WO2011048931A1 - シリコン又はシリコン合金溶解炉 - Google Patents
シリコン又はシリコン合金溶解炉 Download PDFInfo
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- WO2011048931A1 WO2011048931A1 PCT/JP2010/067336 JP2010067336W WO2011048931A1 WO 2011048931 A1 WO2011048931 A1 WO 2011048931A1 JP 2010067336 W JP2010067336 W JP 2010067336W WO 2011048931 A1 WO2011048931 A1 WO 2011048931A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/037—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/06—Metal silicides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/003—Heating or cooling of the melt or the crystallised material
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/04—Crucible or pot furnaces adapted for treating the charge in vacuum or special atmosphere
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/06—Crucible or pot furnaces heated electrically, e.g. induction crucible furnaces with or without any other source of heat
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B5/00—Muffle furnaces; Retort furnaces; Other furnaces in which the charge is held completely isolated
- F27B5/04—Muffle furnaces; Retort furnaces; Other furnaces in which the charge is held completely isolated adapted for treating the charge in vacuum or special atmosphere
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B5/00—Muffle furnaces; Retort furnaces; Other furnaces in which the charge is held completely isolated
- F27B5/06—Details, accessories, or equipment peculiar to furnaces of these types
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B5/00—Muffle furnaces; Retort furnaces; Other furnaces in which the charge is held completely isolated
- F27B5/06—Details, accessories, or equipment peculiar to furnaces of these types
- F27B5/16—Arrangements of air or gas supply devices
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D7/00—Forming, maintaining, or circulating atmospheres in heating chambers
- F27D7/06—Forming or maintaining special atmospheres or vacuum within heating chambers
Definitions
- the present invention relates to a silicon or silicon alloy melting method and a melting furnace capable of melting silicon or a silicon alloy raw material at low cost.
- the processing speed and production capacity of Si ingots with a single device are far superior to single crystal growth devices in the current polycrystalline melting furnace, but when investing in equipment for further production expansion, The amount of money equivalent to or larger than that is necessary, and considering the burden of depreciation, etc., the cost of crystalline silicon is at a standstill.
- the reason why the polycrystalline silicon melting apparatus becomes very expensive is that high vacuum processing is currently performed before and at the time of melting the metal Si raw material.
- a pressure vessel (tank) and a pump are always required for this high vacuum process.
- the pressure tank needs to be designed to be thick, and the larger the size, the higher the material cost and the more parts that must be completely welded to prevent leakage, resulting in an increase in cost.
- the pump needs to be used in combination with a plurality of rotary, mechanical booster, oil diffusion pump, turbo molecular pump, etc. in order to obtain a high vacuum, resulting in an increase in cost.
- a cooling function is provided on the furnace body side face and the lid.
- the cooling function is a jacket type that is attached to the surface of the furnace, but most current Si melting furnaces have this function, ensuring the utility of cooling water Including the burden.
- FIG. 3 shows an example of a vacuum furnace in which a cylindrical heat-resistant partition wall 12 is provided around a silicon melting crucible 11 and a carbon heater 13 is arranged around the cylindrical heat-resistant partition wall 12.
- the partition wall 12 is used to prevent the silicon melted from the heater 13 having a higher vapor pressure than the furnace temperature from being contaminated by carbon and to uniformly heat the melting crucible.
- a heat resistant pressure vessel 14 is disposed on the outer periphery of the heater 13.
- SS general structural rolled steel
- SUS stainless steel
- a cooling device 15 such as a water-cooled jacket or a water-cooled channel is attached around the pressure vessel 14 or in the vicinity of the surface layer.
- a vacuum pump 16 is coupled to the pressure vessel 14 and an inert gas is introduced from the pipe 17 and at the same time, the pressure vessel 14 is exhausted.
- FIG. 4 is another example of the conventional vacuum vessel.
- molybdenum or tungsten is used as the heater 13, and in this case, since there is no carbon contamination of the dissolved silicon, it is not necessary to provide the partition wall 12 shown in FIG. Accordingly, the structure is simplified compared to FIG.
- carbon may be used as a material for the heater 13 unless carbon contamination is a particular problem.
- the degree of vacuum when using a vacuum vessel depends on the type of pump, but when a rotary pump is used, the oxygen partial pressure is about 0.14 Pa, and when a mechanical booster pump is used, the oxygen content is When using an oil diffusion pump with a pressure of about 0.03 Pa, the oxygen partial pressure can be set to about 0.00002 Pa, but in any case, an expensive vacuum pump must be used. Therefore, there is a problem that the equipment cost and the maintenance cost are inevitably high.
- FIG. 5 is an example of a conventional high-temperature atmospheric furnace.
- a heater 13 of molybdenum silicide (MoSi 2 ) or silicon carbide (SiC) is often used around the heat-treated crucible 11.
- MoSi 2 molybdenum silicide
- SiC silicon carbide
- a heat insulating material such as a ceramic fiber board is generally used for the outer wall of the furnace.
- the ceramic fiber board has a very low thermal conductivity and a high heat insulation effect, so there are times when it is not necessary to provide a sufficient thickness to provide a water cooling function.
- the structure of the furnace is much simpler than that shown in FIGS. 3 and 4, and it is easy to reduce the cost.
- FIG. 6 shows a multipurpose melting furnace having a structure in which the atmospheric furnace of FIG. 5 is surrounded by a pressure-resistant tank.
- a vacuum pump 16 to provide a vacuum atmosphere, an inert atmosphere in which nitrogen or argon is flowed from a gas inlet (pipe) 17, or a reducing atmosphere in which hydrogen or carbon monoxide is flowed.
- a high-strength pressure tank is used for the outer tank.
- the inner partition 12 is designed to be thinner than FIG. 5 in order to facilitate gas replacement and to have a compact size. For this reason, the pressure tank is provided with a water cooling function, and accordingly, the structure in the furnace and the surrounding structure are complicated, resulting in high costs.
- silicon dissolution in the conventional resistance heating furnace is of the type shown in FIGS. 3, 4, and 6, but in order to prevent Si oxidation, oxygen in the atmosphere is exhausted by a vacuum pump, and the oxygen partial pressure is rotary. Dissolution was performed at a pressure of about 0.14 Pa by a pump, usually by using a mechanical booster pump or an oil diffusion pump in combination with a pressure of about 0.03 Pa to 0.00002 Pa. On the other hand, in the furnace of FIG. 5, oxygen was very high at about 21,000 Pa because of the atmosphere, and it was not a condition that silicon was dissolved very much.
- the use of silicon includes the use of sputtering targets in addition to semiconductor silicon wafers and substrates of crystalline silicon solar cells.
- Examples of the use of the silicon used as the sputtering target include an antireflection film for window glass for automobiles, a light absorption layer that is a key for solar energy conversion efficiency for solar cells, and a protective layer.
- a silicon target used for an antireflection film for a window glass or a protective layer for a solar cell does not necessarily require such high characteristics as a polycrystalline silicon used for a semiconductor wafer or a solar cell.
- the demand in such a target field is still small, so far, expensive single crystals and polycrystalline silicon used in solar cells have been used.
- the silicon may be fully utilized. This application is also expected to grow greatly in the future, and it is necessary to supply a large amount of polycrystalline silicon at a low cost.
- the sputtering method is used as a thin film forming means, but there are several sputtering methods such as bipolar DC sputtering method, high frequency sputtering method, magnetron sputtering method, each utilizing its own sputtering properties.
- bipolar DC sputtering method high frequency sputtering method
- magnetron sputtering method each utilizing its own sputtering properties.
- a substrate serving as an anode and a target serving as a cathode are opposed to each other, and an electric field is generated by applying a high voltage between these substrate and target in an inert gas atmosphere. Electrons and inert gas collide with each other to form a plasma. The cations in this plasma collide with the target surface and strike out target constituent atoms, and the ejected atoms adhere to the opposing substrate surface to form a film. It uses the principle that it is formed.
- a dissolved silicon target As such a sputtering target, a dissolved silicon target has been proposed. However, in recent years, this target tends to increase in size, and in order to increase the film formation efficiency, a large and large rectangular or disk-shaped target is used. It is requested. In any case, it is necessary to dissolve silicon (Si) or silicon-based alloy as a raw material. Silicon is an element that is easily oxidized, and oxygen is considered to be a transition crystal when incorporated into the crystal, leading to device defects and a decrease in conversion efficiency. Therefore, conventionally, after completely removing atmospheric components in a high-vacuum furnace, it is replaced with an inert atmosphere in a highly airtight state or dissolved in a vacuum state and solidified in the vacuum furnace. It was taken.
- the melting equipment for silicon or silicon-based alloys requires a pressure-resistant vessel (furnace) having airtightness, and the furnace has a heating device, a cooling device, and high heat resistance that does not cause contamination.
- various devices for holding or transporting made of high-strength materials and a high-performance vacuum pump coupled to the high-pressure vessel are required, so that the manufacturing cost of the melting furnace is remarkably high, and the capital investment at the time of production increase was there. This cost increases as the silicon target becomes larger.
- Patent Document 1 when a crystalline silicon is produced by applying a temperature gradient upward from the inner bottom surface of the mold, an inert gas is blown onto the silicon melt surface from above during crystallization. A technique of swinging to such an extent that a cavity is formed on the surface is described.
- Patent Document 2 a gas supply lance composed of an inner tube and an outer tube is disposed when a crystalline silicon is produced by applying a temperature gradient upward from the inner bottom surface of the mold.
- an inert gas that covers the surface of the silicon melt is supplied between the double tubes, and an inert gas is blown onto the surface of the silicon melt from above during crystallization, so that a cavity is formed on the surface. The technique of rocking is described.
- Patent Document 3 describes that the position of the tip of the gas supply pipe is adjusted when an inert gas is blown onto the surface of the silicon melt from above to form a cavity on the surface.
- an inert gas is supplied to the surface and, as a result, a structure in which the melt surface is shielded with an inert gas is essential, and the presence of oxygen is completely recognized.
- oxygen partial pressure or the structure of the furnace body When producing crystalline silicon by applying a temperature gradient upward from the inner bottom surface of the mold, an inert gas is blown from above to the surface of the silicon melt during crystallization, so that a cavity is formed on the surface. It is considered that the technology itself to be moved complicates the structure and that the shielding with an inert gas is indispensable, which further increases the cost.
- Patent Document 1 Japanese Patent Laid-Open No. 2001-10810
- Patent Document 2 Japanese Patent Laid-Open No. 2003-137525
- Patent Document 3 Japanese Patent Laid-Open No. 2005-27178
- the present invention provides a low-cost furnace capable of melting silicon or a silicon-based alloy without increasing the amount of impurities in the raw material under the condition that a high vacuum is not kept even once. Making it possible to procure investment overwhelmingly cheaply, thereby making it a challenge to produce silicon or silicon-based alloys at low cost
- the inventors of the present invention provide a melting apparatus (furnace) that does not require a pressure vessel, does not require a high vacuum apparatus (pump), and has a cooling function for the furnace body.
- the following invention is provided.
- Silicon or silicon which is a method for melting silicon or a silicon-based alloy raw material, wherein the steps from melting of the raw material to solidification are performed in an inert atmosphere having an oxygen partial pressure of 10 to 1000 Pa Melting method of alloys based on the 2)
- Argon gas is introduced into the melting furnace at a flow rate of 5 L / min or more in terms of standard state and discharged, and the silicon or silicon based on any one of 1) to 3) To melt the alloy.
- the present invention also provides the following inventions.
- the process from the melting of the raw material to the solidification by the heating element is performed with an oxygen partial pressure of 10 to
- a melting furnace for silicon or a silicon-based alloy comprising a furnace having a structure for processing in an inert atmosphere of 1000 Pa.
- the heating element is a heater mainly composed of MoSi 2 , and is composed of Al 2 O 3 or SiO 2 ceramic fiber as a heat insulating material surrounding a crucible for melting silicon or silicon-based alloy. 5.
- a melting furnace includes a crucible for melting silicon or a silicon-based alloy and a first casing provided with a heating element surrounding the crucible, and an airtight structure surrounding the first casing and blocking outside air.
- the present invention also provides the following inventions. 8) It is composed of a heat insulating material designed so that the surface temperature of the first housing is 250 ° C. or lower when the furnace temperature is maintained at 1500 ° C. 5) to 7) A melting furnace for silicon or an alloy based on silicon according to any one of the preceding claims. 9) The first casing and the second casing are designed so as to have a clearance of 50 mm or more, and the cooling function is not provided in the second casing. A melting furnace for silicon or a silicon-based alloy as described. 10) The melting furnace for silicon or a silicon-based alloy according to any one of 5) to 9), wherein the crucible has a function of changing a position with respect to a heating element.
- the present invention also provides the following inventions. 12)
- the first housing of the melting furnace has a structure divided into two upper and lower rooms, the upper chamber is a heating chamber provided with a heating element, and the lower chamber is a cooling chamber without a heating element.
- Argon gas is introduced into and discharged from the first and second casings of the melting furnace at a flow rate of 5 L / min or more in terms of standard conditions 5) to 12)
- the inside of the melting furnace is an inert gas atmosphere such as argon, but the presence of a corresponding oxygen partial pressure is allowed. Therefore, a highly functional vacuum device (pump) is not required. As a result, it is possible to provide a melting apparatus (furnace) that does not require a pressure vessel, and has an excellent effect of significantly reducing the manufacturing cost and operating cost of the apparatus. Moreover, since a special cooling device is not required in the melting furnace, there is also an advantage that the utility of the cooling water becomes unnecessary.
- the heating tool is a heater made of MoSi 2 , it can be directly radiated by being placed around the crucible, and can effectively transfer heat. Since most of the heat generated is contained in the first housing, there is an advantage that the apparatus can be made compact. Further, a heater 2 made from MoSi 2 may use a high-purity MoSi 2, less pollution arising from impurities contained in the heater, the effect of suppressing impurity increase in alloy and based on silicon or silicon is there. Further, since the heater of high purity MoSi 2 is a substance having a high oxidation resistance, there is an advantage that the material has a long life when the oxygen partial pressure is 10 to 1000 Pa.
- a carbon heater generally used for conventional Si melting has a short life because oxidation proceeds easily in an atmosphere of 10 to 1000 Pa.
- SiO gas and residual oxygen emitted from the molten silicon react with a carbon heater in the furnace to generate CO and CO 2 . This has the disadvantage of increasing the carbon concentration by being incorporated into the molten silicon penetration crystal.
- the present invention can overcome such drawbacks, and further, the temperature of the first casing is sufficiently lowered, and the initial exhaust to replace with vacuum is not performed. It has the advantage of not requiring materials with high heat resistance and high strength. If confidentiality of oxygen partial pressure of 1000 Pa or less is secured, for example, SUS or aluminum thin plate or foil, or acrylic or vinyl with a density of less than 1.5 g / cm 3 , a lightweight and inexpensive second one. There is an effect that it is possible to provide an extremely cost-competitive manufacturing technology that can be selected as a material for the housing. As described above, the present invention has an excellent effect of significant cost reduction as compared with the conventional case.
- the silicon or silicon-based alloy melting furnace of the present invention heats the raw material with a heating element that generates heat when energized.
- FIG. 1 shows a horizontal cross-sectional view of the central portion showing an outline of the melting furnace of the present invention.
- the heater 2 specifically uses the heater 2 made of MoSi 2 .
- the amount of heat generated by the heater 2 can be controlled, high temperature heating of about 1400 to 1800 ° C. is possible, and rapid heating can be achieved.
- the heater 2 made of this high-purity MoSi 2 is used, since the generation of impurities that volatilize from the heater 2 is small, silicon or an alloy based on silicon is dissolved and hardly contaminated. It has the outstanding effect that can be produced.
- the oxygen partial pressure of the melting furnace is melted in an inert atmosphere of 10 to 1000 Pa.
- the heater 2 made of MoSi 2 is not damaged. Rather, the presence of some oxygen acts to suppress the deterioration of the heater 2 made from MoSi 2 .
- the heater 2 made of high purity MoSi 2 it is expensive.
- carbon and refractory metal heaters are short-lived because they oxidize quickly. Considering that the destruction of the heater induces contamination and maintenance such as replacement, heaters made from high-purity MoSi 2 are Eventually, there is a merit of cost reduction.
- the melting furnace is made an inert atmosphere with argon gas.
- silicon or a silicon-based alloy has a property of oxidizing and requires high purity. Therefore, at least initially, it is replaced with a high vacuum of about 0.00002 to 0.1 Pa.
- the oxygen partial pressure should be about 0.01 to 0.1 Pa in an active atmosphere.
- dissolution is performed in an inert atmosphere of 10 to 1000 Pa, which is 3 to 4 orders of magnitude higher than the conventional oxygen pressure, the extreme surface of the molten silicon is oxidized and no further oxidation proceeds. I understood.
- the oxidized portion at the time of melting moves to the surface, the increase in oxygen in the internal silicon ingot is very small.
- the melting furnace of the present invention includes a first casing 3 including a crucible 1 for melting silicon or a silicon-based alloy and a heating element 2 surrounding the crucible, and surrounds the first casing to block outside air. It can comprise from the 2nd housing
- the double-structured housing also has a function of blocking outside air. In the first place, the melting furnace itself does not need to be made from a pressure-resistant container as in the past, so this housing does not have that much strength, but it is possible to have a double structure to entrain the outside air. The effect of stably maintaining the oxygen partial pressure of the first housing 3 at a low level can be greatly improved.
- the second housing 4 can be manufactured using a material that mainly seals and serves to keep the oxygen partial pressure low.
- the argon gas may be introduced into the first casing 3 and the second casing 4 of the melting furnace through the pipe 5 at a flow rate of 5 L / min or more in terms of standard state and discharged. it can. More preferably, if the argon flow rate is individually adjusted to a positive pressure in the order of the first casing 3, the second casing 4, and the outer side (atmosphere) of the second casing 4, there is less air entrainment. Since the oxygen partial pressure can be kept low, there is an effect of reducing the oxygen content of the obtained ingot.
- ⁇ ⁇ Pipes for introducing gas into the first casing and the second casing may be installed at a plurality of locations in accordance with the size of the furnace body.
- Table 1 shows the results of measuring the oxygen concentration around the melting crucible.
- the target oxygen partial pressure can be lowered to 0% (oxygen partial pressure of about 21000 Pa), 2.8% (oxygen partial pressure of 2840 Pa) in 10 minutes, and 0.2% (oxygen partial pressure of 203 Pa) in 30 minutes. It was possible to control at 0.1% in minutes (oxygen partial pressure of 101 Pa) and 0.1% in the same manner at 180 minutes thereafter.
- the oxygen concentration when argon gas is introduced at 5 L / min in the atmospheric furnace shown in FIG. It reached a peak at 12.3% (oxygen partial pressure 12460 Pa).
- oxygen partial pressure 12460 Pa oxygen partial pressure
- the melting furnace of the present invention can have a function of changing the position of the crucible 1 with respect to the heating element 2.
- a longitudinal sectional view of this example is shown in FIG.
- the melting furnace is divided into two upper and lower chambers, the upper chamber is a heating chamber 6 with a heating element, and the lower chamber is a cooling chamber 7 without a heating element, thereby moving the crucible position.
- casing 3 is arrange
- the crucible 1, the pipe 5, the heater 2, and the second housing 4 are the same as those in FIG.
- the crucible 1 As a material for the crucible 1, it is usually preferable to use silica. In this case, no carbon-based material is used in the present melting furnace, and the carbon concentration in the silicon ingot can be reduced as compared with the conventional melting furnace.
- Table 2 shows changes in the oxygen content and carbon content of the silicon ingot when silicon is melted by changing the oxygen partial pressure and the oxygen content and carbon content of the raw material before melting when silicon is melted. Show. As shown in Table 2, the oxygen content can suppress the increase of oxygen in the ingot by the oxygen partial pressure. On the other hand, it can be seen that the carbon content does not change after dissolution with the carbon content at the time of the raw material.
- the present invention only needs to be able to maintain a certain degree of airtightness, so that it is possible to configure an overwhelmingly low-cost melting facility in which an inexpensive material that does not require heat resistance and high strength can be selected. It has the merit that. And this invention is easy to enlarge. In the conventional enlargement, in order to withstand the pressure when the inside of the furnace is made high vacuum, it is necessary to design a thicker wall, which is expensive. In the case of induction heating, the heater that becomes a coil is enlarged. It was also expensive. The present invention has an effect of reducing the capital investment amount by a difference.
- the furnace body of the melting furnace has a single (casing) structure, even if it is replaced for a long time with the flow of argon gas, the entire interior of the furnace body will be replaced, so there is a risk of entraining residual oxygen around the furnace body Maybe there was. As a result, there is a problem that it is difficult to set the oxygen partial pressure to 1000 Pa or less. In this case, the amount of oxygen in Si exceeded 800 ppm, and it was difficult to obtain the target of reducing oxygen in Si.
- the furnace body of the melting furnace has a double structure.
- the oxygen partial pressure around the crucible 1 was greatly reduced.
- the first housing and the second housing each have an airtight structure that blocks outside air, but it is only necessary to maintain a state where there is no air entrainment, and argon is introduced. It will be readily understood that there is no need to have sex.
- the pressure vessel is not evacuated with a vacuum pump as in the prior art, it is not replaced with argon, so the oxygen partial pressure in the present invention has a lower limit of 10 Pa.
- the oxygen in the ingot was 140 ppm, and when silicon was dissolved at an oxygen partial pressure of 10 to 300 Pa, it was 70 ppm.
- the effect of reducing oxygen in silicon was confirmed.
- ⁇ ⁇ Moreover, it is made of a heat insulating material designed so that the surface temperature of the first housing is 250 ° C. or lower when the furnace temperature is maintained at 1500 ° C.
- the first housing and the second housing are designed so as to ensure a clearance of 50 mm or more.
- Such a silicon ingot sufficiently satisfies the specifications as a sputtering target. Furthermore, if the oxygen partial pressure is controlled so as to be always low, it can be applied to a crystalline silicon solar cell. Further, no increase in carbon impurities was observed by using a silica (SiO 2 ) crucible.
- the inside of the melting furnace is an inert gas atmosphere such as argon, and the existence of a corresponding oxygen partial pressure is allowed, and a highly functional vacuum device (pump) is not required.
- a melting apparatus furnace
- the heating tool is a heater made of MoSi 2 , it can be directly heated by being arranged around the crucible, and there is an advantage that it is not necessary to heat the entire furnace.
- a heater made from MoSi 2 can use the high-purity MoSi 2, for generation of impurities evaporated from the heater is small, and dissolved without hardly contaminate the alloy to based on silicon or silicon There is an effect that an ingot can be produced.
- the heater of MoSi 2 is a substance having a high oxidation resistance, there is an advantage that the material has a long life. Furthermore, heat transfer efficiency is good by a heating method using a heater made of MoSi 2 arranged around the crucible, the temperature is sufficiently lowered in the first housing, and initial evacuation to replace with vacuum is not performed.
- the material of the two housings has an effect of reducing the cost because it does not require high heat resistance and high strength material equipment. Therefore, since silicon or an alloy material based on silicon can be manufactured at a significantly low cost, it is extremely useful industrially.
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Abstract
Description
一方、太陽電池向けのSiは、半導体と同様に単結晶が用いられるケースと多結晶のシリコンが用いられるケースがある。エネルギー変換効率においては、単結晶シリコンの方が優れるが、製造コストにおいては溶解、鋳造して作製できる多結晶シリコンの方が低コストで抑えられるメリットがあり、用途に応じて使い分けされている。
これらの結晶系シリコンは、近年、様々な系の太陽電池が開発されているが最主流であり、今後も需要の急拡大が期待される。一方、全世界で太陽電池を普及させるには、さらなる低コスト化の要求が益々厳しくなってきている。
次に、多結晶シリコン溶解装置が非常に高価になる要因としては、金属Si原料の溶解前および溶解時に現状は高真空の処理が行なわれることに起因している。原料および坩堝等を含めた周辺材料に付着した水分や不純物を除去するためにまずは高真空で初期排気を行なうのが常識となっている。この高真空にするという処理には、耐圧容器(タンク)やポンプが必ず必要になる。耐圧タンクは肉厚に設計する必要があり、大型化するほど材料費を始め、リークが生じないように完全な溶接を行なわないといけない箇所も増え、コストアップとなる。
また、インゴットに引け巣や空隙が生じないようにするためには、坩堝の回転や昇降、天井ヒーターの取り付け、ヒーター位置の昇降等、様々な工夫がなされている。炉内内部を高真空に到達できるように気密性を確保しつつ、これらの機能を設けることも設備費用が高額になる要因となっていた。
ヒーター13の外周には、耐熱性の耐圧容器14を配置する。これは通常、一般構造用圧延鋼(SS)やステンレス(SUS)等を使用する。耐圧容器14の高熱による損壊を防止し、外部への熱放射を抑制するために、耐圧容器14の周囲又は表層付近の内部に、水冷ジャッケット又は水冷チャネル等の冷却装置15を取り付ける。耐圧容器14に真空ポンプ16を結合し、配管17から不活性ガスを導入すると同時に、耐圧容器14内を排気する。
真空容器を使用する場合の真空度は、ポンプの種類にもよるが、ロータリーポンプを使用した場合には、酸素分圧を0.14Pa程度に、メカニカルブースターポンプを使用する場合には、酸素分圧を0.03Pa程度に、さらに油拡散ポンプを使用する場合には、酸素分圧を0.00002Pa程度にすることが可能であるが、いずれにしてもそのための高価な真空ポンプを使用しなければならないので、設備費及び維持管理費が高額にならざるを得ないという問題がある。
また、炉の外壁には、セラミックファイバーボード等の断熱材が一般に使用される。セラミックファイバーボードは、非常に低熱伝導度で断熱効果が高いので、十分な肉厚をとって水冷機能が付与する必要がない時もある。炉の構造は、図3及び図4よりも構造が非常に簡単になっており、低コストが図りやすい。
しかし、当然ながら、大気に曝されているので、溶解品の酸化は抑制できない。一般には、溶解品の酸化を気にする必要がない材料又は既に酸化している材料の溶解に使用される。この場合の酸素濃度は21%、酸素分圧は約21,000Paに達する。
しかし、ガス置換を行なうためには、まずは真空排気をする常識があるため、外槽には高強度の耐圧タンクが用いられる。また内部の隔壁12はガス置換を容易にし、コンパクトなサイズにするために、図5よりに肉薄に設計される。そのため、耐圧タンクには、水冷機能が設けられており、その分炉内の構造や周囲の構造が複雑になり、高コストとなっていた。
しかし、このようなターゲット分野での需要はまだ少量であるため、これまでのところ高価な単結晶や太陽電池で使用される多結晶シリコンが使用されてきた。
ちなみに、スパッタリング法は薄膜を形成手段として使用されているが、これには2極直流スパッタリング法、高周波スパッタリング法、マグネトロンスパッタリング法など、いくつかのスパッタリング法があり、それぞれ固有のスパッタリングの性質を利用して各種電子部品の薄膜が形成されている。
いずれにしても、原料となるシリコン(Si)又はシリコン基合金を溶解する必要がある。シリコンは酸化し易い元素であり、酸素は結晶中に取り込まれると転移結晶となり、デバイス不良や変換効率の低下を招くと考えられている。
そのため従来は高真空炉中で大気成分を完全に排除した後、そのまま気密性の高い状態で不活性雰囲気に置換若しくは真空状態のまま溶解し、これを同真空炉の中で凝固させるという手法が採られていた。
また、特許文献2には、上記特許文献1と同様に、鋳型の内側底面から上方に温度勾配を付与して結晶シリコンを製造する際に、内管と外管からなるガス供給ランスを配置し、この2重管の間にシリコン融液の表面を覆う不活性ガスを供給すると共に、結晶化の際にシリコン融液表面に上方から不活性ガスを吹き付けて、表面にキャビティが形成される程度に揺動させる技術が記載されている。
鋳型の内側底面から上方に温度勾配を付与して結晶シリコンを製造する際に、結晶化の際にシリコン融液表面に上方から不活性ガスを吹き付けて、表面にキャビティが形成される程度に揺動させる技術自体が構造を複雑化させると共に、不活性ガスによるシールドが必須不可欠であることが、さらにコストの上昇を招くと考えられる。
特許文献2:特開2003-137525号公報
特許文献3:特開2005-271078号公報
2)前記酸素分圧を10~300Paで処理することを特徴とする1)記載のシリコン又はシリコンを基とする合金の溶解方法。
3)アルゴンガスを溶解炉内に導入し、不活性雰囲気とすることを特徴とする1)又は2)記載のシリコン又はシリコンを基とする合金の溶解方法。
4)アルゴンガスを溶解炉内に、標準状態換算で5L/分以上の流量で導入し、排出することを特徴とする1)~3)のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解方法。
5)シリコン又はシリコンを基とする合金原料を溶解する炉であって、通電して発熱する発熱体を有し、該発熱体による原料の溶解から凝固までの工程を、酸素分圧が10~1000Paの不活性雰囲気で処理する構造の炉を備えていることを特徴とするシリコン又はシリコンを基とする合金の溶解炉。
6)発熱体が、MoSi2を主成分とするヒーターであり、シリコン又はシリコンを基とする合金を溶解するための坩堝を囲う断熱材に、Al2O3やSiO2系のセラミックファイバーで構成されるボード又はスリーブを用いることを特徴とする5)記載のシリコン又はシリコンを基とする合金の溶解炉。
7)溶解炉が、シリコン又はシリコンを基とする合金を溶解する坩堝及び該坩堝を取り囲む発熱体を備えた第一の筐体と、第一の筐体を取り囲み、外気を遮断する気密構造をもつ第二の筐体とからなることを特徴とする5)又は6)に記載のシリコン又はシリコンを基とする合金の溶解炉。
8)炉内温度を1500°Cに保持した時に、第一筐体の表面温度が250°C以下になるように設計された断熱材で構成されることを特徴とする5)~7)のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
9)第一筐体と第二筐体は50mm以上のクリアランスを有するように設計し、第二筐体には冷却機能を設けないことを特徴とする5)~8)のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
10)前記坩堝が発熱体に対して位置を変える機能を有することを特徴とする5)~9)のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
11)坩堝と発熱体の位置を変える昇降機能を有するモーター等の装置を第一筐体と第二筐体の間に設置することを特徴とする5)~10)のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
12)前記溶解炉の第一筐体が上下2部屋に分割した構造を有し、上の部屋が発熱体を備えた加熱室、下の部屋が発熱体のない冷却室であることを特徴とする5)~11)のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
13)アルゴンガスを、溶解炉の第一の筐体と第二の筐体のそれぞれに、標準状態換算で5L/分以上の流量で導入し、排出することを特徴とする5)~12)のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
14)坩堝の材質をシリカとすることを特徴とする5)~13)のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
また、融解シリコンから出たSiOガスや残留酸素は炉内のカーボンヒーターと反応してCOやCO2が発生する。これは融解シリコン溶け込み結晶中に取り込まれて炭素濃度を高めるという短所があった。
酸素分圧1000Pa以下の機密性が確保されるならば、例えばSUSやアルミニウムの薄板や箔、もしくはアクリルやビニールのような密度が1.5g/cm3未満で、軽量且つ安価なものを第二筐体の材料に選定して良いという、非常にコスト競争力のある製造技術を提供できる効果がある。
以上、従来に比較して著しいコスト低減の優れた効果を有する。
この場合、ヒーター2の発熱量をコントロールすることができ、また1400~1800°C程度の高温加熱が可能であり、また急速加熱もできるという優れた利点を持つ。そして、この高純度MoSi2から作製されたヒーター2を用いる場合には、ヒーター2から揮発する不純物の発生が少ないために、シリコン又はシリコンを基とする合金をほとんど汚染させることなく溶解してインゴットを作製できるという優れた効果を有する。
一般に使用されているカーボンやタングステン等の高融点金属のヒーターに比べ、高純度MoSi2から作製されたヒーター2は高価である。しかしながら、カーボンや高融点金属のヒーターは、すぐ酸化するため短寿命であり、ヒーターの破壊は汚染を誘発すること、さらに交換等のメインテナンスを考慮すると、高純度MoSi2から作製されたヒーターは、最終的にはコスト低減となるメリットが存在する。
本発明の溶解炉は、シリコン又はシリコンを基とする合金を溶解する坩堝1及び該坩堝を取り囲む発熱体2を備えた第一の筐体3と、第一の筐体を取り囲み、外気を遮断する気密構造をもつ第二の筐体4とから構成することができる。二重構造の筐体は、外気を遮断する機能も持つ。
そもそも、溶解炉自体が、従来のような耐圧製の容器から作製する必要はないので、この筐体はそれ程の強度を有していないのであるが、二重構造とすることが、外気の巻き込みを低減し、第一筐体3の酸素分圧を低いレベルで安定し維持する効果を、大きく向上させることができる。
また、前記アルゴンガスを溶解炉の第一の筐体3と第二の筐体4のそれぞれに、配管5を介して、標準状態換算で5L/分以上の流量で導入し、排出することができる。
より好ましくは、アルゴン流量を個別に調整して第一筐体3、第二筐体4、第二筐体4の外側(大気)の順に陽圧にすれば、エアの巻き込みが少なく炉内の酸素分圧を低く維持できるため、得られるインゴットの含有酸素量を減らせる効果がある。
シリコン溶解した場合の、溶解前の原料の酸素含有量及び炭素含有量と、酸素分圧を変化させてシリコンを溶解した場合の、シリコンインゴットの酸素含有量及び炭素含有量の変化を表2に示す。この表2に示すように、酸素含有量は酸素分圧によってインゴットの酸素の増加を抑制することが可能である。一方、炭素含有量は、原料時の炭素含有量と溶解後に変化がないことが分かる。
そして、本願発明は大型化が容易である。従来の大型化においては、炉内を高真空にした場合の圧力に耐えるために、さらに厚肉に設計する必要があり高コストであり、また誘導加熱の場合はコイルとなるヒーターを大型化するにも高コストとなっていた。本発明は、設備投資額をケタ違いに下げられる効果がある。
溶解炉の炉体を、一重(筐体)構造とした場合、アルゴンガスのフローで長時間置換しても、炉体内部全体を置換することになるため、炉体周辺の残存酸素を巻き込む虞が多分にあった。この結果、酸素分圧は1000Pa以下とすることが難しいという問題があった。この場合は、Si中の酸素量は800ppmを超え、Si中の酸素低減という目標を得ることが難しかった。
酸素分圧300~700Paでシリコンを溶解した場合、インゴット中の酸素は140ppm、また酸素分圧10~300Paでシリコンを溶解した場合は70ppmとなった。このように、シリコン中の酸素低減効果が確認できた。
また、溶解炉中には、特別な冷却装置を必要としないというメリットもある。また、加熱用具(ヒーター)は、MoSi2から作製されたヒーターであるため、坩堝周辺に配置することによる直接加熱が可能であり、炉全体を加熱する必要がないという利点がある。また、MoSi2から作製されたヒーターは高純度MoSi2を使用することができ、ヒーターから揮発する不純物の発生が少ないために、シリコン又はシリコンを基とする合金をほとんど汚染させることなく溶解してインゴットを作製できるという効果がある。
したがって、大型化するシリコン又はシリコンを基とする合金材料を、著しく低コストで製造できるので、産業上極めて有用である。
Claims (14)
- シリコン又はシリコンを基とする合金原料を溶解方法であって、原料の溶解から凝固までの工程を、酸素分圧が10~1000Paの不活性雰囲気で処理することを特徴とするシリコン又はシリコンを基とする合金の溶解方法。
- 前記酸素分圧を10~300Paで処理することを特徴とする請求項1記載のシリコン又はシリコンを基とする合金の溶解方法。
- アルゴンガスを溶解炉内に導入し、不活性雰囲気とすることを特徴とする請求項1又は2記載のシリコン又はシリコンを基とする合金の溶解方法。
- アルゴンガスを溶解炉内に、標準状態換算で5L/分以上の流量で導入し、排出することを特徴とする請求項1~3のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解方法。
- シリコン又はシリコンを基とする合金原料を溶解する炉であって、通電して発熱する発熱体を有し、該発熱体による原料の溶解から凝固までの工程を、酸素分圧が10~1000Paの不活性雰囲気で処理する構造の炉を備えていることを特徴とするシリコン又はシリコンを基とする合金の溶解炉。
- 発熱体が、MoSi2を主成分とするヒーターであり、シリコン又はシリコンを基とする合金を溶解するための坩堝を囲う断熱材に、Al2O3やSiO2系のセラミックファイバーで構成されるボード又はスリーブを用いることを特徴とする請求項5記載のシリコン又はシリコンを基とする合金の溶解炉。
- 溶解炉が、シリコン又はシリコンを基とする合金を溶解する坩堝及び該坩堝を取り囲む発熱体を備えた第一の筐体と、第一の筐体を取り囲み、外気を遮断する気密構造をもつ第二の筐体とからなることを特徴とする請求項5又は6に記載のシリコン又はシリコンを基とする合金の溶解炉。
- 炉内温度を1500°Cに保持した時に、第一筐体の表面温度が250°C以下になるように設計された断熱材で構成されることを特徴とする請求項5~7のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
- 第一筐体と第二筐体は50mm以上のクリアランスを有するように設計し、第二筐体には冷却機能を設けないことを特徴とする請求項5~8のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
- 前記坩堝が発熱体に対して位置を変える機能を有することを特徴とする請求項5~9のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
- 坩堝と発熱体の位置を変える昇降機能を有するモーター等の装置を第一筐体と第二筐体の間に設置することを特徴とする請求項5~10のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
- 前記溶解炉の第一筐体が上下2部屋に分割した構造を有し、上の部屋が発熱体を備えた加熱室、下の部屋が発熱体のない冷却室であることを特徴とする請求項5~11のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
- アルゴンガスを、溶解炉の第一の筐体と第二の筐体のそれぞれに、標準状態換算で5L/分以上の流量で導入し、排出することを特徴とする請求項5~12のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
- 坩堝の材質をシリカとすることを特徴とする請求項5~13のいずれか一項に記載のシリコン又はシリコンを基とする合金の溶解炉。
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CN112762711B (zh) * | 2020-12-15 | 2022-09-02 | 山西江淮重工有限责任公司 | 熔体保护装置及熔体保护方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001010810A (ja) | 1999-04-30 | 2001-01-16 | Mitsubishi Materials Corp | 結晶シリコンの製造方法 |
JP2003137525A (ja) | 2001-11-06 | 2003-05-14 | Mitsubishi Materials Corp | 結晶シリコン製造装置 |
JP2005271078A (ja) | 2004-02-25 | 2005-10-06 | Kyocera Corp | 不活性ガス処理構造及びこれを有するシリコン鋳造装置、シリコン鋳造方法及びこれを用いた多結晶シリコンインゴット並びに多結晶シリコン基板 |
JP2007194513A (ja) * | 2006-01-23 | 2007-08-02 | Kyocera Corp | 結晶半導体粒子の製造方法及び光電変換装置 |
JP2007314383A (ja) * | 2006-05-26 | 2007-12-06 | Sharp Corp | 坩堝および薄板製造装置 |
JP2008110914A (ja) * | 2007-12-25 | 2008-05-15 | Kyocera Corp | 粒状単結晶シリコンの製造方法 |
JP2009018958A (ja) * | 2007-07-11 | 2009-01-29 | Sharp Corp | シリコン溶融方法ならびにシリコン精製方法 |
JP2009054769A (ja) * | 2007-08-27 | 2009-03-12 | Sharp Corp | 薄板製造装置および薄板製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0753569B2 (ja) * | 1986-08-07 | 1995-06-07 | 昭和アルミニウム株式会社 | ケイ素の精製方法 |
CN1048330C (zh) * | 1992-05-15 | 2000-01-12 | 冶金工业部钢铁研究总院 | 超高温电加热炉 |
JP2002293526A (ja) * | 2001-03-29 | 2002-10-09 | Kawasaki Steel Corp | 多結晶シリコンの製造装置 |
JP3855082B2 (ja) * | 2002-10-07 | 2006-12-06 | 国立大学法人東京農工大学 | 多結晶シリコンの作製方法、多結晶シリコン、及び太陽電池 |
WO2006059632A1 (ja) * | 2004-11-30 | 2006-06-08 | Space Energy Corporation | 多結晶シリコンインゴットの製造方法 |
CN1905729A (zh) * | 2005-07-29 | 2007-01-31 | 西门子(中国)有限公司 | 分布式天线系统中的无线通信资源配置方法 |
JP2009541193A (ja) * | 2006-06-23 | 2009-11-26 | アール・イー・シー・スキャンウェハー・アー・エス | 半導体級シリコンを生産するための装置および方法 |
CN101353167A (zh) * | 2008-08-08 | 2009-01-28 | 贵阳高新阳光科技有限公司 | 一种超纯冶金硅的制备方法 |
-
2010
- 2010-10-04 KR KR1020127009848A patent/KR101391021B1/ko active IP Right Grant
- 2010-10-04 JP JP2011537191A patent/JP5453446B2/ja active Active
- 2010-10-04 WO PCT/JP2010/067336 patent/WO2011048931A1/ja active Application Filing
- 2010-10-04 CN CN201080046959.9A patent/CN102712480B/zh active Active
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001010810A (ja) | 1999-04-30 | 2001-01-16 | Mitsubishi Materials Corp | 結晶シリコンの製造方法 |
JP2003137525A (ja) | 2001-11-06 | 2003-05-14 | Mitsubishi Materials Corp | 結晶シリコン製造装置 |
JP2005271078A (ja) | 2004-02-25 | 2005-10-06 | Kyocera Corp | 不活性ガス処理構造及びこれを有するシリコン鋳造装置、シリコン鋳造方法及びこれを用いた多結晶シリコンインゴット並びに多結晶シリコン基板 |
JP2007194513A (ja) * | 2006-01-23 | 2007-08-02 | Kyocera Corp | 結晶半導体粒子の製造方法及び光電変換装置 |
JP2007314383A (ja) * | 2006-05-26 | 2007-12-06 | Sharp Corp | 坩堝および薄板製造装置 |
JP2009018958A (ja) * | 2007-07-11 | 2009-01-29 | Sharp Corp | シリコン溶融方法ならびにシリコン精製方法 |
JP2009054769A (ja) * | 2007-08-27 | 2009-03-12 | Sharp Corp | 薄板製造装置および薄板製造方法 |
JP2008110914A (ja) * | 2007-12-25 | 2008-05-15 | Kyocera Corp | 粒状単結晶シリコンの製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2492242A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102849919A (zh) * | 2012-06-14 | 2013-01-02 | 湖北新华光信息材料有限公司 | 一种光学玻璃备料炉 |
CN102849919B (zh) * | 2012-06-14 | 2015-04-08 | 湖北新华光信息材料有限公司 | 一种光学玻璃备料炉 |
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CN102712480A (zh) | 2012-10-03 |
KR101391021B1 (ko) | 2014-04-30 |
JPWO2011048931A1 (ja) | 2013-03-07 |
KR20120068920A (ko) | 2012-06-27 |
EP2492242A4 (en) | 2015-07-22 |
JP5453446B2 (ja) | 2014-03-26 |
EP2492242A1 (en) | 2012-08-29 |
CN102712480B (zh) | 2016-06-01 |
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