CN1668779A - Apparatus for the generation of fluorine gas - Google Patents
Apparatus for the generation of fluorine gas Download PDFInfo
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- CN1668779A CN1668779A CNA038165309A CN03816530A CN1668779A CN 1668779 A CN1668779 A CN 1668779A CN A038165309 A CNA038165309 A CN A038165309A CN 03816530 A CN03816530 A CN 03816530A CN 1668779 A CN1668779 A CN 1668779A
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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
- C25B15/02—Process control or regulation
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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
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Abstract
Provided is an apparatus for the generation of fluorine gas that is capable of very safe and highly reliable operation even during long-term operations. An apparatus (30) for the generation of fluorine gas is provided with an electrolytic cell (32) that generates, in a first gas phase region on the anode side, product gas whose main component is fluorine gas and at the same time generates, in a second gas phase region on the cathode side, by-product gas whose main component is hydrogen gas. A first and second pressure gauges (46 and 48) are provided in order to measure the pressure in the first and second gas phase regions. A first and second conduits (52 and 72) are provided in order to withdraw the product gas and by-product gas. A first and second flow rate control valves are disposed in the first and second conduits (52 and 72). The apertures of the first and second flow rate control valves are adjusted based on the measurement results from the first and second pressure gauges (46 and 48) so as to maintain the pressures in the first and second gas phase regions at first and second set values that are substantially equal.
Description
Invention field
The present invention relates to a kind of device (fluorine gas generator hereinafter referred to as) that generates fluorine gas.More specifically, the present invention relates to fluorine gas generator in a kind of airing system that is placed in semiconductor machining system.In this article, semiconductor machining refers to (for example making semiconducter device and/or semiconducter device syndeton, interconnection, electrode) and accepting in the substrate of handling (target substrate), by on the target substrate of for example semiconductor wafer or LCD substrate and so on, forming the various processing that semi-conductor, dielectric medium and conductive layer carry out with specific pattern.
Description of the Prior Art
In the manufacturing processed of semiconducter device, on the target substrate of for example semiconductor wafer or LCD substrate, carry out the various semiconductor machining of for example film forming, etching and diffusion and so on.Be used for carrying out the process gas of the semiconductor machining system employing fluorine type gas of these processing, for example be used for etching silicon film and silicon oxide film, cleaning Processing Room inside etc. as various uses.As novel etching gas and purge gas, fluorine gas comes on the scene always, but because its security and reliability problems solve the common situ production fluorine gas of not making at semiconducter device fully.
Known device based on electrolyzer is used in gas generation Workshop Production fluorine gas.For example, in Japanese Laid-Open Patent Application (PCT) Hei 9-505853 (505,853/1997) number this type of fluorine gas generator is disclosed.In its disclosed device, the tripping device that extend into the melting salt from the top is divided into middle anolyte compartment and cathode compartment on every side with electrolyzer inside.Two highly different detectors have been installed in the anolyte compartment.These two detectors play the effect of liquid level measuring device, control with the ON/OFF that the electric current of realizing between antianode and the negative electrode applies.Therefore, this device is controlled the generation of fluorine gas by the method that detects the melting salt liquid level.
In Fig. 3, illustrated another kind of prior art fluorine gas generator with synoptic diagram.This device has the structure of improvement, with the charging of control from the fluorine gas of electrolyzer.In this specific device, the fluorine gas that becomes at anode 114 1 adnations of electrolyzer 112 enters in the intermediate receptacle 116 continuously by conduit 120, and temporary storage there.When container 116 reached certain specified pressure, the switching valve that is placed between compressor 118 and the container 116 was temporarily opened, and a certain amount of fluorine gas is inhaled in the compressor 118.Switch valve 122 repeatedly, so that the pressure of second surge tank 124 is increased to certain value.
The problem to be solved in the present invention
In research process, the contriver finds, when fluorine gas generator long-play shown in Figure 3, some safety and integrity problem (vide infra) can occur.From practical term, these problems can not get solving, and can make for example to be difficult to add and use this fluorine gas generator in the system for manufacturing semiconductor device by mechanized production system.
In view of the foregoing problems of prior art, the present invention improves.Even a target of the present invention provide a kind of also can be as safe as a house in long-time operation process and the fluorine gas generator of operation reliably.Objectives of the present invention provide a kind of device that can produce fluorine gas at the scene on demand." scene " used herein is meant fluorine gas generator and specific main processing unit (plant), for example the main processing unit (plant) combination or the assembling of semiconductor machining system." on demand " be meant, provide gas in good time, control its necessary component simultaneously according to the needs of main processing unit (plant).
The method of dealing with problems
A first aspect of the present invention comprises a kind of apparatus for generating fluorine gas, and described device is characterised in that and has been equipped with:
Electrolyzer, it carries out the hydrogen fluoride electrolysis in the electrolyzer of the melting salt that comprises fluorinated hydrogen, and to generate main component in first vapor phase areas of anode side thus be the product gas of fluorine gas, and generating main component in second vapor phase areas of cathode side simultaneously is the byproduct gas of hydrogen;
Initial hydrogen fluoride is sent into feed conduits in the melting salt;
Extract first conduit of product gas from first vapor phase areas;
Extract second conduit of byproduct gas from second vapor phase areas;
First pressure warning unit of pressure in continuously measured first vapor phase areas;
Second pressure warning unit of pressure in continuously measured second vapor phase areas;
Be installed in first flow control valve in first conduit;
Be installed in second flow control valve in second conduit;
First controlling elements, its observed value according to the first pressure warning unit gained are adjusted the open degree of first flow control valve so that the pressure of first vapor phase areas is remained on first set(ting)value; With
Second controlling elements, its observed value according to the second pressure warning unit gained are adjusted the open degree of second flow control valve so that the pressure of second vapor phase areas is remained on second set(ting)value that equals first set(ting)value substantially.
A second aspect of the present invention comprises the device of first aspect, it is characterized in that first and second set(ting)values are the 760-820 holder.
A third aspect of the present invention comprises that according to first or the device of second aspect it is characterized in that also being equipped with first suction unit, it is installed in the downstream of first flow control valve in first conduit, and can aspirate first conduit.
A fourth aspect of the present invention comprises the device of the third aspect, it is characterized in that installing second conduit, so that the second flow control valve downstream is connected with second suction unit that can aspirate second conduit.
A fifth aspect of the present invention comprises the device according to first to the 4th either side, and wherein said device is characterised in that also and has been equipped with:
Be installed in the switching valve in the feed conduits;
Current integrator, the electric current that it will be transported between the electrode of the electrode of electrolytic cell anode side and cathode of electrolytic tank side amasss; With
Controlling elements, its measuring result operation switching valve that obtains according to current integrator is sent into charging in the melting salt with control hydrogen fluoride.
A sixth aspect of the present invention comprises the device of the 5th aspect, it is characterized in that the hydrogen fluoride that imports by feed conduits is gaseous state.
A seventh aspect of the present invention comprises the device of the 6th aspect, it is characterized in that feed conduits installs to such an extent that hydrogen fluoride gas can be imported in the melting salt of cathode of electrolytic tank side, also be and import the downstream that conduit in the feed conduits is connected to aforementioned switching valve to nitrogen, and hydrogen fluoride gas mixed with nitrogen send in the melting salt.
A eighth aspect of the present invention comprises a kind of apparatus for generating fluorine gas, it is characterized in that being equipped with:
Electrolyzer, it carries out the hydrogen fluoride electrolysis in the electrolyzer of the melting salt that comprises fluorinated hydrogen, and to generate main component thus in first vapor phase areas of anode side be the product gas of fluorine gas, and generating main component simultaneously in second vapor phase areas of cathode side is the byproduct gas of hydrogen;
Initial hydrogen fluoride is sent into feed conduits in the melting salt;
Extract first conduit of product gas from first vapor phase areas;
Extract second conduit of byproduct gas from second vapor phase areas;
Be installed in the switching valve in the feed conduits;
Current integrator, it carries out integration to electrode and the electric current between the electrode of cathode of electrolytic tank side that is transported to the electrolytic cell anode side; With
Controlling elements, its measuring result operation switching valve that generates according to current integrator is sent into charging in the melting salt with control hydrogen fluoride.
A ninth aspect of the present invention comprises the device of eight aspect, it is characterized in that, the hydrogen fluoride that imports by feed conduits is gaseous state.
A tenth aspect of the present invention comprises the device of the 9th aspect, it is characterized in that feed conduits installs to such an extent that hydrogen fluoride gas can be imported in the melting salt of cathode of electrolytic tank side, also be and be connected to the downstream of aforementioned switching valve to the conduit that nitrogen imports in the feed conduits, and will send in the melting salt with nitrogen blended hydrogen fluoride gas.
In addition, embodiment of the present invention have been explored various performance of the present invention, can obtain various embodiments of the present invention by the appropriate combination of multiple disclosed assembly.For example, if omit some assemblies from a complete set of assembly that is used for this embodiment, obtain one embodiment of the invention thus, in the actually operating of this deutero-invention embodiment, can realize that by traditional known technology these omit the function of assembly aptly.
The working of an invention scheme
During exploitation the present invention, the contriver has studied and relevant security and the integrity problem of the described prior art fluorine gas generator of reference Fig. 3.As result of study, the contriver has obtained following understanding.
In the operation of the described device of Fig. 3, the pressure in the container 116 arrives to be gone up in limited time, and valve 122 is opened, and in limited time, valve 122 is closed under this pressure arrives.In fluorine gas conduit 120, produce big pressure change like this.Because the fused salt mist that these big pressure change produce accumulates in the ingress of leading to conduit 120, this will make conduit 120 blocked.In addition, because opening-closing valve 122 continually, the base of valve 122 is very easy to be damaged by the chemical action of solid melting salt particulate mechanical effect and fluorine gas.
Another problem about relevant with device shown in Figure 3 it should be noted that, the hydrogen that produces at cathode side passes through the conduit 121 of exhaust system, and discharges from system after being diluted to the minimum value that is low to moderate conventional limits value.Can expect that the pressure in the exhaust system will be as the function of facility environment.For example, when exhaust system has high suction capactity, the pressure of cathode side will automatically become negative pressure, and will be associated, and the horizontal plane of cathode side melting salt will rise.In this case, bigger variation will take place in liquid level, and this will make melting salt be inhaled into hydrogen conduit 121, and thereby occlusion catheter 121.
In case melting salt solidifies in conduit 120 and 121, equipment must be stopped, and carry out maintenance operation, this total system that also causes linking to each other with this equipment enters the shut-down period.In addition, the obstruction of fluorine gas conduit 120 or hydrogen conduit 121 also can destroy the pressure equilibrium in the electrolyzer 122.Pressure equilibrium in the electrolyzer 122 is subjected to havoc, can cause the fluorine gas in the electrolyzer 112 to contact with hydrogen, and this can cause the danger of blast.
The present invention has a kind of structure based on above-mentioned cognition.Hereinafter, with reference to description of drawings embodiment of the present invention.In the following description, specified the common reference marks, only just repeated explanation where necessary them to those assemblies with same general configuration and function.
Fig. 1 has comprised that diagram contains the synoptic diagram of the semiconductor machining system of fluorine gas generator, and this producer is one embodiment of the invention.This semiconductor machining system for example is included in and carries out the semiconductor processing 10 that film forming, etching or diffusion etc. are handled on the target substrate such as semiconductor wafer or LCD substrate.
Fig. 2 has comprised the synoptic diagram of the improvement embodiment 10x of the semiconductor processing that diagram can be used in combination with airing system 20 shown in Figure 1.Semiconductor processing 10x has been equipped with the fixed target substrate, and has carried out the Processing Room 12 of semiconductor machining therein.For the fixed target substrate, assembly floor 14 (support component) has been installed in Processing Room 12.Exhaust system 18 is connected to the lower region of Processing Room 12,, and produces vacuum therein so that find time Processing Room inside.Remote plasma chamber 13 is connected to the upper zone of Processing Room, so that generate plasma body.Aerial coil 17 is being twined in the periphery of this remote plasma chamber 13.Applying RF (high frequency) energy by RF energy source 15 to aerial coil 17, make in the remote plasma chamber 13 and formed induction field, is plasma body so that will handle gas reforming.Airing system 20 is connected to the upper zone of remote plasma chamber 13 handles gas so that supply with.
The fluorine gas generator that comprises embodiment of the present invention also can use with the semiconductor processing equipment that does not use plasma body, and for example, being used for the thermotropism chemical vapor deposition device provides purge gas.
Referring again to Fig. 1, drifting management part 22 has been installed in airing system 20; This drifting management part 22 can for example, be carried out any specified gas the processing gas of semiconductor machining, or be used to clean the processing gas of Processing Room 12 inside, sends in the Processing Room 12 with specified flow velocity, and can switch selectively.Gas storage part 24 is connected on the drifting management part 22.This gas storage part 24 comprises a plurality of gas sources, and stores various activity and/or rare gas element.Be connected to the gas generating portion 26 that can produce fluorine gas class processing gas in addition by reaction process on the drifting management part 22 equally.
The fluorine gas generator 30 that comprises embodiment of the present invention is detachably connected on drifting management part 22 and the gas generating portion 26.More specifically, this producer 30 is directly supplied with fluorine gas to drifting management part 22, perhaps is used for providing initial fluorine gas (not showing switching valve) to gas generating portion 26.Gas generating portion 26 can be for example another kind of halogen gas by initial fluorine gas and chlorine and so on react and produce interhalogen fluorination compound gas.
In electrolytic process, electrolyzer 32 is heated to 80-90 ℃ and keep this temperature by attached well heater 33.It is fluorine gas (F that hydrogen fluoride electrolysis in the electrolyzer causes the vapor phase areas generation main component in anodal compartment 34
2) product gas, generating main component in the vapor phase areas of cathodic compartment 36 is the byproduct gas of hydrogen.According to the vapour pressure dividing potential drop of hydrogen fluoride gas in initial melting salt, in product gas and byproduct gas, all be mixed with hydrogen fluoride gas (for example, 5%).First pressure warning unit 46 is installed on anodal compartment 34, and second pressure warning unit 48 is installed on cathodic compartment 36, so that the pressure of each vapor phase areas of continuous detecting.
First conduit 52 is connected with anodal compartment so that extract product gas, and this product gas is transported to the drifting management part 22 and the gas generating portion 26 of airing system 20.Is first flow control valve 54, absorbing cylinder 56, small-sized surge tank 58, compressor (suction unit) 62 and host buffer jar 64 from upstream one side according to the parts that are installed in to graded first conduit 52.Adopt the suction of compressor 62, the product gas that generates in the anodal compartment 34 is extracted out from anodal compartment 34 by force, and be stored in the main surge tank 64 by first conduit 52.Reference number 66 expression line filter among Fig. 1.
As mentioned above, can be mixed with the hydrogen fluoride of several percentage points (for example, 5%) in the product gas.When product gas passed through absorbing cylinder 56, hydrogen fluoride was removed.Therefore, this absorbing cylinder 56 should be equipped with and can capture the absorption of hydrogen fluoride agent with suction type.For the consideration to processing and pressure-losses aspect, sorbent material should be made up of the bead that is filled in a large number in the absorbing cylinder 56.Sorbent material can be made of the sorbent material that for example Sodium Fluoride (NaF) and so on adsorptive power changes as the function of temperature.Temperature regulation chuck (well heater) 57 is installed to regulate the temperature of absorbing cylinder 56 around absorbing cylinder 56.
By being installed in the pressure warning unit 65 continuous pressure of measuring in the jar 64 on the host buffer jar 64.Measuring result is sent to the controlling elements 39 that links with power supply 38.Controlling elements 39 is according to the measuring result that transmits, by switching on and off the electric current that power supply 38 controls are transported to electrolyzer 32.Therefore, when the pressure in the jar 64 dropped to certain force value, power supply 38 was connected, and begins to produce fluorine gas.When the pressure in the jar 64 was elevated to certain force value, power supply 38 disconnected, and fluorine gas production stops.So just can stop electrolysis and can not form the difference of the melting salt liquid level between the anodal compartment 34 and cathodic compartment 36 in the electrolyzer 32.For instance, the pressure in the jar 64 can be set at atmosphere and be pressed onto normal atmosphere+0.18MPa.
As mentioned above, in electrolytic process, the pressure equilibrium meeting between anodal compartment 34 and the cathodic compartment 36 is destroyed because of multiple reason, and consequently the liquid level in the electrolyzer 32 is easy to change.After gas blocked operation and then, for example finishing after the back handles with nitrogen purging with nitrogen purging electrolyzer 32 inside or in initial hydrogen fluoride gas charging, the liquid level in the electrolyzer 32 also is easy to change usually.These liquid level variation meetings bring disadvantageous effect to the security and the reliability of fluorine gas generator.
In the fluorine gas generator of setting forth as Fig. 1, by the pressure of vapor phase areas in first pressure warning unit, the 46 continuously measured anodal compartment 34, and the pressure by vapor phase areas in second pressure warning unit, the 48 continuously measured cathodic compartment 36.These measuring results are sent to respectively first and second controlling elementss 55 and 75 that link to each other with 74 with first and second flow control valves 54.According to the measuring result that transmits, first and second controlling elementss are regulated the open degree of first and second flow control valves, so that make the pressure in the vapor phase areas of pressure in the vapor phase areas of anodal compartment 34 and cathodic compartment 36 remain basic each other first and second set(ting)values that equate respectively.
Because the pressure in anodal compartment 34 and the cathodic compartment 36 separately continuously and measure independently and control, so the liquid level of melting salt remains on consistent state in anodal compartment 34 and the cathodic compartment 36.In other words, the disadvantageous effect brought of this structure variation that can protect electrolyzer 32 to avoid the operational conditions of the exhaust system 78 of condition, semiconductor manufacturing facility in fluorine working condition, first and second conduits 52 and 72 and compressor 62 and other situation.So just can prevent that for example anode effect can finish the course of processing safely, and electrolysis can not stop suddenly to the damage of expensive electrode.In addition, because the obstruction that the curing by melting salt causes can not take place in the ingress that leads to first and second conduits 52 and 72, thereby frequent maintenance no longer is essential.
In the anodal compartment 34 in first set(ting)value of vapor phase areas and the cathodic compartment second set(ting)value of vapor phase areas be preferably normal atmosphere to 820 holder, normal atmosphere to 770 holder more preferably.For the pressure in stable anode compartment 34 and the cathodic compartment 36, first and second flow control valves 54 and 74 open degree must be can be with high response mode continuously adjustable.For this consideration, preferably use piezo electric valve as first and second flow control valves 54 and 74.
Get back to Fig. 1 once more, in the cathodic compartment 36 of electrolyzer 32, feed conduits 82 is installed, so that hydrogen fluoride gas (for the raw material that consumes) is imported in the melting salt; Feed conduits 82 is immersed in the melting salt.Hydrogen fluoride source 84 and source nitrogen 94 removably by conduit 83 and 93 and feed conduits 82 link.
Switching valve 96 is installed in the conduit 93 that is used for source nitrogen 94, so that conduit 93 is switched between the opening and closing state.Switching valve 96 is always opened in the operational process of fluorine gas generator 30, and, in the operational process of fluorine gas generator 30, always nitrogen is injected the melting salt of electrolyzer 32.When the hydrogen fluoride gas flow velocity was 1 to 50 liter/minute, the flow velocity of nitrogen was arranged between 0.2 to 50 liter/minute, was preferably between 2 to 10 liters/minute.Nitrogen is almost completely insoluble in melting salt, flows through the melting salt of cathode side and is discharged from.
Switching valve 86 is installed in the conduit 83 that is used for hydrogen fluoride source 84, so that conduit 83 is switched between the opening and closing state.Opening and closing switching valve 86 under the control of the controlling elements 87 that is connected thereto.Carry out integration by the electric current that is transported between anode 42 and the negative electrode 44 in 40 pairs of electrolytic processes of current integrator, and this value is sent to controlling elements 87.According to the observed value that is sent to the there, controlling elements is handled switching valve 86 and is entered the charging in the melting salt so that regulate hydrogen fluoride gas (mixture of hydrogen fluoride gas in nitrogen).Determine the set(ting)value of controlling elements 87, so that for example the hydrogen fluoride concentration in the melting salt is remained between 39 to 41%.
The charging that hydrogen fluoride (HF) gas adds in the electrolyzer 32 is according to following theory, by the power integral control that flows of institute.For example, according to Faraday's law, the fluorine gas (F that makes by electrolysis
2) amount be directly proportional with electric weight.Regardless of electrolytic condition (temperature, concentration, electrode type), this law all is suitable for.In described embodiment,, can roughly determine to pass through the fluorine gas that electrolyzer 32 is produced with equation (1) according to the current efficiency relation.
Z＝6.8X (1)
Wherein the Z=fluorine gas is produced flow velocity (ml/min),
X=electric weight (the Faradaic current value (A) in this programme)
Initial hydrogen fluoride concentration in the melting salt for example is set at 41%.Then, the concentration of fluorine in melting salt and before for example reaching 39% concentration limit, is regularly supplied with initial hydrogen fluoride gas after 41% initial density loss.The rising that is reduced to melting salt fusing point when being lower than concentration limit when hydrogen fluoride concentration can cause melting salt to solidify in the worst case, and electrolysis can't be carried out.If hydrogen fluoride concentration surpasses initial concentration, hydrofluoric high vapour pressure can improve the hydrogen fluoride concentration that is blended in the fluorine equally in the consequent melting salt.This can cause very high load to capture hydrofluoric absorption agent (for example, Sodium Fluoride (NaF)) with suction type at absorbing cylinder 56 places.Therefore, hydrogen fluoride concentration must be remained in the aforesaid scope, for example, between 39 to 41%.Relation between equation (2) expression fluorine gas production and hydrogen fluoride gas consume.Here, produce 1 mole of fluorine gas and need 2 moles of hydrogen fluoride.
(2Z+0.05Z+0.05Z)t/1000＝T (2)
Wherein 2Z=produces 1 mole of hydrogen fluoride flow velocity (ml/min) that fluorine gas is required
The hydrogen fluoride flow velocity of carrying secretly in first 0.05Z=1 mole fluorine gas (ml/min)
The hydrogen fluoride flow velocity of carrying secretly in second 0.05Z=1 mol of hydrogen (ml/min)
The t=production time (minute)
The hydrofluoric consumption of T=(liter)
According to equation (1), replace Z in the equation (2) with 6.8X, obtain equation (3).
0.01428X×t＝T (3)
X=electric weight (ampere) wherein
The t=production time (minute)
The hydrofluoric consumption of T=(liter)
Consumable hydrofluoric amount depends on the amount that joins the melting salt in the electrolyzer 32.Suppose electrolysis begin before in the melting salt hydrofluoric concentration be 41%, then hydrofluoric amount is 0.41C in the electrolyzer 32, C is the amount of melting salt here.When in the scope of hydrofluoric concentration at 39-41% in the electrolyzer 32, equation (4) has provided hydrogen fluoride concentration in the melting salt and the relation between the hydrogen fluoride consumption.Equation (5) has provided the amount of consumable hydrofluoric maximum.
(0.41C-HFc)/(C-HFc)＝0.39 (4)
HFc＝0.033C (5)
Wherein, in equation (4) and (5)
The weight of C=melting salt
The hydrofluoric consumption of HFc=
By replace the HFc in the equation (5) with the T in the equation (3), obtain equation (6), obtain equation (7) subsequently.
0.01428X×t＝0.033C (6)
X×t＝2.3C (7)
Wherein, in equation (6) and (7)
X=electric weight (ampere)
The T=production time (minute)
The weight of C=melting salt
Thus, be known if add the weight C of the melting salt (KF/2HF) in the electrolyzer 32 in advance, so for the hydrogen fluoride concentration of used 39-41%, just can determine the relation between electric weight X and the fluorine gas production time t.In this example, the value that can provide by electric quantity integration is determined the selection of time (lower limit of used scope) of hydrogen fluoride gas charging on time shaft, therefore fixing electric weight X.
To discuss the advantage of embodiment of the present invention mentioned above now.
Japanese Laid-Open Patent Application (PCT) Hei 9-505853 number (hereinafter referred to as 853 is open) discloses a kind of fluorine gas groove, it contains the control sensor device of surveying electrolytic solution height in the electrolyzer, and response comes the signal of self-acting control sensor device and responds the current supply arrangement that this signal begins or stop to supply with electric current.In this case, before reaching preposition, liquid level decline continues to carry out fluorine gas production.In this predetermined position, signal sends.Because this signal of response, electrolysis control device stop the electrolyzer power supply, electrolysis stops, and the decline of liquid level of electrolyte height also stops.
Generally speaking, the disclosed technology of this application has a mind to utilize the variation of liquid level to realize the ON/OFF of electric current is controlled, and does not consider this variation is not suppressed.But, in electrolytic process, the variation of liquid level must be reduced to minimum so that when keeping steady state the continuous production fluorine gas.
853 openly point out that also the anodal compartment in the electrolyzer will play the effect of fluorine storing device.But because fluorine gas production is difficult to meet the demands, the fluorine gas generator that is used for semiconductor machining on practical level needs compressor and the container with certain size.Disclosed technology can not adapt to the variation of this type of external conditions in described disclosing.
Therefore, the industrial fluorine gas generation systems that meets 853 publications has been equipped with the bellows type compressor and capacity is the container of several liters.This system is stored in fluorine gas in its surge tank off and on by the action of on/off switch valve.Adopt this method, can generate fluorine gas without a break, and fluorine gas production can not interrupted.But although can stably make fluorine gas in this case, practical experience still shows, following problems can occur in the process of discussing of carrying out long-term production in this case.
In the melting salt mist infiltration gallery of being carried secretly by fluorine gas, or infiltrate in the container between compressor and electrolyzer.Because the fusing point of this mist is about 80 ℃, thereby it can be present in the conduit with solid form.Along with the accumulation of this mist, can cause following problem: (1) conduit stops up the valve seat that damages close/open valve with (2).
Preceding problem causes electrolysis to be interrupted immediately, and need operate to remove the salt of occlusion catheter.Owing to also have reactive fluorine gas in the conduit, thereby this removal operation is dangerous, and needs very careful.Back one problem also can require to stop electrolysis owing to the seepage at the valve place.In addition, frequently repeating on/off operation can cause valve to wear and tear too early.
In addition, because the control method of being discussed can not be avoided liquid level generation variation to a certain degree in the anodal compartment, therefore the contact area between liquid and electrode surface also constantly changes.The variation of current efficiency makes the fluorine gas turnout be difficult to keep stable in the electrolytic process of Chan Shenging like this.Here another problem of Chan Shenging is that anode effect causes (3) electrode must be replaced (carbon commonly used is made anode).
When as 853 open described in by the folding of response control transmitter, when powered-down is controlled the fluorine gas turnout, it also can't adapt to the environmental conditions variation of (linking to each other with compressor) in the example of discussing.And be used under the situation of semiconductor machining, use compressor need carry out last analysis at the electrolyzer place.On the other hand, necessary is, the generation of fluorine gas can not be subjected to the influence in downstream side behind the electrolyzer.Viewpoint be it seems thus, and 853 control methods in open can not adopt, and therefore can not be actually used in semiconductor machining.
A key character of aforementioned embodiment of the present invention is that the influence that it is not changed by the pond postcondition can generate fluorine gas continuously and stably.This fluorine gas feeding mechanism is that specialized designs is used for the semiconductor machining operation, that is to say that its basic premise is to use the suction unit as compressor and so on.
The pressure warning unit that is connected on the surge tank of compressor downstream links to each other with power supply.When pressure dropped to certain value, power supply was opened, and generated fluorine gas.When pressure is increased to certain point, power-off.Adopt this method, need not to resemble 853 open described in the different liquid level of meticulous manufacturing can stop electrolysis.
853 openly point out, because security reason, the preferred pressure in the cathode side exit always is to operate in normal atmosphere (or a little more than atmospheric pressure) time.But, in the semiconductor devices of reality, may keep this point hardly, because in the cathode side conduit, huge pressure change can take place.In addition, 853 openly only pay close attention to the pressure change in the anodal compartment, and this pressure that is based upon in the cathodic compartment is always on the atmospheric prerequisite.
The method of the independent control flow velocity by aforementioned embodiment of the present invention keep-ups pressure, and can make the pressure in two pole compartments of electrolyzer keep constant always.But, can not determine liquid level by pressure in practice, therefore, in order to improve security, can be with liquid surface height sensor in a preferred manner in the male or female side, preferably insert at cathode side.
Initial anhydrous hydrogen fluoride (AHF) is generally gas, and injects the melting salt (preferably at cathode side) of electrolyzer by bubbling.AHF is absorbed in the melting salt very fast, the result, and when AHF supplied with slow speed, cathodic compartment can present negative pressure in moment.When this happens, melting salt rises in the AHF feed conduit, can come to an end with curing in the worst case, and can't continue charging.Therefore, the AHF feeding rate is preferably fast, but to can the actual AHF flow velocity that uses being conditional.
Therefore, in aforementioned embodiment of the present invention, during the AHF charging, AHF is sneaked in the nitrogen, so that in the AHF fill process, improve whole flow velocity.Because nitrogen is almost completely insoluble in melting salt, it flows through the melting salt of cathode side, and is discharged from.No matter whether reality is carried out in electrolysis, and nitrogen is flowed in the cathodic compartment.This can dilute the hydrogen that cathode side in the electrolytic process generates, even and because unexpected and unexpected variation takes place in liquid level when making fluorine gas introducing cathode side, condition is remained on beyond the limits of explosion.Nitrogen flow rate can be adjusted arbitrarily according to the electrolyzer size.
Those skilled in the art can design the various modifications and changes in the technical scope of theory of the present invention, will be appreciated that these modifications and change also drop in protection scope of the present invention.
As mentioned above, though the invention provides a kind of also can be as safe as a house in the long-time running process and the fluorine gas maker of operation highly reliably.
Brief description of drawings
Fig. 1 comprises the synoptic diagram that diagram contains the semiconductor machining system of fluorine gas generator, and this producer is one embodiment of the invention.
Fig. 2 comprises the synoptic diagram of the improvement embodiment of the semiconductor machining system that diagram can be used in combination with airing system 20 shown in Figure 1.
Fig. 3 comprises the synoptic diagram of diagram prior art fluorine gas maker.
Reference symbol:
10,10x ... semiconductor processing
12 ... Processing Room
18 ... exhaust system
20 ... airing system
22 ... the drifting management part
24 ... the gas storage part
26 ... the gas generation part
30 ... producer gas generator
32 ... electrolyzer
34 ... anodal compartment
36 ... cathodic compartment
38 ... power supply
40 ... current integrator
42 ... anode
44 ... negative electrode
46,48 ... pressure warning unit
52,72 ... conduit
54,74 ... flow control valve
55,75 ... controlling elements
56 ... absorbing cylinder
58 ... container
62 ... compressor
64 ... surge tank
76 ... detoxification machine
78 ... exhaust system
82 ... feed conduits
84 ... hydrogen fluoride source
86 ... switching valve
87 ... controlling elements
94 ... source nitrogen
96 ... switching valve
Claims (10)
1. apparatus for generating fluorine gas is characterized in that being equipped with:
Electrolyzer, it carries out the hydrogen fluoride electrolysis in the electrolyzer of the melting salt that contains fluorinated hydrogen, and to generate main component in first vapor phase areas of anode side thus be the product gas of fluorine gas, and generating main component in second vapor phase areas of cathode side simultaneously is the byproduct gas of hydrogen;
Initial hydrogen fluoride is sent into feed conduits in the melting salt;
Shift out first conduit of product gas from first vapor phase areas;
Shift out second conduit of byproduct gas from second vapor phase areas;
First pressure warning unit of pressure in continuously measured first vapor phase areas;
Second pressure warning unit of pressure in continuously measured second vapor phase areas;
Be installed in first flow control valve in first conduit;
Be installed in second flow control valve in second conduit;
First controlling elements, its observed value according to the first pressure warning unit gained are adjusted the open degree of first flow control valve so that the pressure of first vapor phase areas is remained on first set(ting)value; With
Second controlling elements, its observed value according to the second pressure warning unit gained are adjusted the open degree of second flow control valve so that the pressure of second vapor phase areas is remained on second set(ting)value that equals first set(ting)value substantially.
2. according to the apparatus for generating fluorine gas of claim 1, it is characterized in that first and second set(ting)values are 760 to 820 holders.
3. according to the apparatus for generating fluorine gas of claim 1 or 2, it is characterized in that also being equipped with first suction unit, it is installed in the downstream of first flow control valve in first conduit, and can aspirate first conduit.
4. according to the apparatus for generating fluorine gas of claim 3, it is characterized in that the installation of second conduit makes it be able to the downstream of second flow control valve is connected with second suction unit that can aspirate second conduit.
5. according to each apparatus for generating fluorine gas of claim 1 to 4, it is characterized in that also being equipped with:
Be installed in the switching valve in the feed conduits;
Current integrator, the electric current that it will be transported between the electrode of the electrode of electrolyzer aforesaid anode side and the aforementioned cathode side of electrolyzer carries out integration; With
Controlling elements, its measuring result operation switching valve that generates according to current integrator enters charging in the melting salt with control hydrogen fluoride.
6. according to the apparatus for generating fluorine gas of claim 5, it is characterized in that the hydrogen fluoride that imports by feed conduits is gas.
7. according to the apparatus for generating fluorine gas of claim 6, it is characterized in that feed conduits installs to such an extent that hydrogen fluoride gas can be imported in the melting salt of cathode of electrolytic tank side, its feature also is to be connected to the downstream of aforementioned switching valve nitrogen being imported conduit in the feed conduits, and hydrogen fluoride gas is mixed with nitrogen send in the melting salt.
8. apparatus for generating fluorine gas is characterized in that being equipped with:
Electrolyzer, it carries out the hydrogen fluoride electrolysis in the electrolyzer of the melting salt that contains fluorinated hydrogen, generating main component thus in first vapor phase areas of anode side is the product gas of fluorine gas, and generating main component simultaneously in second vapor phase areas of cathode side is the byproduct gas of hydrogen;
Initial hydrogen fluoride is sent into feed conduits in the melting salt;
Shift out first conduit of product gas from first vapor phase areas;
Shift out second conduit of byproduct gas from second vapor phase areas;
Be installed in the switching valve in the feed conduits;
Current integrator, it carries out integration to the electric current between the electrode of the electrode that is transported to electrolyzer aforesaid anode side and the aforementioned cathode side of electrolyzer; With
Controlling elements, its measuring result operation switching valve that generates according to current integrator enters charging in the melting salt with control hydrogen fluoride.
9. apparatus for generating fluorine gas according to Claim 8 is characterized in that the hydrogen fluoride that imports by feed conduits is gas.
10. according to the apparatus for generating fluorine gas of claim 9, it is characterized in that feed conduits installs to such an extent that hydrogen fluoride gas can be imported in the melting salt of cathode of electrolytic tank side, its feature also is to be connected to the downstream of aforementioned switching valve nitrogen being imported conduit in the feed conduits, and hydrogen fluoride gas is mixed with nitrogen send in the melting salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002202734A JP3905433B2 (en) | 2002-07-11 | 2002-07-11 | Fluorine gas generator |
| JP202734/2002 | 2002-07-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1668779A true CN1668779A (en) | 2005-09-14 |
Family
ID=30112643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA038165309A Pending CN1668779A (en) | 2002-07-11 | 2003-06-30 | Apparatus for the generation of fluorine gas |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP3905433B2 (en) |
| KR (1) | KR101065906B1 (en) |
| CN (1) | CN1668779A (en) |
| TW (1) | TWI293342B (en) |
| WO (1) | WO2004007802A2 (en) |
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| CN101248216B (en) * | 2005-08-25 | 2010-06-16 | 东洋炭素株式会社 | Fluorogas generator |
| CN102713009A (en) * | 2010-01-05 | 2012-10-03 | 中央硝子株式会社 | Fluorine gas generation apparatus |
| CN102762772A (en) * | 2009-12-02 | 2012-10-31 | 中央硝子株式会社 | System for generating fluorine gas |
| CN102834549A (en) * | 2010-04-14 | 2012-12-19 | 东洋炭素株式会社 | Gas generation device and gas generation method |
| CN102859040A (en) * | 2010-04-16 | 2013-01-02 | 中央硝子株式会社 | Fluorine gas generation device |
| CN104126031A (en) * | 2011-12-22 | 2014-10-29 | 索尔维公司 | Method of feeding hydrogen fluoride into an electrolytic cell |
| CN113950542A (en) * | 2019-12-27 | 2022-01-18 | 昭和电工株式会社 | Method for producing fluorine gas and apparatus for producing fluorine gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4624699B2 (en) * | 2004-03-18 | 2011-02-02 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Fluorine gas generator |
| JP4494158B2 (en) * | 2004-10-13 | 2010-06-30 | 東洋炭素株式会社 | Gas generator and method for adjusting piping temperature of gas generator |
| WO2006043125A1 (en) * | 2004-10-20 | 2006-04-27 | L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude | Fluorine gas generator |
| JP5332829B2 (en) * | 2009-04-01 | 2013-11-06 | セントラル硝子株式会社 | Fluorine gas generator |
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| KR20130079363A (en) * | 2010-03-26 | 2013-07-10 | 솔베이(소시에떼아노님) | Method for the supply of fluorine |
| JP5716288B2 (en) * | 2010-04-16 | 2015-05-13 | セントラル硝子株式会社 | Fluorine gas generator |
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| CN104651873A (en) * | 2014-12-22 | 2015-05-27 | 四川聚核科技有限公司 | Intelligentized container modularized middle-temperature electrolytic fluorine-preparing device |
| KR20220065864A (en) * | 2019-12-27 | 2022-05-20 | 쇼와 덴코 가부시키가이샤 | Fluorine gas manufacturing method and fluorine gas manufacturing apparatus |
| CN113430543A (en) * | 2021-07-08 | 2021-09-24 | 中核四0四有限公司 | Centralized feeding method for liquid hydrogen fluoride in fluorine-making electrolytic cell |
| TWI820854B (en) * | 2022-08-11 | 2023-11-01 | 亞福儲能股份有限公司 | Battery detecting apparatus |
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| JPS63307289A (en) * | 1987-06-04 | 1988-12-14 | Yokogawa Electric Corp | Pressure control device for ion exchange membrane method electrolytic cell |
| JPH0755807B2 (en) * | 1987-11-04 | 1995-06-14 | 三井東圧化学株式会社 | Method for producing nitrogen trifluoride |
| JPH0678593B2 (en) * | 1989-03-03 | 1994-10-05 | 三井東圧化学株式会社 | Method for producing gas by molten salt electrolysis |
| JPH0353090A (en) * | 1989-07-18 | 1991-03-07 | Asahi Glass Co Ltd | Production of fluorine |
| JP2809811B2 (en) * | 1990-04-27 | 1998-10-15 | 三井化学株式会社 | Method for producing nitrogen trifluoride gas |
| JP3342139B2 (en) * | 1993-12-24 | 2002-11-05 | 三菱重工業株式会社 | Method and apparatus for producing conductive polymer |
| GB9418598D0 (en) * | 1994-09-14 | 1994-11-02 | British Nuclear Fuels Plc | Fluorine cell |
| US6818105B2 (en) * | 2000-04-07 | 2004-11-16 | Toyo Tanso Co., Ltd. | Apparatus for generating fluorine gas |
| JP4085174B2 (en) * | 2002-05-29 | 2008-05-14 | 東洋炭素株式会社 | Fluorine gas generator |
-
2002
- 2002-07-11 JP JP2002202734A patent/JP3905433B2/en not_active Expired - Fee Related
-
2003
- 2003-06-30 KR KR1020057000438A patent/KR101065906B1/en active IP Right Grant
- 2003-06-30 CN CNA038165309A patent/CN1668779A/en active Pending
- 2003-06-30 WO PCT/IB2003/002998 patent/WO2004007802A2/en active Application Filing
- 2003-07-08 TW TW092118556A patent/TWI293342B/en not_active IP Right Cessation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248216B (en) * | 2005-08-25 | 2010-06-16 | 东洋炭素株式会社 | Fluorogas generator |
| CN102762772A (en) * | 2009-12-02 | 2012-10-31 | 中央硝子株式会社 | System for generating fluorine gas |
| CN102713009A (en) * | 2010-01-05 | 2012-10-03 | 中央硝子株式会社 | Fluorine gas generation apparatus |
| CN102834549A (en) * | 2010-04-14 | 2012-12-19 | 东洋炭素株式会社 | Gas generation device and gas generation method |
| CN102834549B (en) * | 2010-04-14 | 2015-11-25 | 东洋炭素株式会社 | Gas generation apparatus and gas generating processes |
| CN102859040A (en) * | 2010-04-16 | 2013-01-02 | 中央硝子株式会社 | Fluorine gas generation device |
| CN104126031A (en) * | 2011-12-22 | 2014-10-29 | 索尔维公司 | Method of feeding hydrogen fluoride into an electrolytic cell |
| CN113950542A (en) * | 2019-12-27 | 2022-01-18 | 昭和电工株式会社 | Method for producing fluorine gas and apparatus for producing fluorine gas |
| CN113950542B (en) * | 2019-12-27 | 2024-03-05 | 株式会社力森诺科 | Method for producing fluorine gas and apparatus for producing fluorine gas |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI293342B (en) | 2008-02-11 |
| TW200400921A (en) | 2004-01-16 |
| WO2004007802A3 (en) | 2004-07-15 |
| KR20050017115A (en) | 2005-02-21 |
| KR101065906B1 (en) | 2011-09-19 |
| JP3905433B2 (en) | 2007-04-18 |
| JP2004043885A (en) | 2004-02-12 |
| WO2004007802A2 (en) | 2004-01-22 |
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