US20050006248A1 - Apparatus for generating f2 gas method for generating f2 gas and f2 gas - Google Patents
Apparatus for generating f2 gas method for generating f2 gas and f2 gas Download PDFInfo
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- US20050006248A1 US20050006248A1 US10/497,158 US49715804A US2005006248A1 US 20050006248 A1 US20050006248 A1 US 20050006248A1 US 49715804 A US49715804 A US 49715804A US 2005006248 A1 US2005006248 A1 US 2005006248A1
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- 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
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- 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
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- 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
- C25B15/021—Process control or regulation of heating or cooling
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- 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
- C25B15/085—Removing impurities
Definitions
- the present invention relates to an apparatus for generating F 2 gas, a method for generating the F 2 gas, and F 2 gas.
- the present invention relates to an F 2 gas generating apparatus for generating high purity F 2 gas, in which a quantity of an impurity is extremely small, for use in a manufacturing process of semiconductor or the like, method for generating F 2 gas, and F 2 gas.
- F 2 gas has been used as a primary gas indispensably, for example, in a field of semiconductor manufacturing.
- the F 2 gas may sometimes be used alone, nitrogen trifluoride gas (hereinafter also referred to as “NF 3 gas”) which has been synthesized based on the F 2 gas has been recently used as a cleaning gas or a dry etching gas for semiconductor.
- NF 3 gas nitrogen trifluoride gas
- NeF gas neon fluoride gas
- ArF gas argon fluoride gas
- KrF gas krypton fluoride gas
- Mixed gas of rare gas and the F 2 gas is in many cases used as a raw material of the excimer laser oscillation gas.
- the F 2 gas is generated by performing electrolysis by using carbon as an anode and nickel as a cathode in an electrolytic cell containing a bath comprising a predetermined quantity of KF.HF.
- the KF.HF contained in the electrolytic cell is used in a form of KF.2HF to be prepared by further appropriately supplying HF into a predetermined quantity of an initially loaded HF. In a case in which KF.2HF is insufficient, KF.HF is loaded and, then, HF is once again added thereto to prepare a predetermined quantity of the bath.
- KF as a component of the bath, is high in hygroscopicity and ordinarily comes to contain moisture at the time of constructing the bath.
- an F 2 gas to be generated in a manner as described above is such a type of F 2 gas as an initially generated F 2 gas contains oxygen by from 45% to 55% therein.
- the F 2 gas to be generated and water in an electrolytic bath are reacted with each other in accordance with the formula (1) described below, thereby ordinarily reducing a quantity of oxygen contained in the F 2 gas. Nevertheless, it is difficult to bring the quantity thereof to 3000 ppm or less.
- the high purity F 2 gas is required as the above-described excimer laser oscillation gas or for performing a surface treatment on a stepper lens (CaF 2 single crystal) of the excimer laser.
- An oxygen concentration to be contained in the F 2 gas is required to be 1000 ppm or less as the excimer laser oscillation gas in the former case and 500 ppm or less as a gas for such surface processing of the stepper lens (CaF 2 single crystal) of the excimer laser in the latter case.
- An object according to the invention is to provide an F 2 gas generating apparatus which can consistently generates a high purity F 2 gas in which a quantity of oxygen to be contained is extremely small amount, an F 2 gas generating method and the high purity F 2 gas.
- an F 2 gas generating apparatus for generating an F 2 gas by subjecting an electrolytic bath comprising KF.2HF to electrolysis, being characterized by comprising:
- KF.2HF is prepared from KF or KF.HF in a closed preparing system
- the thus-prepared KF.2HF is loaded in an electrolytic cell connected with the preparing system in a closed space. Accordingly, KF.2HF loaded in the electrolytic cell is allowed to be an electrolytic bath without absorbing moisture, namely, having a small oxygen content.
- a quantity of oxygen to be contained in the F 2 gas to be obtained by subjecting this electrolytic bath to electrolysis is allowed to be small from an initial stage of generation.
- the F 2 gas generating apparatus is characterized in that a moisture removing device for removing moisture in the KF or KF-HF is attached to the preparing system.
- the F 2 gas generating apparatus is an F 2 gas generating apparatus in which an oxygen concentration in the thus-generated F 2 gas is 2% or less.
- the quantity of oxygen in the F 2 gas is reduced to be 2% or less, preferably 0.2% or less (2000 ppm or less) and more preferably 0.02% or less (200 ppm or less). Accordingly, the F 2 gas can be used as an excimer laser oscillating gas or as a gas for surface treatment of a stepper lens (CaF 2 single crystal) of an excimer laser.
- the F 2 gas generating apparatus is an F 2 gas generating apparatus for generating an F 2 gas by subjecting an electrolytic bath comprising KF.2HF to electrolysis, comprising:
- the moisture controlling device controlling the moisture in the atmosphere outside each of the preparing system, the HF supplying system and the F 2 gas generating systems or all the systems as a whole is provided, contamination of oxygen can surely be controlled.
- the F 2 gas generating apparatus is an F 2 gas generating apparatus in which the moisture controlling device is a box which contains each of the systems or all the systems as a whole and is capable of controlling an atmosphere inside the box.
- the moisture controlling device is a box capable of controlling the atmosphere, adjustment of atmosphere moisture of each of the systems or all the systems as a whole can easily be performed. Accordingly, contamination of oxygen can surely be controlled.
- an F 2 gas generating method is an F 2 gas generating method for generating an F 2 gas by subjecting an electrolytic bath comprising KF.2HF to electrolysis, comprising the steps of:
- the F 2 gas is allowed to be used as the excimer laser oscillating gas or as a gas for surface processing of the stepper lens (CaF 2 single crystal) of the excimer laser.
- the F 2 gas generating method according to the invention is an F 2 gas generating method in which, in the preparing system, the KF or KF.HF is heated at from 200° C. to 300° C. to remove adsorbed water or crystallization water of the KF or KF.HF therefrom.
- the moisture in KF or KF.HF can surely be removed.
- it becomes possible to remove oxygen in the moisture whereupon the oxygen concentration in the F 2 gas to be generated can surely be reduced from an initial stage of F 2 gas generation.
- an F 2 gas according to the invention is an F 2 gas generated by a method comprising the steps of:
- the F 2 gas according to the invention is an F 2 gas in which an oxygen concentration is 2% or less.
- the oxygen concentration is reduced to be preferably 0.2% or less (2000 ppm or less) and more preferably 0.02% or less (200 ppm or less).
- the F 2 gas can be-used as the excimer laser oscillating gas or as the gas for the surface processing of the stepper lens (CaF 2 single crystal) of the excimer laser.
- FIG. 1 is a schematic view of a fluorine gas generating apparatus according to the present invention.
- FIG. 2 is a chart showing a relationship among quantities of electricity in cases of Example 1, Comparative Examples 1 and 3, and a quantity of O 2 in F 2 gas.
- FIG. 1 An example of embodiments according to the present invention will be described with reference to FIG. 1 .
- An F 2 gas generating apparatus G which generates a high purity F 2 gas by subjecting an electrolytic bath 24 comprising KF.2HF to electrolysis, comprises a preparing system A which prepares KF.2HF from KF or KF.HF, an HF supplying system B which supplies HF to the electrolytic bath 24 and the preparing system A, and an F 2 gas generating system C which generates an F 2 gas by subjecting KF.2HF which has been prepared by the preparing system A to electrolysis.
- the preparing system A which prepares KF.2HF from KF or KF.HF comprises a KF.2HF preparing device 7 comprising a vessel 7 a made of Ni which contains KF 10 , and an upper cover 7 b which hermetically seals the vessel 7 a , a heater 9 which covers the vessel 7 a of the KF.2HF preparing device 7 and heats KF 10 inside the vessel 7 a , a cooling water pipe 8 for use in cooling, a vacuum piping 2 , provided in the upper cover 7 b , which is connected with a vacuum-exhausting system D, an inert gas purging piping 3 , and an HF supplying and a KF.2HF sending-out piping 1 which is inserted in KF 10 and connected to both the HF supplying system B and the F 2 gas generating system C.
- a KF.2HF preparing device 7 comprising a vessel 7 a made of Ni which contains KF 10 , and an upper cover 7 b which hermetically seal
- an HF cylinder 11 placed on a load cell 12 is arranged in a box 13 , which is connected to an acrylic scrubber (not shown).
- a surface of the HF cylinder 11 is covered by a heater 14 to maintain an interior of the HF cylinder 11 at a predetermined temperature.
- a quantity of gas inside the HF cylinder 11 is measured by a load cell 12 to measure a quantity of an HF gas to be supplied to both the preparing system A and the F 2 gas generating system C.
- the HF cylinder 11 is connected with the preparing system A via the HF sending-out piping 5 .
- the F 2 gas generating system C comprises, as primary members, an electrolytic bath 24 comprising a KF.2HF mixed molten salt, an electrolytic cell 20 which contains the electrolytic bath 24 , both an anode 22 and a cathode 23 which electrolyze the electrolytic bath 24 .
- the electrolytic cell 20 is integrally formed of a metal, such as Ni, MONEL®, pure iron, and stainless steel.
- the electrolytic cell 20 is separated into an anode chamber 28 and a cathode chamber 29 by a partition wall 27 comprising Ni or MONEL®.
- the anode 22 comprising a low polarized carbon, and the cathode 23 comprising Ni, or Fe are disposed in the anode chamber 28 and the cathode chamber 29 , respectively.
- a discharge port 25 for the F 2 gas to be generated from the anode chamber 28 and the cathode chamber 29 and a discharge port 26 for an H 2 gas to be generated from the cathode chamber 7 are disposed in the upper cover 30 of the electrolytic cell 20 .
- the electrolytic cell 20 is provided with a heater 31 for heating an interior of the electrolytic cell 20 whereupon a heat insulating material (not shown) is provided around the heater 12 .
- the heater 12 is not limited to any particular form but any forms, including a ribbon-type heater, a nichrome wire and the like are permissible.
- the heater 12 is allowed to be in form such that it covers a whole circumference of the electrolytic cell 2 .
- the vacuum-exhausting system D is constructed by molecular sieves 16 and a vacuum pump 17 and sucks moisture which is desorbed from KF 10 when KF 10 contained in the preparing system A is heated by a heater 9 .
- a predetermined quantity of KF 10 is loaded in the vessel 7 a .
- the preparing system A thus loaded with KF is once again heated at from 250° C. to 300° C. either in vacuum or while being purged with an ultra-high purity inert gas and left to stand for from 24 hours to 48 hours to allow KF 10 therein to be dried.
- an interior of the vessel 7 b is exhausted by the vacuum-exhausting system D in a state in which a vacuum piping valve 2 a is opened and a valve 3 a and a valve 4 b are closed.
- KF 10 By subjecting KF 10 to such heating processing for from 24 hours to 48 hours at from 250° C. to 300° C. while being purged by the ultra-high purity inert gas in a manner as described above, adsorbed water and crystallization water in KF 10 can be desorbed therefrom.
- thermogravimetry hereinafter also referred to as “TG” in short
- DTA differential thermal analysis
- the resultant KF is cooled to room temperature, the valve 2 a is closed, and the valve 4 b and the valve 3 a are opened.
- an ultra-purity inert gas piping 4 is previously heated by a line heater 15 to be at from 30° C. to 35° C.
- the HF gas cylinder 11 is heated by a heater 14 to gasify HF and, when a valve 5 is opened, HF is gradually introduced into KF 10 in the preparing system A.
- KF 10 and HF are vigorously reacted with each other to generate heat whereupon water is allowed to flow in a pipe 8 for cooling water in order to cool the KF.2HF adjusting device 7 and prevent the temperature thereof from being 100° C. or more. This is performed because, when the temperature exceeds 100° C. and reaches 200° C., a vigorous bumping of HF is generated to exhibit a state like an explosion.
- HF is introduced into the preparing system A and, when a molar ratio of HF against KF 10 becomes higher than that of KF.HF, a supply speed of HF can be elevated. Then, after it is confirmed by a load cell 12 in the HF supplying system B that a predetermined quantity of HF was supplied into the preparing system A, a valve 5 a is closed and, at the same time, the valve 4 a is opened to allow the high purity inert gas to be introduced through a piping 1 and exhausted through the inert gas purging piping 3 . This is performed to prevent possible flow-back into the piping 1 and solidification therein of KF.2HF which has been prepared from KF 10 to be caused by allowing HF in the piping 1 to be rapidly absorbed in KF.2HF 10 .
- the valve 4 b is closed. Subsequently, the inert gas is supplied through the inert gas purging piping 3 . At the same time, a valve 18 and valve 19 are opened.
- the preparing system A sends out KF.2HF thus prepared therein into the electrolytic cell 20 in the F 2 gas generating system C through the piping 1 by a gas pressure of the inert gas to be introduced through the inert gas purging piping 3 .
- the electrolytic cell 20 has previously been subjected to thermal processing at from 250° C. to 300° C. to allow the adsorbed water and the like to be desorbed.
- the F 2 gas generating apparatus can supply high purity KF.2HF which is small amount in a moisture adsorption quantity into the electrolytic cell in the F 2 gas generating apparatus without allowing high purity KF.2HF to contact with air to construct a high purity electrolytic bath, that is, KF.2HF bath inside the electrolytic cell.
- a high purity electrolytic bath that is, KF.2HF bath inside the electrolytic cell.
- the preparing system A, the HF supplying system B, and the F 2 gas generating system C can be contained in boxes respectively in which atmospheres thereof can be controlled. In this manner, moistures in the atmospheres outside respective systems can be adjusted, and thereby oxygen to be incorporated in respective systems can be controlled.
- all of the systems that is, the F 2 gas generating apparatus G, can be contained in one box. Furthermore, by placing all of the systems in a clean room, same effect as that to be obtained by placing the system in the box in which the atmosphere can be controlled can be obtained. As mentioned above, by controlling such contamination of oxygen, it becomes possible to more surely reduce the oxygen concentration in the F 2 gas to be generated.
- the F 2 gas generating apparatus and the F 2 gas generating method according to the invention are not limited to the aforementioned embodiments.
- an F 2 gas generating apparatus G as shown in FIG. 1 , after a preparing system A was previously subjected to thermal processing at from 250° C. to 300° C. by a heater 9 , KF 10 was loaded in a vessel 7 a . Then, the preparing system A was once again subjected to thermal processing at from 250° C. to 300° C., while being purged by a high purity N 2 gas having a purity of 99.9999%, and left to stand for from 24 hours to 48 hours to allow KF 10 to be dried. Thereafter, the system A is cooled to room temperature and, then, HF was introduced into KF 10 in the preparing system A.
- a constant current electrolysis was performed at an applied current density of 15 A/dm 2 using KF.2HF similar to that in Example 1 as an electrolytic bath while using a carbon electrode as an anode and a Ni electrode as a cathode in an F 2 gas generating system C. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O 2 in such F 2 gas generated was measured by gas chromatography, thereby finding it to be about 450 ppm.
- a constant current electrolysis was performed at an applied current density of 2 A/dm using KF.2HF similar to that in Example 1 as an electrolytic bath, while using a carbon electrode as an anode and a Ni electrode as a cathode in an F 2 gas generating system C. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O 2 in such F 2 gas generated was measured by gas chromatography, thereby finding it to be about 950 ppm.
- a constant current electrolysis was performed at an applied current density of 20 A/dm 2 using KF.2HF similar to that in Example 1 as an electrolytic bath, while using a carbon electrode as an anode and a Ni electrode as a cathode in an F 2 gas generating system C which was contained in a box (not shown), namely, a moisture controlling device, to control moisture inside the box to be 40%. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O 2 in such F 2 gas generated was measured by gas chromatography, thereby finding it to be about 70 ppm.
- a constant current electrolysis was performed at an applied current density of 10 A/dm 2 using KF.2HF prepared in a conventional method as an electrolytic bath, while using a carbon electrode as an anode and a Ni electrode as a cathode in an F 2 gas generating system C. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O 2 in such F 2 gas generated was measured by gas chromatography, thereby finding it to be about 30000 ppm.
- a constant current electrolysis was performed at an applied current density of 15 A/dm 2 using KF.2HF prepared in a conventional method as an electrolytic bath, while using a carbon electrode as an anode and a Ni electrode as a cathode in an F 2 gas generating system C. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O 2 in such F 2 gas generated was measured by gas chromatography, thereby finding it to be about 25000 ppm.
- a constant current electrolysis was performed at an applied current density of 1 A/dm 2 using KF.2HF similar to that in Example 1 as an electrolytic bath, while using a carbon electrode as an anode and a Ni electrode as a cathode in an F 2 gas generating system C. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O 2 in such F 2 gas generated was measured by gas chromatography, thereby finding it to be about 21000 ppm.
- FIG. 2 shown is a relationship among quantities of electricity in cases of Example 1, Comparative Examples 1 and 3, and a quantity of O 2 in the F 2 gas.
- Example 2 it is found that, in Example 1 in which KF.2HF which was prepared after moisture was desorbed from KF by drying it was used as an electrolytic bath, a quantity of O 2 in the F 2 gas was small from an initial stage of F 2 gas generation.
- the present invention is constituted as described above whereupon, by using KF.2HF after KF is dried allowing adsorbed water or crystallization water to be desorbed therefrom, it becomes possible to stably generate an F 2 gas in which an oxygen concentration to be contained is extremely low from an initial stage of the F 2 gas generation.
Abstract
An F2 gas generating apparatus for generating a high purity F2 gas by subjecting an electrolytic bath made of KF.2HF to electrolysis is characterized by comprising a preparing system for preparing KF.2HF from KF or KF.HF, an HF supplying system for supplying HF into the electrolytic bath and the preparing system, and an F2 gas generating system for generating the F2 gas by subjecting KF.2HF prepared by the preparing system to electrolysis.
Description
- The present invention relates to an apparatus for generating F2 gas, a method for generating the F2 gas, and F2 gas. Particularly, the present invention relates to an F2 gas generating apparatus for generating high purity F2 gas, in which a quantity of an impurity is extremely small, for use in a manufacturing process of semiconductor or the like, method for generating F2 gas, and F2 gas.
- F2 gas has been used as a primary gas indispensably, for example, in a field of semiconductor manufacturing. Although the F2 gas may sometimes be used alone, nitrogen trifluoride gas (hereinafter also referred to as “NF3 gas”) which has been synthesized based on the F2 gas has been recently used as a cleaning gas or a dry etching gas for semiconductor. Further, neon fluoride gas (hereinafter also referred to as “NeF gas”), argon fluoride gas (hereinafter also referred to as “ArF gas”), krypton fluoride gas (hereinafter also referred to as “KrF gas”) and the like are excimer laser oscillation gases used for patterning of a semiconductor integrated circuit. Mixed gas of rare gas and the F2 gas is in many cases used as a raw material of the excimer laser oscillation gas.
- The F2 gas is generated by performing electrolysis by using carbon as an anode and nickel as a cathode in an electrolytic cell containing a bath comprising a predetermined quantity of KF.HF. Ordinarily, the KF.HF contained in the electrolytic cell is used in a form of KF.2HF to be prepared by further appropriately supplying HF into a predetermined quantity of an initially loaded HF. In a case in which KF.2HF is insufficient, KF.HF is loaded and, then, HF is once again added thereto to prepare a predetermined quantity of the bath.
- KF, as a component of the bath, is high in hygroscopicity and ordinarily comes to contain moisture at the time of constructing the bath. We have previously made an application (WO 01/77412A1) having a content regarding an apparatus for generating a high purity fluorine gas having a small quantity of impurities.
- However, an F2 gas to be generated in a manner as described above is such a type of F2 gas as an initially generated F2 gas contains oxygen by from 45% to 55% therein. The F2 gas to be generated and water in an electrolytic bath are reacted with each other in accordance with the formula (1) described below, thereby ordinarily reducing a quantity of oxygen contained in the F2 gas. Nevertheless, it is difficult to bring the quantity thereof to 3000 ppm or less.
2F2+H2O→F2O+2HF (1) - The high purity F2 gas is required as the above-described excimer laser oscillation gas or for performing a surface treatment on a stepper lens (CaF2 single crystal) of the excimer laser. An oxygen concentration to be contained in the F2 gas is required to be 1000 ppm or less as the excimer laser oscillation gas in the former case and 500 ppm or less as a gas for such surface processing of the stepper lens (CaF2 single crystal) of the excimer laser in the latter case.
- An object according to the invention is to provide an F2 gas generating apparatus which can consistently generates a high purity F2 gas in which a quantity of oxygen to be contained is extremely small amount, an F2 gas generating method and the high purity F2 gas.
- To solve the above-described problems, the present invention provides an F2 gas generating apparatus for generating an F2 gas by subjecting an electrolytic bath comprising KF.2HF to electrolysis, being characterized by comprising:
-
- a preparing system for preparing KF.2HF from KF or KF.HF;
- an HF supplying system for supplying HF into the electrolytic bath and the preparing system; and
- an F2 gas generating system for generating the F2 gas by subjecting KF.2HF prepared by the preparing system to electrolysis.
- After KF.2HF is prepared from KF or KF.HF in a closed preparing system, the thus-prepared KF.2HF is loaded in an electrolytic cell connected with the preparing system in a closed space. Accordingly, KF.2HF loaded in the electrolytic cell is allowed to be an electrolytic bath without absorbing moisture, namely, having a small oxygen content. By this, a quantity of oxygen to be contained in the F2 gas to be obtained by subjecting this electrolytic bath to electrolysis is allowed to be small from an initial stage of generation.
- Further, the F2 gas generating apparatus according to the invention is characterized in that a moisture removing device for removing moisture in the KF or KF-HF is attached to the preparing system.
- At the time of preparing KF.2HF from KF or KF.HF, a quantity of oxygen can surely be reduced.
- Further, the F2 gas generating apparatus according to the invention is an F2 gas generating apparatus in which an oxygen concentration in the thus-generated F2 gas is 2% or less.
- The quantity of oxygen in the F2 gas is reduced to be 2% or less, preferably 0.2% or less (2000 ppm or less) and more preferably 0.02% or less (200 ppm or less). Accordingly, the F2 gas can be used as an excimer laser oscillating gas or as a gas for surface treatment of a stepper lens (CaF2 single crystal) of an excimer laser.
- Further, the F2 gas generating apparatus according to the invention is an F2 gas generating apparatus for generating an F2 gas by subjecting an electrolytic bath comprising KF.2HF to electrolysis, comprising:
-
- a preparing system for preparing KF.2HF from KF or KF.HF;
- an HF supplying system for supplying HF into the electrolytic bath and the preparing system; and
- an F2 gas generating system for generating the F2 gas by subjecting KF.2HF prepared by the preparing system to electrolysis, being characterized by being provided with a moisture controlling device for adjusting moisture in an atmosphere outside each of the preparing system, the HF supplying system, and the F2 gas generating system or all the systems as a whole.
- Since the moisture controlling device controlling the moisture in the atmosphere outside each of the preparing system, the HF supplying system and the F2 gas generating systems or all the systems as a whole is provided, contamination of oxygen can surely be controlled.
- Further, the F2 gas generating apparatus according to the invention is an F2 gas generating apparatus in which the moisture controlling device is a box which contains each of the systems or all the systems as a whole and is capable of controlling an atmosphere inside the box.
- Since the moisture controlling device is a box capable of controlling the atmosphere, adjustment of atmosphere moisture of each of the systems or all the systems as a whole can easily be performed. Accordingly, contamination of oxygen can surely be controlled.
- Further, an F2 gas generating method according to the invention is an F2 gas generating method for generating an F2 gas by subjecting an electrolytic bath comprising KF.2HF to electrolysis, comprising the steps of:
-
- heat-deaerating KF or KF.HF for a predetermined period of time in an atmosphere of vacuum or an inert gas in a preparing system, for preparing KF.2HF from the KF or KF.HF, which is attached with a moisture removing device for removing moisture in the KF or KF-HF;
- cooling the KF or KF.HF to room temperature in an atmosphere of vacuum or the inert gas in the preparing system;
- supplying HF changed into a vapor phase from an HF supplying system into the preparing system;
- allowing the KF or KF.HF, and the HF to react with each other in the preparing system to generate KF.2HF; supplying the thus-generated KF.2HF into an electrolytic cell in an F2 gas generating system; and
- subjecting the KF.2HF to electrolysis to generate an F2 gas having a low oxygen concentration.
- By providing such arrangement, it becomes possible to allow the quantity of oxygen in the F2 gas generated to be small amount. As a result, the F2 gas is allowed to be used as the excimer laser oscillating gas or as a gas for surface processing of the stepper lens (CaF2 single crystal) of the excimer laser.
- Further, the F2 gas generating method according to the invention is an F2 gas generating method in which, in the preparing system, the KF or KF.HF is heated at from 200° C. to 300° C. to remove adsorbed water or crystallization water of the KF or KF.HF therefrom.
- Accordingly, the moisture in KF or KF.HF can surely be removed. To this end, it becomes possible to remove oxygen in the moisture whereupon the oxygen concentration in the F2 gas to be generated can surely be reduced from an initial stage of F2 gas generation.
- Further, an F2 gas according to the invention is an F2 gas generated by a method comprising the steps of:
-
- heat-deaerating KF or KF-HF for a predetermined period of time in an atmosphere of vacuum or an inert gas in a preparing system, for preparing KF.2HF from KF or KF.HF, which is attached with a moisture removing device for removing moisture in the KF or KF.HF;
- cooling the KF or KF.HF to room temperature in an atmosphere of vacuum or the inert gas in the preparing system;
- supplying HF changed into a vapor phase from an HF supplying system into the preparing system;
- allowing the KF or KF.HF, and the HF to react with each other in the preparing system to generate KF.2HF;
- supplying the thus-generated KF.2HF into an electrolytic cell in an F2 gas generating system; and
- subjecting the KF.2HF to electrolysis. Therefore, since the F2 gas is a high purity F2 gas which is extremely low in the oxygen concentration, it can be used as various types of primary gases for a semiconductor manufacture.
- Further, the F2 gas according to the invention is an F2 gas in which an oxygen concentration is 2% or less.
- The oxygen concentration is reduced to be preferably 0.2% or less (2000 ppm or less) and more preferably 0.02% or less (200 ppm or less). To this end, The F2 gas can be-used as the excimer laser oscillating gas or as the gas for the surface processing of the stepper lens (CaF2 single crystal) of the excimer laser.
-
FIG. 1 is a schematic view of a fluorine gas generating apparatus according to the present invention. -
FIG. 2 is a chart showing a relationship among quantities of electricity in cases of Example 1, Comparative Examples 1 and 3, and a quantity of O2 in F2 gas. - Hereinafter, an example of embodiments according to the present invention will be described with reference to
FIG. 1 . - An F2 gas generating apparatus G according to the present embodiment, which generates a high purity F2 gas by subjecting an
electrolytic bath 24 comprising KF.2HF to electrolysis, comprises a preparing system A which prepares KF.2HF from KF or KF.HF, an HF supplying system B which supplies HF to theelectrolytic bath 24 and the preparing system A, and an F2 gas generating system C which generates an F2 gas by subjecting KF.2HF which has been prepared by the preparing system A to electrolysis. - In
FIG. 1 , the preparing system A which prepares KF.2HF from KF or KF.HF comprises a KF.2HF preparing device 7 comprising a vessel 7 a made of Ni which containsKF 10, and an upper cover 7 b which hermetically seals the vessel 7 a, aheater 9 which covers the vessel 7 a of the KF.2HF preparing device 7 and heatsKF 10 inside the vessel 7 a, a cooling water pipe 8 for use in cooling, avacuum piping 2, provided in the upper cover 7 b, which is connected with a vacuum-exhausting system D, an inertgas purging piping 3, and an HF supplying and a KF.2HF sending-outpiping 1 which is inserted inKF 10 and connected to both the HF supplying system B and the F2 gas generating system C. - In the HF supplying system B which supplies HF to the preparing system A, an
HF cylinder 11 placed on aload cell 12 is arranged in a box 13, which is connected to an acrylic scrubber (not shown). A surface of theHF cylinder 11 is covered by a heater 14 to maintain an interior of theHF cylinder 11 at a predetermined temperature. Further, a quantity of gas inside theHF cylinder 11 is measured by aload cell 12 to measure a quantity of an HF gas to be supplied to both the preparing system A and the F2 gas generating system C. TheHF cylinder 11 is connected with the preparing system A via the HF sending-outpiping 5. - The F2 gas generating system C comprises, as primary members, an
electrolytic bath 24 comprising a KF.2HF mixed molten salt, anelectrolytic cell 20 which contains theelectrolytic bath 24, both ananode 22 and acathode 23 which electrolyze theelectrolytic bath 24. - The
electrolytic cell 20 is integrally formed of a metal, such as Ni, MONEL®, pure iron, and stainless steel. Theelectrolytic cell 20 is separated into ananode chamber 28 and a cathode chamber 29 by apartition wall 27 comprising Ni or MONEL®. Theanode 22 comprising a low polarized carbon, and thecathode 23 comprising Ni, or Fe are disposed in theanode chamber 28 and the cathode chamber 29, respectively. Adischarge port 25 for the F2 gas to be generated from theanode chamber 28 and the cathode chamber 29 and adischarge port 26 for an H2 gas to be generated from thecathode chamber 7 are disposed in theupper cover 30 of theelectrolytic cell 20. Further, theelectrolytic cell 20 is provided with aheater 31 for heating an interior of theelectrolytic cell 20 whereupon a heat insulating material (not shown) is provided around theheater 12. Theheater 12 is not limited to any particular form but any forms, including a ribbon-type heater, a nichrome wire and the like are permissible. Preferably, theheater 12 is allowed to be in form such that it covers a whole circumference of theelectrolytic cell 2. - The vacuum-exhausting system D is constructed by
molecular sieves 16 and avacuum pump 17 and sucks moisture which is desorbed fromKF 10 whenKF 10 contained in the preparing system A is heated by aheater 9. - Next, an operation of the F2 gas generating apparatus G will be explained.
- After the preparing system A is subjected to thermal processing at from 250° C. to 300° C. by the
heater 9, a predetermined quantity ofKF 10 is loaded in the vessel 7 a. The preparing system A thus loaded with KF is once again heated at from 250° C. to 300° C. either in vacuum or while being purged with an ultra-high purity inert gas and left to stand for from 24 hours to 48 hours to allowKF 10 therein to be dried. On this occasion, an interior of the vessel 7 b is exhausted by the vacuum-exhausting system D in a state in which a vacuum piping valve 2 a is opened and a valve 3 a and a valve 4 b are closed. By subjectingKF 10 to such heating processing for from 24 hours to 48 hours at from 250° C. to 300° C. while being purged by the ultra-high purity inert gas in a manner as described above, adsorbed water and crystallization water inKF 10 can be desorbed therefrom. - When thermogravimetry (hereinafter also referred to as “TG” in short) and differential thermal analysis (hereinafter also referred to as “DTA” in short) were performed, endothermic peaks were observed at 43.4° C., 64.4° C., 90.8° C. and 151.6° C. The endothermic peaks at 43.4° C., 64.4° C., and 90.8° C. thereamong are attributable to desorption of adsorbed water while the endothermic peak at 151.6° C. is attributable to desorption of crystallization water. It is considered that the adsorbed water of KF as a starting material can easily be decomposed by a reaction represented by the formula (1). On the other hand, since not only the crystallization water corresponding to the endothermic peak which appears at 151.6° C. of the DTA is strong in an interaction with KF, but also HF contained in the electrolytic bath as a major component forms a network by hydrogen bonds, it is considered that, when the crystallization water becomes extremely small in quantity, it becomes hardly diffused, thereby allowing it difficult to be removed. Therefore, as described above, by subjecting KF to thermal processing such that it is once again heated at from 250° C. to 300° C. while being purged by the ultra-high purity inert gas for from 24 hours to 48 hours and preferably for from 10 hours to 30 hours, the crystallization water became capable of being desorbed.
- Thereafter, the resultant KF is cooled to room temperature, the valve 2 a is closed, and the valve 4 b and the valve 3 a are opened. On this occasion, an ultra-purity
inert gas piping 4 is previously heated by a line heater 15 to be at from 30° C. to 35° C. Then, theHF gas cylinder 11 is heated by a heater 14 to gasify HF and, when avalve 5 is opened, HF is gradually introduced intoKF 10 in the preparing system A. At such introduction,KF 10 and HF are vigorously reacted with each other to generate heat whereupon water is allowed to flow in a pipe 8 for cooling water in order to cool the KF.2HF adjusting device 7 and prevent the temperature thereof from being 100° C. or more. This is performed because, when the temperature exceeds 100° C. and reaches 200° C., a vigorous bumping of HF is generated to exhibit a state like an explosion. - In a manner as described above, HF is introduced into the preparing system A and, when a molar ratio of HF against
KF 10 becomes higher than that of KF.HF, a supply speed of HF can be elevated. Then, after it is confirmed by aload cell 12 in the HF supplying system B that a predetermined quantity of HF was supplied into the preparing system A, a valve 5 a is closed and, at the same time, the valve 4 a is opened to allow the high purity inert gas to be introduced through apiping 1 and exhausted through the inertgas purging piping 3. This is performed to prevent possible flow-back into thepiping 1 and solidification therein of KF.2HF which has been prepared fromKF 10 to be caused by allowing HF in thepiping 1 to be rapidly absorbed inKF.2HF 10. - Then, after an interior of the preparing system A is purged by the inert gas for an appropriate duration of time, the valve 4 b is closed. Subsequently, the inert gas is supplied through the inert
gas purging piping 3. At the same time, avalve 18 andvalve 19 are opened. The preparing system A sends out KF.2HF thus prepared therein into theelectrolytic cell 20 in the F2 gas generating system C through thepiping 1 by a gas pressure of the inert gas to be introduced through the inertgas purging piping 3. On this occasion, theelectrolytic cell 20 has previously been subjected to thermal processing at from 250° C. to 300° C. to allow the adsorbed water and the like to be desorbed. - In such a manner as described above, the F2 gas generating apparatus according to the invention can supply high purity KF.2HF which is small amount in a moisture adsorption quantity into the electrolytic cell in the F2 gas generating apparatus without allowing high purity KF.2HF to contact with air to construct a high purity electrolytic bath, that is, KF.2HF bath inside the electrolytic cell. In such a manner as described above, an oxygen concentration in the electrolytic bath is extremely reduced.
- Further, the preparing system A, the HF supplying system B, and the F2 gas generating system C can be contained in boxes respectively in which atmospheres thereof can be controlled. In this manner, moistures in the atmospheres outside respective systems can be adjusted, and thereby oxygen to be incorporated in respective systems can be controlled. Alternatively, all of the systems, that is, the F2 gas generating apparatus G, can be contained in one box. Furthermore, by placing all of the systems in a clean room, same effect as that to be obtained by placing the system in the box in which the atmosphere can be controlled can be obtained. As mentioned above, by controlling such contamination of oxygen, it becomes possible to more surely reduce the oxygen concentration in the F2 gas to be generated.
- Still further, the F2 gas generating apparatus and the F2 gas generating method according to the invention are not limited to the aforementioned embodiments.
- Hereinafter, the F2 gas generating apparatus according to the invention will specifically be explained with reference to Examples.
- In an F2 gas generating apparatus G as shown in
FIG. 1 , after a preparing system A was previously subjected to thermal processing at from 250° C. to 300° C. by aheater 9,KF 10 was loaded in a vessel 7 a. Then, the preparing system A was once again subjected to thermal processing at from 250° C. to 300° C., while being purged by a high purity N2 gas having a purity of 99.9999%, and left to stand for from 24 hours to 48 hours to allowKF 10 to be dried. Thereafter, the system A is cooled to room temperature and, then, HF was introduced intoKF 10 in the preparing system A. On this occasion, water was allowed to flow in a cooling water pipe 8 for cooling a KF.2HF adjusting device 7 to be 100° C. or less. Next, after it was confirmed by aload cell 12 in an HF supplying system B that a predetermined quantity of HF was supplied in the preparing system A, an interior of the preparing system A was purged by a high purity N2 gas for an appropriate duration of time and, then, a high purity N2 gas was supplied therein and, thereafter, such KF.2HF prepared was sent out into anelectrolytic cell 20 in a F2 gas generating system C through piping 1 to construct an electrolytic bath having a bath volume of 7 1. Subsequently, in the F2 gas generating system C, a constant current electrolysis was performed at an applied current density of 10 A/dm2 while using a carbon electrode and a Ni electrode as an anode and a cathode, respectively. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O2 in such F2 gas generated was measured by gas chromatography, thereby finding it to be about 650 ppm. - A constant current electrolysis was performed at an applied current density of 15 A/dm2 using KF.2HF similar to that in Example 1 as an electrolytic bath while using a carbon electrode as an anode and a Ni electrode as a cathode in an F2 gas generating system C. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O2 in such F2 gas generated was measured by gas chromatography, thereby finding it to be about 450 ppm.
- A constant current electrolysis was performed at an applied current density of 2 A/dm using KF.2HF similar to that in Example 1 as an electrolytic bath, while using a carbon electrode as an anode and a Ni electrode as a cathode in an F2 gas generating system C. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O2 in such F2 gas generated was measured by gas chromatography, thereby finding it to be about 950 ppm.
- A constant current electrolysis was performed at an applied current density of 20 A/dm2 using KF.2HF similar to that in Example 1 as an electrolytic bath, while using a carbon electrode as an anode and a Ni electrode as a cathode in an F2 gas generating system C which was contained in a box (not shown), namely, a moisture controlling device, to control moisture inside the box to be 40%. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O2 in such F2 gas generated was measured by gas chromatography, thereby finding it to be about 70 ppm.
- A constant current electrolysis was performed at an applied current density of 10 A/dm2 using KF.2HF prepared in a conventional method as an electrolytic bath, while using a carbon electrode as an anode and a Ni electrode as a cathode in an F2 gas generating system C. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O2 in such F2 gas generated was measured by gas chromatography, thereby finding it to be about 30000 ppm.
- A constant current electrolysis was performed at an applied current density of 15 A/dm2 using KF.2HF prepared in a conventional method as an electrolytic bath, while using a carbon electrode as an anode and a Ni electrode as a cathode in an F2 gas generating system C. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O2 in such F2 gas generated was measured by gas chromatography, thereby finding it to be about 25000 ppm.
- A constant current electrolysis was performed at an applied current density of 1 A/dm2 using KF.2HF similar to that in Example 1 as an electrolytic bath, while using a carbon electrode as an anode and a Ni electrode as a cathode in an F2 gas generating system C. Then, when a quantity of electricity reached about 100 Ahr, a quantity of O2 in such F2 gas generated was measured by gas chromatography, thereby finding it to be about 21000 ppm.
- In
FIG. 2 , shown is a relationship among quantities of electricity in cases of Example 1, Comparative Examples 1 and 3, and a quantity of O2 in the F2 gas. - As shown in
FIG. 2 , it is found that, in Example 1 in which KF.2HF which was prepared after moisture was desorbed from KF by drying it was used as an electrolytic bath, a quantity of O2 in the F2 gas was small from an initial stage of F2 gas generation. - The present invention is constituted as described above whereupon, by using KF.2HF after KF is dried allowing adsorbed water or crystallization water to be desorbed therefrom, it becomes possible to stably generate an F2 gas in which an oxygen concentration to be contained is extremely low from an initial stage of the F2 gas generation.
Claims (9)
1. An F2 gas generating apparatus for generating an F2 gas by subjecting an electrolytic bath comprising KF.2HF to electrolysis, being characterized by comprising:
a preparing system for preparing KF.2HF from KF or KF.HF;
an HF supplying system for supplying HF into the electrolytic bath and the preparing system; and
an F2 gas generating system for generating the F2 gas by subjecting KF.2HF prepared by the preparing system to electrolysis.
2. The F2 gas generating apparatus as set forth in claim 1 , being characterized in that a moisture removing device for removing moisture in said KF or KF.HF is attached to the preparing system.
3. The F2 gas generating apparatus as set forth in claim 1 , wherein an oxygen concentration in the thus-generated F2 gas is 2% or less.
4. An F2 generating apparatus for generating an F2 gas by subjecting an electrolytic bath comprising KF.2HF to electrolysis, comprising:
a preparing system for preparing KF.2HF from KF or KF.HF;
an HF supplying system for supplying HF into the electrolytic bath and the preparing system; and
an F2 gas generating system for generating the F2 gas by subjecting KF.2HF prepared by the preparing system to electrolysis, being characterized by being provided with a moisture controlling device for adjusting moisture in an atmosphere outside each of the preparing system, the HF supplying system, and the F2 gas generating system or all the systems as a whole.
5. The F2 gas generating apparatus as set forth in claim 4 , wherein the moisture controlling device is a box which contains each of the systems or all the systems as a whole and is capable of controlling an atmosphere inside the box.
6. An F2 gas generating method for generating an F2 gas by subjecting an electrolytic bath comprising KF.2HF to electrolysis, comprising the steps of:
heat-deaerating KF or KF.HF for a predetermined period of time in an atmosphere of vacuum or an inert gas in a preparing system, for preparing KF.2HF from said KF or KF.HF, which is attached with a moisture removing device for removing moisture in said KF or KF.HF;
cooling said KF or KF.HF to room temperature in an atmosphere of vacuum or the inert gas in the preparing system;
supplying HF changed into a vapor phase from an HF supplying system into said preparing system;
allowing said KF or KF.HF, and said HF to react with each other in the preparing system to generate KF.2HF;
supplying the thus-generated KF.2HF into an electrolytic cell in an F2 gas generating system; and
Subjecting said KF.2HF to electrolysis to generate an F2 gas having a low oxygen concentration.
7. The F2 gas generating method as set forth in claim 6 , wherein, in the preparing system, said KF or KF.HF is heated at from 200° C. to 300° C. to remove adsorbed water or crystallization water of said KF or KF.HF therefrom.
8. An F2 gas generated by a method comprising the steps of:
heat-deaerating KF or KF.HF for a predetermined period of time in an atmosphere of vacuum or an inert gas in a preparing system, for preparing KF.2HF from KF or KF.HF, which is attached with a moisture removing device for removing moisture in said KF or KF.HF;
cooling said KF or KF.HF to room temperature in an atmosphere of vacuum or the inert gas in the preparing system;
supplying HF changed into a vapor phase from an HF supplying system into said preparing system;
allowing said KF or KF-HF, and said HF to react with each other in the preparing system to generate KF.2HF;
supplying the thus-generated KF.2HF into an electrolytic cell in an F2 gas generating system; and
Subjecting said KF.2HF to electrolysis.
9. The F2 gas as set forth in claim 8 , wherein an oxygen concentration is 2% or less.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP2001-382722 | 2001-12-17 | ||
JP2001382722 | 2001-12-17 | ||
PCT/JP2002/012868 WO2003052167A1 (en) | 2001-12-17 | 2002-12-09 | Apparatus for generating f2 gas and method for generating f2 gas, and f2 gas |
Publications (1)
Publication Number | Publication Date |
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US20050006248A1 true US20050006248A1 (en) | 2005-01-13 |
Family
ID=19187509
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US10/497,158 Abandoned US20050006248A1 (en) | 2001-12-17 | 2002-12-09 | Apparatus for generating f2 gas method for generating f2 gas and f2 gas |
Country Status (8)
Country | Link |
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US (1) | US20050006248A1 (en) |
EP (1) | EP1457586A4 (en) |
JP (1) | JP3569279B2 (en) |
KR (1) | KR100712345B1 (en) |
CN (1) | CN1327032C (en) |
AU (1) | AU2002349510A1 (en) |
TW (1) | TW593774B (en) |
WO (1) | WO2003052167A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040238374A1 (en) * | 2003-05-28 | 2004-12-02 | Toyo Tanso Co., Ltd. | Electric current control method and apparatus for use in gas generators |
US20090205952A1 (en) * | 2008-02-14 | 2009-08-20 | Snecma Propulsion Solide | Electrolysis installation |
JP2013540964A (en) * | 2010-09-16 | 2013-11-07 | ソルヴェイ(ソシエテ アノニム) | Hydrogen fluoride supply device |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5584904B2 (en) * | 2008-03-11 | 2014-09-10 | 東洋炭素株式会社 | Fluorine gas generator |
JP2011058015A (en) * | 2009-09-07 | 2011-03-24 | Toyo Tanso Kk | Electrolytic device |
JP5375673B2 (en) * | 2010-03-01 | 2013-12-25 | セントラル硝子株式会社 | Fluorine gas generator |
TWI586842B (en) * | 2010-09-15 | 2017-06-11 | 首威公司 | Plant for fluorine production and a process using it |
JP5906742B2 (en) * | 2012-01-05 | 2016-04-20 | セントラル硝子株式会社 | Fluorine gas generator |
WO2020085066A1 (en) * | 2018-10-24 | 2020-04-30 | 昭和電工株式会社 | Fluorine gas production device |
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GB1570004A (en) * | 1976-10-19 | 1980-06-25 | British Nuclear Fuels Ltd | Electrolytic production of fluorine |
JPS5867877A (en) * | 1981-10-20 | 1983-04-22 | Asahi Glass Co Ltd | Preparation of fluorine |
CA2071235C (en) * | 1991-07-26 | 2004-10-19 | Gerald L. Bauer | Anodic electrode for electrochemical fluorine cell |
US5628894A (en) * | 1995-10-17 | 1997-05-13 | Florida Scientific Laboratories, Inc. | Nitrogen trifluoride process |
JP2000313981A (en) * | 1999-04-27 | 2000-11-14 | Toyo Tanso Kk | Carbon electrode for fluorine electrolysis |
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2002
- 2002-12-09 CN CNB02825158XA patent/CN1327032C/en not_active Expired - Fee Related
- 2002-12-09 KR KR1020047007949A patent/KR100712345B1/en not_active IP Right Cessation
- 2002-12-09 AU AU2002349510A patent/AU2002349510A1/en not_active Abandoned
- 2002-12-09 US US10/497,158 patent/US20050006248A1/en not_active Abandoned
- 2002-12-09 WO PCT/JP2002/012868 patent/WO2003052167A1/en active Application Filing
- 2002-12-09 JP JP2003553033A patent/JP3569279B2/en not_active Expired - Fee Related
- 2002-12-09 EP EP02783802A patent/EP1457586A4/en not_active Ceased
- 2002-12-12 TW TW091136005A patent/TW593774B/en not_active IP Right Cessation
Patent Citations (4)
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US5840266A (en) * | 1993-01-19 | 1998-11-24 | British Nuclear Fuels Plc - Springfield Works | Dehydration of fluoride mixtures |
US6113769A (en) * | 1997-11-21 | 2000-09-05 | International Business Machines Corporation | Apparatus to monitor and add plating solution of plating baths and controlling quality of deposited metal |
US6818105B2 (en) * | 2000-04-07 | 2004-11-16 | Toyo Tanso Co., Ltd. | Apparatus for generating fluorine gas |
US20040028600A1 (en) * | 2001-06-29 | 2004-02-12 | Junichi Torisu | High-purity fluorine gas, production and use thereof, and method for analyzing trace impurities in high-purity fluorine gas |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20040238374A1 (en) * | 2003-05-28 | 2004-12-02 | Toyo Tanso Co., Ltd. | Electric current control method and apparatus for use in gas generators |
US7288180B2 (en) * | 2003-05-28 | 2007-10-30 | Toyo Tanso Co., Ltd. | Electric current control method and apparatus for use in gas generators |
US20090205952A1 (en) * | 2008-02-14 | 2009-08-20 | Snecma Propulsion Solide | Electrolysis installation |
US8038854B2 (en) * | 2008-02-14 | 2011-10-18 | Snecma Propulsion Solide | Electrolysis installation |
JP2013540964A (en) * | 2010-09-16 | 2013-11-07 | ソルヴェイ(ソシエテ アノニム) | Hydrogen fluoride supply device |
Also Published As
Publication number | Publication date |
---|---|
CN1604970A (en) | 2005-04-06 |
TW200301316A (en) | 2003-07-01 |
EP1457586A1 (en) | 2004-09-15 |
EP1457586A4 (en) | 2005-07-13 |
JPWO2003052167A1 (en) | 2005-04-28 |
AU2002349510A1 (en) | 2003-06-30 |
WO2003052167A1 (en) | 2003-06-26 |
TW593774B (en) | 2004-06-21 |
KR20040062648A (en) | 2004-07-07 |
CN1327032C (en) | 2007-07-18 |
JP3569279B2 (en) | 2004-09-22 |
KR100712345B1 (en) | 2007-05-02 |
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