[go: up one dir, main page]

WO2004007802A2 - Appareil de production de gaz fluore - Google Patents

Appareil de production de gaz fluore Download PDF

Info

Publication number
WO2004007802A2
WO2004007802A2 PCT/IB2003/002998 IB0302998W WO2004007802A2 WO 2004007802 A2 WO2004007802 A2 WO 2004007802A2 IB 0302998 W IB0302998 W IB 0302998W WO 2004007802 A2 WO2004007802 A2 WO 2004007802A2
Authority
WO
WIPO (PCT)
Prior art keywords
gas
conduit
hydrogen fluoride
molten salt
phase region
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2003/002998
Other languages
English (en)
Other versions
WO2004007802A3 (fr
Inventor
Jun Sonobe
Minoru Ino
Muneuyki Fukuoka
Takako Kimura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA a Directoire et Conseil de Surveillance pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA a Directoire et Conseil de Surveillance pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of WO2004007802A2 publication Critical patent/WO2004007802A2/fr
Publication of WO2004007802A3 publication Critical patent/WO2004007802A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/245—Fluorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes

Definitions

  • This invention relates to an apparatus that generates fluorine gas (referred to below as a fluorine gas generator). More particularly, this invention relates to a fluorine gas generator that is disposed in the gas supply system of a semiconductor processing system.
  • Semiconductor processing refers in this context to the various processes carried out in order to fabricate semiconductor devices and/or semiconductor device-connecting structures (e.g., interconnects, electrodes) on the substrate undergoing the processing (the target substrate) by the formation of semiconductor, dielectric, and conductive layers in specific patterns on the target substrate, such as a semiconductor wafer or LCD substrate.
  • a variety of semiconductor processes such as film formation, etching, and diffusion, are carried out on the target substrate, e.g., a semiconductor wafer or LCD substrate, during the fabrication of semiconductor devices.
  • the semiconductor processing systems used to carry out these treatments employ fluorine-type gases as process gases in a variety of applications, such as for the etching of silicon films and silicon oxide films and to clean the interior of process compartments.
  • Fluorine gas has been receiving attention as a new etching gas and cleaning gas, but it is generally not produced at the actual site of semiconductor device fabrication because its safety and reliability issues have not been completely addressed.
  • Electrolytic cell-based apparatuses are known for the production of fluorine gas at gas production plants.
  • a fluorine gas generator of this type is disclosed, for example, in Japanese Laid Open Patent Application (PCT) Number Hei 9-505853 (505,853/1997).
  • a separation means extending from the top into the molten salt functions to partition the interior of the electrolytic cell into a central anode compartment and a surrounding cathode compartment.
  • Two probes that end at different heights are disposed within the anode compartment. These two probes function as surface level gauges in order to effect ON/OFF control of the current fed between the anode and cathode.
  • this apparatus controls the generation of fluorine gas by detecting the surface level of the molten salt.
  • FIG. 3 Another prior art fluorine gas generator is schematically illustrated in Figure 3.
  • This apparatus has an improved structure for controlling the feed of fluorine gas from the electrolytic cell.
  • the fluorine gas generated at the anode 114 side of an electrolytic cell 112 is continuously fed through a conduit 120 into an intermediate capacitor 116 and is temporarily stored therein.
  • a switching valve 122 disposed between a compressor 118 and the capacitor 116 is temporarily opened and a certain specified amount of the fluorine gas is suctioned into the compressor 118.
  • the valve 122 is repeatedly operated in order to raise the pressure of the secondary buffer tank 124 to a specified value.
  • An object of this invention is to provide a fluorine gas generator that is capable of very safe and highly reliable operation even during long-term operations.
  • a particular object of this invention is to provide an apparatus that can produce fluorine gas both on-site and on-demand.
  • on-site means that the fluorine gas generator is combined or assembled with the particular main process apparatus, for example, the main process apparatus of a semiconductor processing system.
  • On-demand means that the gas can be supplied, with accompanying control of its required components, with a timing that responds to the requirements of the main process apparatus.
  • the first aspect of this invention comprises an apparatus for the generation of fluorine gas, said apparatus being characteristically provided with an electrolytic cell that carries out the electrolysis of hydrogen fluoride in an electrolytic bath comprising hydrogen fluoride-containing molten salt and thereby generates, in a first gas phase region on the anode side, product gas whose main component is fluorine gas and at the same time generates, in a second gas phase region on the cathode side, byproduct gas whose main component is hydrogen gas, a starting material conduit that feeds starting hydrogen fluoride into the molten salt, a first conduit that withdraws the product gas from the first gas phase region, a second conduit that withdraws the by-product gas from the second gas phase region, a first pressure gauge that continuously measures the pressure in the first gas phase region, a second pressure gauge that continuously measures the pressure in the second gas phase region, a first flow rate control valve disposed in the first conduit, a second flow rate control valve disposed in the second conduit, a first control member that based on the measurement result from
  • the second aspect of this invention comprises the apparatus of the first aspect, characterized in that the first and second set values are 760-820 Torr.
  • the third aspect of this invention comprises an apparatus according to the first or second aspect, that is characteristically additionally provided with a first suction means that is disposed in the first conduit downstream from the first flow rate control valve and that can suction the first conduit.
  • the fourth aspect of this invention comprises the apparatus of the third aspect, characterized in that the second conduit is disposed so as to connect downstream from the second flow rate control valve to a second suction means that can suction the second conduit.
  • the fifth aspect of this invention comprises an apparatus according to any of the first through fourth aspects, wherein said apparatus is characteristically also provided with a switching valve disposed in the starting material conduit, a current integrator that integrates the electric current fed between the electrode on the anode side of the electrolytic cell and the electrode on the cathode side of the electrolytic cell, and a control member that based on the measurement result produced by the current integrator operates the switching valve so as to control the feed of hydrogen fluoride into the molten salt.
  • the sixth aspect of this invention comprises the apparatus of the fifth aspect, with the characteristic feature that the hydrogen fluoride fed through the starting material conduit is a gas.
  • the seventh aspect of this invention comprises the apparatus of the sixth aspect, characterized in that the starting material conduit is disposed so as to feed the hydrogen fluoride gas into the molten salt on the cathode side of the electrolytic cell and in that a conduit that can feed nitrogen gas into the starting material conduit is connected thereto downstream from the aforesaid switching valve and the hydrogen fluoride gas is fed mixed with nitrogen gas into the molten salt.
  • the eighth aspect of this invention comprises a fluorine gas generator that is characteristically provided with an electrolytic cell that carries out the electrolysis of hydrogen fluoride in an electrolytic bath comprising hydrogen fluoride-containing molten salt and thereby generates, in a first gas phase region on the anode side, product gas whose main component is fluorine gas and at the same time generates, in a second gas phase region on the cathode side, byproduct gas whose main component is hydrogen gas, a starting material conduit that feeds starting hydrogen fluoride into the molten salt, a first conduit that withdraws the product gas from the first gas phase region, a second conduit that withdraws the by-product gas from the second gas phase region, a switching valve disposed in the starting material conduit, a current integrator that integrates the electric current fed between the electrode on the anode side of the electrolytic cell and the electrode on the cathode side of the electrolytic cell, and a control member that based on the measurement result produced by the current integrator operates the switching valve so as to control
  • the ninth aspect of this invention comprises the apparatus of the eighth aspect with the characteristic feature that the hydrogen fluoride fed through the starting material conduit is a gas.
  • the tenth aspect of this invention comprises the apparatus of the ninth aspect, characterized in that the starting material conduit is disposed so as to feed the hydrogen fluoride gas into the molten salt on the cathode side of the electrolytic cell and in that a conduit that can feed nitrogen gas into the starting material conduit is connected thereto downstream from the aforesaid switching valve and the hydrogen fluoride gas is fed mixed with nitrogen gas into the molten salt.
  • the embodiments of this invention explore a variety of executions of this invention, and various embodiments of this invention can be derived by suitable combination of the plural number of disclosed constituent elements. For example, when an embodiment of the invention has been derived in which some constituent elements have been omitted from the overall set of constituent elements presented for the embodiment, these omitted elements can be suitably fulfilled by conventional well-known technologies in the actual working of the derived inventive embodiment.
  • valve 122 is opened at the upper limit for the pressure in the capacitor 116 and the valve 122 is closed at the lower limit for this pressure. This results in the generation of large pressure variations in the fluorine gas conduit 120.
  • the molten salt mist caused by these large pressure variations accumulates at the inlet to the conduit 120, which causes the conduit 120 to become clogged.
  • the seat of the valve 122 is quite prone to damage by the mechanical action of solidified molten salt particles and the chemical action of the fluorine gas.
  • the hydrogen gas produced on the cathode side passes through the conduit 121 of the exhaust system and is discharged from the system after dilution at a minimum down to the usual regulatory value.
  • the pressure in the discharge system will vary as a function of the plant environment. For example, when the exhaust system has a high suction capacity, the pressure on the cathode side will spontaneously become a negative pressure and in association therewith the molten salt level on the cathode side will rise. The surface level undergoes a major change in this case, which results in molten salt being pulled into the hydrogen gas conduit 121 and hence in clogging of the conduit 121.
  • FIG. 1 contains a schematic drawing that illustrates a semiconductor processing system that incorporates a fluorine gas generator that is an embodiment of this invention.
  • This semiconductor processing system contains a semiconductor processing apparatus 10 that executes a process, e.g., film formation, etching, or diffusion, on a target substrate, e.g., a semiconductor wafer or LCD substrate.
  • the semiconductor processing apparatus 10 is provided with a process chamber 12 that holds the target substrate and in which the semiconductor process is implemented.
  • a mounting platform 14 (support member) that functions both as a lower electrode and as a platform for mounting the target substrate.
  • An upper electrode 16 is also disposed within the process chamber 12 facing the mounting platform 14.
  • RF (high frequency) power can be applied from an RF power source 15 across the two electrodes 14 and 16 in order to form an RF field in the process chamber 12 for the purpose of converting the process gas into a plasma.
  • An exhaust system 18 is connected to the lower region of the process chamber 12 for the purpose of evacuating the interior of the chamber and establishing a vacuum therein.
  • a gas supply system 20 is connected to the upper region of the process chamber 12 for the purpose of supplying the process gas.
  • FIG 2 contains a schematic drawing that illustrates a modified example 10x of the semiconductor processing apparatus that can be used in combination with the gas supply system 20 illustrated in Figure 1.
  • This semiconductor processing apparatus 10x is provided with a process chamber 12 that holds the target substrate and in which the semiconductor process is implemented.
  • a mounting platform 14 (support member) is disposed within the process chamber 12 for the purpose of mounting the target substrate.
  • An exhaust system 18 is connected to the lower region of the process chamber 12 for the purpose of evacuating the interior of the chamber and establishing a vacuum therein.
  • a remote plasma chamber 13 is connected to the upper region of the process chamber 12 for the purpose of forming a plasma. The periphery of this remote plasma chamber 13 is wrapped with a coil antenna 17.
  • RF radio frequency
  • the fluorine gas generator comprising the embodiment of this invention can also be used with semiconductor process equipment that does not employ a plasma, for example, to supply cleaning gas to a thermal CVD apparatus.
  • a flow management section 22 is disposed in the gas supply system 20; this flow management section 22 can feed any designated gas, for example, process gas for carrying out a semiconductor process or process gas for cleaning the interior of the process chamber 12, into the process chamber 12 at a specified flow rate and is also capable of selective switching.
  • a gas storage section 24 is connected to the flow management section 22. This gas storage section 24 contains a plurality of gas sources and stores various active and/or inert gases. Also connected to the flow management section 22 is a gas production section 26 that produces fluorine gas-type process gas by a reaction process.
  • a fluorine gas generator 30 comprising an embodiment of this invention is detachably connected to the flow management section 22 and the gas production section 26. More specifically, this generator 30 either directly supplies fluorine gas to the flow management section 22 or is used to supply starting fluorine gas to the gas production section 26 (switching valve not shown).
  • the gas production section 26 can produce, for example, an interhalogen fluorine compound gas by reacting the starting fluorine gas with another halogen gas such as chlorine.
  • the generator 30 contains an airtight electrolytic cell 32 that holds an electrolytic bath comprising hydrogen fluoride-containing molten salt.
  • This molten salt comprises a mixture (KF/2HF) of potassium fluoride (KF) and hydrogen fluoride (HF) or a mixture of hydrogen fluoride and Fremy's salt.
  • the electrolytic cell 32 is divided into an anode compartment 34 and a cathode compartment 36 by a partition sheet 35 that extends from the top into the molten salt.
  • a carbon electrode (anode) 42 is immersed in the molten salt in the anode compartment 34 while a nickel electrode (cathode) 44 is immersed in the molten salt in the cathode compartment 36.
  • Attached to the electrolytic cell 32 are a current source 38 that can supply current between the anode 42 and cathode 44 and a current integrator 40 that integrates the supplied current.
  • Electrolysis of the hydrogen fluoride in the electrolytic bath results in the production in the gas phase region of the anode compartment 34 of product gas whose main component is fluorine gas (F 2 ) and in the production in the gas phase region of the cathode compartment 36 of by-product gas whose main component is hydrogen gas.
  • Hydrogen fluoride gas is admixed (for example, at 5%) in both the product gas and by-product gas in accordance with the vapor pressure contribution of the hydrogen fluoride gas in the starting molten salt.
  • a first pressure gauge 46 is disposed on the anode compartment 34 and a second pressure gauge 48 is disposed on the cathode compartment 36 in order to continuously measure the pressure of the respective gas phase regions.
  • a first conduit 52 is connected to the anode compartment 34 in order to withdraw product gas and transport same to the flow management section 22 and gas production section 26 of the gas supply system 20. Disposed in this first conduit 52, in the given sequence from the upstream side, are a first flow rate control valve 54, an adsorption cartridge 56, a minibuffer tank 58, a compressor (suction means) 62, and a main buffer tank 64.
  • the product gas produced in the anode compartment 34 is forcibly withdrawn from the anode compartment 34 by suction of the first conduit 52 by the compressor 62 and is stored in the main buffer tank 64.
  • Reference number 66 in Figure 1 denotes a line filter.
  • hydrogen fluoride will be admixed at several percent (for example, 5%) in the product gas. This hydrogen fluoride is removed when the product gas passes through the adsorption cartridge 56.
  • This cartridge 56 should therefore hold adsorbent capable of adsorptively capturing hydrogen fluoride.
  • the adsorbent should be composed of a large number of pellets filled in the cartridge 56.
  • the adsorbent may be composed, for example, of adsorbent whose adsorption capacity varies as a function of temperature, such as sodium fluoride (NaF).
  • a temperature-regulating jacket (heater) 57 is disposed over the circumference of the cartridge 56 in order to regulate the temperature of the cartridge 56.
  • the pressure within the main buffer tank 64 is continuously measured by a pressure gauge 65 disposed on the tank 64. This measurement result is transmitted to the control member 39 connected to the current source 38.
  • the control member 39 controls the feed of current to the electrolytic cell 32 based on the transmitted measurement result by switching the current source 38 on and off.
  • the current source 38 is switched on and fluorine gas production is begun.
  • the pressure within the tank 64 has increased to a certain pressure, the current source 38 is switched off and fluorine gas production is halted. This enables electrolysis to be stopped without setting up differences in the molten salt surface levels within the electrolytic cell 32 between the anode compartment 34 and cathode compartment 36.
  • the pressure within the tank 64 is set, for example, to atmospheric pressure to atmospheric pressure + 0.18 MPa.
  • a second conduit 72 is connected to the cathode compartment 36 in order to withdraw the by-product gas.
  • This second conduit 72 is detachably connected to a conduit of the exhaust system (suction means) 78 of, for example, a semiconductor fabrication plant.
  • a second flow rate control valve 74 and a detoxifier 76 are disposed in this second conduit 72.
  • the by-product gas produced in the cathode compartment 36 is forcibly suctioned from the cathode compartment 36 by the suction in the second conduit 72 due to the exhaust system 78 and is moved through the detoxifier 76 and transported into the exhaust system 78.
  • the pressure balance between the anode compartment 34 and cathode compartment 36 can for various reasons become disturbed during the electrolytic process, with the result that changes in the surface level within the electrolytic cell 32 are prone to occur.
  • the surface level in the electrolytic cell 32 is also generally prone to change immediately after a gas-switching operation, such as a nitrogen purge of the interior of the electrolytic cell 32 or the nitrogen purge process after the end of feed of starting hydrogen fluoride gas. These surface level variations can have adverse effects on the safety and reliability of the fluorine gas generator.
  • the pressure of the gas phase region in the anode compartment 34 is continuously measured by a first pressure gauge 46 and the pressure of the gas phase region in the cathode compartment 36 is continuously measured by a second pressure gauge 48.
  • These measurement results are transmitted to first and second control members 55 and 75 connected, respectively, to first and second flow rate control valves 54 and 74.
  • the first and second control members 55 and 75 adjust the apertures of the first and second flow rate control valves 54 and 74 so as to maintain the pressure in the gas phase region of the anode compartment 34 and the pressure in the gas phase region of the cathode compartment 36, respectively, at first and second set values that are substantially equal to each other.
  • this structure protects the electrolytic cell 32 from the adverse effects of variations in the conditions of fluorine production, in the conditions within the first and second conduits 52 and 72, in the operating conditions of the exhaust system 78 of the semiconductor fabrication plant and the compressor 62, and in other circumstances. This makes it possible to prevent damage to the expensive electrodes, for example, the anode effect, and to carry out the process safely and without abrupt stoppages in electrolysis. In addition, frequent maintenance is no longer necessary since clogging due to the solidification of molten salt at the inlets to the first and second conduits 52 and 72 does not occur.
  • the first set value for the gas phase region in the anode compartment 34 and the second set value for the gas phase region in the cathode compartment 36 are preferably atmospheric pressure to 820 Torr and more preferably atmospheric pressure to 770 Torr.
  • the aperture of the first and second flow rate control valves 54 and 74 must be continuously adjustable in a highly responsive manner. This consideration makes it preferable to use a piezovalve for the first and second flow rate control valves 54 and 74.
  • a starting material conduit 82 is disposed in the cathode compartment 36 of the electrolytic cell 32 in order to feed hydrogen fluoride gas (consumable starting material) into the molten salt; this starting material conduit 82 is disposed immersed in the molten salt.
  • a hydrogen fluoride source 84 and a nitrogen source 94 are detachably connected through conduits 83 and 93 to the starting material conduit 82.
  • a switching valve 96 is disposed in the conduit 93 for the nitrogen source 94 in order to switch the conduit 93 between open and closed states.
  • the switching valve 96 is always open during operation of the fluorine gas generator 30 and nitrogen gas is always fed into the molten salt of the electrolytic cell 32 during operation of the fluorine gas generator 30.
  • the nitrogen gas flow rate is set at 0.2 to 50 L/min and preferably 2 to 10 L/min for a hydrogen fluoride gas flow rate of 1 to 50 L/min.
  • the nitrogen gas is almost completely insoluble in the molten salt and passes through the moiten salt on the cathode side and is discharged.
  • a switching valve 86 is disposed in the conduit 83 for the hydrogen fluoride source 84 in order to switch the conduit 83 between open and closed states.
  • This switching valve 86 is opened and closed under control by the control member 87 attached thereto.
  • the current fed during the electrolysis process between the anode 42 and the cathode 44 is integrated by the current integrator 40 and this value is transmitted to the control member 87.
  • the control member 87 operates the switching valve 86 so as to regulate the feed of hydrogen fluoride gas (mixture of hydrogen fluoride gas in nitrogen) into the molten salt.
  • the set value for the control member 87 is established, for example, so as to maintain the hydrogen fluoride concentration in the molten salt in the range from 39 to 41%.
  • the feed of hydrogen fluoride (HF) gas to the electrolytic cell 32 is controlled, based on the following theory, by integration of the supplied current.
  • X amount of electricity (in this case the electrolysis current value (A))
  • the initial hydrogen fluoride concentration in the molten salt is set, for example, to 41%.
  • the supply of starting hydrogen fluoride gas is then timed to occur after the hydrogen fluoride concentration in the molten salt has fallen from its initial 41% concentration and prior to reaching a lower concentration limit, for example, 39%.
  • a lower concentration limit for example, 39%.
  • the increase in the melting point of the molten salt when the hydrogen fluoride concentration falls below the lower concentration limit can in the worst case result in solidification of the molten salt and make it impossible to carry out electrolysis.
  • the hydrogen fluoride concentration exceeds the initial concentration the resulting high vapor pressure of the hydrogen fluoride in the molten salt will also raise the concentration of hydrogen fluoride mixed in the fluorine.
  • Equation (2) shows the relationship between fluorine gas production and hydrogen fluoride gas consumption.
  • 2 moles hydrogen fluoride are required for the production of 1 mole fluorine.
  • Equation (3) hydrogen fluoride consumption (L) Equation (3) is obtained by substituting, based on equation (1), 6.8X for Z in equation (2).
  • the amount of consumable hydrogen fluoride depends on the amount of molten salt introduced into the electrolytic cell 32. Given that the hydrogen fluoride concentration in the molten salt prior to the start of electrolysis is 41%, the amount of hydrogen fluoride in the electrolytic cell 32 is then 0.41 C where C is the amount of molten salt. The relationship between the hydrogen fluoride concentration in the molten salt and hydrogen fluoride consumption is given by equation (4) when the electrolytic cell 32 is' used in the 39-41 % hydrogen fluoride concentration range. The maximum amount of consumable hydrogen fluoride is then given by equation (5).
  • Equation (6) and then equation (7) are obtained by substituting T in equation (3) for HFc in equation (5).
  • the relationship between the amount of electricity X and the fluorine production time t for the hydrogen fluoride concentration range used of 39-41 % can be determined if the weight C of the molten salt (KF/2HF) preliminarily introduced into the electrolytic cell 32 is known.
  • the timing (lower limit of the range used) of hydrogen fluoride gas feed can be specified by the value afforded by integration of the amount of electricity along the time axis, and as a consequence the amount of electricity X need not be fixed.
  • Japanese Laid Open Patent Application (PCT) Number Hei 9-505853 discloses a fluorine cell that contains a control sensor means that detects the electrolyte level in the electrolytic cell and a current supply means that responds to a signal from the control sensor means and starts or stops the supply of current in response to this signal. In this case, fluorine production continues until the decline in the surface level reaches a preset position at which a signal is issued. Since in response to this signal the electrolysis controlling apparatus stops the supply of current to the cell, electrolysis is stopped and the fall in the surface level of the electrolyte is also stopped.
  • PCT Japanese Laid Open Patent Application
  • the 853 publication also makes it clear that the anode compartment in the electrolytic cell is to function as a fluorine reservoir.
  • the fluorine generators used for semiconductor processing at a practical level require a compressor and a capacitor of a certain size.
  • the technology disclosed in the publication under consideration cannot accommodate such changes in the external environment.
  • the fine molten salt mist entrained by the fluorine infiltrates into the conduit or into the capacitor present between the compressor and electrolytic cell. Since this mist has a melting point around 80°C, it will be present as a solid in the conduit. As this mist accumulates, it will cause such problems as (1) clogging of the conduit and (2) damage to the valve seat of the ON/OFF valve.
  • An important feature of the above-described embodiment of this invention is that it is not influenced by changes in the post-cell environment and can continuously and stably generate fluorine.
  • This fluorine-supplying apparatus is consciously designed for semiconductor processing service, i.e., it is essentially premised on the use of a suction apparatus such as a compressor.
  • the pressure gauge connected to the buffer tank downstream from the compressor is linked to the current source.
  • the power source is switched on and fluorine is generated.
  • the power source is switched off when the pressure has increased up to a certain point.
  • the 853 publication teaches that for safety reasons it is preferable that operations always be carried out with the pressure at the cathode side outlet at atmospheric pressure (or at a pressure slightly above atmospheric pressure). However, it is almost impossible to maintain this in an actual semiconductor plant due to the large pressure variations occurring therein in the cathode side conduit. Moreover, the 853 publication focuses only on pressure changes in the anode compartment and bases this on the premise that the pressure in the cathode compartment is always atmospheric pressure. Pressure maintenance by independent flow rate controls in the above-described embodiment of this invention enables the pressure in the two electrode compartments of the electrolytic cell to be maintained constant at all times. However, in practice the surface level cannot be determined from the pressure, and for this reason in order to enhance safety one surface level sensor is inserted in a preferred modality on the anode or cathode side and preferably on the cathode side.
  • the starting anhydrous hydrogen fluoride is ordinarily a gas and is fed by bubbling into the molten salt (preferably on the cathode side) of the electrolytic cell.
  • AHF exhibits a very fast rate of absorption into the molten salt, and as a result the cathode compartment can instantaneously assume a negative pressure when the AHF is supplied at a slow flow rate.
  • the AHF feed flow rate is therefore preferably rapid, but there are limitations on the AHF flow rate that can be used in practice.
  • the AHF is mixed into nitrogen gas during the AHF feed interval with the goal of raising the overall flow rate during AHF feed. Since nitrogen gas is almost completely insoluble in the molten salt, it passes through the molten salt on the cathode side and is discharged. This flow of nitrogen gas into the cathode compartment is maintained at all times regardless of whether electrolysis is actually underway. This results in dilution of the hydrogen generated on the cathode side during electrolysis and makes it possible to maintain conditions outside the explosive limit even when fluorine gas is introduced to the cathode side due to a sudden and unexpected change in surface levels.
  • the nitrogen flow rate is regulated optimally on the basis of the size of the electrolytic cell.
  • the fluorine gas generator 30 is detachably incorporated in the semiconductor processing system in the embodiment described above, but the generator may also be permanently installed in this system.
  • components disposed within the semiconductor fabrication plant itself can be used for several of the components assigned to the fluorine gas generator 30, e.g., the compressor 62, main buffer tank 64, detoxifier 76, and so forth.
  • the fluorine gas may be alternately fed to the flow management section 22 or gas production section 26 or may be directly fed to the process chamber 12 separately from the other process gases.
  • the gas production section 26 can also be configured to produce other fluorine-system process gases rather than interhalogen fluorine compounds.
  • this invention provides a fluorine gas generator that is capable of very safe and highly reliable operation even during long-term operations.
  • Figure 1 contains a schematic drawing that illustrates a semiconductor processing system that incorporates a fluorine gas generator that is an embodiment of this invention.
  • Figure 2 contains a schematic drawing that illustrates a modified example of the semiconductor processing system used in combination with the gas feed system illustrated in Figure 1.
  • Figure 3 contains a schematic drawing that illustrates a prior art fluorine gas generator.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un appareil de production de gaz fluoré, qui peut fonctionner de manière très sûre et très fiable, même pendant des opérations à long terme. Elle concerne également un appareil (30) de production de gaz fluoré, qui comprend une cellule d'électrolyse (32) générant, dans une première zone de phase gazeuse, côté anode, un gaz produit dont le constituant principal est le gaz fluoré; et dans une seconde zone de phase gazeuse, côté cathode, un gaz dérivé dont le constituant principal est le gaz hydrogène. Un premier et un second manomètres de contrôle (46 et 48) sont mis en place pour mesurer la pression dans la première et la seconde zones de phase gazeuse. Un premier et un second conduits (52 et 72) extraient le gaz produit et le gaz dérivé. Une première et une seconde soupapes de régulation du débit sont disposées dans le premier et le second conduits (52 et 72). Les ouvertures de la première et de la seconde soupapes de régulation du débit sont réglées sur la base des résultats des mesures obtenues du premier et du second manomètres de contrôle (46 et 48), de façon à maintenir les pressions dans la première et la seconde zones de phase gazeuse conformément à une première et une seconde valeurs définies, sensiblement égales.
PCT/IB2003/002998 2002-07-11 2003-06-30 Appareil de production de gaz fluore Ceased WO2004007802A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002202734A JP3905433B2 (ja) 2002-07-11 2002-07-11 フッ素ガス生成装置
JP2002-202734 2002-07-11

Publications (2)

Publication Number Publication Date
WO2004007802A2 true WO2004007802A2 (fr) 2004-01-22
WO2004007802A3 WO2004007802A3 (fr) 2004-07-15

Family

ID=30112643

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2003/002998 Ceased WO2004007802A2 (fr) 2002-07-11 2003-06-30 Appareil de production de gaz fluore

Country Status (5)

Country Link
JP (1) JP3905433B2 (fr)
KR (1) KR101065906B1 (fr)
CN (1) CN1668779A (fr)
TW (1) TWI293342B (fr)
WO (1) WO2004007802A2 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006043125A1 (fr) * 2004-10-20 2006-04-27 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Generateur de gaz fluor
US8366886B2 (en) 2005-08-25 2013-02-05 Toyo Tanso Co., Ltd. Fluorogas generator
US20130032471A1 (en) * 2010-04-16 2013-02-07 Central Glass Company, Limited. Fluorine gas generating apparatus
WO2013092772A1 (fr) * 2011-12-22 2013-06-27 Solvay Sa Procédé d'introduction de fluorure d'hydrogène dans une cellule électrolytique
CN104651873A (zh) * 2014-12-22 2015-05-27 四川聚核科技有限公司 智能化集装箱模组式中温电解制氟装置
CN113430543A (zh) * 2021-07-08 2021-09-24 中核四0四有限公司 一种制氟电解槽液态氟化氢集中供料方法
CN113874554A (zh) * 2019-12-27 2021-12-31 昭和电工株式会社 氟气的制造方法和氟气制造装置
EP4083265A4 (fr) * 2019-12-27 2024-09-11 Resonac Corporation Procédé et appareil de production de gaz fluor
EP4083261A4 (fr) * 2019-12-27 2024-09-11 Resonac Corporation Procédé de production de fluor gazeux et dispositif de production de fluor gazeux
EP4083605A4 (fr) * 2019-12-27 2024-09-25 Resonac Corporation Dispositif de production de gaz fluoré et détecteur à diffusion de lumière
EP4083263A4 (fr) * 2019-12-27 2024-10-02 Resonac Corporation Procédé de fabrication de fluor gazeux et dispositif de fabrication de fluor gazeux
EP4083264A4 (fr) * 2019-12-27 2024-10-02 Resonac Corporation Procédé de production de fluor gazeux et appareil de production de fluor gazeux
EP4083260A4 (fr) * 2019-12-27 2024-10-09 Resonac Corporation Procédé de production de fluor gazeux et appareil de production de fluor gazeux

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4624699B2 (ja) * 2004-03-18 2011-02-02 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード フッ素ガス生成装置
JP4494158B2 (ja) * 2004-10-13 2010-06-30 東洋炭素株式会社 ガス発生装置及びガス発生装置の配管温度調節方法
JP5572981B2 (ja) 2009-04-01 2014-08-20 セントラル硝子株式会社 フッ素ガス生成装置
JP5332829B2 (ja) * 2009-04-01 2013-11-06 セントラル硝子株式会社 フッ素ガス生成装置
JP5581676B2 (ja) 2009-12-02 2014-09-03 セントラル硝子株式会社 フッ素ガス生成装置
JP5577705B2 (ja) * 2010-01-05 2014-08-27 セントラル硝子株式会社 フッ素ガス生成装置
JP5544895B2 (ja) * 2010-01-21 2014-07-09 セントラル硝子株式会社 フッ素ガス生成装置
MY162759A (en) * 2010-03-26 2017-07-14 Solvay Method for the supply of fluorine
JP5567375B2 (ja) * 2010-04-14 2014-08-06 東洋炭素株式会社 気体発生装置および気体発生方法
JP5716288B2 (ja) * 2010-04-16 2015-05-13 セントラル硝子株式会社 フッ素ガス生成装置
JP5757168B2 (ja) * 2011-06-10 2015-07-29 セントラル硝子株式会社 フッ素ガス生成装置
TWI820854B (zh) * 2022-08-11 2023-11-01 亞福儲能股份有限公司 電池檢測裝置

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB817071A (en) * 1944-03-15 1959-07-22 Kenneth E Stuart Improved electrolytic cell
US3349326A (en) * 1963-03-12 1967-10-24 Int Standard Electric Corp Electrolytic current integrator
JPS63307289A (ja) * 1987-06-04 1988-12-14 Yokogawa Electric Corp イオン交換膜法電槽圧力制御装置
JPH0755807B2 (ja) * 1987-11-04 1995-06-14 三井東圧化学株式会社 三弗化窒素の製造方法
JPH0678593B2 (ja) * 1989-03-03 1994-10-05 三井東圧化学株式会社 溶融塩電解法によるガスの製造方法
JPH0353090A (ja) * 1989-07-18 1991-03-07 Asahi Glass Co Ltd フッ素の製造方法
JP2809811B2 (ja) * 1990-04-27 1998-10-15 三井化学株式会社 三弗化窒素ガスの製造方法
JP3342139B2 (ja) * 1993-12-24 2002-11-05 三菱重工業株式会社 導電性高分子製造方法及び製造装置
GB9418598D0 (en) * 1994-09-14 1994-11-02 British Nuclear Fuels Plc Fluorine cell
CN1307325C (zh) * 2000-04-07 2007-03-28 东洋炭素株式会社 氟气发生装置
JP4085174B2 (ja) * 2002-05-29 2008-05-14 東洋炭素株式会社 フッ素ガス発生装置

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006043125A1 (fr) * 2004-10-20 2006-04-27 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Generateur de gaz fluor
US8366886B2 (en) 2005-08-25 2013-02-05 Toyo Tanso Co., Ltd. Fluorogas generator
US20130032471A1 (en) * 2010-04-16 2013-02-07 Central Glass Company, Limited. Fluorine gas generating apparatus
US9139918B2 (en) * 2010-04-16 2015-09-22 Central Glass Company, Limited Fluorine gas generating apparatus
WO2013092772A1 (fr) * 2011-12-22 2013-06-27 Solvay Sa Procédé d'introduction de fluorure d'hydrogène dans une cellule électrolytique
CN104651873A (zh) * 2014-12-22 2015-05-27 四川聚核科技有限公司 智能化集装箱模组式中温电解制氟装置
CN113874554B (zh) * 2019-12-27 2024-01-05 株式会社力森诺科 氟气的制造方法和氟气制造装置
CN113874554A (zh) * 2019-12-27 2021-12-31 昭和电工株式会社 氟气的制造方法和氟气制造装置
EP4083265A4 (fr) * 2019-12-27 2024-09-11 Resonac Corporation Procédé et appareil de production de gaz fluor
EP4083261A4 (fr) * 2019-12-27 2024-09-11 Resonac Corporation Procédé de production de fluor gazeux et dispositif de production de fluor gazeux
EP4083262A4 (fr) * 2019-12-27 2024-09-11 Resonac Corporation Procédé et dispositif de production de gaz fluor
EP4083605A4 (fr) * 2019-12-27 2024-09-25 Resonac Corporation Dispositif de production de gaz fluoré et détecteur à diffusion de lumière
EP4083263A4 (fr) * 2019-12-27 2024-10-02 Resonac Corporation Procédé de fabrication de fluor gazeux et dispositif de fabrication de fluor gazeux
EP4083264A4 (fr) * 2019-12-27 2024-10-02 Resonac Corporation Procédé de production de fluor gazeux et appareil de production de fluor gazeux
EP4083260A4 (fr) * 2019-12-27 2024-10-09 Resonac Corporation Procédé de production de fluor gazeux et appareil de production de fluor gazeux
CN113430543A (zh) * 2021-07-08 2021-09-24 中核四0四有限公司 一种制氟电解槽液态氟化氢集中供料方法

Also Published As

Publication number Publication date
WO2004007802A3 (fr) 2004-07-15
JP2004043885A (ja) 2004-02-12
KR101065906B1 (ko) 2011-09-19
JP3905433B2 (ja) 2007-04-18
TWI293342B (en) 2008-02-11
KR20050017115A (ko) 2005-02-21
TW200400921A (en) 2004-01-16
CN1668779A (zh) 2005-09-14

Similar Documents

Publication Publication Date Title
WO2004007802A2 (fr) Appareil de production de gaz fluore
CN1307325C (zh) 氟气发生装置
JP3645495B2 (ja) フッ素ガス発生装置
JP4624699B2 (ja) フッ素ガス生成装置
EP2559789A1 (fr) Dispositif de génération de gaz fluoré
JP4926318B2 (ja) ガス配送システム
JP4584549B2 (ja) フッ素ガス生成装置
JP3527735B1 (ja) フッ素ガス発生装置
JP4085174B2 (ja) フッ素ガス発生装置
WO2005031039A2 (fr) Unite de production de fluor gazeux
JP3725822B2 (ja) フッ素ガス生成及び供給装置
CN101248216B (zh) 氟系气体产生装置
JP2003190762A (ja) フッ化水素を含むフッ素ガスの生成装置
WO2006043125A1 (fr) Generateur de gaz fluor
TW201331419A (zh) 氟氣生成裝置
JP2009191362A (ja) 溶融塩電解装置及びフッ素ガスの発生方法
CN102369314B (zh) 氟气生成装置
JP5716288B2 (ja) フッ素ガス生成装置
JP2009280862A (ja) フッ素発生装置及びフッ素原料の再生方法並びにフッ素利用システム
WO2010113612A1 (fr) Dispositif de génération de gaz de fluor
CN119642104A (zh) 一种气体纯化设备使用的再生气体生成装置
CN120099540A (zh) 一种气体纯化设备使用的再生气体生成装置
JP2004216233A (ja) ガス供給ライン構造
JPS62277729A (ja) ドライエツチング装置

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): CN KR SG US

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 1020057000438

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 20038165309

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 1020057000438

Country of ref document: KR

122 Ep: pct application non-entry in european phase