Linear and nonlinear propagation of localised plasmon in metallic nanostructures

A major challenge in modern photonics and nano-optics is the diffraction limit of light which does not allow field localisation into regions with dimensions smaller than half the wavelength. Localisation of light into nanoscale regions (beyond its diffraction limit) has applications ranging from the design of optical sensors and measurement techniques with resolutions as high as a few nanometres, to the effective delivery of optical energy into targeted nanoscale regions such as quantum dots, nano-electronic and nano-optical devices. This field has become a major research direction over the last decade. The use of strongly localised surface plasmons in metallic nanostructures is one of the most promising approaches to overcome this problem. Therefore, the aim of this thesis is to investigate the linear and non-linear propagation of surface plasmons in metallic nanostructures. This thesis will focus on two main areas of plasmonic research –– plasmon nanofocusing and plasmon nanoguiding. Plasmon nanofocusing – The main aim of plasmon nanofocusing research is to focus plasmon energy into nanoscale regions using metallic nanostructures and at the same time achieve strong local field enhancement. Various structures for nanofocusing purposes have been proposed and analysed such as sharp metal wedges, tapered metal films on dielectric substrates, tapered metal rods, and dielectric V-grooves in metals. However, a number of important practical issues related to nanofocusing in these structures still remain unclear. Therefore, one of the main aims of this thesis is to address two of the most important of issues which are the coupling efficiency and heating effects of surface plasmons in metallic nanostructures. The method of analysis developed throughout this thesis is a general treatment that can be applied to a diversity of nanofocusing structures, with results shown here for the specific case of sharp metal wedges. Based on the geometrical optics approximation, it is demonstrated that the coupling efficiency from plasmons generated with a metal grating into the nanofocused symmetric or quasi-symmetric modes may vary between ~50% to ~100% depending on the structural parameters. Optimal conditions for nanofocusing with the view to minimise coupling and dissipative losses are also determined and discussed. It is shown that the temperature near the tip of a metal wedge heated by nanosecond plasmonic pulses can increase by several hundred degrees Celsius. This temperature increase is expected to lead to nonlinear effects, self-influence of the focused plasmon, and ultimately self-destruction of the metal tip. This thesis also investigates a different type of nanofocusing structure which consists of a tapered high-index dielectric layer resting on a metal surface. It is shown that the nanofocusing mechanism that occurs in this structure is somewhat different from other structures that have been considered thus far. For example, the surface plasmon experiences significant backreflection and mode transformation at a cut-off thickness. In addition, the reflected plasmon shows negative refraction properties that have not been observed in other nanofocusing structures considered to date. Plasmon nanoguiding – Guiding surface plasmons using metallic nanostructures is important for the development of highly integrated optical components and circuits which are expected to have a superior performance compared to their electronicbased counterparts. A number of different plasmonic waveguides have been considered over the last decade including the recently considered gap and trench plasmon waveguides. The gap and trench plasmon waveguides have proven to be difficult to fabricate. Therefore, this thesis will propose and analyse four different modified gap and trench plasmon waveguides that are expected to be easier to fabricate, and at the same time acquire improved propagation characteristics of the guided mode. In particular, it is demonstrated that the guided modes are significantly screened by the extended metal at the bottom of the structure. This is important for the design of highly integrated optics as it provides the opportunity to place two waveguides close together without significant cross-talk. This thesis also investigates the use of plasmonic nanowires to construct a Fabry-Pérot resonator/interferometer. It is shown that the resonance effect can be achieved with the appropriate resonator length and gap width. Typical quality factors of the Fabry- Pérot cavity are determined and explained in terms of radiative and dissipative losses. The possibility of using a nanowire resonator for the design of plasmonic filters with close to ~100% transmission is also demonstrated. It is expected that the results obtained in this thesis will play a vital role in the development of high resolution near field microscopy and spectroscopy, new measurement techniques and devices for single molecule detection, highly integrated optical devices, and nanobiotechnology devices for diagnostics of living cells.

Two-dimensional coordination polymers in rubidium and caesium complexes with orthanilic acid

The crystal structures of the rubidium and caesium complexes with 2-aminobenzenesulfonic acid (orthanilic acid), [Rb4(C6H6NO3S)4(H2O)]n (1) and [Cs(C6H6NO3S)]n (2) and have been determined at 200 K. Complex 1 has a repeating unit comprising four independent and different Rb coordination centres, (RbO8), (RbO7), (RbN2O4) and (RbO10), each having irregular stereochemistry and involving a number of bidentate chelate sulfonate-O,O’-metal and bridging interactions, giving a two-dimensional polymeric layered structure. Anhydrous complex 2 is also polymeric with the irregular (CsO7) coordination polyhedron comprising six sulfonate oxygen donors from three separate bidentate chelate sulfonate ligands and one monodentate bridging sulfonate oxygen, giving a two-dimensional layered structure.

Near infrared spectroscopy for non-destructive evaluation of articular cartilage

There is a need for an accurate real-time quantitative system that would enhance decision-making in the treatment of osteoarthritis. To achieve this objective, significant research is required that will enable articular cartilage properties to be measured and categorized for health and functionality without the need for laboratory tests involving biopsies for pathological evaluation. Such a system would provide the capability of access to the internal condition of the cartilage matrix and thus extend the vision-based arthroscopy that is currently used beyond the subjective evaluation of surgeons. The system required must be able to non-destructively probe the entire thickness of the cartilage and its immediate subchondral bone layer. In this thesis, near infrared spectroscopy is investigated for the purpose mentioned above. The aim is to relate it to the structure and load bearing properties of the cartilage matrix to the near infrared absorption spectrum and establish functional relationships that will provide objective, quantitative and repeatable categorization of cartilage condition outside the area of visible degradation in a joint. Based on results from traditional mechanical testing, their innovative interpretation and relationship with spectroscopic data, new parameters were developed. These were then evaluated for their consistency in discriminating between healthy viable and degraded cartilage. The mechanical and physico-chemical properties were related to specific regions of the near infrared absorption spectrum that were identified as part of the research conducted for this thesis. The relationships between the tissue's near infrared spectral response and the new parameters were modeled using multivariate statistical techniques based on partial least squares regression (PLSR). With significantly high levels of statistical correlation, the modeled relationships were demonstrated to possess considerable potential in predicting the properties of unknown tissue samples in a quick and non-destructive manner. In order to adapt near infrared spectroscopy for clinical applications, a balance between probe diameter and the number of active transmit-receive optic fibres must be optimized. This was achieved in the course of this research, resulting in an optimal probe configuration that could be adapted for joint tissue evaluation. Furthermore, as a proof-of-concept, a protocol for obtaining the new parameters from the near infrared absorption spectra of cartilage was developed and implemented in a graphical user interface (GUI)-based software, and used to assess cartilage-on-bone samples in vitro. This conceptual implementation has been demonstrated, in part by the individual parametric relationship with the near infrared absorption spectrum, the capacity of the proposed system to facilitate real-time, non-destructive evaluation of cartilage matrix integrity. In summary, the potential of the optical near infrared spectroscopy for evaluating articular cartilage and bone laminate has been demonstrated in this thesis. The approach could have a spin-off for other soft tissues and organs of the body. It builds on the earlier work of the group at QUT, enhancing the near infrared component of the ongoing research on developing a tool for cartilage evaluation that goes beyond visual and subjective methods.

Studies on the surface properties of biodegradable polymer carriers in respiratory delivery of drug from Dry Powder Inhaler formulations

Dry Powder Inhaler (DPI) technology has a significant impact in the treatment of various respiratory disorders. DPI formulations consist of a micronized drug (<5ìm) blended with an inert coarse carrier, for which lactose is widely used to date. DPIs are one of the inhalation devices which are used to target the delivery of drugs to the lungs. Drug delivery via DPI formulations is influenced by the physico-chemical characteristics of lactose particles such as size, shape, surface roughness and adhesional forces. Commercially available DPI formulations, which utilise lactose as the carrier, are not efficient in delivering drug to the lungs. The reasons for this are the surface morphology, adhesional properties and surface roughness of lactose. Despite several attempts to modify lactose, the maximum efficient drug delivery to the lungs remains limited; hence, exploring suitable alternative carriers for DPIs is of paramount importance. Therefore, the objective of the project was to study the performance of spherical polymer microparticles as drug carriers and the factors controlling their performance. This study aimed to use biodegradable polymer microspheres as alternative carriers to lactose in DPIs for achieving efficient drug delivery into the lungs. This project focused on fabricating biodegradable polymer microparticles with reproducible surface morphology and particle shape. The surface characteristics of polymeric carriers and the adhesional forces between the drug and carrier particles were investigated in order to gain a better understanding of their influence on drug dispersion. For this purpose, two biodegradable polymers- polycaprolactone (PCL) and poly (DL-lactide-co-glycolide) (PLGA) were used as the carriers to deliver the anti-asthmatic drug - Salbutamol Sulphate (SS). The first study conducted for this dissertation was the aerosolization of SS from mixtures of SS and PCL or PLGA microparticles. The microparticles were fabricated using an emulsion technique and were characterized by laser diffraction for particle size analysis, Scanning Electron Microscopy (SEM) for surface morphology and X-ray Photoelectron Spectroscopy (XPS) to obtain surface elemental composition. The dispersion of the drug from the DPI formulations was determined by using a Twin Stage Impinger (TSI). The Fine particle Fraction (FPF) of SS from powder mixtures was analyzed by High Performance Liquid Chromatography (HPLC). It was found that the drug did not detach from the surface of PCL microspheres. To overcome this, the microspheres were coated with anti-adherent agents such as magnesium stearate and leucine to improve the dispersion of the drug from the carrier surfaces. It was found that coating the PCL microspheres helped in significantly improving the FPF of SS from the PCL surface. These results were in contrast to the PLGA microspheres which readily allowed detachment of the SS from their surface. However, coating PLGA microspheres with antiadherent agents did not further improve the detachment of the drug from the surface. Thus, the first part of the study demonstrated that the surface-coated PCL microspheres and PLGA microspheres can be potential alternatives to lactose as carriers in DPI formulations; however, there was no significant improvement in the FPF of the drug. The second part of the research studied the influence of the size of the microspheres on the FPF of the drug. For this purpose, four different sizes (25 ìm, 48 ìm, 100 ìm and 150 ìm) of the PCL and PLGA microspheres were fabricated and characterized. The dispersion of the drug from microspheres of different sizes was determined. It was found that as the size of the carrier increased there was a significant increase in the FPF of SS. This study suggested that the size of the carrier plays an important role in the dispersion of the drug from the carrier surface. Subsequent experiments in the third part of the dissertation studied the surface properties of the polymeric carrier. The adhesion forces existing between the drug particle and the polymer surfaces, and the surface roughness of the carriers were quantified using Atomic Force Microscopy (AFM). A direct correlation between adhesion forces and dispersion of the drug from the carrier surface was observed suggesting that adhesion forces play an important role in determining the detachment potential of the drug from the carrier surface. However, no direct relationship between the surface roughness of the PCL or PLGA carrier and the FPF of the drug was observed. In conclusion, the body of work presented in this dissertation demonstrated the potential of coated PCL microspheres and PLGA microspheres to be used in DPI formulations as an alternative carrier to sugar based carriers. The study also emphasized the role of the size of the carrier particles and the forces of interaction prevailing between the drug and the carrier particle surface on the aerosolization performances of the drug.

Water-based exercise for patients with chronic arm lymphedema : a randomized controlled pilot trial

Objective: To evaluate the feasibility and effect of a water-based exercise (WBE) program on lymphedema status and shoulder range of motion (ROM) among women with breast cancer related lymphedema. Design: Single-blinded, randomized controlled pilot trial. Twenty-nine eligible breast cancer survivors (median 10 years after surgery) with arm lymphedema (median 21% inter limb difference) were included and randomized into intervention (n= 15) or control (n=14). Twenty-five participants completed the study. The intervention was at least twice weekly WBE for 8 weeks; supervised initially but performed independently during the study period. Outcomes of interest were feasibility as measured by retention and adherence, lymphedema status as measured by optoelectronic perometry, bioimpedance spectroscopy and tissue dielectric constant, and shoulder range of motion (ROM) as measured by goniometer. Results: Four participants were not measured at post-intervention and were not included in the analysis (retention). Four participants in the intervention group did not perform the minimum WBE criteria set (adherence). No effect was found on lymphedema status. Compared to the control group, median ROM change for flexion was 6 (1-10) degrees (p<0.001) and 6 (0-15.5) degrees (p=0,07) for external rotation. Clinically relevant increase in the intervention group was found for 36% in flexion (p≤0.05) and (57%) in external rotation (p≤0.05) compared to controls. Conclusions: This study shows WBE is feasible for breast cancer survivors with arm lymphedema and that shoulder ROM can be improved years after cancer treatment has been completed.

Characterisation of multi wall carbon nanotube–polymer composites for strain sensing applications

Carbon nanotubes (CNTs) have excellent electrical, mechanical and electromechanical properties. When CNTs are incorporated into polymers, electrically conductive composites with high electrical conductivity at very low CNT content (often below 1% wt CNT) result. Due to the change in electrical properties under mechanical load, carbon nanotube/polymer composites have attracted significant research interest especially due to their potential for application in in-situ monitoring of stress distribution and active control of strain sensing in composite structures or as strain sensors. To sucessfully develop novel devices for such applications, some of the major challenges that need to be overcome include; in-depth understanding of structure-electrical conductivity relationships, response of the composites under changing environmental conditions and piezoresistivity of different types of carbon nanotube/polymer sensing devices. In this thesis, direct current (DC) and alternating current (AC) conductivity of CNT-epoxy composites was investigated. Details of microstructure obtained by scanning electron microscopy were used to link observed electrical properties with structure using equivalent circuit modeling. The role of polymer coatings on macro and micro level electrical conductivity was investigated using atomic force microscopy. Thermal analysis and Raman spectroscopy were used to evaluate the heat flow and deformation of carbon nanotubes embedded in the epoxy, respectively, and related to temperature induced resistivity changes. A comparative assessment of piezoresistivity was conducted using randomly mixed carbon nanotube/epoxy composites, and new concept epoxy- and polyurethane-coated carbon nanotube films. The results indicate that equivalent circuit modelling is a reliable technique for estimating values of the resistance and capacitive components in linear, low aspect ratio-epoxy composites. Using this approach, the dominant role of tunneling resistance in determining the electrical conductivity was confirmed, a result further verified using conductive-atomic force microscopy analysis. Randomly mixed CNT-epoxy composites were found to be highly sensitive to mechanical strain and temperature variation compared to polymer-coated CNT films. In the vicinity of the glass transition temperature, the CNT-epoxy composites exhibited pronounced resistivity peaks. Thermal and Raman spectroscopy analyses indicated that this phenomenon can be attributed to physical aging of the epoxy matrix phase and structural rearrangement of the conductive network induced by matrix expansion. The resistivity of polymercoated CNT composites was mainly dominated by the intrinsic resistivity of CNTs and the CNT junctions, and their linear, weakly temperature sensitive response can be described by a modified Luttinger liquid model. Piezoresistivity of the polymer coated sensors was dominated by break up of the conducting carbon nanotube network and the consequent degradation of nanotube-nanotube contacts while that of the randomly mixed CNT-epoxy composites was determined by tunnelling resistance between neighbouring CNTs. This thesis has demonstrated that it is possible to use microstructure information to develop equivalent circuit models that are capable of representing the electrical conductivity of CNT/epoxy composites accurately. New designs of carbon nanotube based sensing devices, utilising carbon nanotube films as the key functional element, can be used to overcome the high temperature sensitivity of randomly mixed CNT/polymer composites without compromising on desired high strain sensitivity. This concept can be extended to develop large area intelligent CNT based coatings and targeted weak-point specific strain sensors for use in structural health monitoring.

Poly(2-oxazoline) hydrogel monoliths via thiol-ene coupling

Copoly(2-oxazoline)s, prepared by cationic ring-opening polymerization of 2-(dec-9-enyl)-2-oxazoline with either 2-methyl-2-oxazoline or 2-ethyl-2-oxazoline, have been crosslinked with small dithiol molecules under UV-irradiation to form homogeneous networks. In-situ monitoring of the crosslinking reaction by photo-rheology revealed network formation within minutes. The degree of swelling in water was found to be tunable by the hydrophilicity of the starting macromers and the proportion of alkene side arms. Furthermore, degradable hydrogels have been prepared based on a hydrolytically cleavable dithiol crosslinker.

The analogue shear zone : from rheology to associated geometry

The geometry of ductile strain localization phenomena is related to the rheology of the deformed rocks. Both qualitative and quantitative rheological properties of natural rocks have been estimated from finite field structures such as folds and shear zones. We apply physical modelling to investigate the relationship between rheology and the temporal evolution of the width and transversal strain distribution in shear zones, both of which have been used previously as rheological proxies. Geologically relevant materials with well-characterized rheological properties (Newtonian, strain hardening, strain softening, Mohr-Coulomb) are deformed in a shear box and observed with Particle Imaging Velocimetry (PIV). It is shown that the width and strain distribution histories in model shear zones display characteristic finite responses related to material properties as predicted by previous studies. Application of the results to natural shear zones in the field is discussed. An investigation of the impact of 3D boundary conditions in the experiments demonstrates that quantitative methods for estimating rheology from finite natural structures must take these into account carefully.

Auger spectroscopy of stratospheric particles : the influence of aerosols on interplanetary dust

Particle collections from the stratosphere via either the JSC Curatorial Program or the U2 Program (NASA Ames) occur between 16km and 19km altitude and are usually part of ongoing experiments to measure parameters related to the aerosol layer. Fine-grained aerosols (<0.1µm) occur in the stratosphere up to 35km altitude and are concentrated between 15km and 25km altitude[1]. All interplanetary dust particles (IDP's) from these stratospheric collections must pass through this aerosol layer before reaching the collection altitude. The major compounds in this aerosol layer are sulfur rich particulates (<0.1µm) and gases and include H2S04, OCS, S02 and CS2 [2].In order to assess possible surface reactions of interplanetary dust particles (IDP's) with ambient aerosols in the stratosphere, we have initiated a Surface Auger Microprobe (SAM) and electron microscope study of selected particles from the JSC Cosmic Dust Collection.