Este trabalho apresenta um método desenvolvido pela autora para, através de simulações multifísicas pelo Método dos Elementos Finitos (MEF), servir como ferramenta de apoio ao projeto e fabricação de guias de onda e moduladores eletro-ópticos em óptica integrada, além de possibilitar a análise da performance de moduladores eletro-ópticos. A técnica adotada para a fabricação dos guias de onda ópticos foi a de tensão mecânica. Os parâmetros de geometria (espessura do filme e larguras das trincheiras) e de temperatura de deposição do filme são definidos nas simulações e utilizados no processo de fabricação de guias de ondas em óptica integrada, que servem de base para a fabricação de moduladores eletro-ópticos em substrato cristalino de retículo cúbico. As trincheiras dos guias de onda do tipo canal são construídas em Germanato de Bismuto (BGO - Bi4Ge3O12), a partir da deposição sobre o substrato de um filme fino indutor de tensão mecânica (stress) Nitreto de Silício (Si3N4) e definidas pelos processos de litografia óptica e corrosão seletiva por plasma. Os moduladores são obtidos através da deposição dos eletrodos de alumínio sobre o filme, seguida de Si3N4 dos processos de litografia óptica e corrosão, obtendo-se eletrodos. O processo iterativo proposto inicia-se com os resultados das simulações, em que são definidos os parâmetros de fabricação do filme, da trincheira e dos eletrodos. Após a fabricação desses elementos, o componente é caracterizado e são medidos os parâmetros reais filme e do substrato. Esses valores são realimentados nas simulações para refinar o projeto do componente. O trabalho, além de apresentar todos os passos do processo interativo de simulações, projeto, fabricação e caracterização do componente desejado, indica as dificuldades encontradas na implementação do processo e as atividades futuras a serem desenvolvidas para o aperfeiçoamento do mesmo. / This work presents a method developed by the author to support the project and fabrication of integrated optic waveguides and electro-optic modulators by means of Finite Element Method (FEM) multiphysics simulations, also enabling the electro-optic modulators performance analysis. The technique used for fabricating the optical waveguides was the thermally induced residual stress (ISS). The geometry parameters (film thicknesses and trenches widths) and the film deposition temperature are obtained in the simulations and subsequently used in the integrated optical waveguides fabrication process, which serve as a basic building block for the electrooptic modulators on crystalline cubic lattice substrate. The channel waveguide trenches are built on Bismuth Germanate (BGO Bi4Ge3O12) by depositing a Silicon Nitride (Si3N4) Stress-inducing thin film, being later defined by optical lithography and plasma etching process. Modulators are obtained depositing aluminum on the Si3N4 film followed by the optical lithography and corrosion process, defining electrodes. The proposed iterative process starts with the simulation results that define the fabrication parameters of the film, trench and electrodes. After the fabrication of these elements, the device is characterized and the actual parameters of the film and substrate are measured. These values are fed back into the simulations to refine the component design. The work besides presenting all the simulation-design-fabrication-characterization iterative process for obtaining the devised device also highlights the difficulties encountered in the implementation process along with suggestions of future activities aiming at improving it.

Am Beispiel von ferroelektrischen Systemen auf Bismut-Basis (Bismutmolybdat, Bismutwolframat und Bismuttitanat) und von Strontiumbariumniobat werden neue Möglichkeiten zur Synthese solcher Nanopartikel aufgezeigt. Die Integration der Nanopartikel in transparente Nanokompositmaterialien und die Entwicklung neuer Precursoren für die Herstellung von Dünnschichtproben gehen den Untersuchungen zur Anwendung als elektrooptische aktive Materialien voraus. Durch weitere Anwendungsmöglichkeiten in der Photokatalyse, dem Test dampfadsorptiver Eigenschaften mit Hilfe eines neuartigen Adsorptionstesters (Infrasorb) und auch mit Hilfe der Ergebnisse der ferroelektrischen Charakterisierung von gesinterten Probenkörpern aus einem Spark-Plasma-Prozess wird ein gesamtheitlicher Überblick über die vielfältigen Aspekte in der Arbeit mit nanoskaligen, ferroelektrischen Materialien gegeben.

Made available in DSpace on 2016-06-02T20:16:51Z (GMT). No. of bitstreams: 1 5339.pdf: 3033412 bytes, checksum: 3e684081236853aacfacccef70bd4635 (MD5) Previous issue date: 2009-10-02 / Financiadora de Estudos e Projetos / Lead titanate zirconate modified with lanthanum, or PLZT, is one the most ferroelectric compounds utilized in electronic devices, due to its versatility and low production costs in comparison with single-crystalline materials. When adequately prepared, this system presents good optical (high optical transmission) properties, in the visible and near infrared range, and can be electro-optically characterized. Recently, in the end of 90 s, it was verified its high potential as host of photoluminescent ions, as the lanthanide (rare-earth) family. The possibility to use its electro-optic properties (due to its ferroelectric characteristics) and its photoluminescent properties (achieved by the doping process) together ,enlarges the range of application of this system. In this way, the electro-optical characterization of doped PLZT ceramics becomes essential, besides the photonic characterization. In this work, the Senarmont compensator method for electro-optical characterization, or dynamic method, was instrumented, and the values of the induced (due to the quadratic electrooptic effect, Kerr) and permanent (due to the linear electro-optic effect, Pockels) birefringence were determined as a function of the temperature, wave-length and electric-field frequency, of the rare-earth (Nd2O3, Ho2O3, Er2O3, Tm2O3 e Yb2O3) doped PLZT, with La/Zr/Ti=9/65/35, ceramics. The results shown a relationship between of the electro-optic (electro-optic coefficients, or birefringence values) and the dielectric, ferroelectric and structural properties (studied in others works) of the ceramics, that were related with the site occupancy and the structural defects due to the aliovalent dopant. It also can be identified two distinct birefringence dependence as a function of the electric field, for the same electro-optic effect (Kerr, or Pockels), identified as a function of the doping process. In the case of electro-optical characterizations in function of the variable frequency, was observed an agreement with the characterization ferroelectric results made in other works in GCFerr, being evidenced the reduction of electro-optical properties with increasing frequency, where if it observed the occurrence of anomalies in the Pockels response with direct influence on the response Kerr. The characterization as a function of wavelength showed the occurrence of two types of behavior depending on the dopant ion used, being one of them the reduction of the values of birefringence with increasing wavelength (the samples pure and doped ions neodymium (Nd) and ytterbium (Yb)), with a tendency to expected behavior in the literature, however, in the second was seen irregular increase birefringence with increase wavelength (for samples doped with ions holmio ( Ho), erbium (Er) and thulium (Tm),not existing relation with to the theoretical models adopted. In relation the characterization as a function of temperature, this was carried through in a temperature interval that understood the characteristic temperatures of systems relaxores (freezing temperature (TF), the maximum dielectric permittivity (TM (e)) and Burns (TB)), except for the sample doped with neodymium ions, whose freezing temperature is below interval worked. By the curve of birefringence (Δn) as a function of temperature was possible to determine the temperature of maximum birefringence for each of the samples, correlated them with each other. Through the curve (d Δn / dt) vs. T was possible to identify a relationship between the maximum variations, positive and negative birefringence with the temperature characteristics TF and TB. / Entre os sistemas ferroelétricos, o sistema titanato zirconato de chumbo modificado com lantânio (PLZT) é um dos mais amplamente utilizados em dispositivos eletrônicos, dada sua versatilidade em aplicações e relação de custo quando comparado aos materiais monocristalinos utilizados nessa mesma área. Quando preparado pelo devido método de síntese, apresenta excelentes propriedades óticas (altos valores de transmissão ótica) desde a região do visível ao infravermelho próximo, possibilitando uma adequada caracterização de suas propriedades óticas e eletro-óticas. Recentemente, a partir do final da década de 90, foi verificada sua alta potencialidade como matriz hospedeira para íons fotoluminescentes, como os da família dos lantanídeos (ou terras-raras). A possibilidade do uso conjunto das propriedades eletro-óticas (dado seu caráter ferroelétrico) e de suas propriedades luminescentes (devido à incorporação de dopantes laser-ativos) aumentou ainda mais a possibilidade de aplicação desses materiais. Desse modo, a caracterização eletro-ótica das cerâmicas de PLZT dopado torna-se indispensável, além de sua caracterização fotônica. Sendo assim, neste trabalho foi instrumentado um sistema de caracterização eletro-ótica, utilizando o método do compensador Senarmont, também conhecido como método dinâmico, para determinar os valores da birrefringência induzida (devido ao efeito eletro-ótico quadrático, Kerr) e a permanente (devido ao efeito eletro-ótico linear, Pockels) em função da temperatura, comprimento de onda e frequência do campo elétrico de prova para composições cerâmicas de PLZT na razão La/Zr/Ti=9/65/35, dopadas com os óxidos terras-raras Nd2O3, Ho2O3, Er2O3, Tm2O3 e Yb2O3, na quantidade de 1,0% em peso. Os resultados mostraram que há uma relação entre as propriedades eletro-óticas encontradas (seja na forma de valores dos coeficientes eletro-óticos, ou na variação da birrefringência) com as propriedades dielétricas, ferroelétricas e estruturais (já observadas em outros trabalhos do grupo de pesquisa no qual esta dissertação foi realizada) das cerâmicas que, por sua vez, foram relacionadas com o tipo de ocupação e de defeitos gerados devido à incorporação dos dopantes. Além disso, foi possível observar que para uma mesma composição pode ocorrer a presença dos dois tipos de efeitos eletro-óticos - Kerr e Pockels - com proporções distintas em função do tipo de dopante. Através desse método, para esse conjunto de amostras, também foi possível identificar dois tipos distintos de variações da birrefringência em função do campo elétrico para um mesmo efeito eletro-ótico (Kerr, ou Pockels), que também puderam ser associados com o tipo de ocupação dos dopantes. Em se tratando das caracterizações eletro-óticas em função da variável frequência, foi observada uma concordância com os resultados da caracterização ferroelétrica, realizada em outros trabalhos no GCFErr, sendo evidenciada a redução das propriedades eletro-óticas com o aumento da frequência, em que se observou a ocorrência de anomalias na resposta Pockels com influência direta na resposta Kerr. A caracterização como uma função do comprimento de onda mostrou a ocorrência de dois tipos de comportamentos, dependendo do íon dopante utilizado, sendo um deles a redução dos valores da birrefringência com o aumento do comprimento de onda (caso das amostras pura e dopadas com os íons neodímio (Nd) e itérbio (Yb)), havendo certa tendência ao comportamento previsto em literatura, no entanto, no segundo caso foi constatado o aumento irregular da birrefringência com o aumento do comprimento de onda (caso das amostras dopadas com os íons holmio (Ho), érbio (Er) e túlio (Tm), não havendo relação com os modelos teóricos adotados. Quanto à caracterização em função da temperatura, esta foi realizada em um range de que compreendeu as temperaturas características de sistemas relaxores (de freezing (TF(e)), máxima permissividade dielétrica (TM(e)) e Burns (TB(e))), exceto para a amostra dopada com o íon neodímio, cuja TF(e) estava abaixo do intervalo considerado. Através da curva de birrefringência (Δn) em função da temperatura foi possível determinar a temperatura de máxima birrefringência para cada uma das amostras, correlacionado-as entre si. Através da curva de (dΔn/dt) vs. T, foi possível constatar uma relação entre as máximas variações, positiva e negativa, da birrefringência com as temperaturas características TF e TB.

Este trabalho apresenta um método desenvolvido pela autora para, através de simulações multifísicas pelo Método dos Elementos Finitos (MEF), servir como ferramenta de apoio ao projeto e fabricação de guias de onda e moduladores eletro-ópticos em óptica integrada, além de possibilitar a análise da performance de moduladores eletro-ópticos. A técnica adotada para a fabricação dos guias de onda ópticos foi a de tensão mecânica. Os parâmetros de geometria (espessura do filme e larguras das trincheiras) e de temperatura de deposição do filme são definidos nas simulações e utilizados no processo de fabricação de guias de ondas em óptica integrada, que servem de base para a fabricação de moduladores eletro-ópticos em substrato cristalino de retículo cúbico. As trincheiras dos guias de onda do tipo canal são construídas em Germanato de Bismuto (BGO - Bi4Ge3O12), a partir da deposição sobre o substrato de um filme fino indutor de tensão mecânica (stress) Nitreto de Silício (Si3N4) e definidas pelos processos de litografia óptica e corrosão seletiva por plasma. Os moduladores são obtidos através da deposição dos eletrodos de alumínio sobre o filme, seguida de Si3N4 dos processos de litografia óptica e corrosão, obtendo-se eletrodos. O processo iterativo proposto inicia-se com os resultados das simulações, em que são definidos os parâmetros de fabricação do filme, da trincheira e dos eletrodos. Após a fabricação desses elementos, o componente é caracterizado e são medidos os parâmetros reais filme e do substrato. Esses valores são realimentados nas simulações para refinar o projeto do componente. O trabalho, além de apresentar todos os passos do processo interativo de simulações, projeto, fabricação e caracterização do componente desejado, indica as dificuldades encontradas na implementação do processo e as atividades futuras a serem desenvolvidas para o aperfeiçoamento do mesmo. / This work presents a method developed by the author to support the project and fabrication of integrated optic waveguides and electro-optic modulators by means of Finite Element Method (FEM) multiphysics simulations, also enabling the electro-optic modulators performance analysis. The technique used for fabricating the optical waveguides was the thermally induced residual stress (ISS). The geometry parameters (film thicknesses and trenches widths) and the film deposition temperature are obtained in the simulations and subsequently used in the integrated optical waveguides fabrication process, which serve as a basic building block for the electrooptic modulators on crystalline cubic lattice substrate. The channel waveguide trenches are built on Bismuth Germanate (BGO Bi4Ge3O12) by depositing a Silicon Nitride (Si3N4) Stress-inducing thin film, being later defined by optical lithography and plasma etching process. Modulators are obtained depositing aluminum on the Si3N4 film followed by the optical lithography and corrosion process, defining electrodes. The proposed iterative process starts with the simulation results that define the fabrication parameters of the film, trench and electrodes. After the fabrication of these elements, the device is characterized and the actual parameters of the film and substrate are measured. These values are fed back into the simulations to refine the component design. The work besides presenting all the simulation-design-fabrication-characterization iterative process for obtaining the devised device also highlights the difficulties encountered in the implementation process along with suggestions of future activities aiming at improving it.

L’objectif de cette thèse consistait à développer des colorants de la famille des polyméthines absorbant dans le proche infrarouge et présentant des propriétés d’optique non-linéaire (ONL) prononcées. De nouveaux chromophores ont été préparés et leurs propriétés spectroscopiques ont été systématiquement étudiées afin d’établir des relations structures-propriétés. Cette stratégie a permis l’identification des facteurs permettant d’exalter la réponse ONL des polyméthines et de prédire leur comportement face à de subtiles modifications structurales. Trois familles de colorants ont été préparées : des monométhines aza-dipyrrométhènes de bore, des heptaméthines symétriques ainsi que des heptaméthines dissymétriques.Dans un premier temps, des aza-bodipys possédant des groupements donneurs périphériques sont synthétisés. Une étude spectroscopique approfondie permet d’identifier les structures présentant une absorption à deux photons importante en vue d’applications en limitation optique aux longueurs d’onde des télécommunications (1500 nm). Le chapitre suivant a pour but de rationaliser les équilibres de la limite cyanine. L’étude de la substitution centrale de nombreux dérivés heptaméthines a permis de moduler leurs propriétés optiques sur une large gamme spectrale et de mettre en évidence une nouvelle structure électronique limite de type bis-dipôle. Parmi cette famille de colorants, des dérivés keto-heptaméthines ont été utilisées en imagerie biologique (cellules et cerveau) par microscopie non-linéaire. Enfin, l’élaboration de structures heptaméthines dissymétriques originales est détaillée dans le dernier chapitre. Ces chromophores ont révélé des propriétés ONL du second ordre idéales pour des applications en modulation électro-optique. / The aim of this thesis consisted in developing dyes from the polymethine family absorbing in the near-infrared (NIR) region and featuring pronounced nonlinear optical (NLO) properties. Several new chromophores have been prepared and their spectroscopic properties have been systematically investigated in order to establish structure-properties relationships. This strategy has permitted the identification of the factors that enhance the NLO response of polymethines and allowed the prediction of their optical behaviour depending on subtle structural modifications. Three families of dyes have been prepared and investigated: boron aza-dipyrro-monomethines (aza-bodipys), symmetrical heptamethines and unsymmetrical heptamethines.In a first time, aza-bodipys possessing electro-donating peripherical substituants has been synthesized. A detailed spectroscopic study allow the identification of structures that present a high two-photon absorption (TPA), towards optical limiting applications at telecommunication wavelengths (1500 nm). The next chapter rationalizes the equilibrium surrounding the cyanine limit. The study of the central substitution of several heptamethines derivatives permitted the fine tuning of their optical properties upon a large spectral region and evidenced a new bis-dipolar electronic structure. Within this dye family, keto heptamethine derivatives has been tested in bio-imaging experiments (living cells and brain) using non-linear microscopy. Finally, the elaboration of original unsymmetrical heptamethines is detailed in the last chapter. These chromophores revealed ideal second order NLO properties for applications in electro-optic modulation.

This thesis deals with optical synthesis of unmodulated and modulated microwave signals. Generation of microwave signals based on optical heterodyning is discussed in detail. The effect of phase noise of laser on heterodyned output has been studied for different phase noise profiles. Towards this, we propose a generic algorithm to numerically model the linewidth broadening of a laser due to phase noise. Generation of microwave signals is demonstrated practically by conducting an optical heterodyning experiment. Signals ranging in frequency from 12.5 MHz to 27 GHz have been generated. Limitations of optical heterodyning based approach in terms of phase noise performance and frequency stability are discussed and practically demonstrated. A hardware-efficient Optical Phase Locked Loop (OPLL) is proposed to overcome these issues. Phase noise tracking performance of the proposed OPLL has been experimentally demonstrated. Phase noise values as low as -105 dBc/Hz at 10 KHz offset have been achieved. Optical modulators, owing to their extremely low electro-optic response time, can support high frequency modulating signals. This makes them highly attractive in comparison to their microwave counterparts. In this thesis, we propose techniques to generate microwave signals modulated at very high bit rates by down-converting the corresponding modulated optical signals to microwave domain. Down-conversion required for this process is achieved by optical heterodyning. The proposed concept has been theoretically analyzed, simulated and experimentally validated. Amplitude Modulated and ASK modulated microwave signals have been generated as Proof-of-Concept. Limitations posed by OPLL in generation of angle modulated microwave signals by optical heterodyning have been brought out. Schemes overcoming these limitations have been proposed towards generation of BPSK and QPSK modulated microwave signals. Integrated Optics (IO) technology has been studied as a means of implementation of the proposed concepts. IO components like Sinusoidal bends, Y-branch splitters and Electro-Optic-Modulators (EOMs) have been designed towards optical synthesis of modulated microwave signals. Propagation of modulated optical signal through these IO components has also been studied. An all-optic scheme based on Optical Beam Forming is proposed for transmission of QPSK modulated signal. Limitation of phase-shifting based approach, in terms of beam-squint, has been brought out. True-Time-Delay based approach has been proposed for applications demanding wide instantaneous bandwidth to avoid beam-squint. Algorithms / numerical methods required for analyses and simulations associated with the above-mentioned tasks have been evolved. This study is envisaged to provide useful insight into the realization of high-speed, compact, light-weight data transmitting systems based on Integrated Optics for future onboard spacecraft applications. This work, we believe, is a step towards realization of an Integrated Optic System-on-Chip solution for specific microwave data transmission applications.

[ES] La búsqueda de nuevas soluciones e ideas innovadoras en el campo de la fotónica de silicio mediante la integración de nuevos materiales con prestaciones únicas es un tema de alta actualidad entre la comunidad científica en fotónica y con un impacto potencial muy alto. Dentro de esta temática, esta tesis pretende contribuir hacia una nueva generación de dispositivos fotónicos basados en la integración de óxidos metálicos en tecnología de silicio. Los óxidos metálicos elegidos pertenecen a la familia de óxidos conductores transparentes (TCO), concretamente el óxido de indio y estaño (ITO) y el óxido de cadmio (CdO), y materiales de cambio de fase (PCM) como el dióxido de vanadio (VO2). Dichos materiales se caracterizan especialmente por una variación drástica de sus propiedades optoelectrónicas, tales como la resistividad o el índice de refracción, frente a un estímulo externo ya sea en forma de temperatura, aplicación de un campo eléctrico o excitación óptica. De esta forma, nuestro objetivo es diseñar, fabricar y demostrar experimentalmente nuevas soluciones y dispositivos clave tales como dispositivos no volátiles, desfasadores y dispositivos con no linealidad óptica. Tales dispositivos podrían encontrar potencial utilidad en diversas aplicaciones que comprenden las comunicaciones ópticas, redes neuronales, LiDAR, computación, cuántica, entre otros. Las prestaciones clave en las que se pretende dar un salto disruptivo son el tamaño y capacidad para una alta densidad de integración, el consumo de potencia, y el ancho de banda. / [CA] La recerca de noves solucions i idees innovadores al camp de la fotònica de silici mitjançant la integració de nous materials amb prestacions úniques és un tema d'alta actualitat entre la comunitat científica en fotònica i amb un impacte potencial molt alt. D'aquesta temàtica, aquesta tesi pretén contribuir cap a una nova generació de dispositius fotònics basats en la integració d'òxids metàl·lics en tecnologia de silici. Els òxids metàl·lics elegits pertanyen a la família d'òxids conductors transparents (TCO), concretament l'òxid d'indi i estany (ITO) i l'òxid de cadmi (CdO), i materials de canvi de fase (PCM) com el diòxid de vanadi (VO2). Aquests materials es caracteritzen especialment per una variació dràstica de les propietats optoelectròniques, com ara la resistivitat o l'índex de refracció, davant d'un estímul extern ja siga en forma de temperatura, aplicació d'un camp elèctric o excitació òptica. D'aquesta manera, el nostre objectiu és dissenyar, fabricar i demostrar experimentalment noves solucions i dispositius clau com ara dispositius no volàtils, desfasadors i dispositius amb no-linealitat òptica. Aquests dispositius podrien trobar potencial utilitat en diverses aplicacions que comprenen les comunicacions òptiques, xarxes neuronals, LiDAR, computació, quàntica, entre d'altres. Les prestacions clau en què es pretén fer un salt disruptiu són la grandària i la capacitat per a una alta densitat d'integració, el consum de potència i l'amplada de banda. / [EN] The search for new solutions and innovative ideas in the field of silicon photonics through the integration of new materials featuring unique optoelectronic properties is a hot topic among the photonics scientific community with a very high potential impact. Within this topic, this thesis aims to contribute to a new generation of photonic devices based on the integration of metal oxides in silicon technology. The chosen metal oxides belong to the family of transparent conducting oxides (TCOs), namely indium tin oxide (ITO) and cadmium oxide (CdO), and phase change materials (PCMs) such as vanadium dioxide (VO2). These materials are characterized by a drastic variation of their optoelectronic properties, such as resistivity or refractive index, in response to an external stimulus either in the form of temperature, application of an electric field, or optical excitation. Therefore, our objective is to design, fabricate and experimentally demonstrate new solutions and key devices such as non-volatile devices, phase shifters, and devices with optical nonlinearity. Such devices could find potential utility in several applications, including optical communications, neural networks, LiDAR, computing, and quantum. The key features in which we aim to take a leapfrog are footprint and capacity for high integration density, power consumption, and bandwidth. / This work is supported in part by grants ACIF/2018/172 funded by Generaliltat Valenciana, and FPU17/04224 funded by MCIN/AEI/10.13039/501100011033 and by “ESF Investing in your future”. / Parra Gómez, J. (2022). Toward a new generation of photonic devices based on the integration of metal oxides in silicon technology [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/190883

This dissertation presents the novel creation of a hybrid D-fiber electro-optic polymer electric field sensor. The sensor is made by removing a portion of the cladding from a D-shaped optical fiber, thus exposing the core to interaction with external stimulus. Then, an electro-optic polymer is deposited, partially replacing the core of the fiber. Next, the polymer is poled to endow it with electro-optic properties. This sensor is packaged in order to restore its mechanical strength. Because D-fiber is not intrinsically compatible with standard optical equipment it is fusion spliced to standard polarization maintaining fiber. Finally the sensor is tested for electro-optic sensitivity. The hybrid D-fiber electric field sensors designed and fabricated in this work meet the requirements of mechanical strength, temporal stability, minimal perturbation of the electric field by the sensor, and a small and flexible cross-sectional area so that it can be embedded into the device under test. A fully packaged hybrid electro-optic polymer D-fiber electric field sensor which is capable of detecting electric fields of 50 V/m at a frequency of 6 GHz is produced. The sensor's electro-optic response is shown to be temporally stable. Additionally, the sensor is physically robust, and physically and electrically non-intrusive. This work also adds a thorough understanding of the design and fabrication of D-fiber waveguides with a polymer material deposited in the core. Several new fabrication techniques are developed and presented. A path to greater electric field sensitivity is outlined for future research.

Am Beispiel von ferroelektrischen Systemen auf Bismut-Basis (Bismutmolybdat, Bismutwolframat und Bismuttitanat) und von Strontiumbariumniobat werden neue Möglichkeiten zur Synthese solcher Nanopartikel aufgezeigt. Die Integration der Nanopartikel in transparente Nanokompositmaterialien und die Entwicklung neuer Precursoren für die Herstellung von Dünnschichtproben gehen den Untersuchungen zur Anwendung als elektrooptische aktive Materialien voraus. Durch weitere Anwendungsmöglichkeiten in der Photokatalyse, dem Test dampfadsorptiver Eigenschaften mit Hilfe eines neuartigen Adsorptionstesters (Infrasorb) und auch mit Hilfe der Ergebnisse der ferroelektrischen Charakterisierung von gesinterten Probenkörpern aus einem Spark-Plasma-Prozess wird ein gesamtheitlicher Überblick über die vielfältigen Aspekte in der Arbeit mit nanoskaligen, ferroelektrischen Materialien gegeben.:Inhaltsverzeichnis...........................................................................................................5 Abkürzungsverzeichnis ...................................................................................................9 1. Motivation....................................................................................................................11 2. Stand der Forschung und theoretischer Teil ...............................................................14 2.1. Nanoskalige Materialien...........................................................................................15 2.1.1. Nanopartikel und Nanokompositmaterialien ....................................................... 15 2.1.2. Dünnschichten..................................................................................................... 21 2.1.3. Anwendungen in der Photokatalyse.................................................................... 22 2.1.4. Anwendungen in der Gas- und Dampfsensorik.................................................... 24 2.2. Ferroelektrika .........................................................................................................26 2.2.1. Bismutmolybdat................................................................................................... 32 2.2.2. Bismutwolframat.................................................................................................. 34 2.2.3. Bismuttitanat ....................................................................................................... 36 2.2.4. Strontiumbariumniobat......................................................................................... 37 2.3. Verwendete Methoden.............................................................................................40 2.3.1. Spark-Plasma-Sintering ........................................................................................40 2.3.2. Bestimmung ferroelektrischer Eigenschaften ...................................................... 42 2.3.3. Charakterisierung nichtlinearer, elektrooptischer Eigenschaften......................... 43 3. Experimenteller Teil ....................................................................................................51 3.1. Synthesevorschriften................................................................................................52 3.1.1. Verwendete Chemikalien und Substrate.............................................................. 52 3.1.2. Solvothermalsynthese von Bi2MO6 (M = Mo, W)................................................... 55 3.1.3. Phasentransfersynthese von Bi2MO6 (M = Mo, W)............................................... 56 3.1.4. Präparation von Bi2MO6/PLA Nanokompositmaterialien (M = Mo, W) ................... 57 3.1.5. Sol-Gel-Synthese von Bi2MO6 (M = Mo, W), Bi4Ti3O12 und Ba0.25Sr0.75Nb2O6 und Dünnschichten..................... 57 3.1.6. Mikroemulsionssynthese von Bi4Ti3O12 ............................................................... 59 3.1.7. Sol-Gel-Synthese von Bi2Ti2O7............................................................................. 60 3.1.8. Synthese von BiOH(C2O4), BiOCH3COO und Bi(CH3COO)3................................... 61 3.2. Vorschriften zur Durchführung und Charakterisierung...............................................62 3.2.1. Verwendete Geräte und Einstellungen ................................................................ 62 3.2.2. Spark Plasma Sintering von Bi2MO6 (M = Mo,W) und Bestimmung ferroelektrischer Eigenschaften ........................ 65 3.2.3. Prüfung elektrooptischer Eigenschaften, Präparation der Bauteile und Messaufbau .............................................. 67 3.2.4. Durchführung photokatalytischer Messungen ....................................................... 69 3.2.5. Messung der Dampfadsorption an Nanopartikeln mit Hilfe berührungsloser Detektion ........................................... 70 4. Ergebnisse und Diskussion...........................................................................................71 4.1. Synthese und Eigenschaften von nanoskaligen Materialien......................................72 4.1.1. Synthese von Bi2MO6 (M = Mo, W) Nanopartikeln................................................. 72 4.1.2. Nanokompositmaterialien mit Bi2MO6 (M = Mo, W)................................................ 81 4.1.3. Synthese der Bismuttitanate Bi4Ti3O12 und Bi2Ti2O7 .......................................... 84 4.1.4. Herstellung von Dünnschichten der Systeme Bi2MO6 (M = Mo, W), Bi4Ti3O12 und Sr0.75Ba0.25Nb2O6 ................. 88 4.2. Funktion der nanoskaligen Materialien .....................................................................100 4.2.1. Bismuthaltige Nanopartikel in der Photokatalyse ..................................................100 4.2.2. Spark-Plasma-Sintern von Bi2MO6-Nanopartikel (M = Mo, W)................................103 4.2.3. Elektrooptische Eigenschaften von Dünnschichten und Kompositmaterialien ............................................................108 4.2.4. Messung der Dampfadsorption an Bi2MO6 (M = Mo, W)-Nanopartikeln mit Hilfe berührungsloser Detektion ............114 4.3. Synthese von BiOH(C2O4), BiO(CH3COO) und Bi(CH3COO)3....................................118 5. Zusammenfassung ......................................................................................................127 6. Ausblick .......................................................................................................................131 7. Literatur ......................................................................................................................132 8. Abbildungs- und Tabellenverzeichnis ..........................................................................146 8.1. Abbildungsverzeichnis...............................................................................................146 8.2. Tabellenverzeichnis...................................................................................................152 9. Anhang ........................................................................................................................154 9.1. Synthese und Eigenschaften von nanoskaligen Materialien......................................155 9.1.1. Solvothermalsynthese von Bi2MO6 (M = Mo, W).....................................................155 9.1.2. Phasentransfersynthese von Bi2MO6 (M = Mo, W).................................................156 9.1.3. Synthese der Bismutmolybdate Bi4Ti3O12 und Bi2Ti2O7 .......................................156 9.1.4. Herstellung von Dünnschichten der Systeme Bi2MO6 (M = Mo, W), Bi4Ti3O12 und Sr0.75Ba0.25Nb2O6 .................159 9.2. Funktion der nanoskaligen Materialien ......................................................................164 9.2.1. Spark-Plasma-Sintern..............................................................................................164 9.2.2. Elektro-optische Eigenschaften von Dünnschichten und Kompositmaterialien .........................................................166 9.2.3. Messung der Dampfadsorption an Bi2MO6 (M = Mo, W)-Nanopartikeln mit Hilfe berührungsloser Detektion ...........174 9.3. Synthese von BiOH(C2O4), BiO(CH3COO) und Bi(CH3COO)3.....................................175 9.3.1. DTA-TG-Ergebnisse .................................................................................................175 9.3.2. Kristalldaten und Strukturverfeinerung ...................................................................177 9.4. Quelltexte ..................................................................................................................181 9.4.1. MATLAB-Skript zur Auswertung elektrooptischer Koeffizienten................................181 9.4.2. MATLAB-Skript zur Auswertung dampfadsorptiver Eigenschaften............................182