abstract: Polymer fibers have broad applications in wearable electronics, bulletproof vests, batteries, fuel cells, filters, electrodes, conductive wires, and biomedical materials. Polymer fibers display light density and flexibility but are mostly weak and compliant. The ceramic, metallic, and carbon nanoparticles have been frequently included in polymers for fabricating continuous, durable, and functional composite fibers. Nanoparticles display large specific areas, low defect density and can transfer their superior properties to polymer matrices. The main focus of this thesis is to design, fabricate and characterize the polymer/nanocarbon composite fibers with unique microstructures and improved mechanical/thermal performance. The dispersions and morphologies of graphene nanoplatelets (GNPs), the interactions with polyvinyl alcohol (PVA) molecules and their influences on fiber properties are studied. The fibers were fabricated using a dry-jet wet spinning method with engineered spinneret design. Three different structured fibers were fabricated, namely, one-phase polymer fiber (1-phase), two-phase core-shell composite fiber (2-phase), and three-phase co-axial composite fiber (3-phase). These polymer or composite fibers were processed at three stages with drawing temperatures of 100˚C, 150˚C, and 200˚C. Different techniques including the mechanical tester, wide-angle X-Ray diffraction (WAXD), scanning electron microscope (SEM), thermogravimetric analysis (TGA), and differential scanning calorimeter (DSC) have been used to characterize the fiber microstructures and properties. / Dissertation/Thesis / Masters Thesis Mechanical Engineering 2018

Surfactant assisted solution exfoliation of expanded graphite by means of sonication was carried out in an attempt to produce non-covalent charge functionality on the surface of graphene for the directed self assembly of graphene films on patterned substrates via electrostatic interactions. This thesis includes the results of experimental research associated with: 1) quantifying the effectiveness of various di-functionalized dithienothiophene surfactant small molecules, 2) further understanding the surface affinity and interaction mechanism between these surfactant molecules and the surface of expanded graphite and graphene and 3) experimentally testing the feasibility of the directed self-assembly of graphene films by means of charge functionalization of graphene by the surfactant molecules adsorbed onto the surface of exfoliated graphene.

Graphene is a single sheet of graphite. While bulk graphite is semimetal, graphene is a zero bandgap semiconductor. Band structure calculations show graphene has a linear energy dispersion relation in the low energy region close to the Dirac points where the conduction band and the valence band touch. Carriers in graphene are described as massless Dirac fermions in contrast to massive carriers in normal metals and semiconductors that obey a parabolic energy dispersion relation. The uniqueness of graphene band structure indicates its peculiar electronic transport properties. In this thesis work, single- and multi-layer graphene films epitaxially grow on either the Si face or the C face of SiC substrates in a homemade induction vacuum chamber by thermal decomposition of SiC at high temperatures. The surface morphology and crystal structure of epitaxial graphene are studied with surface analysis tools. The transport properties of epitaxial graphene are studied by magnetotransport experiments. An epitaxial graphene film turns out to be a multilayered graphene because carriers in epitaxial graphene act as those in single layer graphene. Top gated and side gated epitaxial graphene field effect transistors (FETs) have also been successfully fabricated. These systematic studies unambiguously demonstrate the high quality of epitaxial graphene and the great potential of epitaxial graphene for electronic applications

Covalent functionalization significantly enhances the utility of carbon nanomaterials for many applications. In this study, we investigated the functionalization of double nitrogen doped graphene by the addition of different alkyl and phenyl functional groups at N atoms in syn and anti-configurations. Density functional theory calculations at the B3LYP/def-SV(P) level were employed to understand the syn versus anti preference on functionalization. The bond lengths, bond angles, relative energies, deformation energies and HOMO-LUMO energy gaps, of the syn and anti-configurations of the functionalized 2N-doped graphenes, have been compared. Functionalization with two groups leads to considerable deformation of 2N-doped graphene, which is confirmed by the change in C–N bond lengths by attachment of the functional groups. The attachment of larger functional groups deforms 2N-doped graphene to a greater extent than smaller functional groups. The HOMO-LUMO energy gap values are the least for the alkyl functionalized products, indicating that these structures are kinetically less stable than the phenyl functionalized products.

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The graphitic systems have attracted intensive attention recently due to the discovery of graphene, a single layer of graphite. The low-energy band structure of graphene exhibits an unusual linear dispersion relation which hosts massless Dirac fermions and leads to intriguing electronic and optical properties. In particular, due to the high mobility and tunability, graphene and graphitic materials have been recognized as promising candidates for future nanoelectronics and optoelectronics. Electron-phonon coupling (EPC) plays a significant role in electronic and optoelectronic devices. Therefore, it is crucial to understand EPC in graphitic materials and then manipulate it to achieve better device performance. In the first part of this thesis, we explore EPC between Dirac-like fermions and infrared active phonons in graphite via infrared magneto-spectroscopy. We demonstrate that the EPC can be tuned by varying the magnetic field. The second part of this thesis deals with magnetoplasmons in quasineutral graphene nanoribbons. Multilayer epitaxial graphene grown on the carbon terminated silicon carbide surface behaves like single layer graphene. Plasmons are excited in the nanoribbons of undoped multilayer epitaxial graphene. In a magnetic field, the cyclotron resonance can couple with the plasmon resonance forming the so-called upperhybrid mode. This mode exhibits a distinct dispersion relation, radically different from that expected for conventional two dimensional systems.

A transparent conductive electrode (TCE) is an important component in many of our modern optoelectronic devices like photovoltaics, light emitting diodes and touch screens. These devices require good current injection and spreading as well as a high transparency. In this thesis we explore the use of graphene as an alternative to the current widely used indium tin oxide (ITO) as TCE in gallium nitride (GaN) based light emitting diodes (LEDs). Monolayer crystalline graphene can be produced on copper foils using chemical vapor deposition (CVD), where metals (especially copper) has a catalysing effect on the formation of graphene. However, transfer of graphene from copper foils is not suitable for an industrial scale and it results in a poor contact with the target substrate. We investigate the possibility of directly integrating graphene on GaN-based LEDs by using plasma-enhanced chemical vapor deposition (PECVD). We try to obtain the optimal conditions under these catalyst-free circumstances and propose a recipe adapted for the setup that we used. We will also study ideas of using a metal (we tried copper and nickel) to assist the direct growth that could help to increase the fraction of sp2 carbon bonds and reduce the sheet resistance. The metals are evaporated onto our samples either before or after we grow a carbon film to either assist the growth or rearrange the carbon respectively. The focus was not on trying to optimize the conditions for one metal treatment but rather to briefly explore multiple methods to find a suitable path for further studies. The direct grown pristine carbon films shows indications from Raman measurements of being nanocrystalline graphene with a sheet resistance ranging from about 20-50 kΩ/sq having a transmittance of approximately 96 % at 550 nm. A transmittance at this level is closely related to the value of an ideal monolayer graphene, which indicates that our carbon films could be close to one atom in thickness while being visually homogeneous and complete in coverage. Due to the use of a temperature close to the melting point of copper we struggled to keep the assisting copper from evaporating too fast or staying homogeneous after the treatment. Nickel has a higher melting temperature, but it appears as if this metal might be diffusing into the GaN substrate which changes the properties of both the GaN and carbon film. Even though the metal treatments that we tested did not provide any noticeable improvements, there is need for further investigations to obtain suitable treatment conditions. We suggest that the treatments involving copper are a more promising path to pursue as nickel seem to cause unavoidable intermixing problems.

Graphene nanostructures directly grown on SiC are appealing for their potential application to nano-scale electronic devices. In particular, epitaxial sidewall graphene nanoribbons have been a promising candidate in ballistic transport and band gap engineering. In this thesis, we study graphene nanoribbons by utilizing both nano-lithography and natural step bunching to control the step morphology of the SiC(0001) surface in order to guide the growth of graphene which initiates at step edges, and study their respective characteristics. With scanning tunneling microscopy and spectroscopy (STM/STS), we explore the local atomic and electronic structures of the graphene nanoribbons down to atomic scale. It is found that nanoribbon formation depends critically on nanofacet orientation, nanofacet density, and growth conditions. Under some conditions, nanoribbons grow predominantly on the nanofacet. Significant electronic density-of-states features, resolved by STS, are found to depend strongly on proximity to strained graphene near the step edge. Experimental results are compared to Molecular Dynamics simulations to better understand the origin of the discrete electronic states.

Diamond has since many years been applied in electronic fields due to its extraordinary properties. Substitutional dopants and surface functionalization have also been introduced in order to improve the electrochemical properties. However, the basic mechanism at an atomic level, regarding the effects of dopants and terminations, is still under debate. In addition, theoretical modelling has during the last decades been widely used for the interpretation of experimental results, prediction of material properties, and for the guidance of future materials. Therefore, the purpose of this research project has been to theoretically investigate the influence of dopants and adsorbates on electronic and geometrical structures by using density functional theory (DFT) under periodic boundary conditions. Both the global and local effects of dopants (boron and phosphorous) and terminations have been studied. The models have included H-, OH-, F-, Oontop-, Obridge- and NH2-terminations on the diamond surfaces. For all terminating species studied, both boron and phosphorous have been found to show a local impact, instead of a global one, on diamond structural geometry and electronic properties. Therefore, the terminating species only affect the DOS of the surface carbon layers. In addition, Oontop-terminated (111) diamond surfaces present reactive surface properties and display metallic conductivity. Moreover, the conductivity of the diamond surface can be dramatically increased by the introduction of a phosphorous dopant in the lattice. The work function of a diamond surface has also been found to be influenced to a large extent by the various adsorbates and the dopant levels. Diamond can also be used as a promising substrate for an epitaxial graphene adlayer. The effects of dopants and terminations on the graphene and diamond (111) interfacial systems have been investigated theoretically in great detail. The interfacial interaction is of the Van der Waal type with an interfacial distance around 3 Å. The interactions between graphene and a terminated diamond substrate were found to be relatively weaker than those for a non-terminated diamond substrate (even with dopants). For all interface systems between graphene and diamond, a diamond-supported graphene adlayer without induced defects can still keep its intrinsic high carrier mobility. A minor charge transfer was observed to take place from the graphene adlayer to a non-terminated diamond substrate (with or without dopants) and to Oontop-, OH- or Obridge-terminated diamond substrates. However, for the situation with an H-terminated diamond surface, the electron transfer took place from the diamond surface to graphene. On the contrary, an interfacial system with a non-terminated diamond surface offers a more pronounced charge transfer than that of the terminated diamond substrates. A small finite band gap at the Dirac point was also observed for the Oontop-terminated diamond-supporting graphene adlayer.