Estudo da influência da temperatura de brasagem nas uniões zircônia/aço inox 304 utilizando metalização mecânica

Metal-Ceramic (M/C) Zirconia-stainless steel interfaces have been processed through brazing techniques due to the excellent combination of properties such as high temperature stability, high corrosion resistance and good mechanical properties. However, some M/C interfaces show some defects, like porosity and cracks results in the degradation of the interfaces, leading even to its total rupture. Most of time, those defects are associated with an improper brazing parameters selection to the M/C system. In this work, ZrO2 Y-TZP and ZrO2 Mg - PSZ were joint with the stainless steel grade 304 by brazing using a eutectic silver-copper (Ag28Cu) interlayer alloy with different thermal cycles. Ceramic surfaces were previous mechanically metallized with titanium to improve adhesion of the system. The effect of temperature on the M/C interface was studied. SEM-EDS and 3 point flexural bend test were performed to evaluate morphology, chemical composition and mechanical resistance of the M/C interfaces. Lower thermal cycle temperatures produced better results of mechanical resistance, and more regular/ homogeneous reaction layers between braze alloy and metal-ceramic surfaces. Also was proved the AgCu braze alloy activation in situ by titanium

Metalização mecânica de ZrO2 com Ti para brasagem ZrO2/Aço com ligas de adição sem metal ativo

Metal/ceramic interfaces using zirconia have dominated the industrial applications in the last decade, due to the high mechanical strength and fracture toughness of zirconia, especially at temperatures below 300 ºC. Also noteworthy is the good ionic conductivity in high temperatures of this component. In this work joining between ZrO2 Y-TZP and ZrO2 Mg-PSZ with austenitic stainless steel was studied. These joints were brazed at high-vacuum after mechanical metallization with Ti using filler alloys composed by Ag-Cu and Ag-Cu-Ni. The influence of the metallization, and the affinity between the different groups (ceramic / filler alloys) was evaluated, in order to achieve strong metal/ceramic joints. Evaluation of joints and interfaces, also the characterization of base materials was implemented using various techniques, such as: x-ray diffraction, leak test, three-point flexural test and scanning electron microscopy with chemical analysis. The microstructural analysis revealed physical and chemical bonds in the metal/ceramic interfaces, providing superior leak proof joints and stress cracking, in order to a good joint in all brazed samples. Precipitation zones and reaction layers with eutetic characteristics were observed between the steel and the filler metal

Ultrasonic density measurement cell design and simulation of non-ideal effects

This paper presents a theoretical analysis of a density measurement cell using an unidimensional model composed by acoustic and electroacoustic transmission lines in order to simulate non-ideal effects. The model is implemented using matrix operations, and is used to design the cell considering its geometry, materials used in sensor assembly, range of liquid sample properties and signal analysis techniques. The sensor performance in non-ideal conditions is studied, considering the thicknesses of adhesive and metallization layers, and the effect of residue of liquid sample which can impregnate on the sample chamber surfaces. These layers are taken into account in the model, and their effects are compensated to reduce the error on density measurement. The results show the contribution of residue layer thickness to density error and its behavior when two signal analysis methods are used. (c) 2006 Elsevier B.V. All rights reserved.

Preparation and antibacterial activity of silver nanoparticles impregnated in bacterial cellulose

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Superfícies eletromagnéticas de microondas com controle do regime de trapped-mode

Neste trabalho foram investigadas (FSSs) com ressonância de alto fator de qualidade (fator Q) e independência da polarização para uma onda plana com incidência normal. Estas FSSs são baseadas em um arranjo planar de metalizações sobre um substrato. Um alto fator Q é obtido por meio da excitação do trapped-mode e a independência da polarização, por meio da alta simetria rotacional dos elementos que compõe o arranjo. Para o projeto de FSSs com controle do regime de trapped-mode, foram utilizados substratos feitos de materiais com possibilidade de controle de suas propriedades elétricas ou magnéticas (ferrite magnetizada ou silício ativado oticamente). O arranjo de dois anéis concêntricos em um substrato dielétrico analisado neste trabalho apresenta uma ressonância de trapped-mode com fator Q em torno de 12 e transmitância máxima de 70 %. Com a utilização de um substrato de ferrite magnetizada nesse arranjo, é mostrado que é possível deslocar a frequência de ressonância do trappedmode em torno de 20 %, sem degradação significativa da ressonância de transmisão. Com o emprego de um substrato de silício ativado opticamente, é demonstrado que é possível realizar um chaveamento praticamente completo da banda de transmissão desse arranjo. Para realização das simulações computacionais foram utilizados o método dos momentos no domínio espectral (SDMM) e os programas comerciais Ansoft Designer 5 Planar EM e CST 2009.

Design and fabrication of MOMS-based ultrasonic probes for minimally invasive endoscopic applications

A Micro-opto-mechanical systems (MOMS) based technology for the fabrication of ultrasonic probes on optical fiber is presented. Thanks to the high miniaturization level reached, the realization of an ultrasonic system constituted by ultrasonic generating and detecting elements, suitable for minimally invasive applications or Non Destructive Evaluation (NDE) of materials at high resolution, is demonstrated. The ultrasonic generation is realized by irradiating a highly absorbing carbon film patterned on silicon micromachined structures with a nanosecond pulsed laser source, generating a mechanical shock wave due to the thermal expansion of the film induced by optical energy conversion into heat. The short duration of the pulsed laser, together with an appropriate emitter design, assure high frequency and wide band ultrasonic generation. The acoustic detection is also realized on a MOMS device using an interferometric receiver, fabricated with a Fabry-Perot optical cavity realized by means of a patterned SU-8 and two Al metallization levels. In order to detect the ultrasonic waves, the cavity is interrogated by a laser beam measuring the reflected power with a photodiode. Various issues related to the design and fabrication of these acoustic probes are investigated in this thesis. First, theoretical models are developed to characterize the opto-acoustic behavior of the devices and estimate their expected acoustic performances. Tests structures are realized to derive the relevant physical parameters of the materials constituting the MOMS devices and determine the conditions theoretically assuring the best acoustic emission and detection performances. Moreover, by exploiting the models and the theoretical results, prototypes of acoustic probes are designed and their fabrication process developed by means of an extended experimental activity.

Nanostructuring by templated synthesis of nanowires and controlled crystallization of calcium phosphate on self-assembled monolayers

The idea was to obtain nanowires in a chemical laboratory under convenient and simple conditions by employing templates. Thus it was possible to produce nanochains by interlinking of gold colloids synthesized by the two-phase-method of M. Brust with by making use of vanadiumoxide nanotubes as template. The length of the resulting nanowires is varying between 1100 nm and 200 nm with a diameter of about 16 nm. Due to a flexible linker the obtained nanowires are not completely rigid. These unique structural features could make them interesting objects for structuring and assembling in the nanoscale range. Another way to produce gold nanowires was realized by a two-step surface metallization procedure, using type I collagen fibres as a template. Gold colloids were used to label the collagen fibres by direct electrostatic interaction, followed by growth steps to enhance the size of the adsorbed colloidal gold crystals, resulting in a complete metallization of the template surface. The length of the resulting gold nanowires reaches several micrometers, with a diameter ~ 100 to 120 nm. To gain a deeper insight into the process of biomineralization the cooperative effect of self-assembled monolayers as substrate and a soluble counterpart on the nucleation and crystal growth of calcium phosphate was studied by diffusion techniques with a pH switch as initiator. As soluble component Perlucin and Nacrein were used. Both are proteins originally extracted from marine organisms, the first one from the Abalone shell and the second one from oyster pearls. Both are supposed to facilitate the calcium carbonate formation in vivo. Studies with Perlucin revealed that this protein shows a clear cooperative effect at a very low concentration with a hydrophobic surface promoting the calcium phosphate precipitation resulting in a sponge like structure of hydroxyapatite. The Perlucin molecule is very flexible and is unfolded by adsorbing to the hydrophobic surface and uncovers its active side. Hydrophilic surfaces did not have a deeper impact. Studies with Nacrein as additive have shown that the protein stabilizes octacalcium phosphate at room temperature on carboxylic self-assembled monolayer and at 34 °C on all other employed surfaces by interaction with the mineral. On the hydroxyl-, alkyl-, and amin-terminated self-assembled monolayers at room temperature the octacalcium phosphate get transformed to hydroxyapatite. Main analytical techniques which are used in this work are transmission electron microscopy, high resolution scanning electron microscopy, surface plasmon resonance spectroscopy, atomic force microscopy, Raman micro-spectroscopy and quartz crystal microbalance.

Homo- and Heterometal Carbonyl Nanoclusters

In this thesis, the syntheses and the characterizations of several new bimetallic carbonyl clusters have been outlined. X-ray crystallography is a key technique in order to elucidate their structures which can be related to their chemical and physical properties. In particular, electrochemical studies are very useful in order to understand how the physical properties of metal aggregates change with increasing size and when the molecular behavior fades into bulk behavior. Moreover, the incipient metallization of the cluster has be assessed (not measured) via UV-vis analyses even if this technique revealed to be not very useful in order to distinguish the different species present in solution. Overall, this work demonstrates that molecular nanoclusters are ideal models in order to better understand the structures and properties of ultrasmall metal nanoparticles.

Adsorption behavior of redox-active suppressor additives: Combined electrochemical and STM studies

The redox chemistry and the related surface phase behavior of Safranine (SAF) and Janus Green B (JGB) have been studied by means of cyclic voltammetry in combination with in situ Scanning Tunneling Microscopy using HOPG (Highly Oriented Pyrolytic Graphite) and single crystalline Cu(1 0 0) as model substrates, both revealing different widths of the accessible potential windows. JGB and SAF serve as prototypical heterocyclic suppressor/leveler additives that are used for the metallization of 3D-TSVs (3D Through Silicon Vias) following a classical "leveling" concept. SAF can be considered as the reductive decomposition product of JGB that is formed at the copper/electrolyte interface upon electroplating. Both additives reveal a pronounced pH-dependent redox-chemistry with redox-transitions lying close to or even beyond the anodic limit of the copper potential window. Affected by these redox-processes are in particular the aromatic cores of those heterocycles that can be (quasi)reversibly reduced by a two electron transfer process within the potential window of copper. Therefore we identify the reduced form of those dyes as the active components for the suppressing/leveling effect in copper plating. STM data clearly shows a dye surface phase behavior that is crucially determined by its potential-dependent redox-chemistry. This will be exemplarily discussed for the SAF dye. On chloride-modified Cu(1 0 0) mono-reduced SAF forms a structurally well-defined monolayer of cationic stacking polymers. However, this coupled anion/cation layer reveals only minor suppressing capabilities with respect to the copper dissolution and deposition processes. Complete reduction of the aromatic heterocycle finally leads to the 3D precipitation of hydrophobic reaction products. 3D clusters of this SAF precipitate are discussed as the active structural motif for the suppressing effect of these dyes. (C) 2011 Elsevier Ltd. All rights reserved.

High-Resolution Chemical Depth Profiling of Solid Material Using a Miniature Laser Ablation/Ionization Mass Spectrometer

High-resolution chemical depth profiling measurements of copper films are presented. The 10 μm thick copper test samples were electrodeposited on a Si-supported Cu seed under galvanostatic conditions in the presence of particular plating additives (SPS, Imep, PEI, and PAG) used in the semiconductor industry for the on-chip metallization of interconnects. To probe the trend of these plating additives toward inclusion into the deposit upon growth, quantitative elemental mass spectrometric measurements at trace level concentration were conducted by using a sensitive miniature laser ablation ionization mass spectrometer (LIMS), originally designed and developed for in situ space exploration. An ultrashort pulsed laser system (τ ∼ 190 fs, λ = 775 nm) was used for ablation and ionization of sample material. We show that with our LIMS system, quantitative chemical mass spectrometric analysis with an ablation rate at the subnanometer level per single laser shot can be conducted. The measurement capabilities of our instrument, including the high vertical depth resolution coupled with high detection sensitivity of ∼10 ppb, high dynamic range ≥10(8), measurement accuracy and precision, is of considerable interest in various fields of application, where investigations with high lateral and vertical resolution of the chemical composition of solid materials are required, these include, e.g., wafers from semiconductor industry or studies on space weathered samples in space research.

A two-dimensional finite element model of front surface current flow in cells under non-uniform, concentrated illumination

A two-dimensional finite element model of current flow in the front surface of a PV cell is presented. In order to validate this model we perform an experimental test. Later, particular attention is paid to the effects of non-uniform illumination in the finger direction which is typical in a linear concentrator system. Fill factor, open circuit voltage and efficiency are shown to decrease with increasing degree of non-uniform illumination. It is shown that these detrimental effects can be mitigated significantly by reoptimization of the number of front surface metallization fingers to suit the degree of non-uniformity. The behavior of current flow in the front surface of a cell operating at open circuit voltage under non-uniform illumination is discussed in detail.

InN/GaN heterojunction electrical behavior

Indium nitride (InN) has been the subject of intense research in recent years. Some of its most attractive features are its excellent transport properties such as its small band edge electron effective mass, high electron mobilities and peak drift velocities, and high frequency transient drift velocity oscillations [1]. These suggest enormous potential applications for InN in high frequency electronic devices. But to date the high unintentional bulk electron concentration (n~1018 cm-3) of undoped InN samples and the surface electron accumulation layer make it a hard task to create a reliable metalsemiconductor Schottky barrier. Some attempts have been made to overcome this problem by means of material oxidation [2] or deposition of insulators [3]. In this work we present a way to obtain an electrical rectification behaviour by means of heterojunction growth. Due to the big band gap differences among nitride semiconductors, it’s possible to create a structure with high band offsets. In InN/GaN heterojunctions, depending on the GaN doping, the magnitude of conduction and valence band offset are critical parameters which allow distinguishing among different electrical behaviours. The earliest estimate of the valence band offset at an InN–GaN heterojunction in a wurtzite structure was measured to be ~0.85 eV [4], while the Schottky barrier heights were determined to be ~ 1,4 eV [5].We grew In-face InN layer with varying thickness (between 150 nm and 1 mm) by plasma assisted molecular beam epitaxy (PA-MBE) on GaNntemplates (GaN/Al2O3), with temperatures ranging between 300°C and 450°C. The different doping in GaN template (Si doping, Fe doping and Mg doping) results in differences in band alignments of the two semiconductors changing electrical barriers for carriers and consequently electrical conduction behaviour. The processing of the devices includes metallization of the ohmic contacts on InN and GaN, for which we used Ti/Al/Ni/Au. Whereas an ohmic contact on InN is straightforward, the main issue was the fabrication of the contact on GaN due to the very low decomposition temperature of InN. A standard ohmic contact on GaN is generally obtained by high temperature rapid thermal annealing (RTA), typically done between 500ºC and 900ºC[6]. In this case, the limitation due to the presence of In-face InN imposes an upper limit on the temperature for the thermal annealing process and ohmic contact formation of about 450°C. We will present results on the morphology of the InN layers by X-Ray diffraction and SEM, and electrical measurements, in particular current-voltage and capacitance-voltage characteristics.

Microprocesos láser para la mejora de dispositivos fotovoltaicos basados en silicio cristalino

En los últimos años la tecnología láser se ha convertido en una herramienta imprescindible en la fabricación de dispositivos fotovoltaicos, ayudando a la consecución de dos objetivos claves para que esta opción energética se convierta en una alternativa viable: reducción de costes de fabricación y aumento de eficiencia de dispositivo. Dentro de las tecnologías fotovoltaicas, las basadas en silicio cristalino (c-Si) siguen siendo las dominantes en el mercado, y en la actualidad los esfuerzos científicos en este campo se encaminan fundamentalmente a conseguir células de mayor eficiencia a un menor coste encontrándose, como se comentaba anteriormente, que gran parte de las soluciones pueden venir de la mano de una mayor utilización de tecnología láser en la fabricación de los mismos. En este contexto, esta Tesis hace un estudio completo y desarrolla, hasta su aplicación en dispositivo final, tres procesos láser específicos para la optimización de dispositivos fotovoltaicos de alta eficiencia basados en silicio. Dichos procesos tienen como finalidad la mejora de los contactos frontal y posterior de células fotovoltaicas basadas en c-Si con vistas a mejorar su eficiencia eléctrica y reducir el coste de producción de las mismas. En concreto, para el contacto frontal se han desarrollado soluciones innovadoras basadas en el empleo de tecnología láser en la metalización y en la fabricación de emisores selectivos puntuales basados en técnicas de dopado con láser, mientras que para el contacto posterior se ha trabajado en el desarrollo de procesos de contacto puntual con láser para la mejora de la pasivación del dispositivo. La consecución de dichos objetivos ha llevado aparejado el alcanzar una serie de hitos que se resumen continuación: - Entender el impacto de la interacción del láser con los distintos materiales empleados en el dispositivo y su influencia sobre las prestaciones del mismo, identificando los efectos dañinos e intentar mitigarlos en lo posible. - Desarrollar procesos láser que sean compatibles con los dispositivos que admiten poca afectación térmica en el proceso de fabricación (procesos a baja temperatura), como los dispositivos de heterounión. - Desarrollar de forma concreta procesos, completamente parametrizados, de definición de dopado selectivo con láser, contactos puntuales con láser y metalización mediante técnicas de transferencia de material inducida por láser. - Definir tales procesos de forma que reduzcan la complejidad de la fabricación del dispositivo y que sean de fácil integración en una línea de producción. - Mejorar las técnicas de caracterización empleadas para verificar la calidad de los procesos, para lo que ha sido necesario adaptar específicamente técnicas de caracterización de considerable complejidad. - Demostrar su viabilidad en dispositivo final. Como se detalla en el trabajo, la consecución de estos hitos en el marco de desarrollo de esta Tesis ha permitido contribuir a la fabricación de los primeros dispositivos fotovoltaicos en España que incorporan estos conceptos avanzados y, en el caso de la tecnología de dopado con láser, ha permitido hacer avances completamente novedosos a nivel mundial. Asimismo los conceptos propuestos de metalización con láser abren vías, completamente originales, para la mejora de los dispositivos considerados. Por último decir que este trabajo ha sido posible por una colaboración muy estrecha entre el Centro Láser de la UPM, en el que la autora desarrolla su labor, y el Grupo de Investigación en Micro y Nanotecnologías de la Universidad Politécnica de Cataluña, encargado de la preparación y puesta a punto de las muestras y del desarrollo de algunos procesos láser para comparación. También cabe destacar la contribución de del Centro de Investigaciones Energéticas, Medioambientales y Tecnológicas, CIEMAT, en la preparación de experimentos específicos de gran importancia en el desarrollo del trabajo. Dichas colaboraciones se han desarrollado en el marco de varios proyectos, tales como el proyecto singular estratégico PSE-MICROSIL08 (PSE-iv 120000-2006-6), el proyecto INNDISOL (IPT-420000-2010-6), ambos financiados por el Fondo Europeo de Desarrollo Regional FEDER (UE) “Una manera de hacer Europa” y el MICINN, y el proyecto del Plan Nacional AMIC (ENE2010-21384-C04-02), cuya financiación ha permitido en gran parte llevar a término este trabajo. v ABSTRACT. Last years lasers have become a fundamental tool in the photovoltaic (PV) industry, helping this technology to achieve two major goals: cost reduction and efficiency improvement. Among the present PV technologies, crystalline silicon (c-Si) maintains a clear market supremacy and, in this particular field, the technological efforts are focussing into the improvement of the device efficiency using different approaches (reducing for instance the electrical or optical losses in the device) and the cost reduction in the device fabrication (using less silicon in the final device or implementing more cost effective production steps). In both approaches lasers appear ideally suited tools to achieve the desired success. In this context, this work makes a comprehensive study and develops, until their implementation in a final device, three specific laser processes designed for the optimization of high efficiency PV devices based in c-Si. Those processes are intended to improve the front and back contact of the considered solar cells in order to reduce the production costs and to improve the device efficiency. In particular, to improve the front contact, this work has developed innovative solutions using lasers as fundamental processing tools to metalize, using laser induced forward transfer techniques, and to create local selective emitters by means of laser doping techniques. On the other side, and for the back contact, and approached based in the optimization of standard laser fired contact formation has been envisaged. To achieve these fundamental goals, a number of milestones have been reached in the development of this work, namely: - To understand the basics of the laser-matter interaction physics in the considered processes, in order to preserve the functionality of the irradiated materials. - To develop laser processes fully compatible with low temperature device concepts (as it is the case of heterojunction solar cells). - In particular, to parameterize completely processes of laser doping, laser fired contacts and metallization via laser transfer of material. - To define such a processes in such a way that their final industrial implementation could be a real option. - To improve widely used characterization techniques in order to be applied to the study of these particular processes. - To probe their viability in a final PV device. Finally, the achievement of these milestones has brought as a consequence the fabrication of the first devices in Spain incorporating these concepts. In particular, the developments achieved in laser doping, are relevant not only for the Spanish science but in a general international context, with the introduction of really innovative concepts as local selective emitters. Finally, the advances reached in the laser metallization approached presented in this work open the door to future developments, fully innovative, in the field of PV industrial metallization techniques. This work was made possible by a very close collaboration between the Laser Center of the UPM, in which the author develops his work, and the Research Group of Micro y Nanotecnology of the Universidad Politécnica de Cataluña, in charge of the preparation and development of samples and the assessment of some laser processes for comparison. As well is important to remark the collaboration of the Centro de Investigaciones Energéticas, Medioambientales y Tecnológicas, CIEMAT, in the preparation of specific experiments of great importance in the development of the work. These collaborations have been developed within the framework of various projects such as the PSE-MICROSIL08 (PSE-120000-2006-6), the project INNDISOL (IPT-420000-2010-6), both funded by the Fondo Europeo de Desarrollo Regional FEDER (UE) “Una manera de hacer Europa” and the MICINN, and the project AMIC (ENE2010-21384-C04-02), whose funding has largely allowed to complete this work.

New laser-based approaches to improve the passivation and rear contact quality in high effiency crystalline silicon solar cells

Laser processing has been the tool of choice last years to develop improved concepts in contact formation for high efficiency crystalline silicon (c-Si) solar cells. New concepts based on standard laser fired contacts (LFC) or advanced laser doping (LD) techniques are optimal solutions for both the front and back contacts of a number of structures with growing interest in the c-Si PV industry. Nowadays, substantial efforts are underway to optimize these processes in order to be applied industrially in high efficiency concepts. However a critical issue in these devices is that, most of them, demand a very low thermal input during the fabrication sequence and a minimal damage of the structure during the laser irradiation process. Keeping these two objectives in mind, in this work we discuss the possibility of using laser-based processes to contact the rear side of silicon heterojunction (SHJ) solar cells in an approach fully compatible with the low temperature processing associated to these devices. First we discuss the possibility of using standard LFC techniques in the fabrication of SHJ cells on p-type substrates, studying in detail the effect of the laser wavelength on the contact quality. Secondly, we present an alternative strategy bearing in mind that a real challenge in the rear contact formation is to reduce the damage induced by the laser irradiation. This new approach is based on local laser doping techniques previously developed by our groups, to contact the rear side of p-type c-Si solar cells by means of laser processing before rear metallization of dielectric stacks containing Al2O3. In this work we demonstrate the possibility of using this new approach in SHJ cells with a distinct advantage over other standard LFC techniques.

Free-form optical systems for nonimaging applications : Sistemas ópticos anamórficos para aplicaciones anidólicas

La óptica anidólica es una rama de la óptica cuyo desarrollo comenzó a mediados de la década de 1960. Este relativamente nuevo campo de la óptica se centra en la transferencia eficiente de la luz, algo necesario en muchas aplicaciones, entre las que destacamos los concentradores solares y los sistemas de iluminación. Las soluciones de la óptica clásica a los problemas de la transferencia de energía de la luz sólo son adecuadas cuando los rayos de luz son paraxiales. La condición paraxial no se cumple en la mayoría de las aplicaciones para concentración e iluminación. Esta tesis contiene varios diseños free-form (aquellos que no presentan ninguna simetría, ni de rotación ni lineal) cuyas aplicaciones van destinadas a estos dos campos. El término nonimaging viene del hecho de que estos sistemas ópticos no necesitan formar una imagen del objeto, aunque no formar la imagen no es una condición necesaria. Otra palabra que se utiliza a veces en lugar de nonimaging es la palabra anidólico, viene del griego "an+eidolon" y tiene el mismo significado. La mayoría de los sistemas ópticos diseñados para aplicaciones anidólicas no presentan ninguna simetría, es decir, son free-form (anamórficos). Los sistemas ópticos free-form están siendo especialmente relevantes durante los últimos años gracias al desarrollo de las herramientas para su fabricación como máquinas de moldeo por inyección y el mecanizado multieje. Sin embargo, solo recientemente se han desarrollado técnicas de diseño anidólicas capaces de cumplir con estos grados de libertad. En aplicaciones de iluminación el método SMS3D permite diseñar dos superficies free-form para controlar las fuentes de luz extensas. En los casos en que se requiere una elevada asimetría de la fuente, el objeto o las restricciones volumétricos, las superficies free-form permiten obtener soluciones de mayor eficiencia, o disponer de menos elementos en comparación con las soluciones de simetría de rotación, dado que las superficies free-form tienen más grados de libertad y pueden realizar múltiples funciones debido a su naturaleza anamórfica. Los concentradores anidólicos son muy adecuados para la captación de energía solar, ya que el objetivo no es la reproducción de una imagen exacta del sol, sino sencillamente la captura de su energía. En este momento, el campo de la concentración fotovoltaica (CPV) tiende hacia sistemas de alta concentración con el fin de compensar el gasto de las células solares multi-unión (MJ) utilizadas como receptores, reduciendo su área. El interés en el uso de células MJ radica en su alta eficiencia de conversión. Para obtener sistemas competitivos en aplicaciones terrestres se recurre a sistemas fotovoltaicos de alta concentración (HCPV), con factores de concentración geométrica por encima de 500x. Estos sistemas se componen de dos (o más) elementos ópticos (espejos y/o lentes). En los sistemas presentados a lo largo de este trabajo se presentan ejemplos de concentradores HCPV con elementos reflexivos como etapa primaria, así como concentradores con elementos refractivos (lente de Fresnel). Con la necesidad de aumentar la eficiencia de los sistemas HCPV reales y con el fin de proporcionar la división más eficiente del espectro solar, células conteniendo cuatro o más uniones (con un potencial de alcanzar eficiencias de más del 45% a una concentración de cientos de soles) se exploran hoy en día. En esta tesis se presenta una de las posibles arquitecturas de división del espectro (spectrum-splitting en la literatura anglosajona) que utilizan células de concentración comercial. Otro campo de aplicación de la óptica nonimaging es la iluminación, donde es necesario proporcionar un patrón de distribución de la iluminación específico. La iluminación de estado sólido (SSL), basada en la electroluminiscencia de materiales semiconductores, está proporcionando fuentes de luz para aplicaciones de iluminación general. En la última década, los diodos emisores de luz (LED) de alto brillo han comenzado a reemplazar a las fuentes de luz convencionales debido a la superioridad en la calidad de la luz emitida, elevado tiempo de vida, compacidad y ahorro de energía. Los colimadores utilizados con LEDs deben cumplir con requisitos tales como tener una alta eficiencia, un alto control del haz de luz, una mezcla de color espacial y una gran compacidad. Presentamos un colimador de luz free-form con microestructuras capaz de conseguir buena colimación y buena mezcla de colores con una fuente de LED RGGB. Una buena mezcla de luz es importante no sólo para simplificar el diseño óptico de la luminaria sino también para evitar hacer binning de los chips. La mezcla de luz óptica puede reducir los costes al evitar la modulación por ancho de pulso y otras soluciones electrónicas patentadas para regulación y ajuste de color. Esta tesis consta de cuatro capítulos. Los capítulos que contienen la obra original de esta tesis son precedidos por un capítulo introductorio donde se presentan los conceptos y definiciones básicas de la óptica geométrica y en el cual se engloba la óptica nonimaging. Contiene principios de la óptica no formadora de imagen junto con la descripción de sus problemas y métodos de diseño. Asimismo se describe el método de Superficies Múltiples Simultáneas (SMS), que destaca por su versatilidad y capacidad de controlar varios haces de rayos. Adicionalmente también se describe la integración Köhler y sus aplicaciones en el campo de la energía fotovoltaica. La concentración fotovoltaica y la iluminación de estado sólido son introducidas junto con la revisión de su estado actual. El Segundo y Tercer Capítulo contienen diseños ópticos avanzados con aplicación en la concentración solar principalmente, mientras que el Cuarto Capítulo describe el colimador free-form con surcos que presenta buena mezcla de colores para aplicaciones de iluminación. El Segundo Capítulo describe dos concentradores ópticos HCPV diseñados con el método SMS en tres dimensiones (SMS3D) que llevan a cabo integración Köhler en dos direcciones con el fin de proporcionar una distribución de irradiancia uniforme libre de aberraciones cromáticas sobre la célula solar. Uno de los diseños es el concentrador XXR free-form diseñado con el método SMS3D, donde el espejo primario (X) y la lente secundaria (R) se dividen en cuatro sectores simétricos y llevan a cabo la integración Köhler (proporcionando cuatro unidades del array Köhler), mientras que el espejo intermedio (X) presenta simetría rotacional. Otro concentrador HCPV presentado es el Fresnel-RXI (FRXI) con una lente de Fresnel funcionando como elemento primario (POE) y una lente RXI como elemento óptico secundario (SOE), que presenta configuración 4-fold con el fin de realizar la integración Köhler. Las lentes RXI son dispositivos nonimaging conocidos, pero su aplicación como elemento secundario es novedosa. Los concentradores XXR y FRXI Köhler son ejemplos académicos de muy alta concentración (más de 2,000x, mientras que los sistemas convencionales hoy en día no suelen llegar a 1,000x) preparados para las células solares N-unión (con N>3), que probablemente requerirán una mayor concentración y alta uniformidad espectral de irradiancia con el fin de obtener sistemas CPV terrestres eficientes y rentables. Ambos concentradores están diseñados maximizando funciones de mérito como la eficiencia óptica, el producto concentración-aceptancia (CAP) y la uniformidad de irradiancia sobre la célula libre de la aberración cromática (integración Köhler). El Tercer Capítulo presenta una arquitectura para la división del espectro solar basada en un módulo HCPV con alta concentración (500x) y ángulo de aceptancia alto (>1º) que tiene por objeto reducir ambas fuentes de pérdidas de las células triple unión (3J) comerciales: el uso eficiente del espectro solar y la luz reflejada de los contactos metálicos y de la superficie de semiconductor. El módulo para la división del espectro utiliza el espectro solar más eficiente debido a la combinación de una alta eficiencia de una célula de concentración 3J (GaInP/GaInAs/Ge) y una de contacto posterior (BPC) de concentración de silicio (Si), así como la técnica de confinamiento externo para la recuperación de la luz reflejada por la célula 3J con el fin de ser reabsorbida por la célula. En la arquitectura propuesta, la célula 3J opera con su ganancia de corriente optimizada (concentración geométrica de 500x), mientras que la célula de silicio trabaja cerca de su óptimo también (135x). El módulo de spectrum-splitting consta de una lente de Fresnel plana como POE y un concentrador RXI free-form como SOE con un filtro paso-banda integrado en él. Tanto POE como SOE realizan la integración Köhler para producir homogeneización de luz sobre la célula. El filtro paso banda envía los fotones IR en la banda 900-1,150nm a la célula de silicio. Hay varios aspectos prácticos de la arquitectura del módulo presentado que ayudan a reducir la complejidad de los sistemas spectrum-splitting (el filtro y el secundario forman una sola pieza sólida, ambas células son coplanarias simplificándose el cableado y la disipación de calor, etc.). Prototipos prueba-de-concepto han sido ensamblados y probados a fin de demostrar la fabricabilidad del filtro y su rendimiento cuando se combina con la técnica de reciclaje de luz externa. Los resultados obtenidos se ajustan bastante bien a los modelos y a las simulaciones e invitan al desarrollo de una versión más compleja de este prototipo en el futuro. Dos colimadores sólidos con surcos free-form se presentan en el Cuarto Capítulo. Ambos diseños ópticos están diseñados originalmente usando el método SMS3D. La segunda superficie ópticamente activa está diseñada a posteriori como una superficie con surcos. El diseño inicial de dos espejos (XX) está diseñado como prueba de concepto. En segundo lugar, el diseño RXI free-form es comparable con los colimadores RXI existentes. Se trata de un diseño muy compacto y eficiente que proporciona una muy buena mezcla de colores cuando funciona con LEDs RGB fuera del eje óptico como en los RGB LEDs convencionales. Estos dos diseños son dispositivos free-form diseñados con la intención de mejorar las propiedades de mezcla de colores de los dispositivos no aplanáticos RXI con simetría de revolución y la eficiencia de los aplanáticos, logrando una buena colimación y una buena mezcla de colores. La capacidad de mezcla de colores del dispositivo no-aplanático mejora añadiendo características de un aplanático a su homólogo simétrico sin pérdida de eficiencia. En el caso del diseño basado en RXI, su gran ventaja consiste en su menor coste de fabricación ya que el proceso de metalización puede evitarse. Aunque algunos de los componentes presentan formas muy complejas, los costes de fabricación son relativamente insensibles a la complejidad del molde, especialmente en el caso de la producción en masa (tales como inyección de plástico), ya que el coste del molde se reparte entre todas las piezas fabricadas. Por último, las últimas dos secciones son las conclusiones y futuras líneas de investigación. ABSTRACT Nonimaging optics is a branch of optics whose development began in the mid-1960s. This rather new field of optics focuses on the efficient light transfer necessary in many applications, among which we highlight solar concentrators and illumination systems. The classical optics solutions to the problems of light energy transfer are only appropriate when the light rays are paraxial. The paraxial condition is not met in most applications for the concentration and illumination. This thesis explores several free-form designs (with neither rotational nor linear symmetry) whose applications are intended to cover the above mentioned areas and more. The term nonimaging comes from the fact that these optical systems do not need to form an image of the object, although it is not a necessary condition not to form an image. Another word sometimes used instead of nonimaging is anidolic, and it comes from the Greek “an+eidolon” and has the same meaning. Most of the optical systems designed for nonimaging applications are without any symmetry, i.e. free-form. Free-form optical systems become especially relevant lately with the evolution of free-form tooling (injection molding machines, multi-axis machining techniques, etc.). Nevertheless, only recently there are nonimaging design techniques that are able to meet these degrees of freedom. In illumination applications, the SMS3D method allows designing two free-form surfaces to control very well extended sources. In cases when source, target or volumetric constrains have very asymmetric requirements free-form surfaces are offering solutions with higher efficiency or with fewer elements in comparison with rotationally symmetric solutions, as free-forms have more degrees of freedom and they can perform multiple functions due to their free-form nature. Anidolic concentrators are well suited for the collection of solar energy, because the goal is not the reproduction of an exact image of the sun, but instead the collection of its energy. At this time, Concentration Photovoltaics (CPV) field is turning to high concentration systems in order to compensate the expense of multi-junction (MJ) solar cells used as receivers by reducing its area. Interest in the use of MJ cells lies in their very high conversion efficiency. High Concentration Photovoltaic systems (HCPV) with geometric concentration of more than 500x are required in order to have competitive systems in terrestrial applications. These systems comprise two (or more) optical elements, mirrors and/or lenses. Systems presented in this thesis encompass both main types of HCPV architectures: concentrators with primary reflective element and concentrators with primary refractive element (Fresnel lens). Demand for the efficiency increase of the actual HCPV systems as well as feasible more efficient partitioning of the solar spectrum, leads to exploration of four or more junction solar cells or submodules. They have a potential of reaching over 45% efficiency at concentration of hundreds of suns. One possible architectures of spectrum splitting module using commercial concentration cells is presented in this thesis. Another field of application of nonimaging optics is illumination, where a specific illuminance distribution pattern is required. The Solid State Lighting (SSL) based on semiconductor electroluminescence provides light sources for general illumination applications. In the last decade high-brightness Light Emitting Diodes (LEDs) started replacing conventional light sources due to their superior output light quality, unsurpassed lifetime, compactness and energy savings. Collimators used with LEDs have to meet requirements like high efficiency, high beam control, color and position mixing, as well as a high compactness. We present a free-form collimator with microstructures that performs good collimation and good color mixing with RGGB LED source. Good light mixing is important not only for simplifying luminaire optical design but also for avoiding die binning. Optical light mixing may reduce costs by avoiding pulse-width modulation and other patented electronic solutions for dimming and color tuning. This thesis comprises four chapters. Chapters containing the original work of this thesis are preceded by the introductory chapter that addresses basic concepts and definitions of geometrical optics on which nonimaging is developed. It contains fundamentals of nonimaging optics together with the description of its design problems, principles and methods, and with the Simultaneous Multiple Surface (SMS) method standing out for its versatility and ability to control several bundles of rays. Köhler integration and its applications in the field of photovoltaics are described as well. CPV and SSL fields are introduced together with the review on their background and their current status. Chapter 2 and Chapter 3 contain advanced optical designs with primarily application in solar concentration; meanwhile Chapter 4 portrays the free-form V-groove collimator with good color mixing property for illumination application. Chapter 2 describes two HCPV optical concentrators designed with the SMS method in three dimensions (SMS3D). Both concentrators represent Köhler integrator arrays that provide uniform irradiance distribution free from chromatic aberrations on the solar cell. One of the systems is the XXR free-form concentrator designed with the SMS3D method. The primary mirror (X) of this concentrator and secondary lens (R) are divided in four symmetric sectors (folds) that perform Köhler integration; meanwhile the intermediate mirror (X) is rotationally symmetric. Second HCPV concentrator is the Fresnel-RXI (FRXI) with flat Fresnel lens as the Primary Optical Element (POE) and an RXI lens as the Secondary Optical Element (SOE). This architecture manifests 4-fold configuration for performing Köhler integration (4 array units), as well. The RXI lenses are well-known nonimaging devices, but their application as SOE is novel. Both XXR and FRXI Köhler HCPV concentrators are academic examples of very high concentration (more than 2,000x meanwhile conventional systems nowadays have up to 1,000x) prepared for the near future N-junction (N>3) solar cells. In order to have efficient and cost-effective terrestrial CPV systems, those cells will probably require higher concentrations and high spectral irradiance uniformity. Both concentrators are designed by maximizing merit functions: the optical efficiency, concentration-acceptance angle (CAP) and cell-irradiance uniformity free from chromatic aberrations (Köhler integration). Chapter 3 presents the spectrum splitting architecture based on a HCPV module with high concentration (500x) and high acceptance angle (>1º). This module aims to reduce both sources of losses of the actual commercial triple-junction (3J) solar cells with more efficient use of the solar spectrum and with recovering the light reflected from the 3J cells’ grid lines and semiconductor surface. The solar spectrum is used more efficiently due to the combination of a high efficiency 3J concentration cell (GaInP/GaInAs/Ge) and external Back-Point-Contact (BPC) concentration silicon (Si) cell. By employing external confinement techniques, the 3J cell’s reflections are recovered in order to be re-absorbed by the cell. In the proposed concentrator architecture, the 3J cell operates at its optimized current gain (at geometrical concentration of 500x), while the Si cell works near its optimum, as well (135x). The spectrum splitting module consists of a flat Fresnel lens (as the POE), and a free-form RXI-type concentrator with a band-pass filter embedded in it (as the SOE), both POE and SOE performing Köhler integration to produce light homogenization. The band-pass filter sends the IR photons in the 900-1,150nm band to the Si cell. There are several practical aspects of presented module architecture that help reducing the added complexity of the beam splitting systems: the filter and secondary are forming a single solid piece, both cells are coplanar so the heat management and wiring is simplified, etc. Two proof-of-concept prototypes are assembled and tested in order to prove filter manufacturability and performance, as well as the potential of external light recycling technique. Obtained measurement results agree quite well with models and simulations, and show an opened path to manufacturing of the Fresnel RXI-type secondary concentrator with spectrum splitting strategy. Two free-form solid V-groove collimators are presented in Chapter 4. Both free-form collimators are originally designed with the SMS3D method. The second mirrored optically active surface is converted in a grooved surface a posteriori. Initial two mirror (XX) design is presented as a proof-of-concept. Second, RXI free-form design is comparable with existing RXI collimators as it is a highly compact and a highly efficient design. It performs very good color mixing of the RGGB LED sources placed off-axis like in conventional RGB LEDs. Collimators described here improve color mixing property of the prior art rotationally symmetric no-aplanatic RXI devices, and the efficiency of the aplanatic ones, accomplishing both good collimation and good color mixing. Free-form V-groove collimators enhance the no-aplanatic device's blending capabilities by adding aplanatic features to its symmetric counterpart with no loss in efficiency. Big advantage of the RXI design is its potentially lower manufacturing cost, since the process of metallization may be avoided. Although some components are very complicated for shaping, the manufacturing costs are relatively insensitive to the complexity of the mold especially in the case of mass production (such as plastic injection), as the cost of the mold is spread in many parts. Finally, last two sections are conclusions and future lines of investigation.