WO2009130786A1 - Procédé de fabrication d'une matière à base de silicium pour cellule solaire - Google Patents
Procédé de fabrication d'une matière à base de silicium pour cellule solaire Download PDFInfo
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- WO2009130786A1 WO2009130786A1 PCT/JP2008/058067 JP2008058067W WO2009130786A1 WO 2009130786 A1 WO2009130786 A1 WO 2009130786A1 JP 2008058067 W JP2008058067 W JP 2008058067W WO 2009130786 A1 WO2009130786 A1 WO 2009130786A1
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- Prior art keywords
- silicon
- raw material
- solar cell
- ingot
- producing
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000008569 process Effects 0.000 title claims abstract description 12
- 239000002210 silicon-based material Substances 0.000 title abstract 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 156
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 156
- 239000010703 silicon Substances 0.000 claims abstract description 156
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000006698 induction Effects 0.000 claims abstract description 39
- 230000008018 melting Effects 0.000 claims abstract description 32
- 238000002844 melting Methods 0.000 claims abstract description 32
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001868 water Inorganic materials 0.000 claims abstract description 23
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 57
- 238000004519 manufacturing process Methods 0.000 claims description 46
- 238000001816 cooling Methods 0.000 claims description 44
- 239000007864 aqueous solution Substances 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 16
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- -1 silicate alkali salt Chemical class 0.000 claims description 5
- 150000004760 silicates Chemical class 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 24
- 238000007670 refining Methods 0.000 abstract description 23
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 38
- 229910002804 graphite Inorganic materials 0.000 description 29
- 239000010439 graphite Substances 0.000 description 29
- 239000012535 impurity Substances 0.000 description 29
- 229910052751 metal Inorganic materials 0.000 description 28
- 239000002184 metal Substances 0.000 description 27
- 239000007789 gas Substances 0.000 description 21
- 238000005204 segregation Methods 0.000 description 21
- 238000007711 solidification Methods 0.000 description 20
- 230000008023 solidification Effects 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 18
- 229910052796 boron Inorganic materials 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 14
- 239000008188 pellet Substances 0.000 description 14
- 239000011574 phosphorus Substances 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 13
- 239000004115 Sodium Silicate Substances 0.000 description 12
- 229910052911 sodium silicate Inorganic materials 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000011449 brick Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000000498 cooling water Substances 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000011044 quartzite Substances 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 150000003388 sodium compounds Chemical class 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NCZAACDHEJVCBX-UHFFFAOYSA-N [Si]=O.[C] Chemical compound [Si]=O.[C] NCZAACDHEJVCBX-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 230000005674 electromagnetic induction Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WENVJNOLTLNPQS-UHFFFAOYSA-N tetrachlorosilane zinc Chemical compound [Zn].[Si](Cl)(Cl)(Cl)Cl WENVJNOLTLNPQS-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
- C01B33/025—Preparation by reduction of silica or free silica-containing material with carbon or a solid carbonaceous material, i.e. carbo-thermal process
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
- H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a method for producing a silicon raw material of solar cell grade purity used for a silicon substrate for a solar cell.
- the present silicon raw material for solar cells is manufactured by the method shown in FIG.
- the trichlorosilane hydrogen reduction method is the most important among the current production methods, and supplies most of the current semiconductor grade and solar cell grade silicon raw materials.
- Silane pyrolysis can produce the most pure silicon, but the production cost is high.
- the silicon tetrachloride zinc reduction method is the first industrialized method for semiconductor silicon production, but the purity of the produced silicon is insufficient, and it is difficult to continue the production equipment. Not used.
- the above three production methods are called gas production methods because silicon is reacted with chlorine, hydrogen, or both to produce a gaseous silicon compound.
- the semiconductor silicon gas production method has a drawback that the volume of the apparatus is large and the production cost is small because the production volume is small compared to the size of the apparatus.
- the metallurgical refining method similarly shown in FIG. 1 is a silicon manufacturing method proposed to solve the manufacturing cost limitation of the gas manufacturing method.
- Silicon for solar cells usually does not require higher purity than silicon for semiconductor devices.
- the purity of silicon raw materials for semiconductor devices usually needs to be 9N (99.9999999%) or higher, but silicon raw materials for solar cells are used if they have a purity of 7N (99.99999%) excluding carbon, oxygen and boron. can do.
- the metallurgical refining method was devised to produce such a medium-purity silicon raw material for solar cells, and impurities were removed to the purity of solar cell grade silicon by melting and refining metal grade silicon in a high purity vessel. (Refer nonpatent literature 1).
- metal grade silicon (about 99% purity) is melted in a high vacuum by electron beam melting to preferentially evaporate and remove vaporizable elements such as phosphorus, and then to silicon dissolved in an electromagnetic induction furnace.
- Irradiation with a plasma jet of argon containing a small amount of oxygen gas oxidizes boron, carbon, etc. to generate volatile oxide compounds, evaporates and removes them, and further dissolves silicon to unidirectionally solidify metal impurities.
- the solidification segregation accumulates the final solidified portion of the ingot, and the final solidified portion of the ingot is cut and discarded to reduce the impurity concentration of the remaining ingot portion.
- the above metallurgical refining method has the following drawbacks. That is, among impurities contained in metal silicon, an electron beam melting and refining process is mainly used to remove phosphorus by vaporization refining, and further, plasma jet irradiation irradiation is mainly performed to remove boron by oxidative vaporization refining. Two steps are used.
- metal refining by electron beam melting requires the installation of a complex apparatus consisting of a vacuum exhaust system in order to maintain a high vacuum.
- a complex apparatus consisting of a vacuum exhaust system in order to maintain a high vacuum.
- metal refining by plasma jet irradiation generates a plasma gas with a temperature of 10,000 degrees and irradiates the metal, so that if the refining time is long, it becomes inevitable that it becomes a refining method with high energy consumption.
- the removal reaction rate is low and the refining time is long because the concentration of removed phosphorus and boron is in a low region of 1 ppm or less.
- the metallurgical refining method has a problem that although the productivity is improved by downsizing the manufacturing apparatus as compared with the gas manufacturing method, the improvement in the productivity is extremely insufficient.
- the present invention has been made in view of the above-described problems, and provides a silicon raw material manufacturing method capable of manufacturing a silicon raw material for solar cells with low energy consumption and a short refining time without requiring a complicated apparatus. Is an issue.
- the present invention includes a first step in which a silicon oxide raw material, an alkali metal compound, and water are mixed and heated and reacted in a container to prepare an alkali silicate aqueous solution; A second step in which hydrochloric acid or sulfuric acid is added to the alkali silicate aqueous solution to precipitate silicic acid to separate and dry high-purity silicon oxide, and the separated and dried silicon oxide is reduced at a high temperature in an electric furnace with a carbon material.
- the rock resource quartzite is mainly composed of silicon oxide, but it contains oxides such as calcium, magnesium, aluminum, iron, boron and phosphorus as gangue.
- Rock quartzite cannot be easily dissolved with acids such as hydrochloric acid or sulfuric acid, but can be melted by mixing with alkali oxides such as sodium or potassium.
- the molten alkali silicate salt is water-soluble and can be combined with water to produce an aqueous alkali silicate salt solution.
- the silica and the alkali metal compound are melted at a high temperature (usually 800 to 1200 ° C.) and cooled, and then combined with water to form an alkali silicate aqueous solution.
- the alkali silicate aqueous solution is produced by the production method or by the method of simultaneously mixing silica stone, an alkali metal compound, and water and reacting them at a low temperature (usually 80 to 180 ° C.) to produce the alkali silicate aqueous solution.
- hydrochloric acid or sulfuric acid is added to the manufactured aqueous alkali silicate salt solution to precipitate a high-purity silicic acid component, which is separated by filtration and dehydrated to produce high-purity silicon oxide.
- FIG. 2 shows the change in Gibbs free energy as a function of temperature when a sodium compound reacts with silicon oxide to produce an alkali silicate salt. Under normal conditions, the reaction proceeds when the Gibbs free energy is negative.
- alkali silicate is produced by the reaction of silicon oxide and sodium hydroxide or the reaction of silicon oxide and sodium carbonate. The reaction between silicon oxide and sodium hydroxide proceeds from room temperature, but the reaction between silicon oxide and sodium carbonate proceeds only at about 700K or higher. Therefore, the production of sodium silicate by melting of sodium carbonate and quartzite proceeds efficiently at a temperature of about 800 ° C. or higher, which is a temperature at which sodium silicate softens and has fluidity.
- Fig. 3 shows the change in Gibbs free energy related to the production of alkali silicate by the reaction of industrially available alkali metal (lithium, potassium) compounds and silicon oxide.
- the reaction between lithium hydroxide and potassium hydroxide and silicon oxide proceeds at room temperature or higher.
- the reaction between lithium carbonate and silicon oxide proceeds at 500K or more, and the reaction between potassium carbonate and silicon oxide proceeds at about 700K or more.
- alkali metal compound and reaction temperature for producing alkali silicate aqueous solution are preferably sodium, potassium and lithium hydroxides and carbonates.
- FIG. 4 shows the equilibrium vapor pressure with respect to the temperature change of water.
- Water has a vapor pressure of 1 atm at 100 ° C. and reaches a seaside pressure with a vapor pressure of 218 at 374 ° C.
- An industrial pressure vessel usually has a simple structure when 10 atmospheres or less is used. In order to carry out an aqueous solution reaction at 10 atm or less in a pressure vessel having a simple structure, it is necessary to carry out the reaction at a temperature of 180 ° C.
- the reactions that proceed at 180 ° C. (453 K) or less are lithium, sodium, and potassium hydroxides having a negative Gibbs free energy change. Was found to be preferred.
- FIG. 5 As an example of the reaction between an alkali silicate aqueous solution and an acid, the reaction of an aqueous sodium silicate salt solution with hydrochloric acid and sulfuric acid is illustrated together with a change in Gibbs free energy with respect to temperature.
- the free energy change of Gibbs becomes negative, so sodium chloride and hydrated silicic acid are generated.
- Sodium chloride is contained in the liquid as an aqueous solution, but silicic acid is not dissolved in an acidic aqueous solution and thus precipitates as hydrated silicic acid.
- a small amount of elements other than silicon present in the aqueous solution are contained in the liquid as an aqueous chloride solution or an aqueous sulfide solution.
- the precipitated hydrated silicic acid is separated from the aqueous solution by filtration, and the hydrated silicic acid separated by filtration is further thermally decomposed to separate moisture, whereby high-purity silicon oxide is produced.
- a method of removing impurities in silicon by unidirectional solidification while induction melting in a longitudinally electrically insulated crucible is performed in a metal by a “zone melt method”. This is the same as the method for removing impurities.
- This method is based on the thermodynamic principle that when the metal solidifies, the chemical potential of the solute element between the solid phase and the liquid phase is equal.
- the segregation coefficient of solute elements in silicon is K
- C0 is the initial concentration of the solute
- X is the length of the solidification phase
- L is the length of the dissolution zone.
- FIG. 6 shows segregation coefficients of solute elements in silicon.
- the concentration of the solute relating to each segregation coefficient due to the unidirectional solidification segregation of silicon is shown as a ratio to the initial concentration.
- the concentration in silicon after solidification segregation is about 0.01 ppm.
- the concentration of boron after solidification segregation is about 4 ppm.
- a method used as one of the combination techniques in the present invention that is, a method of casting a vertically long ingot by solidifying in one direction while inducing and melting silicon in a crucible electrically insulated in a longitudinal direction, This is a silicon casting method using the “crucible induction melting method”.
- Fig. 8 shows the configuration of the cooling crucible induction melting apparatus.
- the cooling crucible (cold crucible) induction melting method is a container formed by arranging vertically divided conductive segments electrically insulated from each other and cooled by cooling water in the circumferential direction.
- the cooling crucible current (53) flows into each conductive segment of the cooling crucible (50) according to the principle of electromagnetic induction. Is induced as a skin current to form a loop current in each segment according to the principle of current conservation.
- the cooling crucible current (53) further induces a skin current of the molten metal current (55) in the conductive molten metal (54) inside the copper cooled crucible (50).
- the molten metal current (55) heats the molten metal (54) and acts on the induced magnetic field to cause a force (Lorentz force) that pushes the surface of the molten metal (54) inward.
- a force Lorentz force
- the molten metal can be held in the air in a non-contact manner. By this method, it is possible to dissolve and hold the material while eliminating the contamination of the impurities from the crucible, so that the high-purity metal can be melted and continuously cast.
- a solar cell grade silicon raw material can be manufactured by a combination of the first to fifth simple processes. For this reason, the complicated apparatus in the conventional metallurgical refining method is unnecessary. In addition, since the two processes of dephosphorization using an electron beam that consumes a lot of energy and boron refining using a plasma jet are not used, low energy consumption and a short refining time can be realized.
- aqueous sodium silicate solution by reaction of silica, sodium hydroxide and water As an example of preparing an alkali silicate aqueous solution by mixing a silicon oxide raw material, an alkali metal hydroxide, and water and raising the temperature and reacting in a vessel, pressure is obtained by mixing silica stone, sodium hydroxide, and water. The reaction was carried out by raising the temperature in the reaction vessel (1).
- a pressure reaction vessel (1) having a volume of about 15 liters shown in FIG. 9 was prepared.
- the material of the pressure reaction vessel (1) is stainless steel, the body is 8 mm thick, and the thickness of the disk-shaped material that seals the raw material inlet (101) is 10 mm.
- a pressure gauge (102) and a thermocouple thermometer (103) are attached to the pressure reaction vessel (1), and a gas burner (104) is installed at the bottom.
- the reaction procedure is as follows. 1.32 kg of silicic acid, 0.88 kg of sodium hydroxide and 8 liters of water were weighed and charged into the pressure reaction vessel (1). After charging the reactants, the raw material inlet (101) was sealed and the gas burner (104) installed at the bottom of the vessel was ignited. About 20 minutes after heating by the gas burner (104) started, the thermocouple thermometer (103) indicated 170 ° C. The pressure gauge (102) simultaneously showed 8.4 atmospheres. Once the temperature reached 170 ° C, the temperature was adjusted to indicate between 170 ° C and 180 ° C. The pressure gauge (102) exhibited between about 8.4 atmospheres and 10.5 atmospheres. The reaction in this state was maintained for 6 hours.
- the gas burner (104) was turned off and the pressure reaction vessel (1) was cooled to room temperature. After cooling, the raw material inlet (101) was opened, and the reaction product in the pressure reaction vessel (1) was taken out. The reaction product was an aqueous solution with slight turbidity. When this aqueous solution was filtered, a colorless and transparent aqueous solution (sodium silicate aqueous solution) was obtained as the filtrate.
- ⁇ Second step Production of high-purity silicon oxide by reaction of aqueous sodium silicate solution and hydrochloric acid> Examples for producing high-purity silicon oxide by depositing and drying silicic acid by adding hydrochloric acid or sulfuric acid to an aqueous solution of alkali silicate, and adding silica to an aqueous solution of sodium silicate, separating and drying, This was carried out in the example of producing pure silicon oxide.
- a resin reaction vessel (2) shown in FIG. 10 was prepared.
- the container (2) was made of metal, but the inner surface was lined with polypropylene, and a rotary stirrer (201) coated with polypropylene was installed, and the internal volume was about 100 liters.
- a hydrochloric acid feeder (202) made of polypropylene material was installed on the upper part of the container (2), and a stopcock for adjusting the amount of hydrochloric acid to be supplied was installed.
- the reaction was performed according to the following procedure. That is, 30 liters of the sodium silicate aqueous solution produced and filtered in the first step was charged into the container (2).
- the aqueous solution in which precipitation of silicic acid was completed by the reaction in the container (2) was taken out, and the silicic acid was separated from the aqueous solution by a centrifugal filter. Further, the operation of adding water to the silicic acid separated in the centrifugal filter and washing it with water and further filtering it by centrifugation was repeated four times. Thereafter, silicic acid washed and separated with a centrifugal filter was placed in a thermostatic bath and dried at about 180 ° C. to produce high purity silicon oxide.
- the chemical concentration of the raw silica and the high-purity silicon oxide produced by the above procedure was performed to determine the impurity concentration.
- the result was shown in FIG. Boron in the raw silica was 1.7 ppmw, phosphorus was 3.0 ppmw, aluminum, iron, and titanium were 14 ppmw to 136 ppmw.
- boron was 0.5 ppmw or less, phosphorus was 0.5 ppmw or less and other metal impurities were reduced from 0.8 ppmw to 4.0 ppmw.
- ⁇ Third step carbon reduction of silicon oxide by electric furnace>
- the maximum output of the DC power supply is 160 kW
- the diameter in the furnace is 40 cm
- the height is 50 cm
- the furnace volume is 0.06 cubic meters
- the furnace bottom is made of graphite brick (301)
- the furnace wall is made of alumina brick (302).
- the furnace body (303) has a structure in which bricks (301) and (302) are wrapped with an iron plate having a thickness of 3 mm.
- the graphite electrode (304) was a graphite rod having a diameter of 12 cm, and could move up and down to adjust the voltage during energization.
- Two raw material addition ports (306) having a diameter of 10 cm were provided in the furnace lid portion (305).
- a metal fitting (307) which was water-cooled was used for the conductive wire portion electrically connected to the graphite electrode (304) and the graphite brick (301).
- the electric furnace reduction procedure for silicon is as follows. First, 85 kg of silicon oxide prepared in the second step, 38 kg of carbon powder prepared by pyrolysis of natural gas, and a small amount of sugar are mixed well with a small amount of water, and this mixed silicon oxide-carbon mixture is a rotating drum type. About 120 kg of silicon oxide-carbon mixed pellets having a diameter of about 2 cm. The mixed pellets were thoroughly dried with an incubator and then used as a reducing material for the DC arc electric furnace (3).
- the mixed pellets were additionally charged from the raw material addition port (306) to proceed the reduction. Such an operation was continued for about 5 hours.
- the total amount of the mixed pellets charged was 120 kg.
- the voltage gradually increased slightly to about 60 V, and the current was maintained at 2500A.
- the upper layer portion of the stacked mixed pellets was heated red, and the supply of power was stopped after the ejection of the gas generated by the reaction almost disappeared.
- the furnace body (303) was disassembled and the silicon in the furnace was taken out. About 29 kg of silicon was produced.
- the results of impurity analysis of the produced silicon were 0.2 ppmw or less for both boron and phosphorus, 75 ppmw for aluminum, 164 ppmw for iron, 2 ppmw for titanium, 1 ppmw for chromium, and 1100 ppmw for carbon.
- the boron and phosphorus concentrations in the reduced silicon were lowered, and it became clear that the conditions that the silicon raw material for solar cells should satisfy with respect to the boron and phosphorus concentrations were achieved by the present invention.
- an electric furnace that uses a plasma jet of argon gas or the like as a heat source in a method of generating silicon from high temperature reduction in an electric furnace and taking it out of the electric furnace. If an electric furnace using a plasma jet as a heat source is used, there is no fear that impurities in the graphite material are mixed due to exhaustion of the graphite material as in the case of using an electric furnace of a graphite electrode. Therefore, an electric furnace using a plasma jet as a heat source can be used to manufacture silicon containing even lower impurities.
- ⁇ 4th step Solidification segregation of silicon by cooling crucible induction melting method> An example of solidification segregation in which a vertically long ingot was cast by inducing and melting silicon in a water-cooled copper crucible electrically insulated in the vertical direction was performed as follows.
- the cooling crucible induction melting furnace (4) of this example is shown in FIG. That is, a cooling crucible (401) and an induction coil (402) surrounding the cooling crucible (401) are installed in a closed furnace in which the internal pressure can be controlled, and the ingot up-and-down moving device is directly below the cooling crucible (401). (403) was installed to continuously pull down silicon (S). Furthermore, a raw material supply device (404), a graphite lump (405), and a graphite lump vertical movement device (406) were installed above the furnace body. The graphite mass (405) is inserted into the height level of the induction coil (402) in the cooling crucible (401) from above to induce heat generation at the time of initial melting of silicon to assist the silicon (S). It is for heating. Reference numerals (407) and (408) denote gas ports.
- the cross section of silicon (S) in the casting direction is circular and its diameter is 15 cm. Therefore, the inner diameter of the cooling crucible (401) was 15 cm, the outer diameter was 19 cm, and the number of divisions for electrically insulating the cooling crucible (401) in the vertical direction was 20.
- Each segment of the copper crucible divided into 20 was processed so that cooling water circulated inside, and an electrically insulating mica was inserted between the segments.
- the cooling water in the cooling crucible (401) has a total flow rate of 150 liters per minute.
- the induction power supply used a maximum output of 200 kW and a frequency of about 20 kHz.
- the induction coil (402) has three turns with an inner diameter of 21 cm and a coil height of 15 cm.
- the procedure of this example is as follows. First, a graphite pedestal having a diameter of 15 cm in cross section with respect to the pulling-down direction is placed on the ingot vertical movement device (403) so that the upper surface of the pedestal is the same as the lower end position of the induction coil (402), and the crucible ( 401) was inserted from below, and 4.5 kg of silicon (S) was placed on the pedestal.
- a graphite block (405) having a circular cross section with respect to the pulling direction, a diameter of 14 cm, and a height of 5 cm is inserted 2 cm above the top surface of the inserted silicon (S) from above.
- the induction coil (402) After the pressure in the melting furnace (4) was reduced to 0.1 Torr with a vacuum pump, argon gas was sent to atmospheric pressure, and an alternating current with a frequency of 20 kHz was applied to the induction coil (402) to an output of 200 kW.
- the induction coil (402) When the induction coil (402) is energized, the graphite mass (405) inserted above the silicon (S) is first heated by induction heat to turn red, and then the charged silicon (S) The temperature was raised by the radiant heat of the red graphite block (405).
- the temperature of the silicon (S) reached about 500 ° C., the electric resistance value of the silicon (S) decreased, the induced current in the silicon (S) increased, and self-heating started.
- the silicon (S) produced in the third step and crushed and washed is supplied from the raw material supply device (404) located above.
- the ingot up-and-down moving device (403) holding the dissolved silicon (S) was lowered to start casting. Since the descent of the ingot moving device (403) starts and the molten silicon (S) descends below the position of the lower end of the induction coil (402), the electromagnetic force received by the molten silicon (S) decreases rapidly.
- the melted silicon (S) has a small amount of heat generation and is cooled and solidified.
- continuous casting was carried out by simultaneously supplying the raw material and continuously solidifying the silicon (S) ingot.
- the casting speed was 2.0 mm / min, and the induction power output during steady casting was about 130 kW. Casting was stopped when the total length of the ingot reached 60 cm.
- ⁇ Fifth step a part of the head of the cast silicon ingot is cut and separated> After cooling the ingot of silicon (S) cast in the fourth step, a part of the head of the cast ingot is cut and separated, and the remaining most of the ingot is used as a silicon raw material for solar cells. .
- the impurity concentration in silicon produced by electric furnace reduction was 0.2 ppmw or less for both boron and phosphorus, 11 ppmw for aluminum, 167 ppmw for iron, 2 ppmw for titanium, 0.5 ppmw for chromium, and 770 ppmw for carbon.
- the results of solidification segregation by the melting method show that the average concentration of impurities is 0.2 ppmw or less for both boron and phosphorus, 0.1 ppmw for aluminum and 0.1 ppmw for iron in the lower 50 cm ingot portion of the ingot 60 cm. 1 ppmw or less, titanium 0.1 ppmw or less, chromium 0.1 ppmw or less, and carbon 7 ppmw.
- the production of a silicon (S) ingot to be segregated and purified by the cooling crucible induction melting method of the above-described embodiment was repeated to produce a total of 51 kg of solar cell grade silicon raw material.
- the 51 kg of silicon (S) was used for production of a polycrystalline ingot for solar cells by a normal mold unidirectional solidification method and production of a polycrystalline substrate for solar cells by a wire saw slice method.
- the silicon (S) is placed in a high-purity silica square mold, melted and unidirectionally solidified, and formed into an ingot having a width of 33 cm ⁇ 33 cm and a height of 20 cm.
- the silicon (S) ingot was divided by a diamond cutting machine, it was processed into a silicon polycrystalline substrate for solar cells having a width of 15 cm ⁇ 15 cm and a thickness of 250 ⁇ m by a wire saw slicing machine.
- FIG. 12 shows the stirring pressure reaction vessel (1).
- the stirrer (105) was charged into the pressure reaction vessel (1) used in “Example 1” from the raw material charging port (101) at the top of the vessel and fixed.
- the material of the stirrer (105) was stainless steel.
- the reaction procedure was the same as “Example 1” except that the reaction was carried out with stirring. That is, 1.32 kg of silicic acid, 0.88 kg of sodium hydroxide and 8 liters of water were charged into the container (1), and stirring was started. The stirring speed was kept constant at 20 rpm. After the gas burner (104) was ignited and the thermocouple thermometer indicated 170 ° C, the temperature was adjusted between 170 ° C and 180 ° C. This stirred reaction was held for 1 hour. After 1 hour of reaction, the reaction product was taken out. The reaction product was an aqueous solution with slight turbidity. When this aqueous solution was filtered, the filtrate showed a colorless and transparent aqueous solution (sodium silicate aqueous solution).
- the colorless and transparent aqueous solution produced by the above procedure was reacted with hydrochloric acid in the same procedure as in “Example 1” to precipitate silicic acid, and further dehydrated to produce silicon oxide.
- the results of chemical analysis of the produced silicon oxide were the same as those of “Example 1” for the concentrations of boron and phosphorus, but the concentrations of the other metal elements were subject to variations in analysis. Matched within range.
- FIG. 16 shows a cooled crucible induction melting furnace (5) to which plasma jet heating is applied in the atmosphere for the present embodiment. That is, in order to install a cooling crucible (501) and an induction coil (502) surrounding the cooling crucible (501) in the atmosphere, and to pull down the silicon (S) ingot directly below the cooling crucible (501).
- the lowering shaft (503) and the vertical movement drive device (504) were installed so that the silicon (S) ingot was continuously pulled down.
- a plasma jet device (505) and a raw material inlet (506) capable of moving up and down and rotating were installed above the furnace body.
- the cross section of the silicon (S) ingot with respect to the casting direction was square, and one side thereof was 20 cm. Therefore, the inner diameter of the cooling crucible (501) was a square with a side of 20 cm, the outer diameter was also square with a side of 25 cm, and the number of divisions for electrically insulating the cooling crucible (501) in the vertical direction was 32.
- Each segment of the cooling crucible (501) divided into 32 was processed so that cooling water circulated therein, and mica of an electrically insulating material was inserted between the segments.
- the cooling water in the cooling crucible (501) flowed at a flow rate of 200 liters per minute as a whole.
- the induction power supply used a maximum output of 300 kW and a frequency of about 12 kHz.
- the induction coil (502) was a square with an inner diameter of 28 cm, the number of turns was 3 turns, and the coil height was 20 cm.
- the plasma jet device (505) for heating the molten silicon (S ′) from the top is a water-cooled plasma torch having a diameter of 9.8 cm and a length of 1.3 m, a DC power supply with a maximum output of 150 kW, and plasma gas ignition. It consisted of a high-frequency transmission device and an argon gas flow rate controller. The diameter of the plasma injection port of the plasma jet apparatus (505) was 18 mm.
- the procedure of this example was performed in the air as follows. First, a graphite pedestal (507) having a square cross section with respect to the pull-down direction and a side of 20 cm is placed on the vertical movement drive device (504) so that the upper surface of the pedestal is the same as the lower end position of the induction coil (502). The cooling crucible (501) was inserted from below, and about 8 kg of silicon (S) was placed on the pedestal.
- the plasma jet device (505) is lowered so that the tip thereof approaches the silicon (S) on the pedestal (507), and argon is further introduced into the plasma torch at 150 liters per minute so that DC plasma is supplied to the cathode of the plasma torch. And ignited between silicon (S). After confirming the ignition of the plasma, an induction power source having a frequency of about 12 kHz was transmitted to apply power to the silicon (S).
- the silicon prepared and crushed and washed in the third step is continuously charged into the cooling crucible (501) from the raw material charging port (506) located above, Casting was started by lowering the vertical movement driving device (504) holding (S).
- the vertical drive unit (504) began to descend, continuous raw material supply and continuous ingot solidification were simultaneously performed, and continuous casting was performed.
- the casting speed is 3.0 mm / min
- the induction power output during steady casting is about 150 kW
- the output for plasma generation is about 65 kW with a voltage of about 130 V and a current of about 500 A. It was. Casting was stopped when the total length of the silicon (S) ingot reached 60 cm.
- impurity concentrations in silicon (S) produced by electric furnace reduction were 0.2 ppmw or less for both boron and phosphorus, aluminum 8 ppmw, iron 108 ppmw, titanium 2 ppmw, chromium 0.8 ppmw, and carbon 920 ppmw.
- silicon (S) was dissolved in the atmosphere so that oxygen in the air was mixed in the silicon.
- silicon monoxide gas Is removed from the silicon (S). That is, in the process of producing a polycrystalline ingot for a solar cell using the silicon raw material produced according to the present embodiment, the process is usually performed by melting and solidifying in an inert gas of argon. Since oxygen generates silicon monoxide gas and is removed from the silicon, there is no problem even if the initial oxygen concentration in the raw material is high.
- the process of making a prototype of the silicon raw material produced in this example into a solar cell was performed as follows.
- the silicon raw material 51 kg produced in this example was used for the production of a polycrystalline ingot for a solar cell by a normal mold unidirectional solidification method. That is, the silicon was charged into a high-purity silica square mold and melted and unidirectionally solidified under an inert gas of argon, and produced into an ingot having a width of 33 cm ⁇ 33 cm and a height of 20 cm. .
- this ingot was divided by a diamond cutting machine, and then processed into a silicon polycrystalline substrate for solar cells having a width of 15 cm ⁇ 15 cm and a thickness of 250 ⁇ m by a wire saw slicing machine.
- the silicon raw material for use in a crystalline silicon solar cell having sufficient quality can be produced at low cost by the method for producing silicon for solar cells of the present invention. Moreover, the manufacturing method of this invention can manufacture the silicon
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Abstract
Cette invention porte sur un procédé de fabrication d'une matière à base de silicium pour une cellule solaire. Ce procédé consiste à mélanger une matière d'oxyde de silicium avec de l'hydroxyde de sodium et de l'eau dans un récipient ; à élever la température du mélange dans un récipient pour permettre à une réaction de se dérouler pour préparer une solution aqueuse de silicate alcalin ; à ajouter de l'acide chlorhydrique à la solution aqueuse de silicate alcalin pour faire précipiter de l'acide silicique ; et à séparer et à sécher de l'oxyde de silicium de pureté élevée. L'oxyde de silicium séparé et séché est réduit par une matière carbonée à une température élevée dans un four électrique pour produire du silicium. Le silicium est ensuite soutiré du four électrique et solidifié de façon unidirectionnelle sous fusion par induction dans un creuset verticalement électriquement isolé pour la coulée d'un lingot verticalement allongé. Une partie de la partie tête du lingot de silicium est coupée et séparée, et la plus grande partie restante est utilisée comme matière à base de silicium pour une cellule solaire. Conformément à la structure ci-dessus, une matière à base de silicium pour cellule solaire peut être obtenue sans devoir utiliser un appareil compliqué, en consommant peu d’énergie et avec un temps d'affinage court.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2011055650A1 (fr) * | 2009-11-06 | 2011-05-12 | 三菱化学株式会社 | Procédé et appareil de production de silicium |
WO2011104795A1 (fr) * | 2010-02-24 | 2011-09-01 | 株式会社Sumco | Tranche de silicium polycristallin |
WO2013080606A1 (fr) * | 2011-11-29 | 2013-06-06 | シャープ株式会社 | Procédé de contrôle d'une masse métallique purifiée, procédé de fabrication d'un métal de haute pureté la comprenant et leurs utilisations |
US10766777B2 (en) | 2009-11-20 | 2020-09-08 | Consarc Corporation | Method for electromagnetic casting of silicon in a conductive crucible using a highest- and lowest-disposed induction coil |
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JPS6456311A (en) * | 1987-08-27 | 1989-03-03 | Kawasaki Steel Co | Production of high-purity silicon |
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JPS60204613A (ja) * | 1984-03-30 | 1985-10-16 | Nippon Sheet Glass Co Ltd | 高純度シリカゲルの製造方法 |
JPS6456311A (en) * | 1987-08-27 | 1989-03-03 | Kawasaki Steel Co | Production of high-purity silicon |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2011055650A1 (fr) * | 2009-11-06 | 2011-05-12 | 三菱化学株式会社 | Procédé et appareil de production de silicium |
US10766777B2 (en) | 2009-11-20 | 2020-09-08 | Consarc Corporation | Method for electromagnetic casting of silicon in a conductive crucible using a highest- and lowest-disposed induction coil |
WO2011104795A1 (fr) * | 2010-02-24 | 2011-09-01 | 株式会社Sumco | Tranche de silicium polycristallin |
WO2013080606A1 (fr) * | 2011-11-29 | 2013-06-06 | シャープ株式会社 | Procédé de contrôle d'une masse métallique purifiée, procédé de fabrication d'un métal de haute pureté la comprenant et leurs utilisations |
JP2013112570A (ja) * | 2011-11-29 | 2013-06-10 | Sharp Corp | 金属精製塊の検査方法およびそれを含む高純度金属の製造方法 |
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