In this talk, I will discuss three problems related to the novel physics of two-dimensional quantum materials such as graphene, group-VI dichalcogenides family (TMDCs viz. MoS2 , WS2, MoSe2 , etc) and Silicene-Germanene class of materials. The first problem poses a simple question - how do the quantum excitations in a graphene membrane affect adsorption? Using the tools of diagrammatic perturbation theory, I will derive the scattering rates of a neutral atom on a graphene membrane. I will show how this seemingly naive model can serve as a non-relativistic condensed matter analogue of the infamous infrared problem in Quantum Electrodynamics. In the second problem, I will move from the framework of a single atom adsorption to a collective behavior of fluids near graphene and TMDC - interfaces. Following the seminal work of Dzyaloshinskii-Lifshitz-Pitaevskii on van der Waals interactions, I will develop a theory of liquid film growth on 2 dimensional surfaces. Additionally, I will report an exotic phenomenon of critical wetting instability which is a result of the dielectric engineering and discuss experimental and technological implications. Finally, the last problem will see the introduction of spin-orbit coupling effects in the 2D topological insulator family of Silicene-Germanene class of materials. I will present a unified theory for their in-plane magnetic field response leading to "anomalous", i.e electron interaction-dependent spin-flip transition moment. Can this correction to spin-flip transition moment be measured? I will propose magneto-optical experimental techniques that can probe the effects.

Graphene can be used to create circuits that are almost superconducting, potentially speeding electronic components by as much as 1000 times [1]. Such blazing speed might also help produce ever-tinier computing devices with more power than your clunky laptop [2]. Graphite is a polymorph of the element carbon [3]. Graphite is made up of tiny sheets of graphene. Graphene sheets stack to form graphite with an interplanar spacing of 0.335 nm, which means that a stack of 3 million sheets would be only one millimeter thick. [1] This nano scale 2 dimensional sheet is graphene. Novoselov and Geim's discovery is now the stuff of scientific legend, with the two men being awarded the Nobel Prize in 2010 [4]. In 2004, two Russian-born scientists at the University of Manchester stuck Scotch tape to a chunk of graphite, then repeatedly peeled it back until they had the tiniest layer possible [2]. Graphene has exploded on the scene over the past couple of years. "Six years ago, it didn't exist at all, and next year we know that Samsung is planning to release their first mobile-phone screens made of graphene." - Dr Kostya Novoselov [4]. It is a lattice of hexagons, each vertex tipped with a carbon atom. At the molecular level, it looks like chicken wire [4]. There are two common lattice formations of graphene, armchair and zigzag. The most studied edges, zigzag and armchair, have drastically different electronic properties. Zigzag edges can sustain edge surface states and resonances that are not present in the armchair case Rycerz et al., 2007 [5]. This research focused on the armchair graphene nanoribbon formation (acGNR). Graphene has several notable properties that make it worthy of research. The first of which is its remarkable strength. Graphene has a record breaking strength of 200 times greater than steel, with a tensile strength of 130GPa [1]. Graphene has a Young's modulus of 1000, compared to just that of 150 for silicon [1]. To put it into perspective, if you had a sheet of graphene as thick as a piece of cellophane, it would support the weight of a car. [2] If paper were as stiff as graphene, you could hold a 100-yard-long sheet of it at one end without its breaking or bending. [2] Another one of graphene's attractive properties is its electronic band gap, or rather, its lack thereof. Graphene is a Zero Gap Semiconductor. So it has high electron mobility at room temperature. It's a Superconductor. Electron transfer is 100 times faster than Silicon [1]. With zero a band gap, in the massless Dirac Fermion structure, the graphene ribbon is virtually lossless, making it a perfect semiconductor. Even in the massive Dirac Fermion structure, the band gap is 64meV [6]. This research began, as discussed in Chapter 2, with an armchair graphene nanoribbon unit cell of N=8. There were 16 electron approximation locations (ψ) provided per unit cell that spanned varying Fermi energy levels. Due to the atomic scales of the nanoribbon, the carbon atoms are separated by 1.42Å. The unit vector is given as, ~a = dbx, where d = 3αcc and αcc = 1.42°A is the carbon bond length [5]. Because of the close proximity of the carbon atoms, the 16 electron approximations could be combined or summed with their opposing lattice neighbors. Using single line approximation allowed us to reduce the 16 points down to 8. These approximations were then converted into charge densities (ρ). Poisson's equation, discussed in Chapter 3, was expanded into the 3 dimensional space, allowing us to convert ρ into voltage potentials (φ). Even though graphene is 2 dimensional; it can be used nicely in 3 dimensional computations without the presence of a substrate, due to the electric field lines and voltage potential characteristics produced being 3 dimensional. Subsequently it was found that small graphene sheets do not need to rest on substrates but can be freely suspended from a scaffolding; furthermore, bilayer and multilayer sheets can be prepared and characterized.

Ce travail présente une évaluation des performances des transistors à effet de champ à base de graphène (GFET) grâce à des simulations électriques des modèles compact dédiés à des applications à haute fréquence. Les transistors à base de graphène sont parmi les nouvelles technologies et sont des candidats prometteurs pour de futures applications à hautes performances dans le cadre du plan d’action « au-delà du transistor CMOS ». Dans ce contexte, cette thèse présente une évaluation complète des transistors à base de graphène tant au niveau du dispositif que du circuit grâce au développement de modèles compacts précis pour des GFETs, de l’analyse de la fiabilité, en étudiant les mécanismes critiques de dégradation des GFETs, et de la conception des architectures de circuits basés sur des GFETs.Dans cette thèse nous présentons, à l’aide de certaines notions bien particulières de la physique, un modèle compact grand signal des transistors FET à double grille à base de graphène monocouche. Ainsi, en y incluant une description précise des capacités de grille et de l’environnement électromagnétique (EM), ce travail étend également les aptitudes de ce modèle à la simulation RF. Sa précision est évaluée en le comparant à la fois avec un modèle numérique et avec des mesures de différentes technologies GFET. Par extension, un modèle grand signal pour les transistors FET à double grille à base de graphène bicouche est présenté. Ce modèle considère la modélisation de l’ouverture et de la modulation de la bande interdite (bandgap) dues à la polarisation de la grille. La polyvalence et l’applicabilité de ces modèles compacts des GFETs monocouches et bicouches ont été évalués en étudiant les GFETs avec des altérations structurelles.Les aptitudes du modèle compact sont encore étendues en incluant des lois de vieillissement qui décrivent le piégeage de charges et la génération d’états d’interface qui sont responsables de la dégradation induite par les contraintes de polarisation. Enfin, pour évaluer les aptitudes du modèle compact grand signal développé, il a été implémenté au niveau de différents circuits afin de prédire les performances par simulations. Les trois architectures de circuits utilisées étaient un amplificateur triple mode, un circuit amplificateur et une architecture de circuit « balun ». / This work presents an evaluation of the performances of graphene-based Field-Effect Transistors (GFETs) through electrical compact model simulation for high-frequency applications. Graphene-based transistors are one of the novel technologies and promising candidates for future high performance applications in the beyond CMOS roadmap. In that context, this thesis presents a comprehensive evaluation of graphene FETs at both device and circuit level through development of accurate compact models for GFETs, reliability analysis by studying critical degradation mechanisms of GFETs and design of GFET-based circuit architectures.In this thesis, an accurate physics-based large-signal compact model for dual-gate monolayer graphene FET is presented. This work also extends the model capabilities to RF simulation by including an accurate description of the gate capacitances and the electro-magnetic environment. The accuracy of the developed compact model is assessed by comparison with a numerical model and with measurements from different GFET technologies.In continuation, an accurate large-signal model for dual-gate bilayer GFETs is presented. As a key modeling feature, the opening and modulation of an energy bandgap through gate biasing is included to the model. The versatility and applicability of the monolayer and bilayer GFET compact models are assessed by studying GFETs with structural alterations.The compact model capabilities are further extended by including aging laws describing the charge trapping and the interface state generation responsible for bias-stress induced degradation.Lastly, the developed large-signal compact model has been used along with EM simulations at circuit level for further assessment of its capabilities in the prediction of the performances of three circuit architectures: a triple-mode amplifier, an amplifier circuit and a balun circuit architecture.

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.

A theoretical methodology and study of charge transport through GNRs, as well as in metallic and semiconducting CNTs, with randomly distributed functional groups covalently attached to the system surface is presented. By resorting to both first principles calculations, to obtain a suitable parametrization of the electronic structure, and a fully ab initio transport approach calculation to explore conduction regimes through large and disordered systems. The quantum transport modeling is based on the Green function formalism, combining an iterative scheme for the calculation of transmission coefficients with the Landauer formula for the coherent conductance. The results describe how the conductance of the hybrid systems is altered as a function of incident electron energy and molecules coverage density. Comparing two different types of functional groups, transport regimes are explored. Phenyls and hydroxyl groups induce a local orbital rehybridization of the CNTs and GNRs anchor carbon atoms from sp2-type to sp3-type yielding a localized transport regime. On the other hand, carbene groups do not disrupt the original sp2 network of armchair and small diameter zigzag CNTs which allows for good conductance preservation.

Chitosan is widely investigated for biomedical applications due to its excellent properties, such as biocompatibility, biodegradability, bioadhesivity, antibacterial, etc. In the field of neural engineering, it has been extensively studied in forms of film and hydrogel, and has been used as scaffolds for nerve regeneration in the peripheral nervous system and spinal cord. One of the main issues in neural engineering is the incapability of neuron to attach on biomaterials. The present study, from a new aspect, aims to take advantage of the bio-adhesive property of chitosan to develop chitosan-based materials for neural engineering, specifically in the fields of brain repair and neuroprosthetics. Neuronal responses to the developed biomaterials will also be investigated and discussed. In the first part of this study (Chapter II), chitosan was blended with a well-studied hydrogel material (agarose) to form a simply prepared hydrogel system. The stiffness of the agarose gel was maintained despite the inclusion of chitosan. The structure of the blended hydrogels was characterized by light microscopy and scanning electron microscopy. In vitro cell studies revealed the capability of chitosan to promote neuron adhesion. The concentration of chitosan in the hydrogel had great influence on neurite extension. An optimum range of chitosan concentration in agarose hydrogel, to enhance neuron attachment and neurite extension, was identified based on the results. A “steric hindrance” effect of chitosan was proposed, which explains the origin of the morphological differences of neurons in the blended gels as well as the influence of the physical environment on neuron adhesion and neurite outgrowth. This chitosan-agarose (C-A) hydrogel system and its multi-functionality allow for applications of simply prepared agarose-based hydrogels for brain tissue repair. In the second part of this study (Chapter III), chitosan was blended with graphene to form a series of graphene-chitosan (G-C) nanocomposites for potential neural interface applications. Both substrate-supported coatings and free standing films could be prepared by air evaporation of precursor solutions. The electrical conductivity of graphene was maintained after the addition of chitosan, which is non-conductive. The surface characteristic of the films was sensitively dependent on film composition, and in turn, influenced neuron adhesion and neurite extension. Biological studies showed good cytocompatibility of graphene for both fibroblast and neuron. Good cell-substrate interactions between neurons and G-C nanocomposites were found on samples with appropriate compositions. The results suggest this unique nanocomposite system may be a promising substrate material used for the fabrication of implantable neural electrodes. Overall, these studies confirmed the bio-adhesive property of chitosan. More importantly, the developed chitosan-based materials also have great potential in the fields of neural tissue engineering and neuroprosthetics.

Before Moire patterns are discovered in graphene, graphene was assumed to be found in only the rhombohedral form in nature. After transfer of graphene layer over another substrate was achieved by Andre Geim and Konstantin Novoselov, studies on graphene gained momentum. Following this, moire paterns were observed by scanning tunelling microscopy (STM) and high resolution transmision electron microscopy (HR-TEM). However, stability of these structures are still unknown. In this thesis, for the first time in literature, molecular dynamics of double layer graphene based Moire patterns are investigated as a result of the rotation of two graphene layers with LAMMPS (Large-scale Atomic/Molecular Massively Parallel Simulator) which has a GNU general public license. To model the two graphene layers, hexagonal graphene layers are generated by home writen Octave code. Then, periodicity condition for the Moire patterns are derived in chapter 2 according to rotation of graphene layers around their central axis, perpendicular to the layers. Then these layers with different angles or temperature or size are simulated by LAMMPS. There are 4 kind of molecular dynamics simulations studied according to modeled flakes. These are grouped under the name of &rsquo / Experiment #&rsquo / according to the modeling structure. Experiment-1 simulates double layer hexagonal flakes of graphene at a temperature of 0.1K. Experiment-2 simulates periodic moire patterns under periodic boundary conditions and represents the infinitely large graphene layers at 10K. Experiment 3 is dierent version of the experiment 1 but at higher temperature (10K). Finally, experiment 4 is modeled to show the behaviour of the graphene flake on a growth or attached region. The atoms around the flakes are modeled as a rigid body and constructs some stress on the graphene flakes.

Photophysical, electronic, and compositional properties of single-walled carbon nanotubes (SWCNTs) and bulk nanotube samples were investigated together with graphene oxide photoluminescence. First, we studied the effect of external electric fields on SWCNT photoluminescence. Fields of up to 10 7 V/m caused dramatic, reversible decreases in emission intensity. Quenching efficiency was proportional to the projection of the field on the SWCNT axis, and showed inverse correlation with optical band gap. The magnitude of the effect was experimentally related to exciton binding energy, as consistent with a proposed field-induced exciton dissociation model. Further, the electronic composition of various SWCNT samples was studied. A new method was developed to measure the fraction of semiconducting nanotubes in as- grown or processed samples. SWCNT number densities were compared in images from near-IR photoluminescence (semiconducting species) and AFM (all species) to compute the semiconducting fraction. The results provide important information about SWCNT sample compositions that can guide controlled growth methods and help calibrate bulk characterization techniques. The nature of absorption backgrounds in SWCNT samples was also studied. A number of extrinsic perturbations such as extensive ultrasonication, sidewall functionalization, amorphous carbon impurities, and SWCNT aggregation were applied and their background contributions quantified. Spectral congestion backgrounds from overlapping absorption bands were assessed with spectral modeling. Unlike semiconducting nanotubes, metallic SWCNTs gave broad intrinsic absorption backgrounds. The shape of the metallic background component and its absorptivity coefficient were determined. These results can be used to minimize and evaluate SWCNT absorption backgrounds. Length dependence of SWCNT optical properties was investigated. Samples were dispersed by ultrasonication or shear processing, and then length-fractionated by gel electrophoresis or controlled ultrasonication shortening. Fractions from both methods showed no significant absorbance variations with SWCNT length. The photoluminescence intensity increased linearly with length, and the relative quantum yield gradually increased, approaching a limiting value. Finally, a strong pH dependence of graphene oxide photoluminescence was observed. Sharp and structured excitation/emission features resembling the spectra of molecular fluorophores were obtained in basic conditions. Based on the observed pH-dependence and quantum calculations, these spectral features were assigned to quasi-molecular fluorophores formed by the electronic coupling of oxygen-containing addends with nearby graphene carbon atoms.

The terahertz (THz) frequency range. 0.1 - 20 THz, exists between the microwave and infrared ranges and contains abundant information on the dynamics of charge and spin carriers in condensed matter systems. Since its advent two decades ago, THz spectroscopy has been extensively used to study a wide range of solid state materials, including typical semiconductors, conducting polymers, insulators, superconductors, and artificially grown structures such as quantum wells. In these systems, electronic and photonic events tend to occur on the time scale of tens to hundreds of femtoseconds, which results in many important excitations, resonances and dynamical phenomena in the THz frequency range. In this dissertation work, we have developed a typical THz time-domain spectroscopy (TDS) system to investigate the THz dynamics of quantum-confined electrons in two important types of carbon nanomaterial: single-walled carbon nanotubes (SWNTs) and graphene. Polarization dependent THz transmission measurements were conducted on a highly-aligned SWNT film on a sapphire substrate, revealing extremely high anisotropy: virtually no attenuation was observed when the polarization of the THz beam was perpendicular to the nanotube axis, while the THz beam was strongly absorbed when its polarization was parallel to the tube axis. From the measured absorption anisotropy, we calculated the reduced linear dichrosim to be 3, corresponding to a nematic order parameter of 1. These observations are a direct result of the one-dimensional nature of conduction electrons in the nanotubes and at the same time, demonstrate that any misalignment of nanotubes in the film mast have characteristic length scales much smaller than the wavelengths used in these experiments (1.5 mm - 150 μm). Based on this work, an ideal THz linear polarizer built with parallel stacks of such aligned SWNT films was synthesized, exhibiting a degree of polarization of 99.9% throughout the frequency range 0.2 - 2.2 THz and a high extinction ratio of 10 -3 (or 30 dB). The THz complex conductivity of the thin SWNT film was extracted through a proper model directly from the TDS data without Kramers-Kronig analysis. Both real and imaginary parts of the conductivity showed a non-Drude frequency dependence, indicating the presence of plasmon-dipole resonance at higher frequencies. Finally, the optical conductivity of large-area. graphene grown from solid state carbon source was studied in a wide spectral range (7 cm -1 - 9500 cm -1 ) using THz-TDS and Fourier transform infrared spectroscopy. We observed that the Fermi level E f of graphene could be tuned by both electrical gating and thermal annealing. The optical conductivity measured at different carrier concentrations exhibited Drude-like frequency dependence, and different 2 E f onsets in the spectrum were probed as well.

Graphene, a two dimensional single layer of graphite, attracts a lot of attention of researchers around the globe due to its remarkable physical properties and application potential. The origin can thereby be found in the peculiar electronic structure since graphene is a zero gap semi-conductor with a linear energy dispersion in the vicinity of the Fermi level. Consequently, the charge carriers in graphene mimic massless Dirac Fermions which brings principles of quantum electrodynamics and exotic effects like Klein tunneling into a bench-top experiment. Modifying the electronic and/or crystal structure structure by functionalization might therefore as well lead to new tantalizing physical properties, novel compound materials based on graphene like graphane (fully hydrogenated graphene) or flourographene (fluorinated graphene), and ultimately new applications. In this work, the influences on the electronic structure of graphene are investigated with photoemission spectroscopies after covalent functionalization by atomic hydrogen and ionic functionalization with potassium. Regarding hydrogenation, the formation of tunable bandgap is observed along with a full recovery of the electronic properties of graphene upon removing the hydrogen by thermal annealing. Using high resolution x-ray photoemission and molecular dynamics simulations, the formation of a C4H structure is predicted for substrate supported graphene at a saturation H-coverage of 25%, due to a preferential para- arrangement of hydrogen atoms. In fully electron doped, hydrogenated graphene the formation of dispersionless hydrogen impurity state is observed with angle-resolved photoemission spectroscopy. This flat state is extended over the whole Brillouin zone and according to calculations not localized. Potassium-doped graphene shows a similar doping level as its 3D parent component, the graphite intercalation compound KC8. Investigating the electron-phonon coupling in doped graphene, by direct derivation of the Eliashberg-function, shows an asymmetric coupling strength along the high-symmetry directions in the Brillouin Zone of graphene. In the K-M direction additional low energetic contributions could be identified which may originate from out-of-plane phonon modes. Regarding the electron-phonon-coupling strength of the high energy in-plane phonon modes a reasonable agreement with theoretical predictions is found.