WO2011045881A1 - 多結晶シリコン製造用芯線ホルダおよび多結晶シリコンの製造方法 - Google Patents
多結晶シリコン製造用芯線ホルダおよび多結晶シリコンの製造方法 Download PDFInfo
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- WO2011045881A1 WO2011045881A1 PCT/JP2010/004773 JP2010004773W WO2011045881A1 WO 2011045881 A1 WO2011045881 A1 WO 2011045881A1 JP 2010004773 W JP2010004773 W JP 2010004773W WO 2011045881 A1 WO2011045881 A1 WO 2011045881A1
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- core wire
- wire holder
- polycrystalline silicon
- silicon
- annular slit
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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
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/035—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition or reduction of gaseous or vaporised silicon compounds in the presence of heated filaments of silicon, carbon or a refractory metal, e.g. tantalum or tungsten, or in the presence of heated silicon rods on which the formed silicon is deposited, a silicon rod being obtained, e.g. Siemens process
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/53—Means to assemble or disassemble
- Y10T29/53796—Puller or pusher means, contained force multiplying operator
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/53—Means to assemble or disassemble
- Y10T29/53961—Means to assemble or disassemble with work-holder for assembly
Definitions
- the present invention relates to a core wire holder used for manufacturing polycrystalline silicon and a method for manufacturing polycrystalline silicon.
- Siemens method is known as a method for producing polycrystalline silicon which is a raw material of single crystal silicon for semiconductor production or silicon for solar cell production.
- the Siemens method is a method in which a source gas containing chlorosilane is brought into contact with a heated silicon core wire, and polycrystalline silicon is vapor-phase grown on the surface of the silicon core wire using a CVD (Chemical Vapor Deposition) method.
- CVD Chemical Vapor Deposition
- the metal electrode penetrates the base plate with an insulator in between and is connected to another metal electrode through wiring or connected to a power source arranged outside the reactor.
- the metal electrode, the base plate, and the reactor are cooled using a refrigerant.
- the core wire holder fixed to the metal electrode is also cooled by the metal electrode.
- the polycrystalline silicon rod may fall during or after the vapor phase growth process of polycrystalline silicon.
- Patent Document 2 discloses a heat conductivity having a thermal conductivity higher than 145 W / m ⁇ K and suitable for the thermal expansion coefficient of silicon. It has been proposed to use a core wire holder having an expansion coefficient.
- the fall of the silicon core wire occurs when the bonding strength between the silicon core wire and the core wire holder is insufficient. This is considered to be caused by non-uniform growth of polycrystalline silicon.
- the core wire holder is usually made of graphite, and one end side (first end side) is formed with a cavity that is opened to insert and hold the silicon core wire, and the other end side (second end side) is metal. Fixed to the electrode. Then, the current supplied from the metal electrode to the second end side of the core wire holder flows to the first end side end of the low resistance core wire holder, and flows into the silicon core wire for the first time in the vicinity of the opening of the cavity.
- the silicon core wire generally has a quadrangular cross section, and is inserted into a cavity having a quadrangular cross section formed in the core wire holder, and is in close contact with two adjacent surfaces of the quadrangular cross section.
- the current flows from the core wire holder to the core wire at the two contact surface portions near the cavity opening. Since the current flows above the core wire at the shortest distance, heat generation is promoted on the close contact two-surface portion side compared to the non-contact two-surface portion side.
- the temperature in the vicinity of the core wire holder contact portion of the silicon core wire is polycrystalline because the metal electrode in contact with the core wire holder is water-cooled. It is lower than the straight silicon body, so that the polycrystalline silicon at the site has a slower deposition rate and a smaller diameter than the straight body.
- the present invention has been made to solve the above-mentioned problems, and its object is to make the bonding strength between the silicon core wire and the core wire holder sufficient in a short time, and as a result, to suppress the growth rate at the initial stage of the reaction.
- An object of the present invention is to provide a method for producing polycrystalline silicon that can shorten the period.
- a core wire holder according to the present invention is a core wire holder used in the production of polycrystalline silicon by the Siemens method, and includes one end provided with a hollow opening for inserting a silicon core wire, The heat insulation part is provided between the other end used as the contact part with the metal electrode for sending an electric current through a silicon
- the core wire holder is, for example, a graphite carbon electrode.
- the heat insulating portion may include at least one annular slit formed from the outer peripheral surface near the opening toward the cavity.
- the formation depth of the annular slit is 70% or more and less than 100%, more preferably 90% or more and less than 100%, of the thickness of the core wire holder in the annular slit formation region.
- the distance between the inner peripheral surface of the annular slit and the outer peripheral surface of the silicon core wire is preferably 0.1 mm or more, and the width of the annular slit is preferably 0.5 mm or more.
- the one end side is formed in a truncated cone shape, and the annular slit is formed in the inclined surface of the truncated cone.
- the core wire holder of the present invention may be configured such that the annular slit is filled with an insulating material having a lower thermal conductivity than the material of the core wire holder.
- the thermal conductivity of the core wire holder of the present invention is preferably 145 W / m ⁇ K or less.
- the method for producing polycrystalline silicon according to the present invention is a method for producing polycrystalline silicon using the above-described core wire holder, and the cross-sectional current density of the annular slit forming portion is 0. 0 at the beginning of the vapor phase growth of polycrystalline silicon.
- a current is supplied to the core wire holder so that the current is from 05 A / mm 2 to 4.9 A / mm 2 .
- one end side of the core wire holder receives conduction heat and radiation heat from the silicon core wire or polycrystalline silicon. In the conventional core wire holder, this heat is cooled by the metal electrode. It escapes to the metal electrode through the other end side of the holder, heating on one end side becomes insufficient, and the deposition rate of polycrystalline silicon on the portion becomes low.
- the core wire holder of the present invention has one end (upper side) provided with a hollow opening for inserting a silicon core wire and the other end (contact portion) with a metal electrode for flowing a current through the silicon core wire ( Since the heat insulating part is provided between the silicon wire and the polycrystalline silicon, the heat conduction and radiant heat from the silicon core wire are difficult to escape to the metal electrode side.
- the one end side is uniformly heated by the heat accumulated in.
- one end side (upper surface side) of the core wire holder can be easily maintained at a high temperature, the temperature distribution in the region becomes uniform, and the deposition efficiency of polycrystalline silicon on the silicon core wire near the upper surface increases. Polycrystalline silicon is deposited evenly in the region.
- the area where the upper surface of the core wire holder is covered with polycrystalline silicon can be made sufficiently large, so that the bonding strength between the silicon core wire and the core wire holder is sufficient in a short time, It is possible to shorten the growth rate suppression period.
- FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the core wire holder of the present invention, and the core wire holder 20 of the present invention can be a carbon electrode made of graphite, for example.
- one end side (first end side) has a shape having a truncated cone-like slope, and an opening 22 is provided at the end, and the silicon core wire 5 is inserted and held.
- a cavity 21 is formed.
- the polycrystalline silicon 6 is vapor-phase grown on the surface of the silicon core wire 5 by the Siemens method, and a polycrystalline silicon rod is manufactured.
- the other end side (second end side) of the core wire holder 20 is a contact portion with a metal electrode (indicated by reference numeral 2 in FIG. 2) for flowing a current through the silicon core wire 5 as will be described later.
- the holder 20 is fixed to the metal electrode 2.
- An annular slit 23 (23a to 23c) is formed on the frustoconical slope near the opening 22 as a heat insulating layer from the outer peripheral surface near the opening toward the cavity 21.
- the annular slit 23 acts as a heat insulating portion (heat insulating layer) and suppresses escape of conduction heat and radiation heat from the silicon core wire 5 or the polycrystalline silicon 6 to the metal electrode.
- the slit as the heat insulation part is easy to manufacture and easy to use the one with a notch as shown in the figure, but as other shapes, it is a straight notch from the opposite position of the side surface of the core wire holder. It is also possible to use two substantially semicircular slits that sandwich the bisector of the cross-sectional circle of the core wire holder.
- the groove portion (space) of the annular slit 23 acts as an effective heat insulating layer.
- the polycrystalline silicon 6 is deposited on the core wire holder 20 to fill the groove of the annular slit 23, the annular slit 23 does not function as a heat insulating layer. Therefore, when it is desired to lengthen the heating period on the first end side, a plurality of annular slits 23 may be formed as shown in FIG.
- a heat insulating portion heat insulating layer
- conduction heat and radiant heat from the silicon core wire or polycrystalline silicon received at one end during the vapor phase growth process of polycrystalline silicon are caused by a metal electrode. Since it escapes to a metal electrode through the other end side of the core wire holder being cooled, the heating at one end side becomes insufficient, and the deposition rate of polycrystalline silicon on the portion becomes low. Further, in the portion where the silicon core wire is not in contact with the core wire holder in the cavity 21 (non-contact portion), the temperature is low and the deposition rate is low at the initial stage of growth of polycrystalline silicon.
- the shape of the upper end side (one end side) of the core wire holder in the initial stage of deposition of the polycrystalline silicon 6 is as shown by the broken line p in FIG. 1, and the contact area with the upper end surface of the core wire holder is low. It is difficult to ensure sufficient bonding strength between the silicon core wire 5 and the core wire holder.
- the annular slit 23 is provided in the core wire holder 20 as in the present invention, conduction heat and radiant heat from the silicon core wire 5 or the polycrystalline silicon 6 are difficult to escape to the metal electrode 2 side.
- the one end side is uniformly heated by the heat accumulated between the one end side and the heat insulating portion.
- the current flows in the core wire holder 20 toward the cavity side, and the current density of the portion increases.
- the one end side of the core wire holder 20 is formed in a truncated cone shape as shown in FIG. 1 and the annular slit 23 is formed on the inclined surface of the truncated cone, the current tends to flow toward the cavity side. That is, the current flow path is limited by such an annular slit 23, and the heating amount on one end side is increased.
- the formation depth (x) of the annular slit 23 is the thickness of the core wire holder 20 in the formation region of the annular slit 23 (y ) Is preferably 70% or more and less than 100%, more preferably 90% or more and less than 100%.
- the distance (s) between the inner peripheral surface of the annular slit 23 and the outer peripheral surface of the silicon core wire 5 is preferably 0.1 mm or more. Furthermore, when the width (w) of the annular slit 23 is less than 0.5 mm, sparks may be generated between the slits.
- the cross-sectional current density of the annular slit forming portion is 0.05 A / mm 2 or more 4 at the start of vapor phase growth of the polycrystalline silicon 6.
- Current is supplied to the core wire holder 20 so as to be 9 A / mm 2 or less.
- the thermal conductivity of the core wire holder 20 is desirably 145 W / m ⁇ K or less.
- FIG. 2 is a schematic explanatory diagram showing an example of a vapor phase growth apparatus 100 in which the present invention is used.
- the vapor phase growth apparatus 100 is an apparatus for vapor growth of polycrystalline silicon 6 on the surface of the silicon core wire 5 by the Siemens method, and is roughly constituted by the base plate 1 and the reaction furnace 10.
- the core wire holder 20 is a carbon electrode made of graphite.
- the base plate 1 is provided with a metal electrode 2 for supplying a current to the silicon core wire 5, a gas nozzle 3 for supplying a process gas such as nitrogen gas, hydrogen gas and trichlorosilane gas, and an exhaust port 4 for discharging exhaust gas. .
- the metal electrode 2 passes through the base plate 1 with the insulator 7 interposed therebetween, and is connected to another metal electrode through wiring or connected to a power source arranged outside the reactor.
- the metal electrode 2, the base plate 1, and the reaction furnace 10 are cooled using a refrigerant.
- the silicon core wire 5 is assembled into a torii type with two vertical directions and one horizontal direction in the reaction furnace 10, and the torii type silicon core wire 5 is assembled.
- the silicon core wire 5 is assembled into a torii type with two vertical directions and one horizontal direction in the reaction furnace 10, and the torii type silicon core wire 5 is assembled.
- the core wire holder 20 is made of graphite having a thermal conductivity of 145 W / m ⁇ K or less, and has an opening for inserting and holding the silicon core wire 5 on one end side (first end side) having a truncated cone-shaped slope.
- the cavity 21 is formed, and the other end side (second end side) is fixed to the metal electrode 2.
- annular slit 23 is formed toward the cavity 21 as a heat insulating layer.
- the depth of the annular slit 23 is preferably 90% or more and less than 100% of the thickness of the annular slit forming region, and the width of the annular slit 23 is preferably 0.5 mm or more.
- the distance from the bottom of the annular slit 23 to the core wire 5 is preferably 0.1 mm or more. In FIG. 2, only one annular slit 23 is shown, but a plurality of annular slits may be provided.
- the reactor 10 is placed in close contact with the base plate 1, and nitrogen gas is supplied from the gas nozzle 3 to replace the air in the reactor 10 with nitrogen. Air and nitrogen in the reaction furnace 10 are exhausted from the exhaust port 4. After the inside of the reaction furnace 10 is replaced with a nitrogen atmosphere, hydrogen gas is supplied from the gas nozzle 3 instead of the nitrogen gas, and the inside of the reaction furnace 10 is made a hydrogen atmosphere.
- the silicon core wire 5 is preheated to a temperature of 250 ° C. or higher by using a heater (not shown) so that the silicon core wire 5 becomes conductive enough to allow current to flow efficiently.
- a current is supplied from the metal electrode 2 to the silicon core wire 5 via the core wire holder 20 to heat the silicon core wire 5 to 900 ° C. or higher.
- trichlorosilane gas is supplied at a low flow rate as a raw material gas together with hydrogen gas, and vapor phase growth is started.
- the cross-sectional current density of the current flowing between the annular slit 23 formed in the graphite core wire holder 20 and the cavity 21 is 0.05 A / mm 2 or more and 4.9 A / mm 2 or less.
- 3A to 3E are conceptual diagrams showing the heating state of the core wire holder 20 when the polycrystalline silicon 6 is deposited near the first end of the core wire holder 20.
- the first end of the core wire holder 20 and the annular slit are received by conduction heat and radiant heat from the silicon core wire 5 and the polycrystalline silicon 6.
- the space between 23 gradually becomes reddish.
- a total of three annular slits 23a, 23b, 23c
- the space between the first end of the core wire holder 20 and the annular slit 23a is uniformly heated.
- the bonding strength between the silicon core wire 5 and the core wire holder 20 becomes sufficient, so that the supply flow rate of the source gas can be increased. Accordingly, the polycrystalline silicon 6 is vapor-phase grown in the temperature range of 900 ° C. or more and 1200 ° C. or less on the silicon core wire 5 while further increasing the supply amount of the source gas hydrogen gas and trichlorosilane gas and the current supply amount. Unreacted gas and by-product gas are discharged from the exhaust port 4.
- the supply of the source gas is stopped, the temperature in the reaction furnace 10 is lowered, the atmosphere in the reaction furnace is replaced with hydrogen from nitrogen, and the reaction furnace 10 is opened to the atmosphere.
- Example Example 1 when the core wire holder 20 is provided with a diameter-inclined portion (expanded or inclined portion) 24 at the first end of the core wire holder 20, the silicon core wire 5 and the polycrystalline silicon 6 In addition to the heat conduction, the radiant heat can be received more efficiently, so that the heating amount on the first end side of the core wire holder 20 can be increased.
- Example Example 1
- a circular slit 23 having a width of 1 mm and a depth of 3.5 mm toward the cavity 21 is formed on the inclined surface of the truncated cone having a truncated cone shape on the first end side and 4 mm away from the opening 22 of the cavity 21.
- a graphite core wire holder 20 was used. When the silicon core wire 5 held in the core wire holder 20 is heated to 1063 ° C. and trichlorosilane gas is supplied as a raw material gas together with hydrogen gas, the core wire holder 20 has a first growth rate suppression period of 28 hours after the start of vapor phase growth. One end side was evenly coated by the deposition of polycrystalline silicon 6. At that time, the polycrystalline silicon 6 had a diameter of 38 mm and a current value of 605A.
- a graphite core wire holder 20 of the same type as in Example 1 was used, and while the silicon core wire 5 held by the core wire holder 20 was heated to 1055 ° C., trichlorosilane gas was supplied as a raw material gas together with hydrogen gas.
- the first end side of the core wire holder 20 was uniformly coated by the deposition of the polycrystalline silicon 6.
- the polycrystalline silicon 6 had a diameter of 36 mm and a current value of 590A. Comparative example
- a graphite core wire holder 20 of the same type as in Example 1 is used except that an annular slit is not formed.
- the raw material gas was supplied.
- the first end side of the core wire holder 20 was evenly coated by the deposition of polycrystalline silicon 6.
- the polycrystalline silicon 6 had a diameter of 56 mm and a current value of 1110 A.
- the opening of the core wire holder can be uniformly covered with polycrystalline silicon at about half the current value of the core wire holder without slits.
- the entire circumference of the first end of the core wire holder 20 can be heated, the deposition of polycrystalline silicon is uniform, and the collapse due to local growth does not occur.
- the bonding strength between the silicon core wire 5 and the core wire holder 20 can be sufficient in a short time, and the growth rate suppression period in the initial stage of the reaction Can be greatly shortened.
- a method for producing polycrystalline silicon that makes it possible to make the bonding strength between the silicon core wire and the core wire holder sufficient in a short time, and as a result, to shorten the growth rate suppression period in the initial reaction.
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Abstract
Description
実施例
実施例1
実施例2
比較例
2 金属電極
3 ガスノズル
4 排気口
5 シリコン芯線
6 多結晶シリコン
7 絶縁物
10 反応炉
20 芯線ホルダ
21 空洞
22 開口部
23、23a、23b、23c 環状スリット
24 芯線ホルダの拡径傾斜部
100 気相成長装置
Claims (11)
- シーメンス法による多結晶シリコンの製造に用いられる芯線ホルダであって、
シリコン芯線を挿入する空洞の開口部が設けられた一方端と前記シリコン芯線に電流を流すための金属電極との接触部となる他方端との間に断熱部が設けられていることを特徴とする芯線ホルダ。 - 前記芯線ホルダはグラファイト製炭素電極である請求項1に記載の芯線ホルダ。
- 前記断熱部は、前記開口部近傍の外周面から前記空洞に向かって形成された少なくとも一つの環状スリットを含む、請求項1又は2に記載の芯線ホルダ。
- 前記環状スリットの形成深さは該環状スリット形成領域の芯線ホルダ肉厚の70%以上100%未満である請求項3に記載の芯線ホルダ。
- 前記環状スリットの形成深さは該環状スリット形成領域の芯線ホルダ肉厚の90%以上100%未満である請求項3に記載の芯線ホルダ。
- 前記環状スリットの内周面と前記シリコン芯線の外周面との距離が0.1mm以上である請求項3に記載の芯線ホルダ。
- 前記環状スリットの幅は0.5mm以上である請求項3に記載の芯線ホルダ。
- 前記一方端側は円錐台状に形成されており、前記環状スリットが該円錐台の斜面に形成されている、請求項3に記載の芯線ホルダ。
- 前記環状スリット内に、前記芯線ホルダの材料よりも熱伝導度の小さい絶縁材料が充填されている請求項3に記載の芯線ホルダ。
- 前記芯線ホルダの熱伝導率は145W/m・K以下である請求項1又は2に記載の芯線ホルダ。
- 請求項3に記載の芯線ホルダを用いる多結晶シリコンの製造方法であって、
多結晶シリコンの気相成長開始時において、前記環状スリット形成部の断面電流密度が0.05A/mm2以上4.9A/mm2以下となるように前記芯線ホルダへの電流供給を行うことを特徴とする多結晶シリコンの製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP10823150.7A EP2489634B1 (en) | 2009-10-14 | 2010-07-27 | Core wire holder for producing polycrystalline silicon and method for producing polycrystalline silicon |
CN201080046255.1A CN102574691B (zh) | 2009-10-14 | 2010-07-27 | 多晶硅制造用芯线支架及多晶硅的制造方法 |
AU2010307921A AU2010307921B2 (en) | 2009-10-14 | 2010-07-27 | Core wire holder for producing polycrystalline silicon and method for producing polycrystalline silicon |
US13/502,015 US8793853B2 (en) | 2009-10-14 | 2010-07-27 | Core wire holder for producing polycrystalline silicon and method for producing polycrystalline silicon |
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JP2009237017A JP5560018B2 (ja) | 2009-10-14 | 2009-10-14 | 多結晶シリコン製造用芯線ホルダおよび多結晶シリコンの製造方法 |
JP2009-237017 | 2009-10-14 |
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EP (1) | EP2489634B1 (ja) |
JP (1) | JP5560018B2 (ja) |
CN (1) | CN102574691B (ja) |
AU (1) | AU2010307921B2 (ja) |
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Cited By (2)
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WO2012147300A1 (ja) * | 2011-04-27 | 2012-11-01 | 信越化学工業株式会社 | 多結晶シリコン製造装置および多結晶シリコンの製造方法 |
WO2014168116A1 (ja) * | 2013-04-10 | 2014-10-16 | 株式会社トクヤマ | シリコン製造用芯線ホルダ |
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JP5560018B2 (ja) * | 2009-10-14 | 2014-07-23 | 信越化学工業株式会社 | 多結晶シリコン製造用芯線ホルダおよび多結晶シリコンの製造方法 |
JP5666983B2 (ja) * | 2011-05-09 | 2015-02-12 | 信越化学工業株式会社 | シリコン芯線ホルダおよび多結晶シリコンの製造方法 |
JP5719282B2 (ja) * | 2011-11-29 | 2015-05-13 | 信越化学工業株式会社 | 多結晶シリコンの製造方法 |
JP2014001096A (ja) * | 2012-06-18 | 2014-01-09 | Shin Etsu Chem Co Ltd | 多結晶シリコンの結晶配向度評価方法、多結晶シリコン棒の選択方法、多結晶シリコン棒、多結晶シリコン塊、および、単結晶シリコンの製造方法 |
JP6373724B2 (ja) | 2014-11-04 | 2018-08-15 | 株式会社トクヤマ | 芯線ホルダ及びシリコンの製造方法 |
CN112424121A (zh) * | 2018-07-23 | 2021-02-26 | 株式会社德山 | 芯线支架、硅制造装置及硅制造方法 |
WO2020249188A1 (de) * | 2019-06-11 | 2020-12-17 | Wacker Chemie Ag | Verfahren zur herstellung von polykristallinem silicium |
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- 2010-07-27 EP EP10823150.7A patent/EP2489634B1/en active Active
- 2010-07-27 US US13/502,015 patent/US8793853B2/en active Active
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WO2012147300A1 (ja) * | 2011-04-27 | 2012-11-01 | 信越化学工業株式会社 | 多結晶シリコン製造装置および多結晶シリコンの製造方法 |
JP2012229144A (ja) * | 2011-04-27 | 2012-11-22 | Shin-Etsu Chemical Co Ltd | 多結晶シリコン製造装置および多結晶シリコン製造方法 |
WO2014168116A1 (ja) * | 2013-04-10 | 2014-10-16 | 株式会社トクヤマ | シリコン製造用芯線ホルダ |
Also Published As
Publication number | Publication date |
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EP2489634B1 (en) | 2019-12-11 |
JP5560018B2 (ja) | 2014-07-23 |
EP2489634A1 (en) | 2012-08-22 |
US8793853B2 (en) | 2014-08-05 |
AU2010307921B2 (en) | 2013-07-25 |
US20120201976A1 (en) | 2012-08-09 |
CN102574691A (zh) | 2012-07-11 |
EP2489634A4 (en) | 2014-12-31 |
AU2010307921A1 (en) | 2012-05-03 |
CN102574691B (zh) | 2014-04-23 |
JP2011084419A (ja) | 2011-04-28 |
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