EP3160903A1 - Réacteur à lit fluidisé et procédé de production de silicium polycristallin granulaire - Google Patents

Réacteur à lit fluidisé et procédé de production de silicium polycristallin granulaire

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Publication number
EP3160903A1
EP3160903A1 EP15734088.6A EP15734088A EP3160903A1 EP 3160903 A1 EP3160903 A1 EP 3160903A1 EP 15734088 A EP15734088 A EP 15734088A EP 3160903 A1 EP3160903 A1 EP 3160903A1
Authority
EP
European Patent Office
Prior art keywords
reactor
silicon
fluidized bed
gas
polycrystalline silicon
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP15734088.6A
Other languages
German (de)
English (en)
Inventor
Simon PEDRON
Bernhard Baumann
Gerhard FORSTPOINTNER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
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 Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP3160903A1 publication Critical patent/EP3160903A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • B01J8/1836—Heating and cooling the reactor
    • 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
    • B01J8/1872—Details of the fluidised bed reactor
    • 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
    • C01B33/021—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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/442—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using fluidised bed 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
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00761—Discharging
    • 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
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B01J2208/00902—Nozzle-type feeding elements

Definitions

  • the invention relates to a fluidized bed reactor and a method for producing polycrystalline silicon granules.
  • silicon-containing educt gas there are described silicon-halogen compounds (e.g., chlorosilanes or bromosilanes), monosilane (SiH4), and mixtures of these gases with hydrogen.
  • silicon-halogen compounds e.g., chlorosilanes or bromosilanes
  • SiH4 monosilane
  • No. 4,90041,1 A discloses a process for obtaining high-purity polycrystalline silicon by precipitation of silicon onto high-purity silicon particles of silicon-containing gas, such as silane, dichlorosilane, trichlorosilane or tribromosilane, characterized by a reactor with a fluidized bed, in which together with Silicon seed particles, a reaction gas is introduced through an introduction tube, microwaves are supplied to heat the fluidized particles, so that deposited on it polysilicon.
  • silicon-containing gas such as silane, dichlorosilane, trichlorosilane or tribromosilane
  • US 4786477 A discloses an apparatus for carrying out the process comprising a reactor having a gas inlet tube for the reaction gas mixture at the lower end, a gas outlet tube at the top and a feed tube for the silicon seed particles, characterized in that the reactor made of quartz vertically on the Center line of a heat generator is located in which a shield against microwave in the middle part is installed and which communicates with microwave generators via microwave guide tubes, below the reactor, a gas distribution plate and within each microwave guide tube a Gasabsperrmembran is arranged and that cooling channels between the wall of the heat generator and the outer wall of the reactor and in the gas distribution plate are provided.
  • the Siliziumimpfteilchen be heated by means of microwave radiation to a temperature of 600-1200 ° C.
  • US Pat. No. 6,007,869 A discloses a process for producing silicon granules having a chlorine contamination of less than 50 ppm by weight by precipitation of elemental silicon on silicon particles in a fluidized bed reactor having a heating zone and a reaction zone, wherein the silicon particles in the heating zone are heated by means of an inert, silicon-free carrier gas are fluidized and heated by means of microwave energy, and exposed in the reaction zone to a reaction gas consisting of a silicon-containing feed gas and the carrier gas, characterized in that the average temperature of the reaction gas in the reaction zone, while flowing through the fluidized silicon particles, below 900 ° C is.
  • US7029632 B2 discloses a fluidized bed reactor consisting of:
  • All product-contacting components of the reactor are preferably made of an inert material or are coated with such a material.
  • Particularly suitable materials for this purpose are silicon or quartz.
  • the inner reactor tube must also have a high transmission for the heat radiation emitted by the selected heater.
  • the transmission for infrared radiation with wavelengths smaller than 2.6 pm is greater than 90%.
  • quartz in combination with an infrared radiation heater (range from 0.7 to 2.5 ⁇ m), for example a radiator with SiC surface whose maximum of the emitted radiation lies at a wavelength of 2.1 ⁇ m, is particularly good suitable.
  • the material should have a similarly high degree of transmission as quartz glass or a combination of high emissivity and high thermal conductivity.
  • the materials should also be inert against chemical attack, in particular by H 2 , chlorosilanes, HCl, N 2 at high temperatures.
  • Metals form silicides with chlorosilanes.
  • Free silicon reacts with nitrogen to form silicon nitride.
  • Nitrogen is often used as an inert gas in the pressure-bearing shell or in the heating chamber, which limits the reaction space, cf. e.g. US 490041 1 A. If nitrogen is used in the pressure-bearing casing, the reactor tube should be gas-tight in order to prevent nitrogen from passing from the casing into the interior of the reactor tube.
  • reactor tubes can cause abrasion on the walls.
  • the reactor tube can also be exposed to high voltages, namely compressive stress due to the clamping of the tube, thermal stresses due to high temperature gradients in the axial and radial directions. The latter occur preferably when the fluidized bed is locally heated from the outside.
  • EP1337463B1 discloses a reactor for producing high-purity, granular silicon by decomposition of a silicon-containing gas, characterized in that the reactor consists of a carbon-fiber-reinforced material based on silicon carbide, wherein the heat-insulating regions at the bottom of the reactor, and at the reactor head of a carbon fiber reinforced Silicon carbide material with low thermal conductivity exist, while the remaining areas are made of a carbon fiber-reinforced silicon carbide material with high thermal conductivity.
  • US 8075692 B2 describes a fluidized bed reactor having a metal alloy reactor tube and a removable concentric sleeve inside the reactor tube, the sleeve being silicon carbide, silicon nitride, silicon, quartz, a molybdenum alloy, molybdenum, graphite, a cobalt alloy or a nickel alloy or a coating can have with the materials mentioned.
  • the sleeve should withstand a temperature of at least 870 ° C, the temperatures in the vicinity of the sleeve amount to 700-900 ° C.
  • EP1984297 B1 discloses a fluidized bed reactor for the production of granular polycrystalline silicon comprising a) a reactor tube; b) a reactor shell surrounding the reactor tube; c) an inner zone formed in the reactor tube and an outer zone between the reactor shell and the reactor tube, wherein a silicon particle bed is present in the inner zone and a silicon deposition takes place while in the outer zone does not have a silicon particle bed and no silicon deposition takes place; d) a gas distributor device for introducing a gas into the silicon particle bed; e) an outlet for polycrystalline silicon particles and an outlet for reacted gas from the fluidized bed f) an inert gas inlet for maintaining a substantially inert gas atmosphere in the outer zone; g) a pressure control means for measuring and controlling the inner zone pressure Pi or the outer zone pressure Po; h) pressure difference control means for maintaining the value of Po - Pi within a range of 0 to 1 bar; wherein the inner zone pressure or the outer zone pressure is in the range of 1 to 15 bar.
  • the reactor tube preferably consists of an inorganic material which has a high temperature resistance, such as e.g. Quartz, silica, silicon nitride, boron nitride, silicon carbide, graphite, amorphous carbon.
  • US 8431032 B2 discloses a process for producing polysilicon by means of a fluidized bed reactor for the production of granular polysilicon
  • (iii) a step of removing silicon deposits following the silicon particle removal step, wherein the silicon deposits are removed by supplying an etching gas into the reaction zone which reacts with the silicon deposits to form gaseous silicon mixtures.
  • the deposition temperature is 600 ⁇ 850 ° C for monosilane as feed gas and 900-1 150 ° C for trichlorosilane.
  • the following materials are mentioned: quartz, silica, silicon nitride, silicon carbide, graphite, amorphous carbon.
  • Such a reactor tube is not inert to nitrogen in the intermediate jacket.
  • the etching process described in US Pat. No. 8431032 B2 makes it possible to etch wall covering on the reactor tube and on internals by means of a gas mixture.
  • the etching gas comprises e.g. HCl.
  • JP 63225514 A discloses a reactor tube of silicon carbide having a lining or coating of silicon for use in fluidized bed separation of high purity polysilicon from monosilane (SiH) at a deposition temperature of 550-1000 ° C. In an etching process to remove wall covering, the coating would be attacked by silicon.
  • a fluidized bed reactor for the production of polycrystalline silicon granules comprising a reactor vessel (1), a reactor tube (2) and a reactor bottom (15) within the reactor vessel (1), wherein between an outer wall of the reactor tube (2) and a Inner wall of the reactor container (1), further comprising a heating device (5), at least one bottom gas nozzle (9) for supplying fluidizing gas and at least one secondary gas nozzle (10) for supplying reaction gas, a supply device (1 1) to silicon To supply seed particles, a removal line (14) for polycrystalline silicon granules and a device for removing reactor exhaust gas (16), characterized in that a base body of the reactor tube (2) consists of at least 60 wt .-% of silicon carbide and at least on its inner side a CVD coating having a layer thickness of at least 5 ⁇ m, which is at least 99.995% by weight of silicon carbide.
  • the fluidized-bed reactor according to the invention provides for the use of silicon carbide for the main body of the reactor tube and for the coating of the reactor tube.
  • Silicon carbide (SiC) has a high thermal conductivity of 20 to 150 W / m-K at 1000 ° C and an emissivity of 80 to 90%.
  • the CVD coating with SiC preferably has a layer thickness of 30 to 500 ⁇ m, particularly preferably a layer thickness of 50 to 200 ⁇ m.
  • both the pipe inside and the pipe outside are coated.
  • the main body preferably consists of sintered SiC (SSiC).
  • SSiC is temperature resistant up to 1800-1900 ° C and already gas-tight without further treatment.
  • compounds containing electron acceptors e.g., boron
  • the SiC content of the SSiC basic body in this case is more than 90% by weight.
  • the main body can also consist of nitride-bonded SiC. This material is temperature resistant up to about 1500 ° C. Main constituents are SiC (65-90% by weight) and less than 6% by weight of metallic impurities or sintering aids. Other ingredients are Si 3 N 4 and free silicon.
  • nitride-bonded SiC is not gas-tight.
  • the CVD coating however, the gas tightness is accomplished.
  • the main body can also consist of recrystallized SiC (RSiC).
  • RSiC is temperature resistant up to about 1800-2000 ° C and has a high purity of greater than 99 wt% SiC.
  • the material is open-porous without further treatment and thus not gas-tight.
  • One possible treatment to achieve gas tightness is to infiltrate with liquid silicon to fill the pores. As a result, the maximum operating temperature is lowered to about 1400 ° C. Subsequent CVD coating ensures chemical inertness and required surface cleanliness. The CVD coating would be obsolete if no wall covering is to be etched and high-purity polysilicon is used for infiltration.
  • the gas tightness can be ensured by a SiC-CVD coating with a layer thickness of 200 to 800 ⁇ .
  • the main body can also consist of reaction-bonded SiC (RBSiC or SiSiC). This consists of 65 to 95 wt .-% of SiC and less than 1 wt .-% of metallic impurities. Other ingredients are free silicon and free carbon.
  • the material can be used up to 1400 ° C, but is not inert to a corrosive atmosphere due to an excess of silicon. If C-fibers are used for mechanical stabilization and control of thermal conductivity of the material, free carbon may be present on the surface. This is prone to methanation and thereby affects the gas tightness.
  • the preferred materials can be used up to a temperature of at least 1400 ° C, which has an advantage, e.g. compared with the silicon nitride proposed in the prior art, which is stable only up to 1250 ° C.
  • the base body and the coating have essentially the same coefficient of thermal expansion.
  • a fluidized bed reactor for the production of polycrystalline silicon granules comprising a reactor vessel (1), a reactor tube (2) and a reactor bottom (15) within the reactor vessel (1), wherein between an outer wall of the reactor tube (2) and an inner wall of the reactor vessel (1) is an intermediate casing (3), further comprising a heating device (5), at least one bottom gas nozzle (9) for supplying fluidizing gas and at least one secondary gas nozzle (10) for supplying reaction gas, a feed device (1 1) to supply silicon seed particles, a polycrystalline silicon granule discharge line (14) and a reactor exhaust gas discharge device (16), characterized in that a main body of the sapphire glass reactor tube (2) containing at least 99.99% by weight of a -AI 2 0 3 , exists.
  • a reactor tube of high-purity sapphire glass (a-Al 2 0 3 ) with a purity of at least 99.99 wt .-% can be used up to 1900 ° C and has similar transmission properties as glass, a high abrasion resistance and is chemically resistant to all reaction gases ,
  • the material can be provided with a SiC-CVD coating because of an almost identical coefficient of thermal expansion (4.6- 10 "6 K -1 at 1000 ° C.), which is preferred.
  • the reactor tube at least on its inside a CVD coating containing at least 99.995 wt .-% SiC and a layer thickness of at least 5 pm.
  • the CVD coating with SiC preferably has a layer thickness of 30-500 ⁇ m, more preferably between 50 and 200 ⁇ m.
  • the intermediate casing preferably contains an insulating material and is filled with an inert gas or is purged with an inert gas. Nitrogen is preferably used as the inert gas.
  • the pressure in the intermediate jacket is preferably higher than in the reaction space.
  • the high purity of the SiC coating of at least 99.995% by weight of SiC ensures that dopants (electron donors and acceptors, for example B, Al, As, P), metals, carbon, oxygen or chemical compounds of these substances in the near-surface Regions of the reactor tube are present only in low concentrations, so that the individual elements can reach neither by diffusion nor by abrasion in appreciable amount in the fluidized bed. There is no free silicon and no free carbon on the surface. This gives inertness to H 2 , chlorosilanes, HCl and N 2 .
  • dopants electron donors and acceptors, for example B, Al, As, P
  • metals, carbon, oxygen or chemical compounds of these substances in the near-surface Regions of the reactor tube are present only in low concentrations, so that the individual elements can reach neither by diffusion nor by abrasion in appreciable amount in the fluidized bed.
  • Contamination of the polycrystalline silicon granules with carbon is prevented by using a high-purity CVD coating on the SiC reactor tube. Notable amounts of carbon would be transferred from pure SiC only to contact with liquid silicon.
  • the invention also relates to a process for the production of polycrystalline silicon granules in one of the above-described fluidized bed reactors with a novel reactor tube, comprising fluidizing silicon seed particles by means of a gas flow in a fluidized bed, which is heated by means of a heater, wherein polycrystalline silicon by addition of a silicon-containing reaction gas the hot Siliziumkeimpumbleobervid is deposited, whereby the polycrystalline silicon granules formed.
  • the resulting polycrystalline silicon granules are removed from the fluidized bed reactor.
  • Siiiciumablagerungen are preferably removed on walls of the reactor tube and other reactor components by supplying an etching gas into the reaction zone.
  • etchant gas to poly Si silicon deposits on the hot silicon seed particle surfaces to provide silicon deposits on reactor tube and other reactor wall walls avoid.
  • the supply of the etching gas is preferably carried out locally in the so-called. Free board zone, which designates the gas space above the fluidized bed.
  • the wall covering can therefore be etched cyclically in alternation with the deposition process.
  • locally etching gas can be continuously added in the deposition operation in order to avoid the formation of wall covering.
  • the process is preferably operated continuously by removing particles grown by deposition from the reactor and metering in fresh silicon seed particles.
  • trichlorosilane is used as the silicon-containing reaction gas.
  • the temperature of the fluidized bed in the reaction zone in this case is more than 900 ° C and preferably more than 1000 ° C.
  • the temperature of the fluidized bed is at least 1100 ° C, more preferably at least 1 150 ° C and most preferably at least 1200 ° C.
  • the temperature of the fluidized bed in the reaction zone may also be 1300-1400 ° C.
  • the temperature of the fluidized bed in the reaction zone 1 is particularly preferably from 150 ° C. to 1250 ° C. In this temperature range, a maximum of the deposition rate is achieved, which drops again at even higher temperatures.
  • the temperature of the fluidized bed in the reaction zone is preferably 550-850 ° C.
  • the temperature of the fluidized bed in the reaction region is preferably 600-1000 ° C.
  • the fluidizing gas is preferably hydrogen.
  • the reaction gas is injected via one or more nozzles in the fluidized bed.
  • the local gas velocities at the outlet of the nozzles are preferably 0.5 to 200 m / s.
  • the concentration of the silicon-containing reaction gas is preferably from 5 mol% to 50 mol%, particularly preferably from 15 mol% to 40 mol%, based on the total amount of gas flowing through the fluidized bed.
  • the concentration of the silicon-containing reaction gas in the reaction gas nozzles is preferably 20 mol% to 80 mol%, particularly preferably 30 mol% to 60 mol%, based on the total amount of gas flowing through the reaction gas nozzles.
  • the silicon-containing reaction gas is preferably trichlorosilane.
  • the reactor pressure ranges from 0 to 7 barü, preferably in the range 0.5 to 4.5 barü.
  • the mass flow of silicon-containing reaction gas is preferably 200 to 600 kg / h.
  • the hydrogen volume flow is preferably 100 to 300 NrrrVh.
  • higher amounts of silicon-containing reaction gas and H 2 are preferred.
  • the specific mass flow of silicon-containing reaction gas is preferably 1600-6500 kg / (h * m 2 ).
  • the specific hydrogen volume flow is preferably 800-4000
  • the specific bed weight is preferably 700-2000 kg / m 2 .
  • the specific silicon seed particle dosage rate is preferably 7-25 kg / (h * m 2 ).
  • the specific reactor heating power is preferably 800-3000 kW / m 2 .
  • the residence time of the reaction gas in the fluidized bed is preferably 0.1 to 10 s, more preferably 0.2 to 5 s.
  • Fig. 1 shows the schematic structure of a fluidized bed reactor.
  • the fluidized bed reactor consists of a reactor vessel 1 into which a reactor tube 2 is inserted.
  • the intermediate casing 3 contains insulating material and is filled with an inert gas or is purged with an inert gas.
  • the pressure in the intermediate jacket 3 is higher than in the reaction space, which is limited by the walls of the reactor tube 2.
  • the fluidized bed 4 of polysilicon granules Inside the reactor tube 2 is the fluidized bed 4 of polysilicon granules.
  • the gas space above the fluidized bed (above the dashed line) is commonly referred to as a "free board zone”.
  • the fluidized bed 4 is heated by means of a heater 5.
  • the fluidizing gas 7 and the reaction gas mixture 6 are fed.
  • the gas supply takes place specifically via nozzles.
  • the fluidizing gas 7 is supplied via bottom gas nozzles 9 and the reaction gas mixture via so-called secondary gas nozzles (reaction gas nozzles) 10.
  • the height of the secondary gas nozzles 10 may differ from the height of the bottom gas nozzles 9.
  • the reactor head 8 may have a larger cross section than the fluidized bed 4.
  • Hydrogen is used as the fluidizing gas.
  • the deposition takes place at a pressure of 3 bar (abs) in a reactor tube with an inner diameter of 500 mm.
  • Product is continuously withdrawn and the seed supply is controlled so that the Sauter diameter of the product is 1000 ⁇ 50 ⁇ .
  • the intermediate coat is purged with nitrogen.
  • the residence time of the reaction gas in the fluidized bed is 0.5 s.
  • a total of 800 kg / h of gas is supplied, 17.5 mol% of which consist of trichlorosilane and the remainder of hydrogen.
  • the reactor tube consists of SSiC with a SiC content of 98% by weight and with a 150 ⁇ thick CVD coating, a fluidized bed temperature of 1200 ° C. can be achieved.
  • reaction gas reacts to equilibrium.
  • 38.9 kg of silicon can be deposited per hour.
  • the reactor tube is made of quartz glass, only a fluidized bed temperature of 980 ° C can be achieved, since otherwise a temperature of 1 150 ° C is exceeded long term on the heated reactor tube outside.
  • the reaction temperature is chosen to be similar to that used for the deposition process in order to avoid thermal stresses between reactor pipe and wall covering.
  • the reactor tube consists of SSiC with a SiC content of 98% by weight with a high-purity SiC coating with a thickness of 150 ⁇ m, the reactor tube is not chemically attacked and can continue to be used without restriction after the etching process.
  • the reactor tube is made of silicon or SiSiC without surface treatment
  • the reactor lining is also etched with the wall covering.
  • hydrogen can react with a carbon-containing heater and the nitrogen used as the inert gas to the toxic product HCN.
  • Chlorosilanes react on the hot surface of the heater to form silicon nitride, which forms white growths there.
  • the reactor must still be taken out of service during the etching.
  • the reactor tube is no longer usable for further runs.

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

Abstract

L'invention concerne un réacteur à lit fluidisé, destiné à la production de silicium polycristallin granulaire, qui comprend une cuve de réacteur (1), un tube de réacteur (2) et un fond de réacteur (15) à l'intérieur de la cuve (1), une chemise intermédiaire (3) étant disposée entre une paroi extérieure du tube (2) et une paroi intérieure de la cuve (1). Le réacteur comprend en outre un dispositif chauffant (5), au moins une buse à gaz (9) traversant le fond pour l'admission de gaz de fluidisation ainsi qu'au moins une buse à gaz secondaire (10) pour l'admission de gaz réactionnel, un système (11) d'alimentation de particules de silicium d'ensemencement, une conduite (14) de prélèvement du silicium polycristallin granulaire, ainsi qu'un système (16) d'évacuation des effluents gazeux du réacteur. Le corps de base du tube de réacteur (2) est constitué à au moins 60 % en poids de carbure de silicium et il est doté d'un revêtement CVD, ayant une épaisseur de couche d'au moins 5 µm, constitué à au moins 99,995 % en poids de SiC, ou bien le corps de base du tube de réacteur (2) est constitué de verre de saphir contenant au moins 99,99 % en poids d'α-Al2O3. L'invention concerne en outre un procédé de production de silicium polycristallin granulaire dans un tel réacteur à lit fluidisé.
EP15734088.6A 2014-06-24 2015-06-19 Réacteur à lit fluidisé et procédé de production de silicium polycristallin granulaire Withdrawn EP3160903A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014212049.7A DE102014212049A1 (de) 2014-06-24 2014-06-24 Wirbelschichtreaktor und Verfahren zur Herstellung von polykristallinem Siliciumgranulat
PCT/EP2015/063860 WO2015197498A1 (fr) 2014-06-24 2015-06-19 Réacteur à lit fluidisé et procédé de production de silicium polycristallin granulaire

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EP3160903A1 true EP3160903A1 (fr) 2017-05-03

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Country Link
US (1) US20170158516A1 (fr)
EP (1) EP3160903A1 (fr)
KR (1) KR101914535B1 (fr)
CN (1) CN106458608B (fr)
DE (1) DE102014212049A1 (fr)
TW (1) TWI555888B (fr)
WO (1) WO2015197498A1 (fr)

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Publication number Publication date
KR20160148601A (ko) 2016-12-26
WO2015197498A1 (fr) 2015-12-30
CN106458608A (zh) 2017-02-22
US20170158516A1 (en) 2017-06-08
DE102014212049A1 (de) 2015-12-24
KR101914535B1 (ko) 2018-11-02
TWI555888B (zh) 2016-11-01
TW201600655A (zh) 2016-01-01
CN106458608B (zh) 2019-05-03

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