Bandwidth demands in global telecommunication infrastructures continue to rise and new optical techniques are needed to deal with massive data flows. Generating high bandwidth signals (> 40 GHz) using conventional modulation techniques is hindered by material limitations and fabrication complexities. Similarly, controlling such high bandwidths in both the temporal and spectral domain becomes more problematic using conventional electronic processes. Advances in electro-optic organic materials, fibers/micro-fluidics integration, and nonlinear optics have significant potential for higher bandwidth modulation and temporal/spectral control. The work presented in this dissertation demonstrates the use of various nonlinear optical effects in new photonic device and system designs towards the generation and manipulation of highspeed optical pulses. First, an all fiber-based system utilizing an integrated carbon disulfide-filled liquidcore optical fiber (i-LCOF) and co-propagating pulses of comparable temporal lengths is presented. The slow light effect was observed in 1-meter of i-LCOF, where 18 ps pulses were delayed up to 34 ps through the use of stimulated Raman scattering. Delays greater than a pulse width indicate a potential application as an ultrafast controllable delay line for time division multiplexing in multi-Gb/s telecommunication systems. Similarly, an optically tunable frequency shift was observed using this system. Pulses experienced a full spectral bandwidth shift at low peak pump powers when utilizing the Raman-induced frequency shift and slow light effects. Numerical simulations of the pulse-propagation equations agree well with the observed shifts. Included in our simulations are the contributions of both the Raman cross-frequency shift and slow light effects to the overall frequency shift. These results make the system suitable for numerous applications including low power wavelength converters. Second, a silica/electro-optic (EO) polymer phase modulator with an embedded bowtie antenna is proposed for use as a microwave radiation receiver. The detection of high-frequency electromagnetic fields has been heavily studied for wireless data transfer. Recently there has been growing interest in the field of microwave photonics. We present the design and optimization of a waveguide with an EO polymer core and silica/sol-gel cladding. The effect of electrodes on the insertion losses and poling efficiency are also analyzed, and conditions for low-loss and high poling efficiency are established. Experimental results for a fabricated device with microwave-response between 10 - 14 GHz are presented. Finally, we present the design for a fast optical switch incorporating silicon as the passive waveguide structure and EO polymer as the active material. The design uses a simple directional coupler with coplanar electrodes and promises to have low cross-talk and high switching speed (on the order of nanoseconds). An initial design for a 1x2 switch is fabricated and tested, and future optimization processes are also presented.

Two experiments explore the application of plasmonic nanoparticles to cellular pathology. The first devised a platform by which gold-silver nanoparticles act as differentiable labels for cell surface receptors under dark field imaging. By conjugating particles of various constitutions with receptor-targeting antibodies, particles scatter characteristically according to their plasmon peak. The second experiment programmed receptor placement via the patterning of two substrates and used the binding of SERS nanoparticles to explore the quantification of such targets at high-density. On one substrate, anchor pairs established receptors at specified distances in order to define the relationship between scattering intensity and the distance between SERS particles. On the second, anchor regions are filled with increasing densities of receptors and the particle-saturated substrates are probed to relate scattering intensity to particle density. This should discover the density-threshold between linear and non-linear scattering and inform the quantification of particles in the exponential density regime.

Two experiments explore the application of plasmonic nanoparticles to cellular pathology. The first devised a platform by which gold-silver nanoparticles act as differentiable labels for cell surface receptors under dark field imaging. By conjugating particles of various constitutions with receptor-targeting antibodies, particles scatter characteristically according to their plasmon peak. The second experiment programmed receptor placement via the patterning of two substrates and used the binding of SERS nanoparticles to explore the quantification of such targets at high-density. On one substrate, anchor pairs established receptors at specified distances in order to define the relationship between scattering intensity and the distance between SERS particles. On the second, anchor regions are filled with increasing densities of receptors and the particle-saturated substrates are probed to relate scattering intensity to particle density. This should discover the density-threshold between linear and non-linear scattering and inform the quantification of particles in the exponential density regime.

Aseptic loosening of artificial joints is caused by an osteolytic reaction to wear debris mediated by macrophages and other cells. Imaging these wear particles within cells can be a key process in understanding particle-cell interactions. However, the compounds used in surgical implants are not easily visualised as no tagging molecule can be added without altering the properties of the material. We were interested in using a label free optical technique known as coherent anti-Stokes Raman scattering spectroscopy (CARS) to image these particles in cells. In this thesis we studied how to use CARS to image physiologically relevant wear particles within cells. We characterised the responses from our CARS system and found them to be in good agreement to the Raman spectra we obtained for the same materials. We showed that the forward scattered CARS signal was consistently larger than the backwards scattered signal for the same size particles, and also generated a larger contrast, especially between sub-micron sized particles and the non-resonant background. Wear particles of polyethylene isolated from a pin-on-plate wear simulator were shown to be in a similar size range to those retrieved from revision tissue. When incubated in our model macrophage cells we were able to image areas of CARS signal that indicated the location of these particles in the cell. Furthermore, using multiple CARS images taken at different Raman resonances we were able to distinguish between three different polymeric compounds added to cells, showing the specificity of the technique. The inherent 3D sectioning capabilities of multiphoton microscopy were used to generate projected images of the cells and contents, as well as estimating the particle loads within cells. These results show that CARS could be an important tool in imaging intra-cellular polyethylene and characterising the interactions of wear particles with cells and the surrounding tissue.

This thesis is focused on nanofabrication and its application in plasmonic chemical and bio- sensors. The contribution thus is the development of novel nanofabrication techniques and nano- structures for the sensors based on surface plasmon (SP). Part I (Chapter 1-3) is about novel nanofabrication techniques, especially nanoimprint lithography (NIL) and electron beam lithography (EBL). For NIL, the four major aspects of NIL were discussed, including the resist, mold, imprint process and equipment for NIL. Combined with NIL and soft lithography, hybrid nanoimprint-soft lithography was investigated. To overcome the difficulty of mold fabrication, a more robust solution of mold fabrication through a sacrificial poly(dimethyl glutarimide) (PMGI) master mold was designed in this work. Based on this method, the mold was fabricated without structure distortion, and pattern replication with sub-10 nm resolution was demonstrated. For EBL, several aspects were discussed to improve the performance of EBL, including the resist, development, and exposure condition. The charging effect to the pattern distortion was studied systemically for the electron beam exposure in large area with high current (>nA). Tilted periodic nanostructure was achieved by electron beam scanning on tilted sample with dynamic focus mode. EBL on irregular surface was realized by the exposure on evaporated polystyrene. Part II (Chapter 4-6) is the application in surface plasmonic chemical and bio-sensors. The first type of sensors is surface enhanced Raman scattering (SERS) sensor based on localized SP. Bowtie-shape nano-antenna structures of sub-10 nm gap were fabricated with the breakthrough of EBL resolution to 3 nm by exposing resist on Si3N4 membrane. By controlling the gap size during lithography, the surface plasmon enhancement was tuned accurately. High sensitivity of Au bowties antenna with sub-10 nm gap was achieved at low concentration of the target molecule (10^-7 mM, 1,2-di(4-pyridyl)ethylene in ethanol solution) and high enhancement of 10^7 resulting from the corresponding bowtie structure. The second type of sensors is extraordinary optical transmission (EOT) sensor based on propagating SP. The process of double liftoff was developed for the fabrication of nano-hole arrays on 100 nm-thick Au film utilizing EBL. This technique is versatile for the fabrication of many kinds of high-aspect-ratio noble metal structures. Additionally, annealing method was employed in this work to improve the smoothness of Au film. It was found that the RMS roughness of the deposited film was reduced by 72 % and the sensitivity was increased by 32 nm/RIU as a result of annealing. It was also found that the optical transmission intensity of the annealed NHA of similar hole diameter was increased more than twice which is due to the smaller absorption/scattering of the incident light and surface waves from the Au film surface. Besides the double liftoff process, several techniques were developed for EOT structures, including electroplating, imprint method, and deposition on membrane.

<p>There is an urgent need to develop practical and effective systems to detect diseases, such as cancer, infectious diseases and cardiovascular diseases.</p><p>Nanotechnology is a new, maturing field that employs specialized techniques to detect and diagnose infectious diseases. To this end, there have been a wealth of techniques that have shown promising results, with fluorescence and surface-enhanced Raman scattering being two important optical modalities that are utilized extensively. The progress in this specialized niche is staggering and many research groups in academia, as well as governmental and corporate organizations, are avidly pursuing leads which have demonstrated optimistic results.</p><p>Although much fundamental science is still in the pipeline under the guise of both ex-vivo and in-vivo testing, it is ultimately necessary to develop diagnostic devices that are able to impact the greatest number of people possible, in a given population. Such systems make state-of-the-art technology platforms accessible to a large population pool. The development of such technologies provide opportunities for better screening of at-risk patients, more efficient monitoring of disease treatment and tighter surveillance of recurrence. These technologies are also intrinsically low cost, facilitating the large scale screening for disease prevention.</p><p>Fluorescence has long been established as the optical transduction method of choice, because of its wealth of available dyes, simple optical system, and long heritage from pathology. The intrinsic limitations of this technique, however, have given rise to a complementary, and more recent, modality: surface-enhanced Raman scattering (SERS). There has been an explosive interest in this technique for the wealth of information it provides without compromising its narrow spectral width.</p><p>A number of novel studies and advances are successively presented throughout this study, which culminate to an advanced SERS-based platform in the last chapter.</p><p>The finite element method algorithm is critically evaluated against analytical solutions as a potential tool for the numerical modeling of complex, three-dimensional nanostructured geometries. When compared to both the multipole expansion for plane wave excitation, and the Mie-theory with dipole excitation, this algorithm proves to provide more spatially and spectrally accurate results than its alternative, the finite-difference time domain algorithm.</p><p>Extensive studies, both experimental and numerical, on the gold nanostar and Nanowave substrate for determining their potential as SERS substrates, constituted the second part of this thesis. The tuning of the gold nanostar geometry and plasmon band to optimize its SERS properties were demonstrated, and significant 3-D modeling was performed on this exotic shape to correlate its geometry to the solution's exhibited plasmon band peak position and large FWHM. The Nanowave substrate was experimentally revived and its periodic array of E-field hotspots, which was until recently only inferred, was finally demonstrated via complex modeling.</p><p>Novel gold- and silver- coated magnetic nanoparticles were synthesized after extensive tinkering of the experimental conditions. These plasmonics-active magnetic nanoparticles were small and displayed high stability, were easy to synthesize, exhibited a homogeneous distribution, and were easily functionalizable with Raman dye or thiolated molecules.</p><p>Finally, bowtie-shaped cobalt micromagnets were designed, modeled and fabricated to allow the controllable and reproducible concentrating of plasmonics-active magnetic nanoparticles. The external application of an oscillating magnetic field was accompanied by a cycling of the detected SERS signal as the nanoparticles were concentrated and re-dispersed in the laser focal spot. This constituted the first demonstration of magnetic-field modulated SERS; its simplicity of design, fabrication and operation opens doors for its integration into diagnostic devices, such as a digital microfluidic platform, which is another novel concept that is touched upon as the final section of this thesis.</p> / Dissertation

No description available.

No presente trabalho é feito um estudo sistemático do efeito do campo cristalino nas propriedades ópticas do íon Er3+. Para tal propósito utilizamos três diferentes sistemas cristalinos dopados com Er3+: Ortovanadato de cálcio [Ca3(VO4)2], Niobato de lítio [LiNb03] e Titanato de bismuto [Bi12TiO20]. Os cristais foram crescidos no formato de fibras, pela técnica LHPG (Laser Heated Pedestal Growth). O uso deste método de crescimento permitiu não apenas o estudo do efeito do campo cristalino da matriz no Er3+ como também, a influência de diferentes condições crescimento. As composições dos cristais foram determinadas através de EDX (Energy Dispersive X Ray), XPS (X Ray Photoelectron Spectroscopy) e microscopia Auger. As amostras também foram investigadas através de absorção óptica e emissão, incluindo a determinação de seus índices de refração, gap óptico, identificação e análise de várias transições, medidas de emissão dependentes do tempo e da temperatura. A estrutura de todos os cristais foram investigadas pelas técnicas de difração de raios X e espalhamento Raman. Baseados nos resultados experimentais foi possível inferir sobre as regras impostas pelas condições de crescimento nas propriedades finais das fibras cristalinas de Ca3(VO4)2, LilNbO3 e Bi12Ti020 dopados com Er3+. Especificamente relacionado com as fibras cristalinas de Ca3(VO4)2 e LiNBbO3 dopadas com Er3+, a inserção de diferentes pressões de oxigênio molecular, durante o crescimento, induz mudanças significativas na sua estrutura cristalina. A inserção de íons Er3+ na matiz Bi12Ti020 produz uma luminescência fraca, quando comparada a do Ca3(VO4)2 e LiNbO3, porém esta luminescência apresenta um aumento considerável quando as amostras são co-dopada com íons Ga3+ / In this work we performed a systematic study of the crystal field effect on the optical properties of the Er3+ ion. For such a purpose we used three different crystalline Er3+ doped systems: calcium orthovanadate [Ca3(VO4)2, lithium niobate [LiNbO3] and bismuth titanate [Bi12TiO20]. The crystals were grown in the shape of fibers by the Laser Heated Pedestal Growth (LHPG) technique. By using this growth technique it was possible to explore not only the effects of different crystal fields on the Er3+ ion but also, the influence of different growth conditions. The composition of each fiber was determined from EDX (Energy, Dispersive X Ray , analysis), XPS (X Ray Photoelectron Spectroscopy) and Auger microprobe. The fibers were also optically investigated through optical absorption and emission and included the determination of their index of refraction, optical band gap, the identification and analysis of several different transitions, temperature and time-dependent measurements, etc. The structure of all crystals were investigated by X ray diffraction and Raman scattering techniques. Based on these experimental results it was possible to infer the role played by the growth technique and conditions on the final properties of these Er3+ -doped Ca3(VO4)2, LiNbO3 and Bi12Ti020 crystalline fibers. Specifically related to the Er3+ -doped Ca3(VO4)2 and LiNbO3 fibers, different pressures of molecular oxygen, during the groNvt.h., induces significant changes on their atomic (and electronic) structure. The insertion of Er3+ ions in the Bi12Ti020 matrix produces a small photoluminescence intensity, when compared with Ca3(VO4)2 and LINbO3, which is considerably increased by co-doping with Ga3+ ions

Neste trabalho apresentamos um cálculo teórico para o espalhamento Raman eletrônico via flutuações de densidade de spin de uma super-rede &#948-dopada de GaAs. A estrutura eletrônica da super-rede é determinada utilizando-se a teoria do funcional densidade dentro da aproximação de densidade local. O cálculo da seção de choque revela que sob condições de extrema ressonância existe uma forte dependência das formas de linha com a freqüência de excitação indicando a coexistência de um gás bi e tri-dimensional de elétrons nesta estrutura. Os resultados obtidos mostram excelente acordo entre teoria e experimento. / In this work we theoretically investigate the electronic Raman scattering by spin density fluctuations in periodically &#948-doped GaAs. The electronic structure of the superlattice is determined using density functional theory within the local-density-functional approximation. The calculation of the cross section reveals a strong dependence of the line shape on the exciting frequency under conditions of extreme resonance, which indicates the coexistence of a two and three-dimensional electron gas. The results show an excellent agreement between theory and experiment.

O presente trabalho aborda o estudo de correlações entre estrutura e propriedade de uma nova composição de vidros fluorofosfato. O trabalho compreende na síntese e caracterização de vidros fluorofosfatos com a seguinte composição: [80Ba(PO3)2 - 20Al(PO3)3]1-x[80BaF2 - 20AlF3]x(0 &le; x &le; 40 - mol%).Ressonância Magnética Nuclear e Espalhamento Raman são técnicas indicadas no estudo estrutural de materiais amorfos, como por exemplo, os vidros. Através dos resultados obtidos por difração de raios-X (DRX) e análise térmica diferencial (DTA) confirmam a formação de um sólido amorfo com concentrações de íons fluoretos de até 30 mol%. No entanto, a partir dos resultados da quantificação dos íons fluoretos via 19F RMN sugerem que houve uma quantidade significativa de perda de fluoreto ou ainda troca dos íons fluoretos por óxidos. Os espectros de 31P e Raman indicam uma gradual conversão das unidades Q2m em Q1m com o aumento de x. 19F RMN indica que os átomos de flúor estão em dois ambientes químicos distintos, onde os íons fluoretos estão ligados com átomos de fósforo ou distribuídos em um ambiente misto de Al/Ba. Resultados obtidos via 19F{31P}-REDOR confirmam a formação da ligação P-F. Os espectros de 27Al mostram a predominância dos átomos de alumínio com geometria octaédrica e ainda os resultados de 27Al{31P}-REDOR sugerem uma coordenação preferencial dos Al com unidades fosfato. Através dos resultados dos acoplamentos dipolares homonucleares via 31P{31P}-DRENAR corroboram com a deconvolução dos espectros de 31P na atribuição das espécies Q1m e Q2m. / In this work was studied the development of structure/property correlations for new fluorophosphate glasses compositions: [80Ba(PO3)2 - 20Al(PO3)3]1-x[80BaF2 - 20AlF3]x(0 &le; x &le; 40 - mol%). Most suitable techniques for the structural analysis in case of disordered and amorphous material are Nuclear Magnetic Resonance (NMR) Spectroscopy and Raman scattering. Results from X-ray diffraction (XRD) and differential thermal analysis (DTA) reveal that amorphous samples were obtained for all glass compositions up to x &le; 30. However, the fluorine quantification via 19F MAS NMR suggests significant fluoride loss and/or fluoride/oxide replacement. Both 31P and Raman results indicate gradual conversion of Q2m units to Q1m units with increasing the fluorine concentration. 19F MAS NMR spectra indicate fluorine atoms in two different chemical environments bonded wither covalently to P-atoms or located in a mixed Al/Ba environment. The P-F assignment is confirmed by 19F{31P}-REDOR experiments. 27Al NMR spectra shows dominantly six-coordinated aluminium, and the 27Al{31P}-REDOR data suggest nearly exclusive coordination of Al with phosphate species. The dipolar coupling constant obtained by 31P{31P}-DRENAR are roughly consistent with 31P spectral deconvolution suggesting the presence of Q1and Q2 species.