There is a compelling need to explore different material options as well as device structures to facilitate smooth transistor scaling for higher speed, higher density and lower power. The enormous potential of nanoelectronics, and nanotechnology in general, offers us the possibility of designing devices with added functionality. However, at the same time, the new materials come with their own challenges that need to be overcome. In this work, we have addressed some of these challenges in the context of quasi-2D Silicon, III-V semiconductor and graphene. Bulk Si is the most widely used semiconductor with an indirect bandgap of about 1.1 eV. However, when Si is thinned down to sub-10nm regime, the quasi-2D nature of the system changes the electronic properties of the material significantly due to the strong geometrical confinement. Using a tight-binding study, we show that in addition to the increase in bandgap due to quantization, it is possible to transform the original in direct bandgap to a direct one. The effective masses at different valleys are also shown to vary uniquely in an anisotropic way. This ultra-thin Si, when used as a channel in a double gate MOSFET structure, creates so called “volume in version” which is extensively investigated in this work. It has been found that the both the quantum confinement as well as the gating effect play a significant role in determining the spatial distribution of the charge, which in turn has an important role in the characteristics of transistor. Compound III-V semiconductors, like Inx Ga1-xAs, provide low effective mass and low density of states. This, when coupled with strong confinement in a nanowire channel transistor, leads to the “Ultimate Quantum Capacitance Limit” (UQCL) regime of operation, where only the lowest subband is occupied. In this regime, the channel capacitance is much smaller than the oxide capacitance and hence dominates in the total gate capacitance. It is found that the gate capacitance change qualitatively in the UQCL regime, allowing multi-peak, non-monotonic capacitance-voltage characteristics. It is also shown that in an ideal condition, UQCL provides improved current saturation, on-off ratio and energy-delay product, but a degraded intrinsic gate delay. UQCL shows better immunity towards series resistance effect due to increased channel resistance, but is more prone to interfacial traps. A careful design can provide a better on-off ratio at a given gate delay in UQCL compared to conventional MOSFET scenario. To achieve the full advantages of both FinFET and HEMT in III-V domain, a hybrid structure, called “HFinFET” is proposed which provides excellent on performance like HEMT with good gate control like FinFET. During on state, the carriers in the channel are provided using a delta-doped layer(like HEMT) from the top of a fin-like non-planar channel, and during off state, the gates along the side of the fin(like FinFET) help to pull-off the carriers from the channel. Using an effective mass based coupled Poisson-Schrodinger simulation, the proposed structure is found to outperform the state of the art planar and non-planar MOSFETs. By careful optimization of the gate to source-drain underlap, it is shown that the design window of the device can be increased to meet ITRS projections at similar gate length. In addition, the performance degradation of HFinFET in presence of interface traps has been found to be significantly mitigated by tuning the underlap parameter. Graphene is a popular 2D hexagonal carbon crystal with extraordinary electronic, mechani-cal and chemical properties. However, the zero band gap of grapheme has limited its application in digital electronics. One could create a bandgap in grapheme by making quasi-1D strips, called nanoribbon. However, the bandgap of these nanoribbons depends on the the type of the edge, depending on which, one can obtain either semiconducting or metallic nanoribbon. It has been shown that by the application of an external transverse field along the sides of a nanoribbon, one could not only modulate the magnitude of the bandgap, but also change it from direct to indirect. This could open up interesting possibilities for novel electronic and optoelectronic applications. The asymmetric potential distribution inside the nanoribbon is found to result in such direct to indirect bandgap transition. The corresponding carrier masses are also found to be modulated by the external field, following a transition from a“slow”electron to a“fast” electron and vice-versa. Experimentally, it is difficult to control the bandgap in nanoribbons as precise edge control at nanometer scale is nontrivial. One could also open a bandgap in a bilayer graphene, by the application of vertical electric field, which has raised a lot of interest for digital applications. Using a self-consistent tight binding theory, it is found that, inspite of this bandgap opening, the intrinsic bias dependent electronic structure and the screening effect limit the subthreshold slope of a metal source drain bilayer grapheme transistor at a relatively higher value-much above the Boltzmann limit. This in turn reduces the on-off ratio of the transistor significantly. To overcome this poor on-off ratio problem, a semiconductor source-drain structure has been proposed, where the minority carrier injection from the drain is largely switched off due to the bandgap of the drain. Using a self-consistent Non-Equilibrium Green’s Function(NEGF) approach, the proposed device is found to be extremely promising providing unipolar grapheme devices with large on-off ratio, improved subthreshold slope and better current saturation. At high drain bias, the transport properties of grapheme is extremely intriguing with a number of nontrivial effects. Optical phonons in monolayer grapheme couple with carriers in a much stronger way as compared to a bilayer due to selection rules. However, it is difficult to experimentally probe this through transport measurements in substrate supported grapheme as the surface polar phonons with typical low activation energy dominates the total scattering. However, at large drain field, the carriers obtain sufficient energy to interact with the optical phonons, and create so called ‘hot phonons’ which we have experimentally found to result in a negative differential conductance(NDC). The magnitude of this NDC is found to be much stronger in monolayer than in bilayer, which agrees with theoretical calculations. This NDC has also been shown to be compensated by extra minority carrier injection from drain at large bias resulting in an excellent current saturation through a fundamentally different mechanism as compared to velocity saturation. A transport model has been proposed based on the theory, and the experimental observations are found to be in agreement with the model.

Nanoscience dominates almost all areas of science and technology in the 21st century. Nanoparticles are of fundamental interest since they possess unique size dependent properties (optical, electrical, mechanical, chemical, magnetic etc.), which are quite different from the bulk and the atomic state. The research work presented in the thesis is on the preparation, characterization and studies on Ir, Os and graphene oxide-based systems. Interconnected Ir and Os nanochains are prepared under environmentally friendly conditions in aqueous media and subsequently used as substrates for surface enhanced Raman scaterring studies and also as electrocatalysts for oxygen reduction and formaldehyde oxidation. Ir and IrOx nanostructures are prepared using borohydride at different temperatures. The nature of interaction of heme proteins with IrOx is studied using spectroscopic techniques. Electrochemical studies on reduced graphene oxide include sensing of biomolecules with high sensitivity and oxygen reduction reaction (ORR) in aqueous alkaline medium. rGO is also used as support for anchoring Ir nanoparticles and the catalyst is used for the oxidation of benzyl amines to corresponding imines. The thesis is divided in to seven chapters and details are given below. Chapter 1 gives an introduction about the synthetic strategies and properties of metal nanostructures. This is followed by literature survey on Ir, Os and graphene oxide-based systems relevant to the present study. Aim and scope of the present investigation is given at the end. Chapter 2 discusses the experimental procedures and characterization techniques used in the present study. Chapter 3 involves the preparation, characterization and studies on interconnected Ir nanochains. Assemblies of small sized nanoparticles forming network-like structures have attracted enormous interest and different metal nanoassemblies have been reported using different procedures. Ir3+ reduction is kinetically not a very favourable process and hence there are not many attempts to synthesize Ir-based nanostructures. Assemblies of interconnected Ir nanoparticles have been synthesized in the present studies using borohydride as reducing agent and ascorbic acid as capping agent, at high temperatures. Polyfunctional capping molecules such as ascorbic acid and vitamin P play important role for the formation of network- like Ir nanostructures. Optical properties of the networks are probed using UV-Vis spectroscopy and evolution of coupled plasmon of Ir nanochains at 418 nm (figure 1) is observed. The nanochains are used as substrates for SERS studies while the catalytic activity is followed for the reduction of nitroaromatics. Electrocatalytic activity of Ir nanochains is exemplified using oxygen reduction and formaldehyde oxidation. Ir nanochains show better electrocatalytic activities than nanoparticles as shown in figure 2. Figure 1. Time dependent UV-Vis absorption spectra of Ir nanoparticles recorded at various time intervals of (a) 5; (b) 15; (c) 30 and (d) 60 minutes of reduction of Ir3+ using borohydride and the corresponding TEM images. Figure 2. Polarization curves for oxygen reduction on (i) Ir nanochains and (ii) Ir nanoparticles in (A) 0.5 M H2SO4 and (B) 0.1 M KOH at a scan rate of 0.005 V/s. Rotation speed used is 1000 rpm. Chapter 4 discusses the preparation of Ir and IrOx using borohydride. The reaction temperature determines the product. Various physicochemical, microscopic and spectroscopic techniques have been used to understand the evolution of nanostructures. Borohydride reduces Ir3+ at high temperatures to form high surface area foams, while at 25oC, it results in an alkaline environment that helps in the hydrolysis of the Ir precursor to form IrOx nanoparticles. Porous IrOx is formed when Ir foams are annealed at high temperatures. Water oxidation has been demonstrated using IrOx nanoparticles and foams. Biocompatibility of IrOx is used to study the nature of interaction of heme proteins and the formation of bioconjugates using spectroscopic techniques. IrOx forms bioconjugates with substantial changes observed in secondary and tertiary structures of proteins. Chapter 5 explores the synthesis of interconnected ultrafine Os nanoclusters and the nanostructured materials are used as SERS substrates. Os nanochains are prepared under environmentally friendly conditions using polyfunctional molecules like ascorbic acid and vitamin P as both reducing agent and capping agent in aqueous media. Small sized (1-1.5 nm) Os nanoparticles spontaneously self-assemble to form clusters of few tens of nm that in turn self-organize to form branched nanochains of several microns in size. The as-formed nanochains show surface plasmon absorption in the visible region 540 nm which make them active substrates for surface enhanced Raman scattering (SERS) studies. High SERS activity is observed for fluorescent analyte, rhodamine 6G and non-fluorescent analyte, mercaptopyridine, with different laser excitation sources. Efficient energy transfer from fluorescent R6G dye to Os nanochains is observed based on steady state and time resolved fluorescence measurements.Figure 3. (I) Time dependent UV-Vis absorption spectra of Os nanochains recorded at different time intervals of (a) 5; (b) 7; (c) 15; (d) 30 and (e) 60 minutes. Inset shows the TEM images of Os nanochains after 60 minutes of reduction. (II) SERS spectra of 4-MPy adsorbed on Os nanochains from (a) 1 mM; (b) 10 µM and (c) 1 µM solutions using 514 nm laser excitation. Chapter 6 discusses the studies based on reduced graphene oxide. Reduced graphene oxide (rGO) is explored as electrodes for simultaneous determination of dopamine (DA), ascorbic acid (AA) and uric acid (UA) at low concentrations useful in medical diagnostics (figure 4A). It is also used as metal-free electrocatalyst for ORR (figure 4B). The use of rGO as a support for anchoring Ir nanoparticles is probed and subsequently the Ir/rGO is used as catalyst for direct aerobic oxidation of benzyl amine derivatives to corresponding imines. Chapter 7 describes the summary of the work and scope for further studies. Appendix 1 discusses the preparation of different Ir nanostructures using simple galvanic displacement reaction on copper foil while appendix 2 describes the preparation of different sized Ir nanoparticles and their electrocatalytic activity towards oxygen reduction reaction

Cette thèse présente des mesures de transport électronique dans des systèmes bi-dimensionels et uni-dimensionels à base de graphène sous champ magnétique pulsé (60T). L'objectif de ces travaux consiste à sonder la dynamique des porteurs de charge en modifiant la densité d'états du système par l'application d'un champ magnétique. Une première partie est consacrée à l'étude de l'influence des îlots électrons-trous sur les propriétés de transport du graphène au voisinage du point de neutralité de charge. Nous avons constaté l'apparition de fluctuations de la magnéto-résistance liée à la transition progressive des îlots de taille finie dans le régime quantique lorsque le champ magnétique augmente. Nous avons aussi montré que la variation de l'énergie de Fermi, liée à l'augmentation de la dégénérescence orbitale des niveaux de Landau, est directement responsable d'une modification du ratio entre électrons et trous. Dans une deuxième partie consacrée à l'étude des nanorubans de graphène, nous avons exploré deux gammes de largeur différentes. Dans les rubans larges (W>60nm), la quantification de la résistance a été observée révélant ainsi une signature évidente de la quantification du spectre énergétique en niveaux de Landau. Le confinement magnétique des porteurs de charge sur les bords des nanorubans a permis de mettre en évidence, pour la première fois, la levée de dégénérescence de vallée liée à la configuration armchair du ruban. Pour des rubans plus étroits (W<30nm), en présence de défauts de bord et d'impuretés chargées, la formation progressive des états de bords chiraux donne lieu à une magnéto-conductance positive quelque soit la densité de porteurs. Enfin, la dernière partie traite du magnéto-transport dans le graphene multi-feuillet. En particulier, nous avons observé l'effet Hall quantique dans les systèmes tri-couche de graphène. Une étude comparative des résultats expérimentaux avec des simulations numériques a permis de déterminer l'empilement rhombohedral des trois couches de graphene constituant l'échantillon / This thesis presents transport measurements on two-dimensional and one-dimensional graphene-based systems under pulsed magnetic field (60T). The objective of this work is to probe the dynamics of charge carriers by changing the density of states of the system by applying a strong magnetic field. The first part is devoted to the study of the influence of electron-hole pockets on the transport properties of graphene near the charge neutrality point. We found the appearance of fluctuations in the magneto-resistance due to the progressive transition of the electron/hole puddles of finite size in the quantum regime as the magnetic field increases. We have also shown that the variation of the Fermi energy, due to the increase of orbital Landau level degeneracy, is directly responsible of a change in the electron and hole ratio. The second part is devoted to the study of graphene nano-ribbons, we explored two different ranges of width. In the broad nano-ribbons of width W larger than 60 nm, the quantification of the resistance is observed, revealing a clear signature of the quantization of the energy spectrum into Landau levels. We show for the first time the effect of valley degeneracy lifting induced by the magnetic confinement of charge carriers at the edges of the armchair nano-ribbons. For narrower nano-ribbons (W <30 nm) in presence of edge defects and charged impurities, the progressive formation of chiral edge states leads to a positive magneto-conductance whatever the carrier density. Finally, the last part of this thesis deals with magneto-transport fingerprints in multi-layer graphene as we observed the quantum Hall effect in tri-layer graphene. A comparative study of the experimental results with numerical simulations was used to determine the rhombohedral stacking of three layers of graphene in the sample

[pt] Este trabalho investiga o impacto de suspensões de grafeno funcionalizado sobre reologia de uma dispersão aquosa de Carbopol. Os derivados de grafeno usados foram óxido de grafeno (GO) e óxido de grafeno amino funcionalizado (AFGO). A variação da concentração e do grau de oxidação do grafeno funcionalizado foram avaliadas e relacionadas à reologia das suspensões. O GO foi produzido a partir da síntese de óxido de grafite pelo método de Hummers modificado, e caracterizado pelas técnicas de DRX, Raman, TGA, FTIR, XPS, TEM e AFM. O GO foi funcionalizado com trietilenotetramina por reação assistida por microondas para produzir AFGO, caracterizado por TGA e XPS. As suspensões foram caracterizadas por experimentos de potencial zeta e testes reológicos de escoamento em estado estacionário e oscilatório. A caracterização do GO mostra que grupos funcionais oxigenados foram incorporados em sua superfície grafítica. O GO oxidado por 96 horas (GO 96 h) apresentou maior distância interplanar e também apresentou menos camadas quando comparado com GO oxidado por 2 horas (GO 2 h). A caracterização do AFGO aponta que grupos aminados foram covalentemente ligados às nanofolhas GO e o GO com maior grau de oxidação produziu AFGO com maior nível de aminação. Todas as nanofolhas sintetizadas são coloidalmente estáveis quando suspensas em meio neutro. Todas as suspensões foram bem modeladas pela equação de Hershel-Bulkley. O aumento da concentração de nanofolhas nas suspensões prejudica a microestrutura do fluido e leva a uma diminuição da viscosidade, tensão de escoamento e elasticidade. O GO 96 h promoveu menor decréscimo na viscosidade, tensão de escoamento e elasticidade do que a suspensão GO 2 h. No caso do AFGO, o maior grau de aminação pode levar a uma queda mais pronunciada nas propriedades reológicas da suspensão. Para a suspensão com maior concentração de GO 96 h, observou-se o aparecimento de histerese em baixas taxas de cisalhamento. Esses resultados mostram que pequenas mudanças na superfície das nanofolhas de grafeno funcionalizado podem influenciar as respostas reológicas de um fluido não newtoniano. / [en] This work investigates the impact of functionalized graphene suspensions on the rheology of a Carbopol aqueous dispersion. The graphene derivatives used were graphene oxide (GO) and amino-functionalized graphene oxide (AFGO). The variation of the functionalized graphene concentration and oxidation was evaluated and related with the suspensions rheology. GO nanosheets were produced from synthesis of graphite oxide by modified Hummers method, and they were characterized by XRD, Raman,TGA, FTIR, XPS, TEM and AFM techniques. The GO was functionalized with triethylenetetramine by microwave assisted reaction to produce the AFGO, which was characterized by TGA and XPS techiniques. The suspensions were characterized by zeta potential experiments and rheological tests through steady-state and oscillatory flow. The GO characterization shows that oxygenated functional groups were incorporated in its graphitical surface. GO oxidized for 96 hours (GO 96 h) showed higher interplanar distance and also presented fewer layers when compared with GO oxidized for 2 hours (GO 2 h). The AFGO characterization points out that aminated groups were covalently attached to the GO nanosheets and the GO with a higher oxidation degree produced an AFGO with higher amination level. All synthesized nanosheets are colloidally stable when suspended at neutral media. All suspensions were well modeled by the Hershel-Bulkley equation. The increase of the nanosheets concentration in the suspensions impairs the level of fluid structure and leads to a decrease in viscosity, yield stress, and elasticity. The GO 96 h promoted a lower decrease in viscosity, yield stress and elasticity than the GO 2 h suspension. In the case of AFGO, the greater amination degree can lead to a more pronounced drop in the suspension rheological properties. For the suspension with a higher concentration of GO 96 h, it was observed the appearance of hysteresis at low shear rates. These results show that small changes in the graphene functionalized nanosheets surface can influence the rheological responses of a non-Newtonian fluid.

D. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / In this study, few layer graphene (Gr) and heteroatom graphene (HGr) were synthesized by chemical vapour deposition (CVD) method. Acetylene gas was used as carbon source for the synthesis of graphene, while a mixture of nitrobenzene and dichloromethane (ratio 1:1) were used as both carbon and dopant sources for the synthesis of the heteroatom graphene (HGr). A mixture of argon and nitrogen gases were carefully combined and used as carrier gasses and purge for both the synthesis of graphene and the synthesis of heteroatom graphene. X-ray diffraction (XRD) characterized showed that the as synthesized materials were crystalline materials, Raman spectroscopy indicated that the synthesized materials consist of sp2 hybridized carbon atoms, while scanning electron microscopy (SEM) and atomic force microscopy (AFM) results showed that the synthesized materials possess regions of 2 to 7 nm of thickness. Transmission electron microscopy (TEM) characterization also showed that the synthesized heteroatom graphene possesses about 5 to 7 layers with about 2 nm thickness, and x-ray photoelectron spectroscopy (XPS) result showed the presence of nitrogen, oxygen and chlorine in the lattice of the synthesized heteroatom graphene while the synthesized material still retained about 80% sp2 hybridization. The synthesized materials were used in the fabrication of modified bioelectrodes for electrobiocatalytic biosensing of glucose and hydroquinone. The fabricated bioelectrodes were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The CV characterization showed a diffusion-controlled electrode processes in al modified electrodes, while the EIS characterization showed the presence of both diffusion controlled and kinetic controlled impedance at the electrode-electrolyte interface. The fabricated GC/PEDOT-PSS/HGr/Lac modified bioelectrode exhibited a kinetic controlled impedance of 3150 Ω, while the fabricated GC/PEDOT-PSS/Gr/Lac modified bioelectrode exhibited a kinetic controlled impedance of 4138 Ω. Chronoamperometric experiments showed that the fabricated bioelectrodes exhibited swift electrobiocatalytic activity towards glucose and hydroquinone sensing respectively for graphene and heteroatom graphene. The graphene modified bioelectrode exhibited a linear response of 0.2 to 9.8 mM glucose concentration and a sensitivity of 87.0 μA/mM/cm2, while the heteroatom modified bioelectrode also exhibited a swift response to step by step addition of hydroquinone with a limit of detection of 2.07 μM and dynamic range of 2.07μM to 2.97 mM, thus indicating the tremendous potential of the materials in a wide range of electrobiocatalytic and bioelectronics applications.

No description available.

Like cell to the human body, transistors are the basic building blocks of any electronics circuits. Silicon has been the industries obvious choice for making transistors. Transistors with large size occupy large chip area, consume lots of power and the number of functionalities will be limited due to area constraints. Thus to make the devices smaller, smarter and faster, the transistors are aggressively scaled down in each generation. Moore's law states that the transistors count in any electronic circuits doubles every 18 months. Following this Moore's law, the transistor has already been scaled down to 14 nm. However there are limitations to how much further these transistors can be scaled down. Particularly below 10 nm, these silicon based transistors hit the fundamental limits like loss of gate control, high leakage and various other short channel effects. Thus it is not possible to favor the silicon transistors for future electronics applications. As a result, the research has shifted to new device concepts and device materials alternative to silicon. Carbon is the next abundant element found in the Earth and one of such carbon based nanomaterial is graphene. Graphene when extracted from Graphite, the same material used as the lid in pencil, have a tremendous potential to take future electronics devices to new heights in terms of size, cost and efficiency. Thus after its first experimental discovery of graphene in 2004, graphene has been the leading research area for both academics as well as industries. This dissertation is focused on the analysis and optimization of graphene based circuits for future electronics. The first part of this dissertation considers graphene based transistors for analog/radio frequency (RF) circuits. In this section, a dual gate Graphene Field Effect Transistor (GFET) is considered to build the case study circuits like voltage controlled oscillator (VCO) and low noise amplifier (LNA). The behavioral model of the transistor is modeled in different tools: well accepted EDA (electronic design automation) and a non-EDA based tool i.e. \simscape. This section of the dissertation addresses the application of non-EDA based concepts for the analysis of new device concepts, taking LC-VCO and LNA as a case study circuits. The non-EDA based approach is very handy for a new device material when the concept is not matured and the model files are not readily available from the fab. The results matches very well with that of the EDA tools. The second part of the section considers application of multiswarm optimization (MSO) in an EDA tool to explore the design space for the design of LC-VCO. The VCO provides an oscillation frequency at 2.85 GHz, with phase noise of less than -80 dBc/Hz and power dissipation less than 16 mW. The second part of this dissertation considers graphene nanotube field effect transistors (GNRFET) for the application of digital domain. As a case study, static random access memory (SRAM) hs been design and the results shows a very promising future for GNRFET based SRAM as compared to silicon based transistor SRAM. The power comparison between the two shows that GNRFET based SRAM are 93% more power efficient than the silicon transistor based SRAM at 45 nm. In summary, the dissertation is to expected to aid the state of the art in following ways: 1) A non-EDA based tool has been used to characterize the device and measure the circuit performance. The results well matches to that obtained from the EDA tools. This tool becomes very handy for new device concepts when the simulation needs to be fast and accuracy can be tradeoff with. 2)Since an analog domain lacks well-design design paradigm, as compared to digital domain, this dissertation considers case study circuits to design the circuits and apply optimization. 3) Performance comparison of GNRFET based SRAM to the conventional silicon based SRAM shows that with maturation of the fabrication technology, graphene can be very useful for digital circuits as well.

In this thesis, we have explored the possibilities to realize a Graphene Based Hybrid structures (GBHs) by the functionalization of a graphene layer on both sides. The first chapter gives a general introduction about graphene and a literature review of different metal intercalations on graphene. The second chapter explains the experimental techniques used in this work. In chapter 3, we studied the functionalization of epitaxial graphene on SiC(0001) by gold intercalation. With the help of Scanning Tunneling Microscopy, we have evidenced and characterized different intercalation modes such as the formation of aggregates of individual gold atoms and the formation of a continuous gold layer between the top graphene and the buffer layer. The free standing nature of the intercalated gold atoms was examined by differential charge density plot, projected density of states calculations and further by X-ray photoelectron spectroscopy. The band structure modification of graphene due to these intercalated gold atoms was evidenced by Angle-resolved photoemission spectroscopy, which reveals a strong Van Hove extension and an increase of the Fermi velocity. Extend to this research, to obtain an extended Van Hove singularity usually observed in highly doped graphene; we studied highly electron donor molecules, TetraThioFullvalene (TTF) on pristine and gold intercalated graphene and on graphite (chapter 4). The dependence of charge transfer of these molecules with their conformation and the reactivity of photochromic with conjugated molecules on graphene were also discussed. To understand the structural properties of these molecules photophysical measurements were performed in chapter 5.

Ag is a widely used electrical contact material due to its excellent electrical properties. The problems with Ag are that it is soft and has poor tribological properties (high friction and wear in Ag/Ag sliding contacts). For smart grid applications, friction and wear became increasingly important issues to be improved, due to much higher sliding frequency in the harsh operation environment. The aim of this thesis is to explore several different concepts to improve the properties of Ag electrical contacts for smart grid applications. Bulk Ag-X (X=Al, Sn In) alloys were synthesized by melting of metals. An important result was that the presence of a hcp phase in the alloys significantly reduced friction coefficients and wear rates compared to Ag. This was explained by a sliding-induced reorientation of easy-shearing planes in the hexagonal structure. The Ag-In system showed the best combination of properties for potential use in future contact applications.  This thesis has also demonstrated the strength of a combinatorial approach as a high-throughput method to rapidly screen Ag-based alloy coatings. It was also used for a rapid identification of optimal deposition parameters for reactive sputtering of a complex AgFeO2 oxide with narrow synthesis window. A new and rapid process was developed to grow low frictional AgI coatings and a novel designed microstructure of nanoporous Ag filled with AgI (n-porous Ag/AgI) using a solution chemical method was also explored. The AgI coatings exhibited low friction coefficient and acceptable contact resistance. However, under very harsh conditions, their lifetime is too short. The initial tribotests showed high friction coefficient of the n-porous Ag/AgI coating, indicating an issue regarding its mechanical integrity. The use of graphene as a solid lubricant in sliding electrical contacts was investigated as well. The results show that graphene is an excellent solid lubricant in Ag-based contacts. Furthermore, the lubricating effect was found to be dependent on chemical composition of the counter surface. As an alternative lubricant, graphene oxide is cheaper and easier to produce. Preliminary tests with graphene oxide showed a similar frictional behavior as graphene suggesting a potential use of this material as lubricant in Ag contacts.

In this thesis, graphene (i.e. monolayer carbon film) and carbon clusters supported on a transition metal surface are systematically studied by local probe techniques, with respect to their structures, electronic properties and formation mechanisms. The main tools used are low-temperature scanning tunnelling microscopy and spectroscopy (STM and STS), which are introduced in Chapter 2. The mechanism of the resonance tunnelling at electron energies higher than the work function of the surface is discussed in detail, and a qualitative explanation of the Gundlach oscillations in the corresponding spectroscopy is presented. Epitaxial graphene synthesised on the Rh(111) surface by ethylene dehydrogenation is investigated by STM in Chapter 4. Such carbon film exhibits a hexagonal Moiré pattern due to a lattice mismatch between graphene and the rhodium substrate. The periodicity and local registries of the graphene/Rh(111) superstructure are carefully analysed. Based on a thorough discussion about the “commensurate vs. incommensurate” nature of the Moiré pattern in surface science field, the graphene/Rh(111) system is identified to have a non-simple-commensurate superstructure. The surface electronic properties and geometric buckling of graphene/Rh(111) are investigated by resonance tunnelling spectroscopy (RTS) and density functional theory (DFT) calculations in Chapter 5. Spectroscopy measurements reveal a modulation of the electronic surface potential (or work function Φ) across the supercell of epitaxial graphene. Based on the microscopy/spectroscopy data and the extended DFT calculations, we examined the electronic coupling of the various local C-Rh registries, and identified both experimentally and theoretically the local atomic configurations of maximum and minimum chemical bonding between graphene and the rhodium substrate. We studied in Chapter 6 the growth mechanism of graphene on Rh(111) at elevated temperatures. This part starts by investigating the dehydrogenation of ethylene into ethylidyne. When the dehydrogenation process is complete, monodispersed carbon species, identified as 7C6, are found to dominate the cluster population on the rhodium terraces. A significant coalescence of the 7C6 clusters into graphene islands occurs at temperatures higher than 873 K. The structural and electronic properties of the 7C6 carbon clusters are examined by high-resolution STM and STS, and compared with coronene molecules, i.e. the hydrogenated analogues of 7C6. DFT calculations are further used to explain the stability of 7C6 supported on the Rh(111) surface, and also the structural characteristics of such magic-sized carbon clusters.