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

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

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.

Application of photoreflectance to advanced multilayer structures for photovoltaics

Photoreflectance (PR) is a convenient characterization tool able to reveal optoelectronic properties of semiconductor materials and structures. It is a simple non-destructive and contactless technique which can be used in air at room temperature. We will present experimental results of the characterization carried out by means of PR on different types of advanced photovoltaic (PV) structures, including quantum-dot-based prototypes of intermediate band solar cells, quantum-well structures, highly mismatched alloys, and III?V-based multi-junction devices, thereby demonstrating the suitability of PR as a powerful diagnostic tool. Examples will be given to illustrate the value of this spectroscopic technique for PV including (i) the analysis of the PR spectra in search of critical points associated to absorption onsets; (ii) distinguishing signatures related to quantum confinement from those originating from delocalized band states; (iii) determining the intensity of the electric field related to built-in potentials at interfaces according to the Franz?Keldysh (FK) theory; and (v) determining the nature of different oscillatory PR signals among those ascribed to FK-oscillations, interferometric and photorefractive effects. The aim is to attract the interest of researchers in the field of PV to modulation spectroscopies, as they can be helpful in the analysis of their devices.

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.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

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.