[pt] Neste trabalho foram obtidos filmes de grafeno usando um precursor sólido, a Trifenilfosfina, num processo de deposição química na fase vapor em alto vácuo (HVCVD). A microscopia eletrônica de Varredura permitiu observar a presença de pequenas regiões inomogêneas na superfície das amostras crescidas. Estas regiões foram observadas na microscopia antes e após o processo de transferência da folha de cobre para o substrato de silício oxidado. Medidas realizadas por XPS permitiram comprovar a incorporação de fósforo no filme crescido. A espectroscopia Raman foi usada para determinar a temperatura de trabalho adequada no sistema de crescimento. A presença de grafeno foi confirmada em todas as amostras, mas observou-se que, em geral, a quantidade de defeitos nas amostras cresceu com o aumento da massa do precursor utilizado no crescimento. Os resultados obtidos são discutidos à luz de recentes trabalhos teóricos que tratam do uso da técnica Raman no estudo de defeitos em grafeno. / [en] In this work graphene films were obtained using a solid precursor, Triphenylphosphine, by chemical vapor deposition in high vacuum (HVCVD). Scanning electron microscopy allowed to observe the presence of small inhomogeneus regions on the surface of the grown samples. These regions were observed in the microscopy before and after the transfer process from the copper foil to silicon oxidized wafer. XPS measurements checked the incorporation of phosphorus in the film grown. Raman spectroscopy was used to determine the suitable working temperature in the growth system. The presence of graphene was confirmed in all samples, but it was observed that in general, the amount of defects in the samples increased with increasing the mass of the precursor used in growth. The results are discussed in light of recent theoretical works that address the use of Raman technique in the study of defects in graphene.

Por duas décadas, as nanoestruturas conhecidas como nanotubos de carbono (CNT), tem chamado a atenção de muitos centros de pesquisa, devido a suas propriedades físicas e químicas, que tornam este material uma ferramenta de primeira ordem em diferentes aplicações. Este trabalho pretende pesquisar a fabricação e caracterização destas estruturas, utilizando as técnicas de deposição química a vapor (CVD), e deposição química a vapor assistida por plasma (PECVD), visto que são as que reportam melhores resultados em termos de qualidade e quantidade, além de facilidade. A pesquisa está encaminhada pelo ajuste fino das variáveis que intervém nestes dois tipos de processo, tais como a temperatura, os gases precursores a usar, seus fluxos, e relação entre eles, o tipo de catalizador etc. assim como das variáveis que só fazem parte de cada processo diferenciado, no caso do CVD as altas temperaturas, e no caso do PECVD a pressão, a potência de RF aplicada para a formação do plasma etc. A forma de avaliar os resultados obtidos foi mediante as técnicas mais idôneas relativas aos nanotubos de carbono, as quais são a microscopia Raman, a microscopia eletrônica tanto de varredura como de transmissão, e a dispersão de raios X. Desta forma pretende-se fazer um trabalho exaustivo com a finalidade de conseguir uma síntese idônea das nanoestruturas de carbono para diferentes tipos de aplicações encaminhadas principalmente a dispositivos elétricos. / For the past two decades, the nanostructures known as carbon nanotubes (CNT), have been the center of attention of many research centers, due mainly to its physical and chemical properties, turning them into a first order tool in many kind of applications. This work pretends to study the fabrication and characterization of these nanostructures, using the chemical vapor deposition (CVD), and the plasma enhanced chemical vapor deposition (PECVD) techniques, since they are reported as the best ones in terms of quality, quantity and ease of use. The research is routed by the fine tuning of the variables involved in both processes, such as the temperature, the gas precursors, the gas flows, the flow ratio, the metal catalyst etc. as well as the variables involved in just one of the processes, in the case of CVD, the high temperatures, and in the case of PECVD, the pressure, the RF power for plasma formation etc. The way to evaluate the obtained results was through the most suitable techniques relative to CNT analysis , as Raman microscopy, electron microscopy, both scanning and transmission, and x-ray diffraction. Thus we pretend to perform an exhaustive research with the aim to find a synthesis of carbon nanostructures suitable for different kind of applications, routed principally to electronic devices.

Este estudo in vitro avaliou a microinfiltração marginal de restaurações de classe V em resina composta, preparadas utilizando-se três técnicas de preparo cavitário: Alta-rotação (AR), ultrassom (US) e a associação das duas técnicas (AR+US); e restauradas após a aplicação de 3 sistemas adesivos, sendo um de condicionamento total (Single-Bond (SB)) e dois autocondicionantes (Clearfil SE Bond (CSE) e Prompt L-Pop (POP)). Foram formados nove grupos (n=14) com terceiros molares que tiveram cavidades preparadas em suas faces vestibular e lingual, e foram classificados como: Grupo1- AR/SB; Grupo 2 AR/CSE; Grupo 3 AR/POP; Grupo 4 US/SB; Grupo 5 US/CSE; Grupo 6 US/POP; Grupo 7 AR+US/SB; Grupo 8 - AR+US/CSE; Grupo 9 - AR+US/POP. Após a aplicação do adesivo as cavidades foram preenchidas com resina composta Z250-3M ESPE e armazenadas em água destilada a 37°C durante 24 horas. Posteriormente, as restaurações foram polidas e os espécimes termociclados (1000 ciclos/ 5 e 55°C), impermeabilizados, imersos em solução de nitrato de prata 50% por 8 horas, seccionados em 3 fatias, imersos em solução fotoreveladora por 16 horas e observados em microscópio óptico acoplado à uma câmera de vídeo. As imagens foram digitalizadas e um software foi utilizado para medir a microinfiltração marginal dos lados oclusal e cervical. Foi realizado ANOVA Split-plot que demonstrou não haver diferenças estatisticamente significantes para os lados oclusal e cervical (p<0.05). A média dos lados oclusal e cervical foi realizada e os dados submetidos à ANOVA 2 Fatores (p=0,05), que mostrou haver diferenças estatisticamente significante entre os grupos, sendo necessário a utilização de um Teste de Tukey (p=0,05). Este teste mostrou não haver diferenças estatisticamente significantes entre os grupos restaurados com o sistema adesivo de condicionamento total (SB), no entanto, os grupos restaurados com os adesivos CSE e POP apresentaram menor microinfiltração para os grupos preparados com US e AR+US. O Grupo US/CSE apresentou o menor índice de microinfiltração e o AR/POP o maior. Nas condições deste estudo, podemos concluir que o método de preparo das cavidades pode alterar a microinfiltração marginal para restaurações que utilizem sistema adesivo autocondicionante. / This in vitro study compared the microleakage of class V resin composite restorations placed in cavities prepared with high-speed dental bur (AR), ultrasonic preparation devices (US) and high-speed dental bur plus ultrasonic preparation devices(AR+US), and restored using three different adhesive systems (One all etch Single Bond (SB) , and two Self-etch Clearfil CSE bond (CSE), Prompt L-Pop (POP)). Nine groups (n= 14) of human third molars each were prepared on the bucal and lingual surfaces were formed: Group 1- AR/SB; Group 2 AR/CSE; Group3 AR/POP; Group4 US/SB; Group 5 US/CSE; Group 6 US/POP; Group 7 AR+US/SB; Group 8 - AR+US/CSE; Group 9 - AR+US/POP. Specimens were built up with Z250/3M ESPE composite and stored in distilled water at 37°C for 24 hours. Then, the restorations were polished and the specimens thermocycling (1000 cycles/ 5°- 55°C), put impermeable, immersed in a 50% silver nitrate solution for 8 hours, sectioned, immersed in a photographic developer solution at darkness for 16 hours, and analyzed for leakage at the oclusal and cervical interface using an optical microscope connected to a video camera. The images were digitalized and software was utilized for microleakage assessment. Upon analyzing the results using a Split-plot ANOVA no statistically significant differences (p<0,05) between the cervical and oclusal interfaces for all groups was observed. The average of the interfaces was held and a Two-Way ANOVA revealed differences in microleakage among the tested groups (p=0,05). Tukey Test for Multiple Comparisons (p=0,05) demonstrated no significant difference between the groups restored with total etch adhesive system (SB), the groups restored with CSE and POP showed the least microleakage for the group prepared with the US and AR/US. The group US/CSE had the lowest microleakage and the group AR/POP had the highest. In the conditions of this study, we can conclude that the method of cavity preparation may affect the microleakage when a selfetch adhesive system is used.

Recentemente surgiram os instrumentos abrasivos diamantados obtidos pela técnica Chemical Vapor Deposition (CVD) utilizados em ultra -som como uma nova possibilidade na técnica do preparo de cavidade. Tradicionalmente, os preparos cavitários são realizados com instrumentos abrasivos diamantados rotatórios convencionais (IADR) formando uma espessa camada de esfregaço. Com o desenvolvimento dos sistemas adesivos, tornou-se muito importante saber a qualidade e a espessura da camada de esfregaço e a topografia dentinária produzida. Com esse objetivo, foram avaliadas in vitro as características da superfície desgastada e a camada de esfregaço produzida em dentina após serem instrumentadas. Foram preparados 24 corpos de prova (cps) e divididos em 4 grupos (grupo 1 – cps preparados com IADR, grupo 2 – cps preparados com CVD rotatório, grupo 3 - cps preparado com CVD Tangencial por ultra-som e grupo 4 - cps preparados com CVD Impacto por ultra-som). Após os desgastes dentinários descritos, os corpos de prova foram desidratados e devidamente preparados para a observação em MEV. Em análise qualitativa as fotomicrografias realizadas no MEV demonstraram significantes diferenças. Os corpos de prova instrumentados com o sistema rotatório (IADR e CVD rotatório) apresentaram ranhuras com traçado retilíneo e paralelo, maior produção de espessura de esfregaço e maior comprimento de smear plug. Os corpos de prova instrumentados com o sistema ultra-sônico (CVD Tangencial eCVD Impacto) apresentaram padrões de ranhuras e traçados próprios, com menores espessuras de esfregaço e menor comprimento de smear plug. / Abrasive diamond instruments are a recent development, obtained through a technique called Chemical Vapor Deposition (CVD), used in ultrasound as a new possibility in dental cavity preparation. Traditionally, cavity preparations are made with conventional abrasive rotary diamond burs (IADR), forming a thick smear layer. Upon the development of new adhesive systems, it has become very important to know the quality and thickness of the smear layer, as well as the dentin topography produced after preparati on. For this purpose, we conducted an in vitro evaluation of the drilled surface and the smear layer produced in dentin after instrumentation. Twenty-four (24) samples were divided into four (4) groups: (group 1 – samples prepared with IADR, group 2 – samples prepared with rotary CVD, group 3 – samples prepared with Tangential ultrasound -guided CVD, and group 4 – groups prepared with Impact ultrasound-guided CVD). After the dentin drilling described, the samples were dehydrated and adequately prepared for SEM observation. A qualitative analysis conducted by SEM microphotography yielded significant differences. The samples worked with the rotary systems (IADR and rotary CVD) showed straight, parallel grooves, with thicker smear layers and longer smear plugs. The samples submitted to ultrasound-guided drilling (Tangential CVD and Impact CVD) showed distinctive groove and contour patterns, with the lowest smear thicknesses and smear plug lengths.

Das Wachstum makroskopischen und einlagigen Graphens und dessen Implementierung in großflächige Bauelementen ist von großem Interesse. Großflächiges Graphen wird mit Hilfe eines optimierten CVD-Prozesses auf polykristalliner Kupferfolie bei hohen Temperaturen gewachsen und durch einen eigens entwickelten Transferprozess auf geeignete Substrate transferiert. Transmissionsspektroskopische Untersuchungen zeigen, dass sich die hergestellten Graphenschichten im Wellenlängenbereich von 450-800 nm durch eine Transmission auszeichnen, die nicht wesentlich von 97.6% abweicht. NEXAFS-, XPS und Raman-Experimente belegen, dass die sp2-Hybridstruktur des Graphens arm an Defekten ist. Aufgrund der unterschiedlichen thermischen Ausdehnungskoeffizienten von Graphen und Kupfer, wird großflächiges Graphen während des Abkühlprozesses biaxial und kompressiv verspannt. Unter Verwendung von AFM- und Raman-Experimenten werden der Mechanismus des schrittweisen Verspannungsabbaus vollständig aufgeklärt und die Teil- sowie Restverspannungen quantifiziert. Interessanterweise führt der erste Schritt des Verspannungsabbaus während des Abkühlprozesses zur Ausbildung einer ausgeprägten Rillenstruktur auf der Cu-Substratoberfläche und zum Aufwerfen von Graphenfalten. Die Relaxation weiterer Verspannung während des Graphentransfers vom Cu-Wachstumssubstrat auf SiO2-bedecktes Si führt zu einer Frequenzverschiebung der 2D Phonon-Mode um -27 cm-1. Hall-Effekt-Messungen einer 8x8 mm2 großen Graphenschicht auf Corning Eagle Borosilikatglas zeigen eine Ladungsträgerbeweglichkeit von 2070 cm2 V-1 s-1 im Graphen. Weiterhin ergeben diese Messungen eine Lochkonzentration von 3.6E12 cm-2 in diesen Schichten. Der durch Raman-Experimente gezeigte Erhalt der Graphenstruktur nach Bedeckung mit kristallinem Si, weckt Erwartungen, Graphen zukünftig beispielsweise als vergrabenen Frontkontakt in flüssigphasenkristalliserten Dünnschichtsolarzellen in Superstratkonfiguration implementieren zu können. / The growth of macroscopic single-layer graphene and its implementation in large-area electronic devices is of major interest. Large area graphene is grown by an optimized CVD-process on polycrystalline copper foil and transferred to suitable substrates by a self-developed transfer process. Transmission-spectroscopic investigations indicate that the manufactured graphene exhibits almost constant transmission of 97.6 % between 450-800 nm. NEXAFS-, XPS-, as well as Raman experiments were conducted to demonstrate the low defect density in the sp2 hybrid structure of the manufactured graphene. Large internal biaxial compressive strain is introduced in graphene due to the thermal expansion mismatch between graphene and copper. The mechanism of the stepwise strain relaxation is fully revealed by AFM and Raman measurement techniques. The remaining strain in the material is thoroughly quantified. Interestingly, the first step of the strain relaxation process results in a pronounced ripple structure on the Cu substrate and in graphene wrinkle formation. Removing graphene from the Cu substrate and transferring it to SiO2 results in a shift of the 2D phonon mode by 27cm-1 to lower frequencies. Hall effect measurements of an 8x8mm2 graphene layer on corning eagle borosilicate glass exhibit a charge carrier mobility of 2070 cm2 V-1 s-1 at hole concentrations of 3.6E12 cm-2, respectively. Expectations for further applications in liquid phase crystallized superstrate thin film solar cells are raised by the retention of the basic structure of graphene after burial under crystalline Si.

Por duas décadas, as nanoestruturas conhecidas como nanotubos de carbono (CNT), tem chamado a atenção de muitos centros de pesquisa, devido a suas propriedades físicas e químicas, que tornam este material uma ferramenta de primeira ordem em diferentes aplicações. Este trabalho pretende pesquisar a fabricação e caracterização destas estruturas, utilizando as técnicas de deposição química a vapor (CVD), e deposição química a vapor assistida por plasma (PECVD), visto que são as que reportam melhores resultados em termos de qualidade e quantidade, além de facilidade. A pesquisa está encaminhada pelo ajuste fino das variáveis que intervém nestes dois tipos de processo, tais como a temperatura, os gases precursores a usar, seus fluxos, e relação entre eles, o tipo de catalizador etc. assim como das variáveis que só fazem parte de cada processo diferenciado, no caso do CVD as altas temperaturas, e no caso do PECVD a pressão, a potência de RF aplicada para a formação do plasma etc. A forma de avaliar os resultados obtidos foi mediante as técnicas mais idôneas relativas aos nanotubos de carbono, as quais são a microscopia Raman, a microscopia eletrônica tanto de varredura como de transmissão, e a dispersão de raios X. Desta forma pretende-se fazer um trabalho exaustivo com a finalidade de conseguir uma síntese idônea das nanoestruturas de carbono para diferentes tipos de aplicações encaminhadas principalmente a dispositivos elétricos. / For the past two decades, the nanostructures known as carbon nanotubes (CNT), have been the center of attention of many research centers, due mainly to its physical and chemical properties, turning them into a first order tool in many kind of applications. This work pretends to study the fabrication and characterization of these nanostructures, using the chemical vapor deposition (CVD), and the plasma enhanced chemical vapor deposition (PECVD) techniques, since they are reported as the best ones in terms of quality, quantity and ease of use. The research is routed by the fine tuning of the variables involved in both processes, such as the temperature, the gas precursors, the gas flows, the flow ratio, the metal catalyst etc. as well as the variables involved in just one of the processes, in the case of CVD, the high temperatures, and in the case of PECVD, the pressure, the RF power for plasma formation etc. The way to evaluate the obtained results was through the most suitable techniques relative to CNT analysis , as Raman microscopy, electron microscopy, both scanning and transmission, and x-ray diffraction. Thus we pretend to perform an exhaustive research with the aim to find a synthesis of carbon nanostructures suitable for different kind of applications, routed principally to electronic devices.

Les composites à matrice céramique SiC/SiC sont des matériaux prometteurs pour le remplacement des superalliages dans les moteurs pour l’aviation civile et militaire. La matrice de SiC des composites est réalisée par dépôt chimique en phase vapeur (CVD). Le précurseur actuellement utilisé à l’échelle industrielle est le méthyltrichlorosilane (MTS, CH3SiCl3) dilué dans le dihydrogène (H2). Ce système chimique peut dans certains cas conduire à des écarts à la stoechiométrie des dépôts ainsi qu’à des gradients de densification au sein du composite final. Deux nouvelles molécules ont été envisagées dans le cadre de la thèse pour remédier aux inconvénients du MTS. Le vinyltrichlorosilane (VTS, C2H3SiCl3), composé d’un groupement vinyle (deux carbones doublement liés), susceptible de stabiliser la liaison Si-C de la molécule et favoriser une réactivité couplée de silicium et du carbone, propice au dépôt de SiC pur. Le méthylsilane (MS, CH3SiH3), qui ne possède pas d’atomes de chlore limitant la réactivité hétérogène. Son utilisation devrait en outre permettre de réduire le traitement des effluents en sortie de réacteur.La pertinence de ces deux précurseurs a été évaluée par une approche expérimentale mettant en évidence les régimes cinétiques associés aux deux molécules et en s’intéressant à la nature du solide déposé. Cette approche est couplée à une modélisation de la phase homogène et à des mesures IRTF des gaz froids sortant du réacteur, dans le but de comprendre les phénomènes chimiques mis en jeu pendant le dépôt.À basse température, la décomposition du VTS produit des hydrocarbures réactifs qui inhibent le dépôt de SiC et conduisent à un large excès de carbone libre. Le solide devient stoechiométrique à température moyenne, au-delà d’un domaine de bi-stabilité de la vitesse de dépôt (R). C2H4 et SiCl4 sont alors majoritairement formés. Les transferts de masse (TM) limitent la vitesse de dépôt à haute température et un léger excès de C réapparait dans le solide, associé à la formation C2H2.Le système MS/Ar réagit à plus basse température que VTS/H2 et le rendement en solide est beaucoup plus élevé (seules des traces de CH4 sont détectées à haute température en sortie du réacteur). Inversement à VTS/H2, le solide est excédentaire en Si à basse température, stoechiométrique à température moyenne et, dans certains cas, riche en C à haute température (R est alors limitée par les TM).La composition, la structure et la texture des dépôts de SiC issus des deux systèmes ont été corrélées avec les conditions expérimentales (température, pression, temps de séjour). Sur substrat dense, les transitions observées traduisent des variations de concentration des précurseurs effectifs de C et de Si, voire des changements du mécanisme de dépôt. L’aptitude à l’infiltration (CVI) a également été jugée à l’aide de substrats poreux modèles. Les profils d’épaisseurs et de composition le long d’un canal traduisent l’effet du temps de diffusion des gaz le long du pore, mais aussi l’appauvrissement local en réactifs. Comparativement au système MTS/H2 testé dans des conditions de référence, des conditions plus favorables à la CVI ont été établies pour les systèmes VTS/H2 et MS/Ar. / The aim of this thesis is to understand the gas-phase mechanisms that occured during the chemical vapor deposition of silicon carbide from two precursors with different chemistry (chlorinated precursor and non-chrloinated one). Thanks to this study, optimal conditions for infiltration with these two precursors should be found.

Nesta dissertação discutem-se os resultados do estudo do efeito da modificação superficial de filmes de diamante dopados com boro (DDB) com partículas de Pt depositadas eletroquimicamente, sobre a reação de oxidação anódica de etanol em meio ácido. Foram investigadas a influência do potencial de deposição, da carga de deposição e do pré-tratamento eletroquímico em potenciais de reação de geração de H2 (RGH) e de O2 (RGO) no grau de dispersão da Pt e na eficiência do eletrodo de BDD-Pt para a reação de oxidação anódica de etanol. Pré-tratamentos catódicos tendem a aumentar a atividade do eletrodo para a RGO, embora este efeito não seja permanente e só seja observado em filmes novos. Polarizações anódicas contribuem para o aumento do sobrepotencial de RGO, assim como causam a diminuição da eficiência de corrente para a deposição de Pt,embora surpreendentemente origine depósitos de Pt com maior área superficial e maior atividade para a oxidação anódica do etanol. Um modelo baseado em interações entre a superfície do diamante e o íon complexo de Pt é proposto para explicar a influência destes parâmetros nas características dos depósitos. / The results from the study of the surfacial modification of boron doped diamond (BDD) films with electrodeposited Pt particles for the anodic oxidation of ethanol in acidic media are discussed. It was investigated the influence of deposition potential, catalyst loading and electrochemical pre-treatment at H2 or O2 evolution reaction (HER and OER, respectively) potentials made prior to catalyst deposition, on the dispersion degree and electrode efficiency for ethanol anodic oxidation. HER polarizations tend to increase the film activity for the OER reaction, though this effect was not found to be permanent and was only observed in recently prepared BDD films. Anodic polarizations on the BDD contribute to the increase of OER overpotential as well as for the decreasing of the current efficiency for the Pt deposition, though it surprisingly resulted in more dispersed (higher surfacial area), more ethanol oxidation active Pt deposits. A tentative model based on interactions between Pt complex ion and O (or H) terminated BDD surfaces is presented.

Les propriétés physiques et chimiques exceptionnelles du matériau diamant ont suscité l'intérêt des chercheurs pour le développement d'applications industrielles, comme par exemple dans les domaines de la dissipation thermique ou de l'électronique de puissance. En particulier, les propriétés mécaniques remarquables de ce matériau peuvent être exploitées avantageusement pour la conception de résonateurs MEMS (Micro-Electro-Mechanical Systems). Même si certains dispositifs MEMS à base de diamant avaient été décrits dans la littérature, les propriétés mécaniques de ce matériau n'avaient jamais été associées à ses propriétés chimiques pour la réalisation de transducteurs chimiques ou biochimiques à base de résonateurs MEMS. Ainsi, l'objectif cette thèse a été de démontrer l'intérêt de ce matériau innovant pour la fabrication de ces capteurs. Les MEMS offrent la possibilité de faire de la détection en temps réel de manière directe (sans marqueur), rapide et sensible, sur de faibles quantités d'analytes. De plus ils permettent d'adresser des cibles non électro-actives qui ne peuvent pas être détectées par des capteurs électrochimiques. Dans cette étude, nous avons développé dans un premier temps des procédés de micro-structuration spécifiques du diamant. Ces procédés entièrement compatibles avec des techniques de salle blanche ont permis d'aboutir à la réalisation de nombreux transducteurs à base de micro-leviers en diamant sur des substrats en silicium de 4 pouces. De plus les approches développées permettent d'éviter la gravure fastidieuse du matériau diamant. Leur caractérisation mécanique en régime dynamique a permis de caractériser le module d'Young E du matériau diamant synthétisé en fonction des conditions de croissance. Dans le meilleur cas une valeur de E très élevée de l'ordre de 1100 GPa a été obtenue, ce qui est très proche de la valeur du diamant monocristallin (1200GPa). Par ailleurs, nous avons pu vérifier que les propriétés de résonance (fréquence de résonance et facteur de qualité) des structures en diamant réalisées étaient supérieures à celles de structures identiques en silicium. En particulier, cela rend ces résonateurs plus aptes à être exploités en milieux liquides. Nous avons montré que dans de tels milieux les micro-leviers en diamant étaient très peu sensibles à une variation massique. En revanche leur sensibilité à une variation de masse volumique du liquide est de l'ordre de 3Hz.kg-1.m3 et donc significative. Par ailleurs, en fonctionnalisant des micro-leviers en diamant par de l'acide caproïque, nous avons mis en évidence que des variations de densité de charges à la surface des micro-leviers pouvaient induire des variations de fréquence de résonance de plusieurs dizaines de Hz dans le cas de structures vibrant à quelques kHz. Ceci a permis de mettre en évidence la grande sensibilité de nos transducteurs en diamant à des interactions moléculaires. Dans ce contexte nous avons pu réaliser un capteur d'ADN permettant la reconnaissance spécifique en temps réel de brins d'ADN cibles de 24 paires de bases sans marqueur. En parallèle de ces travaux, des structures d'actionnement et de lecture ont été intégrées et évalué sur des dispositifs résonants à base de diamant. Ceci a permis de les interfacer à un premier prototype de système d'acquisition électronique portable dédié réalisé au cours de cette thèse / Diamond material is very promising for future technological applications due to its outstanding physical and chemical properties. In particular, its remarkable mechanical features may be used advantageously for MEMS (Micro-Electro-Mechanical Systems) devices development. However, even though several diamond-based MEMS devices have been reported in the literature, the mechanical properties of this material have never been combined to its chemical properties for developing resonating MEMS-based biochemical transducers. Thus, the purpose of this study was to demonstrate the interest of such diamond transducers for chemical or biochemical sensing applications. MEMS devices are indeed attractive because they allow fast, label free and sensitive detection in real time on small volumes due to their miniaturized size. Moreover they offer the possibility to address non electroactive target species which are undetectable using classical electrochemical methods. In this study, we developed specific clean room compatible processes for diamond micro-structuring. The bottom-up approaches undertaken here were based on diamond patterns growth. Hence they avoid time consuming diamond etching steps. These processes allowed fabricating several diamond micro-cantilever transducers over 4-inches substrates. The mechanical characterization of the cantilevers in oscillating regime was performed in order to extract the material Young's modulus E when the structures were made of different polycrystalline diamond qualities. In the best case, a value of E as high as 1100 GPa and very close to the Young's modulus of monocrystalline diamond (1200 GPa) was achieved. In parallel, we verified that both cantilevers resonance frequency and Q-factor were significantly higher than those of identical silicon structures (on average twice higher). This makes diamond mechanical structures more suitable for use in liquid media. In such damping media a very poor sensitivity to mass changes was determined. Nevertheless, their sensitivity to liquid density changes was found to be significant (-3Hz.kg-1.m3). More importantly, by functionalizing diamond micro-cantilevers with caproic acid, an evidence of these transducers high sensitivity to surface molecular interactions was shown. Especially, when charge density variations occurs several tens Hz changes were measured on kHz-range oscillating cantilevers. In this context, a label free DNA sensor was achieved and allowed the specific detection of 24-mer target DNA in real time. In parallel to this work, actuation and boron doped diamond-based readout gauges were integrated to the resonant cantilevers and characterized. They allowed interfacing the cantilevers to a dedicated acquisition electronic prototype developed in the course of this study

Nous vous proposons un procédé de fabrication pour obtenir des dispositifs de graphène suspendu avec rendement élevé (~ 90%). Surtout, nous nous concentrons sur l'intégrabilité de procédé ainsi que sa compatibilité avec les technologies existantes de silicium. Pour répondre à ces questions, nous avons développé un système de fabrication à base de graphène qui était synthétisé par dépôt chimique en phase vapeur (CVD).L'étape la plus importante dans le processus de fabrication est liée à la gravure du substrat de SiO2 sous-jacente à suspendre les rubans de graphène. Il est souvent rapporté dans la littérature que, à ce stade, les forces capillaires peuvent provoquer l'effondrement des rubans de graphène. En dehors de cet effet, nous avons trouvé que la qualité de l'interface entre le masque de gravure et le substrat est essentielle pour suspendre les dispositifs de graphène avec succès. Ce n'est que lorsque la qualité de cette interface a été amélioré, nous avons atteint des rendements remarquablement élevés d'environ 90%. Caractérisation par spectroscopie Raman, la microscopie électronique à balayage (MEB) et microscopie à force atomique (AFM), qui était effectuée après chaque étape de fabrication, ont attesté que notre méthodologie n'a aucune dommage sur la qualité du graphène.Par la suite, nous avons utilisé la spectroscopie Raman pour étudier le dopage et la contrainte dans nos dispositifs de graphène CVD. Alors que nous avons observé une forte dopage de type p sur graphène supporté sur SiO2 dans l'air, le dopage seul ne peut pas tenir compte des spectres observés. Au lieu de cela, nous concluons que les échantillons de graphène mesurées présentent une contrainte interne de compression, qui ne se relâche pas complètement pendant la fabrication. Nous attribuons cette contrainte au budget de la température de CVD et au polymère rigide de transfert.Enfin, nous avons étudié les caractéristiques électriques de nos dispositifs à température ambiante ainsi qu'à basse température. Les mesures ont confirmé la forte dopage de type p de graphène, et en suite, ‘back-gating' ont donné une modulation faible de courant. Mesures magnéto-transport, qui sont effectuées à 20 K et 4, ont été utilisés pour extraire la densité de porteurs et la mobilité des dispositifs supportés sur SiO2. Faibles valeurs de mobilité sont attribuées à la diffusion par les joints de grains. À des champs magnétiques faibles, nous avons observé des signatures de localisation faible, ce qui implique que ‘intervalley scattering' est le mécanisme dominant dans nos échantillons. À des champs magnétiques élevés, la résistivité longitudinale a montré oscillations robuste à température qui pourraient être identifiés comme niveaux de Landau. / We propose a high-yield (~ 90%) fabrication route to obtain suspended graphene devices. Importantly, we focus on the scalability of the process as well as its compatibility with existing Si technologies. To address these issues, we developed a fabrication scheme based on graphene grown by chemical vapor deposition (CVD).The most crucial step in the fabrication process relates to the etching of the underlying SiO2 substrate to suspend the graphene ribbons. It is often reported in the literature that at this stage, capillary forces can lead to the collapse of the graphene beams. We have found that apart from this effect, the quality of the interface between the etch mask and the substrate is key to successfully suspend graphene devices. Only when the quality of this interface was improved, were we able to achieve remarkably high yields of approximately 90%. Characterization by Raman spectroscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM), performed after each step of fabrication, attested that our methodology does not impact the quality of the graphene.We have subsequently employed Raman spectroscopy to investigate doping and strain in our CVD graphene devices. While we did observe a strong p-type doping of graphene supported on SiO2 in air, doping alone cannot account for the observed spectra. Instead, we conclude that the measured graphene samples display a compressive internal strain, which does not fully relax during fabrication. We attribute this strain to the large temperature budget of the CVD process and to the rigid transfer polymer.