Metal-Organic Semiconductor Nanostructures for Surface-Enhanced Raman Scattering

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

Unusual bismuth-containing surface layers of III-V compound semiconductors

The understanding and engineering of bismuth (Bi) containing semiconductor surfaces are signi cant in the development of novel semiconductor materials for electronic and optoelectronic devices such as high-e ciency solar cells, lasers and light emitting diodes. For example, a Bi surface layer can be used as a surfactant which oats on a III-V compound-semiconductor surface during the epitaxial growth of IIIV lms. This Bi surfactant layer improves the lm-growth conditions if compared to the growth without the Bi layer. Therefore, detailed knowledge of the properties of the Bi/III-V surfaces is needed. In this thesis, well-de ned surface layers containing Bi have been produced on various III-V semiconductor substrates. The properties of these Bi-induced surfaces have been measured by low-energy electron di raction (LEED), scanning-tunneling microscopy and spectroscopy (STM), and synchrotron-radiation photoelectron spectroscopy. The experimental results have been compared with theoretically calculated results to resolve the atomic structures of the studied surfaces. The main ndings of this research concern the determination of the properties of an unusual Bi-containing (2×1) surface structure, the discovery and characterization of a uniform pattern of Bi nanolines, and the optimization of the preparation conditions for this Bi-nanoline pattern.

Research and development of III-V semiconductor surfaces for improved device interfaces

This thesis is devoted to understanding and improving technologically important III-V compound semiconductor (e.g. GaAs, InAs, and InSb) surfaces and interfaces for devices. The surfaces and interfaces of crystalline III-V materials have a crucial role in the operation of field-effect-transistors (FET) and highefficiency solar-cells, for instance. However, the surfaces are also the most defective part of the semiconductor material and it is essential to decrease the amount of harmful surface or interface defects for the next-generation III-V semiconductor device applications. Any improvement in the crystal ordering at the semiconductor surface reduces the amount of defects and increases the material homogeneity. This is becoming more and more important when the semiconductor device structures decrease to atomic-scale dimensions. Toward that target, the effects of different adsorbates (i.e., Sn, In, and O) on the III-V surface structures and properties have been investigated in this work. Furthermore, novel thin-films have been synthesized, which show beneficial properties regarding the passivation of the reactive III-V surfaces. The work comprises ultra-high-vacuum (UHV) environment for the controlled fabrication of atomically ordered III-V(100) surfaces. The surface sensitive experimental methods [low energy electron diffraction (LEED), scanning tunneling microscopy/spectroscopy (STM/STS), and synchrotron radiation photoelectron spectroscopy (SRPES)] and computational density-functionaltheory (DFT) calculations are utilized for elucidating the atomic and electronic properties of the crucial III-V surfaces. The basic research results are also transferred to actual device tests by fabricating metal-oxide-semiconductor capacitors and utilizing the interface sensitive measurement techniques [capacitance voltage (CV) profiling, and photoluminescence (PL) spectroscopy] for the characterization. This part of the thesis includes the instrumentation of home-made UHV-compatible atomic-layer-deposition (ALD) reactor for growing good quality insulator layers. The results of this thesis elucidate the atomic structures of technologically promising Sn- and In-stabilized III-V compound semiconductor surfaces. It is shown that the Sn adsorbate induces an atomic structure with (1×2)/(1×4) surface symmetry which is characterized by Sn-group III dimers. Furthermore, the stability of peculiar ζa structure is demonstrated for the GaAs(100)-In surface. The beneficial effects of these surface structures regarding the crucial III-V oxide interface are demonstrated. Namely, it is found that it is possible to passivate the III-V surface by a careful atomic-scale engineering of the III-V surface prior to the gate-dielectric deposition. The thin (1×2)/(1×4)-Sn layer is found to catalyze the removal of harmful amorphous III-V oxides. Also, novel crystalline III-V-oxide structures are synthesized and it is shown that these structures improve the device characteristics. The finding of crystalline oxide structures is exploited by solving the atomic structure of InSb(100)(1×2) and elucidating the electronic structure of oxidized InSb(100) for the first time.

Modified rare earth semiconductor oxide as a new nucleotide probe

Recent rapid developments in biological analysis, medical diagnosis, pharmaceutical industry, and environmental control fuel the urgent need for recognition of particular DNA sequences from samples. Currently, DNA detection techniques use radiochemical, enzymatic, fluorescent, or electrochemiluminescent methods; however, these techniques require costly labeled DNA and highly skilled and cumbersome procedure, which prohibit any in-situ monitoring. Here, we report that hybridization of surface-immobilized single-stranded oligonucleotide on praseodymium oxide (evaluated as a biosensor surface for the first time) with complimentary strands in solution provokes a significant shift of electrical impedance curve. This shift is attributed to a change in electrical characteristics through modification of surface charge of the underlying modified praseodymium oxide upon hybridization with the complementary oligonucelotide strand. On the other hand, using a noncomplementary single strand in solution does not create an equivalent change in the impedance value. This result clearly suggests that a new and simple electrochemical technique based on the change in electrical properties of the modified praseodymium oxide semiconductor surface upon recognition and transduction of a biological event without using labeled species is revealed.

The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

In order to evaluate the interactions between Au/Cu atoms and clean Si(l 11) surface, we used synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations. Optimized geometries and energies on different adsorption sites indicate that the binding energies at different adsorption sites are high, suggesting a strong interaction between metal atom and silicon surface. The Au atom showed higher interaction than Cu atom. The theoretical and experimental data showed good agreement. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A theoretical analysis of the TiO2/Sn doped (110) surface properties

We have used the periodic quantum-mechanical method with density functional theory at the B3LYP level in order to study TiO2/Sn doped (1 1 0) surfaces and have investigated the structural, electronic and energy band properties of these oxides. Our calculated relaxation directions for TiO2 is the experimental one and is also in agreement with other theoretical results. We also observe for the doped systems relaxation of lattice positions of the atoms. Modification of Sri, O and Ti charges depend on the planes and positions of the substituted atoms. Doping can modify the Fermi levels, energy gaps as well as the localization and composition of both valence and conduction band main components. Doping can also modify the chemical, electronic and optical properties of these oxides surfaces increasing their suitability for use as gas sensors and optoelectronic devices. (c) 2005 Elsevier B.V. All rights reserved.

Strategies to unblock the n-GaAs surface when electrodepositing Bi from acidic solutions

Bismuth ultra-thin films grown on n-GaAs electrodes via electrodeposition are porous due to a blockade of the electrode surface caused by adsorbed hydrogen when using acidic electrolytes. In this study, we discuss the existence of two sources of hydrogen adsorption and we propose different routes to unblock the n-GaAs surface in order to improve Bi films compactness. Firstly, we demonstrate that increasing the electrolyte temperature provides compact yet polycrystalline Bi films. Cyclic voltammetry scans indicate that this low crystal quality might be a result of the incorporation of Bi hydroxides within the Bi film as a result of the temperature increase. Secondly, we have illuminated the semiconductor surface to take advantage of photogenerated holes. These photocarriers oxidize the adsorbed hydrogen unblocking the surface, but also create pits at the substrate surface that degrade the Bi/GaAs interface and prevent an epitaxial growth. Finally, we show that performing a cyclic voltammetry scan before electrodeposition enables the growth of compact Bi ultra-thin films of high crystallinity on semiconductor substrates with a doping level low enough to perform transport measurements.

Driving forces for the adsorption of cyclopentene on InP(001)

In this work the interaction of cyclopentene with a set of InP(001) surfaces is investigated by means of the density functional theory. We propose a simple approach for evaluating the surface strain and based on it we have found a linear relation between bond and strain energies and the adsorption energy. Our results also indicate that the higher the bond energy, the more disperse the charge distribution is around the adsorption site associated to the high occupied state, a key feature that characterizes the adsorption process. Different adsorption coverages are used to evaluate the proposed equation. Our results suggest that the proposed approach might be extended to other systems where the interaction of the semiconductor surface and the molecule is restricted to first neighbor sites. (C) 2011 Elsevier B.V. All rights reserved.

Photocatalytic Degradation of Phenol by Thermal Titanium Dioxide Thin Layer Electrodes

Electrochemical processes in industrial effluents have been studied as a means to obtain higher efficiency in wastewater treatment. Heterogeneous photocatalysis appears as a low-cost alternative through the use of lower wattage lamps and thermal TiO2 films. Photocatalysis became a clean process for water treatment due to hydroxyl radicals generated on semiconductor surface. Such radicals are able to degrade several organic compounds. This study used different electrodes and analytical methods for degradation of phenol molecules to reduce treatment costs, improve efficiency, and identify compounds formed during the decomposition of phenolic molecules. Thermal growth of TiO2 film was observed on the titanium electrode in rutile form. Application of an electrical potential on the Ti/TiO2 working electrode increases efficiency in reducing concentration of phenol after photocatalytic treatment. Still, high energy radiation (UVC) showed best degradation rates in photolytic process. Different compounds formed during the degradation of phenol were also identified in the UVC-PE treatment.

Heterogeneous photocatalytic treatment of organic dyes in air and aqueous media

This review focuses on the heterogeneous photocatalytic treatment of organic dyes in air and water. Representative studies spanning approximately three decades are included in this review. These studies have mostly used titanium dioxide (TiO2) as the inorganic semiconductor photocatalyst of choice for decolorizing and decomposing the organic dye to mineralized products. Other semiconductors such as ZnO, CdS, WO3, and Fe2O3 have also been used, albeit to a much smaller extent. The topics covered include historical aspects, dark adsorption of the dye on the semiconductor surface and its role in the subsequent photoreaction, semiconductor preparation details, photoreactor configurations, photooxidation kinetics/mechanisms and comparison with other Advanced Oxidation Processes (e.g., UV/H2O2, ozonation, UV/O3, Fenton and photo-Fenton reactions), visible light-induced dye decomposition by sensitization mechanism, reaction intermediates and toxicity issues, and real-world process scenarios. © 2008 Elsevier B.V. All rights reserved.

Desinfecção de águas pelo processo fotocatalítico utilizando eletrodos térmicos de dióxido de titânio para inativação de Escherichia coli e Staphylococcus aureus

Pós-graduação em Ciências Biológicas (Microbiologia Aplicada) - IBRC

Charge generation and recombination in solid-state dye-sensitized solar cells

Diese Doktorarbeit befasst sich mit Ladungsgeneration und – rekombination in Feststoff-Farbstoffsolarzellen, die spiro-OMeTAD als Lochleiter verwenden. Die vorliegende Arbeit ist in drei Fallstudien unterteilt: i.) Kern-erweiterte Rylen-Farbstoffe, ii.) ein Perylenmonoimid-Farbstoff und iii.) Donor-π verbrückte (Cyclopentadithiophen)-Akzeptor-Farbstoffe. Trotz ihres hohen molaren Extinktionskoeffizienten und der hohen Absorbanz der sensibilisierten Filme, zeigen einige dieser Farbstoffmoleküle nur geringe photovoltaischen Effizienzen. Um den Ursprung des geringen Wirkungsgrades herauszufinden, wurde breitbandige, ultraschnelle transiente Absorptionsspektroskopie an Solarzellen durchgeführt.rnInsbesondere die Auswirkungen verschiedender Ankergruppen, Dipolmomente, Photolumineszenzlebenszeiten, Lithium-Kationensensitivität und Ladungsträgerdynamik, die alle einen großen Einfluss auf den Wirkungsgrad der Solarzelle besitzen, wurden untersucht. In der ersten Fallstudie zeigte ein kurzer Rylen-Farbstoff aufgrund deutlich verlängerter Lebenszeiten die beste Effizienz im Vergleich zu größeren Kern-erweiterten Rylen-Farbstoffen. Die Lebenszeit wurde weiter reduziert, wenn Maleinsäure als Ankergruppe unter einer Ringöffnungsreaktion an die mesoporöse Oberfläche des Metalloxid-Halbleiters adsorbierte. Dies konnte mit Hilfe von Berechnungen mittels der Dichtefunktionaltheorie (DFT, B3LYP) auf die Differenz des Dipolmoments zwischen Grundzustand und angeregtem Zustand zurückgeführt werden. Die Berechnungen bekräftigen die unvorteilhafte Injektion von Ladungen durch die Änderung der Richtung des Dipolmoments, wenn eine Ringöffnung der Anhydridgruppe stattfindet. In der zweiten Studie zeigte das Perylenmonoimid-Derivat ID889 einen Wirkungsgrad von 4.5% in Feststoff-Farbstoffsolarzellen, wobei ID889 sogar ohne Zuhilfenahme eines Additivs in der Lage ist langlebige Farbstoffkationen zu bilden. Die Verwendung von Lithium-Kationen stabilisiert jedoch sowohl den Prozess der Ladungsgeneration als auch den der Ladungsregeneration. Des Weiteren wurde in ID889-sensitivierten Bauteilen kein reduktives Löschen beobachtet. Dabei wurde die Dynamik der Exzitonen mittels einer soft-modelling Methode Kurvenanalyse aus den Daten der transienten Absorptionsspektroskopie gewonnen. Zuletzt wurden Strukturen mit Cyclopentadithiophen(CPDT)-Baustein untersucht, die eine typische D-π-A Molekülstruktur bilden. FPH224 und 233 zeigten dabei eine bessere Effizienz als FPH231 und 303 aufgrund einer großen Injektionseffizienz (IE) und längerer Lebenszeit der angeregten Zustände. Dies kann auf reduktives Löschen in FPH231 und 303 zurückgeführt werden, wohingegen FPH224 und 233 einen moderaten Zerfall des Spirokationensignals zeigten.

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.

Why is it possible to detect doped regions of semiconductors in low voltage SEM:a review and update

There is an urgent need for fast, non-destructive and quantitative two-dimensional dopant profiling of modern and future ultra large-scale semiconductor devices. The low voltage scanning electron microscope (LVSEM) has emerged to satisfy this need, in part, whereby it is possible to detect different secondary electron yield values (brightness in the SEM signal) from the p-type to the n-type doped regions as well as different brightness levels from the same dopant type. The mechanism that gives rise to such a secondary electron (SE) contrast effect is not fully understood, however. A review of the different models that have been proposed to explain this SE contrast is given. We report on new experiments that support the proposal that this contrast is due to the establishment of metal-to-semiconductor surface contacts. Further experiments showing the effect of instrument parameters including the electron dose, the scan speeds and the electron beam energy on the SE contrast are also reported. Preliminary results on the dependence of the SE contrast on the existence of a surface structure featuring metal-oxide semiconductor (MOS) are also reported. Copyright © 2005 John Wiley & Sons, Ltd.