No description available.

No description available.

No description available.

Charge transfer salts of Tetracyanoquinodimethane (TCNQ) were synthesised and their electrical and magnetic properties were investigated. These salts show unusual electrical and magnetic behaviour in contrast to conventional organic compounds. These salts have crystal structures which in general consist of TCNQ radical ions stacked in chains, isolated from each other by the diamagnetic cations. They are thus regarded as "one-dimensional" electrical and magnetic systems. The ESR spectra of these salts are attributed to triplet excitons showing that the spin-spin and electronelectron correlation effects are important. In the ESR spectra (Chapter III) of some TCNQ salts dipolar splitting is observed confirming the spin-spin interaction. These triplet excitons are regarded as bound electron-hole pairs. The experimentally determined dipolar splitting tensors are presented in Chapter III and the intensity data in Chapter IV. A large number of fine structure lines are observed in the ESR spectra of Pyridinium-TCNQ and 4-Aminopyridinium-TCNQ apart from regular triplet exciton lines (Chapter III). These lines are attributed to the trapping of excitons on an extended formula finit (TCNQ2 )n. In Chapter IV the temperature dependent magnetic susceptibilities are discussed in terms of Heisenberg antiferromagnetism and Pauli paramagnetism. In Chapter V temperature dependent behaviour of electrical conductivity is discussed in terms of an exciton band model, the lattice structure of the salts and one-dimensional lattice consisting of defects giving rise to high and low conducting segments. Low temperature electrical and magnetic phases are discussed (Chapters IV and VII) in terms of a band and hopping mechanisms.In Chapter VI self consistent field calculations are made with reference to the tight binding one electron band theory using simplified Roothaan equations considering CNDO approximations. Theoretical results are related to experimental band gaps, spinspin interactions and charge alteration.

No description available.

Este trabalho descreve o estudo de preparação dos filmes de polianilina, Pani, depositados pelo método de polimerização in-situ para serem utilizados em dispositivos poliméricos emissores de luz (PLEDs) e em sensores químicos e de flexão mecânica. É descrita a síntese química da Pani, a produção de filmes pelo método de polimerização in-situ, o estudo do seu crescimento usando a espectroscopia de UV-Vis e as características morfológicsa da superfície pela técnica de varredura de AFM. Filmes de Pani depositados pela técnica in-situ sobre eletrodos interdigitados foram caracterizados através de medidas de condutividade elétrica contínua e alternada em função da temperatura e da dopagem do material. Os resultados elétricos obtidos, típicos de sistemas sólidos desordenados, foram interpretados usando o modelo de condução de Dyre. Investigou-se o uso de filmes finos de Pani como camada injetora de portadores de carga em PLEDs para diferentes métodos de conversão do precursor poli(xilideno tetrahidrotiofeno), PTHT, em poli(-fenileno vinileno), PPV. Mostrou-se que a camada de Pani pode ser usada como janela transparente da emissão luminosa do PPV, o que diminui a tensão de operação do PLED e protege o eletrodo de ITO contra a corrosão durante o processo de conversão. São mostrados estudos exploratórios de sensores de Pani depositados sobre o substrato de poli (tereftalato de etileno) (PET) para aplicação em dispositivos para medidas de pH de solução e de flexão mecânica. / This work shows the study of Pani film prepared by the in-situ deposition technique aiming its use im polymeric light emission diodes (PLEDs) and in chemical sensors and of flection mechanics. The sysnthesis of the Pani, the production of films by the in-situ method, the film growth probed by UV-Vis spectroscopy and its surface morphology characteristics probed by the scanning AFM microscope are presented. Such in-situ films were deposited on the top of interdigitated electrodes and characterized usign ac and dc conductivity measurements as function of temperature and of the material doping level. The electric results were typical of non ordered materials and interpreted using the Dyre´s conduction model. It was investigated the use of Pani films as carrier layer injection in PLEDs employing different of conversion of poly(xylylidene tetrahydrothiophenium), PTHT, in to poly(-phenylene vinylene), PPV. It was showed that the Pani film act as a transparent window for the PPV light emission, the onset voltage of the PLED decreased and the Pani layers protects the ITO electrode against the corrosion during the conversion of the PTHT in to PPV. Exploratory studies were also performed using the Pani layer deposited on the top of a poly (ethylene terephtalate) substrate aiming its application for measuring the pH of a solution and as mechanical bending sensor.

Cette thèse est consacrée à l'étude d'encres, de composites et de dépôts de nanotubes de carbone monofeuillets (SWNT). Le contrôle de la dispersion et de l'orientation des nanotubes dans ces matériaux composites nanostructurés vise à optimiser leurs propriétés, en particulier électriques et optiques.La première partie du travail est consacrée à l'optimisation de la dispersion des SWNT dans des suspensions aqueuses stabilisées par des tensio-actifs, des sels biliaires, et à l'étude de leurs propriétés optiques, et en particulier de leur photoluminescence (PL) dans le proche infrarouge. La spectroscopie d'absorption nous permet de sonder la dispersion des SWNT et de mesurer leur coefficient d'absorption. Nous montrons que ce dernier est très sensible au degré d'individualisation des nanotubes. Par ailleurs, nous revisitons l'interprétation des spectres de PL excités dans le proche infrarouge (en particulier à 1,17 et 1,58 eV) et attribuons les différents pics mesurés à différents mécanismes : transitions excitoniques directes, à des couplages exciton-phonon ou à des transferts d'énergie entre nanotubes. Nous montrons que l'évolution de l'intensité de PL avec l'individualisation permet de distinguer ces différents mécanismes.La seconde partie du travail est dédiée à la préparation de suspensions aqueuses stabilisées par des polymères hydrosolubles (PVA et PVP), et de composites SWNT/polymère, sans tensio-actifs. Les suspensions de nanotubes sont mélangées à des solutions de polymère, puis dialysées pour éliminer le tensio-actif. Le rendement, i.e. la concentration de la suspension finale, est de l'ordre de 75 fois plus élevée que pour une suspension préparée directement avec des polymères. Par ailleurs, les spectres de PL sont sensibles à l'environnement diélectrique des nanotubes et leur étude permet de mettre en évidence un échange entre les agents dispersants tensio-actifs/PVA à la surface des nanotubes, échange qui n'est pas observé dans le cas du PVP. Dans la troisième partie de la thèse, nous utilisons la technique d'impression jet d'encre pour imprimer des lignes continues micrométriques de SWNT, et proposons des méthodes originales pour étudier leur morphologie et leur anisotropie. La morphologie des dépôts peut varier entre deux cas limites, le dépôt homogène et la ‘‘paire de rails'', en faisant varier la concentration de nanotubes dans les encres, la distance entre gouttes et la température du substrat. L'orientation des nanotubes au bord des dépôts est très élevée (paramètre d'ordre orientationnel S entre 0,6 et 0,9), les nanotubes sont également bien orientés dans les rails (S~0.5) et dans une moindre mesure dans les lignes homogènes S~0.3. / This thesis focus on the study of inks, composites and deposits of single-wall carbon nanotubes (SWNT). The control of dispersion and orientation of nanotubes in such nanostructured composites materials allows to optimize their properties, and especially their electrical and optical properties.The first part of the work is devoted to the optimization of dispersion of SWNT in aqueous suspensions stabilized by bile salts surfactants, and to the study of their optical properties, and especially their near infrared photoluminescence (PL). Dispersion of the nanotubes is probed by absorption spectroscopy. We show that their absorption coefficient is very sensitive to the individualization of the nanotubes. On the other hand, we revisit the interpretation of the PL spectra excited in the near infrared (especially at 1.17 and 1.58 eV), and we assign the different peaks to different mechanisms, namely direct excitonic transitions, exciton-phonon coupling, and energy transfer between nanotubes. We show that the evolution of PL intensity as a function of individualization allows to distinguish the different mechanisms.The second part of the work is dedicated to the preparation of aqueous suspensionsstabilized by hydrosoluble polymers (PVA and PVP), and SWNT/polymer composites, without surfactants. SWNT suspensions are mixed with polymer solutions, and then the surfactant is removed by dialysis. The yield, i.e. the relative concentration of SWNT in the dialyzed suspension, is ~75 times higher than for a suspension prepared directly with polymers. On the other hand, PL signatures are sensitive to the dielectric environment of the nanotubes which allows to evidence an exchange between the dispersing agents bile salts/PVA on the nanotube surface, such an exchange is not observed in the case of PVP.In the third part of the thesis, we use the inkjet printing technique to print continuous micrometric lines of SWNT, and we propose original methods to study their morphology and their anisotropy. The morphology of the deposits varies between two limit cases, an homogeneous deposit and a ‘‘pair of tracks'', by varying nanotube concentration in the inks, inter-drop distance and substrate temperature. The orientation of the nanotubes is very high at the edge of the deposits (orientational order parameter S between 0.6 y 0.9), the nanotubes are well-oriented as well in the tracks (S~0.5) and to a lesser extent in the homogeneous lines (S~0.3).

Silício amorfo hidrogenado depositado por descarga luminescente tem adquirido posição de destaque entre os vários materiais foto-sensíveis, principalmente devido à sua fácil obtenção e versatilidade em propriedades. Neste trabalho, preparamos amostras de a-Si:H (Silício amorfo hidrogenado) utilizando o método de descarga de RF em atmosfera de gás SiH4, utilizando como substrato vidro e silício cristalino. As amostras depositadas sobre vidro foram utilizadas para estudo de formação de defeitos meta-estáveis no filme morfo devido a exposição à Raios-X. Os mecanismos de formação e recuperação dos defeitos foram analisados através do estudo da fotocondutividade, revelando a possível natureza de tais defeitos. Acreditamos que se trata da quebra de ligações Si-H e Si-Si, formando armadilhas para elétrons condutores. Analisamos a resposta espectral da fotocondutividade e absorção óptica, que forneceram informações a respeito do gap óptico do material. As amostras preparadas sobre c-Si foram utilizadas para a espectroscopia no infra-vermelho, onde analisamos o espectro das vibrações no material, bem como procuramos evidências da existência de hidrogênio molecular. / Hydrogenated amorphous silicon deposited by the glow discharge technique has been prominent among several photosensitive materials, mainly due to their easy obtention process and versatile properties. In this work, we have prepared hydrogenated amorphous silicon (a-Si:H) samples using the RF discharge method in SiH gaseous atmosphere. We have used glass and crystalline silicon as substrate. The samples which were deposited on glasses were used for the study on the creation of metastables defects in amorphous films due to X-Ray exposition. The creation and annealing process were analyzed through photoconductivity measurements which showed the possible origin of such defects. We believe that this behavior takes place due the breaking of Si-Si and Si-H bounds, which build up traps for free electrons. We have analyzed the photoconductivity spectral response and the optical absorption which give us information about the optical gap of this material. The samples which were prepared on crystalline silicon materials were used for infra-red spectroscopy, were we have analyzed the vibration spectra of a-Si:H, and also have been looking for evidences about the existence of molecular hydrogen.

L’accouchement prématuré est un problème de santé publique dans le monde et notamment dans les pays économiquement développés avec un taux variant entre 7 et 12 % des naissances. Le diagnostic du risque d’accouchement prématuré est difficile à faire et les outils à notre disposition ont peu évolué ces dernières années. La contraction utérine est la conséquence directe de l’activité électrique au niveau du myomètre. Le type de contraction est lié à l’importance de l’excitabilité cellulaire et de sa diffusion à l’ensemble du myomètre. Le recueil et l’analyse de cette activité électrique par des électrodes de surface est aujourd’hui le seul moyen non invasif d’étudier, pendant la grossesse, les mécanismes qui sont à l’origine de la contraction. L’enregistrement de l’électromyogramme utérin ou électrohystérogramme (EHG) est donc prometteur pour réaliser un diagnostic et une surveillance des femmes à risque d’accouchement prématuré. Dans ce travail de thèse 3 études cliniques ont été réalisées. Dans la première, j’ai étudié différentes électrodes de surface permettant d’enregistrer les signaux électriques. Je propose à la fin de cette première partie un système d’électrodes pour permettre à la fois un enregistrement de qualité et une pose aisée compatible avec une application clinique. Dans la deuxième étude j’ai étudié la détection automatique des contractions par l’EHG avec des résultats encourageants pour l’application clinique et notamment en ambulatoire. Enfin dans la troisième étude j’ai étudié la prédiction du risque d’accouchement prématuré par l’analyse de paramètres électriques issus de l’EHG. Les résultats obtenus permettent d’améliorer la prédiction du risque d’accouchement prématuré par rapport aux outils utilisés en routine. / Premature birth is a public health problem in the world, particularly in economically developed countries with a rate varying between 7% and 12% of births. The diagnosis of the risk of premature labor is difficult to make and the tools at our disposal have changed little in recent years. Uterine contraction is a direct consequence of electrical activity at the level of the myometrium. The type of contraction is related to the importance of cell excitability and its diffusion to the entire myometrium. The analysis of this electrical activity by surface electrodes is currently the only non-invasive way to study the mechanisms that are at the origin of the contraction. The recording of the uterine electromyogram or electrohysterogram (EHG) is therefore promising for the diagnosis and surveillance of women at risk of preterm birth. In this thesis work 3 clinical studies have been carried out. In the first clinical study, different surface electrodes to record electrical signals were tested. I propose at the end of this first part a system of electrodes to allow at the same time a recording of quality and an easy pose compatible with a clinical application. In the second study , the automatic detection of contractions by the El-IG was studied with encouraging results for the clinical application and especially in ambulatory. Finally, in the third clinical experiment, I studied the prediction of the risk of premature delivery by the analysis of electrical parameters extracted from the EHG. The results obtained make it possible to improve the prediction of the risk of premature delivery compared to the tools used routinely.

Fundamental thermodynamic investigations have been carried out regarding the phase equilibria of La0.8Sr0.2MnO3±δ (LSM), a cathode of a solid oxide fuel cell (SOFC), utilizing the CALculation of PHAse Diagram (CALPHAD) approach. The assessed thermodynamic databases developed for LSM perovskite in contact with YSZ fluorite and the other species have been discussed. The application of computational thermodynamics to the cathode is comprehensively explained in detail, including the defect chemistry analysis as well as the quantitative Brouwer diagrams, electronic conductivity, cathode/electrolyte interface stability, thermomechanical properties of the cathode and the impact of gas impurities, such as CO2 as well as humidity, on the phase stability of the cathode. The quantitative Brouwer diagrams for LSM at different temperatures are developed and the detailed analysis of the Mn3+ charge disproportionation behavior and the electronic conductivity in the temperature range of 1000-1200°C revealed a good agreement with the available experimental observations. The effects of temperature, CO2 partial pressure, O2 partial pressure, humidity level and the cathode composition on the formation of secondary phases have been investigated and correlated with the available experimental results found in the literature. It has been indicated that the CO2 exposure does not change the electronic/ionic carriers’ concentration in the perovskite phase. The observed electrical conductivity drop is predicted to occur due to the formation of secondary phases such as LaZr2O7, SrZrO3, SrCO3 and Mn oxides at the LSM/YSZ interface, resulting in the blocking of the electron/ion transfer paths. For the thermo-mechanical properties of LSM, a new weight loss Mechanism for (La0.8Sr0.2)0.98MnO3±δ using the La-Sr-Mn-O thermodynamic database is modeled with respect to the compound energy formalism model. This newly proposed mechanism comprehensively explains the defect formation as a result of volume/weight change during the thermal cycles. According to the proposed mechanism the impact of cation vacancies regarding the volume change of cathode was explained.