Interplay between atomic and mesoscopic order on gold vicinal surfaces

Self-organization on Au(1,1,1) vicinal surfaces provides a unique opportunity to study the interplay between atomic and mesoscopic order. First, experimental results demonstrate the different interactions between steps and surface reconstruction on Au(1,1,1) vicinal surfaces. Depending on the step atomic structure, lines of discommensurations are found to be either parallel or perpendicular to the step edges. This leads to a complete understanding of the mesoscopic self-organization on theses surfaces, which drastically depends on the step structure. This points out the crucial role played by the edge energy cost which can monitor the faceting periodicity in a wide range of values.     

Theory of semiconductor surfaces

Three kinds of recent theories of the atomic and electronic structure of semiconductor surfaces are relevant to experiment. Self-consistent calculations have provided a firm basis for understanding covalent bonding at the surface. Realistic tight-binding models can study larger unit cells which commonly occur on reconstructed surfaces. Thermochernical analysis explains the atomic arrangements obtained by annealing clean covalent surfaces.     

C2H2在金刚石（001）-（2×1）重构面上吸附的分子动力学模拟

利用Brenner半经验多体相互作用势和分子动力学模拟方法，研究了乙块（C₂H₂）分子在金刚石（001）-（2×1）重构表面上的碰撞动力学过程与化学吸附构型的关系.观察到C₂H₂在金刚石表面的6种吸附结构.约95％的吸附呈C₂H₂与表面形成两个σ单键的形式.讨论了轰击能量、入射位置及金刚石表面原子的空间位形对各种吸附构型形成的影响.还给出了化学吸附过程的分子快照，并讨论了C₂H₂分子与表面的能量交换关系. 关键词：     

硅晶体表面石墨烯褶皱形貌的分子动力学模拟研究

本文利用分子动力学的方法和模拟退火技术从原子尺度分析研究了Si (100), Si (111)和Si (211)表面单原子层石墨烯的褶皱形貌及其演化特点. 研究表明, 分别置于Si晶体的三种不同原子表面的石墨烯都展现出原子尺度的褶皱形貌. 石墨烯与Si晶体表面原子的晶格失配是引起石墨烯褶皱的主要原因. 研究发现, Si晶体表面石墨烯的褶皱形貌强烈的依赖于退火温度. 石墨烯的褶皱形貌还将直接影响其在Si晶体表面的吸附稳定性. 这些研究结果有助于人们认识基于Si晶体衬底的石墨烯的结构形貌及其稳定性, 为石墨烯的进一步应用提供理论参考.     

Surface structure of cubic diamond nanowires

Presented are results of our ab initio study of the surface reconstruction and relaxation of (1 0 0) surfaces on diamond nanowires. We have used a density function theory within the generalized-gradient approximation using the Vienna ab initio simulation package, to consider dehydrogenated and hydrogenated surfaces. Edges of nanowires offer a new challenge in the determination of surface structure. We have applied the methodology for stepped diamond (1 0 0) surfaces to this problem, and consider it useful in describing diamond nanowire edges to first approximation. We have found that dimer lengths and atomic layer depths of the C(1 0 0)(2 × 1) and C(1 0 0)(2 × 1):H nanowire surfaces differ slightly from those of bulk diamond and nanodiamond surfaces. The aim of this study is provide a better understanding of the effects of nano-scale surfaces on the stability of diamond nanostructures.     

Structure and energetics changes during hydrogenation of 4H-SiC{0001} surfaces: a DFT study

The changes in the atomic and electronic structure of Si- and C-terminated hexagonal SiC{0001} surfaces resulting from on-surface and subsurface hydrogen adsorption have been studied within the density functional theory framework. Hydrogen coverages ranging from a submonolayer to one monolayer were considered. Our results show that a monolayer of adsorbed H almost completely suppresses the relaxation of the SiC surface atomic layers. On both terminations H binds strongly to the surface and the binding is about 2?eV stronger in on-surface sites than subsurface. Hydrogen binding to the C-terminated surface varies very little with coverage and is distinctly stronger than to the Si-terminated surface.     

Atomic structures of silicon and metal surfaces; pulsed-laser tof atom-probe and field ion microscopy

The atomic structure of a solid surface can be imaged with the field ion microscope and the chemical species of surface atoms can be identified by the time-of-flight atom-probe. By combining a pulsed-laser technique to field ion microscopy, atomic processes in surface reconstruction and growth of thin films can be studied with a resolution of 2.5 Å, and in time steps of a few nanoseconds. The mass resolution and material applicability of a pulsed-laser time-of-flight atom-probe are greatly improved. Thus materials of poor conductivity such as high purity silicon can be analyzed with excellent mass resolution. It is also ionion energy analyzer with an accuracy and resolution of 2 parts per 100 000 and an ion reaction and dissociation time analyzer of 20 fs time resolution. Some recent studies with these techniques such as (1) surface reconstruction of Pt and Ir(001) and (110) surfaces, (2) observation of well ordered and atomically resolved images of pure silicon surfaces and surface reconstruction of many surfaces of silicon, and (3) formation of multiple charge cluster ions and dissociation of compound ions by atomic tunneling in an electric field etc., will be briefly described. We want to emphasize that recent studies of Si and metal surfaces are concerned with atomic structures of thermally equilibrated surfaces, and not with field evaporated surfaces as in earlier studies.     

Atomic reconstructions and electronic states on the GaAs(001) surface with the adsorbed Sb and Cs layers

In experiments on the adsorption and thermal desorption of Cs on GaAs(001) surfaces with various atomic reconstructions and compositions including those enriched in the cation (gallium) and in the anions (arsenic and antimony), the correlation in the behavior of the atomic structure and the surface electronic states, which determine the band bending, has been established. The cesium adsorption on the anion-rich surfaces results in both the similar disordering of the atomic structure and in the close dose dependences of the band bending, while the adsorption on the Ga-rich surface is ordered and results in the qualitatively different dose dependence, which has several maxima and minima. In the Cs desorption and the subsequent adsorption-desorption cycles, the stabilizing effect of Sb on the atomic structure and the electronic states of the Cs/Sb/GaAs(001) surface has been revealed.     

Hydrogen chemisorption on metal surfaces

The adsorption of H atoms on metal (jellium) surfaces has been investigated using linear response theory within the density functional formalism. The adsorbate is represented initially by a 1S orbital on the H atom, which perturbs the jellium surface and indirectly the adsorbate itself. The interaction energy curves, atomic binding energies, induced dipole moments, chemical shifts associated with the adsorbate, and vibrational excitation energies at the equilibrium internuclear separation have been calculated for a single H atom chemisorbed on metal surfaces. The sum of the atomic binding energy and the ionization potential of the H 1S level may be regarded as the initial state energy in the case of photoemission from the chemisorbed H. The rather satisfactory overall agreement between the theory and the experimental results for binding energies, vibrational excitation energies, and dipole moments suggests that this simple formalism could also have useful applications in more complicated chemisorbed systems.     

Angle resolved photoemission study of surface states on the Pt(997) vicinal surface

One-dimensional atomic chains can be synthesized on stepped surfaces and the electronic structure of the high vicinal surface plays an essential role in determining the physical properties of atomic chains grown on top of it. We have applied surface analysis techniques to study the surface of a Pt(997) single crystal. The STM image of the surface showed that the surface was uniform with a well defined distance between the terraces. Angle resolved photoemission spectroscopy (ARPES) was used to characterize the electronic states of the Pt(997) surface, and confinement of electrons with wave vector perpendicular to the step direction was observed.     

An atomic view of crystal growth

The ability to routinely observe individual metal atoms adsorbed on metal surfaces using field ion microscopy has made it possible to directly examine atomic events important in the growth of crystals from the vapor. On the atomically smooth (111) plane of iridium, there are now available observations of the binding sites for atoms and of condensation from the vapor, together with measurements of the diffusion of atoms over the surface, as well as studies of their subsequent incorporation at both ascending and descending steps. These results are briefly reviewed, revealing a picture generally more varied and interesting than envisioned in classical theories of crystal growth.     

Metallicity of atomic wires

The variety of atomic “dimensional” wires can now be synthesized on furrowed and stepped surfaces. These adlayers provide a variety of opportunities for systematically tailoring the surface properties. One of key issue is the metallicity of an atomic wire (even a “supported” atomic wire). Monte-Carlo simulations provide insight into the parameters of indirect interaction that are the basis for the formation of the atomic wires and their stability. In some cases, these results can be directly compared with density functional theory (DFT) calculations of energies of the lateral interactions between adsorbed atoms—one of the most transparent example of Sr/Mo(1 1 2) is presented here as well. It is the surface band structure calculations that provide insights on how metallicity in such surface structures might be altered.Surprisingly, like most of “metallic” wires on semiconductor surfaces, linear chains of alkaline earth on the furrowed transition metal surfaces, such as the Mo(1 1 2) surface, also do not exhibit strong metallic character but, rather, may be considered dielectric atomic chains. The adsorption bonds result in a loss in electron itinerancy, leading to greater valence electron localization in the adlayer in some cases. The localized character of the bands near the Fermi level, associated with the adlayer, is replaced by a metallic band structure when the lattice period of the adsorbed layer becomes incommensurate with the substrate periodicity along the furrows with increasing coverage of the adlayer. With changes in adlayer coverage, both theory and experiment indicate that the adsorbed layers can undergo a Wilson type nonmetal-to-metal transition.     

Erosion of polyimide modified by amorphous silica sol in the stream of oxygen plasma

Polymeric coatings derived from Kapton H polyimide, thermoplastic polyimide (PI), and a composite with amorphous silica sol (PI-SS) were irradiated in a magnetoplasma dynamic accelerator of oxygen plasma simulating the action of atomic oxygen (AO). The volumetric erosion coefficients of polymers were calculated, and the comparative analysis of the stability of coatings was performed. The changes in morphology of polymer surfaces before and after irradiation were studied by means of scanning electron microscopy. It was shown that the PI-SS composite has increased resistance to atomic oxygen. The composition of the PI-SS composite was found at which the particles of silica sol are uniformly dispersed over the polymer volume that explains a better resistance of PI-SS polymeric-inorganic compositions to the action of atomic oxygen. The lowest stability was registered for the coating based on Kapton H polyimide. The surfaces of all coatings after irradiation were found to possess a carpetlike morphology. Each polymer featured a number of distinctive peculiarities of the surface structure caused by the differences in the chemical structure of the polymides under investigation.     

Vibrations at surfaces

This special issue is dedicated to the phenomenon of vibrations at surfaces-a topic that was indispensible a couple of decades ago, since it was one of the few phenomena capable of revealing the nature of binding at solid surfaces. For clean surfaces, the frequencies of modes with characteristic displacement patterns revealed how surface geometry, as well as the nature of binding between atoms in the surface layers, could be different from that in the bulk solid. Dispersion of the surface phonons provided further measures of interatomic interactions. For chemisorbed molecules on surfaces, frequencies and dispersion of the vibrational modes were also critical for determining adsorption sites. In other words, vibrations at surfaces served as a reliable means of extracting information about surface structure, chemisorption and overlayer formation. Experimental techniques, such as electron energy loss spectroscopy and helium-atom-surface scattering, coupled with infra-red spectroscopy, were continually refined and their resolutions enhanced to capture subtleties in the dynamics of atoms and molecules at surfaces. Theoretical methods, whether based on empirical and semi-empirical interatomic potential or on ab initio electronic structure calculations, helped decipher experimental observations and provide deeper insights into the nature of the bond between atoms and molecules in regions of reduced symmetry, as encountered on solid surfaces. Vibrations at surfaces were thus an integral part of the set of phenomena that characterized surface science. Dedicated workshops and conferences were held to explore the variety of interesting and puzzling features revealed in experimental and theoretical investigations of surface vibrational modes and their dispersion. One such conference, Vibrations at Surfaces, first organized by Harald Ibach in Juelich in 1980, continues to this day. The 13th International Conference on Vibrations at Surfaces was held at the University of Central Florida, Orlando, in March 2010. Several speakers at this meeting were invited to contribute to the special section in this issue. As is clear from the articles in this special section, the phenomenon of vibrations at surfaces continues to be a dynamic field of investigation. In fact, there is a resurgence of effort because the insights provided by surface dynamics are still fundamental to the development of an understanding of the microscopic factors that control surface structure formation, diffusion, reaction and structural stability. Examination of dynamics at surfaces thus complements and supplements the wealth of information that is obtained from real-space techniques such as scanning tunneling microscopy. Vibrational dynamics is, of course, not limited to surfaces. Surfaces are important since they provide immediate deviation from the bulk. They display how lack of symmetry can lead to new structures, new local atomic environments and new types of dynamical modes. Nanoparticles, large molecules and nanostructures of all types, in all kinds of local environments, provide further examples of regions of reduced symmetry and coordination, and hence display characteristic vibrational modes. Given the tremendous advance in the synthesis of a variety of nanostructures whose functionalization would pave the way for nanotechnology, there is even greater need to engage in experimental and theoretical techniques that help extract their vibrational dynamics. Such knowledge would enable a more complete understanding and characterization of these nanoscale systems than would otherwise be the case. The papers presented here provide excellent examples of the kind of information that is revealed by vibrations at surfaces. Vibrations at surface contents Poisoning and non-poisoning oxygen on Cu(410)L Vattuone, V Venugopal, T Kravchuk, M Smerieri, L Savio and M Rocca Modifying protein adsorption by layers of glutathione pre-adsorbed on Au(111)Anne Vallée, Vincent Humblot, Christophe Méthivier, Paul Dumas and Claire-Marie Pradier Relating temperature dependence of atom scattering spectra to surface corrugationW W Hayes and J R Manson Effects of the commensurability and disorder on friction for the system Xe/CuA Franchini, V Bortolani, G Santoro and K Xheka Switching ability of nitro-spiropyran on Au(111): electronic structure changes as a sensitive probe during a ring-opening reactionChristopher Bronner, Gunnar Schulze, Katharina J Franke, José Ignacio Pascual and Petra Tegeder High-resolution phonon study of the Ag(100) surfaceK L Kostov, S Polzin and W Widdra On the interpretation of IETS spectra of a small organic molecule Karina Morgenstern.     

用X射线光电子能谱测定InP(100)清洁表面的原子浓度比

根据XPS的强度测量和作者先前确定的原子灵敏度因子,测定了InP(100)表面的In/P原子比。实验结果表明氩离子轰击有择优溅射作用,在1keV刻蚀能量下,In/P浓度比为2.2,随氩离子能量增加而单调上升。样品在超高真空中300℃附近退火30分钟后,表面In/P比降为1.2,接近于体内化学计量比的值。从XPS强度的角度关系和In3d_5/2结合能的化学位移中可以推测,离子轰击造成In—P化学键的破裂,在退火后又重新键合,使得表面成为有序结构,而最外层原子是富铟的。 关键词：     

UHV-HREM and diffraction of surfaces

Characterization of the structure of surfaces is very important in order to develop a fundamental understanding of the electronic, mechanical and chemical properties of a material. While transmission electron microscopy imaging (TEM) and diffraction (TED) techniques are capable of providing surface structural information at the atomic level, such data would be suspect if obtained under conventional vacuum conditions (10^-6–10^-8 Torr). Ultrahigh vacuum (UHV) conditions are imperative during both preparation and observation of clean surfaces/interfaces. Conventional TEM techniques are very powerful for UHV-TEM investigations; however, the marriage of surface science and conventional TEM to yield an UHV-TEM is a complex task. These complexities and some of the results obtained using UHV-TEM and UHV-TED techniques for surfaces i.e. solid-vacuum interfaces will be illustrated.     

Observation of Simplest Water Chains on Surface Stabilized by a Hydroxyl Group at One End

The key to fully understanding water-solid interfaces relies on the microscopic nature of hydrogen bond networks,including their atomic structures, interfacial interactions, and dynamic behaviors. Here, we report the observation of two types of simplest water chains on Au(111) surface which is expected unstable according to the rules of hydrogen network on noble metal surfaces. A common feature at the end of chain structures is revealed in high resolution scanning tunneling microscopy images. To explain the stability in observed hydrogen bond networks,we propose a structure model of the water chains terminated with a hydroxyl group. The model is consistent with detailed image analysis and molecular manipulation. The observation of simplest water chains suggests a new platform for exploring fundamental physics in hydrogen bond networks on surfaces.     

Adsorption on the surface of ionic crystals and the effect of applied electric field

Adsorption of molecules on an ideal surface of ionic crystals and the effect of an external uniform electric field on this process have been investigated using a model Hamiltonian, which takes account of the Coulomb interaction between electrons and atomic cores of the system under consideration, all valence orbitals of the admolecule, as well as their nonorthogonality to the crystal wavefunctions, the substrate band structure. The binding energy as a function of the adsorbate-to-substrate distance is calculated for H₂O and CO on NaCl and MgO (001) surfaces. The main attention is focused on the contributions of admolecule-substrate interaction of various types to the binding energy.     

Geometric and electronic structure of positively and negatively poled LiNbO3 (0 0 0 1) surfaces

The effect of ferroelectric poling direction on the structure and electronic properties of the LiNbO₃ (0 0 0 1) surface was characterized. Low energy and reflection high energy electron diffraction indicated that both the positively and negatively poled surfaces were (1 × 1) with no evidence of longer range periodic reconstructions. Low energy ion scattering spectra from both surfaces were dominated by scattering from oxygen atoms. X-ray and ultraviolet photoelectron spectra also showed little difference between the positively and negatively poled surfaces, with the exception of a high binding energy shoulder on the O 1s core level of the negative surface. Exposure of the surfaces to atomic hydrogen caused reduction of the surface Nb rather than an increase in intensity on the high binding energy side of the O 1s peak, indicating that the shoulder on the O 1s peak on the negative surface was not due to surface hydroxyl groups. Temperature programmed desorption measurements indicated that the nearly stoichiometric LiNbO₃ samples were susceptible to loss of Li₂O starting at temperatures as low as 500 K, independent of the poling direction. An adatom/vacancy model is proposed in which oxygen ad-anions accumulate on one side of the crystal while oxygen anion vacancies are created on the opposite surface. This model can explain the apparent oxygen termination of both surfaces and the observed (1 × 1) periodicity of the surfaces, and also effectively screens the thickness dependent electric field associated with the polar orientation of the crystal.     

Vibrational states of a cobalt dimer on the (111) and (001) copper surfaces

The results of calculations of the total (lateral and vertical) relaxation of the (001) and (111) copper surfaces in the presence of a small cluster of cobalt adatoms, local vibrational density of states and polarizations of these states are presented. The calculations were performed using the atomic interaction potentials in a tight binding approximation. An analysis of the results obtained showed that the presence of a cobalt dimer gives rise to modification of the vibrational states of the copper surface and generation of new modes localized both on the adatoms of the cluster and the surface atoms of the substrate. The revealed anisotropy of surface relaxation along [001] results in deformation of atomic bonding and splitting of the vibrational modes of the dimer. The lifetimes of the vibrational states of the dimer are found to be nearly equal for both surfaces under study, with a frequency shift being however observed. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp.73–78, December, 2008.