Les dispersions de nanocomposite à base aqueuse sont produites pour des applications diverses telles que les adhésifs, les revêtements et plus récemment les encres. Ce projet consiste à réaliser des encres conductrices nanocomposites comprenant des particules de polymère (latex) à basse température de transition vitreuse, Tg, pour la formation de films à température ambiante, et des plaquettes de graphène, en raison de leurs excellentes propriétés conductrices. Les charges conductrices, appelées multi-feuillets de graphène, sont réalisées par broyage en voie aqueuse de graphite (1-10 µm) stabilisées par différents tensio-actifs et/ou stabilisants. Cette méthode sans solvant et à bas coût permet de produire des suspensions de multi-feuillets (1-10 feuillets) de graphène. Les particules de polymères utilisées sont synthétisées par polymérisation en émulsion de monomères acrylates. Dans un second temps, des mélanges physiques de suspensions de graphène et de latex acrylates ont permis d’obtenir des encres nanocomposites. L’ajout de graphène permet l’obtention d’un seuil de percolation à bas taux de charge et une nette amélioration des propriétés électriques et du renfort. Le diamètre des billes de latex a une influence importante sur ces propriétés et a également été étudié. Afin d’augmenter la stabilité des suspensions et les interactions graphène/latex, des nanocomposites structurés ont été synthétisés par polymérisation in situ en émulsion, miniemulsion ou dispersion en présence de graphène. Les excellentes propriétés électriques associées à leur flexibilité font de ces matériaux des candidats adaptés pour la réalisation d’encres conductrices pour impression sur textile. / Printed electronics, particularly on flexible and textile substrates, raised a strong interest during the past decades. This project presents a procedure that provides a complete and consistent candidate for conductive inks based on a graphene/polymer nanocomposite material. It consists in the synthesis of conductive inks nanocomposites comprising polymer particles (latex) with low glass transition temperature, Tg, and graphene platelets, for the conductive properties. The conductive particles, named Nanosize Multilayered Graphene (NMG), are prepared by wet grinding delamination of micro-graphite suspensions stabilized by various surfactants and/or polymeric stabilizers. This solvent-free procedure allows the formation of NMG suspensions with low thickness (1-10 sheets). Polymer particles are synthetized by surfactant-free emulsion polymerization with acrylates monomers.Physical blending of latex particles and NMG platelets are performed to obtain conductive nanocomposites inks. Adding NMG induce a low percolation threshold and a sharp increase of the electrical and mechanical properties of the nanocomposites. Moreover, the polymer particles diameters have an impact on these properties.To increase the formation of a well-defined cellular microstructure, the nanocomposites are also synthetized by in situ polymerization in presence of NMG platelets, using emulsion, miniemulsion or dispersion polymerization. The excellent electrical properties of these nanocomposites associated to their flexibility make these materials suitable candidates for the production of conductive inks for textile printing applications.

Le graphène est un matériau carboné exceptionnel de par ses propriétés électriques (mobilité électronique à température ambiante de 200 000 cm²V-¹s-¹), mécaniques (module d'Young de 1,5 TPA) et sa capacité à protéger un substrat de l’atmosphère. Cela en fait un candidat idéal comme revêtement de protection pour les dispositifs de connexion dont la partie active (le contact électrique) peut subir des dégradations sévères au cours du temps.. Un tel revêtement de protection doit en effet avoir des propriétés de robustesse et de conduction la plupart du temps antinomiques. La première étape de ce travail a consisté à mettre en œuvre un procède d’exfoliation en phase liquide afin de produire des suspensions de graphène ou de matériaux de type graphène. Différents type de caractérisations structurelles et électriques à l’échelle microscopique ont permis de déterminer des conditions d’exfoliation favorables en variant la nature du solvant et les conditions de sonication. Il s’est agi ensuite d’évaluer différents modes de dépôts permettant d’obtenir un revêtement de protection à partir de feuillets individuels. Les méthodes de trempé, évaporation, spray et filtration ont été caractérisées et ont montré leurs avantages et inconvénients. La méthode de filtration donne les films les plus couvrants mais pose le problème du transfert vers la surface à protéger : on a mis en évidence une contamination résiduelle difficile à éliminer. Les premiers résultats avec une méthode de spray industriel sans buse ont montré une grande réduction du frottement mais aussi la complexité des mécanismes régissant la qualité des dépôts. Les limites des différentes méthodes de dépôt pourraient être dépassées par l’utilisation de films composites polymère-graphène. / Graphene is a special carbon material due to its electrical properties (electron mobility at room temperature 200 000 cm²V-¹s-¹), mechanical (Young modulus of 1.5 TPA) and ability to protect a substrate of atmosphere. This makes it an ideal candidate as a protective coating for connecting devices including the active portion (electrical contact) may suffer severe damage over time .. Such a protective coating must indeed have properties and robustness conducting most of the contradictory time. The first step of this work was to implement an exfoliation proceeds in the liquid phase to produce suspensions of graphene and graphene-like materials.Different types of structural and electrical properties at the microscopic scale have determined favorable conditions for exfoliation by varying the nature of the solvent and conditions of sonication. He then acted deposits evaluate different methods to obtain a protective coating from individual sheets. The methods of dip coating, drop casting, spray and filtration have been characterized and have shown their advantages and disadvantages. The filtration method gives the most covering films, but the problem of the transfer to the surface to be protected: it showed residual contamination difficult to remove. The first results with an industrial spray without nozzle method showed a large reduction in friction but also the complexity of the mechanisms governing the quality of deposits. Limitations of different deposit methods could be exceeded by the use of graphene-polymer composite films.

CSÁKI, Štefan: Thermophysical and electrical properties of illite-based ceramics. [Doctoral thesis]. Constantine the Philosopher University in Nitra. Faculty of Natural Sciences. Charles University. Faculty of Mathematics and Physics. Supervisor: prof. RNDr. Libor Vozár, CSc. (Constantine the Philosopher University in Nitra), doc. Ing. Patrik Dobroň, PhD. (Charles University). Nitra & Prague, 2018. 107 p. Illitic clays are of special importance in the ceramic industry. Therefore, a deep knowledge of the thermophysical processes, as well as the electric properties, is of special importance. The illitic clay originated in Northeastern Hungary was used in this thesis. The reactions, occurring during firing, were studied using thermal analyses (Differential thermal analysis, Thermogravimetry, Thermodilatometry) and special attention was paid to the measurement of the electrical conductivity (both DC and AC). Up to 250 řC, where the removal of the physically bond water (PBW) takes place, the dominant charge carriers were the H+ and OH- ions. After the PBW was removed, Na+ and K+ ions became the dominant charge carriers. During dehydroxylation (450 - 750 řC) H+ and OH- ions were freed from the illite structure, which supported the electrical conduction in the samples. At ~ 970 řC glassy phase appeared...

Indiana University-Purdue University Indianapolis (IUPUI) / This study represents a cost-effective method to advance the physical and mechanical properties of carbon fiber-reinforced polymer (CFRP) prepreg composite materials, where electrospun multiwalled carbon nanotubes (CNTs)/epoxy nanofibers fabricated and deposited in between the layers of traditional CFRP prepreg composite. CNT-aligned epoxy nanofibers were uniformly formed by an optimized electrospinning method. Electrospinning is considered one of the most flexible, low-cost, and globally recognized methods for generating continuous filaments from submicron to tens of nanometer diameter. Nanofilaments were incorporated precisely on the layers of prepreg to accomplish increased adhesion and interfacial bonding, leading to increased strength and enhancements in more mechanical properties. As a result, the modulus of the epoxy and CNT/epoxy nanofibers were revealed to be 3.24 GPa and 4.84 GPa, leading to 49% enhancement. Furthermore, interlaminar shear strength (ILSS) and fatigue performance at high-stress regimes improved by 29% and 27%, respectively. Barely visible impact damage (BVID) energy improved considerably by up to 45%. The thermal and electrical conductivities were also increased considerably because of the highly conductive CNT networks present in between the CFRP layers. The newly introduced approach was able to deposit high content uniform CNTs at the ply interface of prepregs to enhance the CFRP properties, that has not been achieved in the past because of the randomly oriented high viscosity CNTs in epoxy resins.

This study represents a cost-effective method to advance the physical and mechanical properties of carbon fiber-reinforced polymer (CFRP) prepreg composite materials, where electrospun multiwalled carbon nanotubes (CNTs)/epoxy nanofibers fabricated and deposited in between the layers of traditional CFRP prepreg composite. CNT-aligned epoxy nanofibers were uniformly formed by an optimized electrospinning method. Electrospinning is considered one of the most flexible, low-cost, and globally recognized methods for generating continuous filaments from submicron to tens of nanometer diameter. Nanofilaments were incorporated precisely on the layers of prepreg to accomplish increased adhesion and interfacial bonding, leading to increased strength and enhancements in more mechanical properties. As a result, the modulus of the epoxy and CNT/epoxy nanofibers were revealed to be 3.24 GPa and 4.84 GPa, leading to 49% enhancement. Furthermore, interlaminar shear strength (ILSS) and fatigue performance at high-stress regimes improved by 29% and 27%, respectively. Barely visible impact damage (BVID) energy improved considerably by up to 45%. The thermal and electrical conductivities were also increased considerably because of the highly conductive CNT networks present in between the CFRP layers. The newly introduced approach was able to deposit high content uniform CNTs at the ply interface of prepregs to enhance the CFRP properties, that has not been achieved in the past because of the randomly oriented high viscosity CNTs in epoxy resins.

We studied the effect of low energy (30 keV) ionic implantation of Ga+ in the direction parallel to the graphene planes (perpendicular to the c-axis) in oriented graphite ribbons with widths around 500 nm. Our experiments have reproducibly shown a reduction of electrical resistance upon implantation consistent with the occurrence of ionic channeling in our devices. Our results allow for new approaches in the modulation of the charge carrier concentration in mesoscopic graphite.

L’objet de cette thèse est d’étudier le dopage ex-situ de nanofils semiconducteurs IV pour des applications en électronique, spintronique ou encore thermoélectricité. Deux techniques de dopage ont été explorées : l’implantation par faisceaux d’ions et le Spin-On-Doping (SOD).L’implantation d’ions Mn a été testée dans les nanofils de Ge avec l’objectif de synthétiser un matériau semi-conducteur ferromagnétique dilué. Une concentration en Mn de quelques pourcents peut être atteinte sans amorphisation du fil ni formation de précipités, ce qui est très encourageant. Lors d’expériences d’implantation réalisées in situ dans un microscope électronique en transmission, une forte exaltation de la pulvérisation sous irradiation électronique a été constatée.La technique SOD consiste à faire diffuser thermiquement les impuretés de type p ou n contenues une résine de type HSQ (Hydrogen silsesquioxane) qui enrobe les nanofils. Le recuit de la HSQ (dopée ou non) engendre une modification structurale des nanofils (bien que cette technique soit considérée comme non destructive). Lors du recuit, une transformation partielle de la phase diamant 3C vers la phase hexagonale 2H, a en effet été observée dans les nanofils de Si et de Ge, au-delà de 500 et 400°C respectivement. Les paramètres essentiels de la transformation de phase sont la contrainte de cisaillement résultant de la densification de la résine et le budget thermique. Les nanofils de Ge deviennent amorphes au-delà de 650°C, ce qui interdit en pratique leur dopage par SOD.Les caractérisations électriques ont été réalisées sur des nanofils de Si réalisés par gravure ionique réactive sur substrats orientés (111) et contactés en matrice ou individuellement. Pour le contactage de nanofils uniques en configuration NW-FET (nanowire field effect transistors), un procédé technologique basé sur la lithographie électronique a dû être développé. Les difficultés à surmonter étaient relatives à la faible longueur des nanofils. Diverses techniques de caractérisation ont été mises en œuvre (I-V en configuration verticale ou horizontale de type TLM (Transient Linear Measurement), SSRM (scanning spreading resistance microscopy), EBIC (electron beam induced current). Les mesures collectives concernent des ensembles de nanofils de type p enrobés dans une résine qu’elle soit dopante ou non. Pour observer un courant notable dans la structure, un recuit est nécessaire. Au-delà d’une température de recuit de 600°C, une polarisation négative du substrat induit un comportement conforme au mécanisme SCLC (space charge limited current) attendu pour des nanofils faiblement dopés enrobés dans une matrice isolante. En positif, on observe une caractéristique I(V) ohmique et une densité de courant jusqu’à 500 fois plus élevée dans les nanofils que dans le substrat. Ce comportement pourrait être dû à l’influence des états d’interface provenant de la technique de gravure. Cette hypothèse est confortée par le fait qu’après recuit à 900°C, le courant en direct s’explique en considérant dans les fils un dopage proche de celui du substrat, et surtout par l’observation en SSRM d’une couche conductrice interfaciale entre fils et HSQ. Elle permet aussi d’interpréter les mesures sous pointes faites sur les fils de type n. Le mode de transport SCLC a également été observé pour des nanofils individuels contactés sous pointe ou par lithographie. Ces mesures n’ont pas mis directement en évidence l’influence de la transformation de phase.Le dopage de type n ou p par SOD s’avère efficace après recuit à 900°C. Dans ce cas, les comportements observés, contacts ohmiques et jonctions p-n, peuvent être interprétés plus simplement en considérant des niveaux de dopage supérieurs à 3×10¹⁶ cm⁻³ en type p et 2×10¹⁶ cm⁻³ en type n. Ces valeurs déduites des résistivités mesurées sont sans doute très sous-estimées puisque la mobilité dans les fils est sans doute inférieure à celle du volume. / This thesis aims at studying the ex-situ doping of semiconducting nanowires (NWs) for applications in electronics, spintronics or thermoelectricity. Two widely used techniques have been envisaged: ion beam implantation and Spin-On-Doping (SOD).The ion beam implantation of Mn ions has been tested in Ge NWs in an attempt to form a 1D diluted magnetic semiconductor structure. A Mn concentration of few percents can be achieved without amorphization of the nanowire nor clustering, what is very promizing. During implantation done in situ in a transmission electron microscope, a strong enhancement of the sputtering under electron irradiation has been observed.The doping by SOD results from the thermal diffusion of p-type or n-type impurities contained in a HSQ (Hydrogen silsesquioxane) resist in which the NWs are embedded. The curing of the HSQ resist (doped or not) leads to a structural modification of nanowires (while SOD is generally assumed to be non-destructive). As a result of the annealing, a partial transformation of the 3C diamond phase towards the 2H hexagonal phase is observed in Si and Ge nanowires, above 500 et 400°C respectively. The main parameters of that phase transformation are the shear stress due to the HSQ densification and the thermal budget. Ge NWs are found to turn to amorphous above 650°C, what renders SOD practically unusable for Ge NWs. Two methods are currently used for the fabrication of nanowires, the VLS (vapor-liquid-solid) growth and reactive ion etching of (111) Si wafers. For practical reasons, etched NWs were used for the study of their electrical properties.The electrical characterizations were done on arrays of Si NWs embedded in a HSQ matrix or on single NWs. For contacting single NWs in the NW-FET(nanowire field effect transistors) configuration , a process based on electron beam lithography has been developed. The issues to be solved were related to the low length of NWs. Various measurement techniques were used: I-V in two tips or TLM (Transient Linear Measurement) arrangement, SSRM (scanning spreading resistance microscopy), EBIC (electron beam induced current). Collective measurements were done on arrays of p-type NWs embedded in a HSQ resist, doped or not. It was firstly observed that an annealing is needed to observe a noticeable current in the structure. Above an annealing temperature of 600°C, for a negative bias applied to the substrate, the observed behavior can be described by the SCLC (space charge limited current) mechanism expected for poorly doped NWs in an isolating matrix, while a positive bias applied to the substrate results in an ohmic characteristic and in a current density up to 500 times higher in the NWs than in the substrate. This unexpectedly high intensity in direct bias may be attributed to electrically active surface states resulting from the etching process. This hypothesis is conforted by the fact that an annealing at 900°C (without extra doping) the measured intensity can be explained by assuming the same doping level in NWS than in the substrate. In addition, an interfacial conductive between resist and nanowires can be observed by SSRM. These interfacial states can be also involved for understanding the measurements done on n-type NWS. The SCLC mechanism of transport has been also observed for single NWs contacted by tips or by lithographied contacts. These measurements were not able to evidence the effect of the phase transformation on the electrical properties.P-type and n-type doping by SOD becomes effective after annealing at 900°C. After doping, ohmic or rectifying behaviours on p-type substrate are observed as expected. That renders more easy the interpretation of results, by assuming doping levels in the NWs of 3×10¹⁶ cm⁻³ and 2×10¹⁶ cm⁻³ for p-type and n-type respectively. These values as deduced from resistivities are probably very underestimated as the mobilities in NW are probably much lower than in the bulk.

Orientador: Eudes Borges de Araújo / Resumo: Nos últimos anos, grande atenção tem sido dada ao desenvolvimento de células solares com o iodeto de chumbo e metilamônio (MAPbI3) em virtude de suas excelentes propriedades fotovoltaicas. Apesar de altas eficiências de conversão de energia terem sido atingidas com essas células, a síntese desse material e algumas de suas características elétricas permanecem em estudo. No presente trabalho, mostrou-se que a síntese desse material na forma de filmes finos via spin-coating deve ser executada preferencialmente com soluções precursoras de dimetilsulfóxido depositadas sobre platina, com maiores tempos e temperaturas de secagem e aumento da taxa de remoção do solvente. Por sua vez, pastilhas de MAPbI3 tiveram condições ótimas de sinterização a 120°C por 2h. O material foi caracterizado em termos de suas propriedades elétricas por meio da espectroscopia de impedância, com tensões de frequências na faixa de 300 Hz a 1 MHz e temperaturas no intervalo entre 100 e 430K, tendo sido observada uma histerese entre o aquecimento e o resfriamento nos comportamentos da permissividade elétrica, impedância, módulo elétrico e condutividade elétrica, que se mostraram sensíveis à temperatura e às frequências da tensão de teste. Ainda, foram observadas alterações dessas propriedades elétricas associadas às transições de fase, cujas temperaturas em que ocorrem se mostraram independentes da frequência da tensão. A fim de separar os efeitos diferenciados dos grãos e contornos de grão nas propriedades e... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In recent years, great attention has been paid to the manufacture of solar cells with methylammonium lead iodide (MAPbI3) due to its excellent photovoltaic properties. Although high energy conversion efficiencies have been achieved with these cells, the synthesis of this material and some of its electrical characteristics remain under study. In the present research, it was shown that the synthesis of this material in the form of spin-coating thin films should be performed preferably with dimethylsulfoxide precursor solutions deposited over platinum surfaces, with higher drying times and temperatures and increasing the solvent removal rate. In turn, MAPbI3 pellets had optimum sintering conditions at 120°C for 2h. The material was characterized in terms of it’s electrical properties by impedance spectroscopy, with frequency voltages in the range of 300 Hz to 1 MHz and temperatures in the range 100 to 430K, and a hysteresis between heating and cooling was observed on permissivity, impedance, electrical modulus and conductivity behaviors, which were sensitive to temperature and applied voltage frequencies. In addition, changes in these electrical properties associated with phase transitions were observed, whose temperatures at which they occurred were independent of the voltage frequency. In order to separate the differentiated effects of grains and grain boundaries on the electrical properties of MAPbI3, an equivalent circuit was proposed that was efficient to describe the exper... (Complete abstract click electronic access below) / Mestre

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18982号 / 工博第4024号 / 新制||工||1620(附属図書館) / 31933 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 酒井 明, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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