Advances in the modeling, characterization and reliability of concentrator multijunction solar cells

Los sistemas de concentración fotovoltaica (CPV) parecen ser una de las vías más prometedoras para generar electricidad a gran escala a precios competitivos. La investigación actual se centra en aumentar la eficiencia y la concentración de los sistemas para abaratar costes. Al mismo tiempo se investiga sobre la fiabilidad de los diferentes componentes que integran un sistema de concentración, ya que para que los sistemas de concentración sean competitivos es necesario que tengan una fiabilidad al menos similar a los sistemas basados en células de silicio. En la presente tesis doctoral se ha llevado a cabo el estudio de aspectos avanzados de células solares multi-unión diseñadas para trabajar a concentraciones ultra-altas. Para ello, se ha desarrollado un modelo circuital tridimensional distribuido con el que simular el comportamiento de las células solares triple-unión bajo distintas condiciones de funcionamiento, así mismo se ha realizado una caracterización avanzada de este tipo de células para comprender mejor su modo de operación y así poder contribuir a mejorar su eficiencia. Finalmente, se han llevado a cabo ensayos de vida acelerados en células multiunión comerciales para conocer la fiabilidad de este tipo de células solares. Para la simulación de células solares triple-unión se ha desarrollado en la presente tesis doctoral un modelo circuital tridimensinal distribuido el cuál integra una descripción completa de la unión túnel. De este modo, con el modelo desarrollado, hemos podido simular perfiles de luz sobre la célula solar que hacen que la densidad de corriente fotogenerada sea mayor a la densidad de corriente pico de la unión túnel. El modelo desarrollado también contempla la distribución lateral de corriente en las capas semiconductoras que componen y rodean la unión túnel. Por tanto, se ha podido simular y analizar el efecto que tiene sobre el funcionamiento de la célula solar que los concentradores ópticos produzcan perfiles de luz desuniformes, tanto en nivel de irradiancia como en el contenido espectral de la luz (aberración cromática). Con el objetivo de determinar cuáles son los mecanismos de recombinación que están limitando el funcionamiento de cada subcélula que integra una triple-unión, y así intentar reducirlos, se ha llevado a cabo la caracterización eléctrica de células solares monouni ón idénticas a las subcelulas de una triple-unión. También se ha determinado la curva corriente-tensión en oscuridad de las subcélulas de GaInP y GaAs de una célula dobleunión mediante la utilización de un teorema de reciprocidad electro-óptico. Finalmente, se ha analizado el impacto de los diferentes mecanismos de recombinación en el funcionamiento de la célula solar triple-unión en concentración. Por último, para determinar la fiabilidad de este tipo de células, se ha llevado a cabo un ensayo de vida acelerada en temperatura en células solares triple-unión comerciales. En la presente tesis doctoral se describe el diseño del ensayo, el progreso del mismo y los datos obtenidos tras el análisis de los resultados preliminares. Abstract Concentrator photovoltaic systems (CPV) seem to be one of the most promising ways to generate electricity at competitive prices. Nowadays, the research is focused on increasing the efficiency and the concentration of the systems in order to reduce costs. At the same time, another important area of research is the study of the reliability of the different components which make up a CPV system. In fact, in order for a CPV to be cost-effective, it should have a warranty at least similar to that of the systems based on Si solar cells. In the present thesis, we will study in depth the behavior of multijunction solar cells under ultra-high concentration. With this purpose in mind, a three-dimensional circuital distributed model which is able to simulate the behavior of triple-junction solar cells under different working conditions has been developed. Also, an advanced characterization of these solar cells has been carried out in order to better understand their behavior and thus contribute to improving efficiency. Finally, accelerated life tests have been carried out on commercial lattice-matched triple-junction solar cells in order to determine their reliability. In order to simulate triple-junction solar cells, a 3D circuital distributed model which integrates a full description of the tunnel junction has been developed. We have analyzed the behavior of the multijunction solar cell under light profiles which cause the current density photo-generated in the solar cell to be higher than the tunnel junction’s peak current density. The advanced model developed also takes into account the lateral current spreading through the semiconductor layers which constitute and surround the tunnel junction. Therefore, the effects of non-uniform light profiles, in both irradiance and the spectral content produced by the concentrators on the solar cell, have been simulated and analyzed. In order to determine which recombination mechanisms are limiting the behavior of each subcell in a triple-junction stack, and to try to reduce them when possible, an electrical characterization of single-junction solar cells that resemble the subcells in a triplejunction stack has been carried out. Also, the dark I-V curves of the GaInP and GaAs subcells in a dual-junction solar cell have been determined by using an electro-optical reciprocity theorem. Finally, the impact of the different recombination mechanisms on the behavior of the triple-junction solar cell under concentration has been analyzed. In order to determine the reliability of these solar cells, a temperature accelerated life test has been carried out on commercial triple-junction solar cells. In the present thesis, the design and the evolution of the test, as well as the data obtained from the analysis of the preliminary results, are presented.

Voltage recovery in intermediate band solar cells

The intermediate band solar cell (IBSC) is based on a novel photovoltaic concept and has a limiting efficiency of 63.2%, which compares favorably with the 40.7% efficiency of a conventional, single junction solar cell. It is characterized by a material hosting a collection of energy levels within its bandgap, allowing the cell to exploit photons with sub-bandgap energies in a two-step absorption process, thus improving the utilization of the solar spectrum. However, these intermediate levels are often regarded as an inherent source of supplementary recombination, although this harmful effect can in theory be counteracted by the use of concentrated light. We present here a novel, low-temperature characterization technique using concentrated light that reveals how the initially enhanced recombination in the IBSC is reduced so that its open-circuit voltage is completely recovered and reaches that of a conventional solar cell.

Understanding intermediate-band solar cells

The intermediate-band solar cell is designed to provide a large photogenerated current while maintaining a high output voltage. To make this possible, these cells incorporate an energy band that is partially filled with electrons within the forbidden bandgap of a semiconductor. Photons with insufficient energy to pump electrons from the valence band to the conduction band can use this intermediate band as a stepping stone to generate an electron-hole pair. Nanostructured materials and certain alloys have been employed in the practical implementation of intermediate-band solar cells, although challenges still remain for realizing practical devices. Here we offer our present understanding of intermediate-band solar cells, as well as a review of the different approaches pursed for their practical implementation. We also discuss how best to resolve the remaining technical issues.

Symmetry considerations in the empirical k.p Hamiltonian for the study of intermediate band solar cells

With the purpose of assessing the absorption coefficients of quantum dot solar cells, symmetry considerations are introduced into a Hamiltonian whose eigenvalues are empirical. In this way, the proper transformation from the Hamiltonian's diagonalized form to the form that relates it with Γ-point exact solutions through k.p envelope functions is built accounting for symmetry. Forbidden transitions are thus determined reducing the calculation burden and permitting a thoughtful discussion of the possible options for this transformation. The agreement of this model with the measured external quantum efficiency of a prototype solar cell is found to be excellent.

Impact of MOVPE Environment on Silicon Substrates for III-V-on-Si Multijunction Solar Cells

With the final goal of integrating III-V materials to silicon for tandem solar cells, the influence of the metal-organic vapor phase epitaxy (MOVPE) environment on the minority carrier properties of silicon wafers has been evaluated. These properties will essentially determine the photovoltaic performance of the bottom cell in a III-V-on-Si tandem solar cell device. A comparison of the base minority carrier lifetimes obtained for different thermal processes carried out in a MOVPE reactor on Czochralski silicon wafers has been carried out. The effect of the formation of the emitter by phosphorus diffusion has also been evaluated.

Extended description of tunnel junctions for distributed modeling of concentrator multi-junction solar cells

One of the key components of highly efficient multi-junction concentrator solar cells is the tunnel junction interconnection. In this paper, an improved 3D distributed model is presented that considers real operation regimes in a tunnel junction. This advanced model is able to accurately simulate the operation of the solar cell at high concentraions at which the photogenerated current surpasses the peak current of the tunnel junctionl Simulations of dual-junction solar cells were carried out with the improved model to illustrate its capabilities and the results have been correlated with experimental data reported in the literature. These simulations show that under certain circumstances, the solar cells short circuit current may be slightly higher than the tunnel junction peak current without showing the characteristic dip in the J-V curve. This behavior is caused by the lateral current spreading toward dark regions, which occurs through the anode/p-barrier of the tunnel junction.

Understanding phosphorus diffusion into silicon in a MOVPE environment for III-V on silicon solar cells

Dual-junction solar cells formed by a GaAsP or GaInP top cell and a silicon bottom cell seem to be attractive candidates to materialize the long sought-for integration of III?V materials on silicon for photovoltaic applications. When manufacturing a multi-junction solar cell on silicon, one of the first processes to be addressed is the development of the bottom subcell and, in particular, the formation of its emitter. In this study, we analyze, both experimentally and by simulations, the formation of the emitter as a result of phosphorus diffusion that takes place during the first stages of the epitaxial growth of the solar cell. Different conditions for the Metal-Organic Vapor Phase Epitaxy (MOVPE) process have been evaluated to understand the impact of each parameter, namely, temperature, phosphine partial pressure, time exposure and memory effects in the final diffusion profiles obtained. A model based on SSupremIV process simulator has been developed and validated against experimental profiles measured by ECV and SIMS to calculate P diffusion profiles in silicon formed in a MOVPE environment taking in consideration all these factors.

On-site measurement of limiting subcell in multijunction solar devices

It is well known that the response of any photovoltaic solar cell is dependent on the spectral characteristics of the incident radiation. This dependency is crucial in the output characteristics of a multijunction (MJ) cell where the spectral composition of the radiation determines the overall photocurrent produced, as either the top or the middle subcell will be limiting its response. The current mismatching between top and middle subcell is translated into energy losses, affecting the yield of the system. For research and commercial purposes it is interesting to measure accurately the incident solar radiation on a MJ cell, in terms of its spectral composition. This measurement will allows us to determine the photocurrent generated in each band of the multijunction device. Nowadays, the only way of measuring the photocurrent generated by each subcell is done with isotype cells or with spectroradiometers but there is no device capable of directly measuring each subcell photocurrent. In this paper it is described a device based on a commercial multijunction solar cell that is capable of measuring the direct irradiance for the top and middle bands thus it offers information of the limiting subcell (top or middle) in outdoors conditions.

Nano-imprinted rear-side diffraction gratings for absorption enhancement in solar cells

As wafer-based solar cells become thinner, light-trapping textures for absorption enhancement will gain in importance. In this work, crystalline silicon wafers were textured with wavelength-scale diffraction grating surface textures by nanoimprint lithography using interference lithography as a mastering technology. This technique allows fine-tailored nanostructures to be realized on large areas with high throughput. Solar cell precursors were fabricated, with the surface textures on the rear side, for optical absorption measurements. Large absorption enhancements are observed in the wavelength range in which the silicon wafer absorbs weakly. It is shown experimentally that bi-periodic crossed gratings perform better than uni-periodic linear gratings. Optical simulations have been made of the fabricated structures, allowing the total absorption to be decomposed into useful absorption in the silicon and parasitic absorption in the rear reflector. Using the calculated silicon absorption, promising absorbed photocurrent density enhancements have been calculated for solar cells employing the nano-textures. Finally, first results are presented of a passivation layer deposition technique that planarizes the rear reflector for the purpose of reducing the parasitic absorption.

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.

The unstoppable rise of photovoltaic solar energy: PV vs. PV

Photovoltaic (PV) solar energy has been growing during the last decade an explosive rate. Last year (2011) the solar cell production amounted to more than 37 GW. It is the energy technology most installed nowadays. The power generated by the 37 GW is similar to the one generated by about 7 nuclear units of 1 GW each. The solar industry is already a huge industry dominated by Asian countries led by China. It is not anymore a promise. It is just a reality.

ARXPS analysis of a GaAs/GaInP heterointerface with application in III-V multijunction solar cells

In this contribution, angle-resolved X-ray photoelectron spectroscopy is used to explore the extension and nature of a GaAs/GaInP heterointerface. This bilayer structure constitutes a very common interface in a multilayered III-V solar cell. Our results show a wide indium penetration into the GaAs layer, while phosphorous diffusion is much less important. The physico-chemical nature of such interface and its depth could deleteriously impact the solar cell performance. Our results probe the formation of spurious phases which may profoundly affect the interface behavior.

Sistema de medida de mapa de electroluminiscencia para células solares de concentración

En este Trabajo Fin de Master se desarrolla una aplicación basada en Labview diseñada para la adquisición automática de mapas de electroluminiscencia de células solares en general y células solares multiunión de concentración como caso particular, para diferentes condiciones de polarización. Este sistema permitirá la adquisición de mapas de electroluminescencia de cada una de las sub-células de una célula multiunión. Las variaciones espaciales en la intensidad de electroluminescencia medida podrán ser analizadas y correlacionadas con defectos de distintos tipos en la estructura semiconductora o en los contactos metálicos que forman el dispositivo de célula solar. En la parte teórica se presenta el estado del arte referente a la caracterización de células solares basada en la técnica de electroluminiscencia, así como los antecedentes del Instituto de Energía Solar (IES) referidos a este tema. Para el desarrollo de la parte práctica ha sido necesario diseñar dos drivers en Labview. El primer driver controla una fuente-medidor, que inyecta corriente a la célula solar y recoge datos de la tensión asociada. El segundo driver se utiliza para controlar y automatizar el proceso de adquisición, mediante sensor CCD, de la imagen electroluminiscente de la célula solar sometida a unas condiciones de polarización determinadas. Estos drivers se incluyen dentro de la aplicación final desarrollada, que ofrece al usuario una interfaz para la aplicación de diferentes condiciones de polarización a la célula solar y la adquisición de los mapas de electroluminescencia. La utilización de este sistema es fundamental en los estudios de degradación de células solares que se llevan a cabo actualmente en el Instituto de Energía Solar. De hecho, en este Trabajo Fin de Máster se han realizado las primeras medidas al respecto, cuyos resultados se presentan en la parte final de esta memoria. SUMMARY. This Master Final Project develops a Labview application designed to perform the automatic acquisition of solar cell electroluminescence maps in general, and concentrator multijunction solar cells as a special case, under forward biased conditions. This system allows the acquisition of electroluminescence maps of each of the sub-cells in a multijunction cell. The spatial variations in the intensity of the electroluminescence measured can be analyzed and correlated with defects in the semiconductor structure or in the metal contacts of the solar cell. In the theory section of this memory, the state of the art of the electroluminescence-based characterization techniques for solar cells is presented, and the previous work carried out at I.E.S. is summarized. For the development of the practice part it has been necessary to design two drivers using Labview software. The first driver handles the source-meter injecting current in the solar cell and measuring voltage between its terminals. The second driver is used to handle and automate the acquisition of the solar cell electroluminescence image under forward biased conditions, using a CCD sensor. These drivers are included in the final application, which offers the user an interface to apply different bias conditions to the solar cell and for the acquisition of electroluminescence maps. The use of this system is essential in the studies of degradation of solar cells which is currently underway at the I.E.S. – U.P.M. In this Master Final Project the results of the first measurements are carried out which are presented in the final part of this memory.

Estudio teórico de propiedades termodinámicas y optoelectronicas de nuevos materiales fotovoltaicos de banda intermedia = Theoretical study of thermodynamic and optoelectronic properties of new intermediate band photovoltaic materials

Los materiales de banda intermedia han atraido la atención de la comunidad científica en el campo de la energía solar fotovoltaica en los últimos años. Sin embargo, con el objetivo de entender los fundamentos de las células solares de banda intermedia, se debe llevar a cabo un estudio profundo de la características de los materiales. Esto se puede hacer mediante un modelo teórico usando Primeros Principios. A partir de este enfoque se pueden obtener resultados tales como la estructura electrónica y propiedades ópticas, entre otras, de los semiconductores fuertemente dopados y sus precursores. Con el fin de desentrañar las estructuras de estos sistemas electrónicos, esta tesis presenta un estudio termodinámico y optoelectrónico de varios materiales fotovoltaicos. Específicamente se caracterizaron los materiales avanzados de banda intermedia y sus precursores. El estudio se hizo en términos de caracterización teórica de la estructura electrónica, la energética del sistema, entre otros. Además la estabilidad se obtuvo usando configuraciones adaptadas a la simetría del sistema y basado en la combinatoria. Las configuraciones de los sitios ocupados por defectos permiten obtener información sobre un espacio de configuraciones donde las posiciones de los dopantes sustituidos se basan en la simetría del sólido cristalino. El resultado puede ser tratado usando elementos de termodinámica estadística y da información de la estabilidad de todo el espacio simétrico. Además se estudiaron otras características importantes de los semiconductores de base. En concreto, el análisis de las interacciones de van der Waals fueron incluidas en el semiconductor en capas SnS2, y el grado de inversión en el caso de las espinelas [M]In2S4. En este trabajo además realizamos una descripción teórica exhaustiva del sistema CdTe:Bi. Este material de banda-intermedia muestra características que son distintas a las de los otros materiales estudiados. También se analizó el Zn como agente modulador de la posición de las sub-bandas prohibidas en el material de banda-intermedia CuGaS2:Ti. Analizándose además la viabilidad termodinámica de la formación de este compuesto. Finalmente, también se describió el GaN:Cr como material de banda intermedia, en la estructura zinc-blenda y en wurtztite, usando configuraciones de sitios ocupados de acuerdo a la simetría del sistema cristalino del semiconductor de base. Todos los resultados, siempre que fue posible, fueron comparados con los resultados experimentales. ABSTRACT The intermediate-band materials have attracted the attention of the scientific community in the field of the photovoltaics in recent years. Nevertheless, in order to understand the intermediate-band solar cell fundamentals, a profound study of the characteristics of the materials is required. This can be done using theoretical modelling from first-principles. The electronic structure and optical properties of heavily doped semiconductors and their precursor semiconductors are, among others, results that can be obtained from this approach. In order to unravel the structures of these crystalline systems, this thesis presents a thermodynamic and optoelectronic study of several photovoltaic materials. Specifically advanced intermediate-band materials and their precursor semiconductors were characterized. The study was made in terms of theoretical characterization of the electronic structure, energetics among others. The stability was obtained using site-occupancy-disorder configurations adapted to the symmetry of the system and based on combinatorics. The site-occupancy-disorder method allows the formation of a configurational space of substitutional dopant positions based on the symmetry of the crystalline solid. The result, that can be treated using statistical thermodynamics, gives information of the stability of the whole space of symmetry of the crystalline lattice. Furthermore, certain other important characteristics of host semiconductors were studied. Specifically, the van der Waal interactions were included in the SnS2 layered semiconductor, and the inversion degree in cases of [M]In2S4 spinels. In this work we also carried out an exhaustive theoretical description of the CdTe:Bi system. This intermediate-band material shows characteristics that are distinct from those of the other studied intermediate-band materials. In addition, Zn was analysed as a modulator of the positions of the sub-band gaps in the CuGaS2:Ti intermediate-band material. The thermodynamic feasibility of the formation of this compound was also carried out. Finally GaN:Cr intermediate-band material was also described both in the zinc-blende and the wurtztite type structures, using the symmetry-adapted-space of configurations. All results, whenever possible, were compared with experimental results.

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.