Bibliography: leaves 140-151 / 151, [2] leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Mawson Institute, 1989

abstract: Obtaining local electrochemical (EC) information is extremely important for understanding basic surface reactions, and for many applications. Scanning electrochemical microscopy (SECM) can obtain local EC information by scanning a microelectrode across the surface. Although powerful, SECM is slow, the scanning microelectrode may perturb reaction and the measured signal decreases with the size of microelectrode. This thesis demonstrates a new imaging technique based on a principle that is completely different from the conventional EC detection technologies. The technique, referred to as plasmonic-based electrochemical imaging (PECI), images local EC current (both faradaic and non-faradaic) without using a scanning microelectrode. Because PECI response is an optical signal originated from surface plasmon resonance (SPR), PECI is fast and non-invasive and its signal is proportional to incident light intensity, thus does not decrease with the area of interest. A complete theory is developed in this thesis work to describe the relationship between EC current and PECI signal. EC current imaging at various fixed potentials and local cyclic voltammetry methods are developed and demonstrated with real samples. Fast imaging rate (up to 100,000 frames per second) with 0.2×3µm spatial resolution and 0.3 pA detection limit have been achieved. Several PECI applications have been developed to demonstrate the unique strengths of the new imaging technology. For example, trace particles in fingerprint is detected by PECI, a capability that cannot be achieved with the conventional EC technologies. Another example is PECI imaging of EC reaction and interfacial impedance of graphene of different thicknesses. In addition, local square wave voltammetry capability is demonstrated and applied to study local catalytic current of platinum nanoparticle microarray. This thesis also describes a related but different research project that develops a new method to measure surface charge densities of SPR sensor chips, and micro- and nano-particles. A third project of this thesis is to develop a method to expand the conventional SPR detection and imaging technology by including a waveguide mode. This innovation creates a sensitive detection of bulk index of refraction, which overcomes the limitation that the conventional SPR can probe only changes near the sensor surface within ~200 nm. / Dissertation/Thesis / Video for Figure 3.2 C to H / Video for Figure 3.5 / Video for Figure 5.5 / Video for Figure 6.7 / Video for Figure 6.11 / Ph.D. Electrical Engineering 2011

Durant les 15 dernières années, le couplage fort lumière-matière avec des matériaux organiques a attiré un intérêt croissant, notamment à cause des valeurs extrêmes que peut atteindre l'écart énergétique entre les modes couplés dans ces systèmes. Ces modes couplés sont des hybrides lumière-matière, aussi appelés états polaritons et notés habituellement P+ et P-. La valeur de I' écart énergétique entre les modes couplés, également appelé énergie de Rabi-splitting, est provoqué par une transition efficace de dipôle moments entre des molécules et aussi par des cavités ou des plasmons en surface de petits volumes en mode de micro-Fabry-Pérot métalliques (FP) qui sont utilisés dans ces études. Rabi-splittings - 1eV représente souvent une fraction importante de l'énergie de transition électronique, dans ce cas, le système est appelé dans le régime de couplage ultra-forte. Dans ce régime, la physico-chimie des molécules ou des propriétés des matériaux du système couplé peuvent être modifié. En effet, d'effet a déjà été montré sur les voies de relaxation dans le système couplé, les taux de réactions photochimiques, le travail d'extraction et de la conductivité des semi-conducteurs organiques dans l'obscurité, entre autres choses. Une étude récente a pu montrer que l'énergie de l'état non-excité dans une étude thermodynamique peut également être décalée dans le régime de couplage ultra-fort. De plus, le couplage fort ne se limite pas à des transitions électroniques, mais peut aussi être utilisé pour perturber les vibrations de l'état non-excité de molécules dans la région infrarouge. Tous ces résultats montrent que le couplage fort en lumière-molécule a beaucoup de potentiel pour le matériel et la science moléculaire et mérite donc une étude plus approfondie. / Over the past 15 years, light-matter strong coupling involving organic materials has been of increasing interest due to the very large energy splitting such systems exhibit between the two hybrid light-matter states, also known as the polaritonic states typically denoted P+ and P-. The large energy splitting, so-called Rabi splitting, is the result of the high transition dipole moments of the molecules and the small mode volumes of micro-metallic Fabry-Pérot (FP) cavities or surface plasmons used in these studies. Rabi-splittings -1 eV have been observed, often representing a significant fraction of the electronic transition energy in which case the system is said to be in the ultra-strong coupling regime. ln this regime the physical chemistry of molecules or the properties of materials of the coupied system should be modified. lndeed, it has already been shown to affect the relaxation pathways in the coupled system, the rates of photochemical reactions, thework-function and conductivity of organic-semiconductors in the dark, among other things. A recent thermodynamic study demonstrated that the ground state energy can also be shifted in theultra-strong coupling regime. Moreover, the strong coupling is not limited to electronic transitions, but also can be used to perturb the ground-state vibrations of molecules in the infrared region. Ali these results suggest that light-molecule strong coupling has much potential for material and molecular science and therefore merits further study.

Compared with the detector devices made of inorganic semiconductors, organic photodetectors are granted with additional strengths, such as flexibility, high scalability and bio-compatibility. However, in the family of organic optoelectronic devices, the detectors that are capable of detecting photons at two or multiple specific wavelengths are still missing. Such photodetectors are highly interesting because they could identify the target objects or materials much more precisely by detecting the reflected, transmitted or emitted photons at two or multiple characteristic wavelengths. In this thesis project, the optical simulations using Transfer Matrix Method (TMM) were performed on the organic devices to achieve the dual wavelength narrowband detection in the near-infrared (NIR) spectral range of 700 ~ 1100 nm. The devices use the fact that, at the interface of the blended organic electron donating and accepting materials, the charge-transfer (CT) states with the transition energies that are lower than the optical gap of the neat materials are formed. Combined with a Fabry-Perot resonant cavity, the CT absorption can be dramatically enhanced at certain wavelengths. The simulation results show that the two detection wavelengths can be tuned independently from 650 to 1100 nm. The spectral resolution (full with at half maximum - FWHM) of the detection bands varies between 10 and 30 nm. The simulated external quantum efficiency (EQE) is ~35% at 700 nm and ~10% at 1000 nm, respectively. A possible application of such photodetectors is for example moisture detection, where two of the characteristic absorption peaks of water are located at around 750 and 960 nm. By optimizing the thickness of the two photo-absorbing layers in a tandem device structure, the detection bands can be tuned to match with those two wavelengths for simultaneous and precise detection.

[pt] Nanopartículas metálicas apresentam um pico no espectro de absorção devido ao efeito de LSPR (Localized Surface Plasmon Resonance – Ressonância de Plasmon de Superfície Localizado). A posição espectral do pico depende da forma, do tamanho, do material das nanopartículas e do índice de refração do meio em que se encontra. Conhecendo como a posição espectral deste pico varia de acordo com o índice de refração externo, pode-se utilizar, em princípio, estas nanopartículas como elemento sensor para medir a refração de líquidos e gases. Um sensor de índice de refração foi desenvolvido fabricando-se nanopartículas metálicas na extremidade de uma fibra óptica. Estas nanopartículas foram fabricadas a partir de um filme de ouro evaporado na extremidade de uma fibra óptica que depois foi aquecida. As nanopartículas assim formadas possuem uma distribuição não homogênea de forma e tamanho. De forma a se obter um maior controle do tamanho e da forma das nanopartículas metálicas fabricadas para o desenvolvimento de um sensor óptico com maior controle dos parâmetros, foi investigada nesta dissertação a formação de nanopartículas de prata por síntese química. Diferentes processos para a síntese foram investigados. As nanopartículas de prata localizadas na extremidade da fibra óptica foram caracterizadas quanto à resposta do sinal de LSPR quando as nanopartículas estavam em contato com meios com diferentes índices de refração. Visando ainda a investigação de sistemas de fibras ópticas com aplicação em sensoriamento, foi realizada uma simulação da deformação de cavidades elípticas formadas no interior de fibras ópticas quando estas estão sujeitas à aplicação de uma tensão longitudinal da fibra. Este tipo de cavidade pode ser usada como sensor de deformação devido à interferência das múltiplas reflexões no interior da cavidade. / [en] Metallic nanoparticles show a peak in the absorption spectrum due to the Localized Surface Plasmon Resonance (LSPR) effect. The position of this peak depends on the shape, size and the type of the nanoparticles as well as on the refractive index of the surrounding media. From the dependence of the position of the peak with the external refractive index, it is possible to use these nanoparticles as a sensor element to measure the refractive index of liquids and gas. A refractive index sensor was developed with nanoparticles deposited at the end face of an optical fiber. These nanoparticles, fabricated from a heated gold film deposited at the end face of the fiber, have a non homogenous distribution of size and form. In order to obtain a better control of the size and form of the fabricated metallic nanoparticles, aiming the development of an optical sensor with control of the involved parameters, it was investigated in this work the formation of silver nanoparticles by chemical synthesis. Furthermore, extending the investigation of fiber optics systems with applications on sensing, it was performed a simulation of the deformation of elliptical air cavities, formed in the interior of optical fibers, under the effect of longitudinal stress along the fiber. This type of system can be used as a deformation sensor due to the multiple interference reflections in the interior of the cavity.

L’objet de cette thèse de doctorat est la conception et la construction d’une horloge atomique réalisée sur un microcircuit à atomes (TACC) et améliorée par l’intrication. L’élément principal de cette nouvelle expérience est un micro-résonateur Fabry Pérot qui permet la génération d’états de spin comprimés de l'ensemble atomique grâce aux interactions entre la lumière et les atomes. Il a déjà été montré que ces états peuvent améliorer les performances métrologiques des horloges atomiques. Cependant, les expériences ayant permis cette démonstration de principe n'ont pas encore atteint un niveau de précision présentant un intérêt métrologique. C’est précisément l'objectif de la nouvelle configuration expérimentale que nous proposons ici. Afin de conserver la compacité et la stabilité de notre installation, nous avons choisi d’utiliser une cavité Fabry-Pérot fibrée (fibered Fabry-Pérot, FFP) comme résonateur optique, dans lequel les miroirs du résonateur sont réalisés sur la pointe de fibres optiques. Pour répondre aux exigences de notre expérience, une nouvelle génération de résonateurs FFP a été développée au cours de cette thèse, les plus longs réalisés à ce jour. A cette fin, nous avons développé une procédure d’ablation par tirs multiples à l'aide d'un laser CO$_2$ focalisé, qui permet la mise en forme des surfaces de silice fondue avec une précision et une polyvalence sans précédent.L'intégration du résonateur optique au dispositif expérimental TACC nécessite une conception nouvelle du microcircuit à atomes, qui doit permettre le transport du nuage atomique jusqu’au résonateur. Nous présenterons donc la conception et la fabrication de ce microcircuit à atomes. / This thesis describes the conception and construction of an “entanglement-enhanced” trapped atom clock on an atom chip (TACC). The key feature of this new experiment is the integration of two optical Fabry-Pérot micro resonators which enable generation of spin-squeezed states of the atomic ensemble via atom-light interactions and non-destructive detection of the atomic state. It has been shown before that spin-squeezed states can enhance the metrological performance of atomic clocks, but existing proof-of-principle experiments have not yet reached a metrologically relevant level of precision. This is the first goal of the new setup. To retain the compactness and stability of our setup, we chose the optical resonator to be a fiber Fabry-Pérot (FFP) resonator where the resonator mirrors are realized on the tip of optical fibers. To meet the requirements of our experiment, a new generation of FFP resonators was developed in the context of this thesis, demonstrating the longest FFP resonators to date. For this purpose, we developed a “dot milling” procedure using a focused CO2-laser that allows shaping of fused silica surfaces with unprecedented precision and versatility. Incorporating optical resonators in the TACC system requires a new atom chip design, allowing transportation of the atom cloud into the resonator. We present the design and the fabrication of this atom chip. The completed setup will enable investigations of the interplay of spin-dynamics in presence of light mediated correlations and spin-squeezing at a metrologically relevant stability level of $10^{-13}$ at 1 s.

Der Einsatz von Computern, zur unterstützenden Durchführung physikalischer Experimente, gewinnt immer mehr an Bedeutung. Computer, unter anderem auch Personal Computer (kurz PC), können durch ihre heutige Leistungsfähigkeit, immer mehr nützliche Funktionen während eines physikalischen Experimentes übernehmen. Diese Arbeit beschäftigt sich mit dem Vorbereiten eines solchen PC, welcher für die Umsetzung einer Regelschaltung für ein physikalisches Experiment genutzt werden kann. Dazu werden Gentoo-Linux, RTAI, Scilab/Scicos und Comedi verwendet. Besonderer Schwerpunkt der Arbeit ist dabei die Regelung in Echtzeit auszuführen. Im Verlauf der Arbeit werden Hardware- sowie Software-Ansprüche und deren Anpassungen besprochen, so dass alle Voraussetzungen des Experiment-PC, zur Umsetzung eines zuverlässigen Regelprozesses, erfüllt werden. Aus Gründen, welche in dieser Arbeit erläutert werden, wurde der Experiment-PC mit der Open-Source Linux-Distribution namens Gentoo ausgestattet. Zusätzlich verfügt der Experiment-PC über eine Mess- und Steuerkarte, welche es dem Experiment-PC erlaubt Signale aus dem Experiment aufzunehmen und eine entsprechende Regelung, durch die Ausgabe von Signalen, vorzunehmen.

Realising Si-based electrically driven light emitters in a process technology compatible with mainstream microelectronics CMOS technology is key requirement for the implementation of low-cost Si-based optoelectronics and thus one of the big challenges of semiconductor technology. This work has focused on the development of microcavity enhanced silicon LEDs (MCLEDs), including their design, fabrication, and experimental as well as theoretical analysis. As a light emitting layer the abrupt pn-junction of a Si-diode was used, which was fabricated by ion implantation of boron into n-type silicon. Such forward biased pn-junctions exhibit room-temperature EL at a wavelength of 1138 nm with a reasonably high power efficiency of 0.1% [1]. Two MCLEDs emitting light at the resonant wavelength about 1150 nm were demonstrated: a) 1 MCLED with the resonator formed by 90 nm thin metallic CoSi2 mirror at the bottom and semitranparent distributed Bragg reflector (DBR) on the top; b) 5:5 MCLED with the resonator formed by high reflecting DBR at the bottom and semitransparent top DBR. Using the appoach of the 5:5 MCLED with two DBRs the extraction efficiency is enhanced by about 65% compared to the silicon bulk pn-junction diode.:List of Abbreviations and Symbols 1 Introduction and motivation 2 Theory 2.1 Electronic band structure of semiconductors 2.2 Light emitting diodes (LED) 2.2.1 History of LED 2.2.2 Mechanisms of light emission 2.2.3 Electrical properties of LED 2.2.4 LED e ciency 2.3 Si based light emitters 2.4 Microcavity enhanced light emitting pn-diode 2.4.1 Bragg reflectors 2.4.2 Fabry-Perot resonators 2.4.3 Optical mode density and emission enhancement in coplanar Fabry-Perot resonator 2.4.4 Design and optical properties of a Si microcavity LED 3 Preparation and characterisation methods 3.1 Preparation techniques 3.1.1 Thermal oxidation of silicon 3.1.2 Photolithography 3.1.3 Wet chemical cleaning and etching 3.1.4 Ion implantation 3.1.5 Plasma Enhanced Chemical Vapour Deposition (PECVD) of silicon nitride 3.1.6 Magnetron sputter deposition 3.2 Characterization techniques 3.2.1 Variable Angle Spectroscopic Ellipsometry (VASE) 3.2.2 Fourier Transform Infrared Spectroscopy (FTIR) 3.2.3 Microscopy 3.2.4 Electroluminescence and photoluminescence measurements 4 Experiments, results and discussion 4.1 Used substrates 4.1.1 Silicon substrates 4.1.2 Silicon-On-Insulator (SOI) substrates 4.2 Fabrication and characterization of distributed Bragg reflectors 4.2.1 Deposition and characterization of SiO2 4.2.2 Deposition of Si 4.2.3 Distributed Bragg Reflectors (DBR) 4.2.4 Conclusions 4.3 Design of Si pn-junction LED 4.4 Resonant microcavity LED with CoSi2 bottom mirror 4.4.1 Device preparation 4.4.2 Electrical Si diode characteristics 4.4.3 EL spectra 4.4.4 Conclusions 4.5 Si based microcavity LED with two DBRs 4.5.1 Test device 4.5.2 Device fabrication 4.5.3 LED on SOI versus MCLED 4.5.4 Conclusions 5 Summary and outlook 5.1 Summary 5.2 Outlook A Appendix A.1 The parametrization of optical constants A.1.1 Kramers-Kronig relations A.1.2 Forouhi-Bloomer dispersion formula A.1.3 Tauc-Lorentz dispersion formula A.1.4 Sellmeier dispersion formula A.2 Wafer holder List of publications Acknowledgements Declaration / Versicherung

Fabry disease (FD) is an X-linked recessive lysosomal storage disorder (LSD) known to affect approximately 1 in every 40,000 males, and a smaller number of females. FD results from a deficiency of functional α-galactosidase (α-GAL), which leads to the accumulation of terminally α-galactosylated substrates in the lysosome. The predominant treatment is Enzyme Replacement Therapy (ERT), requiring the regular infusion of recombinant human α-GAL. More than half of individuals receiving ERT experience a range of adverse infusion reactions, and it has been reported that as many as 88% of patients receiving ERT develop neutralizing IgG antibodies against the drug. In aim of designing a non-immunogenic treatment candidate for Fabry disease ERT, we have engineered the active sites of α-GAL and another homologous family 27 exoglycosylase named α-N-acetylgalactosaminidase (α-NAGAL) to have interconverted substrate specificities. 11 of 13 active site residues are conserved between these two enzymes, and we have shown that their substrate specificities can be interconverted by mutating the two non-conserved active-site residues. We report the kinetic properties of these two mutants along with wild type controls, and use western blotting to show that both mutant enzymes retain their respective wild type enzyme antigenicity. Structural data obtained by X-ray crystallography on the α-GAL mutant (called α-GALSA ) reveals the mechanism by which substrate specificity is dictated between these two proteins, and provides explanations for the mutant’s reduced catalytic efficiency.

Optofluidics is a relatively new and exciting field that includes the integration of optical waveguides into microfluidic platforms. The purpose of this field of study is to miniaturize previously developed optical systems used for biological and chemical analysis with the end goal of placing bench-top optics into microscopic packages. Mundane optical alignment and sample manipulation procedures would then be intrinsic to the platform and allow measurements to be completed quickly and with reduced human interaction. Biosensors based on AntiResonant Reflecting Optical Waveguides (ARROWs) consist of hollow-core waveguides used for fluid sample manipulation and analysis, as well as solid-core waveguides used in interfacing external components located at the chip edges. Hollow-core ARROWs are particularly useful for their ability to provide specifically tailored analyte volumes that are easily configurable depending upon the target experiment. Adaptations of standard planar microfabrication methods allow for complex integrated ARROW designs. Integrated spectral filtering with high rejection can be implemented on-chip, removing the need for additional off-chip components and increasing device sensitivity. Additional techniques to increase device sensitivity and utility, such as hybrid ARROW platforms and optical manipulation of samples, are also explored.