Loline alkaloids (LA) are secondary metabolites produced by Epichloandamp;euml; (anamorph, Neotyphodium) grass endophytes. They are toxic and deterrent to a broad range of herbivorous insects but not to livestock. This protective bioactivity has spurred considerable research into the LA biosynthetic pathway. LOL, the gene cluster containing nine genes, is required for LA biosynthesis. The regulation of LOL genes during LA production in culture and in symbio is of interest. In this study, coordinate regulation between LOL gene expression and LA production level was investigated in both MM culture and symbiota. Results showed that expression of LOL genes in N. uncinatum MM culture were tightly correlated with each other (p andamp;lt; 0.0005), and all presented a significant temporal quadratic pattern during LA production. Gene expression started before LA were detectable, and increased while LA accumulated. The highest gene expression level was reached before the highest amounts of LA were detected, and gene expression level declined to a very low level after amounts of LA plateaued. Observations suggested that the hierarchical clusters based on the correlation coefficient could help to predict the roles of LOL genes in the LA pathway. In symbiota, coordinate coregulation of LOL gene expression with LA was found in E. festucae-meadow fescue inflorescences and stromata, whereby lower LOL gene expression corresponded with the lower LA level in stromata. In N. uncinatum (or N. siegelii)-meadow fescue vegetative tissues, dramatically higher LA levels were found in younger leaf tissue than in older leaf tissue, yet no evidence was found to relate this difference to LOL gene expression differences. Instead, substrate availability may regulate the LA level. In particular, asparagine was more than 10-fold higher in young leaf tissue than in old tissue, although proline was significantly lower in young tissue. Therefore, different regulatory mechanisms underlie LOL gene expression and LA production in different circumstances. The GUS activity of Pro-lolC2-GUS and Pro-lolA2-GUS in Neotyphodium species was almost undetectable in culture, though the activity could be detected in symbiota. The mRNA of GUS did not exhibit the same pattern as lolC2 or lolA2 in culture during LA production time course. A Pro-lolC2-cre transgene was expressed in complex medium, in which lolC2 mRNA was not detectable. These results suggest that proper regulation of LOL genes in culture or symbiota is dependent on the LOL cluster.

There are currently three known crystal packing motifs of boronsubphthalocyanine derivatives. Each motif is associated with a particular class of BsubPc derivatives, and none are ideal for organic electronic applications according to the criteria we defined for evaluation: having a continuous pathway for charge-carrier conduction in the solid-state, resistance to hydrolysis, good electrochemical and optical properties, and possession of a robust crystal form. In this thesis, we present five methods for altering the crystal packing structure of phenoxy-BsubPc derivatives in order to meet the above four criteria. We find that neither addition of steric bulk to the axial derivative nor changing the symmetry of the compounds is sufficient for creating a new crystal packing motif. We do find that reducing the symmetry of the axial group does increase the solubility greatly, however. We identify a new motif for BsubPc crystals that occurs when the intermolecular interactions between the axial phenoxy segment and the BsubPc ligand are increased. We present two methods for achieving this new motif, one is through addition of a π-Br interaction and the other is through creation of a strong π-acid/ π-base stacking by making the axial phenoxy more π-electron rich. Unfortunately, the p-bromophenoxy-BsubPc forms this new motif as a kinetic product, isolation of which is unreliable. Attaching a naphthol fragment axially to the BsubPc creates a stable version of this new motif. We also synthesized a new class of BsubPc pseudohalides based on sulfonate derivatives. Of the derivatives in this new class, we found that mesylate-BsubPc forms into a crystal packing structure that possesses a one-dimensional pathway for charge carrier mobility, but is still resistant to hydrolysis under the conditions tested. Overall, we show four compounds that meet the criteria for further study as organic electronic materials: p-methoxyphenoxy-BsubPc, α-naphthoxy-BsubPc, β-naphthoxy-BsubPc, and mesylate-BsubPc.

There are currently three known crystal packing motifs of boronsubphthalocyanine derivatives. Each motif is associated with a particular class of BsubPc derivatives, and none are ideal for organic electronic applications according to the criteria we defined for evaluation: having a continuous pathway for charge-carrier conduction in the solid-state, resistance to hydrolysis, good electrochemical and optical properties, and possession of a robust crystal form. In this thesis, we present five methods for altering the crystal packing structure of phenoxy-BsubPc derivatives in order to meet the above four criteria. We find that neither addition of steric bulk to the axial derivative nor changing the symmetry of the compounds is sufficient for creating a new crystal packing motif. We do find that reducing the symmetry of the axial group does increase the solubility greatly, however. We identify a new motif for BsubPc crystals that occurs when the intermolecular interactions between the axial phenoxy segment and the BsubPc ligand are increased. We present two methods for achieving this new motif, one is through addition of a π-Br interaction and the other is through creation of a strong π-acid/ π-base stacking by making the axial phenoxy more π-electron rich. Unfortunately, the p-bromophenoxy-BsubPc forms this new motif as a kinetic product, isolation of which is unreliable. Attaching a naphthol fragment axially to the BsubPc creates a stable version of this new motif. We also synthesized a new class of BsubPc pseudohalides based on sulfonate derivatives. Of the derivatives in this new class, we found that mesylate-BsubPc forms into a crystal packing structure that possesses a one-dimensional pathway for charge carrier mobility, but is still resistant to hydrolysis under the conditions tested. Overall, we show four compounds that meet the criteria for further study as organic electronic materials: p-methoxyphenoxy-BsubPc, α-naphthoxy-BsubPc, β-naphthoxy-BsubPc, and mesylate-BsubPc.

L’effet thermoélectrique permet la conversion directe et réversible d’un flux de chaleur en courant électrique via l’utilisation de semi-conducteurs de type-p et de type n. Les polymères conjugués, comme le poly(3,4-éthylènedioxythiophène) (PEDOT) sont pressentis pour être des alternatives aux alliages de tellurure de bismuth (Bi2Te3) coûteux, toxiques et difficiles à synthétiser.Cette thèse se propose d’améliorer la conductivité électrique d’un PEDOT et de faciliter sa mise en œuvre par une technique d’impression grande surface comme le spray.La première partie porte sur l’amélioration de la synthèse par tournette du PEDOT : OTf dont le dopage est stabilisé par le contre-ion trifluorométhanesulfonate (OTf-). Plusieurs co-solvants sont testés comme la pyridine ou la NMP. Ces co-solvants permettent de ralentir la polymérisation et d’améliorer ainsi la structure du matériau. Des conductivités électriques de 3600 S.cm-1 avec un coefficient Seebeck aux environs de 20 µV.K-1 sont atteintes.La seconde partie étudie les avantages et les inconvénients d’une synthèse de ce PEDOT : OTf amélioré par spray ultrasonique. Cette technique permet de conserver la formulation développée pour le dépôt par tournette. Il est possible d’obtenir des films épais (~ 1 µm) avec une conductivité électrique supérieure à 1650 S.cm-1. Des études par diffraction des rayons X et de transports permettent de comparer les deux méthodes de dépôt et d’orienter les choix de formulation et de procédé.Finalement, avec ces améliorations apportées, des exemples de modules thermoélectriques imprimés sont présentés et évalués. Ainsi en imprimant plus de 300 thermocouples connectés en série puis roulés, un tel module thermoélectrique occupe une surface inférieure à une pièce de 50 centimes d’euro et peut générer 1 µW avec un gradient de température de 35 °C.Cette thèse souhaite pouvoir apporter des éléments de réponse sur la relation entre la mise en œuvre et les propriétés électriques des polymères conducteurs. / Thermoelectricity can convert directly and reversibly a heat flux into an electric current with p and n-type semiconductors. Conjugated polymers, such as poly(3,4-ethylenedioxithiophene) (PEDOT), offers an alternative to the best room temperature thermoelectric materials based on bismuth telluride alloys which used scarce, hazardous and hard to process raw materials.This PhD work aims to enhance the electrical conductivity of an in-situ polymerised PEDOT and make it easy to process with large scale printing techniques like spray-coating.The first part focus on the optimisation of this synthetized PEDOT through spin-coating. The doping of this PEDOT is stabilised with the counter-ion trifluoromethanesulfonate (OTf-). One way of enhancement is to add co-solvents like pyridine and NMP in order to slow down the polymerisation rate. Consequently, PEDOT:OTf get a better structure and reach an outstanding electrical conductivity of 3,600 S.cm-1 without decreased the Seebeck coefficient which remains around 20 µv.K-1.The second part studies pro and cons of the ultrasonic spray as a coating technic to this enhanced PEDOT:OTf. This technic allows to keep an ink formulation closed of the spin-coating one and can print thick films (~ 1 µm) with an electrical conductivity above 1650 S.cm-1. XRD and transport measurements are achieved in order to understand and compare both spray and spin-coating techniques. And therefore, to enlighten improvement on formulation and process.At last, several examples of spray-coated thermoelectric generators are shown and tested. Thus by printing more than 300 thermocouples connected in series and rolled into a cylinder, such devices could produce 1 µW with a gradient of temperature of 35 °C on a surface less than a 5 cm2 (size of a coin).This thesis work wishes to provide insight on the process-electrical relationship in conducting polymers.

Para que a tecnologia de eletrônica orgânica alcance todo o seu potencial é primordial que o processo de fabricação seja rápido e barato, e uma das maneiras de alcançar isto é com a utilização de processos gráficos especialmente adaptados para a produção de eletrônica, processo esse conhecido por roll-to-roll. Uma grande carência mundial se encontra em equipamentos de produção roll-to-roll de porte laboratorial, que possam ser utilizados para estudos de construção dos dispositivos e, mais importante, a transferência das tecnologias desenvolvidas em laboratório para processos que possam ser facilmente expandidos para a indústria. Neste sentido, durante este trabalho foi desenvolvido um sistema roll-to-roll compacto para produção e estudo de dispositivos orgânicos que apresenta as técnicas de deposição por rotogravura, wire-bar e knife-over-edge comutáveis, sendo empregada uma técnica por vez. O equipamento foi projetado e fabricado de forma a permitir a maior quantidade possível de ajustes das variáveis, com um pequeno consumo de material polimérico e de substrato. Além disto, desenvolveu-se um software de controle operado empregando-se o programa LabVIEW para regulagem da temperatura de secagem, velocidades do substrato e impressão. Como primeiro dispositivo fabricado optou-se por células eletroquímicas emissoras de luz (PLEC) por estas apresentarem baixa tensão de operação e uma baixa influência da espessura e dos eletrodos em suas propriedades optoeletrônicas. Desta forma, foi produzido um dispositivo luminescente sobre papel alumínio, flexível, de baixo custo, sem ITO e todo fabricado no equipamento roll-to-roll aqui desenvolvido. Além disto, o processo foi projetado para ser executado no ambiente, isto é, sem etapas que necessitem vácuo ou atmosfera controlada. Estes dispositivos comprovaram a aplicabilidade do sistema desenvolvido para a produção e desenvolvimento da eletrônica orgânica em laboratório visando a produção industrial final. / To develop the entire potential of Organic Electronic (OE) industry, it is necessary to generate processing methods that include high speed production at low cost. One technique that is emerging as very promising is that known as roll-to-roll. Despite the existence of several roll-to-roll machinery in the market, a small prototype that can be used in laboratories certainly will be very useful for research and as first experiments for production. In this work, we developed a compact roll-to-roll system devoted specifically to the production of printable electronic devices. In particular, this machine disposes deposition techniques as rotogravure, wire-bar and knife-over-edge. It is a versatile machine, which allows the operation of several technical parameters, using a relatively low amount of polymer material and substrate. In addition, we developed a numerical control system that is operated by a computer trough a LabWIEW program. This regulates the drying temperature and the substrate speed, parameters of fundamental importance for a good printed product. As first test we opted for building a coated Light Emitting Electrochemical Cell (PLEC), which are optoelectronic devices that uses relatively low operation voltage and does not exhibit critical thickness dependence. We printed this low cost and flexible device onto aluminum paper, then avoiding any other process and the use of ITO. All the coating processing was carried out in environmental conditions, being not necessary vacuum or accurate control of atmosphere. This application gives a strong evidence that this compact roll-to-roll machine presents a good performance in the fabrication of organic optoelectronic devices, being adequate for research and as guide for industrial production.

Au cours de cette thèse, une technique de mesure du potentiel de surface par AFM (KPFM) a été développée et exploitée. Elle permet la caractérisation locale et quantitative de transistors organiques (OTFT) polarisés à plusieurs dizaines de volts, en condition ambiante. Cependant tout type de composants polarisés dont la surface est accessible peut être étudié. La méthode a été utilisée de façon complémentaire à l’étude conventionnelle des caractéristiques courant-tension des transistors et à la simulation, elle contribue ainsi à une meilleure compréhension des mécanismes de transport et d’injection des porteurs dans les OTFT. Nous avons étudié des transistors en structure empilée ou planaire et à base de semi-conducteurs variés (PTAA, DNTT, P3HT). Nous avons obtenu des caractéristiques courant-tension intrinsèques du contact de source, ohmique ou non-linéaire, suivant les cas. Les résultats sont 10 fois plus précis qu’avec la méthode dite « transmission line method (TLM) » et permettent d’étudier chaque transistor individuellement. La modélisation des contacts s’est appuyée sur l’implémentation du modèle d’injection d’Arkhipov dans un simulateur quasi-2D. Une nouvelle méthode de mesure de la mobilité et de la tension de seuil à partir des profils de potentiel a été introduite. Nous avons ainsi mesuré la mobilité du canal indépendamment des effets des contacts. Etonnamment la mobilité a été trouvée indépendante du champ électrique et de la densité de charges pour tous les OTFT étudiés. Enfin l’analyse des profils de potentiel dans le canal a mis en lumière des effets inattendus comme une diminution de la mobilité proche des contacts ou une évolution de la tension de seuil. / In this work, a surface potential measurement technique based on the Kelvin Force Probe Microscopy (KPFM), has been developed and applied to operating electronic devices. Potential profiles in the channel of organic transistors operated under high voltage (>10V) have been measured under ambient conditions. This original technique was used together with conventional current-voltage characterization and numerical simulation to gain a better understanding of carrier injection and transport properties in organic thin film transistors (TFTs). Various TFT structures and materials were studied (PTAA, DNTT, P3HT). The source intrinsic current-voltage characteristic was found either linear or non-linear depending on the device technology. Contact resistance measurements are 10 times more accurate than using the conventional « transmission line method» (TLM), and allow individual TFT characterization. Contact modeling was carried out using a quasi-2D numerical model, including an injection model from Arkhipov, and compared to measurements. New mobility and threshold voltage measurement methods, extracted from the KPFM potential profiles, are introduced. The KPFM measured channel mobility does not suffer from any contact influence. Surprisingly, the channel mobility was also found independent from the carrier concentration and from the electric field, on all the measured devices. Finally, unexpected effects could be evidenced from the potential profiles on some TFT structures: a reduction of the channel mobility occurs close to the contacts in some planar structures, and a shift of the threshold voltage was observed in staggered devices.

No description available.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Ce travail de thèse a été réalisé grâce à une collaboration entre le laboratoire IMS (Université Bordeaux 1, CNRS) et la société STANTUM dans le cadre d’une bourse CIFRE.La thématique étudiée se positionne dans le domaine en pleine expansion des interfaces tactiles intégrées dans les écrans. La mise en production ces dernières années des systèmes multi-touches a permis l’arrivée sur le marché grand public de nombreux dispositifs tels que les GPS, les Smartphones ou encore les tablettes. Malgré tout, de nombreux problèmes sont encore à résoudre, en particulier la possibilité d’avoir une écriture naturelle via un stylet, en posant la main sur la tablette comme sur une feuille de papier. Après un rappel sur l’historique et sur l’intérêt des dalles tactiles comme interface homme/machine, le premier chapitre présente les principales technologies actuelles et la technologie iVSM développée par STANTUM. La structure des dalles tactiles et les différentes étapes de fabrication de ces dernières sont abordées dans le deuxième chapitre. Nous avons ensuite développé un modèle théorique permettant de décrire le fonctionnement et les limitations de la technologie. Ces dernières peuvent survenir lorsque l’utilisateur écrit sur la dalle tactile et peuvent empêcher, dans certaines configurations, une bonne reconnaissance d’écriture. Deux approches sont proposées dans le quatrième chapitre pour corriger ces phénomènes inhérents : la couche résistive et les diodes intercalées. Le dernier chapitre est dévolu à la partie expérimentale. Tout d’abord, les différentes approches dédiées à la réalisation d’une couche résistive, que ce soit par enduction par sol-gel ou encore par pulvérisation cathodique, sont présentées. Pour la caractérisation des dalles tactiles, nous avons mis en place des facteurs de qualité permettant de juger efficacement de l’amélioration des performances et avons également pris en compte les paramètres de dureté, d’adhésion et surtout d’état de surface des couches intermédiaires. La seconde partie de ce chapitre se focalise sur la réalisation des diodes par les approches couches minces (jonction tunnel par PVD, diode organique et jonction PN en silicium amorphe). / This work comes from close collaboration between IMS laboratory (University of Bordeaux 1, CNRS) and STANTUM. This thesis is focused on tactile interface integrated on display. Recently multitouch systems became compatible for consumer electronic market which led to incoming devices such as GPS, Smartphones and tablet PC. However troubles still remained. Performing the discrimination between finger, palm and stylus was still an insuperable technology step to provide natural handwriting input on a display. After reminding a brief historic and the interest as human to machine interface, the first chapter presents the dominating touch screen technologies at the moment and the iVSM STANTUM technology. Touch screen structure and fabrication processes are approached, including industrial step as laser patterning or stencil printing. Then a theoretical model is detailed to explain the iVSM scanning engine and the inherent phenomena. These latter can occur when user is writing on the display with stylus in certain configurations. Two approaches are discussed in the third chapter in order to cut off or at least decrease those phenomena amplitude: the resistive layer and the embedded matrix diodes. The last chapter is dedicated to experimental results. Firstly, several processes, as doctor-blade and physical vapor deposition, are explained. Characterization is performed in using quality factors, to specifically evaluate inherent phenomena decreasing. Hardness, roughness and surface morphology are also discussed in this chapter. The second part is focused on embedded matrix diodes using thin film technologies (tunnel junction, organic diode and a-Si PN junction).