WO2011007491A1 - シリカ容器及びその製造方法 - Google Patents

シリカ容器及びその製造方法 Download PDF

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Publication number
WO2011007491A1
WO2011007491A1 PCT/JP2010/003651 JP2010003651W WO2011007491A1 WO 2011007491 A1 WO2011007491 A1 WO 2011007491A1 JP 2010003651 W JP2010003651 W JP 2010003651W WO 2011007491 A1 WO2011007491 A1 WO 2011007491A1
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WIPO (PCT)
Prior art keywords
silica
substrate
container
silica container
gas
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/003651
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English (en)
French (fr)
Japanese (ja)
Inventor
山形茂
笛吹友美
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Quartz Products Co Ltd
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Shin Etsu Quartz Products Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Shin Etsu Quartz Products Co Ltd filed Critical Shin Etsu Quartz Products Co Ltd
Priority to EP10799555A priority Critical patent/EP2455349A1/en
Priority to KR1020117012685A priority patent/KR101268483B1/ko
Priority to US13/123,629 priority patent/US8733127B2/en
Priority to CN201080003082.5A priority patent/CN102197002B/zh
Publication of WO2011007491A1 publication Critical patent/WO2011007491A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/09—Other methods of shaping glass by fusing powdered glass in a shaping mould
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/09—Other methods of shaping glass by fusing powdered glass in a shaping mould
    • C03B19/095—Other methods of shaping glass by fusing powdered glass in a shaping mould by centrifuging, e.g. arc discharge in rotating mould
    • 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
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10—Crucibles or containers for supporting the melt
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the present invention relates to a silica container having silica as a main constituent and a method for producing the same, and more particularly, to a low-cost, high dimensional accuracy, high heat deformation deformable silica container and a method for producing the same.
  • Silica glass is a lens for projection exposure equipment (lithography equipment) for manufacturing large-scale integrated circuits (LSIs), prisms, photomasks and TFT substrates for displays, tubes for ultraviolet or infrared lamps, window materials, reflectors, and cleaning for the semiconductor industry. It is used as a container, a silicon semiconductor melting container, and the like.
  • LSIs large-scale integrated circuits
  • TFT substrates for displays
  • tubes for ultraviolet or infrared lamps tubes for ultraviolet or infrared lamps
  • window materials ultraviolet or infrared lamps
  • reflectors and cleaning for the semiconductor industry.
  • cleaning for the semiconductor industry a container, a silicon semiconductor melting container, and the like.
  • expensive compounds such as silicon tetrachloride must be used, and since the melting temperature and processing temperature of silica glass are about 2000 ° C., the energy consumption is large. It causes mass emission of carbon dioxide, which is considered as one of the global warming gases. Therefore, conventionally, a method for producing silica glass using a
  • Patent Document 1 discloses a method (sol-gel method) in which silicon alkoxide is hydrolyzed to form a silica sol, then gelled to form a wet gel, dried to a dry gel, and finally a high-temperature calcination to obtain a transparent silica glass body.
  • Patent Document 2 discloses a method for obtaining transparent silica glass by a sol-gel method from a silica sol mixed solution composed of tetramethoxysilane or tetraethoxysilane and a silica sol solution containing silica fine particles.
  • Patent Document 3 in a method for producing transparent silica glass using silicon alkoxide and silica glass fine particles as main raw materials, heat treatment at 200 ° C. to less than 1300 ° C. is performed in an oxygen gas-containing atmosphere and further increased to 1700 ° C. or higher. It is shown that the heat treatment for heating is performed in an atmosphere containing hydrogen gas, and the reduced-pressure atmosphere heat treatment is performed between the two heat treatments.
  • these conventional sol-gel methods are not only problematic in terms of initial dimensional accuracy of the produced silica glass and heat resistance during subsequent use at high temperatures, but are also not very inexpensive in terms of cost.
  • Patent Document 4 at least two different silica glass particles, for example, silica glass fine powder and silica glass particles are mixed to form a water-containing suspension, then pressure-molded, and sintered at high temperature to contain silica.
  • a method of obtaining a composite is shown.
  • opaque silica is produced by preparing a mixed liquid (slurry) containing silica glass particles having a size of 100 ⁇ m or less and silica glass granules having a size of 100 ⁇ m or more, injecting the mixture into a mold, and then drying and sintering.
  • a method of making a glass composite is shown.
  • these conventional slip casting methods have a large shrinkage of the molded body in the drying process and the sintering process, and it has not been possible to produce a thick silica glass molded body with high dimensional accuracy.
  • the method for producing a silica glass molded body from a powder raw material has the above-described problems. Therefore, even now, as a method for producing a silica crucible for producing single crystal silicon for LSI, production methods as described in Patent Document 6 and Patent Document 7 are used. In these methods, natural quartz powder or synthetic cristobalite powder treated with ultra-high purity is put into a rotating formwork, and after molding, the carbon electrode is pushed in from the top, and electric discharge is applied to the carbon electrode to cause arc discharge. The quartz raw material powder is melted and sintered by raising the ambient temperature to the melting temperature range of quartz powder (estimated to be about 1800 to 2100 ° C.).
  • Patent Document 8 discloses an outer layer made of natural quartz glass and an intermediate layer made of synthetic quartz glass having a high aluminum concentration by an arc discharge melting method of silica powder raw material (the atmosphere during melting is estimated to be air).
  • a silica crucible having an inner three-layer structure made of high-purity synthetic quartz glass is shown. And the effect of preventing impurity migration by the intermediate layer is shown.
  • the three-layer structure having such a structure is not only expensive, but the problem of heat distortion resistance has not been solved.
  • Patent Document 9 discloses a technique for reducing bubbles in the melted quartz crucible wall by sucking under reduced pressure from the outer periphery of the molding die during arc discharge melting of the silica powder raw material compact. Yes.
  • the dissolved gas in the melted quartz crucible wall could not be completely removed by simply vacuuming the air present in the silica powder.
  • only a crucible with a large residual gas of H 2 O could be obtained.
  • Patent Document 10 discloses a silica crucible having a three-layer structure containing a crystallization accelerator by a similar arc discharge melting method.
  • the crucible does not necessarily crystallize uniformly, and there is a lot of outgassing from the crucible, so there are voids in the grown single crystal silicon.
  • defects such as pinholes were generated and that heat deformation was caused when the crucible was used.
  • a silica container mainly composed of silica having high dimensional accuracy and high heat distortion resistance is used, and a powder mainly composed of silica is used as a main raw material.
  • An object of the present invention is to provide a method for producing a silica container that can be produced at low cost, and to provide such a silica container.
  • the present invention has been made to solve the above-mentioned problems, and is a method for producing a silica container comprising at least a silica substrate having silica as a main component and having rotational symmetry, the silica substrate A raw material powder for a substrate, which is silica particles for forming a carbon, and rotating a carbon outer mold frame that has rotational symmetry and is formed by distributing holes for decompression to the inner wall
  • the base material powder is introduced into the inner wall of the outer mold frame, and the base material powder is temporarily molded into a predetermined shape corresponding to the inner wall of the outer mold frame to form a silica substrate temporary molded body.
  • H 2 gas was supplied at 10 vol.
  • Degassing by depressurizing the temporary molding body of the silica substrate from the outer peripheral side by supplying a reducing gas containing at a ratio exceeding% by reducing the pressure through the pressure reducing holes formed in the outer mold.
  • the outer peripheral portion of the silica substrate temporary molded body is made a sintered body, and the silica substrate temporary molding is performed.
  • a method for producing a silica container comprising a step of forming a silica base body by forming an inner portion of a body as a molten glass body.
  • an oxygen deficiency type defect can be included in a silica substrate by heating under a strong reducing atmosphere. Due to the presence of this oxygen deficiency type defect, high heat distortion resistance can be imparted to the silica substrate.
  • this invention since this invention can be implemented without adding a special apparatus and process with respect to the conventional method, it manufactures the silica container which has high heat-resistant deformation with high dimensional accuracy, high productivity, and low cost. be able to.
  • the amount of H 2 O molecules dissolved in the manufactured silica container can be suppressed by heating in the presence of H 2 gas. Therefore, when the silica container is used, H 2 O molecules released from the silica container can be suppressed, so that adverse effects due to the H 2 O molecules on the contents accommodated in the silica container can be reduced. .
  • Al is added to the base material powder at 10 to 1000 wt. If it is contained at a concentration of ppm, it is possible to suppress the diffusion of metal impurities in the silica substrate, and to reduce the contamination of impurities in the accommodation.
  • the silica substrate is made of crystalline silica from the inside of the silica substrate, and has a silica purity higher than that of the raw material powder for the substrate.
  • the method may further include a step of forming an inner layer made of transparent silica glass on the inner surface of the silica substrate by heating from the inner side by a discharge heating melting method while spraying a raw material powder having a high inner layer.
  • the method further includes a step of forming an inner layer made of transparent silica glass on the inner surface of the obtained silica substrate, the silica container is accommodated in the manufactured silica container. It is possible to more effectively reduce the contamination of impurities in the contained material.
  • each concentration of Li, Na, and K in the inner layer raw material powder is set to 60 wt.
  • the concentration of Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Mo, and W is 30 wt. It is preferable to set it to ppb or less. If the density
  • cooling after discharge heating in the step of forming a silica substrate by the discharge heating melting method or the step of forming an inner layer is performed in an oxidizing gas atmosphere containing O 2 gas.
  • the O 2 gas content ratio of the oxidizing gas is 1 to 30 vol. % Is preferable.
  • the cooling after the discharge heating in the step of forming the silica substrate by the discharge heating melting method or the step of forming the inner layer is performed by oxidizing gas containing O 2 gas. If it is carried out in an atmosphere, the carbon particles scattered from the carbon electrode are oxidized and gasified to obtain a silica container with little adhesion of carbon fine particles. Further, the O 2 gas content ratio of the oxidizing gas is set to 1 to 30 vol. By setting it as%, the adhered carbon fine particles can be more effectively removed.
  • the present invention is a silica container comprising at least a silica substrate having silica as a main constituent and having rotational symmetry, wherein the silica substrate includes an oxygen deficient defect, and an outer peripheral portion.
  • a silica container having a white opaque layer portion containing bubbles and a colorless transparent layer portion made of silica glass containing substantially no bubbles in an inner peripheral portion.
  • Such a silica container can have high heat distortion resistance because it contains oxygen-deficient defects.
  • the density of oxygen-deficient defects contained in the silica substrate is preferably such that the colorless transparent layer portion has a light transmittance of 80% or less at a wavelength of 240 nm per 10 mm of the optical path length.
  • the silica substrate is Since a sufficiently high-density oxygen deficiency type defect is included, a more reliable silica container having heat distortion resistance can be obtained.
  • H 2 O molecules that emit colorless and transparent layer part of the silica substrate when heated to 1000 ° C. under vacuum is not more than 1 ⁇ 10 17 molecules / cm 3.
  • the H 2 O molecules released when the colorless and transparent layer portion of the silica substrate is heated to 1000 ° C. under vacuum is 1 ⁇ 10 17 molecules / cm 3 or less, the container accommodated in the silica container The adverse effect of H 2 O gas molecules on can be suppressed.
  • H 2 molecule concentration in the colorless and transparent layer part of the silica substrate is 5 ⁇ 10 16 molecules / cm 3 or less.
  • the H 2 molecule concentration in the colorless and transparent layer portion of the silica substrate is 5 ⁇ 10 16 molecules / cm 3 or less, the adverse effect of the H 2 gas molecules on the contents accommodated in the silica container is suppressed. Can do.
  • the viscosity at 1400 ° C. of the colorless and transparent layer portion of the silica substrate is 10 10.5 Pa ⁇ s or more.
  • the silica container having higher reliability of heat distortion can be obtained.
  • the silica substrate has an OH group concentration of 60 wt. It is preferably at most ppm. Further, the silica substrate contains 10 to 1000 wt. It is preferably contained at a concentration of ppm. Thus, if the silica substrate contains OH groups and Al at the above concentrations, the diffusion of metal impurities in the silica substrate can be suppressed, and the contamination of the contained material can be reduced. Can do.
  • an inner layer made of transparent silica glass having a silica purity higher than that of the silica substrate can be provided on the inner surface of the silica substrate.
  • any one of the above silica containers is provided with an inner layer made of transparent silica glass having a silica purity higher than that of the silica base on the inner surface of the silica base, the container to be stored in the silica container. Impurity contamination can be reduced more effectively.
  • the inner layer has an OH group concentration of 30 wt. ppm or less, and each concentration of Li, Na, and K is 60 wt. ppb or less, and each concentration of Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Mo, W is 30 wt. It is preferably ppb or less. If the OH group concentration and the concentration of each metal contained in the inner layer are such concentrations, it is possible to more effectively reduce the contamination of impurities contained in the manufactured silica container.
  • oxygen deficient defects can be included in the silica substrate. Due to the presence of this oxygen deficiency type defect, high heat distortion resistance can be imparted to the silica substrate. And the silica container which has such a high heat deformation property can be manufactured with high dimensional accuracy, high productivity, and low cost. Further, it is possible to produce a silica container H 2 O molecules dissolved was suppressed. Therefore, when the silica container is used, H 2 O molecules released from the silica container can be suppressed, so that adverse effects due to the H 2 O molecules on the contents accommodated in the silica container can be reduced. . Moreover, if it is a silica container according to this invention, in order to contain an oxygen deficiency type defect, it can have high heat-deformability.
  • the manufacture of conventional silica containers has problems in terms of heat resistance, dimensional accuracy, and cost.
  • the ultra-high purity quartz raw material powder is used in the entire container, there is a problem that the cost is very high.
  • the present inventors have studied in view of such problems, and have found the following problems.
  • a silica container such as a crucible or a boat for melting metal silicon and producing silicon crystals
  • temperature uniformity inside the container in a heated high temperature atmosphere is required.
  • the silica container has a multi-layer structure
  • the outer side of the container is a porous white opaque silica glass
  • the inner side of the container is a colorless transparent silica glass having substantially few bubbles.
  • silica containers such as crucibles and boats for producing silicon crystals have been required to have large silica containers as the diameter of silicon crystals has increased, and at a high temperature (for example, 1400 to 1600 ° C.) when melting metal silicon.
  • the second problem is to prevent softening and deformation of the silica container itself, that is, to improve the heat deformation resistance.
  • the third problem is to make the amount of dissolved gas small (low emission gas). This is because, when a gas molecule such as O 2 gas, H 2 gas, H 2 O gas, CO gas, and CO 2 gas is taken into the silica container, in the case of a silica container used for pulling up a silicon single crystal, a silicon crystal At the time of fabrication, such gas molecules are released into the silicon melt and become bubbles and are taken into the grown silicon single crystal. The gas taken in this way forms voids and pinholes when the silicon single crystal is used as a wafer, and significantly reduces the yield. Therefore, the third problem is to reduce the amount of gas molecules released from the silica container.
  • a fourth problem is to use a low-cost silica raw material that does not have a high-purification treatment and to make a low-cost manufacturing method.
  • silica container solar grade crucible
  • metal silicon melting container used as a material for solar cells (solar power generation, solar power generation)
  • the present invention is not limited to this, and can be widely applied to all silica containers having rotational symmetry having silica as a main constituent.
  • FIG. 1 shows a schematic cross-sectional view of an example of a silica container according to the present invention.
  • the silica container 71 according to the present invention has rotational symmetry, and its basic structure is composed of a silica substrate 51.
  • the silica substrate 51 includes oxygen deficient defects. Further, the silica substrate 51 has a white opaque layer portion 51a containing bubbles in the outer peripheral portion and a colorless transparent layer portion 51b made of silica glass containing substantially no bubbles in the inner peripheral portion.
  • the silica container of the present invention may further include other layers as long as it has at least the silica substrate 51.
  • FIG. 2 shows a silica container 71 ′ having an inner layer 56 made of transparent silica glass on the inner surface of the silica substrate 51 as another example of the silica container according to the present invention.
  • the silica purity of the inner layer 56 is preferably higher than that of the silica substrate 51.
  • substrate 51 which comprises the silica container which concerns on this invention is demonstrated concretely.
  • the silica substrate 51 includes oxygen-deficient defects as described above.
  • oxygen-deficient defects in the silica substrate 51 By including oxygen deficient defects in the silica substrate 51, the viscosity of the silica glass at a high temperature can be increased, and as a result, the heat distortion resistance of the silica container can be improved. It has been reported that oxygen-deficient defects in silica glass show an absorption band at a light wavelength of about 240 nm to about 250 nm. For example, what is called a B 2 ⁇ band is estimated to be absorption due to a Schottky type defect of oxygen (O), and shows maximum absorption at 5.06 eV (246 nm).
  • O Schottky type defect of oxygen
  • the so-called B 2 ⁇ band is presumed to be absorption by a lone electron pair (silicon loan pair) of silicon (Si), and shows maximum absorption at 5.14 eV (242 nm).
  • the so-called 5 eV band is presumed to be absorbed by silicon clusters in silica glass, and exhibits a very wide absorption in the vicinity of 5 eV (250 nm).
  • the absorption band in the silica substrate 51 of the present invention shows maximum absorption in the vicinity of about 5.17 eV (wavelength 240 nm), and it is unclear which kind of oxygen deficiency type defect is related to the above-mentioned. It is. Further, the mechanism by which the oxygen deficiency type defect improves the viscosity of silica glass at high temperatures is unknown. However, if the silica container 51 contains oxygen-deficient defects, the heat resistance of the silica substrate 51 can be improved.
  • the oxygen deficiency type defect contained in the silica substrate 51 has a density (concentration) of light transmittance at a wavelength of 240 nm per 10 mm optical path length in the colorless transparent layer portion 51b (here, the silica glass surface or It is a transmittance that does not take into account reflection on the back surface or light scattering inside the silica glass, and so-called linear transmittance) is preferably 80% or less, preferably 1 to 60%. It is more preferable to indicate the range. If it is such a range, the heat-resistant deformation property of the silica base
  • substrate 51 can be improved reliably.
  • a transparent silica glass free of bubbles that does not contain oxygen-deficient defects shows a light transmittance of about 90% at a wavelength of 240 nm per optical path length of 10 mm.
  • the silica substrate 51 has the white opaque layer portion 51a containing bubbles in the outer peripheral portion and the colorless and transparent layer portion 51b made of silica glass substantially free of bubbles in the inner peripheral portion. . Since the silica substrate 51 includes the white opaque layer portion 51a and the colorless transparent layer portion 51b, it is possible to improve the heat uniformity inside the silica container under heating.
  • the bulk density of the white opaque layer portion 51a can be, for example, 1.90 to 2.20 (g / cm 3 ), and the bulk density of the colorless and transparent layer portion 51b is typically 2.20 (g / cm 3). However, the present invention is not particularly limited to these.
  • the silica containers 71 and 71 ′ are often used under high temperature and reduced pressure, and at this time, it is necessary to reduce the amount of gas released from the silica containers 71 and 71 ′.
  • the H 2 O molecules released when the colorless transparent layer portion 51b is heated to 1000 ° C. under vacuum is preferably 1 ⁇ 10 17 molecules / cm 3 or less, and 5 ⁇ 10 16 molecules / cm 3 or less. More preferably.
  • the H 2 molecule concentration in the colorless transparent layer portion 51b is preferably 5 ⁇ 10 16 molecules / cm 3 or less.
  • H 2 gas when the thickness of silica glass as a measurement sample is thin (for example, 1 mm or less), the amount of H 2 gas released per unit volume under vacuum at 1000 ° C. and the Raman scattering measurement at room temperature.
  • the dissolved H 2 molecule concentration value per unit volume by the method is equivalent.
  • the adverse effects of the gas molecules on the contents accommodated in the silica container can be reduced.
  • the silica container 71 of the present invention is used for pulling up a silicon single crystal, when the above gas release occurs, it is taken into the silicon crystal, and a structural defect such as a void or a pinhole is generated in the crystal.
  • this adverse effect can be reduced.
  • the silica substrate 51 preferably has an Al concentration of 10 to 1000 wt. ppm, more preferably 50 to 500 wt.
  • the impurity metal element can be adsorbed and fixed.
  • the OH group is preferably added to the silica substrate at 60 wt. ppm or less, more preferably 10 to 30 wt. By containing ppm, the adsorption and fixing action of impurity metal elements can be greatly improved.
  • the silica substrate 51 can be made to contain Al by increasing the viscosity of the silica glass at a high temperature to improve the heat distortion resistance of the silica substrate 51 at a high temperature. It can improve the heat resistance of '.
  • the OH group concentration was 60 wt. ppm or less, preferably 30 wt. If it is set to ppm or less, it is possible to suppress the reduction of the viscosity of the silica glass at a high temperature due to the effect of the OH group, and to obtain the above-described impurity metal element adsorption and fixation.
  • the viscosity of the silica substrate 51 can be improved by the presence of the above-described oxygen deficient defects, the addition of Al, and the like, and the heat distortion resistance of the silica containers 71 and 71 ′ can be improved.
  • the viscosity at 1400 ° C. of the colorless and transparent layer portion 51b of the silica substrate 51 may be 10 10.5 Pa ⁇ s or more.
  • the inner layer 56 of the silica container 71 ′ shown in FIG. 2 will be described.
  • the inner layer 56 is formed on the inner wall surface of the silica substrate 51 and is made of transparent silica glass having a silica purity higher than that of the silica substrate.
  • the silica purity of the silica substrate 51 is set to 99.9 to 99.999 wt. % And a relatively low purity.
  • the silica container 71 ′ having the inner layer 56 it is possible to sufficiently prevent impurities from being contained in the accommodated material while the silica substrate 51 is a silica container having such a silica purity and a low cost.
  • the inner layer 56 has an OH group concentration of 30 wt. It is preferable to set it as ppm or less. More preferably, it is at most ppm. Inclusion of OH groups in the inner layer 56 has an effect of reducing the diffusion rate of the impurity metal element, but also has an adverse effect of reducing the etching resistance, so that the appropriate concentration range is limited.
  • the inner layer 56 has a Li, Na, and K element concentration of 60 wt.
  • the element concentration of Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Mo, and W is 30 wt. It is preferable to set it to ppb or less. More preferably, each of Li, Na, and K is 20 wt.
  • each of Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Mo, W is 10 wt. ppb or less. This can reduce the adverse effects of these impurity elements on the object to be processed.
  • the object to be processed is a silicon crystal for solar, it is possible to prevent the photoelectric conversion efficiency from being lowered and to improve the quality thereof.
  • silica containers 71 and 71 are demonstrated concretely.
  • an example of a method for producing a low-cost silica container (solar grade crucible) that can be used as a container for melting and single crystal pulling of metal silicon (Si), which is used as a material for a photovoltaic power generation device, will be described.
  • the outline of the manufacturing method of the silica container 71 which concerns on this invention is shown in FIG.
  • substrates which is a silica particle is prepared (process 1).
  • the base material powder 11 is a main constituent material of the silica base 51 in the silica containers 71 and 71 ′ (see FIGS. 1 and 2) according to the present invention.
  • This base material powder can be produced, for example, by crushing and sizing the silica lump as follows, but is not limited thereto.
  • a natural silica lump (naturally produced crystal, quartz, silica, siliceous rock, opal stone, etc.) with a diameter of about 5 to 50 mm is heated in a temperature range of 600 to 1000 ° C. for about 1 to 10 hours in an air atmosphere.
  • 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 by a crusher or the like, and the particle size is preferably adjusted to 10 to 1000 ⁇ m, more preferably 50 to 500 ⁇ m 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, and is kept at 700 to 1100 ° C.
  • the high-purity treatment is performed by heating for about 1 to 100 hours. However, in a product application that does not require high purity, the process may proceed to the next process without performing the purification process.
  • the base material powder 11 obtained after the above steps is crystalline silica.
  • amorphous silica glass scrap can be used as the base material powder 11.
  • the particle size of the base material powder 11 is preferably 10 to 1000 ⁇ m, and more preferably 50 to 500 ⁇ m.
  • the silica purity of the raw material powder 11 for substrate is 99.99 wt. % Or more, preferably 99.999 wt. % Or more is more preferable.
  • substrates will be 99.999 wt.
  • the manufactured silica container can fully prevent the impurity contamination to the accommodation to accommodate. Therefore, a silica container can be manufactured at a lower cost than before. Moreover, when manufacturing silica container 71 'provided with the inner layer 56 as shown in FIG. 2 mentioned later, especially the silica purity of the raw material powder 11 for base
  • substrates can also be made low, for example, 99.9 wt. % Or more.
  • the concentration of OH groups contained in the substrate raw material powder 11 is 10 to 1000 wt. It is preferable to set it to about ppm.
  • the OH group contained in the raw material powder 11 for the substrate can be adjusted depending on the gas atmosphere, treatment temperature, and time in the subsequent drying process, which is included in the natural quartz from the beginning, or moisture mixed in the intermediate process.
  • Silica glass synthesized by the flame hydrolysis method or manufactured by the flame Bernoulli method has 200 to 2000 wt. ppm OH groups are contained, and the OH group concentration can be adjusted by mixing an appropriate amount of these OH group-containing amorphous silica powders.
  • the base material powder 11 further contains Al, preferably 10 to 1000 wt. It is good also as what is contained in the range of ppm.
  • Al can be obtained, for example, by putting nitrate, acetate, carbonate, chloride or the like into water or an alcohol solution, putting silica powder in these solutions, immersing them, and then drying them.
  • FIG. 5 is a cross-sectional view illustrating an outline of an outer mold for temporarily forming the raw material powder 11 for a substrate.
  • the carbon outer mold 101 used in the present invention is made of a carbon member such as graphite and has rotational symmetry.
  • pressure reducing holes 103 are distributed and formed in the inner wall 102 of the carbon outer mold 101.
  • the decompression hole 103 is continuous with the decompression passage 104.
  • a pressure reducing passage 105 also passes through a rotating shaft 106 for rotating the carbon outer mold 101, and vacuuming can be performed from here.
  • the base material powder 11 is introduced into the inner wall 102 of the carbon outer mold frame 101, and the base material powder 11 is temporarily formed into a predetermined shape corresponding to the shape of the inner wall 102 of the carbon outer mold frame 101, and then a silica base.
  • the temporary molded body 41 see FIG. 6). Specifically, while rotating the carbon outer mold 101, the raw material powder 11 for the substrate is gradually put into the inner wall 102 of the carbon outer mold 101 from a raw material powder hopper (not shown), and centrifugal force is used. And molded into a container shape. Further, the thickness of the silica base temporary molded body 41 may be adjusted to a predetermined amount by bringing a plate-shaped inner mold (not shown) from the inside into contact with the rotating powder.
  • the method for supplying the base material powder 11 to the carbon outer mold 101 is not particularly limited.
  • a hopper provided with a stirring screw and a measuring feeder can be used.
  • the base material powder 11 filled in the hopper is stirred with a stirring screw, and is supplied while adjusting the supply amount with a measuring feeder.
  • a silica substrate 51 is formed by a reduced pressure / discharge heat melting method (step 3). Specifically, as shown in FIG. 7 and FIG. 8, the silica substrate temporary molded body 41 is converted into a silica substrate temporary molded by reducing the pressure through the decompression hole 103 formed in the carbon outer mold 101. While depressurizing and degassing from the outer peripheral side of the body 41, it is heated from the inside of the temporary preform of the silica substrate by a discharge heating melting method.
  • the silica base 51 is formed by using the outer peripheral portion of the silica base temporary molding 41 as a sintered body and the inner portion of the silica base temporary molding 41 as a molten glass body.
  • the apparatus for forming the silica substrate 51 includes a rotary carbon outer mold 101 having the rotational axis symmetry described above, a rotary motor (not shown), a molten atmosphere gas regulator (not shown), and a discharge. It consists of a carbon electrode 212, an electric wire 212a, a high-voltage power supply unit 211, and a lid 213, which are heat sources for heat melting (also called arc melting or arc discharge melting). In addition, this apparatus can be used continuously when forming the inner layer 56 on the inner surface of the silica base
  • the carbon outer mold frame 101 containing the silica-based temporary molded body 41 is rotated at a constant speed, and a degassing vacuum pump (see FIG. (Not shown), the pressure is reduced from the outside of the temporary molded body 41 through the pressure reducing hole 103 and the pressure reducing passages 104 and 105, and the carbon electrode 212 is started to be charged.
  • the inner surface portion of the silica-based preform 41 is in the melting temperature range of silica powder (estimated to be about 1800 to 2000 ° C.), and the outermost layer. Melting starts from the part.
  • the degree of vacuuming by the degassing vacuum pump is increased (the pressure is suddenly reduced), and the dissolved gas contained in the base material powder 11 is degassed to the fused silica glass layer. Changes from the inside to the outside.
  • the inner half of the total thickness of the silica substrate is melted to form a transparent (translucent) layer 51b (transparent layer part), and the remaining outer half is sintered white opaque silica (opaque layer part) 51a.
  • the degree of vacuum is preferably 10 3 Pa or less.
  • the atmosphere gas at the time of discharge heating and melting inside the silica substrate 51 is hydrogen gas (H 2 ) of 10 vol. Mix to exceed%.
  • Components other than hydrogen gas are mainly composed of an inert gas such as nitrogen (N 2 ), argon (Ar), or helium (He) for the purpose of reducing consumption of the carbon electrode 212.
  • N 2 nitrogen
  • Ar argon
  • He helium
  • an oxygen deficient defect structure can be generated in the fused silica substrate 51, and the dissolved gas in the fused silica substrate 51 can be reduced.
  • the reason why the dissolved gas in the silica gas 51 can be reduced is that oxygen gas (O 2 ) that is difficult to degas from silica glass reacts with hydrogen to produce water (H 2 O), and the water molecules are converted into oxygen molecules.
  • the diffusion coefficient is likely to be released to the outside of the substrate.
  • hydrogen gas (H 2 ) has a small molecular radius and a large diffusion coefficient, even if it is contained in the atmospheric gas, it is easily released to the outside of the substrate.
  • the silica container 71 of the present invention can be formed only by the silica substrate 51 formed so far, but if necessary, the inner layer 56 is formed on the inner surface of the silica substrate 51 as shown in FIG.
  • the silica container 71 ′ formed and provided with the silica substrate 51 and the inner layer 56 may be used. A method of manufacturing the silica container 71 ′ having the inner layer 56 as shown in FIG. 2 will be described with reference to FIG.
  • the steps up to the step of forming the silica substrate 51 are performed (see FIGS. 4 (1) to (3)).
  • FIG. 4 (4) while heating the inner layer raw material powder 12 made of crystalline silica and having a silica purity higher than that of the base material powder 11, the discharge heating is performed.
  • the inner layer 56 is formed on the inner surface of the silica substrate 51 by heating from the inside by a melting method (step 4).
  • FIG. The basic formation method of the inner layer 56 follows the contents shown in Patent Document 6 and Patent Document 7, for example.
  • the inner layer raw material powder 12 is prepared.
  • the material of the inner layer raw material powder 12 include highly purified natural quartz powder, natural crystal powder, synthetic cristobalite powder, and synthetic silica glass powder.
  • crystalline silica powder is preferable, and for the purpose of making a high-purity transparent layer, synthetic powder is preferable.
  • the particle size is 10 to 1000 ⁇ m, preferably 100 to 500 ⁇ m.
  • Purity is silica component (SiO 2 ) 99.9999 wt. % Or more and each of the alkali metal elements Li, Na, K is 60 wt. ppb or less, preferably 20 wt.
  • each of Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Mo, W is 30 wt. ppb or less, preferably 10 wt. It is below ppb.
  • a method of forming the inner layer 56 will be described with reference to FIG. As in the previous step, the apparatus for forming the inner layer 56 on the inner surface of the silica substrate 51 is a rotatable carbon outer mold 101 on which a silica substrate 51 having rotational axis symmetry is installed, a rotary motor (not shown).
  • a melting atmosphere gas regulator (not shown), a raw material powder hopper 303 containing the inner layer raw material powder 12 for forming the inner layer 56, a stirring screw 304, a metering feeder 305, and a heat source for discharge heating melting A carbon electrode 212, an electric wire 212 a, a high-voltage power supply unit 211, and a lid 213.
  • the carbon outer mold 101 is set to a predetermined rotation speed, and a high voltage is gradually applied from the high-voltage power supply unit 211.
  • the inner layer 56 is gradually formed from the raw material hopper 303.
  • the inner layer raw material powder (high purity silica powder) 12 is sprayed from the upper part of the silica substrate 51.
  • the discharge is started between the carbon electrodes 212, and the silica base 51 is in the melting temperature range of silica powder (estimated to be about 1800 to 2000 ° C.). It becomes particles and adheres to the inner surface of the silica substrate 51.
  • the carbon electrode 212, the raw material powder inlet, and the lid 213 installed in the upper opening of the silica substrate 51 have a mechanism in which the position can be changed to a certain extent with respect to the silica substrate 51. By changing these positions, The inner layer 56 can be formed with a uniform thickness on the entire inner surface of the silica substrate 51.
  • the atmosphere gas inside the silica base 51 during discharge heating melting for forming the inner layer 56 is mainly composed of an inert gas such as N 2 gas, Ar gas, He gas, etc. in order to reduce the consumption of the carbon electrode.
  • H 2 gas in an amount of 1 to 30 vol.
  • the H 2 gas content in the mixed gas atmosphere is 1 vol. % Or more, the effect of reducing bubbles contained in the inner layer 56 (transparent silica glass) can be further increased, and the content of H 2 gas is 30 vol. If it is less than or equal to%, the bubble reduction effect of the inner layer 56 can be sufficiently obtained, and the cost of the mixed gas can be suppressed.
  • dissolved H 2 O molecules can be effectively reduced by using a dry gas atmosphere containing no water vapor.
  • oxygen gas (O 2 ) 1-30 vol. % Of the mixed gas atmosphere oxidizes the carbon (C, carbon) fine particles generated at the time of discharge heating and melting to CO, CO 2 , whereby the inner layer 56 with few carbon (C) fine particles can be obtained. .
  • the content of O 2 gas in the mixed gas atmosphere is 1 vol. % Or more, the effect of reducing the carbon fine particles contained in the inner layer 56 (transparent silica glass) can be further increased, and the content of O 2 gas is 30 vol. If it is less than or equal to%, the effect of reducing the carbon fine particles of the inner layer 56 can be sufficiently obtained, and the consumption of the carbon electrode can be suppressed. At this time, CO and CO 2 are generated as described above, but can be removed due to reduced pressure.
  • the step of forming the silica substrate 51 by the discharge heating melting method (step 3 shown in FIGS. 3 and 4) or the step of forming the inner layer 56 (step 4 shown in FIG. 4). ) Can be performed in an oxidizing gas atmosphere containing O 2 gas.
  • gas atmosphere was carried out discharge heating, in the case of such N 2 gas containing H 2 gas as described above, it is necessary to replace the oxidizing gas containing O 2 gas.
  • carbon particles generated from the carbon electrode and attached to the silica substrate 51 or the inner layer 56 or remaining in the surrounding atmosphere are removed.
  • a silica container can be obtained which can be gasified by oxidation treatment and has little adhesion of carbon fine particles.
  • the O 2 gas content ratio of the oxidizing gas is 1 to 30 vol. % Is preferable.
  • the process of cooling the silica substrate 51 to room temperature in an oxidizing gas atmosphere containing O 2 gas is performed when a silica container 71 ′ for forming the inner layer 56 as shown in FIGS.
  • a silica container 71 ′ for forming the inner layer 56 As shown in FIGS.
  • the silica substrate 51 is formed and then cooled once, it may be performed at that time, or after the silica substrate 51 is formed, the inner layer 56 is formed while maintaining the high temperature, and then the cooling is performed. May be done at that time. Of course, both may be performed.
  • the silica containers 70 and 71 ′ of the present invention can be obtained, but the silica container is washed as follows as necessary.
  • silica container cleaning and drying For example, surface etching is performed with about 1 to 10% hydrofluoric acid aqueous solution (HF) for 5 to 30 minutes, then washed with pure water and dried in clean air to obtain a silica container.
  • HF hydrofluoric acid aqueous solution
  • the silica containers 71 and 71 ′ according to the present invention shown in FIGS. 1 and 2 as described above can be manufactured.
  • Example 1 According to the method for producing a silica container of the present invention shown in FIG. 3, a silica container was produced as follows.
  • the base material powder 11 was prepared as follows (step 1). 100 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 then pulverized using a crusher to obtain a particle size of 50 to 500 ⁇ m and a silica (SiO 2 ) purity of 99.999 wt. % Or more and a total weight of about 90 kg of silica powder (natural quartz powder).
  • the base body is connected to the inner wall 102 of a rotating cylindrical carbon (graphite) outer mold frame 101 in which a decompression hole 103 is formed in the inner wall 102.
  • the raw material powder 11 was introduced, the shape of the base material powder 11 was adjusted so as to have a uniform thickness according to the shape of the carbon outer mold 101, and the silica base temporary compact 41 was obtained (step 2). ).
  • a silica substrate 51 was formed by a discharge heating melting method while reducing the pressure (step 3). Specifically, the dried N 2 (nitrogen) 80 vol. % And H 2 (hydrogen) 20 vol. %, The silica base temporary molded body 41 is reduced to the outer peripheral side of the silica base temporary molded body 41 by reducing the pressure through the decompression hole 103 formed in the carbon outer mold 101. The gas is decompressed and degassed, and the outer peripheral portion of the silica base temporary compact 41 is formed into a sintered body by heating at a high temperature from the inside of the silica base temporary compact 41 by the discharge heating melting method using the carbon electrode 212.
  • the inner portion of the silica substrate temporary molding 41 was made of a molten glass body to form a silica substrate 51, which was used as a silica container 71. Thereafter, N 2 (nitrogen) 80 vol. % And O 2 (oxygen) 20 vol.
  • the silica substrate 51 (silica container 71) was cooled to room temperature in a mixed gas atmosphere of%.
  • the silica container 71 manufactured in this way is 3 wt. After washing with an aqueous hydrofluoric acid solution (HF) for 3 minutes, it was washed with pure water and dried.
  • HF aqueous hydrofluoric acid solution
  • Example 2 Basically in the same manner as in Example 1, except that N 2 (nitrogen) 60 vol. % And H 2 (hydrogen) 40 vol.
  • the silica container 71 was manufactured as a mixed gas of%.
  • Example 3 In accordance with the method for producing a silica container of the present invention shown in FIG. 4, a silica container 71 ′ was produced as follows. In step 1 shown in FIG. 4 (1), 20 wt. It carried out like Example 1 except having added Al so that it might contain ppm. Next, the steps (steps 2 to 3) of FIGS. 4 (2) and 4 (3) were performed in the same manner as in Example 1, but the next step (step 4) was performed without once cooling the silica substrate 51. It moved to.
  • high-purity synthetic cristobalite powder (particle size: 100 to 300 ⁇ m, silica purity: 99.99999 wt.% Or more) was prepared as the inner layer raw material powder 12.
  • the inner layer raw material powder 12 is sprayed from the inside of the silica substrate 51 in a mixed gas atmosphere and heated from the inside by the discharge heating melting method, so that the transparent silica glass is formed on the inner surface of the silica substrate 51.
  • the inner layer 56 formed was formed as a silica container 71 ′.
  • the silica container 71 ′ was cooled to room temperature in a mixed gas atmosphere of% (step 4).
  • the silica container 71 ′ thus produced was treated with 3 wt. After washing with an aqueous hydrofluoric acid solution (HF) for 3 minutes, it was washed with pure water and dried.
  • HF aqueous hydrofluoric acid solution
  • Example 4 Basically the same as in Example 3, except that the atmosphere gas at the time of melting of the silica-based preform 41 in Step 3 was dried by N 2 (nitrogen) 60 vol. % And H 2 (hydrogen) 40 vol.
  • the silica container 71 ′ was manufactured as a mixed gas of%.
  • Example 5 The silica container 71 ′ was manufactured basically in the same manner as in Example 3, but the following points were changed.
  • Al is 30 wt. Al was added so as to contain ppm.
  • the discharge heating for forming the inner layer 56 in Step 4 is performed using N 2 (nitrogen) 90 vol. % And H 2 (hydrogen) 10 vol. % In a mixed gas atmosphere.
  • Example 6 Basically in the same manner as in Example 5, except that the atmosphere gas at the time of melting of the silica-based preform 41 in Step 3 was dried with N 2 (nitrogen) 20 vol. % And H 2 (hydrogen) 80 vol. % Mixed gas.
  • Example 7 Basically in the same manner as in Example 1, except that N 2 (nitrogen) 85 vol. % And H 2 (hydrogen) 15 vol.
  • the silica container 71 made of the silica substrate 51 was manufactured with a mixed gas of%.
  • Example 8 Basically the same as in Example 3, except that the atmosphere gas at the time of melting the silica-based preform 41 in Step 3 was dried by N 2 (nitrogen) 85 vol. % And H 2 (hydrogen) 15 vol.
  • a silica container (silica crucible) was prepared according to a conventional method. That is, the portion corresponding to the silica substrate of the silica container of the present invention was also formed by a discharge heating melting method using high-purity raw material powder.
  • silica powder of 99.9999 wt. % Natural quartz powder (particle size 100 to 300 ⁇ m) having a high purity of at least 100% was prepared.
  • high-purity natural quartz powder is directly injected into a carbon (graphite) rotating frame and the centrifugal force is used in the rotating frame, particularly in an air atmosphere where humidity is not adjusted.
  • a quartz powder layer was formed, and this was discharge-heated and melted with a carbon electrode to form a silica substrate (corresponding to the silica substrate 51 of the present invention shown in FIG. 2). This is 60 minutes, and the temperature of the silica substrate is estimated to be about 2000 ° C.
  • the same synthetic cristobalite powder as in Examples 3 to 8 was prepared, and this high-purity synthetic cristobalite powder was sprayed from the hopper onto the inner surface of the silica substrate, particularly humidity adjustment
  • the inner layer portion (corresponding to the inner layer 56 in the silica container 71 ′ of the present invention shown in FIG. 2) was formed by discharge heating and melting with a carbon electrode in an air atmosphere without performing the above.
  • Comparative Example 2 Basically the same as Comparative Example 1, except that the silica substrate (corresponding to the silica substrate 51 of the present invention shown in FIG. 2) is melted in an alumina mold, and in particular, decompressed air without humidity adjustment. It was carried out by an electric discharge heating melting method in an atmosphere.
  • Example 3 Basically in the same manner as in Example 1, except that N 2 (nitrogen) 90 vol. % And H 2 (hydrogen) 10 vol.
  • the silica container 71 made of the silica substrate 51 was manufactured with a mixed gas of%.
  • Example 4 Basically in the same manner as in Example 3, except that N 2 (nitrogen) 90 vol. % And H 2 (hydrogen) 10 vol.
  • Impurity metal element concentration analysis When the impurity metal element concentration is relatively low (the glass is highly pure), plasma emission analysis (ICP-AES, Inductively Coupled Plasma-Atomic Emission Spectroscopy) or plasma mass spectrometry (ICP-MS, Inductively Coupled Pladded) When the impurity metal element concentration is relatively high (the glass is of low purity), atomic absorption spectrophotometry (AAS, Atomic Absorption Spectroscopy) was used.
  • ICP-AES Inductively Coupled Plasma-Atomic Emission Spectroscopy
  • ICP-MS Inductively Coupled Pladded
  • Particle size measurement method for 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).
  • Transmittance measurement Optical polishing finish of dimensions 6 ⁇ 6 ⁇ thickness 10 mm, parallel at both ends, from the bubble-free portion (colorless transparent layer portion) inside the silica substrate of each silica container of each example and each comparative example A sample was prepared, and the linear light transmittance at a wavelength of 240 nm was measured using an ultraviolet spectrophotometer. Therefore, the value of the light transmittance does not take into account the surface reflection loss of the incident light to the sample and the back surface reflection loss of the emitted light, and is expressed by the following equation.
  • Light transmittance (%) 100 ⁇ (emitted light intensity) / (incident light intensity)
  • the area with few bubbles to the extent that the transmittance measurement can be sufficiently measured did not exist in a size that allows the sample with the above dimensions to be collected, and thus the transmittance could not be measured.
  • Layer thickness measurement The thickness of the silica substrate and the inner layer was determined by measuring the cross section of the container at half the full height of the side wall of the silica container with a scale.
  • Measuring method of gas molecule emission from each of silica substrate and inner layer From each of the silica container of each of the Examples and Comparative Examples, 10 ⁇ 50 from each of the inner portion of the silica substrate (the colorless transparent layer portion, the portion having relatively few inner bubbles as much as possible in Comparative Example 1) and the inner layer.
  • X Prepare a sample for measurement of double-sided mirror-finished surface with a thickness of 1 mm, place it in a vacuum chamber, and measure the gas release under 1000 ° C vacuum with a mass spectrometer for the type of gas and the amount of gas released did.
  • H 2 and H 2 O gas were expressed as the number of molecules released per unit volume (molecules / cm 3 ), assuming that the entire amount was released.
  • the H 2 gas as dissolved gas concentration in the silica glass, it was confirmed that the same value can be obtained by the following measuring method literature. Khotimchenko, V.M. S. et al. (1987) “Determining the content of hydrodissolved in quartz glassing the methods of Raman scattering and mass spectrometry in Japan.” 46, no. 6, pp. 632-635.
  • Viscosity First, a material of about 10 ⁇ 10 cm was cut out from each silica container, washed, placed in an electric furnace, and held at 1150 ° C. for 3 hours in an air atmosphere. Thereafter, the temperature was lowered to 900 ° C. at a temperature lowering rate of 10 ° C./hour, then the power was turned off, and the mixture was naturally cooled to room temperature in an electric furnace. The heat history of the material cut out from each silica container by this heat treatment was matched. Next, 3 ⁇ 10 ⁇ length from each portion of this material corresponding to a portion free of bubbles in the inner portion of the silica substrate (colorless transparent layer portion, a portion having relatively few inner bubbles as much as possible in Comparative Example 1).
  • Silicon single crystal continuous pulling (multi pulling) evaluation In the produced silica container, the purity was 99.99999 wt. % Metal polysilicon was added, the temperature was raised to obtain a silicon melt, and then the silicon single crystal was pulled three times repeatedly (multi-pulling), and the success rate of single crystal growth was evaluated.
  • the pulling conditions were as follows: the inside of the CZ apparatus was an argon (Ar) gas 100% atmosphere at a pressure of 10 3 Pa, the pulling rate was 1 mm / min, the rotation speed was 10 rpm, the silicon single crystal dimensions were 150 mm in diameter and 150 mm in length. The operation time for one batch was about 12 hours.
  • the evaluation classification of the success rate of three times of single crystal growth was as follows. 3 times ⁇ (good) Twice ⁇ (somewhat bad) Once ⁇ (Bad)
  • the dissolved amount of H 2 O molecules is significantly smaller than those in Comparative Examples 1 and 2, and accordingly, voids and voids are contained in silicon single crystals produced using these silica containers. Defects such as pinholes are difficult to occur.
  • Example 2 the ratio of H 2 gas was made higher than that in Example 1 in the step of forming the silica substrate 51 from the silica substrate temporary molded body 41 (Step 3). Many oxygen deficient defects were generated, and the amount of H 2 O gas released was reduced. Therefore, generation of voids and pinholes could be further reduced.
  • the viscosity of the silica substrate 51 could be increased as compared with Examples 1 and 2 by increasing the concentration of Al in the silica substrate 51.
  • the concentration of Al in the silica substrate 51 is high, and the inner layer 56 is formed, so that the effect of preventing impurity diffusion is higher than in Examples 1 and 2. I was able to.
  • Example 5 the ratio of H 2 gas in the step of forming the silica substrate 51 from the silica substrate temporary molded body 41 (Step 3) was made higher than in Example 3, so that the oxygen-deficient defects in the silica substrate The amount could be further increased, the viscosity at high temperature could be increased, and a silica container having high heat distortion resistance could be obtained. In Example 6, the tendency became more remarkable.
  • the atmosphere gas at the time of melting of the silica-based temporary molded body in Step 3 was 10 vol. Of H 2 gas. . It was found that it was necessary to contain it in a ratio exceeding%.
  • 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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011032147A (ja) * 2009-08-05 2011-02-17 Shinetsu Quartz Prod Co Ltd シリカ容器及びその製造方法

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8272234B2 (en) * 2008-12-19 2012-09-25 Heraeus Shin-Etsu America, Inc. Silica crucible with pure and bubble free inner crucible layer and method of making the same
EP2431338B1 (en) * 2009-04-28 2021-08-25 Shin-Etsu Quartz Products Co., Ltd. Silica vessel
CN102395535B (zh) * 2009-05-26 2014-07-02 信越石英株式会社 二氧化硅容器及其制造方法
US9003832B2 (en) * 2009-11-20 2015-04-14 Heraeus Shin-Etsu America, Inc. Method of making a silica crucible in a controlled atmosphere
EP2703526A4 (en) * 2012-03-23 2014-12-31 Shinetsu Quartz Prod SILICONE CONTAINER FOR BREEDING A SILICON CRYSTAL AND MANUFACTURING METHOD THEREFOR
WO2014167788A1 (ja) * 2013-04-08 2014-10-16 信越石英株式会社 単結晶シリコン引き上げ用シリカ容器及びその製造方法
US10308541B2 (en) 2014-11-13 2019-06-04 Gerresheimer Glas Gmbh Glass forming machine particle filter, a plunger unit, a blow head, a blow head support and a glass forming machine adapted to or comprising said filter
JP6220772B2 (ja) * 2014-12-26 2017-10-25 クアーズテック株式会社 石英ガラスルツボの製造方法
US10822716B2 (en) * 2016-09-13 2020-11-03 Sumco Corporation Quartz glass crucible and manufacturing method thereof
JP6769893B2 (ja) * 2017-02-24 2020-10-14 東ソ−・エスジ−エム株式会社 Ｏｈ基拡散抑制能を有する石英ガラス材料及びその製造方法
US10710918B1 (en) 2018-02-19 2020-07-14 Owens-Brockway Glass Container Inc. Method of manufacturing a hollow glass article having a container shape
CN111122373B (zh) * 2018-10-30 2024-01-02 贝特瑞新材料集团股份有限公司 一种纳米硅基材料中硅含量的测试方法
JP7724066B2 (ja) * 2021-03-05 2025-08-15 信越石英株式会社 石英ガラスるつぼの評価方法及び製造方法
US20240141546A1 (en) * 2021-03-05 2024-05-02 Shin-Etsu Quartz Products Co., Ltd. Method for evaluating quartz glass crucible, method for manufacturing the same, and quartz glass crucible

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0422861A (ja) 1990-05-17 1992-01-27 Matsushita Seiko Co Ltd 炭酸ガス検知装置
JPH0729871A (ja) 1993-06-25 1995-01-31 Toshiba Corp 表面処理方法および表面処理装置
JPH07206451A (ja) 1993-12-29 1995-08-08 Nippon Steel Corp 合成石英ガラスの製造方法
JPH07277744A (ja) 1994-04-04 1995-10-24 Nippon Steel Corp 合成石英ガラスの製造方法
JPH07277743A (ja) 1994-04-04 1995-10-24 Nippon Steel Corp 合成石英ガラスの製造方法
JP2559604B2 (ja) * 1987-12-15 1996-12-04 東芝セラミックス株式会社 石英ガラスルツボの製造方法
JPH09255476A (ja) 1996-03-18 1997-09-30 Shinetsu Quartz Prod Co Ltd 単結晶引き上げ用石英ガラスるつぼ及びその製造方法
JPH1025184A (ja) 1996-07-09 1998-01-27 Shinetsu Quartz Prod Co Ltd 石英ルツボの製造装置及び方法
JPH11171684A (ja) 1997-09-30 1999-06-29 Shinetsu Quartz Prod Co Ltd シリコン単結晶製造用石英ガラスるつぼおよび その製造方法
JPH11199369A (ja) * 1998-01-08 1999-07-27 Toshiba Ceramics Co Ltd シリコン単結晶引上げ用石英ガラスルツボおよびその製造方法
JP2000086383A (ja) * 1998-09-04 2000-03-28 Toshiba Ceramics Co Ltd シリコン単結晶引上げ用石英ガラスルツボおよびその製造方法
JP2002362932A (ja) 2001-03-24 2002-12-18 Shinetsu Quartz Prod Co Ltd ＳｉＯ２含有複合材料の製造方法、その製造方法により得られる複合材料及び複合材料の使用
JP2004131380A (ja) 2002-09-20 2004-04-30 Heraeus Quarzglas Gmbh & Co Kg 不透明石英ガラス複合材の製造方法、前記方法による複合材、およびその利用法
JP2004292211A (ja) * 2003-03-26 2004-10-21 Kuramoto Seisakusho Co Ltd 石英ルツボの内面透明層形成方法
JP2008308383A (ja) * 2007-06-18 2008-12-25 Covalent Materials Corp シリコン単結晶の製造方法
WO2009041684A1 (ja) * 2007-09-28 2009-04-02 Japan Super Quartz Corporation シリカガラスルツボとその製造方法および引き上げ方法

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01148718A (ja) 1987-12-03 1989-06-12 Shin Etsu Handotai Co Ltd 石英るつぼの製造方法
JPH0729871B2 (ja) 1987-12-03 1995-04-05 信越半導体 株式会社 単結晶引き上げ用石英るつぼ
US4935046A (en) 1987-12-03 1990-06-19 Shin-Etsu Handotai Company, Limited Manufacture of a quartz glass vessel for the growth of single crystal semiconductor
DE69109026T2 (de) 1990-09-07 1995-12-07 Mitsubishi Chem Corp Silica-Glas Pulver und Verfahren seiner Herstellung und daraus hergestellter Silica-Glasgegenstand.
JP3100836B2 (ja) 1994-06-20 2000-10-23 信越石英株式会社 石英ガラスルツボとその製造方法
DE19541372A1 (de) * 1994-11-15 1996-05-23 Gen Electric Tiegel aus geschmolzenem Quarz sowie Verfahren zu dessen Herstellung
US5976247A (en) 1995-06-14 1999-11-02 Memc Electronic Materials, Inc. Surface-treated crucibles for improved zero dislocation performance
EP0911429A1 (en) 1997-09-30 1999-04-28 Heraeus Quarzglas GmbH Quartz glass crucible for producing silicon single crystal and method for producing the crucible
US6553787B1 (en) * 1999-04-06 2003-04-29 Nanwa Quartz, Inc. Method for manufacturing quartz glass crucible
US6546754B1 (en) * 2000-10-27 2003-04-15 General Electric Company Apparatus for silica crucible manufacture
US6510707B2 (en) * 2001-03-15 2003-01-28 Heraeus Shin-Etsu America, Inc. Methods for making silica crucibles
US7118789B2 (en) 2001-07-16 2006-10-10 Heraeus Shin-Etsu America Silica glass crucible
JP4841764B2 (ja) * 2001-07-23 2011-12-21 信越石英株式会社 シリコン単結晶引上げ用石英ガラスるつぼの製造方法及び装置
JP4339003B2 (ja) * 2003-04-02 2009-10-07 ジャパンスーパークォーツ株式会社 石英ガラスルツボの製造方法
TW200730672A (en) * 2005-11-29 2007-08-16 Japan Super Quartz Corp Quartz glass crucible, method of producing the same, and application thereof
WO2009017071A1 (ja) * 2007-07-27 2009-02-05 Japan Super Quartz Corporation 石英ガラスルツボの製造方法
US8196429B2 (en) * 2007-07-28 2012-06-12 Japan Super Quartz Corporation Method and apparatus for manufacturing vitreous silica crucible
WO2009069773A1 (ja) * 2007-11-30 2009-06-04 Japan Super Quartz Corporation 石英ガラスルツボの製造方法および製造装置
JP4918473B2 (ja) * 2007-12-14 2012-04-18 ジャパンスーパークォーツ株式会社 高強度を有する大径シリコン単結晶インゴット引上げ用高純度石英ガラスルツボ
JP5377930B2 (ja) * 2008-10-31 2013-12-25 株式会社Ｓｕｍｃｏ シリコン単結晶引上用石英ガラスルツボの製造方法
US8272234B2 (en) * 2008-12-19 2012-09-25 Heraeus Shin-Etsu America, Inc. Silica crucible with pure and bubble free inner crucible layer and method of making the same
WO2011030657A1 (ja) * 2009-09-10 2011-03-17 ジャパンスーパークォーツ株式会社 シリコン単結晶引き上げ用シリカガラスルツボ及びその製造方法
JP4969632B2 (ja) * 2009-10-14 2012-07-04 信越石英株式会社 シリカ粉及びシリカ容器並びにそれらの製造方法
US9003832B2 (en) * 2009-11-20 2015-04-14 Heraeus Shin-Etsu America, Inc. Method of making a silica crucible in a controlled atmosphere
JP4951057B2 (ja) * 2009-12-10 2012-06-13 信越石英株式会社 シリカ容器及びその製造方法
FR2963341B1 (fr) * 2010-07-27 2013-02-22 Saint Gobain Quartz Sas Creuset a ouverture polygonale

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2559604B2 (ja) * 1987-12-15 1996-12-04 東芝セラミックス株式会社 石英ガラスルツボの製造方法
JPH0422861A (ja) 1990-05-17 1992-01-27 Matsushita Seiko Co Ltd 炭酸ガス検知装置
JPH0729871A (ja) 1993-06-25 1995-01-31 Toshiba Corp 表面処理方法および表面処理装置
JPH07206451A (ja) 1993-12-29 1995-08-08 Nippon Steel Corp 合成石英ガラスの製造方法
JPH07277744A (ja) 1994-04-04 1995-10-24 Nippon Steel Corp 合成石英ガラスの製造方法
JPH07277743A (ja) 1994-04-04 1995-10-24 Nippon Steel Corp 合成石英ガラスの製造方法
JPH09255476A (ja) 1996-03-18 1997-09-30 Shinetsu Quartz Prod Co Ltd 単結晶引き上げ用石英ガラスるつぼ及びその製造方法
JPH1025184A (ja) 1996-07-09 1998-01-27 Shinetsu Quartz Prod Co Ltd 石英ルツボの製造装置及び方法
JPH11171684A (ja) 1997-09-30 1999-06-29 Shinetsu Quartz Prod Co Ltd シリコン単結晶製造用石英ガラスるつぼおよび その製造方法
JPH11199369A (ja) * 1998-01-08 1999-07-27 Toshiba Ceramics Co Ltd シリコン単結晶引上げ用石英ガラスルツボおよびその製造方法
JP2000086383A (ja) * 1998-09-04 2000-03-28 Toshiba Ceramics Co Ltd シリコン単結晶引上げ用石英ガラスルツボおよびその製造方法
JP2002362932A (ja) 2001-03-24 2002-12-18 Shinetsu Quartz Prod Co Ltd ＳｉＯ２含有複合材料の製造方法、その製造方法により得られる複合材料及び複合材料の使用
JP2004131380A (ja) 2002-09-20 2004-04-30 Heraeus Quarzglas Gmbh & Co Kg 不透明石英ガラス複合材の製造方法、前記方法による複合材、およびその利用法
JP2004292211A (ja) * 2003-03-26 2004-10-21 Kuramoto Seisakusho Co Ltd 石英ルツボの内面透明層形成方法
JP2008308383A (ja) * 2007-06-18 2008-12-25 Covalent Materials Corp シリコン単結晶の製造方法
WO2009041684A1 (ja) * 2007-09-28 2009-04-02 Japan Super Quartz Corporation シリカガラスルツボとその製造方法および引き上げ方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DODD, D. M.; FRASER, D. B.: "Optical determination of OH in fused silica", JOURNAL OF APPLIED PHYSICS, vol. 37, 1966, pages 3911
KHOTIMCHENKO, V. S. ET AL.: "Determining the content of hydrogen dissolved in quartz glass using the methods of Raman scattering and mass spectrometry", JOURNAL OF APPLIED SPECTROSCOPY, vol. 46, no. 6, 1987, pages 632 - 635, XP009149953, DOI: doi:10.1007/BF00661243
NASU, S. ET AL.: "Gas release of various kinds of vitreous silica", JOURNAL OF ILLUMINATING ENGINEERING INSTITUTE OF JAPAN, vol. 74, no. 9, 1990, pages 595 - 600
YOSHIKAZU KIKUCHI ET AL.: "OH Content Dependence of Viscosity of Vitreous Silica", JOURNAL OF THE CERAMICS SOCIETY OF JAPAN, vol. 105, no. 8, 1997, pages 645 - 649

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011032147A (ja) * 2009-08-05 2011-02-17 Shinetsu Quartz Prod Co Ltd シリカ容器及びその製造方法

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