Room-temperature chemisorption of hexacyclic aromatic hydrocarbons on the 2x1, sputtered, oxidized and H-terminated Si(100) surfaces, as well as those upon post treatments of hydrogenation, oxidization and electron irradiation have been investigated by using thermal desorption spectrometry (TDS), Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). This work focuses on the effects of the functional groups (phenyl, methyl, vinyl, heteroatom, and H atom) in the chemisorbed aromatic hydrocarbons (benzene, toluene, xylene isomers, styrene and pyridine) on organic functionalization of the Si(100) surface, particularly on such surface processes as cycloaddition, dative adsorption, hydrogen abstraction, desorption, dissociation, diffusion, and condensation polymerization. Unlike the earlier notion that hydrogen evolution in the hydrocarbon/Si(100) systems is the result of hydrocarbon dissociation (into smaller hydrocarbon fragments and H atoms) on the surface, condensation polymerization of the adsorbed aromatic hydrocarbons is proposed in the present work, in order to explain the higher-temperature hydrogen evolution feature in the toluene/Si(100) system. This hypothesis is supported by our TDS results for other hydrocarbon adsorbates, especially in the pyridine/Si(100) system where electron-induced condensation polymerization has been observed at room temperature. The improved techniques in the TDS experiments developed in the present work have enabled us to observe condensation polymerization and the effect of H on the surface processes (via surface reconstruction) on Si(100) for the first time. New analysis methods have also been developed to determine the adsorption coverage from the AES data, and this work has not only improved the accuracy of the elemental-coverage evaluation, but also provided a means to estimate the rate and the order of chemisorption. By using the density functional theory with the Gaussian 98 program, the adsorption geometries and the corresponding adsorption energies of various adsorption phases have been calculated. These computational results have provided useful insights into the chemisorption structures on the Si(100) surface. The present work also presents the development of three kinetics models for hydrogen evolution in the aforementioned aromatic-hydrocarbon systems on Si(100). Based on a modified collision theory with consideration of diffusion, these theoretical models have proven to be quite successful in simulating the observed TDS profiles and in estimating the kinetic parameters for the analysis of condensation polymerization in 2-dimensional diffusion systems. The present work illustrates that TDS experiments can be used effectively with quantum computation and theoretical kinetics modelling to elucidate the intricate nature of organosilicon surface chemistry.

An experimental study on impaction of a single drop on solid surfaces was conducted to show the effects of particles on the impact process. The parameters were: volume fraction of particles (0 to 0.3), particle size (0.47 to 250 micron), and ratio of particle size to drop size (0.00017 to 0.074). The effect of particle volume fraction on the spreading process depended on impact speed and substrate. At low impact speed, particles had little effect on the spreading except for surfaces where the equilibrium contact angle was low. For high impact speed, the influence of particles on spreading can be described by the effective viscosity. The effect of particle size on the spreading process also depended on impact speed and substrate. At low impact speed, the drop did not have enough kinetic energy to overcome the energy barrier associated with the large particles. For particle-laden liquids, retraction was affected by particle parameters. When pure liquid drops retracted from the maximum spreading ratio, the retraction appeared to be symmetric around the point of impaction while retraction of the particle-laden drop was sometimes asymmetric. Rebounding on the Teflon film depended on impact speed, particle volume fraction, and particle size. The impact speed must reach a critical value for rebounding to occur. Bouncing results suggested that the probability of bouncing decreased as viscosity increased, impact speed increased, and surface tension decreased. The non-wetting behavior and bouncing probably involved an air layer between the surface and the drop. When a low-velocity liquid drop impacts on a surface, ejection of a secondary drop from the top of the impacting drop was sometimes observed. When Renardy et al.'s (2003) criterion for the range of velocities for existence of a capillary wave was applied to for a 3.2-mm water drop; the range was between 0.2 to 1.5 m/s. However, drop ejection was observed at lower impact speed. When apparent viscosity of the particle-laden liquid obtained from Krieger's equation (1972) was used in the pure liquid models for predicting the maximum spreading ratio, good agreement between model predictions and experimental results was obtained when Park et al's model (2003) was used.

The classical theory of colloids and surface science has universally been applied in modeling and calculations involving solid-liquid interfaces encountered in natural and engineered environments. However, several discrepancies between the observed behavior of charged solid-liquid interfaces and predictions by classical theory have been reported in the past decades. The hypothesis that the mean-field, pseudo-one-component approximation adopted within the framework of the classical theory is responsible for the differences observed is tested in this work via the application of modeling and experimental techniques at a molecular level. Silica and silicon nitride are selected as model charged solid surfaces, and mixtures of symmetric and asymmetric indifferent and non-indifferent electrolytes are used as liquid phases. Canonical Monte Carlo simulations (CMC) of the electrical double layer (EDL) structure of a discretely charged planar silica surface, embedded in solutions of indifferent electrolytes, reveal the presence of a size exclusion effect that is enhanced at larger values of surface charge densities. That effect translates into an unexpected behavior of the interaction forces between a charged planar surface and a spherical particle. CMC simulations of the electrostatic interactions and calculations of the EDL force between a spherical particle and a planar surface, similarly charged, reveal the presence of two attractive force components: a depletion effect almost at contact and a long-range attractive force of electrostatic origin due to ion-ion correlation effects. Those two-force components result from the consideration of discreteness of charge in the interaction of solid-liquid interfaces, and they contradict the classical theory predictions of electrostatic repulsive interaction between similarly charged surfaces. Direct interaction force measurements between a charged planar surface and a colloidal particle, performed by atomic force microscopy (AFM), reveal that, when indifferent and non-indifferent electrolytes are present in solution, surface charge modification occurs in addition to the effects on the EDL behavior reported for indifferent electrolytes. Non-uniformity and even heterogeneity of surface charge are detected due to the action of non-indifferent, asymmetric electrolytes. The phenomena observed explain the differences between the classical theory predictions and the experimental observations reported in the open literature, validating the hypothesis of this work.

Colloidal particles suspended in a liquid or gas phase often interact with a solid-liquid or solid-gas interface. In this study, experimental data through atomic force microscopy and neutron reflectometry and theoretical results of colloidal particle-surface interactions were obtained and compared. Atmospheric and aquatic environments were considered for the interactions of microbial colloidal particles and nano-sized silica particles with planar surfaces. Spores of Bacillus thuringiensis, members of the Bacillus cereus group, were examined as the microbial particles, simulating the pathogens Bacillus cereus and Bacillus anthracis which are potentially dangerous to human health. Model planar surfaces used in this study include gold which is an electrically conductive surface, mica which is a highly charged, nonconductive surface, and silica. In atmospheric systems, the interaction forces were found to be strongly affected by the relative humidity, and the total adhesion force of a particle onto a surface was modeled as the addition of the capillary, van der Waals, and electrostatic forces. Each component is influenced by the properties of the particle and surface materials, including hydrophobicity and surface roughness, as well as the humidity of the surrounding atmosphere. In aquatic systems, the interaction forces are mainly affected by the solution chemistry, including pH and ionic strength. The main components of the interaction force between a microbial colloidal particle and a planar surface were found to be the van der Waals and electrostatic forces. The results obtained in this research provide insights into the fundamental mechanisms of colloidal particle interactions with environmental surfaces in both atmospheric and aquatic systems, contributing to the understanding of the phenomena driving such interfacial processes as deposition, aggregation, and sedimentation. Thus, the results can help us describe the behavior of contaminant colloidal particles in environmental systems and subsequently devise better means for their removal from environmental surfaces.

Nanoscience dominates virtually every field of science and technology in the 21st century. Nanoparticles are of fundamental interest since they possess unique size- dependent properties (optical, electrical, mechanical, chemical, magnetic etc.), which are quite different from the bulk and the atomic state. Bimetallic nanoparticles are of particular interest since they combine the advantages of the individual monometallic counterparts. The present study focuses on bimetallic nanoparticles containing gold as one of the constituents. Au-Pd, Au-Pt and Au-Ag bimetallic/alloy nanoparticles have been prepared by four different synthetic methods, and characterised by a variety of techniques, with an emphasis on Au-Ag alloy systems in the solution phase as well as in the form of nanostructured films on solid substrates. Au- Ag alloy nanoparticles have been used to demonstrate two different applications. The first is the use of Au-Ag monolayer protected alloy clusters in demonstrating single electron charging events in the solution phase as well as in the dry state. Single electron transfer events involving nanosized particles are being probed extensively due to their potential applications in the field of electronics. The second is an analytical application, involving the use of trisodium citrate capped Au-Ag alloy hydrosols as substrates for surface enhanced Raman and resonance Raman scattering [SE(R)RS] studies. The sols have been used for single molecule detection purposes. Various organic molecules such as quinones, phthalocyanines and methyl violet have been self- assembled in a stepwise manner on the nanoparticulate as well as bulk Au, Ag and Au-Ag surfaces, and characterised extensively by spectroscopic, electrochemical and spectroelectrochemical techniques.

The condition of no relative velocity of fluid past solid is termed as ‘no-slip boundary condition’. This condition is a general observation in fluid mechanics. However, several research groups have recently reported slip of water for surfaces with water repelling chemistry (referred to as hydrophobic surfaces). The effect has been attributed to disruption of H-bonding network of water molecules at such surfaces and resulting nucleation of dissolved gases and even reduced water density locally in absence of dissolved air. Slip of water on hydrophobic surfaces has been demonstrated to get amplified by high degree of roughness and patterning. Trapping of air in the surface asperities has been cited as the possible reason. The present work focuses on the study of effect of surface chemistry and roughness on flow behavior close to solid surfaces. Superhydrophobic surfaces have been generated by novel methods and wet-etching has been used to generate well-defined patterns on silicon surfaces. For flow characterisation, a micrometre resolution Particle Image Velocimetry (micro-PIV) facility has been developed and flow measurements have been carried out with a spatial resolution of less than 4 µm. It has been found from the experiments that flow of water on smooth surfaces, with or without chemical modification, conforms to the no-slip within the resolution limits of experiments. Deviation is observed in case of rough and patterned hydrophobic surfaces, possibly because of trapped air in asperities. Total Internal Reflection experiments, used to visualise the air pockets, confirmed the trapping of air at asperities. Diffusion of air out of the crevices seems to be the limiting factor for the utility of these surfaces in under-water applications.

<p>The cellular response to a biomaterial, such as a dental implant, is mainly governed by the surface properties, and can thus be altered by the introduction of a surface coating. In this thesis the buildup of a biomacromolecule-based coating formed by layerby-layer (LbL) deposition of the charged polypeptides poly(L-lysine) (PLL) and poly(L-glutamic acid) (PGA) has been studied. In an attempt to make these coatings bioactive and useful for bone-anchored implants, an amelogenin protein mixture (EMD), has been immobilized in these thin polyelectrolyte multilayer (PEM) films. Multilayers were also built by LbL deposition of the natural biomacromolecules collagen (Col) and hyaluronic acid (HA). Multilayer films of these two extra-cellular biomacromolecules should be of interest for use as a scaffold for tissue engineering.</p><p>The buildup of the multilayer films has been followed in situ, using ellipsometry, quartz crystal microbalance with dissipation (QCM-D), and dual polarization interferometry (DPI). The studied PLL/PGA multilayers were found to be highly hydrated, and to exhibit a two-regime buildup behavior, with an initial “slow-growing” regime, and a second “fast-growing” regime with a linear growth in film thickness and more than linear growth in mass. A net diffusion of polypeptides into the film during the buildup led to an increase in density of the films for each layer adsorbed. A change in density was also observed in the Col/HA film, where HA penetrated and diffused into the porous fibrous Col network.</p><p>The formed PLL/PGA films were further found to be rather stable during drying, and post-buildup changes in temperature and pH, not losing any mass as long as the temperature was not raised too rapidly. The film thickness responded to changes in the ambient media and collapsed reversibly when dried. A swelling/de-swelling behavior of the film was also observed for changes in the temperature and pH.</p><p>The EMD protein adsorbed to silica surfaces as nanospheres, and could by itself form multilayers. The adsorption of EMD onto PLL/PGA multilayer films increased at lower pH (5.0), and EMD could be immobilized in several layers by alternate deposition of EMD and PGA.</p>

No description available.

Designing novel nanostructures which exploit the self-assembly capabilities of biomolecules yields a promising approach to control matter at the nanoscale. Here, the homochiral molecular self-assemblies of the methionine and tyrosine amino acids on the monocrystalline Ag(111) and Cu(111) surfaces are characterized by means of scanning tunneling microscopy (STM) and spectroscopy (STS), helium atom scattering (HAS), x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) in ultrahigh vacuum (UHV). On Ag(111), methionine self-assembles into supramolecular chains following the <110> substrate axis, forming regular nanogratings with tunable periodicity. Within the nanowires, a zwitterionic dimerization scheme is revealed. STS shows that the biomolecular nanostructures act as tunable one-dimensional quantum resonators for the surface state electrons. Zero-dimensional electronic confinement is achieved by positioning single iron atoms in the molecular trenches. This shows a novel approach to control the dimensionality of surface state electrons. The nanogratings were exploited to steer the spontaneous one-dimensional ordering of cobalt and iron atoms. For T > 15 K, the metal species self-align into homogeneously distributed chains in between the biomolecular trenches with ~25 Å interatomic distace. For Co, the dynamics of the self-alignment was monitored, revealing a reduced mobility in comparison with isolated Co atoms on bare Ag(111). On Cu(111), the self-assembly of methionine is influenced by the substrate reactivity and its temperature during molecular deposition. For T < 273 K, the biomolecules assemble in anisotropic extended clusters oriented with a -10° rotation off the <110> substrate orientations, whereas above 283 K a regularly ordered 1D phase arises with a +10° rotation off these high-symmetry axis. XPS reveals a structural transformation triggered by a thermally activated deprotonation of the zwitterionic ammonium group. On Ag(111), tyrosine self-assembles above a critical temperature into linear structures primarily following the substrate crystalline symmetry. A zwitterionic non-covalent molecular dimerization is demonstrated, NEXAFS data providing evidence of a non-flat adsorption of the phenyl ring. This recalls the geometrical pattern of methionine on Ag(111) and supports a universal self-assembling scheme for amino acids on close-packed noble metal surfaces, the different mesoscopic ordering being determined by the side chain reactivity.

This talk was presented in the 14th International Conference on Atomic Layer Deposition (ALD 2014) in Kyoto, Japan on 18th June 2014. Abstract Atomic Layer Deposition (ALD) is emerging as a ubiquitous method for the deposition of conformal and homogeneous ultra-thin films on complex topographies and large substrates in microelectronics. Electrochemical deposition (ECD) is the first choice for the deposition of copper (Cu) into the trenches and vias of the interconnect system for ULSI circuits. The ECD of Cu necessitates an electrically conductive seed layer for filling the interconnect structures. ALD is now considered as a solution for conformal deposition of Cu seed layers on very high aspect ratio (AR) structures also for technology nodes below 20 nm, since physical vapor deposition is not applicable for structures with high AR. Cu seed layer deposition by the reduction of Cu2O, which has been deposited from the Cu(I) β-diketonate [(nBu3P)2Cu(acac)] (1) used as Cu precursor, has been successfully carried out on different substrates like Ta, TaN, SiO2, and Ru [1, 2]. It was found that the subsequent gas-phase reduction of the Cu2O films can be aided by introducing catalytic amounts of a Ru precursor into the Cu precursor, so that metallic copper films could potentially obtained also on non-catalytic substrates [3, 4]. In this work, in situ X-ray photoelectron spectroscopy (XPS) investigation of the surface chemistry during Cu2O ALD from the mixture of 99 mol % of 1 and 1 mol % of [Ru(η5 C5H4SiMe3)(η5-C7H11)] (2) as ruthenium precursor, and the reduction of Cu2O to metallic Cu by formic acid carried out on SiO2 substrate are demonstrated. Oxidation states of the Cu in the film are identified by comparing the Cu Auger parameter (α) [5] with literature data. α calculated after ALD equals 362.2 eV and after reduction equals 363.8 eV, comparable to the Cu2O and metallic Cu in thin-films [6] respectively. In addition, <10 % of Cu(I), Cu(II), and Cu(OH)2 species are identified from the Cu 2p3/2 and Cu L3VV Auger spectrum after reduction. Consequently, the ALD Cu2O is successfully reduced to metallic copper by in-situ thermal reduction using formic acid. [1] T. Waechtler et al., J. Electrochem. Soc., 156 (6), H453 (2009). [2] T. Waechtler et al., Microelectron. Eng., 88, 684 (2011). [3] S. Mueller et al., Conference Proceedings SCD 2011, Semiconductor Conference Dresden, pp. 1-4. [4] T. Waechtler et al., US Patent Application Publication, US 2013/0062768. [5] C. D. Wagner, Faraday Discuss. Chem. Soc., 60, 291 (1975). [6] J. P. Espinós et al., J. Phys. Chem. B, 106, 6921 (2002).