Engineering metal precipitate size distributions to enhance gettering in multicrystalline silicon

The extraction of metal impurities during phosphorus diffusion gettering (PDG) is one of the crucial process steps when fabricating high-efficiency solar cells using low-cost, lower-purity silicon wafers. In this work, we show that for a given metal concentration, the size and density of metal silicide precipitates strongly influences the gettering efficacy. Different precipitate size distributions can be already found in silicon wafers grown by different techniques. In our experiment, however, the as-grown distribution of precipitated metals in multicrystalline Si sister wafers is engineered through different annealing treatments in order to control for the concentration and distribution of other defects. A high density of small precipitates is formed during a homogenization step, and a lower density of larger precipitates is formed during extended annealing at 740º C. After PDG, homogenized samples show a decreased interstitial iron concentration compared to as-grown and ripened samples, in agreement with simulations.

Electronic property analysis of O-doped Cu3SbS3

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

Analysis of the surface state of epi-ready Ge wafers

The surface state of Ge epi-ready wafers (such as those used on III-V multijunction solar cells) supplied by two different vendors has been studied using X-ray photoemission spectroscopy. Our experimental results show that the oxide layer on the wafer surface is formed by GeO and GeO2. This oxide layer thickness differs among wafers coming from different suppliers. Besides, several contaminants appear on the wafer surfaces, carbon and probably chlorine being common to every wafer, irrespective of its origin. Wafers from one of the vendors show the presence of carbonates at their surfaces. On such wafers, traces of potassium seem to be present too.

Laser ablation modelling of aluminium, silver and crystalline silicon for applications in photovoltaic technologies

Laser material processing is being extensively used in photovoltaic applications for both the fabrication of thin film modules and the enhancement of the crystalline silicon solar cells. The two temperature model for thermal diffusion was numerically solved in this paper. Laser pulses of 1064, 532 or 248 nm with duration of 35, 26 or 10 ns were considered as the thermal source leading to the material ablation. Considering high irradiance levels (108–109 W cm−2), a total absorption of the energy during the ablation process was assumed in the model. The materials analysed in the simulation were aluminium (Al) and silver (Ag), which are commonly used as metallic electrodes in photovoltaic devices. Moreover, thermal diffusion was also simulated for crystalline silicon (c-Si). A similar trend of temperature as a function of depth and time was found for both metals and c-Si regardless of the employed wavelength. For each material, the ablation depth dependence on laser pulse parameters was determined by means of an ablation criterion. Thus, after the laser pulse, the maximum depth for which the total energy stored in the material is equal to the vaporisation enthalpy was considered as the ablation depth. For all cases, the ablation depth increased with the laser pulse fluence and did not exhibit a clear correlation with the radiation wavelength. Finally, the experimental validation of the simulation results was carried out and the ability of the model with the initial hypothesis of total energy absorption to closely fit experimental results was confirmed.

Study of the brittle fracture of monocrystalline silicon wafers

There is a growing trend towards using thinner wafers in order to reduce the costs of solar energy. But the current tools employed during the solar cells production are not prepared to work with thinner wafers, decreasing the industrial yield due to the high number of wafers broken. To develop new tools, or modify existing ones, the mechanical properties have to be determined. This paper tackles an experimental study of the mechanical properties of wafers. First, the material characteristics are detailed and the process to obtain wafers is presented. Then, the complete test setup and the mechanical strength results interpreted by a described numerical model are shown.

Mechanical characterization of multicrystalline silicon wafers

The possibility of using more economical silicon feedstock, i.e. as support for epitaxial solar cells, is of interest when the cost reduction and the properties are attractive. We have investigated the mechanical behavior of two blocks of upgraded metallurgical silicon, which is known to present high content of impurities even after being purified by the directional solidification process. The impurities are mainly metals like Al and silicon compounds. Thus, it is important to characterize their effect in order to improve cell performance and to ensure the survival of the wafers throughout the solar value chain. Microstructure and mechanical properties were studied by means of ring on ring and three point bending tests. Additionally, Young’s modulus, hardness and fracture toughness were measured. These results showed that it is possible to obtain marked improvements in toughness when impurities act as microscopic internal crack arrestors. However, the same impurities can be initiators of damage due to residual thermal stresses introduced during the crystallization process.

Progress on the development of a technology for silicon purification

The polysilicon market is experiencing tremendous changes due to the strong demand from Photovoltaics (PV), which has by far surpassed the demand from Microelectronics. The need of solar silicon has induced a large increase in capacity, which has now given a scenario of oversupply, reducing the polysilicon price to levels that put a strong pressure on the cost structure of the producers. The paper reports on the R&D efforts carried out in the field of solar silicon purification via the chlorosilane route by a private-public consortium that is building a pilot plant of 50-100 tonnes/year, that will synthesize trichlorosilane, purify it and deposit ultrapure silicon in an industrial-size Siemens type reactor. It has also capabilities for ingot growth and material characterization. A couple of examples of the progress so far are given, the first one related to the recycling scheme of chlorinated compounds, and the second to the minimization of radiation losses in the CVD deposition process, which account for a relevant part of the total energy consumption. In summary, the paper gives details on the technology being developed in our pilot plant, which offers a unique platform for field-testing of innovative approaches that can lead to a cost reduction of solar silicon produced via the chlorosilane route.

Fracture strength of drilled wafers: study of the stress concentration factor and determination of the weibull distribution of the fracture stress

In the photovoltaic field, the back contact solar cells technology has appeared as an alternative to the traditional silicon modules. This new type of cells places both positive and negative contacts on the back side of the cells maximizing the exposed surface to the light and making easier the interconnection of the cells in the module. The Emitter Wrap-Through solar cell structure presents thousands of tiny holes to wrap the emitter from the front surface to the rear surface. These holes are made in a first step over the silicon wafers by means of a laser drilling process. This step is quite harmful from a mechanical point of view since holes act as stress concentrators leading to a reduction in the strength of these wafers. This paper presents the results of the strength characterization of drilled wafers. The study is carried out testing the samples with the ring on ring device. Finite Element models are developed to simulate the tests. The stress concentration factor of the drilled wafers under this load conditions is determined from the FE analysis. Moreover, the material strength is characterized fitting the fracture stress of the samples to a three-parameter Weibull cumulative distribution function. The parameters obtained are compared with the ones obtained in the analysis of a set of samples without holes to validate the method employed for the study of the strength of silicon drilled wafers.

Intermediate Band to Conduction Band optical absorption in ZnTe:O

ZnTe doped with high concentrations of oxygen has been proposed in previous works as intermediate band (IB) material for photovoltaic applications. The existence of extra optical transitions related to the presence of an IB has already been demonstrated in this material and it has been possible to measure the absorption coefficient of the transitions from the valence band (VB) to the IB. In this work we present the first measurement of the absorption coefficient associated to transitions from the IB to the conduction band (CB) in ZnTe:O. The samples used are 4 ?m thick ZnTe layers with or without O in a concentration ~ 1019 cm-3, which have been grown on semi-insulating GaAs substrates by molecular beam epitaxy (MBE). The IB-CB absorption coefficient peaks for photon energies ~ 0.4 eV. It is extracted from reflectance and transmittance spectra measured using Fourier Transform Infrared (FTIR) spectroscopy. Under typical FTIR measurement conditions (low light intensity, broadband spectrum) the absorption coefficient in IB-to-CB transitions reaches 700 cm-1. This is much weaker than the one observed for VB-IB absorption. This result is consistent with the fact that the IB is expected to be nearly empty of electrons under equilibrium conditions in ZnTe(:O). The absorption for VB to IB transitions is also observed in the same samples through reflectance measurements performed in the visible range using a monochromator. These measurements are compared with the quantum efficiency (QE) from solar cells fabricated under similar conditions.

Analytic free-form lens design for tracking integration in concentrating photovoltaics

In this work the concept of tracking integration in concentrating photovoltaics (CPV) is revisited and developed further. With respect to conventional CPV, tracking integration eliminates the clear separation between stationary units of optics and solar cells, and external solar trackers. This approach is capable of further increasing the concentration ratio and makes high concentrating photovoltaics (> 500x) available for single-axis tracker installations. The reduced external solar tracking effort enables possibly cheaper and more compact installations. Our proposed optical system uses two laterally moving plano-convex lenses to achieve high concentration over a wide angular range of ±24°. The lateral movement allows to combine both steering and concentration of the incident direct sun light. Given the specific symmetry conditions of the underlying optical design problem, rotational symmetric lenses are not ideal for this application. For this type of design problems, a new free-form optics design method presented in previous papers perfectly matches the symmetry. It is derived directly from Fermat's principle, leading to sets of functional differential equations allowing the successive calculation of the Taylor series coeficients of each implicit surface function up to very high orders. For optical systems designed for wide field of view and with clearly separated optical surfaces, this new analytic design method has potential application in both fields of nonimaging and imaging optics.

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.

Free-form optics for Fresnel-lens-based photovoltaic concentrators

The Concentrated Photovoltaics (CPV) promise relies upon the use of high-efficiency triple-junction solar cells (with proven efficiencies of over 44%) and upon high-performance optics that allow for high concentration concurrent with relaxed manufacturing tolerances (all key elements for low-cost mass production). Additionally, uniform illumination is highly desirable for efficiency and reliability reasons. All of these features have to be achieved with inexpensive optics containing only a few (in general no more than 2) optical elements. In this paper we show that the degrees of freedom using free-forms allow the introduction of multiple functionalities required for CPV with just 2 optical elements, one of which is a Fresnel lens.

Low-cost irradiance sensors for irradiation assessments inside tree canopies.

The solar irradiation that a crop receives is directly related to the physical and biological processes that affect the crop. However, the assessment of solar irradiation poses certain problems when it must be measured through fruit inside the canopy of a tree. In such cases, it is necessary to check many test points, which usually requires an expensive data acquisition system. The use of conventional irradiance sensors increases the cost of the experiment, making them unsuitable. Nevertheless, it is still possible to perform a precise irradiance test with a reduced price by using low-cost sensors based on the photovoltaic effect. The aim of this work is to develop a low-cost sensor that permits the measurement of the irradiance inside the tree canopy. Two different technologies of solar cells were analyzed for their use in the measurement of solar irradiation levels inside tree canopies. Two data acquisition system setups were also tested and compared. Experiments were performed in Ademuz (Valencia, Spain) in September 2011 and September 2012 to check the validity of low-cost sensors based on solar cells and their associated data acquisition systems. The observed difference between solar irradiation at high and low positions was of 18.5% ± 2.58% at a 95% confidence interval. Large differences were observed between the operations of the two tested sensors. In the case of a-Si cells based mini-modules, an effect of partial shadowing was detected due to the larger size of the devices, the use of individual c-Si cells is recommended over a-Si cells based mini-modules.

Wide-angle, high-concentration photovoltaics to compete with flat plate systems

A novel photovoltaic concentrator enables highly uniform irradiance on a small number of efficient solar cells. The maximum electrical power of a photovoltaic (PV) energy installation depends on three factors: the available irradiance, the size of the systems collecting sunlight, and the rate at which the device transforms light into electricity (the conversion efficiency). Developers can maximize the irradiance by carefully selecting the site and orientation of the solar facility. But they can only expand their sunlight collection systems for standard flat plate PV devices by increasing the number of solar cells, at greater cost. Here, we consider the advantages of an alternative PV system that produces more energy without increasing the number of cells used (actually, reducing it), by improving the conversion rates.We also present a new device that may enhance the commercial viability of such technologies.

Development and characterization of an FK photovoltaic concentrator for maximum conversion efficiency

The outdoor measurements of a single-cell concentrator PV module reaching a regressed 35.6% efficiency and a maximum peak efficiency of 36.0% (both corrected @Tcell=25ºC) are presented. This is the result of the joint effort by LPI and Solar Junction to demonstrate the potential of combining their respective state-of-the-art concentrator optics and solar cells. The LPI concentrator used is an FK, which is an advanced nonimaging concentrator using 4-channel Köhler homogenization, with a primary Fresnel lens and a refractive secondary made of glass. Solar Junction’s cell is a triplejunction solar cell with the A-SLAMTM architecture using dilute-nitrides.