WO2010098797A1 - Fluidized bed reactor for production of high purity silicon - Google Patents

Fluidized bed reactor for production of high purity silicon Download PDF

Info

Publication number
WO2010098797A1
WO2010098797A1 PCT/US2009/065345 US2009065345W WO2010098797A1 WO 2010098797 A1 WO2010098797 A1 WO 2010098797A1 US 2009065345 W US2009065345 W US 2009065345W WO 2010098797 A1 WO2010098797 A1 WO 2010098797A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon
fluidized bed
chamber
bed reactor
reactor
Prior art date
Application number
PCT/US2009/065345
Other languages
French (fr)
Inventor
Javier San Segundo Sanchez
Jose Luis Montesinos Barona
Evaristo Ayuso Conejero
Manuel Vicente Vales Canle
Xavier Benavides Rel
Pedro-Tomas Lujan Garcia
Matthew S. Bethards
Original Assignee
Siliken Chemicals S.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siliken Chemicals S.L. filed Critical Siliken Chemicals S.L.
Priority to CN2009801490221A priority Critical patent/CN102239115A/en
Priority to RU2011139109/05A priority patent/RU2011139109A/en
Priority to MX2011008790A priority patent/MX2011008790A/en
Priority to EP09840944.4A priority patent/EP2318313A4/en
Priority to BRPI0924261-9A priority patent/BRPI0924261A2/en
Priority to CA2753354A priority patent/CA2753354A1/en
Priority to AU2009341100A priority patent/AU2009341100A1/en
Priority to JP2011552017A priority patent/JP2012519130A/en
Publication of WO2010098797A1 publication Critical patent/WO2010098797A1/en

Links

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
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
    • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • 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
    • C01B33/029—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of monosilane
    • 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
    • C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
    • B01J2208/00407—Controlling the temperature using electric heating or cooling elements outside the reactor bed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
    • B01J2208/00415—Controlling the temperature using electric heating or cooling elements electric resistance heaters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00433—Controlling the temperature using electromagnetic heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00433—Controlling the temperature using electromagnetic heating
    • B01J2208/0046—Infrared radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
    • B01J2219/0236—Metal based

Definitions

  • the present disclosure relates to methods for producing high purity electronic grade silicon. More particularly, this disclosure relates to methods for producing high purity silicon beads by chemical vapor deposition (CVD) of a silicon- bearing gas on seed particles by decomposition in a fluidized bed reactor.
  • CVD chemical vapor deposition
  • FIG. 1 shows one embodiment of a process for the purification of silicon.
  • FIG. 2 shows one embodiment of a fluidized bed reactor used for the purification of silicon.
  • FIG. 3 shows a close-up cross section of one embodiment of a fluidized bed reactor as disclosed herein.
  • Polycrystalline silicon may be used in the production of electronic components and solar panel construction.
  • One conventional method of producing polycrystalline silicon is feeding a mixture comprising hydrogen and silane (SiH 4 ) or a mixture comprising hydrogen and a halosilane, such as thchlorosilane (HSiCIs), is fed to a decomposition reactor containing a hot wire or hot substrate rods.
  • This method requires a high amount of energy per unit of mass of produced silicon, and the silicon rods produced by this method need further processing to be used in a silicon ingot growing process.
  • An alternate silicon production method is to feed a mixture comprising hydrogen and silane or a mixture comprising hydrogen and thchlorosilane to a fluidized bed containing silicon beads that are maintained at high temperature.
  • Decomposition of silane or thchlorosilane causes the deposition of elemental silicon on the surface of the beads. Therefore, the silicon beads grow in size, and when large enough, are passed out of the fluidized bed reactor as a high purity silicon product.
  • fluidized bed reactors allow for a much larger contact area between the beads and the silicon-bearing gases in a heated chamber, enhancing the thermal
  • the purity of the silicon produced using a fluidized bed reactor may be preserved by constructing the reactor out of materials that do not contaminate the silicon product.
  • a fluidized bed reactor, or reactor, or reactor system used for the production of high purity silicon may be constructed out of a material that prevents or minimizes the contamination of the polycrystalline silicon product due to the diffusion of impurities from the materials used to construct the reactor.
  • the reactor may be constructed or lined or coated with a material that is inert or resistant to the reactor feed gases and fluidized gases and the other gases or products that may be produced during the use of a fluidized bed reactor.
  • a fluidized bed reactor may include an elongate chamber or column comprising one or more inlet openings and one or more outlet openings.
  • a fluidized bed reactor may include a bed of granular solid materials, such as a bed of silicon beads that can be used as seed beads to seed a silicon decomposition reaction during which the seed beads can increase in size because of the deposition of additional silicon on the surface of the seed beads.
  • the seed beads with the added silicon product may be eventually removed from the reactor to recover the high purity silicon product.
  • the seed beads may be "fluidized", or suspended in the reactor, by injecting fluidizing gases into the reactor at sufficient velocities to agitate the beads.
  • the fluidizing gases may be injected into the reactor through one or more inlet openings located around the reactor such as at the ends of the column and at the sides of the reactor column.
  • the fluidizing gases or the silicon product may be removed from the reactor through one or more outlet openings.
  • the reactor may be constructed or lined or coated with a material that is inert or resistant to the fluidizing gases used to fluidize the bed of silicon beads.
  • a silicon-bearing gas may be injected into a fluidized bed reactor that may be constructed, lined or coated with a material that is inert or resistant to the silicon- bearing gas.
  • the silicon-bearing gas may be trichlorosilane (TCS) that can be injected into the reactor at the same location or a location adjacent to the fluidizing gas. When heated, TCS decomposes in the reactor to form silicon
  • SaltLake-499981 1 0031299-00010 2 on the seed silicon beads thereby increasing the diameter of the seed silicon beads over time and producing the desired high purity silicon product.
  • One reason that the resulting polycrystalline silicon product is of high purity is because the reactor has been constructed out of a material that prevents or minimizes the contamination of the silicon during decomposition. The resulting silicon product beads may then be recovered from the reactor and used for the production of semiconductors and photovoltaic cells.
  • Methods for the production of high purity silicon may include the use of a fluidized bed reactor configured to avoid reactor corrosion and prevent the contamination of a silicon product.
  • a method of silicon production may include the conversion of metallurgical grade silicon (MGS) into a hydrohalosilane such as thchlorosilane (TCS); the purification of the hydrohalosilane, such as by distillation; and the decomposition of the hydrohalosilane back to silicon.
  • MGS metallurgical grade silicon
  • TCS thchlorosilane
  • the conversion of MGS into hydrohalosilane may be accomplished by reacting silicon with silicon tetrachloride (STC), hydrogen and hydrogen chloride to form TCS and hydrogen.
  • STC silicon tetrachloride
  • the result of the reaction in area 101 may be a mix of gases including TCS, STC, and H 2 that can be removed from area 101 and then introduced in area 102 for purification by distillation.
  • the purification of TCS by distillation of the hydrohalosilanes may occur in area 102 as shown in FIG. 1.
  • the gas stream from area 101 including TCS, STC and other hydrohalosilanes, may be injected into a distillation column in area 102 resulting in high purity TCS. Hydrogen may be recycled for use in area 101 after further purity removal.
  • the resulting TCS vapor is a silicon-bearing gas that may be injected into a fluidized bed reactor that may be used for a silicon decomposition process in area 103.
  • Area 103 may comprise multiple elements for the conversion of TCS into high purity silicon.
  • area 103 may comprise one or more of the following: fluidized bed reactor, storage tank, evaporator, reactor heater, gas separator, granular separator, cyclone, heat recovery system, product recovery
  • hydrohalosalines refers to any silane species having one or more halide atoms and one or more hydrogen atoms bonded to silicon and includes, but is not limited to monochlorosilane (H 3 SiCI), dichlorosilane (H 2 SiCb), thchlorosilane (HSiCIs) and various chlorinated disilanes such as pentachlorodisilane.
  • a silicon-bearing gas such as a TCS vapor
  • TCS silicon-bearing gas
  • the conversion of TCS into high purity silicon may be accomplished using a fluidized bed reactor 200 as shown in FIG. 2, in which the following reaction may occur:
  • the fluidized bed reactor 200 used in the decomposition process may include an elongate chamber or column 205 which includes a bed of silicon beads 210, which may be used to seed silicon a decomposition reaction.
  • the beads 210 may be "fluidized” by initially injecting gases, such as fluidizing gases 215 from inlet 220 into the column 205 to agitate or fluidize the silicon beads 210.
  • the fluidizing gases 215 may include hydrogen and silicon tetrachloride SiCI 4 .
  • the fluidizing gas may be one or a mixture selected from the group consisting of hydrogen, helium, argon, silicon tetrachloride, silicon tetrabromide and silicon tetraiodide.
  • the fluidizing gases 215 may be injected into the column 205 from several areas of the reactor 200 such as at the bottom or sides of the column 205, such as through inlet 220.
  • the fluidized bed reactor 200 may be heated by one or more heaters 240 placed around or near the body of reactor 200.
  • the heaters 240 may be radiant, conductive, electromagnetic, infrared or other type of heaters known by those of skill in the art.
  • the surface of the reactor wall 250 may be textured, etched or sand-blasted in order to increase the thermal emissivity or the thermal power transfer efficiency of the reactor wall 250 and improve heating by the heater 240 of the column 205 and the inside of the reactor 200.
  • a heating device such as heater 240
  • the heater 240 may be in total or partial contact with the reactor wall 250.
  • the heater 240 may have no direct contact with reactor wall 250.
  • the heater 240 may be positioned outside the reactor wall 250 and configured as a group of cylinders partially or completely covering one or more outlet surfaces of the reactor 200.
  • the heater 240 may be
  • SaltLake-499981 1 0031299-00010 4 configured to use radiation or a mix of direct heat conduction and heat radiation to heat the silicon beads 210 and the silicon-bearing gases to a temperature sufficient for the decomposition reaction.
  • the fluidized bed reactor 200 may be heated during the production of high purity silicon to temperatures ranging from approximately 500 C to approximately 1200 C.
  • the fluidized bed reactor 200 may be heated by the heaters 240 such that the silicon beads 210, the silicon-bearing gases, and the fluidizing gases 215 within the column 205 are heated to a temperature ranging from approximately 600 0 C to 1100 0 C, or from 700 0 C to 1000 0 C, or from 700 0 C to 900 0 C, or from 750 0 C to 850 0 C, or from 800 0 C to 1000 0 C.
  • the fluidized bed reactor 200 may be configured to withstand the conditions during the decomposition reaction including temperatures ranging from approximately 500 0 C to approximately 1200 0 C and internal pressures ranging from approximately 50 mbar to approximately 6000 mbar.
  • the fluidized bed reactor 200 as described herein may be constructed to withstand pressures of approximately up to 50 mbar, 100 mbar, 200 mbar, 500 mbar, 750 mbar, 1000 mbar, 1500 mbar, 2000 mbar, 2500 mbar, 3000 mbar, 3500 mbar, 4000 mbar, 4500 mbar, 5000 mbar, 5500 mbar and 6000 mbar.
  • the fluidized bed reactor 200 may be contained within another structure or enclosure configured to support pressures ranging from approximately 50 mbar to approximately 6000 mbar.
  • one or more silicon-bearing gases such as TCS, may be injected into the reactor 200.
  • the silicon-bearing gas may be injected into the reactor 200 through the inlet 220 into the column 205.
  • a silicon-bearing gas like TCS, decomposes to form silicon on the beads 210, increasing the diameter of the beads 210 over time until they may become a silicon product bead 212.
  • the silicon-bearing gas may comprise a gas which decomposes when heated to form silicon and is a gas or a mixture of gases selected from the group of monosilane, disilane, thsilane, thchlorosilane, dichlorosilane, monochlorosilane, thbromosilane, dibromosilane, monobromosilane, thiodosilane, diiodosilane and monoiodosilane.
  • the high purity silicon product beads 212 may be recovered from the reactor 200 near the top of the column 205 at outlet 230 along with the effluent gas stream 235 that may include hydrogen, STC, HCI, unreacted TCS and monochlorosilane (MCS) and dichlorosilane (DCS).
  • the effluent gas stream 235 may include hydrogen, STC, HCI, unreacted TCS and monochlorosilane (MCS) and dichlorosilane (DCS).
  • the concentration of the silicon-bearing gases in the feed stream to the fluidized bed reactor 200 may range from approximately 20 mol % to 100 mol %.
  • the average diameter of the fluidized silicon beads 210 may range from 0.5 mm to 4 mm. In another embodiment, the average diameter of the silicon beads 210 may range from 0.25 mm to 1.2 mm, or alternatively, 0.6 mm to 1.6 mm. In one embodiment, the silicon beads 210 may remain in the reactor 200 until a desired size is reached and the silicon product beads 212 are extracted from the reactor 200.
  • the time that the silicon beads 210 may remain in the reactor 200 may depend on the starting size of silicon beads 210.
  • the growth rate of the silicon beads 21 may depend, among other things, on the reaction conditions including gas concentrations, temperature and pressure.
  • the minimum fluidization velocity and design operational velocity may be determined by one of ordinary skill in the art based on various factors.
  • the minimum fluidization velocity may be influenced by factors including gravitational acceleration, fluid density, fluid viscosity, solid density, and solid particle size.
  • the operational velocity may be influenced by factors including heat transfer and kinetic properties, such as height of the fluidized bed, total surface area, flow rate of silicon precursor in the feed gas stream, pressure, gas and solids temperature, concentrations of species, and thermodynamic equilibrium point.
  • one or more surfaces of the fluidized bed reactor 200 may be made of a metal or a metal alloy.
  • one or more surfaces of the reactor 200 may include a metal or metal alloy capable of withstanding the reaction temperatures.
  • the reactor wall 250 may be constructed of iron based-alloys, such as: stainless steel alloys, chromium-nickel alloys, and nickel based alloys including nickel-chromium alloys and nickel- chromium-molybdenum alloys, which may optionally include manganese, molybdenum, silicon, cobalt, tungsten, etc., which would be apparent to those having skill in the art with the aid of the present disclosure.
  • the metal alloys may be chosen from: steel 1.4841 , steel 1.4959, steel 2.4856, steel 2.4819 or steel 2.4617.
  • the reactor wall 250 may be configured to be thermoresistant to temperatures in the range of approximately 500 0 C to 1 ,200 0 C.
  • the reactor wall 250 can be constructed to tolerate temperatures ranging from approximately 500 0 C to 600 0 C, or from 500 0 C to 700 0 C, or from 600
  • the inside surface of the reactor wall 250 may be partially or completely coated with a protective layer 260 to avoid or minimize the contamination of the product beads 212 by diffusion of impurities from the reactor 200 or the reactor wall 250.
  • the protective layer 260 may comprise materials that are inert or resistant to the conditions in the reactor 200, such as a metal or metal alloy capable of withstanding the reaction conditions within the reactor 200 and be compatible with the application of the protective layer 260.
  • the protective layer 260 may comprise materials that are resistant to heat, pressure, and corrosion by the fluidizing gases 215 or the silicon-bearing gases that are injected into the reactor 200.
  • the fluidized bed reactor 200 may be lined with a protective layer 260 comprising a ceramic material that is resistant to corrosion or breakdown by the conditions in the reactor 200.
  • the protective layer 260 may comprise at least one of the following materials: Alumina (AI 2 O 3 ), Zirconium dioxide (ZrO 2 ) and Zirconium dioxide - yttrium stabilized.
  • the protective layer is a ceramic material made from a composition other than silicon-based or carbon-based.
  • the protective layer 260 may comprise at least one of Alumina (AI 2 Os), Zirconium dioxide (ZrO 2 ) and Zirconium dioxide - yttrium stabilized in combination with at least one of polycrystalline silicon, silicon carbide, silicon carbide coated graphite, silica, silicon nitride, tungsten carbide or molybdenum.
  • the fluidized bed reactor 200 may include at least one of Alumina (AI 2 Os), Zirconium dioxide (ZrO 2 ) and Zirconium dioxide - yttrium stabilized in combination with one of: quartz, graphite, carbon fiber, or combinations thereof.
  • FIG. 3 is close-up view of a cross section of a wall of a fluidized bed reactor as described herein with silicon beads 310 disposed therein.
  • the reactor wall 350 comprises a protective layer 360 and an adhesion layer 365 applied to the reactor wall 350 before the deposition of the protective layer 360.
  • the adhesion layer 365 may provide a substrate to which the protective layer 360 may bind or attach improving the durability and function of the protective layer 360.
  • an adhesion layer 365 may comprise
  • SaltLake-499981 1 0031299-00010 a nickel based alloy with or without yttrium, particularly when iron based alloys, such as Cr-Ni alloys, comprise the reactor wall 250.
  • the protective layer 260 may comprise a coating which has a depth of approximately 3 to 1000 microns.
  • the protective layer 260 has a depth ranging from approximately 5 to 900 microns, 10 to 700 microns, 20 to 500 microns, 25 to 400 microns or 40 to 300 microns.
  • the protective coating may have a depth of up to 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 95, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, or 900 microns.
  • the protective layer such as protective layer 260 shown in FIG. 2, or protective layer 360 shown in FIG. 3, can be formed or deposited by one or more methods known by those of skill in the art including thermal projection, chemical vapor deposition, physical vapor deposition, solgel, electrophoretic deposition and aerosol thermal spraying.
  • the deposition of the protective layer 260 or protective layer 360 may be followed by a thermal treatment.
  • the protective layer 260 may be annealed with a thermal treatment of temperatures ranging from approximately 900 0 C to 1 ,300 0 C.
  • the thermal treatment may comprise temperatures ranging from 900 0 C to 1 ,000 0 C, or from 900 0 C to 1 ,100 0 C, or from 1 ,000 0 C to 1 ,200 0 C, or from 1 ,000 0 C to 1 ,300 0 C.
  • compositions referred to and used in the following examples are either commercially available or can be prepared according to standard literature procedures by those skilled in the art.
  • thermoresistant steel 1.4841 was subjected to decomposition conditions at 900 0 C in the presence of silicon beads and a N 2 gas stream. After 100 hours under reaction conditions, the sample steel 1.4841 was removed from the reactor and cooled to room temperature.
  • SaltLake-499981 1 0031299-00010 8 [0033] Cross sections of the sample steel 1.4841 were then prepared for analysis with a scanning electron microscope (SEM). The SEM analysis revealed that the steel had been corroded as evidenced by a suicide layer extending into the metal to a depth of approximately 2 microns.
  • thermoresistant steel 1.4841 was subjected to decomposition conditions at 900 0 C in the presence of silicon beads and HCI and H 2 (5:1 ). After 100 hours under reaction conditions, the sample steel 1.4841 was removed from the reactor and cooled to room temperature.
  • the SEM analysis revealed a 50 micron suicide layer on the metal resulting from corrosion of the metal substrate by the chloride.
  • the SEM analysis also revealed the formation of chlorides including iron and chromium chlorides.
  • a sample of steel 1.4841 was coated with a 50 micron layer of Cr 2 O 3 using chemical vapor deposition.
  • the Cr 2 O 3 coated steel was heated to 900 0 C in the presence of silicon beads and N 2 gas. After 100 hours, the Cr 2 O 3 coated steel was cooled to room temperature. SEM analysis showed the presence of silica and chromium on the surface of the steel, potentially due to the following reaction: 2Cr 2 O 3 + 3Si ⁇ 4Cr + 3SiO 2 .
  • a sample of steel 1.4841 was prepared with a nickel alloy adhesion layer to improve the adhesion of the ceramic layer.
  • the nickel alloy adhesion layer (NiCrAIY) was deposited using an atmospheric plasma spray process.
  • the sample was covered with a 100 micron ceramic coating Of ZrO 2 — yttrium stabilized, and heated to 900 0 C, as before, in conditions simulating a fluidized bed reactor with silicon beads and in the presence of HCI and H 2 (5:1 ).
  • the ZrO 2 — yttrium stabilized coated steel was cooled to room temperature.
  • SEM analysis showed the steel 1.4841 with the ceramic coating of ZrO 2 — yttrium stabilized resisted corrosion or degradation thereby minimizing or eliminating likely contamination of a silicon product. More particularly, SEM data showed that there was no migration of
  • a sample of steel 1.4841 was prepared with a nickel alloy adhesion layer followed by the addition of an AI 2 O 3 protective layer.
  • the prepared sample was heated for 100 hours at 900 0 C in a fluidized bed reactor with silicon beads fluidized with HCI and H 2 (5:1 ). After cooling to room temperature, SEM analysis showed that the AI 2 O 3 protective layer prevented corrosion of the steel sample.
  • Example 2 Heat transfer by a radiant heater [0043]
  • a stainless steel tube approximately 0.5 meters long and with an outside diameter of 21.3 mm and a thickness of 2.77 mm was used to measure radiation heat transfer.
  • a radiation heater with an inside diameter of 40 mm was positioned around the steel tube without contacting the surface of the steel tube.
  • the steel tube and the radiation heater were insulated with 300 mm thick ceramic fiber.
  • a stream of N 2 gas at mass flow rate of 15 Kg/h was passed along the inside of the steel tube horizontally. Thermowells were used to measure the temperature of the radiation heater, the external temperature of the steel tube at the inlet and outlet points of the N 2 gas stream, and the temperature of the N 2 gas stream at the inlet and outlet points.
  • N 2 inlet temperature 21 0 C
  • N 2 outlet temperature 315 0 C
  • the thermal power absorbed in the system was 1.325 W.
  • the calculation model introduced the concept of mean logarithmic difference of universal coefficients of heat transfer, and temperatures, because U and ⁇ T vary along the heat exchanger.
  • the emissivity of stainless steel is 0.18 at 500 0 C.
  • the values of the first test were implemented in order to adjust the model, and in a second stage the values of the second test were implemented in order to obtain the new emissivity values through an iterative process.
  • the sand-blasted stainless steel emissivity calculated was 0.52. Hence, the radiation heat transfer ratio was increased approximately 3 times by the sand-blasting surface treatment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Silicon Compounds (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

Methods and apparatus for the production of high purity silicon including a fluidized bed reactor with one or more protective layers deposited on an inside surface of the fluidized bed reactor. The protective layer may be resistant to corrosion by fluidizing gases and silicon-bearing gases.

Description

FLUIDIZED BED REACTOR FOR PRODUCTION OF HIGH PURITY SILICON
Technical Field
[0001] The present disclosure relates to methods for producing high purity electronic grade silicon. More particularly, this disclosure relates to methods for producing high purity silicon beads by chemical vapor deposition (CVD) of a silicon- bearing gas on seed particles by decomposition in a fluidized bed reactor.
Brief Description of the Drawings
[0002] FIG. 1 shows one embodiment of a process for the purification of silicon. [0003] FIG. 2 shows one embodiment of a fluidized bed reactor used for the purification of silicon.
[0004] FIG. 3 shows a close-up cross section of one embodiment of a fluidized bed reactor as disclosed herein.
Detailed Description
[0005] Polycrystalline silicon may be used in the production of electronic components and solar panel construction. One conventional method of producing polycrystalline silicon is feeding a mixture comprising hydrogen and silane (SiH4) or a mixture comprising hydrogen and a halosilane, such as thchlorosilane (HSiCIs), is fed to a decomposition reactor containing a hot wire or hot substrate rods. This method requires a high amount of energy per unit of mass of produced silicon, and the silicon rods produced by this method need further processing to be used in a silicon ingot growing process.
[0006] An alternate silicon production method is to feed a mixture comprising hydrogen and silane or a mixture comprising hydrogen and thchlorosilane to a fluidized bed containing silicon beads that are maintained at high temperature. Decomposition of silane or thchlorosilane causes the deposition of elemental silicon on the surface of the beads. Therefore, the silicon beads grow in size, and when large enough, are passed out of the fluidized bed reactor as a high purity silicon product. In comparison to the substrate used in wire or rod substrate reactors, fluidized bed reactors allow for a much larger contact area between the beads and the silicon-bearing gases in a heated chamber, enhancing the thermal
SaltLake-499981 1 0031299-00010 1 decomposition of the silicon-bearing gases thereby forming high purity elemental silicon on the surface of existing beads.
[0007] As described herein, the purity of the silicon produced using a fluidized bed reactor may be preserved by constructing the reactor out of materials that do not contaminate the silicon product. In one such embodiment, a fluidized bed reactor, or reactor, or reactor system used for the production of high purity silicon may be constructed out of a material that prevents or minimizes the contamination of the polycrystalline silicon product due to the diffusion of impurities from the materials used to construct the reactor. In another embodiment, the reactor may be constructed or lined or coated with a material that is inert or resistant to the reactor feed gases and fluidized gases and the other gases or products that may be produced during the use of a fluidized bed reactor.
[0008] In one embodiment, a fluidized bed reactor according to the disclosure herein may include an elongate chamber or column comprising one or more inlet openings and one or more outlet openings. In one such embodiment, a fluidized bed reactor may include a bed of granular solid materials, such as a bed of silicon beads that can be used as seed beads to seed a silicon decomposition reaction during which the seed beads can increase in size because of the deposition of additional silicon on the surface of the seed beads. The seed beads with the added silicon product may be eventually removed from the reactor to recover the high purity silicon product. The seed beads may be "fluidized", or suspended in the reactor, by injecting fluidizing gases into the reactor at sufficient velocities to agitate the beads. The fluidizing gases may be injected into the reactor through one or more inlet openings located around the reactor such as at the ends of the column and at the sides of the reactor column. In one embodiment, the fluidizing gases or the silicon product may be removed from the reactor through one or more outlet openings. In one such embodiment, the reactor may be constructed or lined or coated with a material that is inert or resistant to the fluidizing gases used to fluidize the bed of silicon beads.
[0009] A silicon-bearing gas may be injected into a fluidized bed reactor that may be constructed, lined or coated with a material that is inert or resistant to the silicon- bearing gas. In one embodiment, the silicon-bearing gas may be trichlorosilane (TCS) that can be injected into the reactor at the same location or a location adjacent to the fluidizing gas. When heated, TCS decomposes in the reactor to form silicon
SaltLake-499981 1 0031299-00010 2 on the seed silicon beads thereby increasing the diameter of the seed silicon beads over time and producing the desired high purity silicon product. One reason that the resulting polycrystalline silicon product is of high purity is because the reactor has been constructed out of a material that prevents or minimizes the contamination of the silicon during decomposition. The resulting silicon product beads may then be recovered from the reactor and used for the production of semiconductors and photovoltaic cells.
[0010] Methods for the production of high purity silicon may include the use of a fluidized bed reactor configured to avoid reactor corrosion and prevent the contamination of a silicon product. In one embodiment, a method of silicon production may include the conversion of metallurgical grade silicon (MGS) into a hydrohalosilane such as thchlorosilane (TCS); the purification of the hydrohalosilane, such as by distillation; and the decomposition of the hydrohalosilane back to silicon. [0011] In one embodiment, the conversion of MGS into hydrohalosilane may be accomplished by reacting silicon with silicon tetrachloride (STC), hydrogen and hydrogen chloride to form TCS and hydrogen. With reference to FIG. 1 , the following reactions may occur inside area 101 :
3SiCI4 + 2H2 + Si → 4 HSiCI3 SiCI4 + H2 → HSiCI3 + HCI 3 HCI + Si → HSiCI3 + H2
[0012] In one embodiment, the result of the reaction in area 101 may be a mix of gases including TCS, STC, and H2 that can be removed from area 101 and then introduced in area 102 for purification by distillation.
[0013] The purification of TCS by distillation of the hydrohalosilanes may occur in area 102 as shown in FIG. 1. In one embodiment, the gas stream from area 101 , including TCS, STC and other hydrohalosilanes, may be injected into a distillation column in area 102 resulting in high purity TCS. Hydrogen may be recycled for use in area 101 after further purity removal. The resulting TCS vapor is a silicon-bearing gas that may be injected into a fluidized bed reactor that may be used for a silicon decomposition process in area 103.
[0014] Area 103 may comprise multiple elements for the conversion of TCS into high purity silicon. For example, area 103 may comprise one or more of the following: fluidized bed reactor, storage tank, evaporator, reactor heater, gas separator, granular separator, cyclone, heat recovery system, product recovery
SaltLake-499981 1 0031299-00010 3 system and other devices and systems for the production of high purity silicon. The term hydrohalosalines refers to any silane species having one or more halide atoms and one or more hydrogen atoms bonded to silicon and includes, but is not limited to monochlorosilane (H3SiCI), dichlorosilane (H2SiCb), thchlorosilane (HSiCIs) and various chlorinated disilanes such as pentachlorodisilane.
[0015] In one embodiment, a silicon-bearing gas, such as a TCS vapor, may be used for the production of high purity silicon. The conversion of TCS into high purity silicon may be accomplished using a fluidized bed reactor 200 as shown in FIG. 2, in which the following reaction may occur:
4SiHCI3 → Si + 3SiCI4 + 2H2 (thermal decomposition)
[0016] The fluidized bed reactor 200 used in the decomposition process may include an elongate chamber or column 205 which includes a bed of silicon beads 210, which may be used to seed silicon a decomposition reaction. The beads 210 may be "fluidized" by initially injecting gases, such as fluidizing gases 215 from inlet 220 into the column 205 to agitate or fluidize the silicon beads 210. In one embodiment, the fluidizing gases 215 may include hydrogen and silicon tetrachloride SiCI4. In another embodiment, the fluidizing gas may be one or a mixture selected from the group consisting of hydrogen, helium, argon, silicon tetrachloride, silicon tetrabromide and silicon tetraiodide. In one such embodiment, the fluidizing gases 215 may be injected into the column 205 from several areas of the reactor 200 such as at the bottom or sides of the column 205, such as through inlet 220. [0017] The fluidized bed reactor 200 may be heated by one or more heaters 240 placed around or near the body of reactor 200. The heaters 240 may be radiant, conductive, electromagnetic, infrared or other type of heaters known by those of skill in the art. In one embodiment, the surface of the reactor wall 250 may be textured, etched or sand-blasted in order to increase the thermal emissivity or the thermal power transfer efficiency of the reactor wall 250 and improve heating by the heater 240 of the column 205 and the inside of the reactor 200.
[0018] In another embodiment, a heating device, such as heater 240, may be in total or partial contact with the reactor wall 250. In yet another embodiment, the heater 240 may have no direct contact with reactor wall 250. In one such embodiment, the heater 240 may be positioned outside the reactor wall 250 and configured as a group of cylinders partially or completely covering one or more outlet surfaces of the reactor 200. In still another embodiment, the heater 240 may be
SaltLake-499981 1 0031299-00010 4 configured to use radiation or a mix of direct heat conduction and heat radiation to heat the silicon beads 210 and the silicon-bearing gases to a temperature sufficient for the decomposition reaction.
[0019] In one embodiment, the fluidized bed reactor 200 may be heated during the production of high purity silicon to temperatures ranging from approximately 500 C to approximately 1200 C. For example, the fluidized bed reactor 200 may be heated by the heaters 240 such that the silicon beads 210, the silicon-bearing gases, and the fluidizing gases 215 within the column 205 are heated to a temperature ranging from approximately 600 0C to 1100 0C, or from 700 0C to 1000 0C, or from 700 0C to 900 0C, or from 750 0C to 850 0C, or from 800 0C to 1000 0C. [0020] The fluidized bed reactor 200 may be configured to withstand the conditions during the decomposition reaction including temperatures ranging from approximately 500 0C to approximately 1200 0C and internal pressures ranging from approximately 50 mbar to approximately 6000 mbar. For example, the fluidized bed reactor 200 as described herein, may be constructed to withstand pressures of approximately up to 50 mbar, 100 mbar, 200 mbar, 500 mbar, 750 mbar, 1000 mbar, 1500 mbar, 2000 mbar, 2500 mbar, 3000 mbar, 3500 mbar, 4000 mbar, 4500 mbar, 5000 mbar, 5500 mbar and 6000 mbar. In another embodiment, the fluidized bed reactor 200 may be contained within another structure or enclosure configured to support pressures ranging from approximately 50 mbar to approximately 6000 mbar. [0021] In one embodiment, one or more silicon-bearing gases, such as TCS, may be injected into the reactor 200. For example, the silicon-bearing gas may be injected into the reactor 200 through the inlet 220 into the column 205. In one such embodiment, a silicon-bearing gas, like TCS, decomposes to form silicon on the beads 210, increasing the diameter of the beads 210 over time until they may become a silicon product bead 212. In still another embodiment, the silicon-bearing gas may comprise a gas which decomposes when heated to form silicon and is a gas or a mixture of gases selected from the group of monosilane, disilane, thsilane, thchlorosilane, dichlorosilane, monochlorosilane, thbromosilane, dibromosilane, monobromosilane, thiodosilane, diiodosilane and monoiodosilane. In one embodiment, the high purity silicon product beads 212 may be recovered from the reactor 200 near the top of the column 205 at outlet 230 along with the effluent gas stream 235 that may include hydrogen, STC, HCI, unreacted TCS and monochlorosilane (MCS) and dichlorosilane (DCS).
SaltLake-499981 1 0031299-00010 5 [0022] In one embodiment, the concentration of the silicon-bearing gases in the feed stream to the fluidized bed reactor 200 may range from approximately 20 mol % to 100 mol %. In one embodiment, the average diameter of the fluidized silicon beads 210 may range from 0.5 mm to 4 mm. In another embodiment, the average diameter of the silicon beads 210 may range from 0.25 mm to 1.2 mm, or alternatively, 0.6 mm to 1.6 mm. In one embodiment, the silicon beads 210 may remain in the reactor 200 until a desired size is reached and the silicon product beads 212 are extracted from the reactor 200. In another embodiment, the time that the silicon beads 210 may remain in the reactor 200 may depend on the starting size of silicon beads 210. In one embodiment, the growth rate of the silicon beads 21 may depend, among other things, on the reaction conditions including gas concentrations, temperature and pressure. The minimum fluidization velocity and design operational velocity may be determined by one of ordinary skill in the art based on various factors. The minimum fluidization velocity may be influenced by factors including gravitational acceleration, fluid density, fluid viscosity, solid density, and solid particle size. The operational velocity may be influenced by factors including heat transfer and kinetic properties, such as height of the fluidized bed, total surface area, flow rate of silicon precursor in the feed gas stream, pressure, gas and solids temperature, concentrations of species, and thermodynamic equilibrium point.
[0023] In one embodiment, one or more surfaces of the fluidized bed reactor 200 may be made of a metal or a metal alloy. In one such embodiment, one or more surfaces of the reactor 200 may include a metal or metal alloy capable of withstanding the reaction temperatures. For example, the reactor wall 250 may be constructed of iron based-alloys, such as: stainless steel alloys, chromium-nickel alloys, and nickel based alloys including nickel-chromium alloys and nickel- chromium-molybdenum alloys, which may optionally include manganese, molybdenum, silicon, cobalt, tungsten, etc., which would be apparent to those having skill in the art with the aid of the present disclosure. In certain embodiments, the metal alloys may be chosen from: steel 1.4841 , steel 1.4959, steel 2.4856, steel 2.4819 or steel 2.4617. For example, the reactor wall 250 may be configured to be thermoresistant to temperatures in the range of approximately 500 0C to 1 ,200 0C. For example, the reactor wall 250 can be constructed to tolerate temperatures ranging from approximately 500 0C to 600 0C, or from 500 0C to 700 0C, or from 600
SaltLake-499981 1 0031299-00010 6 °C to 800 0C, or from 800 0C to 900 0C, or from 800 0C to 1000 0C, or from 900 0C to 1100 0C, or from 900 0C to 1200 0C.
[0024] As shown by FIG. 2, the inside surface of the reactor wall 250 may be partially or completely coated with a protective layer 260 to avoid or minimize the contamination of the product beads 212 by diffusion of impurities from the reactor 200 or the reactor wall 250. In one such embodiment, the protective layer 260 may comprise materials that are inert or resistant to the conditions in the reactor 200, such as a metal or metal alloy capable of withstanding the reaction conditions within the reactor 200 and be compatible with the application of the protective layer 260. For example, the protective layer 260 may comprise materials that are resistant to heat, pressure, and corrosion by the fluidizing gases 215 or the silicon-bearing gases that are injected into the reactor 200.
[0025] In one embodiment, the fluidized bed reactor 200 may be lined with a protective layer 260 comprising a ceramic material that is resistant to corrosion or breakdown by the conditions in the reactor 200. In one such embodiment, the protective layer 260 may comprise at least one of the following materials: Alumina (AI2O3), Zirconium dioxide (ZrO2) and Zirconium dioxide - yttrium stabilized. In another embodiment, the protective layer is a ceramic material made from a composition other than silicon-based or carbon-based. In yet another embodiment, the protective layer 260 may comprise at least one of Alumina (AI2Os), Zirconium dioxide (ZrO2) and Zirconium dioxide - yttrium stabilized in combination with at least one of polycrystalline silicon, silicon carbide, silicon carbide coated graphite, silica, silicon nitride, tungsten carbide or molybdenum. In still another embodiment, the fluidized bed reactor 200 may include at least one of Alumina (AI2Os), Zirconium dioxide (ZrO2) and Zirconium dioxide - yttrium stabilized in combination with one of: quartz, graphite, carbon fiber, or combinations thereof.
[0026] FIG. 3 is close-up view of a cross section of a wall of a fluidized bed reactor as described herein with silicon beads 310 disposed therein. In the embodiment shown by FIG. 3, the reactor wall 350 comprises a protective layer 360 and an adhesion layer 365 applied to the reactor wall 350 before the deposition of the protective layer 360. The adhesion layer 365 may provide a substrate to which the protective layer 360 may bind or attach improving the durability and function of the protective layer 360. In one such embodiment, an adhesion layer 365 may comprise
SaltLake-499981 1 0031299-00010 a nickel based alloy with or without yttrium, particularly when iron based alloys, such as Cr-Ni alloys, comprise the reactor wall 250.
[0027] In one embodiment, the protective layer 260 may comprise a coating which has a depth of approximately 3 to 1000 microns. In one such example, the protective layer 260 has a depth ranging from approximately 5 to 900 microns, 10 to 700 microns, 20 to 500 microns, 25 to 400 microns or 40 to 300 microns. In another embodiment, the protective coating may have a depth of up to 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 95, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, or 900 microns.
[0028] The protective layer, such as protective layer 260 shown in FIG. 2, or protective layer 360 shown in FIG. 3, can be formed or deposited by one or more methods known by those of skill in the art including thermal projection, chemical vapor deposition, physical vapor deposition, solgel, electrophoretic deposition and aerosol thermal spraying.
[0029] In one embodiment, the deposition of the protective layer 260 or protective layer 360 may be followed by a thermal treatment. For example, the protective layer 260 may be annealed with a thermal treatment of temperatures ranging from approximately 900 0C to 1 ,300 0C. In one such embodiment, the thermal treatment may comprise temperatures ranging from 900 0C to 1 ,000 0C, or from 900 0C to 1 ,100 0C, or from 1 ,000 0C to 1 ,200 0C, or from 1 ,000 0C to 1 ,300 0C.
Examples
[0030] The specific examples included herein are for illustrative purposes only and are not to be considered as limiting to this disclosure. The compositions referred to and used in the following examples are either commercially available or can be prepared according to standard literature procedures by those skilled in the art.
Example 1: Effects of decomposition conditions on steel 1.4841
[0031] A. Nitrogen Gas
[0032] A sample of thermoresistant steel 1.4841 was subjected to decomposition conditions at 900 0C in the presence of silicon beads and a N2 gas stream. After 100 hours under reaction conditions, the sample steel 1.4841 was removed from the reactor and cooled to room temperature.
SaltLake-499981 1 0031299-00010 8 [0033] Cross sections of the sample steel 1.4841 were then prepared for analysis with a scanning electron microscope (SEM). The SEM analysis revealed that the steel had been corroded as evidenced by a suicide layer extending into the metal to a depth of approximately 2 microns.
[0034] B. HCI and Hydrogen Gas
[0035] A sample of thermoresistant steel 1.4841 was subjected to decomposition conditions at 900 0C in the presence of silicon beads and HCI and H2 (5:1 ). After 100 hours under reaction conditions, the sample steel 1.4841 was removed from the reactor and cooled to room temperature.
[0036] Cross sections of the sample steel 1.4841 were prepared as before for
SEM analysis. The SEM analysis revealed a 50 micron suicide layer on the metal resulting from corrosion of the metal substrate by the chloride. The SEM analysis also revealed the formation of chlorides including iron and chromium chlorides.
[0037] C. Steel with Cr2O3 Layer
[0038] A sample of steel 1.4841 was coated with a 50 micron layer of Cr2O3 using chemical vapor deposition. The Cr2O3 coated steel was heated to 900 0C in the presence of silicon beads and N2 gas. After 100 hours, the Cr2O3 coated steel was cooled to room temperature. SEM analysis showed the presence of silica and chromium on the surface of the steel, potentially due to the following reaction: 2Cr2O3 + 3Si→ 4Cr + 3SiO2.
[0039] D. Steel with Adhesion Layer and ZrO2 — yttrium Stabilized Protective Layer [0040] A sample of steel 1.4841 was prepared with a nickel alloy adhesion layer to improve the adhesion of the ceramic layer. The nickel alloy adhesion layer (NiCrAIY) was deposited using an atmospheric plasma spray process. Next, the sample was covered with a 100 micron ceramic coating Of ZrO2 — yttrium stabilized, and heated to 900 0C, as before, in conditions simulating a fluidized bed reactor with silicon beads and in the presence of HCI and H2 (5:1 ). After 100 hours, the ZrO2 — yttrium stabilized coated steel was cooled to room temperature. SEM analysis showed the steel 1.4841 with the ceramic coating of ZrO2 — yttrium stabilized resisted corrosion or degradation thereby minimizing or eliminating likely contamination of a silicon product. More particularly, SEM data showed that there was no migration of
SaltLake-499981 1 0031299-00010 9 aluminum outside of the NiCrAIY adhesion layer. Likewise, there was no migration of chromium, manganese, and nickel outside of the steel 1.4841 and the NiCrAIY adhesion layer. Additionally, the SEM analysis showed that only a few particles of iron from the steel 1.4841 were present in the base of the NiCrAIY adhesion layer and, there was no iron migration into the ZrO2 — yttrium stabilized protective layer. Therefore, there was no contamination of the ZrO2 — yttrium stabilized protective layer that would threaten the purity of a silicon product.
[0041] E. Steel with Adhesion Layer and AI2O3 Protective Layer
[0042] As before, a sample of steel 1.4841 was prepared with a nickel alloy adhesion layer followed by the addition of an AI2O3 protective layer. The prepared sample was heated for 100 hours at 900 0C in a fluidized bed reactor with silicon beads fluidized with HCI and H2 (5:1 ). After cooling to room temperature, SEM analysis showed that the AI2O3 protective layer prevented corrosion of the steel sample.
Example 2: Heat transfer by a radiant heater [0043] A. Untreated Stainless Steel
[0044] A stainless steel tube (AISI316L) approximately 0.5 meters long and with an outside diameter of 21.3 mm and a thickness of 2.77 mm was used to measure radiation heat transfer. A radiation heater with an inside diameter of 40 mm was positioned around the steel tube without contacting the surface of the steel tube. The steel tube and the radiation heater were insulated with 300 mm thick ceramic fiber. A stream of N2 gas at mass flow rate of 15 Kg/h was passed along the inside of the steel tube horizontally. Thermowells were used to measure the temperature of the radiation heater, the external temperature of the steel tube at the inlet and outlet points of the N2 gas stream, and the temperature of the N2 gas stream at the inlet and outlet points. In steady state, the following temperatures were measured: N2 inlet temperature = 210C; N2 outlet temperature = 315 0C; outer wall tube temperature at the inlet = 569 0C, and at the outlet = 773 0C. The thermal power absorbed in the system was 1.325 W.
SaltLake-499981 1 0031299-00010 1 0 [0045] B. Sand-Blasted Stainless Steel
[0046] A stainless steel tube was prepared as previously described followed by sand-blasting the surface of the steel tube. After sand-blasting, the following temperatures from the stainless steel tube were measured: N2 inlet temperature = 2O0C; N2 outlet temperature = 445 0C; outer wall tube temperature at the inlet = 953 0C, and at the outlet = 1 ,055 0C. With the surface treatment, the thermal power absorbed in the system was 1.970 W.
[0047] The analysis showed that the thermal power transfer with the sand-blasting treatment was approximately 1.5 times greater that the untreated steel tube. The thermal power transfer to the N2 gas stream is due to a combination of radiation from the heater to the outlet wall of the steel tube, conduction through the wall of the steel tube, and convection from the inner wall of the steel tube to the N2 gas stream. The surface treatment resulted in a decreased reflectivity of the steel tube and an increased ability of the steel tube to absorb heat, thereby increasing the efficiency of heat transfer to the gas stream inside the steel tube. An estimation of the new emissivity value was calculated using the combination of the radiation, conduction and convection heat transfer. Values of the theoretical thermal power transfer were calculated in order to estimate the new value of the emissivity. [0048] Not being bound by any particular theory, a calculation model using the following equations was used: [0049] Dittus-boelter equation:
Nu D = 0.023 - RC -Pr* Kx = Nu ' k
D
[0050] A grey body completely enclosed into another grey body equivalent convection coefficient due to radiation:
Figure imgf000013_0001
[0051] Universal coefficient of heat transfer at the inlet and at the outlet of the pipe:
SaltLake-499981 1 0031299-00010 1 1
Figure imgf000014_0001
[0052] The calculation model introduced the concept of mean logarithmic difference of universal coefficients of heat transfer, and temperatures, because U and ΔT vary along the heat exchanger.
[0053] The emissivity value of the heater was ε = 0.7 according to the manufacturer datasheet. The emissivity of stainless steel is 0.18 at 500 0C. [0054] The values of the first test were implemented in order to adjust the model, and in a second stage the values of the second test were implemented in order to obtain the new emissivity values through an iterative process. The sand-blasted stainless steel emissivity calculated was 0.52. Hence, the radiation heat transfer ratio was increased approximately 3 times by the sand-blasting surface treatment. [0055] It will be obvious to those having skill in the art that many changes may be made to the details of the above-described embodiments without departing from the underlying principles of the invention. The scope of the present invention should, therefore, be determined only by the following claims.
SaltLake-499981 1 0031299-00010 1 2

Claims

Claims
1. A fluidized bed reactor comprising: a chamber having dimensions to contain particles capable of being fluidized therein, the chamber having a wall constructed of a metal alloy; a gas inlet in the chamber configured to receive a gas to fluidize the particles inside the chamber; an outlet in the chamber configured to allow an effluent to leave the chamber; and a ceramic protective layer deposited on at least a portion of an inside surface of the chamber; wherein the protective layer comprises a ceramic or non-silicon or non-carbon based composition and is configured to be resistant to corrosion by the fluidizing gas.
2. The fluidized bed reactor of claim 1 , wherein the metal alloy is an iron- based alloy selected from at least one of the following: a stainless steel alloy and a chromium-nickel alloy.
3. The fluidized bed reactor of claim 2, wherein the metal alloy further includes at least one of the following: manganese, molybdenum, silicon, cobalt and tungsten.
4. The fluidized bed reactor of claim 1 , wherein the metal alloy is a nickel- based alloy selected from at least one of the following: a nickel-molybdenum alloy and a nickel-chromium-molybdenum alloy.
5. The fluidized bed reactor of claim 4, wherein the metal alloy further includes at least one of the following: manganese, molybdenum, silicon, cobalt and tungsten.
6. The fluidized bed reactor of claim 1 , wherein the ceramic protective layer comprises at least one of the following: Alumina (AI2O3), Zirconium dioxide (Zrθ2) and Zirconium dioxide-yttrium stabilized.
7. The fluidized bed reactor of claim 1 , further comprising an adhesion layer positioned between the protective layer and the inside surface of the chamber.
8. The fluidized bed reactor of claim 7, wherein the adhesion layer comprises at least one of the following: a nickel alloy layer and a nickel-chromium- yttrium layer
SaltLake-499981 1 0031299-00010 1 3
9. The fluidized bed reactor of claim 1 , wherein the ceramic protective layer deposited on the inside surface of the chamber is deposited by at least one of the following: thermal projection, chemical vapor deposition, physical vapor deposition, solgel, electrophoretic deposition and aerosol thermal spraying.
10. The fluidized bed reactor of claim 1 , wherein the chamber comprises an external surface and, wherein at least a portion of the external surface of the chamber has been treated to improve the thermal power transfer efficiency of the chamber compared to an untreated external surface.
11. The fluidized bed reactor of claim 10, wherein the external surface of the chamber is sand-blasted to improve the thermal power transfer efficiency of the chamber.
12. The fluidized bed reactor of claim 1 , wherein the chamber is constructed of a material configured to withstand internal pressures ranging from approximately 50 mbar to approximately 5000 mbar.
13. The fluidized bed reactor of claim 1 , wherein the chamber is constructed of a material configured to withstand temperatures ranging from approximately 500 °C to approximately 1200 °C.
14. The fluidized bed reactor of claim 1 , wherein the particles comprise silicon particles and the gas comprises at least one of the following: hydrogen, helium, argon, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, monosilane, disilane, trisilane, trichlorosilane, dichlorosilane, monochlorosilane, thbromosilane, dibromosilane, monobromosilane, triiodosilane, diiodosilane and monoiodosilane.
15. The fluidized bed reactor of claim 1 , further comprising at least one reactor heater, wherein the at least one reactor heater comprises at least one of the following: a radiation heater and a conduction heater.
16. The fluidized bed reactor of claim 1 , wherein the gas inlet in the chamber is configured to also receive a silicon-bearing gas to fluidize the particles inside the chamber.
17. A method of producing high purity silicon, the method comprising: injecting at least one fluidizing gas into a fluidized bed reactor, wherein the fluidized bed reactor comprises: a chamber constructed of a metal alloy, the chamber including a gas inlet and an effluent outlet;
SaltLake-499981 1 0031299-00010 14 a ceramic protective layer deposited on an inside surface of the chamber; a bed of silicon beads disposed within the chamber; and at least one reactor heater; injecting at least one silicon-bearing gas into the fluidized bed reactor, heating the fluidized bed reactor with the at least one reactor heater to a temperature sufficient for thermal decomposition of silicon; and collecting the high purity silicon that has been produced and deposited on the fluidized silicon beads; wherein the ceramic protective layer is resistant to corrosion by the at least one fluidizing gas or the at least one silicon-bearing gas.
18. The method of claim 17, wherein the metal alloy is an iron-based alloy selected from at least one of the following: a stainless steel alloy and a chromium- nickel alloy.
19. The method of claim 17, wherein the metal alloy is a nickel-based alloy selected from at least one of the following: a nickel-molybdenum alloy and a nickel- chromium-molybdenum alloy.
20. The method of claim 17, wherein the ceramic protective layer comprises at least one of the following: Alumina (AI2O3), Zirconium dioxide (Zrθ2) and Zirconium dioxide-yttrium stabilized.
21. The method of claim 17, further comprising an adhesion layer positioned between the protective layer and the inside surface of the chamber.
22. The method of claim 21 , wherein the adhesion layer comprises a nickel alloy layer, or a nickel-chromium-yttrium alloy layer.
23. The method of claim 17, wherein the protective layer is deposited on the inside surface of the chamber by at least one of the following: thermal projection, chemical vapor deposition, physical vapor deposition, solgel, electrophoretic deposition and aerosol thermal spraying.
24. The method of claim 17, wherein an external surface of the chamber is sand-blasted to improve the thermal power transfer efficiency of the chamber compared to an untreated external surface.
25. The method of claim 17, wherein the fluidizing gas is at least one of the following: hydrogen, helium, argon, silicon tetrachloride, silicon tetrabromide and silicon tetraiodide.
SaltLake-499981 1 0031299-00010 1 5
26. The method of claim 17, wherein the silicon-bearing gas is at least one of the following: monosilane, disilane, thsilane, thchlorosilane, dichlorosilane, monochlorosilane, tribromosilane, dibromosilane, monobromosilane, thiodosilane, diiodosilane and monoiodosilane.
27. The method of claim 17, wherein heating the fluidized bed reactor with the at least one reactor heater to a temperature sufficient for thermal decomposition of silicon comprises heating the fluidized bed reactor to a temperature of between approximately 500 °C to approximately 1200 °C.
28. The method of claim 27, wherein the fluidized bed reactor is heated to a temperature ranging from approximately 700 0C to approximately 900 0C.
SaltLake-499981 1 0031299-00010 1 6
PCT/US2009/065345 2009-02-26 2009-11-20 Fluidized bed reactor for production of high purity silicon WO2010098797A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CN2009801490221A CN102239115A (en) 2009-02-26 2009-11-20 Fluidized bed reactor for production of high purity silicon
RU2011139109/05A RU2011139109A (en) 2009-02-26 2009-11-20 PSEUDO-LIQUIDED REACTOR FOR HIGH PURITY SILICON
MX2011008790A MX2011008790A (en) 2009-02-26 2009-11-20 Fluidized bed reactor for production of high purity silicon.
EP09840944.4A EP2318313A4 (en) 2009-02-26 2009-11-20 Fluidized bed reactor for production of high purity silicon
BRPI0924261-9A BRPI0924261A2 (en) 2009-02-26 2009-11-20 Fluid bed reactor for high purity silicon production
CA2753354A CA2753354A1 (en) 2009-02-26 2009-11-20 Fluidized bed reactor for production of high purity silicon
AU2009341100A AU2009341100A1 (en) 2009-02-26 2009-11-20 Fluidized bed reactor for production of high purity silicon
JP2011552017A JP2012519130A (en) 2009-02-26 2009-11-20 Fluidized bed reactor for producing high purity silicon

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12/393,852 2009-02-26
US12/393,852 US8168123B2 (en) 2009-02-26 2009-02-26 Fluidized bed reactor for production of high purity silicon

Publications (1)

Publication Number Publication Date
WO2010098797A1 true WO2010098797A1 (en) 2010-09-02

Family

ID=42631134

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/065345 WO2010098797A1 (en) 2009-02-26 2009-11-20 Fluidized bed reactor for production of high purity silicon

Country Status (12)

Country Link
US (3) US8168123B2 (en)
EP (1) EP2318313A4 (en)
JP (1) JP2012519130A (en)
KR (1) KR20110132338A (en)
CN (1) CN102239115A (en)
AU (1) AU2009341100A1 (en)
BR (1) BRPI0924261A2 (en)
CA (1) CA2753354A1 (en)
MX (1) MX2011008790A (en)
RU (1) RU2011139109A (en)
TW (1) TW201034757A (en)
WO (1) WO2010098797A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2766149C2 (en) * 2015-10-09 2022-02-08 МИЛУОКИ СИЛИКОН, ЭлЭлСи Purified silicon, as well as devices and systems for its production

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103787336B (en) 2008-09-16 2016-09-14 储晞 The method producing high purity granular silicon
JP2010171388A (en) * 2008-12-25 2010-08-05 Hitachi Kokusai Electric Inc Substrate processing apparatus, method of manufacturing semiconductor device, and reaction tube for processing substrate
US8168123B2 (en) * 2009-02-26 2012-05-01 Siliken Chemicals, S.L. Fluidized bed reactor for production of high purity silicon
TW201113391A (en) * 2009-03-19 2011-04-16 Ae Polysilicon Corp Silicide-coated metal surfaces and methods of utilizing same
JP2012523963A (en) * 2009-04-20 2012-10-11 エーイー ポリシリコン コーポレーション Reactor with metal surface coated with silicide
US8235305B2 (en) * 2009-04-20 2012-08-07 Ae Polysilicon Corporation Methods and system for cooling a reaction effluent gas
US8029756B1 (en) * 2010-03-30 2011-10-04 Peak Sun Sillcon Corporation Closed-loop silicon production
CN101935038B (en) * 2010-08-13 2013-04-10 镇江环太硅科技有限公司 Silicon ingot cutting waste material recovery method and silicon ingot treatment device
US20120148728A1 (en) * 2010-12-09 2012-06-14 Siliken Sa Methods and apparatus for the production of high purity silicon
KR20140005199A (en) * 2011-01-19 2014-01-14 알이씨 실리콘 인코포레이티드 Reactor system and method of polycrystalline silicon production therewith
DE102011077970A1 (en) * 2011-06-22 2012-12-27 Wacker Chemie Ag Apparatus and process for the temperature treatment of corrosive gases
US8875728B2 (en) 2012-07-12 2014-11-04 Siliken Chemicals, S.L. Cooled gas distribution plate, thermal bridge breaking system, and related methods
WO2014026588A1 (en) * 2012-08-13 2014-02-20 江苏中能硅业科技发展有限公司 Method for preparing high sphericity seed crystal and fluidized bed particle silicon
US9452403B2 (en) * 2012-10-19 2016-09-27 Sunedison, Inc. Using wavelet decomposition to determine the fluidization quality in a fluidized bed reactor
US9212421B2 (en) 2013-07-10 2015-12-15 Rec Silicon Inc Method and apparatus to reduce contamination of particles in a fluidized bed reactor
US9587993B2 (en) 2012-11-06 2017-03-07 Rec Silicon Inc Probe assembly for a fluid bed reactor
JP2016503377A (en) * 2012-11-06 2016-02-04 アールイーシー シリコン インコーポレイテッド Method and apparatus for reducing particle contamination in a fluidized bed reactor
JP2016509662A (en) * 2012-12-21 2016-03-31 アールイーシー シリコン インコーポレイテッド High temperature grade steel for fluidized bed reactors
US9297765B2 (en) * 2013-03-14 2016-03-29 Sunedison, Inc. Gas decomposition reactor feedback control using Raman spectrometry
DE102013206339A1 (en) 2013-04-10 2014-10-16 Wacker Chemie Ag Apparatus and method for removing polycrystalline silicon rods from a reactor
WO2015138512A1 (en) * 2014-03-10 2015-09-17 Sitec Gmbh Hydrochlorination reactor
US9446367B2 (en) 2014-08-15 2016-09-20 Rec Silicon Inc Joint design for segmented silicon carbide liner in a fluidized bed reactor
US9662628B2 (en) 2014-08-15 2017-05-30 Rec Silicon Inc Non-contaminating bonding material for segmented silicon carbide liner in a fluidized bed reactor
US20160045881A1 (en) * 2014-08-15 2016-02-18 Rec Silicon Inc High-purity silicon to form silicon carbide for use in a fluidized bed reactor
US9238211B1 (en) 2014-08-15 2016-01-19 Rec Silicon Inc Segmented silicon carbide liner
CN104383865B (en) * 2014-11-20 2016-09-21 江苏科技大学 A kind of magnetically fluidized bed device and use control method and the test method of this device
DE102015205727A1 (en) 2015-03-30 2016-10-06 Wacker Chemie Ag Fluidized bed reactor for the production of chlorosilanes
KR102393833B1 (en) * 2015-06-16 2022-05-02 버슘머트리얼즈 유에스, 엘엘씨 Halidosilane compounds and compositions and processes for depositing silicon-containing films using same
WO2019079879A1 (en) 2017-10-27 2019-05-02 Kevin Allan Dooley Inc. A system and method for manufacturing high purity silicon
RU2744449C1 (en) * 2019-12-27 2021-03-09 Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской Академии наук (ФГБУН ИПХФ РАН) Silicon-containing active material for negative electrode and method for its production
US20230338915A1 (en) * 2020-09-21 2023-10-26 Dsm Ip Assets B.V. Ceramic coating on metal parts to reduce deposit of metallic transition metals in hydrogenation reactions

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516345A (en) * 1994-06-30 1996-05-14 Iowa State University Research Foundation, Inc. Latent heat-ballasted gasifier method
US5798137A (en) * 1995-06-07 1998-08-25 Advanced Silicon Materials, Inc. Method for silicon deposition
US5910290A (en) * 1994-10-03 1999-06-08 Foster Wheeler Energia Oy Arrangement in a wall and a method of coating a wall
US5976247A (en) * 1995-06-14 1999-11-02 Memc Electronic Materials, Inc. Surface-treated crucibles for improved zero dislocation performance
US6007869A (en) 1997-08-14 1999-12-28 Wacker-Chemie Gmbh Process for preparing highly pure silicon granules
US20070154382A1 (en) 2003-11-21 2007-07-05 Emil Edwin Method
US20070178028A1 (en) 2004-02-23 2007-08-02 Eiichi Fukasawa Apparatus for production of metal chloride

Family Cites Families (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2843458A (en) * 1955-10-20 1958-07-15 Cabot Godfrey L Inc Process for producing silicon tetrachloride
GB1159823A (en) * 1965-08-06 1969-07-30 Montedison Spa Protective Coatings
US4393013A (en) * 1970-05-20 1983-07-12 J. C. Schumacher Company Vapor mass flow control system
US3906605A (en) * 1973-06-18 1975-09-23 Olin Corp Process for preparing heat exchanger tube
US4084024A (en) * 1975-11-10 1978-04-11 J. C. Schumacher Co. Process for the production of silicon of high purity
US4134514A (en) * 1976-12-02 1979-01-16 J C Schumacher Co. Liquid source material container and method of use for semiconductor device manufacturing
US4298037A (en) * 1976-12-02 1981-11-03 J. C. Schumacher Co. Method of shipping and using semiconductor liquid source materials
US4140735A (en) * 1977-08-15 1979-02-20 J. C. Schumacher Co. Process and apparatus for bubbling gas through a high purity liquid
US4227291A (en) * 1978-06-22 1980-10-14 J. C. Schumacher Co. Energy efficient process for continuous production of thin semiconductor films on metallic substrates
US4341610A (en) * 1978-06-22 1982-07-27 Schumacher John C Energy efficient process for continuous production of thin semiconductor films on metallic substrates
US4318942A (en) * 1978-08-18 1982-03-09 J. C. Schumacher Company Process for producing polycrystalline silicon
US4298942A (en) * 1979-12-19 1981-11-03 The United States Of America As Represented By The Secretary Of The Air Force Nonlinear amplitude detector
US4436674A (en) * 1981-07-30 1984-03-13 J.C. Schumacher Co. Vapor mass flow control system
US4891201A (en) * 1982-07-12 1990-01-02 Diamond Cubic Liquidation Trust Ultra-pure epitaxial silicon
US4818495A (en) * 1982-11-05 1989-04-04 Union Carbide Corporation Reactor for fluidized bed silane decomposition
US4979643A (en) * 1985-06-21 1990-12-25 Air Products And Chemicals, Inc. Chemical refill system
US4859375A (en) * 1986-12-29 1989-08-22 Air Products And Chemicals, Inc. Chemical refill system
KR880000618B1 (en) * 1985-12-28 1988-04-18 재단법인 한국화학연구소 Preparation for silicon multy crystal
US4820587A (en) * 1986-08-25 1989-04-11 Ethyl Corporation Polysilicon produced by a fluid bed process
US4883687A (en) * 1986-08-25 1989-11-28 Ethyl Corporation Fluid bed process for producing polysilicon
JPS63117906A (en) * 1986-11-07 1988-05-21 Shin Etsu Chem Co Ltd Member for production apparatus of polycrystalline silicon
JPS63230504A (en) * 1987-03-18 1988-09-27 Mitsui Toatsu Chem Inc Production of chlorine
DE3711444A1 (en) * 1987-04-04 1988-10-13 Huels Troisdorf METHOD AND DEVICE FOR PRODUCING DICHLORSILANE
US5139762A (en) * 1987-12-14 1992-08-18 Advanced Silicon Materials, Inc. Fluidized bed for production of polycrystalline silicon
US5242671A (en) * 1988-10-11 1993-09-07 Ethyl Corporation Process for preparing polysilicon with diminished hydrogen content by using a fluidized bed with a two-step heating process
US5326547A (en) * 1988-10-11 1994-07-05 Albemarle Corporation Process for preparing polysilicon with diminished hydrogen content by using a two-step heating process
JPH02233514A (en) * 1989-03-06 1990-09-17 Osaka Titanium Co Ltd Production of polycrystalline silicon
US5284676A (en) * 1990-08-17 1994-02-08 Carbon Implants, Inc. Pyrolytic deposition in a fluidized bed
JPH06127922A (en) * 1992-10-16 1994-05-10 Tonen Chem Corp Fluidized bed reactor for producing polycrystalline silicon
GB2271518B (en) * 1992-10-16 1996-09-25 Korea Res Inst Chem Tech Heating of fluidized bed reactor by microwave
US5445742A (en) * 1994-05-23 1995-08-29 Dow Corning Corporation Process for purifying halosilanes
JP3705623B2 (en) * 1995-03-24 2005-10-12 株式会社トクヤマ Silane decomposition / reduction reaction apparatus and method for producing high-purity crystalline silicon
US5776416A (en) * 1995-11-14 1998-07-07 Tokuyama Corporation Cyclone and fluidized bed reactor having same
US6060021A (en) * 1997-05-07 2000-05-09 Tokuyama Corporation Method of storing trichlorosilane and silicon tetrachloride
US5910295A (en) * 1997-11-10 1999-06-08 Memc Electronic Materials, Inc. Closed loop process for producing polycrystalline silicon and fumed silica
GB9902099D0 (en) 1999-01-29 1999-03-24 Boc Group Plc Vacuum pump systems
DE19948395A1 (en) * 1999-10-06 2001-05-03 Wacker Chemie Gmbh Fluidized bed reactor with radiative heating, useful for producing high purity polycrystalline silicon, e.g. for electronics, by passing silicon-containing gas over hot silicon particles
WO2002012122A1 (en) * 2000-08-02 2002-02-14 Mitsubishi Materials Polycrystalline Silicon Corporation Process for producing disilicon hexachloride
ATE274471T1 (en) * 2000-09-14 2004-09-15 Solarworld Ag METHOD FOR PRODUCING TRICHLOROSILANE
DE10057481A1 (en) * 2000-11-20 2002-05-23 Solarworld Ag Production of high-purity granular silicon comprises decomposing a silicon-containing gas in a reactor made of carbon-fiber-reinforced silicon carbide
DE10060469A1 (en) * 2000-12-06 2002-07-04 Solarworld Ag Process for the production of high-purity, granular silicon
DE10061680A1 (en) * 2000-12-11 2002-06-20 Solarworld Ag Process for the production of silane
DE10062419A1 (en) * 2000-12-14 2002-08-01 Solarworld Ag Process for the production of high-purity, granular silicon
DE10063862A1 (en) * 2000-12-21 2002-07-11 Solarworld Ag Process for the production of high-purity, granular silicon
KR100411180B1 (en) * 2001-01-03 2003-12-18 한국화학연구원 Method for preparing polycrystalline silicon
DE10118483C1 (en) * 2001-04-12 2002-04-18 Wacker Chemie Gmbh Continuous direct synthesis of silane and mono-, di-, tri- and tetra-chlorosilanes, used e.g. in production of linear polysiloxanes or pyrogenic silica, in fluidized bed includes recycling dust containing silicon as suspension in liquid
DE10124848A1 (en) * 2001-05-22 2002-11-28 Solarworld Ag Production of high-purity granular silicon by thermal decomposition of silanes or halosilanes in a fluidized-bed reactor comprises separating particles of the desired size in an external classifier
US7033561B2 (en) * 2001-06-08 2006-04-25 Dow Corning Corporation Process for preparation of polycrystalline silicon
US20020187096A1 (en) * 2001-06-08 2002-12-12 Kendig James Edward Process for preparation of polycrystalline silicon
WO2003040036A1 (en) 2001-10-19 2003-05-15 Tokuyama Corporation Method for producing silicon
WO2003069027A2 (en) * 2002-02-14 2003-08-21 Advanced Silicon Materials Llc Energy efficient method for growing polycrystalline silicon
WO2004035472A1 (en) * 2002-09-12 2004-04-29 Takayuki Shimamune Process for producing high-purity silicon and apparatus
NO321276B1 (en) * 2003-07-07 2006-04-18 Elkem Materials Process for the preparation of trichlorosilane and silicon for use in the preparation of trichlorosilane
US20050161158A1 (en) * 2003-12-23 2005-07-28 Schumacher John C. Exhaust conditioning system for semiconductor reactor
DE102004010055A1 (en) 2004-03-02 2005-09-22 Degussa Ag Process for the production of silicon
US7141114B2 (en) * 2004-06-30 2006-11-28 Rec Silicon Inc Process for producing a crystalline silicon ingot
US20060105105A1 (en) * 2004-11-12 2006-05-18 Memc Electronic Materials, Inc. High purity granular silicon and method of manufacturing the same
US8029914B2 (en) * 2005-05-10 2011-10-04 Exxonmobile Research And Engineering Company High performance coated material with improved metal dusting corrosion resistance
US7462211B2 (en) * 2005-06-29 2008-12-09 Exxonmobil Chemical Patents Inc. Gas-solids separation device and method
CN101316651B (en) 2005-07-19 2011-03-02 瑞科硅公司 Silicon spout-fluidized bed
DE102005039118A1 (en) * 2005-08-18 2007-02-22 Wacker Chemie Ag Method and device for comminuting silicon
DE102005042753A1 (en) * 2005-09-08 2007-03-15 Wacker Chemie Ag Method and device for producing granular polycrystalline silicon in a fluidized bed reactor
NO20054402L (en) 2005-09-22 2007-03-23 Elkem As Method of production of trichlorosilane and silicon for use in the production of trichlorosilane
KR101450346B1 (en) * 2006-03-15 2014-10-14 알이에스씨 인베스트먼츠 엘엘씨 Method for making silicon for solar cells and other applications
CN101460398B (en) * 2006-04-13 2012-08-29 卡伯特公司 Production of silicon through a closed-loop process
US7935327B2 (en) * 2006-08-30 2011-05-03 Hemlock Semiconductor Corporation Silicon production with a fluidized bed reactor integrated into a siemens-type process
DE102007021003A1 (en) * 2007-05-04 2008-11-06 Wacker Chemie Ag Process for the continuous production of polycrystalline high-purity silicon granules
US7927984B2 (en) * 2008-11-05 2011-04-19 Hemlock Semiconductor Corporation Silicon production with a fluidized bed reactor utilizing tetrachlorosilane to reduce wall deposition
US8168123B2 (en) * 2009-02-26 2012-05-01 Siliken Chemicals, S.L. Fluidized bed reactor for production of high purity silicon

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516345A (en) * 1994-06-30 1996-05-14 Iowa State University Research Foundation, Inc. Latent heat-ballasted gasifier method
US5910290A (en) * 1994-10-03 1999-06-08 Foster Wheeler Energia Oy Arrangement in a wall and a method of coating a wall
US5798137A (en) * 1995-06-07 1998-08-25 Advanced Silicon Materials, Inc. Method for silicon deposition
US5976247A (en) * 1995-06-14 1999-11-02 Memc Electronic Materials, Inc. Surface-treated crucibles for improved zero dislocation performance
US6007869A (en) 1997-08-14 1999-12-28 Wacker-Chemie Gmbh Process for preparing highly pure silicon granules
US20070154382A1 (en) 2003-11-21 2007-07-05 Emil Edwin Method
US20070178028A1 (en) 2004-02-23 2007-08-02 Eiichi Fukasawa Apparatus for production of metal chloride

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2318313A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2766149C2 (en) * 2015-10-09 2022-02-08 МИЛУОКИ СИЛИКОН, ЭлЭлСи Purified silicon, as well as devices and systems for its production

Also Published As

Publication number Publication date
US20100215562A1 (en) 2010-08-26
CA2753354A1 (en) 2010-09-02
RU2011139109A (en) 2013-11-20
EP2318313A4 (en) 2013-05-01
MX2011008790A (en) 2011-12-14
JP2012519130A (en) 2012-08-23
TW201034757A (en) 2010-10-01
KR20110132338A (en) 2011-12-07
BRPI0924261A2 (en) 2015-08-25
US8168123B2 (en) 2012-05-01
EP2318313A1 (en) 2011-05-11
US20110027160A1 (en) 2011-02-03
US20120171102A1 (en) 2012-07-05
AU2009341100A1 (en) 2011-09-08
CN102239115A (en) 2011-11-09
US8158093B2 (en) 2012-04-17

Similar Documents

Publication Publication Date Title
US8168123B2 (en) Fluidized bed reactor for production of high purity silicon
KR101914535B1 (en) Fluidized bed reactor and method for producing polycrystalline silicon granules
US8425855B2 (en) Reactor with silicide-coated metal surfaces
KR20140071394A (en) Production of polycrystalline silicon by the thermal decomposition of silane in a fluidized bed reactor
US8875728B2 (en) Cooled gas distribution plate, thermal bridge breaking system, and related methods
TW201221474A (en) Production of polycrystalline silicon by the thermal decomposition of trichlorosilane in a fluidized bed reactor
CN107253723B (en) Production of polycrystalline silicon by thermal decomposition of silane in a fluidized bed reactor
US20180297852A1 (en) Fluidized bed reactor and process for producing polycrystalline silicon granules
US7727483B2 (en) Reactor for chlorosilane compound
US20040042950A1 (en) Method for producing high-purity, granular silicon
WO2010108065A1 (en) Silicide - coated metal surfaces and methods of utilizing same
JPH0317768B2 (en)
EP1798199B1 (en) Reactor for chlorosilane compound
JP3341314B2 (en) Polycrystalline silicon manufacturing method

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980149022.1

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09840944

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2009840944

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2009840944

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2009341100

Country of ref document: AU

Ref document number: 2011552017

Country of ref document: JP

Ref document number: MX/A/2011/008790

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2011002060

Country of ref document: CL

Ref document number: 2753354

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 20117019738

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 6613/DELNP/2011

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 2009341100

Country of ref document: AU

Date of ref document: 20091120

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 7311/DELNP/2011

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 2011139109

Country of ref document: RU

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: PI0924261

Country of ref document: BR

ENP Entry into the national phase

Ref document number: PI0924261

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20110824