Fabrication and characterization of doped and porous silicon nanowires as anodes for lithium ion batteries

By using Si(100) with different dopant type (n++-type (As) or p-type (B)), it is shown how metal-assisted chemically (MAC) etched silicon nanowires (Si NWs) can form with rough outer surfaces around a solid NW core for p-type NWs, and a unique, defined mesoporous structure for highly doped n-type NWs. High resolution electron microscopy techniques were used to define the characteristic roughening and mesoporous structure within the NWs and how such structures can form due to a judicious choice of carrier concentration and dopant type. Control of roughness and internal mesoporosity is demonstrated during the formation of Si NWs from highly doped n-type Si(100) during electroless etching through a systematic investigation of etching parameters (etching time, AgNO3 concentration, %HF and temperature). Raman scattering measurements of the transverse optical phonon confirm quantum size effects and phonon scattering in mesoporous wires associated with the etching condition, including quantum confinement effects for the nanocrystallites of Si comprising the internal structure of the mesoporous NWs. Laser power heating of NWs confirms phonon confinement and scattering from internal mesoporosity causing reduced thermal conductivity. The Li+ insertion and extraction characteristics at n-type and p-type Si(100) electrodes with different carrier density and doping type are investigated by cyclic voltammetry and constant current measurements. The insertion and extraction potentials are demonstrated to vary with cycling and the occurrence of an activation effect is shown in n-type electrodes where the charge capacity and voltammetric currents are found to be much higher than p-type electrodes. X-ray photo-electron spectroscopy (XPS) and Raman scattering demonstrate that highly doped n-type Si(100) retains Li as a silicide and converts to an amorphous phase as a two-step phase conversion process. The findings show the succinct dependence of Li insertion and extraction processes for uniformly doped Si(100) single crystals and how the doping type and its effect on the semiconductor-solution interface dominate Li insertion and extraction, composition, crystallinity changes and charge capacity. The effect of dopant, doping density and porosity of MAC etched Si NWs are investigated. The CV response is shown to change in area (current density) with increasing NW length and in profile shape with a changing porosity of the Si NWs. The CV response also changes with scan rate indicative of a transition from intercalation or alloying reactions, to pseudocapactive charge storage at higher scan rates and for p-type NWs. SEM and TEM show a change in structure of the NWs after Li insertion and extraction due to expansion and contraction of the Si NWs. Galvanostatic measurements show the cycling behavior and the Coulombic efficiency of the Si NWs in comparison to their bulk counterparts.

Development of block copolymer lithography for device structure fabrication

This thesis investigated well-ordered block copolymer (BCP) thin film characteristics and their use for nanoscale pattern formation using a series of polystyrene-block-polymethylmethacrylate (PS-b-PMMA), polystyrene-blockpolydimethylsiloxane (PS-b-PDMS) and polystyrene-block-poly(ethylene oxide) (PS-b-PEO) systems of various molecular weights. BCP thin films, which act as an ‘on-chip’ etch mask and material templates, are highly promising self-assembling process for future scalable nanolithography. Unlike conventional BCP processing methods, the work in this thesis demonstrates that well-ordered patterns can be achieved in a few seconds compared to several hours by use of a non-conventional microwave assisted technique. As a result, well-ordered BCP nanoscale structures can be developed in industry appropriate periods facilitating their incorporation into current technologies. An optimised and controlled plasma dry etch process was used for successful pattern transfer to the underlying silicon substrate. Long range ordered BCP templates were further modified by selective metal inclusion technique to form a hard mask template towards fabrication of high aspect ratio nanopillars and nanowires. The work described here is centred on how these templates might be used to generate function at substrate surfaces. Herein we describe a number of innovations which might allow their successful uptake in a number of applications.

Plasmonic Nanoparticles and Nanowires: Design, Fabrication and Application in Sensing.

This study involves two aspects of our investigations of plasmonics-active systems: (i) theoretical and simulation studies and (ii) experimental fabrication of plasmonics-active nanostructures. Two types of nanostructures are selected as the model systems for their unique plasmonics properties: (1) nanoparticles and (2) nanowires on substrate. Special focus is devoted to regions where the electromagnetic field is strongly concentrated by the metallic nanostructures or between nanostructures. The theoretical investigations deal with dimers of nanoparticles and nanoshells using a semi-analytical method based on a multipole expansion (ME) and the finite-element method (FEM) in order to determine the electromagnetic enhancement, especially at the interface areas of two adjacent nanoparticles. The experimental study involves the design of plasmonics-active nanowire arrays on substrates that can provide efficient electromagnetic enhancement in regions around and between the nanostructures. Fabrication of these nanowire structures over large chip-scale areas (from a few millimeters to a few centimeters) as well as FDTD simulations to estimate the EM fields between the nanowires are described. The application of these nanowire chips using surface-enhanced Raman scattering (SERS) for detection of chemicals and labeled DNA molecules is described to illustrate the potential of the plasmonics chips for sensing.

Fabrication of Poly (D,L-Lactic-Co-Glycolic Acid) Microparticles for Improved Human Papillomavirus Vaccine Delivery

Human papillomavirus (HPV) is the leading cause of cervical cancer and the most prevalent sexually transmitted disease worldwide. HPV vaccines require a multi-dose regimen to provide immunity, contributing to low patient compliance. We addressed this problem by formulating biodegradable poly(D,L-lactic-co-glycolic acid) (PLGA) microparticles and assessing their viability for use in controlled-release vaccines. We hypothesized that we could alter fabrication parameters to produce 1-10 μm microparticles in order to encapsulate ovalbumin (OVA) and HPV virus-like particles (VLPs). Microparticles were fabricated using a double emulsion method and used to elicit an immune response in JAWSII cells. Our results contribute to knowledge of vaccine delivery mechanisms and controlled-release technology, and could contribute to the creation of a viable controlled-release HPV vaccine.

Multi-physics modelling for the fabrication, packaging and reliability of micro-systems components

The latest advances in multi-physics modelling both using high fidelity techniques and reduced order and behavioural models will be discussed. Particular focus will be given to the application and validation of these techniques for modelling the fabrication, packaging and subsequent reliability of micro-systems based components. The paper will discuss results from a number of research projects with particular emphasis on the techniques being developed in a major UK Goverment funded project - 3D-MINTEGRATION (www.3d-mintegration.com).

Evaluating the process of borosilicate glass capillaries used for fabrication of in-vitro fertilization (IVF) micro-pipettes

In this paper we investigate a number of gas flames for fire polishing borosilicate glass capillaries used in the manufacturing of IVF micro-pipettes. Hydrofluoric acid (HF) was also used as an alternative to finish the pipette end. Glass micro tools in the IVF industry are drawn from hollow glass capillaries of diameter 1 mm. These capillaries are cut manually to a length of 100 mm from hollow glass rods resulting in sharp and chipped edges. These capillaries are held in a customised holder having padding of soft silicone or rubber. Sharp and uneven edges of these capillaries pick up particles of rubber or soft silicone shavings, rendering them ineffective for IVF treatments. The working range of borosilicate glass is 800-1,200 degrees C. The experiments involved analysis of fire polishing process for borosilicate glass capillaries using candle, butane, propane, 2350 butane propane, oxyacetylene gas flames, finding the optimum distance of the capillary relative to the flame, optimum time for which the capillary should be held in the flame and optimum region of the flame which gives the required temperature range. The results show that 2350 butane propane gas mix is optimum for fire polishing of borosilicate glass capillaries. The paper is concluded by comparing the results of fire polishing with the results of acid polishing, in which HF of 1.6% concentration is used to etch the ends of the borosilicate glass pipettes.

Fabrication of Ti-Al coatings by mechanical alloying method

By means of the mechanical alloying (MA) method, Al and Ti + Al coatings were deposited on Ti alloy substrates. During the mechano-activation processing, the substrate surface was impacted by a large number of flying balls along with particles of powder. The repeated ball collisions with the substrate resulted in the deposition of powder on its surface. MA technique produced Ti + Al coating with a thickness of 200 µm and Al one with a thickness of 50 µm after 2 h milling at room temperature. The as-synthesized coatings showed structures with high apparent density and free of porosity. The surface morphology of the MA-coatings was very rough. Annealing treatment led to the leveling of this uneven morphology. Annealing at temperatures ranging between 600 °C and 1100 °C gave different aluminide phases on the samples. In the case of Al coating, Al3Ti and Ti3Al compound were observed upon heating up to 1100 °C. In the case of Ti + Al coating, Al3Ti, Al2Ti, TiAl and Ti3Al were formed on the surface.