La formation des ondes de densité de charge (ODC) est un phénomène de brisure de symétrie qui apparaît dans systèmes électroniques, et particulièrement dans les conducteurs quasi-unidimensionnels. Elle est observée aussi bien dans les matériaux très anisotropes que les isotropes comme par exemple les supraconducteurs pnictures. L'ODC peut être vue comme une déformation sinusoïdale de la densité électronique et de la modulation du réseau, ou également comme un cristal de singulets électroniques. Dans un état d'ODC, les cellules élémentaires peuvent être modifiées en absorbant ou en rejetant des paires d'électrons. Un tel processus passe par des configurations topologiquement non triviales: des solitons et des dislocations, ou plus généralement des vortex d'ODC. Ces états inhomogènes peuvent être obtenus expérimentalement dans des nano-produits appelés ''mésa-jonctions'', et observés à l'aide d'un microscope à effet tunnel ou d’une radiographie par micro-diffraction. Afin de simuler ces expériences, nous avons réalisé un programme modélisant les états stationnaires d'ODC ainsi que leur dynamique transitoire à travers des géométries restreintes auxquelles sont appliquées une tension ou un courant. Le modèle prend en compte plusieurs champs en interaction non linéaire: le paramètre d'ordre complexe d'ODC, la distribution de champ électrique, ainsi que la densité et le courant des autres porteurs de charge. Nous avons utilisé une approche de type Ginzburg-Landau ainsi qu'une extension basée sur une propriété d'invariance chirale. A l'aide de ce programme, nous avons observé la création progressive de dislocations statiques dans les jonctions. La dynamique transitoire est alors très riche avec notamment des créations, des annihilations et des balayages de vortex multiples. Des chutes de tension apparaissent au centre des dislocations, créant ainsi des jonctions tunnel microscopiques à travers lesquelles transitent des paires électron-trou. Les résultats qualitatifs obtenus sont en très bon accord avec les observations expérimentales. Ce model peut aussi être étendu à tout type de cristaux électronique comme les cristaux de Wigner dans les hétéro-jonctions et les nano-fils, les ODC dans les composés de chaîne, les ondes de densité de spin dans les conducteurs organiques, ou encore les structures de bandes dans les oxydes dopés. La reconstruction des ODC dans les jonctions tunnel peut aussi trouver son importance dans l'étude des effets de champs sur les matériaux fortement corrélés induisant des brisures spontanées de symétries. / Formation of charge density waves (CDW) is a symmetry breaking phenomenon found in electronic systems, which is particularly common in quasi-one-dimensional conductors. It is widely observed from highly anisotropic materials to isotropic ones like the superconducting pnictides. The CDW is seen as a sinusoidal deformation of coupled electronic density and lattice modulation; it can be also viewed as a crystal of singlet electronic pairs. In the CDW state, the elementary units can be readjusted by absorbing or rejecting pairs of electrons. Such a process should go via topologically nontrivial configurations: solitons and dislocations - the CDW vortices. An experimental access to these inhomogeneous CDW states came from studies of nano-fabricated mesa-junctions, from the STM and from the X-ray micro-diffraction. Following these requests, we have performed a program of modeling stationary states and of their transient dynamic for the CDW in restricted geometries under applied voltage or at passing normal currents. The model takes into account multiple fields in mutual nonlinear interactions: the two components of the CDW complex order parameter, and distributions of the electric field, the density and the current of normal carriers. We were using the Ginzburg-Landau type approach and also we have derived its extension based on the property of the chiral invariance. We observed the incremental creation of static dislocations within the junctions. The transient dynamics is very rich showing creation, annihilation and sweeping of multiple vortices. The dislocations cores concentrate the voltage drops thus providing self-tuned microscopic junctions where the tunneling creation of electron-hole pairs can take place. The results obtained from this model agree with experiment observations. The methods can be extended to other types of charge organization known under the general name of the Electronic Crystal. It takes forms of Wigner crystals at hetero-junctions and in nano-wires, CDWs in chain compounds, spin density waves in organic conductors, and stripes in doped oxides. The studied reconstruction in junctions of the CDW may be relevant also to modern efforts of the field-effect transformations in strongly correlated materials with a spontaneous symmetry breaking.

A eletrônica digital desempenha papel essencial no desenvolvimento e manutenção dos padrões de vida em prática hoje no mundo. A peça fundamental para a criação desta era tecnológica é sem dúvidas o transistor. Com o advento de novos materiais, a busca por transistores que oferecem novas oportunidades de processamento e aplicação permitiu que uma nova área fosse criada: a eletrônica orgânica. Transistores de efeito de campo baseados em filmes finos de materiais orgânicos têm recebido grande atenção nas últimas décadas. Apresentamos um estudo experimental e teórico de transistores de efeito de campo a base de filmes finos orgânicos. Foram caracterizados transistores usando um derivado do pentaceno (TMTES-pentaceno) como camada ativa em um dispositivo feito sobre Si/SiO2. Mostramos que a inclusão do semicondutor orgânico em uma matriz polimérica isolante ajuda a manter a estabilidade termo mecânica do dispositivo. Foi desenvolvido um modelo que levasse em conta as resistências parasíticas para explicar o comportamento do transistor em função da temperatura. Também foram construídos e caracterizados transistores usando rr-P3HT como semicondutor e PMMA como isolantes. Apresentamos transistores do tipo Top-Gate e Bottom-Gate com mobilidade máxima de 7 x 10-3 cm2/V.s. Valores de razão ON/OFF de ~ 900 foram encontrados nos transistores otimizados. O comportamento dos transistores é analisado em função da temperatura e os modelos de aproximação de canal gradual e de Vissenberg-Matters foram aplicados para extração dos parâmetros de interesse. Por fim, apresentamos um modelo de corrente de canal baseado na resolução 2D numérica da equação de Poisson usando as idéias de Vissenberg-Matters para a concentração de cargas em função do potencial local. O modelo, embora ainda nos primeiros estágios de desenvolvimento, prevê a saturação da corrente nas curvas de saída simuladas sem limitações de regime de validade. / Digital electronics plays an essential role in the development and maintenance of living standards into practice in the world today. The cornerstone for the creation of this technological age is undoubtedly the transistor. With the advent of new materials, the search for transistors that offer new opportunities in processing and application allowed a new area to be created: the organic electronics. Field effect transistors based on organic thin films have received great attention in recent decades. We report an experimental and theoretical study of field effect transistors based on organic thin films. We characterized transistors manufactured using a derivative of pentacene (TMTES-pentacene) as the active layer in a device and using Si/SiO2 as gate and insulator. We show that the inclusion of the organic semiconductor in an insulating polymeric matrix helps to maintain the termo-mechanical stability of the device. A model was developed that take into account the parasitic resistances and to explain the behavior of the transistor as a function of temperature. We also present the manufacturing and characterization process of transistors using rr-P3HT as semiconductor and PMMA as insulator. We report Top-Gate and Bottom-Gate transistors with maximum mobility of 7 x 10-3 cm2/V.s. The maximun ON/OFF ratio of ~ 900 was found for the optimized transistors. The behavior of the transistors was analyzed as a function of temperature and both gradual channel approximation and Vissenberg-Matters models were applied for extracting the parameters. Finally, we present a channel current model based on the resolution of 2D numerical Poisson equation using the ideas of Vissenberg-Matters to the calculate the concentration of charges due to the local potential. The model, although still in the early stages of development, predicts the saturation current at output simulated curves with no limitation of regime validity.

Biossensores que empregam dispositivos de efeitos de campo podem ser obtidos em diversas arquiteturas, incluindo dispositivos Eletrólito-Isolante-Semicondutor (EIS), que são capacitores em que o eletrodo metálico é substituído por um filme e uma solução. Medindo-se a capacitância em função do potencial aplicado, é possível detectar variações de pH oriundas de reações ou interações entre o filme e o analito. Nesta dissertação, sensores foram produzidos com a adsorção de filmes automontados de dendrímero (PAMAM) e nanotubos de carbono (SWNT) num chip. Medidas de espectroscopia de impedância foram realizadas para investigar o crescimento de cada bicamada do filme automontado, e os dados foram analisados com circuitos equivalentes que continham uma capacitância de dupla camada, um elemento de fase constante e uma capacitância para a região de depleção. Para o chip, os melhores ajustes foram obtidos na frequência de 2 kHz, em que a concentração de dopantes foi 6,6x1020 m-3 para o chip com isolante de SiO2 e de 1,1x1021 m-3 para o chip com isolante de SiO2/Ta2O5. O potencial de banda plana foi -0,2 V e -0,06V, respectivamente. Para os chips recobertos com os filmes de PAMAM/SWNT, observamos que a região de depleção é causada pelas cargas positivas do PAMAM. Com relação às implicações para biossensores, verificamos que o desempenho ótimo deve ser obtido com 3 bicamadas de PAMAM/SWNT. Isso pode explicar a observação empírica na literatura de que existe uma espessura ideal dos filmes para um desempenho otimizado. / Biosensors based on field effect devices can be produced with several architectures, including Electrolyte-Insulator-Semiconductor (EIS) devices, which are capacitors where conventional metal electrodes are replaced by a sensing layer and an electrolyte solution. By measuring the capacitance as a function of the bias voltage, it is possible to detect pH changes that may originate from reactions or interactions between the film in the sensing unit and the analyte. In this study sensors were obtained by adsorbing layer-by-layer (LbL) films made with dendrimers (PAMAM) and carbon nanotubes (SWNT) on a semiconductor chip. Impedance spectroscopy measurements were performed to monitor the growth of each bilayer in the LbL film, whose data were analyzed with equivalent circuits containing a double-layer capacitance, a constant phase element and a capacitance for the depletion region. The results for the semiconductor chip could be best fitted for a frequency of 2 kHz, where the doping concentration was 6.6 x1020 m-3 for the insulating SiO2 layer and 1.1 x1021 m-3 for the SiO2/Ta2O5 layer. The flat band voltage was -0.2 V and -0.06 V, respectively. In the analysis of the chip coated with different numbers of PAMAM/SWNT bilayers, we found that the depletion region appears as a contribution from the positive charges in the PAMAM layer. With regard to implications for biosensors, we found that optimized performance should be reached with three PAMAM/SWNT bilayers, which may explain the empirical finding in the literature that an ideal thickness exists for enhanced performance.

The phase diagram of complex oxides is very diverse due to the strong interaction between electrons in the electronic structure. It is possible to probe those interactions by changing electrostatically the carrier density, the main concept behind the Field-Effect Transistors (FET) which is the building blocks of nanoelectronics devices. In the case of high-TC superconductor copper oxides, it is possible to use this concept to switch between superconducting and insulator phases, for example using an adjacent liquid electrolyte layer to inject charges in a superconducting film. With that in mind, the objective of this work was to establish protocols to grow superconductor and ferroelectric films for future fabrication of superconducting FET devices. We optimized the deposition conditions for the growth of a single layer of superconductor YBa2Cu3O7–x and the ferroelectric barium titanate on SrTiO3 substrates by pulsed laser deposition (PLD). Several techniques were employed to study the properties of the thin films, such as X-ray diffraction, atomic force microscope, X-ray photoelectron spectroscopy, resistance vs temperature and ferroelectric hysteresis. Regarding the superconductors thin films, we observed several relations between the superconducting features and the growth parameters. For instance, lower growth temperatures contribute to the nucleation of a-axis oriented grains meanwhile higher growth temperature tends to be c-axis oriented. Regarding the frequency of the laser (proportional to the growth rate), it seems that lower frequency is related to higher surface roughness and the presence of non-superconducting contributions. As it increases, the roughness decrease and the sample presents a sharper superconducting transition. Finally, we also did the first steps towards the field effect device by growing a heterostructure thin film consisting of a superconductor and ferroelectric material. The sample grew c-axis oriented on strontium titanate substrate, though with a high value of surface roughness. / O diagrama de fase dos óxidos complexos é muito diverso devido à forte interação entre os elétrons na estrutura eletrônica. É possível sondar essas interações alterando eletrostaticamente a densidade da portadores, o principal conceito por trás dos transistores de efeito de campo (FET), que é o elemento fundamental dos dispositivos nanoeletrônicos. No caso de supercondutores de alta temperatura a base de óxidos de cobre, é possível usar este conceito para alternar entre fases supercondutoras e isolantes, por exemplo utilizando uma camada adjacente de eletrólito líquido para injetar cargas no filme supercondutor. Com isso em mente, o objetivo desse trabalho foi estabelecer protocolos para crescer filmes supercondutores e ferroelétricos para fabricações futuras de dipositivos FET supercodutores. Nós optimizamos as condições de deposição para o crescimento de uma única camada do supercondutor YBa2Cu3O7–x e do ferroeléctrico titanato de bário em substratos SrTiO3 por deposição de laser pulsado (PLD). Diversas técnicas foram empregadas para estudar as propriedades dos filmes finos, como difração de raios-X, microscopia de força atômica, espectroscopia de fotoelétrons de raios-X, resistência vs temperatura e histerese ferroelétrica. Em relação aos filmes finos supercondutores, observamos várias relações das propriedades supercondutoras com os parâmetros de crescimento. Por exemplo, temperaturas de crescimento mais baixas contribuem para a nucleação de grãos orientados no eixo a, enquanto a temperatura de crescimento mais alta tende a ser orientada para o eixo c. Em relação à frequência do laser (proporcional à taxa de crescimento), há um indício que valores menores de frequência está relacionada à maior rugosidade superficial e à presença de contribuições não supercondutoras. À medida que aumenta a frequência, a rugosidade diminui e a amostra apresenta uma transição supercondutora mais nítida. Por fim, também fizemos os primeiros passos em direção ao dispositivo de efeito de campo, desenvolvendo um filme fino de heteroestrutura com um material supercondutor e ferroelétrico. A amostra cresceu orientada no eixo c em substrato de titanato de estrôncio com alto valor de rugosidade superficial.

O desenvolvimento de sensores em sistemas para controle ambiental tem-se mostrado uma área de elevado interesse científico e técnico. Os principais desafios nesta área estão relacionados ao desenvolvimento de sensores com capacidade de detecção de várias substâncias. Neste contexto, os capacitores MOS apresentam-se como dispositivos versáteis para a geração de imagens químicas com potencial de detecção e classificação de diferentes substâncias a partir de apenas um único sensor. No presente trabalho, foi proposto um sensor MOS com um perfil geométrico de porta em forma de cata-vento composta por Pd, Au e Pt. A resposta do sensor mostrou ter alta sensibilidade a moléculas ricas em átomos de H, como os gases H2 e NH3. As medidas de capacitância mostraram que o sensor tem uma resposta não linear para H2 e NH3 obedecendo à lei da isoterma de Langmuir. O sensor MOS mostrou-se eficiente na geração de imagens químicas através da técnica de escaneamento por luz pulsada. As imagens químicas correspondentes aos gases H2 e NH3 mostraram diferentes padrões quando o N2 foi utilizado como gás transportador. A diferença entre os padrões aconteceu principalmente devido ao perfil geométrico da porta metálica. A sensibilidade do sensor mostrou dependência com o potencial de polarização. Nas medidas de capacitância, a maior sensibilidade foi observada para potenciais próximos da tensão de banda plana. Já para as imagens químicas, a maior sensibilidade foi observada para potenciais inteiramente na região de depleção. A sensibilidade do sensor também se mostrou dependente do gás transporta- dor. O sensor mostrou ser mais sensível com N2 como gás transportador do que com ar seco. No entanto, o processo de dessorção dos íons H+ resultou ser mais eficiente em ar seco. Os resultados obtidos no presente trabalho sugerem a possibilidade de fabricação de um nariz optoeletrônico utilizando apenas um único sensor MOS. / The development of sensors and systems for environmental control has been shown to be an area of high scientific and technical interest. The main challenges in this area are related to the development of sensors capable of detecting many different substances. In this context, the MOS devices present themselves as versatile devices for chemical imaging with potential for detection and classification of different substances only using one single sensor. In the present work, was proposed a MOS sensor with a wing-vane geometric profile of its gate constituted of Pd, Au and Pt metals. The sensor\'s response showed to have high sensitivity to molecules rich on H atoms, such as H2 and NH3 gases. Capacitance measurements showed that the sensor has a nonlinear response for H2 and NH3 obeying the Langmuir isotherm law. The MOS sensor proved to be efficient in Chemical Imaging generation through the scanned light pulse technique. The chemical images of the H2 and NH3 gases showed different patterns when the N2 was used as carrier gas. The different patterns responses happened mainly due to geometric profile of the metallic gate. The sensor sensitivity showed dependence on the bias potential. In the capacitance measures, greater sensitivity was observed for potential near the flat-band voltage. In the chemical images, the greater sensitivity was observed for bias potential within depletion region. The sensor sensitivity was also dependent on the carrier gas. The sensor showed to be more sensitive with N2 as carrier gas than to dry air. However the desorption process of H+ have been more efficient in dry air. The results obtained in the present work suggest the possibility of manufacturing an optoelectronic nose using only a single MOS sensor.

O desenvolvimento de sensores em sistemas para controle ambiental tem-se mostrado uma área de elevado interesse científico e técnico. Os principais desafios nesta área estão relacionados ao desenvolvimento de sensores com capacidade de detecção de várias substâncias. Neste contexto, os capacitores MOS apresentam-se como dispositivos versáteis para a geração de imagens químicas com potencial de detecção e classificação de diferentes substâncias a partir de apenas um único sensor. No presente trabalho, foi proposto um sensor MOS com um perfil geométrico de porta em forma de cata-vento composta por Pd, Au e Pt. A resposta do sensor mostrou ter alta sensibilidade a moléculas ricas em átomos de H, como os gases H2 e NH3. As medidas de capacitância mostraram que o sensor tem uma resposta não linear para H2 e NH3 obedecendo à lei da isoterma de Langmuir. O sensor MOS mostrou-se eficiente na geração de imagens químicas através da técnica de escaneamento por luz pulsada. As imagens químicas correspondentes aos gases H2 e NH3 mostraram diferentes padrões quando o N2 foi utilizado como gás transportador. A diferença entre os padrões aconteceu principalmente devido ao perfil geométrico da porta metálica. A sensibilidade do sensor mostrou dependência com o potencial de polarização. Nas medidas de capacitância, a maior sensibilidade foi observada para potenciais próximos da tensão de banda plana. Já para as imagens químicas, a maior sensibilidade foi observada para potenciais inteiramente na região de depleção. A sensibilidade do sensor também se mostrou dependente do gás transporta- dor. O sensor mostrou ser mais sensível com N2 como gás transportador do que com ar seco. No entanto, o processo de dessorção dos íons H+ resultou ser mais eficiente em ar seco. Os resultados obtidos no presente trabalho sugerem a possibilidade de fabricação de um nariz optoeletrônico utilizando apenas um único sensor MOS. / The development of sensors and systems for environmental control has been shown to be an area of high scientific and technical interest. The main challenges in this area are related to the development of sensors capable of detecting many different substances. In this context, the MOS devices present themselves as versatile devices for chemical imaging with potential for detection and classification of different substances only using one single sensor. In the present work, was proposed a MOS sensor with a wing-vane geometric profile of its gate constituted of Pd, Au and Pt metals. The sensor\'s response showed to have high sensitivity to molecules rich on H atoms, such as H2 and NH3 gases. Capacitance measurements showed that the sensor has a nonlinear response for H2 and NH3 obeying the Langmuir isotherm law. The MOS sensor proved to be efficient in Chemical Imaging generation through the scanned light pulse technique. The chemical images of the H2 and NH3 gases showed different patterns when the N2 was used as carrier gas. The different patterns responses happened mainly due to geometric profile of the metallic gate. The sensor sensitivity showed dependence on the bias potential. In the capacitance measures, greater sensitivity was observed for potential near the flat-band voltage. In the chemical images, the greater sensitivity was observed for bias potential within depletion region. The sensor sensitivity was also dependent on the carrier gas. The sensor showed to be more sensitive with N2 as carrier gas than to dry air. However the desorption process of H+ have been more efficient in dry air. The results obtained in the present work suggest the possibility of manufacturing an optoelectronic nose using only a single MOS sensor.

Les liquides ioniques sont des fluides non volatiles, constitués de cations et d’anions, qui sont conducteurs ioniques, isolants électriques, et peuvent avoir des valeurs de capacité très élevées. Ces liquides sont susceptibles non seulement de remplacer les électrolytes solides, mais également de susciter des champs électriques intenses (>SI{10}{megavoltpercentimetre}) au sein d’une couche dite double couche électronique (electric double layer, EDL) à l’interface entre le liquide et le matériau sur lequel il est déposé. Ceci conduit à une injection de porteurs de charge bidimensionelle avec des densités allant jusqu’à SI{e15}{cm^{-2}}. Cet effet de grille remarquablement fort des liquides ioniques est réduit en présence d’états piégés ou de rugosité de surface. À cet égard, les dicalchogénures de métaux de transitions, de très haute qualité cristalline et atomiquement plats, font partis des semi-conducteurs les plus adaptés aux grilles EDL.Nous avons réalisé des transistors à effet de champ avec des EDL dans des nanotubes multi-couches de ce{WS2}, avec des performances comparables à celles de transistors EDL sur des ilots de ce{WS2}, et meilleurs que celles de nanotubes de ce{WS2} avec une grille solide. Nous avons obtenu des mobilités allant jusqu’à SI{80}{squarecentimetrepervoltpersecond} pour les porteurs n et p, et des ratios de courants on/off dépassant SI{e5}{} pour les deux polarités. Pour de forts dopages de type électron, les nanotubes ont un comportement métallique jusqu’à basse température. De plus, utiliser un liquide ionique permet de créer une jonction pn de manière purement électrostatique. En prenant avantage de cet effet, nous avons pu réaliser un transistor photoluminescent dans un nanotube.La possibilité de susciter de très forte densités de charges donne la possibilité d’induire des phases métalliques ou supraconductrices dans des semi-conducteurs a large bande interdite. Nous avons ainsi réussi à induire par effet de champ une phase métallique à basse température dans du diamant intrinsèque avec une surface hydrogénée, et nous avons obtenu un effet de champ dans du silicone dopé métallique.Les liquides ioniques offrent beaucoup d’avantages, mais leur champ d’application est encore réduit par l’instabilité du liquide, ainsi que par les courants de fuites et l’absorption graduelle d’impuretés. Un moyen efficace de s’affranchir de ces inconvénients, tout en conservant la possibilité d’induire de très fortes densités de porteurs, est de gélifier le liquide ionique. Nous sommes allés plus loin en fabriquant des gels ioniques modifiés, avec les cations fixés sur une seule surface et les anions libres de se mouvoir au sein du gel. Cet outil nous a permis de réaliser une nouvelle diode à effet de champ de faible puissance. / Ionic liquids are non-volatile fluids, consisting of cations and anions, which are ionically conducting and electrically insulating and hold very high capacitances. These liquids have the ability to not only to replace solid electrolytes, but to create strongly increased electric fields (>SI{10}{megavoltpercentimetre}) in the so-called electric double layer (EDL) on the electrolyte/channel interface, which leads to the injection of 2D charge carrier densities up to SI{e15}{cm^{-2}}. The remarkably strong gate effect of ionic liquids is diminished in the presence of trapped states and roughness-induced surface disorder, which points out that atomically flat transition metal dichalcogenides of high crystal quality are some of the semiconductors best suited for EDL-gating.We realised EDL-gated field-effect transistors based on multi-walled ce{WS2} nanotubes with operation performance comparable to that of EDL-gated thin flakes of the same material and superior to the performance of backgated ce{WS2} nanotubes. For instance, we observed mobilities of up to SI{80}{squarecentimetrepervoltpersecond} for both p- and n-type charge carriers and our current on-off ratios exceed SI{e5}{} for both polarities. At high electron doping levels, the nanotubes show metallic behaviour down to low temperatures. The use of an electrolyte as topgate dielectric allows the purely electrostatic formation of a pn-junction. We successfully fabricated a light-emitting transistor taking advantage of this utility.The ability of high charge carrier doping suggests an electrostatically induced metal phase or superconductivity in large gap semiconductors. We successfully induced low temperature metallic conduction into intrinsic diamond with hydrogen-terminated surface via field-effect and we observed a gate effect in doped, metallic silicon.Ionic liquids have many advantageous properties, but their applicability suffers from the instability of their liquid body, gate leakage currents and absorption of impurities. An effective way to bypass most of these problems, while keeping the ability of ultra-high charge carrier injection, is the gelation of ionic liquids. We even went one step further and fabricated modified ion gel films with the cations fixed on one surface and the anions able to move freely through the film. With this tool, we realised a novel low-power field-effect diode.

Kwok Pui-ho. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2000. / Includes bibliographical references (leaves [79]-85). / Abstracts in English and Chinese. / Chapter CHAPTER 1 --- INTRODUCTION --- p.1 / Chapter CHAPTER 2 --- NONLINEAR BEHAVIOR OF RF POWER AMPLIFIERS --- p.5 / Chapter 2.1 --- Single Tone Excitation --- p.6 / Chapter 2.1.1 --- AM-AM Conversion --- p.7 / Chapter 2.1.2 --- AM-PM Conversion --- p.9 / Chapter 2.2 --- Two-Tone Excitation --- p.11 / Chapter 2.2.1 --- Intermodulation Distortion --- p.12 / Chapter 2.3 --- Digitally Modulated Signal Excitation --- p.13 / Chapter 2.3.1 --- Spectral Regeneration --- p.14 / Chapter 2.3.2 --- Adjacent Channel Power Ratio (ACPR) --- p.16 / Chapter CHAPTER 3 --- LINEARIZATION TECHNIQUES --- p.18 / Chapter 3.1 --- pre-distortion --- p.20 / Chapter 3.2 --- Feed-forward Techniques --- p.23 / Chapter 3.3 --- Harmonics Control Techniques --- p.24 / Chapter CHAPTER 4 --- SPECTRAL REGROWTH ANALYSIS USING VOLTERRA SERIES METHOD --- p.26 / Chapter 4.1 --- Introduction To Volterra Series Analysis --- p.27 / Chapter 4.1.1 --- Linear and Nonlinear Systems --- p.27 / Chapter 4.1.2 --- Evaluation of Volterra transfer function --- p.29 / Chapter 4.1.3 --- Volterra Series Analysis of Spectral Regrowth --- p.31 / Chapter 4.2 --- Nonlinear Model of GaAs MESFET Device --- p.33 / Chapter 4.3 --- Evaluation Of Nonlinear Responses --- p.35 / Chapter 4.3.1 --- First-Order Response --- p.36 / Chapter 4.3.2 --- Second-Order Response --- p.38 / Chapter 4.3.3 --- Third-Order Response --- p.39 / Chapter CHAPTER 5 --- EFFECT OF HARMONIC TUNING ON SPECTRAL REGROWTH --- p.42 / Chapter 5.1 --- Simulation of Digitally Modulated Signal --- p.43 / Chapter 5.2 --- Effect of Source Second Harmonic Termination --- p.44 / Chapter CHAPTER 6 --- EXPERIMENTAL VERIFICATION --- p.48 / Chapter 6.1 --- Circuit Design and Construction --- p.49 / Chapter 6.2 --- Setup and Measurement --- p.55 / Chapter 6.3 --- Experimental Results --- p.56 / Chapter 6.3.1 --- Small Signal Measurement --- p.56 / Chapter 6.3.2 --- Single Tone Characterization --- p.57 / Chapter 6.3.3 --- Two-Tone Characterization --- p.59 / Chapter 6.3.4 --- ACPR Characterization --- p.60 / Chapter 6.4 --- Comparison of Measurement and Simulation --- p.66 / Chapter CHAPTER 7 --- NONLINEAR TRANSCONDUCTANCE COEFFICIENTS EXTRACTION --- p.68 / Chapter 7.1 --- Large Signal Model --- p.69 / Chapter 7.2 --- Extraction of Nonlinear Transconductance --- p.71 / Chapter 7.2.1 --- Extraction of g1 --- p.71 / Chapter 7.2.2 --- Extraction of g2 and g3 --- p.72 / Chapter CHAPTER 8 --- CONCLUSION --- p.76 / FUTURE WORK RECOMMENDATION --- p.78 / REFERENCE

Un des enjeux principaux de l’électronique organique est le développement de circuits associant des transistors organiques à effet de champ (OFETs) de type p et de type n stables à l’air ainsi que leur fabrication par voie liquide. Si de nombreux matériaux de type p existent, les exemples de matériaux de type n stables sont plus rares. L’objectif de ce travail de thèse a ainsi été de concevoir, de synthétiser, et de caractériser de nouvelles molécules π-conjuguées électrodéficientes solubles afin de les intégrer dans des transistors organiques à effet de champ de type n (OFETs) stables à l’air. Dans ce but, le coeur aromatique d’un pigment reconnu très stable chimiquement, la triphénodioxazine (TPDO), a été fonctionnalisé avec des fonctions solubilisantes et des groupements électroattracteurs pour moduler ses propriétés de solubilité et augmenter son affinité électronique. Les nombreuses variations structurales réalisées ont conduit à une famille complète de dérivés électrodéficients. Les nouveaux composés, caractérisés à l’état liquide et solide, ont été intégrés dans des OFETs et ont démontré, pour la plupart, un transport de charges négatives efficace. Au-delà de la rationalisation des résultats obtenus lors des synthèses, des caractérisations des matériaux et des performances des dispositifs électroniques, un dérivé tétracyané a rempli l'ensemble du cahier des charges initial (solubilité, mobilité de type n, stabilité à l’air), ce qui valide la démarche adoptée. / One the main challenges of organic electronics is the fabrication of electronic circuits combining p-type and n-type organic field effect transistors which can be processed by liquid route and are stable in air. Even though many efficient p-type organic materials have been reported, the examples of n-type analogues are rare. The aim of this PhD research work was therefore to design, synthesize and characterize new soluble and electron-acceptor π-conjugated molecules and determine their ability to transport electrons in organic field effect transistors (OFETs) under air. In this aim, the aromatic core of a well-known stable pigment, the Triphenodioxazine (TPDO), was functionalized with solubilizing groups and electron-withdrawing functions to tune the solubility and to yield a higher electron affinity. The various structural modifications achieved provided a complete family of electro-deficient materials. The new compounds were characterized in liquid and solid state, and then integrated in OFETs. Most of them led to an efficient negative charge carrier transport. Hereafter of the rationalization of the results during synthesis, characterization of new materials and physical characterizations of devices, a tetracyano derivative has fulfilled the initial project specifications in terms of solubility, electron mobility and air stability of the performances

Le travail réalisé durant cette thèse s’est axé sur la compréhension des mécanismes de transport de charges impliqués dans l’électronique organique ainsi que sur l’ingénierie des propriétés semiconductrices d’interfaces supramoléculaires hybrides. Tout d’abord, l’origine intrinsèque des propriétés de transport de charges a été étudiée dans de petites molécules semiconductrices, similaires en structure chimiques, mais présentant des propriétés électriques nettement différentes. Puis, les propriétés électroniques de matériaux 2D ont été modulées à l’aide de monocouches auto-assemblées induisant des propriétés de dopage antagonistes. Enfin, des pérovskites hybrides ainsi que des petites molécules semiconductrices ont été utilisées comme matériaux actifs dans la détection d’oxygène et d’humidité, respectivement, formant alors des détecteurs à haute performance. L’ensemble de ces projets utilise les principes de la chimie supramoléculaire dans leur réalisation. / The work realized during this thesis was oriented toward the comprehension of the charge transport mechanism involved in organic electronics, and on the engineering of the semiconducting properties of hybrid supramolecular interfaces. Firstly, the intrinsic origin of the charge transport properties was studied for two semiconducting small molecules which are similar in terms of chemical structure but exhibit different electrical properties. Secondly, the electronic properties of 2D material were modulated with the help of self-assembled monolayers inducing antagonist doping properties. Finally, hybrid perovskites and semiconducting small molecules were used as active materials in oxygen and humidity sensing respectively, forming high-performance sensors. All the project employed the principles of the supramolecular chemistry in their realisation.