This thesis investigates pool boiling heat transfer from bare and graphene-coated NiCr wires in a saturated liquid of FC 770, a fluorocarbon fluid. Of particular interest was the effect of graphene-oxide platelets, dip-coated onto the heater surface, in enhancing the nucleate boiling heat transfer (BHT) rates and the critical heat flux (CHF) value. In the course of the pool boiling experiment, the primary focus was on the reduction mechanism of graphene oxide. The transition from hydrophilic to hydrophobic behavior of the graphene oxide-coated surface was captured, and the attendant effects on surface wettability, porosity and thermal activity were observed. A parametric sensitivity analysis of these surface factors was performed to understand the CHF and BHT enhancement mechanisms. In the presence of graphene-oxide coating, the data indicated an increase of 50% in CHF. As the experiment continued, a partial reduction of graphene oxide occurred, accompanied by (a) further enhancement in the CHF to 77% larger compared to the bare wire. It was shown that the reduction of graphene oxide progressively altered the porosity and thermal conductivity of the coating layer without changing the wettability of FC 770. Further enhancement in CHF was explained in terms of improved porosity and thermal activity that resulted from the partial reduction of graphene-oxide. An implication of these results is that a graphene-oxide coating is potentially a viable option for thermal management of high-power electronics by immersion cooling technology. / Master of Science

Imposing dimensional restrictions on graphene sheets and adding impurities can give rise to carbon nanostructures with magnetic properties. In this work, zigzag graphene nanoribbons, zGNRs, with nitrogen and fluorine adatoms are investigated for magnetic properties of interest for spin devices. Geometry optimizations were done determining which position along a zGNR electrode that N and F would favorably attach to. Edge positions were determined as the most stable attachment site. M-cell zGNR electrodes (M = 1-3) edge-functionalized by N and F adatoms were investigated with respect to their band structures and spin densities in antiferromagnetic and ferromagnetic, AFM and FM, configurations. Focus was placed on band structures showing spin gaps, indicating potential for magnetoresistive devices. Devices were modeled for 2-cell and 3-cell electrodes with nitrogen adatoms, and the respective transmission spectra were compared. Attaching N adatoms to zGNRs turned out to be a mode of controlled manipulation of their spin configurations. Spin gaps were identified in units based on 3-cell-zGNR electrodes.

The direct growth of graphene by scalable methods on magnetic insulators is important for industrial development of graphene-based spintronic devices, and a route towards substrate-induced spin polarization in graphene without spin injection. X-ray photoelectron spectroscopy (XPS), low energy electron diffraction LEED, electron energy loss spectroscopy (EELS) and Auger electron spectroscopy (AES) demonstrate the growth of Co3O4(111) and CoO(111) to thicknesses greater than 100 Å on Ru(0001) surfaces, by molecular beam epitaxy (MBE). The results obtained show that the formation of the different cobalt oxide phases is O2 partial pressure dependent under same temperature and vacuum conditions and that the films are stoichiometric. Electrical I-V measurement of the Co3O4(111) show characteristic hysteresis indicative of resistive switching and thus suitable for advanced device applications. In addition, the growth of Co0.5Fe0.5O(111) was also achieved by MBE and these films were observed to be OH-stabilized. C MBE yielded azimuthally oriented few layer graphene on the OH-terminated CoO(111), Co0.5Fe0.5O(111) and Co3O4(111). AES confirms the growth of (111)-ordered sp2 C layers. EELS data demonstrate significant graphene-to-oxide charge transfer with Raman spectroscopy showing the formation of a graphene-oxide buffer layer, in excellent agreement with previous theoretical predictions. XPS data show the formation of C-O covalent bonding between the oxide layer and the first monolayer (ML) of C. LEED data reveal that the graphene overlayers on all substrates exhibit C3V. The reduction of graphene symmetry to C3V – correlated with C-O bond formation – enables spin-orbit coupling in graphene. Consequences may include a significant band gap and room temperature spin Hall effect – important for spintronic device applications. The results suggest a general pattern of graphene/graphene oxide growth and symmetry lowering for graphene formation on the (111) surfaces of rocksalt-structured oxides.

This thesis work contains electrical transport and low frequency (1/f) noise measurements in ultrathin graphene and Molybdenum disulphide (MoS2) field effect transistors (FET). From the measurements, We mainly focus on the origin of disorder in both the materials. To address the orgin of disorder in graphene, we study single and bilayer graphene-FET devices on SiO2 substrate. We observe that both conductivity and mobility are mainly determined by substrate induced long range, short range, and polar phonon scattering. For further confirmation, we fabricate suspended graphene devices which show extremely high mobility. We find that, in contrast to substrate-supported graphene, conductivity and mobility in suspended graphene are governed by the longitudinal acoustic phonon scattering at high temperature and the devices reach a ballistic limit at low temperature. We also conduct low frequency 1/f noise measurements, known to be sensitive to disorder dynamics, to extract more information on the nature of disorder. The measurements are carried out both in substrate-supported and suspended graphene devices. We find that 1/f noise in substarted graphene is mainly determined by the trap charges in the SiO2 substrate. On the other hand, noise behaviour in suspended graphene devices can not be explained with trap charge dominated noise model. More-over, suspended devices exhibit one order of magnitude less noise compared to graphene on SiO2 substrate. We believe noise in suspended graphene devices probably originate from metal-graphene contact regions. In the second part of our work, We present low temperature electrical transport in ultrathin MoS2 fields effect devices, mechanically exfoliated onto Si/SiO2 substrate. Our experiments reveal that the electronic states in MoS2 are localized well up to the room temperature over the experimentally accessible range of gate voltage. This manifests in two dimensional (2D) variable range hopping (VRH) at high temperatures, while below ~ 30 K the conductivity displays oscillatory structures in gate voltage arising from resonant tunneling at the localized sites. From the correlation energy (T0) of VRH and gate voltage dependence of conductivity, we suggest that the charged impurities are the dominant source of disorder in MoS2. To explore the origin of the disorder, we perform temperature dependent I - V measurements at high source-drain bias. These measurements indicate presence of an exponentially distributed trap states in MoS2 which originate from the structural inhomogeneity. For more detailed investigation, we employ 1/f noise which further confirms possible presence of structural disorder in the system. The origin of the localized states is also investigated by spectroscopic studies, which indicate a possible presence of metallic 1T-patches inside semiconducting 2H phase. From all these evidences, we suggest that the disorder is internal, and achieving high mobility in MoS2 FET requires a greater level of crystalline homogeneity.

This work deals with issues of application of the graphene material in the field of electrochemical energy storage. It includes basic graphene properties, the overview of methods for the production of lithium-iron-phosphate/graphene composites and results of different research approaches. The general aim is to present growing opportunity of application of graphene based composites in the electrochemical energy storage field. In the experimental part of this work, a electrochemical exfoliation of graphite and a production of LFP/G composites with different amount of graphene material and with different types of graphene material are carried out. This work includes also x-ray diffraction spectroscopy measurements and the evaluation of impacts of graphene additives on final properties of the electrochemical energy storage.

Radionuclide liquid wastes generated from nuclear facilities can affect humans and the environment, thus substantial attention for their safe management has been received worldwide. Treatment of radionuclide liquid wastes is an important step in its management. In the present work, new composite nanomaterials, graphene oxide base nanomaterial (GO) are developed for treatment purpose. Graphene oxide (GO), one of the most graphene derivatives, its unique properties, such as chemical stability, hydrophilicity, large surface area and functional groups, make them able to form strong chemical bonds with radionuclides. GO was successfully synthesized via Hummers method, characterized by Raman spectroscopy, X-Ray Diffraction (XRD), UV/Vis Spectroscopy, Fourier transform infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM) and applied as an adsorbent in removal of the metallic long-lived radionuclide 68Ge from of aqueous solution The method used for evaluation of nanomaterials retention properties was sorption experiment, being based on contact of solid material with tracer solution under defined boundary conditions (solid/solution ratio, solution composition etc.). Two sorption experimental methods were used in this study. Firstly, an aqueous solution of 68Ge radionuclide solution mixed with GO solution, the solution was filtered using syringe filter membrane unit and the aliquot was quantified by gamma spectrometry. Secondly, the 68Ge radionuclide was mixed with GO solid powder, suspension rotated in a mechanical shaker, centrifuged, an aliquot of 1.0 ml sample taken for gamma spectroscopy and the supernatant was put in an oven to dry overnight for characterization analysis. The results obtained from experiments were the evaluated, using sorption percentage equation and showed that the GO had much low sorption capacity for the pre-concentration of radionuclides from aqueous solutions. The function of the pH, the ionic strength and the reduction of GO will be investigated for future studies for the improvement of the research results. / Physics / M. Sc. (Physics)

The two-dimensional phase of carbon known as graphene is actively being pursued as a primary material in future electronic devices. The goals of this thesis are to investigate the growth and electronic properties of epitaxial graphene on SiC, with a particular focus on nanostructured graphene. The first part of this thesis examines the kinetics of graphene growth on SiC(0001) and SiC(0001 ̅) by high-temperature sublimation of the substrate using a custom-built, ultra-high vacuum induction furnace. A first-principles kinetic theory of silicon sublimation and mass-transfer is developed to describe the functional dependence of the graphene growth rate on the furnace temperature and pressure. This theory can be used to calibrate other graphene growth furnaces which employ confinement controlled sublimation. The final chapter in this thesis involves a careful study of self-organized epitaxial graphene nanoribbons (GNRs) on SiC(0001). Scanning tunneling microscopy of the sidewall GNRs confirms that these self-organized nanostructures are susceptible to overgrowth onto nearby SiC terraces. Atomic-scale imaging of the overgrown sidewall GNRs detected local strained regions in the nanoribbon crystal lattice, with strain coefficients as high as 15%. Scanning tunneling spectroscopy (STS) of these strained regions demonstrate that the graphene electronic local density of states is strongly affected by distortions in the crystal lattice. Room temperature STS in regions with a large strain gradient found local energy gaps as high as 400 meV. Controllable, strain-induced quantum states in epitaxial graphene on SiC could be utilized in new electronic devices. / Per request of the author and the advisor, and with the approval of the graduate office, the Acknowledgements page was replaced with an errata.

In this thesis work several manufacturing methods for graphene is discussed followed by an indepth study of graphene grown by a high temperature sublimation method (sublimation of siliconcarbide). The graphene surfaces studied have been grown by Graphensic AB, both graphenegrown on the Si-face and the C-face of the silicon carbide were studied. Six graphene samplesgrown 4H-SiC substrates were examined for homogeneity and surface morphology as well assome surface roughness parameters using Atomic Force Microscopy (AFM). The graphene wasstudied to get a better understanding of the surfaces and the growth mechanisms to improvemanufacturing parameters while also being informative for graphene sample customers. Anadditional graphene sample grown on 6H-SiC epitaxial layer was also studied to get a betterunderstanding of the sublimation mechanism. If graphene could be manufactured in a cheaprepeatable way the applications are endless and a new era of technology could emerge muchlike the silicon era that began several decades ago. In this thesis work the results are presentedas topography images as well as tables and histograms in the results section. The growth onthe Si-face is found to be well ordered when compared to the C-face which shows signs of alargely complex growth. The graphene on the Si-face lies on top of silicon carbide steps like acarpet with a buer layer interface against the silicon carbide. On the C-face this buer layeris not present but the graphene is deformed by buckling which is suspected to originate fromdierences in thermal properties between the graphene and the C-face. The in uence of AFMsettings for characterization of graphene while using intermittent mode have been evaluated andrecommendations are given. Finally a method for evaluating the homogeneity of the graphenelm is proposed but is in need of further verication.

Made available in DSpace on 2016-03-15T19:36:55Z (GMT). No. of bitstreams: 0 Previous issue date: 2015-08-18 / Fundo Mackenzie de Pesquisa / A two-dimensional structure with a thickness of one atom in a Bravais lattice in a "honeycomb". So it is known graphene, with interesting property both in basal plane as the edges of the material. Consisting of carbon atoms in its sp2 hybridization, graphene has applications to mechanical areas, electrical, optical, chemistry, biology. This requires mastered the techniques of obtaining graphene. This paper presents the study of obtaining exfoliated material, seeking to control the process as well as obtain graphene by electrochemical. The process of obtaining exfoliation is important because through it can obtain more control over the exfoliated material. The material obtained was analyzed by Raman spectroscopy. Our results show that it is possible to obtain exfoliated material, and as the spectra material by analyzing the intensity of the peaks. / Uma estrutura bidimensional com a espessura de um átomo, em uma rede de bravais em forma de favos de mel . Assim é conhecido o grafeno, com propriedade interessante tanto no plano basal como nas bordas do material. Constituído de átomos de carbono em sua hibridização sp2, o grafeno possui aplicações às áreas de mecânica, elétrica, ótica, química, biologia. Para isso é necessário dominar as técnicas de obtenção de grafeno. Este trabalho apresenta o estudo da obtenção de material esfoliado, buscando controle no processo, além de se obter grafeno por via eletroquímica. O processo de obtenção por esfoliação eletroquímica é importante, pois por meio dele pode-se adquirir mais controle sobre o material esfoliado. O material obtido foi analisado através da técnica de Espectroscopia Raman. Os resultados mostraram que é possível obter material esfoliado e a análise deste material através da intensidade das bandas de seu espectro Raman.

Les couches de graphene épitaxiées sur la face carbone du carbure de silicium sont tournées les unes par rapport aux autres. Cette rotation préserve la structure de bande linéaire du graphene mono-couche et permet un transport balistique des porteurs de charge. Parmi les propriétés intéressantes développées dans le chapitre 2, la possibilité de former de pleines couches de graphene sur le substrat isolant qu'est le SiC est un avantage majeur de cette technique comparé aux autres méthodes de croissance du graphene (exfoliation et épitaxie en phase vapeur sur métaux). Les grandes surfaces produites permettent aux expérimentateurs de faire facilement des mesures STM car la localisation de la partie utile de l’échantillon n'est pas un problème dans ce cas.Dans ce travail de thèse, j'ai réalisé la croissance de graphene sur la face carbone du SiC dans le but d'étudier la supraconductivité induite dans le graphene par la proximité d'un supraconducteur. Cette supraconductivité induite dont le principe expliqué dans le chapitre 3 se développe d'autant plus loin de l'interface que le matériau non supraconducteur possède un grand libre parcours moyen. D'où notre choix du graphene. Dans le chapitre 3 je présente aussi les efforts que j'ai mené pour fabriquer des jonctions graphene/supraconducteur par une technique de lithographie propre : la lithographie par microsphères. Cette méthode utilise des micro-sphères de silice comme masque dur durant le dépôt par évaporation d'un matériaux supraconducteur tel le vanadium. Malgré la propreté de cette méthode telle qu'avérée par les images STM des échantillons, nous n'avons pas réussi à induire la supraconductivité dans le graphene. Suite à ce résultat négatif, nous avons développé une seconde approche décrite dans le chapitre 4. Un matériau supraconducteur réfractaire, le niobium, est cette fois-ci déposé sur le substrat avant la croissance du graphene. A l'issue de la croissance, nous avons eu la surprise de constater que la température critique du matériaux supraconducteur s'était élevée de 7 à 12 K. Cela s'explique par la carburation du Niobium lors du recuit. Par ailleurs, nous avons bien démontré que des couches graphitiques sont aussi crues sur le NbC permettant ainsi de réaliser des jonctions. Néanmoins, nous n'avons à nouveau pas réussi à observer de supraconductivité induite dans le graphene.Outre les propriétés intéressantes pour l'étude de la supraconductivité induite, les couches de graphene en rotation constituent en elle même un sujet d'étude intéressant. En effet, la densité d'état de ce système présente des singularités de van Hove dont la position en énergie dépend de l'angle de rotation. Ce système ouvre donc la porte à l'étude de la physique associée à ces singularités (supraconductivité, magnétisme) à des énergies accessibles par dopage électrostatique. De plus, une localisation des fonctions d'onde électroniques a été prédite pour les faibles angles de rotation et cette localisation a été confirmée par des résultats expérimentaux préliminaires. Cependant, il manquait une étude systématique des propriétés électriques des systèmes à faible angle de rotation. Les mesures que j'ai réalisé dans ce régime sont présentées dans la dernière partie de ce mémoire. Ces mesures de spectroscopie sont comparées à un modèle de liaison fortes. Le modèle sans désordre et en présence de désordre ne permettent pas de décrire correctement les expériences menées pour des angles inférieurs à 2°. Mon travail souligne qu'une physique riche existe aux faibles angles de rotation et qu'il reste encore beaucoup de travail à faire pour la comprendre. / Epitaxial graphene on carbon-terminated face (C-face) of SiC substrates consists of graphene layers rotated from each other. This rotation of layers grants this material single-layer like properties, such as a linear dispersion band structure and a ballistic transport. As discussed in chapter 2, the full-wafer size and the insulating SiC substrate are two of many advantages of graphene films grown on SiC compared to those prepared differently (exfoliation method and chemical vapour deposition method). These two advantages allow experimentalists to perform scanning tunneling microscopic (STM) experiments and to study graphene properties easily.In this PhD work, we grew graphene on C-face of SiC substrates to investigate the induced superconducting proximity effect in ballistic regime. The physics of this phenomenon is explained in chapter 3 as the formation of time-reversed pairs of electrons and holes. Concerning the superconducting materials, we relied on vanadium and niobium carbide to induce the proximity effect. These two approaches are discussed in detail in chapter 3 (for V) and chapter 4 (for NbC). STM characterizations performed on fabricated samples show a superconducting gap in V and a part of the NbC surface, but no induced gap in graphene. Several possible reasons, like a poor interface between superconductors and graphene, the unability of the STM to reach the true graphene-superconductor interface, and the degradation of the surface of NbC, were suggested and discussed. However, our high-quality epitaxial NbC films meet the requirements for hot-electron bolometers.Besides their single-layer like properties, the rotation of layers also leads to tunable van Hove singularities and the localization of states, which are thoroughly discussed in chapter 5 and 6. Once one of these singularities stays at the Fermi level, graphene is predicted to gain intrinsic superconductivity and magnetic properties. This condition can be achieved by reducing the rotation angle towards zero, as these singularities converge to the Dirac point or the Fermi level for undoped graphene. In addition to the intrinsic superconductivity, the localization of states also appears for layers rotated with a small angle, as observed in several STM experiments. Experimentally, we found regions in rotated layers, which appear as periodic Moiré patterns in our STM images. The rotation angles were estimated from the Fast Fourier Transform of the recorded STM images. Comparing our experimental results with tight-binding calculations for disorder-free layers rotated with the same angles leads to a qualitatively good agreement for the positions of van Hove peaks. However, the appearance of new peaks in proximity to the Dirac point for layers rotated with θ=1.5º and a spatial evolution of of spectroscopic features for the small rotation angles cannot be explained by the calculations for disorder-free layers. In order to explain these two phenomena, we considered the influence of disorder. This indeed improved the agreement between theoretical and experimental results. But, since no electronic disorder could be evidenced from our STM images, other explanations, like strain, need to be considered too.