<p>Ferroelectrics are a group of advanced electronic materialswith a wide variety of properties useful in applications suchas memory devices, resonators and filters, infrared sensors,microelectromechanical systems, and optical waveguides andmodulators. Among the oxide perovskite-structured ferroelectricthin film materials sodium potassium niobate or Na0.5K0.5NbO3(NKN) has recently emerged as one of the most promisingmaterials in microwave applications due to high dielectrictunability and low dielectric loss. This licentiate thesispresents results on growth and structural, optical, andelectrical characterization of Na0.5K0.5NbO3 thin films. Thefilms were deposited by rf-magnetron sputtering of astoichiometric, high density, ceramic Na0.5K0.5NbO3 target ontosingle crystal LaAlO3 and Al2O3, and polycrystalline Pt80Ir20substrates. By x-ray diffractometry, NKN films on c-axisoriented LaAlO3 substrates were found to grow epitaxially,whereas films on hexagonal sapphire and polycrystallinePt80Ir20 substrates were found to be preferentially (00l)oriented. Optical and waveguiding properties of theNa0.5K0.5NbO3/Al2O3 heterostructure were characterized using aprism-coupling technique. Sharp and distinguishable transversemagnetic (TM) and electric (TE) propagation modes wereobserved. The extraordinary and ordinary refractive indiceswere calculated to ne = 2.216±0.003 and no =2.247±0.002 for a 2.0 μm thick film at λ = 632.8nm. This implies a birefringence Δn = ne - no =-0.031±0.003 in the film. The ferroelectric state inNKN/Pt80Ir20 films at room temperature was indicated by apolarization loop with polarization as high as 33.4 μC/cm2at 700 kV/cm, remnant polarization of 9.9 μC/cm2 andcoercive field of 91 kV/cm. Current-voltage characteristics ofvertical Au/NKN/Pt80Ir20 capacitive cells and planar Au/NKN/LaAlO3 interdigital capacitors (IDCs) showed very goodinsulating properties, with the leakage current density for anNKN IDC on the order of 30 nA/cm2 at 400 kV/cm. Rf dielectricspectroscopy demonstrated low loss, low frequency dispersion,and high voltage tunability. At 1 MHz NKN/LaAlO3 showed adissipation factor tan δ of 0.010 and a tunability of 16.5% at 200 kV/cm. For the same structure the frequencydispersion, Δεr, between 1 kHz and 1 MHz was 8.5%.</p><p><b>Key words:</b>ferroelectrics, sodium potassium niobates,thin films, rf-magnetron sputtering, waveguiding, refractiveindex, prism coupling, dielectric tunability</p>

Fotoninis kristalas sudarytas iš medžiagų su skirtingais lūžio rodikliais. Dėl stop juostos valdymas fotoniniame kristale yra diskutuotinas klausimas.Vienas iš metodų valdyti stop juostą, užpildyti jį skystuoju kristalu. užpildant opalą skystuoju kristalu, buvo sukurtas LC defektas. Keičiant elektrinį laiuką, intervale nuo 1V iki 6V, defektą galima valdyti. defekto poslinkis gautas per 4m.defektas opale juda šviesos greičiu 300 000 km/s, o stop juostoje greitis lygus 0m/s. / Photonic crystals (PCs) are periodic dielectric materials that can control the propagation of photons. Control of stop band position in photonic crystals was discussed.A method was developed to adjust the opal stop band position by controlling the refractive index.When filling in the opal LC the result was a LC defect. Changing the electric field wichin the interval from 1 V to 6 V it is possible handle the defect. The movement of the defect was 4nm. The defect in the opal in moving with light speed that is 300 000 km/s and the speed on the bang is 0 m/s.

Chemical detection, including analysis of gases and liquids, is a large field in environmental research and industry. It requires sensitive, rapid, and inexpensive chemical sensors. Many industrial materials such as coatings and adhesives readily absorb chemical analytes, which may result in changes of their chemical, mechanical, and optical properties. This uptake of volatile organic compounds either from the gas phase or from an aqueous solution into a thin film is frequently accompanied by a change in material refractive index and film thickness. While the undesired swelling of thin film coatings and their refractive index changes affect their use in harsh environments, the sensitivity of some polymers to solvent vapours can also be exploited for sensing applications. In this project, a method is reported for real-time monitoring of vapour uptake by simultaneous detection of the refractive index, n, and thickness, d, of thin transparent films with a precision of 10-4 for refractive index and 100 nm for thickness. The setup combines a total internal reflection refractometer with an interferometric imaging method. Two setups using 1550 nm and 635 nm measurement wavelengths were developed, with a detection rate of 1 second per measurement. Two processing methods using a fast Fourier transform algorithm to calculate n and d are applied to the experimental results and compared. Both methods could extract n and d simultaneously from each image captured by the refractometer. The results show that the setup is capable of monitoring film RI and thickness change in real-time. The partitioning of volatile organic compound vapours into polydimethylsiloxane (PDMS) and PDMS-polydiphenylsiloxane (PDPS) copolymers is described. The system is also suited for characterization of other solid and liquid films like SU-8 photoresist and crude oil. It shows great potential in commercial applications of thin film characterization. / Thesis (Master, Electrical & Computer Engineering) -- Queen's University, 2013-09-19 22:21:38.836

The purpose of this thesis is to describe the development of an anatomically based, young adult eye model, which includes a crystalline lens with a gradient refractive index (GRIN). This model will then be used to investigate the effect of laser refractive surgery. The first step in this process involved developing a symmetrical eye model that was found to be a better predictor of empirical longitudinal spherical aberration than any previous model. Myopia was simulated by either a purely axial or refractive technique. While these models were found to be good predictors of the spherical aberration measured in young adults, they did not predict the total amount of high-order aberrations. The techniques used to simulate a single type of myopia caused the myopic models to become anatomically inaccurate. To improve the eye models a biconic surface was used to quantify the anterior corneal shape as a function of myopia. A method to describe the refractive error and biconic shape parameters in Jackson Cross Cylinder terms was implemented to determine correlations. Results indicate that a biconic accurately models the average shape of the anterior corneal surface as a function of myopia. Adopting the biconic model for the anterior corneal surface and adding average misalignments of the ocular components transformed the models from symmetrical to asymmetrical. Refractive error was now simulated by the anatomically accurate changes in both the anterior corneal shape and axial length. The asymmetrical aberrations resulted from the misalignment of the ocular components and provided a good prediction of average empirical aberrations but underestimated the aberrations of individual subjects. Photorefractive keratectomy, a form of laser refractive surgery, was simulated by theoretically calculated and by empirically measured changes in the shape of the anterior corneal surface. Applying the change in anterior corneal shape to the asymmetrical models was used to develop postoperative models. Changes in corneal shape and model aberrations attributed to theoretical calculations do not match empirical observations. The prediction of increased high-order aberrations in postoperative models based on empirically measured changes in the anterior corneal topography was similar to clinical results. Average anatomically based, GRIN eye models have been developed that accurately predict the average aberrations of emmetropic and myopic young adults. These models underestimate the asymmetrical and total high-order aberrations that have been measured in individual subjects but are still useful for investigating the average effects of procedures like refractive surgery.

Over the last three decades, the performance of OLEDs has been improved rapidly, however, as an important assessment for OLED, the EQE data are still quite low. As outlined in the theoretical background, the EQE is the product of out-coupling efficiency and internal quantum efficiency (IQE). Therefore, this thesis focuses on designing two types of polymers with different optical functionalities, to increase the EQE addressing the two aforementioned determining factors. Thus, the first part of the thesis addresses the light out-coupling efficiency in OLED devices. Here high refractive index (HRI) polymers are aimed for as potential material for the out-coupling layer, which are so far scarily reported for application in OLED devices, due to existing limitations, such as limited transparency, extra fluorescence, tedious synthesis, poor thermal stability and low solubility. However, if suitable polymers are becoming easily available, they will offer the unique advantage, compared to low molar mass HRI compounds, of being able to using cost-effective solution based technology for large area film preparation. In addition, polymeric materials will allow to introducing fully new concepts for increasing the light-out-coupling efficiency, like patterning allowing micro-lens preparation, or the incorporation of light scattering particles into the out-coupling layer. The approach described in this thesis is based on a previous work where HRI polymers were prepared via metal-free thiol-yne “A2+B3” polyaddition reaction, which led in an easy one-pot synthesis to hyperbranched polyvinylsulfides of high solubility and already reasonable high RI. For further increasing RI, in this work B3 as well as finally A2 monomers with high naphthalene content were chosen which should, in addition to the positive effect of the sulfur-containing units, render polymers with even higher RI, and hopefully also of high solubility due to the branching. A challenging aspect of this work was to find reaction conditions which allow the preparation of high molar mass as well as highly soluble, highly aromatic polymers by that A2+B3 approach, even so very sterically demanding monomers are used. In addition, the material properties should be fine-tuned by careful selection of the monomer ratio. It was expected that these new, easily available HRI polymers will be of high potential in OLED application. Thus, the work in this part of the thesis comprises on the one hand monomer and polymer synthesis as well as detailed characterization of the structure and the solution and thermal properties of the new materials. But on the other hand, the elucidation of the thin film preparation and the quality and optical properties of the resulting polymer films are major objectives. Finally, evaluation of the performance of the polymer films in an OLED device compared to conventionally low molar mass our-coupling layers was aimed for, which could be realized with the help of partners from the Institute of Applied Photophysics at TU Dresden. For increasing the IQE in OLEDs, this thesis focuses on the development of a new type of polymeric thermally activated delayed fluorescence (TADF) material. TADF materials have the potential of theoretical 100% IQE and are considered as key materials for the next generation of OLEDs. So far, a significant amount of low molar mass TADF molecules has been developed, however, only a limited number of design rules are reported so far for polymers, even though polymers would offer, as already outlined above, significant advantages with regard to processing cost-effectively more efficient OLEDs for large area application. The new concept described in this thesis for TADF polymers is based on a new monomer which exhibits individual promising structural units for achieving TAFD properties but does not emit TADF itself due to its large ΔEST (the energy gap between singlet S1 and triple T1 state). However, it has to be expected that once the monomer is polymerized, the resulting polymeric product will have reduced ΔEST due to the increased conjugation length and thus can be expected to emit TADF. This new concept has the potential to significantly increase the scope of polymeric materials with TADF properties. Thus the second part on the thesis focuses on the design of a new monomer based on carbazole units with a pendant benzophenone moiety and its polymerization and full structural elucidation with the help of model compounds involving intensive NMR and MALDI-TOF analysis. In addition to the expect TADF properties, the benzophenone unit will also provide the possibility for film stabilization and even photopatterning due to photo-crosslinking. Thus the study of film formation and photo-crosslinking of the new TADF polymers was a further objective of this thesis. Finally, first theoretical as well as experimental studies of the photo physical properties of the monomer, a low molar mass model compound and the polymer, again together with the partners from the Institute of Applied Photophysics, should provide evidence on the suitability of the new polymer design principle.

The nonlinear refractive index (n2) of room temperature liquid CS2 in the wavelength range of 9 to 11 micrometers is measured. A line tunable hybrid C02 TEA laser and amplifier system is used for the experiments. In these measurements the well known photoacoustic method is utilized to observe the onset of whole beam self-focusing. The photoacoustic signal in a CS2 cell, much longer than the confocal parameter, is monitored. The departure of the acoustic signal from linear growth marks the critical power for the onset of nonlinearity. It is experimentally verified that the phenomenon is power dependent as expected from self-focusing theory. The value of n2 is then calculated from the theoretical model of self focusing. Measurements of the on-axis irradiance transmitted through the nonlinear material as well as the measurements of beam distortion are used to verify the validity of the photoacoustic method. In all the measurements the on-axis intensity was smaller than the calculated threshold intensity for stimulated Brillouin scattering. The back reflection was monitored to make sure that stimulated Brillouin scattering was not playing a role in the phenomenon.

This thesis describes the work carried out at Brunel University to develop novel optical fibre sensors capable of monitoring the cure state of an epoxy/amine resin system. The sensors were of simple construction, consisting of an optical fibre from which the silicone cladding layer had been removed over a short length. This stripped length was embedded into the curing resin system. The sensor was successfully used in two ways: i) as an evanescent absorption sensor to monitor specific absorption bands of the resin system. The absorption of energy from the evanescent wave of the optical fibre by absorbing media allows evanescent absorption spectra to be obtained. Absorption spectra were obtained from sensors embedded in a model curing resin system over narrow wavelength ranges. These wavelength ranges corresponded to positions of known absorptions in the spectra of active components in epoxy/amine systems. By monitoring the change in these absorptions it was possible to obtain information about concentration of the amine hardener functional group throughout cure; ii) as a refractive index sensor capable of monitoring the changes in the refractive index of the resin system during cure. A laser diode was used to launch light into the sensor and the intensity of light emerging from the other end of the fibre was monitored. Changes in the resin system refractive index caused changes in the guiding properties of this the sensor. This resulted in a significant change in the intensity of light recorded by the detector and allowed the cure process to be followed. This sensor was also embedded into a unidirectional pre-preg system and was able to follow the cure of the system. The results from the two sensing methods have been compared with data obtained using FTIR spectroscopy and Abbe refractometry during the resin system cure. A theoretical model of sensor response has been developed and compared with the experimental data obtained. The sensor response has also been compared to predictions made by several models of evanescent sensor systems obtained from the literature. These models have been modified so that they can be applied to a sensor embedded into a curing resin system. An analysis of the correspondence between theory and experiment is presented.

The objective of this thesis is to develop a sequential algorithm to determine accurately and quickly, at which point in time a product is well mixed or reaches a steady state plateau, in terms of the Refractive Index (RI). An algorithm using sequential non-linear model fitting and prediction is proposed. A simulation study representing typical scenarios in a liquid manufacturing process in pharmaceutical industries was performed to evaluate the proposed algorithm. The data simulated included autocorrelated normal errors and used the Gompertz model. A set of 27 different combinations of the parameters of the Gompertz function were considered. The results from the simulation study suggest that the algorithm is insensitive to the functional form and achieves the goal consistently with least number of time points.

Les métamatériaux sont des matériaux artificiels qui possèdent de nouvelles propriétés optiques grâce à leur structuration à l’échelle nanométrique. Un des principaux axes de recherche dans le domaine des métamatériaux s’intéresse aux indices de réfraction négatifs qui permettent la réalisation de lentilles « parfaites » ainsi que d’autres applications excitantes. Dans cette thèse, nous étudions théoriquement les propriétés de métamatériaux optiques de type « fishnet », en particulier l’origine de leur indice de réfraction négatif, ainsi que d’autres problèmes théoriques associés. La thèse peut être divisée en quatre parties.Dans la première partie, nous étudions la diffusion de la lumière à l’interface entre l’air et un métamatériau fishnet semi-infini. A l’aide d’une méthode numérique vectorielle, nous calculons les coefficients de diffusion de l’interface et nous démontrons que le transport de l’énergie est dû à un seul mode de Bloch, le mode fondamental du fishnet. Puis, en s’appuyant sur les coefficients de diffusion de l’interface et sur l’indice effectif de ce mode de Bloch, nous proposons un nouvel algorithme d’extraction des paramètres effectifs du métamatériau. Notre approche met l’accent sur le rôle clé joué par le mode de Bloch fondamental et elle permet d’extraire des paramètres effectifs plus stables que ceux obtenus avec les méthodes classiques basées sur le calcul de la réflexion et la transmission d’une couche de métamatériau d’épaisseur finie. Dans la deuxième partie, nous dérivons grâce à l’orthogonalité des modes de Bloch des expressions analytiques pour les coefficients de diffusion à l’interface entre deux milieux périodiques de périodes légèrement différentes. Nous montrons que les expressions analytiques permettent d’obtenir des résultats très précis pour différentes géométries allant de guides d’onde périodiques diélectriques à des métamatériaux métalliques. Ces expressions analytiques constituent donc un outil utile pour la conception et l’ingénierie de structures photoniques périodiques.Le mode de Bloch fondamental est central pour expliquer le phénomène de réfraction négative dans les métamatériaux fishnet. Dans la troisième partie, nous avons développé un modèle semi-analytique pour la constante de propagation complexe du mode de Bloch fondamental du fishnet. Le modèle est basé sur une analyse fine de la propagation et de la diffusion de la lumière à l’intérieur de la structure. Le modèle montre que l’origine des valeurs négatives de l’indice de réfraction sur une large bande spectrale peut être essentiellement comprise comme le résultat d’une résonance plasmonique dans les canaux transverses métal-insolant-métal du fishnet. La résonance plasmonique exalte la réponse « magnétique » du fishnet et les pertes associées à cette résonance peuvent être compensées en incluant du gain dans les couches diélectriques. En outre, le modèle simplifie l’ingénierie des paramètres géométriques des métamatériaux fishnet. C’est la résonance plasmonique dans des structures de type métal-isolant-métal (MIM) qui induit l’indice de réfraction négatif dans les métamatériaux de type fishnet. Dans la dernière partie, nous étudions le comportement asymptotique de nanorésonateurs MIM lorsque leur taille est réduite sous la limite de diffraction. En particulier, nous montrons que le facteur de qualité augmente d’un ordre de grandeur quand le volume du résonateur passe de (λ/2n)3 à (λ/50)3. Une étude complète est réalisée avec un modèle Fabry-Perot semi-analytique. Le modèle reste précis sur toute la gamme de tailles étudiées, même dans le régime quasi-statique où des effets de retard ne sont pas attendus. Ce résultat important et contre-intuitif indique que les résonances plasmoniques localisées dans des nanoparticules peuvent être comprises de la même manière que les résonances délocalisées dans des nanofils métalliques, c’est-à-dire comme des problèmes d’antennes basés sur des effets de retard. / Optical metamaterials are artificial media that exhibit new properties from structuring on the nanometric scale. One of the main researches in metamaterials investigates materials with negative refractive index, which can allow the development of perfect lens and other exciting potential applications. In this thesis, we theoretically study the properties of negative-index optical fishnet metamaterials, especially the origin of their negative-valued refractive index, and also associated theoretical problems. The thesis can be divided into 4 parts. In the first part we study the light scattering at an interface between air and a semi-infinite fishnet metamaterial. With a fully-vectorial numerical method, we calculate the scattering coefficients of the interface and find that the energy transport inside the fishnet is due to a single Bloch mode, the fundamental one. Based on the single-interface scattering coefficients and the effective index of this Bloch mode we propose a new algorithm for retrieving effective optical parameters of the metamaterial. The approach emphasizes the key role played by the fundamental Bloch mode and provides retrieved parameters that are more accurate or stable than those obtained by classical methods based only on light reflection and transmission through finite-thickness metamaterial slabs. Due to the importance of the fundamental Bloch mode in the light transport in metamaterials, in the second part, based on the Bloch mode orthogonality we derive closed-form expressions for the scattering coefficients at an interface between two periodic media with slightly different geometrical parameters, which is a computationally demanding electromagnetic problem. We show that the analytical expressions are very accurate for various geometries, including dielectric waveguides and metallic metamaterials. Thus they can be useful for designing and engineering stacks of periodic structures. As shown in the first part, the fundamental Bloch mode is central to explain the negative refraction phenomenon in fishnet metamaterials. In the third part, we derive an accurate semi-analytical model for the complex propagation constant of the fishnet fundamental Bloch mode. This is achieved by analyzing light propagation and scattering inside the fishnet. The model shows that the origin of broad-band negative index of fishnets can be mainly understood as a plasmon resonance in the transversal metal-insulator-metal (MIM) channels. The plasmon resonance enhances the ‘magnetic’ response of fishnet and the losses associated to this resonance can be compensated by including gain in the dielectric layers of the fishnet. Furthermore, the model allows an easy and precise geometrical tailoring of fishnet metamaterials. As shown in the third part, it is the plasmon resonance in metal-insulator-metal (MIM) structures that induces the negative index of fishnet metamaterials. In the last part, we study the asymptotic behavior of 3D MIM nanoresonators, as the resonator size is shrunk below the diffraction limit. In particular we show that the quality factor increases from 10 to 100 when the resonator volume is scaled down from (λ/2n)3 to (λ/50)3. We provide a comprehensive study with a semi-analytical Fabry-Perot model. The model remains accurate over the whole size scale even in the quasi-static regime for which retardation effects are not expected. This important and counterintuitive result indicates that both localized plasmon resonances in nanoparticles and delocalized resonance in elongated plasmonic nanowires can be possibly understood as a wave-retardation based antenna problem.

Neste trabalho investigamos as duas contribuições mais importantes ao índice de refração não-linear, n2, em sólidos dopados: o efeito de Lente Térmica (LT) e o efeito de Lente de População (LP). Nós estudamos cristais fluoretos dopados com Cr+3 e vidros fluoretos dopados com Nd+3. As medidas de n2 foram feitas com a técnica de Z-scan resolvida no tempo, que é uma técnica simples mas muito sensível. Também realizamos medidas usando a técnica de Lente Térmica de modo descasado onde usou-se dois feixes de laser (um de excitação e outro de prova). Nós mostramos que pode-se separar temporalmente as contribuições a n2 devido a LT e LP, através da variação da freqüência do chopper / In this work we investigated the two more important contributions to the index of no-lineal refraction, n2, in ion doped solid: the effects of Thermal Lens (LT) and Population Lens (LP). We studied Cr+3 doped fluoride crystals and Nd+3 doped fluoride glasses. The n2 measurements were made with the time-resolved Z-scan technique that is a simple but very sensitive technique. We also performed time¬ resolved Mode-mismatched Thermal Lens measurements, where two laser beams were used (one excitation beam and another probe beam). We showed that it is possible to temporally separate the contributions of LT and LP for n2, through the variation of the chopper frequency