WO2012104948A1 - Contenant rectangulaire de silice pour la fabrication d'un lingot de silicium polycristallin, plaque de silice poreuse et son procédé de fabrication - Google Patents

Contenant rectangulaire de silice pour la fabrication d'un lingot de silicium polycristallin, plaque de silice poreuse et son procédé de fabrication Download PDF

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Publication number
WO2012104948A1
WO2012104948A1 PCT/JP2011/006699 JP2011006699W WO2012104948A1 WO 2012104948 A1 WO2012104948 A1 WO 2012104948A1 JP 2011006699 W JP2011006699 W JP 2011006699W WO 2012104948 A1 WO2012104948 A1 WO 2012104948A1
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Prior art keywords
silica
container
raw material
porous silica
material powder
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PCT/JP2011/006699
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English (en)
Japanese (ja)
Inventor
茂 山形
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信越石英株式会社
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Priority claimed from JP2011049356A external-priority patent/JP5762777B2/ja
Priority claimed from JP2011067263A external-priority patent/JP5762784B2/ja
Application filed by 信越石英株式会社 filed Critical 信越石英株式会社
Publication of WO2012104948A1 publication Critical patent/WO2012104948A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/02—Forming molten glass coated with coloured layers; Forming molten glass of different compositions or layers; Forming molten glass comprising reinforcements or inserts
    • 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
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/06—Forming glass sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/20—Uniting glass pieces by fusing without substantial reshaping
    • C03B23/203—Uniting glass sheets
    • 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
    • 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
    • C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
    • C30B35/002—Crucibles or containers

Definitions

  • the present invention relates to a square (square tank type) silica container for solidifying a silicon melt to produce a polycrystalline silicon ingot.
  • Polycrystalline silicon is one of the materials constituting the photovoltaic part of solar cells. Polycrystalline silicon is often produced as polycrystalline silicon ingots by cooling and solidifying a silicon melt. As a container for solidifying a silicon melt to produce a polycrystalline silicon ingot, a silica (silicon dioxide) container or a graphite container is used.
  • a release layer in advance.
  • Various materials are used as a release agent for forming the release layer.
  • a release agent slurry containing Si, Si 3 N 4 , Si 3 N 4 + SiO 2 or Si + Si 3 N 4 + SiO 2 is used as a release agent in an inner layer of a silicon melting container made of quartz glass. The formation of a layer is described.
  • Patent Document 2 describes a silicon casting mold made of silicon dioxide in which a release material layer containing silicon nitride is formed on the inner surface.
  • Patent Document 3 describes a release layer made of porous silicon nitride or porous silicon oxynitride.
  • Patent Documents 4 to 6 describe a release layer containing solid particles having a composition of SiO X N Y (X> 0, Y> 0).
  • a release layer is generally formed on the inner surface of a container for producing a polycrystalline silicon ingot by solidifying the silicon melt in the container.
  • a material that becomes an impurity in the polycrystalline silicon ingot is used as a mold release agent, the impurity in the polycrystalline silicon ingot is removed because the release layer is peeled off and taken into the silicon melt. There was a problem that mixing was inevitable.
  • the release agent is not used, the polycrystalline silicon ingot is fused to the container when the silicon melt is solidified, and the surface portion of the polycrystalline silicon ingot is damaged during cooling or removal. There was a problem. As a result, for example, when a solar cell is manufactured from a polycrystalline silicon ingot, the cost of the manufactured solar cell is increased due to deterioration of the quality of the manufactured solar cell and a decrease in yield.
  • the silica container for accommodating the silicon melt must also be enlarged.
  • the manufacture of such a large silica container requires a large-sized device, resulting in a significant increase in container manufacturing cost.
  • the present invention has been made in view of the problems as described above, and suppresses impurity contamination of the silicon melt and the polycrystalline silicon ingot, is excellent in releasability, and produces a very low cost polycrystalline silicon ingot.
  • An object of the present invention is to provide a rectangular silica container.
  • the present invention has been made in order to solve the above problems, and is a rectangular silica container for producing a polycrystalline silicon ingot by solidifying a silicon melt, and is a parallel plate-like porous material made of porous silica.
  • a rectangular silica for producing a polycrystalline silicon ingot, comprising a combination of silica plates, wherein the bulk density of the porous silica plate is lower in the inner part than the surface parts of both parallel planes Provide a container.
  • the bulk density of the porous silica plate is lower in the inner part than the surface parts of both parallel planes, the square silica container containing the produced polycrystalline silicon ingot Therefore, the polycrystalline silicon ingot can be easily removed without being damaged. Moreover, since it is not necessary to use a mold release agent in addition to the container made of silica, it is possible to suppress impurity contamination to the contained silicon (silicon melt and polycrystalline silicon ingot). Moreover, since such a silica container is a combination of plates, the manufacturing cost of the container can be remarkably reduced compared to a single body.
  • the square silica container may contain a release accelerator that promotes release of the polycrystalline silicon ingot in at least a part of the inner surface portion.
  • the bulk density of the porous silica plate is lower in the inner part than the surface parts of both parallel planes, and at least part of the inner surface part of the rectangular silica container is polycrystalline. Impurity contamination to the contained silicon (silicon melt and polycrystalline silicon ingot) is sufficiently prevented and produced by containing a mold release accelerator that promotes mold release of the silicon ingot.
  • the polycrystalline silicon ingot can be easily removed from the rectangular silica container containing the polycrystalline silicon ingot without being damaged.
  • the manufacturing cost of the container can be remarkably reduced compared to a single body.
  • the bulk density of the porous silica plate is 1.60 to 2.10 g / cm 3
  • the bulk density at a depth of 3 mm from the surface of both parallel planes of the porous silica plate is the center. It is preferably larger than the bulk density of the partial thickness of 3 mm and having a difference of 0.05 g / cm 3 or more.
  • the strength of the rectangular silica container for producing a polycrystalline silicon ingot can be maintained and the releasability can be further increased.
  • the square silica container has an Al concentration of 3 to 500 wt. ppm, and the OH group concentration is 5 to 500 wt. Preference is given to ppm.
  • each of Li, Na and K contained in the square silica container is 1 to 100 wt. ppm, and each concentration of Ti, Cr, Fe, Ni, Cu, Zn, Mo, Au is 0.01 to 5.0 wt. Preference is given to ppm.
  • each concentration of Li, Na, and K is 100 wt. ppm or less, each concentration of Ti, Cr, Fe, Ni, Cu, Zn, Mo, Au is 5.0 wt. If it is less than or equal to ppm, the diffusion of impurities into the contained silicon can be suppressed.
  • each concentration of Li, Na, and K is 1 wt. ppm or more, each concentration of Ti, Cr, Fe, Ni, Cu, Zn, Mo, Au is 0.01 wt. It does not have to be so high as in the case of ppm or more, and the manufacturing cost can be suppressed.
  • the present invention also relates to a parallel flat plate-like porous silica plate made of porous silica for constituting a square silica container for producing a polycrystalline silicon ingot by solidifying a silicon melt.
  • the density is 1.60 to 2.10 g / cm 3
  • the bulk density of the thickness portion of 3 mm depth from the surfaces of both parallel planes is larger than the bulk density of the central portion thickness of 3 mm
  • 0.05 g A porous silica plate having a density difference of at least / cm 3 is provided.
  • Such a porous silica plate can be combined to form a square silica container.
  • the rectangular silica container is an extremely low-cost rectangular silica container for producing a polycrystalline silicon ingot, which suppresses impurity contamination to the silicon (silicon melt and polycrystalline silicon ingot) contained therein, has excellent releasability, and can do.
  • the porous silica plate may include a release accelerator that promotes the release of the polycrystalline silicon ingot in at least a part of the surface portion.
  • Such a porous silica plate can be combined to form a square silica container.
  • the rectangular silica container should be a rectangular silica container for manufacturing a polycrystalline silicon ingot that is sufficiently prevented from being contaminated with impurities and has excellent releasability. it can.
  • the porous silica plate has an Al concentration of 3 to 500 wt. ppm, and the OH group concentration is 5 to 500 wt. Preference is given to ppm.
  • the concentration of each of Li, Na and K contained in the porous silica plate is 1 to 100 wt. ppm, and each concentration of Ti, Cr, Fe, Ni, Cu, Zn, Mo, Au is 0.01 to 5.0 wt. Preference is given to ppm.
  • Such a porous silica plate having an impurity concentration can sufficiently suppress the diffusion of impurities into the contained silicon when combined with a rectangular silica container while suppressing the manufacturing cost.
  • the present invention also relates to a method for producing a parallel flat plate-like porous silica plate made of porous silica for constituting a rectangular silica container for producing a polycrystalline silicon ingot by solidifying a silicon melt.
  • a step of producing silica powder as a raw material powder a step of replacing the inside of a melting vessel arranged in an electric heating furnace with an inert gas atmosphere containing any one or more of nitrogen, neon, argon, and krypton, While maintaining the inside of the melting container in the inert gas atmosphere, supplying the raw material powder into the melting container, and maintaining the pressure of the inert gas atmosphere in the melting container at or above atmospheric pressure
  • a step of melting and softening the raw material powder by heating the temperature of the melting container to 1700 ° C.
  • a porous silica plate body characterized by comprising a step of pulling out continuously while forming a parallel plate with.
  • the bulk density of the produced porous silica plate can be made lower in the inner part than the surface parts of both parallel planes. That is, by melting and softening the raw material powder in an inert gas atmosphere containing any one or more of nitrogen, neon, argon, and krypton, bubbles can be included in the fused silica glass. By forming this into a parallel plate shape through a shape forming tool, it is possible to manufacture a porous silica plate having fewer bubbles in the surface portion of the plate than in the central portion. Moreover, the porous silica plate manufactured in this way is low in cost and can be combined to form a square silica container.
  • Such a rectangular silica container suppresses impurity contamination to the silicon (silicon melt and polycrystalline silicon ingot) to be accommodated, is excellent in releasability, and has a very low cost for producing a rectangular silicon ingot for polycrystalline silicon ingot.
  • Can be a container.
  • a mold release accelerator for promoting mold release of the polycrystalline silicon ingot can be contained in at least a part of the surface portion of the porous silica plate.
  • the release accelerator when a release accelerator that promotes release of the polycrystalline silicon ingot is included in at least a part of the surface portion of the porous silica plate, the release accelerator is included in the surface of the porous silica plate.
  • the rectangular silica container By configuring the rectangular silica container so that the contained surface is on the inside, the rectangular silica container can accommodate the silicon contained due to the configuration related to the bulk density of the porous silica plate and the presence of the release accelerator. Impurity contamination is sufficiently prevented, and it is excellent in releasability, and can be a very low cost rectangular silica container for producing a polycrystalline silicon ingot.
  • a first raw material powder made of silica powder having a particle size of 0.003 to 3.0 mm and a mass-based cumulative distribution in the step of producing a second raw material powder made of silica powder having an average particle size compared with the particle size value at 50% smaller than the first raw material powder, and supplying the raw material powder into the melting container, While supplying the supply position of the first raw material powder as the center side in the melting container, supplying the second raw material powder to the outside of the supply position of the first raw material powder in the melting container. Can do.
  • the release accelerator can be contained in the second raw material powder by adding (doping) the release accelerator. Further, in the method for producing a porous silica plate of the present invention, the release accelerator is contained in at least a part of the surface portion of the porous silica plate after the porous silica plate is produced. A mold release accelerator can also be contained by application (coating).
  • a release accelerator that promotes release of the polycrystalline silicon ingot can be more easily contained in at least a part of the surface portion of the porous silica plate.
  • the concentration of each of Li, Na and K contained in the raw material powder is 1 to 100 wt.
  • the concentration of each of Ti, Cr, Fe, Ni, Cu, Zn, Mo, and Au contained in the raw material powder is 0.01 to 5.0 wt. It is preferable to set it as ppm.
  • the impurity metal element concentration contained in the raw material powder is set in this manner, the diffusion of impurities to the contained silicon can be sufficiently achieved when the manufactured plate is combined into a rectangular silica container while suppressing the manufacturing cost. Can be suppressed.
  • the atmospheric gas in the melting container is 80 vol. % Or more is preferable.
  • the bulk density of the porous silica plate can be more reliably lowered in the inner portion than the surface portions of both parallel planes.
  • the rectangular silica container for producing a polycrystalline silicon ingot according to the present invention contains the produced polycrystalline silicon ingot because the bulk density of the porous silica plate is lower in the inner part than the surface parts of both parallel planes.
  • the polycrystalline silicon ingot can be easily removed from the rectangular silica container. Further, in the case where a release agent is not used in addition to the container made of silica, impurity contamination to the contained silicon (silicon melt and polycrystalline silicon ingot) can be suppressed.
  • the bulk density of the porous silica plate is lower in the inner part than the surface parts of both parallel planes, and further promotes the release of the polycrystalline silicon ingot on at least a part of the inner surface part of the square silica container.
  • the release accelerator When the release accelerator is contained, impurity contamination of the contained silicon is sufficiently prevented, and the polycrystalline silicon is removed from the rectangular silica container containing the manufactured polycrystalline silicon ingot. It is easy to remove without damaging the ingot. Moreover, since the silica container like these is a combination of plates, the container manufacturing cost can be significantly reduced as compared with a single body.
  • porous silica board which concerns on this invention, it can be set as the porous silica board for comprising such a square silica container for polycrystalline silicon ingot manufacture. Further, according to the method for producing a porous silica plate according to the present invention, such a silica plate can be produced at low cost.
  • a high-quality, low-cost rectangular polycrystalline silicon ingot can be manufactured, which is particularly suitable for a solar cell.
  • FIG. 1 It is a figure which shows the example of installation of the square silica container which concerns on this invention, (a) is a schematic top view, (b) is a schematic sectional drawing. It is a schematic sectional drawing which shows an example of the apparatus used for manufacture of the porous silica board which concerns on this invention. It is a schematic sectional drawing which shows an example of the apparatus used for manufacture of the porous silica board which concerns on this invention from another angle. It is a schematic sectional drawing which shows another example of the apparatus used for manufacture of the porous silica board which concerns on this invention. It is a schematic sectional drawing which shows another example of the apparatus used for manufacture of the porous silica board which concerns on this invention from another angle.
  • a rectangular silica container for producing a polycrystalline silicon ingot which can obtain a rectangular polycrystalline silicon ingot suitable for use in a solar cell, has the following problems.
  • a rectangular silica container having excellent releasability having excellent releasability (improving releasability).
  • the polycrystalline silicon ingot can be easily removed from the rectangular silica container.
  • a rectangular silica container capable of preventing impurity contamination. This means that various impurity metal elements contained in the square silica container move and diffuse to the contained silicon (silicon melt, polycrystalline silicon ingot, etc.) even at high temperatures during the production of polycrystalline silicon. As a result, impurity contamination of the silicon melt and the polycrystalline silicon ingot is sufficiently prevented.
  • the above-mentioned excellent releasability and prevention of impurity contamination are realized at low cost. This means that, for the production of rectangular silica containers, the cost of parts can be reduced and inexpensive silica raw materials can be used, and the silica raw materials are continuously melted and molded in a relatively short time. To reduce energy consumption.
  • FIG. 1 shows an outline of an example of a rectangular silica container for producing a polycrystalline silicon ingot according to the present invention.
  • 1A is a schematic top view
  • FIG. 1B is a schematic cross-sectional view.
  • the shape of the silica container 10 according to the present invention is a square (also called a square tank type).
  • the rectangular silica container 10 includes a side part (side wall part) 11 and a bottom part 21.
  • the square silica container 10 according to the present invention is configured by combining parallel flat plate-like porous silica plates.
  • the four side portions 11 and the one bottom portion 21 are each made of a parallel flat plate-like porous silica plate, and according to the present invention.
  • the square silica container 10 is configured by combining these.
  • the method for combining the porous silica plates constituting the rectangular silica container 10 according to the present invention is not particularly limited, but it is preferable not to fall inside when combined.
  • the parallel flat porous silica plates can be combined such that each inclined portion is an inclined surface and the inclined surfaces face each other (grinding (ground glass bonding) type).
  • FIG. 2 shows an outline of another example of a rectangular silica container for producing a polycrystalline silicon ingot according to the present invention.
  • FIG. 2A is a schematic top view
  • FIG. 2B is a schematic cross-sectional view.
  • each combination portion of the parallel flat plate-like porous silica plates can be formed so as to be fitable, and can be combined (fit type).
  • each side and bottom of the square is not limited to being assembled with a single porous silica plate, but each side and bottom with a plurality of porous silica plates as shown in FIGS. Can be configured.
  • 3A is a schematic top view
  • FIG. 3B is a schematic cross-sectional view
  • FIG. 4A is a schematic top view
  • FIG. 4B is a schematic cross-sectional view.
  • the rectangular container is composed of a porous silica plate having eight side portions 11a and 11b and two bottom portions 21a and 21b each having a parallel plate shape.
  • the porous silica plate according to the present invention has a parallel plate shape.
  • the parallel plate shape is two flat surfaces having a large area among the flat plate-shaped surfaces. Means substantially parallel.
  • a shape for combination may be formed in the peripheral portion of the flat plate shape.
  • FIG. 5 shows an installation example of the square silica container 10 according to the present invention.
  • FIG. 5A is a schematic top view
  • FIG. 5B is a schematic cross-sectional view.
  • FIG. 5 shows a typical example in which the square silica container 10 is configured by a combination of the combination types as shown in FIG. 1, but other combinations, for example, the configurations shown in FIGS. Good.
  • the porous silica plate constituting the rectangular silica container 10 can be fixed by a susceptor 80 made of carbon or the like.
  • the rectangular silica container 10 according to the present invention configured by combining the porous silica plates is a container for solidifying the silicon melt to produce a rectangular polycrystalline silicon ingot. Therefore, the manufacturing cost can be significantly reduced as compared with the case where the entire container is manufactured integrally. Also, if the manufactured polycrystalline silicon ingot is rectangular, it can be sliced to obtain a rectangular polycrystalline silicon wafer, and when a wafer obtained by slicing a cylindrical polycrystalline silicon ingot is used as a solar cell. In comparison, there is no waste of light receiving area, which is very suitable.
  • the bulk density of the porous silica plate is lower in the inner part than the surface parts of both parallel planes. That is, with reference to FIGS. 1 to 4, the porous silica plates 11, 11a, 11b constituting the side portions are portions of the side inner surfaces 12, 12a, 12b and the side outer surfaces 13, 13a, 13b. The bulk density is lower in the portion inside the plate. Further, the porous silica plate bodies 21, 21a, 21b constituting the bottom portion have a bulk density at the portion inside the plate body rather than the portions at the bottom portion inner surfaces 22, 22a, 22b and the bottom portion outer surfaces 23, 23a, 23b. Is low.
  • the bulk density of the porous silica plate is made lower in the inner part (more specifically, the part deeper than about 3 mm from the surface) than the surface parts of both parallel planes ( That is, the strength of the central portion of the porous silica plate is set low due to the large amount of bubbles.
  • a polycrystalline silicon ingot is produced by solidifying the silicon melt in such a square silica container, the strength of the container itself is appropriately maintained, so that a predetermined shape corresponding to the shape of the square silica container is obtained. It is possible to produce a polycrystalline silicon ingot.
  • the strength of the inner part of the porous silica plate is weak, so that the surface part of the polycrystalline silicon ingot is not damaged or microcracks are not easily formed on the surface.
  • the crystalline silicon ingot can be taken out. Further, if necessary, the polycrystalline silica ingot can be easily detached from the container by breaking the square silica container.
  • the rectangular silica container 10 need not use a release agent made of other materials (for example, silicon carbide SiC, silicon nitride Si 3 N 4, carbon C, etc.). Impurity contamination due to the release agent itself to the contained silicon (silicon melt and polycrystalline silicon ingot) can be suppressed. Moreover, since such a silica container is a combination of plates, the manufacturing cost of the container can be remarkably reduced compared to a single body.
  • a release agent made of other materials for example, silicon carbide SiC, silicon nitride Si 3 N 4, carbon C, etc.
  • the square silica container 10 according to the present invention may further contain a release accelerator that promotes release of the polycrystalline silicon ingot in at least a part of the inner surface portion.
  • the inner surfaces of the square silica container 10 are the side inner surfaces 12, 12a, 12b and the bottom inner surfaces 22, 22a, 22b.
  • the release accelerator when peeling the polycrystalline silicon ingot from the container, in addition to the weakness of the internal portion of the porous silica plate, the release accelerator is contained, so the surface portion of the polycrystalline silicon ingot The polycrystalline silicon ingot can be taken out more easily without causing defects or generating microcracks on the surface. Also in this case, since the strength of the portion inside the porous silica plate is weak, if necessary, the rectangular silica container can be easily broken and the polycrystalline silicon ingot can be removed from the container.
  • Examples of the release accelerator that can be used in the present invention include alkaline earth metal elements such as calcium Ca, strontium Sr, and barium Ba, and compounds such as sulfates, chlorides, carbonates, halides, and the like. It can be contained in the square silica container 10 in the form.
  • examples of the release accelerator that can be used in the present invention include silicon carbide SiC, silicon nitride Si 3 N 4 , silicon oxynitride SiO x N y (x> 0, y> 0), magnesium oxide MgO, Examples include zirconium oxide ZrO 2 and carbon C.
  • preferable release accelerators are alkaline earth metal elements Ca, Sr, and Ba.
  • the inner surface layer of the rectangular silica container 10 can be transferred from silica glass to a microcrystalline phase such as cristobalite or opal, thereby generating microcracks.
  • the polycrystalline silicon ingot is removed when removing the polycrystalline silicon ingot from the rectangular silica container 10. It can be removed without breaking or forming irregularities on the surface portion of the polycrystalline silicon ingot or causing progressive cracks.
  • the alkaline earth metal elements Ca, Sr, Ba have a correlation with the segregation coefficient, and are applied to the polycrystalline silicon ingot produced by solidification from the melt. Incorporation is small, that is, process contamination of the polycrystalline silicon ingot can be reduced.
  • Ba is most preferable as a mold release accelerator used in the present invention because it has less diffusion contamination into the polycrystalline silicon ingot.
  • the range in which the mold release accelerator is contained may be at least part of the inner surface portion of the rectangular silica container 10 as described above.
  • the entire inner surface portion up to a height at which the silicon melt is accommodated and solidified is more preferable, and the entire inner surface portion of the square silica container 10 is further preferable.
  • a method of containing the release accelerator in the inner surface portion of the rectangular silica container a method by coating (coating) on the surface of the porous silica plate constituting the rectangular silica container, or in the production of the porous silica plate There is a method of adding (doping) to the raw material powder. From the viewpoint of cost, a method of applying an aqueous solution such as barium sulfate or barium chloride to the inner surface of the square silica container and drying it is effective at low cost.
  • the application concentration of the mold release accelerator is 50 to 50% as the total value of alkaline earth metal elements such as Ca, Sr and Ba when an alkaline earth metal element such as Ca, Sr and Ba is used as the mold release accelerator. It is preferably 5000 ⁇ g / cm 2 (50 to 5000 ⁇ g per cm 2 of the inner surface of the square silica container), more preferably 100 to 1000 ⁇ g / cm 2 .
  • the bulk density of each porous silica plate constituting the rectangular silica container 10 is 1.60 to 2.10 g / cm 3 (this means that the bulk density of the porous silica plate is within this range, that is, the lower limit of the bulk density 1.60 g / cm 3 or more, the upper limit means that is 2.10 g / cm 3 or less), the depth from the surface of both the parallel plane of the porous silica plate member of It is preferable that the bulk density of the 3 mm thick part is larger than the bulk density of the central part thickness of 3 mm and has a difference of 0.05 g / cm 3 or more.
  • the bulk density of the porous silica plate is more preferably in the range of 1.70 to 2.00 g / cm 3 .
  • the difference in bulk density between the surface portion and the central portion is more preferably 0.1 g / cm 3 or more, and particularly preferably 0.2 g / cm 3 or more.
  • the bulk density of the portion of each porous silica plate constituting the rectangular silica container 10 on the inner surface as the container is 2.10 g / If the value is not more than cm 3, the fusion between the polycrystalline silicon ingot and the square silica container 10 does not become too strong, and the release property can be sufficiently provided.
  • each porous silica plate constituting the rectangular silica container 10 is a value of 1.60 g / cm 3 or more, the releasability can be further improved, and the strength of the container is increased. It will not drop too much. Further, if the bulk density of the central portion of the porous silica plate is 1.90 g / cm 3 or less, the fusion between the polycrystalline silicon ingot produced in the square silica container and the silica container becomes weak, and the container Since the strength is appropriately reduced, the releasability is further improved.
  • the bulk density of the central part thickness of 3 mm of the porous silica plate is 1.60 to 1.90 g / cm 3 (that is, the lower limit is 1. in the part of the porous silica plate having the central part thickness of 3 mm). 60 g / cm 3 or more, it is preferable that the upper limit of the bulk density and 1.90 g / cm 3 or less), more preferably in the range of 1.70 ⁇ 1.85g / cm 3.
  • the square silica container 10 has an Al concentration (Al element concentration) of 3 to 500 wt. ppm, and the OH group concentration is 5 to 500 wt. Preference is given to ppm.
  • the rectangular silica container 10 preferably contains an OH group simultaneously with the Al element.
  • the Al concentration is 10 to 100 wt. More preferably, the OH group concentration is 30 to 300 wt. More preferably, it is ppm.
  • Al and OH groups are converted when impurity metal elements in the porous silica plate, especially when the carrier lifetime of polycrystalline silicon under light irradiation is reduced or when a polycrystalline silicon ingot is used as a solar cell material. It prevents migration and diffusion in the silica of alkali metal elements such as Li, Na and K which are considered to reduce the efficiency and transition metal elements such as Ti, Cr, Fe, Ni, Cu, Zn, Mo and Au.
  • alkali metal elements such as Li, Na and K which are considered to reduce the efficiency and transition metal elements such as Ti, Cr, Fe, Ni, Cu, Zn, Mo and Au.
  • the details of the mechanism are unknown, but by replacing the Al atom with the Si atom, the cation (cation) of the impurity metal element is incorporated from the difference in coordination number, and the charge balance in the silica glass network is maintained. Therefore, it is presumed to prevent adsorption and diffusion.
  • the OH group has an effect of adsorbing or preventing diffusion of these
  • the Al concentration is 3 wt. If it is ppm or more, a sufficient impurity contamination preventing effect is recognized. On the other hand, the Al concentration is 500 wt. If it is less than or equal to ppm, contamination of the polycrystalline silicon ingot to be produced by Al or Al 2 O 3 itself can be suppressed.
  • OH group concentration is 5 wt. If it is ppm or more, a sufficient impurity contamination preventing effect is recognized. On the other hand, the OH group concentration is 500 wt. If it is ppm or less, the viscosity of the porous silica plate at a high temperature will not be excessively lowered.
  • the OH group serves as a silica glass network structure of Si and O, that is, a terminal portion (network terminator) of the glass network. For this reason, it is considered that the inclusion of a high concentration of OH groups tends to cause deformation of the porous silica plate at a high temperature.
  • the purity of the silica powder which is the raw material for the porous silica plate constituting the rectangular silica container 10
  • the purity of the silica raw material powder is 99.99 wt. %
  • the concentration of each of Li, Na, and K is 1 to 100 wt.
  • the polycrystalline silicon ingot is produced with the rectangular silica container of the present invention with sufficient prevention of process contamination. It becomes possible to do. In this way, if the polycrystalline silicon ingot is sufficiently prevented from being contaminated with a process, when a solar power generation device (solar cell) is manufactured, its photoelectric conversion efficiency can be significantly increased.
  • a solar power generation device solar cell
  • silica powder is produced as raw material powder.
  • High-purity silica raw material powder high-purity quartz powder, high-purity natural quartz powder, ultra-high-purity synthetic silica glass powder
  • Silica (SiO 2 ) purity is 99.9 to 99.999 wt. % Of relatively low purity silica raw material powder is preferably used.
  • the silica raw material powder it is preferable to use low-cost crystalline natural quartz powder, but it is not necessarily limited to the case where only crystalline natural quartz powder is used.
  • crystalline natural quartz powder may be used as the main raw material (for example, 50% or more by weight), and amorphous silica powder (fused natural quartz glass powder, synthetic silica glass powder) or the like may be mixed to obtain the raw material powder.
  • the particle size of the silica raw material powder is preferably a raw material powder having a relatively large particle size of, for example, a particle size of 0.01 to 3 mm (more preferably 0.1 to 1 mm). It is not limited to.
  • a raw material powder having a relatively large particle diameter of 0.01 to 3 mm mixed with a highly active synthetic silica glass powder having a particle diameter of about 0.1 to 10 ⁇ m or more, or more Various types of silica powder may be mixed to form a raw material powder.
  • amorphous fused natural quartz glass powder, synthetic silica glass powder or the like may be used instead of crystalline silica powder as raw material powder.
  • the particle size is preferably a relatively large particle size of 0.01 to 3 mm as described above, and more preferably 0.1 to 1 mm.
  • the purity of silica (SiO 2 ) of the raw material powder is 99.9 wt. % Or more, preferably 99.99 wt. % Or more is more preferable.
  • the concentration of each of Li, Na, and K is set to 100 wt. ppm or less, and the concentration of each of Ti, Cr, Fe, Ni, Cu, Zn, Mo, Au is 5.0 wt. It is preferable to set it as ppm or less.
  • flour is 99.999 wt.
  • the manufactured rectangular silica container can sufficiently prevent impurity contamination of the silicon melt and polycrystalline silicon ingot. Therefore, a rectangular silica container for producing a polycrystalline silicon ingot can be produced at a lower cost than before.
  • the production of a relatively large particle diameter raw material having a particle diameter of 0.01 to 3 mm can be made, for example, by pulverizing and sizing a quartzite lump as follows, but is not limited thereto.
  • a natural quartzite block naturally produced crystal, quartz, quartzite, siliceous rock, opal stone, etc.
  • the natural silica mass is put into water, taken out after rapid cooling, and dried. This process facilitates the subsequent crushing and sizing process using a crusher or the like, but the process may proceed to the crushing process without performing the heating and quenching process.
  • the natural silica mass is pulverized and sized with a crusher or the like, and the particle size is adjusted to, for example, 0.03 to 3 mm, preferably 0.1 to 1 mm to obtain natural silica powder.
  • this natural silica powder is put into a rotary kiln composed of a silica glass tube having an inclination angle, and the inside of the kiln is made into an atmosphere containing hydrogen chloride (HCl) or chlorine (Cl 2 ) gas at 700 to 1100 ° C.
  • the high-purity treatment is performed by heating for about 1 to 100 hours.
  • the process may proceed to the next process without performing this high-purification process.
  • the raw material powder obtained after the above steps is crystalline silica powder. From the viewpoint of cost, it is preferable to use such natural crystalline silica powder as the main raw material powder.
  • the porous silica plate in order to improve the heat-resistant deformation property of the porous silica plate, it is preferable to contain Al (Al element) in the raw material powder.
  • the method of adding Al to the raw material powder is not particularly limited.
  • metal Al or a salt thereof (aluminum nitrate, aluminum carbonate, aluminum chloride, etc.) is directly mixed into the raw material powder, or dissolved and mixed in water or alcohol. Later, it can be mixed into the raw material powder.
  • the amount of Al to be added is such that the Al concentration of the porous silica plate to be produced is 3 to 500 wt. It is preferable to make it ppm, 10 to 100 wt. It is more preferable to adjust to ppm.
  • FIGS. 7 is a cross-sectional view when viewed from a direction perpendicular to FIG.
  • This electric heating furnace 200 has a raw material powder supply port 203, a melting container for charging and melting and softening the raw material powder (preferably, but not limited to, a high melting point metal crucible such as molybdenum or tungsten) 208, melting Heating means 207 for heating the container 208 (electric resistance heating, high-frequency induction heating, etc.
  • a melting container for charging and melting and softening the raw material powder preferably, but not limited to, a high melting point metal crucible such as molybdenum or tungsten
  • melting Heating means 207 for heating the container 208 (electric resistance heating, high-frequency induction heating, etc.
  • High melting point metal tool is preferred (but not limited to this) 212, atmosphere gas supply in the melting vessel for adjusting the atmosphere gas in the melting vessel 208 Melting vessel outside atmosphere gas supply for adjusting the outside of the atmosphere gas of the melting vessel 208 in the exhaust port 202, an electric furnace, an exhaust port 204, the heating means atmospheric gas supply, consisting like outlet 205.
  • a gap 211 can be formed between the rectifying jig 210 and the shape forming tool 212 as shown in the figure, and the rectifying jig 210 and the shape forming tool 212 can be in close contact with each other.
  • a porous silica plate body take-out chamber 213 is arranged at the lower part of the electric heating furnace, and a porous silica plate body take-out chamber atmosphere gas supply, an exhaust port 214, a porous silica plate body drawing roller 216, and the like are arranged. .
  • the basic structure and operating conditions of this electric heating furnace are shown in documents such as JP-A-1-320234, JP-A-2-296740, and JP-A-6-24785.
  • conventional electric furnaces such as those described in these documents are designed to produce transparent rod-like or tubular silica glass that does not contain bubbles, and parallel that contains bubbles as in the present invention.
  • This is different from an electric heating furnace structure for producing a flat porous silica plate.
  • the first difference is the shape of the electric heating furnace and the shape of the melting vessel.
  • the electric heating furnace that can be used in the present invention preferably has a substantially cylindrical shape or a substantially elliptical cylinder shape together with the melting vessel 208 in order to produce a parallel flat plate-like porous silica plate.
  • the second difference is the type and pressure of the atmospheric gas when heating the silica raw material powder.
  • an inert gas containing any one or more of nitrogen, neon, argon, and krypton is set to a pressure equal to or higher than atmospheric pressure in order to contain bubbles in the porous silica plate.
  • These gases are inert gases having a larger molecular radius than hydrogen or helium.
  • the third difference is the shape of the shape forming tool for forming the fused silica body.
  • the shape of the opening of the shape forming tool 212 is substantially rectangular (see the shape forming tool 212 in FIGS. 6 and 7).
  • the porous silica plate of the present invention is produced using the electric heating furnace shown in FIGS. Specifically, it is performed as follows.
  • (A) Atmospheric gas adjustment in melting container First, the inside of the melting container 208 disposed in the electric heating furnace is replaced with an inert gas atmosphere containing at least one of nitrogen, neon, argon, and krypton. Nitrogen gas is 80 vol. % Or more is preferable. In order to extend the life of the container under high temperature, hydrogen gas is added at 1 to 4 vol. % May be used in combination.
  • Atmospheric gas adjustment in the electric heating furnace (outside of the melting vessel)
  • the outside of the melting vessel 208 is also preferably replaced with an inert gas such as nitrogen, neon, argon, or krypton.
  • Nitrogen gas is 80 vol. % Or more is preferable.
  • hydrogen gas is added at 1 to 4 vol. % May be used in combination.
  • the raw material powder is supplied into melting container 208 while maintaining the inside of melting container 208 in the above inert gas atmosphere.
  • the raw material powder 206 adjusted to have a predetermined particle size and a predetermined purity as described above can be supplied from the raw material powder supply port 203 arranged in the upper part of the electric heating furnace in FIGS.
  • the raw material powder is heated by heating the temperature of the melting vessel 208 to 1700 ° C. or higher while maintaining the pressure of the inert gas atmosphere in the melting vessel 208 at atmospheric pressure or higher.
  • 206 is melted and softened.
  • the temperature range is set to 1700 ° C. to 2300 ° C., although it varies slightly depending on the heating means 207 by the electric resistance heating method or the high frequency induction heating method, and the structure of the raw material powder, for example, crystalline silica or amorphous silica.
  • the temperature is preferably 1800 ° C. to 2100 ° C.
  • the rectifying jig 210 When the raw material powder 206 is sufficiently heated and softened to become a silica glass body containing bubbles, the rectifying jig 210 is pulled up. At this time, by controlling the size of the gap 211 between the rectifying jig 210 and the shape forming tool 212 and the gas pressure in the melting vessel 208, the parallel-plate-shaped porous silica plate 215 having a predetermined size is made to be a porous silica plate. The body can be pulled out in the body pulling direction 217.
  • the dimensional accuracy of the porous silica plate is controlled by controlling the temperature of the melting vessel, the atmospheric gas pressure, the size of the gap 211 between the rectifying jig 210 and the shape forming tool 212, the drawing speed of the porous silica plate 215, and the like. Can be increased.
  • the cross-sectional dimensions of the porous silica plate 215 drawn out continuously can be, for example, a width of 100 to 1000 mm and a thickness of 10 to 30 mm.
  • the bulk density of the porous silica plate 215 can be made lower in the inner portion than the surface portions of both parallel planes. That is, when the porous silica plate 215 is pulled out from the lower part of the melting vessel 208 through the shape forming tool 212, the temperature of the surface portion is higher than the inside of the porous silica plate and softens as silica glass (viscosity decreases). ), And the bubble content in the surface portion is relatively reduced. Further, while cooling, due to outward diffusion of bubbles, bubbles are reduced near the surface of the porous silica plate 215, while bubbles are hardly reduced at the inner portion. The internal bulk density can be relatively low.
  • the bulk density (g / cm 3 ) of the porous silica plate 215 can be controlled to a predetermined value by adjusting the particle size of the raw material powder, the type of gas in the melting vessel 208, the pressure, and the like.
  • a mold release accelerator can be contained by applying (coating) at least part of the surface of the porous silica plate thus obtained. If the release accelerator is a water-soluble substance, an aqueous solution of the release accelerator can be contained on the surface of the porous silica plate by spray coating or the like and then dried, etc., and the release accelerator is insoluble If it is a substance, it can be contained by mixing fine particles of a release accelerator with a solvent, spray-coating the surface in the same manner, and drying.
  • an alkaline earth metal element such as Ca, Sr, or Ba
  • at least one compound mixed solution of Ca, Sr, and Ba is added to at least a part of the porous silica plate.
  • a coating process is performed by applying and drying on the surface by a spray method, an air brush method, or the like.
  • the coating concentration, Ca, Sr preferably to 50 ⁇ 5000 ⁇ g / cm 2 as an alkaline earth metal element sum of such Ba, and even more preferably from 100 ⁇ 1000 ⁇ g / cm 2.
  • the release accelerator when contained in the surface portion of the porous silica plate by the above-described application, it is preferably performed after combining the porous silica plates to form a square silica container.
  • the OH group concentration contained in the porous silica plate can be adjusted by selecting the type of raw material powder, changing the raw material powder drying process, and the atmosphere, temperature, and time conditions of the melting process. As a result, 5 to 500 wt. It is preferable that it be contained at a concentration of ppm, 30 to 300 wt. More preferably, it is in the range of ppm.
  • the parallel flat porous silica plates manufactured as described above are combined in a susceptor 80 made of carbon to form a square silica container 10.
  • a susceptor 80 made of carbon When the whole is heated in such an arrangement, the porous silica plates are welded together, and the square silica container 10 can be easily integrated.
  • porous silica plates may be joined to each other by using a SiO 2 -containing joined body as described in JP-A-2008-511527 alone or supplementarily.
  • silica powder is produced as raw material powder.
  • two types of raw material powders having different average particle diameters are prepared.
  • silica powder having a particle size of 0.003 to 3.0 mm is prepared. This is 99 wt.% In the particle size range of 0.003 to 3.0 mm in the silica powder of the first raw material powder. % Of silica powder is included.
  • a silica powder having an average particle size compared with the particle size value (D 50 ) at 50% of the mass-based cumulative distribution is smaller than that of the first raw material powder.
  • the particle size value (D 50 ) at 50% of the mass-based cumulative distribution (also referred to herein simply as “average particle size”) is determined by particle size distribution measurement.
  • the particle size distribution measurement is performed, for example, by a screening method or a laser diffraction / scattering method according to JIS R 1639-1 (fine ceramics—or (condylar) particle property measurement method—Part 1: particle size distribution). .
  • the first raw material powder can have a particle size range of 0.1 to 3.0 mm and an average particle size of 0.2 mm (200 ⁇ m), and the second raw material powder can have a particle size range of 0.1 mm.
  • the average particle size can be set to 01 to 0.3 mm and 0.04 mm (40 ⁇ m).
  • both the silica purity and the impurity concentration of the first raw material powder and the second raw material powder are in the same range as in the first aspect described above.
  • the method for producing the first raw material powder and the second raw material powder can be produced, for example, by pulverizing and sizing a silica stone lump, as in the first embodiment, but is not limited thereto. Further, in order to improve the heat distortion resistance of the porous silica plate, it is preferable that Al (Al element) is contained in the first raw material powder and the second raw material powder as in the first embodiment. .
  • the release accelerator since the release accelerator is contained in the porous silica plate after production, the release accelerator can be added (doping) to the second raw material powder.
  • the concentration of the release accelerator can be controlled by the amount added to the raw material powder.
  • concentration of the mold release accelerator for example, when an alkaline earth metal element such as Ca, Sr, Ba or the like is used as the mold release accelerator, each element is formed at a depth of 2 mm from the inner surface of the porous silica substrate. 50 to 5000 wt. ppm is preferable, and 100 to 1000 wt. More preferably, it is ppm.
  • FIGS. 9 A schematic cross-sectional view of the electric heating furnace is shown in FIGS.
  • FIG. 9 is a cross-sectional view when viewed from a direction perpendicular to FIG.
  • the electric heating furnace 300 needs to have a structure necessary for setting the supply positions of the first raw material powder and the second raw material powder to predetermined positions when the raw material powder is supplied into the melting container. There is.
  • This electric heating furnace is provided with a first raw material powder supply port 303a, a second raw material powder supply port 303b, a melting vessel for melting and softening both raw material powders (high melting point metal such as molybdenum and tungsten).
  • a melting vessel for melting and softening both raw material powders high melting point metal such as molybdenum and tungsten.
  • Crucible is preferable, but is not limited to this.
  • heating means for heating the melting vessel 308 electric resistance heating, high-frequency induction heating, etc.
  • a heat insulating material 309 that blocks the release of heat a shape forming tool of a fused silica body (a high melting point metal tool such as molybdenum and tungsten is preferred, but not limited to this)
  • the atmosphere gas outside the melting container for adjusting the atmosphere gas outside the melting container 308 among the atmosphere gas supply inside the melting container, the exhaust port 302, and the electric heating furnace.
  • Supply consisting of the exhaust port 305 and the like.
  • the second raw material powder supply port 303b is configured to surround the first raw material powder supply port 303a.
  • FIGS. 8 and 9 show a case where the rectifying jig illustrated in FIGS. 6 and 7 is not provided.
  • a rectifying jig for adjusting the flow of the fused silica body in which the raw material powder is heated, melted and softened may be provided, but may not be provided as shown in FIGS.
  • the shape of the opening of the shape forming tool 312 is substantially rectangular.
  • An opening / closing plate 322 at the bottom of the melting vessel that can move in the direction of the arrow 323 is provided below the shape forming tool 312.
  • a porous silica plate body take-out chamber 313 is arranged, and a porous silica plate body take-out chamber atmosphere gas supply, an exhaust port 314, a porous silica plate body drawing roller 316 and the like are arranged. Yes.
  • the porous silica plate of the present invention is produced using the electric heating furnace shown in FIGS. Specifically, it is performed as follows.
  • (A) Atmospheric gas adjustment in melting container First, the inside of the melting container 308 disposed in the electric heating furnace is replaced with an inert gas atmosphere containing at least one of nitrogen, neon, argon, and krypton. Nitrogen gas is 80 vol. % Or more is preferable. In order to extend the life of the container under high temperature, hydrogen gas is added at 1 to 4 vol. % May be used in combination.
  • the outside of the melting vessel 308 is also preferably replaced with an inert gas such as nitrogen, neon, argon, krypton, etc. .
  • Nitrogen gas is 80 vol. % Or more is preferable.
  • hydrogen gas is added at 1 to 4 vol. % May be used in combination.
  • Such raw material powder is supplied from the first raw material powder supply port 303a and the second raw material powder supply port 303b arranged in the upper part of the electric heating furnace 300 shown in FIGS. It can be carried out by supplying the first raw material powder 306a and the second raw material powder 306b, which are adjusted to have a predetermined particle size range and average particle size, and a predetermined purity, respectively.
  • the temperature of the melting vessel 308 is heated to 1700 ° C. or higher while maintaining the pressure of the inert gas atmosphere in the melting vessel 308 at atmospheric pressure or higher.
  • the raw material powder 306a and the second raw material powder 306b are melted and softened. Thereby, raw material powder turns into fused silica glass bodies 321a and 321b.
  • the silica glass body 321a on the center side in the melting vessel 308 has a lot of silica components derived from the first raw material powder 306a having a relatively coarse particle size, and the silica glass body 321b on the peripheral side in the melting vessel 308 has a particle size.
  • the silica component derived from the relatively fine second raw material powder 306b increases.
  • the second raw material powder contains a release accelerator
  • the peripheral silica glass body in the melting vessel 308 is used. 321b comes to contain a lot of mold release accelerator.
  • the parallel-plate-shaped porous silica plate 315 having a predetermined size is taken out. It becomes possible.
  • the dimensional accuracy of the porous silica plate 315 controls the temperature of the melting vessel 308, the atmospheric gas pressure, the position adjustment of the opening / closing plate 322, the gap size of the shape forming tool 312, the drawing speed of the porous silica plate 315, and the like. Can be increased.
  • the bulk density (g / cm 3 ) of the porous silica plate 315 is determined based on the average particle size, particle size range, and particle size distribution setting of the first raw material powder and the second raw material powder, and the gas in the melting vessel 308. It can be controlled to a predetermined value by adjusting the type, gas pressure and the like.
  • the bulk density of the porous silica plate 315 can be made lower in the inner part than the surface parts of both parallel planes.
  • the difference in density between the surface portion of both parallel planes of the porous silica plate 315 and the inner portion can be easily increased.
  • the difference in bulk density between the surface portion and the central portion can be more easily realized to be 0.1 g / cm 3 or more.
  • the bulk density of the porous silica plate is preferably 1.60 to 2.10 g / cm 3 as described above, but may be 1.40 to 2.20 g / cm 3 in some cases. You can also.
  • Such a porous silica plate can be more easily realized according to the second aspect using the raw material powder having two kinds of average particle diameters.
  • the silica glass body 321b on the peripheral side in the melting vessel 308 contains a lot of the release accelerator, so that the extracted porous silica A mold release accelerator can be contained outside the plate body 315, that is, on the surface side.
  • a parallel flat plate-like porous silica plate body 315 continuously manufactured from the lower part of the electric heating furnace is provided. Cut when a predetermined length is reached. Then, if necessary, the end of the porous silica plate is cut, ground, and polished to obtain a porous silica plate having a shape and a size that can be used for the assembled square silica container for producing a polycrystalline silicon ingot.
  • a release accelerator can be contained by applying (coating) at least a part of the surface to the porous silica plate thus obtained.
  • the release accelerator may be added to the second raw material powder and applied to the surface of the porous silica plate, or only one method may be used.
  • molten silicon as a raw material is put into a rectangular silica container according to the present invention.
  • the molten silicon is heated and kept at a predetermined temperature.
  • the polycrystalline silicon ingot is taken out from the rectangular silica container.
  • the strength of the container is set to be moderately low, and the polycrystalline silicon ingot is easily taken out by making it easy to break, and the polycrystalline silicon ingot is prevented from being damaged. be able to.
  • the presence of the mold release accelerator makes it possible to more effectively take out the polycrystalline silicon ingot from the rectangular silica container and prevent the polycrystalline silicon ingot from being damaged.
  • the taken polycrystalline silicon ingot is sliced to a predetermined thickness and polished to obtain a polycrystalline silicon substrate.
  • Example 1 In accordance with the method for producing a porous silica plate according to the present invention (first aspect), a porous silica plate was produced as follows, and a rectangular silica container was further produced.
  • the raw material powder was produced as follows. 50 kg of natural silica was prepared, heated in an air atmosphere at 1000 ° C. for 10 hours, put into a water tank containing pure water, and rapidly cooled. This was dried and pulverized using a crusher to obtain a particle size of 100 to 1000 ⁇ m and a silica purity of 99.99 wt. % And a total weight of 40 kg of silica powder (natural quartz powder).
  • a porous silica plate was produced by an electric heating furnace (high frequency induction heating) shown in FIGS.
  • the atmosphere gas was a nitrogen atmosphere containing 3% hydrogen (nitrogen 97%).
  • the dimensions of the porous silica plate were 250 mm long ⁇ 390 mm wide ⁇ 10 mm thick (for the side), 400 mm long ⁇ 400 mm wide ⁇ 10 mm thick (for the bottom portion). It was made to become.
  • the peripheral portion of the parallel flat plate-like porous silica plate produced in this way was processed, and five pieces were combined as shown in FIG.
  • the dimension of the square silica container after the combination was 400 ⁇ 400 ⁇ height 260 mm.
  • Example 2 A porous silica plate was produced in substantially the same manner as in Example 1, and a square silica container was further produced. However, the following conditions were changed. The particle size of the raw material powder was increased to 200 to 2000 ⁇ m. Thereby, air bubbles easily entered the porous silica plate and the bulk density was lowered. Moreover, the Al concentration contained in the raw material powder was 10 times.
  • Example 3 A porous silica plate was produced in substantially the same manner as in Example 2, and a square silica container was further produced. However, the following conditions were changed. The particle size of the raw material powder was further increased to 300 to 3000 ⁇ m. Thereby, air bubbles easily entered the porous silica plate and the bulk density was lowered.
  • Example 4 A porous silica plate was produced in substantially the same manner as in Example 2, and a square silica container was further produced. However, the following conditions were changed. The silica purity of the raw material powder is made high, and 99.999 wt. %. Moreover, Al was not added to the raw material powder.
  • Example 5 A porous silica plate was produced in substantially the same manner as in Example 2, and a square silica container was further produced. However, the following conditions were changed. The silica purity of the raw material powder is reduced to 99.9 wt. %. Moreover, the Al concentration contained in the raw material powder was 5 times (50 times that of Example 1).
  • Example 6 A porous silica plate was produced in substantially the same manner as in Example 2, and a square silica container was further produced. However, the molten gas atmosphere of the raw material powder was an Ar 100% atmosphere.
  • Example 7 In accordance with the method for producing a porous silica plate according to the present invention (second embodiment), a porous silica plate was produced as follows, and a rectangular silica container was further produced.
  • a first raw material powder was produced. 50 kg of natural silica was prepared, heated in an air atmosphere at 1000 ° C. for 10 hours, put into a water tank containing pure water, and rapidly cooled. This was dried and pulverized using a crusher to obtain a particle size range of 100 to 1000 ⁇ m and a silica purity of 99.99 wt. % And a total weight of 40 kg of silica powder (natural quartz powder). The average particle size (particle size value at 50% of the mass-based cumulative distribution, D 50 ) was 530 ⁇ m. The second raw material powder was prepared by the same process as the first raw material powder, but the particle size range was 10 to 500 ⁇ m and the average particle size was 100 ⁇ m.
  • a porous silica plate was produced by an electric heating furnace (high frequency induction heating) shown in FIGS.
  • the atmosphere gas was a nitrogen atmosphere containing 3% hydrogen (nitrogen 97%).
  • the dimensions of the porous silica plate were 200 mm long x 400 mm wide x 10 mm thick.
  • the peripheral portion of the parallel flat plate-like porous silica plate produced in this way was processed, and 10 pieces were combined into a square silica container 10 as shown in FIG.
  • the dimension of the square silica container after the combination was 400 ⁇ 400 ⁇ height 400 mm.
  • Example 8 A porous silica plate was produced in substantially the same manner as in Example 7, and a square silica container was further produced. However, the following conditions were changed.
  • the particle sizes of the first raw material powder and the second raw material powder were coarsened. Specifically, the first raw material powder has a particle size range of 200 to 2000 ⁇ m and an average particle size of 700 ⁇ m, and the second raw material powder has a particle size range of 10 to 600 ⁇ m and an average particle size of 150 ⁇ m.
  • the Al concentration contained in the first raw material powder and the second raw material powder was 10 times.
  • Example 9 As in Example 8, except that the first raw material powder and the second raw material powder are further coarsened (the first raw material powder has a particle size range of 300 to 3000 ⁇ m, an average particle size of 910 ⁇ m, The particle size range was 10 to 700 ⁇ m and the average particle size was 220 ⁇ m.), A porous silica plate was manufactured, and a square silica container was further manufactured.
  • Example 10 A porous silica plate was produced by substantially the same process as in Example 8, and a square silica container was further produced. However, the following conditions were changed. The silica purity of the first raw material powder and the second raw material powder is 99.999 wt. %. Moreover, the process which contains Al in the 1st raw material powder and the 2nd raw material powder was not performed.
  • Example 11 A porous silica plate was produced by substantially the same process as in Example 7, and a square silica container was further produced. However, the following conditions were changed.
  • the silica purity of the first raw material powder was set to low purity (99.9 wt.%), And the particle size was coarsened (particle size range 200 to 2000 ⁇ m, average particle size 680 ⁇ m).
  • the second raw material powder was the same as in Example 7.
  • the silica purity was low, the Al concentration contained in the first raw material powder and the second raw material powder was about 30 times that in Example 7.
  • Example 1 Comparative Example 1 Compared with Example 1, the following conditions were changed, a silica plate was manufactured, and a square silica container was further manufactured.
  • the raw material powder was highly purified (silica purity 99.9999 wt.%), And the particle size was adjusted to 50 to 500 ⁇ m.
  • the molten gas atmosphere was 80% H 2 and 20% He. Thereby, there were almost no air bubbles in the porous silica plate, and the silica plate was transparent. Moreover, Al was not added to the raw material powder.
  • Comparative Example 2 (Comparative Example 2) Compared to Comparative Example 1, the following conditions were changed to produce a silica plate, and a square silica container was further produced.
  • the silica purity of the raw material powder was 99.99 wt. %.
  • Example 12 In accordance with the method for producing a porous silica plate according to the present invention (first aspect), a porous silica plate was produced as follows, and a rectangular silica container was further produced.
  • the raw material powder was produced as follows. 50 kg of natural silica was prepared, heated in an air atmosphere at 1000 ° C. for 10 hours, put into a water tank containing pure water, and rapidly cooled. This was dried and pulverized using a crusher to obtain a particle size of 100 to 1000 ⁇ m and a silica purity of 99.99 wt. % And a total weight of 40 kg of silica powder (natural quartz powder).
  • a porous silica plate was produced by an electric heating furnace (high frequency induction heating) shown in FIGS.
  • the atmosphere gas was a nitrogen atmosphere containing 3% hydrogen (nitrogen 97%).
  • the dimensions of the porous silica plate were 200 mm long x 400 mm wide x 10 mm thick.
  • the peripheral portion of the parallel flat plate-like porous silica plate produced in this way was processed, and 10 pieces were combined into a square silica container 10 as shown in FIG.
  • the dimensions of the square silica container after the combination were 400 ⁇ 400 ⁇ 400 mm in height.
  • a barium chloride aqueous solution was applied to the entire inner surface portion of the square silica container by a spray method and dried.
  • Example 13 A porous silica plate was produced in substantially the same manner as in Example 12, and a square silica container was further produced. However, the following conditions were changed. The particle size of the raw material powder was increased to 200 to 2000 ⁇ m. Thereby, air bubbles easily entered the porous silica plate and the bulk density was lowered. Moreover, the Al concentration contained in the raw material powder was 10 times.
  • Example 14 A porous silica plate was produced in substantially the same manner as in Example 13, and a square silica container was further produced. However, the following conditions were changed. The particle size of the raw material powder was further increased to 300 to 3000 ⁇ m. Thereby, air bubbles easily entered the porous silica plate and the bulk density was lowered.
  • Example 15 A porous silica plate was produced in substantially the same manner as in Example 13, and a square silica container was further produced. However, the following conditions were changed. The silica purity of the raw material powder is made high, and 99.999 wt. %. Moreover, Al was not added to the raw material powder.
  • Example 16 A porous silica plate was produced in substantially the same manner as in Example 13, and a square silica container was further produced. However, the following conditions were changed. The silica purity of the raw material powder is reduced to 99.9 wt. %. The Al concentration contained in the raw material powder was 5 times (50 times that of Example 12).
  • Example 17 A porous silica plate was produced in substantially the same manner as in Example 13, and a square silica container was further produced. However, the molten gas atmosphere of the raw material powder was an Ar 100% atmosphere.
  • Example 18 In accordance with the method for producing a porous silica plate according to the present invention (second embodiment), a porous silica plate was produced as follows, and a rectangular silica container was further produced.
  • a first raw material powder was produced. 50 kg of natural silica was prepared, heated in an air atmosphere at 1000 ° C. for 10 hours, put into a water tank containing pure water, and rapidly cooled. This was dried and pulverized using a crusher to obtain a particle size range of 100 to 1000 ⁇ m and a silica purity of 99.99 wt. % And a total weight of 40 kg of silica powder (natural quartz powder). The average particle size (particle size value at 50% of the mass-based cumulative distribution, D 50 ) of this first raw material powder was 530 ⁇ m. The second raw material powder was prepared by the same process as the first raw material powder, but the particle size range was 10 to 500 ⁇ m and the average particle size was 100 ⁇ m.
  • aluminum nitrate was added as an aqueous solution to the first raw material powder, and aluminum nitrate and barium nitrate were added as an aqueous solution to the second raw material powder and dried.
  • a porous silica plate was produced by an electric heating furnace (high frequency induction heating) shown in FIGS.
  • the atmosphere gas was a nitrogen atmosphere containing 3% hydrogen (nitrogen 97%).
  • the dimensions of the porous silica plate were 200 mm long x 400 mm wide x 10 mm thick.
  • the peripheral portion of the parallel flat plate-like porous silica plate produced in this way was processed, and 10 pieces were combined into a square silica container 10 as shown in FIG.
  • the dimensions of the square silica container after the combination were 400 ⁇ 400 ⁇ 400 mm in height.
  • the mold release accelerator was not applied to the inner surface portion of the square silica container.
  • Example 19 A porous silica plate was produced in substantially the same manner as in Example 18, and a square silica container was further produced. However, the following conditions were changed.
  • the particle sizes of the first raw material powder and the second raw material powder were coarsened. Specifically, the first raw material powder has a particle size range of 200 to 2000 ⁇ m and an average particle size of 700 ⁇ m, and the second raw material powder has a particle size range of 10 to 600 ⁇ m and an average particle size of 150 ⁇ m.
  • the Al concentration contained in the first raw material powder and the second raw material powder was 10 times.
  • the Ba concentration contained in the second raw material powder was also 10 times.
  • Example 20 As in Example 19, except that the first raw material powder and the second raw material powder are further coarsened (the first raw material powder has a particle size range of 300 to 3000 ⁇ m, an average particle size of 910 ⁇ m, The particle size range was 10 to 700 ⁇ m and the average particle size was 220 ⁇ m.), A porous silica plate was manufactured, and a square silica container was further manufactured.
  • Example 21 A porous silica plate was produced by substantially the same process as in Example 19, and a square silica container was further produced. However, the following conditions were changed.
  • the silica purity of the first raw material powder and the second raw material powder is 99.999 wt. %.
  • Al was not contained in the first raw material powder and the second raw material powder.
  • Ba was contained in the second raw material powder.
  • Example 22 A porous silica plate was produced by substantially the same process as in Example 19, and a square silica container was further produced. However, the following conditions were changed.
  • the silica purity of the first raw material powder was set to low purity (99.9 wt.%), And the particle size was coarsened (particle size range 200 to 2000 ⁇ m, average particle size 680 ⁇ m).
  • the Al concentration contained in the first raw material powder and the second raw material powder was about three times that in Example 19.
  • Example 23 In accordance with substantially the same process as in Example 19, a porous silica plate was produced as follows, and a rectangular silica container was further produced.
  • the aluminum nitrate was added to the first raw material powder as an aqueous solution and dried to contain Al. Moreover, aluminum nitrate and barium nitrate were added to the second raw material powder as an aqueous solution and dried to contain Al and Ba.
  • a porous silica plate was produced by an electric heating furnace (high frequency induction heating) shown in FIGS.
  • the atmosphere gas was an Ar atmosphere (Ar 99%) containing 1% hydrogen.
  • the dimensions of the porous silica plate were 200 mm long x 400 mm wide x 10 mm thick.
  • the peripheral portion of the parallel flat plate-like porous silica plate produced in this way was processed, and 10 pieces were combined into a square silica container 10 as shown in FIG.
  • the dimension of the square silica container after the combination was 400 ⁇ 400 ⁇ height 400 mm.
  • the aqueous solution containing Ba was not applied to the inner surface of the square silica container.
  • Example 3 (Comparative Example 3) Compared with Example 12, the following conditions were changed, a silica plate was produced, and a square silica container was further produced.
  • the raw material powder was highly purified (silica purity 99.9999 wt.%), And the particle size was adjusted to 50 to 500 ⁇ m.
  • the molten gas atmosphere was 80% H 2 and 20% He. Thereby, there were almost no air bubbles in the porous silica plate, and the silica plate was transparent. Moreover, Al was not added to the raw material powder.
  • Comparative Example 4 Compared to Comparative Example 3, the following conditions were changed to produce a silica plate, and a square silica container was further produced.
  • the silica purity of the raw material powder was 99.99 wt. %.
  • Measurement of particle size range of each raw material powder Two-dimensional shape observation and area measurement of each raw material powder were performed with an optical microscope or an electron microscope. Next, assuming that the shape of the particle is a perfect circle, the diameter was calculated from the area value. This method was repeated statistically to obtain a value within the range of the particle size (in this range, 99 wt.% Or more of the raw material powder was included).
  • Average particle size measurement of each raw material powder Using a plurality of powder sieves, particle size distribution was measured according to a screening method (JIS R 1639-1). As a sieve, a standard sieve of JIS Z 8801 was used. In addition to the above sieving method, the particle size distribution was measured according to a laser diffraction and scattering method (also JIS R 1639-1). From these two types of data, the correlation between the particle diameter ( ⁇ m) and the mass-based cumulative distribution (wt.%) was determined. Finally, 50 wt. The particle diameter (D 50 ) in% cumulative mass value was shown as the average particle diameter.
  • Metal element concentration analysis In the concentration analysis other than barium used as a mold release accelerator, a sample was prepared by cutting out a sample piece from the center of the thickness of the porous silica plate and dissolving it in an aqueous hydrofluoric acid solution. . In the barium concentration analysis, a plurality of 20 mm ⁇ 20 mm ⁇ 2 mm samples were cut out from the inner surface layer portion of the square silica container to obtain a silica sample piece for analysis.
  • ICP-AES Inductively Coupled Plasma-Atomic Emission Spectroscopy
  • ICP-MS Inductively Coupled Plasma-Plasma
  • AS Atomic Absorption Spectroscopy
  • OH group concentration measurement A powdery sample having a particle size of 10 to 100 ⁇ m was prepared from the central portion of the thickness of the silica plate, and was performed by infrared diffuse reflection spectrophotometry. Conversion to the OH group concentration follows the literature below. Dodd, D.D. M.M. and Fraser, D.A. B. (1966) Optical determination of OH in fused silica. Journal of Applied Physics, vol. 37, P.I. 3911.
  • Anti-diffusion effect from rectangular silica container to polycrystalline silicon ingot Si purity 99.99999999 wt. %
  • High-purity silicon melt was charged and cooled to room temperature to prepare a polycrystalline silicon ingot having dimensions of 380 mm ⁇ 380 mm ⁇ 240 mm.
  • a silicon piece was sampled at a depth of 3 mm from the surface of the ingot, and this was treated with an acidic solution to obtain a solution sample, and then analyzed for Na concentration by ICP-AES.
  • the effect of preventing impurity diffusion from the rectangular silica container to the polycrystalline silicon ingot was evaluated by the Na concentration value.
  • High impurity diffusion prevention effect ⁇ (Na concentration is less than 10wt.ppb) During impurity diffusion prevention effect ⁇ (Na concentration is 10 wt. Ppb or more and less than 100 wt. Ppb) Small impurity diffusion prevention effect ⁇ (Na concentration is 100wt.ppb or more)
  • a polycrystalline silicon ingot was prepared in the same manner as described above, and then the four side wall corners of the square silica container and the welded portions of the four side walls and the bottom corner were cut with a cutter, and the square shape was cut from the ingot.
  • the four side walls and bottom plate of the silica container were peeled off.
  • the silica pieces adhering to the surface of the polycrystalline ingot were dissolved and removed with an aqueous hydrofluoric acid solution.
  • the releasability was evaluated by measuring the depth of unevenness and cracks remaining on the surface of the ingot from the position in contact with the inner surface of the square silica container to the inner direction with a scale.
  • Moderate releasability ⁇ depth 2mm or more and less than 5mm
  • Good releasability ⁇ depth 5mm or more
  • Manufacturing cost (relative) evaluation The manufacturing cost of the square silica container was examined. For Examples 1 to 11 and Comparative Examples 1 and 2, the reference is Comparative Example 1, and for Examples 12 to 23 and Comparative Examples 3 and 4, the reference is Comparative Example 3, especially the raw material cost and adjustment cost of silica powder, The total cost of the entire manufacturing process such as the melting cost was relatively evaluated. Cost is very low ⁇ (30% or less) Low cost ⁇ (about 30-50%) Medium cost ⁇ (about 50-90%) Cost is high ⁇ (Comparative Example 1 or Comparative Example 3 is 100%)
  • Tables 1 to 10 summarize the production conditions, measured physical property values, and evaluation results of the porous silica plates and square silica containers produced in Examples 1 to 23 and Comparative Examples 1 to 4.
  • the present invention is not limited to the above embodiment.
  • the above embodiment is merely an example, and the present invention has the same configuration as that of the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne un contenant rectangulaire de silice pour fabriquer un lingot de silicium polycristallin par solidification d'une masse fondue de silicium. Le contenant rectangulaire de silice pour la fabrication d'un lingot de silicium polycristallin est configuré par combinaison de plaques de silice poreuse planes et parallèles qui sont formées de silice poreuse. La masse volumique apparente des plaques de silice poreuse est plus faible dans les parties internes que dans les parties de surface des surfaces planes et parallèles. En conséquence, une contamination par des impuretés de la masse fondue de silicium et du lingot de silicium polycristallin est supprimée et un contenant rectangulaire de silice à coût extrêmement faible pour la fabrication d'un lingot de silicium polycristallin ayant une excellente aptitude au démoulage est proposé.
PCT/JP2011/006699 2011-02-01 2011-11-30 Contenant rectangulaire de silice pour la fabrication d'un lingot de silicium polycristallin, plaque de silice poreuse et son procédé de fabrication WO2012104948A1 (fr)

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JP2011019830 2011-02-01
JP2011-019830 2011-02-01
JP2011-049356 2011-03-07
JP2011049356A JP5762777B2 (ja) 2011-02-01 2011-03-07 多結晶シリコンインゴット製造用角形シリカ容器並びに多孔質シリカ板体及びその製造方法
JP2011-067263 2011-03-25
JP2011067263A JP5762784B2 (ja) 2011-03-25 2011-03-25 多結晶シリコンインゴット製造用角形シリカ容器並びに多孔質シリカ板体及びその製造方法

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JP2016034896A (ja) * 2014-08-04 2016-03-17 ヘレーウス クヴァルツグラース ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフトＨｅｒａｅｕｓ Ｑｕａｒｚｇｌａｓ ＧｍｂＨ ＆ Ｃｏ． ＫＧ シリコンブロック、該シリコンブロックを製造する方法、該方法を実施するのに適した透明又は不透明な溶融シリカのルツボ及び該ルツボの製造方法

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JP2005046851A (ja) * 2003-07-29 2005-02-24 Kyocera Corp シリコン鋳造用鋳型およびその製造方法
JP2006273664A (ja) * 2005-03-29 2006-10-12 Kyocera Corp シリコン鋳造用鋳型及びシリコン鋳造装置並びに多結晶シリコンインゴットの鋳造方法

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JP2005046851A (ja) * 2003-07-29 2005-02-24 Kyocera Corp シリコン鋳造用鋳型およびその製造方法
JP2006273664A (ja) * 2005-03-29 2006-10-12 Kyocera Corp シリコン鋳造用鋳型及びシリコン鋳造装置並びに多結晶シリコンインゴットの鋳造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016034896A (ja) * 2014-08-04 2016-03-17 ヘレーウス クヴァルツグラース ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフトＨｅｒａｅｕｓ Ｑｕａｒｚｇｌａｓ ＧｍｂＨ ＆ Ｃｏ． ＫＧ シリコンブロック、該シリコンブロックを製造する方法、該方法を実施するのに適した透明又は不透明な溶融シリカのルツボ及び該ルツボの製造方法
US9828691B2 (en) 2014-08-04 2017-11-28 Heraes Quarzglas GmbH & Co. KG Silicon block, method for producing the same, crucible of transparent or opaque fused silica suited for performing the method, and method for the production thereof

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