Gettering and Defect Engineering in Semiconductor Technology XIII

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Authors: Otwin Breitenstein, Jan Bauer, Pietro P. Altermatt, Klaus Ramspeck
Abstract: The current-voltage (I-V) characteristics of most industrial silicon solar cells deviate rather strongly from the exponential behavior expected from textbook knowledge. Thus, the recombination current may be orders of magnitude larger than expected for the given material quality and often shows an ideality factor larger than 2 in a wide bias-range, which cannot be explained by classical theory either. Sometimes, the cells contain ohmic shunts although the cell’s edges have been perfectly insolated. Even in the absence of such shunts, the characteristics are linear or super-linear under reverse bias, while a saturation would be classically expected. Especially in multicrystalline cells the breakdown does not tend to occur at -50 V reverse bias, as expected, but already at about -15 V or even below. These deviations are typically caused by extended defects in the cells. This paper reviews the present knowledge of the origin of such non-ideal I-V characteristics of silicon solar cells and introduces new results on recombination involving coupled defect levels.
Authors: Mariana I. Bertoni, Clémence Colin, Tonio Buonassisi
Abstract: Dislocations are known to be among the most deleterious performance-limiting defects in multicrystalline silicon (mc-Si) based solar cells. In this work, we propose a method to remove dislocations based on a high temperature treatment. Dislocation density reductions of >95% are achieved in commercial ribbon silicon with a double-sided silicon nitride coating via high temperature annealing under ambient conditions. The dislocation density reduction follows temperature-dependent and time-dependent models developed by Kuhlmann et al. for the annealing of dislocations in face-centered cubic metals. It is believed that higher annealing temperatures (>1170°C) allow dislocation movement unconstrained by crystallographic glide planes, leading to pairwise dislocation annihilation within minutes.
Authors: Jun Chen, Bin Chen, Woong Lee, Masayuki Fukuzawa, Masayoshi Yamada, Takashi Sekiguchi
Abstract: We report the electrical, structural and mechanical properties of grain boundaries (GBs) in multicrystalline Si (mc-Si) based on electron-beam-induced current (EBIC), transmission electron microscope (TEM), and scanning infrared polariscope (SIRP) characterizations. The recombination activities of GBs are clearly classified with respect to GB character and Fe contamination level. The decoration of Fe impurity at boundary has been approved by annular dark field (ADF) imaging in TEM. Finally, the distribution of residual strain around GBs, and the correlations between strain and electrical properties are discussed.
Authors: Antti Haarahiltunen, Ville Vähänissi, Marko Yli-Koski, H. Talvitie, Hele Savin
Abstract: Iron precipitation in multicrystalline silicon has been modeled aiming at the optimization of intrinsic gettering of iron in multicrystalline silicon. Iron precipitation during both crystal growth and following phosphorus diffusion gettering (PDG) are simulated and compared to experimental results as the iron precipitate density after these processes is essential in the modeling of intrinsic gettering in multicrystalline silicon solar cell processing. The PDG decreases the density of iron precipitates compared to the as-grown state and as expected the effect is larger at lower initial iron concentrations. Due to this effect the iron precipitation is significantly reduced almost throughout the whole ingot height and it can be concluded that intrinsic gettering has a beneficial effect only in the case of high initial iron concentration, in accordance with the experimental results. The simulated change in interstitial iron concentration as a function of intrinsic gettering temperature suggests the same optimum intrinsic gettering temperature as the experiments. With the given model it is however much easier to find optimal parameters compared to expensive and time consuming experiments.
Authors: Hans Joachim Möller, Claudia Funke, Jan Bauer, S. Köstner, H. Straube, Otwin Breitenstein
Abstract: This work introduces two different approaches to explain the growth of silicon carbide (SiC) filaments, found in the bulk material and in grain boundaries of solar cells made from multicrystalline (mc) silicon. These filaments are responsible for ohmic shunts. The first model proposes that the SiC filaments grow at the solid-liquid interface of the mc-Si ingot, whereas the second model proposes a growth due to solid state diffusion of carbon atoms in the solid fraction of the ingot during the block-casting process. The melt interface model can explain quantitatively the observed morphologies, diameters and mean distances of SiC filaments. The modeling of the temperature- and time-dependent carbon diffusion to a grain boundary in the cooling ingot shows that solid state diffusion based on literature data is not sufficient to transport the required amount of approximately 3.4  1017 carbon atoms per cm2 to form typical SiC filaments found in grain boundaries of mc-Si for solar cells. However, possible mechanisms are discussed to explain an enhanced diffusion of carbon to the grain boundaries.
Authors: M. Holla, Tzanimir Arguirov, Winfried Seifert, Martin Kittler
Abstract: We report on the optical and mechanical properties of Si3N4 inclusions, formed in the upper part of mc-Si blocks during the crystallization process. Those inclusions usually appear as crystalline hexagonal tubes or rods. Here we show that in many cases the Si3N4 inclusions contain crystalline Si in their core. The presence of the Si phase in the centre was proven by means of cathodoluminescence spectroscopy and imaging, electron beam induced current measurements and Raman spectroscopy. The crystalline Si3N4 phase was identified as β-Si3N4. Residual stress was revealed at the particles. While the stress is compressive in the Si material surrounding the Si3N4 particles tensile stress is found in the Si core. We assume that the stress is formed during cool down of the Si block and is a consequence of the larger thermal expansion coefficient of Si in comparison to that of β-Si3N4. Iron assisted nitridation of Si at temperatures below 1400 °C is considered a possible mechanism of Si3N4 formation.
Authors: Lutz Raabe, Jan Ehrig, Sindy Würzner, Olf Pätzold, Michael Stelter, Hans Joachim Möller
Abstract: The influence of the CO concentration in the gas phase on the distribution of carbon in Bridgman-grown, multicrystalline silicon is studied. The growth experiments were conducted in a high-vacuum induction furnace either under a CO enriched atmosphere or under CO free conditions. Furthermore, thermodynamic calculations in the system silicon/oxygen/carbon were done. In crystal growth under a CO enriched atmosphere a SiC-containing layer is formed on the top surface of the melt in agreement with the calculated phase diagram. In this case, the level of substitutional carbon in the cystal was found to be almost constant, whereas the axial carbon concentration in crystals grown under CO free conditions increases monotonously according to Scheil's law.
Authors: B.R. Mansfield, David E.J. Armstrong, Peter R. Wilshaw, John D. Murphy
Abstract: As the thickness of multi-crystalline silicon solar cells continues to reduce, understanding the mechanical properties of the material is of increasing importance. In this study, a variety of techniques are used to study multi-crystalline silicon. Fracture tests are performed using four- and three-point bending. The fracture stress of as-sawn material reduces with increasing beam width and is increased in beams with a polished front surface. This indicates that fracture initiates from surface flaws. Modifications to standard fracture testing, including testing under liquid, are made so that beams fracture into just two pieces. By determining the crystallography either side of the location of fracture, multi-crystalline silicon was found to fail by transgranular fracture in the samples studied. Further evidence for this is gained from indentation experiments at grain boundaries. In order to understand the relative strength of grain boundaries, new approaches need to be considered. Therefore, a novel micromechanical technique, which enables individual grain boundaries to be studied, has started to be applied to multi-crystalline silicon. A focused ion beam is used to mill micron-scale cantilevers across notched grain boundaries, which are then loaded to fracture using the tip of a nanoindenter. The technique is shown to reproduce the known fracture toughness of {110} planes in single-crystal silicon, giving a value of 0.7 ± 0.3MPam1/2. Preliminary results are presented for fracture of multi-crystalline silicon.

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