Band structure of Au layers on the Ru(0001) and graphene/Ru(0001) surfaces

The electronic structures of Au monolayers on the Ru(0001) and graphene-coated Ru(0001) surfaces have been calculated by DFT method using the supercell (repeated-slab) approach. The local densities of states (LDOS) and band structures of the monolayer and bilayer Au films adsorbed on the graphene/Ru(0001) and those of free hexagonal Au layers are found to be very similar. This result indicates that the monolayer graphene almost completely screens the Au layers from the Ru(0001) substrate surface, so that electronic properties of Au films adsorbed on graphene are determined predominantly by the electronic structure of the Au adlayers, essentially independent on the electronic structure of the substrate surface.     

Surface strain versus substrate interaction in heteroepitaxial metal layers: Pt on Ru(0001)

By studying the adsorption of CO on up to 30 layers of Pt deposited on Ru(0001) the influence of surface strain on the adsorption energy has been disentangled from the residual chemical interaction with the substrate. While the electronic influence of the substrate has largely vanished for three Pt layers, the effect of surface strain due to the 2.5% lattice mismatch of Pt and Ru remains initially intact and is only gradually released for n>/=5 Pt layers. Electronic structure calculations confirm the experimental observations, in particular, the dramatic decrease of the CO adsorption energy on a single Pt layer which is caused by the strong Pt-Ru interlayer coupling.     

Graphene on Ru(0001): contact formation and chemical reactivity on the atomic scale

Graphene on Ru(0001) is contacted with Au tips of a cryogenic scanning tunneling microscope. The formation and conductance of single-atom contacts vary within the moiré unit cell. Density functional calculations reveal that elastic distortions of the graphene lattice occur at contact due to a selectively enhanced chemical reactivity of C atoms at hollow sites of Ru(0001). Concomitant quantum transport calculations indicate that the graphene-Ru distance determines the conductance variations.     

OPCOT在Ru(0001)表面上的紫外光电子能谱研究

采用紫外光电子能谱,研究了新型有机发光材料八芳基环辛四烯(OPCOT)在金属Ru(0001)表面上的电子结构,以及它们之间的相互作用.位于费米能级以下43,69,93和114eV处的4个谱峰分别来自于OPCOT材料中苯环的πCC,σCC,σCH和σHH轨道,位于30eV处的谱峰反映了8个苯环聚合后具有π轨道特性的C—C键.OPCOT材料的价带顶位于费米能级以下25eV处,OPCOT材料在Ru(0001)表面上的功函数为395eV.150℃以下,OPCOT材料可以在Ru(0001)表面稳定存在.随温度的升高,OPCOT材料主要以脱附的形式减少 关键词： 八芳基环辛四烯 光电子能谱 价电子结构 脱附     

Formation of graphene on Ru（0001） surface

We report on the formation of a graphene monolayer on a Ru(0001) surface by annealing the Ru(0001) crystal. The samples are characterized by scanning tunnelling microscopy (STM) and Auger electron spectroscopy (AES). STM images show that the Moir\'{e} pattern is caused by the graphene layer mismatched with the underlying Ru(0001) surface and has an $N\times N$ superlattice. It is further found that the graphene monolayer on a Ru(0001) surface is very stable at high temperatures. Our results provide a simple and convenient method to produce a graphene monolayer on the Ru(0001) surface, which is used as a template for fabricating functional nanostructures needed in future nano devices and catalysis.     

Phase transitions in physisorbed films on cadmium (0001): comparison with graphite (0001)

Physical adsorption of simple molecules has been studied experimentally on cadmium (0001). Adsorption isotherms of Kr and CF₄ at 77.3 K show a first-order phase transition in the first layer, characteristic of adsorption on uniform substrates.

The nature of the phase transition on cadmium (0001) in the first layer is investigated for Kr and CF₄ by a thermodynamic approach in comparison with results obtained earlier on graphite (0001).

From the comparison between the two uniform substrates, we show that (1) cadmium (0001) has a less attractive force field than graphite (0001); and (2) like graphite (0001), cadmium (0001) is a very uniform surface suitable for studying two-dimensional phases according to the Gibbsian formulation.     

Ge在Ru(0001)表面上生长及其性质研究

报道Ge在Ru(0001)表面上生长以及相互作用行为的扫描隧道显微镜（STM）和x射线光电子能谱（XPS）研究. STM的实验结果表明Ge在Ru(0001)表面的生长呈典型的Stranski_Krastanov生长模式，Ge的覆盖度小于单原子层时呈层状生长，而从第二层开始呈岛状生长. XPS测量显示衬底Ru(0001)与Ge的相互作用很弱. Ru(0001)表面的Ru 3d5/2和Ru 3d3/2芯态结合能分别处于2798和2840 eV. 随着Ge的生长，到Ge层的厚度为20个单原子层，衬底Ru 3d芯态结合能减小了约02 eV，而Ge 3d芯态结合能从Ge低覆盖度时的289 eV增加到了290 eV，其相对位移约为01 eV. 关键词： Ge Ru表面 生长 相互作用     

Adsorbate band dispersions for C on Ru(0001)

We have studied carbon-induced two-dimensional energy bands on Ru(0001) using angleresolved photoelectron spectroscopy and have compared them with ab initio calculations. We find a nearly parabolic band (bottom at E_F ?9.8 eV at k_∥ = 0, effective mass ～ 1.5 m_e) which we assign to the C 2p_z valence states of a graphitic carbon overlayer. Compared to graphite, these states are bound more tightly by 2.3 eV.     

Theory of H bonding and vibration on Ru(0001)

Self-consistent linear augmented plane wave total energy calculations have been carried out for a 1 × 1 H monolayer on the Ru(0001) surface. They give an HRu layer separation of 1.06 Å and vibrational frequencies of 140 meV for the symmetric stretch mode and 100 meV for the asymmetric stretch mode. These compare very well with measured values of 138 and 105 meV, but reverse the original mode assignments which appeared to be consistent with a nearest neighbor harmonic force model. Our results are qualitatively inconsistent with such a model. Another simple model, the effective medium theory, also fails to account for our results in the absence of significant covalent correction terms.     

Multidimensional effects on dissociation of N2 on Ru(0001)

The applicability of the Born-Oppenheimer approximation to molecule-metal surface reactions is presently a topic of intense debate. We have performed classical trajectory calculations on a prototype activated dissociation reaction, of N2 on Ru(0001), using a potential energy surface based on density functional theory. The computed reaction probabilities are in good agreement with molecular beam experiments. Comparison to previous calculations shows that the rotation of N2 and its motion along the surface affect the reactivity of N2 much more than nonadiabatic effects.     

Ferromagnetic hcp chromium in Cr/Ru(0001) superlattices

We report the first observation of a weak ferromagnetic state of Cr in Cr/Ru(0001) superlattices, based on magnetic hysteresis and corroborated by x-ray magnetic circular dichroism at the CrL(2,3) edges. In situ reflection high-energy electron diffraction, x-ray diffraction, and Cr K-edge polarized x-ray absorption investigations have shown that the Cr layers thinner than 8 angstroms adopt a slightly distorted hcp structure, accompanied by a large atomic volume expansion of up to 14% compared to the bcc packing volume. The expanded hcp structure clearly induces the observed ferromagnetism, in agreement with theory.     

Formation of and phase transitions in electrodeposited tellurium atomic layers on Au(1 1 1)

Detailed studies of the structures formed by the electrodeposition of atomic layers of Te on Au(1 1 1) surfaces from aqueous solutions were performed using in situ scanning tunneling microscopy (STM), as well as by UHV-EC techniques such as low energy electron diffraction and Auger electron spectroscopy. There are two features in the voltammetry that may be considered underpotential deposition (UPD). However, from the voltammetry, it is clear that the deposition process is kinetically slow, and from this study it appears that several atomic layer structures are actually formed at overpotentials. Prior to deposition, a surface excess of a tellurium oxide species coats the surface. This layer is then converted to a Au(1 1 1)(√3×√3)R30°–Te structure with an array of domain walls, at 1/3 ML. The initial structure appears to have a symmetric array of walls, resulting in a (13×13) periodicity, which then converts to a less symmetric structure where the domain walls form rhombi, with a larger periodicity. During the second UPD feature, the coverage increases, forming a (√7×√13) unit cell at 0.36 ML and then a (3×3) at 0.44 ML. Commensurate with the formation of these higher coverage structures, a roughening transition takes place, where the surface becomes pitted, resulting in about 40% of the surface being covered with single atom deep pits. This process appears to be related to the pits formed in the surfaces of self-assembled monolayers (SAM) of thiols on Au surfaces, and layers of Se and S on Au surfaces. Several theories have been suggested to account for these pits. The model that appears to best explain the pits is based on shrinking of the size of the underlying Au atoms, reconstructing the underlying Au. There also appears to be a high coverage structure, near 0.9 ML, that forms at potentials near where the (3×3) forms, but only by holding the potential for an extended period of time. Subsequent dissolution of this high coverage structure produces domains of disordered Te atoms, which gradually decrease in coverage until the (3×3) is again formed at 0.44 ML.     

A molecular beam study of the adsorption dynamics of CO on Ru(0001), Cu(111) and a pseudomorphic Cu monolayer on Ru(0001)

We have investigated the sticking coefficient of CO on Ru(0001), a pseudomorphic Cu monolayer on Ru(0001), and a fully relaxed Cu(111) multilayer as function of kinetic energy, surface coverage, and surface temperature. At a low kinetic energy of 0.09 eV, the initial sticking coefficients, S₀, on these surfaces are determined to be 0.92, 0.96 and 0.87, respectively. In all cases, a decrease of S₀ with increasing beam energy was observed, yielding values of 0.58, 0.14 and 0.07, respectively, at a kinetic energy of 2.0 eV. For all three surfaces the coverage dependent sticking coefficients, S(Θ), display very characteristic behavior at low kinetic energies: S(Θ) remains more or less constant up to coverages close to saturation, indicative of precursor adsorption kinetics. However, characteristic minima at intermediate coverages are observed, which are correlated to the formation of well ordered adsorbate phases. For high kinetic energies we observe a transition towards a linear decrease of S(Θ) for Ru(0001). In contrast, for the pseudomorphic Cu monolayer and for Cu(111) we find an increase in the sticking coefficients at low coverages, followed by a decrease close to saturation. This behavior is attributed to adsorbate assisted sticking, that is, to a higher sticking coefficient on adsorbate covered regions than on the bare surface. The comparison between the pseudomorphic monolayer and Cu(111) reveals that the CO bond strength to the former is larger by 40%. The initial sticking coefficients for both surfaces are very similar at low kinetic energies; at high kinetic energies, S₀ for the pseudomorphic Cu monolayer is, however, larger by a factor of two.     

Site-selective adsorption of xenon on a stepped Ru(0001) surface

The adsorption of xenon has been studied with UV photoemission (UPS), flash desorption (TDS) and work function measurements on differently conditioned Ru(0001) surfaces at 100 K and at pressures up to 3 × 10^?5 Torr. Low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) served to ascertain the surface perfectness. On a perfect Ru(0001) surface only one Xe adsorption state is observed, which is characterized by$\text{Xe}\text{5}\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$,$\text{1}\text{2}$ electron binding energies of 5.40 and 6.65 eV, an adsorption energy of E_ad≈ 5 kcal/mole and dipole moment of μ'_T ≈ 0.25 D. On a stepped-kinked Ru(0001) surface, the terrace-width, the step-height and step-orientation of which are well characterized with LEED, however, two coexisting xenon adsorption states are distinguishable by an unprecedented separation in$\text{Xe}\text{5}\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$,$\text{1}\text{2}$ electron binding energies of 800 meV, by their different UPS intensities and line shapes, by their difference in adsorption energy ofΔE_ad ≈ 3 kcal/mole and finally by their strongly deviating dipole moments of μ_S = 1.0 D and μ_T = 0.34 D. The two xenon states (which are also observed on a slightly sputtered surface) are identified as corresponding to xenon atoms being adsorbed at step and terrace sites, respectively. Their relative concentrations as deduced from the UPS intensities quantitatively correlate with the abundance of step and terrace sites of the ideal TLK surface structure model as derived from LEED. Furthermore, ledge-sites and kink-sites are distinguishable via E_ad. The E_ad heterogeneity on the stepped-kinked Ru(0001) surface is interpreted in terms of different coordination and/or different charge-transfer-bonding at the various surface sites. The enormous increase in Xe 5p electron binding energy of 0.8 eV for Xe atoms at step sites is interpreted as a pure surface dipole potential shift. —The observed effects suggest selective xenon adsorption as a tool for local surface structure determination.     

Growth and structure of crystalline silica sheet on Ru(0001)

Thin SiO? films were grown on a Ru(0001) single crystal and studied by photoelectron spectroscopy, infrared spectroscopy and scanning probe microscopy. The experimental results in combination with density functional theory calculations provide compelling evidence for the formation of crystalline, double-layer sheet silica weakly bound to a metal substrate.     

Graphene on Ru(0001): a 25 x 25 supercell

The structure of a single layer of graphene on Ru(0001) has been studied using surface x-ray diffraction. A surprising superstructure containing 1250 carbon atoms has been determined, whereby 25 x 25 graphene unit cells lie on 23 x 23 unit cells of Ru. Each supercell contains 2 x 2 crystallographically inequivalent subcells caused by corrugation. Strong intensity oscillations in the superstructure rods demonstrate that the Ru substrate is also significantly corrugated down to several monolayers and that the bonding between graphene and Ru is strong and cannot be caused by van der Waals bonds. Charge transfer from the Ru substrate to the graphene expands and weakens the C-C bonds, which helps accommodate the in-plane tensile stress. The elucidation of this superstructure provides important information in the potential application of graphene as a template for nanocluster arrays.