The impact of structure on the electrical transport properties of nitrogen-doped carbon microspheres

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. April 2016.Chemical vapour deposition was used to synthesise four carbon microspheres (CMS) samples. Introduction of acetonitrile in different quantities produced spheres of differing nitrogen concentration. The structure of the spheres was investigated using Raman spectroscopy, scanning electron microscopy and X-ray photoelectron spectroscopy techniques. The Raman investigation revealed a decrease in average graphitic flake size which forms the surface layers of the spheres with nitrogen incorporation. XPS showed that increased nitrogen doping caused a larger proportion of pyridinic nitrogen, which process likely restricts the growth of the crystallite flakes detected with the Raman technique. Microscopy revealed spheres with differing morphologies which did not correlated with the level of nitrogen doping. Electron paramagnetic resonance techniques were employed to investigate the impact of nitrogen doping on the spin system of the samples. Electrical transport and Hall effect data were collected with an automated experiment station purpose built for this work. Samples displayed semiconducting behaviour at low temperatures which was ascribed to fluctuation assisted tunnelling. At higher temperatures all four samples display a transition to metallic behaviour. Models for conduction, which were tested but ultimately rejected, include variable range hopping in all its dimensional forms, Efros-Shklovskii VRH and weak localisation. A comparison of the conduction results and the structural information showed the conductivity to be more closely affected by the structure of the spheres than the overall doping level. A case is made for the dominant conduction mechanism being determined by the intersphere rather than the intrasphere conduction. This research shows that creating carbon microspheres with specific electrical properties requires control of the structure induced during synthesis. Nitrogen doping alone does not determine the final physical and electrical transport properties.LG201

The impact of structure on the electrical transport properties of nitrogen-doped carbon microspheres

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. April 2016.Chemical vapour deposition was used to synthesise four carbon microspheres (CMS) samples. Introduction of acetonitrile in different quantities produced spheres of differing nitrogen concentration. The structure of the spheres was investigated using Raman spectroscopy, scanning electron microscopy and X-ray photoelectron spectroscopy techniques. The Raman investigation revealed a decrease in average graphitic flake size which forms the surface layers of the spheres with nitrogen incorporation. XPS showed that increased nitrogen doping caused a larger proportion of pyridinic nitrogen, which process likely restricts the growth of the crystallite flakes detected with the Raman technique. Microscopy revealed spheres with differing morphologies which did not correlated with the level of nitrogen doping. Electron paramagnetic resonance techniques were employed to investigate the impact of nitrogen doping on the spin system of the samples. Electrical transport and Hall effect data were collected with an automated experiment station purpose built for this work. Samples displayed semiconducting behaviour at low temperatures which was ascribed to fluctuation assisted tunnelling. At higher temperatures all four samples display a transition to metallic behaviour. Models for conduction, which were tested but ultimately rejected, include variable range hopping in all its dimensional forms, Efros-Shklovskii VRH and weak localisation. A comparison of the conduction results and the structural information showed the conductivity to be more closely affected by the structure of the spheres than the overall doping level. A case is made for the dominant conduction mechanism being determined by the intersphere rather than the intrasphere conduction. This research shows that creating carbon microspheres with specific electrical properties requires control of the structure induced during synthesis. Nitrogen doping alone does not determine the final physical and electrical transport properties.LG201