WO2012133986A1 - Procédé d'affinage des impuretés dans du silicium métallurgique utilisant la différence de densité entre les scories et le silicium - Google Patents

Procédé d'affinage des impuretés dans du silicium métallurgique utilisant la différence de densité entre les scories et le silicium Download PDF

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Publication number
WO2012133986A1
WO2012133986A1 PCT/KR2011/004518 KR2011004518W WO2012133986A1 WO 2012133986 A1 WO2012133986 A1 WO 2012133986A1 KR 2011004518 W KR2011004518 W KR 2011004518W WO 2012133986 A1 WO2012133986 A1 WO 2012133986A1
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slag
refining
silicon
cao
impurities
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PCT/KR2011/004518
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English (en)
Korean (ko)
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민동준
정은진
김완호
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연세대학교 산학협력단
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Publication of WO2012133986A1 publication Critical patent/WO2012133986A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/037—Purification
    • 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
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • 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 method for producing economical Si for solar cells (hereinafter, SoG-Si) from metal-grade Si (hereinafter, MG-Si), and more particularly, to remove impurities in Si.
  • the device is designed to solve the limitations of gas phase refining methods, such as the Siemens process, which is complex and low-cost, and enables the simultaneous refining of the impurities in the silicon and the evaporation at the same time by optimizing the process atmosphere and the density difference between the slag and silicon.
  • the present invention relates to a method for refining impurities in MG-Si using slag.
  • the Si manufacturing technology for solar cells is a gas phase process via Trichloro-silane (TCS) or Mono-silane (MS), and Siemens process technology is mainly applied.
  • the gas phase gas oil process is a method of producing high purity polysilicon by repeating the process of repurifying gaseous silicon (MG-Si) made of silica ore using HCl and then re-reducing it to H 2 . It is known to be suitable.
  • this method has been pointed out as a problem of large facility investment cost (capital investment> 100 million won / ton-Si) and low energy efficiency (about 120 kWh / kg). There is a need to improve.
  • the advantage of the metallurgical refining method is MG-Si as a starting material through the high temperature refining process, the main advantage is high energy efficiency and productivity, and has been reported to be able to produce a facility investment of about 25% compared to the meteorological method.
  • the environmental problems legal and technical
  • silane chloride in the meteorological method, it is a technological process suitable for fostering small and medium-sized industries as a low facility investment and environmental load industry. Therefore, Elkem has set the goal of producing polysilicon at the 25% energy level compared to the meteorological method with commercialization of the world's first 2500-ton production facility in 2008.
  • Impurities in MG-Si a raw material of polysilicon, are determined by the raw material used, the quality of the reducing agent, and the carbon reduction method, which is a manufacturing process.
  • the main impurities are P, B, and ore / coke originating elements such as Ca and Mg. Development of refining technology is the key, and various refining technologies are required.
  • the present invention has been made to solve the above-mentioned problems in the prior art, by using a slag with a higher density than silicon containing impurities in the MG-Si slag reduction refining, so that the slag is placed below the silicon in the crucible by the density difference
  • Impurity in MG-Si using the difference in density of the slag and silicon including the step of vaporizing and refining the impurities in the MG-Si through the reduction refining at the interface between the injected slag and the molten Si as well as the vaporization reaction of the molten Si of the upper Of refining method.
  • the crucible is preferably made of one selected from graphite, SiO 2 and SiC.
  • the slag is preferably a binary slag system comprising SiO 2 and one selected from CaF 2 , CaO, FeO, MgO and MnO.
  • the slag is SiO 2 and, Al 2 O 3 -CaO, Al 2 O 3 -FeO, Al 2 O 3 -MgO, CaO-CaF 2, CaO-FeO, CaO-MgO, CaO-MnO, FeO-MgO, FeO It is preferred that it is a ternary slag system comprising one selected from -MnO and FeO-Na 2 O.
  • the slag is SiO 2 and, Al 2 O 3 -CaF 2 -MgO , CaO-Al 2 O 3 -MgO, CaO-Al 2 O 3 -MnO, Al 2 O 3 -FeO-MgO, Al 2 O 3 -CaO It is preferred that it is a quaternary slag system comprising one selected from -Na 2 O, FeO-MgO-Na 2 O and CaO-FeO-MnO.
  • the present invention by applying the metallurgical refining process, it is possible to continuously work by using the slag refining and vaporization refining of the impurities at the same time to increase the productivity and the process stability of the silicon product as well.
  • FIG. 1 is a schematic diagram showing an arrangement of silicon and slag in a crucible due to density differences in silicon refining using slag of the present invention.
  • FIG. 2 is a schematic diagram showing a slag refining and vaporization refining process of impurities at an interface between silicon and slag and from an interface between silicon and air in the apparatus of FIG. 1.
  • Figure 3 is a schematic diagram showing the results when the slag refining and vaporization refining at the same time in the present invention.
  • the present invention relates to a process technology for manufacturing SoG-Si from MG-Si, impurities of high segregation coefficient in silicon is difficult to remove using segregation in a conventional one-way solidification system. Therefore, in order to effectively remove impurities in MG-Si, the present invention utilizes a density difference between silicon and slag to reduce impurities at the lower part of the molten metal through a refining reaction at the interface between the slag and molten Si, and at the surface of the molten metal. The present invention relates to a method for effectively refining impurities in MG-Si through evaporation of.
  • the atmosphere of the refining crucible is adjusted to a reducing atmosphere.
  • FIG. 1 is a schematic diagram showing a refining apparatus for refining silicon using slag of the present invention.
  • the atmosphere of the refining crucible is controlled to a reducing gas atmosphere, specifically, to a mixed reducing gas atmosphere of Ar + H 2 (H 2 O).
  • an inert gas as an atmosphere gas as described above is to relatively suppress the partial pressure of oxygen in the crucible and to remove the slag from the molten Si to the Phosphate (PO 4 3- ) state due to the oxidative refining effect.
  • H 2 is used as the reducing gas as the atmosphere gas in order to more effectively lower the oxygen partial pressure in the refining crucible so that P in the molten Si can be removed in the slag in the form of Phosphide (P 3- ) ions.
  • the crucible is desirably made of one selected from graphite, SiO 2 and SiC.
  • the MG-Si raw material is charged and melted into the crucible adjusted to the atmosphere, in which case it is preferable to manage the temperature of the crucible to 1450 °C or more for sufficient melting.
  • a slag containing SiO 2 having a higher density than silicon is introduced into the MG-Si melted crucible.
  • the slag is placed under the molten Si in the crucible due to the density difference.
  • various slag systems having a relatively higher density than molten Si may be used, and are not limited to specific slag systems.
  • the slag may be a binary slag system comprising SiO 2 and one selected from CaF 2 , CaO, FeO, MgO and MnO.
  • the slag is SiO 2 and, Al 2 O 3 -CaO, Al 2 O 3 -FeO, Al 2 O 3 -MgO, CaO-CaF 2, CaO-FeO, CaO-MgO, CaO-MnO, FeO-MgO, It may be a ternary slag system comprising a selected one of FeO-MnO and FeO-Na 2 O.
  • Table 1 shows the density of binary or higher SiO 2 based system slag meeting the conditions of the present invention.
  • the impurities in the MG-Si are refined through the gasification reaction of the molten Si on the upper side as well as the reduction refining at the interface between the slag and the molten Si.
  • FIG. 2 is a schematic diagram showing a slag refining and vaporization refining process of impurities at an interface between silicon and slag and from an interface between silicon and air in the present invention.
  • the reduction refining process through the reduction reaction at the interface between molten Si and the slag of the present invention undergoes an interfacial reaction with M, which is an impurity such as phosphorus in silicon, by oxygen partial pressure control through a reduction refining reaction in a hydrogen atmosphere. It moves to the slag side below with M ion.
  • the present invention separates and removes impurities P in MG-Si by changing ion stability of, for example, impurities P in slag according to the equilibrium oxygen partial pressure control at the interface in the refining process of molten silicon and slag. can do.
  • the stability of the impurity P in the silicon is changed by the control of the interfacial oxygen partial pressure of Si / SiO 2 , the critical oxygen partial pressure is different depending on the composition of the slag, but p O2 is about 10 -16.5 atm (critical oxygen partial pressure) It is known that the reaction mechanism changes in the vicinity.
  • P which is an impurity in molten Si
  • P is effectively removed in the slag underneath in the form of Phosphide (P 3- ) ion. You can do it.
  • the stability of the P ion in the slag in the present invention is greatly affected by the affinity with the cation (basic oxide ion) in the refining slag, the slag design described above for controlling the interaction between the oxygen partial pressure and the cation is It can be important.
  • impurities having a vapor pressure higher than that of silicon are vaporized and removed through the interface between the molten silicon and the atmosphere.
  • Table 2 below shows the vapor pressure of silicon and impurities in the silicon in accordance with the conditions of the present invention.
  • the impurity element removed by vaporization and refining may be vaporized and refined to all impurity elements whose vapor pressure is higher than that of silicon, and is not limited to the description of Table 2.
  • vaporizable impurities (B, Na, K, Fe, etc.) not shown in Table 2 can be obtained by knowing the activity coefficient and thermodynamic data of the element in silicon, and thus the vapor pressure higher than that of silicon. All of them can be subject to vaporization.
  • Figure 3 is a schematic diagram showing the results when the slag refining and vaporization refining at the same time by changing the mixing ratio of Ar gas and H 2 gas in the present invention.
  • Figure 3 when compared to the results of polishing by mixing as those incorporated by feeding only the Ar gas Ar gas and H 2 gas, that of phosphorus slag reduction refining of the impurity supplying a mixture of Ar gas and H 2 gas, that of phosphorus slag reduction refining of the impurity supplying a mixture of Ar gas and H 2 gas It can be seen that the effect is larger, and furthermore, H 2 gas is effective for removing impurity P by forming a gaseous compound of PH 3 .
  • the present invention uses the slag relatively higher than the molten silicon to place the slag in the lower portion of the molten silicon to reduce and refine the impurities through the interfacial reaction between the molten silicon and the slag and at the same time contact with the atmosphere
  • the upper part of can refine the impurities such as P through evaporation refining according to the difference in vapor pressure.
  • the present invention can reduce the oxidation loss of the silicon by using a reduction refining method applying a metallurgical refining process, it is possible to work continuously, high productivity and improve the quality and process stability of the silicon product.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne un procédé d'affinage des impuretés dans du silicium métallurgique (MG-Si) utilisant la différence de densité entre les scories et le silicium. Ledit procédé d'affinage consiste à : transformer l'atmosphère d'un creuset d'affinage en une atmosphère gazeuse réductible constituée d'un mélange d'Ar et H2 gazeux ; charger du MG-Si brut à l'intérieur du creuset dans l'atmosphère ajustée, puis chauffer et faire fondre le MG-Si brut ; insérer des scories contenant du SiO2 ayant une densité supérieure à celle du silicium dans le creuset de MG-Si fondu ; et effectuer un affinage par réduction à l'interface entre les scories insérées et le silicium fondu, mais aussi un affinage par vaporisation des impuretés dans le MG-Si par une réaction de vaporisation du Si fondu dans la partie supérieure.
PCT/KR2011/004518 2011-03-31 2011-06-21 Procédé d'affinage des impuretés dans du silicium métallurgique utilisant la différence de densité entre les scories et le silicium WO2012133986A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2011-0029530 2011-03-31
KR1020110029530A KR101222175B1 (ko) 2011-03-31 2011-03-31 슬래그와 실리콘의 밀도차이를 이용한 ＭＧ－Ｓｉ중 불순물의 정련 방법

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108031815A (zh) * 2017-11-30 2018-05-15 重庆嘉萌鸿业科技有限公司 铝合金铸件组合冷却工艺
CN114349009A (zh) * 2022-01-21 2022-04-15 贵州理工学院 一种用于工业硅炉外精炼脱铁和钛的渣剂
CN114538449A (zh) * 2022-02-10 2022-05-27 贵州理工学院 一种用微硅粉为原料制备工业硅精炼渣剂的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998016466A1 (fr) * 1996-10-14 1998-04-23 Kawasaki Steel Corporation Procede et appareil de preparation de silicium polycristallin et procede de preparation d'un substrat en silicium pour cellule solaire
JPH11312683A (ja) * 1998-04-28 1999-11-09 Sumitomo Metal Ind Ltd 半導体単結晶シリコンの製造方法
WO2006059632A1 (fr) * 2004-11-30 2006-06-08 Space Energy Corporation Procede pour fabriquer un lingot de silicium polycristallin
KR20100050307A (ko) * 2008-11-05 2010-05-13 한국에너지기술연구원 고순도 실리콘의 연속주조 장치 및 방법

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2933164A1 (de) * 1979-08-16 1981-02-26 Consortium Elektrochem Ind Verfahren zum reinigen von rohsilicium
NO180532C (no) * 1994-09-01 1997-05-07 Elkem Materials Fremgangsmåte for fjerning av forurensninger fra smeltet silisium
KR20100099396A (ko) * 2009-03-03 2010-09-13 미리넷실리콘(주) 고순도 실리콘 정제장치 및 그 정제방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998016466A1 (fr) * 1996-10-14 1998-04-23 Kawasaki Steel Corporation Procede et appareil de preparation de silicium polycristallin et procede de preparation d'un substrat en silicium pour cellule solaire
JPH11312683A (ja) * 1998-04-28 1999-11-09 Sumitomo Metal Ind Ltd 半導体単結晶シリコンの製造方法
WO2006059632A1 (fr) * 2004-11-30 2006-06-08 Space Energy Corporation Procede pour fabriquer un lingot de silicium polycristallin
KR20100050307A (ko) * 2008-11-05 2010-05-13 한국에너지기술연구원 고순도 실리콘의 연속주조 장치 및 방법

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108031815A (zh) * 2017-11-30 2018-05-15 重庆嘉萌鸿业科技有限公司 铝合金铸件组合冷却工艺
CN114349009A (zh) * 2022-01-21 2022-04-15 贵州理工学院 一种用于工业硅炉外精炼脱铁和钛的渣剂
CN114538449A (zh) * 2022-02-10 2022-05-27 贵州理工学院 一种用微硅粉为原料制备工业硅精炼渣剂的方法

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