Diffusion of tungsten clusters on tungsten (110) surface

Using molecular dynamics simulation and modified analytic embedded-atom method, we have investigated the self-diffusion of clusters on a tungsten (110) surface. As compared to the linear-chain configuration, the close-packed islands for tungsten clusters containing more than nine adatoms have been predicted to be more stable with the relatively lower binding energies. The migration energies show an interesting and oscillating behavior with increasing cluster size. The tetramer, hexamer and octamer have obviously higher migration energies than the others. The different atomic configurations and diffusion mechanisms have been determined during the diffusion processes. It is clear that the dimer-shearing mechanism occurs inside the hexamer, while it occurs at the periphery of heptamer. The successive hopping mechanism of individual atom is of critical importance in the migration of the clusters containing five or fewer adatoms. In addition, the diffusion of a cluster with nine adatoms is achieved through the changes of the cluster shape.     

Femtosecond laser nanostructuring of a tungsten surface

Tungsten surface nanostructuring is performed using the radiation of a Yb:KGW femtosecond laser in air and in liquid nitrogen. Arrays of linear nanostructures and nanorods of tungsten and tungsten nitride are fabricated on the surfaces of targets. Possible scenarios of transforming surface nanostructures of one type into another and the formation of network-like relief are considered.     

Europium adsorption on a tungsten surface with various degrees of oxidation

The kinetics of europium adsorption on a W(100) face with various degrees of oxidation were studied by thermal desorption and Auger electron spectroscopy. The spectrum of Eu atoms desorbed thermally from the W(100) face consists of three successively filling desorption phases whose desorption activation energy decreases from 3 to 2.1 eV with an increase in the surface coverage. The thermodesorption spectrum of Eu atoms from the W(100) face coated with a monatomic oxygen film contains five successively forming desorption phases, with the desorption activation energy increasing to 4 eV for the high-temperature phase. The oxidized W is reduced by europium, and the desorption of the W oxides is replaced by that of EuO. After a monolayer film has formed, the Eu film adsorbed on tungsten starts to grow in the form of three-dimensional crystallites. As the degree of W oxidation increases, the Eu film becomes less nonuniform, until a solid Eu film starts to grow on bulk W oxides and completely screens the tungsten Auger signal.     

Site competition in surface segregation

Observations have been made, by Auger electron spectroscopy, of site competition between tin, sulphur and calcium co-segregating to the free surface of otherwise pure iron in the temperature range 600–800°C. The correlations between the segregation levels of the species are explained for sub-monolayer and multilayer tin adsorption, in terms of a simple model. In the absence of calcium the reduction in available adsorption sites for tin is a function of both the tin and sulphur coverages. With calcium present the formation of surface precipitates of calcium compounds is observed. Excellent agreement is obtained between the observed interrelated behaviour of the segregants and the predictions of the model, over a wide range of experimental conditions. A similar behaviour is expected, and must be allowed for, in all studies of segregation thermodynamics and kinetics of surfaces and interfaces exhibiting more than two components.     

The scattering of hydrogen from a cesiated tungsten surface

The reflection of protons from a partially cesiated tungsten surface is studied in the energy domain between 100 and 2000 eV and in the angular domain between 75° and 85° with respect to the surface normal. The study is performed by measuring the angular and energy distribution of the scattered negative ions. The reflection can take place along two paths. One path is reflection from the cesium surface layer, the other one is reflection from the tungsten substrate. A dependence of the final charge state on the path is observed. It is inferred that this phenomenon is due to incomplete neutralization of the protons scattered from the cesium layer. The energy loss of the reflected ions cannot be accounted for by using only the binary collision model. Also the electronic stopping of the atoms by the metal electrons is shown to be an important energy loss mechanism. Total conversion measurements of H⁺ to H^- combined with the measurements of the negatively charged fraction of the scattered particles, as reported in the proceeding paper, yield the particle reflection coefficient as a function of the angle of incidence. These reflection coefficients show that for angles of incidence less than 75° already more than 50% of the particles do not reflect from the surface. Total conversion efficiency measurements with H^- ions as primary ions show that the influence of the initial charge state on the total conversion is very small.     

Electron-induced Ti-rich surface segregation on SrTiO3 nanoparticles

Atomic surface structures of nanoparticles are of interest in catalysis and other fields. Aberration-corrected HREM facilitates direct imaging of the surfaces of nanoparticles. A remaining concern of surface imaging arises from beam damage. It is important to identify the intrinsic surface structures and the ones created by electron beam irradiation in TEM. In this study, we performed aberration-corrected HREM and EELS to demonstrate that TiO and bcc type Ti islands form due to intense electron irradiation. The formation of Ti-rich islands is in agreement with previous high temperature annealing experiments on the surfaces of SrTiO₃ single crystals.     

Scanning tunneling microscopy study of thermal-diffusion-assisted self-organization on a tungsten crystal surface

The initial stage of faceting on the tungsten (110) vicinal plane during annealing in conditions close to thermodynamic equilibrium or favoring thermal-diffusion-assisted mass transport is studied by scanning tunneling microscopy. In the first case, the initial nanofacets (the traces left after electrochemical polishing) arrayed at a repeat frequency q=(3–4)·10⁵ cm⁻¹ merge to form microsteps with clearly pronounced faceting. In the second, the nanofacet pattern is overlaid by a wavelike, sinusoidally corrugated structure. The corrugation frequency is in a good agreement with the theoretical estimate obtained within the surface mass-transport model. Fiz. Tverd. Tela (St. Petersburg) 39, 968–971 (June 1997)     

Diffusion of rhodium layers on the stepped surface of a tungsten micro-crystal

We have investigated the spreading of rhodium at coverages of 0.25, 0.5, 1, 2 and 3 ML over the curved surface of a field emitter tip using field electron microscopy. We have found that the activation energy of spreading as well as the prefactor for the diffusivity depend strongly on the thickness of the layer diffusing, due to a change in interactions in the adsorbate-substrate system. The derived average activation energy for spreading first decreases from E_dif = 1.32 eV/atom at Θ = 0.25 ML to E_dif = 0.71 eV at Θ ≈ 2 ML and than rises again to E_dif = 1.20 eV at Θ ≈ 3 ML. The prefactor for the diffusivity D₀ also decreases with increasing coverage from 0.5 to 1 ML, and stays almost constant for multilayer diffusion in a range of few orders of magnitude lower than for single atom diffusion. We register typical spreading behavior with a sharp moving boundary in the (0 1 1)-(0 0 1) zone of the tip and an unusual picture of diffusion in the (0 1 1)-(1 1 2) region of the tip. In the second region diffusion proceeds without a sharp boundary, independent of the thickness of the moving layer. We think that such an unusual picture can be caused by the change in composition of the second and next layers of adsorbing material due to the early stage of faceting observed in this region of the tip at higher temperature. The results are compared with data for diffusion of individual Rh atoms and small clusters; to understand the observed diffusion we propose taking account of the atomic surface structure of the substrate, modified by strong interactions of the Rh adsorbate with the W micro-crystal surface.     

A Spin—Orbit-induced surface resonance on tungsten

A three-band model tight binding Greens function formalism is used to calculate the electronic structure of the (100) surface of tungsten in the vicinity of the Fermi level. The results exhibit a large surface resonance, which provides an explanation for a surface-sensitive peak observed in recent field- and photoemission experiments.     

Study of a surface critical phenomenon associated with surface segregation in Cu---Ag alloys

This paper presents a modified regular solution formalism for surface segregation in substitutional alloys which distinguishes between bond energies at the surface and in the bulk of a solid solution. The differences between surface and bulk energies are ascribed to strain energy effects associated with misfitting solutes. Experimental measurements of surface composition on (111) surfaces of Cu---Ag alloys dilute in Ag are reported and show the existence of a surface phase transition, which manifests itself as an abrupt surface composition change at temperatures below 788 K. Similar measurements on (100) surfaces show no comparable critical phenomena down to temperatures as low as 523 K, indicating a strong anisotropic behavior of the surface phase transition. The data are compared with the model to obtain model-based estimates of the surface critical temperatures and the surface regular solution constants for both surface orientations.     

Carbon interaction with rhodium surface: Adsorption, dissolution, segregation, growth of graphene layers

Carbon interaction with rhodium (111) surface has been studied by Auger electron spectroscopy in ultrahigh vacuum within a broad temperature interval of 300-1800 K. It has been shown that the graphene monolayer remains stable on the metal surface within a relatively narrow temperature interval of ～50 K below the carbonization point, and when heated above this point, graphene breaks up gradually by transferring first to the island state, and after that, to chemisorbed carbon “gas.“ As the temperature decreases, a stable multilayer graphite film forms.     

Kinetics of surface segregation in alloys

The kinetics of surface segregation in ordering alloys are studied with the help of a multilayer model in slabs of different thicknesses. The time evolution of the concentrations of atomic layers perpendicular to the (100) planes of an AB-type BCC ordering alloy (CoFe) are calculated. As a result of the competition between the surface segregation of A atoms and ordering in the bulk, a metastable configuration with two anti-phase boundaries (APB) inside the slab, with odd numbers of layers, was obtained if we started from an ordered initial state with B atoms on the free surfaces (B-termination). The effect of the temperature was also investigated for a slab with 41 layers and from the calculation of the free energies of the metastable and stable states it was shown that the metastable state can exist below T₁ = 0.95T_c, where T_c is the critical temperature of the order-disorder transition in bulk. It was obtained that T₁ decreases with decreasing thickness of the slab, while the difference of free energies of the metastable and stable states slightly increases. The effect of the slab thickness is a typical size effect: the time necessary to reach the steady state decreases with decreasing number of layers.     

Electron spectroscopy studies of surface In-Ag alloy formation on the tungsten surface

XPS and UPS investigations of ultrathin films of In/Ag and Ag/In, deposited onto the W(1 1 0) surface in the ultrahigh vacuum conditions have been performed. Indium and silver films were formed by “in-situ” evaporation on W(1 1 0) substrate. XPS and UPS studies have been performed by means of SCIENTA ESCA200 instrument. The changes of In4d core-level and Ag4d valence band emissions with increasing Ag and In coverage were monitored to observe the energy shift and shape of the spin-orbit doublet of In4d and Ag4d lines in the Ag/In/W and In/Ag/W systems. UPS (HeI and HeII) measurements were supported by XPS AlK_α measurements of In3d and W4p levels, as well as by investigations of Ag3d levels. XPS and UPS data allowed to evaluate the coverage and make conclusions concerning intermixing and surface alloying in the In/Ag/W and Ag/In/W systems. W(1 1 0) substrate can be cleaned after each deposition by thermal desorption and no alloying in the In/W and Ag/W systems is observed.     

Athermal luminescence of a tungsten surface irradiated with laser pulses

An investigation of athermal luminescence triggered at a tungsten surface by thermal deformations produced by laser pulses is reported. The spectral composition and time dependence of individual spectral components of the luminescence are investigated. Oscillations of the luminescence intensity are observed, and they are interpreted as a definite sequence of emergence of dislocations at the surface. Fiz. Tverd. Tela (St. Petersburg) 41, 1538–1542 (September 1999)     

Long-range effect of ion irradiation on Cu surface segregation in a CuNi system

Ni films were deposited on one side of single crystal Cu substrate discs of 1.0 and 1.5 mm thickness. These discs were irradiated on the Cu side with argon ions. Evidence for enhanced Cu segregation at the Ni surface was found for both thicknesses. This effect decreased with increasing distance between the diffusion zone and the irradiated surface. Slow positron annihilation results indicate lower vacancy-like defects at the subsurface layer after Ar irradiation on the other surface of Cu disks. Such long-range effect is here interpreted on the basis of a particular type of mobile discrete breather called quodon.     

Properties of ultrathin layers of palladium on a tungsten {110} surface

The growth mode, structure, thermal stability and work function of Pd films up to several monolayers in thickness on a W{110} surface are studied. At room temperature, layer-by-layer growth occurs, at least up to 4 layers. Layers in excess of the first monolayer are metastable and agglomerate at substrate temperatures above 700 K. Pd-W and Pd-Pd interactions within the first layer are investigated with thermal desorption techniques. The binding energy for single Pd atoms to the substrate is 3.6 eV/atom, the energy per lateral bond between nearest Pd atoms is about 0.05–0.12 eV/bond dependent upon range of interaction. These data are based on a phase transition occurring during the desorption of the first layer. The desorption of Pd in excess of the first monolayer is similar to the sublimation of bulk Pd.