TW592797B - Exhaust gas treatment process and treatment system - Google Patents
Exhaust gas treatment process and treatment system Download PDFInfo
- Publication number
- TW592797B TW592797B TW092103139A TW92103139A TW592797B TW 592797 B TW592797 B TW 592797B TW 092103139 A TW092103139 A TW 092103139A TW 92103139 A TW92103139 A TW 92103139A TW 592797 B TW592797 B TW 592797B
- Authority
- TW
- Taiwan
- Prior art keywords
- gas
- exhaust gas
- combustion chamber
- nickel
- combustion
- Prior art date
Links
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Treating Waste Gases (AREA)
- Incineration Of Waste (AREA)
- Drying Of Semiconductors (AREA)
Abstract
Description
592797 C1) 玖、發明說明 【發明所屬之技術領域】 本發明是關於廢氣的處理方法及處理裝置，特別是於 半導體製程中的蝕刻過程或淸淨過程所排放之含有含氟氣 fk或S氣化鹵氣體〆；廢氣的處理方法及裝置以及應用該方 法或裝置的半導體裝置之製造方法。 【先行技術】 製造半導體的各過程所排放之廢氣會有含有半導體材 料用氣體、蝕刻用氣體、淸淨用氣體等的氣體，且會有這 些氣體爲有害氣體的情況。另外也有含有對環境造成破壞 之氣體的情況，含有此種成分的廢氣無法直接排放到大氣 中 〇 因此’此類廢氣的處理方法，過去以來已知有下列幾 種方法： (1 ) 應用苛性鈉（氫氧化鈉）等的中和劑使其氧 化反應或中和反應之濕式除害方法。 (2 ) 觸媒層所引發的反應分解法。 (3 )吸附到氧化物等之乾式除害方法。 (4 ) 裝設電熱器之熱分解方法。 (5 ) 燃燒式除害方法。 ，然則廢氣處理方法則是利用上述各方法的特徵點加以活 用。 近年’半導體製程中所排放之廢氣中所含有的有害成 ί>4·κ (2) (2)592797 分已是多樣化；進而晶圓或液晶面板等顯著大型化，因而 製造裝置也大型化，製程所使用之氣體的量大幅增加。另 外，隨著單片處理裝置的普及，由於多室化、製造過程複 雜化’因而造成必須同時處理不同路徑所排放大量的廢氣 ’或用相同的處理裝置安全處理同一路徑上改變循環時間 所流通大量不同的廢氣之情形。因有此情形，所以將高溫 下燃燒可燃性氣體而含在廢氣中的有毒成分或對環境造成 影響的廢氣成分轉換成無害的物質，或是轉換成容易處理 的物質之除害方法’經檢討有燃燒方式或熱分解方的熱處 理式除害方法。 不過’特別是以燃燒除害方式的情況，由於用天然瓦 斯、LPG、甲烷等的燃料氣體與空氣或氧氣等的助燃氣體 一起在高溫下燃燒處理半導體製程中所排放的廢氣，因而 會有經由含在廢氣中的氮元素或空氣中的氮等而衍生N〇 x 的副生成物之問題。 含在燃燒後的廢氣中之Ν ο X的生成量，依據所使用的 裝置或燃燒條件’會有產生1〜3 〇 %的非常高濃度的情況， 爲了使其不超過TLV(NO爲25ppm，N02爲3ppm)而檢討 種種的方法。例如日本專利特開2 0 0 1 - 1 9 3 9 1 8號公報中載 示爲了降低Ν Ο X的生成量而針對燃燒室的形狀、噴嘴的形 狀等進行種種的檢討。不過當使蝕刻及淸淨過程中大量使 用之含有NF3氣體的廢氣燃燒時，因會有產生多量的n〇x 之情況所以期望加以改善。 此外，半導體製造過程中，更高性能的淸淨用氣體， -8 - (3) (3)592797 嘗試使用含氟氣體或含氟化鹵氣體或這些的混合氣體進行 淸淨。例如，在 J. APPL. Phys. p 29 3 9，56(10)，No.15, 1 9 84中，已有含氟氣體及含氟化鹵氣體的淸淨性能比用 NF3氣體的淸淨性能更優良之硏究報告。 不過，含氟氣體或含氟化鹵氣體爲活性非常強的氧化 劑，化學反應性較強，會有在常溫下與氧化性物質起化學 反應而著火的情況；另外對裝置材料具較大的腐蝕性。因 此，裝置材料必須從特定的高耐蝕性金屬當中選用，即使 設足爲禁油禁水或設定日局耐触性樹脂而大多用於半導體 製造裝置之四氟化乙烯樹脂也會有依使用條件而不適用的 情況。 另外’含氟氣體或三氟化氯氣體等含氟化鹵氣體的除 害裝置，採用以苛性納或苛性鉀等鹼性水溶液之淸淨器來 中和吸收之濕式吸收裝置或是以活性氧化鋁或鹼石灰等的 固體吸附劑來吸附除去之乾式除害裝置。不過其課題爲用 任何一種裝置都無法處理含有高濃度的含氟氣體或含氟化 鹵氣體的廢氣。而且含氟氣體或含氟化鹵氣體的使用量增 大，當以鹼式淸淨器的濕式除害裝置時，則會有吸收塔大 型化、吸收液的廢液處理過度煩雜、運轉成本上升等的問 題。另外，乾式分解除害裝置或吸附除去除害裝置，也會 發生對於大流量的除害裝置化會有困難，又固體分解劑或 吸附劑的更換頻率增加而增大運轉經費，且維修操作的增 加而容易引起管理安全上困擾之問題。 (4) (4)592797 【發明內容】 〔發明所欲解決之課題〕 本發明的課題爲提供在於上述狀況下能夠處理從含有 高濃度且大量的含氟氣體或含氟化鹵氣體的半導體製程中 所排放的廢氣，且能安全又省能量而更有效率進行除害處 理之除害方法及除害裝置。 如同前述，在於半導體製程中使用含氟氣體或含氟化 鹵氣體時，用專用的除害裝置單獨進行廢氣處理，不過用 本發明之方法，半導體裝置的大型化、多次化、複雜都能 解決，另外除害裝置的設置空間也能縮小，而能解決上述 的課題。 〔用以解決課題之手段〕 本發明者爲了解決上述的課題而經詳加檢討的結果： 發現經由將蝕刻過程或淸淨過程所排放之含有含氟氣體或 含氟化鹵氣體的廢氣，導入到備有表面形成有氟化鈍態膜 的燃燒室之燃燒裝置中，採行使前述廢氣燃燒的處理方法 就能解決前述的課題，而硏發完成本發明。 即是本發明提供包括使蝕刻過程或淸淨過程所排放之 含有含氟氣體或含氟化鹵氣體的廢氣在於表面形成有氟化 鈍態膜的燃燒室內燃燒之廢氣的處理方法。 前述的氟化鈍態膜由氟化鎳所形成較爲理想。 含氟氣體或含氟化鹵氣體的濃度爲5 vol%以下較佳。 含在燃燒後的廢氣中之氮氧化物的含量未滿5volppm -10- (5) (5)592797 較佳。 本發明提供備有廢氣導入口、燃料導入□、燃燒前室 、空氣導入口以及排氣管，至少在燃燒室表面形成有氟化 鈍態膜之廢氣的處理裝置。 燃燒室由從含有局鎳合金及筒強度耐蝕銅合金的群組 中選出的至少1種材料所形成，在該材料的表面形成有氟 化鈍態膜較爲理想。 燃燒室由從不銹鋼及鋼鐵材的群組中選出的至少1種 材料所形成，在該材料的表面具有由鎳、電鍍鎳合金、電 f尋鍍金、無電解電鍍鎳合金所形成的薄膜或是由氧化鋁或 炎^化iS所形成的陶瓷溥膜，在該薄膜的表面形成有化鈍 態膜較佳。 另外’本發明針對包括有使用含氟氣體或含氟化鹵氣 體作爲蝕刻用氣體或淸淨用氣體之蝕刻過程或淸淨過程， 及使上述製程中所排放之含有含氟氣體或含氟化鹵氣體的 氣體燃燒之除害過程的半導體裝置之製造方法，提供該除 害過程在表面形成有氟化鈍態膜之燃燒室內進行的半導體 裝置之製造方法。 前述気化鈍態膜由氟化鎳所形成較佳。 【實施方式】 以下，詳細說明本發明。 本發明的廢氣處理方法是蝕刻過程或淸淨過程所排放 Z含有含E氣體或含氟化鹵氣體的廢氣，在於表面形成有 -11 - (6) (6)592797 氟化鈍態膜的燃燒室內燃燒。即是本發明包括含有例如當 作成膜氣體使用之SiH4等的氣體或其他氣體之半導體製程 中所排出的廢氣與含氟氣體或含氟化鹵氣體一起以一定的 溫度進行無害化處理。 本發明的處理方法，比不含含氟氣體或含氟化鹵氣體 的一般燃燒條件更削減燃料的供應量，在於使燃燒溫度降 低的條件下能充分進行無害化處理，即是能處理易於無害 化的化合物，以此條件下運轉，能顯著削減除害裝置所排 放的分解副產物之二氧化碳及NOx的量。 本發明則是用燃燒方式的除害裝置，同時將製造半導 體的過程中常用的 SiH4 、SiH2Cl2 、NH3、PH3、WF6、 Si ( 〇C2H5 ) 4、NF3、H2、B2H6、CH4、C2H2等的成膜用 氣體’淸淨用氣體或其他的半導體製造過程所排放的氣體 成分與含氟氣體和含氟化鹵氣體進行除害處理。此情況， 含在廢氣中的被處理成分只有含氟氣體或含氟化鹵氣體亦 可。含在廢氣中之含氟氣體或含氟化鹵氣體的濃度爲 5vol%以下較爲理想。 當運轉本發明的燃燒式除害裝置之際，與所導入的廢 氣中未含有含氟氣體或含氟化鹵氣體的燃燒條件（例如爲 了分解三氟化氮氣體所必要的燃燒條件）作比較，燃料的 供應量削減1 〇〜3 0%，即使在於燃燒溫度爲5 0 °C以上的運 轉條件’仍能使有毒氣體成分無害化或是轉換成容易分解 除去的物質。因此若是採用本發明的處理方法，則可以與 所使用燃料氣體的削減量成比例削減除害裝置所排放的分592797 C1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a method and a device for treating exhaust gas, especially a fluorine-containing gas fk or S gas emitted during an etching process or a cleaning process in a semiconductor process. Halogen gas radon; method and device for processing exhaust gas, and method for manufacturing semiconductor device using the method or device. [Preceding technology] Exhaust gas emitted from various semiconductor manufacturing processes may contain gases for semiconductor materials, etching gases, cleaning gases, etc., and these gases may be harmful gases. In addition, there are also cases that contain gases that cause damage to the environment. Exhaust gas containing such components cannot be directly discharged into the atmosphere. Therefore, the following methods have been known for the treatment of such exhaust gases: (1) Application of caustic soda (Sodium hydroxide) A wet detoxification method using a neutralizing agent such as an oxidation reaction or a neutralization reaction. (2) The reaction decomposition method initiated by the catalyst layer. (3) Dry-type detoxification method adsorbed to oxides and the like. (4) Thermal decomposition method of electric heater. (5) Burning method of harm elimination. However, the exhaust gas treatment method is utilized by utilizing the characteristic points of the above methods. In recent years, the harmful components contained in the exhaust gas emitted from semiconductor manufacturing processes have been diversified; > 4 · κ (2) (2) 592,797 points have been diversified; furthermore, wafers, liquid crystal panels, and the like have grown significantly in size, and thus manufacturing equipment has also been enlarged. The amount of gas used in the process has increased significantly. In addition, with the popularization of single-chip processing equipment, due to the multi-chamber and complicated manufacturing process, it is necessary to simultaneously process a large amount of exhaust gas emitted from different paths, or to use the same processing device to safely process the circulation time and change the circulation time on the same path A large number of different exhaust gas situations. Because of this situation, the toxic components contained in the exhaust gas that burn flammable gas at high temperature or the components of the exhaust gas that have an impact on the environment are converted into harmless substances, or the methods for eliminating harmful substances that are converted into easily handled substances are reviewed. There are combustion methods or thermal decomposition methods for heat treatment. However, 'especially in the case of combustion detoxification method, since natural gas, LPG, methane, and other fuel gases are used together with air or oxygen-supporting combustion gases to combust the exhaust gas emitted from the semiconductor process at a high temperature, there will be The problem of the by-products of Nox derived from the nitrogen contained in the exhaust gas or nitrogen in the air. The amount of N ο X contained in the exhaust gas after combustion may produce a very high concentration of 1 to 30% depending on the device or combustion conditions used. In order to prevent it from exceeding TLV (NO is 25 ppm, N02 is 3ppm) and review various methods. For example, Japanese Patent Laid-Open Nos. 2000-1 1 9 3 9 1 8 describes various reviews of the shape of the combustion chamber, the shape of the nozzle, and the like in order to reduce the amount of NOx produced. However, when a large amount of exhaust gas containing NF3 gas used in the etching and cleaning processes is burned, a large amount of n0x may be generated, so improvement is desired. In addition, in the semiconductor manufacturing process, higher performance cleaning gas, -8-(3) (3) 592797, try to use fluorine-containing gas or halogen-fluoride-containing gas or a mixture of these gases to perform cleaning. For example, in J. APPL. Phys. P 29 3 9, 56 (10), No. 15, 1 9 84, the performance of the plutonium of fluorine-containing gas and halogen-fluoride gas is better than that of NF3 gas. Research report with better performance. However, fluorine-containing gas or halogen-fluoride-containing gas is a very active oxidant and has a strong chemical reactivity, which may cause a chemical reaction with an oxidizing substance at room temperature to catch fire; in addition, it has a large corrosion of the device material Sex. Therefore, device materials must be selected from specific high-corrosion-resistant metals, and even if it is set to be oil- and water-resistant or daily-resistant resins, most of the tetrafluoroethylene resins used in semiconductor manufacturing devices will be used according to the conditions of use. Not applicable. In addition, 'Fluoride-containing gas or chlorine trifluoride gas and other halogen-containing gas detoxification devices, using a caustic soda or caustic potassium alkaline aqueous solution to neutralize the absorption of wet absorption device or active A dry type detoxification device for adsorption and removal of solid adsorbent such as alumina or soda lime. However, the problem is that the exhaust gas containing a high concentration of a fluorine-containing gas or a halogen-containing gas cannot be processed by any of the devices. In addition, the use of fluorine-containing gas or halogen-containing halogen gas is increased. When the wet type detoxification device of an alkaline decontamination device is used, there will be an increase in the size of the absorption tower, excessive waste liquid treatment of the absorption liquid, and operating costs. Rising issues. In addition, dry-type separation detoxification devices or adsorption removal and removal devices can also cause difficulties in the use of large-flow detoxification devices, and increase the replacement frequency of solid decomposers or adsorbents, increasing operating expenses, and maintenance operations. Increase and easily cause problems in management security. (4) (4) 592797 [Summary of the Invention] [Problems to be Solved by the Invention] The object of the present invention is to provide a semiconductor process capable of processing a semiconductor gas containing a high concentration of a large amount of a fluorine-containing gas or a halogen-containing halogen gas under the above-mentioned conditions. Exhaust gas discharged from the environment, and a method and a device for removing harmful gas which are safe and energy-saving, and more efficiently perform harmful treatment. As mentioned above, when a fluorine-containing gas or a halogen-containing halogen gas is used in a semiconductor manufacturing process, the exhaust gas treatment is performed separately by a dedicated detoxification device. However, the method of the present invention can increase the size, multiple times, and complexity of a semiconductor device. In addition, the installation space of the harm removal device can be reduced, and the above-mentioned problem can be solved. [Means to solve the problem] As a result of a detailed review by the present inventor in order to solve the above-mentioned problems, it was found that the exhaust gas containing a fluorine-containing gas or a halogen-containing gas emitted through the etching process or the cleaning process was introduced into In a combustion device equipped with a combustion chamber having a fluorinated passive film formed on its surface, the aforementioned problems can be solved by using the above-mentioned treatment method of exhaust gas combustion, and the present invention has been completed. That is, the present invention provides a method for treating exhaust gas including a fluorine-containing gas or a halogen-containing halogen gas discharged in an etching process or a cleaning process in a combustion chamber in which a fluorinated passive film is formed on the surface. The aforementioned fluorinated passive film is preferably formed of nickel fluoride. The concentration of the fluorine-containing gas or halogen-containing gas is preferably 5 vol% or less. The content of nitrogen oxides in the exhaust gas after combustion is preferably less than 5 volppm -10- (5) (5) 592797. The present invention provides an exhaust gas treatment device provided with an exhaust gas inlet, a fuel inlet, a pre-combustion chamber, an air inlet, and an exhaust pipe, and at least a fluorinated passive film is formed on the surface of the combustion chamber. The combustion chamber is formed of at least one material selected from the group consisting of a local nickel alloy and a tube-strength corrosion-resistant copper alloy, and it is preferable to form a fluorinated passive film on the surface of the material. The combustion chamber is formed of at least one material selected from the group of stainless steel and steel. The surface of the material has a thin film formed of nickel, electroplated nickel alloy, electroplated gold, or electroless nickel electroplated alloy. It is preferred that a ceramic film made of alumina or sulfonium iS be formed with a passive film on the surface of the film. In addition, the present invention is directed to an etching process or a decontamination process including the use of a fluorine-containing gas or a halogen-containing gas as an etching gas or a cleaning gas, and the fluorine-containing gas or fluorinated gas discharged in the above process. A method for manufacturing a semiconductor device in the detoxification process of halogen gas gas combustion is provided, and a method for manufacturing a semiconductor device in the combustion chamber in which a fluorinated passivation film is formed on the surface is provided. It is preferable that the halogenated passive film is formed of nickel fluoride. [Embodiment] Hereinafter, the present invention will be described in detail. The exhaust gas treatment method of the present invention is an exhaust gas containing Z gas containing E gas or halogen fluoride gas, which is emitted during the etching process or cleaning process, and the combustion of a fluorinated passive film with -11-(6) (6) 592797 is formed on the surface. Burning indoors. That is, in the present invention, the exhaust gas discharged from a semiconductor process including a gas such as SiH4 used as a film-forming gas or other gas is detoxified at a constant temperature together with a fluorine-containing gas or a halogen-containing gas. The treatment method of the present invention reduces the supply of fuel more than ordinary combustion conditions that do not contain a fluorine-containing gas or a halogen-containing halogen gas, and can fully detoxify under the condition that the combustion temperature is reduced, that is, it can be treated easily and harmlessly. Chemical compounds that operate under these conditions can significantly reduce the amount of carbon dioxide and NOx in the decomposition byproducts emitted by the detoxification device. The invention uses a combustion-type detoxification device, and simultaneously forms SiH4, SiH2Cl2, NH3, PH3, WF6, Si (〇C2H5) 4, NF3, H2, B2H6, CH4, C2H2 and the like commonly used in the manufacturing of semiconductors. The gas for the membrane is used as a purifying gas or other components emitted from the semiconductor manufacturing process, and the fluorine-containing gas and the halogen-fluoride-containing gas are subjected to decontamination treatment. In this case, the component to be treated contained in the exhaust gas may be a fluorine-containing gas or a halogen-containing halogen gas. The concentration of the fluorine-containing gas or halogen-containing gas contained in the exhaust gas is preferably 5 vol% or less. When operating the combustion type detoxification device of the present invention, compare with the combustion conditions (for example, the combustion conditions necessary to decompose the nitrogen trifluoride gas) in the exhaust gas which does not contain a fluorine-containing gas or a halogen-containing gas. The supply of fuel is reduced by 10 to 30%. Even under operating conditions where the combustion temperature is above 50 ° C, toxic gas components can be rendered harmless or converted into substances that are easily decomposed and removed. Therefore, if the treatment method of the present invention is adopted, the amount of emissions from the detoxification device can be reduced in proportion to the reduction amount of the used fuel gas.
-12- (7) (7)592797 解副產物的二氮化碳。另外降低燃燒溫度也能顯著削減 ΝΟχ的生成量，而能將N0x的生成量設成未滿5 volppm 〇 另外，降低燃燒溫度後運轉對運轉管理層面’安全層 面都有很大助益已能明白’因燃燒廢氣的部位或其前室部 位之機器上的材料表面溫度降低’所以大幅減低對裝置材 料的腐蝕負擔。因此裝置維修的頻率減少’對裝置的使用 壽命則明顯具成本優勢。 另外，經燃燒處理過的廢氣’在於最後連接到燃燒式 除害塔的排氣管之鹼性淸淨器的濕式除害裝置中，吸收處 理氟化氫等的鹵化氫、NO X 、其他分解物質的四氟化矽 等。 本發明的廢氣處理裝置具備有廢氣導入口、燃料導入 口、燃燒前室、燃燒室、空氣導入口以及排氣管，至少在 燃燒室的表面形成有氟化鈍態膜。 第1圖表示能實施本發明的廢氣處理方法之處理裝置 的範例，也是將含有含氟氣體或含氟化鹵氣體之混合廢氣 通過火焰壁後導入到助燃氣體的渦流中，用燃燒分解處理 的方式之裝置的範例。 第1圖中裝置的材質，因使其流通含氟氣體或含氟化 鹵氣體’所以必須是高耐蝕性的材料。燃燒室8因燃燒熱 而變高濕所以由鎳，含有高鎳合金或高強度耐熱銅合金屬 所形成’在其表面形成有氟化鈍態膜較爲理想。另外，燃 燒室由一般的不銹鋼或一般的鋼鐵材所形成，在其表面具 -13 · (8) (8)592797 有由感、電鍍鎳合金、電纟#電鍍或無電解電鍍鎳合金所形 成的薄膜或是由經熔射法等而耐含氟氣體性優良又具有耐 熱性的氧化鋁或氮化鋁所形成之陶瓷薄膜，且在該薄膜的 表面形成有氟化鈍態膜較爲理想。電鍍鎳時爲耐熱性優良 之鎳硼元素類的無電解電鍍處理較佳。另外，燃燒前室7 也是同樣地在其表面形成有氟化鈍態膜較爲理想。 針對裝置零件預先用含氟氣體實施鈍態化處理較佳。 特別是燃燒廢氣之部位的周圍部分經由從燃燒部位的輻射 熱、傳導熱而曝露在相當的高溫下。因此，此部位由鎳、 含有高鎳合金、高強度耐熱銅合金等製成較爲理想。若爲 對一般的不銹鋼或鋼鐵材施予電鍍鎳、電鑄電鍍、無電解 電鍍鎳等的耐蝕處理亦可。另外，至於裝置構件也是同樣 地預先用含氟氣體實施鈍態化處理較佳。 用含氟氣體實施鈍態化處理之方法採用眾知的方法， 例如採用日本專利特開平1 1 -929 1 2號公報中所記載的方法 。即是例如將作爲裝置零件使用之鎳的表面一度強制氧化 ，之後使該氧化皮膜與含氟氣體起反應而形成氟化鈍態膜 。另外，例如使用不銹鋼表面形成有鎳的薄膜之裝置零件 時也是同樣地經由進行氧化及氟化的處理而在表面形成氟 化鈍化膜。 如前述，依據本發明，將蝕刻過程或淸淨過程所排放 之含有含氟氣體或含氟化鹵的廢氣，導入到具備有表面形 成有氟化鈍態膜的燃燒室之燃燒裝置中，經由使前述廢氣 燃燒就能有效率進行廢氣處理。-12- (7) (7) 592797 Decompose carbon dioxide as a by-product. In addition, lowering the combustion temperature can also significantly reduce the amount of NOx generated, and the amount of NOx generated can be set to less than 5 volppm. In addition, operation after reducing the combustion temperature can greatly help the operation management level. Because the surface temperature of the material on the machine where the exhaust gas is burned or its front chamber is lowered, the burden of corrosion on the device materials is greatly reduced. Therefore, reducing the frequency of device maintenance 'obviously has a cost advantage for the service life of the device. In addition, the combustion-treated exhaust gas is a wet-type detoxification device of an alkaline purifier that is finally connected to the exhaust pipe of the combustion-type detoxification tower, and absorbs and treats hydrogen halide, NOx, and other decomposed substances. Silicon tetrafluoride and so on. The exhaust gas treatment device of the present invention includes an exhaust gas introduction port, a fuel introduction port, a pre-combustion chamber, a combustion chamber, an air introduction port, and an exhaust pipe, and a fluorinated passive film is formed on at least the surface of the combustion chamber. FIG. 1 shows an example of a processing device capable of implementing the exhaust gas treatment method of the present invention. The mixed exhaust gas containing a fluorine-containing gas or a halogen-containing halogen gas is introduced into a vortex of a combustion-supporting gas after passing through a flame wall, and is processed by combustion decomposition. An example of a device of the way. The material of the device in Fig. 1 must be a material having a high corrosion resistance because a fluorine-containing gas or a halogen-containing halogen gas is allowed to flow therethrough. The combustion chamber 8 is made high in humidity due to the heat of combustion, and is preferably formed of nickel, a high-nickel alloy or a high-strength heat-resistant copper alloy metal, and a fluorinated passive film is formed on the surface. In addition, the combustion chamber is formed of general stainless steel or general steel materials, and its surface has -13 · (8) (8) 592797. It is formed by feel, electroplated nickel alloy, electroplated nickel alloy or electroless nickel electroplated alloy. Or a ceramic thin film made of alumina or aluminum nitride with excellent resistance to fluorine-containing gases and heat resistance by spraying method, etc., and a fluorinated passive film is preferably formed on the surface of the thin film . In the case of nickel plating, electroless plating treatment of nickel-boron elements with excellent heat resistance is preferred. It is also desirable that the pre-combustion chamber 7 has a fluorinated passive film formed on the surface. It is preferable to perform passivation treatment with a fluorine-containing gas on the device parts in advance. In particular, the surrounding area of the part where the exhaust gas is burned is exposed to a relatively high temperature via radiant heat and conducted heat from the burned part. Therefore, this portion is preferably made of nickel, a high-nickel-containing alloy, a high-strength heat-resistant copper alloy, or the like. It is also possible to apply a corrosion-resistant treatment such as electroplated nickel, electroforming electroplating, or electroless nickel plating to general stainless steel or steel materials. In addition, as for the device members, it is also preferable to perform passivation treatment with a fluorine-containing gas in advance. A known method is used for the passivation treatment using a fluorine-containing gas, for example, a method described in Japanese Patent Laid-Open No. 1 1-929 1. That is, for example, the surface of nickel used as a device part is forcibly oxidized once, and then the oxide film is reacted with a fluorine-containing gas to form a fluorinated passive film. In addition, for example, when using a device part in which a thin film of nickel is formed on a stainless steel surface, a fluorinated passivation film is formed on the surface by similarly performing an oxidation and fluorination treatment. As described above, according to the present invention, the exhaust gas containing fluorine-containing gas or halogen-containing fluoride emitted during the etching process or cleaning process is introduced into a combustion device having a combustion chamber having a fluorinated passive film formed on the surface, and Combustion of the exhaust gas can efficiently perform exhaust gas treatment.
-14 - (9) (9)592797 本發明也是包括有用含氟氣體或含氟化鹵氣體作爲蝕 刻用氣體或淸淨用氣體之蝕刻過程或淸淨過程，及使上述 過程中所排放的含有含氟氣體或含氟化鹵氣體的氣體燃燒 之除害過程的半導體裝置之製造方法，提供該除害過程在 於表面形成有氟化鈍態膜之燃燒室內進行的半導體裝置之 製造方法。 〔實施例〕 以下，用實施例及比較例進一步說明本發明，然則本 發明並不侷限於這些實施例。 (實施例1 ) 對燃燒式除害裝置中不銹鋼製的燃燒室及其周圍的零 件施予電鍍鎳及氟化鈍態化處理後，用含氟氣體進行燃燒 除害實驗。燃燒室除害裝置的運轉條件及氟導入條件記載 在表1中，燃燒除害後所排放之廢氣的組成分析結果記載 在表2中。燃燒室溫度是以安裝在燃燒室外壁的熱電偶加 以測定。含在燃燒後的廢氣中之一氧化氮及二氧化氮的濃 度是瓦斯偵測管加以測定，氟化氫氣體的濃度是以紅外分 光法加以測定。三氟化氮是用檢測器加以測定。另外，進 行碘化鉀水溶液的抽樣，以抽樣液的硫代硫酸鈉溶液的滴 定法測定含氟氣體旳濃度，再以抽樣液之誘發結合電漿發 光分析法測定金屬濃度。 (10)592797 〈表1 > 燃料甲 燃燒輔助 冷卻空氣 Μ流量 稀釋氮 燃燒室 烷流量 空氣流量 排氣風量 流量 溫度 (L / m i η ) (L / m i η) (m3/min) (L / m i η) (L/m i η) (°C ) 25 3 0 3 0 13.5 240 3 05〜3 1 5 〈表2> 氟化氫氣 氟化氫氣 氟測定 一氧化氮 二氧化氮 其他燃燒 體計算濃 體測定濃 濃度 測定濃度 測定濃度 反應衍生 度 度 物 (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 900 <10 <0.1 <0.1 未檢測出 從表2中能明白，燃燒後的廢氣中完全未含有一氧化 氮及二氧化氮，導入到燃燒式除害裝置中的氟全部都反應 而轉換成氟化氫氣體。另外，燃燒廢氣中沒有氟化氫氣體 、水蒸氣及二氧化碳以外的燃燒反應衍生物，經由紅外分 光法及抽樣液的誘發結合電漿發光分析法的測定加以確認 (比較例1 ) 導入氣體取代含氟氣體改而以三氟化氮，進行三戴化 氮的流量設爲9. OL/min之燃燒除害實驗。燃燒室除害裝置 的運轉條件及二氛化氮的導入條件記載在表3中，燃燒廢 -16 --14-(9) (9) 592797 The present invention also includes an etching process or a decontamination process using a fluorine-containing gas or a halogen-fluoride-containing gas as an etching gas or a cleaning gas, and the content of A manufacturing method of a semiconductor device for a detoxification process of a fluorine-containing gas or a halogen-containing halogen-containing gas is provided, and a method for manufacturing a semiconductor device in which the detoxification process is performed in a combustion chamber having a fluorinated passive film formed on a surface is provided. [Examples] Hereinafter, the present invention will be further described using examples and comparative examples. However, the present invention is not limited to these examples. (Example 1) After a stainless steel combustion chamber and surrounding parts in the combustion type detoxification device were subjected to nickel plating and fluorinated passivation treatment, a combustion detoxification experiment was performed using a fluorine-containing gas. Table 1 shows the operating conditions and fluorine introduction conditions of the combustion chamber detoxification device, and Table 2 shows the composition analysis results of the exhaust gas emitted after combustion and detoxification. The temperature of the combustion chamber was measured using a thermocouple mounted on the outside wall of the combustion chamber. The concentration of one of nitrogen oxides and nitrogen dioxide in the exhaust gas after combustion is measured by a gas detection tube, and the concentration of hydrogen fluoride gas is measured by infrared spectrometry. Nitrogen trifluoride is measured with a detector. In addition, the potassium iodide aqueous solution was sampled, and the concentration of fluorine-containing gas tritium was measured by titration of the sodium thiosulfate solution of the sampling solution, and then the metal concentration was measured by the induction of the sampling solution and the plasma light emission analysis method. (10) 592797 <Table 1> Fuel A combustion auxiliary cooling air M flow dilution nitrogen combustion chamber alkane flow air flow exhaust air flow temperature (L / mi η) (L / mi η) (m3 / min) (L / mi η) (L / mi η) (° C) 25 3 0 3 0 13.5 240 3 05 ~ 3 1 5 <Table 2 > Hydrogen fluoride Hydrogen fluoride Hydrogen fluoride Determination of nitric oxide Nitrogen dioxide Other combustors calculation Concentration measurement Concentration measurement Concentration response Derivative degree (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 900 < 10 < 0.1 < 0.1 As can be seen in Table 2, the exhaust gas after combustion does not contain nitrogen monoxide and nitrogen dioxide at all, and all the fluorine introduced into the combustion type detoxification device reacts and is converted into hydrogen fluoride gas. In addition, there are no combustion reaction derivatives other than hydrogen fluoride gas, water vapor, and carbon dioxide in the combustion exhaust gas, and it was confirmed by infrared spectrometry and induction of the sample liquid combined with plasma luminescence analysis (Comparative Example 1) The introduction gas replaced the fluorine-containing gas Instead, the nitrogen trifluoride was used to perform a combustion detoxification experiment with the flow rate of nitrogen nitrogen set to 9. OL / min. The operating conditions of the combustion chamber detoxification device and the introduction conditions of dinitrogenated nitrogen are shown in Table 3. Combustion waste -16-
.8 W (11)592797 氣的組成分析結果記載在表4中。 <表3> 燃料甲 燃燒輔助 冷卻空氣 三氟化氮 稀釋氮 燃燒室 烷流量 空氣流量 排氣風量 流量 流量 溫度 (L/ m i η ) (L/min) (m3/min) (L/min) fL/min) (°C ) 3 0 3 I 1 3 0 9.0 240 3 5 0〜360 〈表 4> Φ 氟化氫氣 氟化氫氣 三氟化氮 一氧化氮 二氧化氮 其他燃燒 體計算濃 體測定濃 測定濃度 測定濃度 測定濃度 反應衍生 度 度 物 (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 900 <1 72 12 未檢測出 表3中所記載的運轉條件爲廢氣中未被檢測出三氟化 氮氣體之燃燒運轉條件。因此，導入到燃燒室除害裝置中 之三氟化氮全部起反應而轉換成氟化氫氣體，不過在廢氣 中分別衍生出一氧化氮及二氧化氮，且大幅超出容許濃度 (比較例2 ) 與實施例1作比較，除了燃料甲烷流量增加爲3〇L/min ’燃燒溫度提高到3 5 0 °C以上之外，進行與實施例1相同 的燃燒除害實驗。燃燒式除害裝置的運轉條件及氟導入條 -17- (12)592797 件記載在表5中，燃燒廢氣的組成分析結果記載在表6中。 〈表 5> —________ 燃料甲 燃燒輔助 冷卻空氣 氯流量 稀釋氮 燃燒室 院流量 空氣流量 排氣風量 流量 溫度 (L/min) (L/min) (m3/min) (L/min) (L/min) (°C ) 3 0 34 1 30 13.5 240 3 60〜3 70 <表6 > 氟化氫氣 體計算濃 度 氟化氫氣 體測定濃 度 氟測定濃 度 一氧化氮 測定濃度 二氧化氮 測定濃度 其他燃燒反 應衍生物 (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 850 <10 0.5 1.0 未檢測出 由表6中能明白，導入到燃燒式除害裝置中之氟的一 部分成未被當作氟化氫排出，與燃燒室及其周圍的構件表 面起反應而被消耗掉。另外一部分形成爲金屬氟化物，經 微粉化被確認。廢氣分析的結果也確認出衍生一氧化氮及 二氧化氮。 (比較例3 ) 除了不施行燃燒室的塗敷（氟化鈍態化處理），使用 原來的不錄鋼（S U S 3 0 4材）之外，進行與實施例i相同的 燃燒除害實驗。燃燒式除害裝置的運轉條件及氟的導入條 -18- (13) 件記載在表7中，燃燒廢氣的組成分析結果記載在表8中。 〈表7> 燃料甲 燃燒輔助 冷卻空氣 氟流量 稀釋氮 燃燒室 院流量 空氣流量 排氣風量 流量 溫度 (L / m i η ) (L / m i η ) Γ m3/mi π) (L/min) (L/min) CC ) 25 3 08 3 0 13.5 240 3 10〜320 〈表8> 氟化氫氣 體計算濃 度 氟化氫氣 體測定濃 度 氟測定濃 度 一氧化氮 測定濃度 二氧化氮 測定濃度 其他燃燒反 應衍生物 (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 700 <10 <0.1 <0· 1 鉻化合物 592797 由表8中能明白，未被確認出導入到燃燒式除害裝置 中的氟相當程度成爲氟化氫，也沒有衍生出如同氟化鉻的 氣體成分。 (比較例4 ) 除了燃燒室的塗層只電鍍鎳而未施行含氟處理之外， 進行與實施例相同的燃燒除害處理。燃燒式除害裝置的運 轉條件及氟的導入條件記載在表9中，燃燒廢氣的組成分 析結果記載在表1 〇中。 (14)592797 〈表9> 燃料甲 燃燒輔助 冷卻空氣 氟流量 稀釋氮 燃燒室 院流量 空氣流量 排氣風量 流量 溫度 (L/min) (L/min) (m3/min) (L/min) (L/min) (°C ) 25 299 30 13.5 240 3 1 0〜3 20 < 表 1 Ο > 氟化氫氣 體計算濃 度 氟化氫氣 體測定濃 度 氟測定濃 度 一氧化氮 測定濃度 二氧化氮 測定濃度 其他燃燒反 應衍生物 (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 820 <10 <0· 1 <0.1 未檢測出The composition analysis results of .8 W (11) 592797 gas are shown in Table 4. < Table 3 > Fuel nail combustion auxiliary cooling air nitrogen trifluoride diluted nitrogen combustion chamber alkane flow air flow exhaust air flow flow temperature (L / min) (L / min) (m3 / min) (L / min) fL / min) (° C) 3 0 3 I 1 3 0 9.0 240 3 5 0 ~ 360 <Table 4> Φ Hydrogen fluoride, hydrogen fluoride, nitrogen trifluoride, nitric oxide, nitrogen dioxide Concentration measurement Concentration measurement Concentration reaction derivative degree (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 900 < 1 72 12 The operating conditions are the combustion operating conditions in which no nitrogen trifluoride gas is detected in the exhaust gas. Therefore, all the nitrogen trifluoride introduced into the combustion chamber detoxification device reacted to be converted into hydrogen fluoride gas, but nitrogen monoxide and nitrogen dioxide were respectively derived from the exhaust gas, and the allowable concentrations were significantly exceeded (Comparative Example 2) and In Example 1, for comparison, the same combustion detoxification experiment was performed as in Example 1 except that the fuel methane flow rate was increased to 30 L / min and the combustion temperature was increased to more than 350 ° C. The operating conditions of the combustion type detoxification device and the fluorine introduction bar are listed in Table 5 and (12) 592797, and the composition analysis results of the combustion exhaust gas are shown in Table 6. <Table 5> --________ Fuel Auxiliary Cooling Air Chlorine Flow Dilution Nitrogen Combustion Chamber Flow Air Flow Exhaust Air Flow Flow Temperature (L / min) (L / min) (m3 / min) (L / min) (L / min) (° C) 3 0 34 1 30 13.5 240 3 60 ~ 3 70 < Table 6 > Calculated concentration of hydrogen fluoride gas Measured concentration of hydrogen fluoride gas Fluorine measurement concentration Nitric oxide measurement concentration Nitrogen dioxide measurement concentration Other combustion reaction derivatives (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 850 < 10 0.5 1.0 Not detected It can be understood from Table 6 that it was introduced into a combustion type detoxification device Part of the fluorine is not discharged as hydrogen fluoride, and is consumed by reacting with the surface of the combustion chamber and the surrounding components. The other part was formed as a metal fluoride and was confirmed by micronization. The results of the exhaust gas analysis also confirmed that nitrogen monoxide and nitrogen dioxide were derived. (Comparative Example 3) A combustion detoxification experiment was performed in the same manner as in Example i, except that the coating of the combustion chamber (fluorinated passivation treatment) was not performed, and the original non-recording steel (SUS 304) was used. The operating conditions of the combustion type detoxification device and the introduction of fluorine (13) are listed in Table 7, and the results of the analysis of the composition of the combustion exhaust gas are shown in Table 8. <Table 7> Fuel Auxiliary Combustion Cooling Air Fluorine Flow Dilution Nitrogen Combustion Chamber Flow Air Flow Exhaust Air Flow Flow Temperature (L / mi η) Γ m3 / mi π) (L / min) (L / min) CC) 25 3 08 3 0 13.5 240 3 10 ~ 320 <Table 8> Calculated concentration of hydrogen fluoride gas Measured concentration of hydrogen fluoride gas Fluorine measured concentration Nitric oxide measured concentration Nitrogen dioxide measured concentration Other combustion reaction derivatives (vol-ppm ) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 700 < 10 < 0.1 < 0 · 1 Chromium compound 592797 As can be understood from Table 8, it was not confirmed that The fluorine in the combustion type detoxification device becomes a considerable amount of hydrogen fluoride, and no gas component like chromium fluoride is derived. (Comparative Example 4) Except that the coating of the combustion chamber was electroplated with only nickel and no fluorine-containing treatment was performed, the same combustion removal treatment was performed as in the example. The operating conditions of the combustion type detoxification device and the introduction conditions of fluorine are shown in Table 9, and the results of the composition analysis of the combustion exhaust gas are shown in Table 10. (14) 592797 <Table 9> Fuel A combustion auxiliary cooling air fluorine flow dilution nitrogen combustion chamber courtyard flow air flow exhaust air flow temperature (L / min) (L / min) (m3 / min) (L / min) ( L / min) (° C) 25 299 30 13.5 240 3 1 0 ~ 3 20 < Table 1 〇 > Calculated concentration of hydrogen fluoride gas Measured concentration of hydrogen fluoride gas Fluorine determined concentration Nitric oxide measured concentration Nitrogen dioxide measured concentration Other combustion reactions Derivatives (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 820 < 10 < 0 · 1 < 0.1 Not detected
由表1 〇中能明白，導入到燃燒式除害裝置中的含氟氣 體些微與燃燒裝置材料表面起反應而被消耗掉。 (比較例5 ) 除了將導入氣體設爲三氧化氮，三氟化氮的流量設爲 9. OL/m in之外’進行與實施例1相同的燃燒除害實驗。只 不過燃燒室的表面未作任何處理，使用原狀的不銹鋼（ S US 3 (Μ )。燃燒式除害裝置的運轉條件及三氟化氮的導 入條件記載在表1 1中’燃燒廢氣的組成分析結果記載在表 1 2中。 -20- (15) 〈表Η > 燃料甲 燃燒輔助 冷卻空氣 三氟化氮 稀釋氮 燃燒室 院流量 空氣流量 排氣風量 流量 流量 溫度 (L / m i η ) (L/min) (m3/mi η) (L/min) (L/min) (°C ) 30 305 3 0 9.0 240 350〜360 〈表 12〉 氟化氫氣 體計算濃 度 氟化氫氣 體測定濃 度 三氟化氮 測定濃度 一氧化氮 測定濃度 二氧化氮 測定濃度 其他燃燒反 應衍生物 (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 860 <1 70 11 未檢測出 592797 由表1 2中能明白，導入到燃燒式除害裝置中之三氟化 氮起反應而轉換成氟化氫氣體，不過一部分與裝置材料起 反應而消失掉，其他一氧化氮及二氧化氮分別都大幅超過 容許濃度。 進而，燃燒除害運轉結束後，針對實施例1及比較例1 、比較例2 、比較例3 、比較例4 、比較例5中之燃燒室 的內面進行金屬表面分析。測定則是以能量分散型X線分 析裝置來進行。 -21 - (16)592797 < 表 1 3 > 被檢測出金屬（質量％ )As can be understood from Table 10, the fluorine-containing gas introduced into the combustion type detoxification device reacts slightly with the surface of the material of the combustion device and is consumed. (Comparative Example 5) The same experiment as in Example 1 was performed except that the introduction gas was nitrogen trioxide and the flow rate of nitrogen trifluoride was 9. OL / min. Only the surface of the combustion chamber is not treated, and the original stainless steel (S US 3 (M)) is used. The operating conditions of the combustion type detoxification device and the introduction conditions of nitrogen trifluoride are described in Table 11 'Composition of the combustion exhaust gas The analysis results are listed in Table 12. -20- (15) <Table Η > Fuel A combustion auxiliary cooling air nitrogen trifluoride diluted nitrogen combustion chamber courtyard flow air flow exhaust air flow flow temperature (L / mi η) (L / min) (m3 / mi η) (L / min) (L / min) (° C) 30 305 3 0 9.0 240 350 ~ 360 <Table 12> Calculated concentration of hydrogen fluoride gas Measured concentration of hydrogen fluoride gas Nitrogen trifluoride Measuring concentration Nitric oxide Measuring concentration Nitrogen dioxide Measuring concentration Other combustion reaction derivatives (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) (vol-ppm) 900 860 < 1 70 11 Not It was found that 592797 was shown in Table 12. The nitrogen trifluoride introduced into the combustion type detoxification device reacted to convert to hydrogen fluoride gas, but part of it reacted with the device material and disappeared. Other nitric oxide and dioxide Each of the nitrogens significantly exceeds the allowable concentration. After the detoxification operation is completed, the metal surface analysis is performed on the inner surfaces of the combustion chambers in Example 1 and Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, and Comparative Example 5. The measurement is based on the energy dispersive X -21-(16) 592797 < Table 1 3 > Detected metal (% by mass)
Ni Fe Cr 其他 實施例1 1 00 0 0 0 比較例1 100 0 0 0 比較例2 1 0 0 0 0 0 比較例3 7.7 75.8 16.5 0 比較例4 1 00 0 0 0 比較例5 7.5 73.5 19 0 參考 SUS316L 12 69.5 16 Mo2.5 參考S U S 3 0 4 8 74 18 0Ni Fe Cr Other Examples 1 1 0 0 0 0 0 Comparative Example 1 100 0 0 0 Comparative Example 2 1 0 0 0 0 0 Comparative Example 3 7.7 75.8 16.5 0 Comparative Example 4 1 0 0 0 0 0 Comparative Example 5 7.5 73.5 19 0 Reference SUS316L 12 69.5 16 Mo2.5 Reference SUS 3 0 4 8 74 18 0
以鎳作表面處理之燃燒室顯示出沒有大損傷而對含氟 氣體，三氟化氮具有較大的耐蝕性。 其次，針對實施例1及比較例1 、比較例2 、比較例 3 、比較例4 、比較例5中進行燃燒除害後之燃燒前室的 內面，進行金屬表面分析。測定則是以能量分散型X線分 析裝置來進行。 -22- (17)592797 〈表 14> 被檢測出金屬(質量％ )The combustion chamber with nickel as the surface treatment showed no large damage and had a large corrosion resistance to fluorine-containing gas and nitrogen trifluoride. Next, the inner surface of the pre-combustion chamber after combustion detoxification in Example 1 and Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, and Comparative Example 5 was analyzed for metal surface. The measurement was performed using an energy dispersive X-ray analysis apparatus. -22- (17) 592797 <Table 14> Metals detected (% by mass)
Ni Fe Cr 其他 實施例1 1 00 0 0 0 比較例1 1 00 0 0 0 比較例2 100 0 0 0 比較例3 7.9 88.1 7.9 0 比較例4 100 0 0 0 比較例5 9.6 75.8 14.7 0 參考 SUS316L 12 69.5 16 Mo2.5 參考SUS304 8 74 18 0 比較例3中明顯確認出從素材中正在消失C r。另外在 於比較例5的情況也是C r濃度稍微減少。用顯微鏡觀察 則也發現有撕裂，引起形成Cr*的氟化物且氣化的現象或不 銹鋼材的Fe從二價轉爲三價之高次氟化物形成反應等，而 造成氟化形成膜脫落。 燃燒室及燃燒前室之不銹鋼的損傷，與燃燒含氟氣體 及三氟化氮作比較，燃燒含氟氣體之比較例中的Cr濃度 都有較大變化，外觀上也顯著劣化。 另外，與燃燒室及燃燒前室之不銹鋼的損傷狀態燃燒 室作比較，燃燒前室比燃燒室在於含氟氣體、三氟化氮的 任一情況都是燃燒前室的Cr濃度起較大的變化，外觀上 顯著劣化。此情況被認爲是因燃燒室，特別是其壁的部位 -23- (18) (18)592797 ，當燃料氣體燃燒之際氧化火焰較具氧化反應優勢之故。 〔發明之效果〕 如以上所述，採用本發明的處理方法，而高濃度且大 量排放含氟氣體或含氟化鹵氣體時，可以同時用相同的除 害裝置來處理含有上述氣體且不同性質的氣體。本發明的 方法適於半導體的製造過程中使用，且是充分考慮到安全 性之有效率又具經濟性之除害處理方法，從維護地球環境 層面上，對產業具有高利用價値。 【圖式簡單說明】 第1圖是顯示能夠實施本發明的廢氣之處理方法的處理 裝置之一例的示意圖。 【符號說明】 1 處理廢氣 2 稀釋用氣體 3 助燃用氣體 4 燃燒用可燃性氣體 5 空氣 6 大氣中放出氣體 7 燃燒前室 8 燃燒室 9 燃燒氣體冷卻裝置 -24- (19)592797 10 鹼性淸淨器 11 排氣鼓風機Ni Fe Cr Other Examples 1 1 0 0 0 0 0 Comparative Example 1 1 0 0 0 0 0 Comparative Example 2 100 0 0 0 Comparative Example 3 7.9 88.1 7.9 0 Comparative Example 4 100 0 0 0 Comparative Example 5 9.6 75.8 14.7 0 Reference SUS316L 12 69.5 16 Mo2.5 Reference SUS304 8 74 18 0 In Comparative Example 3, it was confirmed that C r was disappearing from the material. In the case of Comparative Example 5, the C r concentration was slightly reduced. Observation with a microscope also revealed tearing, which caused the formation of Cr * fluoride and gasification, or the formation of a higher-order fluoride from a bivalent to a trivalent Fe in stainless steel, which caused the formation of a fluorinated film. Fall off. Compared with the combustion of fluorine-containing gas and nitrogen trifluoride, the damage of the stainless steel in the combustion chamber and the pre-combustion chamber has a large change in the Cr concentration in the comparative example of burning the fluorine-containing gas, and the appearance is also significantly deteriorated. In addition, compared with the damaged combustion chamber of the combustion chamber and the pre-combustion stainless steel, the pre-combustion chamber has a higher Cr concentration in the pre-combustion chamber than the combustion chamber in the case of fluorine-containing gas and nitrogen trifluoride. Changes, the appearance is significantly deteriorated. This situation is considered to be due to the combustion chamber, especially its wall part -23- (18) (18) 592797. When the fuel gas is burned, the oxidation flame has the advantage of oxidation reaction. [Effects of the Invention] As described above, when the treatment method of the present invention is adopted and a high concentration and large amount of fluorine-containing gas or halogen fluoride gas is discharged, the same detoxification device can be used to treat the above-mentioned gases with different properties simultaneously. gas. The method of the present invention is suitable for use in the manufacturing process of semiconductors, and is an efficient and economical decontamination treatment method that fully considers safety, and has a high utilization price for the industry in terms of maintaining the global environment. [Brief Description of the Drawings] Fig. 1 is a schematic diagram showing an example of a processing apparatus capable of implementing the method for treating exhaust gas of the present invention. [Symbol description] 1 Treatment of exhaust gas 2 Dilution gas 3 Combustion gas 4 Combustible gas 5 Air 6 Gas released from the atmosphere 7 Pre-combustion chamber 8 Combustion chamber 9 Combustion gas cooling device-24- (19) 592797 10 Alkaline Purifier 11 exhaust blower
-25* •Kf>4-25 * • Kf > 4
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002037344A JP4172938B2 (en) | 2002-02-14 | 2002-02-14 | Exhaust gas treatment method and treatment apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200303236A TW200303236A (en) | 2003-09-01 |
| TW592797B true TW592797B (en) | 2004-06-21 |
Family
ID=27678109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW092103139A TW592797B (en) | 2002-02-14 | 2003-02-14 | Exhaust gas treatment process and treatment system |
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 |
| KR101970807B1 (en) * | 2012-08-20 | 2019-04-19 | 사빅 글로벌 테크놀러지스 비.브이. | 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 Corp | Method for measuring fluorine gas concentration in halogen-fluoride-containing gas using mass spectrometer |
| CN113785190A (en) * | 2019-11-27 | 2021-12-10 | 昭和电工株式会社 | Method for measuring fluorine gas concentration in halogen-containing fluoride 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 |
Family Cites Families (13)
| 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 |
| DE68907366T2 (en) * | 1988-04-11 | 1993-12-02 | Mitsui Toatsu Chemicals | Process for refining nitrogen trifluoride gas. |
| JPH01261208A (en) * | 1988-04-11 | 1989-10-18 | Mitsui Toatsu Chem Inc | Method 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 CN CNB038001454A patent/CN1259524C/en not_active Expired - Fee Related
- 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
- 2003-02-14 TW TW092103139A patent/TW592797B/en not_active IP Right Cessation
-
2004
- 2004-11-18 HK HK04109106A patent/HK1066262A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| US20050115674A1 (en) | 2005-06-02 |
| CN1498328A (en) | 2004-05-19 |
| JP4172938B2 (en) | 2008-10-29 |
| CN1259524C (en) | 2006-06-14 |
| WO2003069228A1 (en) | 2003-08-21 |
| KR20030085596A (en) | 2003-11-05 |
| AU2003211966A1 (en) | 2003-09-04 |
| JP2003236337A (en) | 2003-08-26 |
| HK1066262A1 (en) | 2005-03-18 |
| KR100544760B1 (en) | 2006-01-24 |
| TW200303236A (en) | 2003-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW592797B (en) | Exhaust gas treatment process and treatment system | |
| JP7297834B2 (en) | Vapor Plasma Arc Hydrolysis of Ozone Depleting Substances | |
| KR100766749B1 (en) | An apparatus and method for treatment waste gas contains perfluoro compounds | |
| EP1340533A1 (en) | A method of treatment for decomposing fluorine compounds, and catalyst and apparatus therefor | |
| KR20110123375A (en) | High efficient plasma reactor for thermal destruction processes of high concentrated perfluorocompounds gases | |
| US7005117B2 (en) | Method for removing harmful components in an exhaust gas | |
| US6126906A (en) | Apparatus for removing harmful components in a semiconductor exhaust gas | |
| JP2002058961A (en) | Exhaust gas treating equipment | |
| JP2002058961A5 (en) | ||
| US9393519B2 (en) | Waste disposal | |
| TW539570B (en) | Method and apparatus for removing harmful perfluorocarbon gas or a perfluoro compound | |
| JP2007162959A (en) | Waste gas cleaning treatment device | |
| CN1227054C (en) | Evil-removing method of perfluocarbon or perfluoride and evil-removing device | |
| JP2010058009A (en) | Method of decomposing nitrogen trifluoride and device using this method | |
| JP3869184B2 (en) | Method for decomposing halides | |
| JP4400067B2 (en) | Halogen corrosion resistant member and perfluoro compound decomposition treatment equipment | |
| KR20040007676A (en) | Exhaust gas treating method and treating device | |
| US6635229B1 (en) | Method for low perfluorocarbon compound emission | |
| JP2007237150A (en) | Catalyst detoxifying treatment method of emission gas | |
| CN209782220U (en) | Low-concentration gas treatment device | |
| JP2006305410A (en) | Method for decomposing hardly decomposable chlorofluocarbon gas | |
| JP2005111433A (en) | Treating method for fluorine compound-containing exhaust gas and apparatus therefor | |
| TW557346B (en) | Method and device for disposing of exhaust gas | |
| TWI317387B (en) | A plasma method and apparatus to dispose of process waste gases and particles | |
| JP2005007341A (en) | Method and apparatus for treating halogenated organic compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |