WO2013132629A1 - 高純度シリコンの製造方法、及びこの方法で得られた高純度シリコン、並びに高純度シリコン製造用シリコン原料 - Google Patents
高純度シリコンの製造方法、及びこの方法で得られた高純度シリコン、並びに高純度シリコン製造用シリコン原料 Download PDFInfo
- Publication number
- WO2013132629A1 WO2013132629A1 PCT/JP2012/055937 JP2012055937W WO2013132629A1 WO 2013132629 A1 WO2013132629 A1 WO 2013132629A1 JP 2012055937 W JP2012055937 W JP 2012055937W WO 2013132629 A1 WO2013132629 A1 WO 2013132629A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silicon
- ppmw
- molten
- raw material
- purity
- Prior art date
Links
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 250
- 239000010703 silicon Substances 0.000 title claims abstract description 250
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 249
- 239000002994 raw material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000007711 solidification Methods 0.000 claims abstract description 23
- 230000008023 solidification Effects 0.000 claims abstract description 23
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 18
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 18
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 57
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 57
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 26
- 229910052796 boron Inorganic materials 0.000 claims description 26
- 239000012535 impurity Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000002019 doping agent Substances 0.000 claims description 19
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 4
- 238000005266 casting Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000010453 quartz Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 230000007547 defect Effects 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000007664 blowing Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 229910052581 Si3N4 Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001782 photodegradation Methods 0.000 description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/037—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/007—Mechanisms for moving either the charge or the heater
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table
- H01L31/0288—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table characterised by the doping material
-
- 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
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
- C30B13/08—Single-crystal growth by zone-melting; Refining by zone-melting adding crystallising materials or reactants forming it in situ to the molten zone
- C30B13/10—Single-crystal growth by zone-melting; Refining by zone-melting adding crystallising materials or reactants forming it in situ to the molten zone with addition of doping materials
-
- 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
- C30B21/00—Unidirectional solidification of eutectic materials
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a production method for producing high-purity silicon that can be suitably used for applications such as solar cell production by solidifying molten silicon as a raw material in one direction, and a high-temperature obtained by this method.
- the present invention relates to pure silicon and a silicon raw material for producing high-purity silicon used in this method.
- metal impurity elements such as Fe, Ni, and Ti that are contained in the molten silicon and reduce the carrier lifetime are solidified in the mold container.
- highly purified silicon can be obtained by segregating to the upper portion and removing the portion where impurities are concentrated by this segregation.
- a mold made of quartz is mainly used as a mold container in which the molten silicon is put.
- powder such as silicon nitride, silicon oxide, silicon carbide, etc. is applied to the inner wall surface of polyvinyl alcohol (PVA).
- PVA polyvinyl alcohol
- Non-Patent Document 1 A part of the oxygen dissolved in the molten silicon becomes silicon monoxide and evaporates as a gas from the surface of the molten silicon, but the distribution coefficient (segregation coefficient) of oxygen in the molten silicon is close to 1, so the molten silicon In particular, at the lower part of the mold container far from the surface, the oxygen concentration remains high and the silicon is taken into the solidified silicon.
- Patent Document 3 a method using gallium instead of boron has been proposed.
- Such photodegradation is caused by the combination of boron and oxygen dissolved in silicon.
- oxygen concentration exceeds the solid solubility limit, oxygen precipitates as silicon oxide (SiOx), which is a dislocation growth source.
- SiOx silicon oxide
- fixing to dislocations causes a decrease in the quality of the solar cell, such as a decrease in photoelectric conversion efficiency when used as a silicon substrate of the solar cell. Therefore, in order to obtain silicon having a low oxygen concentration, a method of melting by increasing the degree of vacuum in the apparatus using a plasma melting apparatus has been proposed (Patent Document 4).
- the carbon in the silicon becomes a nucleus that promotes oxygen precipitation, and when used as a silicon substrate of a solar cell, the photoelectric conversion efficiency decreases, and the carbon itself It may precipitate as silicon carbide (SiC) and increase the leakage current. Furthermore, when slicing and cutting out the substrate, it may cause the silicon substrate to become defective, such as scratches on the substrate. .
- Patent Document 5 As a method for removing carbon, an inert gas containing an oxidizing agent is blown through a decarburizing lance to completely remove carbon.
- a method for removing carbon oxide as a gas from the surface of molten silicon (for example, Patent Document 5), and a method for removing precipitated silicon carbide include adding a temperature gradient to molten silicon (Patent Document 6) or a magnetic field. (Patent Document 7) has been proposed, in which silicon carbide is locally accumulated and removed.
- Non-patent Document 2 the addition of germanium to silicon improves the quality as a solar cell, and the addition of 0.5 to 5% by mass improves the photoelectric conversion efficiency. It has also been reported that the strength is improved by adding 50 to 200 ppmw (Patent Document 8).
- Patent Document 5 when an oxidizing agent or an oxidizing gas is introduced into molten silicon for the purpose of lowering the carbon concentration, the oxygen concentration is increased, and the method described in Patent Document 4 is followed. Even if the deoxidized silicon raw material is used, oxygen is taken into the molten silicon as long as silicon is produced by unidirectional solidification using a quartz mold.
- Patent Document 3 proposes a method of using gallium instead of boron, but gallium has a larger atomic weight than boron and a distribution coefficient of 0.8 for boron. Since it is very small as 0.008, the addition amount for generating carriers necessary for the solar cell must be very large, and most of the addition amount is other metal impurities during unidirectional solidification. At the same time, it is concentrated in the upper part of the mold container, and there is a problem that the amount used effectively is small and the loss is large, and further, there is a demerit that it is difficult to handle because it is liquid at 30 ° C. or higher.
- silicon oxide precipitates and becomes a dislocation growth source, and it also causes a decrease in photoelectric conversion efficiency. It is also conceivable to use a carbon mold container while avoiding the use of a mold container.
- ingot-shaped silicon silicon ingot
- ingot-shaped silicon can be obtained by unidirectionally solidifying molten silicon and then damaging it. When it is used, it is expensive per se, and if it is damaged at a time, the cost becomes very high.
- the coefficient of thermal expansion of carbon is larger than that of silicon nitride or silicon oxide, which is a mold release material, the mold release material is easy to peel off, causing molten silicon to adhere to the inner wall surface of the mold container.
- silicon nitride or silicon oxide which is a mold release material
- the present inventors have conducted intensive studies to solve the various problems described above in producing high-purity silicon used for solar cell production and the like by unidirectional solidification of molten silicon.
- molten silicon containing carbon and germanium at a predetermined concentration as raw materials, even when a quartz mold container used in general industrial production is used, the oxygen concentration in solidified silicon and High-purity silicon that can produce a good-quality silicon substrate for solar cells without photodegradation at low cost and industrially, even when boron concentration is added as a dopant.
- the present invention was completed.
- an object of the present invention is to produce inexpensively and industrially easily high-purity silicon having a low oxygen concentration and a low carbon concentration and suitable for applications such as solar cell production by unidirectional solidification of molten silicon.
- Another object of the present invention is to provide a method for producing high purity silicon.
- Another object of the present invention is to provide high-purity silicon which has a low oxygen concentration and a low carbon concentration and can be suitably used for applications such as solar cell production.
- An object of the present invention is to provide a silicon raw material for producing high-purity silicon suitable for producing such high-purity silicon having a low oxygen concentration and low carbon concentration.
- the present invention is a method for producing high-purity silicon in which molten silicon as a raw material is unidirectionally solidified in a mold container to produce high-purity silicon, and the raw material contains a carbon content of 100 to 1000 ppmw and a germanium content of 0.
- the present invention is high-purity silicon produced by the above method, and the carbon concentration measured by Fourier transform infrared spectroscopy (FT-IR) is 10 ⁇ 10 17 atoms / cm 3 or less, The oxygen concentration is 3 ⁇ 10 17 atoms / cm 3 or less, and the number of remaining silicon carbide of 100 ⁇ m or more measured by infrared transmission method (IR-TM) is 10 / dm 3 or less, preferably 5 / High-purity silicon characterized by a dm of 3 or less.
- FT-IR Fourier transform infrared spectroscopy
- the present invention is a silicon raw material used for producing high-purity silicon, comprising carbon at a rate of 100 to 1000 ppmw and germanium at a rate of 0.5 to 2000 ppmw. It is a silicon raw material for silicon production.
- a holding step for holding the molten state of the molten silicon in the mold vessel is provided, and in this holding step, the inner wall surface of the mold vessel is provided. It is preferable to form a silicon carbide adhesion layer having a thickness of 20 ⁇ m or more on the surface, so that even if a quartz mold container is used, the silicon carbide adhesion layer on the inner wall surface of the mold container is solidified during unidirectional solidification of molten silicon. It is possible to effectively suppress the dissolution of oxygen in the molten silicon and reduce the carbon concentration in the solidified silicon.
- the contact area between the molten silicon and the inner wall surface of the mold vessel is relatively small compared to the volume of the molten silicon, and silicon carbide deposited in the molten silicon can be obtained only by natural convection of the molten silicon.
- stirring that gives forced convection to the molten silicon in the mold container is performed, or after such stirring is performed It is preferable to stop and hold the stirring, thereby forming a silicon carbide adhesion layer having a desired thickness on the inner wall surface of the mold container.
- the present invention during the heat removal step of the molten silicon raw material, it is preferable to perform stirring that gives forced convection to the molten silicon raw material in the mold vessel, thereby solidifying the molten silicon in one direction.
- the carbon concentration in the molten silicon increases.
- the silicon carbide is deposited on the surface of the molten silicon or in the mold container. It can be moved to the inner wall surface side and can be prevented as much as possible from being taken into the solidified silicon.
- the molten silicon used as a raw material contains carbon at a rate of 100 to 1000 ppmw and germanium at a rate of 0.5 to 2000 ppmw.
- the metal impurity concentration is 1000 ppmw or less and that boron is contained as a dopant. According to the present invention, even when boron is added as a dopant, it is possible to produce high-purity silicon that can produce a good-quality silicon substrate without photodegradation.
- high-purity silicon having low oxygen concentration and low carbon concentration and few crystal defects can be produced inexpensively and industrially easily.
- High-purity silicon suitable for manufacturing a silicon substrate having good quality without photodegradation can be provided, and the product yield when making a wafer can be improved, and defects due to an increase in leakage current can be provided. Can be suppressed.
- the raw material molten silicon used in the present invention has a carbon content of 100 ppmw to 1000 ppmw, preferably 200 ppmw to 500 ppmw, and germanium is 0.5 ppmw to 2000 ppmw, preferably 50 ppmw to 1000 ppmw.
- a continuous silicon carbide adhesion layer is formed on the inner wall surface of the mold container, and the entire inner wall surface of the mold container is surely covered with the silicon carbide adhesion layer.
- the thickness of the silicon carbide layer to be formed varies considerably at the position of the inner wall surface of the mold container, but in order to suppress the dissolution of oxygen, the thinnest part is 20 ⁇ m or more, preferably 50 ⁇ m or more and 2000 ⁇ m.
- the thickness at the thinnest part is less than 20 ⁇ m, the effect of suppressing the dissolution of oxygen may be insufficient, and conversely, if the thickness exceeds 2000 ⁇ m, the effect of suppressing the dissolution of oxygen Is achieved, but it becomes too thick in the parts other than the thinnest part, and the product yield is lowered accordingly.
- molten silicon is always in coexistence with silicon carbide, carbon is dissolved in the molten silicon in a saturated state, and oxygen dissolved from the inner wall surface of the mold vessel is immediately removed as carbon monoxide gas. Is done.
- the appropriate carbon content in the molten silicon for forming a silicon carbide layer having such a thickness on the inner wall surface of the mold container depends on the volume of the molten silicon and the ratio of the contact area between the molten silicon and the inner wall surface of the mold container. , 100 ppmw or more is necessary, and at most 1000 ppmw is sufficient.
- the upper part where metal impurities and the like are condensed is removed, and further, the side part and the bottom part are cut and then sliced into a solar cell wafer, but the carbon content exceeds 1000 ppmw. Then, silicon carbide tends to remain in the interior, and the silicon carbide layer formed on the inner wall surface of the mold container becomes too thick, resulting in an increase in the amount of cutting at the side surface or the bottom and a decrease in product yield.
- the silicon carbide layer formed on the inner surface of the mold container is formed not only on the side surface but also on the bottom of the mold container. This will adversely affect crystal growth at the initial stage of solidification. Silicon carbide acts as a nucleation site for silicon crystals, and the probability of generating crystal grains having random grain boundaries increases. Since random grain boundaries are likely to be the starting point of crystal defects, many crystal defects are formed, resulting in a problem that the carrier lifetime is reduced. Therefore, in the present invention, germanium is added to molten silicon at a ratio of 0.5 ppmw or more and 2000 ppmw or less, so that even if a silicon carbide layer is formed at the bottom of the mold container, silicon with few crystal defects is formed. Crystals can be produced. The concentration of germanium is preferably 50 ppmw or more, but even if added over 2000 ppmw, the effect of suppressing crystal defects does not increase, and conversely, the cost increases due to the cost of germanium.
- the precipitated silicon carbide moves in the mold container by natural convection, and the one that has reached the surface of the molten silicon floats, Anything that reaches the wall will be deposited and deposited there.
- the contact area between the molten silicon and the inner wall of the mold container is small compared to the volume of the molten silicon, the silicon carbide precipitated in the molten silicon can be transferred to the inner surface of the mold container only by natural convection of the molten silicon. It may be difficult to move.
- the silicon carbide adhesion layer can be efficiently formed on the inner wall surface of the mold vessel by stirring, but depending on the manner of stirring, the surface of the molten silicon and the inner wall surface of the mold vessel are not closed. If silicon carbide enters the flow, the silicon carbide is taken into the solidified silicon ingot without reaching the surface of the molten silicon or the inner wall of the mold vessel. End up. Therefore, in the present invention, if necessary, the stirring is preferably stopped and held after stirring. Silicon carbide generated in the molten silicon has a specific gravity larger than that of the molten silicon, and silicon carbide is clustered by stirring. Therefore, if stirring is stopped, the silicon carbide easily settles and adheres to the bottom of the mold container.
- the holding time is usually 30 minutes to 8 hours, preferably 1 hour to 5 hours.
- the agitation time depends on the flow rate of forced convection caused by this agitation and the ratio of the volume of molten silicon to the contact area between the molten silicon and the inner surface of the mold vessel. Depending on the above, it is usually 10 minutes or more and 3 hours or less, and preferably 30 minutes or more and 2 hours or less. Although it depends on the height, it is usually from 10 minutes to 5 hours, preferably from 30 minutes to 3 hours.
- the silicon carbide adhering layer may not be a continuous layer. Conversely, even if the holding time is longer than 8 hours, the silicon carbide adhering layer does not become thick and the productivity is lowered. Will be invited.
- the present invention if necessary, it is preferable to stir the molten silicon during the heat removal step of unidirectional solidification, thereby further reducing the carbon concentration in the molten silicon. Even if silicon carbide is generated during the single heat extraction process, it can be moved to the surface side of the molten silicon or the inner wall surface of the mold container.
- gas blowing stirring As a method for stirring molten silicon performed in the holding step and the heat removal step described above, methods such as gas blowing stirring, electromagnetic stirring, and mechanical stirring can be applied. From the viewpoint of manufacturing a silicon ingot at low cost, gas Stirring by blowing is preferred. As a gas used for this purpose, there are options such as helium, neon, and argon, but argon is desirable for the same reason as described above.
- the gas blowing operation involves immersing a lance made of carbon, quartz, or a ceramic lance such as silicon carbide, silicon nitride, or aluminum oxide in the molten silicon.
- the lance has an outer diameter of 5 to 30 mm and an inner diameter of 3 to 20 mm.
- the gas to be blown from the flow rate is 0.2 liters (L) to 5 L / min, preferably 0.5 L to 2 L / min.
- the tip of the lance is always about 0.5 to 5 cm away from the rising solidification interface so that the lance is not swallowed by the solidified silicon ingot.
- the lance may be moved upward as the coagulation progresses so as to maintain a distant position.
- the molten silicon used as a raw material when producing high-purity silicon used for solar cell production, should have a metal impurity concentration of 1000 ppmw or less, preferably 0.05 ppmw boron as a dopant. It should be contained in the range of 0.5 ppmw or less, preferably 0.1 ppmw or more and 0.3 ppmw or less. According to the method of the present invention, by using such a silicon raw material, and even when boron is added as a dopant, it is possible to produce a silicon substrate for solar cells of good quality without photodegradation. Pure silicon can be easily produced at low cost and industrially.
- Example 1 A silicon raw material 10 kg prepared by adding boron (B) as a dopant at a concentration of 0.1 ppmw to a silicon raw material having a carbon concentration (C concentration) of 150 ppmw, a germanium concentration (Ge concentration) of 1 ppmw, and a metal impurity concentration of 0.1 ppmw or less was prepared. .
- the silicon raw material is charged into the mold container, and then 1500 ° C.
- the silicon raw material was melted by heating to 1450 ° C. for 1 hour while maintaining the molten state of the generated molten silicon (holding step).
- heat removal was started from the bottom of the mold container, and gradually solidified in one direction from the bottom to the top to produce a silicon ingot (heat removal). Process).
- the silicon ingot thus produced was cut into about 15 mm at the upper part of the solidification direction, about 15 mm at the lower part (bottom part) of the solidification direction, and about 15 mm at the peripheral part to obtain a silicon block of 155 mm ⁇ 155 mm ⁇ 98 mm.
- the continuity and the minimum thickness were examined by observing the silicon carbide adhering layer with a microscope at the lower part (bottom part) in the solidification direction and the cross section of the peripheral part.
- the carrier lifetime depends on the boron concentration, the metal impurity concentration, and the defect density, which are the generation sources of carriers, the boron concentration is the same, and the metal impurity concentration is negligible.
- a relative comparison of defect density is possible by time. Therefore, acid etching is performed on the test plate cut out in the horizontal direction at a position 25% from the bottom of the silicon ingot obtained in Comparative Example 1 below to extract the defective portion, and the carrier lifetime in five portions without the defect.
- the average value is taken as LTmax, and the ratio of the LTmax value to the in-plane average value of the carrier lifetime measured at five locations at each height position (evaluation position) is obtained, and the in-plane average value ratio Furthermore, the average value of the in-plane average value ratio calculated
- the carrier lifetime was determined as an in-plane average value excluding that portion because it was influenced by the diffusion of metal impurities from the release material in the vicinity of the contact portion with the inner wall surface of the mold container. The results are shown in Table 1.
- the infrared transmission method (IR-TM) is performed according to the method described in “Proc 25th EU PVSEC (2010) pp1624”, and the microwave photoconductive decay method ( ⁇ -PCD method) is used. It was carried out according to the method described in “Kobe Steel Engineering Reports Vol.52, No.2, pp87-93 (Sep. 2002)”, and further, for Fourier transform infrared spectroscopy (FT-IR), “Kanagawa This was carried out in accordance with the method described in Research Report No. 15/2009, pp.19-23 ”, Industrial Technology Center.
- FT-IR Fourier transform infrared spectroscopy
- Example 1 For comparison, a silicon ingot was prepared and evaluated in the same manner as in Example 1 by adding only boron as a dopant in a proportion of 0.1 ppmw to a silicon raw material having a metal impurity concentration of 0.1 ppmw or less. The results are shown in Table 1.
- Example 1 of the present invention From the comparison between Example 1 and Comparative Examples 1 and 2 shown in Table 1, in Example 1 of the present invention, the oxygen concentration can be reduced without increasing the carbon concentration or the residual silicon carbide concentration. It was found that a silicon ingot having a high carrier lifetime can be obtained.
- Example 2 A silicon ingot was prepared and evaluated in the same manner as in Example 1 except that boron was added as a dopant at a ratio of 0.3 ppmw. Photodegradation was conducted after measuring the carrier lifetime using a test plate at a height of 25% obtained from the silicon ingot obtained in Example 2 and then irradiating with halogen light of 200 mW / cm 2 for 10 minutes. The carrier lifetime was measured and investigated by comparing the in-plane average values before and after the light irradiation.
- Example 3 For comparison, a silicon ingot was prepared and evaluated in the same manner as in Example 2 by adding only boron as a dopant at a rate of 0.3 ppmw to a silicon raw material having a metal impurity concentration of 0.1 ppmw or less. The results are shown in Table 1.
- Example 3 A silicon raw material 400 kg prepared by adding boron (B) as a dopant at a concentration of 0.15 ppmw to a silicon raw material having a carbon concentration (C concentration) of 400 ppmw, a germanium concentration (Ge concentration) of 200 ppmw, and a metal impurity concentration of 0.1 ppmw or less was prepared. .
- the silicon raw material is charged into the mold container, and then 1500 ° C. After the silicon raw material is melted by heating, a carbon lance having an outer diameter of 12.5 mm and an inner diameter of 6 mm from above is placed in the mold container, and the tip is positioned at a height of 50 mm from the bottom of the mold container. Then, Ar gas was blown through the carbon lance at a rate of 1 L / min (Ar blowing), and the molten silicon in the mold container was stirred for 1 hour. Was maintained for 3 hours while maintaining the molten state (holding step).
- Example 4 A silicon raw material in which boron (B) is added as a dopant at a concentration of 0.15 ppmw to a silicon raw material having a carbon concentration (C concentration) of 400 ppmw, a germanium concentration (Ge concentration) of 30 ppmw, and a metal impurity concentration of 0.1 ppmw or less is used. Except for the above, a silicon ingot was prepared in the same manner as in Example 3, and the oxygen concentration and carbon concentration, the remaining silicon carbide, and the carrier lifetime were measured. The results are shown in Table 1.
- Example 5 Use of silicon raw material in which boron (B) is added at a concentration of 0.15 ppmw as a dopant to a silicon raw material having a carbon concentration (C concentration) of 1000 ppmw, a germanium concentration (Ge concentration) of 2000 ppmw, and a metal impurity concentration of 0.1 ppmw or less. Except for the above, a silicon ingot was prepared in the same manner as in Example 3, and the oxygen concentration and carbon concentration, the remaining silicon carbide, and the carrier lifetime were measured. The results are shown in Table 1.
- Example 3 From the comparison between Example 3 and Comparative Example 4 shown in Table 1, in Comparative Example 4, the carbon concentration was high and the number of residual silicon carbide was also observed. In the upper part of the silicon ingot, a large number of silicon carbides were observed in a band shape, and a decrease in carrier lifetime due to high carbon concentration or residual silicon carbide was also observed.
- Example 5 A silicon raw material in which boron (B) is added as a dopant at a concentration of 0.15 ppmw to a silicon raw material having a carbon concentration (C concentration) of 80 ppmw, a germanium concentration (Ge concentration) of 200 ppmw, and a metal impurity concentration of 0.1 ppmw or less is used. Except for the above, a silicon ingot was prepared in the same manner as in Example 3, and the oxygen concentration and carbon concentration, the remaining silicon carbide, and the carrier lifetime were measured. The results are shown in Table 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Silicon Compounds (AREA)
Abstract
Description
炭素濃度(C濃度)150ppmw、ゲルマニウム濃度(Ge濃度)1ppmw、及び金属不純物濃度0.1ppmw以下のシリコン原料に、ドーパントとしてホウ素(B)を0.1ppmwの濃度で添加したシリコン原料10kgを用意した。
結果を表1に示す。
比較として、金属不純物濃度が0.1ppmw以下のシリコン原料に、ドーパントとしてホウ素のみを0.1ppmwの割合で添加し、実施例1と同様にしてシリコンインゴットを作製し、その評価を行った。
結果を表1に示す。
更に比較として、金属不純物濃度が0.1ppmw以下のシリコン原料に、ゲルマニウムを0.3ppmwの割合で添加すると共に、ドーパントとしてホウ素を0.1ppmwの割合で添加し、実施例1と同様にしてシリコンインゴットを作製し、その評価を行った。
結果を表1に示す。
ドーパントとしてホウ素を0.3ppmwの割合で添加したこと以外は、上記の実施例1と同様にしてシリコンインゴットを作製し、その評価を行った。
光劣化は、この実施例2で得られたシリコンインゴットから得られた高さ25%位置の試験板を用い、キャリアライフタイムを測定した後、200mW/cm2のハロゲン光を10分照射した後のキャリアライフタイムを測定し、光照射前後の面内平均値を比較することにより調査した。
比較として、金属不純物濃度が0.1ppmw以下のシリコン原料に、ドーパントとしてホウ素のみを0.3ppmwの割合で添加し、実施例2と同様にしてシリコンインゴットを作製し、その評価を行った。
結果を表1に示す。
炭素濃度(C濃度)400ppmw、ゲルマニウム濃度(Ge濃度)200ppmw、及び金属不純物濃度0.1ppmw以下のシリコン原料に、ドーパントとしてホウ素(B)を0.15ppmwの濃度で添加したシリコン原料400kgを用意した。
結果を表1に示す。
炭素濃度(C濃度)400ppmw、ゲルマニウム濃度(Ge濃度)30ppmw、及び金属不純物濃度0.1ppmw以下のシリコン原料に、ドーパントとしてホウ素(B)を0.15ppmwの濃度で添加したシリコン原料を用いたこと以外は、上記実施例3と同様にして、シリコンインゴットを作製し、酸素濃度及び炭素濃度、残存炭化珪素、及びキャリアライフタイムを測定した。
結果を表1に示す。
炭素濃度(C濃度)1000ppmw、ゲルマニウム濃度(Ge濃度)2000ppmw、及び金属不純物濃度0.1ppmw以下のシリコン原料に、ドーパントとしてホウ素(B)を0.15ppmwの濃度で添加したシリコン原料を用いたこと以外は、上記実施例3と同様にして、シリコンインゴットを作製し、酸素濃度及び炭素濃度、残存炭化珪素、及びキャリアライフタイムを測定した。
結果を表1に示す。
比較として炭素濃度(C濃度)が400ppmwであって、金属不純物濃度が0.1ppmw以下のシリコン原料に、ドーパントとしてホウ素を0.15ppmwの割合で添加したシリコン原料400kgを用い、シリコン原料を溶解した後にAr吹込みを行わずに4時間保持し、抜熱工程でのAr吹込みとを行わなかったこと以外は、上記実施例3と同様にして一方向凝固させてシリコンインゴットを作製し、実施例3と同様にしてその評価を行った。
結果を表1に示す。
炭素濃度(C濃度)80ppmw、ゲルマニウム濃度(Ge濃度)200ppmw、及び金属不純物濃度0.1ppmw以下のシリコン原料に、ドーパントとしてホウ素(B)を0.15ppmwの濃度で添加したシリコン原料を用いたこと以外は、上記実施例3と同様にして、シリコンインゴットを作製し、酸素濃度及び炭素濃度、残存炭化珪素、及びキャリアライフタイムを測定した。
結果を表1に示す。
Claims (9)
- 鋳型容器内で原料の溶融シリコンを一方向凝固させて高純度シリコンを製造する高純度シリコンの製造方法であり、
前記原料として、炭素含有量100~1000ppmw及びゲルマニウム含有量0.5~2000ppmwの溶融シリコンを用いることを特徴とする高純度シリコンの製造方法。 - 前記一方向凝固のための抜熱工程に先駆けて、前記鋳型容器内で溶融シリコンの溶融状態を保持する保持工程を設け、この保持工程で前記鋳型容器の内壁面に厚さ20μm以上の炭化珪素付着層を形成する請求項1に記載の高純度シリコンの製造方法。
- 前記溶融シリコンの保持工程の際に、鋳型容器内の溶融シリコンに強制対流を与える攪拌を行う請求項2に記載の高純度シリコンの製造方法。
- 前記溶融シリコンの保持工程の際に、鋳型容器内の溶融シリコンに強制対流を与える攪拌を行った後に、この攪拌を停止して保持する請求項2に記載の高純度シリコンの製造方法。
- 前記溶融シリコンの抜熱工程の際に、鋳型容器内の溶融シリコンに強制対流を与える攪拌を行う請求項1~4に記載の高純度シリコンの製造方法。
- 前記高純度シリコンが太陽電池用シリコンであり、原料の溶融シリコンが、金属不純物濃度1000ppmw以下であると共に、ドーパントとしてホウ素を含有する請求項1~5のいずれかに記載の高純度シリコンの製造方法。
- 請求項1~6に記載のいずれかの方法で製造された高純度シリコンであり、フーリエ変換赤外分光法(FT-IR)で測定された炭素濃度が10×1017atoms/cm3以下であって、酸素濃度が3×1017atoms/cm3以下であり、かつ、赤外透過法(IR-TM)で測定された100μm以上の残存炭化珪素数が10個/dm3以下であることを特徴とする高純度シリコン。
- 高純度シリコンを製造するために用いられるシリコン原料であり、炭素を100~1000ppmwの割合で含むと共に、ゲルマニウムを0.5~2000ppmwの割合で含むことを特徴とする高純度シリコン製造用シリコン原料。
- 前記高純度シリコンが太陽電池用シリコンであり、金属不純物濃度が1000ppmw以下であると共に、ドーパントとしてホウ素を含有する請求項8に記載の高純度シリコン製造用シリコン原料。
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014503378A JP5938092B2 (ja) | 2012-03-08 | 2012-03-08 | 高純度シリコンの製造方法、及びこの方法で得られた高純度シリコン、並びに高純度シリコン製造用シリコン原料 |
US14/383,321 US10167199B2 (en) | 2012-03-08 | 2012-03-08 | Method for manufacturing highly pure silicon, highly pure silicon obtained by this method, and silicon raw material for manufacturing highly pure silicon |
CN201280073015.XA CN104271506B (zh) | 2012-03-08 | 2012-03-08 | 用于制造高纯硅的方法、通过该方法得到的高纯硅、以及用于制造高纯硅的硅原料 |
PCT/JP2012/055937 WO2013132629A1 (ja) | 2012-03-08 | 2012-03-08 | 高純度シリコンの製造方法、及びこの方法で得られた高純度シリコン、並びに高純度シリコン製造用シリコン原料 |
SI201231510T SI2824070T1 (sl) | 2012-03-08 | 2012-03-08 | Metoda za izdelavo visoko čistega silikona |
LTEP12870715.5T LT2824070T (lt) | 2012-03-08 | 2012-03-08 | Didelio grynumo silicio gamybos būdas |
PL12870715T PL2824070T3 (pl) | 2012-03-08 | 2012-03-08 | Sposób wytwarzania krzemu o wysokiej czystości |
EP12870715.5A EP2824070B1 (en) | 2012-03-08 | 2012-03-08 | Method for manufacturing highly pure silicon |
ES12870715T ES2704906T3 (es) | 2012-03-08 | 2012-03-08 | Método para la fabricación de silicio altamente puro |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2012/055937 WO2013132629A1 (ja) | 2012-03-08 | 2012-03-08 | 高純度シリコンの製造方法、及びこの方法で得られた高純度シリコン、並びに高純度シリコン製造用シリコン原料 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013132629A1 true WO2013132629A1 (ja) | 2013-09-12 |
Family
ID=49116145
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/055937 WO2013132629A1 (ja) | 2012-03-08 | 2012-03-08 | 高純度シリコンの製造方法、及びこの方法で得られた高純度シリコン、並びに高純度シリコン製造用シリコン原料 |
Country Status (9)
Country | Link |
---|---|
US (1) | US10167199B2 (ja) |
EP (1) | EP2824070B1 (ja) |
JP (1) | JP5938092B2 (ja) |
CN (1) | CN104271506B (ja) |
ES (1) | ES2704906T3 (ja) |
LT (1) | LT2824070T (ja) |
PL (1) | PL2824070T3 (ja) |
SI (1) | SI2824070T1 (ja) |
WO (1) | WO2013132629A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103469303A (zh) * | 2013-09-24 | 2013-12-25 | 江西赛维Ldk太阳能高科技有限公司 | 多晶硅锭及其制备方法、多晶硅片和多晶硅铸锭用坩埚 |
CN104556045A (zh) * | 2014-12-11 | 2015-04-29 | 中国科学院等离子体物理研究所 | 一种利用Al-Si合金熔体机械搅拌去除Si中杂质P的方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110344113A (zh) * | 2019-08-23 | 2019-10-18 | 江苏美科硅能源有限公司 | 一种减少多晶硅锭或铸造单晶锭氧含量和杂质点的装料方法 |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63166A (ja) | 1986-06-19 | 1988-01-05 | Toshiba Corp | 不揮発性半導体記憶装置 |
JPS6350308A (ja) * | 1986-08-14 | 1988-03-03 | バイエル・アクチエンゲゼルシヤフト | 溶融ケイ素からの炭素の除去方法 |
JPH02267110A (ja) | 1989-04-07 | 1990-10-31 | Kawasaki Steel Corp | 金属シリコン脱炭用ランスおよび脱炭方法 |
JPH0574783A (ja) * | 1991-09-13 | 1993-03-26 | Fujitsu Ltd | シリコンウエハーおよびウエハーゲツタリングの処理方法 |
JPH11314911A (ja) | 1998-05-07 | 1999-11-16 | Sumitomo Sitix Amagasaki:Kk | 多結晶シリコンインゴットの製造方法 |
JP2001000064A (ja) | 1999-06-18 | 2001-01-09 | Kazumi Kimura | 子豚圧死防止具 |
WO2006093089A1 (ja) * | 2005-02-28 | 2006-09-08 | Kyocera Corporation | 多結晶シリコン基板、多結晶シリコンインゴット及びそれらの製造方法、光電変換素子、並びに光電変換モジュール |
WO2006104107A1 (ja) * | 2005-03-29 | 2006-10-05 | Kyocera Corporation | 多結晶シリコン基板及びその製造方法、多結晶シリコンインゴット、光電変換素子、並びに光電変換モジュール |
JP2007000261A (ja) | 2005-06-22 | 2007-01-11 | Chugoku Electric Power Co Inc:The | 発光機能付き歩行補助具 |
JP2008000127A (ja) | 2006-05-25 | 2008-01-10 | Nof Corp | 液状コーヒーホワイトナー用油脂組成物 |
JP2008127254A (ja) * | 2006-11-22 | 2008-06-05 | Kyocera Corp | シリコンインゴットの製造方法 |
JP2008156227A (ja) * | 2006-12-22 | 2008-07-10 | Schott Solar Gmbh | 結晶化シリコンの製造方法および結晶化シリコン |
JP2011000524A (ja) | 2009-06-17 | 2011-01-06 | Ryobi Shoji Kk | 塗膜除去方法並びに装置 |
JP2011524849A (ja) * | 2008-06-16 | 2011-09-08 | カリソーラー インコーポレイテッド | 太陽電池製造用のゲルマニウム濃縮シリコン材料 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5961944A (en) * | 1996-10-14 | 1999-10-05 | Kawasaki Steel Corporation | Process and apparatus for manufacturing polycrystalline silicon, and process for manufacturing silicon wafer for solar cell |
US5972107A (en) * | 1997-08-28 | 1999-10-26 | Crystal Systems, Inc. | Method for purifying silicon |
CN1648041A (zh) * | 2004-01-19 | 2005-08-03 | 吴尔盛 | 从金属硅制备超纯硅的方法和装置 |
CN101367522A (zh) * | 2007-08-13 | 2009-02-18 | 侯振海 | 生产高纯硅的新材料及工艺 |
US8758507B2 (en) * | 2008-06-16 | 2014-06-24 | Silicor Materials Inc. | Germanium enriched silicon material for making solar cells |
WO2010127184A1 (en) * | 2009-04-29 | 2010-11-04 | Calisolar, Inc. | Quality control process for umg-si feedstock |
TWI403461B (zh) * | 2010-07-21 | 2013-08-01 | Masahiro Hoshino | Method and apparatus for improving yield and yield of metallurgical silicon |
-
2012
- 2012-03-08 JP JP2014503378A patent/JP5938092B2/ja active Active
- 2012-03-08 LT LTEP12870715.5T patent/LT2824070T/lt unknown
- 2012-03-08 US US14/383,321 patent/US10167199B2/en active Active
- 2012-03-08 ES ES12870715T patent/ES2704906T3/es active Active
- 2012-03-08 PL PL12870715T patent/PL2824070T3/pl unknown
- 2012-03-08 EP EP12870715.5A patent/EP2824070B1/en active Active
- 2012-03-08 CN CN201280073015.XA patent/CN104271506B/zh active Active
- 2012-03-08 WO PCT/JP2012/055937 patent/WO2013132629A1/ja active Application Filing
- 2012-03-08 SI SI201231510T patent/SI2824070T1/sl unknown
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63166A (ja) | 1986-06-19 | 1988-01-05 | Toshiba Corp | 不揮発性半導体記憶装置 |
JPS6350308A (ja) * | 1986-08-14 | 1988-03-03 | バイエル・アクチエンゲゼルシヤフト | 溶融ケイ素からの炭素の除去方法 |
JPH02267110A (ja) | 1989-04-07 | 1990-10-31 | Kawasaki Steel Corp | 金属シリコン脱炭用ランスおよび脱炭方法 |
JPH0574783A (ja) * | 1991-09-13 | 1993-03-26 | Fujitsu Ltd | シリコンウエハーおよびウエハーゲツタリングの処理方法 |
JPH11314911A (ja) | 1998-05-07 | 1999-11-16 | Sumitomo Sitix Amagasaki:Kk | 多結晶シリコンインゴットの製造方法 |
JP2001000064A (ja) | 1999-06-18 | 2001-01-09 | Kazumi Kimura | 子豚圧死防止具 |
WO2006093089A1 (ja) * | 2005-02-28 | 2006-09-08 | Kyocera Corporation | 多結晶シリコン基板、多結晶シリコンインゴット及びそれらの製造方法、光電変換素子、並びに光電変換モジュール |
WO2006104107A1 (ja) * | 2005-03-29 | 2006-10-05 | Kyocera Corporation | 多結晶シリコン基板及びその製造方法、多結晶シリコンインゴット、光電変換素子、並びに光電変換モジュール |
JP2007000261A (ja) | 2005-06-22 | 2007-01-11 | Chugoku Electric Power Co Inc:The | 発光機能付き歩行補助具 |
JP2008000127A (ja) | 2006-05-25 | 2008-01-10 | Nof Corp | 液状コーヒーホワイトナー用油脂組成物 |
JP2008127254A (ja) * | 2006-11-22 | 2008-06-05 | Kyocera Corp | シリコンインゴットの製造方法 |
JP2008156227A (ja) * | 2006-12-22 | 2008-07-10 | Schott Solar Gmbh | 結晶化シリコンの製造方法および結晶化シリコン |
JP2011524849A (ja) * | 2008-06-16 | 2011-09-08 | カリソーラー インコーポレイテッド | 太陽電池製造用のゲルマニウム濃縮シリコン材料 |
JP2011000524A (ja) | 2009-06-17 | 2011-01-06 | Ryobi Shoji Kk | 塗膜除去方法並びに装置 |
Non-Patent Citations (5)
Title |
---|
JOURNAL OF APPLIED PHYSICS, vol. 96, 2004, pages 1238 |
JOURNAL OF CRYSTAL GROWTH, vol. 310, 2008, pages 2204 |
KANAGAWA PREFECTURE INDUSTRIAL TECHNOLOGY CENTRE RESEARCH REPORT NO. 15/2009, pages L9 - 23 |
KOBE SEIKO GIHOU, vol. 52, no. 2, September 2002 (2002-09-01), pages 87 - 93 |
See also references of EP2824070A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103469303A (zh) * | 2013-09-24 | 2013-12-25 | 江西赛维Ldk太阳能高科技有限公司 | 多晶硅锭及其制备方法、多晶硅片和多晶硅铸锭用坩埚 |
CN103469303B (zh) * | 2013-09-24 | 2016-08-10 | 江西赛维Ldk太阳能高科技有限公司 | 多晶硅锭及其制备方法、多晶硅片和多晶硅铸锭用坩埚 |
CN104556045A (zh) * | 2014-12-11 | 2015-04-29 | 中国科学院等离子体物理研究所 | 一种利用Al-Si合金熔体机械搅拌去除Si中杂质P的方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2013132629A1 (ja) | 2015-07-30 |
CN104271506B (zh) | 2015-11-11 |
LT2824070T (lt) | 2019-04-25 |
US20150028268A1 (en) | 2015-01-29 |
EP2824070B1 (en) | 2018-12-12 |
JP5938092B2 (ja) | 2016-06-22 |
SI2824070T1 (sl) | 2019-05-31 |
US10167199B2 (en) | 2019-01-01 |
EP2824070A4 (en) | 2015-10-14 |
CN104271506A (zh) | 2015-01-07 |
ES2704906T3 (es) | 2019-03-20 |
EP2824070A1 (en) | 2015-01-14 |
PL2824070T3 (pl) | 2019-09-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100945517B1 (ko) | 다결정 실리콘 잉곳의 제조방법 | |
TWI546401B (zh) | Cu-Ga alloy sputtering target and its manufacturing method | |
JP4528995B2 (ja) | Siバルク多結晶インゴットの製造方法 | |
TWI532891B (zh) | Polycrystalline silicon wafers | |
SU et al. | Preparation, microstructure and dislocation of solar-grade multicrystalline silicon by directional solidification from metallurgical-grade silicon | |
JP5938092B2 (ja) | 高純度シリコンの製造方法、及びこの方法で得られた高純度シリコン、並びに高純度シリコン製造用シリコン原料 | |
JP2012193423A (ja) | Cu−Ga合金材およびその製造方法 | |
TW201137191A (en) | Method of exocasting an article of semiconducting material | |
KR101074304B1 (ko) | 금속 실리콘과 그 제조 방법 | |
JP6233114B2 (ja) | 半導体装置用シリコン部材及び半導体装置用シリコン部材の製造方法 | |
JP5861770B2 (ja) | 多結晶シリコンおよびその鋳造方法 | |
JP4748187B2 (ja) | Si結晶インゴットの製造方法 | |
JP6401051B2 (ja) | 多結晶シリコンインゴットの製造方法 | |
JP2008162865A (ja) | 石英ガラスルツボ | |
JP5201446B2 (ja) | ターゲット材およびその製造方法 | |
JP2007045682A (ja) | シリコン単結晶の育成方法およびシリコンウェーハ | |
JP2011138866A (ja) | 多結晶シリコンブロック材の製造方法、多結晶シリコンウエハの製造方法及び多結晶シリコンブロック材 | |
JP2016088822A (ja) | シリコン部品用シリコン結晶及びこのシリコン結晶から加工されたシリコン部品 | |
JP2013079411A (ja) | Cu−Ga合金スパッタリングターゲット及びその製造方法 | |
JP2004161575A (ja) | 多結晶シリコンインゴット及び部材の製造方法 | |
JP2007063048A (ja) | 半導体インゴット及び太陽電池素子の製造方法 | |
JP2009023851A (ja) | シリコン単結晶製造用原料の製造方法およびシリコン単結晶の製造方法 | |
JP6147788B2 (ja) | Cu−Ga合金スパッタリングターゲット | |
JP6016849B2 (ja) | Cu−Ga合金スパッタリングターゲット | |
JP2016222520A (ja) | 太陽電池用シリコン単結晶インゴット、およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12870715 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014503378 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012870715 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14383321 Country of ref document: US |