The possibility of creating superconductivity in Highly Oriented Pyrolytic Graphite (HOPG) by means of doping was investigated. Bulk HOPG samples were doped with phosphorous using either ion-implantation or by Chemical Vapor Deposition growth with phosphine in the gas mixture. The methods for testing the graphene samples, once doped, were done by performing R vs. T measurements, and determining via observation suppressed superconductive characteristics signaling the presence of the Meissner Effect in a strong applied magnetic field. Before doping, the resistance vs. temperature (R vs. T) characteristic of the HOPG was measured. The R vs. T characteristic was again measured after doping, and for surface multilayers of graphene exfoliated from the post doped bulk sample. A 100 to 350 mT magnetic field was supplied, and the R vs. T characteristic was re-measured on a number of samples. Phosphorous-implanted HOPG samples exhibit deviations from the expected rise in resistance as the temperature is reduced to some point above 100 K. The application of a modest magnetic field reverses this trend. A step in resistance at a temperature of approximately 50-60 K in all of the samples is clearly observed, as well as a second step at 100-120 K, a third at a temperature range of 150-180 K and a fourth from about 200-240 K. A response consistent with the presence of magnetic field flux pancake vortices in phosphorous implanted HOPG and in phosphorous-doped exfoliated multilayer graphene has been observed. The lack of zero resistance at low temperatures is also consistent with pancake vortex behaviour in the flux-flow regime. The presence of magnetic vortices requires, and is direct evidence of superconductivity.

Controlling molecular orientation is of great importance in organic thin films due to the fact that the fundamental properties of functional nanomaterials depend on molecular orientation at the nanoscale. However, controlling molecular orientation cannot be achieved without having an extensive understanding about the controlling factors in the organic film growth processes. Most previous studies have been devoted to monolayer structures. The structure of multilayer films has not been well investigated. This study was performed using a phenomenological approach, in which the morphology and orientation of n-alkane thin films were studied as a function of substrate identity, interface treatment, substrate temperature and deposition rate. The experimental techniques that were used include IR-spectroscopy, polarized optical microscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray microscopy. The kinetic and thermodynamic factors that govern the orientation of organic thin films were extracted from the experimental results, and generalized to make a framework by which the morphology and orientation of organic films can be predicted. Epitaxial growth was specifically considered as a method to pattern organic thin films. In epitaxial growth, the oriented crystals of an organic film grow on a crystalline substrate such that the structure of the substrate is copied by the deposit crystals. For epitaxy it is required that the lattice planes of two crystals are parallel and similar in the lattice points spacing. A minor part of this dissertation is devoted to epitaxy in an inorganic system. One of the favorable consequences of epitaxial growth in inorganic systems is lattice strain that alters the electronic properties of semiconductor devices. A synchrotron based experimental method has been developed to quantitatively measure the degree of strain in Si1-xGex alloy films grown epitaxially on the Si(100) substrate.

Diamond is widely known for its extraordinary properties, such as high hardness, thermal conductivity, electron mobility, energy bandgap and durability making it a very attractive material for many applications. Synthetic diamonds retain most of the attractive properties of natural diamond. Among the types of synthetic diamonds, nanocrystalline diamond (NCD) is being developed for electrical, tribological, optical, and biomedical applications. In this research work, NCD films were grown by the pulsed electron beam ablation (PEBA) method at different process conditions such as accelerating voltage, pulse repetition rate, substrate material and temperature. PEBA is a relatively novel deposition technique, which has been developed to provide researchers with a new means of producing films of equal or better quality than more conventional methods such as Pulsed Laser Deposition, Sputtering, and Cathodic Vacuum Arc. The deposition process parameters have been defined by estimating the temperature and pressure of the plasma particles upon impact with the substrates, and comparing the data with the carbon phase diagram. Film thickness was measured by visible reflectance spectroscopy technique and was in the range of 40 – 230 nm. The nature of chemical bonding, namely, the ratio (sp3/sp3+sp2) and nanocrystallinity percentage were estimated using visible Raman spectroscopy technique. The films prepared from the ablation of a highly ordered pyrolytic graphite (HOPG) target on different substrates consisted mainly of nanocrystalline diamond material in association with a diamond-like carbon phase. The micro-structural properties and surface morphology of the films were studied by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The mechanical properties of the NCD films were evaluated by nano-indentation.

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La problématique énoncée par l’utilisation de matériaux composites C/C denses implique la connaissance et la maîtrise des processus de dégradation auxquels ils sont soumis. L’utilisation de moyens de caractérisation in-situ de ces voies de dégradation constitue alors un atout considérable pour leur anticipation. Ainsi, l’utilisation de la MEBE en Température associée à une caractérisation cristallographique par MET et une confrontation ex-situ par Analyse thermogravimétrique a abouti à l’obtention de lois cinétiques caractérisant la propagation de l’oxydation dans toutes les directions de l’espace. A la suite de cette étape expérimentale, une approche numérique basée sur l’utilisation d’algorithmes de Monte-Carlo Cinétique, a alors été mise en place pour modéliser ces observations tant sur le plan atomique avec la modélisation de la loi cinétique d’oxydation linéique, que meso et macroscopique par la simulation de la loi cinétique de perte de masse dans le cas particulier du HOPG. / The problem stated by the use of composites C / C dense implies knowledge and control of degradation processes to which they are subjected. The use of in-situ characterization of these means of degradation pathways then is a considerable asset for their advance. Thus, the use of ESEM in temperature associated with a crystallographic characterization by TEM and ex situ confrontation by thermogravimetric analysis resulted in obtaining kinetic laws characterizing the propagation of oxidation in all directions. Following this experimental stage, a numerical approach based on the use of algorithms Kinetic Monte-Carlo, was then introduced to model these observations both at the atomic level with the modeling of the oxidation kinetics law linear, as meso-and macro-simulation by the kinetic law of mass loss in the case of HOPG.

Les nanoparticules présentent des propriétés liées à la taille qui diffèrent fortement de celles observées dans des matériaux massifs. D'intenses recherches sur les nanoparticules sont actuellement en cours du fait de leurs grandes potentialités. Il a été montré que certaines nanoparticules métalliques sont catalytiquement actives et efficaces, comme par exemple le Palladium. L'objectif de la thèse est d'étudier la formation de nanoparticules de Pd déposées sur des surfaces pré-structurées de HOPG (Highly Ordered Pyrolytic Graphite) afin d'en optimiser la taille, la densité de surface et la stabilité. Trois étapes principales ont été menées dans nos études : la préparation des substrats, le dépôt de Pd et la caractérisation des échantillons par microscopie à effet tunnel (STM). La préparation des substrats contient elle-même deux étapes : la création de défauts par l'implantation d'agrégats Aun+ ou le bombardement de Co2, suivie d'une oxydation thermique. On obtient ainsi la formation de trous contrôlés en profondeur et en diamètre, qui serviront de sites d'ancrage pour les nanoparticules de Pd. Les mesures STM nous ont permis d'établir la relation entre la quantité de Pd déposée et la taille des nanoparticules de Pd formées à la surface du HOPG. Deux modes de croissance ont clairement été mis en évidence. Ils sont liés à la taille des défauts dans le HOPG. Les nanoparticules se présentent soit sous la forme de colliers soit sous la forme de particules isolées. Ces échantillons ont ensuite été caractérisés par des mesures de catalyse en chimie organique (Heck) ainsi qu'en catalyse gaz (oxydation du CO). / Nanoparticles exhibit size-related properties that different from those observed in bulk materials. Nanoparticle research has attracted intense interest due to its great potential applications. It has been shown that some metallic nanoparticles are catalytically active and effective, such as-Palladium.The aim of this thesis is to study the formation of Pd nanoparticles deposited on pre-structured HOPG (Highly Ordered Pyrolytic Graphite) surfaces in order to optimize their size, density and surface stability. Three major steps were taken in our studies: preparation of substrates, deposition of Pd and characterization of samples by scanning tunneling microscopy (STM). Substrats preparations itself contains two steps : the creation of defects by Aun+ clusters implantation or by bombardment of Co2 ions, followed by thermal oxidation. These steps give the formation of hales with controlled depth and diameter, which serve as anchoring sites for Pd nanoparticles.The STM measurements have allowed us to establish the relationships between the quantity of deposited Pd and the size of Pd nanoparticles formed on the HOPG surface. Two growth modes were clearly observed which are related to the defect sizes created on the HOPG surface. Nanoparticles are present either in the form of pearl necklace or in the form of isolated particles. These samples were then characterized by catalytic measurements in organic synthesis (Heck) and gas catalysis (CO oxidation).

Des assemblages linéaires de porphyrines reliées par des cations métalliques ont été obtenus en solution et visualisés à l’interface HOPG-solvant par STM. Afin de contrôler la taille des assemblages synthétisés en solution, une stratégie par différenciation de la réactivité des deux sites de coordination externes des porphyrines a été exploitée. De fortes interactions électroniques ont été mises en évidence entre les sous-unités des assemblages multi-porphyriniques. Atteignant la limite de solubilité et de caractérisation en solution avec les molécules comportant six porphyrines, une seconde stratégie a été développée, afin de synthétiser les oligomères à l’interface HOPG-phényloctane. L’auto-assemblage de monomères de porphyrines possédant deux sites de coordination externes a été étudié par STM. Après ajout de l’ion connecteur, des nanorubans comportant plusieurs dizaines de porphyrines reliées par des cations métalliques ont été observés par STM à l’interface HOPG-solvant. / Linear assemblies of porphyrins linked by metal ions were prepared both in solution and at an HOPG/phenyloctane interface. In the first part of the project, controlling the size of the linear assemblies generated in solution was the main goal. Porphyrins bearing two different external coordination sites were used to prepare finite oligomers. Strong interactions between the subunits were found in these compounds. In a second part of the project, the organization of monomeric or dimeric porphyrins at a solid/liquid interface was studied. Finally, linear porphyrin oligomers were prepared directly by self-assembly at an HOPG/phenyloctane interface. These porphyrin nano-ribbons were visualized by STM and presented sizes of several dozen nanometers.

The studies presented in this work are aimed towards a better understanding of the fundamental physics of the electrode/organic molecule interface in both the ground and excited state manifolds. Systematic investigations of single systems using two-photon photoemission (TPPE) and ultraviolet photoelectron spectroscopy (UPS) were undertaken in order to assess the evolution of the electronic structure and molecular organization at the interface. The adsorbate molecule vanadyl naphthalocyanine (VONc) was used whose properties are well-suited to this purpose. Interfacial electronic states of thin films of VONc were studied with two different substrates: highly ordered pyrolytic graphite (HOPG) and Au(111).The substrate of HOPG is a surface which does not possess reactive dangling bonds and the electron density close to the Fermi edge is very low, permitting high resolution spectroscopic band analysis of VONc and revealing subtle changes to the electronic structure. From interfacial studies of this weakly interacting substrate/ adsorbate system, it is shown in this work that molecular electronic levels in both the ground and excited state manifolds can shift independently of the vacuum level. Further, electron transfer between close lying electron donor and acceptor energy levels may be influenced by energy level shifts caused by depolarization effects as a function of dipole density.The VONc/Au(111) interface is investigated in order to examine energy level alignment in a system with the additional complexity of molecule/substrate interactions. The electron rich Au(111) surface leads to a strong interface dipole upon addition of VONc. Joint experimental and computational data is presented showing that the underlying cause of this interface dipole is Pauli repulsion. Additionally, investigations of energy level alignment in the excited state manifold are presented and the possibility of quantum interference is discussed.The interfacial electronic structure is quite different among these two model systems. The interfacial alignment observed in the HOPG/VONc system was largely due to depolarization of the intrinsic molecular dipole as a function of density, whereas the Au(111)/VONc interface is dominated by interfacial Pauli repulsion interactions.

The objective of this master s thesis is the preparation and characterization of ribonucleic acid (RNA)/inorganic material interfaces by electrospray deposition and photoemission spectroscopy. This was done through investigation of the chemical and electronic structure of the surface of Highly Ordered Pyrolytic Graphite (HOPG) and gold before and after multiple steps of RNA thin film deposition by electrospray. Great interest has been shown by researchers into RNA due to its self-assembling ability. A series of experiments was conducted depositing RNA Poly adenosine, RNA Poly cytidine, and (for control purposes) DI water on HOPG. RNA Poly adenosine was also deposited on Gold. Gold is a more practical surface for use with RNA, but HOPG is useful for this study because it allows the precise determination of the density of states (DOS) of RNA. X-ray photoemission spectroscopy (XPS) and ultraviolet photoemission spectroscopy (UPS) were used to characterize the RNA-interfaces. The work function, high binding energy cutoff, and HOMO energies were determined. The clean, in-vacuum deposition of RNA was carried out using an electrospray thin film deposition device. The HOPG and gold substrates were prepared by in-situ cleavage and sputtering respectively. The electrospray method can be used for many different types of molecules including Polymers, metal-organics, crystals, and biological materials including RNA or DNA. These measurements provided data that will be helpful in determining the electronic properties of biological and substrate interfaces.

1-D and 2-D organic nanostructures formed by supramolecular self-assembly on HOPG(0001)from molecules containing amide and carboxylic moieties have been investigated with scanning tunneling and force microscopy operated in ambient conditions. A Precise determination of the structure of the monolayer of arachidic acid on graphite was found from moire pattern resulting from tunneling current contributions from both the monolayer and the substrate. Wedge-shaped benzamide amphiphilic molecules deposited on HOPG mainly showed 1-D structures. Systematically varied molecular geometry and head groups reveal the architecture of nanowires which are distinctly different from their columnar mesophase in solution.