WO2014065233A1 - Method and device for supplying hydrogen-selenide mixed gas - Google Patents
Method and device for supplying hydrogen-selenide mixed gas Download PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- hydrogen selenide
- flow rate
- gas supply
- mixed gas
- Prior art date
Links
- 229910000058 selane Inorganic materials 0.000 title claims abstract description 317
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 title claims abstract 34
- 238000000034 method Methods 0.000 title claims description 73
- 239000007789 gas Substances 0.000 claims abstract description 612
- 238000004519 manufacturing process Methods 0.000 claims description 100
- 238000012937 correction Methods 0.000 claims description 54
- 239000011261 inert gas Substances 0.000 claims description 49
- 238000005259 measurement Methods 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000691 measurement method Methods 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 296
- 239000002994 raw material Substances 0.000 description 30
- 239000011669 selenium Substances 0.000 description 14
- 229910052711 selenium Inorganic materials 0.000 description 13
- 238000011144 upstream manufacturing Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen gas selenide Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Metallurgy (AREA)
- Computer Hardware Design (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Fluid Mechanics (AREA)
- Chemical Vapour Deposition (AREA)
- Photovoltaic Devices (AREA)
- Flow Control (AREA)
- Fuel Cell (AREA)
Abstract
Description
本願は、2012年10月22日に、日本に出願された特願2012-232832号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a method and apparatus for supplying a hydrogen selenide mixed gas.
This application claims priority based on Japanese Patent Application No. 2012-2327282 filed in Japan on October 22, 2012, the contents of which are incorporated herein by reference.
すなわち、(1)ベースガス供給流路から供給される不活性ガスと、原料ガス供給流路から供給されるセレン化水素ガスと、を混合して、所定の濃度に調製されたセレン化水素混合ガスを製造する工程と、前記混合ガスを供給する工程を有する、セレン化水素混合ガスの供給方法であって、更に、セレン化水素混合ガスを製造する工程を停止している間に、原料ガスの流量設定値を補正する工程を含み、前記補正工程が、前記原料ガス供給流路に設けられて前記セレン化水素ガスの流量を制御する流量制御手段と、校正用の流量測定手段とに、同一流量の校正用ガスを流す工程と、前記流量制御手段及び前記流量測定手段によって測定された前記校正用ガスのそれぞれの流量値の差分を得る工程と、前記差分に応じて、前記流量制御手段が流す前記セレン化水素ガスの流量値を補正する工程と、を含むことを特徴とするセレン化水素混合ガスの供給方法が提供される。 In order to solve the above problems, the following method is provided as a first aspect of the present invention.
(1) 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. A step of flowing a calibration gas with the same flow rate, a step of obtaining a difference between the flow rate values of the calibration gas measured by the flow rate control means and the flow rate measurement means, and the flow rate control means according to the difference Flow 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.
(2)前記校正用ガスを、前記流量制御手段と前記流量測定手段とに、順不同で、連続して流す。
(3)前記流量制御手段と前記流量測定手段とに、同一の仕様の流量測定方法を用いる。
(4) 上記(1)~(3)のいずれかにおいて、前記校正用ガスとして、前記不活性ガスを用いる。
(5) 上記(1)~(4)のいずれかにおいて、前記セレン化水素混合ガスを製造する際に、前記セレン化水素ガスを校正用の前記流量測定手段に流さない。 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.
(4) In any one of the above (1) to (3), the inert gas is used as the calibration gas.
(5) In any one of the above (1) to (4), when the hydrogen selenide mixed gas is produced, the hydrogen selenide gas is not allowed to flow to the flow rate measuring means for calibration.
(6) 本発明の第二の態様として、以下の装置が提供される。
すなわち、ベースガス供給流路から供給される不活性ガスと、原料ガス供給流路から供給されるセレン化水素ガスと、を混合して、所定の濃度に調製されたセレン化水素混合ガスを製造し、その後、供給する、セレン化水素混合ガスの供給装置であって、
前記原料ガス供給流路に設けられて前記セレン化水素ガスの流量を制御する流量制御手段と;前記セレン化水素混合ガスの製造停止時に、校正用ガスを前記原料ガス供給流路の前記流量制御手段の一次側へと供給する校正用ガス供給流路と;前記セレン化水素混合ガスの製造停止時に前記校正用ガスが流れるとともに前記セレン化水素混合ガスの製造時には前記セレン化水素ガスが流れない流路に設けられた校正用の流量測定手段と;前記流量制御手段及び前記流量測定手段に同一流量の前記校正用ガスを流した際に、それぞれ測定された校正用ガスの流量値の差分に応じて、流量制御手段が流す前記セレン化水素ガスの流量値を補正する制御手段と、を備えることを特徴とするセレン化水素混合ガスの供給装置が提供される。
(6) As the second aspect of the present invention, 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 gas supply passage for calibration to be supplied to the primary side of the means; the calibration gas flows when the production of the hydrogen selenide mixed gas is stopped, and the hydrogen selenide gas does not flow when the hydrogen selenide mixed gas is produced. 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.
(8) 上記(6)において、前記校正用ガス供給流路が、前記ベースガス供給流路と前記原料ガス供給流路の前記流量制御手段の一次側とを接続するバイパス流路である。
(9) 上記(8)において、前記バイパス流路には、前記セレン化水素混合ガスの製造時に閉状態となり、前記不活性ガスを校正用ガスとして前記ベースガス供給流路から前記原料ガス供給流路へと供給する際に開状態となる、第1の開閉弁が設けられており、前記バイパス流路の前記第1の開閉弁の一次側に、前記流量測定手段が設けられている。 (7) In the above (6), 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. Yes.
(8) In the above (6), 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.
(9) In the above (8), 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.
(11) 上記(6)~(10)のいずれかにおいて、前記流量制御手段と前記流量測定手段とが、同一の仕様の流量測定方法である。 (10) In the above (6) or (8), 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. There is provided 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.
(11) In any one of the above (6) to (10), the flow rate control unit and the flow rate measurement unit are flow rate measurement methods having the same specifications.
なお、以下の説明で用いる図面は、特徴をわかりやすくするために、便宜上特徴となる部分を拡大して示している場合があり、各構成要素の寸法比率などが実際と同じであるとは限らない。また本発明は、以下の例のみに限定されるものではない。本発明の範囲内において、必要に応じて、変更、省略、交換及び/又は追加することも可能である。装置の数や位置も、必要に応じて変更してもよい。また、本明細書中で用いる単位については、濃度は体積濃度、圧力はゲージ圧力、流量は体積流量を表している。さらに、本明細書中に示す体積は、基準状態(0℃、1atm(大気圧))での体積である。また本発明において、“手段”という記載は、装置、工程、部材、システム、及び部分などを意味してよい。 Hereinafter, a hydrogen selenide mixed gas supply method and a hydrogen selenide mixed gas supply apparatus according to an embodiment to which the present invention is applied will be described in detail with reference to the drawings.
In addition, in the drawings used in the following description, in order to make the features easy to understand, there are cases where the portions that become the features are enlarged for the sake of convenience, and the dimensional ratios of the respective components are not always the same as the actual ones. Absent. The present invention is not limited to the following examples. Changes, omissions, replacements and / or additions may be made as necessary within the scope of the present invention. The number and position of the devices may be changed as necessary. As for the units used in this specification, the concentration represents volume concentration, the pressure represents gauge pressure, and the flow rate represents volume flow rate. Furthermore, the volume shown in this specification is a volume in a reference state (0 ° C., 1 atm (atmospheric pressure)). In the present invention, the term “means” may mean an apparatus, a process, a member, a system, a part, and the like.
先ず、本実施形態のセレン化水素混合ガスの供給装置(以下、単に「供給装置」という)101の構成について、太陽電池製造装置向けの供給装置として、図1を参照しながら説明する。なお、ここでは太陽電池製造装置向けの供給装置として記載するが、本発明の供給装置は、セレン化水素混合ガスを消費する装置向けの供給装置であれば特に限定されず、何にでも使用できる。例えばセレン化水素混合ガスをドーピングガスとして消費する半導体製造装置向けの供給装置などが、例としてあげられる。なお上記“装置A向けの装置B”などの表現は、装置Aとは別途に用意される装置Bを意味しても良く、あるいは、装置Aの一部として含まれる装置Bを意味しても良い。 (Hydrogen selenide mixed gas supply device)
First, 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. Although described here as a supply device for a solar cell manufacturing apparatus, 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. . For example, 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. Note that 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.
ベースガス供給流路L1は、一端が図示略のベースガス供給源に接続されており、他端が混合器2に接続されている。ベースガスは、希釈用途の不活性ガスであれば特に限定されるものではない。本発明で使用される不活性ガスとしては、例えば、窒素(N2)ガス、あるいは、アルゴン(Ar)、ヘリウム(He)や、ネオン(Ne)などの希ガス等が挙げられる。 (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
圧力調整器5は、ベースガス供給源から供給される不活性ガスの圧力を所望の圧力へと減圧するために設けられている。本実施形態の供給装置101では、圧力調整器5がベースガス供給流路L1に1つだけ設けられている。しかしながら、1つに限定されるものではなく、圧力調整器5が流路L1の任意に選択される箇所に2以上設けられていてもよい。
なお、マスフローコントローラ6の直前の流路L1中のガスの圧力は、太陽電池製造装置への供給圧力に応じて、適宜設定することができる。例えば、マスフローコントローラ6の直前のガスの圧力としては、0.3~0.8MPaの範囲とすることができる。 The on-off
The
In addition, the pressure of the gas in the flow path L1 immediately before the
また、マスフローコントローラ6は、混合器2で混合されたセレン化水素混合ガス中のセレン化水素濃度が所定値を維持するように、不活性ガスの流量を制御する。
図1には、ベースガス供給流路L1に1つのマスフローコントローラ6が設けられた供給装置101を例示しているが、本発明はこれに限定されるものではない。例えば、マスフローコントローラ6がベースガス供給流路L1に並列で2以上設けられていてもよい。
マスフローコントローラ6には、質量流量センサが搭載される。マスフローコントローラ6に搭載される質量流量センサは、特に限定されるものではなく、例えば、熱式質量流量センサ、差圧式質量流量センサ、コリオリ式質量流量センサ等の一般的なものを用いることができる。 The
The
Although FIG. 1 illustrates the
A mass flow sensor is mounted on the
原料ガス供給流路L2は、一端が図示略の原料ガス供給源に接続されており、他端が混合器2に接続されている。原料ガスは、セレン化水素ガスである。 (Raw material gas supply flow path L2)
One end of the source gas supply flow path L <b> 2 is connected to a source gas supply source (not shown), and the other end is connected to the
また、マスフローコントローラ11は、混合器2で混合されたセレン化水素混合ガス中のセレン化水素濃度が所定値になるように、セレン化水素ガスの流量を制御する。
また、マスフローコントローラ11では、セレン化水素混合ガスの製造停止時に、バイパス流路L3を介してマスフローコントローラ11の一次側(上流側)へ供給される校正用ガスの、流量制御及び質量流量計測がなされる。
さらに、マスフローコントローラ11には、後述する配線E1によって制御手段19が接続されており、校正用ガスの流量の測定結果(流量測定値)をマスフローコントローラ11から制御手段19へと送信可能とされている。制御手段19では、必用な情報を得ると演算処理などを行い、その結果をマスフローコントローラ11の制御に反映させることができる。 The
The
The
Further, a control means 19 is connected to the
混合器2は、ベースガス供給流路L1の他端と原料ガス供給流路L2の他端とが合流する位置に設けられている。混合器2は、ベースガス供給流路L1を通って供給される不活性ガスと、原料ガス供給流路L2を通って供給されるセレン化水素ガスとを混合して、所定の濃度に調整されたセレン化水素混合ガスを製造し、製造したガスを下流側に供給できるものであれば、特に限定されず、任意のものを選択できる。混合器2により、原料ガス供給流路L2への不活性ガスの流入、及びベースガス供給流路L1へのセレン化水素ガスの流入が、防止される。 (Mixer 2)
The
混合器2とバッファタンク3とは、流路L5により接続される。なお、流路L5には、図示略の開閉バルブが設けられていてもよい。 (Flow path L5)
The
バッファタンク3は、混合器2によって所定の濃度に調整されたセレン化水素混合ガスを貯留するための貯留槽である。バッファタンク3の内容積は、特に限定されるものではなく、太陽電池製造装置へのセレン化水素混合ガスの供給量に応じて適宜選択することができる。バッファタンク3におけるセレン化水素混合ガスの貯留量は、バッファタンク3の内容積及び太陽電池製造装置へのセレン化水素混合ガスの供給量に応じて適宜選択することができる。例えば、太陽電池製造装置へのセレン化水素混合ガス供給量が100~200L/minの場合、バッファタンク内容量は20~400Lとすることができる。 (Buffer tank 3)
The
バッファタンク3には流路L6の一端が接続されており、流路L6の他端が混合ガスの出口となっており、この出口は太陽電池製造装置に接続されている。これにより、バッファタンク3から太陽電池製造装置へとセレン化水素混合ガスを供給可能となっている。また、流路L6の出口より上流位置、すなわち流路L6の供給口側には、開閉バルブ21が設けられている。
太陽電池製造装置にセレン化水素混合ガスをバッファタンク3から供給する場合には、開閉バルブ21を開ける。一方、太陽電池製造装置にセレン化水素混合ガスをバッファタンク3から供給しない場合には、開閉バルブ21を閉じる。
なお、太陽電池製造装置にセレン化水素混合ガスを一定圧力で供給する場合は、流路L6に図示略の圧力調整器を設けてもよい。
また、複数の太陽電池製造装置にセレン化水素混合ガスを供給する場合は、開閉バルブ21を2以上設けてもよい。この時、流路L6は分岐させてもよい。 (Flow path L6)
One end of the flow path L6 is connected to the
When supplying the hydrogen selenide mixed gas from the
In addition, 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.
Moreover, when supplying a hydrogen selenide mixed gas to a plurality of solar cell manufacturing apparatuses, two or more open /
また、バッファタンク3には、流路L7の一端が接続されており、流路L7の他端が圧力計22に接続されている。圧力計22により、バッファタンク3内のセレン化水素混合ガスの圧力を計測することができる。また、流路L7には、開閉バルブ23が設けられている。開閉バルブ23は通常は開いている。
さらに、バッファタンク3には、図示略の真空ポンプ等が接続されていることが好ましい。これにより、バッファタンク3に残留する窒素等のパージガスを除く場合、パージガスを真空ポンプ等によって排気することができる。 (Flow path L7)
In addition, one end of a flow path L7 is connected to the
Furthermore, it is preferable that a vacuum pump or the like (not shown) is connected to the
なお、本発明では、バッファタンク3は省略してもよい。バッファタンク3を採用しない本実施形態の供給装置(図示略)においては、図1に示す流路L5と流路L6とが直結しており、バッファタンク3に接続する流路L7、圧力計22、開閉バルブ23は設けられていなくてもよい。 (Omitted buffer tank)
In the present invention, the
バイパス流路L3は、一端がベースガス供給源あるいはベースガス供給流路L1に接続されており、他端がマスフローコントローラ11の一次側(上流側)に位置する流路L2に接続されている。バイパス流路L3には、自動弁(第1の開閉弁)14が設けられている。自動弁14は、セレン化水素混合ガスの製造時に閉状態とされ、セレン化水素混合ガスの製造停止時に開状態とされる。自動弁14が開状態のとき、校正用ガスがベースガス供給流路L1からバイパス流路L3を介して、原料ガス供給流路L2へと供給される。 (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
さらに、バイパス流路L3には、図示略の圧力調整器が設けられていてもよい。 Further, the 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.
分岐流路L4は、一端がマスフローコントローラ11の二次側(下流側)の原料ガス供給流路L2に接続されており、他端が図示略の排気ダクトに接続されている。分岐流路L4には、上流側から下流側に向かって、自動弁(第2の開閉弁)15、マスフローメータ16が順次設けられている。自動弁15は、セレン化水素混合ガスの製造時に閉状態とされ、セレン化水素混合ガスの製造停止時に開状態とされる。自動弁15が開状態のとき(セレン化水素混合ガスが製造停止のとき)、校正用ガスがベースガス供給流路L1からバイパス流路L3及び原料ガス供給流路L2を介して分岐流路L4へと供給される。
セレン化水素混合ガスの製造時には、分岐流路L4と原料ガス供給流路L2とが自動弁15により遮断される。かつ、セレン化水素混合ガスの製造停止時には分岐流路L4と原料ガス供給流路L2とが自動弁15により遮断されない、すなわち連通する。セレン化水素混合ガスの製造時には、分岐流路L4と原料ガス供給流路L2とが遮断されるため、分岐流路L4の自動弁15の二次側には、セレン化水素ガスが流れない。 (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
During the production of the hydrogen selenide mixed gas, the branch flow path L4 and the raw material gas supply flow path L2 are shut off by the
また、マスフローコントローラ11におけるセレン化水素ガスの流量値をより正確に補正するため、本実施形態のマスフローメータ16は、セレン化水素混合ガスの製造時にセレン化水素ガスが流れない流路に設置されていることが好ましい。マスフローメータ16へのセレン結晶の析出を防止することができる。具体的には、マスフローメータ16は、図1に示すように、セレン化水素混合ガスの製造時に閉状態となる自動弁15の二次側(下流側)に設けられていることが好ましい。 The
Further, in order to more accurately correct the flow rate value of the hydrogen selenide gas in the
マスフローメータ16には、質量流量センサが搭載されることが好ましい。マスフローメータ16に搭載される質量流量センサは、特に限定されるものではなく、例えば、熱式質量流量センサ、差圧式質量流量センサ、コリオリ式質量流量センサ等の一般的なものを用いることができる。 The
The
マスフローメータ16は、配線E2によって、制御手段19に接続されている。すなわち、分岐流路L4へ供給される校正用ガスの流量測定値は、配線E2により、マスフローメータ16から制御手段19へと送信可能とされている。
なお前述したように、制御手段19には、マスフローコントローラ11に接続する配線E1も接続されている。 (Control means 19 and wirings E1 and E2)
The
As described above, the control means 19 is also connected to the wiring E1 connected to the
例えば、マスフローコントローラ11が熱式質量流量センサを搭載しており、セレン化水素で校正された流量計測のフルスケールが10[L/min]の仕様のものであれば、マスフローメータ16には、同様のもの、すなわち、熱式質量流量センサを搭載するとともにセレン化水素で校正された流量計測のフルスケールが10[L/min]の仕様のものを用いることが極めて好ましい。
マスフローコントローラ11及びマスフローメータ16として使用する機器として、このように類似の、または同じものを選択することにより、以下の効果をえることができる。すなわち、マスフローコントローラ11とマスフローメータ16で測定された校正用ガスの流量測定値は、異種ガスを用いた場合に必要である流量換算処理を必要とすることなく、校正用ガスの測定後、直ちに制御手段19により、マスフローコントローラ11のために、セレン化水素ガスの流量値の補正量または補正されたセレン化水素ガスの流量値を算出することができる。 In each of the
For example, if the
By selecting similar or identical devices as the
なお、校正用ガスの流量測定値は、セレン化水素混合ガス製造停止時に、マスフローコントローラ11及びマスフローメータ16で測定される。その後、セレン化水素混合ガスの製造が再開された時には、セレン化水素ガスの補正を加味した流量値を、マスフローコントローラ11の流量設定値とする。 The control means 19 receives the calibration gas flow rate values measured by the
The flow rate measurement value of the calibration gas is measured by the
次に、供給装置101を用いた本実施形態のセレン化水素混合ガスの供給方法(以下、単に「供給方法」という)について説明する。 (Method for supplying hydrogen selenide mixed gas)
Next, a method for supplying a hydrogen selenide mixed gas of the present embodiment using the supply device 101 (hereinafter simply referred to as “supply method”) will be described.
先ず、マスフローコントローラ6で流量制御された不活性ガスと、マスフローコントローラ11で流量制御された原料ガスとを、混合器2で混合して、所定のセレン化水素濃度設定値になるように、セレン化水素混合ガスを製造する。そして製造された混合ガスを、バッファタンク3に貯留する。(セレン化水素混合ガスの製造プロセス(I))。
その後、バッファタンク3内のそのセレン化水素混合ガスを、供給装置101の後段に設けられた、太陽電池製造装置等の二次側に位置する消費設備に供給する(セレン化水素混合ガスの供給プロセス(III))。
セレン化水素混合ガス製造プロセスの後、すなわち、セレン化水素混合ガスの製造を停止した後に、同一流量の校正用ガスを、好ましくは同じ校正用ガスを、マスフローコントローラ11及びマスフローメータ16に流通させる。マスフローコントローラ11及びマスフローメータ16によって測定された、校正用ガスのそれぞれの流量値の差分に応じて、マスフローコントローラ11に流すセレン化水素ガスの流量値を補正する(原料ガスの流量設定値の補正プロセス(II))。
なおここでは、セレン化水素混合ガスの二次側(下流側)に位置する消費設備として、太陽電池製造装置と記載したが、セレン化水素混合ガスを消費する装置であれば何でもよい。例えばセレン化水素混合ガスをドーピングガスとして消費する半導体製造装置などがあげられる。 The supply method of this embodiment includes the following processes.
First, the inert gas whose flow rate is controlled by the
Thereafter, the hydrogen selenide mixed gas in the
After the hydrogen selenide mixed gas production process, that is, after the production of the hydrogen selenide mixed gas is stopped, the calibration gas having the same flow rate, preferably the same calibration gas, is passed through the
In addition, although 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. For example, a semiconductor manufacturing apparatus that consumes a hydrogen selenide mixed gas as a doping gas can be used.
先ず、セレン化水素混合ガスの製造前の準備を行う。具体的には、図1に示す供給装置101を用意し、この装置において、開閉バルブ4、21、23、自動弁9を開閉操作しながら窒素等のパージガスを流通させ、流路内のパージを行う。上記パージを完了した後、自動弁14,15を閉状態にするとともに、自動弁14、15以外の全ての開閉バルブ及び自動弁を開状態にして、製造準備を完了する。
なお、バッファタンク3に残留する窒素等のパージガスは、除いておくことが好ましい。例えば、バッファタンク3に接続する図示略の真空排気用バルブ等から、図示略の真空ポンプ等を用いて真空排気することが好ましい。 (Manufacturing preparation process)
First, preparation before manufacture of hydrogen selenide mixed gas is performed. Specifically, a
The purge gas such as nitrogen remaining in the
次に、ベースガス供給流路L1から不活性ガスを、原料ガス供給流路L2からセレン化水素ガスを、それぞれ混合器2へと供給する。すなわち、不活性ガスの流量(流量設定値V1[L/min])とセレン化水素ガスの流量(流量設定値V2[L/min])とを、予め設定された流量に制御しながら供給する。
より具体的には、不活性ガスの流量とセレン化水素ガスの流量とを、予め設定された、太陽電池製造装置に供給するセレン化水素混合ガス中のセレン化水素濃度の設定値(セレン化水素濃度C[%]、C=V2/(V1+V2)×100)から決定された各流量となるように、それぞれ制御する。このようにして、ベースガス供給流路L1から不活性ガスを、原料ガス供給流路L2からセレン化水素ガスを、それぞれ混合器2へと供給する。 (Process for producing hydrogen selenide mixed gas (I))
Next, 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
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). Control is performed so that each flow rate is determined from the hydrogen concentration C [%], C = V 2 / (V 1 + V 2 ) × 100). In this manner, 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
ここで、セレン化水素混合ガスの濃度は、特に限定されるものではなく、太陽電池製造装置の要求に応じて、適宜選択することができる。具体的には、例えば、セレン化水素混合ガス中のセレン化水素の濃度を、5~20vol%とすることができる。 Next, the inert gas and hydrogen selenide gas supplied at a predetermined flow rate are mixed by the
Here, 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%.
バッファタンク3内に貯留されたセレン化水素混合ガスを、太陽電池製造装置におけるセレン化水素混合ガスの消費状況に応じて、太陽電池製造装置へ供給する。 (Hydrogen selenide mixed gas supply process (III))
The hydrogen selenide mixed gas stored in the
このようにして、セレン化水素の濃度が安定したセレン化水素混合ガスを、太陽電池製造装置に、連続的に供給する。 In the supply method of the present embodiment that does not use the
In this way, the hydrogen selenide mixed gas having a stable hydrogen selenide concentration is continuously supplied to the solar cell manufacturing apparatus.
バッファタンク3へのセレン化水素混合ガスの製造を停止した後に、以下に説明する原料ガスの流量設定値の補正プロセスを行う。この補正プロセスにより、マスフローコントローラ11の二次側(下流側)へ流す、セレン化水素ガスの流量設定値を補正する。
具体的には、原料ガス供給流路L2に設けられてセレン化水素の流量を制御するマスフローコントローラ11と、校正用のマスフローメータ16とに、同一流量の校正用ガスを流す。連続して流れる校正用ガスの流れが、それぞれの位置で測定される。そして、マスフローコントローラ11及びマスフローメータ16によって測定された校正用ガスのそれぞれの流量値の差分に応じて、マスフローコントローラ11に流すセレン化水素ガスの流量設定値を補正する。 (Source gas flow rate setting value correction process (II))
After the production of the hydrogen selenide mixed gas in the
Specifically, the calibration gas having the same flow rate is supplied to the
先ず、自動弁9を閉状態にして、セレン化水素ガスの供給を停止する。自動弁8と13も閉じられる。 Further, the correction process will be described.
First, the
なお、校正時と混合ガス製造時のガスの種類が異なる場合、あるいは、必要に応じて別途マスフローコントローラやマスフローメータのそれぞれの校正を行う際に校正時と流量測定時のガスの種類が異なる場合、流量誤差の算出前に、コンバージョンファクターと呼ばれる流量補正係数を用いて流量を換算することが好ましい。 Next, each flow rate value of the calibration gas is measured by the
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.
流量誤差の算出にあたっては、先ず、マスフローコントローラ11により、校正用ガスの流量の制御を行い、また、同時に校正用ガスの流量V3[L/min]を測定する。さらに、同時に、下流側に位置するマスフローメータ16により、校正用ガスの流量V4[L/min]を測定する。
セレン化水素混合ガス製造時において、マスフローコントローラ11を含む原料ガス供給流路L2にセレン結晶が多く析出されると、マスフローコントローラ11の流量制御精度が低下する。このとき、セレン結晶の存在の為に、セレン化水素混合ガス製造停止時にマスフローコントローラ11で測定された校正用ガスの流量V3[L/min]が、本来測定されるべき校正用ガスの流量より小さくなる傾向がある。
これに対し、マスフローメータ16は、セレン化水素混合ガス製造時において、セレン化水素ガスが流れない位置に配置されている。このため、マスフローメータ16で測定された校正用ガスの流量V4[L/min]は、本来測定されるべき校正用ガスの流量と等しくなる。
このように、セレン化水素混合ガス製造停止時に、マスフローコントローラ11及びマスフローメータ16のそれぞれで測定された校正用ガスの流量値V3,V4[L/min]の差分は、マスフローコントローラ11の流量制御精度の低下具合、さらには、マスフローコントローラ11を含む原料ガス供給流路L2のセレン結晶の析出量の程度を、正確に示している。
なお、ここではマスフローコントローラ11で測定された校正用ガスの流量V3[L/min]が本来測定されるべき校正用ガスの流量より小さくなる場合を記載している。しかしながら、本来測定されるべき校正用ガスの流量より大きくなる場合でも、同様に処理すること、すなわち補正することができる。 The calculation of the flow rate error in the present invention will be described in more detail.
In calculating the flow rate error, first, the
When a large amount of selenium crystals are precipitated in the source gas supply flow path L2 including the
On the other hand, the
As described above, when the production of the hydrogen selenide mixed gas is stopped, the difference between the flow values V 3 and V 4 [L / min] of the calibration gas measured by the
Here, the case where the flow rate V 3 [L / min] of the calibration gas measured by the
流量誤差A=(|V3-V4|/V4)×100[%]
補正係数B=V4/V3
但し、マスフローコントローラにおいて、校正時と混合ガス製造時のガスの種類が異なる場合、あるいは、必要に応じて別途マスフローコントローラの校正を行う際に校正時と流量測定時で使用されるガスの種類が一致していない場合には、コンバージョンファクターと呼ばれる流量補正係数で補正する必要がある。流量補正係数を用いてV3とV4を、校正用ガスの種類による流量値に補正した後、流量誤差A及び補正係数Bを算出する。 Specifically, 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 = (| V 3 −V 4 | / V 4 ) × 100 [%]
Correction coefficient B = V 4 / V 3
However, in the mass flow controller, if 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.
流量設定値V5[L/min]=B×V2[L/min] After calculating the flow rate error A and the correction coefficient B, the corrected hydrogen selenide gas flow rate set value V 5 [L / min] to be transmitted to the
Flow rate setting value V 5 [L / min] = B × V 2 [L / min]
なお、補正係数Bを使用するのはセレン化水素ガスの流量制御時のみとする。すなわち、校正用ガスの流量測定時は、マスフローコントローラ11に対して補正係数Bを用いた補正は行わない。 Suitable for supplying to the solar cell manufacturing apparatus using the hydrogen selenide gas flow rate setting value V 5 [L / min] corrected according to the amount of selenium crystals precipitated by the
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
例えば、セレン化水素の混合ガス製造プロセス(I)と、原料ガスの流量設定値の補正プロセス(II)を交互に2単位以上繰り返し実施した場合、1回目の製造プロセスにおける流量測定値がV3a[L/min]、この値を用いた補正プロセスにおいて得られた補正係数がBa、2回目の製造プロセスにおける流量測定値がV3b[L/min]、この値を用いた補正プロセスにおいて得られた補正係数がBbで、V3a<V3bとする。その場合、その後の製造及び補正プロセスにおいて、セレン化水素ガスの流量測定値が0~V3a[L/min]の場合に適用する補正係数はBa、V3a~V3b[L/min]の場合に適用する補正係数はBbとすることができる。 When the hydrogen selenide mixed gas production process (I) and the correction process (II) of the raw material gas flow rate setting value are alternately repeated two or more units, the raw material gas flow rate setting value correction process (II) The process 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.
For example, when the hydrogen gas selenide mixed gas production process (I) and the raw material gas flow rate setting value correction process (II) are repeated two or more units alternately, 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], and obtained in the correction process using this value. The obtained correction coefficient is Bb , and V 3a <V 3b . In that case, in the subsequent manufacturing and correction processes, 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]. the correction factor to be applied to the case of can be B b.
例えば、上記実施形態の供給装置101は、マスフローメータ16を分岐流路L4に設けた構成とした。しかしながら、図6に記載の供給装置102のように、マスフローメータ16を自動弁14の一次側(上流側)のバイパス流路L3に設けてもよい。前述したように、自動弁14の一次側のバイパス流路L3にはセレン化水素ガスが流れない。このため、上述した供給装置101と同様に、セレン化水素ガスが流れない流路にマスフローメータ16を設けることができる。従って、分岐流路L4を設けなくてもよくなり、上述の実施形態の効果に加えて、供給装置を小型にすることができる。その結果、短時間周期のバルブ開閉等の緻密な機器操作や大容量のバッファタンクを必要とすることなく、長期的に安定したセレン化水素濃度のセレン化水素混合ガスが太陽電池製造装置等に供給される。 The technical scope of the present invention is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention.
For example, the
以下、本発明の好ましい具体例を示す。
(実施例)
図1に示す供給装置101を用いてセレン化水素混合ガスを製造し、太陽電池製造装置にセレン化水素混合ガスを、連続して長期間供給した。供給装置101のセレン化水素混合ガスの製造プロセスを行う際には、表1の条件を用いた。また、供給装置101の原料ガスの流量設定値の補正プロセスを行う際には、表2の条件を用いた。 Examples Hereinafter, preferred specific examples of the present invention will be shown.
(Example)
The hydrogen selenide mixed gas was manufactured using the
・表2に記載される“1回”とは、1回の流量設定値の補正を行う為に行われる製造プロセスと補正プロセスの組み合わせの回数であり、本実施例ではこれが複数回繰り返される。 In Table 2, the flow rate measurement value V3 of the
“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.
供給装置101の原料ガスの流量設定値の補正プロセスを実施する時に、マスフローコントローラ11のセレン化水素の流量設定値V2[L/min]の補正に補正係数Bを使用しないこと以外は、実施例と同じ条件で、セレン化水素混合ガスを製造し、太陽電池製造装置にセレン化水素混合ガスを連続して供給した。すなわち、補正プロセスは実施するものの、マスフローコントローラ11で補正された流量を使用せずに、製造及び供給を行った。実施例と同じく、流路L6に設置したセレン化水素濃度分析計を用いてセレン化水素混合ガス中のセレン化水素濃度の経時変化を測定した。このときのセレン化水素混合ガス中のセレン化水素濃度の時間(日数)依存性を図2に示す。 (Comparative example)
When the correction process of the flow rate setting value of the raw material gas of the
図2に示すように、比較例では測定開始から約40日が過ぎるまでは、セレン化水素混合ガス中のセレン化水素濃度が所定濃度の10.0%付近を保っている。しかしながら、さらに日数が経過すると、セレン化水素濃度が急激に増大している。
また、図3に示す流量誤差Aのセレン化水素濃度の時間(日数)依存性においても、測定開始から約40日以降の日数が経過すると、流量誤差Aが急激に増大している。その結果、比較例において測定開始から100日目には、セレン化水素混合ガス中のセレン化水素濃度が13.8%に達した。
このようにセレン化水素濃度が上昇する要因としては、補正係数Bを用いたマスフローコントローラ11のセレン化水素の流量設定値V2[L/min]の補正がなされなかったために、マスフローコントローラ11の流量制御精度が低下したことが挙げられる。 (Comparison of measurement results of Examples and Comparative Examples)
As shown in FIG. 2, in the comparative example, the hydrogen selenide concentration in the hydrogen selenide mixed gas is maintained around 10.0% of the predetermined concentration until about 40 days have passed since the start of measurement. However, as the number of days elapses, the concentration of hydrogen selenide increases rapidly.
Moreover, also in the time (days) dependence of the hydrogen selenide concentration of the flow rate error A shown in FIG. 3, the flow rate error A rapidly increases when the number of days after about 40 days has elapsed since the start of measurement. As a result, the hydrogen selenide concentration in the hydrogen selenide mixed gas reached 13.8% on the 100th day from the start of measurement in the comparative example.
As a factor for increasing the hydrogen selenide concentration in this manner, the correction of the hydrogen selenide flow rate setting value V 2 [L / min] of the
3,118…バッファタンク
4,21,23,104,114,115…開閉バルブ
5,10,105,110…圧力調整計
6,11,106,111…マスフローコントローラ(流量制御手段)
7,12,107,112…逆止弁
8,9,13,108,109,113…自動弁
14,15…自動弁(開閉弁)
16…マスフローメータ(流量測定手段)
19…制御手段
22,116…圧力計
L1,L101…ベースガス供給流路
L2,L102…原料ガス供給流路
L3,L105…バイパス流路
L4…分岐流路
L5,L6,L7,L103,L104…流路
E1,E2…配線
101,102、103、201,202…供給装置 2, 117 ...
7, 12, 107, 112 ...
16. Mass flow meter (flow rate measuring means)
19 ... Control means 22, 116 ... Pressure gauge L1, L101 ... Base gas supply flow path L2, L102 ... Raw material gas supply flow path L3, L105 ... Bypass flow path L4 ... Branch flow paths L5, L6, L7, L103, L104 ... Flow path E1, E2 ...
Claims (11)
- ベースガス供給流路から供給される不活性ガスと、原料ガス供給流路から供給されるセレン化水素ガスと、を混合して、所定の濃度に調製されたセレン化水素混合ガスを製造する工程と、前記混合ガスを供給する工程を有する、セレン化水素混合ガスの供給方法であって、
更に、セレン化水素混合ガスを製造する工程を停止している間に、原料ガスの流量設定値を補正する工程を含み、
前記補正工程が、
前記原料ガス供給流路に設けられて前記セレン化水素ガスの流量を制御する流量制御手段と、校正用の流量測定手段とに、同一流量の校正用ガスを流す工程と、
前記流量制御手段及び前記流量測定手段によって測定された前記校正用ガスのそれぞれの流量値の差分を得る工程と、
前記差分に応じて、前記流量制御手段が流す前記セレン化水素ガスの流量値を補正する工程と、
を含むことを特徴とするセレン化水素混合ガスの供給方法。 A process for producing a hydrogen selenide mixed gas prepared at a predetermined concentration by mixing an inert gas supplied from a base gas supply channel and a hydrogen selenide gas supplied from a source gas supply channel And a method for supplying a hydrogen selenide mixed gas, comprising the step of supplying the mixed gas,
Furthermore, the process of correcting the flow rate setting value of the source gas while stopping the process of producing the hydrogen selenide mixed gas,
The correction step includes
A flow control means for controlling the flow rate of the hydrogen selenide gas provided in the source gas supply flow path, and a flow of calibration gas having the same flow rate to the flow measurement means for calibration;
Obtaining a difference between the flow rate values of the calibration gas measured by the flow rate control means and the flow rate measurement means;
Correcting the flow rate value of the hydrogen selenide gas that the flow rate control means flows according to the difference; and
A method for supplying a hydrogen selenide mixed gas, comprising: - 前記校正用ガスを、前記流量制御手段と前記流量測定手段とに、順不同で連続して流すことを特徴とする請求項1に記載のセレン化水素混合ガスの供給方法。 2. The method for supplying a hydrogen selenide mixed gas according to claim 1, wherein the calibration gas is continuously flowed through the flow rate control means and the flow rate measurement means in any order.
- 前記流量制御手段と前記流量測定手段とに、同一の仕様の流量測定方法を用いることを特徴とする請求項1又は2に記載のセレン化水素混合ガスの供給方法。 The method for supplying a hydrogen selenide gas mixture according to claim 1 or 2, wherein a flow rate measuring method having the same specifications is used for the flow rate control means and the flow rate measuring means.
- 前記校正用ガスとして、前記不活性ガスを用いることを特徴とする請求項1乃至3のいずれか一項に記載のセレン化水素混合ガスの供給方法。 The method for supplying a hydrogen selenide mixed gas according to any one of claims 1 to 3, wherein the inert gas is used as the calibration gas.
- 前記セレン化水素混合ガスを製造する際に、前記セレン化水素ガスを前記流量測定手段に流さないことを特徴とする請求項1乃至4のいずれか一項に記載のセレン化水素混合ガスの供給方法。 The supply of hydrogen selenide mixed gas according to any one of claims 1 to 4, wherein when the hydrogen selenide mixed gas is produced, the hydrogen selenide gas is not passed through the flow rate measuring means. Method.
- ベースガス供給流路から供給される不活性ガスと、原料ガス供給流路から供給されるセレン化水素ガスと、を混合して、所定の濃度に調製されたセレン化水素混合ガスを製造し、その後、供給する、セレン化水素混合ガスの供給装置であって、
前記原料ガス供給流路に設けられて前記セレン化水素ガスの流量を制御する流量制御手段と、
前記セレン化水素混合ガスの製造停止時に、校正用ガスを前記原料ガス供給流路の前記流量制御手段の一次側へと供給する校正用ガス供給流路と、
前記セレン化水素混合ガスの製造停止時には前記校正用ガスが流れるとともに前記セレン化水素混合ガスの製造時に前記セレン化水素ガスが流れない流路に設けられた校正用の流量測定手段と、
前記流量制御手段及び前記流量測定手段に同一流量の前記校正用ガスを流した際に、それぞれ測定された校正用ガスの流量値の差分に応じて、前記流量制御手段が流す前記セレン化水素ガスの流量値を補正する制御手段と、を備えることを特徴とするセレン化水素混合ガスの供給装置。 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 to a predetermined concentration, Thereafter, a hydrogen selenide mixed gas supply device to be supplied,
A flow rate control means for controlling the flow rate of the hydrogen selenide gas provided in the source gas supply flow path;
A calibration gas supply flow path for supplying a calibration gas to the primary side of the flow rate control means of the source gas supply flow path when production of the hydrogen selenide mixed gas is stopped;
A flow rate measuring means for calibration provided in a flow path through which the calibration gas flows when the production of the hydrogen selenide mixed gas stops and the hydrogen selenide gas does not flow during the production of the hydrogen selenide mixed gas;
The hydrogen selenide gas that is flowed by the flow control means according to the difference in the flow rate value of the calibration gas measured when the same flow of the calibration gas is passed through the flow control means and the flow measurement means. And a control means for correcting the flow rate value of the hydrogen selenide mixed gas supply device. - 前記校正用ガス供給流路には、前記セレン化水素混合ガスの製造時に閉状態となり、前記校正用ガスを前記校正用ガス供給流路から前記原料ガス供給流路へと供給する際に開状態となる、第1の開閉弁が設けられており、
前記校正用ガス供給流路の前記第1の開閉弁の一次側に、前記流量測定手段が設けられていることを特徴とする請求項6に記載のセレン化水素混合ガスの供給装置。 The calibration gas supply channel is closed when the hydrogen selenide mixed gas is produced, and is opened when the calibration gas is supplied from the calibration gas supply channel to the source gas supply channel. A first on-off valve is provided,
The hydrogen selenide mixed gas supply apparatus according to claim 6, wherein the flow rate measuring means is provided on a primary side of the first on-off valve of the calibration gas supply flow path. - 前記校正用ガス供給流路が、前記ベースガス供給流路と前記原料ガス供給流路の前記流量制御手段の一次側とを接続するバイパス流路であることを特徴とする請求項6に記載するセレン化水素混合ガスの供給装置。 7. The calibration gas supply flow path is a bypass flow path that connects the base gas supply flow path and a primary side of the flow rate control means of the source gas supply flow path. Hydrogen selenide mixed gas supply device.
- 前記バイパス流路には、前記セレン化水素混合ガスの製造時に閉状態となり、前記不活性ガスを校正用ガスとして前記ベースガス供給流路から前記原料ガス供給流路へと供給する際に開状態となる、第1の開閉弁が設けられており、
前記バイパス流路の前記第1の開閉弁の一次側に、前記流量測定手段が設けられていることを特徴とする請求項8に記載のセレン化水素混合ガスの供給装置。 The bypass channel is closed when the hydrogen selenide mixed gas is produced, and is opened when the inert gas is supplied as a calibration gas from the base gas supply channel to the source gas supply channel. A first on-off valve is provided,
9. The hydrogen selenide mixed gas supply device according to claim 8, wherein the flow rate measuring means is provided on a primary side of the first on-off valve of the bypass passage. - 前記原料ガス供給流路の前記流量制御手段の二次側に、分岐流路が設けられ、
前記分岐流路には、前記セレン化水素混合ガスの製造時に閉状態となり、前記不活性ガスを校正用ガスとして前記ベースガス供給流路から前記原料ガス供給流路へと供給する際に開状態となる、第2の開閉弁が設けられており、
前記分岐流路の前記第2の開閉弁の二次側に、前記流量測定手段が設けられていることを特徴とする請求項6又は8に記載のセレン化水素混合ガスの供給装置。 A branch channel is provided on the secondary side of the flow rate control means of the source gas supply channel,
The branch channel is closed when the hydrogen selenide mixed gas is produced, and is opened when the inert gas is supplied as a calibration gas from the base gas supply channel to the source gas supply channel. A second on-off valve is provided,
9. The hydrogen selenide mixed gas supply device according to claim 6, wherein the flow rate measuring means is provided on the secondary side of the second on-off valve of the branch flow path. - 前記流量制御手段と前記流量測定手段とが、同一の仕様の流量測定方法であることを特徴とする請求項6乃至10のいずれか一項に記載の太陽電池用セレン化水素混合ガスの供給装置。 The apparatus for supplying a hydrogen selenide mixed gas for a solar cell according to any one of claims 6 to 10, wherein the flow rate control means and the flow rate measurement means are flow rate measurement methods having the same specifications. .
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014543279A JP6065329B2 (en) | 2012-10-22 | 2013-10-21 | Method and apparatus for supplying hydrogen selenide mixed gas |
CN201380052051.2A CN104769727B (en) | 2012-10-22 | 2013-10-21 | The supply method of Selenium hydride. mixed gas and feedway |
KR1020157006775A KR101661483B1 (en) | 2012-10-22 | 2013-10-21 | Method and device for supplying hydrogen-selenide mixed gas |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-232832 | 2012-10-22 | ||
JP2012232832 | 2012-10-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014065233A1 true WO2014065233A1 (en) | 2014-05-01 |
Family
ID=50544613
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/078444 WO2014065233A1 (en) | 2012-10-22 | 2013-10-21 | Method and device for supplying hydrogen-selenide mixed gas |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6065329B2 (en) |
KR (1) | KR101661483B1 (en) |
CN (1) | CN104769727B (en) |
TW (1) | TWI618672B (en) |
WO (1) | WO2014065233A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109865440A (en) * | 2019-03-29 | 2019-06-11 | 国网山东省电力公司电力科学研究院 | A kind of standard gas preparation device |
JP2020105577A (en) * | 2018-12-27 | 2020-07-09 | 株式会社フジキン | Fluid supply device |
CN113874547A (en) * | 2019-11-12 | 2021-12-31 | 昭和电工株式会社 | Method for removing deposit and method for forming film |
WO2024038827A1 (en) * | 2022-08-17 | 2024-02-22 | 大陽日酸株式会社 | Mixed gas supply device |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102016003875A1 (en) * | 2016-03-31 | 2017-10-05 | Linde Aktiengesellschaft | Volumetric and gravimetric level for the production of gas mixtures |
JP6904231B2 (en) * | 2017-12-13 | 2021-07-14 | 東京エレクトロン株式会社 | Substrate processing method, storage medium and raw material gas supply device |
KR20200050607A (en) | 2018-11-02 | 2020-05-12 | 알엠아이텍(주) | Method for producing hydrogen selenide based on zinc selenide |
CN112097114A (en) * | 2020-08-07 | 2020-12-18 | 安徽亚格盛电子新材料有限公司 | Device for accurately preparing liquid MO source and hydrogen mixed gas |
KR102431346B1 (en) * | 2022-02-11 | 2022-08-09 | 박재기 | Gas supply system that can replace the flow controller without interruption of the process |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11265218A (en) * | 1998-03-18 | 1999-09-28 | Kokusai Electric Co Ltd | Automatic flow/flow ratio conversion data calibrating device and gas supplying device |
JP2011057455A (en) * | 2009-09-04 | 2011-03-24 | Taiyo Nippon Sanso Corp | Method and apparatus for supplying hydrogen selenide-mixed gas for solar cell |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011027663A1 (en) * | 2009-09-04 | 2011-03-10 | 大陽日酸株式会社 | Method and apparatus for supplying hydrogen selenide mixed gas for solar cell |
JP5663488B2 (en) | 2009-10-14 | 2015-02-04 | 大陽日酸株式会社 | Method and apparatus for supplying hydrogen selenide mixed gas for solar cell |
-
2013
- 2013-10-21 WO PCT/JP2013/078444 patent/WO2014065233A1/en active Application Filing
- 2013-10-21 JP JP2014543279A patent/JP6065329B2/en not_active Expired - Fee Related
- 2013-10-21 CN CN201380052051.2A patent/CN104769727B/en not_active Expired - Fee Related
- 2013-10-21 KR KR1020157006775A patent/KR101661483B1/en active IP Right Grant
- 2013-10-22 TW TW102138027A patent/TWI618672B/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11265218A (en) * | 1998-03-18 | 1999-09-28 | Kokusai Electric Co Ltd | Automatic flow/flow ratio conversion data calibrating device and gas supplying device |
JP2011057455A (en) * | 2009-09-04 | 2011-03-24 | Taiyo Nippon Sanso Corp | Method and apparatus for supplying hydrogen selenide-mixed gas for solar cell |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020105577A (en) * | 2018-12-27 | 2020-07-09 | 株式会社フジキン | Fluid supply device |
CN109865440A (en) * | 2019-03-29 | 2019-06-11 | 国网山东省电力公司电力科学研究院 | A kind of standard gas preparation device |
CN109865440B (en) * | 2019-03-29 | 2021-08-31 | 国网山东省电力公司电力科学研究院 | Standard gas preparation device |
CN113874547A (en) * | 2019-11-12 | 2021-12-31 | 昭和电工株式会社 | Method for removing deposit and method for forming film |
WO2024038827A1 (en) * | 2022-08-17 | 2024-02-22 | 大陽日酸株式会社 | Mixed gas supply device |
Also Published As
Publication number | Publication date |
---|---|
KR101661483B1 (en) | 2016-09-30 |
TWI618672B (en) | 2018-03-21 |
CN104769727A (en) | 2015-07-08 |
JPWO2014065233A1 (en) | 2016-09-08 |
KR20150044437A (en) | 2015-04-24 |
JP6065329B2 (en) | 2017-01-25 |
CN104769727B (en) | 2016-12-07 |
TW201427896A (en) | 2014-07-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6065329B2 (en) | Method and apparatus for supplying hydrogen selenide mixed gas | |
US9556518B2 (en) | Raw material gas supply apparatus for semiconductor manufacturing equipment | |
JP3174856B2 (en) | Mixed gas supply device | |
US8794261B2 (en) | Fluid control system and fluid control method | |
EP2466412B1 (en) | Gas concentration controller system | |
JP5518404B2 (en) | Method and apparatus for supplying hydrogen selenide mixed gas for solar cell | |
US20120227816A1 (en) | Dynamic gas blending | |
KR101641194B1 (en) | Method And Apparatus For Supplying Hydrogen Selenide Mixed Gas For Solar Cells | |
JP5548208B2 (en) | Method and apparatus for supplying hydrogen selenide mixed gas for solar cell | |
CN111408289A (en) | Method and system for industrially continuously mixing gas with high precision | |
CN107519773B (en) | Large-concentration-range standard gas distribution instrument with calibration function and calibration method thereof | |
CN111394789A (en) | Gas inlet structure, gas inlet method and gas inlet equipment of chemical vapor deposition equipment | |
CN103309369B (en) | The accurate gas control method of optical system internal chamber and device thereof | |
JP5873231B2 (en) | Supply device and supply method of hydrogen selenide mixed gas for solar cell | |
JP6008688B2 (en) | Method for supplying hydrogen selenide mixed gas for solar cell | |
KR20080082818A (en) | Gas dilution apparatus using mass flow controller | |
JP5378122B2 (en) | Method and apparatus for supplying hydrogen selenide mixed gas for solar cell | |
US20230285911A1 (en) | Facility and method for distributing a gas mixture for doping silicon wafers | |
JP2021159900A (en) | Mixed gas supply device and method | |
JP2010232521A (en) | Processing liquid supply device, and processing liquid supply method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13848823 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014543279 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20157006775 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13848823 Country of ref document: EP Kind code of ref document: A1 |