X-ray photoelectron diffraction study of discommensurate Cu/Ge(111)

We have studied the atomic structure in the interior of discommensurate domains of the Cu/Ge(111) surface by using scanned-angle X-ray photoelectron diffraction (XPED). XPED patterns of Cu 2p_3/2 intensity provided direct information on the local structure in the vicinity of photoelectron emitters. It has been found that a certain number of Cu atoms are embedded within the surface layer, so that the surface has some structural similarity with the discommensurate Cu/Si(111)-‘5×5’.     

X-ray diffraction analysis of the silicon (111) surface during alkaline etching

We present a surface X-ray diffraction determination of the silicon (111)-liquid interface structure during alkaline etching. Preparation of an atomically smooth surface was realized by an in-situ procedure using an aqueous NH₄F solution devoid of oxygen. Using diluted aqueous potassium hydroxide (KOH) and ammonium fluoride (NH₄F) etchant, we have observed that the crystal surface is hydrogen terminated and is not reconstructed at open circuit potential. In addition, a partial liquid ordering of two water layers on top of the crystal surface was found, indicating a weak interaction with the hydrophobic, hydrogen terminated surface. We have followed in-situ the development of the oxide layer by a birth and spread mechanism during anodic passivation of the silicon surface.     

Static investigation of the small clusters on the Cu(111) and Au(111) surfaces

The diffusion properties of small clusters Ag_n, Cu_n, and Au_n on the Cu(111) and Au(111) surfaces were studied using the molecular statics (MS) in order to understand the atomistic processes underlying the motion. In this work, the atomic interaction potential is modeled by a semi-empirical Embedded Atom Method (EAM), while the drag method is used to determine the static activation energy for each diffusion path. The presented results indicate that the dimer can diffuse on the (111) surface via the zig-zag and concerted motion mechanisms. The trimer diffuses according to the concerted motion mechanism. For the tetramer diffusion, the mechanism that consumes the least amount of energy is the zig-zag motion, in which only two atoms are needed for the diffusion process at one time. This allows finding a static activation energy smaller compared to the trimer diffusion.     

Iodine adlayer structures on Au(111) as discerned by atomic-resolution scanning tunnelling microscopy: relation to iodide electrochemical adsorption

Coverage-dependent adlayer structures of iodine on Au(111) in air or organic solvents obtained by using a high-precision “beetle” — type scanning tunnelling microscope are reported in comparison with those obtained under potential control in aqueous electrochemical environments. The well-known (√3 × √3)R30° structure (Θ_I = 0.33) was only observed at the electrochemical interface at low potentials. Instead, two higher coverage adlattices are evident from the present STM images. The first comprises a (5 × √3) structure (Θ_I = 0.40), with a pair of iodine rows compressed by 20% in the R30° substrate direction. The second high-coverage phase (Θ_I ≈ 0.44) consists of a hexagonal iodine overlayer compressed and rotated a few degrees from the R30° direction, giving rise to a long-range (~ 20 Å) corrugation in the STM image. The virtues of quantitative atomic-resolution STM for deducing such complex adiayer structures are pointed out.     

X-ray photoelectron diffraction investigation of the (2 × 2) overlayers of Cs and K on Cu(111)

X-ray photoelectron diffraction measurements have been made for the Cu(111)(2 × 2)-Cs and Cu(111)(2 × 2)-K systems to explore the possibility of using substrate emission XPD for the elucidation of adsorbate-substrate registry in these cases of strongly scattering adsorbate atoms and anticipated atop adsorption sites. Although scattering effects within the substrate, for sub-surface emitters, clearly complicate the interpretation of the data, simple symmetry arguments do give substantial support to the identification of atop adsorption sites in both systems.     

Comparative study of the electronic structure of the ordered and disordered Cu3Au (100) and Cu3Au (110) surfaces

The influence of structural changes on the electronic structure has been investigated by a comparison of the angle-integrated valence and core level photoelectron spectra of ordered and disordered Cu₃Au(100) and (110) surfaces. The total width of the Au 5d and Cu 3d bands does not change with the ordering state or surface orientation. The spectra for the (100) surface are compared with selfconsistent calculations and good agreement is found, for the ordered state, however with a 0.6 eV correction of the calculated Fermi level position. We observe three Au 5d derived bands at 5.1, 6.0 and 6.9 eV, in contrast to previous experimental findings. Our results indicate the existence of shortrange order above the critical temperature.     

STM study of Au(111) growth on mica

Gold films were thermally evaporated in vacuum on heated cleaved mica substrates. The substrate temperature was immediately decreased after finishing the growth. Samples prepared at various temperatures from 580 K to 890 K and evaporation rates smaller than 1 nm/s were studied by a scanning tunneling microscope (STM) under ambient conditions. Structure and defects of Au(111) surfaces were investigated and discussed with respect to growth conditions.     

Surface density oscillations in disordered binary alloys: X-ray reflectivity study of Cu3Au(001)

3 Au(001) surface using Synchrotron radiation and show that the intensity distribution along the specular rod exhibits the same features as in the case of liquid metals which has been discussed in recent literature. The results are discussed within the framework of the distorted wave Born approximation which allows a straightforward easy-to-apply scheme to analyze such reflectivity data in the entire -range including the total external reflection regime. The data analysis gives a direct evidence for an oscillating average density profile which is analoguous to the socalled surface layering at liquid surfaces. The experimental values for the thermal roughness indicate that surface roughness is suppressed in the ordered phase and allowed to softly grow with temperature above the bulk order-disorder phase transition. The presented experimental and theoretical study of X-ray reflectivity from binary alloys demonstrates the potential of this technique for the study of surface roughening, surface layering and surface segregation phenomena at solid and liquid surfaces. Received: 14 August 1996/Accepted: 7 October 1996     

Cyclic voltammetry and near edge X-ray absorption fine structure spectroscopy at the Ag L3-edge on electrochemical halogenation of Ag layers on Au(111)

One to three layers of Ag grown on a Au(111) electrode were studied by cyclic voltammetry in chloride and bromide solutions and by ex-situ near-edge X-ray absorption fine structure spectroscopy at the Ag L3-edge (Ag L3-NEXAFS). The one and two layers obtained by underpotential deposition exhibited reduced intensity at the absorption edge in the Ag L3-NEXAFS spectra, which suggests the gain of d-electrons in these layers. The cyclic voltammograms and the Ag L3-NEXAFS spectra indicate that the second and third layers of Ag halogenated at positive potentials, whereas the first layer remained in metallic form.     

Cu原子掺杂调控三聚氰胺在Au(111)表面自组装结构

The doping effect of Cu on the self-assembly film of melamine on an Au(111) surface has been investigated with scanning tunneling microscopy (STM). The evaporated Cu adatoms occupy the positions underneath the amino groups and change the hydrogen bonding pattern between the melamine molecules. Accordingly, the self-assembly structure has changed stepwise from a well-defined honeycomb into a track-like and then a triangular structure depending on the amount of Cu adatoms. The interaction between Cu adatom and melamine is moderate thus the Cu adatoms can be released upon mild heating to around 100℃. These findings are different from previous observations of either the coordination assembly or the physically trapped metal adatoms.     

Au(111)表面甲基联二苯丙硫醇盐单层膜的原子结构

利用第一性原理研究了甲基联二苯丙硫醇盐(BP3S)单体、虚拟Au表面BP3S的分子链和单层膜及BP3S/Au(111)吸附系统的原子结构.计算表明BP3S单体呈对称结构,两苯环夹角为35°±10°.首先BP3S单体在虚拟Au(111)表面自组装成稳定的单一分子链.然后在虚拟Au(111)表面,分子链错位排列自组装成两种稳定的单层膜.在虚拟Au(111)-(3~(1/2)×7~(1/2))和Au(111)-(3~(1/2)×13~(1/2))表面,分子链与虚拟表面夹角分别为60°和30°.最后把两种稳定的单层膜吸附在Au(111)表面的四个吸附位,计算表明只有桥位和顶位稳定,且桥位的吸附能比顶位的吸附能低.比较吸附前后BP3S单层膜的结构变化,可知其变化不大,这说明吸附系统的结构参数主要取决于单层膜内的相互作用,衬底对其的影响不大.     

X-ray diffraction study of Si(111)√3 × √3-Au

The structure of the Si(111)√3 × √3-Au surface has been investigated by the use of the surface X-ray diffraction with synchrotron radiation. The structure perpendicular to the surface was determined with respect to the Si bulk crystal. The results of least-squares analysis indicate that Au atoms are adsorbed on the Si substrate in which the first Si layer is missing. The heights of the Au layer and the Si second layer with respect to the intact Si third layer were estimated to be 3.09 ± 0.03 rA and 2.16 ± 0.10 rA, respectively. A possible model of the surface structure is proposed.     

STM study of selenium adsorption on Au(111) surface

Adsorption of chalcogen atoms on metal surfaces has attracted increasing interest for both the fundamental research and industrial applications. Here, we report a systematic study of selenium(Se) adsorption on Au(111) at varies substrate temperatures by scanning tunneling microscopy. At room temperature, small Se clusters are randomly dispersed on the surface. Increasing the temperature up to 200℃, a well-ordered lattice of Se molecules consisting of 8 Se atoms in ringlike structure is formed. Further increasing the temperature to 250℃ gives rise to the formation of Se monolayer with Au(111)-3~(1/2) ×3~(1/2) lattices superimposed with a quasi-hexagonal lattice. Desorption of Se atoms rather than the reaction between the Se atoms and the Au substrate occurs if further increasing the temperature. The ordered structures of selenium monolayers could serve as templates for self-assemblies and our findings in this work might provide insightful guild for the epitaxial growth of the two-dimensional transition metal dichalcogenides.     

Surface interactions of Au(I) cyclo-trimer with Au(111) and Al(111) surfaces: A computational study

A plane-wave density functional theory (DFT) study on surface interactions of a cyclo-[Au(μ-Pz)]₃ monolayer (denoted as T), Pz = pyrazolate, with Au(111) and Al(111) surfaces (denoted as M′) has been performed. Structural and electronic properties at the M′–T interfaces are determined from individually optimized structures of M′, T and M′–T. Results show that the gold pyrazolate trimer (T) binds more strongly on the Au(111) surface than on Al(111). Charge redistribution has been observed at both M′–T interfaces, where charge is “pushed” back towards the Au(111) surface from the trimer monolayer in Au(111)–T system, while the opposite happens in the Al(111)–T system where the charge is being pushed toward the trimer monolayer from the Al(111) surface. Considerable changes to the work function of Au(111) and Al(111) surfaces upon the trimer adsorption which arise from monolayer vacuum level shifts and dipole formation at the interfaces are calculated. The interaction between cyclo-[Au(μ-Pz)]₃ with metal surfaces causes band broadening of the gold pyrazolate trimer in M′–T systems. The present study aids better understanding of the role of intermolecular interactions, bond dipoles, energy-level alignment and electronic coupling at the interface of metal electrodes and organometallic semiconductor to help design metal–organic field effect transistors (MOFETs) and other organometallic electronic devices.