Os filmes moleculares constituídos por complexos polipiridínicos de rutênio, clusters trigonais de acetato de rutênio e porfirinas polimetaladas, tem sido investigados de forma sistemática, proporcionando uma ampla variedade de interfaces funcionais, para uso em dispositivos eletrônicos, sensores, células electrocatalíticas e de fotoconversão de energia. Tais filmes tem sido gerados por meio de métodos conhecidos como dip coating, drop casting, e deposição química/eletroquímica, apresentando aspectos morfológicos extremamente ricos, os quais foram investigados nesta tese, por meio de microscopia de varredura de sonda. Estudos de microscopia de força atômica foram dirigidos para os filmes moleculares gerados por dip coating. As imagens foram analisadas com bons resultados através do Programa da Gwyddion, permitindo a avaliação dos parâmetros de rugosidade envolvidos nas formas e distribuição dos grãos superficiais. Os filmes obtidos por drop casting foram investigados por meio da microscopia de força atômica, MACMode, apresentando uma grande variedade morfológica, associada principalmente com o processo de dewetting, sob a influência de interações moleculares específicas. A eletropolimerização dos complexos foi monitorada por meio de AFM condutivo, permitindo sondar as características condutoras dos filmes poliméricos. Filmes de DNA e nanopartículas magnéticas ancoradas sobre superfície de ouro foram investigados através de AFM MACMode, e AFM magnético, respectivamente. Finalmente, uma nova abordagem de sondas ultrassensitivas, foi explorada através da imobilização de nanopartículas magnéticas sobre MACLevers, ampliando os limites de detecção gravimétrica até sub-picograma. / Molecular films constituted by ruthenium polypyridine complexes, triangular ruthenium acetate clusters, and polymetallated porphyrins have been systematically investigated, providing a wide range of functional interfaces for electronic devices, sensors, photoconversion and electrocatalytical cells. Such films have been generated by dip coating, drop casting and electrochemical deposition, displaying very rich morphological aspects, which have been investigated by means of scanning probe microscopy. AFM studies have been carried out for the molecular films generated by dip coating. The images were successfully analysed using the Gwyddion software, allowing the evaluation of the rugosity parameters determining the grain shapes and distribution over the films. The films obtained by drop casting have been investigated by means of MACMode SFM, exhiting a wide variety of morphologies, mainly associated with the dewetting of the samples, under the influence of specific molecular interactions. Electropolymerization of molecular complexes have been monitored by SFM techniques, including the electroconducting mode to probe the conductivity of the polymeric films. Gold anchored films of DNA and magnetic nanoparticles have also been successfully investigated by MACMode SFM and magnetic SFM techniques, respectively. Finally, a new approach for ultra-sensitive probes, based on the immobilization of magnetic nanoparticles onto the MACLevers has been devised, allowing the detection of sub-picogram amounts of analytes

Os filmes moleculares constituídos por complexos polipiridínicos de rutênio, clusters trigonais de acetato de rutênio e porfirinas polimetaladas, tem sido investigados de forma sistemática, proporcionando uma ampla variedade de interfaces funcionais, para uso em dispositivos eletrônicos, sensores, células electrocatalíticas e de fotoconversão de energia. Tais filmes tem sido gerados por meio de métodos conhecidos como dip coating, drop casting, e deposição química/eletroquímica, apresentando aspectos morfológicos extremamente ricos, os quais foram investigados nesta tese, por meio de microscopia de varredura de sonda. Estudos de microscopia de força atômica foram dirigidos para os filmes moleculares gerados por dip coating. As imagens foram analisadas com bons resultados através do Programa da Gwyddion, permitindo a avaliação dos parâmetros de rugosidade envolvidos nas formas e distribuição dos grãos superficiais. Os filmes obtidos por drop casting foram investigados por meio da microscopia de força atômica, MACMode, apresentando uma grande variedade morfológica, associada principalmente com o processo de dewetting, sob a influência de interações moleculares específicas. A eletropolimerização dos complexos foi monitorada por meio de AFM condutivo, permitindo sondar as características condutoras dos filmes poliméricos. Filmes de DNA e nanopartículas magnéticas ancoradas sobre superfície de ouro foram investigados através de AFM MACMode, e AFM magnético, respectivamente. Finalmente, uma nova abordagem de sondas ultrassensitivas, foi explorada através da imobilização de nanopartículas magnéticas sobre MACLevers, ampliando os limites de detecção gravimétrica até sub-picograma. / Molecular films constituted by ruthenium polypyridine complexes, triangular ruthenium acetate clusters, and polymetallated porphyrins have been systematically investigated, providing a wide range of functional interfaces for electronic devices, sensors, photoconversion and electrocatalytical cells. Such films have been generated by dip coating, drop casting and electrochemical deposition, displaying very rich morphological aspects, which have been investigated by means of scanning probe microscopy. AFM studies have been carried out for the molecular films generated by dip coating. The images were successfully analysed using the Gwyddion software, allowing the evaluation of the rugosity parameters determining the grain shapes and distribution over the films. The films obtained by drop casting have been investigated by means of MACMode SFM, exhiting a wide variety of morphologies, mainly associated with the dewetting of the samples, under the influence of specific molecular interactions. Electropolymerization of molecular complexes have been monitored by SFM techniques, including the electroconducting mode to probe the conductivity of the polymeric films. Gold anchored films of DNA and magnetic nanoparticles have also been successfully investigated by MACMode SFM and magnetic SFM techniques, respectively. Finally, a new approach for ultra-sensitive probes, based on the immobilization of magnetic nanoparticles onto the MACLevers has been devised, allowing the detection of sub-picogram amounts of analytes

This thesis presents the development of a novel atomic force microscope (AFM) based nanofabrication technique termed as thermochemical nanolithography (TCNL). TCNL uses a resistively heated AFM cantilever to thermally activate chemical reactions on a surface with nanometer resolution. This technique can be used for fabrication of functional nanostructures that are appealing for various applications in nanofluidics, nanoelectronics, nanophotonics, and biosensing devices. This thesis research is focused on three main objectives. The first objective is to study the fundamentals of TCNL writing aspects. We have conducted a systematic study of the heat transfer mechanism using finite element analysis modeling, Raman spectroscopy, and local glass transition measurement. In addition, based on thermal kinetics analysis, we have identified several key factors to achieve high resolution fabrication of nanostructures during the TCNL writing process. The second objective is to demonstrate the use of TCNL on a variety of systems and thermochemical reactions. We show that TCNL can be employed to (1) modify the wettability of a polymer surface at the nanoscale, (2) fabricate nanoscale templates on polymer films for assembling nano-objects, such as proteins and DNA, (3) fabricate conjugated polymer semiconducting nanowires, and (4) reduce graphene oxide with nanometer resolution. The last objective is to characterize the TCNL nanostructures using AFM based methods, such as friction force microscopy, phase imaging, electric force microscopy, and conductive AFM. We show that they are useful for in situ characterization of nanostructures, which is particularly challenging for conventional macroscopic analytical tools, such as Raman spectroscopy, IR spectroscopy, and fluorescence microscopy.

Neste trabalho foram obtidos nanotubos de carbono de paredes múltiplas (MWNT). O crescimento apresentou alta densidade de nanotubos orientados perpendicularmente à superfície do substrato, com cerca de 20 m de comprimento e diâmetros entre cerca de 20 e 60 nm. Foram utilizados filmes catalisadores contendo ferro, depositados a partir de solução de nitrato de ferro (Fe(NO3)3.9H2O) em álcool etílico com concentrações que variaram entre 37 mmol/L e 1,2 mmol/L. Não foram notadas diferenças significativas entre os nanotubos crescidos com diferentes concentrações, com exceção da solução de 0,6 mmol/L onde não foi observado o crescimento de nanotubos. Os crescimentos de nanotubos de carbono foram efetuados em um reator CVD a plasma de microonda. Os resultados de espectroscopia Raman sugerem que os nanotubos de carbono obtidos neste trabalho correspondem a MWNT, apresentando alto grau de desordem estrutural. Foram realizados crescimentos diretos de nanotubos de carbono sobre as pontas comerciais de AFM, utilizando filmes de nitrato de ferro. Os nanotubos crescidos nas pontas apresentaram tendência em formarem aglomerados. Não foram obtidas pontas de AFM satisfatórias com este método. Outro método consistiu no crescimento de nanotubos de carbono em amostras planas de silício, utilizando filme catalisador de nitrato de ferro com posterior captura de nanotubos na extremidade da ponta, utilizando um microscópio AFM. Foram realizados 26 procedimentos, onde a maioria dos resultados não foi satisfatória. Apenas em dois dos procedimentos foram obtidos resultados muito bons com nanotubos de carbono retos e protuberantes emergindo das pontas. Ainda neste trabalho foi desenvolvido um método de reciclagem das pontas. O processo é de grande valia, pois a obtenção de pontas de AFM com nanotubos apresenta sucesso em apenas uma fração do número de tentativas, levando a inutilização de um número representativo de pontas. A reciclagem das pontas foi realizada por meio da corrosão dos nanotubos de carbono em plasma de hidrogênio. O equipamento utilizado para essa finalidade foi o próprio reator CVD a plasma de microonda, também utilizado para o crescimento dos nanotubos. / In this work multi walled carbon nanotubes (MWCNT) were obtained. The growth presented high density nanotubes oriented perpendicularly to the substrate, with about 20 m length and diameters between 20 and 60 nm. Catalytic films containing iron were used. These films were deposited from solution of iron nitrate (Fe(NO3)3.9H2O) in ethyl alcohol with concentrations that varied between 37 mmol / L and 1.2 mmol / L. It was not observed significant difference among the grown nanotubes obtained with different concentrations, except from the solution of 0.6 mmol / L, where the nanotubes growth was not observed. The growths of carbon nanotubes were obtained in a microwave plasma CVD reactor. The Raman spectroscopy suggests that the carbon nanotubes obtained in this work correspond to MWCNT, presenting high degree of structural disorder. Direct growths of carbon nanotubes on commercial AFM tips were performed, using films of iron nitrate. The nanotubes grown directly on the tips presented tendency in forming agglomerates. They were not obtained satisfactory AFM tips with this method. Another method consisted of carbon nanotubes growth on flat silicon substrates, using catalytic film of iron nitrate, with subsequent nanotubes capture at the extremity of the tip, using a microscope AFM. Altogether 26 procedures were performed, where most of their results were not satisfactory. In just two of these procedures were obtained very good results with straight and protuberant carbon nanotubes emerging of the tips. Still in this work a method of tip recycling was developed. The process is valuable, since the success in obtaining AFM tips with nanotubes occurs in just a fraction of the attempts, generating a representative number of lost tips. The tips recycling were performed through the corrosion of the carbon nanotubes in hydrogen plasma. The equipment used for this purpose was the microwave plasma CVD reactor, also used for carbon nanotubes growth.

L'état de surface est l'un des paramètres les plus importants pour déterminer la biocompatibilité d'un dispositif médical implantable, tout changement à la surface une fois en contact avec les tissus corporels peut avoir un impact sur la réponse biologique (cytotoxicité, inflammation, irritation, thrombose ... etc.). Pendant le stockage, l’exsudation des additifs peut se produire à la surface des polymères et modifier leurs propriétés. Dans cette étude, nous utilisons du polyuréthane à base de cathéter (Pellethane®), en raison de ses nombreuses applications dans le domaine des dispositifs médicaux, pour évaluer l'impact d’exsudation des additifs sur la biocompatibilité. L'impact des traitements de stérilisation et d'oxydation sur le phénomène d’exsudation a été étudié. L'étude a été réalisée sur du polyuréthane utilisé dans la fabrication de cathéters sur lesquels l’exsudation de cristaux d’additifs a déjà été observée. La stérilisation par rayonnements ionisants (bêta, gamma) a été réalisée sur ce matériau et les échantillons ont été soumis à différents types de processus d'oxydation (UV, H2O2 et action des macrophages). La viabilité des cellules endothéliales a été étudiée. Une évaluation préliminaire de l'hémocompatibilité a été réalisée par la mesure de l'hémolyse du sang total, ainsi que par l'adhésion des plaquettes en contact avec les différents échantillons de PU. L'étude de la production pro-inflammatoire d'IL-alpha; et de TNF-alpha; par des macrophages en contact avec des échantillons a également été rapportée. / Surface state is one of the most important parameter determining the biocompatibility of animplantable medical device, any change on the surface once in contact with body tissues canimpact the biological response (Cytotoxicity, inflammation, irritation, thrombosis …etc). During storage, the blooming of additives may occur on the surface of polymers and modify their properties. In this study, we use (Pellethane®) catheter-based polyurethane, because of its many applications in the field of medical devices, to evaluate the impact of additives blooming on the biocompatibility. The impact of sterilizing and oxidation treatments on blooming was studied. The study was realized on polyurethane used in the fabrication of catheters on which the blooming of antioxidant crystals has been previously observed. Sterilization by ionizing radiations (beta, gamma) was performed on this material and samples were submitted to different kinds of oxidation process (UV, H2O2 and macrophages action). Endothelial cells viability was studied. A preliminary haemocompatibility evaluation was performed through the measurement of whole blood hemolysis, as well as platelet adhesion in contact with the different PU samples. The study of the pro-inflammatory IL-alpha; and TNF-alpha; production by macrophages in contact with samplesis also reported.

The quality of atomic force microscope (AFM) data strongly depends on scan and controller parameters. Data artifacts can result from poor dynamic response of the instrument. In order to achieve reliable data, dynamic interactions between AFM components need to be well understood and controlled. In this paper we present a summary of our work in this direction. It includes models for the probe-sample interaction, scanner lateral and longitudinal dynamics, scanner creep, and cantilever dynamics. The models were used to study the effect of scan parameters on the system dynamics. Simulation results for both frequency response and imaging were presented. Experimental results were given supporting the simulations and demonstrating the competence of the models. The results within will be used to develop algorithms that allow automated choice of key system parameters, guaranteeing reliable and artifact-free data for any given operating condition (sample, cantilever, environment). Consequently, expanding the AFM capabilities and permitting its use in a wider range of applications. / Singapore-MIT Alliance (SMA)

Holes with different sizes from microscale to nanoscale were directly fabricated by focused ion beam (FIB) milling in this paper. Maximum aspect ratio of the fabricated holes can be 5:1 for the hole with large size with pure FIB milling, 10:1 for gas assistant etching, and 1:1 for the hole with size below 100 nm. A phenomenon of volume swell at the boundary of the hole was observed. The reason maybe due to the dose dependence of the effective sputter yield in low intensity Gaussian beam tail regions and redeposition. Different materials were used to investigate variation of the aspect ratio. The results show that for some special material, such as Ni-Be, the corresponding aspect ratio can reach 13.8:1 with Cl₂ assistant etching, but only 0.09:1 for Si(100) with single scan of the FIB. / Singapore-MIT Alliance (SMA)

Removal of emulsified water is a challenge in oil sands and heavy oil processing. The flocculation and coagulation of emulsified water droplets depend on the interactions between the water droplets covered mainly by asphaltenes and oil-contaminated fine solids. To quantitatively evaluate the stability of water-in-diluted bitumen emulsions, this research determined the interactions between asphaltene surfaces in model oils, heptane, toluene or a mixture of the two known as heptol, by colloidal force measurements using atomic force microscopy (AFM) in combination with the Langmuir-Blodgett technique. The effect of aromaticity of the solvents, temperature and water content of the solvents on asphaltenes-asphaltenes interactions was systematically investigated. The results showed that the interaction forces between asphaltenes are highly sensitive to the aromaticity of the organic solvents. In solvents of higher aromaticity, a repulsive force existed between asphaltene surfaces; whereas in solvents of lower aromaticity, a weak attraction was detected. The transition from repulsion to attraction indicates that it is possible to control asphaltenes-asphaltenes interactions, and ultimately to control the stability of asphaltene-stabilized water droplets in oil, through tuning the aromaticity of the organic solvents. By fitting the measured force profiles with theoretical models, the nature of the forces was determined, which provides insights into the mechanisms of asphaltene-stabilized water-in-oil emulsions. The concomitant benefit of the results from the direct force measurement is to predict asphaltene precipitation with change of solvent composition. Oil-contaminated fine solids not only help stabilize water-in-diluted bitumen emulsions but are detrimental to bitumen upgrading. To control the wettability of these fine solids, a preliminary study was carried out in this work to explore the potential of ethyl cellulose (EC), an effective demulsifier for water-in-diluted bitumen emulsion, as a surface wettability modifier of the oil-contaminated solids. It was found that EC is able to reduce the surface hydrophobicity of the asphaltene- and bitumen-contaminated solids and thus enhances their removal from bitumen froth. The mechanism of increased wettability by EC addition was determined by quartz crystal microbalance with dissipation (QCM-D) and AFM topographical imaging. The results from this study can help establish the criteria for selecting and developing chemical modifiers for applications in wettability control of oil-contaminated solids. / Chemical Engineering

A magnetic force microscope (MFM) is a special type of scanning force microscope which measures the stray field above a ferromagnetic sample with the help of a ferromagnetic cantilever. The aim of this project was to design and build a MFM head and interface it with a commercial scanning probe electronics controller with the help of an appropriate force sensor. The MFM head and the force sensor were to be designed to work at low temperatures (down to 4 K) and in high vacuum. During this work, a magnetic force microscope (MFM) head was designed. Its design is symmetrical and modular. Two dimensional views were prepared to ensure proper geometry and alignment for the various modules. Based on these views, individual parts in the various modules were manufactured and combined for the final assembly of the head. This MFM head has many essential and advanced features which were incorporated during the design process. Our MFM head has an outside diameter of 5 cm and thus has a low thermal mass. The head operates inside a 100 cm long vacuum can which is kept in a cold bath inside a superinsulated dewar. Other features of this MFM head include thermal compensation of the important parts, flexibility to use commercial MFM cantilevers and a large scan range compared to the previous designs. Some of the anticipated system specifications are: 1) room temperature scanning range of 175?? 175 ??m, 2) low temperature scanning range between 35-50 ??m, 3) smallest detectable magnetic force in the range of one pN and 4) smallest detectable magnetic force gradient in the range of 10-3 to 10 -5 N/m. This MFM head was interfaced to a commercial scanning probe electronics apparatus by designing a fiber-optic interferometer as the sensor for the detection of the cantilever deflection. The fiber-optic sensor also has features of its own such as stability, compactness and low susceptibility to noise because of all-fiber construction. With this MFM head, we hope to image many magnetic samples which were previously impossible to image at Texas A&M.

The atomic force microscope (AFM) was used to study a series of self-assembled systems: alkanethiol self-assembled monolayer (SAM), diblock copolymer thin film, solid supported lipid bilayer membrane, and microgel with double interpenetrating polymer network. In the first system, packing and restructuring of self-assembled monolayers as exhibited by several alkanethiol systems (1-hexanethiol, 1-decanethiol, 11-ferrocenyl-1-undecanethiol) is demonstrated using conducting probe AFM (CP-AFM). Pressure is induced by an AFM tip, and simultaneously, electrical behavior is measured via detection of tunneling currents between metallic tip and substrate. The behavior is fit using a mechanical model that attempts to predict the observed junction resistance as a function of applied force with consideration for mechanical restructuring of the monolayer at higher loads. CP-AFM is also used to study self-assembled thin film of the diblock copolymer polystyrene- block-polyferrocenylsilane (PS-b-PFS) on gold substrate. Simultaneous height and electrical current imaging verify the phase separation of the two blocks of the polymer and additionally, distinguish each block due to differential conductivity. The phase separation of multi-component phospholipid bilayers (phosphatidylcholine/ sphingomyelin/ cholesterol) on supporting substrate into liquid-ordered and liquid-disordered phases is demonstrated using both topographical imaging, and the use of force map analysis through tip indentation and rupture measurements. The segregation and differential mechanical stiffness of the phases help to understand the important role of mechanical stability and rigidity membranes. An automated batch analysis process was implemented to facilitate the procedure. The mechanical properties of microfluidically produced microgels (cross-linked sodium alginate and poly(N-isopropylacrylamide)) are measured using indentation experiments, to evaluate the suitability of these gels as cell-mimics. Nanoscale heterogeneities were avoided by using a tipless cantilever. This body of work shows that the alginate content of these microgels can be varied to tune their mechanical properties and that a platform for mechanical measurement of cell and cell-mimics is possible.