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.

Integration of III-V materials on Silicon Substrates for Multi-junction Solar Cell Applications

The work presented here aims to reduce the cost of multijunction solar cell technology by developing ways to manufacture them on cheap substrates such as silicon. In particular, our main objective is the growth of III-V semiconductors on silicon substrates for photovoltaic applications. The goal is to create a GaAsP/Si virtual substrates onto which other III-V cells could be integrated with an interesting efficiency potential. This technology involves several challenges due to the difficulty of growing III-V materials on silicon. In this paper, our first work done aimed at developing such structure is presented. It was focused on the development of phosphorus diffusion models on silicon and on the preparation of an optimal silicon surface to grow on it III-V materials.

Si(100) versus Ge(100): Watching the interface formation for the growth of III-V-based solar cells on abundant substrates

We investigated the atomic surface properties of differently prepared silicon and germanium (100) surfaces during metal-organic vapour phase epitaxy/chemical vapour deposition (MOVPE/MOCVD), in particular the impact of the MOVPE ambient, and applied reflectance anisotropy/difference spectroscopy (RAS/RDS) in our MOVPE reactor to in-situ watch and control the preparation on the atomic length scale for subsequent III-V-nucleation. The technological interest in the predominant opto-electronic properties of III-V-compounds drives the research for their heteroepitaxial integration on more abundant and cheaper standard substrates such as Si(100) or Ge(100). In these cases, a general task must be accomplished successfully, i.e. the growth of polar materials on non-polar substrates and, beyond that, very specific variations such as the individual interface formation and the atomic step structure, have to be controlled. Above all, the method of choice to grow industrial relevant high-performance device structures is MOVPE, not normally compatible with surface and interface sensitive characterization tools, which are commonly based on ultrahigh vacuum (UHV) ambients. A dedicated sample transfer system from MOVPE environment to UHV enabled us to benchmark the optical in-situ spectra with results from various surfaces science instruments without considering disruptive contaminants. X-ray photoelectron spectroscopy (XPS) provided direct observation of different terminations such as arsenic and phosphorous and verified oxide removal under various specific process parameters. Absorption lines in Fourier-transform infrared (FTIR) spectra were used to identify specific stretch modes of coupled hydrides and the polarization dependence of the anti-symmetric stretch modes distinguished different dimer orientations. Scanning tunnelling microscopy (STM) studied the atomic arrangement of dimers and steps and tip-induced H-desorption proved the saturation of dangling bonds after preparati- n. In-situ RAS was employed to display details transiently such as the presence of H on the surface at lower temperatures (T <; 800°C) and the absence of Si-H bonds at elevated annealing temperature and also surface terminations. Ge buffer growth by the use of GeH4 enables the preparation of smooth surfaces and leads to a more pronounced amplitude of the features in the spectra which indicates improvements of the surface quality.

Optimizing Bottom Subcells for III-V-on-Si MultiJunction 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. Such integration would offer a cost breakthrough for photovoltaic technology, unifying the low cost of silicon and the efficiency potential of III-V multijunction solar cells. In this study, we analyze several factors influencing the performance of the bottom subcell of this dual-junction, namely, 1) the formation of the emitter as a result of the phosphorus diffusion that takes place during the prenucleation temperature ramp and during the growth of the III-V layers; 2) the degradation in surface morphology during diffusion; and 3) the quality needed for the passivation provided by the GaP layer on the emitter.

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.

Statistical Calculation of the Main Reliability Functions of GaAs Concentrator III-V Solar Cells

This paper presents some of the results of a method to determine the main reliability functions of concentrator solar cells. High concentrator GaAs single junction solar cells have been tested in an Accelerated Life Test. The method can be directly applied to multi-junction solar cells. The main conclusions of this test carried out show that these solar cells are robust devices with a very low probability of failure caused by degradation during their operation life (more than 30 years). The evaluation of the probability operation function (i.e. the reliability function R(t)) is obtained for two nominal operation conditions of these cells, namely simulated concentration ratios of 700 and 1050 suns. Preliminary determination of the Mean Time to Failure indicates a value much higher than the intended operation life time of the concentrator cells.

E-beam nanopatterning for the selective area growth of III-V nitride nanorods

GaN/InGaN nanorods have attracted much scientific interest during the last decade because of their unique optical and electrical properties [1,2]. The high crystal quality and the absence of extended defects make them ideal candidates for the fabrication of high efficiency opto-electronic devices such as nano-photodetectors, light-emitting diodes, and solar cells [1-3]. Nitrides nanorods are commonly grown in the self-assembled mode by plasma-assisted molecular beam epitaxy (MBE) [4]. However, self-assembled nanorods are characterized by inhomogeneous heights and diameters, which render the device processing very difficult and negatively affect the electronic transport properties of the final device. For this reason, the selective area growth (SAG) mode has been proposed, where the nanorods preferentially grow on pre-defined sites on a pre-patterned substrate [5].

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.

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.

In situ control of Si(100) and Ge(100) surface preparation for the heteroepitaxy of III-V solar cell architectures

Si(100) and Ge(100) substrates essential for subsequent III-V integration were studied in the hydrogen ambient of a metalorganic vapor phase epitaxy reactor. Reflectance anisotropy spectroscopy (RAS) enabled us to distinguish characteristic configurations of vicinal Si(100) in situ: covered with oxide, cleaned by thermal removing in H2, and terminated with monohydrides when cooling in H2 ambient. RAS measurements during cooling in H2 ambient after the oxide removal process revealed a transition from the clean to the monohydride terminated Si(100) surface dependent on process temperature. For vicinal Ge(100) we observed a characteristic RA spectrum after annealing and cooling in H2 ambient. According to results from X-ray photo electron spectroscopy and Fourier-transform infrared spectroscopy the spectrum corresponds to the monohydride terminated Ge(100) surface.

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.

Optimization of the silicon subcell for III-V on silicon multijunction solar cells: key differences with conventional silicon technology

Dual-junction solar cells formed by a GaAsP or GaInP top cell and a silicon (Si) bottom cell seem to be attractive candidates to materialize the long sought-for integration of III-V materials on Si for photovoltaic (PV) applications. Such integration would offer a cost breakthrough for PV technology, unifying the low cost of Si and the efficiency potential of III-V multijunction solar cells. The optimization of the Si solar cells properties in flat-plate PV technology is well-known; nevertheless, it has been proven that the behavior of Si substrates is different when processed in an MOVPE reactor In this study, we analyze several factors influencing the bottom subcell performance, namely, 1) the emitter formation as a result of phosphorus diffusion; 2) the passivation quality provided by the GaP nucleation layer; and 3) the process impact on the bottom subcell PV properties.

Preliminary temperature Accelerated Life Test (ALT) on III-V commercial concentrator triple-junction solar cells

A quantitative temperature accelerated life test on sixty GaInP/GaInAs/Ge triple-junction commercial concentrator solar cells is being carried out. The final objective of this experiment is to evaluate the reliability, warranty period, and failure mechanism of high concentration solar cells in a moderate period of time. The acceleration of the degradation is realized by subjecting the solar cells at temperatures markedly higher than the nominal working temperature under a concentrator Three experiments at three different temperatures are necessary in order to obtain the acceleration factor which relates the time at the stress level with the time at nominal working conditions. . However, up to now only the test at the highest temperature has finished. Therefore, we can not provide complete reliability information but we have analyzed the life data and the failure mode of the solar cells inside the climatic chamber at the highest temperature. The failures have been all of them catastrophic. In fact, the solar cells have turned into short circuits. We have fitted the failure distribution to a two parameters Weibull function. The failures are wear-out type. We have observed that the busbar and the surrounding fingers are completely deteriorate

Influence of PH3 exposure on silicon substrate morphology in the MOVPE growth of III-V on silicon multijunction 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. One of the first issues to be considered in the development of this structure will be the strategy to create the silicon emitter of the bottom subcell. In this study, we explore the possibility of forming the silicon emitter by phosphorus diffusion (i.e. exposing the wafer to PH3 in a MOVPE reactor) and still obtain good surface morphologies to achieve a successful III-V heteroepitaxy as occurs in conventional III-V on germanium solar cell technology. Consequently, we explore the parameter space (PH3 partial pressure, time and temperature) that is needed to create optimized emitter designs and assess the impact of such treatments on surface morphology using atomic force microscopy. Although a strong degradation of surface morphology caused by prolonged exposure of silicon to PH3 is corroborated, it is also shown that subsequent anneals under H-2 can recover silicon surface morphology and minimize its RMS roughness and the presence of pits and spikes.

Effects of internal luminescence and internal optics on V-oc and J(sc) of III-V solar cells

For solar cells dominated by radiative recombination, the performance can be significantly enhanced by improving the internal optics. Internally radiated photons can be directly emitted from the cell, but if confined by good internal reflectors at the front and back of the cell they can also be re-absorbed with a significant probability. This so-called photon recycling leads to an increase in the equilibrium minority carrier concentration and therefore the open-circuit voltage, Voc. In multijunction cells, the internal luminescence from a particular junction can also be coupled into a lower bandgap junction where it generates photocurrent in addition to the externally generated photocurrent, and affects the overall performance of the tandem. We demonstrate and discuss the implications of a detailed model that we have developed for real, non-idealized solar cells that calculates the external luminescent efficiency, accounting for wavelength-dependent optical properties in each layer, parasitic optical and electrical losses, multiple reflections within the cell and isotropic internal emission. The calculation leads to Voc, and we show data on high quality GaAs cells that agree with the trends in the model as the optics are systematically varied. For multijunction cells the calculation also leads to the luminescent coupling efficiency, and we show data on GaInP/GaAs tandems where the trends also agree as the coupling is systematically varied. In both cases, the effects of the optics are most prominent in cells with good material quality. The model is applicable to any solar cell for which the optical properties of each layer are well-characterized, and can be used to explore a wide phase space of design for single junction and multijunction solar cells.