L'objectif principal de ce travail est l'étude fondamentale de nanostructures à base de carbone individuelles dans le but d'améliorer la compréhension de leurs propriétés vibrationnelles et optiques intrinsèques ainsi que d'estimer et de quantifier les effets d'environnement. Dans ce but, nous avons synthétisé des nanotubes de carbone mono- et multi-feuillets par décomposition catalytique en phase vapeur sur des substrats dédiés. L'aspect principal du travail est basé sur l'utilisation combinée de plusieurs sondes expérimentales sur la même nanostructure carbonée individuelle. Nous avons effectué une analyse structurale complète par diffraction électronique et microscopie électronique haute résolution et mesuré les spectres Raman de ces nanostructures individuelles. Plusieurs effets environnementaux importants ont été mis en évidence pour la première fois, comme par exemple l'effet d'un couplage mécanique (due à l'interaction de van-der-Waals) entre les parois des nanotubes bi-feuillets conduisant à une modification des modes Raman de basse fréquence et des conditions de résonances optiques. De plus, le comportement des modes de haute fréquence des nanotubes bi-feuillets a été analysé. Suite à ce travail plusieurs critères expérimentaux permettant un diagnostic de la structure des nanotubes multi-feuillets ont été proposés. / The main objective of this work is the fundamental physical study of individual isolated carbon nanostructures in order to address their intrinsic vibrational and optical properties and also to estimate and quantify the environmental effects. For these purposes, we synthesized individual single- and multi-walled carbon nanotubes by chemical vapour deposition method on dedicated substrates. The main aspect of the work involves the combined use of different experimental probes on the same individual nanostructures. We performed a complete structure analysis by electron diffraction and high-resolution electron microscopy and the measurement of the Raman spectra on these individual nanostructures. Several important environmental effects were evidenced for the first time, e.g. the effect of mechanical coupling (van-der-Waals interaction) between the layers of double-walled carbon nanotubes leading to the change in the low-frequency Raman modes and the optical resonance conditions. Moreover the behaviour of high-frequency modes of double-walled tubes was also analysed and described. As a result of this work several experimental criteria for structure diagnostics of multi-walled carbon nanotubes were proposed.

Selon l’ITRS, le transistor à nanotube de carbone est une des alternatives prometteuses au transistor MOS Silicium notamment en termes de taille de composant et d’architectures de circuits innovantes. Cependant, à l’heure actuelle, la maturité des procédés de fabrication de ces technologies ne permet pas de contrôler finement les caractéristiques électriques. C’est pourquoi, nous proposons un modèle compact basé sur les principes physiques qui gouvernent le fonctionnement du transistor à nanotube. Cette modélisation permet de lier les activités technologiques à celles de conception de circuit dans le contexte de prototypage virtuel. Pour peu qu’elle inclut des paramètres reflétant la variation des procédés, il est alors possible d’estimer les performances potentielles des circuits intégrés. Le transistor à nanotube de carbone à modulation de hauteur de barrière (C-CNFET), i.e. « MOS-like », est modélisé analytiquement en supposant le transport balistique des porteurs dans le canal. Le formalisme de Landauer est utilisé pour décrire le courant modulé par le potentiel du canal calculé de façon auto-cohérente avec la charge associée selon le potentiel appliqué sur la grille. Le modèle du transistor à nanotube de carbone double grille, DG-CNFET est basé sur celui du C-CNFET. Ce transistor est de type N ou P selon la polarisation de la grille supplémentaire. Ce transistor est modélisé de manière similaire pour les 3 régions : la partie interne modulée par la grille centrale, et les accès source et drain modulés par la grille arrière. La charge, plus complexe à calculer que celle du C-CNFET, est résolue analytiquement en considérant différentes plages de polarisation et d’énergie. Le modèle du DG-CNFET a été mis en œuvre dans le cadre d’architectures de circuits électroniques innovants : une porte logique à 2 entrées comportant 7 transistors CNFET dont 3 DG-CNFET pouvant, selon la polarisation des 3 entrées de configuration, réaliser 8 fonctions logiques différentes. / According to ITRS, the carbon nanotube transistor is one promising alternative to the silicon MOS transistor particularly in terms of device dimensions and novel circuit architectures. However, today, the fabrication processes maturity of these technologies does not allow controlling accurately their electrical characteristics. That’s why we propose a compact model based on physical principles that govern the nanotube transistor operation. That modelling allows linking the technological activities to the circuit design ones in the virtual prototyping context. As it includes parameters that reflect the processes variation, it is possible to estimate the potential performances of integrated circuits. The barrier-height modulated carbon nanotube transistor (C-CNFET), i.e. MOS-like transistor, is analytically modelled assuming ballistic transport of carriers in the channel. The Landauer’s formalism is used to describe the current modulated by the channel potential which is self-consistently calculated with the associated charge according to the gate potential. The model of the double-gate carbon nanotube transistor, DG-CNFET, is based on the C-CNFET one. That transistor is N or P type depending on the additional gate polarisation. That transistor is modelled in a similar way for the 3 regions: the inner part modulated by the central gate, and the source and drain accesses modulated by the back gate. The charge, more complex to calculate than the C-CNFET one, is analytically solved considering different polarisation and energy ranges. Moreover, the DG-CNFET model has been used into novel electronic circuit architectures: a 2 inputs logic gate, composed of 7 CNFET transistors, 3 of which are DG-CNFET, able to realize 8 different logic functions, according to the polarisation of the 3 configuration inputs.

Doctor of Philosophy / Department of Physics / Brian R. Washburn / Optical frequency combs produced by mode-locked fiber lasers are useful tools for high precision frequency metrology and molecular spectroscopy in a robust and portable format. We have specifically investigated erbium doped fiber mode-locked lasers that use single-walled carbon nanotubes as a saturable absorber. We have, for the first time, developed and phase- stabilized a carbon nanotube fiber laser (CNFL) frequency comb. The carbon nanotube saturable absorber, which was fabricated using an optically driven deposition method, permits a high repetition frequency (>150 MHz) since an optical nonlinearity of fibers is not used for mode-locking. The CNFL comb combined with a parabolic pulse erbium doped fiber amplifier (EDFA) has shown a compact, robust, and cost-effective supercontinuum source. The amplified pulse from the parabolic pulse EDFA was compressed with a hollow-core photonic bandgap fiber, which produced a wave-breaking-free pulse with an all-fiber set-up. The stabilized comb has demonstrated a fractional instability of 1.2 ×10[superscript]-11 at 1 sec averaging time, the reference-limited instability. We have performed optical frequency metrology with the CNFL comb and have measured an optical frequency, P(13) which is a molecular overtone transition of C2H2. The measured frequency has shown a good agreement with the known value within an uncertainty of 10 kHz. In order to extend the application of the CNFL comb such as multi-heterodyne dual comb spectroscopy, we have investigated the noise of the CNFL comb and particularly, the broad carrier envelope offset frequency (f[subscript]0) linewidth of the CNFL comb. The primary noise source is shown to be white amplitude noise on the oscillator pump laser combined with the sensitivity of the mode-locked laser to pump power fluctuations. The control bandwidth of f[subscipt]0 was limited by the response dynamics of the CNFL comb. The significant reduction of comb noise has been observed by implementing a phase-lead compensation to extend control bandwidth of the comb and by reducing the pump relative intensity noise simultaneously. Therefore the f[subscipt]0 linewidth has been narrower from 850 kHz to 220 kHz. The integrated phase noise for the f[subscipt]0 lock is 1.6 radians from 100 Hz to 102 kHz.

Compared to conventional fibers, carbon nanotubes possess several significant properties, which make them as an excellent alternative reinforcement in multi-functional material industry. In this study, the possibility of dispersion of the multi-wall carbon nanotube (MWCNTs) in a thermoset bio-based resin (synthesized based on end-functionalized glycerol-lactic acid oligomers, GLA, at university of Borås) was investigated. Furthermore, the addition of the MWCNTs as reinforcement to improve the mechanical and thermal properties of was investigated. The nanocomposites were prepared in three different concentrations of MWCNTs, 0.3 wt.%, 1.0 wt.%, and 2.0 wt.%, and each sample was prepared using three different dispersion methods such as the high speed mixer(HSM), the ultra-sonication (US), and a combined method of HSM & US. The mechanical and thermal properties were analyzed by flexural test, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The results confirm that the nanotubes can be dispersed in GLA but the cured nanocomposite didn’t exhibit any considerable improvement in their thermal properties. Considering to the mechanical properties, the addition of 0.3 wt. % MWCNTs to the GLA increased the flexural strength a little but increasing the nanotubes to 1.0 wt. % decreases the flexural strength to almost 50%. This is mainly due to increase in the brittleness of the produced nanocomposites. Both the distribution methods dispersed the nanomaterials in the matrix initially but they are not efficient enough to stop the re-agglomeration which leads to undesired curing dynamics and low efficiency. Thus, these dispersion methods need to be optimized for improvement of nanocomposites’ properties.

The thesis comprises the two parts in each chapter: the first part focuses on the development and characterization of polyimide (PI) based composite coatings on a steel substrate. In order to improve the tribological performance of polyimide coatings, the fillers i.e. multi-walled carbon nanotubes (MWCNTs) and Graphene (GP) were added into PI and conducted friction test at elevated temperatures ranging from room temperature (RT) to 200°C. Also, the influence of fillers (MWCNTs and GP) materials into PI coatings surface, mechanical and tribological properties of polyimide composites coatings are measured. The addition of MWCNTs and GP reduces the friction coefficient as well as wear volume at elevated temperatures 50°C, 100°C and sometimes at 150°C. These temperatures play a vital role to form a lubrication layer in the contact interfaces at certain load and operating conditions. In these cases, three weight percentage (3wt%) of MWCNTs and GP into polyimide composites showed low friction and high wear-resistant as compared to other PI composites. Besides, by adding these two fillers into pure PI improved the mechanical properties such as micro-hardness and nanoindentation. The scanning electron microscope (SEM) was used to observe the wear mechanism of the composite coatings worn surfaces. The consequences expose that the fatigue wear mechanisms were predominant in the worn surfaces. Moreover, the thermal study of the polyimide composite coatings was conducted using thermal gravimetric (TG) to analyze the behavior of composite coatings at high temperatures. The results showed that the PI coatings with MWCNTs and GP have high thermal stability at 60% sample residue. In the second part-an epoxy coatings with filler materials e.g. hexagonal boron nitride (h-BN) and expanded graphite (EG) were made and conducted their tribological i.e. friction coefficient and wear performance. Also the perfect mixing ratio 4:1 (80 wt% base epoxy matrix and 20 wt% curing agent) was determined on the basis of stoichiometric ratio to cure the epoxy accurately. Therefore, seven samples with a various weight percentage (wt%) were prepared i.e. pure epoxy, epoxy with 5wt%, 10wt%, 15wt% of h-BN and EG. All the prepared samples ran at two different loading 2 N and 4 N conditions with 5 Hz frequency, 300 rpm and 30 minutes duration. The epoxy with h-BN showed low friction as compared to EG where EG has better wear-resistant behavior than h-BN.

Prussian blue (PB) nanoparticles were synthesized from FeCl3.6H2O, K4[Fe(CN)6].3H2O, and from Fe(NO3)3.9H2O and K4[Fe(CN)6].3H2O, and then characterized by Fourier transform infrared (FT-IR), Ultraviolet-visible spectroscopy, X-ray diffraction (XRD), Energy dispersive spectroscopy (EDS), Scanning electron microscopy (SEM), Raman spectroscopy and thermogravimetric analysis. Graphene oxide and carbon nanotubes were also synthesized and characterized. PB nanoparticles, carbon nanotubes (CNT), graphene oxide (GO) and cetyltrimethylammonium bromide (CTAB) were sequentially deposited onto glassy carbon electrode surface to form chemically modified electrode for the detection of hydrogen peroxide (H2O2) and dopamine. The following electrodes were fabricated, GC-PB, GC-MWCNT, GCGO, GC-CTAB, GC-MWCNT-PB, GC-GO-PB and GC-CTAB-PB. Cyclic and Square wave voltammetric techniques were used to measure the hydrogen peroxide detectability of the electrodes at pH ranges of (3 - 7.4) in 0.1M phosphate buffer solution, in the absence or presence of 25 μL of H2O2. The GC-CNT-PB, GC-GO-PB,GC-CTAB-PB electrodes showed a good response for the detection of hydrogen peroxide in both acidic and neutral media while the GCPB electrode only showed good response in acidic media.

Neste trabalho foram realizadas simulações computacionais para investigar as propriedades eletrônicas de nanossistemas baseados em nanotubos de carbono e grafeno por meio de cálculos de primeiros princípios. Um dos nanossistemas investigados é formado por um nanotubo de carbono acoplado a eletrodos de nanofios de paládio encapsulados. Foi mostrado que estados provenientes dos eletrodos interagem fortemente com os estados do nanotubo de carbono. Cálculos de transporte eletrônico foram realizados para investigar a potencialidade desse nanossistema em aplicações como transistor de efeito de campo. Foi mostrado que a intensidade da corrente elétrica desse nanossistema pode ser variada com o campo elétrico de gate. Outro trabalho desenvolvido no presente trabalho tem como base um nanossistema formado pelo grafeno depositado nos substratos SiO2 amorfo e h-BN. Foi determinada a energia de adsorção e a quantidade de carga transferida para investigar a influênicas desses substratos na adsorção da molécula de H2 pelo grafeno. Foi mostrado que a energia de adsorção da molécula de H2 adsorivda na interface grafeno/SiO2 amorfo é menor em comparação com o grafeno suspenso ou disposto sobre o substrato h-BN. Além disso, a adsorção do H2 nessa região resulta em uma transferência de carga de uma ordem de grandeza maior em comparação com a adsorção no grafeno suspenso, sendo observado um deslocamento do Cone de Dirac em relação ao nível de Fermi. Esse estudo poderá contribuir para a construção de futuros sensores de H2 à base de grafeno. / In this work, ab initio calculations were performed within DFT framework to analyse electronic properties of Carbon nanotubes and grapheme nano systems. In this work, computer simulations were performed to investigate the electronic properties of nanosystems based on carbon nanotubes and graphene within DFT framework. One of these systems studied is a Carbon nanotube semiconductor coupled to encapsulated leads of Pd nanowires. It has been shown that leads states interact strongly with the carbon nanotube states. Electronic transport calculations were performed to unfold new applications of this system, such as the field effect transistor. We noticed that charge current intensity can be tuned by electrical field. We also described the influence of amorphous SiO2 and h-BN, in H2 energy adsorption and charge transfer, where both materials are used as graphene substrates. It was shown that the latter adsorption energy in the graphene/Si02 is smaller than graphene/h-Bn and the graphene suspended itself. In fact this adsorption results in a charge transference one order greater than in the suspended graphene, which can be seen as a vertical shift of the Dirac Cone. This study may improve the construction of future H2 sensors based on graphene.

Thesis advisor: Lawrence T. Scott / Carbon nanotubes are theorized to possess many extraordinary properties. To a certain extent, these properties have been demonstrated using the products of current nanotube growth technologies; however, the specific characteristics of distinct nanotube topographies remain untapped on the industrial scale. Carbon vaporization and “flame” methods produce mixtures of various nanotube chiralities and diameters. Although progress has been made, separation techniques are limited. Currently, organic synthesis and subsequent elongation of a select hydrocarbon template is the only approach that promises significant access to specific nanotube topographies without the need for separation. / Thesis (PhD) — Boston College, 2008. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Lawrence T. Scott / This dissertation describes the work that has been carried out towards accessing a C3v [6,6] nanotube end-cap through rational chemical synthesis. Continued advancement in carbon nanotube research has driven scientists to develop a successful route to usable quantities of nanotubes that are homogeneous in structure. Due to the current inability to separate nanotube mixtures efficiently, researchers in fields ranging from chemistry to computer science have been unable to exploit fully all that these unique molecules have to offer. Our envisioned approach to this obstacle involves elongation of a template endcap using iterative growth chemistry. The final stage of the proposed end-cap synthesis involves the execution of a six fold cyclodehydrogenation reaction. To carry out this desired transformation, a new microwave assisted variant of the anionic cyclodehydrogenation reaction has been developed. Through this chemistry we have been able to access a variety of both known and novel polycyclic aromatic hydrocarbons, often in impressively high yields. We hope that this chemistry will be useful to us in accessing the target nanotube end-caps, and to others in providing a new route to accessing a variety of polycyclic aromatic hydrocarbon cores. / Thesis (PhD) — Boston College, 2008. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Ever rising power densities and smaller transistor dimensions are increasing the challenge of thermal management within integrated-circuit chips and their surrounding packaging. In addition, the need for sustainable energy has placed urgent emphasis on energy conversion. Thermoelectric phenomena, involving the conversion of heat to electrical current, provide a central focus for both needs. Specifically, there is a need to engineer materials or composites with low thermal conductivity and high electrical conductivity for energy conversion and the opposite for heat management. In this presentation, experimental results will be presented of the specific heat and thermal conductivity of cobalt nanowires (CoNW), carbon nanotubes (CNT) and polymer-carbon nanotubes, in various composite arrangements with our high precession Calorimetric technique. Due to the nature of these samples, boundary and defect scattering of phonons in nanomaterials can dominate. This scattering phenomena shows decreasing thermal conductivity in metal nanowires, turns to be good for thermoelectric application. For the CNT, and possibly due to the high volume per atom leading to ballistic phonon propagation, the observed thermal conductivity along the nanotube direction, which leads to manage the heat dissipation problem in integrated circuits (ICs) and microprocessors. The thermal conductivity of a single Single-Wall Carbon Nanotube (SWCNT) was found to be 6600 W/mK, theoretically, twice that of diamond. When such high thermal conductivity materials are dispersed in a low thermal conducting polymer (PMMA), the effective thermal conductivity and thermal stability of the composite can change dramatically. The experimental results show good agreement with theoretical model proposed by Nelsen, Hamilton, Crosse, Geometric, and Xue. The thermal relaxation phenomena such as glass transition temperature (Tg) and dynamics of the molecules in the polymer-nanotubes composites, changes significantly different than the pure polymers during thermal treatment and is one of the focusing point of this presentation. Liquid crystalline materials confined to restrictive nano-channels are of great interest in many potential applications of electro-optics and display technology. This part of the presentation investigates the unexplored phenomenon of the coating and filling of 8CB and 10CB liquid crystals inside ~200nm diameter Multi-Wall Carbon nanopipes. The phase transition characteristics of the confined liquid crystal films were studied using MDSC technique and will be the last part of this presentation.