O presente trabalho tem como objetivo o estudo e o desenvolvimento de dispositivos eletrônicos, para o monitoramento de gás de amônia, confeccionados com filmes ultrafinos de polianilina e ftalocianinas metálicas. Foram fabricados três diferentes tipos de sistemas: polianilina/PVS, polianilina/ftalocianina de níquel e polianilina/ftalocianina de cobre, sendo a espessura dos filmes o parâmetro de análise. Foram preparadas amostras com 10, 20 e 40 bicamadas. Os filmes foram caracterizados por profilometria e espectroscopia de absorção na faixa da radiação do UV - visível. Observou-se um aumento linear da espessura dos filmes com o aumento do número de bicamadas depositadas. Os dispositivos foram preparados a partir da deposição dos filmes ultrafinos de polianilina e ftalocianinas sobre substratos de vidro com eletrodos interdigitados de ouro evaporados termicamente. Os dispositivos foram caracterizados eletricamente por medidas de variação da resistência elétrica, em regime de corrente contínua e alternada, para diferentes concentrações de amônia. Também foi analisado o efeito da temperatura e da umidade relativa do ar na sensibilidade dos dispositivos. Todas as estruturas apresentaram uma dependência direta do valor da resistência elétrica com a concentração de amônia. Os dispositivos baseados em filmes de polianilina e ftalocianina de níquel apresentaram a menor variação do valor de resistência elétrica com a umidade relativa do ar. Esta característica é bastante desejável já que os ambientes nos quais se pretende utilizar este tipo de dispositivo para de monitoramento do gás de amônia, pode sofrer grandes variações no valor da umidade relativa do ar, como é o caso de granjas em geral. / The aim of this work is the study and development of electronic devices for ammonia gas monitoring based on polyaniline and metal phthalocyanines ultrathin films. It was produced three different systems: polyaniline/PVS, polyaniline/nickel phthalocyanine of and polyaniline/copper phthalocyanine and the analysis parameter of the films is the thickness. Samples were prepared with 10, 20 and 40 bilayers. The films were characterized by profilometry and spectroscopy of absorption of radiation in the range of UV-visible. There was a linear increase the thickness of the films with the increase in the number of deposited bilayers. The devices were prepared from the deposition of polyaniline and ftalocianines ultrathin films on glass substrates with interdigited electrodes of gold evaporated thermally. The devices were prepared from the polyaniline and phthalocyanine deposition of ultrathin films over glass substrates with gold interdigited electrodes. The devices were characterized electrically by measures of variation of electrical resistance, under the direct current and alternating, for different concentrations of ammonia. It was also examined the effect of temperature and relative humidity of the air in the sensitivity of the devices. All structures had a direct dependence of the value of the electrical resistance with the ammonia concentration. Devices based on films of polyaniline and nickel phthalocyanine of had the slightest variation in the amount of electrical resistance with the relative humidity. This feature is desirable because the environments in which it intends to use this type of device for tracking of ammonia gas, may undergo major changes in the value of the relative humidity of the air, such as poultry houses in general.

Cette thèse est consacrée à l’élaboration de films de nanofils d’argent orientés à l’aide de la technique de pulvérisation à incidence rasante. Couplée à la technique de dépôt couche-par-couche, il est possible de réaliser des films composés de plusieurs couches de nanofils d’argent orientées dans des directions différentes. Les films ainsi formés sont étudiés pour réaliser d’une part des supports conducteurs et transparents ordonnés et d’autre part pour réaliser des structures chirales aux propriétés optiques particulières. Une première étude est menée sur l’influence des différents paramètres de pulvérisation. Ils seront optimisés pour réaliser, dans un premier temps les échantillons transparents et conducteurs, puis dans un second, des structures chirales. Une seconde partie consiste à l’étude de structures hélicoïdales composées de plusieurs couches orientées de nanofils d’argent. Le dichroïsme circulaire de ces échantillons est étudié en fonction de différents paramètres de structure. Enfin une étude consistera à comparer les performances en tant que surface transparente et conductrice, de films orientés et d’argent sans ordre de nanofils. / This study consist in the elaboration of aligned films of silver nanowires by the Grazing Incidence Spraying (GIS) technique. Combined with the Layer-by-Layer (LbL) technique, it is possible to generate films composed of several aligned layers of silver nanowires with different directions of orientation. Optical and conductive properties of these films will be investigated to highlight the impact of these 3D ordered structures. The influence of different parameters of the GIS will be studied. These parameters will be optimized in ordrer to design samples for conductive and transparent films and to elaborate chiral structures. Chiral structures will be realized and their circular dichroism will be investigated in function of structural parameters. A last study will be realized about the influence of order for transparent and conductive electrodes by measuring performances of films with aligned and randomly deposed silver nanowires.

Abstract In this thesis, preparation of carbon nanotube (CNT) inks and inkjet printing of aqueous dispersions of CNTs for certain electrical applications are studied. The nanotube inks prepared in this work are based on chemically oxidized CNTs whose polar side groups enable dispersion in polar solvents. Subsequent centrifugation and decanting processes are used to obtain stable dispersions suitable for inkjet printing. The inks are based on either carboxyl functionalized multi-walled carbon nanotubes (MWCNTs), carboxyl functionalized single wall carbon nanotubes (SWCNTs) or SWCNT-polymer composites. The applicability of MWCNT inks is firstly demonstrated as printed patterns of tangled nanotube networks with print resolution up to ∼260 dpi and surface resistivity of ∼40 kΩ/□. which could be obtained using an ordinary inkjet office printer. In addition, MWCNT inks are found to exhibit spatial ordering in external magnetic fields due to entrapped iron catalyst nanoparticles in the inner-tubular cavity of the nanotubes. Ordering of nanotubes in the inks and in drying droplets placed in relatively weak magnetic fields (B ≤ 1 T) is demonstrated and studied. The high electrical conductivity and optical transparency properties of SWCNTs are utilized for enhancing the conductivity of transparent poly(3,4-ethylenedioxythiophene):poly(styrenesulphonate) (PEDOT:PSS) films. Polymer-nanotube composite materials are inkjet printed on flexible substrates. It is demonstrated that incorporation of SWCNTs in the thin polymer films significantly increases the electrical conductivity of the film without losing the high transparency (> 90%). The structure of composite films is studied using atomic force microscopy (AFM). The electronic properties of deposited random SWCNT networks are studied. The amount of deposited SWCNT is controlled by the inkjet printing technique. In dense networks the current-voltage behaviour is linear whereas for sparse films the behaviour is nonlinear. It is shown that the conduction path in dense films is through the metallic nanotubes, but in sparse films the percolation occurs through random networks of metallic and semiconducting SWCNTs having Schottky-type contacts. The existence of Schottky-junctions in the films is demonstrated with field-effect transistors (FET) on Si-chips and on polymer substrates. The latter is demonstrated as fully printed transistors using a single ink as a material source. FETs are further utilized as chemical-FET sensor applications. The performance of resistive CNT sensors and their comparisons with chem-FETs in terms of selectivity are studied for H2S gas.

Au cours de cette thèse, des dispositifs électrochromes à base de polymères conducteurs électroniques ont été développés pour obtenir des systèmes pouvant passer d’un état coloré cyan, magenta ou jaune à un état incolore. Les polymères électrochromes sont des dérivés du poly(3,4-propylènedioxythiophène) (PProDOT) et du poly(3,4-éthylènedioxythiophène) (PEDOT). Un réseau de polyéthylène glycol incorporant un liquide ionique 1-éthyl-3-méthylimidazolium bis(trifluorométhylsulfonylimide) (EMITFSI) a été utilisé en tant que gel d’électrolyte. Dans un premier temps, les polymères cyan, magenta et jaunes ont été étudiés. La relation entre structure et propriétés colorimétriques des polymères cyan et jaunes a été étudiés par des calculs théoriques avec la théorie de fonctionnelle de densité, la spectroscopie UV/Vis et la colorimétrie. Ces deux dernières techniques ont également été utilisées pour l’étude des polymères magenta. Les polymères présentant les meilleures propriétés optiques ont ensuite été intégrés dans des dispositifs à deux électrodes. Ceux-ci ont été étudiées par des mesures électrochimiques pour évaluer les effets sur le fonctionnement du système et sa durée de vie. Grâce aux données obtenues, nous avons pu montrer que la stabilité des dispositifs était liée à l’efficacité coulombique des polymères cyan, magenta ou jaunes. Pour contourner l’effet de l’efficacité coulombique sur les systèmes en 2 électrodes, nous avons développé des dispositifs intégrant une pseudo-référence. L’application de ces systèmes à 3 électrodes avec un polymère cyan permet de multiplier la gamme de stabilité par 7. Finalement des démonstrateurs ont été produits avec plusieurs dispositifs de chaque couleur. / During the course of this work, electrochromic devices integrating electronically conductive polymers have been developed to obtain systems that could switch from a cyan, magenta or yellow color to an almost colorless one. The electrochromic polymers are derivatives of poly(3,4-propylenedioxythiophene) (PProDOT) and poly(3,4-ethylenedioxythiphene) (PEDOT). A network of polyethyleneglycol swollen with an ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonylimide) (EMITFSI) was used as a gel polymer electrolyte. As a first step, the cyan, magenta and yellow polymers were studied. The relationship between structure and colorimetric properties of the cyan and yellow polymers have been studied with theoretical calculation using the density functional theory, UV/Vis spectroscopy and colorimetry. These last two techniques have also been used to study the magenta polymers. The polymers with the best optical properties have then been integrated inside two electrode devices. They have been characterized with electrochemical measurement to evaluate the effects on the system and its lifetime. The data showed that the stability of the devices was linked to the reversibility of the cyan magenta or yellow polymers. As a workaround to the coulombic efficiency limitation on the 2 electrode systems, we have developed devices with a pseudo-reference. The application of those 3 electrode systems with a cyan polymer leads to a 7 fold increase of the device lifetime. Finally demonstrators have been produced with several devices of each color.

Isotropic conductive adhesives (ICAs) have a growing range of applications in electronics packaging and have recently emerged as an important material in photo-voltaic module interconnections, particularly for thin-film and other non-silicon technologies where soldering processes are often unsuitable due to the nature of the metallisation or the limited maximum temperature the assembly can be exposed to. ICAs typically comprise of a high volume fraction of solid metallic flakes, usually silver, in an adhesive matrix because of its highly conductive oxide however, this thesis will focus on adhesives containing a large volume fraction of silver coated/metalised mono-sized polymer spheres (Ag-MPS). Incorporating silver coated mono-sized polymer spheres is anticipated to deliver specific advantages such as a significant reduction in the required silver content, improvement of the overall mechanical properties and flexibility to tune the properties of the filler according to the application compared with conventional flake filled adhesives. In this research advancements in the understanding of Ag-MPS filled ICAs, both through theory and experiments, have been made. Analytical models to predict an individual Ag-MPS resistance and Ag-MPS filled ICA resistance have been developed. The experiments based on the flat punch nanoindentation technique have been conducted to determine individual Ag-MPS resistances. The theoretical and experimental studies establish Ag-MPS diameter, coating resistivity, coating thickness, contact radius, and contact geometry as the main contributors towards the resistance of an Ag-MPS filled ICAs. These studies showed that Ag-MPS resistance decreases with increasing coating thickness and contact radius but increases with increasing coating resistivity. The experiments have also been conducted to investigate the effect of Ag-MPS volume fraction, diameter, coating thickness, curing conditions and shrinkage (affecting contact radius) on ICA conductivity and comparisons are made with flake filled and commercial ICAs. The results showed that ICA conductivity increases with increasing volume fraction and coating thickness but decreases with diameter. More importantly the results showed that conductivities similar to those of flake filled ICAs, including those commercially available, can be obtained using 70% less silver. The results show that, Ag content can be reduced further to just 7% with use of larger 30μm Ag-MPS but with a lower resulting conductivity. Thus for applications where very high conductivity is not required larger Ag-MPS may offer even greater potential cost benefits, which is something flake filled ICAs cannot offer. This is a significant achievement which can allow tuning of ICA formulations according to the demands of the application, which is not possible with the use of silver flakes as there is only a limited range of silver flake volume fractions that will yield useful levels of conductivity.

The objective of this work is to find an efficient, preferably automated, algorithm or interpretational procedure that can be applied in real time to localise conductors buried in a host rock, with special attention given to a conductor in a conductive environment. The Time Domain Electromagnetic (TDEM) method is considered and more specifically the central loop configuration which can be found in both ground an airborne acquisition systems. The traditional interpretation approach of decay curve analysis is automated and combined with an adapted S-layer differential transform (Sidorov and Tiskshaev, 1969) to produce conductivity-depth sections with superimposed decay behaviour at every station. The adaptations made to the S-layer differential transform include: <ul> <li> a noise filter to improve performance on field data</li> <li> the S-layer differential transform compatibility (SLTC) filter which only allows data conforming to the basic mathematical assumptions made in the transform to be processed (This “compatible” behaviour is derived through a number of synthetic model studies.)</li> <li> a depth correction based on the implications of approximating an infinite number of currents with a single filament. A remaining concern when implementing the S-layer transform is found in two consecutive numerical differentiations and various approaches are analysed to ensure stable differentiation procedures. The automated algorithm is applied to a variety of synthetic models to validate its accuracy and finally examples are shown of its application to both ground and airborne data sets.</li> </ul> / Thesis (PhD (Exploration Geophysics))--University of Pretoria, 2007. / Geology / unrestricted

Lors d’infections, l'identification rapide des micro-organismes est cruciale pour améliorer la prise en charge du patient et mieux contrôler l'usage des antibiotiques. L’électrochimie présente plusieurs avantages pour les tests rapides : elle permet des analyses in situ, faciles et peu chères dans la plupart des liquides. Son utilisation pour l’identification bactérienne est récente et provient de la découverte de molécules donnant de forts signaux redox dans le surnageant de bactéries du genre Pseudomonas.Cette thèse s’intéresse à l’analyse de surnageants de la bactérie Pseudomonas aeruginosa, 4e cause de maladies nosocomiales en Europe. Tout d’abord, l’intérêt de l’analyse électrochimique de surnageants de culture dans une visée d’identification a été évalué. Pour cela, après l’étude de 4 potentiels biomarqueurs de la présence de cette bactérie en solutions modèles, l’analyse électrochimiques de surnageant de plusieurs souches P. aeruginosa a été effectuée. Les résultats obtenus sont prometteurs. Ils mettent en évidence une signature électrochimique complexe et souche-dépendante du surnageant.La suite de la thèse s’est intéressée à l’amplification de la détection électrochimique grâce à l’utilisation du polymère conducteur PEDOT:PSS. Il a été choisi pour ses bonnes propriétés électrochimiques, sa biocompatibilité et sa facilité de mise en forme. Il a tout d’abord été utilisé sous forme de films minces pour confirmer son pouvoir d’amplification. Une électrode 3D a ensuite été fabriquée par lyophilisation. L’utilisation de ce type d’électrode permet d’amplifier encore la détection en augmentant la surface d’échange mais aussi en confinant les bactéries dans l'électrode. / During infections, microorganisms fast identification is critical to improve patient treatment and to better manage antibiotics use. Electrochemistry exhibits several advantages for rapid diagnostic: it enables easy, cheap and in situ analysis in most liquids. Its use for bacterial identification is recent and comes from the discovery of molecules giving strong redox signals in the bacterial supernatant of the Pseudomonas genus.This thesis focuses on the supernatants analysis of the bacterium Pseudomonas aeruginosa. This bacteria is the fourth cause of nosocomial infections in Europe. First, the interest of supernatants electrochemical analysis for identification was evaluated. For this, after the study of four redox biomarkers of this bacterium in model solutions, supernatant electrochemical analysis of several strains of P. aeruginosa was performed. The results are promising. They highlight a complex strain-dependant electrochemical signature of the supernatant.Following, we focused in the amplification of the electrochemical detection through the use of the conductive polymer PEDOT: PSS. This polymer was chosen for its good electrochemical properties, its biocompatibility and its easy shaping. It was first used as a thin films to confirm its amplification power through biomarker adsorption. Then, a 3D electrode was made by freeze drying. The use of this type of electrode can further amplify the detection by increasing the exchange surface as well as confining the bacteria in the electrode.

Les travaux de recherche effectués lors de cette thèse s'articulent autour de deux matériaux carbonés: les nanotubes de carbone et le graphène. Leur point commun réside dans la technique de mise en suspension qu'est la dissolution douce. Cette méthode se base sur la réduction des nanostructures carbonées en polyélectrolytes, autrement dit en nanostructures chargées négativement. Nous nous sommes intéressés d'une part à la préparation et à l'étude de films transparents conducteurs à base de nanotubes de carbone pour des applications en électronique organique en tant qu'électrode transparente et en électrochimie. D'autre part, les travaux présentent une étude des solutions de graphène. Nous nous sommes notamment attachés à démontrer la présence de graphène en suspension dans certains solvants organiques par analyse directe de ces solutions. / Two carbon materials have been studied during this thesis: carbon nanotubes and graphene. Their common point is the method used to prepare suspensions which is the mild dissolution. Using this method, carbon nanostructures can be reduced into polyelectrolytes, id. into negatively charged nanostructures. The first part deals with transparent and conductive films of carbon nanotubes which have been prepared and studied as transparent electrode for electronic applications and for electrochemistry. The second part of this work deals with graphene in solution in different solvents. The aim of this work was to show the presence of graphene by direct analysis of these graphene solutions.

Microarrays enable high throughput analysis with minute amounts of analyte. They are widely used in the ’omics’ fields both as diagnostic and analytical tools. Their ability to dramatically impact an entire field of research has focused our attention on the development of novel methods for the formation, analysis and applications of microarrays to study carbohydrate-protein interactions and the analysis of glycosylation patterns of biomolecules. Availability of appropriately modified ligands is often a limiting factor in the preparation of microarrays. To address this issue robust routes for the synthesis of nine amino ethylglycosides were developed that can be employed for microarray formation. The syntheses of more complex ligands typically deliver small quantities of material despite the requirements for special skills, equipment and long preparation times. Considering the number of complex oligosaccharides that are necessary for systematic microarray studies, the problem of availability of these complex structures is difficult to address solely with synthetic ligands. A modified native chemical ligation (NCL) strategy, in which a surface bound oxo-ester is used instead of a thioester, was optimised and used for efficient chemoselective immobilisation of sugars and peptides carrying N-terminal cysteines. The reaction proceeds under physiological conditions and has the potential to become a valuable tool for immobilisation of N-terminal cysteine-containing molecules from biological samples. The new NCL coupling methodology was developed on gold surfaces and analysed by MALDI-ToF MS. The majority of array systems, however, rely on secondary protein interactions on glass or polystyrene surfaces. A direct, more accurate analytical tool could ease the analysis and significantly improve the quality of data read-out from glass microarrays. MALDI-ToF MS that is applicable to gold microarrays cannot be used on surfaces that do not provide the necessary electrical conductivity. The undertaken experiments indicated that application of conductive tape to the back of glass or polystyrene slides made MALDI-ToF analysis on poorly conducting surfaces possible. Furthermore, the triphenylmethyl (trityl) groups attached to the surface-molecules were shown to act as ’internal-matrix’ and enable the direct MALDI analysis. Once the new array formation and analysis techniques were developed, we turned our attention towards the application of microarrays to analyse carbohydrate-protein interactions. The tools for analysis of glycosylation of biomolecules are laborious and can only be used in specialised labs. As glycosylated biomolecules gain prominence in research, clinical and industrial settings, high throughput analysis of glycosylation patterns is becoming a requirement for quality control. A technique for screening of glycosylation patterns in glycopeptides on microarrays was developed based on biophotonic scattering. This technique enables the detection of glycosylation patterns by screening immobilised glycoproteins with a range of lectins. To study the interactions between enzymes and carbohydrates, a chemoenzymatic synthesis of a mannopeptide, which consisted of four carbohydrate units, was shown in solution and on chip. Three different glycosyl transferases were successfully employed. New methods for microarray formation and analysis were developed and applied to carbohydrate-protein interaction studies. This yielded a new technique to determine protein glycosylation patterns and to produce complex glycans by enzymatic synthesis.

Orientador: Luiz Fernando Zagonel / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-28T03:52:44Z (GMT). No. of bitstreams: 1 Ramos_Raul_M.pdf: 5673835 bytes, checksum: 005e134cbd8cbb241cbdf367a75f35a3 (MD5) Previous issue date: 2015 / Resumo: Eletrodos condutores transparentes (TCE) possuem grande importância para tecnologias de informação e geração de energia. O TCE mais eficiente na atualidade é o ITO (In2O3 dopado com Sn), que pode alcançar resistividades em torno de 2.10-4 ?cm e uma transmitância ótica de 80% a 90% na região do visível. Entretanto, a escassez dos recursos naturais de Índio e sua grande demanda sugerem a necessidade de materiais alternativos. O presente estudo tem por objetivo investigar as propriedades óticas, eletrônicas e estruturais de filmes finos de TiO2 (fase anatase) dopados com Nitrogênio. A deposição dos filmes foi feita por Deposição por Feixe de Íons (IBD) por bombardeamento de um alvo de titânio puro com íons de Ar+ em atmosfera de O2. Os filmes, com uma espessura de ?90 nm, foram depositados em substrato de quartzo amorfo (Herasil-1) a temperaturas de 400 ou 500°C. Depois, os filmes são dopados com implantação iônica, variando o tempo de 10 a 60 minutos, com feixe de íons misto a baixa energia de N2+ e H2+ com 150 eV e sob a mesma temperatura de crescimento. Após a implantação, medidas Hall indicam que a densidade de portadores majoritários nos filmes de anatase dopados com nitrogênio chegam até ?1019 cm?3 (enquanto filmes não dopados tem densidade de cargas de ?1012 cm?3). A resistividade dos filmes dopados chegam até 10?1 ?cm enquanto mantem boa transmissão ótica (>80%). De fato, dependendo do tempo de dopagem e da temperatura do substrato durante o processo, a transmissão de até 85% podem ser obtida em 550 nm com tal resistividade (?10?1 ?cm). Espectroscopia de fotoelétrons emitidos por raio-x (XPS) realizadas in situ mostram que a composição na superfície é compatível com TiO2?xNx com concentração de nitrogênio de até ? 20%. Difração de raio-x com ângulo de incidência rasante (GIXRD) confirmaram a estrutura cristalina anatase dos filmes antes e após a implantação iônica à baixa energia (150 eV). Este estudo indica que é possível dopar a amostra anatase com nitrogênio através do uso de um feixe de íons de baixa energia. Tal abordagem é interessante por permitir um controle da concentração de dopantes (Nitrogênio através de um precursor gasoso) de forma mais controlada do que usualmente obtido por sputtering reativo / Abstract: Transparent conductive electrodes (TCE) have great importance for information and energy technologies. The most efficient TCE is currently the ITO (Sn-doped In2O3), which may have a resistivity lower than 2·10?4 ?cm and an optical transmittance of 80% to 90% in the visible region. However, the scarcity of natural resources of Indium and its great demand suggests the need of alternative materials. The present study aims to investigate the optical, electronic and structural properties of thin films of TiO2 (anatase phase) doped with nitrogen. The films deposition is made by Ion Beam Deposition (IBD) by bombarding a pure titanium target with Ar+ ions in O2 atmosphere to a thickness of about 90 nm. The films are deposited on an amorphous quartz substrate (Herasil-1) at 400 or 500 °C. Afterwards, the films are doped by ion implantation with low-energy ion beam mixed of N2+ and H2+ at 150 eV and under the same temperature of the growth for times ranging from 10 to 60 minutes. After implantation, Hall measurements indicated that the majority carrier density in the nitrogen doped anatase films reaches up to ? 1019 cm?3 (while the undoped films have a carrier density of ? 1012 cm?3). The resistivity of the doped films is as low as 10?1 ? cm while maintaining good optical transmission. Indeed, depending on the doping time and substrate temperature, transmission of up to 90% could be obtained at 550 nm with this resistivity. X-ray photoelectron spectroscopy (XPS) performed in situ shows that the surface composition is compatible with N:TiO2?x with nitrogen concentrations of up to ? 20%. Small angle x-ray diffraction measurements (SAXRD) confirmed the anatase crystal structure of the films before and after the low energy ion implantation. This study indicates that it is indeed possible to dope anatase thin films with nitrogen by low energy ion beam. This approach is interesting for allowing a greater control of doping concentration with respect to what is usually obtained by reactive sputtering / Mestrado / Física / Mestre em Física / 2013/118682-8 / CAPES