Electric current induced flow of liquid metals: Mechanism and substrate-surface effects

Long range, continuous flow of liquid metals occurs upon application of an electric current. Here, we report experimental results elucidating the mechanism of current-induced liquid metal flow, and its dependence on substrate surface condition. It is shown that the observed flow is diffusion-controlled, with the flow-rate depending linearly on applied current density, indicating that it is driven by electromigration. The effective charge number for liquid electromigration, Z*, of several pure metals, such as Al, Bi, Ga, Sn, and Pb, were deduced from the experimental results and were found to be close to the elemental valency. With the exception of liquid Pb, Z* for all liquid metals tested in this study were positive, indicating that: (i) electron wind contributes much less to Z* in liquid metals than in solids, and (ii) with a few exceptions, liquid metals generally flow in the direction of the electric current. On smooth substrates which are wetted well by the liquid metal, flow occurs in a thin, continuous stream. On rough surfaces which are poorly wetted, on the other hand, discrete beads of liquid form, with mass transport between adjacent beads occurring by surface diffusion on the substrate. A rationale for the role of substrate roughness in fostering this observed transition in flow mechanism is presented. (C) 2014 AIP Publishing LLC.

Temperature dependence of surface quantum dots grown under frequent growth interruption

We grow InGaAs quantum dot (QD) at low growth rate with 70 times insertion of growth interruption in MBE system. It is found that because of the extreme growth condition, QDs exhibit a thick wetting layer, large QD height value and special surface morphology which is attributed to the enhanced adatom surface diffusion and In-segregation effect. Temperature dependence of photoluminescence measurement from surface QD shows that this kind of QD has good thermal stability which is explained in terms of the presence of surface oxide. The special distribution of QD may also play a role in this thermal character. (c) 2006 Elsevier B.V. All rights reserved.

Effects of Cu-Wire Surface Fluctuations on Early Failures

Different chemical mechanical polishing （CMP） slurries are used to obtain single-damascene Cu-wires with different surface fluctuations as well as pre-existing surface-defects in wires with rougher surfaces. The presence of such pre-existing defects strongly increases the rate of early failures to almost 100%, reduces electromigration lifetime rapidly to the level of early failures, and changes the multimodal failure distribution into monomodal. The activation energy （0. 74±0.02eV） for the failure mechanism associated with these pre-existing defects confirms a dominant surface diffusion. It shows how a weakest link approximation analysis can he applied to a single wire by dividing the wire into relevant segments and assigning different failure mechanisms to the various segments. The analysis confirms that, although surface-defects are not the fastest early failure mechanism, the ten times higher surface-defectdensity in the rougher wires is responsible for the observed high early-failure rate and unreliable performance.

CHARACTERIZATION OF THE AU SURFACE-STRUCTURE OF AL-L-AU LIGHT-EMITTING TUNNEL-JUNCTIONS

Visible light is emitted from the Au-air interface of Al-I-Au thin-film tunnel junctions (deposited over a thin layer of CaF2 on glass) as a result of the decay of surface plasmon polaritons (SPPs). We show the surface topography of such a Au film and relate its large-scale features to the outcoupling of fast SPP's to photons. The absence of short-scale roughness features is explained by thier disappearance through surface diffusion. To confirm this a controlled sequence of 5-nm, 20-ms scanning tunneling microscope (STM) W tip crashes has been used to produce indentations 3 nm deep with a lateral dimension of 5-7 nm on a Au crystal in air at room temperature. Four sequences of indentations were drawn in the form of a square box. Right from the start, feature decay is observed and over a period of 2 h a succession of images shows that the structure disappears into the background as a result of surface diffusion. The surface diffusion constant is estimated to be 10(-18) cm2 s-1. The lack of light output via slow mode SPPs is an inevitable consequence of surface annealing.

Ab initio diffusional potential energy surface for CO chemisorption on Pd{110} at high coverage:Coupled translation and rotation

The ground state potential energy surface for CO chemisorption across Pd{110} has been calculated using density functional theory with gradient corrections at monolayer coverage. The most stable site corresponds well with the experimental adsorption heat, and it is found that the strength of binding to sites is in the following order: pseudo-short-bridge>atop>long-bridge>hollow. Pathways and transition states for CO surface diffusion, involving a correlation between translation and orientation, are proposed and discussed. (C) 1997 American Institute of Physics.

Surface evolution of amorphous nanocolumns of Fe–Ni grown by oblique angle deposition

The growth of Fe–Ni based amorphous nanocolumns has been studied using atomic force microscopy. The root mean square roughness of the film surface increased with the deposition time but showed a little change at higher deposition time. It was found that the separation between the nanostructures increased sharply during the initial stages of growth and the change was less pronounced at higher deposition time. During the initial stages of the column growth, a roughening process due to self shadowing is dominant and, as the deposition time increases, a smoothening mechanism takes place due to the surface diffusion of adatoms

Swift heavy ion induced surface and microstructural evolution in metallic glass thin films

Swift heavy ion induced changes in microstructure and surface morphology of vapor deposited Fe–Ni based metallic glass thin films have been investigated by using atomic force microscopy, X-ray diffraction and transmission electron microscopy. Ion beam irradiation was carried out at room temperature with 103 MeV Au9+ beam with fluences ranging from 3 1011 to 3 1013 ions/cm2. The atomic force microscopy images were subjected to power spectral density analysis and roughness analysis using an image analysis software. Clusters were found in the image of as-deposited samples, which indicates that the film growth is dominated by the island growth mode. As-deposited films were amorphous as evidenced from X-ray diffraction; however, high resolution transmission electron microscopy measurements revealed a short range atomic order in the samples with crystallites of size around 3 nm embedded in an amorphous matrix. X-ray diffraction pattern of the as-deposited films after irradiation does not show any appreciable changes, indicating that the passage of swift heavy ions stabilizes the short range atomic ordering, or even creates further amorphization. The crystallinity of the as-deposited Fe–Ni based films was improved by thermal annealing, and diffraction results indicated that ion beam irradiation on annealed samples results in grain fragmentation. On bombarding annealed films, the surface roughness of the films decreased initially, then, at higher fluences it increased. The observed change in surface morphology of the irradiated films is attributed to the interplay between ion induced sputtering, volume diffusion and surface diffusion

Hydrogen spillover on carbon-supported metal catalysts studied by inelastic neutron scattering. Surface vibrational states and hydrogen riding modes

Hydrogen spillover on carbon-supported precious metal catalysts has been investigated with inelastic neutron scattering (INS) spectroscopy. The aim, which was fully realized, was to identify spillover hydrogen on the carbon support. The inelastic neutron scattering spectra of Pt/C, Ru/C, and PtRu/C fuel cell catalysts dosed with hydrogen were determined in two sets of experiments: with the catalyst in the neutron beam and, using an annular cell, with carbon in the beam and catalyst pellets at the edge of the cell excluded from the beam. The vibrational modes observed in the INS spectra were assigned with reference to the INS of a polycyclic aromatic hydrocarbon, coronene, taken as a molecular model of a graphite layer, and with the aid of computational modeling. Two forms of spillover hydrogen were identified: H at edge sites of a graphite layer (formed after ambient dissociative chemisorption of H-2), and a weakly bound layer of mobile H atoms (formed by surface diffusion of H atoms after dissociative chernisorption of H-2 at 500 K). The INS spectra exhibited characteristic riding modes of H on carbon and on Pt or Ru. In these riding modes H atoms move in phase with vibrations of the carbon and metal lattices. The lattice modes are amplified by neutron scattering from the H atoms attached to lattice atoms. Uptake of hydrogen, and spillover, was greater for the Ru containing catalysts than for the Pt/C catalyst. The INS experiments have thus directly demonstrated H spillover to the carbon support of these metal catalysts.

Boron nitride nanosheets as improved and reusable substrates for gold nanoparticles enabled surface enhanced Raman spectroscopy.

Atomically thin boron nitride (BN) nanosheets have been found to be excellent substrates for noble metal particles enabled surface enhanced Raman spectroscopy (SERS), thanks to their good adsorption of aromatic molecules, high thermal stability and weak Raman scattering. Faceted gold (Au) nanoparticles have been synthesized on BN nanosheets using a simple but controllable and reproducible sputtering and annealing method. The size and density of the Au particles can be controlled by sputtering time, current and annealing temperature etc. Under the same sputtering and annealing conditions, the Au particles on BN of different thicknesses show various sizes because the surface diffusion coefficients of Au depend on the thickness of BN. Intriguingly, decorated with similar morphology and distribution of Au particles, BN nanosheets exhibit better Raman enhancements than silicon substrates as well as bulk BN crystals. Additionally, BN nanosheets show no noticeable SERS signal and hence cause no interference to the Raman signal of the analyte. The Au/BN substrates can be reused by heating in air to remove the adsorbed analyte without loss of SERS enhancement.

Compositional modulation and surface stability in InGaP films: Understanding and controlling surface properties

We investigate the formation of compositional modulation and atomic ordering in InGaP films. Such bulk properties - as well as surface morphologies - present a strong dependence on growth parameters, mainly the V/III ratio. Our results indicate the importance of surface diffusion and, particularly, surface reconstruction for these processes. Most importantly from the application point of view, we show that the compositional modulation is not necessarily coupled to the surface instabilities, so that smooth InGaP films with periodic compositional variation could be obtained. This opens a new route for the generation of templates for quantum dot positioning and three-dimensional arrays of nanostructures. © 2007 American Institute of Physics.

Diffusion of linear paraffins in nanoporous silica

The diffusion of hexane, heptane, octane, and decane in nanoporous MCM-41 silica at various temperatures is investigated by the zero-length-column method. The diffusion coefficients are derived by a complete-time-range analysis of desorption curves at different purge flow rates and temperatures. The results show that the calculated low-coverage diffusivity values decrease monotonically, and the derived Henry's law constants increase, as the carbon number of paraffins increases. The study reveals that transport is strongly influenced by intracrystalline diffusion and dominated by the sorbate-sorbent interaction. The diffusion activation energy and adsorption isosteric heat at zero loading increase monotonically with the carbon number of linear paraffins, but their ratio is essentially constant for each adsorbate compound.

Diffusion of n-decane in mesoporous MCM-41 silicas

We investigate here the diffusion of n-decane in nanoporous MCM-41 silicas with pore diameters between 3.0 and 4.3 nm, and at various temperatures and purge flow rates, by the Zero Length Column method. A complete-time-range analysis of desorption curves is used to derive the diffusion coefficient, and the effect of pore size, purge flow rate and temperature on the diffusion character is systematically studied. The results show that the calculated low-coverage diffusivity values are strongly dependent on temperature but only weakly dependent on pore size. The study reveals that transport is controlled by intracrystalline diffusion and dominated by sorbate-sorbent interaction, with the experimental isosteric heat matching the potential energy of flat-lying n-decane molecules on the surface, determined using a united atom model. The diffusion activation energy and adsorption isosteric heat at zero loading for the different pore size MCM-41 samples vary in a narrow range respectively, and their ratio is essentially constant over the pore size range studied. The study shows that the ZLC method is an effective tool to investigate the diffusion kinetics of hydrocarbons in mesoporous MCM-41 materials. (c) 2005 Elsevier Inc. All rights reserved.

Effects of adsorbed phase on diffusion of subcritical hydrocarbons in activated carbon at low pressures

Diffusions of free and adsorbed molecules of subcritical hydrocarbons in activated carbon were investigated to study the influence of adsorbed molecules on both diffusion processes at low pressures. A collision reflection factor, defined as the fraction of molecules undergoing collision to the solid surface over reflection from the surface, is incorporated into Knudsen diffusivity and surface diffusivity in meso/macropores. Since the porous structure of activated carbon is bimodal in nature, the diffusion of adsorbed molecules is contributed by that of weakly adsorbed molecules on the meso/macropore surfaces and that of strongly adsorbed molecules in the small confinement of micropores. The mobility of adsorbed molecules on the meso/macropore surface is characterized by the surface diffusivity D-mu 2, while that in the micropore is characterized by D-mu 1. In our study with subcritical hydrocarbons, we have found that the former increases almost linearly with pressure, while the latter exhibits a sharp increase at a very low-pressure region and then decreases beyond a critical pressure. This critical pressure is identified as a pressure at which the micropores are saturated.

Theoretical investigation of thermal tweezers for parallel manipulation of atoms and nanoparticles on surfaces

A major focus of research in nanotechnology is the development of novel, high throughput techniques for fabrication of arbitrarily shaped surface nanostructures of sub 100 nm to atomic scale. A related pursuit is the development of simple and efficient means for parallel manipulation and redistribution of adsorbed atoms, molecules and nanoparticles on surfaces – adparticle manipulation. These techniques will be used for the manufacture of nanoscale surface supported functional devices in nanotechnologies such as quantum computing, molecular electronics and lab-on-achip, as well as for modifying surfaces to obtain novel optical, electronic, chemical, or mechanical properties. A favourable approach to formation of surface nanostructures is self-assembly. In self-assembly, nanostructures are grown by aggregation of individual adparticles that diffuse by thermally activated processes on the surface. The passive nature of this process means it is generally not suited to formation of arbitrarily shaped structures. The self-assembly of nanostructures at arbitrary positions has been demonstrated, though these have typically required a pre-patterning treatment of the surface using sophisticated techniques such as electron beam lithography. On the other hand, a parallel adparticle manipulation technique would be suited for directing the selfassembly process to occur at arbitrary positions, without the need for pre-patterning the surface. There is at present a lack of techniques for parallel manipulation and redistribution of adparticles to arbitrary positions on the surface. This is an issue that needs to be addressed since these techniques can play an important role in nanotechnology. In this thesis, we propose such a technique – thermal tweezers. In thermal tweezers, adparticles are redistributed by localised heating of the surface. This locally enhances surface diffusion of adparticles so that they rapidly diffuse away from the heated regions. Using this technique, the redistribution of adparticles to form a desired pattern is achieved by heating the surface at specific regions. In this project, we have focussed on the holographic implementation of this approach, where the surface is heated by holographic patterns of interfering pulsed laser beams. This implementation is suitable for the formation of arbitrarily shaped structures; the only condition is that the shape can be produced by holographic means. In the simplest case, the laser pulses are linearly polarised and intersect to form an interference pattern that is a modulation of intensity along a single direction. Strong optical absorption at the intensity maxima of the interference pattern results in approximately a sinusoidal variation of the surface temperature along one direction. The main aim of this research project is to investigate the feasibility of the holographic implementation of thermal tweezers as an adparticle manipulation technique. Firstly, we investigate theoretically the surface diffusion of adparticles in the presence of sinusoidal modulation of the surface temperature. Very strong redistribution of adparticles is predicted when there is strong interaction between the adparticle and the surface, and the amplitude of the temperature modulation is ~100 K. We have proposed a thin metallic film deposited on a glass substrate heated by interfering laser beams (optical wavelengths) as a means of generating very large amplitude of surface temperature modulation. Indeed, we predict theoretically by numerical solution of the thermal conduction equation that amplitude of the temperature modulation on the metallic film can be much greater than 100 K when heated by nanosecond pulses with an energy ~1 mJ. The formation of surface nanostructures of less than 100 nm in width is predicted at optical wavelengths in this implementation of thermal tweezers. Furthermore, we propose a simple extension to this technique where spatial phase shift of the temperature modulation effectively doubles or triples the resolution. At the same time, increased resolution is predicted by reducing the wavelength of the laser pulses. In addition, we present two distinctly different, computationally efficient numerical approaches for theoretical investigation of surface diffusion of interacting adparticles – the Monte Carlo Interaction Method (MCIM) and the random potential well method (RPWM). Using each of these approaches we have investigated thermal tweezers for redistribution of both strongly and weakly interacting adparticles. We have predicted that strong interactions between adparticles can increase the effectiveness of thermal tweezers, by demonstrating practically complete adparticle redistribution into the low temperature regions of the surface. This is promising from the point of view of thermal tweezers applied to directed self-assembly of nanostructures. Finally, we present a new and more efficient numerical approach to theoretical investigation of thermal tweezers of non-interacting adparticles. In this approach, the local diffusion coefficient is determined from solution of the Fokker-Planck equation. The diffusion equation is then solved numerically using the finite volume method (FVM) to directly obtain the probability density of adparticle position. We compare predictions of this approach to those of the Ermak algorithm solution of the Langevin equation, and relatively good agreement is shown at intermediate and high friction. In the low friction regime, we predict and investigate the phenomenon of ‘optimal’ friction and describe its occurrence due to very long jumps of adparticles as they diffuse from the hot regions of the surface. Future research directions, both theoretical and experimental are also discussed.