TWI618672B - Method and apparatus for supplying gas mixture including hydrogen selenide - Google Patents
Method and apparatus for supplying gas mixture including hydrogen selenide Download PDFInfo
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- TWI618672B TWI618672B TW102138027A TW102138027A TWI618672B TW I618672 B TWI618672 B TW I618672B TW 102138027 A TW102138027 A TW 102138027A TW 102138027 A TW102138027 A TW 102138027A TW I618672 B TWI618672 B TW I618672B
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- hydrogen
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- selenide
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- 239000007789 gas Substances 0.000 title claims abstract description 596
- 229910000058 selane Inorganic materials 0.000 title claims abstract description 300
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 title claims abstract 29
- 238000000034 method Methods 0.000 title claims description 35
- 239000000203 mixture Substances 0.000 title description 3
- 239000002994 raw material Substances 0.000 claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 claims description 99
- 238000012937 correction Methods 0.000 claims description 62
- 239000011261 inert gas Substances 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 45
- 238000005259 measurement Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 286
- 239000011669 selenium Substances 0.000 description 16
- 229910052711 selenium Inorganic materials 0.000 description 15
- 238000011144 upstream manufacturing Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003346 selenoethers Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 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
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 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
- 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
- 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
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/04—Binary compounds including binary selenium-tellurium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
在設置於原料氣體供給流路控制原料氣體的硒化氫氣體之流量的流量控制器與校正用的流量測定器，流通相同流量的校正用氣體，配合經流量控制器與流量測定器測定的校正用氣體之各別流量值的差分，修正流經流量控制器的硒化氫氣體之流量的設定值。 The flow rate controller that controls the flow rate of the hydrogen selenide gas in the raw material gas supply flow path to control the raw material gas and the flow rate measuring device for calibration flow the calibration gas at the same flow rate, and the calibration is performed by the flow rate controller and the flow rate measuring device. The set value of the flow rate of the hydrogen selenide gas flowing through the flow controller is corrected by the difference between the respective flow values of the gas.
Description
本發明是有關硒化氫混合氣體的供給方法及供給裝置。 The present invention relates to a method and a supply device for supplying a hydrogen-selenide mixed gas.
本申請案基於主張2012年10月22日對日本提出的特願2012一232832號之優先權，在本發明中援用該內容。 The present application is based on the priority of Japanese Patent Application No. 2012-232832, filed on Oct. 22, 2012, to Japan, which is incorporated herein.
近年來，由於環境污染、地球暖化、石化燃料枯竭的問題，而使替代石油能源的太陽能電池受到矚目。現在，太陽能電池的主流，是使用含有銅、銦、鉀及硒的使用硒化氫(H2Se)氣體形成的黃銅礦型之光吸收層的化合物太陽能電池。在此化合物太陽能電池的製造裝置中，必需供給已調整成預定濃度的硒化氫之混合氣體。 In recent years, solar cells that replace petroleum energy have attracted attention due to environmental pollution, global warming, and depletion of fossil fuels. Nowadays, the mainstream of solar cells is a compound solar cell using a chalcopyrite type light absorbing layer formed using hydrogen selenide (H 2 Se) gas containing copper, indium, potassium and selenium. In the apparatus for manufacturing a compound solar cell, it is necessary to supply a mixed gas of hydrogen selenide adjusted to a predetermined concentration.
然而，欲實現化合物太陽能電池的大量生產時，必需供給大量的硒化氫混合氣體至太陽能電池製造裝置中。因此，在使用已填充經調整成預定濃度的混合氣體之氣體缸瓶時，將使缸瓶的交換頻率變多，而有所謂未能確保充分的氣體供給量的問題。 However, in order to realize mass production of a compound solar cell, it is necessary to supply a large amount of hydrogen selenide mixed gas to the solar cell manufacturing apparatus. Therefore, when a gas cylinder bottle that has been filled with a mixed gas adjusted to a predetermined concentration is used, the exchange frequency of the cylinder bottle is increased, and there is a problem that a sufficient gas supply amount cannot be ensured.
為解決上述問題，以往使用第4圖中表示的硒化氫 混合氣體之供給裝置(以下，簡稱「供給裝置」)201。在供給裝置201中，設置基本氣體供給流路L101與原料氣體供給流路L102。各別的流路內，可分別流通惰性氣體與濃度100%的硒化氫氣體(以下，簡稱「硒化氫氣體」)。同時，在基本氣體供給流路L101與原料氣體供給流路L102上，分別設置基本氣體流量控制器106與原料氣體流量控制器111。而且，在基本氣體供給流路L101與原料氣體供給流路L102之下游側，設置貯留已混合惰性氣體與硒化氫氣體的硒化氫混合氣體之緩衝槽118。 In order to solve the above problems, the hydrogen selenide shown in Fig. 4 has been used in the past. A supply device of a mixed gas (hereinafter simply referred to as "supply device") 201. In the supply device 201, a basic gas supply flow path L101 and a raw material gas supply flow path L102 are provided. In the respective flow paths, an inert gas and a hydrogen selenide gas having a concentration of 100% (hereinafter referred to as "selenide gas") may be separately distributed. At the same time, the basic gas flow rate controller 106 and the material gas flow rate controller 111 are provided on the basic gas supply flow path L101 and the material gas supply flow path L102, respectively. Further, on the downstream side of the basic gas supply flow path L101 and the raw material gas supply flow path L102, a buffer tank 118 for storing a hydrogen-selenide mixed gas in which an inert gas and a hydrogen selenide gas are mixed is stored.
在使用供給裝置201的硒化氫混合氣體之供給方法(以下，簡稱「供給方法」)中，以使硒化氫混合氣體之硒化氫濃度成為預定濃度之方式，藉由基本氣體及原料氣體的流量控制器106、111，分別控制惰性氣體與硒化氫氣體的流量。然後，使用混合器117，將經控制流量的惰性氣體與硒化氫氣體混合，然後，將所得的硒化氫混合氣體貯留在緩衝槽118中。貯留在緩衝槽118中的預定硒化氫濃度的硒化氫混合氣體，可連續供給至太陽能電池的製造裝置。 In the method of supplying a hydrogen-selenide mixed gas using the supply device 201 (hereinafter, simply referred to as "supply method"), the basic gas and the material gas are used so that the hydrogen selenide concentration of the hydrogen-selenide mixed gas becomes a predetermined concentration. The flow controllers 106, 111 control the flow rates of the inert gas and the hydrogen selenide gas, respectively. Then, a controlled flow of inert gas is mixed with hydrogen selenide gas using a mixer 117, and then the resulting hydrogen selenide mixed gas is stored in the buffer tank 118. The hydrogen-selenide mixed gas of the predetermined hydrogen selenide concentration stored in the buffer tank 118 can be continuously supplied to the manufacturing apparatus of the solar cell.
然而，供給裝置201中，有以下的問題。即，在可流通硒化氫氣體的原料氣體供給流路L102、開關閥109、113、原料氣體流量控制器111等中，有硒化氫自行分解而造成硒(Se)結晶析出的問題。尤其是，由於在原料氣體流量控制器111中析出硒結晶，而使原料氣體流量控制器111的流量測定精度及流量控制精度降低，其結果是，使預先設定的硒化氫混合氣體之濃度設定值，與實際上經供給裝置201調整的硒化氫混合氣體之濃度實測值之差有變大的問題(此稱為漂移現象)。 However, the supply device 201 has the following problems. In other words, in the raw material gas supply flow path L102 through which the hydrogen selenide gas can flow, the on-off valves 109 and 113, the raw material gas flow rate controller 111, and the like, there is a problem that selenide spontaneously decomposes and selenium (Se) crystals are precipitated. In particular, since selenium crystals are precipitated in the material gas flow rate controller 111, the flow rate measurement accuracy and flow rate control accuracy of the material gas flow rate controller 111 are lowered, and as a result, the concentration of the previously set hydrogen selenide mixed gas is set. The value has a problem that the difference between the measured values of the concentrations of the hydrogen-selenide mixed gas actually adjusted by the supply device 201 becomes large (this is called a drift phenomenon).
可抑制此種漂移現象的技術，例如專利文獻1揭示可使濃度設定值的硒化氫混合氣體安定供給的供給方法及供給裝置。如第5圖中所示，專利文獻1的供給裝置202，除了第4圖中表示的供給裝置201之構成外，也具備可連通基本氣體供給流路L101與原料氣體供給流路L102的旁通流路L105。因此，如專利文獻1中不使用旁通流路L105製造混合氣體而貯留在緩衝槽118之後，將設定量的硒化氫氣體由原料氣體供給流路L102導出至緩衝槽118，並在之後介著旁通流路L105自原料氣體供給流路L102導出設定量的惰性氣體，而調製預定的硒化氫濃度之硒化氫混合氣體，且使殘留在原料氣體供給流路L102中的硒化氫之體積濃度成為10%以下。 A technique for suppressing such a drift phenomenon. For example, Patent Document 1 discloses a supply method and a supply device for stably supplying a hydrogen-selenide mixed gas having a concentration set value. As shown in Fig. 5, the supply device 202 of Patent Document 1 includes a bypass that can communicate with the basic gas supply flow path L101 and the material gas supply flow path L102 in addition to the configuration of the supply device 201 shown in Fig. 4 . Flow path L105. Therefore, in Patent Document 1, after the mixed gas is produced without using the bypass flow path L105 and stored in the buffer tank 118, a set amount of hydrogen selenide gas is led out from the material gas supply flow path L102 to the buffer tank 118, and The bypass flow path L105 derives a predetermined amount of inert gas from the raw material gas supply flow path L102 to prepare a hydrogen selenide mixed gas having a predetermined hydrogen selenide concentration, and causes the hydrogen selenide remaining in the raw material gas supply flow path L102. The volume concentration is 10% or less.
[專利文獻1]國際公開第2011/045983A1號 [Patent Document 1] International Publication No. 2011/045983A1
不過，專利文獻1所述的供給方法中，在介著旁通流路L105而以惰性氣體導出原料氣體供給流路L102內的硒化氫氣體時，有要求例如以0.1秒為單位操作閥般精密之機器操作的問題。同時此時，將使自原料氣體供給流路L102流出的硒化氫氣體濃度由100%大變動至接近0%。因此，如欲抑制緩衝槽內的硒化氫濃度之變動，有需要大容量緩衝槽的問題。 However, in the supply method described in Patent Document 1, when the hydrogen selenide gas in the material gas supply flow path L102 is led out by the inert gas through the bypass flow path L105, it is required to operate the valve in units of, for example, 0.1 second. The problem of precision machine operation. At the same time, the concentration of the hydrogen selenide gas flowing out of the material gas supply flow path L102 is greatly changed from 100% to nearly 0%. Therefore, in order to suppress the fluctuation of the concentration of hydrogen selenide in the buffer tank, there is a problem that a large-capacity buffer tank is required.
並且，在文獻1的方法中，可使殘留在原料氣體供 給流路L102中的硒化氫之體積濃度為10%以下，只有在原料氣體供給流路L102上不供給硒化氫混合氣體時而已，在供給硒化氫混合氣體時，則完全不能防止原料氣體供給流路L102中的硒結晶之析出。因此，如使供給裝置202長期運作，即有顯現漂移現象的問題。 Moreover, in the method of Document 1, it is possible to remain in the raw material gas supply. The volume concentration of the hydrogen selenide in the flow path L102 is 10% or less, and only when the hydrogen-selenide mixed gas is not supplied to the raw material gas supply flow path L102, when the hydrogen-selenide mixed gas is supplied, the raw material cannot be prevented at all. The selenium crystals in the gas supply flow path L102 are precipitated. Therefore, if the supply device 202 is operated for a long period of time, there is a problem that a drift phenomenon appears.
因此本發明的目的是提供一種硒化氫混合氣體的供給方法及供給裝置，其不需要精密的機器操作及大容量的緩衝槽，就能長期抑制漂移現象而供給安定的硒化氫濃度之硒化氫混合氣體。 Therefore, an object of the present invention is to provide a method and a supply device for a hydrogen-selenide mixed gas, which can provide a stable selenide concentration selenium for a long period of time without requiring precise machine operation and a large-capacity buffer tank. Hydrogen mixed gas.
為解決上述問題，本發明的第一形態可提供以下的方法。 In order to solve the above problems, the first aspect of the present invention can provide the following method.
即，(1)可提供一種硒化氫混合氣體的供給方法，其具有：將自基本氣體供給流路供給的惰性氣體與自原料氣體供給流路供給的硒化氫氣體混合而製造調製成預定濃度的硒化氫混合氣體的製造步驟，與供給前述混合氣體的步驟，並且包含：在停止製造硒化氫混合氣體的步驟期間修正原料氣體的流量設定值之步驟，前述修正步驟包含：在設置於前述原料氣體供給流路上而控制前述硒化氫氣體的流量之流量控制器與校正用的流量測定器流通相同流量的校正用氣體步驟；獲得由前述流量控制器及前述流量測定器測定的前述校正用氣體之各別流量值之差分的步驟；以及配合前述差分而修正流經前述流量控制器的前述硒化氫氣體之流量值的步驟。 In other words, (1) a method for supplying a hydrogen-selenide mixed gas, comprising: mixing an inert gas supplied from a basic gas supply flow path and hydrogen selenide gas supplied from a raw material gas supply flow path, and preparing the preparation into a predetermined a step of producing a mixed hydrogen-selenide mixed gas, and a step of supplying the mixed gas, and comprising: a step of correcting a flow rate set value of the raw material gas during the step of stopping the production of the hydrogen-selenide mixed gas, wherein the correcting step includes: setting a flow rate controller for controlling a flow rate of the hydrogen selenide gas on the source gas supply flow path and a flow rate measuring device for correcting a flow rate of a calibration flow rate; and obtaining the flow rate controller and the flow rate measuring device a step of correcting a difference between respective flow rate values of the gas for calibration; and a step of correcting a flow rate value of the hydrogen selenide gas flowing through the flow rate controller in accordance with the difference.
上述(1)的形態，宜具有以下的特徵。 The form of the above (1) preferably has the following features.
(2)使前述校正用氣體以不同順序連續流經前述流量控制器和前述流量測定器。 (2) The calibration gas is continuously flowed through the flow controller and the flow rate measuring device in a different order.
(3)在前述流量控制器與前述流量測定器，使用相同規格的流量測定方法。 (3) The flow rate measuring method of the same specification is used for the flow rate controller and the flow rate measuring device.
(4)上述(1)至(3)的任一項中，使用前述惰性氣體作為前述校正用氣體。 (4) In any one of (1) to (3) above, the inert gas is used as the calibration gas.
(5)上述(1)至(4)的任一項中，在製造前述硒化氫混合氣體之際，不使前述硒化氫氣體流經校正用的前述流量測定器。 (5) In any one of the above (1) to (4), the hydrogen selenide gas is not caused to flow through the flow rate measuring device for calibration when the hydrogen selenide mixed gas is produced.
(6)本發明的第二形態，可提供以下的裝置。 (6) According to a second aspect of the present invention, the following device can be provided.
即，提供一種硒化氫混合氣體的供給裝置，其係將自基本氣體供給流路供給的惰性氣體與自原料氣體供給流路供給的硒化氫氣體混合而製造調製為預定濃度的硒化氫混合氣體，然後進行供給的裝置，其具備：設置於前述原料氣體供給流路而控制前述硒化氫氣體之流量的流量控制器；於停止製造前述硒化氫混合氣體時，對前述原料氣體供給流路的前述流量控制器之一次側供給校正用氣體的校正用氣體供給流路；設置在停止製造前述硒化氫混合氣體時流通前述校正用氣體，並且在製造前述硒化氫混合氣體時不流通前述硒化氫氣體的流路上的校正用流量測定器；以及在前述流量控制器及前述流量測定器流通相同流量的前述校正用氣體流通之際，配合分別測定的校正用氣體流量值的差分，修正流經流量控制器的前述硒化氫氣體之流量值的控制器。 In other words, a hydrogen selenide mixed gas supply device is provided which mixes an inert gas supplied from a basic gas supply flow path with hydrogen selenide gas supplied from a raw material gas supply flow path to produce hydrogen selenide prepared to a predetermined concentration. And a device for supplying a mixed gas, comprising: a flow rate controller installed in the raw material gas supply flow path to control a flow rate of the hydrogen selenide gas; and when the production of the hydrogen-selenide mixed gas is stopped, the raw material gas is supplied a correction gas supply flow path for supplying a correction gas to the primary side of the flow rate controller; and a calibration gas supply flow when the production of the hydrogen-selenide mixed gas is stopped, and not when the hydrogen selenide mixed gas is produced a flow rate measuring device for correcting flow in the flow of the hydrogen selenide gas; and a difference between the flow rates of the corrected gas flows measured when the flow rate controller and the flow rate measuring device flow the same amount of the calibration gas A controller that corrects the flow rate value of the aforementioned hydrogen selenide gas flowing through the flow controller.
(7)上述(6)中，在前述校正用氣體供給流路設置第1開關閥，其在製造前述硒化氫混合氣體時成為關閉狀態， 而在使前述校正用氣體由前述校正用氣體供給流路供給至前述原料氣體供給流路之際成為開啟狀態，在前述校正用氣體供給流路的前述第1開關閥之一次側，設置前述流量測定器。 (7) In the above (6), the first on-off valve is provided in the calibration gas supply flow path, and is turned off when the hydrogen-selenide mixed gas is produced. When the calibration gas is supplied from the calibration gas supply channel to the source gas supply channel, the gas is supplied to the source gas supply channel, and the flow rate is set on the primary side of the first switching valve of the calibration gas supply channel. Tester.
(8)上述(6)中，前述校正用氣體供給流路是旁通流路，其係將前述基本氣體供給流路和前述原料氣體供給流路之前述流量控制器的一次側予以連接。 (8) In the above (6), the calibration gas supply flow path is a bypass flow path that connects the primary side of the flow rate controller of the basic gas supply flow path and the raw material gas supply flow path.
(9)上述(8)中，在前述旁通流路上設置第1開關閥，其在製造前述硒化氫混合氣體時成為關閉狀態，而在使前述惰性氣體作為校正用氣體由前述基本氣體供給流路供給至前述原料氣體流路之際成為開啟狀態，在前述旁通流路的前述第1開關閥之一次側，設置前述流量測定器。 (9) In the above (8), the first on-off valve is provided in the bypass flow path, and is closed when the hydrogen-selenide mixed gas is produced, and the inert gas is supplied as the calibration gas from the basic gas. The flow path is turned on when the flow path is supplied to the material gas flow path, and the flow rate measuring device is provided on the primary side of the first switching valve of the bypass flow path.
(10)上述(6)或(8)中，在前述原料氣體供給流路的前述流量控制器之二次側設置分岐流路，在前述分岐流路設置第2開關閥，其在製造前述硒化氫混合氣體時成為關閉狀態，而在使前述惰性氣體作為校正用氣體由前述基本氣體供給流路供給至前述原料氣體流路之際成為開啟狀態，在前述分岐流路的前述第2開關閥之二次側，設置前述流量測定器。 (10) In the above (6) or (8), a branch flow path is provided on a secondary side of the flow rate controller of the material gas supply flow path, and a second on-off valve is provided in the branch flow path to manufacture the selenium When the hydrogen-mixed gas is turned off, the inert gas is turned on when the inert gas is supplied from the basic gas supply channel to the source gas channel, and the second on-off valve in the branching channel is opened. On the secondary side, the aforementioned flow rate measuring device is provided.
(11)上述(6)至(10)的任一項中，前述流量控制器與前述流量測定器為相同規格的流量測定方法。 (11) In any one of (6) to (10) above, the flow rate controller and the flow rate measuring device are the same as the flow rate measuring method.
依照本發明的硒化氫混合氣體之供給方法，即可在設置於原料氣體的硒化氫氣體供給流路上控制硒化氫氣體之流量的流量控制器，與校正用的流量測定器上，流通相同流量的校正用氣體。而且，形成配合經流量控制器及流量測定器測定的校正 用氣體之各別流量值之差分，修正流經流量控制器的硒化氫氣體之流量值的構成。藉此構成，即可由校正用氣體將滯留在原料氣體供給流路內的硒化氫氣體，自前述原料氣體供給流路內導出。因此，可降低硒化氫的自行分解造成之硒結晶析出。同時，可使用以校正用流量測定器測定的校正用氣體之流量值為基準，修正流經流量控制器的硒化氫氣體之流量值。因此，可使原料氣體供給流路的流量測定誤差或流量控制誤差降為極低，抑制漂移現象。所以，不需要精密的機器操作及大容量的緩衝槽，即可長期將安定的硒化氫濃度之硒化氫混合氣體供給至位於太陽能電池製造裝置等之二次側(下游側)的消耗設備。 According to the method for supplying a hydrogen-selenide mixed gas according to the present invention, a flow rate controller for controlling the flow rate of the hydrogen-selenide gas in the hydrogen selenide gas supply flow path of the source gas can be distributed to the flow rate measuring device for calibration. Calibration gas of the same flow rate. Moreover, the correction is formed in conjunction with the flow controller and the flow meter. The flow rate value of the hydrogen selenide gas flowing through the flow controller is corrected by the difference between the respective flow values of the gas. According to this configuration, the hydrogen selenide gas remaining in the source gas supply passage can be led out from the source gas supply passage by the calibration gas. Therefore, the precipitation of selenium crystals caused by self-decomposition of hydrogen selenide can be reduced. At the same time, the flow rate value of the hydrogen selenide gas flowing through the flow controller can be corrected based on the flow rate value of the calibration gas measured by the flow meter for calibration. Therefore, the flow rate measurement error or the flow rate control error of the material gas supply flow path can be made extremely low, and the drift phenomenon can be suppressed. Therefore, it is possible to supply a stable hydrogen selenide mixed gas of a hydrogen selenide concentration to a secondary device (downstream side) of a solar cell manufacturing apparatus or the like without a precise machine operation and a large-capacity buffer tank. .
同時，本發明的硒化氫混合氣體之供給裝置，具有以下的構成。即，具備流量控制器，其設置於原料氣體供給流路上控制硒化氫氣體流量；旁通流路，其在停止製造硒化氫混合氣體時，可將惰性氣體作為校正用氣體自基本氣體供給流路供給至原料氣體供給流路的流量控制器的一次側；校正用的流量測定器，其設置於在停止製造硒化氫混合氣體時流通校正用氣體、在製造硒化氫混合氣體時不流通硒化氫氣體之流路上；以及修正控制器，其在流量控制器及流量測定器流通相同流量的校正用氣體之際，配合分別測定的校正用氣體流量值的差分，修正流經流量控制器的硒化氫氣體之流量設定值。藉由具備前述構成之供給裝置，可實施上述之供給方法。 Meanwhile, the supply device of the hydrogen-selenide mixed gas of the present invention has the following constitution. That is, a flow controller is provided which is provided on the raw material gas supply flow path to control the flow rate of the hydrogen selenide gas; and a bypass flow path which supplies the inert gas as a correction gas from the basic gas when the production of the hydrogen selenide mixed gas is stopped. The flow path is supplied to the primary side of the flow rate controller of the raw material gas supply flow path, and the flow rate measuring device for calibration is provided when the calibration gas is circulated when the production of the hydrogen-selenide mixed gas is stopped, and when the hydrogen-selenide mixed gas is produced, a flow path through which the hydrogen selenide gas flows; and a correction controller that corrects the flow rate control by adjusting the difference between the corrected gas flow rate values when the flow rate controller and the flow rate measuring device circulate the calibration gas of the same flow rate The flow rate of the hydrogen selenide gas. The above-described supply method can be implemented by the supply device having the above configuration.
2、117‧‧‧混合器 2, 117‧‧ ‧ mixer
3、118‧‧‧緩衝槽 3, 118‧‧‧ buffer tank
4、21、23、104、114、115‧‧‧開關閥 4, 21, 23, 104, 114, 115‧‧‧ switch valves
5、10、105、110‧‧‧壓力調整計 5, 10, 105, 110‧‧‧ pressure adjustment meter
6、11、106、111‧‧‧流量控制器(流量控制機制) 6, 11, 106, 111‧‧‧ flow controller (flow control mechanism)
7、12、107、112‧‧‧逆止閥 7, 12, 107, 112‧‧‧ check valves
8、9、13、108、109、113‧‧‧自動閥 8, 9, 13, 108, 109, 113‧‧‧ automatic valves
14、15‧‧‧自動閥(開關閥) 14, 15‧‧‧Automatic valve (switch valve)
16‧‧‧流量測定器(流量測定機制) 16‧‧‧Flow meter (flow measurement mechanism)
19‧‧‧控制器 19‧‧‧ Controller
22、116‧‧‧壓力計 22, 116‧‧‧ pressure gauge
101、102、103、201、202‧‧‧供給裝置 101, 102, 103, 201, 202‧‧‧ supply devices
E1、E2‧‧‧配線 E1, E2‧‧‧ wiring
L1、L101‧‧‧基本氣體供給流路 L1, L101‧‧‧ basic gas supply flow path
L2、L102‧‧‧原料氣體供給流路 L2, L102‧‧‧ raw material gas supply flow path
L3、L105‧‧‧旁通流路 L3, L105‧‧‧ bypass flow path
L4‧‧‧分岐流路 L4‧‧‧ minute flow path
L5、L6、L7、L103、L104‧‧‧流路 L5, L6, L7, L103, L104‧‧‧ flow paths
第1圖係表示本發明的一實施形態之硒化氫混合氣體的供給 裝置101之示意圖。 Fig. 1 is a view showing the supply of a hydrogen selenide mixed gas according to an embodiment of the present invention. Schematic diagram of device 101.
第2圖係表示實施例中的硒化氫混合氣體之供給時間與硒化氫濃度之關係圖。 Fig. 2 is a graph showing the relationship between the supply time of the hydrogen-selenide mixed gas and the hydrogen selenide concentration in the examples.
第3圖係表示實施例中的硒化氫混合氣體之供給時間與流量誤差A之關係圖。 Fig. 3 is a graph showing the relationship between the supply time of the hydrogen-selenide mixed gas and the flow rate error A in the examples.
第4圖係表示以往的硒化氫混合氣體之供給裝置201的示意圖。 Fig. 4 is a schematic view showing a conventional hydrogen selenide mixed gas supply device 201.
第5圖係表示以往的另一硒化氫混合氣體之供給裝置202的示意圖。 Fig. 5 is a schematic view showing another conventional hydrogen selenide mixed gas supply device 202.
第6圖係表示本發明的另一實施形態之硒化氫混合氣體的供給裝置102之示意圖。 Fig. 6 is a schematic view showing a supply unit 102 of a hydrogen-selenide mixed gas according to another embodiment of the present invention.
第7圖係表示本發明的另一實施形態之硒化氫混合氣體的供給裝置103之示意圖。 Fig. 7 is a schematic view showing a supply unit 103 of a hydrogen-selenide mixed gas according to another embodiment of the present invention.
以下，利用圖面詳細說明有關適用本發明的一實施形態之硒化氫混合氣體的供給方法及硒化氫混合氣體的供給裝置。 Hereinafter, a method of supplying a hydrogen-selenide mixed gas and an apparatus for supplying a hydrogen-selenide mixed gas to which an embodiment of the present invention is applied will be described in detail with reference to the drawings.
又，以下說明中使用的圖面，為易於了解其特徵而在方便上有擴大表示特徵部份的情形，各構成要素的尺寸比率等並不限於與實際相同。同時，本發明並不限定於以下之例。在本發明的範圍內，也可能視需要而變更、省略、交換及/或追加。裝置的個數或位置，也可視需要而變更。同時，本說明書中使用的單位，濃度表示體積濃度、壓力表示壓力計壓力、流量表示體積流量。並且，本說明書中表示的體積，是基準狀態(0℃、1atm(大氣壓)) 中的體積。同時，本發明中所述之”手段(器)”，是指裝置、步驟、構件、系統及部份等之意。 Further, in the drawings used in the following description, in order to facilitate the understanding of the features, it is convenient to expand the feature portions, and the dimensional ratios and the like of the respective constituent elements are not limited to the actual ones. Meanwhile, the present invention is not limited to the following examples. It is also possible to change, omit, exchange, and/or add as needed within the scope of the present invention. The number or location of the devices can also be changed as needed. Meanwhile, the unit used in the present specification, the concentration indicates the volume concentration, the pressure indicates the pressure of the pressure gauge, and the flow rate indicates the volume flow rate. Further, the volume indicated in the present specification is a reference state (0 ° C, 1 atm (atmospheric pressure)). The volume in the middle. Also, the term "means" as used in the present invention means means, steps, components, systems, parts and the like.
(硒化氫混合氣體的供給裝置) (supply device for hydrogen selenide mixed gas)
首先，對於本實施形態的硒化氫混合氣體的供給裝置(以下，簡稱「供給裝置」)101之構成，一邊參照第1圖，一邊說明以太陽能電池製造裝置為對象的供給裝置。又，雖然在此處所述為以太陽能電池製造裝置為對象的供給裝置，但是本發明之供給裝置只要是以消耗硒化氫混合氣體之裝置為對象的供給裝置，即無特別限制，任何裝置均可使用。可舉例如：以將硒化氫混合氣體作為摻雜氣體而消耗的半導體製造裝置為對象之供給裝置等。又上述”以裝置A為對象的裝置B”等的表現，可指裝置A之外另行準備之裝置B，也可指包含裝置B作為裝置A的部份之意。 First, the configuration of the hydrogen selenide mixed gas supply device (hereinafter simply referred to as "supply device") 101 of the present embodiment will be described with reference to Fig. 1, and a supply device for the solar cell manufacturing device will be described. In addition, although the supply device for the solar cell manufacturing apparatus is described here, the supply device of the present invention is not limited to any one of the devices for consuming a hydrogen-selenide mixed gas, and any device is not particularly limited. Can be used. For example, a supply device for a semiconductor manufacturing apparatus that consumes a hydrogen-selenide mixed gas as a doping gas can be used. Further, the expression "the device B for the device A" or the like may be referred to as the device B prepared separately from the device A, or may be the portion including the device B as the device A.
如第1圖中所示，供給裝置101，是配合太陽能電池製造裝置(未圖示)的生產狀況，製造已調製成預定濃度的硒化氫混合氣體，供給至太陽能電池製造裝置的裝置。具體上，供給裝置101的概略構成，是具備基本氣體供給流路L1、原料氣體供給流路L2、流量控制器(流量控制機制)(mass flow controller)6與11、混合器2、及緩衝槽3。更具體說明，供給裝置101的概略構成，是具備供給基本氣體的基本氣體供給流路L1、供給原料氣體的原料氣體供給流路L2、控制基本氣體流量之流量控制器6、控制原料氣體流量之流量控制器11、混合已控制流量的原料氣體與基本氣體的混合器2、以及貯留經混合器2混合的原料氣體與基本氣體之硒化氫混合氣體的緩衝槽3。 As shown in Fig. 1, the supply device 101 is a device that supplies a hydrogen-selenide mixed gas that has been prepared to a predetermined concentration and is supplied to the solar cell manufacturing device in accordance with the production state of the solar cell manufacturing device (not shown). Specifically, the schematic configuration of the supply device 101 includes a basic gas supply flow path L1, a material gas supply flow path L2, flow rate controllers (mass flow controllers) 6 and 11, a mixer 2, and a buffer tank. 3. More specifically, the schematic configuration of the supply device 101 includes a basic gas supply flow path L1 for supplying a basic gas, a raw material gas supply flow path L2 for supplying a raw material gas, a flow rate controller 6 for controlling a basic gas flow rate, and a flow rate for controlling the raw material gas. The flow controller 11 is a mixer 2 that mixes the raw material gas of the controlled flow rate with the basic gas, and a buffer tank 3 that stores the mixed gas of the raw material gas mixed with the basic gas and the hydrogen selenide of the basic gas.
更具體言之，供給裝置101更具備旁通流路L3、流 量測定器(流量測定機制)(mass flow meter)16、及控制器19。又更具體說明，供給裝置101的特徵為：具備旁通流路L3，其在停止製造硒化氫混合氣體時，將基本氣體作為校正氣體，自基本氣體流路L1供給至原料供給流路L2的流量控制器11的一次側(上游側)；流量測定器16，其在製造硒化氫混合氣體時，測定供給至不流通原料氣體的流路之校正用氣體的流量；以及控制器19，其在流量控制器11與流量測定器16使相同流量的校正用氣體流通之際，配合分別測定的校正用氣體流量值的差分，修正流經流量控制器11的原料氣體之流量值。 More specifically, the supply device 101 further has a bypass flow path L3 and a flow A mass spectrometer (mass flow meter) 16, and a controller 19. More specifically, the supply device 101 is characterized in that it includes a bypass flow path L3 that supplies a basic gas as a correction gas and supplies it from the basic gas flow path L1 to the raw material supply flow path L2 when the production of the hydrogen-selenide mixed gas is stopped. The primary side (upstream side) of the flow rate controller 11 and the flow rate measuring device 16 measure the flow rate of the calibration gas supplied to the flow path of the non-circulating material gas when the hydrogen-selenide mixed gas is produced; and the controller 19, When the flow rate controller 11 and the flow rate measuring device 16 circulate the calibration gas of the same flow rate, the flow rate value of the material gas flowing through the flow rate controller 11 is corrected in accordance with the difference between the respective corrected gas flow rate values.
(基本氣體供給流路L1) (basic gas supply flow path L1)
基本氣體供給流路L1，其一端連接在未圖示的基本氣體供給源，另一端連接在混合器2。基本氣體，只要是稀釋用途的惰性氣體，即無特別限定。本發明可使用的惰性氣體，可列舉：例如氮(N2)氣、或氬(Ar)、氦(He)或氖(Ne)等稀有氣體等。 The basic gas supply flow path L1 has one end connected to a basic gas supply source (not shown) and the other end connected to the mixer 2. The basic gas is not particularly limited as long as it is an inert gas for dilution. The inert gas which can be used in the present invention may, for example, be a nitrogen (N 2 ) gas or a rare gas such as argon (Ar), helium (He) or neon (Ne).
在基本氣體供給流路L1上，由上游側朝向下游側，依序設置開關閥4、壓力調整器5、流量控制器6、逆止閥7、自動閥8。又，也可視需要在壓力調整器5的上游側及下游側，設置未圖示的壓力計。藉由此種壓力計的設置，可目視認定壓力調整器5的前後壓力。 On the basic gas supply flow path L1, the on-off valve 4, the pressure regulator 5, the flow rate controller 6, the check valve 7, and the automatic valve 8 are sequentially provided from the upstream side toward the downstream side. Further, a pressure gauge (not shown) may be provided on the upstream side and the downstream side of the pressure regulator 5 as needed. With the setting of such a pressure gauge, the front and rear pressure of the pressure regulator 5 can be visually recognized.
開關閥4，在由開關閥4供給基本氣體至下游時開啟，不供給時關閉。 The on-off valve 4 is opened when the basic gas is supplied from the switching valve 4 to the downstream, and is closed when not supplied.
壓力調整器5，是為了將自基本氣體供給源供給的惰性氣體之壓力減壓至所要求的壓力而設置。本實施形態的供給裝置101中，在基本氣體供給流路L1上僅設置1個壓力調整器5。不過， 並非限定於1個，也可在流路L1的任意選擇處所設置2個以上壓力調整器5。 The pressure regulator 5 is provided to reduce the pressure of the inert gas supplied from the basic gas supply source to a desired pressure. In the supply device 101 of the present embodiment, only one pressure regulator 5 is provided in the basic gas supply flow path L1. but, It is not limited to one, and two or more pressure regulators 5 may be provided at an arbitrary place of the flow path L1.
又，就在流量控制器6前方的流路L1中的氣體壓力，可配合對太陽能電池製造裝置的供給壓力而適宜設定。例如，在流量控制器6前方的氣體壓力，可設定在0.3至0.8MPa的範圍。 Moreover, the gas pressure in the flow path L1 in front of the flow controller 6 can be appropriately set in accordance with the supply pressure to the solar cell manufacturing apparatus. For example, the gas pressure in front of the flow controller 6 can be set in the range of 0.3 to 0.8 MPa.
流量控制器6，是量測惰性氣體的質量流量而執行流量控制的流量控制機器，是為了進行高精度的流量量測及控制而設置。 The flow rate controller 6 is a flow rate control device that measures the mass flow rate of the inert gas and performs flow rate control, and is provided for high-accuracy flow rate measurement and control.
同時，流量控制器6，係以維持經混合器2混合的硒化氫混合氣體中之硒化氫濃度為設定值之方式控制惰性氣體之流量。 At the same time, the flow controller 6 controls the flow rate of the inert gas in such a manner as to maintain the concentration of hydrogen selenide in the hydrogen-selenide mixed gas mixed by the mixer 2 as a set value.
第1圖中，雖然是以在基本氣體供給流路L1上設置1個流量控制器6的供給裝置101為例示，但本發明並不限定於此。例如，也可在基本氣體供給流路L1上並列設置2個以上流量控制器6。 In the first embodiment, the supply device 101 in which one flow controller 6 is provided in the basic gas supply flow path L1 is exemplified, but the present invention is not limited thereto. For example, two or more flow rate controllers 6 may be arranged in parallel on the basic gas supply flow path L1.
在流量控制器6上，可載置質量流量感應器。流量控制器6上載置的質量流量感應器，並無特別限定，例如可使用熱式質量流量感應器、差壓式質量流量感應器、科里奧利(Coriolis)式質量流量感應器等一般的質量流量感應器。 On the flow controller 6, a mass flow sensor can be placed. The mass flow sensor mounted on the flow controller 6 is not particularly limited, and for example, a thermal mass flow sensor, a differential pressure mass flow sensor, a Coriolis mass flow sensor, or the like can be used. Mass flow sensor.
逆止閥7，使經流量控制器6控制流量的惰性氣體僅由上游側流向下游側，同時防止惰性氣體由下游側逆流向上游側。藉此，可使基本氣體供給流路L1內的基本氣體流量之變動減輕。 The check valve 7 causes the inert gas whose flow rate is controlled by the flow rate controller 6 to flow only from the upstream side to the downstream side while preventing the inert gas from flowing backward from the downstream side to the upstream side. Thereby, the fluctuation of the basic gas flow rate in the basic gas supply flow path L1 can be reduced.
自動閥8，是為了控制是否將經流量控制器6控制流量的惰性氣體供給至混合器2而設置。自動閥8為開啟狀態時，可使已控制流量的惰性氣體排放至自動閥8的下游側，而供給至 混合器2。另一方面，自動閥8為關閉狀態時，可使惰性氣體停止供給至自動閥8的下游側，而不能使惰性氣體供給至混合器2。自動閥8的開關狀態，是以可使用壓力計22量測的緩衝槽3之壓力切換。 The automatic valve 8 is provided to control whether or not the inert gas controlled by the flow controller 6 is supplied to the mixer 2. When the automatic valve 8 is in the open state, the inert gas of the controlled flow rate can be discharged to the downstream side of the automatic valve 8, and supplied to Mixer 2. On the other hand, when the automatic valve 8 is in the closed state, the inert gas can be stopped from being supplied to the downstream side of the automatic valve 8, and the inert gas can be supplied to the mixer 2. The switching state of the automatic valve 8 is the pressure switching of the buffer tank 3 which can be measured using the pressure gauge 22.
(原料氣體供給流路L2) (raw material gas supply flow path L2)
原料氣體供給流路L2，其一端連接在未圖示的原料氣體供給源，另一端連接在混合器2。原料氣體是硒化氫氣體。 The material gas supply flow path L2 has one end connected to a source gas supply source (not shown) and the other end connected to the mixer 2. The material gas is hydrogen selenide gas.
在原料氣體供給流路L2，除了設置流量控制器11，也在位於流量控制器11的二次側(下游側)之原料氣體供給流路L2，連接由原料氣體供給流路L2分岐的分岐流路L4。 In the material gas supply flow path L2, in addition to the flow rate controller 11, the material gas supply flow path L2 located on the secondary side (downstream side) of the flow rate controller 11 is connected to the branching flow branched by the material gas supply flow path L2. Road L4.
同時，在原料氣體供給流路L2，由上游側朝向下游側，依序設置自動閥9、壓力調整器10、流量控制器11、逆止閥12、自動閥13。與基本氣體供給流路L1相同，也可視需要而在壓力調整器10的上游側及下游側，設置未圖示的任意數目之壓力計。藉由此種壓力計的設置，即可目視確認壓力調整器10的前後壓力。 At the same time, the raw material gas supply flow path L2 is provided with the automatic valve 9, the pressure regulator 10, the flow rate controller 11, the check valve 12, and the automatic valve 13 in this order from the upstream side to the downstream side. Similarly to the basic gas supply flow path L1, any number of pressure gauges (not shown) may be provided on the upstream side and the downstream side of the pressure regulator 10 as needed. By the setting of such a pressure gauge, the front and rear pressure of the pressure regulator 10 can be visually confirmed.
有關自動閥9、壓力調整器10、逆止閥12、自動閥13之說明，因與基本氣體供給流路L1的開關閥4、壓力調整器5、逆止閥7、自動閥8之說明中，將惰性氣體取代成硒化氫氣體的情形幾乎相同，故省略之。 The descriptions of the automatic valve 9, the pressure regulator 10, the check valve 12, and the automatic valve 13 are described in the description of the switching valve 4, the pressure regulator 5, the check valve 7, and the automatic valve 8 of the basic gas supply flow path L1. The case where the inert gas is substituted with the hydrogen selenide gas is almost the same, and therefore it is omitted.
流量控制器11，是量測流經流路L2的硒化氫氣體之質量流量而執行流量控制的流量控制機器，是為了高精度的量測流量及控制而設置。 The flow rate controller 11 is a flow rate control device that measures the mass flow rate of the hydrogen selenide gas flowing through the flow path L2 and performs flow rate control, and is provided for high-accuracy measurement flow rate and control.
同時，流量控制器11，以可使經混合器2混合的硒化氫混合 氣體中之硒化氫濃度成為設定值的方式控制硒化氫氣體之流量。 At the same time, the flow controller 11 is configured to mix the hydrogen selenide mixed by the mixer 2 The flow rate of the hydrogen selenide gas is controlled in such a manner that the concentration of hydrogen selenide in the gas becomes a set value.
同時，流量控制器11中，在停止製造硒化氫混合氣體時，執行介著旁通流路L3而供給至流量控制器11的一次側(上游側)之校正用氣體的流量控制及量測質量流量。 At the same time, in the flow controller 11, when the production of the hydrogen-selenide mixed gas is stopped, the flow rate control and measurement of the calibration gas supplied to the primary side (upstream side) of the flow rate controller 11 via the bypass flow path L3 is performed. Mass Flow.
並且，在流量控制器11上，是以後述的配線E1連接控制器19，而能夠將校正用氣體的流量測定結果(流量測定值)由流量控制器11送訊至控制器19。控制器19中，進行獲得必用的資訊與演算處理等，可將其結果反應到流量控制器11之控制上。 Further, in the flow controller 11, the wiring E1 to be described later is connected to the controller 19, and the flow rate measurement result (flow rate measurement value) of the calibration gas can be sent from the flow controller 11 to the controller 19. In the controller 19, necessary information, arithmetic processing, and the like are obtained, and the result can be reflected in the control of the flow controller 11.
第1圖中，雖然是以在原料氣體供給流路L2上設置1個流量控制器11的供給裝置為例示，但本發明並不限定於此例示。例如，也可在原料氣體供給流路L2上並列設置2個以上流量控制器11。 In the first embodiment, the supply device in which one flow controller 11 is provided in the material gas supply flow path L2 is exemplified, but the present invention is not limited to this example. For example, two or more flow rate controllers 11 may be arranged in parallel on the material gas supply flow path L2.
在流量控制器11上，可載置質量流量感應器。流量控制器11上載置的質量流量感應器，並無特別的限定，可使用熱式質量流量感應器、差壓式質量流量感應器、科里奧利式質量流量感應器等一般的質量流量感應器。又，流量控制器11雖然宜為經原料氣體的硒化氫氣體校正流量之儀器，但並無特別限定，也可為經硒化氫氣體以外的氣體校正之儀器。 On the flow controller 11, a mass flow sensor can be placed. The mass flow sensor mounted on the flow controller 11 is not particularly limited, and a general mass flow sensor such as a thermal mass flow sensor, a differential pressure mass flow sensor, or a Coriolis mass flow sensor can be used. Device. Further, the flow rate controller 11 is preferably an instrument for correcting the flow rate of the hydrogen selenide gas of the material gas, but is not particularly limited, and may be an instrument for gas calibration other than hydrogen selenide gas.
(混合器2) (Mixer 2)
混合器2，是設在基本氣體供給流路L1的他端與原料氣體供給流路L2的他端合流的位置。混合器2，只要可將通過基本氣體供給流路L1供給的惰性氣體與通過原料氣體供給流路L2供給的硒化氫氣體混合，製造已調整成預定濃度的硒化氫混合氣體，將製造的氣體供給至下游側，即無特別限制，可任意選擇。藉由混 合器2，可防止惰性氣體流入原料氣體供給流路L2及硒化氫氣體流入基本氣體供給流路L1中。 The mixer 2 is a position where the other end of the basic gas supply flow path L1 merges with the other end of the material gas supply flow path L2. The mixer 2 can be produced by mixing the inert gas supplied through the basic gas supply flow path L1 with the hydrogen selenide gas supplied through the raw material gas supply flow path L2 to produce a hydrogen-selenide mixed gas adjusted to a predetermined concentration. The gas is supplied to the downstream side, that is, it is not particularly limited and can be arbitrarily selected. By mixing The combiner 2 prevents the inert gas from flowing into the raw material gas supply flow path L2 and the hydrogen selenide gas into the basic gas supply flow path L1.
(流路L5) (flow path L5)
混合器2與緩衝槽3，是由流路L5連接。又，在流路L5，也可設置未圖示的開關閥。 The mixer 2 and the buffer tank 3 are connected by a flow path L5. Further, an on-off valve (not shown) may be provided in the flow path L5.
第1圖中，是以基本氣體供給流路L1的一端與原料氣體供給流路L2的一端和混合器2連接，在混合器2與緩衝槽3之間設置流路L5的供給裝置101為例示。不過，本發明並不限定於這種例示。例如，也可以是無混合器2的供給裝置，或是無混合器2及流路L5，而使基本氣體供給流路L1及原料氣體供給流路L2的一端分別直接連接在緩衝槽3的供給裝置。即，也可在槽內進行氣體之混合。 In the first drawing, the supply device 101 in which one end of the basic gas supply flow path L1 is connected to one end of the raw material gas supply flow path L2 and the mixer 2, and the flow path L5 is provided between the mixer 2 and the buffer tank 3 is exemplified. . However, the invention is not limited to such an illustration. For example, the supply device without the mixer 2 or the mixer 2 and the flow path L5 may be provided, and one end of the basic gas supply flow path L1 and the raw material gas supply flow path L2 may be directly connected to the supply of the buffer tank 3, respectively. Device. That is, the mixing of the gases can also be carried out in the tank.
(緩衝槽3) (buffer tank 3)
緩衝槽3，是使經混合器2調整至預定濃度的硒化氫混合氣體貯留的貯留槽。緩衝槽3的內容積並無特別限定，可配合對太陽能電池製造裝置的硒化氫混合氣體之供給量而適當選擇。緩衝槽3中的硒化氫混合氣體的貯留量，可配合緩衝槽3的內容積及對太陽能電池製造裝置的硒化氫混合氣體之供給量而適當選擇。例如，對太陽能電池製造裝置的硒化氫混合氣體之供給量為100至200L/分鐘時，緩衝槽3內容量可作成20至400L。 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 in accordance with 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 in accordance with 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 supply amount of the hydrogen-selenide mixed gas to the solar cell manufacturing apparatus is 100 to 200 L/min, the content of the buffer tank 3 can be made 20 to 400 L.
緩衝槽3的上限壓力及下限壓力，並無特別限定，可配合緩衝槽3中硒化氫混合氣體之貯留量及對太陽能電池製造裝置的硒化氫混合氣體之供給量而適當選擇。例如，緩衝槽3內的硒化氫混合氣體之貯留壓力，可為0.1至0.5MPa的範圍。 The upper limit pressure and the lower limit pressure of the buffer tank 3 are not particularly limited, and may be appropriately selected in accordance with the storage amount of the hydrogen-selenide mixed gas in the buffer tank 3 and the supply amount of the hydrogen-selenide mixed gas in the solar cell manufacturing apparatus. For example, the storage pressure of the hydrogen-selenide mixed gas in the buffer tank 3 may be in the range of 0.1 to 0.5 MPa.
(流路L6) (Flow path L6)
在緩衝槽3上連接流路L6的一端，流路L6的另一端成為混合氣體的出口，此出口是連接在太陽能電池製造裝置上。藉此，即可能由緩衝槽3將硒化氫混合氣體供給至太陽能電池製造裝置。同時，在比流路L6的出口更上游的位置，即在流路L6的供給口側，設置開關閥21。 One end of the flow path L6 is connected to the buffer tank 3, and the other end of the flow path L6 serves as an outlet of the mixed gas, and this outlet is connected to the solar cell manufacturing apparatus. Thereby, it is possible to supply the hydrogen-selenide mixed gas to the solar cell manufacturing apparatus from the buffer tank 3. At the same time, the on-off valve 21 is provided at a position upstream of the outlet of the flow path L6, that is, on the supply port side of the flow path L6.
欲將硒化氫混合氣體由緩衝槽3供給至太陽能電池製造裝置時，開啟開關閥21。另一方面，不將硒化氫混合氣體由緩衝槽3供給至太陽能電池製造裝置時，關閉開關閥21。 When the hydrogen-selenide mixed gas is to be supplied from the buffer tank 3 to the solar cell manufacturing apparatus, the on-off 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 on-off valve 21 is closed.
又，欲將硒化氫混合氣體以一定壓力供給至太陽能電池製造裝置時，也可在流路L6設置未圖示的壓力調整器。 Further, when the hydrogen-selenide mixed gas is supplied to the solar cell manufacturing apparatus at a constant pressure, a pressure regulator (not shown) may be provided in the flow path L6.
同時，欲將硒化氫混合氣體由緩衝槽3供給至數個太陽能電池製造裝置時，也可設置2個以上的開關閥21。此時，也可使流路L6分岐。 Meanwhile, when the hydrogen-selenide mixed gas is to be supplied from the buffer tank 3 to a plurality of solar battery manufacturing apparatuses, two or more switching valves 21 may be provided. At this time, the flow path L6 can also be branched.
(流路L7) (Flow path L7)
同時，在緩衝槽3連接流路L7的一端，流路L7的另一端連接在壓力計22。藉由壓力計22，可量測緩衝槽3內的硒化氫混合氣體之壓力。同時，在流路L7，設置開關閥23。關閥23一般是開啟的。 At the same time, one end of the buffer tank 3 is connected to the flow path L7, and the other end of the flow path L7 is connected to the pressure gauge 22. The pressure of the hydrogen-selenide mixed gas in the buffer tank 3 can be measured by the pressure gauge 22. At the same time, on the flow path L7, the on-off valve 23 is provided. The shutoff valve 23 is normally open.
並且，在緩衝槽3，宜連接未圖示的真空泵等。藉此，欲去除殘留在緩衝槽3的氮氣等清洗氣體時，即可由真空泵等排放清洗氣體。 Further, a vacuum pump or the like (not shown) is preferably connected to the buffer tank 3. Thereby, when the cleaning gas such as nitrogen remaining in the buffer tank 3 is to be removed, the cleaning gas can be discharged by a vacuum pump or the like.
(緩衝槽之省略) (Omitted buffer tank)
又，本發明中也可省略緩衝槽3。在不採用緩衝槽3的本實 施形態之供給裝置(未圖示)中，第1圖中表示之流路L5與流路L6直接連結，也可不設置連接在緩衝槽3的流路L7、壓力計22、開關閥23。 Further, in the present invention, the buffer tank 3 can be omitted. In the absence of buffer tank 3 In the supply device (not shown), the flow path L5 shown in Fig. 1 is directly connected to the flow path L6, and the flow path L7 connected to the buffer tank 3, the pressure gauge 22, and the on-off valve 23 may not be provided.
(旁通流路L3) (bypass flow path L3)
旁通流路L3，一端連接在基本氣體供給源或是基本氣體供給流路L1，另一端連接在位於流量控制器11的一次側(上游側)之流路L2。在旁通流路L3，設有自動閥(第1開關閥)14。自動閥14，在製造硒化氫混合氣體時是關閉狀態，在停止製造硒化氫混合氣體時是開啟狀態。自動閥14為開啟狀態時，可使校正用氣體由基本氣體供給流路L1介著旁通流路L3供給至原料氣體供給流路L2。 The bypass flow path L3 has one end connected to the basic gas supply source or the basic gas supply flow path L1, and the other end connected to the flow path L2 located on the primary side (upstream side) of the flow rate controller 11. An automatic valve (first switching valve) 14 is provided in the bypass flow path L3. The automatic valve 14 is in a closed state when manufacturing a hydrogen-selenide mixed gas, and is in an open state when the production of the hydrogen-selenide mixed gas is stopped. When the automatic valve 14 is in the open state, the calibration gas can be supplied from the basic gas supply flow path L1 to the raw material gas supply flow path L2 via the bypass flow path L3.
藉由旁通流路L3及自動閥14的設置，在停止製造硒化氫混合氣體時，可使原料氣體供給流路L2與基本氣體供給流路L1連通。在製造硒化氫混合氣體時，則使原料氣體供給流路L2與基本氣體供給流路L1不連通。因此，在製造硒化氫混合氣體時，由於不使原料氣體供給流路L2與基本氣體供給流路L1連通，故在旁通流路L3的自動閥14之一次側(上游側)，硒化氫氣體不能流通。 By the provision of the bypass flow path L3 and the automatic valve 14, when the production of the hydrogen-selenide mixed gas is stopped, the raw material gas supply flow path L2 can be communicated with the basic gas supply flow path L1. When the hydrogen-selenide mixed gas is produced, the raw material gas supply flow path L2 and the basic gas supply flow path L1 are not communicated. Therefore, when the hydrogen selenide mixed gas is produced, since the raw material gas supply flow path L2 is not communicated with the basic gas supply flow path L1, selenization is performed on the primary side (upstream side) of the automatic valve 14 of the bypass flow path L3. Hydrogen gas cannot flow.
校正用氣體，只要是不含高濃度硒化氫氣體的氣體，即無特別限制。校正用氣體可任意選擇，校正用氣體，例如惰性氣體或是以惰性氣體為主成分的氣體較佳。又，在第1圖中，是使用由基本氣體供給源供給至基本氣體供給流路L1的惰性氣體，作為校正用氣體的構成為例示。不過，也可使旁通流路L3的一端連接在設置於未圖示的他途之校正用氣體供給源或是與別 的裝置共用的惰性氣體供給源，由此等供給源使校正用氣體供給至旁通流路L3(參照第7圖)。不過，為了防止供給裝置101的大型化與不需要追加校正用氣體供給源，宜使旁通流路L3的一端連接在基本氣體供給流路L1。 The gas for calibration is not particularly limited as long as it is a gas containing no high-concentration hydrogen-selenide gas. The gas for calibration can be arbitrarily selected, and a gas for calibration such as an inert gas or a gas containing an inert gas as a main component is preferable. In addition, in the first drawing, an inert gas supplied from the basic gas supply source to the basic gas supply flow path L1 is used as an example of a configuration as a calibration gas. However, one end of the bypass flow path L3 may be connected to a calibration gas supply source or other device provided on the other side of the bypass flow path L3. The inert gas supply source shared by the device is used to supply the calibration gas to the bypass flow path L3 (see FIG. 7). However, in order to prevent an increase in the size of the supply device 101 and the need to add a correction gas supply source, it is preferable to connect one end of the bypass flow path L3 to the basic gas supply flow path L1.
同時，旁通流路L3的一端與基本氣體供給流路L1的連接位置，並無特別限定。不過，宜使旁通流路L3的一端以接近基本氣體供給源的方式，連接在基本氣體供給流路L1。藉由此結構，在使校正用氣體流通於基本氣體供給流路L1之際，可防止不純物混入校正用氣體中。 At the same time, the connection position between one end of the bypass flow path L3 and the basic 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 basic gas supply flow path L1 so as to be close to the basic gas supply source. With this configuration, when the calibration gas flows through the basic gas supply flow path L1, impurities can be prevented from entering the calibration gas.
並且，在旁通流路L3，也可設置未圖示的壓力調整器。 Further, a pressure regulator (not shown) may be provided in the bypass flow path L3.
(分岐流路L4) (divided flow path L4)
分岐流路L4，其一端連接在流量控制器11的二次側(下游側)之原料氣體供給流路L2，另一端連接在未圖示的排氣管。在分岐流路L4，由上游側朝向下游側依序設置自動閥(第2開關閥)15、流量測定器16。自動閥15，在製造硒化氫混合氣體時是關閉狀態，在停止製造硒化氫混合氣體時是開啟狀態。自動閥15為開啟狀態時(停止製造硒化氫混合氣體時)，可使校正用氣體由基本氣體供給流路L1介著旁通流路L3及原料氣體供給流路L2供給至分岐流路L4。 The branch flow path L4 has one end connected to the material gas supply flow path L2 on the secondary side (downstream side) of the flow controller 11, and the other end connected to an exhaust pipe (not shown). In the branching flow path L4, an automatic valve (second switching valve) 15 and a flow rate measuring device 16 are sequentially provided from the upstream side toward the downstream side. The automatic valve 15 is in a closed state when manufacturing a hydrogen-selenide mixed gas, and is in an open state when the production of the hydrogen-selenide mixed gas is stopped. When the automatic valve 15 is in the open state (when the production of the hydrogen-selenide mixed gas is stopped), the calibration gas can be supplied from the basic gas supply flow path L1 to the branch flow path L4 via the bypass flow path L3 and the raw material gas supply flow path L2. .
在製造硒化氫混合氣體時，分岐流路L4與原料氣體供給流路L2是藉由自動閥15隔絶。且在停止製造硒化氫混合氣體時，分岐流路L4與原料氣體供給流路L2則不藉由自動閥15隔絶，即是連通的。在製造硒化氫混合氣體時，由於使分岐流路L4與原料氣體供給流路L2隔絶，故在分岐流路L4的自動閥15之二次側，硒 化氫氣體不能流通。 When the hydrogen selenide mixed gas is produced, the branching flow path L4 and the material gas supply flow path L2 are isolated by the automatic valve 15. When the production of the hydrogen-selenide mixed gas is stopped, the branching flow path L4 and the raw material gas supply flow path L2 are not isolated by the automatic valve 15, that is, they are in communication. When the hydrogen selenide mixed gas is produced, since the branching flow path L4 is isolated from the material gas supply flow path L2, selenium is on the secondary side of the automatic valve 15 of the branching flow path L4. Hydrogen gas cannot be circulated.
流量測定器16，是測量校正用氣體的質量流量之流量測定儀器。具體上，是為了測定流經流量控制器11的校正用氣體之流量而設置。 The flow rate measuring device 16 is a flow rate measuring instrument that measures the mass flow rate of the calibration gas. Specifically, it is provided to measure the flow rate of the calibration gas flowing through the flow controller 11.
同時，為能更正確的修正流量控制器11中的硒化氫氣體之流量值，本實施形態之流量測定器16，宜設置在製造硒化氫混合氣體時不使硒化氫氣體流通的流路上。可防止硒結晶朝流量測定器16析出。具體上，如第1圖所示，流量測定器16宜設置在製造硒化氫混合氣體時成為關閉狀態的自動閥15之二次側(下游側)。 Meanwhile, in order to more accurately correct the flow rate value of the hydrogen selenide gas in the flow controller 11, the flow rate measuring device 16 of the present embodiment is preferably provided with a flow that does not allow the hydrogen selenide gas to flow when the hydrogen selenide mixed gas is produced. On the road. Selenium crystals can be prevented from being precipitated toward the flow rate measuring device 16. Specifically, as shown in Fig. 1, the flow rate measuring device 16 is preferably provided on the secondary side (downstream side) of the automatic valve 15 that is in a closed state when the hydrogen-selenide mixed gas is produced.
流量測定器16中，在停止製造硒化氫混合氣體時，可量測介著旁通流路L3及原料氣體供給流路L2供給至分岐流路L4的校正用氣體之質量流量。此校正用氣體在流經原料氣體供給流路L2之際，可流經流量控制器11。 In the flow rate measuring device 16, when the production of the hydrogen-selenide mixed gas is stopped, the mass flow rate of the calibration gas supplied to the branching flow path L4 via the bypass flow path L3 and the raw material gas supply flow path L2 can be measured. This calibration gas can flow through the flow rate controller 11 while flowing through the material gas supply flow path L2.
在流量測定器16，宜載置質量流量感應器。載置在流量測定器16的質量流量感應器，並無特別限定，可使用例如熱式質量流量感應器、差壓式質量流量感應器、科里奧利式質量流量感應器等一般的質量流量感應器。 At the flow meter 16, a mass flow sensor is preferably placed. The mass flow sensor placed on the flow rate measuring device 16 is not particularly limited, and general mass flow rates such as a thermal mass flow sensor, a differential pressure mass flow sensor, and a Coriolis mass flow sensor can be used. sensor.
(控制器19及配線E1與E2) (Controller 19 and wiring E1 and E2)
流量測定器16藉由配線E2連接在控制器19。即，供給至分岐流路L4的校正用氣體之流量測定值，可藉由配線E2自流量測定器16送訊至控制器19。 The flow rate measuring device 16 is connected to the controller 19 via a wiring E2. That is, the flow rate measurement value of the calibration gas supplied to the branching flow path L4 can be sent from the flow rate measuring device 16 to the controller 19 via the wiring E2.
又如前述，連接在流量控制器11的配線E1，也連接在控制器19。 Further, as described above, the wiring E1 connected to the flow controller 11 is also connected to the controller 19.
在流量控制器11及流量測定器16，分別測定校正用 氣體的流量值而送訊至控制器19。所以，可在控制器19獲得經測定的校正用氣體的流量值之差分。控制器19，可將修正用的數據送達流量控制器11。如此，即可由所得的差分而於再開始製造硒化氫混合氣體時，修正流通至流量控制器11之二次側(下游側)的硒化氫氣體之流量值。流量控制器11及流量測定器16，較佳為流量測定範圍相同的質量流量感應器，並且以經相同成分的氣體校正流量的質量流量感應器為極佳。 In the flow controller 11 and the flow rate measuring device 16, the calibration is measured separately. The flow rate of the gas is sent to the controller 19. Therefore, the difference in the flow rate values of the measured calibration gas can be obtained at the controller 19. The controller 19 can send the data for correction to the flow controller 11. In this manner, when the hydrogen-selenide mixed gas is re-started from the obtained difference, the flow rate value of the hydrogen-selenide gas flowing to the secondary side (downstream side) of the flow rate controller 11 can be corrected. The flow controller 11 and the flow rate measuring device 16 are preferably mass flow sensors having the same flow rate measurement range, and are excellent in mass flow sensors that correct flow rates with gas of the same composition.
例如，若流量控制器11載置熱式質量流量感應器，經硒化氫氣體校正的流量計測之滿量程(full scale)為10[L/分鐘]的規格者，則流量測定器16是以使用相同者，亦即載置熱式質量流量感應器，同時經硒化氫氣體校正的流量計測之滿量程為10[L/分鐘]的規格者為極佳。 For example, if the flow controller 11 is placed with a thermal mass flow sensor and the full scale of the hydrogen selenide gas corrected flow meter is 10 [L/min], the flow meter 16 is It is excellent to use the same one, that is, to place the thermal mass flow sensor, and the flowmeter measured by the hydrogen selenide gas-corrected flow meter has a full scale of 10 [L/min].
使用作為流量控制器11及流量測定器16的儀器，可因選擇類似或相同者，而有以下的效果。即，經流量控制器11及流量測定器16測定的校正用氣體之流量測定值，不需要在使用異種氣體時必要的流量換算處理，在校正用氣體的測定後，即可就由控制器19為流量控制器11計算出硒化氫氣體之流量值的修正量或已修正的硒化氫氣體之流量值。 The use of the instruments as the flow controller 11 and the flow rate measuring device 16 can have the following effects by selecting similar or identical ones. In other words, the flow rate measurement value of the calibration gas measured by the flow rate controller 11 and the flow rate measuring device 16 does not require a flow rate conversion process necessary for the use of the heterogeneous gas, and after the measurement of the calibration gas, the controller 19 can be used. A correction amount of the flow rate value of the hydrogen selenide gas or a flow rate value of the corrected hydrogen selenide gas is calculated for the flow controller 11.
控制器19，可接受由流量控制器11及流量測定器16分別測定的校正用氣體之流量值的訊號。同時，控制器19可配合受訊的各別校正用氣體之流量值的差分，計算出可使用流量控制器11設定的硒化氫氣體之流量值的修正量，或經修正的硒化氫氣體之流量值，傳達至流量控制器11。 The controller 19 receives a signal of the flow rate of the calibration gas measured by the flow controller 11 and the flow rate measuring device 16, respectively. At the same time, the controller 19 can calculate the correction amount of the flow rate value of the hydrogen selenide gas which can be set by the flow controller 11 or the corrected hydrogen selenide gas, in accordance with the difference of the flow values of the respective calibration gases to be sensed. The flow rate value is communicated to the flow controller 11.
又，校正用氣體的流量測定值，在停止製造硒化氫混合氣體 時，可使用流量控制器11及流量測定器16測定。然後，再開始製造硒化氫混合氣體時，可將經加上硒化氫氣體的修正之流量值，作為流量控制器11的流量設定值。 Further, the flow rate measurement value of the calibration gas is stopped at the production of the hydrogen selenide mixed gas The flow rate controller 11 and the flow rate measuring device 16 can be used for measurement. Then, when the hydrogen selenide mixed gas is further produced, the corrected flow rate value of the hydrogen selenide gas can be used as the flow rate setting value of the flow controller 11.
控制器19，只要是可計算出硒化氫氣體的流量值之修正量，或經修正的硒化氫氣體之流量值的儀器，即無特別限定。可任意選擇演算裝置或系統使用。這種控制器19，可使用例如具有中央演算處理裝置的一般電腦或程式邏輯控制器(programmable logic controller)。 The controller 19 is not particularly limited as long as it is a device that can calculate the correction amount of the flow rate value of the hydrogen selenide gas or the corrected flow rate value of the hydrogen selenide gas. The calculation device or system can be used arbitrarily. Such a controller 19 can use, for example, a general computer or a programmable logic controller having a central processing device.
(硒化氫混合氣體的供給方法) (Method of supplying a hydrogen selenide mixed gas)
接著，說明使用供給裝置101的本實施形態之硒化氫混合氣體的供給方法(以下，簡稱「供給方法」)。 Next, a method of 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.
本實施形態之供給方法，包含以下步驟。 The supply method of this embodiment includes the following steps.
首先，使用混合器2，將經流量控制器6控制流量的惰性氣體與經流量控制器11控制流量的原料氣體混合，製造成預定之硒化氫濃度設定值的硒化氫混合氣體。然後將製造的混合氣體貯留在緩衝槽3中。(硒化氫混合氣體的製造步驟(I))。 First, the mixer 2 is used to mix the inert gas controlled by the flow controller 6 with the material gas controlled by the flow controller 11 to produce a hydrogen-selenide mixed gas having a predetermined selenide concentration set value. The produced mixed gas is then stored in the buffer tank 3. (Manufacturing step (I) of the hydrogen selenide mixed gas).
然後，將緩衝槽3內的該硒化氫混合氣體，供給至設置於供給裝置101的後段、位於太陽能電池製造裝置等的二次側之消耗設備(硒化氫混合氣體的供給步驟(Ⅲ))。 Then, the hydrogen-selenide mixed gas in the buffer tank 3 is supplied to a secondary device installed in the rear stage of the supply device 101 and on the secondary side of the solar cell manufacturing apparatus or the like (supply process (III) of the hydrogen-selenide mixed gas) ).
硒化氫混合氣體製造步驟之後，即，停止製造硒化氫混合氣體之後，使相同流量的校正用氣體，宜為相同的校正用氣體，流經流量控制器11及流量測定器16。配合經流量控制器11及流量測定器16測定的校正用氣體之各別流量值的差分，修正流經流量控制器11的硒化氫氣體之流量值(原料氣體的流量設定值的修正 步驟(Ⅱ))。 After the hydrogen selenide mixed gas production step, that is, after the production of the hydrogen-selenide mixed gas is stopped, the calibration gas of the same flow rate is preferably the same calibration gas, and flows through the flow rate controller 11 and the flow rate measuring device 16. The flow rate value of the hydrogen selenide gas flowing through the flow rate controller 11 is corrected in accordance with the difference between the respective flow rate values of the calibration gas measured by the flow rate controller 11 and the flow rate measuring unit 16 (correction of the flow rate setting value of the material gas) Step (II)).
又，此時，位於硒化氫混合氣體的二次側(下游側)之消耗設備，雖然所述為太陽能電池製造裝置，但只要是消耗硒化氫混合氣體的裝置均可。例如，可舉出將硒化氫混合氣體作為渦輪氣體消耗的半導體製造裝置等。 Moreover, in this case, the apparatus for consuming the secondary side (downstream side) of the hydrogen-selenide mixed gas may be a solar cell manufacturing apparatus, but may be any apparatus that consumes a hydrogen-selenide mixed gas. For example, a semiconductor manufacturing apparatus that consumes a hydrogen-selenide mixed gas as a turbine gas can be cited.
(製造準備步驟) (manufacturing preparation step)
首先，進行硒化氫混合氣體製造前之準備。具體上，準備第1圖中表示的供給裝置101，一邊操作此裝置中的開關閥4、21、23、自動閥9的開閉，一邊使氮氣等清洗氣體流通，進行流路內的清洗。結束上述清洗之後，使自動閥14、15成為關閉狀態，同時使自動閥14、15以外的全部開關閥及自動閥成為開啟狀態，完成製造準備。 First, preparation for the production of the hydrogen-selenide mixed gas is carried out. Specifically, the supply device 101 shown in Fig. 1 is prepared, and the opening and closing of the on-off valves 4, 21, and 23 and the automatic valve 9 in the device are operated, and a purge gas such as nitrogen gas is circulated to perform cleaning in the flow path. After the completion of the above-described cleaning, the automatic valves 14 and 15 are brought into a closed state, and all of the on-off valves and the automatic valves other than the automatic valves 14 and 15 are opened, and the manufacturing preparation is completed.
又，宜將殘留在緩衝槽3中的氮氣等清洗氣體去除。例如，宜自連接在緩衝槽3之未圖示的真空排氣用閥等，利用未圖示的真空泵等進行真空排氣。 Further, it is preferable to remove the cleaning gas such as nitrogen remaining in the buffer tank 3. For example, a vacuum exhaust valve (not shown) connected to the buffer tank 3 is preferably evacuated by a vacuum pump or the like (not shown).
(硒化氫混合氣體的製造步驟(I)) (Step (I) of manufacturing a hydrogen-selenide mixed gas)
其次，將惰性氣體自基本氣體供給流路L1、硒化氫氣體自原料氣體供給流路L2，分別供給至混合器2。即，一邊將惰性氣體的流量(流量設定值V1[L/分鐘]與原料氣體的流量(流量設定值V2[L/分鐘])控制成已預先設定之流量，一邊供給。 Next, the inert gas is supplied from the basic gas supply flow path L1 and the hydrogen selenide gas from the raw material gas supply flow path L2 to the mixer 2, respectively. In other words, the flow rate of the inert gas (the flow rate set value V 1 [L/min] and the flow rate of the material gas (the flow rate set value V 2 [L/min]) are controlled so as to be supplied at a predetermined flow rate.
更具體而言，分別控制惰性氣體的流量與硒化氫氣體的流量，使其成為由預先設定的供給太陽能電池製造裝置的硒化氫混合氣體中的硒化氫濃度之設定值(硒化氫濃度C[%]=V2/(V1+V2)×100)決定的各流量。如此進行，將惰性氣體自基本氣體 供給流路L1、將硒化氫氣體自原料氣體供給流路L2分別供給至混合器2。 More specifically, the flow rate of the inert gas and the flow rate of the hydrogen selenide gas are respectively controlled so as to be a set value of the concentration of hydrogen selenide in the hydrogen-selenide mixed gas supplied to the solar cell manufacturing apparatus in advance (hydrogen selenide) Each flow rate determined by the concentration C [%] = V 2 / (V 1 + V 2 ) × 100). In this manner, the inert gas is supplied from the base gas supply flow path L1 to the mixer 2 from the material gas supply flow path L2.
更具體而言，惰性氣體是由基本氣體供給源供給至基本氣體供給流路L1。惰性氣體在基本氣體供給流路L1中，可經壓力調整器5減壓至預定的壓力之後，導入流量控制器6內。在流量控制器6，預先設定惰性氣體之流量值為V1[L/分鐘]。即惰性氣體之流量，是藉由流量控制器6控制成V1[L/分鐘]。而且，在自動閥8為開啟狀態時，介著流量控制器6使預定流量(V1)之惰性氣體供給至混合器2。 More specifically, the inert gas is supplied from the basic gas supply source to the basic gas supply flow path L1. The inert gas is introduced into the flow rate controller 6 after being decompressed to a predetermined pressure by the pressure regulator 5 in the basic gas supply flow path L1. In the flow controller 6, the flow rate of the inert gas is preset to V 1 [L/min]. That is, the flow rate of the inert gas is controlled by the flow controller 6 to be V 1 [L/min]. Further, when the automatic valve 8 is in the open state, the flow controller 6 supplies the inert gas of the predetermined flow rate (V 1 ) to the mixer 2.
同時，硒化氫氣體由原料氣體供給源供給至原料氣體供給流路L2。硒化氫氣體在原料氣體供給流路L2中，是經壓力調整器10減壓至預定的壓力之後，導入流量控制器11內。在流量控制器11，預先設定硒化氫氣體之流量設定值為V2[L/分鐘]。即硒化氫氣體之流量，是藉由流量控制器11控制成V2[L/分鐘]。而且，在自動閥13為開啟狀態時，介著流量控制器11使預定流量(V2)之硒化氫氣體供給至混合器2。 At the same time, the hydrogen selenide gas is supplied from the material gas supply source to the material gas supply flow path L2. The hydrogen selenide gas is introduced into the flow rate controller 11 after being decompressed to a predetermined pressure by the pressure regulator 10 in the material gas supply flow path L2. In the flow controller 11, the flow rate set value of the hydrogen selenide gas is set to V 2 [L/min]. That is, the flow rate of the hydrogen selenide gas is controlled by the flow controller 11 to V 2 [L/min]. Further, when the automatic valve 13 is in the open state, the flow rate controller 11 supplies the hydrogen sulfide gas of a predetermined flow rate (V 2 ) to the mixer 2.
接著，將以預定流量供給的惰性氣體及硒化氫氣體以混合器2混合，製造預定濃度C=(V2/(V1+V2))×100[%]之硒化氫混合氣體。 Next, an inert gas and at a predetermined flow rate of hydrogen selenide gas mixture 2 supplied to the mixer, producing a predetermined concentration C = (V 2 / (V 1 + V 2)) × 100 [%] of a mixed gas of hydrogen selenide.
此時，硒化氫混合氣體之濃度並無特別限定，可視太陽能電池製造裝置的要求而適宜選擇。具體上，例如可使硒化氫混合氣體中硒化氫之濃度為5至20vol%。 In this case, the concentration of the hydrogen-selenide mixed gas is not particularly limited, and may be appropriately selected depending on 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%.
接著，介著流路L5，使混合成預定的硒化氫濃度之硒化氫混合氣體貯留在緩衝槽3中。貯留的硒化氫混合氣體之壓 力，可使用壓力計22量測。製造硒化氫混合氣體直到貯留的硒化氫混合氣體之壓力達到預先設定的上限壓力，藉由流路L5供給至緩衝槽3中。在以壓力計22測定的壓力達到上限壓力之際，使自動閥8、9及13全部為關閉狀態，停止對緩衝槽3的供給，停止硒化氫混合氣體之製造。自動閥9的關閉，是為實施後述的修正步驟。 Next, the hydrogen selenide mixed gas mixed into a predetermined hydrogen selenide concentration is stored in the buffer tank 3 via the flow path L5. The pressure of the stored hydrogen selenide mixed gas The force can be measured using a pressure gauge 22. The hydrogen selenide mixed gas is produced until the pressure of the stored hydrogen-selenide mixed gas reaches a predetermined upper limit pressure, and is supplied to the buffer tank 3 through the flow path L5. When the pressure measured by the pressure gauge 22 reaches the upper limit pressure, the automatic valves 8, 9, and 13 are all turned off, the supply to the buffer tank 3 is stopped, and the production of the hydrogen-selenide mixed gas is stopped. The closing of the automatic valve 9 is to carry out a correction step to be described later.
然後，在由壓力計22檢知緩衝槽3內的硒化氫混合氣體之壓力達到預先設定的下限壓力以下之際，使關閉的自動閥8、9、13為開啟狀態，開始將混合氣體供給至緩衝槽3，即開始硒化氫混合氣體的製造。然後，在以壓力計22檢知緩衝槽3內的壓力達到上限壓力以上之際，使自動閥8、9、13全部為關閉狀態，停止混合氣體對緩衝槽3的供給，即停止硒化氫混合氣體之製造。以後，配合緩衝槽3內的壓力依序重複操作硒化氫混合氣體之製造及停止製造。 Then, when the pressure of the hydrogen-selenide mixed gas in the buffer tank 3 is detected by the pressure gauge 22 to be equal to or lower than a predetermined lower limit pressure, the closed automatic valves 8, 9, and 13 are turned on, and the supply of the mixed gas is started. To the buffer tank 3, the production of a hydrogen-selenide mixed gas is started. Then, when the pressure gauge 22 detects that the pressure in the buffer tank 3 has reached the upper limit pressure or more, the automatic valves 8, 9, and 13 are all turned off, and the supply of the mixed gas to the buffer tank 3 is stopped, that is, the hydrogen selenide is stopped. The manufacture of mixed gases. Thereafter, the production of the hydrogen-selenide mixed gas is repeatedly operated in the buffer tank 3 in accordance with the pressure in the buffer tank 3, and the production is stopped.
(硒化氫混合氣體的供給步驟(Ⅲ)) (Supply step (III) of hydrogen selenide mixed gas)
配合太陽能電池製造裝置中硒化氫混合氣體之消耗狀況，將貯留在緩衝槽3內的硒化氫混合氣體供給至太陽能電池製造裝置。 The hydrogen-selenide mixed gas stored in the buffer tank 3 is supplied to the solar cell manufacturing apparatus in accordance with the consumption state of the hydrogen-selenide mixed gas in the solar cell manufacturing apparatus.
又，在不使用緩衝槽3的本實施形態之供給方法中，硒化氫混合氣體的製造或停止製造之切換，並非配合經壓力計22測定的緩衝槽3內之壓力值而進行，也可配合太陽能電池製造裝置中的硒化氫混合氣體之消耗狀況而進行。例如，在不進行消耗時可停止製造混合氣體，及/或也可在進行消耗時進行製造。 Further, in the supply method of the present embodiment in which the buffer tank 3 is not used, the switching of the production or the stop production of the hydrogen-selenide mixed gas is not performed in accordance with the pressure value in the buffer tank 3 measured by the pressure gauge 22, and may be performed. This is carried out in accordance with the consumption of the hydrogen-selenide mixed gas in the solar cell manufacturing apparatus. For example, the production of the mixed gas can be stopped when the consumption is not performed, and/or the production can be performed while the consumption is being performed.
如此進行，即可使硒化氫之濃度安定的硒化氫混合氣體，連 續的供給至太陽能電池製造裝置。 In this way, the hydrogen selenide mixed gas with a stable concentration of hydrogen selenide can be connected. Continued supply to the solar cell manufacturing apparatus.
(原料氣體流量設定值之修正步驟(Ⅱ)) (Step of correcting the raw material gas flow rate setting value (II))
在停止製造送至緩衝槽3的硒化氫混合氣體之後，進行以下說明的原料氣體流量設定值的修正步驟。藉由此修正步驟，可修正流通至流量控制器11的二次側(下游側)之硒化氫氣體的流量設定值。 After the production of the hydrogen-selenide mixed gas sent to the buffer tank 3 is stopped, the raw material gas flow rate setting value correction step described below is performed. By this correction step, the flow rate set value of the hydrogen selenide gas flowing to the secondary side (downstream side) of the flow controller 11 can be corrected.
具體上，是在設置於原料氣體供給流路L2控制硒化氫氣體流量的流量控制器11與校正用流量測定器16，流通相同流量的校正用氣體。可由各別的位置測定連續流通的校正用氣體之流通。而且，配合經流量控制器11與流量測定器16測定之校正用氣體的各別流量值之差分，修正在流量控制器11流通的硒化氫氣體之流量設定值。 Specifically, the flow rate controller 11 and the calibration flow rate measuring device 16 that control the flow rate of the hydrogen selenide gas in the source gas supply flow path L2 flow the calibration gas at the same flow rate. The flow of the calibration gas that is continuously circulated can be measured from the respective positions. Then, the flow rate setting value of the hydrogen selenide gas flowing through the flow rate controller 11 is corrected in accordance with the difference between the respective flow rate values of the calibration gas measured by the flow rate controller 11 and the flow rate measuring unit 16.
進一步說明修正步驟。 Further explain the correction steps.
首先，使自動閥9為關閉狀態，停止硒化氫氣體的供給。自動閥8與13也關閉。 First, the automatic valve 9 is turned off, and the supply of the hydrogen selenide gas is stopped. The automatic valves 8 and 13 are also closed.
其次，使自動閥14、15為開啟狀態。其結果使來自基本氣體供給源的基本氣體之惰性氣體，在由旁通流路L3、自旁通流路L3與原料供給流路L2的連接位置至分岐流路L4與原料供給流路L2的連接位置之間的原料供給流路L2、與分岐流路L4構成之流路(以下，將此連續流路稱為「校正用氣體流路」)，可連續流通惰性氣體。此惰性氣體也可使用與基本氣體相同的氣體。使用的惰性氣體發揮作為校正用氣體的機能。藉由本步驟，即可使相同流量的校正用氣體，在設置於校正用氣體流路的流量控制器11、流量測定器16，連續流通。 Next, the automatic valves 14, 15 are turned on. As a result, the inert gas of the basic gas from the basic gas supply source is connected to the branch flow path L4 and the raw material supply flow path L2 from the bypass flow path L3, the connection position from the bypass flow path L3 and the raw material supply flow path L2. The raw material supply flow path L2 between the connection positions and the flow path formed by the branch flow path L4 (hereinafter, this continuous flow path is referred to as "correction gas flow path") can continuously flow an inert gas. This inert gas can also use the same gas as the base gas. The inert gas used functions as a calibration gas. According to this step, the calibration gas of the same flow rate can be continuously distributed in the flow rate controller 11 and the flow rate measuring unit 16 provided in the calibration gas flow path.
其次，由設置於校正用氣體流路上的流量控制器11與流量測定器16測定校正用氣體之各別流量值。由控制器19使用此等測定值進行演算處理，以該結果為基準，修正再開始製造硒化氫混合氣體時流經流量控制器11之硒化氫氣體的流量值。 Next, the flow rate controller 11 provided in the calibration gas flow path and the flow rate measuring device 16 measure the respective flow rate values of the calibration gas. The controller 19 performs calculation processing using these measured values, and based on the result, corrects the flow rate value of the hydrogen selenide gas flowing through the flow rate controller 11 when the hydrogen-selenide mixed gas is produced.
又，如校正時與混合氣體製造時的氣體種類不同時，或是視需要而另外進行流量控制器或流量測定器之各別校正之際，校正時與流量測定時的氣體種類不同時，宜在計算出流量誤差之前，利用稱為換算係數(conversion factor)的流量修正係數換算流量。 In addition, when the calibration is different from the type of gas in the production of the mixed gas, or when the flow controller or the flow rate measuring device is separately adjusted as needed, the gas type at the time of the calibration and the flow rate measurement is different. Before calculating the flow error, the flow rate is converted using a flow correction coefficient called a conversion factor.
更詳細說明本發明中流量誤差之計算。 The calculation of the flow error in the present invention will be described in more detail.
在計算流量誤差時，首先由流量控制器11進行校正用氣體的流量控制，同時測定校正用氣體之流量V3[L/分鐘]。並且，由位於下游側的流量測定器16，測定校正用氣體的流量V4[L/分鐘]。 When calculating the flow rate error, first, the flow rate controller 11 performs flow rate control of the calibration gas, and simultaneously measures the flow rate V 3 [L/min] of the calibration gas. Further, the flow rate measuring device 16 located on the downstream side measures the flow rate V 4 [L/min] of the calibration gas.
製造硒化氫混合氣體時，如在含有流量控制器11的原料氣體供給流路L2多量析出硒結晶時，將使流量控制器11的流量控制精度降低。此時，為了硒結晶之存在，在停止製造硒化氫混合氣體時，有使以流量控制器11測定的校正用氣體之流量V3[L/分鐘]，成為小於原來測定的校正用氣體之流量的傾向。 When the selenide mixed gas is produced, if a large amount of selenium crystals are precipitated in the raw material gas supply flow path L2 including the flow rate controller 11, the flow rate control accuracy of the flow rate controller 11 is lowered. At this time, in order to stop the production of the hydrogen selenide mixed gas, the flow rate V 3 [L/min] of the calibration gas measured by the flow rate controller 11 is made smaller than the calibration gas originally measured. The tendency of traffic.
相對於此，流量測定器16，在製造硒化氫混合氣體時，是配置在不能流通硒化氫氣體的位置上。因此，經流量測定器16測定的校正用氣體之流量V4[L/分鐘]，是與原來測定的校正用氣體之流量等量。 On the other hand, when the hydrogen selenide mixed gas is produced, the flow rate measuring device 16 is disposed at a position where the hydrogen selenide gas cannot be circulated. Thus, V 16 measured by the flow rate measuring flow rate of calibration gas 4 [L / min] is the flow rate of the original measured equal amount of calibration gases.
如此，在停止製造硒化氫混合氣體時，經流量控制器11及流量測定器16分別測定的校正用氣體的流量值V3[L/分鐘]、V4[L/分鐘]之差分，將使流量控制器11之流量控制精度的降低適宜， 並且，正確顯示含有流量控制器11的原料氣體供給流路L2的硒結晶之析出量的程度。 As described above, when the production of the hydrogen-selenide mixed gas is stopped, the difference between the flow rate values V 3 [L/min] and V 4 [L/min] of the calibration gas measured by the flow rate controller 11 and the flow rate measuring device 16 will be The flow control accuracy of the flow controller 11 is appropriately reduced, and the degree of deposition of the selenium crystal containing the raw material gas supply flow path L2 of the flow controller 11 is accurately displayed.
又，此處是說明經流量控制器11測定的校正用氣體之流量V3[L/分鐘]小於原來測定的校正用氣體之流量的情形。不過，即使在大於原來測定的校正用氣體之流量時，也可作同樣的處理，亦即可進行修正。 Here, the case where the flow rate V 3 [L/min] of the calibration gas measured by the flow rate controller 11 is smaller than the flow rate of the calibration gas originally measured will be described. However, even if it is larger than the flow rate of the calibration gas originally measured, the same treatment can be performed, and the correction can be performed.
然後，將經流量控制器11及流量測定器16獲得的校正用氣體之流量測定值V3、V4[L/分鐘]，分別介著配線傳達到控制器19。 Then, the flow rate measurement values V 3 and V 4 [L/min] of the calibration gas obtained by the flow rate controller 11 and the flow rate measuring device 16 are transmitted to the controller 19 via the wiring.
其次，配合由流量控制器11獲得的校正用氣體之流量測定值V3[L/分鐘]與由流量測定器16獲得的校正用氣體之流量測定值V4[L/分鐘]之差分，計算出流量控制器11中硒化氫氣體之流量設定值的修正量。 Next, with the flow rate of calibration gas from the flow controller 11 to obtain a measured value V 3 [L / min] and the flow rate measurement value of the correction obtained by the gas flow measuring device 16 V 4 [L / min] of the difference, is calculated The correction amount of the flow rate set value of the hydrogen selenide gas in the flow rate controller 11.
具體上，是由流量測定值V3、V4[L/分鐘]以下式計算出流量誤差A及修正係數B。 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].
流量誤差A=(| V3-V4 |/V4)×100[%] Flow error A=(| V 3 -V 4 |/V 4 )×100[%]
修正係數B=V4/V3 The correction coefficient B = V 4 / V 3
但是，流量控制器11中，如校正時與混合氣體製造時的氣體種類不同時，或是視需要另外進行流量控制器之校正之際，校正時與流量測定時的氣體種類不一致時，必須以稱為換算係數的流量修正係數修正。利用流量修正係數將V3與V4依校正用氣體種類修正流量值之後，計算出流量誤差A及修正係數B。 However, in the flow controller 11, if the type of gas at the time of calibration is different from that in the production of the mixed gas, or when the flow controller is additionally adjusted as necessary, the type of gas at the time of the calibration and the flow rate measurement do not match. A flow correction factor correction called a conversion factor. The flow rate error A and the correction coefficient B are calculated by correcting the flow rate values by V 3 and V 4 depending on the type of gas to be corrected by the flow rate correction coefficient.
計算出流量誤差A及修正係數B後，依下式送訊至流量控制器11，計算出已修正的硒化氫氣體之流量設定值V5[L/ 分鐘]。 After calculating the flow error A and the correction coefficient B, the flow rate is sent to the flow controller 11 to calculate the flow rate set value V 5 [L/min] of the corrected hydrogen selenide gas.
流量設定值V5[L/分鐘]=B×V2[L/分鐘] Flow setting value V 5 [L/min]=B×V 2 [L/min]
其次，將計算出的硒化氫氣體之流量設定值V5[L/分鐘]介著配線E1送訊至流量控制器11。流量設定值V5可使用於以後進行的硒化氫混合氣體的製造步驟。如此進行，在原料氣體流量設定值之修正步驟後，即可使用於再開始製造硒化氫混合氣體時，可獲得修正值。即，流入流量控制器11的二次側(下游側)之硒化氫氣體的流量設定值，可由控制器19計算出的修正量修正。 Next, the calculated flow rate set value V 5 [L/min] of the hydrogen selenide gas is sent to the flow controller 11 via the wiring E1. The flow rate setting value V 5 can be used for the production step of the hydrogen-selenide mixed gas to be performed later. In this way, after the correction step of the raw material gas flow rate setting value, the correction value can be obtained when the production of the hydrogen-selenide mixed gas is resumed. That is, the flow rate setting value of the hydrogen selenide gas flowing into the secondary side (downstream side) of the flow rate controller 11 can be corrected by the correction amount calculated by the controller 19.
由以上的步驟，即完成使用配合流量控制器11中硒結晶之析出量而修正的硒化氫氣體之流量設定值V5[L/分鐘]，製造適合供給至太陽能電池製造裝置之預定硒化氫濃度的硒化氫混合氣體之準備。然後，也可關閉自動閥14、15而開啟自動閥9。亦即因為這樣的開啟，而可將自旁通流路L3與原料氣體供給流路L2之連接位置至分岐流路L4與原料氣體供給流路L2的連接位置之間的原料氣體供給流路內之校正用氣體，取代成硒化氫氣體。此時，自動閥15可就這樣的開啟，也可在預定的時間開啟。 By the above steps, the flow rate set value V 5 [L/min] of the hydrogen selenide gas corrected by the precipitation amount of the selenium crystal in the flow controller 11 is completed, and the predetermined selenization suitable for supply to the solar cell manufacturing apparatus is manufactured. Preparation of hydrogen selenide mixed gas with hydrogen concentration. Then, the automatic valves 14, 15 can also be closed to open the automatic valve 9. In other words, the connection position from the bypass flow path L3 and the material gas supply flow path L2 to the material gas supply flow path between the connection position of the branch flow path L4 and the material gas supply flow path L2 can be achieved by such opening. The calibration gas is replaced by hydrogen selenide gas. At this time, the automatic valve 15 can be opened as such, or can be turned on at a predetermined time.
又，修正係數B是僅在硒化氫氣體的流量控制時使用。即，校正用氣體的流量測定時，對於流量控制器11不進行使用修正係數B的修正。 Further, the correction coefficient B is used only for the flow rate control of the hydrogen selenide gas. In other words, when the flow rate of the calibration gas is measured, the correction of the correction coefficient B is not performed on the flow rate controller 11.
然後，使自動閥14、15為關閉狀態，同時使自動閥14、15以外的全部開關閥及自動閥為開啟狀態，進行上述說明的硒化氫混合氣體製造步驟。在第二次以後的硒化氫混合氣體製造步驟中，可在流量控制器11設定剛以原料氣體流量設定值修正步 驟正確修正之硒化氫氣體之流量設定值V5[L/分鐘]。所以，可在流量控制器11的二次側(下游側)流通原來應流通的流量V2[L/分鐘]之硒化氫氣體。可將流量值V2[L/分鐘]之硒化氫氣體供給至混合器2上。 Then, the automatic valves 14 and 15 are closed, and all of the on-off valves and the automatic valves other than the automatic valves 14 and 15 are opened, and the hydrogen-selenide mixed gas production step described above is performed. In the second and subsequent hydrogen selenide mixed gas production steps, the flow rate controller 11 can set the flow rate set value V 5 [L/min] of the hydrogen selenide gas that has been correctly corrected by the raw material gas flow rate set value correction step. Therefore, the hydrogen selenide gas of the flow rate V 2 [L/min] which should originally flow can be circulated on the secondary side (downstream side) of the flow controller 11. The hydrogen selenide gas having a flow rate value V 2 [L/min] can be supplied to the mixer 2.
以後，重複實施硒化氫混合氣體的製造步驟(I)與原料氣體的流量設定值之修正步驟(Ⅱ)的交互操作。如此進行，即可自供給裝置101長期安定供給適合供給太陽能電池製造裝置的預定硒化氫濃度之硒化氫混合氣體。 Thereafter, the interaction between the manufacturing step (I) of the hydrogen-selenide mixed gas and the correction step (II) of the flow rate set value of the raw material gas is repeated. In this way, the hydrogen selenide mixed gas of a predetermined hydrogen selenide concentration suitable for supply to the solar cell manufacturing apparatus can be stably supplied from the supply apparatus 101 for a long period of time.
在重複實施硒化氫混合氣體的製造步驟(I)與原料氣體的流量設定值之修正步驟(Ⅱ)的交互操作二次以上時，也可視需要變更原料氣體的流量設定值之修正步驟(Ⅱ)中的校正用氣體之流量值後實施步驟。在重複操作數次時，可得數個校正用氣體流量值之差分。因此在變更校正用氣體的流量設定值時，例如可將以各原料氣體的流量設定值之修正步驟獲得之數個修正係數B平均後使用，或是也可依照設定的流量範圍決定適用之修正係數B後使用。 When the interaction between the manufacturing step (I) of the hydrogen-selenide mixed gas and the correction step (II) of the flow rate set value of the raw material gas is repeated two or more times, the flow rate setting value of the raw material gas may be changed as needed (II) The step of performing the flow rate of the calibration gas in the process. When the operation is repeated several times, the difference between the plurality of calibration gas flow values can be obtained. Therefore, when changing the flow rate setting value of the calibration gas, for example, the correction coefficient B obtained by the correction step of the flow rate setting value of each material gas may be averaged, or the applicable correction may be determined according to the set flow rate range. Used after coefficient B.
例如，在重複實施硒化氫混合氣體的製造步驟(I)與原料氣體的流量設定值之修正步驟(Ⅱ)的交互操作二次以上時，第一次的製造步驟中之流量測定值為V3a[L/分鐘]，使用此值的修正步驟中所得的修正係數為Ba，第二次的製造步驟中之流量測定值為V3b[L/分鐘]，使用此值的修正步驟中所得的修正係數為Bb，而V3a<V3b。此時，在其後的製造及修正步驟中，可使適用於硒化氫氣體的流量測定值為0至V3a[L/分鐘]時的修正係數為Ba，適用於V3a至V3b[L/分鐘]時的修正係數為Bb。 For example, when the interaction between the manufacturing step (I) of the hydrogen-selenide mixed gas and the correction step (II) of the flow rate set value of the raw material gas is repeated twice or more, the flow rate measured in the first manufacturing step is V. 3a [L/min], the correction factor obtained in the correction step using this value is B a , and the flow measurement value in the second manufacturing step is V 3b [L/min], which is obtained in the correction step using this value. The correction factor is B b and V 3a <V 3b . At this time, in the subsequent manufacturing and correction steps, the correction coefficient for the flow rate measurement value of 0 to V 3a [L/min] applicable to the hydrogen selenide gas is B a , and is applicable to V 3a to V 3b . The correction factor at [L/min] is B b .
同時，在重複實施硒化氫混合氣體的製造步驟(I)與原料氣體的流量設定值之修正步驟(Ⅱ)的交互操作二次以上時，在連接於緩衝槽的壓力計22低於預定的壓力前，在實施原料氣體的流量設定值之修正步驟(Ⅱ)之後，也可使自動閥14、15為關閉狀態。又，雖然宜使流量誤差A之值為5至30%範圍內，但並未特別限定此範圍，只要在實用上無問題即可適宜選擇。 Meanwhile, when the interaction between the manufacturing step (I) of repeatedly performing the hydrogen-selenide mixed gas and the correction step (II) of the flow rate set value of the raw material gas is twice or more, the pressure gauge 22 connected to the buffer tank is lower than a predetermined one. Before the pressure, the automatic valves 14, 15 may be turned off after the correction step (II) of the flow rate setting value of the material gas is performed. Further, although the value of the flow rate error A is preferably in the range of 5 to 30%, the range is not particularly limited, and may be appropriately selected as long as there is no problem in practical use.
依照上述說明的本實施形態之供給方法，即可由校正用氣體去除滯留在原料氣體供給流路內的硒化氫氣體。因此，可明顯降低原料氣體供給流路L2中由硒化氫自行分解造成的硒結晶析出。同時，在流量控制器11流通流量V2[L/分鐘]的硒化氫氣體時，即使有硒結晶的析出時，也可依據設置在不流通硒化氫氣體的流路上之校正用流量測定器16測定的校正用氣體之流量值，將已修正的流量設定值V5[L/分鐘]送訊至流量控制器11。因此，可極為降低原料氣體供給流路L2的流量控制誤差。 According to the supply method of the present embodiment described above, the hydrogen selenide gas remaining in the source gas supply flow path can be removed by the calibration gas. Therefore, selenium crystallization due to self-decomposition of hydrogen selenide in the raw material gas supply flow path L2 can be remarkably reduced. At the same time, when the flow controller 11 flows the hydrogen sulfide gas having a flow rate of V 2 [L/min], even if selenium crystals are precipitated, the flow rate for calibration can be determined based on the flow path provided on the flow path in which the hydrogen selenide gas is not passed. 16 is a flow value measured by the calibration gas, the corrected flow rate set value V 5 [L / min] to send information to flow controller 11. Therefore, the flow rate control error of the material gas supply flow path L2 can be extremely reduced.
所以，依照本實施形態的硒化氫混合氣體之供給方法，即可不進行短時間週期的開關閥之切換等精密的機器操作及緩衝槽的容積擴張，可比已往更長期降低漂移現象，可將安定的硒化氫濃度之硒化氫混合氣體供給至太陽能電池製造裝置等。 Therefore, according to the method for supplying a hydrogen-selenide mixed gas according to the present embodiment, precise machine operation such as switching of the switching valve for a short period of time and volume expansion of the buffer tank can be performed, and the drift phenomenon can be reduced for a longer period of time than before, and the stability can be stabilized. The hydrogen selenide mixed gas having a hydrogen selenide concentration is supplied to a solar cell manufacturing apparatus or the like.
同時，在本實施形態的供給裝置101中，在硒化氫混合氣體停止製造時，使相同流量的校正用氣體流通設置在原料氣體供給流路L2以控制硒化氫氣體流量的流量控制器11與校正用的流量測定器。藉由此構成，因可使用校正用氣體將滯留在原料氣體供給流路內的硒化氫氣體去除，而降低硒化氫自行分解造成的硒結晶之析出。 At the same time, in the supply device 101 of the present embodiment, when the hydrogen-selenide mixed gas is stopped, the flow rate controller 11 that regulates the flow rate of the hydrogen-selenide gas by circulating the calibration gas of the same flow rate in the raw material gas supply flow path L2 And a flow meter for calibration. According to this configuration, since the hydrogen selenide gas remaining in the source gas supply flow path can be removed by using the calibration gas, precipitation of selenium crystals caused by self-decomposition of hydrogen selenide is reduced.
同時，在硒化氫混合氣體製造時，可配合由設置在流通硒化氫氣體之原料氣體供給流路L2的流量控制器11、設置在不流通硒化氫氣體的流路之流量測定器16，分別測定相同流量之校正用氣體的流量測定值之差分，修正流經流量控制器11的硒化氫氣體之流量設定值。藉此，可使原料氣體供給流路L2的流量控制誤差極為降低，抑制漂移現象。結果不需要短時間週期的閥開關等精密的機器操作或大容量的緩衝槽，即可長期將安定的硒化氫濃度的硒化氫混合氣體供給至太陽能電池製造裝置等。 At the same time, in the production of the hydrogen-selenide mixed gas, the flow rate controller 11 provided in the raw material gas supply flow path L2 through which the hydrogen-selenide gas is supplied, and the flow rate measuring device 16 provided in the flow path through which the hydrogen-selenide gas is not supplied can be blended. The difference between the flow rate measurement values of the calibration gas at the same flow rate is measured, and the flow rate set value of the hydrogen selenide gas flowing through the flow rate controller 11 is corrected. Thereby, the flow rate control error of the material gas supply flow path L2 can be extremely lowered, and the drift phenomenon can be suppressed. As a result, it is possible to supply a stable hydrogen-selenide mixed gas of a hydrogen selenide concentration to a solar cell manufacturing apparatus or the like for a long period of time without requiring a precise machine operation such as a valve switch of a short period of time or a large-capacity buffer tank.
又，本發明的技術範圍並不限定於上述實施的形態，在不脫離本發明的主旨範圍中，可加上各種的變更。 In addition, the technical scope of the present invention is not limited to the above-described embodiments, and various modifications can be added without departing from the spirit and scope of the invention.
例如，上述實施形態的供給裝置101，是將流量測定器16設置於分岐流路L4的構成。然而，如第6圖中所示的供給裝置102，也可將流量測定器16設置於自動閥14的一次側(上游側)之旁通流路L3。如同前述，在自動閥14的一次側之旁通流路L3不能流通硒化氫氣體。因此，與上述的供給裝置101相同，可在不能流通硒化氫氣體的流路上設置流量測定器16。所以，也可形成不設置分岐流路L4，除了上述的實施形態之效果，也可使供給裝置小型化。結果不需要短時間週期的閥開關等精密的機器操作或大容量的緩衝槽，即可長期將安定的硒化氫濃度的硒化氫混合氣體供給至太陽能電池製造裝置等。 For example, in the supply device 101 of the above-described embodiment, the flow rate measuring device 16 is provided in the branching flow path L4. However, as the supply device 102 shown in FIG. 6, the flow rate measuring device 16 may be provided in the bypass flow path L3 on the primary side (upstream side) of the automatic valve 14. As described above, the bypass flow path L3 on the primary side of the automatic valve 14 cannot pass the hydrogen selenide gas. Therefore, similarly to the above-described supply device 101, the flow rate measuring device 16 can be provided on a flow path through which hydrogen selenide gas cannot flow. Therefore, it is also possible to form the branching flow path L4 without being provided, and in addition to the effects of the above-described embodiments, the supply device can be downsized. As a result, it is possible to supply a stable hydrogen-selenide mixed gas of a hydrogen selenide concentration to a solar cell manufacturing apparatus or the like for a long period of time without requiring a precise machine operation such as a valve switch of a short period of time or a large-capacity buffer tank.
同時，另外的實施例，例如流量誤差A超過設定值時，也可將流量控制器11的異常通知供給裝置101的操作員，再由操作員進行流量控制器11的交換。 Meanwhile, in another embodiment, for example, when the flow rate error A exceeds the set value, the operator of the supply controller 101 may be notified of the abnormality of the flow controller 11, and the operator may exchange the flow controller 11.
[實施例] [Examples]
以下，表示本發明的較佳具體例。 Hereinafter, preferred specific examples of the present invention are shown.
使用第1圖中表示的供給裝置101製造硒化氫混合氣體，將硒化氫混合氣體連續長期供給至太陽能電池製造裝置。在進行供給裝置101的硒化氫混合氣體之製造步驟之際，使用表1的條件。同時，在進行供給裝置101的原料氣體流量設定值的修正步驟之際，使用表2的條件。 The hydrogen selenide mixed gas is produced using the supply device 101 shown in Fig. 1, and the hydrogen-selenide mixed gas is continuously supplied to the solar cell manufacturing apparatus for a long period of time. When the manufacturing process of the hydrogen-selenide mixed gas of the supply apparatus 101 is performed, the conditions of Table 1 are used. At the same time, the conditions of Table 2 are used when the raw material gas flow rate setting value of the supply device 101 is corrected.
．表2中，流量控制器11的流量測定值V3，在修正步驟中控制器的流量顯示為10.0L/分鐘時，表示實際流通的氮氣是13.0L/分鐘。 . In Table 2, the flow rate measurement value V3 of the flow rate controller 11 indicates that the actual flow rate of nitrogen gas is 13.0 L/min when the flow rate of the controller is 10.0 L/min in the correction step.
．表2中所述之“1次”，是指為了進行1次流量設定值之修正而進行的製造步驟與修正步驟之組合的次數，本實施例中使此為數次的重複操作。 . The "first time" described in Table 2 refers to the number of times of the combination of the manufacturing step and the correction step performed to correct the flow rate setting value once, and this is repeated several times in the present embodiment.
在一邊以表1、2中表示的實施條件重複進行製造及修正的步驟，一邊將硒化氫混合氣體連續供給至太陽能電池製造裝置之際，使用設置在流路L6的硒化氫濃度分析計(未圖示)，測定硒化氫混合氣體中硒化氫濃度隨時間之變化。使用硒化氫濃度分析計測定的硒化氫混合氣體中硒化氫濃度之時間(日數)依存性，如第2圖所示。同時，重複進行製造及修正步驟之際的流量誤差A之時間(日數)依存性，如第3圖所示。 The step of manufacturing and correcting is repeated in the execution conditions shown in Tables 1 and 2, and the hydrogen selenide mixed gas is continuously supplied to the solar cell manufacturing apparatus, and the hydrogen selenide concentration analyzer provided in the flow path L6 is used. (not shown), the concentration of hydrogen selenide in the hydrogen-selenide mixed gas was measured as a function of time. The time (days) dependence of the concentration of hydrogen selenide in the hydrogen-selenide mixed gas measured using a hydrogen selenide concentration analyzer is shown in Fig. 2. At the same time, the time (days) of the flow error A at the time of the manufacturing and correction steps is repeated, as shown in Fig. 3.
(比較例) (Comparative example)
在實施供給裝置101的原料氣體之流量設定值的修正步驟時，除了在流量控制器11的硒化氫之流量設定值V2[L/分鐘]的修正上不使用修正係數B之外，其餘使用與實施例相同的條件製造硒化氫混合氣體，將硒化氫混合氣體供給至太陽能電池製造裝置。即，雖然實施修正步驟，但不使用經流量控制器11修正的流量而進行製造及供給。與實施例相同，使用設置在流路L6的硒化氫濃度分析計，測定硒化氫混合氣體中硒化氫濃度隨時間之變化。此時硒化氫混合氣體中硒化氫濃度之時間(日數)依存性，如第2圖所示。 When the correction step of the flow rate setting value of the material gas of the supply device 101 is performed, the correction coefficient B is not used except for the correction of the flow rate setting value V 2 [L/min] of the hydrogen selenide flow rate controller 11 The hydrogen selenide mixed gas was produced under the same conditions as in the examples, and the hydrogen-selenide mixed gas was supplied to the solar cell manufacturing apparatus. That is, although the correction step is performed, the manufacturing and supply are performed without using the flow rate corrected by the flow controller 11. Similarly to the examples, the concentration of hydrogen selenide in the hydrogen-selenide mixed gas was measured with time using a hydrogen selenide concentration analyzer provided in the flow path L6. At this time, the time (days) of the concentration of hydrogen selenide in the hydrogen-selenide mixed gas is as shown in Fig. 2.
(實施例及比較例的測定結果之比較) (Comparison of measurement results of the examples and comparative examples)
如第2圖所示，在比較例中自開始測定至大約經過40天中，硒化氫混合氣體中硒化氫濃度保持在預定濃度的10.0%附近。不過，再經過數日後，硒化氫濃度急速的增大。 As shown in Fig. 2, in the comparative example, the concentration of hydrogen selenide in the hydrogen-selenide mixed gas was maintained at about 10.0% of the predetermined concentration from the start of the measurement to about 40 days. However, after a few days, the concentration of hydrogen selenide increased rapidly.
同時，即使在第3圖所示的流量誤差A之硒化氫濃度的時間(日數)依存性中，經過自開始測定至大約經過40天以後的日數，也使流量誤差A急速的增大。其結果，在比較例中自開始測定之第100天時，硒化氫混合氣體中的硒化氫濃度達到13.8%。 At the same time, even in the time (days) dependency of the hydrogen selenide concentration of the flow error A shown in Fig. 3, the flow rate error A is rapidly increased after the number of days from the start of the measurement to about 40 days later. Big. As a result, in the comparative example, the hydrogen selenide concentration in the hydrogen-selenide mixed gas reached 13.8% from the 100th day from the start of the measurement.
如此使硒化氫濃度上昇之主要因素，可舉出由於未進行使用修正係數B的流量控制器11的硒化氫之流量設定值V2[L/分鐘]之修正，而使流量控制器11的流量控制精度降低。 The main factor for increasing the concentration of hydrogen selenide in this manner is that the flow rate controller 11 is corrected by the correction of the flow rate set value V 2 [L/min] of the hydrogen selenide of the flow controller 11 using the correction coefficient B. The flow control accuracy is reduced.
相對於比較例，在實施例中即使自開始測定經過大約100天，硒化氫混合氣體中的硒化氫濃度也是安定的在10.0%附近。所以在本發明中，原料氣體供給流路L2的流量控制誤差極為正確，且可確認至少經過100天左右的長時間可降低誤差。此乃藉由本發明的上述實施形態之供給方法及供給裝置101，配合經校正用的流量測定器16測定的校正用氣體之流量值為基準計算出的流量誤差A及修正係數B，而可將流經流量控制器11的硒化氫氣體的流量設定值V2[L/分鐘]修正為流量設定值V5[L/分鐘]。 With respect to the comparative example, in the examples, the hydrogen selenide concentration in the hydrogen-selenide mixed gas was stabilized at around 10.0% even after about 100 days from the start of the measurement. Therefore, in the present invention, the flow rate control error of the material gas supply flow path L2 is extremely accurate, and it can be confirmed that the error can be reduced by at least a long time of about 100 days. According to the supply method and the supply device 101 of the above-described embodiment of the present invention, the flow rate error A and the correction coefficient B calculated based on the flow rate value of the calibration gas measured by the flow rate measuring device 16 for calibration can be used. The flow rate set value V 2 [L/min] of the hydrogen selenide gas flowing through the flow controller 11 is corrected to the flow rate set value V 5 [L/min].
本發明可適用於硒化氫混合氣體的供給方法及供給裝置。可提供不需要精密的機器操作及大容量的緩衝槽，即可抑制漂移現象且長期供給安定的硒化氫濃度之硒化氫混合氣體的供給方法及供給裝置。 The present invention is applicable to a method and a supply device for supplying a hydrogen selenide mixed gas. It is possible to provide a method and a supply device for a hydrogen-selenide mixed gas which can suppress a drift phenomenon and which can supply a stable hydrogen selenide concentration for a long period of time without requiring a complicated machine operation and a large-capacity buffer tank.
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| 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 |
| JP2020105577A (en) * | 2018-12-27 | 2020-07-09 | 株式会社フジキン | Fluid supply 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 |
| US20220157599A1 (en) * | 2019-11-12 | 2022-05-19 | Showa Denko K.K. | Adhered substance removing method and film-forming method |
| 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 |
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| JPH11265218A (en) * | 1998-03-18 | 1999-09-28 | Kokusai Electric Co Ltd | Automatic flow/flow ratio conversion data calibrating device and gas supplying device |
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