Thesis advisor: Ziqiang Wang / Graphene has emerged as an important two dimensional electron system with novel physical properties due to its relativistic-like linear energy-momentum dispersion relation at low energy. Alongside two dimensional electron systems in semiconductor heterostructures, it has a rich set of integer and fractional quantum Hall states. Significant progresses have been made recently, but a full understanding of these states is still lacking. The prevailing approach for fractional quantum Hall effects in graphene has been the numerical exact diagonalization. In this work, we develop a fermionic Chern-Simons effective theory for Dirac fermions as a complement to the existing theories, and to bring new insights in our understanding of the phenomena. In particular, we study the possibility for quantum Hall plateaus at even-denominator filling factors. We first construct a unitary Chern-Simons transformation to attach even number of flux quanta to Dirac fermions. To deal with the four-fold spin-valley degeneracy, a set of K-matrices is introduced. At even-denominator filling factors in the zeroth Landau level, the fictitious magnetic field of the Chern-Simons field cancels the external magnetic field on average. It is shown that the Chern-Simons field mediates an effective mutual statistical interaction between composite Dirac fermions. We further show the statistical interaction and Coulomb interaction favor the formation of an exciton condensate. Quasi-particles at finite filling factors can be regarded as excita- tions above the exciton condensate, and can be described as massive Dirac fermions. This means a mass is generated dynamically for Dirac fermions. Different types of K-matrices give rise to different mass gaps. The Chern numbers associated with different massive Dirac band structures can be used to classify the K-matrices. In the last part of the thesis, we study the pairing instability of the composite Dirac fermion liquid. We show the statistical interaction drives a complex p-wave pairing among the quasi-particles. As long as the Coulomb pair breaking effect is weak, the system can develop a superconducting energy gap, thus form a fractional quantum Hall state. / Thesis (PhD) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

A Dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in ful lment of the requirements for the degree of Master of Science. Johannesburg 2016. / Low dimensional carbon systems are of immense interest in condensed matter physics due to their exceptional and often startling electric and magnetic properties. In this dissertation we consider two of these materials - graphene and nanocrystalline diamond. The effect of synthesis parameters on the quality of graphene is examined and it is found that controlling the partial pressure of the synthesis gases plays a critical role in determining the quality of the sample. Superconductivity in Boron doped nanocrystalline diamond (B-NCD) is considered and weak localisation along with a Berezinsky-Kosterlitz-Thouless (BKT) transition is identified in the samples. Furthermore we explore theoretically the problem of electric transport through a double quantum dot system coupled to a nanomechanical resonator. We find resonant tunnelling when the difference between the energy levels of the dots equals an integer multiple of the resonator frequency, and that while initially increasing the electron phonon coupling (g) increases the current through the sample further increase in g inhibits electric transport through the quantum dots. / LG2017

We report a method of increasing fracture toughness (KIc) and strain energy release rate (GIc) of vinyl-ester (VE) matrix by adopting a hybrid (dual) reinforcement strategy. The idea of using this strategy was to trigger intrinsic polymer-nanoparticle interaction such as carbon nanotube (CNT) pull-out and interface sliding to enhance energy absorption during fracture. Additionally, we included a second reinforcement, graphene nanoplatelets (GNP), to promote crack-deflection, crack bridging and cross-linking density. Both reinforcements were dispersed into the polymer in three states: non-functionalized (nf>); functionalized with COOH (f>); surface-treated with Triton X-100 (TX100). We embarked on numerous experiments with many combinations of these variables. We measured KIc and GIc using ASTM D5045-14. We conducted an exhaustive iterative investigation with three systems (f>CNT-VE; f>GNP-VE; f>CNT-f>GNP-VE) to determine the best weight-percentage for the nanocomposite system that produced the highest KIc and GIc values when compared to neat-VE. We found that 0.5wt% f>CNT with 0.25wt% f>GNP in the VE matrix resulted in the highest fracture toughness values and was termed the optimized hybrid nanocomposites (OHN) system. Subsequently, we explored further increasing the KIc and GIc of OHN through altering the nanoparticle surface characteristics, which led to four OHN groups: f>CNT-f>GNP-VE; f>CNT-f>GNP-TX100-VE; nf>CNT-nf>GNP-TX100-VE; nf>CNT-nf>GNP-VE. We discovered that the OHN group with non-functionalized nanofillers that were TX100 surface treated (0.5wt%nf>CNT-0.25wt%nf>GNP-TX100-VE) generated the greatest improvements in KIc and GIc. Ultimately, we observed that the KIc of neat-VE increased by 65%, from 1.14 to 1.88 MPa*(m½). The improvement in GIc was even greater with an increase of 166%, from 370 to 985 J/(m2). Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) studies showed a minor shift in glass transition temperature (Tg) by up to 8°C when comparing neat-VE specimens to OHN specimens. A similar increase in maximum thermal decomposition temperature (Tp) of up to 8°C was observed through thermogravimetric analysis (TGA) and derivative TGA (DTG). Scanning electron microscope (SEM) studies revealed that the source of improvements in fracture toughness and thermal properties was primarily the three-dimensional hybrid nanostructures (3DHN) that formed by binding CNT and GNP together, which caused an increase in nanoparticle surface area and inhibited agglomerations. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2018. / FAU Electronic Theses and Dissertations Collection

Grafeno e nanofitas de grafeno vêm, cada vez mais, atraindo o interesse da comunidade científica devido as suas notáveis propriedades. Neste trabalho realizou-se um estudo sistemático da estabilidade de defeitos do tipo divacância, vacância e Stone-Wales em grafeno e nanofitas de grafeno com bordas zigzag. Para tal, fizeram-se cálculos de primeiros princípios, baseados em teoria do funcional da densidade (DFT) na aproximação GGA com o uso de pseudopotenciais ultrasoft e uma base de ondas planas. Também foram feitas simulações de imagens de STM para os defeitos nas nanofitas. Além disso, foram encontrados dois novos defeitos, não publicados em nenhum outro lugar (até onde vai o conhecimento do autor), com energia de formação muito baixa. / Graphene and graphene nanoribbons have been attracting a lot of interest from the scientific community because of their novel properties. In this work, a systematic research has been done on the stability and energetics of divacancy, vacancy and Stone-Wales defects in graphene and zigzag graphene nanoribbons. With this goal in mind, ab initio density functional calculations within the GGA approximation, using ultrasoft pseudopotentials and a plane wave basis were done. Also, STM images were simulated for some selected defects. Besides, two new defects, not published elsewhere (to the best knowledge of the author), with very low formation energy are reported.

In this work the potential of graphene-like particles for mechanical reinforcement is investigated. Different polymer processing methods are studied from traditional ones to more advanced techniques. The potential of graphene as a reinforcement for polymer composites is addressed as a result of polymer modifications and the morphology of the graphene like particles. First, a composites of polycarbonate (PC) and graphite nanoplatelets (GNP) are produced by a traditional melt-mixing method. The GNP composites present a low mechanical reinforcing efficiency which is believed to be due to a poor dispersion of the GNP and a weak interaction between the GNP and the matrix. Secondly, solution cast composites of polyvinyl alcohol (PVA) with very low loadings of graphene oxide (GO) are produced. The polymer morphology undergoes some modifications after the addition of GO. A strong increase of the Tg is observed after the addition of GO which is the result of a reduction in polymer mobility, while a dramatic increase of the mechanical properties is seen as well. Uni-axial drawing is applied in order to align the particles. No polymer modifications are observed between the drawn PVA and the drawn nanocomposites due to the strong alignment of the polymer chains during the drawing. Mechanical reinforcement is observed after addition of the GO showing real reinforcement. Finally, a more advanced processing method is investigated using spraying. The condition of spraying a layer of polymer and GO is studied. Finally a hierarchical composite of PVA - GO is produced by this spraying method. 150 bi-layers are deposited to create a film with improved mechanical properties at a loading of 5.4 wt.% GO. The Young’s modulus and strength of these films doubled or nearly doubled which is believed to be due to the high level of structural organization of the layered nanocomposite incorporating the 2D GO nanofiller, together with hydrogen bonding between the PVA and the GO sheets.

The main technology currently used in diabetic care, monitors blood glucose and involves an invasive “fingerstick” step. However, low patient compliance and non-continuous glucose monitoring imply poor management of diabetes through this technology, which could lead to adverse and potentially life threatening conditions. In this context, non-invasive glucose sensing appears as an alternative that can bring a change in the prevention and management of the diabetic condition, promising to eliminate patient resistance towards more frequent monitoring and, hence, considerably improving diabetic’s control over glycaemia. However, no non-invasive technology has yet succeeded on the market over the long term. The research field is therefore open to innovative and performant non-invasive technologies. This thesis presents the development of a non-invasive biosensor which as a core principle accesses individual, privileged glucose pathways in the skin (such as hair follicles), allowing the extraction of glucose directly from the interstitial fluid, via reverse iontophoresis (RI). The transdermally extracted glucose is then electrochemically detected in a small size sensor with very high sensitivity. A fully developed technology based on this principle will not require fingerpricking and would thus eliminate users’ main barrier to glucose monitoring. The developed sensor is enzymatic (using glucose oxidase), which electrochemically detects the produced H2O2; while the electrode material is graphene produced by Chemical Vapour Deposition, a promising carbon nanomaterial platform for biofunctionalisation and biosensing. The sensor is a miniature one (typically of 9 mm2 area, containing 24 μL of gel encasing the enzyme), with demonstrated performance parameters that are highly competitive (sensitivity of 2.89 μA.mM-1.cm-2 and limit of detection down to 1 μM), with high specificity towards glucose. The combination of this sensor with glucose extraction by reverse iontophoresis was then validated (with proportionality between subdermal and extracted glucose concentrations demonstrated); as well as enhanced extraction through targeting of hair follicles with the miniature device. The electrochemical determination of glucose concentration was further confirmed by 1H quantitative-NMR detection of glucose. Finally, several such sensors were integrated in a multiplex configuration, and independent sensing, with no cross-talk was demonstrated. The steps demonstrated and implemented so far are proof-of-concept of a highly promising non-invasive, transdermal, future technology for diabetic care.

The demand for high performance Lithium-ion batteries (LIBs) is increasing due to widespread use of portable devices and electric vehicles. Silicon (Si) is one of the most attractive candidate anode materials for the next generation LIBs because of its high theoretical capacity (3,578 mAh/g) and low operation potential (~0.4 V vs Li+/Li). However, the high volume change (>300%) during Lithium ion insertion/extraction leads to poor cycle life. The goal of this work is to improve the electrochemical performance of Si/C composite anode in LIBs. Two strategies have been employed: to explore spatial arrangement in micro-sized Si and to use Si/graphene nanocomposites. A unique branched microsized Si with carbon coating was made and demonstrated promising electrochemical performance with a high active material loading ratio of 2 mg/cm2, large initial discharge capacity of 3,153 mAh/g and good capacity retention of 1,133 mAh/g at the 100th cycle at 1/4C current rate. Exploring the spatial structure of microsized Si with its advantages of low cost, easy dispersion, and immediate compatibility with the prevailing electrode manufacturing technology, may indicate a practical approach for high energy density, large-scale Si anode manufacturing. For Si/Graphene nanocomposites, the impact of particle size, surface treatment and graphene quality were investigated. It was found that the electrochemical performance of Si/Graphene anode was improved by surface treatment and use of graphene with large surface area and high defect density. The 100 nm Si/Graphene nanocomposites presented the initial capacity of 2,737 mAh/g and good cycling performance with a capacity of 1,563 mAh/g after 100 cycles at 1/2C current rate. The findings provided helpful insights for design of different types of graphene nanocomposite anodes.

Due to the combination of their electronic, optical and mechanical properties, graphene and other layered materials (GRMs) have great potential for applications such as flexible optoelectronics and energy storage. Given that GRMs can be dispersed in solvents, solution processing is a particularly interesting approach that allows large volume production with tailored properties according to the targeted applications. \par In this dissertation I investigate liquid phase exfoliation and formulation of GRMs-based inks for flexible (opto) electronics, energy and photocatalysis. First I develop a protocol for the characterization of graphene inks, based on the statistical analysis of their Raman spectra. Such a tool is essential because of the scattering of characteristics in liquid-phase exfoliated material. I then report two novel processing techniques. The first consists on the exfoliation of graphene in organic solvents by the means of $\alpha$-functionalized alkanes as stabilising agents, which allows yield by weight ($Y_W$) of $\sim 100\%$. The second is based on exfoliation of graphite by microfluidization, where the material is stabilised in aqueous solution, with concentrations up to 100g/L. Such inks are successfully deposited by blade coating, leading to films of conductivity $\sim$ 2$\cdot$10$^4$ S/m at 25$\mu$m. I then investigate the use of graphene inks in optoelectronics and energy applications: First, I investigate inkjet printed graphene as hole injection layer (HTL). The cells with graphene HTL show high long-term stability, retaining 85$\%$ of the initial fill factor after 900 hrs in damp heat conditions. I then demonstrate flexible displays with graphene-SWNTs as pixel electrode. A 4x4 inch$^2$ demonstrator is realised integrating the ink into 12,700 pixels. I investigate graphene/MoO$_3$ electrode for supercapacitors with a specific capacitance of 342 F/cm$^3$. The electrode shows high cyclic stability, preserving $\sim$96$\%$ of the initial capacitance after 10,000 cycles. I finally report the production of TiO$_2$/exfoliated graphite as efficient photocatalytic composite able to degrade $\sim$100$\%$ more model pollutant with respect to TiO$_2$.

In the last decade, the emerging classes of two-dimensional (2D) materials have been studied as potential candidates for various sensing technologies, including magnetic and optoelectronic detectors. Within the quickly growing portfolio of 2D materials, graphene and semiconducting transition metal dichalcogenides (TMDs) have emerged as attractive candidates for various sensor applications because of their unique properties such as extreme thickness, excellent electrical and optical properties. In this thesis, I have exploited the unique properties of graphene and TMDs materials to develop 2D detectors based on field effect transistors for sensing magnetic field and light. In the first part of this thesis I have shown how the sensitivity of the properties of 2D materials to their surrounding environment can be turned into a feature useful to create new types of magnetic field sensors. The first experimental demonstration of this concept involved the use of graphene deposited on hexagonal Boron Nitride (h-BN), where the inevitable contaminations occurring at the interface of the two materials was used to generate a large magnetoresistance (MR) for a magnetic field sensor. Specifically, I have demonstrated that the contaminations generate an inhomogeneity in the carrier mobility throughout the channel, which is a required ingredient for magnetic field sensing based on linear magnetoresistance (LMR). Another approach I used to make a LMR sensor was by exploiting the large dependence of the mobility in graphene on the Fermi level position. This concept was used to generate two parallel electron gases with different mobility by tuning the Fermi level with an electrical field employing a field effect transistor. The second part of the thesis is focussed on strategies to reduce the impact of the surrounding environment on the properties of 2D materials in order to improve their performance. In particular, I used a 2D heterostructure encapsulated in an ionic polymer to makeii a highly responsive graphene-TMD photodetector. In this device, the ionic polymer covering the heterostructure was employed to screen the long-lived charge traps that limit the speed of such detectors, resulting in a drastic improvement of the detector responsivity properties. Finally, some of the 2D materials properties are very sensitive to the configuration of the electronics measurement setup. For example, effects behind spintronic and valleytronic concepts require non-local electrical transport measurement. We built a novel circuit that enables the detection of such effects without concern about the spurious contributions.

Graphene, an atomically thin material consisting of a hexagonal, highly packed carbon lattice, is of great interests in its magnetic properties. These interests can be categorized in several fields: graphene-based magnetic materials and their applications, large diamagnetism of graphene, and the heterostructures of graphene and other two dimensional materials. In the first aspect, magnetic moments can be in theory introduced to graphene by minimizing its size or introducing structural defects, leading to a very light magnetic material. Furthermore, weak spin-orbital interaction, and long spin relaxation length make graphene promising for spintronics. The first part of this thesis addressed our experimental investigation in defect-induced magnetism of graphene. Non-interacted spins of graphene have been observed by intentionally introducing vacancies and adatoms through ion-irradiation and fluorination, respectively. The defect concentration or the magnetic moments introduced in this thesis cannot provide enough interaction for magnetic coupling. Furthermore, the spins induced by vacancies and adatoms can be controlled through shifting the Fermi energy of graphene using molecular doping, where the adatoms were alternatively introduced by annealing in the inert environment. The paramagnetic responses in graphene induced by vacancy-type defects can only be diverted to half of its maximum, while those induced by sp3 defects can be almost completely suppressed. This difference is supposed that vacancy-type defects induced two localized states (pie and sigma). Only the latter states, which is also the only states induced by sp3 defects, involves in the suppression of magnetic moments at the maximum doping achieved in this thesis. The observation through high resolution transmission electron microscope (HR-TEM) provides more information to the hypothesis of the previous magnetic findings. Reconstructed single vacancy is the majority of defects discovered in proton-irradiated graphene. This result verifies the defect-induced magnetic findings in our results, as well as the electronic properties of defected graphene in the literatures. On the other hand, the diamagnetic susceptibility of neutral graphene is suggested to be larger than that of graphite, and vanish rapidly as a delta-like function when graphene is doped. In our result, surprisingly, the diamagnetic susceptibility varies little when the Fermi level is less than 0.3 eV, in contrast with the theory. When the Fermi energy is higher than 0.3 eV, susceptibility then reduces significantly as the trend of graphite. The little variation in susceptibility near the Dirac point is probably attributed to the spatial confinement of graphene nanoflakes, which are the composition of graphene laminates. In the end of this thesis, we discuss the magnetic properties in one of the other two dimensional materials, molybdenum disulfide (MoS2). It is a potential material for graphene-based heterostructure applications. The magnetic moments in MoS2 are shown to be induced by either edges or vacancies, which are introduced by sonication or proton-irradiation, respectively, similar to the suggestions by theories. However, no significant ferromagnetic finding has been found in all of our cases.