A mixed self assembling monolayer (mSAM) chip with attached heparin was developed to analyze heparin-protein interactions using a Reichert Inc, SR7000, surface plasmon resonance (SPR) instrument. The heparin was attached via streptavidin-biotin linkage where the streptavidin was covalently coupled to the mSAM and biotinylated heparin bound to it. These chips were then used to quantify the interactions of fibroblast growth factor-2 (FGF-2) with the surface bound heparin. Kinetic rate constants of association and disassociation were calculated. The association data of FGF-2 with heparin was fit to a single compartment, well-mixed model as the data did not exhibit mass transfer limitations. The results suggested that rebinding was prevalent and observed disassociation rates differed significantly in the presence of competing soluble heparin during disassociation. Our results indicate that the Reichert instrument and mSAM chips can be used to analyze heparin-protein interactions but that a careful protocol, outlined in this thesis, should be followed to obtain optimal data. / Master of Science

In this paper SAM (self-assembled monolayers) is used to passivate cobalt microbumps for 3D-stacking of Si chips. The SAM deposition process is optimized, using input from characterization techniques such as water contact angle measurement, ATR, AFM and XPS analysis in order to form a monolayer of Thiols-SAM on cobalt microbumps. A 3D stacked Si chips test vehicle was used to demonstrate the effectiveness of the SAM coating on cobalt bumps by measuring the electrical continuity of daisy chains.

A novel electrochemical method to generate nm-scale bubbles at the tips of CNTs can temporarily block the membrane. A 92% blocking efficiency is achieved when the bubbles are stabilized in 30-60 nm diameter „wells‟ at the tips of CNTs. This well is formed by the electrochemical oxidation of the conductive CNTs partially into the polymer matrix of the membrane. Meanwhile, the nanoscale bubbles can be removed with 0.004 atm pressure to recover the transport through the CNT membrane. The CNT membrane with nanoscale bubble valve system was used to demonstrate electrochemical energy storage. Uniform ultrathin Pt films were electrodeposited onto an aligned array of carbon nanotubes (CNTs) for high-area chemically stable methanol fuel cell anodes. Electrochemical treatment of the graphitic CNT surfaces by diazonium benzoic acid allowed for uniform Pt electroplating. The mass activity of the Pt thin film can reach 400 A/g at a scan rate of 20 mV/s and in a solution of 1 M CH3OH/0.5 M H2SO4. A novel programmed pulse potential at 0 V was also seen to nearly eliminate the effects of carbon monoxide poisoning on catalyst Pt. Furthermore, the Pt monolayer was deposited on buckypaper by replacing the precursor Cu monolayer coated on CNTs by the underpotential deposition. The electrochemical surface modification of graphite CNTs by fluorinated benzoic acid was critical to coordinate Cu ions for monolayer formation. The mass activity of the monolayer can be improved to the record value of 2711 A/g. This is about 13 times higher than that of the ~10 nm thick Pt film coated on MWCNTs. Besides the high mass activity, the Pt monolayer coated on buckypaper can be used as catalyst for fuel cells with several advantages such as low cost, high surface area, flexibility, mechanical robustness and enhanced pressure flow. Finally, a new strategy has been developed toward electrochemical water oxidation with Ir complexes catalyst, which was grafted on buckypaper by direct binding to enhance catalyst activity. The TOF (turn over frequency) of the Ir catalyst for water splitting was 7.9 s-1 at the constant potential of 1.4 V vs Ag/AgCl.

Cell adhesion is the first step of cell response to materials and the extracellular matrix (ECM), and is essential to all cell behaviours such as cell proliferation, differentiation, migration and apoptosis for anchor-dependent cells. Therefore, studies of cell attachment have important implications to control and study cell behaviours. During many developed techniques for cell attachment, the manipulation of surface chemistry is a very important method to control initial cell attachment. To control cell adhesion on a two-dimensional surface is a simple model to study cell behaviours, and is a fundamental topic for cell biology, tissue engineering, and the development of biosensors. From the engineering point of view, the preparation of a material with controllable surface chemistry can help studies of cell behaviours and help scientists understand how surface features and chemistry influence cell behaviours. During the fabrication, the challenge is to create a surface with heterogeneous surface properties in the micro scale and subsequently to guide cell initial adhesion. In order to control cell adhesion in a spatial and temporal manner, a photochemical method to control surface chemistry was employed to control the surface property for cell adhesion in this project. Two photocleavable derivatives of the nitrobenzyl group were tried on two types of surfaces: a model self-assembled monolayer (SAM) with alkanethiol-gold surface and biodegradable chitosan. Reactive functional groups on two different surfaces can be inactivated by covalent binding with these photocleavable molecules, and light can be further introduced into the system as a stimulus to recover their reactivity. By simply applying a photomask with diffe

During the synthesis of well arrayed nano/micro structures through wet chemical methods, plenty of parameters are usually involved. Consequently, it is extremely time- and cost-consuming to find out the optimized synthesis conditions by using the conventional "changing one separate factor at a time" (COST) strategy. Instead, the "statistical experimental design" method has been proven in a few works to be an efficient method for experiments involving many parameters.  With this method, the responses could be optimized efficiently by using only a few experiments. Besides, several responses can be optimized simultaneously. Also, models could be built up and the changing tendency can be plotted to predict the required experimental settings for specific tasks. Two types of well arrayed structures including monolayer arrays of silica spheres and vertically aligned ZnO rod arrays were investigated in this work. Monolayer arrays of silica spheres were synthesized by using a dual-speed spin coating method. With assistance of statistical experimental design, the accelerating rate, the second rotation speed and time of the dual-speed spin coating system were found as non-significant parameters to the ordering degree of the obtained monolayer, and thus they can be fixed. This finding could remarkably increase the feasibility of optimizing the practical process. On the other hand, the relative humidity, the first rotation speed and the suspension concentration are identified as the significant parameters to the structures of the monolayer. Moreover, the optimal values for these three parameters were identified: 23% for the relative humidity, 1000 rpm for the first rotation speed and 30 wt.% for the suspension concentration. With these optimized parameters, the area of the obtained silica sphere monolayers reached over 1 cm2 and the defect-free domain size reached over 4000 μm2. These values are considerably higher compared to the previously reported values. Vertically aligned ZnO rod arrays were fabricated by chemical bath deposition. Parameters including precursor concentration, pH value, reaction temperature, reaction time and addition of capping agent were optimized by using statistical experimental design to improve and optimize the growth quality of ZnO rod arrays. Through several stages of optimization, the growth quality of the obtained structures was remarkably enhanced from sparse or clustered ZnO rods to upright and dense ZnO rods. The boundary conditions to achieve vertically aligned ZnO rods, such as a neutral solution and a precursor concentration over 0.02M, were determined. The changing tendency of the texture coefficient and aspect ratio with the factors was also plotted to predict the required experimental settings for specific requests. The points or regions to achieve the optimal properties were identified as well. For instance, the concentration should be as close as to 0.1 M, while the reaction temperature should be limited to 80-90 ◦C, to achieve the ideal preferential growth. With the optimized parameters, the texture coefficient reached almost the perfect value 1, and the aspect ratio was elevated to 21. Moreover, to obtain a dense ZnO thin film, tri-sodium citrate was added to the reaction system. The diameter was systematically controlled through varying the parameters. When both the diameter and the texture coefficient reached the optimal values, the rods were merged together to form a dense ZnO thin film. Furthermore, comments on the statistical experimental method are proposed, and both the advantages and disadvantages are presented according to the present thesis work. This might help the researchers to avoid the disadvantages and thus to employ this method more efficiently in the future. / <p>QC 20150903</p>

The creation of organic electronics is not only an attractive replacement for amorphous silicon devices, but offers the ability to produce novel technologies such as flexible displays and chemical or biological sensors. Control of the semiconducting film for such devices is of great importance. The fabrication of monolayer devices of a high performance offer a desirable way of creating high sensitivity sensors. Achieving a high level of performance for ultra-thin and monolayer devices, where the charge transport layer is effectively the thickness of the film, requires the careful control of deposition conditions. Thin films of the molecule 5,5'-bis(4-n-hexylphenyl)-2,2'-bithiophene (PTTP) were investigated with respect to their crystal structure, growth dynamics and device performance. Optimised conditions led to the highest reported performance for PTTP, to the best of our knowledge, with mobilities greater than 0.1 cm2V-1s-1. These results allowed the creation of monolayer and multilayer devices, resulting in a saturation thickness of approximately 2.1 monolayers, where the bulk performance was reached. This confirmed the presence of the conduction channel within the first few monolayers and could potentially lead to an optimised device for chemical or biological sensing. The development of a solution processed method for creating monlayers of PTTP was also investigated. Creating a compound with the ability to self assemble on a surface, allowing a controlled monolayer to form, involved the use of a trichlorosilane anchoring group attached to a PTTP core by an alkyl spacer. Solution processed self assembled monolayer field effect transistors (SAMFETs) were formed in less than 10 hours, reaching mobilities as high as 1.7 X 10-2 cm2V-1s-1 . This simple method for creating transistors could further the use of monolayer devices in sensing applications and integrated circuits. Furthermore, the development of solution processed PTTP was undertaken. By blending the small molecule with the insulating polymer PMMA, phase separation of the components led to the creation of thin, crystalline films of PTTP. Working devices were fabricated that required as little as 0.05 \% w/v of the small molecule. This attractive method, of reducing the required material and combination of both insulating and semiconducting components, is a versatile approach to greatly simplify the device processing steps required.

Metal and metal oxides are widely used in industry, and to optimize their performance their surfaces are commonly functionalized by the formation of thin films. Self-assembled monolayers (SAMs) are deposited on metals or metal oxides either from solution or by gas deposition. Thiols with polar terminal groups are utilized for creating the responsive surfaces which can interact electrostatically with other adsorbates. Surface charge effects wetting and adhesion, and many other surface properties. Polar terminal groups in thiols could be used to modify these factors. Mixed SAMs can provide more flexible surfaces, and could change the resulting surface properties under the influence of factors such as pH, temperature, and photo-illumination. Therefore, in order to control these phenomena by mixed polar-terminated thiols, it is necessary to understand the composition and conformation of the mixed SAMs and their response to these factors. In this work, mixtures of thiols with carboxylic and amino terminal groups were studied. Carboxylic and amino terminal groups of thiol interact with each other via hydrogen bonding in solution and form a complex. Complexes adsorb to the surface in non-conventional orientations. Unmixed SAMs from each type, either carboxylic terminated thiols or amino terminated thiols are in standing up orientation while SAMs from complexes are in an axially in-plane orientation. Selenol is an alternative to replace thiols for particular applications such as contact with biological matter which has a better compatibility with selenol than sulfur. However, the    Se-C bond is weaker than the S-C bond which limits the application of selenol. Understanding the selenol adsorption mechanism on gold surfaces could shed some light on Se-C cleavage and so is investigated in this work. Se-C cleavage happens in the low coverage areas on the step since atoms at steps have lower coordination making them more reactive than atoms on the terraces.  Another area where the self-assembly of molecules is of importance is for dye sensitized solar cells, which are based on the adsorption of the dye onto metal oxides surfaces such as TiO2.The interface between the SAM of dye and the substrate is an important factor to consider when designing dyes and surfaces in dye sensitized solar cells (DSSCs). The quality of the self-assembled monolayers of the dye on the TiO2 surface has a critical influence on the efficiency of the DSSCs.  Creation of just a monolayer of dye on the surface could lead to an efficient current of photo-excited electrons to the TiO2 and degeneration of the dye by redox. This work, T-PAC dye showed island growth with some ad-layer that is not in contact with the surface, whereas the MP13 dye adsorption is laminar growth.  Cuprite (Cu2O) is the initial and most common corrosion product for copper under atmospheric conditions. Copper could be a good replacement for noble metal as catalysts for methanol dehydrogenation. Knowledge about the structure of Cu2O(100) and Cu2O(111) surfaces could be used to obtain a deeper understanding of methanol dehydrogenation mechanisms with respect to adsorption sites on the surfaces. In this work, a detailed study was done of Cu2O(100) surface which revealed the possible surface structures as the result of different preparation conditions. Studies of the structure of Cu2O(100) and Cu2O(111) surfaces show that Cu2O(100) has a comparatively stable surface and reduces surface reactivity. As a consequence, dehydrogenation of methanol is more efficient on the Cu2O(111) surface. The hydrogen produced from methanol dehydrogenation is stored in oxygen adatom sites on both surfaces. / <p>QC 20161107</p>

C'est la surface, et non le matériau qui interagit avec l'environnement. Par conséquent, en modifiant la surface d'un matériau de manière contrôlée, nous pouvons moduler ces interactions avec son environnement. Les sels d'aryles diazonium semblent très adaptés pour modifier les propriétés de surface de matériaux de par leurs diversités structurelles et leur capacité à modifier des surfaces conductrices par électrochimie. Ce travail de thèse se concentre sur l'étude du transfert électronique au travers de couches organiques de différentes épaisseurs (monocouches, couches ultraminces et multicouches), générées par électro-réduction de sels d'aryles diazonium. La molécule électroactive étudiée peut être alors soit fixée à la surface du matériau ou en solution. Différentes méthodes électrochimiques ont été utilisées au cours de cette thèse : CV, EIS et SECM. Dans un premier temps, l'étude des propriétés électrochimiques de surfaces carbonées modifiées par des monocouches d'alkyle-ferrocène a été entreprise dans différents solvants ; ainsi que leur évaluation pour des applications en stockage d'énergie. La deuxième étude s'intéresse à l'utilisation d'une approche « bottom-up » pour la fabrication de surfaces organisées. Des substrats de carbone et d'or ont été modifiés par électro-réduction d'un sel d'aryle diazonium pré-organisé en forme de tétraèdre. Ceci aboutit à l'obtention d'un film organique ultra-mince possédant des propriétés de tamisage moléculaire et de rectification de courant électrochimique vis-à-vis de sondes redox en solution. La troisième étude s'est ensuite focalisée sur la réaction de réduction du dioxygène et de ses intermédiaires, qui présentent un intérêt général aussi bien dans des processus naturels qu'en industrie. La détection de ces intermédiaires a été entreprise par SECM, utilisant une stratégie « d'empreinte » utilisant différentes couches organiques sensibles. L'influence du potentiel appliqué et de l'électrolyte a été étudiée. Dans ce travail, nous avons démontré que les propriétés électrochimiques de sondes redox en solution ou greffées à la surface d'un matériau peuvent être modulées par l'utilisation de couches organiques. Ces recherches fondamentales présentent un intérêt dans des domaines tels que le stockage d'énergie et la catalyse. / It is the surface, not the bulk material that interacts with the surrounding environment; hence by altering the surface in a controlled manner we can modulate the properties of the material towards its environment. Aryldiazonium salts are suitable to tailor the surface properties since their structural diversity and their electrochemically-assisted bonding ability to modified conducting surfaces. This thesis focuses on the study of the electron transfer through different aryl layers by aryldiazonium electro-reduction at three different thickness levels, monolayer, near-monolayer, and multilayer, when the electroactive molecule is attached to the surface or in solution. Three different electrochemical methods have been used throughout this thesis, CV, EIS and SECM. The first study of this thesis focused on the investigation of the electrochemical properties of alkyl-ferrocene on-carbon monolayers in different solvents and its evaluation for improving the global charge density of carbon materials for energy storage applications. The second study used a bottom-up approach for the fabrication of well-organized surfaces. Carbon and gold substrates were modified by electro-reduction of a tetrahedral-shape preorganized aryldiazonium salt resulting in an ultrathin organic film that showed molecular sieving and current rectification properties towards redox probes in solution. The third study then focused on the oxygen reduction reaction and its intermediates, which are of general importance in natural and industrial processes. Detection of intermediates was achieved by SECM in a foot-printing strategy based on the use of different sensitive aryl multilayers. The role of the applied potential and electrolytes was investigated. Here we have demonstrated that the electrochemical properties of redox probes attached to a surface or in solution can be modulated by introducing aryl layers allowing fundamental research investigations of interest in fields such as energy storage and catalysis.

Films of phospholipids and biologically relevant surfactants at the air-water interface provide a well-defined medium to study molecular alignment, phase behavior and interactions of biomembranes and lung surfactant with exogenous materials. Interactions between lung surfactant interfaces and solid particles are of particular interest due to the increased use of nanomaterials in industrial applications and the promise of polymeric particles in pulmonary drug delivery. Understanding such interactions is necessary to avoid potential adverse effects on surfactant function after exposure to particles. In this thesis, the mechanisms of surfactant inhibition after exposure to submicron particles via different routes were investigated. The effects of carboxyl-modified polystyrene particles (200 nm) on films of dipalmitoyl phosphatidylcholine (DPPC) and Infasurf (calf lung surfactant extract) were studied. Surfactants were exposed to different concentrations of particles in a Langmuir trough with symmetric surface compression and expansion. Surface tension, potential, microstructure and topology were examined to monitor particle effects on surfactant function. Several methods of surfactant exposure to particles were studied: particle injection into the subphase after spreading surfactant monolayers (subphase injection), mixing the particles with the subphase and spreading the surfactant on top (monolayer addition) and particle aerosolization onto surfactant films. Studies with DPPC monolayers revealed that particle-surfactant interactions are dependent on the particle introduction method. In the subphase injection method, particles did not penetrate the monolayer and no inhibitory effects on surfactant function were observed. However, in the monolayer addition method, particles caused a premature monolayer collapse and hindered surfactant respreading likely by penetrating into the DPPC monolayer. Finally, particle aerosolization on surfactant was performed to mimic the physiologically relevant route of surfactant exposure to particles. Particle aerosolization on DPPC monolayers significantly inhibited surfactant function in the lung-relevant surface tension range. When aerosolized on Infasurf, particles caused inhibitory effects as a function of time suggesting adsorption of surfactant components on particle surfaces as the main mechanism of interaction. This research will enhance understanding of the mechanisms of particle-induced surfactant dysfunction, thereby providing information for the safe design of polymeric particles for drug delivery and for developing guidelines for particles used in occupational settings.

Ce travail présente une évaluation des performances des transistors à effet de champ à base de graphène (GFET) grâce à des simulations électriques des modèles compact dédiés à des applications à haute fréquence. Les transistors à base de graphène sont parmi les nouvelles technologies et sont des candidats prometteurs pour de futures applications à hautes performances dans le cadre du plan d’action « au-delà du transistor CMOS ». Dans ce contexte, cette thèse présente une évaluation complète des transistors à base de graphène tant au niveau du dispositif que du circuit grâce au développement de modèles compacts précis pour des GFETs, de l’analyse de la fiabilité, en étudiant les mécanismes critiques de dégradation des GFETs, et de la conception des architectures de circuits basés sur des GFETs.Dans cette thèse nous présentons, à l’aide de certaines notions bien particulières de la physique, un modèle compact grand signal des transistors FET à double grille à base de graphène monocouche. Ainsi, en y incluant une description précise des capacités de grille et de l’environnement électromagnétique (EM), ce travail étend également les aptitudes de ce modèle à la simulation RF. Sa précision est évaluée en le comparant à la fois avec un modèle numérique et avec des mesures de différentes technologies GFET. Par extension, un modèle grand signal pour les transistors FET à double grille à base de graphène bicouche est présenté. Ce modèle considère la modélisation de l’ouverture et de la modulation de la bande interdite (bandgap) dues à la polarisation de la grille. La polyvalence et l’applicabilité de ces modèles compacts des GFETs monocouches et bicouches ont été évalués en étudiant les GFETs avec des altérations structurelles.Les aptitudes du modèle compact sont encore étendues en incluant des lois de vieillissement qui décrivent le piégeage de charges et la génération d’états d’interface qui sont responsables de la dégradation induite par les contraintes de polarisation. Enfin, pour évaluer les aptitudes du modèle compact grand signal développé, il a été implémenté au niveau de différents circuits afin de prédire les performances par simulations. Les trois architectures de circuits utilisées étaient un amplificateur triple mode, un circuit amplificateur et une architecture de circuit « balun ». / This work presents an evaluation of the performances of graphene-based Field-Effect Transistors (GFETs) through electrical compact model simulation for high-frequency applications. Graphene-based transistors are one of the novel technologies and promising candidates for future high performance applications in the beyond CMOS roadmap. In that context, this thesis presents a comprehensive evaluation of graphene FETs at both device and circuit level through development of accurate compact models for GFETs, reliability analysis by studying critical degradation mechanisms of GFETs and design of GFET-based circuit architectures.In this thesis, an accurate physics-based large-signal compact model for dual-gate monolayer graphene FET is presented. This work also extends the model capabilities to RF simulation by including an accurate description of the gate capacitances and the electro-magnetic environment. The accuracy of the developed compact model is assessed by comparison with a numerical model and with measurements from different GFET technologies.In continuation, an accurate large-signal model for dual-gate bilayer GFETs is presented. As a key modeling feature, the opening and modulation of an energy bandgap through gate biasing is included to the model. The versatility and applicability of the monolayer and bilayer GFET compact models are assessed by studying GFETs with structural alterations.The compact model capabilities are further extended by including aging laws describing the charge trapping and the interface state generation responsible for bias-stress induced degradation.Lastly, the developed large-signal compact model has been used along with EM simulations at circuit level for further assessment of its capabilities in the prediction of the performances of three circuit architectures: a triple-mode amplifier, an amplifier circuit and a balun circuit architecture.