WO2003056066A2 - Apparatus for the generation and supply of fluorine gas - Google Patents

Apparatus for the generation and supply of fluorine gas Download PDF

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Publication number
WO2003056066A2
WO2003056066A2 PCT/EP2002/014909 EP0214909W WO03056066A2 WO 2003056066 A2 WO2003056066 A2 WO 2003056066A2 EP 0214909 W EP0214909 W EP 0214909W WO 03056066 A2 WO03056066 A2 WO 03056066A2
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WO
WIPO (PCT)
Prior art keywords
gas
electrolytic cell
section
fluorine gas
fluorine
Prior art date
Application number
PCT/EP2002/014909
Other languages
French (fr)
Other versions
WO2003056066A3 (en
Inventor
Kennedy Colin
Takato Kimura
Minoru Ino
Jun Sonobe
Original Assignee
L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation 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 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude filed Critical L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude
Priority to US10/500,406 priority Critical patent/US20050161321A1/en
Priority to KR10-2004-7010078A priority patent/KR20040075034A/en
Priority to AU2002367093A priority patent/AU2002367093A1/en
Priority to EP02805785A priority patent/EP1461475A2/en
Publication of WO2003056066A2 publication Critical patent/WO2003056066A2/en
Publication of WO2003056066A3 publication Critical patent/WO2003056066A3/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/24Halogens or compounds thereof
    • C25B1/245Fluorine; Compounds thereof
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4405Cleaning of reactor or parts inside the reactor by using reactive gases
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/02Process control or regulation

Definitions

  • This invention relates to an apparatus that is disposed in the gas supply system of a semiconductor processing system and that generates and supplies fluorine gas.
  • 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 or to clean the interior of process compartments, which are not necessarily limited to semiconductor processes.
  • Fluorine-type process gases are generally made available to the gas supply system of a semiconductor processing system as an already prepared fluorine compound filled in a cylinder. Gases of this type are seldom produced on-site from their essential precursors, e.g., fluorine. The reasons for this relate not just to problems with the reliability of the gas composition, but also to the extreme danger associated
  • United States Patent No. 5,688,384 discloses an apparatus that automatically controls the on/off switching of fluorine gas generation in response to demand.
  • this apparatus uses an electrolytic cell that generates fluorine gas by the electrolysis of hydrogen fluoride. Since such electrolytic-type apparatuses can as necessary produce fluorine gas at near atmospheric pressure, they can avoid the safety problems associated with the installation of fluorine cylinders.
  • the object of this invention is to provide a fluorine gas-generating and -supply apparatus that is disposed in the gas supply system of a semiconductor processing system and that in the event of abnormalities in the apparatus enables back up by a safe and inexpensive structure.
  • a particular object of this invention is to provide an apparatus that can generate and supply fluorine gas both on-site and on-demand.
  • on-site means that the mechanism for generating and supplying the fluorine gas 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 is an apparatus that generates and supplies fluorine gas and is disposed in the gas supply system of a semiconductor processing system, said apparatus being characteristically provided with an electrolytic cell that generates fluorine gas by the electrolysis of hydrogen fluoride in an electrolytic bath comprising hydrogen fluoride-containing molten salt, a cylinder that stores a substitute gas selected from the group consisting of nitrogen fluoride, sulfur fluoride, and chlorine fluoride, a gas switching section that is connected to the electrolytic cell and cylinder and that selectively supplies a gas utilization section with fluorine gas from the electrolytic cell or substitute gas from the cylinder, an electrolytic cell detector that detects the state of the electrolytic cell, and a controller that, upon detection of an abnormal state at the electrolytic cell by the electrolytic cell detector, exercises control on the gas switching section so as to feed the substitute gas from the cylinder to the gas utilization section.
  • the second aspect of this invention is an apparatus in accordance with the first aspect with the additional characteristic feature that the electrolytic cell detector detect
  • the third aspect of this invention is an apparatus in accordance with the second aspect with the additional characteristic feature that the electrolytic cell detector detects a state selected from the electrical current characteristics, liquid level, and temperature of the electrolytic bath.
  • the fourth aspect of this invention is an apparatus in accordance with any of the first to third aspects, characterized in that the apparatus is additionally provided with a path detector that can detect an abnormal state in the gas supply path that supplies fluorine gas from the electrolytic cell to the gas utilization section and in that the controller, upon detection of an abnormal state at the electrolytic cell by the electrolytic cell detector or upon detection of an abnormal state in the gas supply path by the path detector, exercises control on the gas switching section so as to feed the substitute gas from the cylinder to the gas utilization section.
  • the fifth aspect of this invention is an apparatus that generates and supplies fluorine gas and is disposed in the gas supply system of a semiconductor processing system, said apparatus being characteristically provided with an electrolytic cell that generates fluorine gas by the electrolysis of hydrogen fluoride in an electrolytic bath comprising hydrogen fluoride-containing molten salt, a cylinder that stores a substitute gas selected from the group consisting of nitrogen fluoride, sulfur fluoride, and chlorine fluoride, a gas switching section that is connected to the electrolytic cell and cylinder and that selectively supplies a gas utilization section with fluorine gas from the electrolytic cell or substitute gas from the cylinder, a path detector that can detect an abnormal state in the gas supply path that supplies fluorine gas from the electrolytic cell to the gas utilization section, and a controller that, upon detection of an abnormal state in the gas supply path by the path detector, exercises control on the gas switching section so as to feed the substitute gas from the cylinder to the gas utilization section.
  • an electrolytic cell that generates fluorine gas by the electrolysis of hydrogen flu
  • the sixth aspect of this invention is an apparatus in accordance with the fourth or fifth aspect, characterized in that the gas supply path is provided with a buffer section that controls the pressure and flow rate of the fluorine gas that is supplied from the electrolytic cell to the gas switching section and in that the path detector is provided with a buffer detector that detects the state of the buffer section.
  • the seventh aspect of this invention is an apparatus in accordance with the sixth aspect, characterized in that the buffer section is provided with a compressor that pressurizes the fluorine gas from the electrolytic cell and in that the buffer detector detects the operational status of the compressor.
  • the eighth aspect of this invention is an apparatus in accordance with the sixth aspect, characterized in that the buffer section is provided with a buffer tank that temporarily stores fluorine gas from the electrolytic cell and in that the buffer detector detects the pressure within the buffer tank.
  • the ninth aspect of this invention is an apparatus in accordance with the sixth aspect, characterized in that the buffer section is provided with a flow controller that supplies fluorine gas from the electrolytic cell to the gas switching section at a specified flow rate and in that the buffer detector detects the fluorine gas flow rate at said flow controller.
  • the tenth aspect of this invention is an apparatus in accordance with any of the first through ninth aspects, characterized in that the substitute gas comprises chlorine fluoride.
  • 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.
  • these omitted elements can be suitably fulfilled by conventional well- known technologies in the actual working of the derived inventive embodiment.
  • FIG. 1 contains a schematic drawing that illustrates a semiconductor processing system that incorporates an embodiment of the inventive apparatus for the generation and supply of fluorine gas.
  • This semiconductor processing system contains a semiconductor processing apparatus 10 that executes a process, such as film formation, etching, or diffusion, on a target substrate such as 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. Disposed within the process chamber 12 is 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
  • 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 gas 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.
  • a gas production section 26 that generates fluorine gas-type process gas by a reaction process.
  • An inventive apparatus 30 for the generation and supply of fluorine gas is connected in the embodiment under consideration to the flow management section 22 and the gas production section 26.
  • this generation and supply apparatus 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 generation and supply apparatus 30 contains an electrolytic cell 34 that generates fluorine gas (F2) by the electrolysis of hydrogen fluoride in 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 34 is connected to a hydrogen fluoride source 32 that supplies hydrogen fluoride, the starting material that undergoes depletion.
  • a detector 36 is disposed within the electrolytic cell 34 for the purpose of detecting, as a state representative of changes in the composition of the electrolytic bath, the electrical current characteristics, liquid level, temperature, etc., of the electrolytic bath.
  • the detection results generated by the detector 36 are fed to a controller 40.
  • the electrolytic cell 34 is replenished with hydrogen fluoride — the consumable starting material — from the hydrogen fluoride source 32 based on the detection result yielded by the detector 36 and under control by the controller 40 using a quantitative threshold value as the criterion.
  • the fluorine gas generated by the electrolytic cell 34 is fed to a gas switching section 56 across a buffer section 42; the purpose of the buffer section 42 is to control the pressure and flow rate of the fluorine gas present in the supply conduit 38.
  • This buffer section 42 is provided with a compressor 44 in order to pressurize the fluorine gas generated at substantially atmospheric pressure at the electrolytic cell 34, a buffer tank 46 that temporarily holds the fluorine gas, and a flow controller 48 that feeds fluorine gas from the buffer tank 46 to the gas switching section 56 at a specified flow rate.
  • An operations detector 50 is disposed at the compressor 44 in order to detect the operational status of the compressor 44.
  • a pressure detector 52 is disposed at the buffer tank 46 in order to detect the pressure within the buffer tank 46.
  • a flow rate detector 54 is disposed at the flow controller 48 in order to detect the flow rate of the fluorine gas in the flow controller 48. The detection results generated by these detectors 50, 52, and 54 are fed to the controller 40.
  • a back-up section 60 is provided against the contingency of the appearance of abnormalities in the electrolytic cell 34 (fluorine gas generator), supply conduit that runs from the electrolytic cell 34 to the gas utilization section, or fluorine gas supply path (including the buffer section 42).
  • This back-up section 60 is provided with a cylinder 62 (or cylinder group) that holds the substitute gas used as a fluorine gas substitute.
  • the substitute gas exiting the valve 64 of the cylinder 62 is supplied, adjusted to a specified flow rate by the flow controller 66, to the gas switching section 56.
  • the substitute gas is selected from the group consisting of nitrogen fluoride, sulfur fluoride, and chlorine fluoride.
  • nitrogen fluoride as the substitute gas, it will be desirable to configure the flow controller to automatically bring the nitrogen fluoride flow rate to approximately two-thirds the fluorine flow rate when a switch is made from fluorine gas to nitrogen fluoride. This configuration can maintain a constant processing capacity at the location where the substitute gas is used.
  • the preferred substitute gas will also vary as a function of the type of process and the nature of the semiconductor processing apparatus. For example, nitrogen fluoride
  • the controller 40 controls the gas switching section 56 in such a manner that substitute gas is supplied to the gas utilization section (the main process facility) from the cylinder 62 when an abnormal state is detected in the electrolytic cell 34 and/or in the buffer section 42. Accompanying this gas switching at the gas switching section 56, the controller 40 also adjusts the status of the valve 64 on the cylinder 62 and adjusts the ON/OFF status of the operation of the buffer section 42 (for example, the operation of the compressor 44).
  • An abnormal state in the electrolytic cell 34 is sensed by the electrolytic cell detector 36.
  • the detector 36 detects, for example, the electric current characteristics, liquid level, or temperature of the electrolytic bath as a state representative of changes in the composition of the electrolytic bath and transmits the result to the controller 40.
  • the controller 40 compares the detected value with a preliminarily set threshold value and determines whether the electrolytic bath 34 resides in a normal state or has entered into an abnormal state.
  • an abnormal state at the buffer section 42 is detected by means of three detectors making up the buffer detector, i.e., the operations detector 50, the pressure detector 52, and the flow rate detector 54.
  • these detectors 50, 52, and 54 detect, respectively, the operational status of the compressor 44, the pressure within the buffer tank 46, and the fluorine gas flow rate at the flow controller 48, and transmit their results to the controller 40. The controller then compares these detected values with preliminarily set threshold values and determines whether the buffer section 42 resides in a normal state or has entered into an abnormal state.
  • the detectors 36, 50, 52, and 54 are respectively disposed in each of the main constituent members on the fluorine gas generation and supply side, which enables the location and type of an abnormal state on the generation and supply side to be recognized by the controller 40.
  • This enables the controller 40 to carry out, in correspondence to the location and type of an abnormal condition, a variety of information processing in connection with control of the gas switching section 56, including, for example, the decision on the timing of gas switching, the execution prior to gas switching of a program that checks the status of each main constituent member, transmission of an alarm signal that alerts the operator of the location, etc., of the abnormal state, and a manual operation indication.
  • the generation and supply apparatus 30 shown in Figure 1 uses a cylinder of the substitute gas as its back-up section rather than providing an additional iteration of the fluorine gas generation and supply structure that runs from the electrolytic cell 34 up to and including the buffer section 42. This results in lower initial costs and lower operating costs for the gas supply system.
  • the substitute gas selected from the group consisting of nitrogen fluoride, sulfur fluoride, and chlorine fluoride, while supplied filled in a cylinder, does not produce the problems associated with high-pressure fluorine cylinders and is therefore preferred from a safety standpoint.
  • Figure 3 contains a schematic diagram of a fluorine gas generation and supply apparatus that is another embodiment of this invention.
  • the controller 40 controls the gas switching section 56 with reference only to the detectors that detect an abnormal state in the gas supply path that supplies fluorine gas from the electrolytic cell 34 to the gas utilization section, and specifically only to the detection results for the state of the buffer section 42 generated by the detectors 50, 52, and 54.
  • the detection results for the liquid level of the electrolytic bath generated by the detector 36 are not transmitted to the controller 40, but rather are used by a controller 70 for replenishment of the electrolytic cell 34 with hydrogen fluoride from the hydrogen fluoride source 32.
  • An abnormal state at the electrolytic cell 34 will generally also cause an abnormality or perturbation in the status of the generated fluorine gas.
  • the basic information necessary for controlling the gas switching section 56 can be obtained by sensing an abnormal state in the gas supply path that supplies fluorine gas from the electrolytic cell 34 to the gas utilization section, for example, an abnormal state for the fluorine gas in the downstream buffer section 42.
  • an abnormal state in the gas supply path that supplies fluorine gas from the electrolytic cell 34 to the gas utilization section for example, an abnormal state for the fluorine gas in the downstream buffer section 42.
  • FIG 4 contains a schematic diagram of a fluorine gas generation and supply apparatus that is another embodiment of this invention.
  • This embodiment lacks detectors for detecting abnormal conditions at the compressor 44, buffer tank 46, and flow controller 48 in the buffer section 42.
  • a detector 72 that detects the pressure and flow rate in the gas supply conduit is provided instead to function as a detector of abnormal conditions in the gas supply path that feeds fluorine gas from the electrolytic cell 34 to the gas utilization section.
  • the controller 40 exercises control on the gas switching section 56 with reference not only to the detection result for the status of the electrolytic cell 34 afforded by the detector 36, but also to the detection results afforded by the detector 72 for the pressure and flow rate in the fluorine gas supply conduit.
  • the detector 72 can also be provided downstream from the gas switching section 56.
  • An abnormal state in the buffer section 42 will generally also cause an abnormal state or condition in the pressure and flow rate in the fluorine gas supply conduit.
  • the basic information necessary for controlling the gas switching section is necessary for controlling the gas switching section
  • the gas switching section 56 may also be disposed between the electrolytic cell 34 and the buffer section 42 in each of the embodiments discussed above. In such a case the controller 40 will exercise control on the gas switching section 56 with reference only to the detection result afforded by the detector 36 for the state of the electrolytic cell 34.
  • the fluorine gas is fed either to the flow management section 22 or to the gas production section 26 in the embodiments discussed above, this gas can be supplied directly to the process chamber 12 separately from other process gases.
  • the gas production section 26 can also be configured to produce other fluorine-type process gases instead of interhalogen fluorine compound gases.
  • a cylinder of fluorine gas can be used in each of the embodiments elaborated hereinabove in place of the cylinder of substitute gas insofar as the corresponding safety issues can be resolved.
  • this invention provides a fluorine gas-generation and -supply apparatus that is disposed in the gas supply system of a semiconductor processing system and that in the event of abnormalities in the apparatus enables back up by a safe and inexpensive structure.
  • Figure 1 contains a schematic drawing that illustrates a semiconductor processing system that incorporates an apparatus for the generation and supply of fluorine gas that is an embodiment of this invention.
  • Figure 2 contains a schematic drawing that illustrates an exemplary modification of the semiconductor processing apparatus that is used in combination with the gas supply system shown in Figure 1.
  • Figure 3 contains a schematic drawing that illustrates an apparatus for the generation and supply of fluorine gas that is another embodiment of this invention.
  • Figure 4 contains a schematic drawing that illustrates an apparatus for the generation and supply of fluorine gas that is yet another embodiment of this invention.

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  • Metallurgy (AREA)
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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Drying Of Semiconductors (AREA)

Abstract

To provide an apparatus for fluorine gas generation and supply that is disposed in the gas supply system of a semiconductor processing system and that in the event of abnormalities in the apparatus enables back up by a safe and inexpensive structure. An apparatus 30 for the generation and supply of gas is disposed in the gas supply system of a semiconductor processing system. This apparatus 30 contains an electrolytic cell 34 that generates fluorine gas and a cylinder 62 that holds a substitute gas selected from the group consisting of nitrogen fluoride, sulfur fluoride, and chlorine fluoride. The electrolytic cell 34 and cylinder 62 are connected to a gas switching section 56 that selectively supplies a gas utilization section with fluorine gas from the electrolytic cell 34 or with substitute gas from the cylinder 62. A controller 40 controls the gas switching section 56 in such a manner that, upon detection of an abnormal state at the electrolytic cell 34 or in the gas supply path by detectors 36, 72, substitute gas is supplied from the cylinder 62 to the gas utilization section.

Description

Apparatus for the generation and supply of fluorine gas
Field of the Invention
This invention relates to an apparatus that is disposed in the gas supply system of a semiconductor processing system and that generates and supplies fluorine gas. 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.
Description of the Prior Art
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 or to clean the interior of process compartments, which are not necessarily limited to semiconductor processes.
Fluorine-type process gases are generally made available to the gas supply system of a semiconductor processing system as an already prepared fluorine compound filled in a cylinder. Gases of this type are seldom produced on-site from their essential precursors, e.g., fluorine. The reasons for this relate not just to problems with the reliability of the gas composition, but also to the extreme danger associated
2 with placing a cylinder filled to high pressures (typically at least 5 kg/cm ) with a strong oxidizer such as fluorine in the gas supply system of a semiconductor processing system.
United States Patent No. 5,688,384, on the other hand, discloses an apparatus that automatically controls the on/off switching of fluorine gas generation in response to demand. As its fluorine gas generation module this apparatus uses an electrolytic cell that generates fluorine gas by the electrolysis of hydrogen fluoride. Since such electrolytic-type apparatuses can as necessary produce fluorine gas at near atmospheric pressure, they can avoid the safety problems associated with the installation of fluorine cylinders.
Problems to Be Solved by the Invention
When a fluorine gas-generating and -supply apparatus as described above is placed in the gas supply system of a semiconductor processing system, it is also necessary to provide a back-up means in order to prevent perturbations in the operation of the main processing apparatus even when abnormalities occur in the fluorine gas- generating and -supply apparatus. In a typical strategy, two fluorine gas-generating and -supply apparatuses are installed in a gas supply system and are operated in rotation as the online apparatus and back-up apparatus. This back-up strategy, however, causes high initial costs and high operating costs for the gas supply system. Moreover, while fluorine cylinders can also be used as a back-up means, safety problems are incurred by the disposition of high-pressure fluorine cylinders in the gas supply system of a semiconductor processing system.
This invention was developed in view of the problems identified above for the prior art. The object of this invention is to provide a fluorine gas-generating and -supply apparatus that is disposed in the gas supply system of a semiconductor processing system and that in the event of abnormalities in the apparatus enables back up by a safe and inexpensive structure.
A particular object of this invention is to provide an apparatus that can generate and supply fluorine gas both on-site and on-demand. As used herein, on-site means that the mechanism for generating and supplying the fluorine gas 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.
Means Solving the Problems The first aspect of this invention is an apparatus that generates and supplies fluorine gas and is disposed in the gas supply system of a semiconductor processing system, said apparatus being characteristically provided with an electrolytic cell that generates fluorine gas by the electrolysis of hydrogen fluoride in an electrolytic bath comprising hydrogen fluoride-containing molten salt, a cylinder that stores a substitute gas selected from the group consisting of nitrogen fluoride, sulfur fluoride, and chlorine fluoride, a gas switching section that is connected to the electrolytic cell and cylinder and that selectively supplies a gas utilization section with fluorine gas from the electrolytic cell or substitute gas from the cylinder, an electrolytic cell detector that detects the state of the electrolytic cell, and a controller that, upon detection of an abnormal state at the electrolytic cell by the electrolytic cell detector, exercises control on the gas switching section so as to feed the substitute gas from the cylinder to the gas utilization section. The second aspect of this invention is an apparatus in accordance with the first aspect with the additional characteristic feature that the electrolytic cell detector detects a state that is representative of the composition of the electrolytic bath.
The third aspect of this invention is an apparatus in accordance with the second aspect with the additional characteristic feature that the electrolytic cell detector detects a state selected from the electrical current characteristics, liquid level, and temperature of the electrolytic bath.
The fourth aspect of this invention is an apparatus in accordance with any of the first to third aspects, characterized in that the apparatus is additionally provided with a path detector that can detect an abnormal state in the gas supply path that supplies fluorine gas from the electrolytic cell to the gas utilization section and in that the controller, upon detection of an abnormal state at the electrolytic cell by the electrolytic cell detector or upon detection of an abnormal state in the gas supply path by the path detector, exercises control on the gas switching section so as to feed the substitute gas from the cylinder to the gas utilization section. The fifth aspect of this invention is an apparatus that generates and supplies fluorine gas and is disposed in the gas supply system of a semiconductor processing system, said apparatus being characteristically provided with an electrolytic cell that generates fluorine gas by the electrolysis of hydrogen fluoride in an electrolytic bath comprising hydrogen fluoride-containing molten salt, a cylinder that stores a substitute gas selected from the group consisting of nitrogen fluoride, sulfur fluoride, and chlorine fluoride, a gas switching section that is connected to the electrolytic cell and cylinder and that selectively supplies a gas utilization section with fluorine gas from the electrolytic cell or substitute gas from the cylinder, a path detector that can detect an abnormal state in the gas supply path that supplies fluorine gas from the electrolytic cell to the gas utilization section, and a controller that, upon detection of an abnormal state in the gas supply path by the path detector, exercises control on the gas switching section so as to feed the substitute gas from the cylinder to the gas utilization section.
The sixth aspect of this invention is an apparatus in accordance with the fourth or fifth aspect, characterized in that the gas supply path is provided with a buffer section that controls the pressure and flow rate of the fluorine gas that is supplied from the electrolytic cell to the gas switching section and in that the path detector is provided with a buffer detector that detects the state of the buffer section.
The seventh aspect of this invention is an apparatus in accordance with the sixth aspect, characterized in that the buffer section is provided with a compressor that pressurizes the fluorine gas from the electrolytic cell and in that the buffer detector detects the operational status of the compressor. The eighth aspect of this invention is an apparatus in accordance with the sixth aspect, characterized in that the buffer section is provided with a buffer tank that temporarily stores fluorine gas from the electrolytic cell and in that the buffer detector detects the pressure within the buffer tank.
The ninth aspect of this invention is an apparatus in accordance with the sixth aspect, characterized in that the buffer section is provided with a flow controller that supplies fluorine gas from the electrolytic cell to the gas switching section at a specified flow rate and in that the buffer detector detects the fluorine gas flow rate at said flow controller.
The tenth aspect of this invention is an apparatus in accordance with any of the first through ninth aspects, characterized in that the substitute gas comprises chlorine fluoride.
In addition, 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.
Embodiments of the Invention
Embodiments of this invention are explained in the following with reference to the drawings appended herewith. In the explanation that follows, those constituent elements that have approximately the same structure and function are assigned a common reference symbol and their explanation will be repeated only when necessary. Figure 1 contains a schematic drawing that illustrates a semiconductor processing system that incorporates an embodiment of the inventive apparatus for the generation and supply of fluorine gas. This semiconductor processing system contains a semiconductor processing apparatus 10 that executes a process, such as film formation, etching, or diffusion, on a target substrate such as 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. Disposed within the process chamber 12 is 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.
Figure 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. The application of RF (high frequency) power from the RF power source 15 to the coil antenna 17 results in the formation in the remote plasma chamber 13 of an induction field for the purpose of converting the process gas to a plasma. A gas supply system 20 is connected to the upper region of the remote plasma chamber 13 in order to supply the process gas.
With reference again to Figure 1 , 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 gas 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 generates fluorine gas-type process gas by a reaction process. An inventive apparatus 30 for the generation and supply of fluorine gas is connected in the embodiment under consideration to the flow management section 22 and the gas production section 26. More specifically, this generation and supply apparatus 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 generation and supply apparatus 30 contains an electrolytic cell 34 that generates fluorine gas (F2) by the electrolysis of hydrogen fluoride in 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 34 is connected to a hydrogen fluoride source 32 that supplies hydrogen fluoride, the starting material that undergoes depletion. A detector 36 is disposed within the electrolytic cell 34 for the purpose of detecting, as a state representative of changes in the composition of the electrolytic bath, the electrical current characteristics, liquid level, temperature, etc., of the electrolytic bath. The detection results generated by the detector 36 are fed to a controller 40. The electrolytic cell 34 is replenished with hydrogen fluoride — the consumable starting material — from the hydrogen fluoride source 32 based on the detection result yielded by the detector 36 and under control by the controller 40 using a quantitative threshold value as the criterion.
The fluorine gas generated by the electrolytic cell 34 is fed to a gas switching section 56 across a buffer section 42; the purpose of the buffer section 42 is to control the pressure and flow rate of the fluorine gas present in the supply conduit 38. This buffer section 42 is provided with a compressor 44 in order to pressurize the fluorine gas generated at substantially atmospheric pressure at the electrolytic cell 34, a buffer tank 46 that temporarily holds the fluorine gas, and a flow controller 48 that feeds fluorine gas from the buffer tank 46 to the gas switching section 56 at a specified flow rate. An operations detector 50 is disposed at the compressor 44 in order to detect the operational status of the compressor 44. A pressure detector 52 is disposed at the buffer tank 46 in order to detect the pressure within the buffer tank 46. A flow rate detector 54 is disposed at the flow controller 48 in order to detect the flow rate of the fluorine gas in the flow controller 48. The detection results generated by these detectors 50, 52, and 54 are fed to the controller 40.
A back-up section 60 is provided against the contingency of the appearance of abnormalities in the electrolytic cell 34 (fluorine gas generator), supply conduit that runs from the electrolytic cell 34 to the gas utilization section, or fluorine gas supply path (including the buffer section 42). This back-up section 60 is provided with a cylinder 62 (or cylinder group) that holds the substitute gas used as a fluorine gas substitute. The substitute gas exiting the valve 64 of the cylinder 62 is supplied, adjusted to a specified flow rate by the flow controller 66, to the gas switching section 56.
The substitute gas is selected from the group consisting of nitrogen fluoride, sulfur fluoride, and chlorine fluoride. Among these, the use of nitrogen fluoride as the substitute gas is particularly desirable due to its low reactivity at room temperature and because it is a relatively safe gas. When nitrogen fluoride (NF3) is used as the substitute gas, it will be desirable to configure the flow controller to automatically bring the nitrogen fluoride flow rate to approximately two-thirds the fluorine flow rate when a switch is made from fluorine gas to nitrogen fluoride. This configuration can maintain a constant processing capacity at the location where the substitute gas is used. The preferred substitute gas will also vary as a function of the type of process and the nature of the semiconductor processing apparatus. For example, nitrogen fluoride
(NF3) is preferably used as the substitute gas in the case of plasma cleaning while chlorine fluoride is preferably used as the substitute gas in the case of thermal cleaning. The controller 40 controls the gas switching section 56 in such a manner that substitute gas is supplied to the gas utilization section (the main process facility) from the cylinder 62 when an abnormal state is detected in the electrolytic cell 34 and/or in the buffer section 42. Accompanying this gas switching at the gas switching section 56, the controller 40 also adjusts the status of the valve 64 on the cylinder 62 and adjusts the ON/OFF status of the operation of the buffer section 42 (for example, the operation of the compressor 44).
An abnormal state in the electrolytic cell 34 is sensed by the electrolytic cell detector 36. In specific terms, the detector 36 detects, for example, the electric current characteristics, liquid level, or temperature of the electrolytic bath as a state representative of changes in the composition of the electrolytic bath and transmits the result to the controller 40. The controller 40 then compares the detected value with a preliminarily set threshold value and determines whether the electrolytic bath 34 resides in a normal state or has entered into an abnormal state. Likewise, an abnormal state at the buffer section 42 is detected by means of three detectors making up the buffer detector, i.e., the operations detector 50, the pressure detector 52, and the flow rate detector 54. In specific terms, these detectors 50, 52, and 54 detect, respectively, the operational status of the compressor 44, the pressure within the buffer tank 46, and the fluorine gas flow rate at the flow controller 48, and transmit their results to the controller 40. The controller then compares these detected values with preliminarily set threshold values and determines whether the buffer section 42 resides in a normal state or has entered into an abnormal state.
Thus, the detectors 36, 50, 52, and 54 are respectively disposed in each of the main constituent members on the fluorine gas generation and supply side, which enables the location and type of an abnormal state on the generation and supply side to be recognized by the controller 40. This enables the controller 40 to carry out, in correspondence to the location and type of an abnormal condition, a variety of information processing in connection with control of the gas switching section 56, including, for example, the decision on the timing of gas switching, the execution prior to gas switching of a program that checks the status of each main constituent member, transmission of an alarm signal that alerts the operator of the location, etc., of the abnormal state, and a manual operation indication.
The generation and supply apparatus 30 shown in Figure 1 uses a cylinder of the substitute gas as its back-up section rather than providing an additional iteration of the fluorine gas generation and supply structure that runs from the electrolytic cell 34 up to and including the buffer section 42. This results in lower initial costs and lower operating costs for the gas supply system. The substitute gas selected from the group consisting of nitrogen fluoride, sulfur fluoride, and chlorine fluoride, while supplied filled in a cylinder, does not produce the problems associated with high-pressure fluorine cylinders and is therefore preferred from a safety standpoint. Figure 3 contains a schematic diagram of a fluorine gas generation and supply apparatus that is another embodiment of this invention. In this embodiment the controller 40 controls the gas switching section 56 with reference only to the detectors that detect an abnormal state in the gas supply path that supplies fluorine gas from the electrolytic cell 34 to the gas utilization section, and specifically only to the detection results for the state of the buffer section 42 generated by the detectors 50, 52, and 54. The detection results for the liquid level of the electrolytic bath generated by the detector 36 are not transmitted to the controller 40, but rather are used by a controller 70 for replenishment of the electrolytic cell 34 with hydrogen fluoride from the hydrogen fluoride source 32. An abnormal state at the electrolytic cell 34 will generally also cause an abnormality or perturbation in the status of the generated fluorine gas. As a consequence, the basic information necessary for controlling the gas switching section 56 can be obtained by sensing an abnormal state in the gas supply path that supplies fluorine gas from the electrolytic cell 34 to the gas utilization section, for example, an abnormal state for the fluorine gas in the downstream buffer section 42. However, in this case it will be desirable to have enabled a separate sensing of any abnormal state at the electrolytic cell 34 unrelated to control of the gas switching section 56.
Figure 4 contains a schematic diagram of a fluorine gas generation and supply apparatus that is another embodiment of this invention. This embodiment lacks detectors for detecting abnormal conditions at the compressor 44, buffer tank 46, and flow controller 48 in the buffer section 42. A detector 72 that detects the pressure and flow rate in the gas supply conduit is provided instead to function as a detector of abnormal conditions in the gas supply path that feeds fluorine gas from the electrolytic cell 34 to the gas utilization section. The controller 40 exercises control on the gas switching section 56 with reference not only to the detection result for the status of the electrolytic cell 34 afforded by the detector 36, but also to the detection results afforded by the detector 72 for the pressure and flow rate in the fluorine gas supply conduit. As illustrated by the dash-and-dot line in Figure 4, the detector 72 can also be provided downstream from the gas switching section 56.
An abnormal state in the buffer section 42 will generally also cause an abnormal state or condition in the pressure and flow rate in the fluorine gas supply conduit. As a consequence, the basic information necessary for controlling the gas switching section
56 can be obtained by sensing an abnormal state in the pressure and flow rate within the fluorine gas supply conduit downstream from the buffer section 42.
The gas switching section 56 may also be disposed between the electrolytic cell 34 and the buffer section 42 in each of the embodiments discussed above. In such a case the controller 40 will exercise control on the gas switching section 56 with reference only to the detection result afforded by the detector 36 for the state of the electrolytic cell 34. Moreover, while the fluorine gas is fed either to the flow management section 22 or to the gas production section 26 in the embodiments discussed above, this gas can be supplied directly to the process chamber 12 separately from other process gases. The gas production section 26 can also be configured to produce other fluorine-type process gases instead of interhalogen fluorine compound gases. A cylinder of fluorine gas can be used in each of the embodiments elaborated hereinabove in place of the cylinder of substitute gas insofar as the corresponding safety issues can be resolved.
While various modifications and alterations within the technical sphere of the concept of this invention can be devised by the individual skilled in the art, it should be understood that such modifications and alterations also fall within the scope of this invention.
Advantageous Effects of the Invention
As has been described in detail hereinabove, this invention provides a fluorine gas-generation and -supply apparatus that is disposed in the gas supply system of a semiconductor processing system and that in the event of abnormalities in the apparatus enables back up by a safe and inexpensive structure. Brief Description of the Drawings
Figure 1 contains a schematic drawing that illustrates a semiconductor processing system that incorporates an apparatus for the generation and supply of fluorine gas that is an embodiment of this invention. Figure 2 contains a schematic drawing that illustrates an exemplary modification of the semiconductor processing apparatus that is used in combination with the gas supply system shown in Figure 1.
Figure 3 contains a schematic drawing that illustrates an apparatus for the generation and supply of fluorine gas that is another embodiment of this invention. Figure 4 contains a schematic drawing that illustrates an apparatus for the generation and supply of fluorine gas that is yet another embodiment of this invention.

Claims

Claims
1. Apparatus that generates and supplies fluorine gas and is disposed in the gas supply system of a semiconductor processing system, said apparatus being characteristically provided with an electrolytic cell that generates fluorine gas by the electrolysis of hydrogen fluoride in an electrolytic bath comprising hydrogen fluoride-containing molten salt, a cylinder that stores a substitute gas selected from the group consisting of nitrogen fluoride, sulfur fluoride, and chlorine fluoride, a gas switching section that is connected to the electrolytic cell and cylinder and that selectively supplies a gas utilization section with fluorine gas from the electrolytic cell or substitute gas from the cylinder, an electrolytic cell detector that detects the state of the electrolytic cell, and a controller that, upon detection of an abnormal state at the electrolytic cell by the electrolytic cell detector, exercises control on the gas switching section so as to feed the substitute gas from the cylinder to the gas utilization section.
2. The apparatus of claim 1 for the generation and supply of fluorine gas, characterized in that the electrolytic cell detector detects a state that is representative of the composition of the electrolytic bath.
3. The apparatus of claim 2 for the generation and supply of fluorine gas, characterized in that the electrolytic cell detector detects a state selected from the electrical current characteristics, liquid level, and temperature of the electrolytic bath.
4. Apparatus according to any of claims 1 to 3 for the generation and supply of fluorine gas, characterized in that the apparatus is additionally provided with a path detector that can detect an abnormal state in the gas supply path that supplies fluorine gas from the electrolytic cell to the gas utilization section and in that the controller, upon detection of an abnormal state at the electrolytic cell by the electrolytic cell detector or upon detection of an abnormal state in the gas supply path by the path detector, exercises control on the gas switching section so as to feed the substitute gas from the cylinder to the gas utilization section.
5. Apparatus that generates and supplies fluorine gas and is disposed in the gas supply system of a semiconductor processing system, said apparatus being characteristically provided with an electrolytic cell that generates fluorine gas by the electrolysis of hydrogen fluoride in an electrolytic bath comprising hydrogen fluoride-containing molten salt, a cylinder that stores a substitute gas selected from the group consisting of nitrogen fluoride, sulfur fluoride, and chlorine fluoride, a gas switching section that is connected to the electrolytic cell and cylinder and that selectively supplies a gas utilization section with fluorine gas from the electrolytic cell or substitute gas from the cylinder, a path detector that can detect an abnormal state in the gas supply path that supplies fluorine gas from the electrolytic cell to the gas utilization section, and a controller that, upon detection of an abnormal state in the gas supply path by the path detector, exercises control on the gas switching section so as to feed the substitute gas from the cylinder to the gas utilization section.
6. The apparatus according to - claim 4 or .5 for the generation and supply of fluorine gas, characterized in that the gas supply path is provided with a buffer section that controls the pressure and flow rate of the fluorine gas that is supplied from the electrolytic cell to the gas switching section and in that the path detector is provided with a buffer detector that detects the state of the buffer section.
7. The apparatus according to claim 6 for the generation and supply of fluorine gas, characterized in that the buffer section is provided with a compressor that pressurizes the fluorine gas from the electrolytic cell and in that the buffer detector detects the operational status of the compressor.
8. The apparatus according to claim 6 for the generation and supply of fluorine gas, characterized in that the buffer section is provided with a buffer tank that temporarily stores fluorine gas from the electrolytic cell and in that the buffer detector detects the pressure within the buffer tank.
9. The apparatus according to claim 6 for the generation and supply of fluorine gas, characterized in that the buffer section is provided with a flow controller that supplies fluorine gas from the electrolytic cell to the gas switching section at a specified flow rate and in that the buffer detector detects the fluorine gas flow rate at said flow controller.
10. Apparatus according to any of claims 1 through 9 for the generation and supply of fluorine gas, characterized in that the substitute gas comprises chlorine fluoride.
PCT/EP2002/014909 2001-12-27 2002-12-20 Apparatus for the generation and supply of fluorine gas WO2003056066A2 (en)

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US10/500,406 US20050161321A1 (en) 2001-12-27 2002-12-20 Apparatus for the generation and supply of fluorine gas
KR10-2004-7010078A KR20040075034A (en) 2001-12-27 2002-12-20 Apparatus for the Generation and Supply of Fluorine Gas
AU2002367093A AU2002367093A1 (en) 2001-12-27 2002-12-20 Apparatus for the generation and supply of fluorine gas
EP02805785A EP1461475A2 (en) 2001-12-27 2002-12-20 Apparatus for the generation and supply of fluorine gas

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JP2001397278A JP3725822B2 (en) 2001-12-27 2001-12-27 Fluorine gas generation and supply equipment

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CN1608146A (en) 2005-04-20
EP1461475A2 (en) 2004-09-29
JP2003193278A (en) 2003-07-09
AU2002367093A8 (en) 2003-07-15
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TW200306950A (en) 2003-12-01
AU2002367093A1 (en) 2003-07-15

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