Organic electrode materials are finding increasing use in energy storage devices due to their attractive properties that allow building of flexible and low weight devices in an environmentally friendlier manner than traditional alternatives. Among these organic electrode materials, conducting redox polymers (CRPs), consisting of conducing polymer (CP) with covalently attached redox active pendant groups (PG), have attracted our interests. This is due to the advantageous synergy between CP and PG, e.g. electronic conductivity, high stability and large charge storage capacity. In this thesis polypyrrole has been selected as CP and quinones as PGs. A series of quinone-pyrrole dyad polymers has been synthesized with a variety of quinone substituents, demonstrating the adjustability of quinone formal potentials by choice of substituents. Importantly, in this series we show that the CP-PG redox match, i.e. that the formal potential of the PG is within the conducting region of the CP, is a requirement for fast charge transfer from the electrode to the PGs. Moreover, a series of quinone-pyrrole dyad polymers with various linkers was synthesized, showing that the choice of linker has a pronounced impact on the interactions between the PG and CP. In addition, the temperature dependence of conductance during doping of the polymers reveals the charge transport mechanism. To summarize, the adjustability of the quinone formal potential as well as the fast charge transport in the bulk material ensures the applicability of the CRPs as electrode materials in organic batteries.

A une époque où les technologies nouvelles fleurissent chaque jour, un domaine particulier se détache : l’électronique organique. Par son utilité et sa facilité de mise en œuvre, l’électronique organique affiche de grandes promesses pour l’avenir. Dans le but d’améliorer le procédé de fabrication et la durée de vie de ces dispositifs, le travail de cette thèse s'est focalisé sur la synthèse de copolymères à architectures variées à base de poly(3-hexylthiophène) (P3HT). Après avoir exposé les problématiques et objectifs de la thèse dans une première partie, la synthèse de différents précurseurs P3HT est décrite. Ces matériaux représentent la base des travaux présentés dans cet ouvrage. Dans un premier temps, l'optimisation de la synthèse des copolymères à blocs rigide-flexible a été réalisée en suivant une stratégie adaptée pour une application en électronique organique. La conception de nouveaux matériaux semi-conducteurs à architectures ramifiées est traitée par la suite. Enfin, le dernier chapitre porte sur l'intégration d’un copolymère, le P3HT-b-Poly(4vinylpyridine), en cellule photovoltaïque organique en tant qu'additif de la couche active. Cette approche s’avère être particulièrement puissante, permettant notamment de diminuer le temps et le coût énergétique de la mise en œuvre de ces cellules en s’affranchissant d’une étape clé de la fabrication, le recuit. / At a time when new technologies emerge every day, a specific domain stands out: the organic electronic. Through its low cost processing or even its utility, the organic electronic constitutes a very promising future.In order to improve the fabrication process and the lifetime of the devices, the work of this thesis was focused on the synthesis of copolymers with various architectures based on poly(3-hexylthiophene) (P3HT). After a first part where main issues and objectives are presented, the synthesis of different P3HT-based precursors is described in a part which could be considered as the heart of these works. Starting with appropriated precursors, the optimization of rod-coil diblock copolymer synthesis was performed following a strategy designed specifically for organic electronic application. Moreover, the precursors were used for the conception of new semi-conducting materials with a variety of architectures, such as graft and star copolymers. Finally, the last part deals with the integration of the P3HT-b-Poly(4-vinylpyridine) copolymer into organic solar cell as an additive of the active layer. This approach turns out to be powerful, especially allowing decreasing the time and the energy cost by avoiding the key step of the fabrication process of those devices, the annealing step.

Cette thèse porte pour l'essentiel sur la synthèse de copolymères à blocs bien définis composés au moins d'un bloc polymère semi-conducteur et d'un segment hydrosoluble pour être utilisés comme agents dispersants de nanotubes de carbone (NTCs) dans des milieux aqueux. Des copolymères de différentes masses molaires ont été synthétisés en suivant des procédés de polymérisation sans métaux et l’influence de la fraction volumique de la partie hydrosoluble a été étudiée au regard de leur solubilité en milieux aqueux. La capacité de ces copolymères à s'organiser ou s'auto-assembler tant en solution qu'en film a été examinée. Enfin, des dispersions de NTCs avec ces copolymères ainsi que leurs films obtenus par différents types de dépôts ont été réalisés et caractérisés pour déterminer notamment leurs caractéristiques électro-optiques. / Our work focused on the synthesis of well-defined copolymers constituted with at least a conductive polymer segment along with hydrophilic moieties in order to disperse CNTs in aqueous media. Using metal free polymerizations, copolymers with different molecular weights were synthesized in order to study the influence of the hydrophilic part on these materials. Besides the self-assembly behavior of these copolymers, both in bulk and in solution, were addressed. This type of copolymers were successfully used to disperse both single and multi wall carbon nanotubes. Electrical and optical characteristics of the dispersions together with their films will also be discussed.

Depuis de nombreuses années des chercheurs imitent le vivant afin d'obtenir des systèmes capables de s'adapter à des environnements de plus en plus complexes. Aujourd'hui aucune des technologies classiques n'est capable de rivaliser complètement avec le fonctionnement d'un muscle. L'objectif de ce travail est de synthétiser et d'intégrer une nouvelle génération d'actionneurs-capteurs à base de réseaux interpénétrés de polymères conducteurs dans des systèmes de perceptions biomimétiques. Nous avons tout d'abord réalisé la synthèse et la caractérisation d'une nouvelle matrice hôte à base de réseaux interprétés de polymères (RIP) combinant de bonnes propriétés mécaniques du caoutchouc nitrile (NBR) et de conductivités ioniques du poly (oxyde d'éthylène). Nous avons ensuite incorporé dans cette matrice hôte un polymère conducteur électronique, le poly (3,4-éthylènedioxythiophène), par polymérisation in situ. Nous avons caractérisé les effets de différents paramètres de synthèse sur la localisation et la morphologie du polymère conducteur au sein de la matrice. Puis nous avons caractérisé les propriétés d'actionneurs et de capteurs de ces matériaux électroactifs. Enfin nous avons réalisé l'intégration de ces matériaux dans deux prototypes de systèmes de perceptions biomimétiques, le premier tactile imitant les vibrisses du rat et le deuxième visuel imitant les muscles oculomoteurs. Finalement, nous concluons que les propriétés et performances de cette nouvelle génération d'actionneurs-capteurs permettent leurs intégrations dans des systèmes de perceptions spécifiques pouvant être utilisés sur un robot mobile. / For many years researchers mimic the living in order to obtain systems that can adapt to complex environments. Today no conventional technology is able to fully compete with the functioning of a muscle. The objective of this work is to synthesize and integrate a new generation of actuators and sensors based on interpenetrating polymer networks of conductive polymers in biomimetic perceptions systems. We first carried out the synthesis and characterization of a novel host matrix based on interpreted polymer networks (IPN) combining good mechanical properties of nitrile rubber (NBR) and ionic conductivities of poly(ethylene oxide ) (PEO). Then, We incorporated into this host matrix an electronically conductive polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), by in situ polymerization. We characterized the effects of various synthesis parameters on the location and morphology of the electrically conductive polymer within the matrix. Then, we characterized the actuation and sensing properties of these électroactive materials. Finally, we completed the integration of these materials into two prototypes of biomimetic perceptions. The first one tactile is imitating and emulating tactile perception of the rat vibrissae. The second one visual is imitating the extraocular muscles. Finally, we conclude that properties and performances of this new generation of sensor-actuators allow their integration into specific perception system that can be used on a mobile robot.

Master of Music / Department of School of Music, Theatre, and Dance / Frank Tracz / The following report is a comprehensive analysis of two works for wind band and one work for small chamber ensemble, prepared by Patrick Sullivan. The report was completed in addition to a Graduate Conducting Recital, taking place on Sunday, March 10, 2013 at 3:00pm. The concert featured the Kansas State University Wind Ensemble and took place on the Kansas State University Campus in McCain Auditorium, the conductors were Andrew Feyes and Patrick Sullivan. Audio and video recordings of the conducted performance can be found within the K-State Research Exchange database. The following report includes three comprehensive Unit Studies or Teacher Research Guides found in the Teaching Music Through Performance in Band book series. The report also includes three Tracz Analysis Grids, newly published in The Art of Interpretation of Band Music. The examined pieces are as follows. Full band works, Flight by Claude T. Smith and Baron Cimetiére’s Mambo by Donald Grantham. A chamber work for double woodwind quintet, Suite Persane by André Caplet.

Master of Music / Department of Music / Frank Tracz / The following report is a comprehensive analysis of two works for wind band and one work for brass ensemble, prepared by Adam Ladd. The report was completed during the Spring semester of 2014 and culminated with live performances of each piece by the Kansas State University Concert Band and Brass Ensemble with Adam Ladd conducting. Audio and video recordings of the conducted performances can be found within the K-State Research Exchange database. The following report includes three comprehensive Unit Studies or Teacher Research Guides in the format that is described in the Teaching Music Through Performance in Band book series. The report also includes three Tracz Analysis Grids in the format that is found in The Art of Interpretation of Band Music. The examined pieces are as follows. Toccatta for Band, by Frank Erickson, Mutations from Bach, by Samuel Barber, and Nobles of the Mystic Shrine, by John Philip Sousa, arranged by Philip Sparke.

Master of Music / Department of Music, Theatre, and Dance / Frank C. Tracz / This report provides a comprehensive research and teaching guide for three works for wind ensemble, brass ensemble, and chamber winds: Three Songs from Sussex by Hugh M. Stuart, Fanfare for Brass and Percussion by Karel Husa, and Serenade No. 10 in Bb, Largo, Allegro molto by Wolfgang Amadeus Mozart. Each chapter provides information on the composer, composition, historical perspective, technical considerations, stylistic considerations, musical elements, form and structure, other listening suggestions, and seating arrangement considerations. Also included are the lesson plan outlines that were used to teach each work, and a detailed score analysis grid. The report documents the full process of selecting, researching, rehearsing, and performing the selected literature with the hope that it will aid in future performances of the works.

Master of Music / Department of Music, Theatre, and Dance / Frank C. Tracz / The following report provides a comprehensive analysis of and teaching guide for one work for brass ensemble and two works for wind band: Legacy by Mark Camphouse, Concert Variations by Claude T. Smith, and Romance for Band by John Zdechlik. A chapter is included for each work, supplying essential information needed to properly prepare the conductor for teaching and rehearsing the work in question. Information is included regarding the composer, the composition, historical perspective, technical considerations, stylistic considerations, musical elements, form and structural analysis, listening suggestions, and a suggested seating arrangement. Outlines of rehearsal plans used by the author are included with self-evaluations of each rehearsal, in addition to a detailed score analysis grid as presented by Dr. Frank Tracz in Mark Walker's book, The Art of Interpretation of Band Music. Chapters are also devoted to the author’s philosophy of music education and philosophy of quality literature selection. All materials are included with the hope that this research can assist in preparation of these works by other conductors and ensembles, as well as to promote a more active programming of these quality, lesser-known works.

Ce travail porte sur la caractérisation de matériaux en couches minces par spectroscopie terahertz dépendant du temps. Dans ce but, nous avons élaboré un banc d’analyse spectroscopique dont l’émission et la détection terahertz reposent sur l’utilisation de laser femtoseconde, de semi-conducteurs, de photocommutateurs ultrarapides ou de cristaux électro-optiques. La réponse diélectrique quantitative de matériaux ferroélectriques (titanate de baryum/ - Ba1-xSrxTiO3) déposés sous forme de couches minces, a permis de mettre en évidence l’importance des modes mous de phonon par une étude en température. Enfin, le comportement électromagnétique de polymères conducteurs à base de polyaniline a été effectué notamment leur efficacité de blindage en bande millimétrique et submillimétrique. / This work concerns the characterization of thin film materials by terahertz time domain spectroscopy. For this purpose, we elaborated a terahertz setup in which the terahertz emission and terahertz detection are based on the use of femtosecond laser, semiconductors, ultrafast photoswitches or electro-optic crystals. The study of dielectric function of ferroelectrics thin film (barium titanate/-Ba1-xSrxTiO3) with temperature, give the importance of soft phonon mode. Finally, the electromagnetic behavior of conducting polymers based on polyaniline was made, in particular their shelding effectiveness in millimeter and sub-millimeter length.

Biosensors based on solid-state field-effect transistor as transducer stage using organic semiconducting materials as sensing stage have been developed. Polyaniline thin films galvanostatic electrodeposited were fabricated. Varied electrodeposition parameters were tested, such as deposited charge, current density, deposition time and monomer concentration, besides the tests of a polymeric blend composed of polyaniline and polypyrrole and tested as pH potentiometric extended gate field-effect transistor sensor. Then, biosensors were produced using the one-step electrochemical immobilization process to obtain thin polyaniline films with entrapped glucose oxidase and urease enzymes, to detection of glucose and urea, respectively. The optimized films presented sensitivity, linearity and detection range to glucose of 14.6 ± 0.4 mV/decade, 99.8 % and from 10-4 mol/L to 10-1 mol/L. Two different biosensors were produced based on the enzymatic catalysis of urea with selectivity to ammonium or hydroxyl ions. For ammonium ion selective films, the sensor presented sensitivity, linearity and detection range of 14.7 ± 0.9 mV/decade, 98.2 % and from 10-5 mol/L to 10-1 mol/L. For the hydroxyl ion selective film, the same parameters were 7.4 ± 0.5 mV/decade, 98.1 % and from 10-5 mol/L to 10-1 mol/L. The same functionalized polyaniline thin films were used in optical and conductometric biosensors due to the polyelectrochromic characteristic of the material. Improvement of the field-effect system was possible with the multimodal array of enzymatic biosensor. The device was built using different enzymatic sensing stages connected to the extended gate field effect transistor. The system decreased the time needed to make distinct measurements, showed good response to the variation in solutions pH, to the presence of the reference film and to injection of target analyte in solution in real time measurement. The electrolyte gated organic field-effect transistor based on a polythiophene organic semiconducting layer was developed. A modular enzymatic biosensor for glucose and urea, with a linear response in the range between 10-6 and 10-3 mol/L, was achieved. This biosensor relies on the immobilization the enzymes on gold rods, used as gate electrodes in the devices. The use of the bioreceptors proved to be selective and cross-selective in the devices. The possibility of exchanging the modified gate electrode to detect specific analytes using the same device system allows the modular sensor to be reused and applied for a broad range of applications. Which is the case for explosives molecules, TNT and DNT, biosensor fabricated in the same terms. This biosensor relies on the immobilization of specific binding peptides for TNT and DNT on the gold rod / Biossensores do estado sólido baseados em transistores de efeito de campo como estágio transdutor fabricados com materiais semicondutores orgânicos como estágio de detecção foram desenvolvidos. Filmes finos de polianilina eletrodepositados galvanostaticamente foram fabricados. Parâmetros de eletrodeposição foram testados, como carga depositada, densidade de corrente, tempo de deposição e concentração de monômero, além de testes com compósito polimérico de polianilina e polipirrol e aplicados como sensor de transistor de efeito de campo de porta estendida potenciométrica de pH. Em seguida, os biossensores foram produzidos utilizando-se o processo de imobilização eletroquímica conjunta para obtenção de filmes finos de polianilina com enzimas glicose oxidase e urease imobilizadas, para detecção de glicose e ureia, respectivamente. Os filmes otimizados apresentaram sensibilidade, linearidade e faixa de detecção para glicose de 14,6 ± 0,4 mV/década, 99,8% e de 10-4 a 10-1 mol/L. Dois biossensores diferentes foram produzidos a partir da catálise enzimática da ureia com seletividade para íons amônio ou hidroxila. Para filmes seletivos ao íon amônio, o sensor apresentou sensibilidade, linearidade e faixa de detecção de 14,7 ± 0,9 mV/década, 98,2% e de 10-5 a 10-1 mol/L. Para o filme seletivo ao íon hidroxila, os mesmos parâmetros foram 7,4 ± 0,5 mV/década, 98,1% e de 10-5 a 10-1 mol/L. Os mesmos filmes finos de polianilina funcionalizados foram utilizados em biossensores ópticos e condutométricos devido à característica polieletrocromática do material. A melhoria do sistema foi possível com o arranjo multimodal do biossensor enzimático. O dispositivo foi construído usando diferentes estágios de detecção enzimática conectados ao transistor de efeito de campo de porta estendido. O sistema diminuiu o tempo necessário para fazer medições distintas, mostrou boa resposta à variação no pH da solução, à presença do filme de referência e à injeção do analito alvo em solução na medição em tempo real. Foi desenvolvido o transistor orgânico de efeito de campo com porta eletrolítica, baseado em uma camada semicondutora orgânica de politiofeno. Um biossensor enzimático modular para glicose e ureia, com uma resposta linear na faixa entre 10-6 e 10-3 mol/L, foi alcançado. Este biossensor depende da imobilização das enzimas no eletrodo ouro utilizado como porta nos dispositivos. O uso dos bioreceptores mostrou-se seletivo nos dispositivos. A possibilidade de trocar o eletrodo de porta modificada para detectar analitos específicos usando o mesmo sistema de dispositivos permite que o sensor modular seja reutilizado e com diversas aplicações. Sendo este o caso de moléculas de explosivos, TNT e DNT, com biossensor fabricado nos mesmos termos. Este biossensor depende da imobilização de peptídeos de ligação específica para TNT e DNT no eletrodo de ouro