Influence of laser wavelength on Laser-Fired contacts for crystalline silicon solar cells

In the Laser-Fired Contact (LFC) process, a laser beam fires a metallic layer through a dielectric passivating layer into the silicon wafer to form an electrical contact with the silicon bulk [1]. This laser technique is an interesting alternative for the fabrication of both laboratory and industrial scale high efficiency passivated emitter and rear cell (PERC). One of the principal characteristics of this promising technique is the capability to reduce the recombination losses at the rear surface in crystalline silicon solar cells. Therefore, it is crucial to optimize LFC because this process is one of the most promising concepts to produce rear side point contacts at process speeds compatible with the final industrial application. In that sense, this work investigates the optimization of LFC processing to improve the back contact in silicon solar cells using fully commercial solid state lasers with pulse width in the ns range, thus studying the influence of the wavelength using the three first harmonics (corresponding to wavelengths of 1064 nm, 532 nm and 355 nm). Previous studies of our group focused their attention in other processing parameters as laser fluence, number of pulses, passivating material [2, 3] thickness of the rear metallic contact [4], etc. In addition, the present work completes the parametric optimization by assessing the influence of the laser wavelength on the contact property. In particular we report results on the morphology and electrical behaviour of samples specifically designed to assess the quality of the process. In order to study the influence of the laser wavelength on the contact feature we used as figure of merit the specific contact resistance. In all processes the best results have been obtained using green (532 nm) and UV (355 nm), with excellent values for this magnitude far below 1 mΩcm2.

Numerical simulation of Ge solar cells using D-AMPS-1D code

A solar cell is a solid state device that converts the energy of sunlight directly into electricity by the photovoltaic effect. When light with photon energies greater than the band gap is absorbed by a semiconductor material, free electrons and free holes are generated by optical excitation in the material. The main characteristic of a photovoltaic device is the presence of internal electric field able to separate the free electrons and holes so they can pass out of the material to the external circuit before they recombine. Numerical simulation of photovoltaic devices plays a crucial role in their design, performance prediction, and comprehension of the fundamental phenomena ruling their operation. The electrical transport and the optical behavior of the solar cells discussed in this work were studied with the simulation code D-AMPS-1D. This software is an updated version of the one-dimensional (1D) simulation program Analysis of Microelectronic and Photonic Devices (AMPS) that was initially developed at The Penn State University, USA. Structures such as homojunctions, heterojunctions, multijunctions, etc., resulting from stacking layers of different materials can be studied by appropriately selecting characteristic parameters. In this work, examples of cells simulation made with D-AMPS-1D are shown. Particularly, results of Ge photovoltaic devices are presented. The role of the InGaP buffer on the device was studied. Moreover, a comparison of the simulated electrical parameters with experimental results was performed.

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.

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

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

Transport properties of CuGaSe(2)-based thin-film solar cells as a function of absorber composition

The transport properties of thin-film solar cells based on wide-gap CuGaSe(2) absorbers have been investigated as a function of the bulk [Ga]/[Cu] ratio ranging from 1.01 to 1.33. We find that (i) the recombination processes in devices prepared from absorbers with a composition close to stoichiometry ([Ga]/[Cu] = 1.01) are strongly tunnelling assisted resulting in low recombination activation energies (E(a)) of approx. 0.95 eV in the dark and 1.36 eV under illumination. (ii) With an increasing [Ga]/[Cu] ratio, the transport mechanism changes to be dominated by thermally activated Shockley-Read-Hall recombination with similar E(a) values of approx. 1.52-1.57 eV for bulk [Ga]/[Cu] ratios of 1.12-1.33. The dominant recombination processes take place at the interface between CdS buffer and CuGaSe(2) absorber independently from the absorber composition. The increase of E(a) with the [Ga]/[Cu] ratio correlates with the open circuit voltage and explains the better performance of corresponding solar cells.

XPS as Characterization Tool for PV: From the Substrate to Complete III-V Multijunction Solar Cells

This contribution aims to illustrate the potential of the X-ray photoelectron spectroscopy (XPS) technique as a tool to analyze different parts of a solar cell (surface state, heterointerfaces, profile composition of ohmic contacts, etc). Here, the analysis is specifically applied to III-V multijunction solar cells used in concentrator systems. The information provided from such XPS analysis has helped to understand the physico-chemical nature of these surfaces and interfaces, and thus has guided the technological process in order to improve the solar cell performance.

The influence of quantum dot size on the sub-bandgap intraband photocurrent in intermediate band solar cells

The effect of quantum dot (QD) size on the performance of quantum dot intermediate band solar cells is investigated. A numerical model is used to calculate the bound state energy levels and the absorption coefficient of transitions from the ground state to all other states in the conduction band. Comparing with the current state of the art, strong absorption enhancements are found for smaller quantum dots, as well as a better positioning of the energy levels, which is expected to reduce thermal carrier escape. It is concluded that reducing the quantum dot size can increase sub-bandgap photocurrent and improve voltage preservation.

Study of the effect of different hole sizes on mechanical strength of wafers for back contact solar cells

Drilling process on wafers to produce EWT or MWT solar cells is a critical fabrication step, which affects on their mechanical stability. The amount of damage introduced during drilling process depends on the density of holes, their size and the chemical process applied afterwards. To quantify the relation between size of the holes and reduction of mechanical strength, several sets of wafers have been prepared, with different hole diameter. The mechanical strength of these sets has been measured by the ring on ring bending test, and the stress state in the moment of failure has been deduced by FE simulation.

Damage reduction of the laser drilling process on back contact solar cells by chemical treatment

Production of back contact solar cells requires holes generations on the wafers to keep both positive and negative contacts on the back side of the cell. This drilling process weakens the wafer mechanically due to the presence of the holes and the damage introduced during the process as microcracks. In this study, several chemical processes have been applied to drilled wafers in order to eliminate or reduce the damage generated during this fabrication step. The treatments analyzed are the followings: alkaline etching during 1, 3 and 5 minutes, acid etching for 2 and 4 minutes and texturisation. To determine mechanical strength of the samples a common mechanical study has been carried out testing the samples by the Ring on Ring bending test and obtaining the stress state in the moment of failure by FE simulation. Finally the results obtained for each treatment were fitted to a three parameter Weibull distribution

A numerical study into the influence of quantum dot size on the sub-bandgap interband photocurrent in intermediate band solar cells

A numerical study is presented of the sub-bandgap interband photon absorption in quantum dot intermediate band solar cells. Absorption coefficients and photocurrent densities are calculated for the valence band to intermediate band transitions using a four-band k · p method. It is found that reducing the quantum dot width in the plane perpendicular to the growth direction increases the photocurrent from the valence band to the intermediate-band ground state if the fractional surface coverage of quantum dots is conserved. This provides a path to increase the sub-bandgap photocurrent in intermediate band solar cells.

Photon Management Structures for Absorption Enhancement in Intermediate Band Solar Cells and Crystalline Silicon Solar Cells

El objetivo de la tesis es investigar los beneficios que el atrapamiento de la luz mediante fenómenos difractivos puede suponer para las células solares de silicio cristalino y las de banda intermedia. Ambos tipos de células adolecen de una insuficiente absorción de fotones en alguna región del espectro solar. Las células solares de banda intermedia son teóricamente capaces de alcanzar eficiencias mucho mayores que los dispositivos convencionales (con una sola banda energética prohibida), pero los prototipos actuales se resienten de una absorción muy débil de los fotones con energías menores que la banda prohibida. Del mismo modo, las células solares de silicio cristalino absorben débilmente en el infrarrojo cercano debido al carácter indirecto de su banda prohibida. Se ha prestado mucha atención a este problema durante las últimas décadas, de modo que todas las células solares de silicio cristalino comerciales incorporan alguna forma de atrapamiento de luz. Por razones de economía, en la industria se persigue el uso de obleas cada vez más delgadas, con lo que el atrapamiento de la luz adquiere más importancia. Por tanto aumenta el interés en las estructuras difractivas, ya que podrían suponer una mejora sobre el estado del arte. Se comienza desarrollando un método de cálculo con el que simular células solares equipadas con redes de difracción. En este método, la red de difracción se analiza en el ámbito de la óptica física, mediante análisis riguroso con ondas acopladas (rigorous coupled wave analysis), y el sustrato de la célula solar, ópticamente grueso, se analiza en los términos de la óptica geométrica. El método se ha implementado en ordenador y se ha visto que es eficiente y da resultados en buen acuerdo con métodos diferentes descritos por otros autores. Utilizando el formalismo matricial así derivado, se calcula el límite teórico superior para el aumento de la absorción en células solares mediante el uso de redes de difracción. Este límite se compara con el llamado límite lambertiano del atrapamiento de la luz y con el límite absoluto en sustratos gruesos. Se encuentra que las redes biperiódicas (con geometría hexagonal o rectangular) pueden producir un atrapamiento mucho mejor que las redes uniperiódicas. El límite superior depende mucho del periodo de la red. Para periodos grandes, las redes son en teoría capaces de alcanzar el máximo atrapamiento, pero sólo si las eficiencias de difracción tienen una forma peculiar que parece inalcanzable con las herramientas actuales de diseño. Para periodos similares a la longitud de onda de la luz incidente, las redes de difracción pueden proporcionar atrapamiento por debajo del máximo teórico pero por encima del límite Lambertiano, sin imponer requisitos irrealizables a la forma de las eficiencias de difracción y en un margen de longitudes de onda razonablemente amplio. El método de cálculo desarrollado se usa también para diseñar y optimizar redes de difracción para el atrapamiento de la luz en células solares. La red propuesta consiste en un red hexagonal de pozos cilíndricos excavados en la cara posterior del sustrato absorbente de la célula solar. La red se encapsula en una capa dieléctrica y se cubre con un espejo posterior. Se simula esta estructura para una célula solar de silicio y para una de banda intermedia y puntos cuánticos. Numéricamente, se determinan los valores óptimos del periodo de la red y de la profundidad y las dimensiones laterales de los pozos para ambos tipos de células. Los valores se explican utilizando conceptos físicos sencillos, lo que nos permite extraer conclusiones generales que se pueden aplicar a células de otras tecnologías. Las texturas con redes de difracción se fabrican en sustratos de silicio cristalino mediante litografía por nanoimpresión y ataque con iones reactivos. De los cálculos precedentes, se conoce el periodo óptimo de la red que se toma como una constante de diseño. Los sustratos se procesan para obtener estructuras precursoras de células solares sobre las que se realizan medidas ópticas. Las medidas de reflexión en función de la longitud de onda confirman que las redes cuadradas biperiódicas consiguen mejor atrapamiento que las uniperiódicas. Las estructuras fabricadas se simulan con la herramienta de cálculo descrita en los párrafos precedentes y se obtiene un buen acuerdo entre la medida y los resultados de la simulación. Ésta revela que una fracción significativa de los fotones incidentes son absorbidos en el reflector posterior de aluminio, y por tanto desaprovechados, y que este efecto empeora por la rugosidad del espejo. Se desarrolla un método alternativo para crear la capa dieléctrica que consigue que el reflector se deposite sobre una superficie plana, encontrándose que en las muestras preparadas de esta manera la absorción parásita en el espejo es menor. La siguiente tarea descrita en la tesis es el estudio de la absorción de fotones en puntos cuánticos semiconductores. Con la aproximación de masa efectiva, se calculan los niveles de energía de los estados confinados en puntos cuánticos de InAs/GaAs. Se emplea un método de una y de cuatro bandas para el cálculo de la función de onda de electrones y huecos, respectivamente; en el último caso se utiliza un hamiltoniano empírico. La regla de oro de Fermi permite obtener la intensidad de las transiciones ópticas entre los estados confinados. Se investiga el efecto de las dimensiones del punto cuántico en los niveles de energía y la intensidad de las transiciones y se obtiene que, al disminuir la anchura del punto cuántico respecto a su valor en los prototipos actuales, se puede conseguir una transición más intensa entre el nivel intermedio fundamental y la banda de conducción. Tomando como datos de partida los niveles de energía y las intensidades de las transiciones calculados como se ha explicado, se desarrolla un modelo de equilibrio o balance detallado realista para células solares de puntos cuánticos. Con el modelo se calculan las diferentes corrientes debidas a transiciones ópticas entre los numerosos niveles intermedios y las bandas de conducción y de valencia bajo ciertas condiciones. Se distingue de modelos de equilibrio detallado previos, usados para calcular límites de eficiencia, en que se adoptan suposiciones realistas sobre la absorción de fotones para cada transición. Con este modelo se reproducen datos publicados de eficiencias cuánticas experimentales a diferentes temperaturas con un acuerdo muy bueno. Se muestra que el conocido fenómeno del escape térmico de los puntos cuánticos es de naturaleza fotónica; se debe a los fotones térmicos, que inducen transiciones entre los estados excitados que se encuentran escalonados en energía entre el estado intermedio fundamental y la banda de conducción. En el capítulo final, este modelo realista de equilibrio detallado se combina con el método de simulación de redes de difracción para predecir el efecto que tendría incorporar una red de difracción en una célula solar de banda intermedia y puntos cuánticos. Se ha de optimizar cuidadosamente el periodo de la red para equilibrar el aumento de las diferentes transiciones intermedias, que tienen lugar en serie. Debido a que la absorción en los puntos cuánticos es extremadamente débil, se deduce que el atrapamiento de la luz, por sí solo, no es suficiente para conseguir corrientes apreciables a partir de fotones con energía menor que la banda prohibida en las células con puntos cuánticos. Se requiere una combinación del atrapamiento de la luz con un incremento de la densidad de puntos cuánticos. En el límite radiativo y sin atrapamiento de la luz, se necesitaría que el número de puntos cuánticos de una célula solar se multiplicara por 1000 para superar la eficiencia de una célula de referencia con una sola banda prohibida. En cambio, una célula con red de difracción precisaría un incremento del número de puntos en un factor 10 a 100, dependiendo del nivel de la absorción parásita en el reflector posterior. Abstract The purpose of this thesis is to investigate the benefits that diffractive light trapping can offer to quantum dot intermediate band solar cells and crystalline silicon solar cells. Both solar cell technologies suffer from incomplete photon absorption in some part of the solar spectrum. Quantum dot intermediate band solar cells are theoretically capable of achieving much higher efficiencies than conventional single-gap devices. Present prototypes suffer from extremely weak absorption of subbandgap photons in the quantum dots. This problem has received little attention so far, yet it is a serious barrier to the technology approaching its theoretical efficiency limit. Crystalline silicon solar cells absorb weakly in the near infrared due to their indirect bandgap. This problem has received much attention over recent decades, and all commercial crystalline silicon solar cells employ some form of light trapping. With the industry moving toward thinner and thinner wafers, light trapping is becoming of greater importance and diffractive structures may offer an improvement over the state-of-the-art. We begin by constructing a computational method with which to simulate solar cells equipped with diffraction grating textures. The method employs a wave-optical treatment of the diffraction grating, via rigorous coupled wave analysis, with a geometric-optical treatment of the thick solar cell bulk. These are combined using a steady-state matrix formalism. The method has been implemented computationally, and is found to be efficient and to give results in good agreement with alternative methods from other authors. The theoretical upper limit to absorption enhancement in solar cells using diffractions gratings is calculated using the matrix formalism derived in the previous task. This limit is compared to the so-called Lambertian limit for light trapping with isotropic scatterers, and to the absolute upper limit to light trapping in bulk absorbers. It is found that bi-periodic gratings (square or hexagonal geometry) are capable of offering much better light trapping than uni-periodic line gratings. The upper limit depends strongly on the grating period. For large periods, diffraction gratings are theoretically able to offer light trapping at the absolute upper limit, but only if the scattering efficiencies have a particular form, which is deemed to be beyond present design capabilities. For periods similar to the incident wavelength, diffraction gratings can offer light trapping below the absolute limit but above the Lambertian limit without placing unrealistic demands on the exact form of the scattering efficiencies. This is possible for a reasonably broad wavelength range. The computational method is used to design and optimise diffraction gratings for light trapping in solar cells. The proposed diffraction grating consists of a hexagonal lattice of cylindrical wells etched into the rear of the bulk solar cell absorber. This is encapsulated in a dielectric buffer layer, and capped with a rear reflector. Simulations are made of this grating profile applied to a crystalline silicon solar cell and to a quantum dot intermediate band solar cell. The grating period, well depth, and lateral well dimensions are optimised numerically for both solar cell types. This yields the optimum parameters to be used in fabrication of grating equipped solar cells. The optimum parameters are explained using simple physical concepts, allowing us to make more general statements that can be applied to other solar cell technologies. Diffraction grating textures are fabricated on crystalline silicon substrates using nano-imprint lithography and reactive ion etching. The optimum grating period from the previous task has been used as a design parameter. The substrates have been processed into solar cell precursors for optical measurements. Reflection spectroscopy measurements confirm that bi-periodic square gratings offer better absorption enhancement than uni-periodic line gratings. The fabricated structures have been simulated with the previously developed computation tool, with good agreement between measurement and simulation results. The simulations reveal that a significant amount of the incident photons are absorbed parasitically in the rear reflector, and that this is exacerbated by the non-planarity of the rear reflector. An alternative method of depositing the dielectric buffer layer was developed, which leaves a planar surface onto which the reflector is deposited. It was found that samples prepared in this way suffered less from parasitic reflector absorption. The next task described in the thesis is the study of photon absorption in semiconductor quantum dots. The bound-state energy levels of in InAs/GaAs quantum dots is calculated using the effective mass approximation. A one- and four- band method is applied to the calculation of electron and hole wavefunctions respectively, with an empirical Hamiltonian being employed in the latter case. The strength of optical transitions between the bound states is calculated using the Fermi golden rule. The effect of the quantum dot dimensions on the energy levels and transition strengths is investigated. It is found that a strong direct transition between the ground intermediate state and the conduction band can be promoted by decreasing the quantum dot width from its value in present prototypes. This has the added benefit of reducing the ladder of excited states between the ground state and the conduction band, which may help to reduce thermal escape of electrons from quantum dots: an undesirable phenomenon from the point of view of the open circuit voltage of an intermediate band solar cell. A realistic detailed balance model is developed for quantum dot solar cells, which uses as input the energy levels and transition strengths calculated in the previous task. The model calculates the transition currents between the many intermediate levels and the valence and conduction bands under a given set of conditions. It is distinct from previous idealised detailed balance models, which are used to calculate limiting efficiencies, since it makes realistic assumptions about photon absorption by each transition. The model is used to reproduce published experimental quantum efficiency results at different temperatures, with quite good agreement. The much-studied phenomenon of thermal escape from quantum dots is found to be photonic; it is due to thermal photons, which induce transitions between the ladder of excited states between the ground intermediate state and the conduction band. In the final chapter, the realistic detailed balance model is combined with the diffraction grating simulation method to predict the effect of incorporating a diffraction grating into a quantum dot intermediate band solar cell. Careful optimisation of the grating period is made to balance the enhancement given to the different intermediate transitions, which occur in series. Due to the extremely weak absorption in the quantum dots, it is found that light trapping alone is not sufficient to achieve high subbandgap currents in quantum dot solar cells. Instead, a combination of light trapping and increased quantum dot density is required. Within the radiative limit, a quantum dot solar cell with no light trapping requires a 1000 fold increase in the number of quantum dots to supersede the efficiency of a single-gap reference cell. A quantum dot solar cell equipped with a diffraction grating requires between a 10 and 100 fold increase in the number of quantum dots, depending on the level of parasitic absorption in the rear reflector.

Interband absorption of photons by extended states in intermediate band solar cells

This paper considers sub-bandgap photon absorption in an InAs/GaAs quantum dot matrix. Absorption coefficients are calculated for transitions from the extended states in the valence band to confined states in the conduction band. This completes a previous body of work in which transitions between bound states were calculated. The calculations are based on the empirical k·p Hamiltonian considering the quantum dots as parallelepipeds. The extended states may be only partially extended?in one or two dimensions?or extended in all three dimensions. It is found that extended-to-bound transitions are, in general, weaker than bound-to-bound transitions, and that the former are weaker when the initial state is extended in more coordinates. This study is of direct application to the research of intermediate band solar cells and other semiconductor devices based on light absorption in semiconductors nanostructured with quantum dots.

In situ control of the GE(100)surface domain structure for III-V multijunction solar cells

Vicinal Ge(100) is the common substrate for state of the art multi-junction solar cells grown by metal-organic vapor phase epitaxy (MOVPE). While triple junction solar cells based on Ge(100) present efficiencies mayor que 40%, little is known about the microscopic III-V/Ge(100) nucleation and its interface formation. A suitable Ge(100) surface preparation prior to heteroepitaxy is crucial to achieve low defect densities in the III-V epilayers. Formation of single domain surfaces with double layer steps is required to avoid anti-phase domains in the III-V films. The step formation processes in MOVPE environment strongly depends on the major process parameters such as substrate temperature, H2 partial pressure, group V precursors [1], and reactor conditions. Detailed investigation of these processes on the Ge(100) surface by ultrahigh vacuum (UHV) based standard surface science tools are complicated due to the presence of H2 process gas. However, in situ surface characterization by reflection anisotropy spectroscopy (RAS) allowed us to study the MOVPE preparation of Ge(100) surfaces directly in dependence on the relevant process parameters [2, 3, 4]. A contamination free MOVPE to UHV transfer system [5] enabled correlation of the RA spectra to results from UHV-based surface science tools. In this paper, we established the characteristic RA spectra of vicinal Ge(100) surfaces terminated with monohydrides, arsenic and phosphorous. RAS enabled in situ control of oxide removal, H2 interaction and domain formation during MOVPE preparation.

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

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

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.