The objective of this thesis is to study the effect of process conditions on structure and electrochemical properties of polyacrylonitrile (PAN)/carbon nanotube (CNT) composite film based electrodes developed for electrochemical capacitors. The process parameters like activation temperature, CNT loading in the composite films are varied to determine optimum process conditions for physical (CO2) and chemical (KOH) activation methods. The PAN/CNT precursors are stabilized in air, carbonized in inert atmosphere (argon), and activated by physical (CO2) and chemical (KOH) methods. The physical activation process is carried out by heat treating the carbon precursors in CO2 atmosphere at activation temperatures. In the chemical activation process, stabilized carbon precursors are immersed in aqueous solutions of activating media (KOH), dried, and subsequently heat treated in an inert atmosphere at the activation temperature. The structure and morphology are probed using scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The specific capacitance, power and energy density of the activated electrodes are evaluated with aqueous electrolytes (KOH) as well as organic electrolyte (ionic liquid in acetonitrile) in Cell Test. The surface area and pore size distribution of the activated composite electrodes are evaluated using nitrogen absorption. Specific capacitance dependence on factors such as surface area and pore size distribution are studied. A maximum specific capacitance of 300 F/g in KOH electrolyte and maximum energy density of 22 wh/kg in ionic liquid has been achieved. BET surface areas in excess of 2500 m2/g with controlled pore sizes in 1 - 5 nm range has been attained in this work.

We investigated dynamic response of Cu46Zr54 metallic glass under adiabatic planar shock wave loading (one-dimensional strain) with molecular dynamics simulations, including Hugoniot (shock) states, shock-induced plasticity, and spallation. The Hugoniot states are obtained up to 60 GPa along with the von Mises shear flow strengths, and the dynamic spall strengths, at different strain rates and temperatures. For the steady shock states, a clear elastic-plastic transition is identified. The local von Mises shear strain analysis is used to characterize local deformation, and the Voronoi tessellation analysis, the corresponding local structures at various stages of shock, release, tension and spallation. The plasticity in this glass, manifested as localized shear transformation zones, is of local structure rather than thermal origin, and void nucleation occurs preferentially at the highly shear-deformed regions. The Voronoi and shear strain analyses show that the atoms with different local structures are of different shear resistances that lead to shear localization. Additionally, we performed large-scale molecular dynamics simulations to investigate plasticity in Cu/Cu46Zr54 glass nanolaminates under uniaxial compression. Partial and full dislocations are observed in the Cu layers, and screw dislocations, near the amorphous−crystalline interfaces (ACIs). Shear bands are directly induced by the dislocations in the crystalline Cu layer through ACIs, and grow from the ACIs into the glass layers and absorb ambient shear transformation zones. Plasticity in the glass layers is realized via pronounced, stable shear banding. As the last part of the dissertation, we investigated with nonreactive molecular dynamics simulations, the dynamic response of phenolic resin and its carbon-nanotube (CNT) composites to shock wave compression. For phenolic resin, our simulations yielded shock states in agreement with experiments on similar polymers, except the "phase change" observed in experiments, indicating that such phase change is chemical in nature. The elastic–plastic transition is characterized by shear stress relaxation and atomic-level slip, and phenolic resin shows strong strain hardening. Shock loading of the CNT-resin composites was applied parallel or perpendicular to the CNT axis, and the composites demonstrated anisotropy in wave propagation, yield and CNT deformation. Our simulations suggested that the bulk shock response of the composites depends on the volume fraction, length ratio, impact cross-section, and geometry of the CNT components; the short CNTs in current simulations had insignificant effect on the bulk response of resin polymer.

Ce travail de thèse est centré autour de deux aspects des technologies quantiques: le calcul quantique et la mesure quantique. Il s'appuie sur la boîte à outils de la lumière micro-onde, développé en électrodynamique quantique, pour sonder des circuits mésoscopiques. Ces circuits, fabriqués ici à base de nanotubes de carbone, peuvent être conçus comme des bits quantiques ou comme des systèmes modèles de la matière condensée, et cette thèse explore les deux aspects. La réalisation d'une interface spin-photon cohérente illustre le premier. L'expérience repose sur l'utilisation de contacts ferro-magnétiques pour induire un couplage spin-orbit artificiel dans une double boîte quantique. Ce couplage hybride les degrés de liberté de charge et de spin de l'électron. En incluant ce circuit dans une cavité micro-onde, dont le champ électrique peut être couplé à la charge, nous réalisons une interface spin-photon. Un second projet est centré sur l'utilisation de boîtes quantiques comme systèmes modèles. Ce projet consiste à coupler, via une cavité micro-onde, un qubit supraconducteur, qui servira de sonde peu invasive, et une boîte quantique unique. Un tel circuit peut exhiber différent comportement dont l'effet Kondo, qui est un effet à N-corps. Dans ce travail, nous présentons à la fois une étude théorique, et des travaux expérimentaux. Finalement, un travail en collaboration, sur une proposition théorique pour détecter le caractère auto-adjoint des fermions de Majorana en utilisant une cavité micro-onde, est présenté. / This thesis work is centered around two key aspects of quantum technologies: quantum information processing and quantum sensing. It builds up onto the microwave light toolbox, developed in circuit quantum electrodynamics, to investigate the properties of mesosocopic circuits. Those circuits, made out here of carbon nanotubes, can be designed to act as quantum bits of information or as condensed matter model system and this thesis explore both aspects. The realization of a coherent spin-photon interface illustrates the first one. The experiment relies on ferromagnetic contacts to engineer an artificial spin-orbit coupling in a double quantum dot. This coupling hybridizes the spin and the charge degree of freedom of the electron in this circuit. By embedding this circuit into a microwave cavity, whose electrical field can be coupled to the charge, we realize an artificial spin-photon interface. A second project, started during this thesis, focuses on using quantum dot circuits as model systems. This project consists in coupling, via a microwave cavity, a superconducting qubit, that will serve as a delicate probe, and single quantum dot circuit. Such a circuit can display several behaviors including the Kondo effect which is intrinsically a many-body effect. In this work, we present both a theoretical study of some possible outcomes of this experiment, and experimental developments. Finally, a theoretical proposition to detect the self-adjoint character of Majorana fermions using a microwave cavity, is presented.

abstract: Nanofluidic devices in which one single-walled carbon nanotube (SWCNT) spans a barrier between two fluid reservoirs were constructed, enabling direct electrical measurement of the transport of ions and molecules. Ion current through these devices is about 2 orders of magnitude larger than that predicted from the bulk resistivity of the electrolyte. Electroosmosis drives excess current, carried by cations, and is found to be the origin of giant ionic current through SWCNT as shown by building an ionic field-effect transistor with a gate electrode embedded in the fluid barrier. Wetting of inside of the semi-conducting SWCNT by water showed the change of its electronic property, turning the electronic SWCNT field-effect transistor to "on" state. These findings provide a new method to investigate and control the ion and molecule behavior at nanoscale. / Dissertation/Thesis / Ph.D. Physics 2011

Actuellement, les recherches sur la fonctionnalisation des surfaces sont en pleine effervescence. Dans ce manuscrit, nous proposons une approche innovante pour mesurer l’efficacité de cette fonctionnalisation. Cette approche est basée sur l’utilisation d’un microscope à force atomique, opérant dans un mode dit de « modulation de fréquence ». Cet outil couplé aux pointes greffées d’un nanotube de carbone, que nous appellerons « sonde », permet d’obtenir des mesures qu’il serait impossible d’effectuer avec des pointes standards. En métrologie, afin d’assurer une bonne reproductibilité des mesures, nous avons besoin d’avoir des sondes ayant des caractéristiques les plus similaires possibles. Ceci a nécessité la mise en oeuvre d’une méthode pour optimiser la fabrication des sondes, ainsi qu’une définition de critères pour les classer dans différents grades de qualités. L’incertitude de répétabilité et de reproductibilité des mesures effectuées avec des sondes de grade « A » a été quantifiée. Ces mesures ont démontré que ces sondes sont compatibles en termes de robustesse et de sensibilité pour la caractérisation de surfaces fonctionnalisées, dont l’épaisseur est supérieure à la monocouche. Des mesures de cartographie effectuées sur de deux types de surfaces fonctionnalisées ont permis de dissocier la mesure de topographie de la réponse mécanique du nanotube en interaction avec la surface. / At present, the researches on the surface functionalization are in full effervescence. In this manuscript, we propose an innovative approach to measure the efficiency of this functionalization. This approach is based on the use of an atomic force microscope, operating in a mode called "frequency modulation". This tool coupled with the grafted tips with a carbon nanotube, which we will call "probe", allows to obtain measurements which would be impossible to make with standard tips. However, in metrology, in order to ensure good reproducibility of the measurements, we need to have probes with characteristics that are as similar as possible. This required the implementation of a method to optimize the manufacture of the probes, as well as a definition of criteria to classify them in different grades of qualities. The uncertainty of repeatability and reproducibility of the measures made with probes of rank "A" were quantified. These measurements have demonstrated that these probes are compatible in terms of robustness and sensitivity for the characterization of functionalized surfaces, whose thickness is superior to the monolayer. Mapping measurements carried out on two types of functionalized surfaces enable to dissociate the topography measurement from the mechanical response of the nanotube in interaction with the surface.

For the past three decades, newly discovered carbon nanostructures such as fullerenes, graphene and carbon nanotubes (CNTs) have revolutionized the field of nanoscience, introducing many practical and potential applications pertaining to their exceptional structural, mechanical, thermal, and optoelectronic properties. Raman spectroscopy has been an instrumental technique for characterizing these materials due to its non-destructive nature and high sensitivity to the material responses. While Raman spectroscopy is broadly used for identifying specific material types and quality, it has also been increasingly useful as a tool for probing the electronic and excitonic properties, as well as their interplay with the vibrational properties in the aforementioned carbon nanomaterials. In this dissertation, we present our Raman-related research on carbon nanotubes and a new member of the nano-carbon family - carbon nanohoops (cycloparaphenylenes, or CPPs). We discuss our new findings on the resonance Raman spectroscopy (RRS) of various semiconducting CNTs, with the focus on the Raman excitation profiles (REPs) for the G-band. The asymmetric lineshapes observed in the G-band REPs for the second excitonic (E22) transition of these CNTs contradict a long-held approximation, the Franck-Condon principle, for the vibronic properties of the carbon nanotubes. In addition, the G-band REPs from the closely spaced E33 and E44 transitions are investigated, and we demonstrate that these excitonic levels exhibit significant quantum interference effects between each other. We also present the first comprehensive study of Raman spectroscopy of CPPs. Analogously to CNTs, we show that Raman spectroscopy can be used to identify CPPs of different sizes. A plethora of Raman modes are observed in these spectra, including modes that are comparable to those of CNTs, such as the G-band, as well as Raman peaks that are unique for CPPs. Calculated Raman spectra using density functional theory (DFT) are compared with the experimental results for the assignment of different modes. Furthermore, we refine our knowledge of the CPP Raman modes by concentrating on the even-numbered CPPs. By taking advantage of the symmetry arguments in the even [n]CPPs, we are able to utilize group theory and accurately identify the size dependences of different Raman-active modes.

abstract: This thesis describes several experiments based on carbon nanotube nanofludic devices and field-effect transistors. The first experiment detected ion and molecule translocation through one single-walled carbon nanotube (SWCNT) that spans a barrier between two fluid reservoirs. The electrical ionic current is measured. Translocation of small single stranded DNA oligomers is marked by large transient increases in current through the tube and confirmed by a PCR (polymerase chain reaction) analysis. Carbon nanotubes simplify the construction of nanopores, permit new types of electrical measurement, and open new avenues for control of DNA translocation. The second experiment constructed devices in which the interior of a single-walled carbon nanotube field-effect transistor (CNT-FET) acts as a nanofluidic channel that connects two fluid reservoirs, permitting measurement of the electronic properties of the SWCNT as it is wetted by an analyte. Wetting of the inside of the SWCNT by water turns the transistor on, while wetting of the outside has little effect. This finding may provide a new method to investigate water behavior at nanoscale. This also opens a new avenue for building sensors in which the SWCNT functions as an electronic detector. This thesis also presents some experiments that related to nanofabrication, such as construction of FET with tin sulfide (SnS) quantum ribbon. This work demonstrates the application of solution processed IV-VI semiconductor nanostructures in nanoscale devices. / Dissertation/Thesis / Ph.D. Physics 2011

This dissertation presents results of a project bringing Scanning Tunneling Microscope (STM) into a regime of unlimited operational time at cryogenic conditions. Freedom from liquid helium consumption was achieved and technical characteristics of the instrument are reported, including record low noise for a scanning probe instrument coupled to a close-cycle cryostat, which allows for atomically resolved imaging, and record low thermal drift. Subsequent studies showed that the new STM opened new prospects in nanoscience research by enabling Scanning Tunneling Spectroscopic (STS) spatial mapping to reveal details of the electronic structure in real space for molecules and low-dimensional nanomaterials, for which this depth of investigation was previously prohibitively expensive. Quantum-confined electronic states were studied in single-walled carbon nanotubes (SWCNTs) deposited on the Au(111) surface. Localization on the nanometer-scale was discovered to produce a local vibronic manifold resulting from the localization-enhanced electron-vibrational coupling. STS showed the vibrational overtones, identified as D-band Kekulé vibrational modes and K-point transverse out-of plane phonons. This study experimentally connected the properties of well-defined localized electronic states to the properties of associated vibronic states. Electronic structures of alkyl-substituted oligothiophenes with different backbone lengths were studied and correlated with torsional conformations assumed on the Au(111) surface. The molecules adopted distinct planar conformations with alkyl ligands forming cis- or trans- mutual orientations and at higher coverage self-assembled into ordered structures, binding to each other via interdigitated alkyl ligands. STS maps visualized, in real space, particle-in-a-box-like molecular orbitals. Shorter quaterthiophenes have substantially varying orbital energies because of local variations in surface reactivity. Different conformers of longer oligothiophenes with significant geometrical distortions of the oligothiophene backbones surprisingly exhibited similar electronic structures, indicating insensitivity of interaction with the surface to molecular conformation. Electronic states for annealed ligand-free lead sulfide nanocrystals were investigated, as well as hydrogen-passivated silicon nanocrystals, supported on the Au(111) surface. Delocalized quantum-confined states and localized defect-related states were identified, for the first time, via STS spatial mapping. Physical mechanisms, involving surface reconstruction or single-atom defects, were proposed for surface state formation to explain the observed spatial behavior of the electronic density of states. This dissertation includes previously published co-authored material.

Ce mémoire est consacré à l'optimisation de la connexion enzymatique d'enzymes pour l'oxydation du glucose et la réduction de O2 sur matrices de nanotube de carbone (CNT) dans les biopiles à glucose.Premièrement, le transfert électronique indirect de la glucose oxydase (GOx) est optimisé dans une matrice nanostructurée de CNT contenant la 1,4-naphtoquinone comme médiateur rédox. Cette bioanode a ensuite été combinée avec des biocathodes similaires à bases d'enzymes à cuivre (laccase et tyrosinase). La biopile GOx-NQ/Lac a permis d'obtenir des puissances maximales de l'ordre de 1,5 mW.cm-2. Les utilisations de cette pile en décharge courte, longue et sa stabilité dans le temps ont également été étudiées. La seconde partie présente la préparation d'une autre anode basée sur la connexion indirecte d'une glucose déshydrogènase NAD+-dépendante (GDH-NAD+) comme alternative pour l'oxydation du glucose. La GDH-NAD+ a été combinée avec un catalyseur d'oxydation de NADH par différentes méthodes. Tout d'abord, elle a été encapsulée au sein du métallopolymère rédox, puis, la modification supramoléculaire a dans un second temps permis d'immobiliser le catalyseur moléculaire et l'enzyme à la surface des CNTs. Ces deux bioanodes ont permis respectivement l'obtention de courants catalytiques d'oxydation du glucose de 1,04 et 6 mA.cm-2. La seconde bioanode a été combinée avec une biocathode à base de BOD et a permis l'obtention de densités de courants maximales de l'ordre de 140 µW.cm-2 La dernière partie concerne l'élaboration d'une biocathode bienzymatique pour la réduction de O2. Le DET de la HRP sur CNTs a dans un premier temps été optimisé par modification de la surface par différents dérivés pyrène. Ensuite, la combinaison de la GOx et de la HRP sur la même électrode a permis de réduire efficacement O2 en 2 étapes. La biocathode est capable de délivrer une densité de courant maximale de l'ordre de 200 µA.cm-2. Cette dernière, combinée avec la bioanode GDH présentée précédemment a permis d'obtenir une biopile opérationnelle en conditions physiologiques et 10 mM de NAD+, en étant capable de débiter une densité de puissance maximale de l'ordre de 57 µW.cm-2. / This work focuses on the optimization of the electrical wiring of glucose oxidizing and dioxygen reducing enzymes on carbon nanotube (CNT) matrixes for glucose biofuel cells.In the first part, glucose oxidase (GOx) mediated electron transfer (MET) is optimized in nanostructured CNTs matrixes by mechanical compression of a CNTs/GOx composite containing 1,4-naphtoquinone as redox mediator. This bioanode was then combined with MCOs (laccase and tyrosinase) based biocathodes. The GOx-NQ/Lac biofuel cell was able to deliver a maximum power density of 1.5 mW.cm-2. The use of this biofuel cell in short/long time discharge and in storage has also been studied. The second part presents the preparation of another bioanode based on the indirect wiring of a NAD+-dependant glucose dehydrogenase (GDH-NAD+) as an alternative for glucose oxidation. The GDH-NAD+ has been combined with an NADH oxidation catalyst by two different techniques. The first one involves the encapsulation of the protein in the metallopolymer redox film, whereas the second one relies on the supramolecular modification of the CNTs by the molecular catalyst and the enzyme. Both bioanodes showed good catalytic properties toward glucose oxidation in presence of NAD+ with respectively 1.04 mA cm-2 and 6 mA cm-2. The latter has been combined with a BOD based biocathode to form a biofuel cell exhibiting maximum power densities of 140 µW cm-2. The last part of this work focuses on the design of a bienzymatic biocathode for O2 reduction. The DET of horseradish peroxidase (HRP) was first investigated and optimized by modification of the CNTs with pyrenes derivatives. The combination of the HRP with the GOx on the same electrode enables an efficient reduction of O2 in a 2-step process. The biocathode could exhibit maximum currents densities of 200 µA cm-2. This cathode along with the previous GDH bioanode formed a biofuel cell functional in physiological conditions and 10 mM NAD+ showing maximum power densities of 57 µW cm-2.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this Thesis we studied through first principles methods the effects of uniform transversal electric fields on the structural and electronic properties of carbon nanotubes. We study the formation of Si-doped carbon nanotubes through the interaction of Si with single-vacant nanotubes and investigate the action of electric fields on semiconducting and metallic carbon nanotubes, both pure carbon, carboxylated or Si-doped nanotubes. All investigations were done using computational first principles simulations based on the density functional theory using the SIESTA code. Firstly, we show that carbon nanotubes with single vacancies are highly reactive centers, which can be used as adsorbing sites for selected substances to form covalent bonds on surface. This feature is used to investigate the possibility of forming Si-doped carbon nanotube, analyzing possible energetic barriers and observing the steps of the structural rearrangement to the complete stabilization. The effect of the transversal electric field applied on carbon nanotubes was also investigated. The applied field has a remarkable influence on electronic structure of the semiconductor carbon nanotubes, leading to a band gap decreasing which is dependent on the field intensity and nanotube radius, including a possible semiconductormetal transition. It is also observed that the electric field induces electric polarization and a comparison between semiconductor and metal tubes is presented. In the same way, the action of transversal electric fields on semiconductor and metallic carbon nanotubes functionalized with carboxylic group was estimated. We observe that the presence of carboxyl in the nanotube surface modifies the response to the electric field, leading to considerable alterations on the electronic structure of the original system, such as energy bands, inducing an electric polarization and charge transfers between the adsorbed molecules and the carbon nanotube. Therefore, we also study the electric fields action on carboxylated Si-doped carbon nanotubes. The electronic and structural properties of these systems are analyzed and the results discussed. / Na presente Tese estudamos através de métodos de primeiros princípios os efeitos de campos elétricos uniformes transversais sobre as propriedades eletrônicas e estruturais de nanotubos de carbono. Apresentamos o estudo da formação de nanotubos de carbono dopados com Si através da interação com nanotubos apresentando vacâncias simples e investigamos a ação de campos elétricos sobre nanotubos de carbono semicondutores e metálicos, sejam eles puros, funcionalizados por ácido carboxílico ou dopados com Si. Toda investigação foi realizada através de simulações computacionais baseadas na teoria do funcional da densidade, utilizando-se, para tanto, o código computacional SIESTA. Uma revisão teórica dos métodos é apresentada, bem como as justificativas de emprego desta metodologia. Mostramos inicialmente que nanotubos de carbono apresentando vacâncias simples constituem um centro de alta reatividade, que pode ser empregado para adsorver substâncias de interesse e formar ligações covalentes com sua superfície. Utilizamos esta característica para investigar a possível formação de um nanotubo dopado com Si, analisando possíveis barreiras de energia e observando os diversos passos de rearranjo estrutural até a estabilização do sistema. Apresentamos, em seguida, os efeitos de campos elétricos transversais sobre nanotubos de carbono. Mostramos que campos elétricos transversais têm efeitos marcantes sobre a estrutura eletrônica de nanotubos semicondutores, provocando uma diminuição do gap de banda que depende da intensidade do campo aplicado e do raio do nanotubo, podendo ocorrer uma transição semicondutor-metal. Observamos que estes campos provocam uma polarização dos nanotubos, e apresentamos as diferenças observadas nesta resposta por nanotubos semicondutores e metálicos. Estudamos a ação de campos elétricos transversais sobre nanotubos semicondutores e metálicos funcionalizados com carboxila. Observamos que a presença deste grupo na superfície permite uma nova resposta aos campos elétricos, levando a alterações substanciais nas propriedades eletrônicas do sistema, como bandas de energia e densidades de estado, além de modificar a população eletrônica, levando à polarização do sistema. Finalizamos esta Tese com o estudo da ação de campos elétricos sobre nanotubos dopados com Si e com o sistema formado por um nanotubo dopado com Si e funcionalizados com ácido carboxílico. A influência destas modificações estruturais sobre as propriedades eletrônicas são apresentadas e os resultados, discutidos. Apresentamos, finalmente, as conclusões pertinentes a este trabalho, com suas implicações e possíveis conexões com a prática de realização experimental.