Energy Efficiency through Thermal Energy Storage : Possibilities for the Swedish Building Stock

The need for heating and cooling in buildings constitutes a considerable part of the total energy use in a country and reducing this need is of outmost importance in order to reach national and international goals for reducing energy use and emissions. One important way of reaching these goals is to increase the proportion of renewable energy used for heating and cooling of buildings. Perhaps the largest obstacle with this is the often occurring mismatch between the availability of renewable energy and the need for heating or cooling, hindering this energy to be used directly. This is one of the problems that can be solved by using thermal energy storage (TES) in order to save the heat or cold from when it is available to when it is needed. This thesis is focusing on the combination of TES techniques and buildings to achieve increased energy efficiency for heating and cooling. Various techniques used for TES as well as the combination of TES in buildings have been investigated and summarized through an extensive literature review. A survey of the Swedish building stock was also performed in order to define building types common in Sweden. Within the scope of this thesis, the survey resulted in the selection of three building types, two single family houses and one office building, out of which the two residential buildings were used in a simulation case study of passive TES with increased thermal mass (both sensible and latent). The second case study presented in the thesis is an evaluation of an existing seasonal borehole storage of solar heat for a residential community. In this case, real measurement data was used in the evaluation and in comparisons with earlier evaluations. The literature reviews showed that using TES opens up potential for reduced energy demand and reduced peak heating and cooling loads as well as possibilities for an increased share of renewable energy to cover the energy demand. By using passive storage through increased thermal mass of a building it is also possible to reduce variations in the indoor temperature and especially reduce excess temperatures during warm periods, which could result in avoiding active cooling in a building that would otherwise need it. The analysis of the combination of TES and building types confirmed that TES has a significant potential for increased energy efficiency in buildings but also highlighted the fact that there is still much research required before some of the technologies can become commercially available. In the simulation case study it was concluded that only a small reduction in heating demand is possible with increased thermal mass, but that the time with indoor temperatures above 24 °C can be reduced by up to 20%. The case study of the borehole storage system showed that although the storage system worked as planned, heat losses in the rest of the system as well as some problems with the system operation resulted in a lower solar fraction than projected. The work presented within this thesis has shown that TES is already used successfully for many building applications (e.g. domestic hot water stores and water tanks for storing solar heat) but that there still is much potential in further use of TES. There are, however, barriers such as a need for more research for some storage technologies as well as storage materials, especially phase change material storage and thermochemical storage.

Final report on heat pump developments in WP 4 - MacSheep Deliverable 4.4 : MacSheep -New Materials and Control for a next generation of compact combined Solar and heat pump systems with boosted energetic and exergetic performance

FP7- MacSheep

Self assembled materials for solar cell application

In der vorliegenden Arbeit wurden Materialien und Aufbauten für Hybrid Solarzellen entwickelt und erforscht. rnDer Vergleich zweier bekannter Lochleitermaterialien für Solarzellen in einfachen Blend-Systemen brachte sowohl Einsicht zur unterschiedlichen Eignung der Materialien für optoelektronische Bauelemente als auch neue Erkenntnisse in Bereichen der Langzeitstabilität und Luftempfindlichkeit beider Materialien.rnWeiterhin wurde eine Methode entwickelt, um Hybrid Solarzelle auf möglichst unkomplizierte Weise aus kostengünstigen Materialien darzustellen. Die „Eintopf“-Synthese ermöglicht die unkomplizierte Darstellung eines funktionalen Hybridmaterials für die optoelektronische Anwendung. Mithilfe eines neu entwickelten amphiphilen Blockcopolymers, das als funktionelles Templat eingesetzt wurde, konnten mit einem TiO2-Precursor in einem Sol-Gel Ansatz verschiedene selbstorganisierte Morphologien des Hybridmaterials erhalten werden. Verschiedene Morphologien wurden auf ihre Eignung in Hybrid Solarzellen untersucht. Ob und warum die Morphologie des Hybridsystems die Effizienz der Solarzelle beeinflusst, konnte verdeutlicht werden. Mit der Weiterentwicklung der „Eintopf“-Synthese, durch den Austausch des TiO2-Precursors, konnte die Solarzelleneffizienz von 0.15 auf 0.4 % gesteigert werden. Weiterhin konnte die Übertragbarkeit des Systems durch den erfolgreichen Austausch des Halbleiters TiO¬2 mit ZnO bewiesen werden.rn

Studies of degradation of organic solar cell materials using electrical scanning probe microscopy

Intense research is being done in the field of organic photovoltaics in order to synthesize low band-gap organic molecules. These molecules are electron donors which feature in combination with acceptor molecules, typically fullerene derivarntives, forming an active blend. This active blend has phase separated bicontinuous morphology on a nanometer scale. The highest recorded power conversionrnefficiencies for such cells have been 10.6%. Organic semiconductors differ from inorganic ones due to the presence of tightly bonded excitons (electron-hole pairs)resulting from their low dielectric constant (εr ≈2-4). An additional driving force is required to separate such Frenkel excitons since their binding energy (0.3-1 eV) is too large to be dissociated by an electric field alone. This additional driving force arises from the energy difference between the lowest unoccupied molecular orbital (LUMO) of the donor and the acceptor materials. Moreover, the efficiency of the cells also depends on the difference between the highest occupied molecular orbital (HOMO) of the donor and LUMO of the acceptor. Therefore, a precise control and estimation of these energy levels are required. Furthermore any external influences that change the energy levels will cause a degradation of the power conversion efficiency of organic solar cell materials. In particular, the role of photo-induced degradation on the morphology and electrical performance is a major contribution to degradation and needs to be understood on a nanometer scale. Scanning Probe Microscopy (SPM) offers the resolution to image the nanometer scale bicontinuous morphology. In addition SPM can be operated to measure the local contact potential difference (CPD) of materials from which energy levels in the materials can be derived. Thus SPM is an unique method for the characterization of surface morphology, potential changes and conductivity changes under operating conditions. In the present work, I describe investigations of organic photovoltaic materials upon photo-oxidation which is one of the major causes of degradation of these solar cell materials. SPM, Nuclear Magnetic Resonance (NMR) and UV-Vis spectroscopy studies allowed me to identify the chemical reactions occurring inside the active layer upon photo-oxidation. From the measured data, it was possible to deduce the energy levels and explain the various shifts which gave a better understanding of the physics of the device. In addition, I was able to quantify the degradation by correlating the local changes in the CPD and conductivity to the device characteristics, i.e., open circuit voltage and short circuit current. Furthermore, time-resolved electrostatic force microscopy (tr-EFM) allowed us to probe dynamic processes like the charging rate of the individual donor and acceptor domains within the active blend. Upon photo-oxidation, it was observed, that the acceptor molecules got oxidized first preventing the donor polymer from degrading. Work functions of electrodes can be tailored by modifying the interface with monomolecular thin layers of molecules which are made by a chemical reaction in liquids. These modifications in the work function are particularly attractive for opto-electronic devices whose performance depends on the band alignment between the electrodes and the active material. In order to measure the shift in work function on a nanometer scale, I used KPFM in situ, which means in liquids, to follow changes in the work function of Au upon hexadecanethiol adsorption from decane. All the above investigations give us a better understanding of the photo-degradation processes of the active material at the nanoscale. Also, a method to compare various new materials used for organic solar cells for stability is proposed which eliminates the requirement to make fully functional devices saving time and additional engineering efforts.

Investigation of P3HT PCBM particle-based solar cells

Die Herstellung von Polymer-Solarzellen aus wässriger Phase stellt eine attraktive Alternative zu der konventionellen lösemittelbasierten Formulierung dar. Die Vorteile der aus wässriger Lösung hergestellten Solarzellen liegen besonders in dem umweltschonenden Herstellungsprozess und in der Möglichkeit, druckbare optoelektronische Bauteile zu generieren. Die Prozessierbarkeit von hydrophoben Halbleitern im wässrigen Milieu wird durch die Dispergierung der Materialien, in Form von Nanopartikeln, erreicht. Der Transfer der Halbleiter in eine Dispersion erfolgt über die Lösemittelverdampfungsmethode. Die Idee der Verwendung von partikelbasierte Solarzellen wurde bereits umgesetzt, allerdings blieben eine genaue Charakterisierung der Partikel sowie ein umfassendes Verständnis des gesamten Fabrikationsvorgangs aus. Deshalb besteht das Ziel dieser Arbeit darin, einen detaillierten Einblick in den Herstellungsprozess von partikelbasierten Solarzellen zu erlangen, mögliche Schwächen aufzudecken, diese zu beseitigen, um so zukünftige Anwendungen zu verbessern. Zur Herstellung von Solarzellen aus wässrigen Dispersionen wurde Poly(3-hexylthiophen-2,5-diyl)/[6,6]-Phenyl-C61-Buttersäure-Methylester (P3HT/PCBM) als Donor/Akzeptor-System verwendet. Die Kernpunkte der Untersuchungen richteten sich zum einen die auf Partikelmorphologie und zum anderen auf die Generierung einer geeigneten Partikelschicht. Beide Parameter haben Auswirkungen auf die Solarzelleneffizienz. Die Morphologie wurde sowohl spektroskopisch über Photolumineszenz-Messungen, als auch visuell mittels Elektronenmikroskopie ermittelt. Auf diese Weise konnte die Partikelmorphologie vollständig aufgeklärt werden, wobei Parallelen zu der Struktur von lösemittelbasierten Solarzellen gefunden wurden. Zudem wurde eine Abhängigkeit der Morphologie von der Präparationstemperatur beobachtet, was eine einfache Steuerung der Partikelstruktur ermöglicht. Im Zuge der Partikelschichtausbildung wurden direkte sowie grenzflächenvermittelnde Beschichtungsmethoden herangezogen. Von diesen Techniken hatte sich aber nur die Rotationsbeschichtung als brauchbare Methode erwiesen, Partikel aus der Dispersion in einen homogenen Film zu überführen. Des Weiteren stand die Aufarbeitung der Partikelschicht durch Ethanol-Waschung und thermische Behandlung im Fokus dieser Arbeit. Beide Maßnahmen wirkten sich positiv auf die Effizienz der Solarzellen aus und trugen entscheidend zu einer Verbesserung der Zellen bei. Insgesamt liefern die gewonnen Erkenntnisse einen detaillierten Überblick über die Herausforderungen, welche bei dem Einsatz von wasserbasierten Dispersionen auftreten. Die Anforderungen partikelbasierter Solarzellen konnten offengelegt werden, dadurch gelang die Herstellung einer Solarzelle mit einer Effizienz von 0.53%. Dieses Ergebnis stellt jedoch noch nicht das Optimum dar und lässt noch Möglichkeiten für Verbesserungen offen.

Charge separation and recombination in novel polymeric absorber materials for organic solar cells : a photophysical study

In dieser Dissertation wird die Ladungsträgergeneration und -rekombination in neuen polymeren Absorbermaterialien für organische Solarzellen untersucht. Das Verständnis dieser Prozesse ist wesentlich für die Entwicklung neuer photoaktiver Materialsysteme, die hohe Effizienzen erzielen und organische Solarzellen konkurrenzfähig im Bereich der erneuerbaren Energien machen. Experimentell verwendet diese Arbeit hauptsächlich die Methode der transienten Absorptionsspektroskopie, die sich für die Untersuchung photophysikalischer Prozesse auf einer Zeitskala von 100 fs bis 1 ms als sehr leistungsfähig erweist. Des Weiteren wird eine soft-modeling Methode vorgestellt, die es ermöglicht, photophysikalische Prozesse aus einer gemessenen transienten Absorptions-Datenmatrix zu bestimmen, wenn wenig a priori Kenntnisse der Reaktionskinetiken vorhanden sind. Drei unterschiedliche Donor:Akzeptor-Systeme werden untersucht; jedes dieser Systeme stellt eine andere Herangehensweise zur Optimierung der Materialien dar in Bezug auf Lichtabsorption über einen breiten Wellenlängenbereich, effiziente Ladungstrennung und schnellen Ladungstransport. Zuerst wird ein Terpolymer untersucht, das aus unterschiedlichen Einheiten für die Lichtabsorption und den Ladungstransport besteht. Es wird gezeigt, dass es möglich ist, den Fluss angeregter Zustände vom Chromophor auf die Transporteinheit zu leiten. Im zweiten Teil wird der Einfluss von Kristallinität auf die freie Ladungsträgergeneration mit einer Folge von ternären Mischungen, die unterschiedliche Anteile an amorphem und semi-kristallinem Polymer enthalten, untersucht. Dabei zeigt es sich, dass mit steigendem amorphen Polymeranteil sowohl der Anteil der geminalen Ladungsträgerrekombination erhöht als auch die nicht-geminale Rekombination schneller ist. Schlussendlich wird ein System untersucht, in dem sowohl Donor als auch Akzeptor Polymere sind, was zu verbesserten Absorptionseigenschaften führt. Die Rekombination von Ladungstransferzuständen auf der unter 100 ps Zeitskala stellt hier den hauptsächliche Verlustkanal dar, da freie Ladungsträger nur an Grenzflächen erzeugt werden können, an denen Donor und Akzeptor face-to-face zueinander orientiert sind. Darüber hinaus wird festgestellt, dass weitere 40-50% der Ladungsträger durch die Rekombination von Grenzflächenzuständen verloren gehen, die aus mobilen Ladungsträgern geminal gebildet werden.

Concentrating solar power technologies. The DESERTEC megaproject

The European strategies on energy have been searching for years to reduce the dependency of Europe from fossil fuels. Underlying this effort, there exist geopolitical, economic, environmental reasons and the reality that oil reservoirs will dry out some day. Renewable energies have become a milestone of this strategy because their huge potential has emerged after years of uncertainty. One of the better developed renewable sources, which is nearer to commercial maturity is solar-thermal energy. In this paper, the current state of this technology will be described as well as the developments that may be expected in the short and mid terms, including the thermoelectric solar megaproject DESERTEC, a German proposal to ensure energy resources to the mayor areas of the EU-MENA countries. The reader will acquire a picture of the current state of the market, of the technical challenges already achieved and of the remaining ones.

Domestic hot water consumption vs. solar thermal energy storage: the optimum size of the storage tank

Many efforts have been made in order to adequate the production of a solar thermal collector field to the consumption of domestic hot water of the inhabitants of a building. In that sense, much has been achieved in different domains: research agencies, government policies and manufacturers. However, most of the design rules of the solar plants are based on steady state models, whereas solar irradiance, consumption and thermal accumulation are inherently transient processes. As a result of this lack of physical accuracy, thermal storage tanks are sometimes left to be as large as the designer decides without any aforementioned precise recommendation. This can be a problem if solar thermal systems are meant to be implemented in nowadays buildings, where there is a shortage of space. In addition to that, an excessive storage volume could not result more efficient in many residential applications, but costly, extreme in space consumption and in some cases too heavy. A proprietary transient simulation program has been developed and validated with a detailed measurement campaign in an experimental facility. In situ environmental data have been obtained through a whole year of operation. They have been gathered at intervals of 10 min for a solar plant of 50 m2 with a storage tank of 3 m3, including the equipment for domestic hot water production of a typical apartment building. This program has been used to obtain the design and dimensioning criteria of DHW solar plants under daily transient conditions throughout a year and more specifically the size of the storage tank for a multi storey apartment building. Comparison of the simulation results with the current Spanish regulation applicable, “Código Técnico de la Edificación” (CTE 2006), offers fruitful details and establishes solar facilities dimensioning criteria.

MOVPE growth of III-V semiconductors on silicon for third generation solar cells

Esta Tesis trata sobre el desarrollo y crecimiento -mediante tecnología MOVPE (del inglés: MetalOrganic Vapor Phase Epitaxy)- de células solares híbridas de semiconductores III-V sobre substratos de silicio. Esta integración pretende ofrecer una alternativa a las células actuales de III-V, que, si bien ostentan el récord de eficiencia en dispositivos fotovoltaicos, su coste es, a día de hoy, demasiado elevado para ser económicamente competitivo frente a las células convencionales de silicio. De este modo, este proyecto trata de conjugar el potencial de alta eficiencia ya demostrado por los semiconductores III-V en arquitecturas de células fotovoltaicas multiunión con el bajo coste, la disponibilidad y la abundancia del silicio. La integración de semiconductores III-V sobre substratos de silicio puede afrontarse a través de diferentes aproximaciones. En esta Tesis se ha optado por el desarrollo de células solares metamórficas de doble unión de GaAsP/Si. Mediante esta técnica, la transición entre los parámetros de red de ambos materiales se consigue por medio de la formación de defectos cristalográficos (mayoritariamente dislocaciones). La idea es confinar estos defectos durante el crecimiento de sucesivas capas graduales en composición para que la superficie final tenga, por un lado, una buena calidad estructural, y por otro, un parámetro de red adecuado. Numerosos grupos de investigación han dirigido sus esfuerzos en los últimos años en desarrollar una estructura similar a la que aquí proponemos. La mayoría de éstos se han centrado en entender los retos asociados al crecimiento de materiales III-V, con el fin de conseguir un material de alta calidad cristalográfica. Sin embargo, prácticamente ninguno de estos grupos ha prestado especial atención al desarrollo y optimización de la célula inferior de silicio, cuyo papel va a ser de gran relevancia en el funcionamiento de la célula completa. De esta forma, y con el fin de completar el trabajo hecho hasta el momento en el desarrollo de células de III-V sobre silicio, la presente Tesis se centra, fundamentalmente, en el diseño y optimización de la célula inferior de silicio, para extraer su máximo potencial. Este trabajo se ha estructurado en seis capítulos, ordenados de acuerdo al desarrollo natural de la célula inferior. Tras un capítulo de introducción al crecimiento de semiconductores III-V sobre Si, en el que se describen las diferentes alternativas para su integración; nos ocupamos de la parte experimental, comenzando con una extensa descripción y caracterización de los substratos de silicio. De este modo, en el Capítulo 2 se analizan con exhaustividad los diferentes tratamientos (tanto químicos como térmicos) que deben seguir éstos para garantizar una superficie óptima sobre la que crecer epitaxialmente el resto de la estructura. Ya centrados en el diseño de la célula inferior, el Capítulo 3 aborda la formación de la unión p-n. En primer lugar se analiza qué configuración de emisor (en términos de dopaje y espesor) es la más adecuada para sacar el máximo rendimiento de la célula inferior. En este primer estudio se compara entre las diferentes alternativas existentes para la creación del emisor, evaluando las ventajas e inconvenientes que cada aproximación ofrece frente al resto. Tras ello, se presenta un modelo teórico capaz de simular el proceso de difusión de fosforo en silicio en un entorno MOVPE por medio del software Silvaco. Mediante este modelo teórico podemos determinar qué condiciones experimentales son necesarias para conseguir un emisor con el diseño seleccionado. Finalmente, estos modelos serán validados y constatados experimentalmente mediante la caracterización por técnicas analíticas (i.e. ECV o SIMS) de uniones p-n con emisores difundidos. Uno de los principales problemas asociados a la formación del emisor por difusión de fósforo, es la degradación superficial del substrato como consecuencia de su exposición a grandes concentraciones de fosfina (fuente de fósforo). En efecto, la rugosidad del silicio debe ser minuciosamente controlada, puesto que éste servirá de base para el posterior crecimiento epitaxial y por tanto debe presentar una superficie prístina para evitar una degradación morfológica y cristalográfica de las capas superiores. En este sentido, el Capítulo 4 incluye un análisis exhaustivo sobre la degradación morfológica de los substratos de silicio durante la formación del emisor. Además, se proponen diferentes alternativas para la recuperación de la superficie con el fin de conseguir rugosidades sub-nanométricas, que no comprometan la calidad del crecimiento epitaxial. Finalmente, a través de desarrollos teóricos, se establecerá una correlación entre la degradación morfológica (observada experimentalmente) con el perfil de difusión del fósforo en el silicio y por tanto, con las características del emisor. Una vez concluida la formación de la unión p-n propiamente dicha, se abordan los problemas relacionados con el crecimiento de la capa de nucleación de GaP. Por un lado, esta capa será la encargada de pasivar la subcélula de silicio, por lo que su crecimiento debe ser regular y homogéneo para que la superficie de silicio quede totalmente pasivada, de tal forma que la velocidad de recombinación superficial en la interfaz GaP/Si sea mínima. Por otro lado, su crecimiento debe ser tal que minimice la aparición de los defectos típicos de una heteroepitaxia de una capa polar sobre un substrato no polar -denominados dominios de antifase-. En el Capítulo 5 se exploran diferentes rutinas de nucleación, dentro del gran abanico de posibilidades existentes, para conseguir una capa de GaP con una buena calidad morfológica y estructural, que será analizada mediante diversas técnicas de caracterización microscópicas. La última parte de esta Tesis está dedicada al estudio de las propiedades fotovoltaicas de la célula inferior. En ella se analiza la evolución de los tiempos de vida de portadores minoritarios de la base durante dos etapas claves en el desarrollo de la estructura Ill-V/Si: la formación de la célula inferior y el crecimiento de las capas III-V. Este estudio se ha llevado a cabo en colaboración con la Universidad de Ohio, que cuentan con una gran experiencia en el crecimiento de materiales III-V sobre silicio. Esta tesis concluye destacando las conclusiones globales del trabajo realizado y proponiendo diversas líneas de trabajo a emprender en el futuro. ABSTRACT This thesis pursues the development and growth of hybrid solar cells -through Metal Organic Vapor Phase Epitaxy (MOVPE)- formed by III-V semiconductors on silicon substrates. This integration aims to provide an alternative to current III-V cells, which, despite hold the efficiency record for photovoltaic devices, their cost is, today, too high to be economically competitive to conventional silicon cells. Accordingly, the target of this project is to link the already demonstrated efficiency potential of III-V semiconductor multijunction solar cell architectures with the low cost and unconstrained availability of silicon substrates. Within the existing alternatives for the integration of III-V semiconductors on silicon substrates, this thesis is based on the metamorphic approach for the development of GaAsP/Si dual-junction solar cells. In this approach, the accommodation of the lattice mismatch is handle through the appearance of crystallographic defects (namely dislocations), which will be confined through the incorporation of a graded buffer layer. The resulting surface will have, on the one hand a good structural quality; and on the other hand the desired lattice parameter. Different research groups have been working in the last years in a structure similar to the one here described, being most of their efforts directed towards the optimization of the heteroepitaxial growth of III-V compounds on Si, with the primary goal of minimizing the appearance of crystal defects. However, none of these groups has paid much attention to the development and optimization of the bottom silicon cell, which, indeed, will play an important role on the overall solar cell performance. In this respect, the idea of this thesis is to complete the work done so far in this field by focusing on the design and optimization of the bottom silicon cell, to harness its efficiency. This work is divided into six chapters, organized according to the natural progress of the bottom cell development. After a brief introduction to the growth of III-V semiconductors on Si substrates, pointing out the different alternatives for their integration; we move to the experimental part, which is initiated by an extensive description and characterization of silicon substrates -the base of the III-V structure-. In this chapter, a comprehensive analysis of the different treatments (chemical and thermal) required for preparing silicon surfaces for subsequent epitaxial growth is presented. Next step on the development of the bottom cell is the formation of the p-n junction itself, which is faced in Chapter 3. Firstly, the optimization of the emitter configuration (in terms of doping and thickness) is handling by analytic models. This study includes a comparison between the different alternatives for the emitter formation, evaluating the advantages and disadvantages of each approach. After the theoretical design of the emitter, it is defined (through the modeling of the P-in-Si diffusion process) a practical parameter space for the experimental implementation of this emitter configuration. The characterization of these emitters through different analytical tools (i.e. ECV or SIMS) will validate and provide experimental support for the theoretical models. A side effect of the formation of the emitter by P diffusion is the roughening of the Si surface. Accordingly, once the p-n junction is formed, it is necessary to ensure that the Si surface is smooth enough and clean for subsequent phases. Indeed, the roughness of the Si must be carefully controlled since it will be the basis for the epitaxial growth. Accordingly, after quantifying (experimentally and by theoretical models) the impact of the phosphorus on the silicon surface morphology, different alternatives for the recovery of the surface are proposed in order to achieve a sub-nanometer roughness which does not endanger the quality of the incoming III-V layers. Moving a step further in the development of the Ill-V/Si structure implies to address the challenges associated to the GaP on Si nucleation. On the one hand, this layer will provide surface passivation to the emitter. In this sense, the growth of the III-V layer must be homogeneous and continuous so the Si emitter gets fully passivated, providing a minimal surface recombination velocity at the interface. On the other hand, the growth should be such that the appearance of typical defects related to the growth of a polar layer on a non-polar substrate is minimized. Chapter 5 includes an exhaustive study of the GaP on Si nucleation process, exploring different nucleation routines for achieving a high morphological and structural quality, which will be characterized by means of different microscopy techniques. Finally, an extensive study of the photovoltaic properties of the bottom cell and its evolution during key phases in the fabrication of a MOCVD-grown III-V-on-Si epitaxial structure (i.e. the formation of the bottom cell; and the growth of III-V layers) will be presented in the last part of this thesis. This study was conducted in collaboration with The Ohio State University, who has extensive experience in the growth of III-V materials on silicon. This thesis concludes by highlighting the overall conclusions of the presented work and proposing different lines of work to be undertaken in the future.

Método experimental para la caracterización de las diferentes tecnologías de integración arquitectónica de la energía fotovoltaica en condiciones de funcionamiento real = Experimental method for characterization of several building integrated photovoltaic technologies under real working conditions

Hoy en día, el proceso de un proyecto sostenible persigue realizar edificios de elevadas prestaciones que son, energéticamente eficientes, saludables y económicamente viables utilizando sabiamente recursos renovables para minimizar el impacto sobre el medio ambiente reduciendo, en lo posible, la demanda de energía, lo que se ha convertido, en la última década, en una prioridad. La Directiva 2002/91/CE "Eficiencia Energética de los Edificios" (y actualizaciones posteriores) ha establecido el marco regulatorio general para el cálculo de los requerimientos energéticos mínimos. Desde esa fecha, el objetivo de cumplir con las nuevas directivas y protocolos ha conducido las políticas energéticas de los distintos países en la misma dirección, centrándose en la necesidad de aumentar la eficiencia energética en los edificios, la adopción de medidas para reducir el consumo, y el fomento de la generación de energía a través de fuentes renovables. Los edificios de energía nula o casi nula (ZEB, Zero Energy Buildings ó NZEB, Net Zero Energy Buildings) deberán convertirse en un estándar de la construcción en Europa y con el fin de equilibrar el consumo de energía, además de reducirlo al mínimo, los edificios necesariamente deberán ser autoproductores de energía. Por esta razón, la envolvente del edifico y en particular las fachadas son importantes para el logro de estos objetivos y la tecnología fotovoltaica puede tener un papel preponderante en este reto. Para promover el uso de la tecnología fotovoltaica, diferentes programas de investigación internacionales fomentan y apoyan soluciones para favorecer la integración completa de éstos sistemas como elementos arquitectónicos y constructivos, los sistemas BIPV (Building Integrated Photovoltaic), sobre todo considerando el próximo futuro hacia edificios NZEB. Se ha constatado en este estudio que todavía hay una falta de información útil disponible sobre los sistemas BIPV, a pesar de que el mercado ofrece una interesante gama de soluciones, en algunos aspectos comparables a los sistemas tradicionales de construcción. Pero por el momento, la falta estandarización y de una regulación armonizada, además de la falta de información en las hojas de datos técnicos (todavía no comparables con las mismas que están disponibles para los materiales de construcción), hacen difícil evaluar adecuadamente la conveniencia y factibilidad de utilizar los componentes BIPV como parte integrante de la envolvente del edificio. Organizaciones internacionales están trabajando para establecer las normas adecuadas y procedimientos de prueba y ensayo para comprobar la seguridad, viabilidad y fiabilidad estos sistemas. Sin embargo, hoy en día, no hay reglas específicas para la evaluación y caracterización completa de un componente fotovoltaico de integración arquitectónica de acuerdo con el Reglamento Europeo de Productos de la Construcción, CPR 305/2011. Los productos BIPV, como elementos de construcción, deben cumplir con diferentes aspectos prácticos como resistencia mecánica y la estabilidad; integridad estructural; seguridad de utilización; protección contra el clima (lluvia, nieve, viento, granizo), el fuego y el ruido, aspectos que se han convertido en requisitos esenciales, en la perspectiva de obtener productos ambientalmente sostenibles, saludables, eficientes energéticamente y económicamente asequibles. Por lo tanto, el módulo / sistema BIPV se convierte en una parte multifuncional del edificio no sólo para ser física y técnicamente "integrado", además de ser una oportunidad innovadora del diseño. Las normas IEC, de uso común en Europa para certificar módulos fotovoltaicos -IEC 61215 e IEC 61646 cualificación de diseño y homologación del tipo para módulos fotovoltaicos de uso terrestre, respectivamente para módulos fotovoltaicos de silicio cristalino y de lámina delgada- atestan únicamente la potencia del módulo fotovoltaico y dan fe de su fiabilidad por un período de tiempo definido, certificando una disminución de potencia dentro de unos límites. Existe también un estándar, en parte en desarrollo, el IEC 61853 (“Ensayos de rendimiento de módulos fotovoltaicos y evaluación energética") cuyo objetivo es la búsqueda de procedimientos y metodologías de prueba apropiados para calcular el rendimiento energético de los módulos fotovoltaicos en diferentes condiciones climáticas. Sin embargo, no existen ensayos normalizados en las condiciones específicas de la instalación (p. ej. sistemas BIPV de fachada). Eso significa que es imposible conocer las efectivas prestaciones de estos sistemas y las condiciones ambientales que se generan en el interior del edificio. La potencia nominal de pico Wp, de un módulo fotovoltaico identifica la máxima potencia eléctrica que éste puede generar bajo condiciones estándares de medida (STC: irradición 1000 W/m2, 25 °C de temperatura del módulo y distribución espectral, AM 1,5) caracterizando eléctricamente el módulo PV en condiciones específicas con el fin de poder comparar los diferentes módulos y tecnologías. El vatio pico (Wp por su abreviatura en inglés) es la medida de la potencia nominal del módulo PV y no es suficiente para evaluar el comportamiento y producción del panel en términos de vatios hora en las diferentes condiciones de operación, y tampoco permite predecir con convicción la eficiencia y el comportamiento energético de un determinado módulo en condiciones ambientales y de instalación reales. Un adecuado elemento de integración arquitectónica de fachada, por ejemplo, debería tener en cuenta propiedades térmicas y de aislamiento, factores como la transparencia para permitir ganancias solares o un buen control solar si es necesario, aspectos vinculados y dependientes en gran medida de las condiciones climáticas y del nivel de confort requerido en el edificio, lo que implica una necesidad de adaptación a cada contexto específico para obtener el mejor resultado. Sin embargo, la influencia en condiciones reales de operación de las diferentes soluciones fotovoltaicas de integración, en el consumo de energía del edificio no es fácil de evaluar. Los aspectos térmicos del interior del ambiente o de iluminación, al utilizar módulos BIPV semitransparentes por ejemplo, son aún desconocidos. Como se dijo antes, la utilización de componentes de integración arquitectónica fotovoltaicos y el uso de energía renovable ya es un hecho para producir energía limpia, pero también sería importante conocer su posible contribución para mejorar el confort y la salud de los ocupantes del edificio. Aspectos como el confort, la protección o transmisión de luz natural, el aislamiento térmico, el consumo energético o la generación de energía son aspectos que suelen considerarse independientemente, mientras que todos juntos contribuyen, sin embargo, al balance energético global del edificio. Además, la necesidad de dar prioridad a una orientación determinada del edificio, para alcanzar el mayor beneficio de la producción de energía eléctrica o térmica, en el caso de sistemas activos y pasivos, respectivamente, podría hacer estos últimos incompatibles, pero no necesariamente. Se necesita un enfoque holístico que permita arquitectos e ingenieros implementar sistemas tecnológicos que trabajen en sinergia. Se ha planteado por ello un nuevo concepto: "C-BIPV, elemento fotovoltaico consciente integrado", esto significa necesariamente conocer los efectos positivos o negativos (en términos de confort y de energía) en condiciones reales de funcionamiento e instalación. Propósito de la tesis, método y resultados Los sistemas fotovoltaicos integrados en fachada son a menudo soluciones de vidrio fácilmente integrables, ya que por lo general están hechos a medida. Estos componentes BIPV semitransparentes, integrados en el cerramiento proporcionan iluminación natural y también sombra, lo que evita el sobrecalentamiento en los momentos de excesivo calor, aunque como componente estático, asimismo evitan las posibles contribuciones pasivas de ganancias solares en los meses fríos. Además, la temperatura del módulo varía considerablemente en ciertas circunstancias influenciada por la tecnología fotovoltaica instalada, la radiación solar, el sistema de montaje, la tipología de instalación, falta de ventilación, etc. Este factor, puede suponer un aumento adicional de la carga térmica en el edificio, altamente variable y difícil de cuantificar. Se necesitan, en relación con esto, más conocimientos sobre el confort ambiental interior en los edificios que utilizan tecnologías fotovoltaicas integradas, para abrir de ese modo, una nueva perspectiva de la investigación. Con este fin, se ha diseñado, proyectado y construido una instalación de pruebas al aire libre, el BIPV Env-lab "BIPV Test Laboratory", para la caracterización integral de los diferentes módulos semitransparentes BIPV. Se han definido también el método y el protocolo de ensayos de caracterización en el contexto de un edificio y en condiciones climáticas y de funcionamiento reales. Esto ha sido posible una vez evaluado el estado de la técnica y la investigación, los aspectos que influyen en la integración arquitectónica y los diferentes tipos de integración, después de haber examinado los métodos de ensayo para los componentes de construcción y fotovoltaicos, en condiciones de operación utilizadas hasta ahora. El laboratorio de pruebas experimentales, que consiste en dos habitaciones idénticas a escala real, 1:1, ha sido equipado con sensores y todos los sistemas de monitorización gracias a los cuales es posible obtener datos fiables para evaluar las prestaciones térmicas, de iluminación y el rendimiento eléctrico de los módulos fotovoltaicos. Este laboratorio permite el estudio de tres diferentes aspectos que influencian el confort y consumo de energía del edificio: el confort térmico, lumínico, y el rendimiento energético global (demanda/producción de energía) de los módulos BIPV. Conociendo el balance de energía para cada tecnología solar fotovoltaica experimentada, es posible determinar cuál funciona mejor en cada caso específico. Se ha propuesto una metodología teórica para la evaluación de estos parámetros, definidos en esta tesis como índices o indicadores que consideran cuestiones relacionados con el bienestar, la energía y el rendimiento energético global de los componentes BIPV. Esta metodología considera y tiene en cuenta las normas reglamentarias y estándares existentes para cada aspecto, relacionándolos entre sí. Diferentes módulos BIPV de doble vidrio aislante, semitransparentes, representativos de diferentes tecnologías fotovoltaicas (tecnología de silicio monocristalino, m-Si; de capa fina en silicio amorfo unión simple, a-Si y de capa fina en diseleniuro de cobre e indio, CIS) fueron seleccionados para llevar a cabo una serie de pruebas experimentales al objeto de demostrar la validez del método de caracterización propuesto. Como resultado final, se ha desarrollado y generado el Diagrama Caracterización Integral DCI, un sistema gráfico y visual para representar los resultados y gestionar la información, una herramienta operativa útil para la toma de decisiones con respecto a las instalaciones fotovoltaicas. Este diagrama muestra todos los conceptos y parámetros estudiados en relación con los demás y ofrece visualmente toda la información cualitativa y cuantitativa sobre la eficiencia energética de los componentes BIPV, por caracterizarlos de manera integral. ABSTRACT A sustainable design process today is intended to produce high-performance buildings that are energy-efficient, healthy and economically feasible, by wisely using renewable resources to minimize the impact on the environment and to reduce, as much as possible, the energy demand. In the last decade, the reduction of energy needs in buildings has become a top priority. The Directive 2002/91/EC “Energy Performance of Buildings” (and its subsequent updates) established a general regulatory framework’s methodology for calculation of minimum energy requirements. Since then, the aim of fulfilling new directives and protocols has led the energy policies in several countries in a similar direction that is, focusing on the need of increasing energy efficiency in buildings, taking measures to reduce energy consumption, and fostering the use of renewable sources. Zero Energy Buildings or Net Zero Energy Buildings will become a standard in the European building industry and in order to balance energy consumption, buildings, in addition to reduce the end-use consumption should necessarily become selfenergy producers. For this reason, the façade system plays an important role for achieving these energy and environmental goals and Photovoltaic can play a leading role in this challenge. To promote the use of photovoltaic technology in buildings, international research programs encourage and support solutions, which favors the complete integration of photovoltaic devices as an architectural element, the so-called BIPV (Building Integrated Photovoltaic), furthermore facing to next future towards net-zero energy buildings. Therefore, the BIPV module/system becomes a multifunctional building layer, not only physically and functionally “integrated” in the building, but also used as an innovative chance for the building envelope design. It has been found in this study that there is still a lack of useful information about BIPV for architects and designers even though the market is providing more and more interesting solutions, sometimes comparable to the existing traditional building systems. However at the moment, the lack of an harmonized regulation and standardization besides to the non-accuracy in the technical BIPV datasheets (not yet comparable with the same ones available for building materials), makes difficult for a designer to properly evaluate the fesibility of this BIPV components when used as a technological system of the building skin. International organizations are working to establish the most suitable standards and test procedures to check the safety, feasibility and reliability of BIPV systems. Anyway, nowadays, there are no specific rules for a complete characterization and evaluation of a BIPV component according to the European Construction Product Regulation, CPR 305/2011. BIPV products, as building components, must comply with different practical aspects such as mechanical resistance and stability; structural integrity; safety in use; protection against weather (rain, snow, wind, hail); fire and noise: aspects that have become essential requirements in the perspective of more and more environmentally sustainable, healthy, energy efficient and economically affordable products. IEC standards, commonly used in Europe to certify PV modules (IEC 61215 and IEC 61646 respectively crystalline and thin-film ‘Terrestrial PV Modules-Design Qualification and Type Approval’), attest the feasibility and reliability of PV modules for a defined period of time with a limited power decrease. There is also a standard (IEC 61853, ‘Performance Testing and Energy Rating of Terrestrial PV Modules’) still under preparation, whose aim is finding appropriate test procedures and methodologies to calculate the energy yield of PV modules under different climate conditions. Furthermore, the lack of tests in specific conditions of installation (e.g. façade BIPV devices) means that it is difficult knowing the exact effective performance of these systems and the environmental conditions in which the building will operate. The nominal PV power at Standard Test Conditions, STC (1.000 W/m2, 25 °C temperature and AM 1.5) is usually measured in indoor laboratories, and it characterizes the PV module at specific conditions in order to be able to compare different modules and technologies on a first step. The “Watt-peak” is not enough to evaluate the panel performance in terms of Watt-hours of various modules under different operating conditions, and it gives no assurance of being able to predict the energy performance of a certain module at given environmental conditions. A proper BIPV element for façade should take into account thermal and insulation properties, factors as transparency to allow solar gains if possible or a good solar control if necessary, aspects that are linked and high dependent on climate conditions and on the level of comfort to be reached. However, the influence of different façade integrated photovoltaic solutions on the building energy consumption is not easy to assess under real operating conditions. Thermal aspects, indoor temperatures or luminance level that can be expected using building integrated PV (BIPV) modules are not well known. As said before, integrated photovoltaic BIPV components and the use of renewable energy is already a standard for green energy production, but would also be important to know the possible contribution to improve the comfort and health of building occupants. Comfort, light transmission or protection, thermal insulation or thermal/electricity power production are aspects that are usually considered alone, while all together contribute to the building global energy balance. Besides, the need to prioritize a particular building envelope orientation to harvest the most benefit from the electrical or thermal energy production, in the case of active and passive systems respectively might be not compatible, but also not necessary. A holistic approach is needed to enable architects and engineers implementing technological systems working in synergy. A new concept have been suggested: “C-BIPV, conscious integrated BIPV”. BIPV systems have to be “consciously integrated” which means that it is essential to know the positive and negative effects in terms of comfort and energy under real operating conditions. Purpose of the work, method and results The façade-integrated photovoltaic systems are often glass solutions easily integrable, as they usually are custommade. These BIPV semi-transparent components integrated as a window element provides natural lighting and shade that prevents overheating at times of excessive heat, but as static component, likewise avoid the possible solar gains contributions in the cold months. In addition, the temperature of the module varies considerably in certain circumstances influenced by the PV technology installed, solar radiation, mounting system, lack of ventilation, etc. This factor may result in additional heat input in the building highly variable and difficult to quantify. In addition, further insights into the indoor environmental comfort in buildings using integrated photovoltaic technologies are needed to open up thereby, a new research perspective. This research aims to study their behaviour through a series of experiments in order to define the real influence on comfort aspects and on global energy building consumption, as well as, electrical and thermal characteristics of these devices. The final objective was to analyze a whole set of issues that influence the global energy consumption/production in a building using BIPV modules by quantifying the global energy balance and the BIPV system real performances. Other qualitative issues to be studied were comfort aspect (thermal and lighting aspects) and the electrical behaviour of different BIPV technologies for vertical integration, aspects that influence both energy consumption and electricity production. Thus, it will be possible to obtain a comprehensive global characterization of BIPV systems. A specific design of an outdoor test facility, the BIPV Env-lab “BIPV Test Laboratory”, for the integral characterization of different BIPV semi-transparent modules was developed and built. The method and test protocol for the BIPV characterization was also defined in a real building context and weather conditions. This has been possible once assessed the state of the art and research, the aspects that influence the architectural integration and the different possibilities and types of integration for PV and after having examined the test methods for building and photovoltaic components, under operation conditions heretofore used. The test laboratory that consists in two equivalent test rooms (1:1) has a monitoring system in which reliable data of thermal, daylighting and electrical performances can be obtained for the evaluation of PV modules. The experimental set-up facility (testing room) allows studying three different aspects that affect building energy consumption and comfort issues: the thermal indoor comfort, the lighting comfort and the energy performance of BIPV modules tested under real environmental conditions. Knowing the energy balance for each experimented solar technology, it is possible to determine which one performs best. A theoretical methodology has been proposed for evaluating these parameters, as defined in this thesis as indices or indicators, which regard comfort issues, energy and the overall performance of BIPV components. This methodology considers the existing regulatory standards for each aspect, relating them to one another. A set of insulated glass BIPV modules see-through and light-through, representative of different PV technologies (mono-crystalline silicon technology, mc-Si, amorphous silicon thin film single junction, a-Si and copper indium selenide thin film technology CIS) were selected for a series of experimental tests in order to demonstrate the validity of the proposed characterization method. As result, it has been developed and generated the ICD Integral Characterization Diagram, a graphic and visual system to represent the results and manage information, a useful operational tool for decision-making regarding to photovoltaic installations. This diagram shows all concepts and parameters studied in relation to each other and visually provides access to all the results obtained during the experimental phase to make available all the qualitative and quantitative information on the energy performance of the BIPV components by characterizing them in a comprehensive way.

The Modelling of Photovoltaic, Solar Thermal, and Photovoltaic/Thermal Domestic Hot Water Systems

Solar heating of potable water has traditionally been accomplished through the use of solar thermal (ST) collectors. With the recent increases in availability and lower cost of photovoltaic (PV) panels, the potential of coupling PV solar arrays to electrically heated domestic hot water (DHW) tanks has been considered. Additionally, innovations in the SDHW industry have led to the creation of photovoltaic/thermal (PV/T) collectors, which heat water using both electrical and thermal energy. The current work compared the performance and cost-effectiveness of a traditional solar thermal (ST) DHW system to PV-solar-electric DHW systems and a PV/T DHW system. To accomplish this, a detailed TRNSYS model of the solar hot water systems was created and annual simulations were performed for 250 L/day and 325 L/day loads in Toronto, Vancouver, Montreal, Halifax, and Calgary. It was shown that when considering thermal performance, PV-DHW systems were not competitive when compared to ST-DHW and PVT-DHW systems. As an example, for Toronto the simulated annual solar fractions of PV-DHW systems were approximately 30%, while the ST-DHW and PVT-DHW systems achieved 65% and 71% respectively. With current manufacturing and system costs, the PV-DHW system was the most cost-effective system for domestic purposes. The capital cost of the PV-DHW systems were approximately $1,923-$2,178 depending on the system configuration, and the ST-DHW and PVT system were estimated to have a capital cost of $2,288 and $2,373 respectively. Although the capital cost of the PVT-DHW system was higher than the other systems, a Present Worth analysis for a 20-year period showed that for a 250 L/day load in Toronto the Present Worth of the PV/T system was approximately $4,597, with PV-DHW systems costing approximately $7,683-$7,816 and the ST-DHW system costing $5,238.

The isotope composition of selenium in chondrites constrains the depletion mechanism of volatile elements in solar system materials

Solar nebula processes led to a depletion of volatile elements in different chondrite groups when compared to the bulk chemical composition of the solar system deduced from the Sun's photosphere. For moderately-volatile elements, this depletion primarily correlates with the element condensation temperature and is possibly caused by incomplete condensation from a hot solar nebula, evaporative loss from the precursor dust, and/or inherited from the interstellar medium. Element concentrations and interelement ratios of volatile elements do not provide a clear picture about responsible mechanisms. Here, the abundance and stable isotope composition of the moderately- to highly-volatile element Se are investigated in carbonaceous, ordinary, and enstatite chondrites to constrain the mechanism responsible for the depletion of volatile elements in planetary bodies of the inner solar system and to define a δ(82/78)Se value for the bulk solar system. The δ(82/78)Se of the studied chondrite falls are identical within their measurement uncertainties with a mean of −0.20±0.26‰ (2 s.d., n=14n=14, relative to NIST SRM 3149) despite Se abundance depletions of up to a factor of 2.5 with respect to the CI group. The absence of resolvable Se isotope fractionation rules out a kinetic Rayleigh-type incomplete condensation of Se from the hot solar nebula or partial kinetic evaporative loss on the precursor material and/or the parent bodies. The Se depletion, if acquired during partial condensation or evaporative loss, therefore must have occurred under near equilibrium conditions to prevent measurable isotope fractionation. Alternatively, the depletion and cooling of the nebula could have occurred simultaneously due to the continuous removal of gas and fine particles by the solar wind accompanied by the quantitative condensation of elements from the pre-depleted gas. In this scenario the condensation of elements does not require equilibrium conditions to avoid isotope fractionation. The results further suggest that the processes causing the high variability of Se concentrations and depletions in ordinary and enstatite chondrites did not involve any measurable isotope fractionation. Different degrees of element depletions and isotope fractionations of the moderately-volatile elements Zn, S, and Se in ordinary and enstatite chondrites indicate that their volatility is controlled by the thermal stabilities of their host phases and not by the condensation temperature under canonical nebular conditions.

Uncertainty in determining thermal performance of liquid-heating flat-plate solar collectors /

"Issued April 1981."