WO2013080556A1 - 多結晶シリコンの製造方法および多結晶シリコン製造用反応炉 - Google Patents

多結晶シリコンの製造方法および多結晶シリコン製造用反応炉 Download PDF

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WO2013080556A1
WO2013080556A1 PCT/JP2012/007674 JP2012007674W WO2013080556A1 WO 2013080556 A1 WO2013080556 A1 WO 2013080556A1 JP 2012007674 W JP2012007674 W JP 2012007674W WO 2013080556 A1 WO2013080556 A1 WO 2013080556A1
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gas
reaction
silicon
temperature
polycrystalline silicon
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French (fr)
Japanese (ja)
Inventor
靖志 黒澤
祢津　茂義
成大 星野
哲郎 岡田
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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Priority to EP12852947.6A priority Critical patent/EP2786963B1/en
Priority to KR1020147017485A priority patent/KR101821851B1/ko
Priority to US14/354,042 priority patent/US9394606B2/en
Priority to RU2014126432/05A priority patent/RU2581090C2/ru
Priority to CN201280058859.7A priority patent/CN103958406B/zh
Publication of WO2013080556A1 publication Critical patent/WO2013080556A1/ja
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    • H01L21/2053—
    • 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
    • C23C16/24—Deposition of silicon only
    • 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
    • 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
    • C23C16/52—Controlling or regulating the coating process

Definitions

  • the present invention relates to a polycrystalline silicon manufacturing technique, and more particularly to a method and a reactor for supplying a raw material gas to the surface of a silicon core wire heated by Siemens method and depositing polycrystalline silicon to manufacture a polycrystalline silicon rod. .
  • the Siemens method is known as a manufacturing method of the polycrystalline silicon used as the raw material of the single crystal silicon for semiconductors, or the silicon
  • the Siemens method is a method of vapor phase growing polycrystalline silicon on the surface of a silicon core wire by using a CVD (Chemical Vapor Deposition) method by bringing a source gas containing chlorosilane into contact with a heated silicon core wire.
  • CVD Chemical Vapor Deposition
  • the number of silicon cores installed in the reactor is increased to increase the production volume per batch, it is difficult to stably supply the source gas to the surface of the silicon cores (the surface of the polycrystalline silicon rod) Become.
  • the surface of the silicon rod is likely to have irregularities called popcorn, and as a result, the diameter (thickness) of the silicon rod differs by about 1 mm to 5 mm in the length direction, for example. It occurs.
  • the surface area per one unevenness (per corn grain) is 20 mm 2 to 200 mm 2
  • a crack-like gap (so-called “sus”) reaching the inside of the silicon rod may occur between the corn grains.
  • the cleaning chemical solution that has entered such a gap is not easily removed, and the efficiency of the cleaning operation is significantly reduced.
  • there is a gap in polycrystalline silicon there is a problem that uniform melting in the growth step of silicon single crystal is hindered.
  • Patent Document 2 In order to prevent the generation of such popcorn, in Patent Document 2 described above, the temperature of the surface of the silicon rod is maintained in a certain range over the entire period of the precipitation reaction, and the concentration of the silicon raw material on the surface of the silicon rod In order to keep the constant, it has been proposed to increase the supply amount of the source gas in accordance with the silicon rod surface area which increases as the deposition reaction proceeds.
  • Patent Document 3 Japanese Patent Laid-Open No. 11-43317
  • the surface temperature of the silicon rod is once greatly reduced at a time when crystal grains of large diameter are easily generated, and precipitation is performed so that only crystal grains of small diameter are generated. Methods have been proposed to control the conditions.
  • JP, 2011-68553 A Japanese Patent Application Publication No. 2003-128492 Japanese Patent Application Laid-Open No. 11-43317 Japanese Patent Application Laid-Open No. 55-15999
  • the mass transfer on the surface of the silicon rod is considered to be mainly the flow of the raw material gas by natural convection, so that popcorn does not occur It was also possible to control the conditions.
  • the precipitation reaction tends to be high pressure and high speed, the pressure in the reactor is higher than before, and a large amount of source gas is supplied, and the mass transfer on the silicon rod surface is natural
  • no methodology has been proposed to control conditions such that popcorn is not generated in such a reaction system.
  • the present invention has been made in view of such problems, and the object of the present invention is to suppress generation of popcorn even in a reaction system in which the pressure is increased, the load is increased, and the speed is increased.
  • the purpose is to propose a technique for stably producing a crystalline silicon rod.
  • the method for producing polycrystalline silicon according to the present invention is a method for producing polycrystalline silicon according to the Siemens method, wherein a source gas comprising chlorosilanes gas and hydrogen gas is reacted from a nozzle port
  • a source gas comprising chlorosilanes gas and hydrogen gas
  • the former process with a relatively low gas supply
  • the latter process with a relatively high gas supply
  • the gas supply are the values of the former process
  • an intermediate step of increasing the value from the second step to the second step wherein all of the three steps are performed at a reaction temperature of 900 to 1250 ° C. and a reaction pressure of 0.3 to 0.9 MPa.
  • the diameter D of the polycrystalline silicon rod changing with the progress of the deposition reaction after the start of the reaction, with the flow velocity at the nozzle opening at the time of gas supply at the maximum feed rate of raw material gas being 150 m / sec or more In response, and performs control of the gas supply and the silicon rod temperature conditions A ⁇ C below.
  • Conditions A supply amount of chlorosilanes gas: Until the D 1 is 40mm or less of the predetermined value or more 15mm is fed in an amount of less than one third of the maximum chlorosilanes gas supply amount, the D 1 reaches The value is increased continuously or in steps until the maximum amount of chlorosilanes gas is supplied until the predetermined value D 2 which is 15 mm or more and 40 mm or less and is later than D 1 is exceeded, and D 2 is exceeded After that, the maximum chlorosilanes gas supply amount is maintained.
  • Condition B the supply amount of hydrogen gas: wherein until the D 1 is supplied such chlorosilanes gas concentration of the raw material gas is less than 30 mol% to 40 mol%, after reaching the D 1 the supply amount ratio with respect to the chlorosilanes gas is increased continuously or stepwise, after reaching the D 2 supplies as chlorosilanes gas concentration of the raw material gas is less than 15 mol% to 30 mol%.
  • Conditions C temperature of the silicon rod: After reaching the D 2 reduces in accordance with the diameter enlargement of the silicon rod.
  • the lowering width of the silicon rod temperature under the condition C is set in the range of 50 to 350.degree.
  • the operation of increasing the ratio of the supplied amount of hydrogen gas to the chlorosilanes gas under the condition B is performed before the diameter of the silicon rod becomes 40 mm.
  • the surface temperature of the bell jar and the base plate of the reactor at the time of the start of the reaction is controlled to 40 ° C. or more.
  • a reaction furnace for producing polycrystalline silicon according to the present invention is a reaction furnace for producing polycrystalline silicon by the Siemens method, and a refrigerant circulation path for controlling surface temperatures of a bell jar and a base plate, and the refrigerant circulation path And a refrigerant temperature control unit capable of controlling the temperature of the refrigerant flowing in the air flow to 40.degree. To 90.degree.
  • a large amount of raw material gas is supplied to the reactor in the initial stage (preceding step) of the deposition reaction.
  • the reaction rate is increased by increasing the concentration of the source gas supplied without raising the reaction rate by increasing the reaction speed, and in the subsequent steps after the previous step, the high speed generated by blowing the source gas into the reactor at high speed Since the probability of popcorn occurrence is reduced by utilizing the effect of forced convection, highly pure polycrystalline silicon rods with less popcorn and high purity can be obtained even in high-pressure, high-load, and high-speed reaction systems. , It becomes possible to manufacture without lowering the production efficiency.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a reaction furnace 100 for producing polycrystalline silicon according to the present invention.
  • the reaction furnace 100 is an apparatus for vapor phase growing polycrystalline silicon on the surface of the silicon core wire 12 by the Siemens method to obtain a polycrystalline silicon rod 13, and includes a base plate 5 and a bell jar 1.
  • a reactor 100 having a diameter of about 1 to 3 m for the base plate 5 and a height of about 1.5 to 3.5 m for the bell jar 1 is preferable.
  • the base plate 5 includes a metal electrode 10 for supplying a current to the silicon core wire 12, a raw material gas supply nozzle 9 for supplying trichlorosilane gas as a silicon raw material, nitrogen or hydrogen as a carrier gas, and the like.
  • a reaction offgas outlet 8 for the gas discharge is provided.
  • the base plate 5 is provided with an electrode 15 for supplying a current to the carbon heater 14 for heating the silicon core wire.
  • silicon cores 12 Although only two silicon cores 12 are shown in this figure, approximately 8 to 100 silicon cores are arranged in a reaction furnace for mass production. Also, the arrangement of the raw material gas supply nozzle 9 and the reaction exhaust gas outlet 8 may have various modes.
  • the bell jar 1 is provided with a temperature control medium inlet 3 and a temperature control medium outlet 4 for circulating a temperature control medium (refrigerant).
  • the medium (refrigerant) circulation for temperature control prevents the chlorosilanes gas from being liquefied because the inner surface temperature at the start of the precipitation reaction of polycrystalline silicon is too low, and the inner surface temperature during the precipitation reaction rises. It is for preventing the bell jar 1 becoming a metal contamination source too much.
  • a viewing window 2 for visually confirming the inside is provided on the side surface of the bell jar 1, a viewing window 2 for visually confirming the inside is provided.
  • the base plate 5 is also provided with a temperature control medium inlet 6 and a temperature control medium outlet 7 for the same purpose as described above.
  • a core holder 11 made of carbon for fixing the silicon core 12 is installed at the top of the metal electrode 10.
  • the silicon core wire 12 is energized, the surface temperature of the silicon core wire 12 becomes a temperature of 900 to 1250 ° C., which is a deposition temperature of polycrystalline silicon, due to self-heating.
  • polycrystalline silicon is deposited to obtain a polycrystalline silicon rod.
  • the base plate 5 has a disk shape, and the metal electrode 10 provided on the base plate 5, the raw material gas supply nozzle 9, and the reaction exhaust gas outlet 8 are also often arranged concentrically.
  • a mixed gas of trichlorosilane and hydrogen is often used as the source gas.
  • the silicon core wire 12 is heated by the radiant heat from the carbon heater 14, and the electrical resistivity of the silicon core wire 12 is reduced. By lowering the electrical resistivity of the silicon core wire 12 in advance, the load at the time of initial energization is reduced. After the initial energization, the surface is maintained at a predetermined temperature by self-heating of the silicon core wire 12, and the reaction of the source gas containing chlorosilane and hydrogen gas supplied from the source gas supply nozzle 9 causes polycrystalline silicon on the silicon core wire 12. Precipitates out.
  • the present invention is a manufacturing technique of polycrystalline silicon for obtaining high purity polycrystalline silicon rods while suppressing generation of popcorn in precipitation reaction of polycrystalline silicon by high pressure, high load and high speed reaction made by the Siemens method.
  • the reaction is performed under a pressure close to the atmospheric pressure, and polycrystalline silicon is deposited under the reaction conditions that the movement of the silicon raw material can be approximated by natural convection, whereas in the present invention
  • the target is the precipitation reaction of polycrystalline silicon by the loaded Siemens method.
  • the reaction pressure is a high pressure of 0.3 to 0.9 MPa, and the silicon raw material has the highest value of silicon rods. It is supplied at 1.0 ⁇ 10 ⁇ 7 mol / sec / mm 2 or more per unit surface area.
  • the raw material gas supply amount (the sum of the supplied amounts of the silicon raw material gas and the carrier gas) becomes large.
  • Forced convection of gas can be used as one of the effective factors for suppressing popcorn generation. That is, in reactions under high pressure, high load, and high speed reaction conditions, both natural convection and forced convection of the source gas can be considered in considering mass transfer for popcorn generation suppression.
  • natural convection is an ascending air flow that is naturally generated due to the temperature difference between the silicon rod 13 and the reaction gas in the reactor 100, and forced convection is ejected from the raw material gas supply nozzle 9 at a high speed.
  • Flow of reactive gas generated in the reactor 100 by the source gas That is, in a high pressure, high load, high speed reaction in which a large amount of high pressure source gas is supplied into the reactor, the silicon rod is generated by forced convection generated by stirring the inside of the reactor using kinetic energy of the source gas.
  • the efficiency of mass transfer on the surface of 13 can be enhanced and the reaction rate can be increased. As a result, the deposition rate of polycrystalline silicon can be increased, and the productivity can be improved.
  • the flow velocity of the raw material gas ejected from the raw material gas supply nozzle 9 at the nozzle port is set to be 150 m / sec or more.
  • Such condition setting can be realized, for example, by shape design of the source gas supply nozzle 9 and supply pressure control of the source gas.
  • the reaction rate at the time of depositing silicon on the surface of the single crystal silicon substrate is determined by the constant determined by the reaction temperature and the type of chlorosilane as the source gas, and the source gas concentration on the substrate surface. Also in the case of depositing silicon on the surface of a polycrystalline silicon rod, basically the same handling as described above can be performed. In addition, the concentration of chlorosilanes on the surface of the silicon rod is determined by the mass transfer amount in the concentration boundary layer and the source gas concentration (bulk gas concentration) outside the concentration boundary layer.
  • popcorn generation is determined from the concentration of chlorosilanes on the surface of the silicon rod 13 and the surface temperature of the silicon rod 13 (v R ) and the surface of the silicon rod 13 through the concentration boundary layer It depends on the magnitude relationship of the amount of chlorosilanes mass transferred to (i.e., mass transfer rate (v T )).
  • Patent Document 2 Such understanding can be achieved by the method disclosed in Patent Document 2, that is, by increasing the concentration of the source gas (bulk gas concentration) to increase the concentration difference between the source gas outside the concentration boundary layer and the surface of the silicon rod 13 There is no contradiction with the basic mechanism of the method of suppressing popcorn generation by increasing the amount of mass transfer through the concentration boundary layer.
  • the thickness of the concentration boundary layer is simply proportional to the thickness of the velocity boundary layer determined by natural convection and forced convection on the surface of the silicon rod 13. Therefore, as the flow velocity of the reaction gas near the surface of the silicon rod 13 decreases and the velocity boundary layer becomes thicker, the concentration boundary layer becomes thicker, and the mass transfer amount passing through the concentration boundary layer decreases even if the bulk gas concentration is constant. Conversely, if the gas flow velocity in the vicinity of the surface of the silicon rod 13 increases, the concentration diffusion layer becomes thinner and the mass transfer rate increases.
  • high-speed forced convection can be obtained by blowing the raw material gas into the reactor at high speed, and the effect of this high-speed forced convection is used for precipitation reaction at high temperatures. Even in this case, it is possible to keep the popcorn occurrence probability low.
  • the silicon core wire 12 used is a rectangle having a cross section of about 5 to 10 mm and a length of about 1500 to 3000 mm. Therefore, if the raw material gas consisting of chlorosilanes gas and hydrogen carrier gas is blown at a high flow rate into the reactor at a high flow rate in a state where the diameter of the silicon rod 13 is not large enough, the silicon core wire 12 and the silicon rod 13 collapse. May occur. For this reason, in an actual manufacturing site, in the initial stage of the precipitation reaction, a method is employed in which the efficiency of mass transfer on the surface of the silicon rod 13 is enhanced to efficiently increase the reaction speed by efficiently using forced convection. It is not possible.
  • the reaction rate is not increased by supplying a large amount of the source gas to the reaction furnace 100, and the concentration of the source gas supplied is made high.
  • the inner wall temperature of the chamber 1 it is not preferable to make the inner wall temperature of the chamber 1 equal to or lower than the dew point of the source gas (bulk gas) outside the concentration boundary layer. This is because when the inner wall temperature of the chamber 1 becomes equal to or lower than the dew point of the bulk gas, liquefaction of the silicon raw material occurs on the inner wall surface of the chamber 1 to clog the exhaust gas pipe of the reaction furnace 100 or secondary to silicon precipitation reaction. This is because there is a risk that the generated powder adheres to the inner wall of the chamber 1 or the inner wall of the exhaust gas pipe, or the performance of the gas heat exchanger attached to the reaction furnace 100 is degraded.
  • the source gas bulk gas
  • the reaction furnace 100 for producing polycrystals according to the present invention includes a refrigerant (for temperature control) which flows in a refrigerant circulation path (3, 4 and 6 and 7) for controlling the inner surface temperature of the bell jar 1 and the base plate 5.
  • the medium 17 is provided with a refrigerant temperature control unit 16 capable of controlling the temperature of the medium 17 to 40 to 90.degree.
  • a chlorosilane gas is used as the silicon source gas, and the inner surface temperatures of the bell jar 1 and the base plate 5 of the reaction furnace 100 at the start of the deposition reaction are controlled to 40.degree.
  • the refrigerant temperature control unit 16 controls the temperature of the refrigerant, it has a function of cooling and heating the refrigerant.
  • water is typically used as a temperature control medium (refrigerant).
  • the refrigerant supplied from the refrigerant temperature control unit 16 is mainly used to control the inner surface temperature of the bell jar 1 and the base plate 5 during the precipitation reaction, but the invention is not limited thereto, and the temperature in the reactor is lowered after the precipitation reaction is completed. It can also be used for cooling in a process (cooling process). Note that, in the case of such use, it is not necessary to manage the refrigerant temperature at 40 to 90 ° C.
  • the high concentration silicon source supply is advantageous from the viewpoint of speeding up of the precipitation reaction, but according to the study of the present inventors, if the high concentration silicon source is continued to be supplied, the secondary reaction is accompanied by the silicon precipitation reaction. It is easy to generate powder which seems to be a gas phase precipitate which is generated. The generation of such powder is particularly remarkable when the diameter of the silicon rod 13 is increased. Such powder adheres to the inner surface of the bell jar 1 to cause heavy metal contamination, and makes it difficult to clean the bell jar 1 and the base plate 5 performed after the reaction. The inventors of the present invention speculate that the cause of the generation of the powder is that when the diameter of the silicon rod 13 becomes large, a local high temperature region is easily generated, and the silicon raw material is thermally decomposed in the high temperature region. ing.
  • the thickness of the velocity boundary layer on the surface of the silicon rod 13 (that is, the thickness of the concentration boundary layer) becomes thicker as the diameter of the silicon rod 13 increases, as long as the gas flow velocity around the silicon rod 13 is the same. For this reason, when the feed gas is continuously supplied to the reaction furnace 100 at a constant flow rate and the flow of forced convection in the reaction furnace is constant, the concentration boundary layer becomes thicker as the silicon rod 13 becomes thicker. As a result, the amount of movement decreases. If the reaction temperature is maintained constant in this state, popcorn is likely to occur.
  • the reactor used in actual production usually has a limit to the ability to supply the raw material gas. .
  • the surface temperature of the silicon rod 13 is controlled to be lowered in the process (post-stage process) after the diameter of the silicon rod 13 has increased to a predetermined value.
  • Such temperature control causes the reaction rate to fall below the mass transfer rate in the concentration boundary layer, and as a result, the generation of popcorn is suppressed.
  • the method for producing polycrystalline silicon of the present invention is carried out under the following conditions.
  • the flow velocity at the nozzle port at the time of gas supply with the maximum raw material gas supply amount is 150 m / sec or more, and the diameter D of polycrystalline silicon rod changes with the progress of the precipitation reaction after the reaction start. Accordingly, control of gas supply and silicon rod temperature is performed under the following conditions A to C.
  • the supply of chlorosilanes gas is supplied in an amount of one third or less of the maximum supply amount of chlorosilanes gas until the diameter of the polycrystalline silicon rod becomes D 1 which is a predetermined value of 15 mm or more and 40 mm or less.
  • D 1 to reach a predetermined value D 2 which is 15 mm or more and 40 mm or less and is larger than D 1 continuously increase in steps until the chlorosilanes gas supply amount is reached, and D 2 is exceeded
  • the maximum supply amount of chlorosilanes gas is maintained (condition A).
  • the supply of hydrogen gas until the diameter of the polycrystalline silicon rod is D 1 is fed so that the chlorosilanes gas concentration in the raw material gas is less than 30 mol% to 40 mol%, to D 1
  • Supply ratio to chlorosilanes gas is increased continuously or stepwise after reaching, and after reaching D 2 , supply is performed so that the concentration of chlorosilanes gas in the source gas becomes 15 mol% or more and less than 30 mol% (conditions B).
  • the temperature of the silicon rod, after reaching the diameter of the polycrystalline silicon rods D 2 reduces in accordance with the diameter enlargement of the silicon rod.
  • the reason for providing the pre-stage with a relatively low gas supply amount is that if a large amount of raw material gas is supplied at a relatively thin stage of the silicon rod, the whole silicon core wire 12 may collapse.
  • the silicon core wire 12 a square prism whose side of a cross section is a rectangle of 6 mm to 8 mm, a cylinder of a cross section of a diameter of 6 mm to 8 mm, or the like is used.
  • the flow rate of the source gas at the start of the reaction is such that the flow velocity at the nozzle port will be described later so that problems such as the collapse and blowout of the silicon core 12 occur due to the ejection pressure of the source gas at the start of the reaction. As limited.
  • the concentration of the chlorosilanes gas in the source gas supplied in the preceding step is increased under the above conditions.
  • the chlorosilanes gas concentration in the source gas is 30 mol% or more and less than 40 mol% until the diameter of the polycrystalline silicon rod reaches D 1 which is a predetermined value of 15 mm or more and 40 mm or less Supply to More preferably, the concentration of chlorosilanes gas in the source gas is 30% by mole or more and less than 35% by mole. Within such a concentration range, liquefaction or generation of powder does not occur in the reaction furnace 100.
  • the reaction temperature can also be kept relatively high at 1000 ° C. to 1250 ° C. And, by setting the reaction temperature relatively high, natural convection and increase in concentration difference diffusion amount can be expected even in the previous step where promotion of mass transfer on the surface of the silicon rod 13 by forced convection accompanying supply of raw material gas can not be expected.
  • the deposition rate can be relatively increased by the
  • reaction temperature is in the range of 900 to 1250 ° C.
  • reaction pressure is in the range of 0.3 to 0.9 MPa.
  • the pressure in the furnace it is preferable to maintain it in the range of ⁇ 20%.
  • the predetermined value is 0.5 MPa
  • reaction temperature surface temperature of the silicon rod
  • the surface temperature of the silicon core wire 12 at the start of the reaction is 1200 ° C.
  • FIG. 2 is a sequence diagram for explaining an example of a polycrystalline silicon production process according to the present invention, showing silicon rod temperature, chlorosilanes gas concentration in raw material gas (chlorosilanes gas supply amount and hydrogen gas The ratio of the supply amount (mol / mol)) and the supply amount of the chlorosilanes gas are illustrated.
  • chlorosilane gas is used as the chlorosilane gas, respectively D 1 and D 2 of the above, it is 20mm and 30 mm.
  • the supply flow rate of the source gas is controlled until the diameter of the silicon rod 13 grows to a thickness of at least 15 mm ⁇ and it becomes difficult to collapse due to the spray pressure of the source gas.
  • the supply amount of the chlorosilanes gas is preferably at least 1/10 or more, more preferably at least 1/6 of the supply amount at the maximum supply.
  • the upper limit is preferably one-third or less, more preferably one-quarter, with respect to the supply amount at the time of maximum amount supply. In this case, if the supply amount of the chlorosilanes gas is within the above range, it is possible to adopt a method of increasing during the process.
  • the diameter (D 2 described above) which does not cause the silicon rod 13 to collapse is generally a value smaller than 40 mm although it depends on the apparatus configuration, after this diameter is reached, the chlorosilane supply amount is maximized, It is preferred to maintain the maximum feed rate until the reaction termination operation is entered.
  • the concentration of chlorosilanes in the source gas is controlled as the bulk concentration as described above, the thickness of the silicon rod 13 can be increased more quickly if the amount of the source gas supplied is large. Therefore, the supply amount of chlorosilanes is increased in multiple stages and / or continuously in accordance with the increase in the thickness of the silicon rod, not by the minimum amount control until the diameter of the silicon rod 13 is not threatened to collapse.
  • D 1 and D 2 are set between 15 mm ⁇ to 40 mm ⁇ , and the chlorosilane supply amount is increased in multiple stages (steps) and / or continuously from the stage after D 1 to make D 2 maximum It is.
  • the diameter of the silicon rod 13 can be calculated from the measurement data of the silicon rod temperature and the resistance value obtained from the conduction data.
  • the amount of supply of hydrogen gas is adjusted according to the amount of supply of chlorosilanes gas so as to maintain the concentration of chlorosilanes in the source gas described above at least until the diameter of the silicon rod 13 becomes 15 mm ⁇ . Then, after the diameter of the silicon rod 13 exceeds 15 mm ⁇ , the ratio of the amount of hydrogen gas supplied to the chlorosilanes gas is continuously and / or one or more in any period or time until the diameter exceeds 70 mm ⁇ . Increase at the stage of After the diameter of the silicon rod 13 reaches 70 mm ⁇ , the concentration of chlorosilanes in the raw material gas is controlled to be 15 mol% or more and less than 30 mol%, preferably 20 mol% or more and 25 mol% or less.
  • the increase in the hydrogen gas supply ratio causes the silicon rod 13 to have a diameter of 15 to 40 mm at the increase timing of the chlorosilanes gas, thereby eliminating the risk of collapse due to the ejection pressure of the source gas. Increase to complete when the supply of
  • the temperature of the silicon rod 13 is controlled to a temperature appropriate for the reaction. It needs to be done. Therefore, the amount of current supplied to the silicon rod 13 is increased to control the temperature with respect to the increase in the amount of cooling caused by the increase in the amount of supply of the source gas. Further, it is preferable that the temperature of the in-furnace source gas is also about 200 to 700 ° C. excluding the vicinity of the source gas supply nozzle 9 and the vicinity of the silicon rod 13. Therefore, even in the case of increasing the supply rate, it is necessary to carry out within the temperature controllable range, and in that sense, it is preferable that the change in the supply rate is not increased once but performed in multiple stages or continuously.
  • the flow velocity of the source gas jetted from the nozzle port of the source gas supply nozzle 9 becomes 150 m / sec or more by the increase of the supply amount of the chlorosilanes gas and the increase of the supply amount of the hydrogen gas described above. Then, the forced convection effect as described above can be obtained.
  • temperature control of the silicon rod 13 is performed to prevent the generation of popcorn. That is, from the time when the increase of the hydrogen gas supply amount described above is completed and the supply of the raw material gas at the fastest speed is started, the reaction is completed at any time from when the diameter of the silicon rod becomes 70 mm ⁇ at the latest In order to prevent the generation of popcorn, the temperature of the silicon rod 13 is lowered. As the diameter of the silicon rod 13 is increased, popcorn generation is performed by performing an operation of gradually decreasing the deposition temperature in order to reduce the reaction rate by an amount corresponding to the decrease in the mass transfer amount on the surface of the silicon rod 13. It can be suppressed.
  • productivity may increase.
  • popcorn may be generated.
  • the control of the deposition temperature relative to the diameter of the silicon rod 13 here is different depending on the condition of the reactor, the pattern for lowering the temperature is several times using the actually operating reactor. Need to test. Since the temperature of the silicon rod 13 is controlled by the amount of current supplied to the silicon rod, a pattern of the amount of current supplied without popcorn may be found by a test and used for producing a polycrystalline silicon rod.
  • the reduction range from the maximum temperature is preferably 50 to 350 ° C., particularly 100 to 350 ° C.
  • the final temperature is The temperature is preferably 1100 ° C to 900 ° C.
  • the pattern for lowering the temperature is from the temperature at which the temperature starts to fall, with the diameter of the silicon rod from the diameter at which the diameter of the silicon rod starts to decrease to the final expected diameter of the silicon rod as the horizontal axis.
  • the diameter and the temperature may be continuously changed and lowered to be approximately linear.
  • two or more points may be provided, and the temperature may be dropped stepwise at that point.
  • productivity drops, and if the temperature is too high, the risk of powder generation increases, so it is preferable to drop in three or more stages.
  • Example 1 Polycrystalline silicon rods were grown using the reactor shown in FIG.
  • 60 silicon core wires 12 with a diameter of 7 mm are built on the base plate 5, and the source gas supply nozzles 9 are arranged so that the necessary amount of source gas can be supplied to all silicon core wires.
  • Water controlled at 55 ° C. was circulated in the refrigerant circulation lines of the bell jar 1 and the base plate 5 (refrigerant inlets 3 and 6 and refrigerant outlets 4 and 7 respectively) from the start of the reaction to the end of the reaction.
  • the pressure in the reactor is maintained at 0.5 MPa, and at the start of the reaction, the temperature of the silicon core wire is 1100 ° C., and the raw material is composed of hydrogen gas and trichlorosilane gas having a trichlorosilane concentration of 32 mol%
  • the gas was supplied at 526 kg / hr (510 kg / hr trichlorosilane gas, 180 Nm 3 / hr hydrogen gas).
  • the diameter of the silicon rod 13 becomes 10 mm ⁇
  • silicon is supplied so that the supply amount of trichlorosilane gas is 1000 kg / hr and the supply amount of hydrogen gas is 350 Nm 3 / hr (trichlorosilane concentration is maintained at 32 mol%).
  • the feed rates of trichlorosilane gas and hydrogen gas were increased in proportion to the diameter of the rod 13.
  • the silicon rod 13 maintains the trichlorosilane gas supply amount of 1000 kg / hr and the hydrogen gas supply amount of 350 Nm 3 / hr until the diameter of the silicon rod 13 is 10 mm ⁇ to 20 mm ⁇ , and then the silicon rod 13 has a diameter of 30 mm ⁇ until the silicon rod
  • the trichlorosilane gas is supplied so that the supply amount of trichlorosilane gas is 3000 kg / hr and the supply amount of hydrogen gas is 2000 Nm 3 / hr (the trichlorosilane concentration in the source gas is 20 mol%)
  • the amount of hydrogen gas supplied was increased in proportion to the diameter of the silicon rod 13 and thereafter maintained until the end of the reaction.
  • the flow rate of the raw material gas at the nozzle port was 180 m / sec when the raw material gas supply amount reached the maximum amount.
  • the temperature of the silicon rod 13 is controlled to maintain 1100 ° C. until the diameter of the silicon rod 13 becomes 30 mm ⁇ by adjusting the amount of supplied current, and then the diameter of the silicon rod becomes 116 mm ⁇
  • the temperature was decreased linearly to 1050 ° C. in proportion to the diameter according to the increase of the diameter of the silicon rod 13 until the reaction was completed.
  • a silicon rod having a diameter of 116 mm is obtained from a 7 mm silicon core wire in 61 hours without producing silicon powder in the reactor, and the productivity of polycrystalline silicon at this time is 43.2 kg / hr. Met.
  • the ratio to the whole chunks containing popcorn was 5% by mass.
  • Example 2 With respect to the process of Example 1, only the supply operation of the raw material gas and the temperature control pattern of the silicon rod were changed to manufacture a polycrystalline silicon rod.
  • the raw material gas was supplied in the same pattern as in Example 1 until the diameter of the silicon rod 13 became 20 mm ⁇ after the start of the reaction, and then the diameter of the silicon rod 13 became 25 mm ⁇
  • the supply amount is increased in proportion to the diameter of the silicon rod 13 so that the supply amount is 3000 kg / hr, and the hydrogen gas supply amount is 2000 Nm 3 / hr when the diameter of the silicon rod 13 becomes 30 mm ⁇ .
  • the supply was made to increase in proportion to the diameter of the silicon rod 13 and thereafter the supply amount of them was maintained.
  • the temperature of the silicon rod 13 is controlled so as to maintain 1100 ° C. until the diameter of the silicon rod 13 becomes 25 mm ⁇ , and then the silicon rod 13 is maintained until the diameter of the silicon rod becomes 119 mm ⁇ .
  • the temperature was decreased linearly to 990 ° C. in proportion to the diameter as the diameter increased.
  • a silicon rod having a diameter of 119 mm is obtained from a 7 mm silicon core wire in 66 hours without generating silicon powder in the reactor, and the productivity of polycrystalline silicon at this time is 42.5 kg / hr. Met.
  • Example 1 With respect to the process of Example 1, the total supply volume of trichlorosilane gas and hydrogen gas is matched with the operation performed in Example 1, and the trichlorosilane concentration from the start to the end of the reaction is fixed at 20 mol%. Furthermore, the reaction temperature was controlled to be 1050 ° C. at the start of the reaction and 990 ° C. at the end of the reaction, except for the temperature control.
  • the amount of trichlorosilane gas supplied is 623 kg / hr and the amount of hydrogen gas supplied is 412 Nm 3 / hr, proportional to the diameter of the silicon rod 13
  • the feed rates of silane gas and hydrogen gas were increased.
  • the amount of trichlorosilane gas supplied is 623 kg / hr and the supplied amount of hydrogen gas 412 Nm 3 / hr is maintained.
  • the ratio was increased proportionally, and then the amount of supplied trichlorosilane gas was maintained at 3000 kg / hr and the amount of supplied hydrogen gas was maintained at 2000 Nm 3 / hr until completion of the reaction.
  • a silicon rod with a diameter of 131 mm was obtained from a 7 mm silicon core in 97 hours without generating silicon powder in the reactor, but using a raw material gas having a low concentration of trichlorosilane from the initial stage of the reaction Therefore, the productivity of polycrystalline silicon decreased to 35.1 kg / hr.
  • Example 2 The procedure of Example 1 was repeated except that the temperature of the silicon rod was fixed at 1050 ° C. from the start to the end of the reaction, in the same manner as the process of Example 1.
  • a silicon rod with a diameter of 131 mm was obtained from a 7 mm silicon core wire in 76 hours without generating silicon powder in the reactor, and the productivity of polycrystalline silicon was 45.2 kg / hr. .
  • a silicon rod with a diameter of 132 mm was obtained from a 7 mm silicon core wire in 73 hours without generating silicon powder in the reactor, and the productivity of polycrystalline silicon was 47.5 kg / hr. .
  • Example 4 With respect to the process of Example 1, the amount of supplied trichlorosilane gas is made to coincide with the operation performed in Example 1, and the hydrogen of the source gas supplied during the reaction is adjusted so that the concentration of trichlorosilane becomes 32 mol%. Adjustment of gas supply amount was performed.
  • the reaction temperature is raised according to the diameter of the silicon rod so that the reaction temperature becomes 1050 ° C. at the start of the reaction and 1100 ° C. when the diameter of the silicon rod becomes 30 mm ⁇ , and then the temperature becomes 990 ° C. at the end of the reaction Temperature control was performed to decrease according to the diameter of the rod. All other operations were performed in the same manner as in the process of Example 1.
  • the raw material gas is supplied in the pattern of Example 1 until the diameter of the silicon rod 13 becomes 20 mm ⁇ , and then the diameter of the silicon rod 13 becomes 30 mm ⁇ until the diameter of the silicon rod becomes 30 mm ⁇ .
  • the feed amounts of the trichlorosilane gas and the hydrogen gas were changed to the silicon rod 13 so that the feed amount of the trichlorosilane gas was 3000 kg / hr and the feed amount of the hydrogen gas was 1050 Nm 3 / hr (trichlorosilane concentration in the source gas was 32 mol%). It increased in proportion to the diameter, and thereafter maintained the amount supplied until the reaction was completed.
  • the flow rate of the raw material gas at the nozzle port was 111 m / sec when the raw material gas supply amount reached the maximum amount.
  • the present invention provides a technology for stably producing high purity polycrystalline silicon rods in which the generation of popcorn is suppressed even in a high pressure, high load, and high speed reaction system.

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PCT/JP2012/007674 2011-11-29 2012-11-29 多結晶シリコンの製造方法および多結晶シリコン製造用反応炉 Ceased WO2013080556A1 (ja)

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US14/354,042 US9394606B2 (en) 2011-11-29 2012-11-29 Production method for polycrystalline silicon, and reactor for polycrystalline silicon production
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WO2017038347A1 (ja) * 2015-09-04 2017-03-09 信越化学工業株式会社 多結晶シリコン棒の製造方法およびｆｚ単結晶シリコンの製造方法
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CN106865551A (zh) * 2017-03-24 2017-06-20 亚洲硅业（青海）有限公司 用于48对棒多晶硅还原炉的喷嘴
CN106865551B (zh) * 2017-03-24 2017-12-19 亚洲硅业（青海）有限公司 用于48对棒多晶硅还原炉的喷嘴
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WO2026034125A1 (ja) * 2024-08-09 2026-02-12 株式会社トクヤマ ポリシリコン塊状物の製造方法

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