The work described in this thesis is concerned with the study of ph-ysisorbed phases by x-ray diffraction using a conventional sealed x-ray tube source. Diffraction data has been collected for a number of adsorption systems using graphite, a montmorillonite clay (Gel White) and zeolite rho as the substrate. It is well known that phases of unique two-dimensional character can be formed on the surface of graphite, and the structure of adsorbed benzene and hexaflurobenzene on graphite have been studied in this thesis. Contrary to current theoretical predictions the >/7x T/7R19" commensurate structure of submonolayer benzene has been confirmed. Submonolayer hexaflurobenzene appears to form a striped domain structure based upon the commensurate x3 lattice in which the molecules are incommensurate with the surface. ' In contrast to the homogeneous surface of graphite, the surface of a clay is microporous and heterogenous, and this gives rise to broad diffraction lines from an adsorbed phase. Despite this, the surface area of Gel White has been deduced from the evolution of the diffraction pattern of a krypton adlayer as a function of krypton loading. The formation of bulk krypton is readily identified and the small size of the three-dimensional crystallites suggests that they are formed within the micropores of the clay. The structure of adlayers of krypton and xenon within the interlayer spacing of Al-pillared Gel White has been studied in order to determine the mean inter-pillar separation. At all the coverages studied, xenon forms a close packed single layer structure whilst krypton appears to form a more complex bilayer phase. A tentative suggestion as to the mean pillar separation from this work is 30X. The adsorption site of krypton, xenon and CH3CI within zeolite rho has been determined using the method of x-ray Rietveld whole profile refinement. The principal site of adsorbed krypton and xenon is at the centre of the octagonal prism. The chlorine atom of CH3CI sits in the centre of the face of the octagonal prism and the methyl group is slightly displaced from the centre of the prism. 37-5354 Hydrodynamics of liquid encapsulation czochralski crystal growth Hicks, T.W. Bristol Ph.D. 1989 Dig. Certain aspects of crystal growth from a melt are investigated. We begin by describing the methods of producing single crystals. Particular emphasis is placed on the need for a better understanding of the hydrodynamics of the encapsulant region of the Liquid Encapsulation Czochralski (LEG) technique. We also introduce the basic physical processes which govern crystal growth. In Chapter 2 we develop a mathematical model of the encapsulant region of the LEC crystal growth system. The equations and boundary conditions that govern the encapsulant flow are formed using a vorticity-stream-function approach, after which the problem is recast in a dimensionless form. In Chapter 3 the equations of motion are represented in a finite difference form and a numerical method for solving the time-marching problem presented by the parabolic equations is developed. The elliptic stream-function equation is solved at each time level using the successive over-relaxation technique. Solutions of the model equations for the growth of GaAs crystals through B3O3 encapsulant are presented in Chapter 4. In all cases considered the flow field tends towards a steady state. For shallow encapsulants, the heat transfer in the encapsulant is conduction dominated, but for deeper encapsulants, advective heat transfer can be significant. In the last chapter we investigate the effect of Soret diffusion on the morphological stability of a freezing interface using linear stability theory. A Soret flux directed towards the interface has a destabilising effect. Over-stable modes of instability exist for very low crystal growth rates, but we are unable to find conditions under which the overstable mode is the most unstable.

The dynamical behaviors of tricarboxylic acid derivative, 1,3,5-tris(carbox- ymethoxy) benzene[TCMB, C6H3(OCH2COOH)3] on an Au surface is investigated by molecular dynamics. A TCMB molecule adsorbed on the Au(111) substrate is first probed into the structure arrangement. It founds that there are four possible conformations of the TCMB molecule that is adsorbed on the Au(111) substrate. The main difference on its conformation is the orientation of its functional group, which lead the molecule that forms the lock-and-key (LAK) behavior and prompts the molecule that become more stable on the substrate. As this result, the LAK behavior directly affects the trajectories of movement and dynamical behaviors. Another topic is to observe the behavior of TCMB molecule on Au(110) and Au(100) surface, respectively. As well as the result of the TCMB molecule adsorbed on the Au(111) substrate, it also shows a different behavior on dynamical behaviors when the TCMB molecule adsorbed on the Au(110) and Au(100) substrate. Moreover, we found that the diffusion direction of TCMB molecule is dependent on the arrangement of the adsorbed surface. From the observation of the trajectory of the TCMB molecule, we found that diffusion range is most wide on Au(100) plane. The translational direction of TCMB molecule tend to move on the <110> direction as the molecule is migrate on the Au(100) plane, whereas that tend to move on the [1ī0] direction as the molecule is migrate on the Au(110) plane. From the description above, we know that TCMB molecule with different conformations on different plane of surface arrangement displays different trajectories of movement and dynamical behaviors. Therefore, in order to understand the dynamical behaviors of TCMB monolayer on gold surface. In this work, the temperature effect on the adsorption behavior and the dynamic behavior of TCMB monolayer structure on the Au(111) substrate are investigated. From the calculation of the cohesive energy between molecules and the interaction energy between the molecule and the Au(111) substrate, we found that there are significant changes in cohesive energy and interaction energy at specific temperatures, which can be attributed to the deformation of the monolayer structure. Finally, the mean square displacement (MSD), diffusion coefficient(D) and distance between the molecule and the Au(111) substrate are calculated to investigate the diffusion property and motion behavior of TCMB monolayer at specific temperatures.

Surface modification has wide ranging implications in lubrication, microelectromechanical systems (MEMS), colloidal systems and biological membranes. Surface modification plays an important role in stabilizing gold nanoparticles, which have applications in targeted drug delivery and catalysis. A variety of surface modification techniques are used for controlling corrosion and wettability, as well as used extensively to understand the nature of interactions between surfaces. This thesis is mainly focused on understanding the kinetics, film growth and surface modification by long chain molecules physisorbed on a surface. The time evolution of film growth and domain formation of octadecylamine on a mica surface is studied using ex-situ AFM and reflectance FTIR. A novel technique of interface creation is developed to measure the height of the adsorbed film. The results show three distinct regions of film growth mechanism. Region I, corresponds to thin film and the interface height is in the monolayer regime. The transient regime (II) consists of a sharp increase in the film thickness, from 1.5 nm to 25 nm within a time span of 180 s. In the final stage of film growth the film thickness is invariant with time, during which domain coarsening is observed. Domain evolution reveals a non-monotonic variation in the domain size as a function of adsorption time. A three stage mechanism is proposed to explain the domain evolution on the surface. In order to explain the observed film thickness variation, we have developed and tested various models to explain the thin to thick film transition observed in the AFM experiments. A model based on adsorption kinetics is solved to obtain the evolution of the adsorbed film. The model with a two-step adsorption isotherm quantitatively captures the thin to thick film transition observed in the AFM experiments. The statistical thermodynamics of adsorption of long chain molecules on a surface has been studied using a lattice model. The molecules are characterized by backbone chain, either lying parallel or perpendicular to the surface. A square lattice with nearest neighbour interactions and a mean field approximation are used to generate the adsorption isotherms for different molecules as a function of chain length. The molecules change their orientation from a surface parallel to an upright configuration with an increase in chemical potential. A similar transition (with time) in the molecular orientation has been observed in the AFM experiments. The transition between these two orientations is accompanied by an entropy maximum The last part of the thesis is concerned with carbon-carbon interactions. More specifically, we are interested in the interactions between graphite surfaces and their modification in the presence of a lubricant or base oil. Diamond like carbon (DLC) AFM tips and highly oriented pyrolitic graphite (HOPG) have been used for this study. Experiments were carried out by treating HOPG graphite in hexadecane oil at different temperatures. It is observed that pull-off forces on bare graphite are smaller when compared to the treated surface. The magnitude of the pull-off forces increases with the temperature of the hexadecane oil bath. Presence of charged patches responsible for the higher adhesion have been confirmed using surface potential microscopy. Results also confirm the presence of a thin liquid-like hexadecane film at room temperature.

Asymmetries in physisorbed systems give rise to interesting phases and phase transitions in two-dimensional (2D) monolayer and multilayer systems. The effects of asymmetric adsorbate and substrate interactions in monolayers of dipolar molecules on ionic substrates and N2 on graphite are studied. In the case of dipolar molecules on ionic substrates, 2D dielectric phase transitions using a modified Blume-Emery-Griffiths (BEG) model are determined theoretically. A dipole adsorbed vertically above a metal ion lattice site, and pointing up (down), is assigned a spin s=+1 (s=-1). An empty lattice site is assigned a spin S=0. Analytic solutions for both ferroelectrically and antiferroelectrically ordered systems are found. The model is applied to CO adsorbed on MgO and NaCl, and preliminary results for the phase diagram of CH3F on NaCl, are presented. Multilayer phase transitions for N2 on graphite are studied experimentally using synchrotron x-ray diffraction. The system is measured to undergo layering transitions, where the number of layers increases as the temperature of the system increases. A new multilayer phase diagram based on our results and the combined results published by other researchers is presented. The effects of capillary condensation on this multilayer system are quantified, and it is determined that its primary effect is to broaden the discrete layering transitions. The results for both studies are put into context with other adsorption systems with asymmetric interactions.

PhD / SYNOPSIS OF THIS THESIS The aim of this thesis is to more fully understand and explain the binding mechanism of organic molecules to the Au(111) surface and to explore the conduction of such molecules. It consists of five discreet chapters connected to each other by the central theme of “The Single Molecule Device: Conductance and Binding”. There is a deliberate concentration on azine linkers, in particular those with a 1,10-phenanthroline-type bidentate configuration at each end. This linker unit is called a “molecular alligator clip” and is investigated as an alternative to the thiol linker unit more commonly used. Chapter 1 places the work in the broad context of Molecular Electronics and establishes the need for this research. In Chapter 2 the multiple break-junction technique (using a Scanning Tunnelling Microscope or similar device) was used to investigate the conductance of various molecules with azine linkers. A major finding of those experiments is that solvent interactions are a key factor in the conductance signal of particular molecules. Some solvents interfere with the molecule’s interaction with and attachment to the gold electrodes. One indicator of the degree of this interference is the extent of the enhancement or otherwise of the gold quantized conduction peak at 1.0 G0. Below 1.0 G0 a broad range for which the molecule enhances conduction indicates that solvent interactions contribute to a variety of structures which could bridge the electrodes, each with their own specific conductance value. The use of histograms with a Log10 scale for conductance proved useful for observing broad range features. vi Another factor which affects the conductance signal is the geometric alignment of the molecule (or the molecule-solvent structure) to the gold electrode, and the molecular alignment is explored in Chapters 3 for 1,10-phenanthroline (PHEN) and Chapter 4 for thiols. In Chapter 3 STM images, electrochemistry, and Density Functional Theory (DFT) are used to determine 1,10-phenanthroline (PHEN) structures on the Au(111) surface. It is established that PHEN binds in two modes, a physisorbed state and a chemisorbed state. The chemisorbed state is more stable and involves the extraction of gold from the bulk to form adatom-PHEN entities which are highly mobile on the gold surface. Surface pitting is viewed as evidential of the formation of the adatom-molecule entities. DFT calculations in this chapter were performed by Ante Bilic and Jeffery Reimers. The conclusions to Chapter 3 implicate the adatom as a binding mode of thiols to gold and this is explored in Chapter 4 by a timely review of nascent research in the field. The adatom motif is identified as the major binding structure for thiol terminated molecules to gold, using the explanation of surface pitting in Chapter 3 as major evidence and substantiated by emergent literature, both experimental and theoretical. Furthermore, the effect of this binding mode on conductance is explored and structures relevant to the break-junction experiment of Chapter 2 are identified and their conductance values compared. Finally, as a result of researching extensive reports of molecular conductance values, and having attempted the same, a simple method for predicting the conductance of single molecules is presented based upon the tunneling conductance formula.

PhD / SYNOPSIS OF THIS THESIS The aim of this thesis is to more fully understand and explain the binding mechanism of organic molecules to the Au(111) surface and to explore the conduction of such molecules. It consists of five discreet chapters connected to each other by the central theme of “The Single Molecule Device: Conductance and Binding”. There is a deliberate concentration on azine linkers, in particular those with a 1,10-phenanthroline-type bidentate configuration at each end. This linker unit is called a “molecular alligator clip” and is investigated as an alternative to the thiol linker unit more commonly used. Chapter 1 places the work in the broad context of Molecular Electronics and establishes the need for this research. In Chapter 2 the multiple break-junction technique (using a Scanning Tunnelling Microscope or similar device) was used to investigate the conductance of various molecules with azine linkers. A major finding of those experiments is that solvent interactions are a key factor in the conductance signal of particular molecules. Some solvents interfere with the molecule’s interaction with and attachment to the gold electrodes. One indicator of the degree of this interference is the extent of the enhancement or otherwise of the gold quantized conduction peak at 1.0 G0. Below 1.0 G0 a broad range for which the molecule enhances conduction indicates that solvent interactions contribute to a variety of structures which could bridge the electrodes, each with their own specific conductance value. The use of histograms with a Log10 scale for conductance proved useful for observing broad range features. vi Another factor which affects the conductance signal is the geometric alignment of the molecule (or the molecule-solvent structure) to the gold electrode, and the molecular alignment is explored in Chapters 3 for 1,10-phenanthroline (PHEN) and Chapter 4 for thiols. In Chapter 3 STM images, electrochemistry, and Density Functional Theory (DFT) are used to determine 1,10-phenanthroline (PHEN) structures on the Au(111) surface. It is established that PHEN binds in two modes, a physisorbed state and a chemisorbed state. The chemisorbed state is more stable and involves the extraction of gold from the bulk to form adatom-PHEN entities which are highly mobile on the gold surface. Surface pitting is viewed as evidential of the formation of the adatom-molecule entities. DFT calculations in this chapter were performed by Ante Bilic and Jeffery Reimers. The conclusions to Chapter 3 implicate the adatom as a binding mode of thiols to gold and this is explored in Chapter 4 by a timely review of nascent research in the field. The adatom motif is identified as the major binding structure for thiol terminated molecules to gold, using the explanation of surface pitting in Chapter 3 as major evidence and substantiated by emergent literature, both experimental and theoretical. Furthermore, the effect of this binding mode on conductance is explored and structures relevant to the break-junction experiment of Chapter 2 are identified and their conductance values compared. Finally, as a result of researching extensive reports of molecular conductance values, and having attempted the same, a simple method for predicting the conductance of single molecules is presented based upon the tunneling conductance formula.

Le procédé de mise en forme des tôles métalliques, généralement oxydées, par emboutissage est en pleine évolutionpour répondre à de nouveaux besoins : intervalles de tolérances dimensionnelles de plus en plus étroits, productionen grande série à faible coût, apparition de nouvelles nuances de matériaux, souci écologique. La réussite d’une telleopération est prédominée par le contrôle du frottement au niveau du contact entre tôle à former et outil enmouvement relatif. Pour ce faire, nous proposons dans cette thèse de fonctionnaliser la surface de la tôle en ygreffant des molécules organiques auto-assemblées, par simple immersion dans une solution contenant les moléculesréactives. Le couple métal/molécule retenu pour cette étude est un substrat massif de cuivre pur avec des moléculesd’acides alkylphosphoniques (CnH2n+1PO(OH)2) dans le but d’établir une corrélation entre les propriétésphysicochimiques des films ainsi formés et leur comportement tribologique. La réponse en frottement a été étudiéepar deux moyens de simulation expérimentale des conditions de contact (tribomètres bille/plan et étirage-plan). Nousavons considéré l’influence des trois facteurs de préparation de substrat suivant μ la nature de surface juste avant safonctionnalisation (présence d’une couche d’oxyde ou d’hydroxyde), le nettoyage de surface aux ultrasons après safonctionnalisation (élimination des espèces physisorbées) et la longueur de chaîne alkyle de la moléculeorganophosphonique (n=4, 12 et 16). Bien que la formulation de cette fonctionnalisation soit simple (élaborée àpartir d’une seule molécule), les techniques d’investigation de surface (PM-IRRAS, XPS, électrochimie, MEB,…)montrent que les films auto-assemblés sont constitués d’une bicouche de bonne qualité de greffage et de propriétésanticorrosion. Cette bicouche est composée d’une première monocouche de molécules chimisorbées à la surface (ouSAM) sur laquelle est déposée une deuxième couche d’amas physisorbés. D’autre part, notre étude a montréégalement que les amas physisorbés ont un rôle primordial dans le comportement tribologique du film auto-assemblé(abaissement et stabilité du coefficient de frottement et prévention contre le grippage). / Sheet metal forming processes are quickly evolving to meet new requirements of deep drawing such as: continuousminimization of dimensional tolerances intervals, cost efficiency at mass production, appearance of new materialstypes, environmental concern. The success of such operation is predominated by controlling friction at the contactbetween the metal sheet and forming tool in relative motion. In the present work, we propose to functionalize themetal sheet surface using grafting of self-assembled organic molecules by simple immersion in a solution containingthe reactive molecules. Consequently, thin film of alkylphosphonic acid (CnH2n+1PO(OH)2) was grafted on copperoxide substrate in order to establish a correlation between the physicochemical properties of the films andtribological behavior. Frictional response was studied by two experimental means of contact conditions (stripdrawing testing and ball-on-plane tribometer). The influence of three factors for the preparation of substrate wasconsidered. Firstly, the nature of its surface just before functionalization including the presence of an oxide orhydroxide layer was studied. Then, the ultrasonic surface cleaning after functionalization (removal physisorbedspecies) and finally, the alkyl chain length of the organophosphonic molecule (n = 4, 12 and 16). Although theformation of this functionalization is simple (made from a single molecule), the surface investigation techniques(PM- IRRAS , XPS, electrochemistry , SEM, .., etc.) show that self-assembled films consist of a bilayer with a goodgrafting quality and anticorrosion properties. The bilayer is composed of a first monolayer of molecules chemisorbedon the surface (or SAM) on which a second layer of physisorbed species is deposited. Furthermore, this study alsoshowed that the physisorbed species have a key role in the tribological behavior of self-assembled film (lower andstable friction coefficient and high resistance to galling).