WO2014065233A1 - セレン化水素混合ガスの供給方法及び供給装置 - Google Patents

セレン化水素混合ガスの供給方法及び供給装置 Download PDF

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Publication number
WO2014065233A1
WO2014065233A1 PCT/JP2013/078444 JP2013078444W WO2014065233A1 WO 2014065233 A1 WO2014065233 A1 WO 2014065233A1 JP 2013078444 W JP2013078444 W JP 2013078444W WO 2014065233 A1 WO2014065233 A1 WO 2014065233A1
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Prior art keywords
gas
hydrogen selenide
flow rate
gas supply
mixed gas
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PCT/JP2013/078444
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English (en)
French (fr)
Japanese (ja)
Inventor
正也 山脇
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大陽日酸株式会社
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Priority to CN201380052051.2A priority Critical patent/CN104769727B/zh
Priority to JP2014543279A priority patent/JP6065329B2/ja
Priority to KR1020157006775A priority patent/KR101661483B1/ko
Publication of WO2014065233A1 publication Critical patent/WO2014065233A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/04—Binary compounds including binary selenium-tellurium compounds
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5866—Treatment with sulfur, selenium or tellurium
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01F—MEASURING VOLUME, VOLUME FLOW, MASS FLOW OR LIQUID LEVEL; METERING BY VOLUME
    • G01F25/00—Testing or calibration of apparatus for measuring volume, volume flow or liquid level or for metering by volume
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01F—MEASURING VOLUME, VOLUME FLOW, MASS FLOW OR LIQUID LEVEL; METERING BY VOLUME
    • G01F25/00—Testing or calibration of apparatus for measuring volume, volume flow or liquid level or for metering by volume
    • G01F25/10—Testing or calibration of apparatus for measuring volume, volume flow or liquid level or for metering by volume of flowmeters
    • G01F25/15—Testing or calibration of apparatus for measuring volume, volume flow or liquid level or for metering by volume of flowmeters specially adapted for gas meters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method and apparatus for supplying a hydrogen selenide mixed gas.
  • a hydrogen selenide mixed gas supply device (hereinafter simply referred to as “supply device”) 201 as shown in FIG. 4 has been used.
  • the supply device 201 is provided with a base gas supply path L101 and a source gas supply path L102.
  • an inert gas and a hydrogen selenide gas having a concentration of 100% (hereinafter simply referred to as “hydrogen selenide gas”) can be circulated.
  • the base gas supply path L101 and the source gas supply path L102 are provided with a base gas flow rate control means 106 and a source gas flow rate control means 111, respectively.
  • a buffer tank 118 for storing a hydrogen selenide mixed gas obtained by mixing an inert gas and a hydrogen selenide gas is provided downstream of the base gas supply path L101 and the source gas supply path L102.
  • the base gas and the source gas are mixed so that the hydrogen selenide concentration of the hydrogen selenide mixed gas becomes a predetermined value.
  • Flow rates of the inert gas and hydrogen selenide gas are controlled by the flow rate control means 106 and 111, respectively.
  • the flow-controlled inert gas and hydrogen selenide gas are mixed by the mixer 117, and then the obtained hydrogen selenide mixed gas is stored in the buffer tank 118.
  • the hydrogen selenide mixed gas having a predetermined hydrogen selenide concentration stored in the buffer tank 118 is continuously supplied to the solar cell manufacturing apparatus.
  • the supply device 201 has the following problems. That is, selenium (Se) crystals due to self-decomposition of hydrogen selenide are precipitated in the source gas supply flow path L102, the on-off valves 109 and 113, the source gas flow rate control means 111, and the like through which hydrogen selenide gas flows. There was a problem. In particular, the deposition of selenium crystals in the source gas flow rate control unit 111 reduces the flow rate measurement accuracy and the flow rate control accuracy of the source gas flow rate control unit 111. As a result, the concentration setting of the hydrogen selenide mixed gas set in advance is reduced. There was a problem that the difference between the measured value and the actually measured concentration value of the hydrogen selenide mixed gas adjusted by the supply device 201 became large (this is called a drift phenomenon).
  • Patent Document 1 discloses a supply method and a supply device capable of stably supplying a hydrogen selenide mixed gas having a concentration set value.
  • the supply device 202 of Patent Document 1 includes a bypass flow that connects the base gas supply channel L ⁇ b> 101 and the source gas supply channel L ⁇ b> 102 in addition to the configuration of the supply device 201 shown in FIG. 4.
  • a path L105 is provided.
  • a mixed gas is produced without using the bypass flow path L105 and stored in the buffer tank 118, and then a predetermined amount of hydrogen selenide gas is supplied from the source gas supply flow path L102 to the buffer tank 118.
  • a predetermined amount of inert gas is led out from the source gas supply flow path L102 via the bypass flow path L105, thereby preparing a hydrogen selenide mixed gas having a predetermined hydrogen selenide concentration.
  • a supply method is disclosed in which the volume concentration of hydrogen selenide remaining in the source gas supply flow path L102 is 10% or less.
  • the volume concentration of hydrogen selenide remaining in the source gas supply channel L102 can be reduced to 10% or less when the hydrogen selenide mixed gas is not supplied to the source gas supply channel L102.
  • the hydrogen selenide mixed gas it was not possible to completely prevent the precipitation of selenium crystals in the source gas supply flow path L102. Therefore, there has been a problem that a drift phenomenon appears when the supply device 202 is operated for a long period of time.
  • An object of the present invention is to provide a method and apparatus for supplying a hydrogen fluoride mixed gas.
  • Hydrogen selenide mixture prepared by mixing an inert gas supplied from a base gas supply channel and hydrogen selenide gas supplied from a source gas supply channel to a predetermined concentration
  • a method for supplying a hydrogen selenide mixed gas comprising a step of producing a gas and a step of supplying the mixed gas, and further, while the step of producing the hydrogen selenide mixed gas is stopped, a source gas
  • the flow rate setting value, and the correction step includes a flow rate control means for controlling the flow rate of the hydrogen selenide gas provided in the source gas supply flow path, and a flow rate measurement means for calibration.
  • the method of supplying hydrogen selenide mixed gas comprising the a step of correcting the flow rate value of the hydrogen selenide gas is provided.
  • the aspect (1) preferably has the following characteristics.
  • (2) The calibration gas is continuously flowed through the flow rate control unit and the flow rate measurement unit in any order.
  • (3) A flow rate measuring method having the same specifications is used for the flow rate control means and the flow rate measuring means.
  • the inert gas is used as the calibration gas.
  • the hydrogen selenide mixed gas is produced, the hydrogen selenide gas is not allowed to flow to the flow rate measuring means for calibration.
  • the following apparatus is provided. That is, an inert gas supplied from the base gas supply channel and a hydrogen selenide gas supplied from the source gas supply channel are mixed to produce a hydrogen selenide mixed gas prepared at a predetermined concentration. And a hydrogen selenide mixed gas supply device to be supplied thereafter, A flow rate control means for controlling the flow rate of the hydrogen selenide gas provided in the source gas supply flow path; and the flow rate control of the source gas supply flow path for the calibration gas when the production of the hydrogen selenide mixed gas is stopped.
  • a flow rate measurement means for calibration provided in the flow path; and when the same flow rate of the calibration gas flows through the flow rate control means and the flow rate measurement means, Accordingly, there is provided a hydrogen selenide mixed gas supply device comprising: control means for correcting the flow rate value of the hydrogen selenide gas that is flowed by the flow rate control means.
  • the calibration gas supply channel is closed during the production of the hydrogen selenide mixed gas, and the calibration gas is supplied from the calibration gas supply channel to the source gas supply channel.
  • a first on-off valve that is open when supplied to the passage is provided, and the flow rate measuring means is provided on a primary side of the first on-off valve of the calibration gas supply channel.
  • the calibration gas supply channel is a bypass channel that connects the base gas supply channel and the primary side of the flow rate control means of the source gas supply channel.
  • the bypass flow path is closed during the production of the hydrogen selenide mixed gas, and the raw material gas supply flow is supplied from the base gas supply flow path using the inert gas as a calibration gas.
  • a first on-off valve that is open when being supplied to the passage is provided, and the flow rate measuring means is provided on the primary side of the first on-off valve of the bypass flow path.
  • a branch channel is provided on the secondary side of the flow rate control means of the source gas supply channel, and the hydrogen selenide mixed gas is provided in the branch channel.
  • a second on-off valve that is closed when the gas is manufactured and opened when the inert gas is supplied as a calibration gas from the base gas supply channel to the source gas supply channel.
  • the flow rate measuring means is provided on the secondary side of the second on-off valve of the branch flow path.
  • the flow rate control means for controlling the flow rate of the hydrogen selenide gas provided in the hydrogen selenide gas supply flow path as the raw material gas, and the flow rate measurement means for calibration
  • the calibration gas with the same flow rate is flowed.
  • the flow rate value of the hydrogen selenide gas flowing by the flow rate control means is corrected.
  • a hydrogen selenide mixed gas having a stable hydrogen selenide concentration is positioned on the secondary side (downstream side) of a solar cell manufacturing apparatus or the like without requiring precise equipment operation and a large-capacity buffer tank. Can be supplied to consumption equipment.
  • the hydrogen selenide mixed gas supply device of the present invention has the following configuration. That is, flow rate control means for controlling the flow rate of hydrogen selenide gas provided in the source gas supply channel; and when the production of the hydrogen selenide mixed gas is stopped, the inert gas is used as a calibration gas and the source gas is supplied from the base gas supply channel A bypass flow path for supplying the flow control means to the primary side of the gas supply flow path; a calibration gas flows when the production of the hydrogen selenide mixed gas is stopped, and a hydrogen selenide gas is produced when the hydrogen selenide mixed gas is produced.
  • a flow rate measuring means for calibration provided in a non-flowing flow path; according to the difference between the flow values of the calibration gas measured when the same flow rate of calibration gas is passed through the flow rate control means and the flow rate measuring means. And control means for correcting the set value of the flow rate of the hydrogen selenide gas that is flowed by the flow rate control means.
  • the above supply method can be implemented by the supply device having the above-described configuration.
  • the concentration represents volume concentration
  • the pressure represents gauge pressure
  • the flow rate represents volume flow rate.
  • the volume shown in this specification is a volume in a reference state (0 ° C., 1 atm (atmospheric pressure)).
  • the term “means” may mean an apparatus, a process, a member, a system, a part, and the like.
  • the configuration of the hydrogen selenide mixed gas supply apparatus (hereinafter simply referred to as “supply apparatus”) 101 of the present embodiment will be described as a supply apparatus for a solar cell manufacturing apparatus with reference to FIG.
  • the supply apparatus of the present invention is not particularly limited as long as it is a supply apparatus for an apparatus that consumes a hydrogen selenide mixed gas, and can be used for anything.
  • a supply device for a semiconductor manufacturing apparatus that consumes a hydrogen selenide mixed gas as a doping gas can be given as an example.
  • expressions such as “apparatus B for apparatus A” may mean apparatus B prepared separately from apparatus A, or may mean apparatus B included as part of apparatus A. good.
  • the supply device 101 is a device that manufactures a hydrogen selenide mixed gas prepared to a predetermined concentration according to the production status of a solar cell manufacturing device (not shown), and supplies it to the solar cell manufacturing device. It is. Specifically, the supply device 101 includes a base gas supply flow path L1, a raw material gas supply flow path L2, mass flow controllers (flow control means) 6 and 11, a mixer 2, and a buffer tank 3. It is schematically configured. More specifically, the supply apparatus 101 controls a base gas supply flow path L1 for supplying a base gas, a raw material gas supply flow path L2 for supplying a raw material gas, and a flow rate of the base gas.
  • the supply device 101 further includes a bypass flow path L3, a mass flow meter (flow rate measuring means) 16, and a control means 19. More specifically, when the production of the hydrogen selenide mixed gas is stopped, the supply apparatus 101 uses the base gas as a calibration gas as a calibration gas on the primary side of the mass flow controller 11 from the base gas supply flow path L1 to the source gas supply flow path L2 ( A bypass flow path L3 for supply to the upstream side), a mass flow meter 16 for measuring the flow rate of the calibration gas supplied to the flow path where the raw material gas does not flow during the production of the hydrogen selenide mixed gas, and mass flow When the calibration gas having the same flow rate is caused to flow through the controller 11 and the mass flow meter 16, the flow rate value of the raw material gas flowing through the mass flow controller 11 is corrected according to the difference in the flow rate value of the calibration gas measured. And a control means 19.
  • Base gas supply flow path L1 One end of the base gas supply channel L ⁇ b> 1 is connected to a base gas supply source (not shown), and the other end is connected to the mixer 2.
  • the base gas is not particularly limited as long as it is an inert gas for dilution use.
  • the inert gas used in the present invention include nitrogen (N 2 ) gas, or rare gases such as argon (Ar), helium (He), and neon (Ne).
  • an opening / closing valve 4 In the base gas supply flow path L1, an opening / closing valve 4, a pressure regulator 5, a mass flow controller 6, a check valve 7, and an automatic valve 8 are sequentially provided from the upstream side to the downstream side.
  • pressure gauges may be provided on the upstream side and the downstream side of the pressure regulator 5. By installing such a pressure gauge, the pressure before and after the pressure regulator 5 can be visually recognized.
  • the on-off valve 4 is opened when the base gas is supplied downstream from the on-off valve 4, and is closed when not supplied.
  • the pressure regulator 5 is provided to reduce the pressure of the inert gas supplied from the base gas supply source to a desired pressure.
  • only one pressure regulator 5 is provided in the base gas supply flow path L1.
  • the number of pressure regulators 5 is not limited to one, and two or more pressure regulators 5 may be provided at arbitrarily selected locations in the flow path L1.
  • the pressure of the gas in the flow path L1 immediately before the mass flow controller 6 can be appropriately set according to the supply pressure to the solar cell manufacturing apparatus.
  • the gas pressure immediately before the mass flow controller 6 can be in the range of 0.3 to 0.8 MPa.
  • the mass flow controller 6 is a flow control device that controls the flow rate by measuring the mass flow rate of the inert gas, and is provided for highly accurate flow rate measurement and control.
  • the mass flow controller 6 controls the flow rate of the inert gas so that the hydrogen selenide concentration in the hydrogen selenide mixed gas mixed in the mixer 2 maintains a predetermined value.
  • FIG. 1 illustrates the supply device 101 in which one mass flow controller 6 is provided in the base gas supply flow path L1
  • the present invention is not limited to this.
  • two or more mass flow controllers 6 may be provided in parallel with the base gas supply flow path L1.
  • a mass flow sensor is mounted on the mass flow controller 6.
  • the mass flow sensor mounted on the mass flow controller 6 is not particularly limited. For example, general mass flow sensors, differential pressure mass flow sensors, Coriolis mass flow sensors, and the like can be used. .
  • the check valve 7 allows the inert gas whose flow rate is controlled by the mass flow controller 6 to flow only from the upstream side to the downstream side, and prevents the reverse flow of the inert gas from the downstream side to the upstream side. Thereby, the fluctuation
  • the automatic valve 8 is provided to control whether or not the inert gas whose flow rate is controlled by the mass flow controller 6 is supplied to the mixer 2.
  • the automatic valve 8 When the automatic valve 8 is in an open state, the inert gas whose flow rate is controlled is discharged downstream of the automatic valve 8 and supplied to the mixer 2.
  • the automatic valve 8 when the automatic valve 8 is in the closed state, the supply of the inert gas to the downstream side of the automatic valve 8 is stopped, and the inert gas is not supplied to the mixer 2.
  • the open / close state of the automatic valve 8 is switched by the pressure of the buffer tank 3 measured by the pressure gauge 22.
  • the source gas is hydrogen selenide gas.
  • the source gas supply channel L2 is provided with the mass flow controller 11, and the source gas supply channel L2 located on the secondary side (downstream side) of the mass flow controller 11 is branched from the source gas supply channel L2.
  • a flow path L4 is connected.
  • an automatic valve 9 In the source gas supply flow path L2, an automatic valve 9, a pressure regulator 10, a mass flow controller 11, a check valve 12, and an automatic valve 13 are sequentially provided from the upstream side to the downstream side. Similar to the base gas supply flow path L1, an arbitrary number of pressure gauges (not shown) may be provided on the upstream side and the downstream side of the pressure regulator 10 as necessary. By installing such a pressure gauge, the pressure before and after the pressure regulator 10 can be visually recognized.
  • the mass flow controller 11 is a flow rate control device that controls the flow rate by measuring the mass flow rate of the hydrogen selenide gas flowing through the flow path L2, and is provided for highly accurate flow rate measurement and control.
  • the mass flow controller 11 controls the flow rate of the hydrogen selenide gas so that the hydrogen selenide concentration in the hydrogen selenide mixed gas mixed in the mixer 2 becomes a predetermined value.
  • the mass flow controller 11 performs flow control and mass flow measurement of the calibration gas supplied to the primary side (upstream side) of the mass flow controller 11 via the bypass flow path L3 when the production of the hydrogen selenide mixed gas is stopped. Made.
  • a control means 19 is connected to the mass flow controller 11 by a wiring E1 which will be described later, and the measurement result (flow rate measurement value) of the calibration gas can be transmitted from the mass flow controller 11 to the control means 19. Yes.
  • the control means 19 obtains necessary information, it can perform arithmetic processing and reflect the result on the control of the mass flow controller 11.
  • FIG. 1 illustrates a supply device 101 in which one mass flow controller 11 is provided in the source gas supply flow path L2, but the present invention is not limited to this.
  • two or more mass flow controllers 11 may be provided in parallel in the source gas supply flow path L2.
  • the mass flow controller 11 is equipped with a mass flow sensor.
  • the mass flow sensor mounted on the mass flow controller 11 is not particularly limited.
  • general mass flow sensors, differential pressure mass flow sensors, Coriolis mass flow sensors, and the like can be used.
  • the mass flow controller 11 is preferably one calibrated with hydrogen selenide gas, which is a raw material gas, but is not particularly limited, and may be calibrated with a gas other than hydrogen selenide gas.
  • the mixer 2 is provided at a position where the other end of the base gas supply flow path L1 and the other end of the source gas supply flow path L2 merge.
  • the mixer 2 is adjusted to a predetermined concentration by mixing the inert gas supplied through the base gas supply flow path L1 and the hydrogen selenide gas supplied through the source gas supply flow path L2. Any hydrogen selenide mixed gas can be selected and any gas can be selected as long as the produced gas can be supplied to the downstream side.
  • the mixer 2 prevents the inflow of the inert gas into the source gas supply channel L2 and the inflow of hydrogen selenide gas into the base gas supply channel L1.
  • Flow path L5 The mixer 2 and the buffer tank 3 are connected by a flow path L5. Note that an open / close valve (not shown) may be provided in the flow path L5.
  • FIG. 1 one end of a base gas supply flow path L1 and one end of a source gas supply flow path L2 are connected to the mixer 2, and a supply apparatus 101 in which a flow path L5 is provided between the mixer 2 and the buffer tank 3 is shown. Is illustrated. However, the present invention is not limited to this.
  • the supply device without the mixer 2 may be used, or the mixer 2 and the flow path L5 are not provided, and one end of the base gas supply flow path L1 and the raw material gas supply flow path L2 is directly connected to the buffer tank 3 respectively. It may be a supply device. That is, gas may be mixed in the tank.
  • the buffer tank 3 is a storage tank for storing the hydrogen selenide mixed gas adjusted to a predetermined concentration by the mixer 2.
  • the internal volume of the buffer tank 3 is not particularly limited, and can be appropriately selected according to the supply amount of the hydrogen selenide mixed gas to the solar cell manufacturing apparatus.
  • the storage amount of the hydrogen selenide mixed gas in the buffer tank 3 can be appropriately selected according to the internal volume of the buffer tank 3 and the supply amount of the hydrogen selenide mixed gas to the solar cell manufacturing apparatus. For example, when the hydrogen selenide mixed gas supply amount to the solar cell manufacturing apparatus is 100 to 200 L / min, the buffer tank capacity can be 20 to 400 L.
  • the upper limit pressure and the lower limit pressure of the buffer tank 3 are not particularly limited, and depending on the storage amount of the hydrogen selenide mixed gas in the buffer tank 3 and the supply amount of the hydrogen selenide mixed gas to the solar cell manufacturing apparatus, It can be selected appropriately.
  • the storage pressure of the hydrogen selenide mixed gas in the buffer tank 3 can be in the range of 0.1 to 0.5 MPa.
  • Flow path L6 One end of the flow path L6 is connected to the buffer tank 3, and the other end of the flow path L6 is an outlet of the mixed gas, and this outlet is connected to the solar cell manufacturing apparatus. Thereby, the hydrogen selenide mixed gas can be supplied from the buffer tank 3 to the solar cell manufacturing apparatus.
  • An opening / closing valve 21 is provided at a position upstream from the outlet of the flow path L6, that is, at the supply port side of the flow path L6. When supplying the hydrogen selenide mixed gas from the buffer tank 3 to the solar cell manufacturing apparatus, the opening / closing valve 21 is opened. On the other hand, when the hydrogen selenide mixed gas is not supplied from the buffer tank 3 to the solar cell manufacturing apparatus, the open / close valve 21 is closed.
  • the pressure regulator when supplying a hydrogen selenide mixed gas to a solar cell manufacturing apparatus with a fixed pressure, you may provide the pressure regulator not shown in the flow path L6.
  • two or more open / close valves 21 may be provided. At this time, the flow path L6 may be branched.
  • Flow path L7 In addition, one end of a flow path L7 is connected to the buffer tank 3, and the other end of the flow path L7 is connected to a pressure gauge 22. The pressure of the hydrogen selenide mixed gas in the buffer tank 3 can be measured by the pressure gauge 22.
  • an opening / closing valve 23 is provided in the flow path L7.
  • the on-off valve 23 is normally open.
  • a vacuum pump or the like (not shown) is connected to the buffer tank 3. As a result, when the purge gas such as nitrogen remaining in the buffer tank 3 is removed, the purge gas can be exhausted by a vacuum pump or the like.
  • the buffer tank 3 may be omitted.
  • the flow path L 5 and the flow path L 6 shown in FIG. 1 are directly connected, and the flow path L 7 connected to the buffer tank 3 and the pressure gauge 22.
  • the opening / closing valve 23 may not be provided.
  • bypass channel L3 One end of the bypass flow path L3 is connected to the base gas supply source or the base gas supply flow path L1, and the other end is connected to the flow path L2 located on the primary side (upstream side) of the mass flow controller 11.
  • An automatic valve (first on-off valve) 14 is provided in the bypass flow path L3. The automatic valve 14 is closed when the hydrogen selenide mixed gas is produced, and is opened when the production of the hydrogen selenide mixed gas is stopped. When the automatic valve 14 is open, the calibration gas is supplied from the base gas supply flow path L1 to the source gas supply flow path L2 via the bypass flow path L3.
  • the source gas supply flow path L2 communicates with the base gas supply flow path L1 when the production of the hydrogen selenide mixed gas is stopped.
  • the source gas supply channel L2 is not communicated with the base gas supply channel L1.
  • the source gas supply flow path L2 is not communicated with the base gas supply flow path L1, so that the primary side (upstream side) of the automatic valve 14 of the bypass flow path L3 has selenization. Hydrogen gas does not flow.
  • the calibration gas is not particularly limited as long as it does not contain high-concentration hydrogen selenide gas.
  • the calibration gas can be arbitrarily selected.
  • As the calibration gas for example, an inert gas or a gas mainly containing an inert gas component is preferable.
  • 1 illustrates a configuration in which an inert gas supplied from the base gas supply source to the base gas supply flow path L1 is used as the calibration gas.
  • one end of the bypass channel L3 is connected to a separately provided calibration gas supply source (not shown) or an inert gas supply source shared with another device, and the calibration source is connected to the bypass channel L3 from these supply sources. Gas may be supplied (see FIG. 7).
  • it is preferable that one end of the bypass flow path L3 is connected to the base gas supply flow path L1 in order to prevent an increase in the size of the supply apparatus 101 and to eliminate the need for adding a calibration gas supply source.
  • connection position between one end of the bypass flow path L3 and the base gas supply flow path L1 is not particularly limited. However, it is preferable that one end of the bypass flow path L3 is connected to the base gas supply flow path L1 so as to be connected to a position close to the base gas supply source. With this structure, it is possible to prevent impurities from being mixed into the calibration gas when the calibration gas flows through the base gas supply channel L1. Furthermore, a pressure regulator (not shown) may be provided in the bypass channel L3.
  • Branch channel L4 One end of the branch flow path L4 is connected to the source gas supply flow path L2 on the secondary side (downstream side) of the mass flow controller 11, and the other end is connected to an exhaust duct (not shown).
  • an automatic valve (second on-off valve) 15 and a mass flow meter 16 are sequentially provided from the upstream side to the downstream side.
  • the automatic valve 15 is closed when the hydrogen selenide mixed gas is produced, and is opened when the production of the hydrogen selenide mixed gas is stopped.
  • the automatic valve 15 is open (when the hydrogen selenide mixed gas is stopped)
  • the calibration gas passes from the base gas supply channel L1 to the branch channel L4 via the bypass channel L3 and the source gas supply channel L2. Supplied to.
  • the branch flow path L4 and the raw material gas supply flow path L2 are shut off by the automatic valve 15.
  • the branch flow path L4 and the source gas supply flow path L2 are not shut off by the automatic valve 15, that is, communicate with each other.
  • the branch flow path L4 and the raw material gas supply flow path L2 are blocked, so that the hydrogen selenide gas does not flow on the secondary side of the automatic valve 15 of the branch flow path L4.
  • the mass flow meter 16 is a flow rate measuring device that measures the mass flow rate of the calibration gas. Specifically, it is provided to measure the flow rate of the calibration gas that has flowed through the mass flow controller 11. Further, in order to more accurately correct the flow rate value of the hydrogen selenide gas in the mass flow controller 11, the mass flow meter 16 of the present embodiment is installed in a flow path where the hydrogen selenide gas does not flow during the production of the hydrogen selenide mixed gas. It is preferable. Precipitation of selenium crystals on the mass flow meter 16 can be prevented. Specifically, as shown in FIG. 1, the mass flow meter 16 is preferably provided on the secondary side (downstream side) of the automatic valve 15 that is closed when the hydrogen selenide mixed gas is produced.
  • the mass flow meter 16 measures the mass flow rate of the calibration gas supplied to the branch flow path L4 via the bypass flow path L3 and the raw material gas supply flow path L2 when the production of the hydrogen selenide mixed gas is stopped.
  • the calibration gas flows through the mass flow controller 11 when flowing through the raw material gas supply flow path L2.
  • the mass flow meter 16 is preferably equipped with a mass flow sensor.
  • the mass flow sensor mounted on the mass flow meter 16 is not particularly limited. For example, general mass flow sensors, differential pressure mass flow sensors, Coriolis mass flow sensors, and the like can be used. .
  • Control means 19 and wirings E1 and E2) The mass flow meter 16 is connected to the control means 19 by the wiring E2. That is, the flow rate measurement value of the calibration gas supplied to the branch flow path L4 can be transmitted from the mass flow meter 16 to the control means 19 via the wiring E2. As described above, the control means 19 is also connected to the wiring E1 connected to the mass flow controller 11.
  • the flow value of the calibration gas is measured and transmitted to the control means 19. Therefore, the difference of the measured flow rate value of the calibration gas is obtained by the control means 19.
  • the control means 19 can send correction data to the mass flow controller 11.
  • the flow rate value of the hydrogen selenide gas flowing to the secondary side (downstream side) of the mass flow controller 11 is corrected by the obtained difference when the hydrogen selenide mixed gas production is resumed.
  • the mass flow controller 11 and the mass flow meter 16 are more preferably mass flow sensors having the same flow rate measurement range, and it is extremely preferable that the flow rate is calibrated with the same component gas.
  • the mass flow controller 11 is equipped with a thermal mass flow sensor and the full scale of flow measurement calibrated with hydrogen selenide is 10 [L / min]
  • the mass flow meter 16 has It is very preferable to use a similar one, that is, a thermal mass flow sensor equipped with a specification with a full scale of flow measurement of 10 [L / min] calibrated with hydrogen selenide.
  • similar or identical devices as the mass flow controller 11 and the mass flow meter 16 the following effects can be obtained. That is, the flow rate measurement value of the calibration gas measured by the mass flow controller 11 and the mass flow meter 16 is immediately after measurement of the calibration gas without requiring a flow rate conversion process that is necessary when a different gas is used.
  • the control means 19 can calculate the corrected hydrogen selenide gas flow rate value or the corrected hydrogen selenide gas flow rate value for the mass flow controller 11.
  • the control means 19 receives the calibration gas flow rate values measured by the mass flow controller 11 and the mass flow meter 16, respectively. Further, the control means 19 determines the correction amount of the flow rate value of hydrogen selenide gas set by the mass flow controller 11 or the corrected flow rate of hydrogen selenide gas according to the difference between the flow rate values of the received calibration gases. The value is calculated and transmitted to the mass flow controller 11. The flow rate measurement value of the calibration gas is measured by the mass flow controller 11 and the mass flow meter 16 when the hydrogen selenide mixed gas production is stopped. After that, when the production of the hydrogen selenide mixed gas is resumed, the flow rate value taking the hydrogen selenide gas correction into account is set as the flow rate setting value of the mass flow controller 11.
  • the control means 19 is not particularly limited as long as it can calculate the correction amount of the hydrogen selenide gas flow rate value or the corrected hydrogen selenide gas flow rate value. Arithmetic devices and systems can be arbitrarily selected and used. As such a control means 19, for example, a general computer or a programmable logic controller having a central processing unit can be used.
  • the supply method of this embodiment includes the following processes. First, the inert gas whose flow rate is controlled by the mass flow controller 6 and the raw material gas whose flow rate is controlled by the mass flow controller 11 are mixed by the mixer 2 so that a predetermined hydrogen selenide concentration setting value is obtained. A hydrogen fluoride mixed gas is produced. The produced mixed gas is stored in the buffer tank 3. (Process for producing hydrogen selenide mixed gas (I)). Thereafter, the hydrogen selenide mixed gas in the buffer tank 3 is supplied to a consumption facility provided on the secondary side of the solar cell manufacturing apparatus or the like provided in the subsequent stage of the supply device 101 (supply of hydrogen selenide mixed gas) Process (III)).
  • the calibration gas having the same flow rate is passed through the mass flow controller 11 and the mass flow meter 16. .
  • the flow rate value of the hydrogen selenide gas flowing to the mass flow controller 11 is corrected according to the difference between the flow rate values of the calibration gas measured by the mass flow controller 11 and the mass flow meter 16 (correction of the flow rate setting value of the source gas) Process (II)).
  • the solar cell manufacturing apparatus was described here as a consumption facility located on the secondary side (downstream side) of the hydrogen selenide mixed gas, any apparatus that consumes the hydrogen selenide mixed gas may be used.
  • a semiconductor manufacturing apparatus that consumes a hydrogen selenide mixed gas as a doping gas can be used.
  • a supply device 101 shown in FIG. 1 is prepared.
  • a purge gas such as nitrogen is circulated while opening / closing the open / close valves 4, 21, 23 and the automatic valve 9 to purge the flow path.
  • the automatic valves 14 and 15 are closed and all the open / close valves and automatic valves other than the automatic valves 14 and 15 are opened to complete the preparation for manufacturing.
  • the purge gas such as nitrogen remaining in the buffer tank 3 is preferably removed. For example, it is preferable to evacuate from a vacuum exhaust valve (not shown) connected to the buffer tank 3 using a vacuum pump (not shown).
  • an inert gas is supplied from the base gas supply flow path L1 and a hydrogen selenide gas is supplied from the source gas supply flow path L2 to the mixer 2, respectively. That is, while controlling the flow rate of the inert gas (flow rate set value V 1 [L / min]) and the flow rate of hydrogen selenide gas (flow rate set value V 2 [L / min]) to a preset flow rate. Supply. More specifically, the flow rate of the inert gas and the flow rate of the hydrogen selenide gas are set in advance as the set value of the hydrogen selenide concentration in the hydrogen selenide mixed gas supplied to the solar cell manufacturing apparatus (selenization).
  • the inert gas is supplied from the base gas supply flow path L1 and the hydrogen selenide gas is supplied from the source gas supply flow path L2 to the mixer 2, respectively.
  • the inert gas is supplied from the base gas supply source to the base gas supply channel L1.
  • the inert gas is decompressed to a predetermined pressure by the pressure regulator 5 in the base gas supply flow path L1, and then introduced into the mass flow controller 6.
  • an inert gas flow rate setting value V 1 [L / min] is set in advance. That is, the flow rate of the inert gas is controlled by the mass flow controller 6 to be V 1 [L / min].
  • the hydrogen selenide gas is supplied from the source gas supply source to the source gas supply flow path L2.
  • the hydrogen selenide gas is decompressed to a predetermined pressure by the pressure regulator 10 in the source gas supply flow path L2, and then introduced into the mass flow controller 11.
  • a flow rate setting value V 2 [L / min] of hydrogen selenide gas is set in advance. That is, the flow rate of the hydrogen selenide gas is controlled by the mass flow controller 11 to be V 2 [L / min].
  • V 2 a predetermined flow rate
  • the concentration of the hydrogen selenide mixed gas is not particularly limited, and can be appropriately selected according to the requirements of the solar cell manufacturing apparatus. Specifically, for example, the concentration of hydrogen selenide in the hydrogen selenide mixed gas can be 5 to 20 vol%.
  • the hydrogen selenide mixed gas mixed to a predetermined hydrogen selenide concentration is stored in the buffer tank 3 through the flow path L5.
  • the pressure of the stored hydrogen selenide mixed gas can be measured by the pressure gauge 22.
  • the hydrogen selenide mixed gas is produced until the pressure of the stored hydrogen selenide mixed gas reaches a preset upper limit pressure, and is supplied to the buffer tank 3 from the flow path L5.
  • all of the automatic valves 8, 9 and 13 are closed, the supply to the buffer tank 3 is stopped, and the hydrogen selenide mixed gas is produced.
  • the automatic valve 9 is also closed in order to implement a correction process described later.
  • the closed automatic valves 8, 9, 13 are turned on.
  • the state is opened, and supply of the mixed gas to the buffer tank 3, that is, production of a hydrogen selenide mixed gas is started.
  • the pressure gauge 22 detects that the pressure in the buffer tank 3 has reached the upper limit pressure or more, all the automatic valves 8, 9, 13 are closed, and the supply of the mixed gas to the buffer tank 3, that is, The production of the hydrogen selenide mixed gas is stopped. Thereafter, the production and stop of production of the hydrogen selenide mixed gas are sequentially repeated according to the pressure in the buffer tank 3.
  • the hydrogen selenide mixed gas stored in the buffer tank 3 is supplied to the solar cell manufacturing apparatus according to the consumption status of the hydrogen selenide mixed gas in the solar cell manufacturing apparatus.
  • the production of hydrogen selenide mixed gas or the switching of the production stop is performed according to the pressure value in the buffer tank 3 measured by the pressure gauge 22. Instead, it may be performed according to the consumption situation of the hydrogen selenide mixed gas in the solar cell manufacturing apparatus. For example, mixed gas production may be stopped when consumption is not performed, and / or production may be performed when consumption is performed. In this way, the hydrogen selenide mixed gas having a stable hydrogen selenide concentration is continuously supplied to the solar cell manufacturing apparatus.
  • the automatic valves 14 and 15 are opened.
  • the inert gas which is the base gas
  • the branch flow path L4 and the source gas supply flow path L2 are connected to a flow path constituted by the source gas supply flow path L2 and the branch flow path L4 (hereinafter referred to as "calibration gas flow path").
  • calibrbration gas flow path a flow path constituted by the source gas supply flow path L2 and the branch flow path L4
  • an inert gas can be flowed.
  • This inert gas may use the same gas as the base gas.
  • the inert gas used functions as a calibration gas.
  • each flow rate value of the calibration gas is measured by the mass flow controller 11 and the mass flow meter 16 provided in the calibration gas flow path.
  • the control means 19 performs arithmetic processing using these measured values, and based on the result, corrects the flow rate value of the hydrogen selenide gas that the mass flow controller 11 flows when the production of the hydrogen selenide mixed gas is resumed. If the gas type at the time of calibration and mixed gas production is different, or if the gas type at the time of calibration is different from that at the time of flow measurement when calibrating each mass flow controller or mass flow meter separately if necessary Before calculating the flow rate error, the flow rate is preferably converted using a flow rate correction coefficient called a conversion factor.
  • the mass flow controller 11 controls the flow rate of the calibration gas, and simultaneously measures the flow rate V 3 [L / min] of the calibration gas. At the same time, the flow rate V 4 [L / min] of the calibration gas is measured by the mass flow meter 16 located on the downstream side.
  • the flow rate V 3 [L / min] of the calibration gas measured by the mass flow controller 11 when the production of the hydrogen selenide mixed gas is stopped is the flow rate of the calibration gas to be originally measured. There is a tendency to become smaller.
  • the mass flow meter 16 is disposed at a position where hydrogen selenide gas does not flow when the hydrogen selenide mixed gas is produced. For this reason, the flow rate V 4 [L / min] of the calibration gas measured by the mass flow meter 16 becomes equal to the flow rate of the calibration gas to be originally measured.
  • the difference between the flow values V 3 and V 4 [L / min] of the calibration gas measured by the mass flow controller 11 and the mass flow meter 16 is The degree of decrease in the flow rate control accuracy and the degree of precipitation of selenium crystals in the source gas supply flow path L2 including the mass flow controller 11 are accurately shown.
  • the case where the flow rate V 3 [L / min] of the calibration gas measured by the mass flow controller 11 is smaller than the flow rate of the calibration gas to be originally measured is described. However, even when the flow rate of the calibration gas to be originally measured is larger, the same processing, that is, correction can be performed.
  • the flow rate error A and the correction coefficient B are calculated from the flow rate measurement values V 3 and V 4 [L / min] by the following equations.
  • Flow rate error A (
  • Correction coefficient B V 4 / V 3
  • the gas type at the time of calibration is different from that at the time of mixed gas production, or if the mass flow controller is separately calibrated if necessary, the type of gas used for calibration and flow rate measurement is different. If they do not match, it is necessary to correct with a flow rate correction coefficient called a conversion factor. After correcting V 3 and V 4 to the flow rate value according to the type of calibration gas using the flow rate correction coefficient, the flow rate error A and the correction coefficient B are calculated.
  • the corrected hydrogen selenide gas flow rate set value V 5 [L / min] to be transmitted to the mass flow controller 11 is calculated by the following equation.
  • Flow rate setting value V 5 [L / min] B ⁇ V 2 [L / min]
  • the calculated hydrogen selenide gas flow rate setting value V 5 [L / min] is transmitted to the mass flow controller 11 via the wiring E1.
  • Flow rate set value V 5 is than this is used later manufacturing process of hydrogen selenide gas mixture takes place.
  • the correction value used when the production of the hydrogen selenide mixed gas is resumed after the process of correcting the flow rate setting value of the source gas is obtained. That is, the flow rate setting value of the hydrogen selenide gas flowing to the secondary side (downstream side) of the mass flow controller 11 is corrected to the correction amount calculated by the control means 19.
  • preparation for producing a hydrogen selenide mixed gas having a predetermined hydrogen selenide concentration is completed.
  • the automatic valves 14 and 15 may be closed and the automatic valve 9 may be opened. That is, by opening in this way, the raw material gas supply flow path L2 between the connection position of the bypass flow path L3 and the raw material gas supply flow path L2 to the connection position of the branch flow path L4 and the raw material gas supply flow path L2.
  • the calibration gas inside may be replaced with hydrogen selenide gas.
  • the automatic valve 15 may remain open or may be opened at a predetermined timing.
  • the correction coefficient B is used only when controlling the flow rate of hydrogen selenide gas. That is, when the flow rate of the calibration gas is measured, the mass flow controller 11 is not corrected using the correction coefficient B.
  • the automatic valves 14 and 15 are closed and all the on-off valves and automatic valves other than the automatic valves 14 and 15 are opened, and the hydrogen selenide mixed gas production process described above is performed.
  • the hydrogen selenide gas flow rate setting value V 5 [L / min] accurately corrected in the immediately preceding raw material gas flow rate setting value correction process is the mass flow controller 11. Is set to Therefore, hydrogen selenide gas having a flow rate V 2 [L / min] that should flow originally to the secondary side (downstream side) of the mass flow controller 11 can be flowed.
  • the flow rate value V 2 [L / min] hydrogen selenide gas can be supplied to the mixer 2.
  • the hydrogen selenide mixed gas production process (I) and the raw material gas flow rate setting value correction process (II) are repeated alternately.
  • a hydrogen selenide mixed gas having a predetermined hydrogen selenide concentration which is suitable for being supplied from the supply device 101 to the solar cell manufacturing apparatus, is stably supplied over a long period of time.
  • the raw material gas flow rate setting value correction process (II) may be performed by changing the flow rate setting value of the calibration gas as necessary. When it is repeated a plurality of times, a plurality of differences in the flow rate values of the calibration gas are obtained. Therefore, when changing the flow rate setting value of the calibration gas, for example, a plurality of correction coefficients B obtained so far obtained in the correction process of the flow rate setting value of each source gas may be averaged and used. Alternatively, the correction coefficient B to be applied may be determined and used for each set flow rate range.
  • the flow rate measurement value in the first production process is V 3a [L / min]
  • the correction coefficient obtained in the correction process using this value is B a
  • the flow rate measurement value in the second manufacturing process is V 3b [L / min]
  • the obtained correction coefficient is Bb
  • V 3a ⁇ V 3b the correction coefficient applied when the flow rate measurement value of hydrogen selenide gas is 0 to V 3a [L / min] is B a
  • V 3a to V 3b [L / min] is B a
  • the correction factor to be applied to the case of can be B b.
  • the pressure gauge 22 connected to the buffer tank has a predetermined value.
  • the automatic valves 14 and 15 may be closed after the correction process (II) of the flow rate setting value of the source gas.
  • the value of the flow rate error A is preferably in the range of 5 to 30%, but is not particularly limited to this range, and can be appropriately selected if there is no practical problem.
  • the hydrogen selenide gas retained in the source gas supply flow path can be removed by the calibration gas. For this reason, precipitation of selenium crystals due to self-decomposition of hydrogen selenide in the source gas supply flow path L2 can be significantly reduced. Further, when hydrogen selenide gas having a flow rate of V 2 [L / min] is flowed to the mass flow controller 11, even if selenium crystals are precipitated, the calibration is provided in a flow path in which hydrogen selenide gas does not flow. Based on the flow rate value of the calibration gas measured by the mass flow meter 16, the corrected flow rate set value V 5 [L / min] can be transmitted to the mass flow controller 11. For this reason, the flow control error of the source gas supply flow path L2 can be extremely reduced.
  • the hydrogen selenide mixed gas supply method of the present embodiment it is possible to perform a longer period of time than before without performing precise equipment operation and buffer tank volume expansion, such as switching of an opening / closing valve in a short cycle.
  • the drift phenomenon can be reduced, and a hydrogen selenide mixed gas having a stable hydrogen selenide concentration can be supplied to a solar cell manufacturing apparatus or the like.
  • the mass flow controller 11 provided in the source gas supply flow path L2 for controlling the flow rate of the hydrogen selenide gas, and the calibration mass flow meter 16, the calibration gas having the same flow rate is supplied.
  • the hydrogen selenide gas staying in the source gas supply channel with the calibration gas is removed, so that the precipitation of selenium crystals due to the self-decomposition of hydrogen selenide is reduced.
  • the mass flow controller 11 provided in the source gas supply flow path L2 through which the hydrogen selenide gas flows and the mass flow meter 16 provided in the flow path through which the hydrogen selenide gas does not flow,
  • the flow rate setting value of the hydrogen selenide gas that is flowed by the mass flow controller 11 is corrected according to the difference between the flow rate measurement values obtained by measuring the calibration gas having the same flow rate.
  • the flow control error of the source gas supply flow path L2 is extremely reduced, and the drift phenomenon is suppressed.
  • long-term stable hydrogen selenide gas mixture with a stable hydrogen selenide concentration without the need for precise equipment operations such as valve opening and closing in a short cycle and a large-capacity buffer tank is a solar cell manufacturing device. Etc.
  • the supply device 101 of the above embodiment has a configuration in which the mass flow meter 16 is provided in the branch flow path L4.
  • the mass flow meter 16 may be provided in the bypass flow path L ⁇ b> 3 on the primary side (upstream side) of the automatic valve 14.
  • the hydrogen selenide gas does not flow through the bypass passage L3 on the primary side of the automatic valve 14.
  • the mass flow meter 16 can be provided in the flow path where hydrogen selenide gas does not flow like the supply device 101 described above.
  • the supply device can be downsized.
  • hydrogen selenide mixed gas with a stable hydrogen selenide concentration in solar cell manufacturing equipment and the like can be used for long-term without requiring precise equipment operation such as valve opening and closing in a short cycle and a large capacity buffer tank. Supplied.
  • an abnormality of the mass flow controller 11 may be notified to the operator of the supply apparatus 101, and the mass flow controller 11 may be replaced by the operator.
  • Example 1 The hydrogen selenide mixed gas was manufactured using the supply apparatus 101 shown in FIG. 1, and the hydrogen selenide mixed gas was continuously supplied to the solar cell manufacturing apparatus for a long period of time.
  • Table 1 The conditions shown in Table 1 were used when the process for producing the hydrogen selenide mixed gas in the supply apparatus 101 was performed.
  • Table 2 The conditions in Table 2 were used when performing the correction process of the flow rate setting value of the source gas of the supply apparatus 101.
  • the flow rate measurement value V3 of the mass flow controller 11 indicates that the nitrogen gas actually flowing is 13.0 L / min when the flow rate display of the controller is 10.0 L / min in the correction process.
  • “One time” described in Table 2 is the number of combinations of the manufacturing process and the correction process performed to correct the flow rate setting value once, and this is repeated a plurality of times in this embodiment.
  • FIG. 2 shows the time (days) dependence of the hydrogen selenide concentration in the hydrogen selenide mixed gas measured with a hydrogen selenide concentration analyzer.
  • FIG. 3 shows the time (days) dependence of the flow rate error A when the manufacturing and correction processes are repeated.
  • the hydrogen selenide concentration in the hydrogen selenide mixed gas is stable at around 10.0% even after about 100 days have elapsed from the start of measurement. Therefore, in the present invention, it has been confirmed that the flow rate control error of the source gas supply flow path L2 can be reduced extremely accurately and over a long period of at least about 100 days. This is based on the flow rate error A and the correction coefficient B calculated based on the flow rate value of the calibration gas measured by the calibration mass flow meter 16 by the supply method and supply device 101 of the above embodiment of the present invention. This is because the flow rate setting value V 2 [L / min] of the hydrogen selenide gas that flows to the mass flow controller 11 can be corrected to the flow rate setting value V 5 [L / min].
  • the present invention can be applied to a hydrogen selenide mixed gas supply method and apparatus.
  • Hydrogen selenide mixed gas supply method and supply capable of supplying a hydrogen selenide mixed gas with a stable hydrogen selenide concentration for a long period of time without requiring a precise equipment operation and a large-capacity buffer tank and suppressing drift phenomenon Equipment can be provided.

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JP2020105577A (ja) * 2018-12-27 2020-07-09 株式会社フジキン 流体供給装置
CN113874547A (zh) * 2019-11-12 2021-12-31 昭和电工株式会社 附着物除去方法及成膜方法
WO2024038827A1 (ja) * 2022-08-17 2024-02-22 大陽日酸株式会社 混合ガス供給装置

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KR20200050607A (ko) 2018-11-02 2020-05-12 알엠아이텍(주) 징크 셀레나이드 기반의 셀렌화수소 제조방법
CN112097114A (zh) * 2020-08-07 2020-12-18 安徽亚格盛电子新材料有限公司 一种精确制备液态mo源和氢气混合气的装置
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