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

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

Performance analysis of AlGaAs/GaAs tunnel junctions for ultra-high concentration photovoltaics

An n(++)-GaAs/p(++)-AlGaAs tunnel junction with a peak current density of 10 100Acm(-2) is developed. This device is a tunnel junction for multijunction solar cells, grown lattice-matched on standard GaAs or Ge substrates, with the highest peak current density ever reported. The voltage drop for a current density equivalent to the operation of the multijunction solar cell up to 10 000 suns is below 5 mV. Trap-assisted tunnelling is proposed to be behind this performance, which cannot be justified by simple band-to-band tunnelling. The metal-organic vapour-phase epitaxy growth conditions, which are in the limits of the transport-limited regime, and the heavy tellurium doping levels are the proposed origins of the defects enabling trap-assisted tunnelling. The hypothesis of trap-assisted tunnelling is supported by the observed annealing behaviour of the tunnel junctions, which cannot be explained in terms of dopant diffusion or passivation. For the integration of these tunnel junctions into a triple-junction solar cell, AlGaAs barrier layers are introduced to suppress the formation of parasitic junctions, but this is found to significantly degrade the performance of the tunnel junctions. However, the annealed tunnel junctions with barrier layers still exhibit a peak current density higher than 2500Acm(-2) and a voltage drop at 10 000 suns of around 20 mV, which are excellent properties for tunnel junctions and mean they can serve as low-loss interconnections in multijunction solar cells working at ultra-high concentrations.

Electronic, structural, and optical properties of the host and Cr-doped cadmium thioindate

The cadmium thioindate spinel CdIn2S4 semiconductor has potential applications for optoelectronic devices. We present a theoretical study of the structural and optoelectronic properties of the host and of the Cr-doped ternary spinel. For the host spinel, we analyze the direct or indirect character of the energy bandgap, the change of the energy bandgap with the anion displacement parameter and with the site cation distribution, and the optical properties. The main effect of the Cr doping is the creation of an intermediate band within the energy bandgap. The character and the occupation of this band are analyzed for two substitutions: Cr by In and Cr by Cd. This band permits more channels for the photon absorption. The optical properties are obtained and analyzed. The absorption coefficients are decomposed into contributions from the different absorption channels and from the inter-and intra-atomic components.

Electronic property analysis of O-doped Cu3SbS3

The ternary Cu-Sb-S semiconductors are considered to be sustainable and potential alternative absorber materials in thin film photovoltaic applications. In these compounds, several phases may coexist, albeit in different proportions depending on experimental growth conditions. Additionally, the photovoltaic efficiency could be increased with isoelectronic doping. In this work we analyze the electronic properties of O-doped Cu3SbS3 in two structures: the wittichenite and the skinnerite. We use first-principles within the density functional formalism with two different exchange-correlation potentials. In addition, we estimate the potential of these compounds for photovoltaic applications.

Effect of concentration on the performance of quantum dot intermediate-band solar cells

Implementation of a high-efficiency quantum dot intermediate-band solar cell (QD-IBSC) must accompany a sufficient photocurrent generation via IB states. The demonstration of a QD-IBSC is presently undergoing two stages. The first is to develop a technology to fabricate high-density QD stacks or a superlattice of low defect density placed within the active region of a p-i-n SC, and the second is to realize half-filled IB states to maximize the photocurrent generation by two-step absorption of sub-bandgap photons. For this, we have investigated the effect of light concentration on the characteristics of QDSCs comprised of multi-layer stacks of self-organized InAs/GaNAs QDs grown with and without impurity doping in molecular beam epitaxy.

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.

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

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

Synthetic strategy of porous ZnO and CdS nanostructures doped ferroelectric liquid crystal and its optical behavior

A simple and scalable chemical approach has been proposed for the generation of 1-dimensional nanostructures of two most important inorganic materials such as zinc oxide and cadmium sulfide. By controlling the growth habit of the nanostructures with manipulated reaction conditions, the diameter and uniformity of the nanowires/nanorods were tailored. We studied extensively optical behavior and structural growth of CdS NWs and ZnO NRs doped ferroelectric liquid crystal Felix-017/100. Due to doping band gap has been changed and several blue shifts occurred in photoluminescence spectra because of nanoconfinement effect and mobility of charges.

Laser Processes for Contact Optimization in c-Si Solar Cells

Solid State Lasers (SSL) have been used in microelectronic and photovoltaic (PV) industry for decades but, currently, laser technology appears as a key enabling technology to improve efficiency and to reduce production costs in high efficiency solar cells fabrication. Moreover, the fact that the interaction between the laser radiation and the device is normally localized and restricted to a controlled volume makes SSL a tool of choice for the implementation of low temperature concepts in PV industry. Specifically, SSL are ideally suited to improve the electrical performance of the contacts further improving the efficiency of these devices. Advanced concepts based on standard laser firing or advanced laser doping techniques are optimal solutions for the back contact of a significant number of structures of growing interest in the c-Si PV industry, and a number of solutions has been proposed as well for emitter formation, to reduce the metallization optical losses or even to remove completely the contacts from the front part of the cell. In this work we present our more recent results of SSL applications for contact optimization in c-Si solar cell technology, including applications on low temperature processes demanding devices, like heterojunction solar cells.

Contaminación y efectos secundarios en suplementos deportivos (proteínas, aminoácidos, creatina y suplementos para la pérdida de peso).

En muchos países la producción de suplementos deportivos no está correctamente regulada a nivel gubernamental. Esto implica la posibilidad de que los ingredientes declarados como componentes del producto no concuerden con los que se indican en la etiqueta del mismo. La literatura ha descrito casos de doping positivo debido a que las sustancias no declaradas en las etiquetas de dichos suplementos se encuentran en la lista de sustancias prohibidas. Este Trabajo Fin de Grado tiene por objetivo realizar una revisión bibliográfica de los estudios y/o análisis que clarifiquen qué suplementos de proteínas, aminoácidos, creatina y orientados a la pérdida de peso y qué marcas o laboratorios son los más fiables y los que no tanto. Dicho estudio se ha enfocado a suplementos que se consumen tanto en el alto rendimiento como a nivel recreativo y social, donde el desconocimiento en este sentido es mucho mayor. También se expondrán los efectos secundarios asociados a su contaminación y/o a su uso inapropiado. ABSTRACT In many countries, the production of sport supplements is not properly regulated by the government. This means that it is possible the ingredients do not match the label claims. In some cases, undeclared substances contained in supplements may include some that are banned by anti-doping laws. This End of Degree Project aims to make a literature review of studies and / or analysis which clarify what kind of protein, amino acids, creatine and fat loss supplements and which brands or laboratories are less reliable, as well as to inform those that do are, not only in high performance sport, but also at the social and recreational level, where the lack of knowledge in this sense is much higher. Also, associated side effects to such contamination and inappropriate use found in the review will be exposed.

Contaminación y efectos secundarios en suplementos deportivos (proteínas, aminoácidos, creatina y suplementos para pérdida de peso).

En muchos países la producción de suplementos deportivos no está correctamente regulada a nivel gubernamental. Esto implica la posibilidad de que los ingredientes declarados como componentes del producto no concuerden con los que se indican en la etiqueta del mismo. La literatura ha descrito casos de doping positivo debido a que las sustancias no declaradas en las etiquetas de dichos suplementos se encuentran en la lista de sustancias prohibidas. Este Trabajo Fin de Grado tiene por objetivo realizar una revisión bibliográfica de los estudios y/o análisis que clarifiquen qué suplementos de proteínas, aminoácidos, creatina y orientados a la pérdida de peso y qué marcas o laboratorios son los más fiables y  los que no tanto. Dicho estudio se ha enfocado a suplementos que se consumen tanto en el alto rendimiento como a nivel recreativo y social, donde el desconocimiento en este sentido es mucho mayor. También se expondrán los efectos secundarios asociados a su contaminación y/o a su uso inapropiado.

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.

Deep level analysis of homoepitaxial ZnO doped with N

High intrinsic carrier concentration (n-type) • Efforts to reduce this effect: • Homoepitaxy1 • Non-polar orientations • Similar samples exhibit residual doping as low as ~1014 cm-3 (2) The path to p-type doping • Many dopants proposed • N is a promising candidate • Simple NO is a deep level • Complex levels have shallower energies • N-related levels observed near the VB by many groups • Energies between 130 meV and 160 meV from VBM

3-D modeling of perimeter recombination in GaAs diodes and its influence on concentrator solar cells

This paper describes a complete modelling of the perimeter recombination of GaAs diodes which solves most unknowns and suppresses the limitations of previous models. Because of the three dimensional nature of the implemented model, it is able to simulate real devices. GaAs diodes on two epiwafers with different base doping levels, sizes and geometries, namely square and circular are manufactured. The validation of the model is achieved by fitting the experimental measurements of the dark IV curve of the manufactured GaAs diodes. A comprehensive 3-D description of the occurring phenomena affecting the perimeter recombination is supplied with the help of the model. Finally, the model is applied to concentrator GaAs solar cells to assess the impact of their doping level, size and geometry on the perimeter recombination.