No description available.

No description available.

No description available.

For graphene to be a viable platform for nanoscale devices, high quality growth and structures are necessary. This means structuring the SiC surface to prevent graphene from having to be patterned using standard microelectronic processes. Presented in this thesis are new processes aimed at improving the graphene as well as devices based on high quality graphene nanoribbons. Amorphous carbon (aC) corrals deposited prior to graphene growth are demonstrated to control SiC step-flow. SiC steps are shown to be aligned by the presence of the corrals and can increase SiC terrace widths. aC contacts deposited and crystallized during graphene growth are shown as a way to contact graphene without metal lift-off. Observation of the Quantum Hall Effect demonstrates the high quality of the graphene grown alongside the nanocrystalline graphite contacts. Continuing the ballistic transport measurements on sidewall graphene nanoribbons, the invasive probe effect is observed using an atomic force microscope (AFM) based technique that spatially maps the invasive probe effect. Cleaning experiments demonstrate the role of scattering due to resist residues and environmental adsorbates on graphene nanoribbons. Finally, switches based on junctions formed in the graphene nanoribbons are shown as a route toward graphene based devices.

Today’s electronic society relies on the functionality of electrical contacts. To achieve good contact properties, surface coatings are normally applied. Such coatings should ideally fulfill a combination of different properties, like high electrical conductivity, high corrosion resistance, high wear resistance and low cost. A common coating strategy is to use noble metals since these do not form insulating surface oxides. However, such coatings are expensive, have poor wear resistance and they are often applied by electroplating, which poses environmental and human health hazards. In this thesis, nanocomposite carbide-based coatings were studied and the aim was to evaluate if they could exhibit properties that were suitable for electrical contacts. Coatings in the Cr-C, Cr-C-Ag and Nb-C systems were deposited by magnetron sputtering using research-based equipment as well as industrial-based equipment designed for high-volume production. To achieve the aim, the microstructure and composition of the coatings were characterized, whereas mechanical, tribological, electrical, electrochemical and optical properties were evaluated. A method to optically measure the amount of carbon was developed. In the Cr-C system, a variety of deposition conditions were explored and amorphous carbide/amorphous carbon (a-C) nanocomposite coatings could be obtained at substrate temperatures up to 500 °C. The amount of a-C was highly dependent on the total carbon content. By co-sputtering with Ag, coatings comprising an amorphous carbide/carbon matrix, with embedded Ag nanoclusters, were obtained. Large numbers of Ag nanoparticles were also found on the surfaces. In the Nb-C system, nanocrystalline carbide/a-C coatings could be deposited. It was found that the nanocomposite coatings formed very thin passive films, consisting of both oxide and a-C. The Cr-C coatings exhibited low hardness and low-friction properties. In electrochemical experiments, the Cr-C coatings exhibited high oxidation resistance. For the Cr-C-Ag coatings, the Ag nanoparticles oxidized at much lower potentials than bulk Ag. Overall, electrical contact resistances for optimized samples were close to noble metal references at low contact load. Thus, the studied coatings were found to have properties that make them suitable for electrical contact applications.

Nanoporous carbons are among the widely studied and promising materials on hydrogen storage for on-board vehicles. However, the nature of nanoporous carbon structures, as well as the relationship between local structure and hydrogen adsorption are still unclear, and hinder the design of carbon materials for optimum hydrogen storage. This dissertation presents a systematic modeling effort of hydrogen storage in nanoporous carbon materials. Tight binding molecular dynamics simulations are utilized to simulate the amorphous carbons over a wide range of density. The resulting structures are in good agreement with experimental data of ultra-microporous carbon (UMC), a wood-based activated carbon, as indicated by a comparison of the microstructure at atomic level, pair distribution function, and pore size distribution. To estimate gas adsorption in complex geometries, an efficient numerical algorithm (based on a continuum gas adsorption model) is developed for calculating the gas uptake at room temperature and moderate pressures. This algorithm is a classical approximation of the quantum mechanical model by Patchkovskii et al.1 and proven to be much faster than other commonly used methods. The gas adsorption calculations in carbon structures from tight-binding simulations demonstrate both a promising hydrogen storage capacity (1.33 wt% at 298K and 5 MPa) and a reasonable heat of adsorption (12-21 kJ/mol). To our knowledge, this is the first work to directly calculate hydrogen adsorption capacity in amorphous carbon. This work demonstrates that increasing the heat of adsorption does not necessarily increase the hydrogen uptake. In fact, the available adsorption volume is as important as the isosteric heat of adsorption for hydrogen storage in nanoporous carbons.

With growing demand for cardiovascular implants, improving the performance of artificial blood-contacting devices is a task that deserves close attention. Current prostheses made of fluorocarbon polymers such as expanded polytetrafluoroethylene (ePTFE) suffer from early thrombosis and require periodic replacement. A great number of attempts have already been made to improve blood compatibility of artificial surfaces, but only few of them found commercial implementation. One of the surfaces under intensive research for cardiovascular use is amorphous carbon-based coatings produced by means of the plasma-assisted deposition. However, this class of coatings can be produced using various techniques leading to a number of coatings with different properties. Carbon coatings produced in different plasmas may be of hard diamond-like type or soft graphite-like type, doping with different elements also changes the surface structure and properties. Taking this into account, the search for blood-compatible coating requires the understanding of surface composition and structure and its influence on blood-compatibility. This work attempts to advance our knowledge of this field. Here, commercial PTFE thin film was used as a working material, which composition corresponds to the composition of modern ePTFE vascular grafts and which compatibility with blood we tried to improve by deposition of nitrogenated amorphous carbon (a-CN) coatings in the plasma. Biocompatibility was assessed by a number of tests including the interaction with whole blood and various cells such as platelets, endothelial cells, neutrophils, and fibroblasts. Most of tests showed the blood compatibility of coated surface is better than that of untreated PTFE. Physico-chemical and morphological properties of coated surfaces were studied in parallel using x-ray photoemission spectroscopy (XPS), electron energy loss spectroscopy (EELS), x-ray absorption spectroscopy (XAS), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM). Some correlation between the structure of coatings and blood compatibility was inferred. It was found that at first nitrogen incorporation into amorphous carbon film stimulates blood compatibility. However, when nitrogen fraction increases over 23-25 %, no further improvement but reduction of blood compatibility was observed. Conclusion is made that for best biomedical performance, nitrogen percentage in a-CN coatings must be adjusted to the optimum value.

Analysis of the electronic structures of nitrogen-doped, amorphous carbon samples and of nanodiamond films are carried out in order to determine their sp2 bonding concentration. The amorphous carbon samples under consideration are deposited onto polytetrafluoroethylene (PTFE) polymer substrates by hot wire plasma sputtering of graphite in varying nitrogen concentration atmospheres. The deposition or modification of the substrates surface may lend itself to increasing hardness and wear resistance. Eventually these polymer substrates may be used for applications in the field of biomaterials, focusing on cardiovascular surgery, where a low blood/surface interaction is important. The primary technique used in this study is x-ray absorption spectroscopy, measured at the Advanced Light Source synchrotron at the Lawrence Berkeley National Laboratory, Berkeley, USA. A method of analyzing these spectra was then developed to determine the sp2 bonding concentrations in carbon films. Through this newly developed analysis method, the sp2 bonding concentrations in these samples increases from 74 to 93% with growing nitrogen doping. The diamond films presented here are deposited on silicon wafer substrates in a methane atmosphere by microwave plasma deposition. Various deposition conditions, such as bias voltage and methane atmosphere concentration, affect the purity of the diamond film. This analysis reveals sp2 bonding concentrations in these samples from, typically, a few percent to 25%.

Analysis of the electronic structures of nitrogen-doped, amorphous carbon samples and of nanodiamond films are carried out in order to determine their sp2 bonding concentration. The amorphous carbon samples under consideration are deposited onto polytetrafluoroethylene (PTFE) polymer substrates by hot wire plasma sputtering of graphite in varying nitrogen concentration atmospheres. The deposition or modification of the substrates surface may lend itself to increasing hardness and wear resistance. Eventually these polymer substrates may be used for applications in the field of biomaterials, focusing on cardiovascular surgery, where a low blood/surface interaction is important. The primary technique used in this study is x-ray absorption spectroscopy, measured at the Advanced Light Source synchrotron at the Lawrence Berkeley National Laboratory, Berkeley, USA. A method of analyzing these spectra was then developed to determine the sp2 bonding concentrations in carbon films. Through this newly developed analysis method, the sp2 bonding concentrations in these samples increases from 74 to 93% with growing nitrogen doping. The diamond films presented here are deposited on silicon wafer substrates in a methane atmosphere by microwave plasma deposition. Various deposition conditions, such as bias voltage and methane atmosphere concentration, affect the purity of the diamond film. This analysis reveals sp2 bonding concentrations in these samples from, typically, a few percent to 25%.

With growing demand for cardiovascular implants, improving the performance of artificial blood-contacting devices is a task that deserves close attention. Current prostheses made of fluorocarbon polymers such as expanded polytetrafluoroethylene (ePTFE) suffer from early thrombosis and require periodic replacement. A great number of attempts have already been made to improve blood compatibility of artificial surfaces, but only few of them found commercial implementation. One of the surfaces under intensive research for cardiovascular use is amorphous carbon-based coatings produced by means of the plasma-assisted deposition. However, this class of coatings can be produced using various techniques leading to a number of coatings with different properties. Carbon coatings produced in different plasmas may be of hard diamond-like type or soft graphite-like type, doping with different elements also changes the surface structure and properties. Taking this into account, the search for blood-compatible coating requires the understanding of surface composition and structure and its influence on blood-compatibility. This work attempts to advance our knowledge of this field. Here, commercial PTFE thin film was used as a working material, which composition corresponds to the composition of modern ePTFE vascular grafts and which compatibility with blood we tried to improve by deposition of nitrogenated amorphous carbon (a-CN) coatings in the plasma. Biocompatibility was assessed by a number of tests including the interaction with whole blood and various cells such as platelets, endothelial cells, neutrophils, and fibroblasts. Most of tests showed the blood compatibility of coated surface is better than that of untreated PTFE. Physico-chemical and morphological properties of coated surfaces were studied in parallel using x-ray photoemission spectroscopy (XPS), electron energy loss spectroscopy (EELS), x-ray absorption spectroscopy (XAS), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM). Some correlation between the structure of coatings and blood compatibility was inferred. It was found that at first nitrogen incorporation into amorphous carbon film stimulates blood compatibility. However, when nitrogen fraction increases over 23-25 %, no further improvement but reduction of blood compatibility was observed. Conclusion is made that for best biomedical performance, nitrogen percentage in a-CN coatings must be adjusted to the optimum value.