CN1259524C - Method and system for treating exhaust gas - Google Patents
Method and system for treating exhaust gas Download PDFInfo
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- CN1259524C CN1259524C CNB038001454A CN03800145A CN1259524C CN 1259524 C CN1259524 C CN 1259524C CN B038001454 A CNB038001454 A CN B038001454A CN 03800145 A CN03800145 A CN 03800145A CN 1259524 C CN1259524 C CN 1259524C
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/061—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating
- F23G7/065—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating using gaseous or liquid fuel
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2215/00—Preventing emissions
- F23J2215/30—Halogen; Compounds thereof
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- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Incineration Of Waste (AREA)
- Treating Waste Gases (AREA)
- Drying Of Semiconductors (AREA)
Abstract
A method for treating an exhaust gas containing a fluorine gas or halogen fluoride gas discharged from an etching or cleaning process, which comprises burning the exhaust gas in a burning chamber having an fluorinated passive film formed on the inner surface thereof. The method can be used for treating an exhaust gas from a semiconductor manufacturing process which contains a fluorine gas or halogen fluoride gas in a high content or in a large amount, is safe and energy-saving, and allows the performance of pretreatment of the exhaust gas with enhanced efficiency.
Description
Technical field
The present invention relates to waste gas processing method and treating apparatus.More particularly, the present invention relates to be used to handle the method and apparatus of the waste gas that contains fluorine gas or halogen fluoride gas, these gases be from the etching of semiconductor fabrication process or cleaning step, discharge and relate to the process for fabrication of semiconductor device that utilizes this method and apparatus.
Background technology
Exhaust gas discharged contains some gases in each step from the semiconductor manufacturing, and as semiconductor material gas, etching gas or purge gas, and these gases usually are harmful to.They comprise disagreeableness gas on the environment sometimes, can not directly be discharged in the atmosphere so contain the waste gas of this type of component.
The method of exhaust-gas treatment is widely known by the people, and comprising:
(1) wet removing method, wherein nertralizer such as caustic soda (NaOH) are used for oxidation reaction or neutralization reaction,
(2) the reactive decomposition method of use catalyst bed,
(3) being adsorbed onto the dried removing method on oxide or the analog,
(4) introduce electric heater thermolysis process and
(5) burning removing method and use these methods according to desirable feature.
In recent years, the diversity of the harmful constituent that is contained in exhaust gas discharged from semiconductor fabrication process and remarkable larger sized silicon wafer and liquid crystal board and corresponding bigger manufacturing installation has increased, and has caused the volume of employed gas in this manufacturing process bigger.In addition, owing to the more uses of the multi-cavity chamber that is used for sheet feeding apparatus and the bigger complexity of corresponding manufacturing process, usually be necessary to handle simultaneously the waste gas from different approaches of large volume, or handle waste gas safely, these waste gas flow in same path, change the time cycle simultaneously, for using identical elimination system that very different performances is arranged.Therefore, in recent years, various heat treatment type removing methods, as burning type or thermal decomposition type method, investigated as removing method, wherein by inflammability fuel gas or analog at high temperature being burnt and poisonous component or the disagreeableness waste gas component of environment that contains in the waste gas changed into harmless material, or they are changed into easy-to-handle material.
Yet, especially eliminate system for burning type, from semiconductor fabrication process exhaust gas discharged at high temperature with fuel gas such as town gas, LPG (liquefied petroleum gas), methane or analog and with the processing of burning of carrying gas such as air and oxygen, and this causes elemental nitrogen from waste gas or the airborne nitrogen gas generation NOx gas as accessory substance.
NOx gas usually in the waste gas of burning the very high concentration with 1-30% produce, this depends on employed device and burning condition, investigated several method with concentration limit to TLV (NO of 25ppm, the NO of 3ppm
2).For example, Japanese uncensored patent publications No.2001-193918 has described the research of combustion-chamber shape and nozzle shape so that reduce the generation of NOx.Yet, when the waste gas of burning contains NF
3Gas is when (it is used for etching and cleaning step in a large number), and the generation of NOx is extra high, and this needs to improve.
On the other hand, clean and also can in semiconductor fabrication process, use fluorine gas or halogen fluoride gas or their mixture to carry out as the purge gas of demonstration superior performance etc.For example, J.Appl.Phys., p.2939, and 56 (10), No.15,1984 have reported result of study, show that the cleaning performance of fluorine gas and halogen fluoride gas compares NF
3Gas is more excellent.
However, fluorine gas or halogen fluoride gas are the high activity strong oxidizers with high chemical reactivity, therefore usually react at normal temperatures with oxidizing substance, cause catching fire, and they are high corrosion to device materials also simultaneously.Therefore this device materials must strictly be selected from the metal of specific high corrosion resistance, and not oil-containing and water; And the TFE that is widely used as the high corrosion resistance resin of semiconductor-fabricating device usually is not suitable for given service condition.
Elimination system as fluorine gas or halogen fluoride gas such as chlorine trifluoride can use wet absorption system, and it is finished neutralization by means of the washer that uses aqueous alkali such as caustic soda or caustic potash and absorbs; Or dried elimination system, it utilizes solid absorbent such as activated bauxite or soda-lime to finish to absorb removes.Yet all these methods all have a shortcoming, and promptly they can't realize containing the treatment of waste gas of high concentration fluorine gas or halogen fluoride gas.The accessory problem that is run into when using wet elimination system such as alkali scrubber for the situation of the fluorine gas of larger volume or halogen fluoride gas is, the size on absorption tower must increase, and it is complicated that the waste disposal of absorbent solution becomes, and operating cost is higher.Remove the elimination system for dry type decomposition elimination system or absorption, not only be difficult to install big mobile elimination system, and the frequency of replacement of solid distintegrant and absorbent is higher, and this causes running cost sharply to increase, and the maintenance program that is added simultaneously tends to cause the safety management problem.
Of the present invention open
In view of this background, the purpose of this invention is to provide removing method and system, this system can handle the waste gas that contains high concentration or a large amount of fluorine gas or halogen fluoride gas that discharges from semiconductor fabrication process, and it be safety and Energy Efficient rate and finish elimination in mode more efficiently.
As mentioned above, when fluorine gas or halogen fluoride gas are used for semiconductor fabrication process, this waste gas is handled by special elimination system separately, but method of the present invention is by improving dimensions of semiconductor devices and complexity and overcoming the problems referred to above for it provides multi-functional, reduced simultaneously should the elimination system installing space.
As result at the effort research that addresses the above problem, the inventor finishes the present invention based on following discovery: the problems referred to above can solve by using a kind of processing method, the waste gas that contains fluorine gas or halogen fluoride gas that wherein discharges from etching or cleaning step is introduced in the burner that the combustion chamber is housed, and has the fluoride passivating film of formation on this combustor surface.
In other words, the invention provides a kind of waste gas processing method, be included in the waste gas that contains fluorine gas or halogen fluoride gas that burning is discharged in the combustion chamber from etching or cleaning step, on this combustor surface, have the fluoride passivating film of formation.
This fluoride passivating film preferably is made up of nickel fluoride.
The concentration of fluorine gas or halogen fluoride gas preferably be not more than by volume 5%.
Preferably be lower than by volume 5ppm at the content of nitrogen oxides of exhaust gas after the burning.
The present invention further provides a kind of exhaust treatment system, it is equipped with waste gas intake, fuel intake, precombustion chamber, combustion chamber, air intake and exhaust duct, and has the fluoride passivating film that forms on this combustor surface at least.
According to embodiment preferred, this combustion chamber is formed by the material that is selected from least a type in nickel, rich nickel alloy and the monel metal, and the fluoride passivating film is to form on the surface of this material.
According to another embodiment preferred, this combustion chamber is formed by the material that is selected from least a type in stainless steel and the steel material, wherein the surface of material has the film be made up of nickel, nickel alloy electricity coating, electric smelting coating layer or nickel alloy chemical plating coating or ceramic membrane of being made up of alumina or aluminium nitride and the fluoride passivating film that forms on this film surface.
The present invention further provides a kind of process for fabrication of semiconductor device, comprising:
Etching or cleaning step wherein adopt fluorine gas or halogen fluoride gas as etching gas or purge gas; With
Removal process wherein makes the gas combustion that contains fluorine gas or halogen fluoride gas of discharging in the step in front,
This removal process is to carry out in the combustion chamber, has the fluoride passivating film of formation on described combustor surface.
This fluoride passivating film preferably is made up of nickel fluoride.
The accompanying drawing summary
Fig. 1 is a schematic diagram, has shown an example of the treatment system that is used to carry out waste gas processing method of the present invention.
In this schematic diagram, the 1st, technology waste gas, the 2nd, diluent gas, the 3rd, carrying gas, the 4th, the fuel gas that is used to burn, the 5th, air, the 6th, airborne release gas, the 7th, precombustion chamber, the 8th, the combustion chamber, the 9th, the burning gases cooling device, the 10th, alkali scrubber and 11 is air exhausters.
Carry out best mode of the present invention
Describe the preferred embodiments of the invention now in detail.
In waste gas processing method of the present invention, the waste gas that contains fluorine gas or halogen fluoride gas that discharges from etching or cleaning step is to burn in the combustion chamber, and this combustion chamber has the fluoride passivating film that forms in its surface.That is to say, present invention resides in the processing under the set point of temperature so that from semiconductor fabrication process, discharge comprise fluorine gas or halogen fluoride gas and as the gas of film forming gas (SiH for example
4) or the waste gas of other gas become harmless.
Processing method of the present invention can reduce significantly as the carbon dioxide of the decomposition by-products of discharging from the elimination system and the amount of NOx gas, this is by allowing fully innoxious processing supply with under the condition with low combustion temperature more (the ordinary combustion condition when not having fluorine gas or halogen fluoride gas is compared) and carry out reducing fuel, or in other words, it allows to handle for being easy to innoxious compound, makes this operation to carry out under this type of appropraite condition.
According to the present invention, eliminate when burning type elimination system is used for following gas and handle: film forming gas such as SiH
4, SiH
2C1
2, NH
3, PH
3, WF
6, Si (OC
2H
5)
4, NF
3, H
2, B
2H
6, CH
4, C
2H
2And analog, purgative gas or other gas component of in semiconductor fabrication process, discharging and in each manufacturing step of semiconductor, use always, and this fluorine gas and halogen fluoride gas.In the case, handled component can be separately fluorine gas or halogen fluoride gas in waste gas.The concentration of fluorine gas or halogen fluoride gas preferably is not more than 5 volume % in waste gas.
Burning type of the present invention is eliminated the operation of system and can be finished the innoxious of toxic gas component and these components are changed into such material, these materials can have the 10-30% inferior fuel supply with and than work as the waste gas of being introduced when not comprising fluorine gas or halogen fluoride gas employed burning condition (for example, for the needed burning condition of the decomposition of gas of nitrogen trifluoride) hang down under these operating conditions of the ignition temperature more than 50 ℃ and easily remove by decomposition.So the processing method of the application of the invention might reduce the amount of carbon dioxide, carbon dioxide is the decomposition by-products of discharging from this elimination system, proportional with the reduction of fuel used gas.Lower ignition temperature also reduces the generation of NOx gas significantly, makes to realize producing the NOx that is lower than 5 volume ppm.
Operation under lower combustion temp is tangible major advantage for the security in operational administrative, and owing to the surface temperature of machine material in the area part of waste gas burning or in the cavity area in front is lower, so the extent of corrosion of device materials is significantly reduced.This makes this system not need too frequent maintenance and is providing tangible cost advantage aspect the life-span that prolongs system.
Waste gas after burning is handled is supplied dewing abatement apparatus such as alkali scrubber at last, and this equipment is connected to and is used to absorb the exhaust duct that the burning type of handling hydrogen halides such as hydrogen fluoride, NOx or other decomposed substance such as ocratation is eliminated tower.
Exhaust treatment system of the present invention is equipped with waste gas intake, fuel intake, precombustion chamber, combustion chamber, air intake and exhaust duct, and forms the fluoride passivating film on the surface of this combustion chamber at least.
Fig. 1 has shown the example of the treatment system that is used to carry out waste gas processing method of the present invention, and its uses combustion decomposition treatment system, wherein makes the mix waste gas that contains fluorine gas or halogen fluoride gas by the flame wall and be incorporated in the carrying gas swirl air-flow.
The material of system shown in Figure 1 must be that the high corrosion resistance material is to withstand flowing of fluorine gas or halogen fluoride gas.Because the heat of burning, combustion chamber 8 is under the high temperature, and it is preferably by nickel or rich nickel alloy or monel metal forms and the fluoride passivating film preferably forms on its surface.As another preferred pattern, combustion chamber 8 can be formed by common stainless steel or steel material, the fluoride passivating film that its surface has the film of being made up of nickel, nickel alloy electricity coating, electric smelting coating layer or nickel alloy chemical plating coating or the ceramic membrane of being made up of alumina or aluminium nitride (these materials have excellent anti-fluorine gas and for the hear resistance of spraying etc.) and forms on this film surface.For the nickel coating layer, it is to obtain excellent heat resistance institute preferably that nickel-boron type chemical plating is handled.Precombustion chamber 7 also preferably has the fluoride passivating film that forms in its surface with the same manner.
Each parts of this system preferably carry out Passivation Treatment with fluorine gas in advance.The vicinity of fluorine gas burning block is exposed to extra high temperature by heat radiation and the heat transmission from this burning block.These zones are therefore preferably with nickel or rich nickel alloy or monel metal structure.Common stainless steel or steel material can carry out anti-corrosion treatment, as nickel plating, electric smelting plating or nickel alloy chemical plating.Each member of this system also preferably carries out Passivation Treatment with the same manner with fluorine gas in advance.
Passivation Treatment with fluorine gas can be carried out according to the known method of the public, for example can use the method for describing in the uncensored patent publications No.11-92912 of Japan.Specifically, for example, forced oxidation can be at first carried out on the surface that is used for the nickel of this system unit, and the reaction of the film of oxidation and fluorine gas forms the fluoride passivating film then.As another example, wherein employed system unit is the stainless steel surfaces that has the nickel film in its surface, and it carries out oxidation and fluorination treatment in the same way so that form the fluoride passivating film from the teeth outwards.
According to aforesaid the present invention, be introduced in the burner that the combustion chamber is housed from the waste gas that contains fluorine gas or halogen fluoride gas of etching or cleaning step discharge, this combustion chamber has the fluoride passivating film of formation in its surface and the efficient processing that the burning of waste gas in this device can realize this waste gas.
The present invention further provides a kind of process for fabrication of semiconductor device, comprise and adopt fluorine gas or halogen fluoride gas as the etching or the cleaning step of etching gas or purge gas with wherein make the removal process of the gas combustion that contains fluorine gas or halogen fluoride gas of discharging in the step in front, this removal process is to carry out in the combustion chamber, and described combustion chamber has the fluoride passivating film that forms in its surface.
To explain the present invention in more detail by following embodiment and Comparative Examples now, precondition is that these embodiment never are limitations of the present invention.
Embodiment 1
Stainless steel combustion chamber and its parts of encirclement that burning type is eliminated system all carry out nickel plating and fluoride Passivation Treatment, and burning-elimination experiment uses fluorine gas to carry out.Burning type eliminates system's operating condition and fluorine introducing condition all is shown in Table 1, and the composition analysis of exhaust gas discharged the results are shown in the table 2 after burning and elimination.Chamber temperature is to measure with the thermocouple that is connected in outer wall of combustion chamber.Nitric oxide after the burning in waste gas and content of nitrogen dioxide are measured with gas detecting tube, and hydrogen fluoride gas concentration is by infrared spectrometry.Nitrogen trifluoride uses detector to measure.Sampling is to carry out with potassium iodide aqueous solution, and the concentration of fluorine of sample solution is by measuring with the sodium thiosulfate solution titration, and the metal concentration of sample solution is to measure by inductively coupled plasma-atomic emission spectrometry.
Table 1
| The fuel methane flow velocity | The carrying air velocity | The cooling air emission flow | The fluorine flow velocity | Dilution nitrogen flow velocity | Chamber temperature |
| (L/ minute) | (L/ minute) | (m 3/ minute) | (L/ minute) | (L/ minute) | (℃) |
| 25 | 30 | 30 | 13.5 | 240 | 305-315 |
Table 2
| The hydrogen fluoride gas concentration of calculating | The hydrogen fluoride gas concentration of measuring | The fluorine concentration of measuring | The nitric oxide concentration of measuring | The content of nitrogen dioxide of measuring | Other combustion reaction products |
| (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | |
| 900 | 900 | ＜10 | ＜0.1 | ＜0.1 | Do not detect |
Can find out that from table 2 waste gas after the burning contains nitric oxide or nitrogen dioxide anything but and is introduced in whole fluorine in the burning type elimination system and all reacted and change into hydrogen fluoride gas.Infrared spectrum and inductively coupled plasma-atomic emission spectrum by sample solution confirm, do not have combustion reaction products, water vapour and carbon dioxide except that fluoridizing hydrogen in burnt gas.
Comparative Examples 1
Burning-elimination experiment replaces fluorine gas to carry out by using Nitrogen trifluoride as introducing gas, and the flow velocity of Nitrogen trifluoride is 9.0L/ minute.During burning type elimination system's operating condition and Nitrogen trifluoride introducing condition all were shown in and glue, the composition analysis of burnt gas the results are shown in the table 4.
Table 3
| The fuel methane flow velocity | The carrying air velocity | The cooling air emission flow | The Nitrogen trifluoride flow velocity | Dilution nitrogen flow velocity | Chamber temperature |
| (L/ minute) | (L/ minute) | (m 3/ minute) | (L/ minute) | (L/ minute) | (℃) |
| 30 | 311 | 30 | 9.0 | 240 | 350-360 |
Table 4
| The hydrogen fluoride gas concentration of calculating | The hydrogen fluoride gas concentration of measuring | The Nitrogen trifluoride concentration of measuring | The nitric oxide concentration of measuring | The content of nitrogen dioxide of measuring | Other combustion reaction products |
| (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | |
| 900 | 900 | ＜1 | 72 | 12 | Do not detect |
Operating condition shown in the table 3 is appointed as the burn operation condition, does not detect gas of nitrogen trifluoride under this condition in waste gas.Therefore, be introduced in whole Nitrogen trifluorides in the burning type elimination system and all react and change into hydrogen fluoride gas, but in waste gas, produced nitric oxide and nitrogen dioxide considerably beyond acceptable concentration.
Comparative Examples 2
According to embodiment 1 in the experiment of burning-eliminate of same mode, just the fuel methane flow velocity is brought up to 30L/ minute, chamber temperature is brought up to more than 350 ℃.Burning type eliminates system's operating condition and fluorine introducing condition all is shown in Table 5, and the composition analysis of burnt gas the results are shown in the table 6.
Table 5
| The fuel methane flow velocity | The carrying air velocity | The cooling air emission flow | The fluorine flow velocity | Dilution nitrogen flow velocity | Chamber temperature |
| (L/ minute) | (L/ minute) | (m 3/ minute) | (L/ minute) | (L/ minute) | (℃) |
| 30 | 341 | 30 | 13.5 | 240 | 360-370 |
Table 6
| The hydrogen fluoride gas concentration of calculating | The hydrogen fluoride gas concentration of measuring | The fluorine concentration of measuring | The nitric oxide concentration of measuring | The content of nitrogen dioxide of measuring | Other combustion reaction products |
| (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | |
| 900 | 850 | ＜10 | 0.5 | 1.0 | Do not detect |
Can find out from table 6, be introduced in the part of the fluorine gas in this burning type elimination system because react with the surface of combustion chamber member and its peripheral region and be consumed, but do not discharge as hydrogen fluoride.Its part has confirmed to form the metal fluoride of fine powder form.The result of waste-gas analysis has also confirmed the generation of nitric oxide and nitrogen dioxide.
Comparative Examples 3
Burning-elimination experiment is carried out according to method similarly to Example 1, and just stainless steel (SUS304 material) itself is used for the combustion chamber, does not have coating (fluoride Passivation Treatment).Burning type eliminates system's operating condition and fluorine introducing condition all is shown in Table 7, and the composition analysis of burnt gas the results are shown in the table 8.
Table 7
| The fuel methane flow velocity | The carrying air velocity | The cooling air emission flow | The fluorine flow velocity | Dilution nitrogen flow velocity | Chamber temperature |
| (L/ minute) | (L/ minute) | (m 3/ minute) | (L/ minute) | (L/ minute) | (℃) |
| 25 | 308 | 30 | 13.5 | 240 | 310-320 |
Table 8
| The hydrogen fluoride gas concentration of calculating | The hydrogen fluoride gas concentration of measuring | The fluorine concentration of measuring | The nitric oxide concentration of measuring | The content of nitrogen dioxide of measuring | Other combustion reaction products |
| (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | |
| 900 | 700 | ＜10 | ＜0.1 | ＜0.1 | Chromium compound |
Can find out that from table 8 the central larger proportion of fluorine that is introduced in this burning type elimination system does not turn out to be hydrogen fluoride, and does not produce gas component such as charomic fluoride.
Comparative Examples 4
According to the experiment of burning-eliminate of the same mode of this embodiment, just this combustion chamber coating is independent nickel coating layer, does not carry out fluorine and handles.Burning type eliminates system's operating condition and fluorine introducing condition all is shown in Table 9, and the composition analysis of burnt gas the results are shown in the table 10.
Table 9
| The fuel methane flow velocity | The carrying air velocity | The cooling air emission flow | The fluorine flow velocity | Dilution nitrogen flow velocity | Chamber temperature |
| (L/ minute) | (L/ minute) | (m 3/ minute) | (L/ minute) | (L/ minute) | (℃) |
| 25 | 299 | 30 | 13.5 | 240 | 310-320 |
Table 10
| The hydrogen fluoride gas concentration of calculating | The hydrogen fluoride gas concentration of measuring | The fluorine concentration of measuring | The nitric oxide concentration of measuring | The content of nitrogen dioxide of measuring | Other combustion reaction products |
| (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | |
| 900 | 820 | ＜10 | ＜0.1 | ＜0.1 | Do not detect |
From table 10, can find out, be introduced in fluorine gas in the burning type elimination system by with burner material surface reaction and slightly consumed.
Comparative Examples 5
According to the experiment of burning-eliminate of mode similarly to Example 1, just Nitrogen trifluoride is as introducing gas, and the flow velocity of Nitrogen trifluoride is 9.0L/ minute.Simultaneously, the surface treatment of combustion chamber is independent stainless steel (SUS304).Burning type eliminates system's operating condition and Nitrogen trifluoride introducing condition all is shown in Table 11, and the composition analysis of burnt gas the results are shown in the table 12.
Table 11
| The fuel methane flow velocity | The carrying air velocity | The cooling air emission flow | The Nitrogen trifluoride flow velocity | Dilution nitrogen flow velocity | Chamber temperature |
| (L/ minute) | (L/ minute) | (m 3/ minute) | (L/ minute) | (L/ minute) | (℃) |
| 30 | 305 | 30 | 9.0 | 240 | 350-360 |
Table 12
| The hydrogen fluoride gas concentration of calculating | The hydrogen fluoride gas concentration of measuring | The Nitrogen trifluoride concentration of measuring | The nitric oxide concentration of measuring | The content of nitrogen dioxide of measuring | Other combustion reaction products |
| (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | (volume ppm) | |
| 900 | 860 | ＜1 | 70 | 11 | Do not detect |
From table 12, can find out, be introduced in Nitrogen trifluoride in the burning type elimination system and reacted and change into hydrogen fluoride gas, but its part produces nitric oxide and nitrogen dioxide considerably beyond acceptable concentration because with the device materials reaction and disappear.
After the operation of having finished burning and having eliminated, analyze the metal surface in the combustion chamber of embodiment 1 and Comparative Examples 1,2,3,4 and 5.This measurement is to carry out with energy dispersive X ray spectroscope.
The metal (quality %) that table 13 detects
| Ni | Fe | Cr | Other | |
| Embodiment 1 | 100 | 0 | 0 | 0 |
| Comparative Examples 1 | 100 | 0 | 0 | 0 |
| Comparative Examples 2 | 100 | 0 | 0 | 0 |
| Comparative Examples 3 | 7.7 | 75.8 | 16.5 | 0 |
| Comparative Examples 4 | 100 | 0 | 0 | 0 |
| Comparative Examples 5 | 7.5 | 73.5 | 19 | 0 |
| Reference material SUS316L | 12 | 69.5 | 16 | Mo 2.5 |
| Reference material SUS304 | 8 | 74 | 18 | 0 |
Carry out the not significantly infringement of surface-treated combustion chamber with nickel, shown high corrosion resistance for fluorine gas and Nitrogen trifluoride.
After the burning of embodiment 1 and Comparative Examples 1,2,3,4 and 5-elimination experiment, the inner surface of precombustion chamber is also carried out the metal surface analyze.This measurement is to carry out with energy dispersive X ray spectroscope.
The metal (quality %) that table 14 detects
| Ni | Fe | Cr | Other | |
| Embodiment 1 | 100 | 0 | 0 | 0 |
| Comparative Examples 1 | 100 | 0 | 0 | 0 |
| Comparative Examples 2 | 100 | 0 | 0 | 0 |
| Comparative Examples 3 | 7.9 | 88.1 | 7.9 | 0 |
| Comparative Examples 4 | 100 | 0 | 0 | 0 |
| Comparative Examples 5 | 9.6 | 75.8 | 14.7 | 0 |
| Reference material SUS316L | 12 | 69.5 | 16 | Mo 2.5 |
| Reference material SUS304 | 8 | 74 | 18 | 0 |
In Comparative Examples 3, confirmed from this material, to have lost considerable Cr.In Comparative Examples 5, this Cr concentration is lower slightly equally.Microscopic observation has shown that crackle and fluoride form peeling off of film, formation by the Cr fluoride and gasification and form reaction and stainless steel material Fe is changed into the trivalent form from divalence by the secondary fluoride.
After the stainless extent of damage of investigating combustion chamber and precombustion chamber, contrast fluorine gas and Nitrogen trifluoride, the variation of the Cr concentration in Comparative Examples 3 (the fluorine gas burning is more violent) is bigger, and outward appearance is also significantly impaired.
When the stainless steel damaged condition of combustion chamber and precombustion chamber compared, precombustion chamber all had the Cr change in concentration bigger than the combustion chamber, no matter for fluorine gas or Nitrogen trifluoride is not always the case, and outward appearance is also significantly impaired.This is owing to the leading position of fuel gas oxidation reaction of oxidisability flame in the combustion chamber and in the process of especially burning on the wall zone.
Industrial applicibility
As explained above, the processing method of the application of the invention, might finish the processing of fluorine gas or halogen fluoride gas, when they discharge with high concentration or high volume, or when they combine with other gas with different performance, thereby by adopting identical elimination system to realize processing simultaneously. Method of the present invention is preferred in the semiconductor fabrication process, and because its realize efficient and economic Processing for removing also with due regard to the protection of safety and environment, so for industry, have very high potentiality.
Claims (11)
1. a waste gas processing method is included in the waste gas that contains fluorine gas or halogen fluoride gas that burning is discharged in the combustion chamber from etching or cleaning step, has the fluoride passivating film of formation on this combustor surface.
2. according to the desired method of claim 1, wherein the fluoride passivating film is made up of nickel fluoride.
3. according to claim 1 or 2 desired methods, wherein the concentration of fluorine gas or halogen fluoride gas be not more than by volume 5%.
4. according to any one method among the claim 1-3, wherein the content in nitrogen oxides of exhaust gas is the 5ppm that is lower than by volume after the burning.
5. exhaust treatment system, it is equipped with waste gas intake, fuel intake, precombustion chamber, combustion chamber, air intake and exhaust duct, and has the fluoride passivating film that forms on this combustor surface at least.
6. according to the desired system of claim 5, wherein this combustion chamber is formed by the material that is selected from least a type in nickel, rich nickel alloy and the monel metal, and the fluoride passivating film is to form on the surface of this material.
7. according to desired system in the claim 5, wherein this combustion chamber is formed by the material that is selected from least a type in stainless steel and the steel material, wherein the surface of material has the film be made up of nickel, nickel alloy electricity coating, electric smelting coating layer or nickel alloy chemical plating coating or ceramic membrane of being made up of alumina or aluminium nitride and the fluoride passivating film that forms on this film surface.
8. semiconductor fabrication process comprises:
Etching or cleaning step wherein adopt fluorine gas or halogen fluoride gas as etching gas or purge gas; With
Removal process wherein makes the gas combustion that contains fluorine gas or halogen fluoride gas of discharging in the step in front,
This removal process is to carry out in the combustion chamber, has the fluoride passivating film of formation on described combustion chamber.
9. desired according to Claim 8 method, wherein the fluoride passivating film is made up of nickel fluoride.
10. method according to Claim 8, wherein this combustion chamber is formed by the material that is selected from least a type in nickel, rich nickel alloy and the monel metal, and the fluoride passivating film is to form on the surface of this material.
11. desired method according to Claim 8, wherein this combustion chamber is formed by the material that is selected from least a type in stainless steel and the steel material, wherein the surface of material has the film be made up of nickel, nickel alloy electricity coating, electric smelting coating layer or nickel alloy chemical plating coating or ceramic membrane of being made up of alumina or aluminium nitride and the fluoride passivating film that forms on this film surface.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002037344A JP4172938B2 (en) | 2002-02-14 | 2002-02-14 | Exhaust gas treatment method and treatment apparatus |
| JP37344/2002 | 2002-02-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1498328A CN1498328A (en) | 2004-05-19 |
| CN1259524C true CN1259524C (en) | 2006-06-14 |
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|---|---|---|---|
| CNB038001454A Expired - Fee Related CN1259524C (en) | 2002-02-14 | 2003-02-13 | Method and system for treating exhaust gas |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20050115674A1 (en) |
| JP (1) | JP4172938B2 (en) |
| KR (1) | KR100544760B1 (en) |
| CN (1) | CN1259524C (en) |
| AU (1) | AU2003211966A1 (en) |
| HK (1) | HK1066262A1 (en) |
| TW (1) | TW592797B (en) |
| WO (1) | WO2003069228A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4751091B2 (en) * | 2005-04-08 | 2011-08-17 | 関東電化工業株式会社 | Exhaust gas treatment method |
| GB0509944D0 (en) * | 2005-05-16 | 2005-06-22 | Boc Group Plc | Gas combustion apparatus |
| JP4912163B2 (en) * | 2007-01-12 | 2012-04-11 | ステラケミファ株式会社 | Carbon steel or special steel formed with a fluorinated passive film and method for forming the same |
| JP5659491B2 (en) * | 2009-01-30 | 2015-01-28 | セントラル硝子株式会社 | Semiconductor manufacturing equipment including fluorine gas generator |
| JP2010276307A (en) * | 2009-05-29 | 2010-12-09 | Japan Pionics Co Ltd | Thermal decomposition device |
| CN102163643B (en) * | 2010-10-09 | 2013-01-02 | 浙江哈氟龙新能源有限公司 | Waste gas treatment thermal cycle drying system |
| EP2893322B1 (en) * | 2012-08-20 | 2018-11-14 | SABIC Global Technologies B.V. | Real-time online determination of caustic in process scrubbers using near infrared spectroscopy and chemometrics |
| JP6257442B2 (en) * | 2014-05-15 | 2018-01-10 | 東京エレクトロン株式会社 | Exhaust gas explosion-proof method in vacuum processing equipment |
| FR3043080B1 (en) * | 2015-11-04 | 2021-01-08 | Haffner Energy | HYPERGAS SYNTHETIC GAS PRODUCTION PROCESS |
| CN106884134B (en) * | 2015-12-16 | 2020-07-03 | 中国科学院上海应用物理研究所 | Surface passivation treatment method of nickel-based alloy |
| GB2554406A (en) * | 2016-09-26 | 2018-04-04 | Edwards Korea Ltd | Plasma abatement |
| CN106524191A (en) * | 2016-10-31 | 2017-03-22 | 江苏优瑞德环境科技有限公司 | Fluorine-contained alkane waste gas incineration treatment process and device |
| EP4067300A4 (en) * | 2019-11-27 | 2024-01-03 | Resonac Corporation | Method for measuring fluorine gas concentration in halogen-fluoride-containing gas using mass spectrometer |
| KR20220005530A (en) * | 2019-11-27 | 2022-01-13 | 쇼와 덴코 가부시키가이샤 | Measurement method of fluorine gas concentration in halogen fluoride-containing gas by ultraviolet spectroscopy |
| CN112827341B (en) * | 2020-12-25 | 2022-05-17 | 北京京仪自动化装备技术股份有限公司 | Waste gas treatment system of semiconductor process and waste gas treatment method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4236464A (en) * | 1978-03-06 | 1980-12-02 | Aerojet-General Corporation | Incineration of noxious materials |
| JPS63166783A (en) * | 1986-12-27 | 1988-07-09 | 三石耐火煉瓦株式会社 | Refractory brick for trash incinerator |
| JPH01261208A (en) * | 1988-04-11 | 1989-10-18 | Mitsui Toatsu Chem Inc | Method for purifying nitrogen trifluoride gas |
| CA1318108C (en) * | 1988-04-11 | 1993-05-25 | Isao Harada | Process for purifying nitrogen trifluoride gas |
| US5009963A (en) * | 1988-07-20 | 1991-04-23 | Tadahiro Ohmi | Metal material with film passivated by fluorination and apparatus composed of the metal material |
| FR2667134B1 (en) * | 1990-09-24 | 1995-07-21 | Pavese Guy | METHOD FOR IMPROVING COMBUSTION FOR A BLOW AIR BURNER AND MEANS FOR CARRYING OUT IT. |
| US5510093A (en) * | 1994-07-25 | 1996-04-23 | Alzeta Corporation | Combustive destruction of halogenated compounds |
| JPH1179871A (en) * | 1997-08-27 | 1999-03-23 | Harima Ceramic Co Ltd | Lining structure of incinerator |
| US6146606A (en) * | 1999-02-09 | 2000-11-14 | Showa Denko Kabushiki Kaisha | Reactive agent and process for decomposing nitrogen fluoride |
| US6630421B1 (en) * | 1999-04-28 | 2003-10-07 | Showa Denko Kabushiki Kaisha | Reactive agent and process for decomposing fluorine compounds and use thereof |
| JP3460122B2 (en) * | 1999-07-14 | 2003-10-27 | 日本酸素株式会社 | Combustion type abatement system and burner for combustion abatement system |
| JP4127447B2 (en) * | 1999-08-26 | 2008-07-30 | 日新製鋼株式会社 | Incinerator body with excellent high temperature corrosion resistance and incinerator facilities |
| KR100729253B1 (en) * | 1999-11-02 | 2007-06-15 | 가부시키가이샤 에바라 세이사꾸쇼 | Combustor for exhaust gas treatment |
-
2002
- 2002-02-14 JP JP2002037344A patent/JP4172938B2/en not_active Expired - Fee Related
-
2003
- 2003-02-13 AU AU2003211966A patent/AU2003211966A1/en not_active Abandoned
- 2003-02-13 KR KR1020037013443A patent/KR100544760B1/en not_active IP Right Cessation
- 2003-02-13 WO PCT/JP2003/001507 patent/WO2003069228A1/en active Application Filing
- 2003-02-13 US US10/474,765 patent/US20050115674A1/en not_active Abandoned
- 2003-02-13 CN CNB038001454A patent/CN1259524C/en not_active Expired - Fee Related
- 2003-02-14 TW TW092103139A patent/TW592797B/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2003236337A (en) | 2003-08-26 |
| HK1066262A1 (en) | 2005-03-18 |
| US20050115674A1 (en) | 2005-06-02 |
| CN1498328A (en) | 2004-05-19 |
| AU2003211966A1 (en) | 2003-09-04 |
| WO2003069228A1 (en) | 2003-08-21 |
| JP4172938B2 (en) | 2008-10-29 |
| TW592797B (en) | 2004-06-21 |
| KR100544760B1 (en) | 2006-01-24 |
| KR20030085596A (en) | 2003-11-05 |
| TW200303236A (en) | 2003-09-01 |
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