WO2012046673A1 - Cuve de fabrication de lingots de silicium - Google Patents

Cuve de fabrication de lingots de silicium Download PDF

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Publication number
WO2012046673A1
WO2012046673A1 PCT/JP2011/072724 JP2011072724W WO2012046673A1 WO 2012046673 A1 WO2012046673 A1 WO 2012046673A1 JP 2011072724 W JP2011072724 W JP 2011072724W WO 2012046673 A1 WO2012046673 A1 WO 2012046673A1
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Prior art keywords
container
silicon
release material
silicon ingot
melt
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PCT/JP2011/072724
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English (en)
Japanese (ja)
Inventor
彰 吉澤
孝幸 清水
朝日　聰明
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Jx日鉱日石金属株式会社
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Priority to JP2012537690A priority Critical patent/JP5788891B2/ja
Priority to CN201180048725.2A priority patent/CN103124693B/zh
Publication of WO2012046673A1 publication Critical patent/WO2012046673A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • 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
    • C30B11/002—Crucibles or containers for supporting the melt
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00939—Uses not provided for elsewhere in C04B2111/00 for the fabrication of moulds or cores
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics

Definitions

  • the present invention relates to a silicon ingot manufacturing container for manufacturing a solar cell grade silicon ingot.
  • a silicon melt is accommodated in a graphite or quartz container (such as a crucible or a mold), and the silicon melt is solidified from below to obtain a silicon polycrystal.
  • a casting method (casting method) for growing the steel is known. According to this casting method, the direction of crystal growth is uniform when the silicon melt is solidified, so that it is possible to manufacture a high-quality wafer in which an increase in specific resistance due to grain boundaries is suppressed. Moreover, according to the casting method, mass production of silicon ingots becomes possible.
  • a release material is formed on the inner surface of a container used in the casting method.
  • silicon ingot When producing a silicon ingot by the casting method, if silicon reacts with the container material when the silicon melt is solidified in the container, the silicon crystals are fixed to the container, making it difficult to take out the ingot. Therefore, a release material is formed on the inner surface of the container so that the silicon crystal does not come into direct contact with the container.
  • silicon nitride (Si 3 N 4 ), silicon dioxide (SiO 2 ), or a mixture thereof is generally used.
  • aqueous slurry prepared by mixing a binder such as polyvinyl alcohol with Si 3 N 4 powder is applied to the inner surface of the container, and then in an oxygen atmosphere.
  • a technique of firing is used.
  • This Si 3 N 4 has low sinterability (the property of solidifying a solid powder aggregate when heated at a temperature lower than the melting point to form a compact object called a sintered body) and sintering metal impurities In the case where no auxiliary agent is added, the strength is known to be low and fragile.
  • the mold release material made of Si 3 N 4 sintered body formed on the inner surface of the container may be damaged in the manufacturing process of the silicon ingot (at the time of holding the silicon melt, at the time of crystal growth, and taking out from the container). high.
  • the density of the silicon melt is 2.5 g / cm 3
  • the solid density is 2.33 g / cm 3 , so that the volume expands by about 7% when the silicon melt is solidified in the container. If excessive stress is generated in the container along with the volume expansion during the solidification of the silicon, the release material is damaged.
  • the release material breaks in a series of silicon ingot manufacturing steps, volume expansion stress remains in the grown silicon ingot, and crystal quality such as an increase in dislocation is deteriorated. Even if the silicon ingot is not damaged, the crystal quality is inevitably deteriorated. In addition, if the release material breaks during crystal growth, the silicon crystal contacts and adheres to the container, so that the take-out property of the silicon ingot is further deteriorated, and the peeled release material is mixed into the silicon ingot and the crystallinity is lowered. Will be invited. Furthermore, since the container cannot be reused as it is, the manufacturing cost increases.
  • Patent Documents 1 to 3 disclose a technique in which Si 3 N 4 , SiO 2 , or a mixture thereof is laminated to form a release material in a multilayer structure.
  • Patent Documents 4 and 5 disclose techniques for mixing a resin into a release material such as Si 3 N 4 .
  • Patent Documents 6 and 7 disclose a technique for forming a release material using aluminum nitride (AlN), cerium dioxide (CeO 2 ), or yttrium oxide (Y 2 O 3 ) as a sintering aid.
  • AlN aluminum nitride
  • CeO 2 cerium dioxide
  • Y 2 O 3 yttrium oxide
  • SiC silicon carbide
  • SiC silicon carbide
  • the produced SiC mixes with a silicon ingot, precipitates in a crystal grain boundary, and becomes the obstacle at the time of processing a silicon ingot into a wafer not only reducing the quality as an ingot.
  • the metal oxide and carbon contained in the mold release material slurry cause the container to deteriorate.
  • a release material formed on the inner surface of a graphite container is easily peeled into a film by carbonization (SiC conversion), so that the release property is not sufficient and the graphite container is consumed.
  • Non-Patent Document 1 silica as a sintering aid in the slurry.
  • Silica reacts, the above problems are accelerated.
  • the release material since the release material has a multilayer structure, it takes time and cost to form the release material.
  • the strength of the release material is high and it is difficult to break, but there is a possibility that the resin or metal contained in the release material is mixed as impurities into the silicon ingot and the crystal quality is lowered.
  • the mold release material and the metal oxide contained in the container serve as a catalyst for generating SiC in the mold release material forming step. The generated SiC becomes a float on the surface of the melt and hinders single crystallization by crystal pulling such as the Czochralski method and the Cairo porous method.
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a container for producing a silicon ingot that can be repeatedly used for producing a silicon ingot and can produce a silicon ingot having a good quality with a high yield. .
  • the invention according to claim 1 is a container for producing a silicon ingot for solidifying a silicon melt to grow a silicon polycrystal.
  • a release material made of silicon nitride is formed on the inner surface of a container body made of a porous body of silicon nitride or silicon carbide.
  • the invention according to claim 2 is the container for manufacturing a silicon ingot according to claim 1,
  • the open porosity of the porous body is 10% or more and 40% or less.
  • the open porosity is a ratio of the total volume of pores communicating with the outside to the apparent volume of the porous body.
  • the invention described in claim 3 is the silicon ingot manufacturing container according to claim 1,
  • the open porosity of the porous body is 20% or more and 30% or less.
  • the invention according to claim 4 is the silicon ingot manufacturing container according to any one of claims 1 to 3,
  • the metal impurities (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body made of the porous silicon nitride are each 1000 ppm or less.
  • the invention according to claim 5 is the silicon ingot production container according to claim 4,
  • the metal impurities (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body made of the porous body of silicon carbide are each 10 ppm or less.
  • the invention according to claim 6 is the silicon ingot manufacturing container according to any one of claims 1 to 3,
  • the metal impurities (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body made of the porous body of silicon carbide are each 100 ppm or less, preferably 10 ppm or less. It is characterized by being.
  • the invention according to claim 7 is the silicon ingot production container according to claim 6,
  • the metal impurities (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body made of the porous body of silicon carbide are each 10 ppm or less.
  • the invention according to claim 8 is the silicon ingot manufacturing container according to any one of claims 1 to 7,
  • the release material has a thickness of 300 to 1000 ⁇ m.
  • the invention according to claim 9 is the silicon ingot manufacturing container according to claim 8,
  • the release agent has a thickness of 350 to 600 ⁇ m.
  • the release material having a good release property is firmly formed on the inner surface of the container body, it is possible to effectively prevent the release material from being damaged by the stress accompanying the volume expansion during the solidification of silicon. it can. Therefore, the silicon ingot can be repeatedly used for manufacturing a silicon ingot, and a silicon ingot having a good quality can be manufactured with a high yield.
  • FIG. 1 is a sectional view of a container for producing a silicon ingot to which the present invention is applied.
  • a container (hereinafter referred to as a container) 10 for producing a silicon ingot includes a container body 11 having heat resistance and a container body 11 for improving the releasability of the grown silicon ingot. And a mold release material 12 formed on the inner surface.
  • the container body 11 is composed of a porous body (porous material) of Si 3 N 4 or SiC.
  • the thickness of the container body 11 is such that warpage does not occur during molding, for example, 5 mm or more.
  • the container body 11 is produced, for example, by sintering and molding Si 3 N 4 or SiC powder, and the open porosity is 10% or more and 40% or less.
  • the open porosity of the porous body constituting the container main body 11 is less than 10%, bubbles remain in the release material 12, so that the release material 12 becomes brittle and easily breaks.
  • the open porosity of the porous body constituting the container main body 11 is desirably 10% or more and 40% or less.
  • the container main body 11 made of a porous molded body of Si 3 N 4 or SiC is superior in heat resistance as compared with a quartz container, and does not deteriorate or deform when the silicon ingot is manufactured at a high temperature. Therefore, when the silicon ingot is manufactured, it is possible to effectively prevent the release material 12 from being damaged due to deterioration and deformation of the container body 11.
  • the container main body 11 consists of a porous molded body of Si 3 N 4 , it contains metal impurities (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr). Is 1000 ppm or less, desirably 10 ppm or less.
  • the metal impurities (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) are each 100 ppm or less, Desirably, it is 10 ppm or less.
  • SiC foreign matter does not float on the melt surface, and single crystallization by a crystal pulling operation such as the Czochralski method or the Cairo porous method is facilitated. Further, when Si polycrystal is produced by a casting method or the like, it is possible to prevent the SiC melt surface suspended matter from being mixed into the crystal, and as a result, the Si crystal quality is improved.
  • the release material 12 is composed of a sintered body of Si 3 N 4 .
  • the release material 12 is prepared by, for example, applying an aqueous slurry prepared by mixing a binder such as polyvinyl alcohol to Si 3 N 4 powder to the inner surface of the container body 11 with a brush or spray, and inactive in an oxygen atmosphere or argon. It is formed by baking at 700 to 1550 ° C. in a gas atmosphere.
  • the release material 12 has a thickness of 300 to 1000 ⁇ m. When it is thinner than 300 ⁇ m, the volume expansion stress relaxation of Si is insufficient, and the crystal is cracked.
  • the mold release material breaks during crystal growth and becomes a float on the melt surface, and single crystallization from the melt surface tends to be hindered.
  • the desirable thickness of the release material is 300 to 600 ⁇ m.
  • the slurry applied to the container body 11 penetrates into the pores of the container body 11 because the container body 11 is composed of a porous body.
  • bubbles in the slurry are degassed by the container body 11 made of a porous material. Since the firing is performed in this state, the release material 12 is firmly formed on the inner surface of the container body 11. Therefore, it is possible to effectively prevent the release material 12 from being damaged when the silicon ingot is manufactured.
  • the mold release material 12 tends to be damaged during the production of the silicon ingot according to the number and size of the residual bubbles.
  • defoaming treatment such as reduced pressure was performed.
  • the container 10 of the present embodiment it is not necessary to perform a defoaming process when forming the release material 12, and the release material 12 can be easily formed.
  • the release material 12 is firmly formed on the inner surface of the container main body 11, it is not necessary to have a multilayer structure as in the prior art. Therefore, the labor and cost for producing the container 10 do not increase, and it is easy to increase the film thickness of the release material 12. Furthermore, since it is not necessary to use a sintering aid such as silica or a metal oxide when forming the release material 12, it is possible to prevent the impurity concentration in the silicon ingot from increasing and the crystallinity from being lowered. That is, during the Si crystal growth, the amount of generated SiO gas due to the thermal decomposition of SiO 2 containing the metal oxide is reduced, and it is possible to prevent the generation of SiC foreign substances that deteriorate the crystal quality. Based on the same principle, it is possible to suppress the generation of SiO gas which is a thermally decomposable product of SiO 2 by not using a conventional quartz container.
  • FIG. 2 is a diagram illustrating an example of a crystal growth apparatus using the container of the embodiment.
  • the crystal growth apparatus 1 shown in FIG. 2 is used when manufacturing a silicon ingot.
  • the container 10 is supported by a susceptor 13 made of graphite, and a heater 14 is disposed on the outer periphery of the susceptor 13.
  • a silicon ingot is manufactured by the casting method using the crystal growth apparatus 1, first, a predetermined amount of silicon raw material (for example, silicon melt) 15 is put into the container 10. Then, by gradually lowering the temperature, the silicon melt is solidified from the melt surface of the container 10 to grow the silicon polycrystal 15a, and a silicon ingot is manufactured.
  • silicon raw material for example, silicon melt
  • the open porosity of the container material is small, the release material is easily peeled off and becomes a floating surface on the melt surface during crystal growth, which prevents single crystallization from the Si melt surface.
  • the open porosity of the container material is too large, the thickness of the release material becomes 300 ⁇ m or less, the volume expansion stress relaxation by the release material becomes insufficient, and cracks are recognized in the ingot.
  • Table 1 shows the results of the test using the Si 3 N 4 crucible.
  • Example 1 When the open porosity was 10%, bubbles when the slurry was brushed remained and a large dent was formed on the surface, and after firing, many cracks originated from the dent were generated. Although it was possible to take out the ingot from the container, there was a tendency for cracks to be large in the R part (curved part of the boundary between the bottom wall and the side wall) at the bottom of the container, and the bottom of the Si ingot solidified from the melt surface was cracked.
  • Example 4 When the open porosity was 40%, the penetration of the release material slurry was large, and it was difficult to increase the thickness of the release material. When the thickness of the mold release material was smaller than 300 ⁇ m, there was a tendency for unevenness to occur on the bottom surface of the ingot. Although the ingot could be removed from the container, cracks were observed in the ingot at the R portion at the bottom of the container.
  • the top inner diameter is 68.2 mm
  • the bottom inner diameter is 36 mm
  • the depth is 48 mm
  • the thickness is 2 mm.
  • All metal impurities Na, Ca, Al, Cr, Cu, Fe
  • a container 10 is used in which a release material 12 having a thickness of 350 to 600 ⁇ m is formed on the inner surface of a SiC container main body (open porosity: 20%) 11 in which Ni, Ti, W, V, Zn, and Zr are each 10 ppm or less.
  • Si was solidified from the melt surface. Specifically, 100 g of silicon raw material was accommodated in the container 10 and heated to 1550 ° C. under an argon atmosphere of 1 atm to melt silicon. Thereafter, the heater was cooled at 10 ° C./min.
  • Example 6 After forming the release material on the inner surface of the SiC container having the same specifications as in Example 5, baking was performed at 1550 ° C. for 12 hours under 1 atm of argon, and then the silicon was melted and solidified by the same method as in Example 5. went.
  • Example 7 the top inner diameter: 84.4 mm, the bottom inner diameter: 48 mm, the depth: 48 mm, the thickness: 10 mm, and metal impurities (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, After forming a release material on the inner surface of the Si 3 N 4 container having W, V, Zn, and Zr) of 10 to 1000 ppm, silicon was melted and solidified in the same manner as in Example 5. These results are shown in Table 2.
  • the stress accompanying the volume expansion during the solidification of the silicon was effective. It is thought that it was relaxed. Moreover, since the mold release material 12 and the container main body 11 were not damaged, the container 10 could be reused, and it could be used repeatedly for producing silicon ingots 10 times or more.
  • Comparative Example 3 In Comparative Example 3, a silicon ingot was manufactured under the same manufacturing conditions as in Example, using a container in which a release material similar to that in Example was formed on the inner surface of a quartz container body. The resulting silicon ingot was severely uneven as compared to the silicon ingot obtained in the examples, and particularly, the ingot was cracked in the ingot due to severe deformation at the top and side surfaces of the ingot. Since the release material peeled off on the surface having the irregularities of the silicon ingot taken out, the release material was damaged due to the volume expansion at the time of solidification of silicon and the thermal deformation of the container due to high temperature, and part of the silicon ingot was It is thought that the ingot was cracked because it was fixed to the container.
  • SiC which is a floating material on the melt surface, is generated during crystal growth, and is mixed into the silicon ingot together with the release material that has been peeled off during growth, and it is considered that the crystal quality of the silicon ingot has deteriorated.
  • Comparative Example 4 In Comparative Example 4, a mold release material was formed on the inner surface of a Si 3 N 4 container having a top inner diameter of 84.4 mm, a bottom inner diameter of 48 mm, a depth of 48 mm, and a thickness of 10 mm, and then baked at 1550 ° C. for 12 hours under 1 atm of argon. Then, melt solidification was performed in the same manner as in Example 5. When the furnace was opened and the container was taken out, it was found that the Si melt leaked from the bottom of the container. Si was distributed by spreading the mold release material, but there was no leakage from the side. Since Si was solidified from the melt surface, it is considered that the melt compressed at the bottom of the container permeated the porous material.
  • the container weight reduction rate was found to be 0.2 wt% / h from the difference in the weight of the container including the release material before and after baking and the baking time. After baking, a large amount of SiO adhered to the furnace. In the case of the SiC container with low metal impurities after baking under the same conditions (Example 6), weight reduction and large amount of SiO generation during crystal growth were not observed. Therefore, there is a possibility that the Si 3 N 4 container main body containing a large amount of SiO 2 and metal oxide and the adjacent Si 3 N 4 release material were thermally decomposed as SiO. That is, it is considered that melt leakage occurred in Comparative Example 4 because the sinterability of the release material Si 3 N 4 particles covered with SiO 2 decreased during baking.
  • the release material 12 made of Si 3 N 4 is formed on the inner surface of the container body 11 made of a porous body of Si 3 N 4 or SiC.
  • the open porosity of the porous body constituting the container body 11 is 10% or more and 40% or less, preferably 20% or more and less than 40%.
  • the release material 12 having good releasability is firmly formed on the inner surface of the container body 11, it is effective for the release material 12 to be damaged due to the stress accompanying the volume expansion at the time of silicon solidification. Can be prevented.
  • porous SiC with low metal impurities produced by the conversion method as the container material, much less metal impurities can be obtained than when using a Si 3 N 4 container produced by the conventional sintering method.
  • Si ingot containing could be manufactured.
  • the SiC container it was possible to perform baking at a temperature higher than that of the Si 3 N 4 container to reduce metal impurities in the Si ingot.
  • the low metal impurity container as a container for producing an Si ingot, it was possible to suppress contamination of SiC foreign matter into the melt. Therefore, the silicon ingot can be repeatedly used for the production of the silicon ingot, and the silicon ingot having a good quality can be produced.
  • the container 10 according to the embodiment can be used not only in the casting method but also in any method for producing a silicon ingot that holds and solidifies the Si melt in the container.
  • the present invention can be used in a chiloporous method in which a seed crystal is brought into contact with the surface of a silicon melt and the silicon crystal is solidified from the surface while the seed crystal is pulled up to grow a silicon single crystal.
  • the problem that the release material breaks down due to the stress associated with the volume expansion at the time of silicon solidification is prevented on the porous container material with low metal impurities is to suppress the occurrence of floating surface of the melt that hinders the single crystallization from the seed crystal. It is because it can solve by forming a mold release material firmly. Further, the container main body 11, not the Si 3 N 4 or SiC only those formed in the crucible shape, assembled type as a template by combining a plurality of plate-like member formed of Si 3 N 4 or SiC in a plate shape Can be applied.

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Abstract

L'invention concerne une cuve de fabrication de lingots de silicium destinée à un usage répété dans la fabrication de lingots de silicium de haute qualité. La cuve selon l'invention sert à solidifier une masse fondue de silicium et à faire croître un polycristal de silicium et elle est configurée de sorte qu'un matériau de démoulage en nitrure de silicium soit formé sur la surface interne d'un corps principale de cuve comprenant un corps poreux en nitrure de silicium ou en carbure de silicium. En outre, la porosité ouverte du corps poreux constituant le corps principal de la cuve est de 10-40%. Comme un matériau de démoulage est formé robuste sur la surface interne du corps principal, les dommages qui pourraient être causés audit matériau par la contrainte accompagnant l'expansion de volume pendant la solidification du silicium sont empêchés de façon efficace. De plus, le maintien de la concentration d'impuretés métalliques de la cuve à 10ppm ou inférieure permet d'empêcher la production de SiC solide suspendu à la surface de la masse fondue, qui entrave la croissance de Si monocristallin.
PCT/JP2011/072724 2010-10-08 2011-10-03 Cuve de fabrication de lingots de silicium WO2012046673A1 (fr)

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JP2012537690A JP5788891B2 (ja) 2010-10-08 2011-10-03 シリコンインゴット製造用容器
CN201180048725.2A CN103124693B (zh) 2010-10-08 2011-10-03 硅锭制造用容器

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JP2010-228607 2010-10-08
JP2010228607 2010-10-08

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WO2012046673A1 true WO2012046673A1 (fr) 2012-04-12

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CN103124693A (zh) 2013-05-29
TW201228934A (en) 2012-07-16

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