Vanadium-Doped In and Sn Sulphides: Photocatalysts able to use the whole visible light spectrum

Using photocatalysis for energy applications depends, more than for environmental purposes or selective chemical synthesis, on converting as much of the solar spectrum as possible; the best photocatalyst, titania, is far from this. Many efforts are pursued to use better that spectrum in photocatalysis, by doping titania or using other materials (mainly oxides, nitrides and sulphides) to obtain a lower bandgap, even if this means decreasing the chemical potential of the electron-hole pairs. Here we introduce an alternative scheme, using an idea recently proposed for photovoltaics: the intermediate band (IB) materials. It consists in introducing in the gap of a semiconductor an intermediate level which, acting like a stepstone, allows an electron jumping from the valence band to the conduction band in two steps, each one absorbing one sub-bandgap photon. For this the IB must be partially filled, to allow both sub-bandgap transitions to proceed at comparable rates; must be made of delocalized states to minimize nonradiative recombination; and should not communicate electronically with the outer world. For photovoltaic use the optimum efficiency so achievable, over 1.5 times that given by a normal semiconductor, is obtained with an overall bandgap around 2.0 eV (which would be near-optimal also for water phtosplitting). Note that this scheme differs from the doping principle usually considered in photocatalysis, which just tries to decrease the bandgap; its aim is to keep the full bandgap chemical potential but using also lower energy photons. In the past we have proposed several IB materials based on extensively doping known semiconductors with light transition metals, checking first of all with quantum calculations that the desired IB structure results. Subsequently we have synthesized in powder form two of them: the thiospinel In2S3 and the layered compound SnS2 (having bandgaps of 2.0 and 2.2 eV respectively) where the octahedral cation is substituted at a â?10% level with vanadium, and we have verified that this substitution introduces in the absorption spectrum the sub-bandgap features predicted by the calculations. With these materials we have verified, using a simple reaction (formic acid oxidation), that the photocatalytic spectral response is indeed extended to longer wavelengths, being able to use even 700 nm photons, without largely degrading the response for above-bandgap photons (i.e. strong recombination is not induced) [3b, 4]. These materials are thus promising for efficient photoevolution of hydrogen from water; work on this is being pursued, the results of which will be presented.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

Simulation of impulse response for indoor visible light communications using 3D CAD models

n this article, a tool for simulating the channel impulse response for indoor visible light communications using 3D computer-aided design (CAD) models is presented. The simulation tool is based on a previous Monte Carlo ray-tracing algorithm for indoor infrared channel estimation, but including wavelength response evaluation. The 3D scene, or the simulation environment, can be defined using any CAD software in which the user specifies, in addition to the setting geometry, the reflection characteristics of the surface materials as well as the structures of the emitters and receivers involved in the simulation. Also, in an effort to improve the computational efficiency, two optimizations are proposed. The first one consists of dividing the setting into cubic regions of equal size, which offers a calculation improvement of approximately 50% compared to not dividing the 3D scene into sub-regions. The second one involves the parallelization of the simulation algorithm, which provides a computational speed-up proportional to the number of processors used.

New concepts and techniques for the development of high-efficiency concentrating photovoltaic modules

El interés por los sistemas fotovoltaicos de concentración (CPV) ha resurgido en los últimos años amparado por el desarrollo de células multiunión de muy alta eficiencia basadas en semiconductores de los grupos III-V. Estas células han permitido obtener módulos de concentración con eficiencias que prácticamente duplican las del panel plano y que llegan al 35% en los módulos récord. Esta tesis está dedicada al diseño y la implementación experimental de nuevos conceptos que permitan obtener módulos CPV que no sólo alcancen una eficiencia alta en condiciones estándar sino que, además, sean lo suficientemente tolerantes a errores de montaje, seguimiento, temperatura y variaciones espectrales para que la energía que producen a lo largo del año sea máxima. Una de las primeras cuestiones que se abordan es el diseño de elementos ópticos secundarios para sistemas cuyo primario es una lente de Fresnel y que permiten, para una concentración fija, aumentar el ángulo de aceptancia y la tolerancia del sistema. Varios secundarios reflexivos y refractivos han sido diseñados y analizados mediante trazado de rayos. En particular, utilizando óptica anidólica y basándose en el diseño de una sola etapa conocido como ‘concentrador dieléctrico que funciona por reflexión total interna‘, se ha diseñado, fabricado y caracterizado un secundario con salida cuadrada que, usado junto con una lente de Fresnel, permite alcanzar simultáneamente una elevada eficiencia, concentración y aceptancia. Además, se ha propuesto y prototipado un método alternativo de fabricación para otro de los secundarios, denominado domo, consistente en el sobremoldeo de silicona sobre células solares. Una de las características que impregna todo el trabajo realizado en esta tesis es la aproximación holística en el diseño de módulos CPV, es decir, se ha prestado especial atención al diseño conjunto de la célula y la óptica para garantizar que el sistema total alcance la mayor eficiencia posible. En este sentido muchos sistemas ópticos desarrollados en esta tesis han sido diseñados, caracterizados y optimizados teniendo en cuenta que el ajuste de corriente entre las distintas subcélulas que comprenden la célula multiunión bajo el concentrador sea muy próximo a uno. La capa antirreflectante sobre la célula funciona, en cierto modo, como interfaz entre la óptica y la célula, por lo que se ha diseñado un método de optimización de capas antirreflectantes que considera no sólo el amplio rango de longitudes de onda para el que las células multiunión son sensibles sino también la distribución angular de intensidad sobre la célula creada por la óptica de concentración. Además, la cuestión de la falta de uniformidad también se ha abordado mediante la comparación de las distribuciones espectrales y espaciales de irradiancia que crean diferentes ópticas (simuladas mediante trazado de rayos y fotografiadas) y las pérdidas de eficiencia que experimentan las células iluminadas por dichas ópticas de concentración medidas experimentalmente. El efecto de la temperatura en la óptica de concentración también ha sido objeto de estudio de esta tesis. En particular, mediante simulaciones de elementos finitos se han dado los primeros pasos para el análisis de las deformaciones que sufren los dientes de las lentes de Fresnel híbridas (vidrio-silicona), así como el cambio de índice de refracción con la temperatura y la influencia de ambos efectos sobre el funcionamiento de los sistemas. Se ha implementado un modelo que tiene por objeto considerar las variaciones ambientales, principalmente temperatura y contenido espectral de la radiación directa, así como las sensibilidades térmica y espectral de los sistemas CPV, con el fin de maximizar la energía producida por un módulo de concentración a lo largo de un año en un emplazamiento determinado. Los capítulos 5 y 6 de este libro están dedicados al diseño, fabricación y caracterización de un nuevo concepto de módulo fotovoltaico denominado FluidReflex y basado en una única etapa reflexiva con dieléctrico fluido. En este nuevo concepto la presencia del fluido aporta algunas ventajas significativas como son: un aumento del producto concentración por aceptancia (CAP, en sus siglas en inglés) alcanzable al rodear la célula con un medio cuyo índice de refracción es mayor que uno, una mejora de la eficiencia óptica al disminuir las pérdidas por reflexión de Fresnel en varias interfaces, una mejora de la disipación térmica ya que el calor que se concentra junto a la célula se trasmite por convección natural y conducción en el fluido y un aislamiento eléctrico mejorado. Mediante la construcción y medida de varios prototipos de unidad elemental se ha demostrado que no existe ninguna razón fundamental que impida la implementación práctica del concepto teórico alcanzando una elevada eficiencia. Se ha realizado un análisis de fluidos candidatos probando la existencia de al menos dos de ellos que cumplen todos los requisitos (en particular el de estabilidad bajo condiciones de luz concentrada) para formar parte del sistema de concentración FluidReflex. Por ´ultimo, se han diseñado, fabricado y caracterizado varios prototipos preindustriales de módulos FluidReflex para lo cual ha sido necesario optimizar el proceso de fabricación de la óptica multicavidad a fin de mantener el buen comportamiento óptico obtenido en la fabricación de la unidad elemental. Los distintos prototipos han sido medidos, tanto en el laboratorio como bajo el sol real, analizando el ajuste de corriente de la célula iluminada por el concentrador FluidReflex bajo diferentes distribuciones espectrales de la radiación incidente así como el excelente comportamiento térmico del módulo. ABSTRACT A renewed interest in concentrating photovoltaic (CPV) systems has emerged in recent years encouraged by the development of high-efficiency multijunction solar cells based in IIIV semiconductors that have led to CPV module efficiencies which practically double that of flat panel PV and which reach 35% for record modules. This thesis is devoted to the design and experimental implementation of new concepts for obtaining CPV modules that not only achieve high efficiency under standard conditions but also have such a wide tolerance to assembly errors, tracking, temperature and spectral variations, that the energy generated by them throughout the year is maximized. One of the first addressed issues is the design of secondary optical elements whose primary optics is a Fresnel lens and which, for a fixed concentration, allow an increased acceptance angle and tolerance of the system. Several reflective and refractive secondaries have been designed and analyzed using ray tracing. In particular, using nonimaging optics and based on the single-stage design known as ‘dielectric totally internally reflecting concentrator’, a secondary with square output has been designed, fabricated and characterized. Used together with a Fresnel lens, the secondary can simultaneously achieve high efficiency, concentration and acceptance. Furthermore, an alternative method has been proposed and prototyped for the fabrication of the secondary named dome. The optics is manufactured by direct overmolding of silicone over the solar cells. One characteristic that permeates all the work done in this thesis is the holistic approach in the design of CPV modules, meaning that special attention has been paid to the joint design of the solar cell and the optics to ensure that the total system achieves the highest attainable efficiency. In this regard, many optical systems developed in the thesis have been designed, characterized and optimized considering that the current matching among the subcells within the multijunction solar cell beneath the optics must be close to one. Antireflective coating over the cell acts, somehow, as an interface between the optics and the cell. Consequently, a method has been designed to optimize antireflective coatings that takes into account not only the broad wavelength range that multijunction solar cells are sensitive to but also the angular intensity distribution created by the concentrating optics. In addition, the issue of non-uniformity has also been addressed by comparing the spectral and spatial distributions of irradiance created by different optics (simulated by ray tracing and photographed) and the efficiency losses experienced by cells illuminated by those concentrating optics experimentally determined. The effect of temperature on the concentrating optics has also been studied in this thesis. In particular, finite element simulations have been use to analyze the deformations experienced by the facets of hybrid (silicon-glass) Fresnel lenses, the change of refractive index with temperature and the influence of both effects on the system performance. A model has been implemented which take into consideration atmospheric variations, mainly temperature and spectral content of the direct normal irradiance, as well as thermal and spectral sensitivities of systems, with the aim of maximizing the energy harvested by a CPV module throughout the year in a particular location. Chapters 5 and 6 of this book are devoted to the design, fabrication, and characterization of a new concentrator concept named FluidReflex and based on a single-stage reflective optics with fluid dielectric. In this new concept, the presence of the fluid provides some significant advantages such as: an increased concentration acceptance angle product (CAP) achievable by surrounding the cell with a medium whose refractive index is greater than one, an improvement of the optical efficiency by reducing losses due to Fresnel reflection at several interfaces, an improvement in heat dissipation as the heat concentrated near the cell is transmitted by natural convection and conduction in the fluid, and an improved electrical insulation. By fabricating and characterizing several elementary-unit prototypes it was shown that there is no fundamental reason that prevents the practical implementation of this theoretical concept reaching high efficiency. Several fluid candidates were investigated proving the existence of at least to fluids that meet all the requirements (including the stability under concentrated light) to become part of the FluidReflex concentrator. Finally, several pre-industrial FluidReflex module prototypes have been designed and fabricated. An optimization process for the manufacturing of the multicavity optics was necessary to attain such an optics quality as the one achieved by the single unit. The module prototypes have been measured, both indoors and outdoors, analyzing the current matching of the solar cells beneath the concentrator for different spectral distribution of the incident irradiance. Additionally, the module showed an excellent thermal performance.

The feasibility of high-efficiency InAs/GaAs quantum dot intermediate band solar cells

In recent years, all the operating principles of intermediate band behaviour have been demonstrated in InAs/GaAs quantum dot (QD) solar cells. Having passed this hurdle, a new stage of research is underway, whose goal is to deliver QD solar cells with efficiencies above those of state-of-the-art single-gap devices. In this work, we demonstrate that this is possible, using the present InAs/GaAs QD system, if the QDs are made to be radiatively dominated, and if absorption enhancements are achieved by a combination of increasing the number of QDs and light trapping. A quantitative prediction is also made of the absorption enhancements required, suggesting that a 30 fold increase in the number of QDs and a light trapping enhancement of 10 are sufficient. Finally, insight is given into the relative merits of absorption enhancement via increasing QD numbers and via light trapping.

Light-Emitting-Diodes based on ordered InGaN nanocolumns emitting in the blue, green and yellow spectral range

The growth of ordered arrays of InGaN/GaN nanocolumnar light emitting diodes by molecular beam epitaxy, emitting in the blue (441 nm), green (502 nm), and yellow (568 nm) spectral range is reported. The device active region, consisting of a nanocolumnar InGaN section of nominally constant composition and 250 to 500 nm length, is free of extended defects, which is in strong contrast to InGaN layers (planar) of similar composition and thickness. The devices are driven under pulsed operation up to 1300 A/cm2 without traces of efficiency droop. Electroluminescence spectra show a very small blue shift with increasing current, (almost negligible in the yellow device) and line widths slightly broader than those of state-of-the-art InGaN quantum wells.

Self assembled and ordered group III nitride nanocolumnar structures for light emitting applications

El objetivo de este trabajo es un estudio profundo del crecimiento selectivo de nanoestructuras de InGaN por epitaxia de haces moleculares asistido por plasma, concentrandose en el potencial de estas estructuras como bloques constituyentes en LEDs de nueva generación. Varias aproximaciones al problema son discutidas; desde estructuras axiales InGaN/GaN, a estructuras core-shell, o nanoestructuras crecidas en sustratos con orientaciones menos convencionales (semi polar y no polar). La primera sección revisa los aspectos básicos del crecimiento auto-ensamblado de nanocolumnas de GaN en sustratos de Si(111). Su morfología y propiedades ópticas son comparadas con las de capas compactas de GaN sobre Si(111). En el caso de las columnas auto-ensambladas de InGaN sobre Si(111), se presentan resultados sobre el efecto de la temperatura de crecimiento en la incorporación de In. Por último, se discute la inclusión de nanodiscos de InGaN en las nanocolumnas de GaN. La segunda sección revisa los mecanismos básicos del crecimiento ordenado de nanoestructuras basadas en GaN, sobre templates de GaN/zafiro. Aumentando la relación III/V localmente, se observan cambios morfológicos; desde islas piramidales, a nanocolumnas de GaN terminadas en planos semipolares, y finalmente, a nanocolumnas finalizadas en planos c polares. Al crecer nanodiscos de InGaN insertados en las nanocolumnas de GaN, las diferentes morfologias mencionadas dan lugar a diferentes propiedades ópticas de los nanodiscos, debido al diferente carácter (semi polar o polar) de los planos cristalinos involucrados. La tercera sección recoge experimentos acerca de los efectos que la temperatura de crecimiento y la razón In/Ga tienen en la morfología y emisión de nanocolumnas ordenadas de InGaN crecidas sobre templates GaN/zafiro. En el rango de temperaturas entre 650 y 750 C, la incorporacion de In puede modificarse bien por la temperatura de crecimiento, o por la razón In/Ga. Controlar estos factores permite la optimización de la longitud de onda de emisión de las nanocolumnas de InGaN. En el caso particular de la generación de luz blanca, se han seguidos dos aproximaciones. En la primera, se obtiene emisión amarilla-blanca a temperatura ambiente de nanoestructuras donde la región de InGaN consiste en un gradiente de composiciones de In, que se ha obtenido a partir de un gradiente de temperatura durante el crecimiento. En la segunda, el apilamiento de segmentos emitiendo en azul, verde y rojo, consiguiendo la integración monolítica de estas estructuras en cada una de las nanocolumnas individuales, da lugar a emisores ordenados con un amplio espectro de emisión. En esta última aproximación, la forma espectral puede controlarse con la longitud (duración del crecimiento) de cada uno de los segmentos de InGaN. Más adelante, se presenta el crecimiento ordenado, por epitaxia de haces moleculares, de arrays de nanocolumnas que son diodos InGaN/GaN cada una de ellas, emitiendo en azul (441 nm), verde (502 nm) y amarillo (568 nm). La zona activa del dispositivo consiste en una sección de InGaN, de composición constante nominalmente y longitud entre 250 y 500 nm, y libre de defectos extendidos en contraste con capas compactas de InGaN de similares composiciones y espesores. Los espectros de electroluminiscencia muestran un muy pequeño desplazamiento al azul al aumentar la corriente inyectada (desplazamiento casi inexistente en el caso del dispositivo amarillo), y emisiones ligeramente más anchas que en el caso del estado del arte en pozos cuánticos de InGaN. A continuación, se presenta y discute el crecimiento ordenado de nanocolumnas de In(Ga)N/GaN en sustratos de Si(111). Nanocolumnas ordenadas emitiendo desde el ultravioleta (3.2 eV) al infrarrojo (0.78 eV) se crecieron sobre sustratos de Si(111) utilizando una capa compacta (“buffer”) de GaN. La morfología y eficiencia de emisión de las nanocolumnas emitiendo en el rango espectral verde pueden ser mejoradas ajustando las relaciones In/Ga y III/N, y una eficiencia cuántica interna del 30% se deriva de las medidas de fotoluminiscencia en nanocolumnas optimizadas. En la siguiente sección de este trabajo se presenta en detalle el mecanismo tras el crecimiento ordenado de nanocolumnas de InGaN/GaN emitiendo en el verde, y sus propiedades ópticas. Nanocolumnas de InGaN/GaN con secciones largas de InGaN (330-830 nm) se crecieron tanto en sustratos GaN/zafiro como GaN/Si(111). Se encuentra que la morfología y la distribución espacial del In dentro de las nanocolumnas dependen de las relaciones III/N e In/Ga locales en el frente de crecimiento de las nanocolumnas. La dispersión en el contenido de In entre diferentes nanocolumnas dentro de la misma muestra es despreciable, como indica las casi identicas formas espectrales de la catodoluminiscencia de una sola nanocolumna y del conjunto de ellas. Para las nanocolumnas de InGaN/GaN crecidas sobre GaN/Si(111) y emitiendo en el rango espectral verde, la eficiencia cuántica interna aumenta hasta el 30% al disminuir la temperatura de crecimiento y aumentar el nitrógeno activo. Este comportamiento se debe probablemente a la formación de estados altamente localizados, como indica la particular evolución de la energía de fotoluminiscencia con la temperatura (ausencia de “s-shape”) en muestras con una alta eficiencia cuántica interna. Por otro lado, no se ha encontrado la misma dependencia entre condiciones de crecimiento y efiencia cuántica interna en las nanoestructuras InGaN/GaN crecidas en GaN/zafiro, donde la máxima eficiencia encontrada ha sido de 3.7%. Como alternativa a las nanoestructuras axiales de InGaN/GaN, la sección 4 presenta resultados sobre el crecimiento y caracterización de estructuras core-shell de InGaN/GaN, re-crecidas sobre arrays de micropilares de GaN fabricados por ataque de un template GaN/zafiro (aproximación top-down). El crecimiento de InGaN/GaN es conformal, con componentes axiales y radiales en el crecimiento, que dan lugar a la estructuras core-shell con claras facetas hexagonales. El crecimiento radial (shell) se ve confirmado por medidas de catodoluminiscencia con resolución espacial efectuadas en un microscopio electrónico de barrido, asi como por medidas de microscopía de transmisión de electrones. Más adelante, el crecimiento de micro-pilares core-shell de InGaN se realizó en pilares GaN (cores) crecidos selectivamente por epitaxia de metal-orgánicos en fase vapor. Con el crecimiento de InGaN se forman estructuras core-shell con emisión alrededor de 3 eV. Medidas de catodoluminiscencia resuelta espacialmente indican un aumento en el contenido de indio del shell en dirección a la parte superior del pilar, que se manifiesta en un desplazamiento de la emisión de 3.2 eV en la parte inferior, a 3.0 eV en la parte superior del shell. Este desplazamiento está relacionado con variaciones locales de la razón III/V en las facetas laterales. Finalmente, se demuestra la fabricación de una estructura pin basada en estos pilares core-shell. Medidas de electroluminiscencia resuelta espacialmente, realizadas en pilares individuales, confirman que la electroluminiscencia proveniente del shell de InGaN (diodo lateral) está alrededor de 3.0 eV, mientras que la emisión desde la parte superior del pilar (diodo axial) está alrededor de 2.3 eV. Para finalizar, se presentan resultados sobre el crecimiento ordenado de GaN, con y sin inserciones de InGaN, en templates semi polares (GaN(11-22)/zafiro) y no polares (GaN(11-20)/zafiro). Tras el crecimiento ordenado, gran parte de los defectos presentes en los templates originales se ven reducidos, manifestándose en una gran mejora de las propiedades ópticas. En el caso de crecimiento selectivo sobre templates con orientación GaN(11-22), no polar, la formación de nanoestructuras con una particular morfología (baja relación entre crecimiento perpedicular frente a paralelo al plano) permite, a partir de la coalescencia de estas nanoestructuras, la fabricación de pseudo-templates no polares de GaN de alta calidad. ABSTRACT The aim of this work is to gain insight into the selective area growth of InGaN nanostructures by plasma assisted molecular beam epitaxy, focusing on their potential as building blocks for next generation LEDs. Several nanocolumn-based approaches such as standard axial InGaN/GaN structures, InGaN/GaN core-shell structures, or InGaN/GaN nanostructures grown on semi- and non-polar substrates are discussed. The first section reviews the basics of the self-assembled growth of GaN nanocolumns on Si(111). Morphology differences and optical properties are compared to those of GaN layer grown directly on Si(111). The effects of the growth temperature on the In incorporation in self-assembled InGaN nanocolumns grown on Si(111) is described. The second section reviews the basic growth mechanisms of selectively grown GaNbased nanostructures on c-plane GaN/sapphire templates. By increasing the local III/V ratio morphological changes from pyramidal islands, to GaN nanocolumns with top semi-polar planes, and further to GaN nanocolumns with top polar c-planes are observed. When growing InGaN nano-disks embedded into the GaN nanocolumns, the different morphologies mentioned lead to different optical properties, due to the semipolar and polar nature of the crystal planes involved. The third section reports on the effect of the growth temperature and In/Ga ratio on the morphology and light emission characteristics of ordered InGaN nanocolumns grown on c-plane GaN/sapphire templates. Within the growth temperature range of 650 to 750oC the In incorporation can be modified either by the growth temperature, or the In/Ga ratio. Control of these factors allows the optimization of the InGaN nanocolumns light emission wavelength. In order to achieve white light emission two approaches are used. First yellow-white light emission can be obtained at room temperature from nanostructures where the InGaN region is composition-graded by using temperature gradients during growth. In a second approach the stacking of red, green and blue emitting segments was used to achieve the monolithic integration of these structures in one single InGaN nanocolumn leading to ordered broad spectrum emitters. With this approach, the spectral shape can be controlled by changing the thickness of the respective InGaN segments. Furthermore the growth of ordered arrays of InGaN/GaN nanocolumnar light emitting diodes by molecular beam epitaxy, emitting in the blue (441 nm), green (502 nm), and yellow (568 nm) spectral range is reported. The device active region, consisting of a nanocolumnar InGaN section of nominally constant composition and 250 to 500 nm length, is free of extended defects, which is in strong contrast to InGaN layers (planar) of similar composition and thickness. Electroluminescence spectra show a very small blue shift with increasing current, (almost negligible in the yellow device) and line widths slightly broader than those of state-of-the-art InGaN quantum wells. Next the selective area growth of In(Ga)N/GaN nanocolumns on Si(111) substrates is discussed. Ordered In(Ga)N/GaN nanocolumns emitting from ultraviolet (3.2 eV) to infrared (0.78 eV) were then grown on top of GaN-buffered Si substrates. The morphology and the emission efficiency of the In(Ga)N/GaN nanocolumns emitting in the green could be substantially improved by tuning the In/Ga and total III/N ratios, where an estimated internal quantum efficiency of 30 % was derived from photoluminescence data. In the next section, this work presents a study on the selective area growth mechanisms of green-emitting InGaN/GaN nanocolumns and their optical properties. InGaN/GaN nanocolumns with long InGaN sections (330-830nm) were grown on GaN/sapphire and GaN-buffered Si(111). The nanocolumn’s morphology and spatial indium distribution is found to depend on the local group (III)/N and In/Ga ratios at the nanocolumn’s top. A negligible spread of the average indium incorporation among different nanostructures is found as indicated by similar shapes of the cathodoluminescence spectra taken from single nanocolumns and ensembles of nanocolumns. For InGaN/GaN nanocolumns grown on GaN-buffered Si(111), all emitting in the green spectral range, the internal quantum efficiency increases up to 30% when decreasing growth temperature and increasing active nitrogen. This behavior is likely due to the formation of highly localized states, as indicated by the absence of a complete s-shape behavior of the PL peak position with temperature (up to room temperature) in samples with high internal quantum efficiency. On the other hand, no dependence of the internal quantum efficiency on the growth conditions is found for InGaN/GaN nanostructures grown on GaN/sapphire, where the maximum achieved efficiency is 3.7%. As alternative to axial InGaN/GaN nanostructures, section 4 reports on the growth and characterization of InGaN/GaN core-shell structures on an ordered array of top-down patterned GaN microrods etched from a GaN/sapphire template. Growth of InGaN/GaN is conformal, with axial and radial growth components leading to core-shell structures with clear hexagonal facets. The radial InGaN growth (shell) is confirmed by spatially resolved cathodoluminescence performed in a scanning electron microscopy as well as in scanning transmission electron microscopy. Furthermore the growth of InGaN core-shell micro pillars using an ordered array of GaN cores grown by metal organic vapor phase epitaxy as a template is demonstrated. Upon InGaN overgrowth core-shell structures with emission at around 3.0 eV are formed. With spatially resolved cathodoluminescence, an increasing In content towards the pillar top is found to be present in the InGaN shell, as indicated by a shift of CL peak position from 3.2 eV at the shell bottom to 3.0 eV at the shell top. This shift is related to variations of the local III/V ratio at the side facets. Further, the successful fabrication of a core-shell pin diode structure is demonstrated. Spatially resolved electroluminescence measurements performed on individual micro LEDs, confirm emission from the InGaN shell (lateral diode) at around 3.0 eV, as well as from the pillar top facet (axial diode) at around 2.3 eV. Finally, this work reports on the selective area growth of GaN, with and without InGaN insertion, on semi-polar (11-22) and non-polar (11-20) templates. Upon SAG the high defect density present in the GaN templates is strongly reduced as indicated by TEM and a dramatic improvement of the optical properties. In case of SAG on non-polar (11-22) templates the formation of nanostructures with a low aspect ratio took place allowing for the fabrication of high-quality, non-polar GaN pseudo-templates by coalescence of the nanostructures.

V-substituted In2S3: an intermediate band material with photocatalytic activity in the whole visible light range

We proposed in our previous work V-substituted In2S3 as an intermediate band (IB) material able to enhance the efficiency of photovoltaic cells by combining two photons to achieve a higher energy electron excitation, much like natural photosynthesis. Here this hyper-doped material is tested in a photocatalytic reaction using wavelength-controlled light. The results evidence its ability to use photons with wavelengths of up to 750 nm, i.e. with energy significantly lower than the bandgap (=2.0 eV) of non-substituted In2S3, driving with them the photocatalytic reaction at rates comparable to those of non-substituted In2S3 in its photoactivity range (λ ≤ 650 nm). Photoluminescence spectra evidence that the same bandgap excitation as in V-free In2S3 occurs in V-substituted In2S3 upon illumination with photons in the same sub-bandgap energy range which is effective in photocatalysis, and its linear dependence on light intensity proves that this is not due to a nonlinear optical property. This evidences for the first time that a two-photon process can be active in photocatalysis in a single-phase material. Quantum calculations using GW-type many-body perturbation theory suggest that the new band introduced in the In2S3 gap by V insertion is located closer to the conduction band than to the valence band, so that hot carriers produced by the two-photon process would be of electron type; they also show that the absorption coefficients of both transitions involving the IB are of significant and similar magnitude. The results imply that V-substituted In2S3, besides being photocatalytically active in the whole visible light range (a property which could be used for the production of solar fuels), could make possible photovoltaic cells of improved efficiency.

New strategies in laser processing of TCOs for light management improvement in thin-film silicon solar cells

Light confinement strategies play a crucial role in the performance of thin-film (TF) silicon solar cells. One way to reduce the optical losses is the texturing of the transparent conductive oxide (TCO) that acts as the front contact. Other losses arise from the mismatch between the incident light spectrum and the spectral properties of the absorbent material that imply that low energy photons (below the bandgap value) are not absorbed, and therefore can not generate photocurrent. Up-conversion techniques, in which two sub-bandgap photons are combined to give one photon with a better matching with the bandgap, were proposed to overcome this problem. In particular, this work studies two strategies to improve light management in thin film silicon solar cells using laser technology. The first one addresses the problem of TCO surface texturing using fully commercial fast and ultrafast solid state laser sources. Aluminum doped Zinc Oxide (AZO) samples were laser processed and the results were optically evaluated by measuring the haze factor of the treated samples. As a second strategy, laser annealing experiments of TCOs doped with rare earth ions are presented as a potential process to produce layers with up-conversion properties, opening the possibility of its potential use in high efficiency solar cells.

Establishing Quercus ilex under Mediterranean dry conditions: sowing recalcitrant acorns versus planting seedlings at different depths and tube shelter light transmissions

Article New Forests November 2015, Volume 46, Issue 5, pp 869-883 First online: 17 June 2015 Establishing Quercus ilex under Mediterranean dry conditions: sowing recalcitrant acorns versus planting seedlings at different depths and tube shelter light transmissionsJuan A. OlietAffiliated withDepartamento de Sistemas y Recursos Naturales, E.T.S. Ingenieros de Montes, Universidad Politécnica de Madrid Email author View author's OrcID profile , Alberto Vázquez de CastroAffiliated withDepartamento de Sistemas y Recursos Naturales, E.T.S. Ingenieros de Montes, Universidad Politécnica de Madrid, Jaime PuértolasAffiliated withLancaster Environment Centre, Lancaster University $39.95 / €34.95 / £29.95 * Rent the article at a discount Rent now * Final gross prices may vary according to local VAT. Get Access AbstractSuccess of Mediterranean dry areas restoration with oaks is a challenging goal. Testing eco-techniques that mimic beneficial effects of natural structures and ameliorate stress contributes to positive solutions to overcoming establishment barriers. We ran a factorial experiment in a dry area, testing two levels of solid wall transmission of tube shelters (60 and 80 %) plus a control mesh, and two depths (shallow and 15 cm depth) of placing either planted seedlings or acorns of Quercus ilex. Microclimate of the planting or sowing spots was characterized by measuring photosynthetically active radiation, temperature and relative humidity. Plant response was evaluated in terms of survival, phenology, acorn emergence and photochemical efficiency (measured through chlorophyll fluorescence). We hypothesize that tube shelters and deep planting improve Q. ilex post-planting and sowing performance because of the combined effects of reducing excessive radiation and improving access to moist soil horizons. Results show that temperature and PAR was reduced, and relative humidity increased, in deep spots. Midsummer photochemical efficiency indicates highest level of stress for oaks in 80 % light transmission shelter. Optimum acorn emergence in spring was registered within solid wall tree shelters, and maximum summer survival of germinants and of planted seedlings occurred when acorns or seedlings were placed at 15 cm depth irrespectively of light transmission of shelter. Survival of germinants was similar to that of planted seedlings. The importance of techniques to keep high levels of viability after sowing recalcitrant seeds in the field is emphasized in the study

Volume Haptics and Dendritic Spine Editing

Esta tesis se ha desarrollado en el contexto del proyecto Cajal Blue Brain, una iniciativa europea dedicada al estudio del cerebro. Uno de los objetivos de esta iniciativa es desarrollar nuevos métodos y nuevas tecnologías que simplifiquen el análisis de datos en el campo neurocientífico. El presente trabajo se ha centrado en diseñar herramientas que combinen información proveniente de distintos canales sensoriales con el fin de acelerar la interacción y análisis de imágenes neurocientíficas. En concreto se estudiará la posibilidad de combinar información visual con información háptica. Las espinas dendríticas son pequeñas protuberancias que recubren la superficie dendrítica de muchas neuronas del cerebro. A día de hoy, se cree que tienen un papel clave en la transmisión de señales neuronales. Motivo por el cual, el interés por parte de la comunidad científica por estas estructuras ha ido en aumento a medida que las técnicas de adquisición de imágenes mejoraban hasta alcanzar una calidad suficiente para analizar dichas estructuras. A menudo, los neurocientíficos utilizan técnicas de microscopía con luz para obtener los datos que les permitan analizar estructuras neuronales tales como neuronas, dendritas y espinas dendríticas. A pesar de que estas técnicas ofrezcan ciertas ventajas frente a su equivalente electrónico, las técnicas basadas en luz permiten una menor resolución. En particular, estructuras pequeñas como las espinas dendríticas pueden capturarse de forma incorrecta en las imágenes obtenidas, impidiendo su análisis. En este trabajo, se presenta una nueva técnica, que permite editar imágenes volumétricas, mediante un dispositivo háptico, con el fin de reconstruir de los cuellos de las espinas dendríticas. Con este objetivo, en un primer momento se desarrolló un algoritmo que proporciona retroalimentación háptica en datos volumétricos, completando la información que provine del canal visual. Dicho algoritmo de renderizado háptico permite a los usuarios tocar y percibir una isosuperficie en el volumen de datos. El algoritmo asegura un renderizado robusto y eficiente. Se utiliza un método basado en las técnicas de “marching tetrahedra” para la extracción local de una isosuperficie continua, lineal y definida por intervalos. La robustez deriva tanto de una etapa de detección de colisiones continua de la isosuperficie extraída, como del uso de técnicas eficientes de renderizado basadas en un proxy puntual. El método de “marching tetrahedra” propuesto garantiza que la topología de la isosuperficie extraída coincida con la topología de una isosuperficie equivalente determinada utilizando una interpolación trilineal. Además, con el objetivo de mejorar la coherencia entre la información háptica y la información visual, el algoritmo de renderizado háptico calcula un segundo proxy en la isosuperficie pintada en la pantalla. En este trabajo se demuestra experimentalmente las mejoras en, primero, la etapa de extracción de isosuperficie, segundo, la robustez a la hora de mantener el proxy en la isosuperficie deseada y finalmente la eficiencia del algoritmo. En segundo lugar, a partir del algoritmo de renderizado háptico propuesto, se desarrolló un procedimiento, en cuatro etapas, para la reconstrucción de espinas dendríticas. Este procedimiento, se puede integrar en los cauces de segmentación automática y semiautomática existentes como una etapa de pre-proceso previa. El procedimiento está diseñando para que tanto la navegación como el proceso de edición en sí mismo estén controlados utilizando un dispositivo háptico. Se han diseñado dos experimentos para evaluar esta técnica. El primero evalúa la aportación de la retroalimentación háptica y el segundo se centra en evaluar la idoneidad del uso de un háptico como dispositivo de entrada. En ambos casos, los resultados demuestran que nuestro procedimiento mejora la precisión de la reconstrucción. En este trabajo se describen también dos casos de uso de nuestro procedimiento en el ámbito de la neurociencia: el primero aplicado a neuronas situadas en la corteza cerebral humana y el segundo aplicado a espinas dendríticas situadas a lo largo de neuronas piramidales de la corteza del cerebro de una rata. Por último, presentamos el programa, Neuro Haptic Editor, desarrollado a lo largo de esta tesis junto con los diferentes algoritmos ya mencionados. ABSTRACT This thesis took place within the Cajal Blue Brain project, a European initiative dedicated to the study of the brain. One of the main goals of this project is the development of new methods and technologies simplifying data analysis in neuroscience. This thesis focused on the development of tools combining information originating from distinct sensory channels with the aim of accelerating both the interaction with neuroscience images and their analysis. In concrete terms, the objective is to study the possibility of combining visual information with haptic information. Dendritic spines are thin protrusions that cover the dendritic surface of numerous neurons in the brain and whose function seems to play a key role in neural circuits. The interest of the neuroscience community toward those structures kept increasing as and when acquisition methods improved, eventually to the point that the produced datasets enabled their analysis. Quite often, neuroscientists use light microscopy techniques to produce the dataset that will allow them to analyse neuronal structures such as neurons, dendrites and dendritic spines. While offering some advantages compared to their electronic counterpart, light microscopy techniques achieve lower resolutions. Particularly, small structures such as dendritic spines might suffer from a very low level of fluorescence in the final dataset, preventing further analysis. This thesis introduces a new technique enabling the edition of volumetric datasets in order to recreate dendritic spine necks using a haptic device. In order to fulfil this objective, we first presented an algorithm to provide haptic feedback directly from volumetric datasets, as an aid to regular visualization. The haptic rendering algorithm lets users perceive isosurfaces in volumetric datasets, and it relies on several design features that ensure a robust and efficient rendering. A marching tetrahedra approach enables the dynamic extraction of a piecewise linear continuous isosurface. Robustness is derived using a Continuous Collision Detection step coupled with acknowledged proxy-based rendering methods over the extracted isosurface. The introduced marching tetrahedra approach guarantees that the extracted isosurface will match the topology of an equivalent isosurface computed using trilinear interpolation. The proposed haptic rendering algorithm improves the coherence between haptic and visual cues computing a second proxy on the isosurface displayed on screen. Three experiments demonstrate the improvements on the isosurface extraction stage as well as the robustness and the efficiency of the complete algorithm. We then introduce our four-steps procedure for the complete reconstruction of dendritic spines. Based on our haptic rendering algorithm, this procedure is intended to work as an image processing stage before the automatic segmentation step giving the final representation of the dendritic spines. The procedure is designed to allow both the navigation and the volume image editing to be carried out using a haptic device. We evaluated our procedure through two experiments. The first experiment concerns the benefits of the force feedback and the second checks the suitability of the use of a haptic device as input. In both cases, the results shows that the procedure improves the editing accuracy. We also report two concrete cases where our procedure was employed in the neuroscience field, the first one concerning dendritic spines in the human cortex, the second one referring to an ongoing experiment studying dendritic spines along dendrites of mouse cortical pyramidal neurons. Finally, we present the software program, Neuro Haptic Editor, that was built along the development of the different algorithms implemented during this thesis, and used by neuroscientists to use our procedure.

Analysis by finite element calculations of light scattering in laser-textured AZO films for PV thin-film solar cells

In the thin-film photovoltaic industry, to achieve a high light scattering in one or more of the cell interfaces is one of the strategies that allow an enhancement of light absorption inside the cell and, therefore, a better device behavior and efficiency. Although chemical etching is the standard method to texture surfaces for that scattering improvement, laser light has shown as a new way for texturizing different materials, maintaining a good control of the final topography with a unique, clean, and quite precise process. In this work AZO films with different texture parameters are fabricated. The typical parameters used to characterize them, as the root mean square roughness or the haze factor, are discussed and, for deeper understanding of the scattering mechanisms, the light behavior in the films is simulated using a finite element method code. This method gives information about the light intensity in each point of the system, allowing the precise characterization of the scattering behavior near the film surface, and it can be used as well to calculate a simulated haze factor that can be compared with experimental measurements. A discussion of the validation of the numerical code, based in a comprehensive comparison with experimental data is included.

Analysis of the behavior of multijunction solar cells under high irradiance Gaussian light profiles showing chromatic aberration with emphasis on tunnel junction performance

In this work, we explain the behavior of multijunction solar cells under non-uniform (spatially and in spectral content) light profiles in general and in particular when Gaussian light profiles cause a photo-generated current density, which exceeds locally the peak current density of the tunnel junction. We have analyzed the implications on the tunnel junction's limitation, that is, in the loss of efficiency due to the appearance of a dip in the I–V curve. For that, we have carried out simulations with our three-dimensional distributed model for multijunction solar cells, which contemplates a full description of the tunnel junction and also takes into account the lateral resistances in the tunnel junction. The main findings are that the current density photo-generated spreads out through the lateral resistances of the device, mainly through the tunnel junction layers and the back contact. Therefore, under non-uniform light profiles these resistances are determinant not only to avoid the tunnel junction's limitation but also for mitigating losses in the fill factor. Therefore, taking into account these lateral resistances could be the key for jointly optimizing the concentrator photovoltaic system (concentrator optics, front grid layout and semiconductor structure)

Light polarization sensitive photodetectors with m- and r-plane homoepitaxial ZnO/ZnMgO quantum wells

Homoepitaxial ZnO/(Zn,Mg)O multiple quantum wells (MQWs) grown with m- and r-plane orientations are used to demonstrate Schottky photodiodes sensitive to the polarization state of light. In both orientations, the spectral photoresponse of the MQW photodiodes shows a sharp excitonic absorption edge at 3.48 eV with a very low Urbach tail, allowing the observation of the absorption from the A, B and C excitonic transitions. The absorption edge energy is shifted by ∼30 and ∼15 meV for the m- and r-plane MQW photodiodes, respectively, in full agreement with the calculated polarization of the A, B, and C excitonic transitions. The best figures of merit are obtained for the m-plane photodiodes, which present a quantum efficiency of ∼11%, and a specific detectivity D* of ∼6.4 × 1010 cm Hz1/2/W. In these photodiodes, the absorption polarization sensitivity contrast between the two orthogonal in-plane axes yields a maximum value of (R⊥/R||)max ∼ 9.9 with a narrow bandwidth of ∼33 meV.

Implications of low breakdown voltage of component subcells on external quantum efficiency measurements of multijunction solar cells

The electrical and optical coupling between subcells in a multijunction solar cell affects its external quantum efficiency (EQE) measurement. In this study, we show how a low breakdown voltage of a component subcell impacts the EQE determination of a multijunction solar cell and demands the use of a finely adjusted external voltage bias. The optimum voltage bias for the EQE measurement of a Ge subcell in two different GaInP/GaInAs/Ge triple-junction solar cells is determined both by sweeping the external voltage bias and by tracing the I–V curve under the same light bias conditions applied during the EQE measurement. It is shown that the I–V curve gives rapid and valuable information about the adequate light and voltage bias needed, and also helps to detect problems associated with non-ideal I–V curves that might affect the EQE measurement. The results also show that, if a non-optimum voltage bias is applied, a measurement artifact can result. Only when the problems associated with a non-ideal I–V curve and/or a low breakdown voltage have been discarded, the measurement artifacts, if any, can be attributed to other effects such as luminescent coupling between subcells.