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Adsorbed sulfur has been investigated on the Ag(110) surface at two different coverages, 0.02 and 0.25 monolayers. At the lower coverage, only sulfur adatoms are present. At the higher coverage, there are additional bright features which we identify as linear, independent AgS2 complexes. This identification is based upon density functional theory (DFT) and its comparison with experimental observations including bias dependence and separation between complexes. DFT also predicts the absence of AgS2 complexes at low coverage, and the development of AgS2 complexes around a coverage of 0.25 monolayers of sulfur, as is experimentally observed. To our knowledge, this is the first example of an isolated linear sulfur-metal-sulfur complex.

Recent experiments indicate that metal intercalation is a very effective method to manipulate the graphene-adatom interaction and control metal nanostructure formation on graphene. A key question is mass transport, i.e., how atoms deposited uniformly on graphene populate different areas depending on the local intercalation. Using first-principles calculations, we show that partially intercalated graphene, with a mixture of intercalated and pristine areas, can induce an alternating electric field because of the spatial variations in electron doping, and thus, an oscillatory electrostatic potential. This alternating field can change normal stochastic adatom diffusion to biased diffusion, leading to selective mass transport and consequent nucleation, on either the intercalated or pristine areas, depending on the charge state of the adatoms.

Pre-adsorbed sulfur controls nucleation of Ag islands on Ag(111), at coverages above a very small critical value. Sulfur can exert opposite effects: it accelerates mass transfer of Ag to steps and hence inhibits nucleation under some conditions, but it impedes mass transfer and hence enhances nucleation under others. The effect depends upon sulfur coverage and temperature. The inhibition or acceleration of mass transfer correlates with the existence or absence of a semi-static, ordered arrangement of Ag3S3 clusters.

We show that friction anisotropy is an intrinsic property of the atomic structure of Al–Ni–Co decagonal quasicrystals and not only of clean and well-ordered surfaces that can be prepared in vacuum [J.Y. Park et al., Science309, 1354 (2005)]. Friction anisotropy is manifested in both nanometer-size contacts obtained with sharp atomic force microscope tips and macroscopic contacts produced in pin-on-disk tribometers. We show that the friction anisotropy, which is not observed when an amorphous oxide film covers the surface, is recovered when the film is removed due to wear. Equally important is the loss of the friction anisotropy when the quasicrystalline order is destroyed due to cumulative wear. These results reveal the intimate connection between the mechanical properties of these materials and their peculiar atomic structure.

The tribological properties of adhesion and friction between 10-fold Al–Ni–Co decagonal quasicrystals and conductive W2C and TiN coated tips were studied in ultrahigh vacuum (UHV) with an atomic force microscope. Contacts between the tip and clean quasicrystals are dominated by strong adhesion forces, which result in irreversible deformations and material transfer. The irreversible adhesion was suppressed following an oxygen exposure of 10 Langmuir, which also reduced the adhesion force by a factor of two. An additional 2/3 reduction in adhesion force occurred after several 100 Langmuir exposure. A much larger decrease (by a factor 10) occurred by air-oxidation. The friction force decreased also with oxygen exposure although not as dramatically. A linear decrease by a factor two, was observed between the clean surface and the surface exposed to 200 Langmuir of oxygen. After that the friction force remained constant. Air-oxidation reduced friction by roughly another factor of two. In contrast with the clean

We have used x-ray photoelectron spectroscopy and Auger electron spectroscopy to examine the characteristics of oxides on two types of quasicrystalline Al–Cu–Fe samples. One type was formed by consolidation of powders, resulting in multiple grains with random surface orientations. The other was a single grain, oriented to expose a fivefold surface. Both were oxidized to saturation in a variety of environments at room temperature. We measured the elemental constituents that oxidized, the extent of oxygen-induced Al segregation, and the depth of the oxide. Under the conditions of our experiments, there was little, if any, significant difference between the two types of samples. Hence, surface orientation and bulk microstructure played little or no role on the final state of the oxide under these conditions.

There is currently great interest in the surface reactivity of quasicrystalline materials, generated largely by a model, proposed by Janot, for the bulk atomic and electronic structure. This {open_quotes}hierarchical cluster{close_quotes} model predicts that quasicrystal surfaces should be intrinsically inert and rough, and is being used to rationalize their practical properties such as low friction coefficients and oxidation resistances Surface structure and surface preparation may play a role in the applicability of this model. In this talk, we examine these factors and present experimental measurements of the surface reactivity of Al-based icosahedral alloys. We make some comparisons with surface reactivity of pure, crystalline aluminum, and with that of crystalline alloys which are similar in composition to the quasicrystal.

Strategies are described for modeling the kinetics of non-equilibrium film growth during deposition of metals on quasicrystalline substrates. We review previous atomistic-level lattice-gas modeling and Kinetic Monte Carlo simulation for pseudomorphic (or commensurate) submonolayer growth based on a “disordered or irregular bond-network” (DBN) of neighboring adsorption sites. We describe extensions to treat strain effects and multilayer growth, and discuss a type of commensurate-incommensurate transition expected around 2-3 layers. We also describe a coarse-grained “step dynamics” modeling which tracks the dynamics of island edges in each layer rather than individual atoms. Step dynamics models can also include key aspects of the physics such as layer-dependent energetics, including quantum size effects, and strain effects.

A surface science experiment has been developed that can be used in both the undergraduate and graduate curriculum. Students study the mechanism of carbon monoxide oxidation using a platinum foil catalyst, and they also get hands-on experience with ultrahigh vacuum equipment. Using temperature programmed desorption, students study the desorption of carbon monoxide and oxygen from platinum foil in vacuum. The study allows students to determine that the Langmuir-Hinshelwood reaction mechanism operates in this catalytic system.

Based on X-ray photoelectron spectroscopy, Gd5Ge4(010) does not show evidence of surface segregation. Scanning tunneling microscopy reveals two types of terraces which alternate laterally on the surface. From the step heights, these two surface terminations are assigned as dense, Gd-pure layers in the bulk structure. There is evidence of reconstruction on one type of terrace.

STM studies reveal that irregular non-equilibrium two-dimensional Al islands form during deposition of Al on NiAl(110) at 300 K. These structures reflect the multiple adsorption sites and diffusion paths available for Al adatoms on the binary alloy surface, as well as the details of inhibited edge diffusion and detachment-attachment kinetics of Al adatoms for numerous distinct step edge configurations. We attempt to capture these features by multi-site lattice-gas modeling incorporating DFT energetics for adatoms both at adsorption sites and transition states. This formulation enables description and elucidation of the observed island growth shapes.

Electrons in a quasicrystal cannot flow as freely as they do in normal metallic crystals because of its nonperiodic structure. It turns out that in a decagonal quasicrystal the electronic behaviour reflects the tenfold symmetry of the crystal structure. Patricia A. Thiel and Jean Marie Dubois

We present experimental results on the structure of Ag thin films grown on high-symmetry surfaces of both quasicrystals and approximants. For coverages above ten monolayers, Ag form fcc nanocrystals with (111) plane parallel to the surface plane. Depending on the substrate surface symmetry, the Ag nanocrystals exist in one, two or five different orientations, rotated by a multiple of 2π/30. The orientation relationship between crystalline films and substrates appears to be determined by the following principles: high atomic density rows of the adsorbate are aligned along high atomic density rows of the substrate.

Near-square islands form during sub-monolayer homoepitaxial growth on metal (100) surfaces. Diffusion of these islands after deposition leads to collision of island pairs, typically corner-to-corner creating dumbbell-shaped clusters. Subsequent coalescence (or sintering) recovers a near-square equilibrium shape. This process is mediated by periphery diffusion (PD) and its study can provide detailed insight into the underlying dynamic processes and energetics. Atomistic modeling reveals that the size scaling of the characteristic relaxation time, τ, depends on the detailed energy barriers of various hopping processes that contribute to PD. Simulations without an extra kink or corner rounding barrier for PD reveals τ ∼ L4, while behavior approaching τ ∼ L3 is observed with a significant extra kink rounding barrier for PD. The latter is consistent with experimental observations for Ag/Ag(100) at 300 K.

Laser vaporization of an icosahedral Al-Pd-Mn sample with detection by time-of-flight mass spectrometry is used to probe metal clusters made from the alloy. After sample vaporization, clusters form by gas aggregation and may contain several to hundreds of atoms. Multi-photon ionization/fragmentation of these clusters yields mass spectra showing many cluster sizes with enhanced intensity. Clusters are identified at masses near those of pseudo- Mackay and Bergman clusters; however, these clusters do not appear special relative to neighboring clusters. Results of this study and its relationship to the proposed cluster structures in quasicrystalline materials are discussed.

An experimental comparison has been made between the properties of the surfaces of an Al70Pd21Mn9 quasicrystal and its Al48Pd42Mn10 approximant. The Al70Pd21Mn9 sample was a single grain icosahedral quasicrystal cut to expose its five-fold symmetric (000001) surface. The approximant was polycrystalline β-phase Al48Pd42Mn10, which has a CsCl-type cubic structure. Surfaces of both were prepared under ultra-high vacuum (UHV) conditions and then used for comparative measurements of their frictional properties and oxidation rates. Both materials are oxidized by reaction with O2 to form a thin film of aluminum oxide that ultimately passivates their surfaces. The interesting difference between the two is that the rate of oxidation of the approximant is significantly higher than that of the quasicrystal in spite of the fact that the bulk Al concentration of the approximant is lower than that of the quasicrystal. Friction measurements were made under UHV conditions between pairs of quasicrystals and pairs of approximants whose surfaces were either clean or oxidized to varying degrees. The friction between pairs of the approximant surfaces is significantly higher than that measured between the quasicrystal surfaces under all conditions of surface oxidation.

Energy-angle distributions of low-energy inert-gas ions scattered from surfaces provide information about surface composition and structure. We have measured energy spectra of He+ scattered from an Al71Pd20Mn9 quasicrystal, which was oriented perpendicular to the 5-fold axis, along various azimuthal directions. Strong scattering signals are seen from Al and Pd, but only a weak Mn signal is observed. From measurements made of He+ at an oblique angle of incidence scattered in the forward direction, we observe a 72° periodicity in the azimuthal dependence of the scattering signal intensity from Al surface atoms. The effect arises from shadowing effects involving neighboring surface atoms and provides direct evidence that Al surface atoms exist in a local environment with 5-fold symmetry. In addition, measuring the variation of the signal intensity with incidence angle provides information about neighboring atom distances, which compare favorably with a model of the quasicrystal surface derived from the bulk structure.

We have used thermal desorption spectroscopy to carry out a comparative study of potassium adsorption on Al(111) and on the fivefold Al-Pd-Mn surface. Potassium adsorption on the quasicrystal was found to be different than on Al(111). The potassium monolayer desorbed from fivefold Al-Pd-Mn at lower temperatures than from Al(111). Potassium is known to form a dense monolayer on Al(111), with an ideal coverage of 0.33, but for the monolayer on fivefold Al Pd Mn we find that the saturation coverage is only one twelfth.

We model the growth of Ag films deposited on Ag(100) below 140K. Our recent Variable-Temperature Scanning Tunneling Microscopy (VTSTM) studies reveal “smooth growth” from 120-140K, consistent with earlier diffraction studies. However, we also find rougher growth for lower temperatures. This unexpected behavior is modeled by describing the deposition dynamics using a “restricted downward funneling” model, wherein deposited atoms get caught on the sides of steep nanoprotrusions (which are prevalent below 120K), rather than always funneling down to lower four-fold hollow adsorption sites. At OK, where no thermal diffusion processes are operative, this leads to the formation of overhangs and internal defects (or voids). Above 40K, low barrier interlayer diffusion processes become operative, producing the observed smooth growth by 120K. We also discuss how the apparent film morphology mapped out by the STM tip “smears” features of the actual film morphology (which are small at low temperature), and also can lead to underestimation of the roughness.

The complete atomic distribution of a binary natural quasicrystal has been achieved by complementing X-ray diffraction patterns with the structure of closely related crystals. The result represents an essential starting point to find the atomic structure of more complex quasicrystals.

We have investigated formation of oxides on quasicrystalline and crystalline alloy surfaces of similar composition, in different oxidizing environments. This includes a comparison between a quaternary orthorhombic approximate of Al-Cu-Fe-Cr quasicrystal and the ternary Al-Cu-Fe quasicrystalline and crystalline phases. We noted that each sample showed the following common trends: preferential oxidation of the Al, enrichment in the concentration of Al present at the surface upon oxidation, water concentration is directly related to oxide thickness, and the oxide thickness displays a strong correlation with the bulk concentration of Al in the sample.

We report the electrochemical potentials at which localized pitting and repassivation occur on icosahedral Al-Cu-Fe, and on a series of related alloys and elemental metals. The electrochemistry occurs in a buffered NaCI solution, pH 8.4. Under these conditions, pitting and repassivation appear to be controlled mainly by the chemical composition of the alloy, although the quasicrystalline phase displays an anomalous resistance to repassivation. Corrosion of this phase proceeds by dissolution of Al and Fe, leaving behind pits which are Cu-enriched.

An Al-Pd-Mn cubic alloy having a bulk chemical composition somewhat analogous to that of the icosahedral Al-Pd-Mn quasicrystal is studied. Our goal is to compare the surface structure and properties of the cubic alloy with those of the quasicrystalline alloy. In this paper, we report the first observations for the (110) surface of the cubic alloy using (primarily) low energy electron diffraction (LEED). The surface is prepared by sputtering and annealing in ultrahigh vacuum (UHV). In addition to the substrate LEED pattern, at least three superstructures evolve sequentially with annealing temperature.

Scanning tunneling microscopy has shown that large, two-dimensional Ag clusters undergo observable diffusion on Ag(100). The variation of the diffusion coefficient with cluster size in the range studied, 100 to 540 atoms per cluster, indicates that two-dimensional evaporation-condensation is the main mechanism of cluster diffusion. The experimental data consistently show evidence for a backward-correlation in the cluster motion. The meaning and origin of this correlation is discussed.

We report a surface science study of fluorinated and hydrogenated ethers adsorbed at a metal surface. Fluorinated ethers bond less strongly to ruthenium surfaces than the hydrogenated analogs, both for atomically-smooth and atomically-rough surfaces. For the hydrogenated ethers, 0.03 to 0.17 monolayers undergo decomposition, while fluorinated ethers do not decompose significantly.