About the origin of low wafer performance and crystal defect generation on seed-cast growth of industrial mono-like silicon ingots

The era of the seed-cast grown monocrystalline-based silicon ingots is coming. Mono-like, pseudomono or quasimono wafers are product labels that can be nowadays found in the market, as a critical innovation for the photovoltaic industry. They integrate some of the most favorable features of the conventional silicon substrates for solar cells, so far, such as the high solar cell efficiency offered by the monocrystalline Czochralski-Si (Cz-Si) wafers and the lower cost, high productivity and full square-shape that characterize the well-known multicrystalline casting growth method. Nevertheless, this innovative crystal growth approach still faces a number of mass scale problems that need to be resolved, in order to gain a deep, 100% reliable and worldwide market: (i) extended defects formation during the growth process; (ii) optimization of the seed recycling; and (iii) parts of the ingots giving low solar cells performance, which directly affect the production costs and yield of this approach. Therefore, this paper presents a series of casting crystal growth experiments and characterization studies from ingots, wafers and cells manufactured in an industrial approach, showing the main sources of crystal defect formation, impurity enrichment and potential consequences at solar cell level. The previously mentioned technological drawbacks are directly addressed, proposing industrial actions to pave the way of this new wafer technology to high efficiency solar cells.

Precipitated iron: a limit on gettering efficacy in multicrystalline silicon

A phosphorus diffusion gettering model is used to examine the efficacy of a standard gettering process on interstitial and precipitated iron in multicrystalline silicon. The model predicts a large concentration of precipitated iron remaining after standard gettering for most as-grown iron distributions. Although changes in the precipitated iron distribution are predicted to be small, the simulated post-processing interstitial iron concentration is predicted to depend strongly on the as-grown distribution of precipitates, indicating that precipitates must be considered as internal sources of contamination during processing. To inform and validate the model, the iron distributions before and after a standard phosphorus diffusion step are studied in samples from the bottom, middle, and top of an intentionally Fe-contaminated laboratory ingot. A census of iron-silicide precipitates taken by synchrotron-based X-ray fluorescence microscopy confirms the presence of a high density of iron-silicide precipitates both before and after phosphorus diffusion. A comparable precipitated iron distribution was measured in a sister wafer after hydrogenation during a firing step. The similar distributions of precipitated iron seen after each step in the solar cell process confirm that the effect of standard gettering on precipitated iron is strongly limited as predicted by simulation. Good agreement between the experimental and simulated data supports the hypothesis that gettering kinetics is governed by not only the total iron concentration but also by the distribution of precipitated iron. Finally, future directions based on the modeling are suggested for the improvement of effective minority carrier lifetime in multicrystalline silicon solar cells.

Experimental verification of intermediate band formation on titanium-implanted silicon

Intermediate band formation on silicon layers for solar cell applications was achieved by titanium implantation and laser annealing. A two-layer heterogeneous system, formed by the implanted layer and by the un-implanted substrate, was formed. In this work, we present for the first time electrical characterization results which show that recombination is suppressed when the Ti concentration is high enough to overcome the Mott limit, in agreement with the intermediate band theory. Clear differences have been observed between samples implanted with doses under or over the Mott limit. Samples implanted under the Mott limit have capacitance values much lower than the un-implanted ones as corresponds to a highly doped semiconductor Schottky junction. However, when the Mott limit is surpassed, the samples have much higher capacitance, revealing that the intermediate band is formed. The capacitance increasing is due to the big amount of charge trapped at the intermediate band, even at low temperatures. Ti deep levels have been measured by admittance spectroscopy. These deep levels are located at energies which vary from 0.20 to 0.28?eV below the conduction band for implantation doses in the range 1013-1014 at./cm2. For doses over the Mott limit, the implanted atoms become nonrecombinant. Capacitance voltage transient technique measurements prove that the fabricated devices consist of two-layers, in which the implanted layer and the substrate behave as an n+/n junction.

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.

Electrical properties of silicon supersaturated with titanium or vanadium for intermediate band material

We have fabricated titanium and vanadium supersaturated silicon layers on top of a silicon substrate by means of ion implantation and pulsed laser melting processes. This procedure has proven to be suitable to fabricate an intermediate band (IB) material, i.e. a semiconductor material with a band of allowed states within the bandgap. Sheet resistance and Hall mobility measurements as a function of the temperature show an unusual behavior that has been well explained in the framework of the IB material theory, supposing that we are dealing with a junction formed by the IB material top layer and the n-Si substrate. Using an analytical model that fits with accuracy the experimental sheet resistance and mobility curves, we have obtained the values of the exponential factor for the thermically activated junction resistance of the bilayer, showing important differences as a function of the implanted element. These results could allow us to engineer the IB properties selecting the implanted element depending on the required properties for a specific application.

Hydrogenated amorphous silicon deposited by high pressure sputtering for HIT solar cells

Hydrogenated amorphous silicon thin films were deposited using a high pressure sputtering (HPS) system. In this work, we have studied the composition and optical properties of the films (band-gap, absorption coefficient), and their dependence with the deposition parameters. For films deposited at high pressure (1 mbar), composition measurements show a critical dependence of the purity of the films with the RF power. Films manufactured with RF-power above 80W exhibit good properties for future application, similar to the films deposited by CVD (Chemical Vapor Deposition) for hydrogenated amorphous silicon.

Performance analysis of a 7-kW crystalline silicon generator after 17 years of operation in Madrid

The degradation observed on a 7-kWp Si-x photovoltaic array after 17 years of exposure on the roof of the Solar Energy Institute of the Polytechnic University of Madrid is presented. The mean peak power degradation has been 9% over this time, or an equivalent to 0.53% per year, whereas peak power standard deviation has remained constant. The main visual defects are backsheet delamination at the polyester/polyvinyl fluoride outer interface and cracks in the terminal boxes and at the joint between the frame and the laminate. Insulation resistance complies well with the requirements of the International Electrotechnical Commission 61215 tests.

Electrical decoupling effect on intermediate band Ti-implanted silicon layers

We investigated the electrical transport properties of ultraheavily Ti-implanted silicon layers subsequently pulsed laser melted (PLM). After PLM, the samples exhibit anomalous electrical behaviour in sheet resistance and Hall mobility measurements, which is associated with the formation of an intermediate band (IB) in the implanted layer. An analytical model that assumes IB formation and a current limitation effect between the implanted layer and the substrate was developed to analyse this anomalous behaviour. This model also describes the behaviour of the function V/Delta V and the electrical function F that can be extracted from the electrical measurements in the bilayer. After chemical etching of the implanted layer, the anomalous electrical behaviour observed in sheet resistance and Hall mobility measurements vanishes, recovering the unimplanted Si behaviour, in agreement with the analytical model. The behaviour of V/Delta V and the electrical function F can also be successfully described in terms of the analytical model in the bilayer structure with the implanted layer entirely stripped.

Far infrared photoconductivity in a silicon based material: vanadium supersaturated silicon

We have analyzed the spectral sub-bandgap photoresponse of silicon (Si) samples implanted with vanadium (V) at different doses and subsequently processed by pulsed-laser melting. Samples with V concentration clearly above the insulator-metal transition limit show an important increase of the photoresponse with respect to a Si reference sample. Their photoresponse extends into the far infrared region and presents a sharp photoconductivity edge that moves towards lower photon energies as the temperature decreases. The increase of the value of the photoresponse is contrary to the classic understanding of recombination centers action and supports the predictions of the insulator-metal transition theory.

Lifetime improvement after phosphorous diffusion gettering on upgraded metallurgical grade silicon

Wide experimental evidence of the phosphorus diffusion gettering beneficial effect on solar grade silicon is found by measuring electron effective lifetime and interstitial iron concentration in as-grown and post processed samples from two ingots of upgraded metallurgical grade silicon produced by Ferrosolar. Results after two different P-diffusion processes are compared: P emitter diffusion at 850ºC followed by fast cool-down (called “standard process”) or followed by slow cool-down (called “extended process”). It is shown that final lifetimes of this low cost material are in the range of those obtained with conventional material. The extended process can be beneficial for wafers with specific initial distribution and concentration of iron, e.g. materials with high concentration of big Fe precipitates, while for other cases the standard process is enough efficient. An analysis based on the comparison of measured lifetime and dissolved iron concentration with theoretical calculations helps to infer the initial iron distribution and concentration, and according to that, choose the more effective type of gettering.

Combining Text and Graphics for Interactive Exploration of Behavior Datasets

Modern sensor technologies and simulators applied to large and complex dynamic systems (such as road traffic networks, sets of river channels, etc.) produce large amounts of behavior data that are difficult for users to interpret and analyze. Software tools that generate presentations combining text and graphics can help users understand this data. In this paper we describe the results of our research on automatic multimedia presentation generation (including text, graphics, maps, images, etc.) for interactive exploration of behavior datasets. We designed a novel user interface that combines automatically generated text and graphical resources. We describe the general knowledge-based design of our presentation generation tool. We also present applications that we developed to validate the method, and a comparison with related work.

Towards a new generation of solar cells: silicon supersaturated with titanium or vanadium

We have analyzed the spectral sub-bandgap photoresponse of silicon (Si) samples implanted with vanadium (V) and titanium (Ti) at different doses and subsequently processed by pulsed-laser melting.

Intermediate band solar cells. The transition metal supersaturated Silicon approach

Within the framework of the third solar cell generation some new ideas to enlarge the spectral response of the solar cells toward the infrared have been proposed. Among them the inclusion of an Intermediate Band (IB) seems to be very promising. This paper will deal with one of the ways to generate the IB namely the deep level center approach. We will discuss not only its existence but also the carriers lifetime recovery which is necessary to obtain the expected increase of the solar cell efficiency.

Impact of Impurities on the Mechanical Strength of Multicrystalline Silicon

The usage of more inexpensive silicon feedstock for crystallizing mc-Si blocks promises cost reduction for the photovoltaic market. For example, less expensive substrates of upgraded metallurgical silicon (UMG-Si) are used as a mechanical support for the epitaxial solar cell. This feedstock has higher content of impurities which influences cell performance and mechanical strength of the wafers. Thus, it is of importance to know these effects in order to know which impurities should be preferentially removed or prevented during the crystallization process. Metals like aluminum (Al) can decrease the mechanical strength due to micro-cracking of the silicon matrix and introduction of high values of thermal residual stress. Additionally, silicon oxide (SiOx) lowers the mechanical strength of mc-Si due to thermal residual stresses and stress intensification when an external load is applied in the surrounding of the particle. Silicon carbide (SiC) introduces thermal residual stresses and intensifies slightly the stress in the surrounding of the particle but can have a toughening effect on the silicon matrix. Finally, silicon nitride (Si3N4) does not influence significantly the mechanical strength of mc- Si and can have a toughening effect on the silicon matrix.

Influence of high aluminium content on the mechanical properties of directionally solidified multicrystalline silicon

The purpose of this research is the mechanical characterisation of multicrystalline silicon crystallised from silicon feedstock with a high content of aluminium for photovoltaic applications. The mechanical strength, fracture toughness and elastic modulus were measured at different positions within the multicrystalline silicon block to quantify the impact of the segregation of impurities on these mechanical properties. Aluminium segregated to the top of the block and caused extensive micro-cracking of the silicon matrix due to the thermal mismatch between silicon and the aluminium inclusions. Silicon nitride inclusions reduced the fracture toughness and caused failure by radial cracking in its surroundings due to its thermal mismatch with silicon. However, silicon carbide increased the fracture toughness and elastic modulus of silicon.