This thesis presented the study of carbon-based materials for ultra-sensitive molecular sensing. Reduced Graphene Oxide (rGO), a 2-dimensional one-atomic layer thick carbon material, had the advantage of low-cost, aqueous and industrial-scalable production route. Using rGO as the transducer platform could potentially lower the cost of sensors down to a few dollars per chip. However, there were still limitations in rGO that prevented its widespread usage as a biosensor transducer or in electronics: its low electrical conductivity and large electrical deviations. This thesis was structured to understand and solve these problems for transducer application. The thesis could be broken down into 3 parts: The first part of the thesis presented the critical review of the background and limitations of graphene research, followed by the background and importance of biosensor developments for the detection of sweat sodium ions and circulatory Interleukin-6 proteins. The second part of the thesis tested the hypothesis that the rGO limitations could be eliminated to create a highly sensitive biosensor transducer via (A) improving rGO synthesis (B) pristine Carbon Nanotubes-rGO hybrid film and (C) growth of rGO. The mechanism of ultra-large graphene oxide synthesis and graphene oxide growth was also elucidated in this section. The third part of the thesis then presented the fabrication and test of the practical and homogenous carbon-based biosensor using the transducer synthesized earlier. The thesis showed that through proving the hypothesis correct, it enabled the synthesis of an all organic sodium ion sensor with integrated pump and an ultra-sensitive interleukin-6 bio-sensor. Both of these novel sensors were able to detect the respective molecules in their physiological ranges.

Le dopage non covalent de nanostructures carbonées par transfert de charge depuis/vers des molécules donneuses ou acceptrices (EDA) ou bien par des molécules d’acide sulfurique H2SO4, est considéré comme potentiellement intéressant pour de nombreuses applications. Parmi celles-ci on peut citer: capteur chimique, transistor à effet de champ, et d’autre l'électronique. Cependant, d'un point de vue théorique, on en sait peu au sujet de ces processus de transfert de charge par électrons ou par trous.Dans un premier temps, nous nous sommes intéressés à l’interaction entre des molécules d’acide sulfurique et des nanostructures modèles, car elles sont capables de doper des nanotubes, de s’intercaler dans le graphite et même d’aligner les tubes dans une phase nématique, ce qui pourrait mener à la création de matériaux composites à forte valeur ajoutée.Bien que certaines études théoriques DFT ont été menées récemment, leurs résultats restent source de confusion. Par exemple, même s’il est rapporté un transfert de charge entre une molécule de H2SO4 et un plan de graphène, tous nos efforts pour reproduire ces calculs ont été infructueux. Nous proposons dans ce travail de thèse, un mécanisme de réaction qui expliquent la "protonation" des parois du tube, tel que proposé dans la littérature. Enfin nous proposons un scénario possible pour une meilleure compréhension de la structuration à grande échelle des molécules d'acide autour de points d'ancrage, telles que des défauts, de la structure carbonée / Non-covalent doping of carbon nanostructures by charge transfer from/to donor/acceptor molecules (EDA) or by H2SO4 molecules, be it with holes or electrons, is usually thought as potentially interesting for many applications of carbon based nano-devices. However, from a theoretical point of view, little is known about such “charge transfer” processes.Employing first-principles method based on Density Functional Theory (DFT), we have studied in details, and proposed a model to rationalize, the interaction between a prototypical donor molecule the tetrathiafulvalene (TTF), a standard acceptor organic molecule, tetracyanoethylene (TCNE) and carbon nanostructures: graphene layer and SWNTs with various chiral indices. Main results concern structural and thermodynamic aspects including dispersion forces effects, and evidently electronic structure modifications of the nanostructures. Various adsorption modes and concentration effects have been investigated. At very low coverage values, we have reported a charge transfer between graphene and TCNE or TTF. Moreover, we have shown that the charge transfer can be enhanced by increasing the concentration of those two EDA molecules, as it has been demonstrated experimentally. Those results are beneficial for comprehending the nonchemical doping mechanism in graphene structure by means of charge transfers. Considering the interaction between these prototypical molecules and carbon nanotubes, we have found that charge transfers tend to decrease while the curvature of nanotube is increasing. Besides, a strong influence of the metallic/semi-conductor character of the SWNTs can be observed and be explained by the change of polarisability of the curved carboneous substrates. Additionally, we have studied the adsorption properties of sulfuric acid molecules, in its non-hydrated form, on carboneous nanostructures. Against the common believe, no charge transfer is observed in the H2SO4@graphene or H2SO4@CNTs cases, even at very high concentrations. Instead, in order to elucidate the origin of p-doping observed experimentally, we have proposed that molecule is responsible of the reversible doping. Besides we have shown that a proton transfer could cause the experimental phenomenon of crystallization of H2SO4 molecules on SWNT’s surface. Finally in such process, defects like vacancy are of first importance, since they could provide anchorage points for hydrogen atoms. The results of the present work will certainly help to understand the charge transfer and doping mechanism of carbon nanostructures by means of non-covalent functionalization, which is a promising method for their future applications

Over the last decade, two dimensional (2D) materials have attracted considerable attention from both the scientific and engineering community due to their unique properties. One important advance of 2D materials is that they can be exfoliated into nanosheets suspended in a liquid phase and that this allows the formulation of 2D nanomaterials inks. Such inks can be deposited as functional components through low-cost inkjet printing techniques. Many 2D materials based inks have been produced over the years. This thesis investigates the use of inkjet printing to deposit 2D materials such as graphene oxide (GO) and black phosphorus (BP).GO, a derivative of graphene, has been widely used to produce graphene-based conductors via inkjet printing owing to its good stability in readily available solvents such as water. In this work, highly conductive reduced graphene oxide (rGO) films with bulk conductivity in excess of 2 × 10^4 Sm-1 have been prepared by inkjet printing a GO aqueous ink, with mean flake size 35.9 micro metre, through a 60 micro metre inkjet printing nozzle followed by a reduction step. Experimental results showed that individual GO flakes up to 200 micro metre diameter can be successfully printed with no instances of nozzle blocking or poor printing performance. The mechanism by which this occurs is believed to be GO sheet folding during drop formation followed by elastic unfolding during drop impact and spreading. In addition, the influence of GO flake size on rGO film conductivity has been investigated. It was found that the rGO film conductivity increased about 60% when the mean flake size of the GO flakes in the ink increases from 0.68 micro metre to 35.9 micro metre. The drying behaviour of printed GO droplets has been studied on eight GO aqueous inks in which the mean flake size of GO was varied over a range from 0.68 to 35.9 micro metre. It was found that the coffee ring effect (inhomogeneous drying of a droplet to leave a ring like deposit) of dried droplets of the GO ink weakened and disappeared when the flake size increasing. It was found that, with a printed deposit around 340 micro metre in diameter, the coffee ring effect (CRE) was suppressed with the mean flake size > 10.3 micro metre. The critical flake size for CRE suppression reduced to 5.97 and 3.68 micro metre when the substrate temperature was 40 and 50 °C, respectively. It was further found that the CRE weakened with decreasing printed drop size, with the critical flake size reducing to 1.58 micro metre with a printed drop diameter of 30 micro metre.The interaction between BP nanometre thickness flakes and humid atmospheres was investigated using an inkjet printed BP sensor. The BP sensor showed was very sensitive to changes in humidity with a response time of a few seconds and the effect is reproducible in minutes. However, long term exposure to humid air with a relative humidity (RH) > 11% leads to a significant chemical change in the BP films, with Fourier transform infra-red spectroscopy (FTIR) indicating partial hydrolysis of the BP to form phosphate and phosphonate ions. Low temperature heat treatment of BP films under dry conditions after exposure to elevated RH leads to a partial recovery of the impedance response and reversion to a chemical state similar to that before exposure to a humid environment. The recovery of BP properties is most complete after exposure to lower humidity environments (RH < 11%), although exact replication of the original impedance response and FTIR spectrum was not possible.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Grafeno à um cristal bidimensional cujo espectro eletrÃnico a baixas energias (E <1 eV) apresenta dispersÃo linear e ausÃncia de gap que, juntamente com a natureza quiral dos portadores de carga, sÃo responsÃveis por uma variedade de propriedades incomuns. Como resultado da sua natureza singular, um grande esforÃo tem sido feito para entender todas as suas propriedades fundamentais e tentar gerar uma nova tecnologia baseada nesse material. Nesta tese, nÃs realizamos um estudo teÃrico de dois tipos de sistemas: nanofitas de grafeno e tricamadas grafeno (TCG). No que diz respeito ao primeiro sistema, um modelo de ligaÃÃo forte (tight-binding) à utilizado para estudar as bandas de energia do grafeno e fitas de grafeno sujeitas a uma tensÃo de cisalhamento. A fita à constituÃda por linhas de Ãtomos de carbono cujas bordas estÃo orientadas nas direÃÃes conhecidas como âarmchairâ ou âzigzagâ. Uma tensÃo de cisalhamento simples à aplicada na direÃÃo x de forma que as distÃncias interatÃmicas na direÃÃo y sÃo mantidas inalteradas. Esta modificaÃÃo na rede cristalina origina bandas de energia que diferem em vÃrios aspectos do sistema original sem qualquer deformaÃÃo. As mudanÃas no espectro dependem do deslocamento entre linhas adjacentes da fita, bem como do parÃmetro de âhoppingâ modificado. Mostra-se tambÃm que este cisalhamento simples modifica as propriedades eletrÃnicas de ambos os sistemas, fitas de grafeno e grafeno, abrindo e fechando gaps de energia para diferentes deslocamentos do sistema. A densidade de estados modificada tambÃm à mostrada. Por fim, o modelo contÃnuo à utilizado a fim de investigar o espectro electrÃnico de trÃs camadas de grafeno acopladas (tricamada de grafeno), na presenÃa de um campo magnÃtico externo. Nesse contexto, obtemos expressÃes analÃticas para os nveis de Landau para ambos os tipos de empilhamento: Bernal (ABA) e romboÃdrico (ABC), verificando-se uma forte dependÃncia dos nÃveis de energia com o tipo de empilhamento. Embora o espectro de Landau para tricamadas ABA seja uma sobreposiÃÃo dos espectros de uma monocamada e de uma bicamada, tricamadas com empilhamento ABC apresentam uma dispersÃo do tipo B3/2 com o campo magnÃtico. Foi mostrado que uma assimetria entre as camadas, que pode ser introduzida por um potencial externo, pode influenciar fortemente as propriedades do sistema. AlÃm disso, as energias de ressonÃncia cÃclotron, assim como forÃas de oscilador correspondentes, e o espectro de absorÃÃo para tricamadas de grafeno sÃo calculadas para ambos os tipos de empilhamento. Verificou-se que um potencial de porta aplicado atravÃs das camadas leva a (1) uma reduÃÃo das energias de transiÃÃo, (2) um levantamento da degenerescÃncia do nÃvel de Landau n=0, e (3) a quebra de simetria entre elÃtrons e buracos. / Graphene is a truly two-dimensional crystal with a gapless linear electronic spectrum at low energies (E<1 eV) which, along with the chiral nature of its charge carriers, is responsible for a variety of unusual properties. As a result of its uniqueness, a great effort has been made in order to understand all its fundamental properties and try to generate a new technology of them. In this thesis we theoretically study two types of graphene-related systems: graphene nanoribbons and trilayer graphene (TLG). Concerning the former, a tight-binding model is used to study the energy band of graphene and graphene ribbon under simple shear strain. The ribbon consists of lines of carbon atoms in an armchair or zigzag orientation where a simple shear strain is applied in the $x$-direction keeping the atomic distances in the $y$-direction unchanged. Such modification in the lattice gives an energy band that differs in several aspects from the one without any shear and with pure shear. The changes in the spectrum depend on the line displacement of the ribbon, and also on the modified hopping parameter. It is also shown that this simple shear strain tunes the electronic properties of both graphene and graphene ribbon, opening and closing energy gaps for different displacements of the system. The modified density of states is also shown. On the latter subject, the continuum model is used in order to investigate the electronic spectrum of three coupled graphene layers (graphene trilayers) in the presence of an external magnetic field. We obtain analytical expressions for the Landau level (LL) spectrum for both the ABA and ABC types of stacking, which exhibit very different dependence on the magnetic field. While the LL spectrum of ABA TLG is found to be a superposition of a monolayer-like and bilayer-like spectra, the ABC TLG present a nearly B^{3/2} field dependence. We show that layer asymmetry and an external gate voltage can strongly influence the properties of the system. In addition, the cyclotron resonance energies, the corresponding oscillator strengths, and the cyclotron absorption spectrum for trilayer graphene are calculated for both ABA and ABC stacking. A gate potential across the stacked layers leads to (1) a reduction of the transition energies, (2) a lifting of the degeneracy of the zero Landau level, and (3) the removal of the electron-hole symmetry.

Cette thèse démontre le potentiel d'utilisation du graphène pour la fabrication de transistors à effet de champ à couche mince. Celui-ci est préparé par exfoliation en phase liquide et co-déposé avec un polymère semiconducteur du type n. Cette stratégie montre que le graphène améliore le comportement ambipolaire du polymère et plus particulièrement le transport des trous ce qui renforce l'application des matériaux composites au graphène dans les circuits logiques.Par la même approche de mélange, de nouveaux nanorubans de graphène dispersés en solution, ont été utilisés pour améliorer la performance des dispositifs basés sur un polymère amorphe de type p. Ces nanorubans forment une voie de percolation pour les charges améliorant ainsi la performance des dispositifs dans l'obscurité ainsi que sous illumination. Finalement, les dispositifs photosensibles multifonctionnels ont été examinés par l'introduction de molécules photochromiques avec différents substituants au sein des films semi-conducteurs à base de polymère ou de molécules de petite taille qui ont été trouvés influer la photocommutation. / This thesis demonstrates that graphene produced by liquid-phase exfoliation can be co-deposited with a polymerie semiconductor for the fabrication of thin film field-effect transistors. The introduction of graphene to the n-type polymeric matrix enhances not only the electrical characteristics of the devices, but also the ambipolar behavior and the hole transport in particular. This provides a prospective pathway for the application of graphene composites for logic circuits.The same approach of blending was adopted to enhance the electrical characteristics of an amorphous p-type polymer semiconductor by addition of an unprecedented solution processable ultra-narrow graphene nanoribbon. GNRs form percolation pathway for the charges resulting in enhanced deviee performance in daras weil as under illumination therefore paving the way for applications in (opto)electronics.Finally, multifunctional photoresponsive devices were examined by introducing photochromic molecules exposing different substituents into small molecule or polymeric semiconductor films that were found to affect the photoswitching behavior.

After the pioneering investigations into graphene-based electronics at Georgia Tech, great strides have been made developing epitaxial graphene on silicon carbide (EG) as a new electronic material. EG has not only demonstrated its potential for large scale applications, it also has become an important material for fundamental two-dimensional electron gas physics. Graphene is generally considered to be a strong candidate to succeed silicon as an electronic material. However, to date, it actually has not yet demonstrated capabilities that exceed standard semiconducting materials. One disadvantage of conventionally fabricated graphene devices is that nanoscopically patterned graphene tends to have disordered edges that severely reduce mobilities thereby obviating its advantage over other materials. The other disadvantage is that pristine graphene does not contain a band gap, which is critical for standard field effect transistor to operate. This thesis will show that graphene grown on structured silicon carbide surfaces overcomes the edge roughness and promises to provide an inroad into nanoscale patterning of graphene. High-quality ribbons and rings can be made using this technique.

Structural properties of pristine and defected graphene nanoribbons have been investigated by stretching them under 5 percent and 10 percent uniaxial strain until fragmentation. The stretching process has been carried out by performing molecular dynamics simulations (MDS) at 1 K and 300 K to determine the temperature effect on the structure of the graphene nanoribbons. Results of the simulations indicated that temperature, edge shape of graphene nanoribbons and stretching speed have a considerable effect on structural properties, however they have a slight effect on the strain value. The maximum strain at which fracture occurs is found to be 46.41 percent whereas minimum strain value is calculated as 21.00 percent. On the other hand, the defect formation energy is strongly affected from temperature and edge shape of graphene nanoribbons. Stone-Wales formation energy is calculated as -1.60 eV at 1 K whereas -30.13 eV at 300 K for armchair graphene nanoribbon.

It is generally believed that the Si technology is going to hit a road block soon. Amongst all the potential candidates, graphene shows the most promise as replacement material for the aging Si technology. This has caused a tremendous stir in the scientific community. This excitement stems from the fact that graphene exhibits unique electronic properties. Physically, it is a two-dimensional network of sp₂bonded carbon atoms. The unique symmetry of two equivalent sublattices gives rise to a linear energy dispersion for the charge carriers. As a consequence, the charge carriers behave like massless Dirac particles with a constant speed of c/300, where c is the speed of light. The sublattice symmetry gives rise to unique half-integer quantum hall effect, Klein's paradox, and weak antilocalization. In this research work, I was able to successfully study the growth and electronic structure of EG on SiC(0001), in ultra-high vacuum and low-vacuum furnace environment. I used STM to study the growth at an atomic scale and macroscopic scale. With STM imaging, I studied the distinct properties of commonly observed interface region (layer 0), first graphene layer, and the second graphene layer. I was able to clearly resolve graphene lattice in both layer 1 and 2. High resolution imaging of the defects showed a unique scattering pattern. Raman spectroscopy measurements were done to resolve the layer dependent signatures of EG. The characteristic Raman 2D peak was found to be suppressed in layer 1, and a single Lorentzian was seen in layer 2. Ni metal islands were grown on EG by e-beam deposition. STM/ STS measurements were done to study the changes in doping and the electronic structure of EG with distance from the metal islands.

The need for post-CMOS nanoelectronics has led to the investigation of innovative device structures and materials. Graphene, a zero bandgap semiconductor with ballistic transport properties, has great potential to extend diversification and miniaturization beyond the limits of CMOS. The goal of this work is to study the growth of graphene on SiC using the novel method of selective graphitization. The major contributions of this research are as follows - First, epitaxial graphene is successfully grown on selected regions of SiC not capped by AlN deposited by molecular beam epitaxy. This contribution enables the formation of electronic-grade graphene in desired patterns without having to etch the graphene or expose it to any detrimental contact with external chemicals. Etching of AlN opens up windows to the SiC in desirable patterns for subsequent graphitization without leaving etch-residues (determined by XPS). Second, the impact of process parameters on the growth of graphene is investigated. Temperature, time, and argon pressure are the primary growth-conditions altered. A temperature of 1400oC in 1 mbar argon for 20 min produced the most optimal graphene growth without significant damage to the AlN capping-layer. Third, first-ever electronic transport measurements are achieved on the selective epitaxial graphene. Hall mobility of about 1550 cm2/Vs has been obtained to date. Finally, the critical limitations of the selective epitaxial graphene growth are enumerated. The advent of enhanced processing techniques that will overcome these limitations will create a multitude of opportunities for applications for graphene grown in this manner. It is envisaged to be a viable approach to fabrication of radio-frequency field-effect transistors.

Following the first report on electronic transport measurements of graphene, an atom-thick carbon material, many scientists have devoted effort to understand its fundamental properties. In this work, the mechanical properties of graphene-based materials, including monolayer graphene oxide and chemical vapor deposition (CVD) grown graphene, were determined using membrane structures. Furthermore, a membrane structure was used to demonstrate thermoacoustic sound generation from monolayer graphene. In order to realize the mechanical characterization, reproducible methods to fabricate graphene membranes were developed using dry and wet transfer techniques. A novel dry transfer technique produced graphene-sealed microchambers without trapping liquid inside. An improved wet transfer technique enabled the transfer of graphene onto perforated substrates. Monolayer graphene oxide was mechanically tested using scanning atomic force microscopy (AFM) combined with finite element analysis of the data. The mechanical deformation was measured by scanning AFM tips over the suspended graphene oxide membranes. The Young’s modulus of the membranes was obtained by analyzing the deformation using finite element analysis together with a mapping technique. In addition, membranes with 2 and 3 layers of graphene oxide were identified using transmission electron microscopy and mechanically characterized. Moreover, these same methods were used for measuring mechanical properties of ultra-thin amorphous carbon membranes. Bulge tests, which apply uniform pressure on the suspended membrane, revealed the mechanical behavior of polycrystalline graphene grown on copper foils by chemical vapor deposition. In particular, the effect of grain boundaries on the elastic properties of polycrystalline graphene was studied by correlating its Young’s modulus with the density of grain boundaries within the membranes. It was observed that a large number of grain boundaries softened the graphene membranes. Graphene, along with monolayer hexagonal boron nitride, is the ultimate limit of thin materials. Thus, it is an ideal candidate as a thermoacoustic sound source because of its low heat capacity per unit area. The work presented here provides the first demonstration of thermoacoustic sound generation from large-area monolayer graphene. A fundamental understanding of the influence of the underlying substrates was achieved by comparing the acoustic performance of graphene membranes on various patterned substrates with different porosities. / text