Nano-urchin: The formation and structure of high-density spherical clusters of vanadium oxide nanotubes

We report the observation of urchin-like nanostructures consisting of high-density spherical nanotube radial arrays of vanadium oxide nanocomposite, successfully synthesized by a simple chemical route using an ethanolic solution of vanadium tri-isopropoxide and alkyl amine hexadecylamine for 7 days at 180oC. The results show that the growth process of the NanoUrchin occurs in stages, starting with a radial self-organized arrangement of lamina followed by the rolling of the lamina into nanotubes. The longest nanotubes are measured to be several micrometers in length with diameters of ~120 nm and hollow centers typically measured to be ~75 nm. The NanoUrchin have an estimated density of nanotubes of ~40 sr-1. The tube walls comprise layers of vanadium oxide with the organic surfactant intercalated between atomic layers. The interlayer distance is measured to be 2.9 ± 0.1 nm and electron diffraction identified the vanadate phase in the VOx nanocomposite as orthorhombic V2O5. These nanostructures may be used as three-dimensional composite materials and as supports for other materials.

Fabrication, characterisation and electroanalysis at 1-dimensional nanostructures

Integrated nanowire electrodes that permit direct, sensitive and rapid electrochemical based detection of chemical and biological species are a powerful emerging class of sensor devices. As critical dimensions of the electrodes enter the nanoscale, radial analyte diffusion profiles to the electrode dominate with a corresponding enhancement in mass transport, steady-state sigmoidal voltammograms, low depletion of target molecules and faster analysis. To optimise these sensors it is necessary to fully understand the factors that influence performance limits including: electrode geometry, electrode dimensions, electrode separation distances (within nanowire arrays) and diffusional mass transport. Therefore, in this thesis, theoretical simulations of analyte diffusion occurring at a variety of electrode designs were undertaken using Comsol Multiphysics®. Sensor devices were fabricated and corresponding experiments were performed to challenge simulation results. Two approaches for the fabrication and integration of metal nanowire electrodes are presented: Template Electrodeposition and Electron-Beam Lithography. These approaches allow for the fabrication of nanowires which may be subsequently integrated at silicon chip substrates to form fully functional electrochemical devices. Simulated and experimental results were found to be in excellent agreement validating the simulation model. The electrochemical characteristics exhibited by nanowire electrodes fabricated by electronbeam lithography were directly compared against electrochemical performance of a commercial ultra-microdisc electrode. Steady-state cyclic voltammograms in ferrocenemonocarboxylic acid at single ultra-microdisc electrodes were observed at low to medium scan rates (≤ 500 mV.s-1). At nanowires, steady-state responses were observed at ultra-high scan rates (up to 50,000 mV.s-1), thus allowing for much faster analysis (20 ms). Approaches for elucidating faradaic signal without the requirement for background subtraction were also developed. Furthermore, diffusional process occurring at arrays with increasing inter-electrode distance and increasing number of nanowires were explored. Diffusion profiles existing at nanowire arrays were simulated with Comsol Multiphysics®. A range of scan rates were modelled, and experiments were undertaken at 5,000 mV.s-1 since this allows rapid data capture required for, e.g., biomedical, environmental and pharmaceutical diagnostic applications.

High speed optical communication systems: From modulation formats to radically new fibres

High volumes of data traffic along with bandwidth hungry applications, such as cloud computing and video on demand, is driving the core optical communication links closer and closer to their maximum capacity. The research community has clearly identifying the coming approach of the nonlinear Shannon limit for standard single mode fibre [1,2]. It is in this context that the work on modulation formats, contained in Chapter 3 of this thesis, was undertaken. The work investigates the proposed energy-efficient four-dimensional modulation formats. The work begins by studying a new visualisation technique for four dimensional modulation formats, akin to constellation diagrams. The work then carries out one of the first implementations of one such modulation format, polarisation-switched quadrature phase-shift keying (PS-QPSK). This thesis also studies two potential next-generation fibres, few-mode and hollow-core photonic band-gap fibre. Chapter 4 studies ways to experimentally quantify the nonlinearities in few-mode fibre and assess the potential benefits and limitations of such fibres. It carries out detailed experiments to measure the effects of stimulated Brillouin scattering, self-phase modulation and four-wave mixing and compares the results to numerical models, along with capacity limit calculations. Chapter 5 investigates hollow-core photonic band-gap fibre, where such fibres are predicted to have a low-loss minima at a wavelength of 2μm. To benefit from this potential low loss window requires the development of telecoms grade subsystems and components. The chapter will outline some of the development and characterisation of these components. The world's first wavelength division multiplexed (WDM) subsystem directly implemented at 2μm is presented along with WDM transmission over hollow-core photonic band-gap fibre at 2μm. References: [1]P. P. Mitra, J. B. Stark, Nature, 411, 1027-1030, 2001 [2] A. D. Ellis et al., JLT, 28, 423-433, 2010.