Graphene is a novel two dimensional material that is revolutionizing many areas of science and it is no surprise that a significant amount of effort is dedicated to its investigation. One of the major areas of graphene research is the development of procedures for large scale production. Among many recently developed methodologies, graphene oxide reduction stands out as a straightforward and scalable procedure for producing final material with properties similar to those of graphene. Laser reduction of graphite oxide is one of the novel approaches for producing multilayer graphene, and this work describes a viable approach in detail. It is determined that a material which is comprised of a combination of laser reduced graphite oxide-coupled to an unreduced graphite oxide layers beneath it, produces a broadband photosensitive material. The efficiency of light conversion into electrical current is greatly dependent upon the oxygen content of the underlying graphite oxide. Developing novel ways for reducing graphite oxide is an ongoing effort. This work also presents a new method for achieving complete reduction of graphite oxide for producing predominantly sp2 hybridized material. This approach is based on the irradiation of graphite oxide with a high flux 3 keV Ar ion beam in vacuum. It is determined that the angle of irradiation greatly influences the final surface morphology of reduced graphite oxide. Also, multilayer epitaxial graphene growth on silicon carbide in ultra-high vacuum was investigated with quadrupole mass spectrometry (QMS). Subliming molecular and atomic species were monitored as a function of temperature and heating time. The grown films were characterized with X-ray photoelectron spectroscopy coupled with Ar ion depth profiling.

Carbon nanotubes are carbon based structures with outstanding electronical and mechanical properties. They are used in a wide range of applications, usually embedded in polymer in the form of composites, in order to affect the electronic behavior of the matrix material. However, as the nanotubes properties are directly dependent on their intrinsic structure, it is necessary to select specific nanotubes depending on the application, which can be a complicated and inefficient process. This makes it attractive to be able to reduce the amount of material used in the composites. In this thesis, focus is placed on the electrical properties of the composites. A simple patterning method is presented which allows the use of extremely low amounts of nanotubes in order to increase the electrical conductivity of diverse polymers such as polystyrene (PS) or poly(3-hexylthiophene) (P3HT). This method is called nanoimprint lithography and uses a flexible mold in order to pattern composite films, leading to the creation of conducting nanotube networks, resulting in vertically conducting samples (from the bottom of the film to the top of the imprinted patterns). In parallel, X-ray diffraction measurements have been conducted on thin P3HT polymer films. These were prepared on either silicon substrate or on graphene, and the influence of the processing conditions as well as of the substrate on the crystallinity of the polymer have been investigated. The knowledge of the crystalline structure of P3HT is of great importance as it influences its electronic properties. Establishing a link between the processing conditions and the resulting crystallinity is therefore vital in order to be able to make opto-electronic devices such as transistor or photovoltaic cells.

Moore's law has defined the semiconductor industry for the past 50 years. Devices continue to become smaller and increasingly integrated into the world around us. Beginning with personal computers, devices have become integrated into watches, phones, cars, clothing and tablets among other things. These devices have expanded in their functionality as well as their ability to communicate with each other through the internet. Further, devices have increasingly been required to have diverse of functionality. This combination of smaller devices coupled with diversification of device functionality has become known as more than Moore. In this thesis, more than Moore applications of graphene are explored in-depth. Graphene was discovered experimentally in 2004 and since then has fueled tremendous research into its various potential applications. Graphene is a desirable candidate for many applications because of its impressive electronic and mechanical properties. It is stronger than steel, the thinnest known material, and has high electrical conductivity and mobility. In this thesis, the potentials of graphene are examined for pressure sensors, humidity sensors and transistors. Through the course of this work, high sensitivity graphene pressure sensors are developed. These sensors are orders of magnitude more sensitive than competing technologies such as silicon nanowires and carbon nanotubes. Further, these devices are small and can be scaled aggressively. Research into these pressure sensors is then expanded to an exploration of graphene's gas sensing properties -- culminating in a comprehensive investigation of graphene-based humidity sensors. These sensors have rapid response and recovery times over a wide humidity range. Further, these devices can be integrated into CMOS processes back end of the line. In addition to CMOS Integration of these devices, a wafer scale fabrication process flow is established. Both humidity sensors and graphene-based transistors are successfully fabricated on wafer scale in a CMOS compatible process. This is an important step toward both industrialization of graphene as well as heterogeneous integration of graphene devices with diverse functionality. Furthermore, fabrication of graphene transistors on wafer scale provides a framework for the development of statistical analysis software tailored to graphene devices. In summary, graphene-based pressure sensors, humidity sensors, and transistors are developed for potential more than Moore applications. Further, a wafer scale fabrication process flow is established which can incorporate graphene devices into CMOS compatible process flows back end of the line. / <p>QC 20160610</p>

We have pioneered a novel approach to the synthesis of high-quality and highly uniform few-layer graphene on silicon wafers, based on solid source growth from epitaxial 3C-SiC films [1,2]. The achievement of transfer-free bilayer graphene directly on silicon wafers, with high adhesion, at temperatures compatible with conventional semiconductor processing, and showing record- low sheet resistances, makes this approach an ideal route for metal replacement method for nanodevices with ultimate scalability fabricated at the wafer –level.

Phonons are primary heat carriers in carbon nanotubes (CNTs) and graphene; a fundamental understanding of phonon transport in these nano-structures is required for the energy efficient design of their devices such as integrated circuit, flexible displays, and transparent electrodes. In this work, atomistic simulations have been performed to investigate thermal transport at interfaces of CNT and graphene that are typically encountered in their applications, e.g., CNT-CNT junctions on silicon oxide substrate, interfaces between shells of double-wall CNTs (DWNTs), and graphene-metal interfaces. Firstly, heat dissipation at CNT junctions supported on the silicon dioxide substrate is investigated using molecular dynamics (MD) simulations and methods for phonon spectrum analysis. The results show the inefficient heat removal from CNTs not making direct contact with the oxide substrate is responsible for the breakdown of CNT network. At interfaces between shells of DWNTs, the radial vibration modes are identified as phonons that are strongly coupled and can efficiently exchange energy between shells of DWNTs. Secondly, the thermal conductivity of suspended single layer graphene (SLG) and SLG supported on Cu is determined using equilibrium MD simulations following Green-Kubo method and relaxation time approximation approach at room temperature. It is demonstrated that the interaction with Cu substrate can significantly reduce the thermal conductivity of SLG, and that the reduction of thermal conductivity from three acoustic phonons is the major reason. Lastly, using atomistic Green’s function method and density function theory calculations, the thermal boundary conductance at interfaces across graphene layers sandwiched by different metals including Cu, Au, and Ti is predicted. The work shows how the bonding strength changes the graphene/metal and graphene/graphene phonon coupling, and demonstrated the transition of thermal transport mechanism from metal/graphene dominated resistance to graphene/graphene dominated resistance as the metal/graphene bonding strength increases in metal/MLG/metal structure.

Carbon nano-onions (CNOs) discovered by Ugarte in 1992 are multi-layered fullerenes that are spherical analogs of multi-walled carbon nanotubes with diameters varying from 6 nm to 30 nm. Among the various methods of synthesis, CNOs prepared by graphitization of nanodiamonds (N-CNOs) and underwater electric arc of graphite rods (A-CNOs) are the subject of our research. N-CNOs are considered as more reactive than A-CNOs due to their smaller size, high curvature and surface defects. This dissertation focuses on structural analysis and surface functionalization of N- CNOs with diameters ranging from 6—10 nm. Synthetic approaches such as oleum- assisted oxidation, Freidel-Crafts acylation and Billups reductive alkylation were used to functionalize N-CNOs to improve their dispersion properties in aqueous and organic solvents. Functionalized N-CNOs were characterized using various techniques such as TGA, TG-MS, Raman spectroscopy and pH-titrimetry. We designed an experimental method to isolate polycyclic aromatic adsorbates formed on the surface of oleum oxidized N-CNOs (ON-CNOs) and characterized them. A-CNOs, on the other hand are bigger than N-CNOs with diameters ranging from 20—40 nm. In this dissertation, we discuss the preparation of graphene structures by unzipping of A-CNOs using KMnO4 as oxidizing agent. These graphene structures were characterized using powder X-ray diffraction, TGA, BET nitrogen adsorption/desorption studies and compressed powder conductivity. This dissertation also focuses on lithiation/delithiation studies of N-CNOs, A- CNOs and A-CNO-derived graphene structures to use them as negative electrode materials in lithium-ion batteries. The cycling performances of these materials at a charge/discharge rate of C/10 were discussed. The cycling performance of N-CNOs was tested at faster charge/discharge rate of C.

The thermomechanical properties of monolayer graphene and the interfacial interactions between graphene and an SiO₂ substrate are investigated in this dissertation using a multiscale approach. The temperature dependent mechanical behavior of graphene with thermal fluctuations is studied by statistical mechanics analysis under harmonic approximation, which is then compared to molecular dynamics simulations. It is found that the amplitude of thermal fluctuation depends nonlinearly on the graphene size due to anharmonic interactions between bending and stretching modes, but a small positive pre-strain could suppress fluctuation amplitude considerably and results in very different scaling behavior. The thermal expansion of graphene depends on two competing effects: positive expansion due to in-plane modes and negative expansion due to out-of-plane fluctuations. The in-plane stress-strain relation of graphene becomes nonlinear even at infinitesimal strain due to the entropic contribution. Consequently, the modulus of graphene depends on strain non-monotonically, with strain stiffening followed by intrinsic softening. Moreover, it is found that the thermomechnical behavior of graphene is dependent on its interactions with environment such as supporting substrate. The interfacial interactions between graphene and SiO₂ substrate is investigated in terms of three perspectives. Firstly, the interaction mechanisms between graphene and SiO₂ substrate are studied by density functional theory (DFT). The dispersion interaction is found to be the predominant mechanism, and the interaction strength is strongly influenced by changes of SiO₂ surface structures due to surface reactions with water. The adhesion energy is reduced when the reconstructed SiO₂ surface is hydroxylated, and further reduced when covered by a monolayer of adsorbed water molecules. Next, we study the interfacial interactions between graphene and a wet substrate that is covered by a liquid-like water film. During the separation of graphene from the wet substrate, MD simulations show evolution of the water from a continuous film to discrete islands. The water bridging effects are further described by continuum models. Finally, a continuum model is developed to predict how the surface roughness may affect the adhesion between graphene membranes and their substrate. / text

<p>Nonlinear optical microscopy serves as a great tool for biomedical imaging due to its high resolution, deep penetration, inherent three dimensional optical sectioning capabilities and superior performance in scattering media. Conventional nonlinear optical microscopy techniques, e.g. two photon fluorescence and second harmonic generation, are based on detecting a small light signal emitted at a new wavelength that is well separated from the excitation light. However, there are also many other nonlinear processes, such as two-photon absorption and self-phase modulation, that do not generate light at new wavelengths and that have not been extensively explored for imaging. This dissertation extends the accessible mechanisms for contrast to the later nonlinear optical processes by combining femtosecond laser pulse shaping and homodyne detection. We developed a rapid pulse shaper with a relatively simple and compact instrument design that modifies the spectrum of individual laser pulses from an 80 MHz mode-locked laser. The pulse shaper enables simultaneous two-photon absorption and self-phase modulation imaging of various nanoparticles in-vitro with high sensitivity. We also applied this imaging technique to study the nonlinear optical response in graphene. Because our technology detects the nonlinear signature encoded within the laser pulse itself, we achieve intrinsic contrast of biological and non-biological samples in highly scattering media. These capabilities have significant implications in biomedical imaging and nanophotonics.</p> / Dissertation

Experimental studies presented in this thesis have shown the first realisation of resonant tunnelling transport through two impurities in a vertical double-barrier tunnelling diode; have proved the chiral nature of charge carriers in graphene by studying ballistic transport through graphene $p$-$n$ junctions; have demonstrated significant differences of $1/f$ noise in graphene compared with conventional two-dimensional systems. Magnetic field parallel to the current has been used to investigate resonant tunnelling through a double impurity in a vertical double-barrier resonant tunnelling diode, by measuring the current-voltage and differential conductance-voltage characteristics of the structure. It is shown that such experiments allow one to obtain the energy levels, the effective electron mass and spatial positions of the impurities. The chiral nature of the carriers in graphene has been demonstrated by comparing measurements of the conductance of a graphene $p$-$n$-$p$ structure with the predictions of diffusive models. This allowed us to find, unambiguously, the contribution of ballistic resistance of graphene $p$-$n$ junctions to the total resistance of the $p$-$n$-$p$ structure. In order to do this, the band profile of the $p$-$n$-$p$ structure has been calculated using the realistic density of states in graphene. It has been shown that the developed models of diffusive transport can be applied to explain the main features of the magnetoresistance of $p$-$n$-$p$ structures. It was shown that $1/f$ noise in graphene has much more complicated concentration and temperature dependences near the Dirac point than in usual metallic systems, possibly due to the existence of the electron-hole puddles in the electro-neutrality region. In the regions of high carrier concentration where no inhomogeneity is expected, the noise has an inverse square root dependence on the concentration, which is also in contradiction with the Hooge relation.

This thesis reports the study of electronic structures for single-walled carbon nanotubes, single layer graphene and thin graphite. A brief introduction is given in Chapter 1 for the geometric and electronic structures of the materials studied while a review for the theory and experimental results relevant to this thesis is given in Chapter 2. The effects of hydrostatic pressure on surfactant-wrapped-single walled carbon nanotubes are studied in Chapter 3 by using photoluminscence and photoluminscence excitation mapping. It is found that the changes to the optical properties can be explained by the compression in carbon-carbon bonds, an effective uniaxial strain exerted on the nanotubes and changes in the surrounding environment leading to changes in the many-body interactions experienced by the nanotubes. Chapter 4 reports the study of cross-polarized photoluminescence of nanotubes isolated by conjugated polymers dispersed in solvents. The effects of Coulomb interactions on the optical bandgaps of the nanotubes are discussed here. Chapter 5 reports Cyclotron resonances studies of graphene monolayers. It is found that a significant asymmetry exists between the electron and hole band structures near the Dirac point, and the asymmetry is bigger than that is expected in a simple tight-binding model. Chapter 6 reports a magnetoabsorption study of the electronic structures near the K- and H- points. It is found that the transitions are not describe well by the conventional Slonczewski-Weiss-McClure model, but can be described instead with a simplified asymmetric effective bilayer model.