with the reported behaviour of copper and silver on W(110).     

Charging of metal atoms on ultrathin MgO/Mo(100) films

The chemical activity of supported metal nanoclusters is enhanced by electronic charging induced by the interaction with surface defects. We use density functional theory plane wave calculations to show that charging of metal atoms with high electron affinity like Au is possible also in the absence of defects by atom deposition on ultrathin MgO films (1 to 3 layers) grown on Mo(100). The Au 6s level falls below the Fermi level of Mo, leading to electron transfer from Mo to Au by direct tunneling through the insulating MgO film. The effect is not observed for Pd, whose 5s empty level falls just above the Fermi level of Mo, or for thicker MgO films.     

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.     

Interaction of cesium and oxygen on W(110): I. Cesium adsorption on oxygenated and oxidized W(110)

Cesium adsorption on oxygenated and oxidized W(110) is studied by Auger electron spectroscopy, LEED, thermal desorption and work function measurements. For oxygen coverages up to 1.5 × 10¹⁵ cm^?2 (oxygenated surface), preadsorbed oxygen lowers the cesiated work function minimum, the lowest (～1 eV) being obtained on a two-dimensional oxide structure with 1.4 × 10¹⁵ oxygen atoms per cm². Thermal desorption spectra of neutral cesium show that the oxygen adlayer increases the cesium desorption energy in the limit of small cesium coverages, by the same amount as it increases the substrate work function. Cesium adsorption destroys the p(2 × 1) and p(2 × 2) oxygen structures, but the 2D-oxide structure is left nearly unchanged. Beyond 1.5 × 10¹⁵ cm^?2 (oxidized surface), the work function minimum rises very rapidly with the oxygen coverage, as tungsten oxides begin to form. On bulk tungsten oxide layers, cesium appears to diffuse into the oxide, possibly forming a cesium tungsten bronze, characterized by a new desorption state. The thermal stability of the 2D-oxide structure on W(110) and the facetting of less dense tungsten planes suggest a way to achieve stable low work functions of interest in thermionic energy conversion applications.     

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.     

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.     

Image charge effect on the light emission of rutile TiO_2(110) induced by a scanning tunneling microscope

The plasmon-enhanced light emission of rutile TiO_2(110) surface has been investigated by a low-temperature scanning tunneling microscope(STM). We found that the photon emission arises from the inelastic electron tunneling between the STM tip and the conduction band or defect states of TiO_2(110). In contrast to the Au(111) surface, the maximum photon energy as a function of the bias voltage clearly deviates from the linear scaling behavior, suggesting the non-negligible effect of the STM tip on the band structure of TiO_2. By performing differential conductance( dI/dV) measurements, it was revealed that such a deviation is not related to the tip-induced band bending, but is attributed to the image charge effect of the metal tip, which significantly shifts the band edges of the TiO_2(110) towards the Femi level(E_F) during the tunneling process. This work not only sheds new lights onto the understanding of plasmon-enhanced light emission of semiconductor surfaces, but also opens up a new avenue for engineering the plasmon-mediated interfacial charge transfer in molecular and semiconducting materials.     

Adsorption of silver on (001), (011) and (111) oriented tungsten single crystals

Work function changes caused by silver adsorption were measured on (001), (011) and (111) tungsten single crystal planes using electron beam method. The decrease of the work function was observed on all planes studied in the small coverage region. The result evidences that the increase previously observed for the average work function in this coverage region can not be connected with negative dipole formation with silver atoms.     

Layer-by-layer analysis of charge state distribution of field evaporated ions from the W(011) plane

A charge state distribution of the field evaporated ions is layer-by-layer analyzed in a W(011) plane by using an atom-probe field ion microscope. A specimen temperature is varied from ～ 20 to ～ 250 K. The results indicate that at any temperature, the surface tungsten atoms field evaporate as triply and quadruply ions from the (011) plane, and the quadruply charged ions are always detected during the final collapse of the plane. They are also discussed on the basis of the post-ionization model.     

Charging of metal adatoms on ultrathin oxide films: Au and Pd on FeO/Pt(111)

We present a combined experimental (STM/scanning tunneling spectroscopy) and theoretical (density functional theory) study on the deposition of Au and Pd metal atoms on FeO/Pt(111) ultrathin films. We show that while the Pd atoms are only slightly oxidized, the Au atoms form positive ions upon deposition, at variance to a charge transfer into the Au atoms as observed for MgO/Ag(100). The modulation of the adsorption properties within the surface Moiré cell and the charging induce the formation a self-assembled array of gold adatoms on FeO/Pt(111), whereas Pd atoms are randomly distributed.     

Adsorption of single alkali atoms on tungsten using field emission and field desorption

Single adatom events have been detected and the binding energies and dipole moments of single sodium, potassium and cesium adatoms have been measured on the (110), (112) and (111) planes of tungsten in a probe hole field emission microscope. The Fowler-Nordheim formulation has been modified to include averaging effects implicit in probe hole measurements on single adsorbed atoms. The work function changes and consequent dipole moments associated with single alkali adatoms on a tungsten surface have been estimated. A model has been proposed to obtain binding energies from measurements of the field required to desorb a single alkali adatom. The results are in good agreement with current theoretical predictions for the adsorption of single alkali atoms on metals.     

Adsorption of molecular nitrogen by the W(110) plane

Characteristics of the adsorption of nitrogen on the (110) plane of tungsten were determined by thermal desorption and work function measurements. The low temperature γ-N₂ state desorbs with first order kinetics and an activation energy of 6 kcal mole^?1. The absence of isotope mixing between ¹⁴N₂ and ¹⁵N₂ demonstrates γ-N₂ is adsorbed molecularly. Monolayer coverage shows a decrease of 0.19 eV in work function. A Topping model plot indicates the layer is immobile at 123 K.