583137 Α7 Β7 五、發明説明（ο 本發明係有關於氣相下使氟氣體飞F 2 )與氨氣體（ ΝΗ3)直接反應後製造三氟化氮（以下稱「NF3」。 )之方法及其用途者。 先行技術中，N F 3係如半導體裝置製造過程中乾蝕 刻用氣體等所使用者，其製造方法通常分爲化學法與電解 法。做爲化學法之例者如公知者有： (1 )於熔融酸性氟化銨中進行吹塑F 2氣體與 N Η 3氣體之方法（特公昭5 5 — 8 9 2 6號公報）， (2 )使固體狀金屬氟化物銨絡合體與F 2氣體相互 反應之方法（特公昭60 - 71503號公報）， (3 )使F2氣體與ΝΗ3氣體直接反應之方法（特 開平2 — 255513號公報），等。 另外，電解法之例如：以熔融酸性氟化銨做爲電解液 ， (4 )以石墨（graphite )做爲陽極之電解法， (5 )以鎳做爲陽極之電解方法 等爲公知者。 又，報告中Ruff等於氣相狀進行F 2與N H3之反應 後，收率爲5%以下者，而NF3藉由化學法進行合成（ Z.anorg.allg.Chem· 1 97,3 95 ( 1 93 1 ) )，Morrow 等亦同樣於氣 1 相下進行 N F 3 之合成（JLAmer.Chem.Soc.82.5301(1960)) 〇 惟，使用先行F 2氣體後，由反應基質之N Η 3進行 合成之直接氟化法由於使用極具反應性之F 2氣體，因此 _____________________________ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） _ 4 - I ^---------^-裝 j — (請先閱讀背面之注意事項再填寫本頁) 訂 .参 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 583137 A7 B7 五、發明説明（2) 有造成基質與F 2氣體產生爆炸。腐蝕之危險。更且，此 等反應其反應熱極大’藉由反應器內溫度之上昇出現 NF3之分解，副反應後，產生N2，HF，NH4F而出 現收率下降等問題。又，特開平2 - 2 5 5 5 1 3號公報 .所載方法係於維持反應器溫度於8 0〜2 5 0 °C下之熱媒 中，針對N F 3使用其3 — 2 0倍之F 2氣體進行製造 N F 3之方法者，F 2基準收率差，造成經濟面不佳之問 題點出現。 使用F 2氣體之直接氟化法係基質中1個氫取代1個 氟時約產生一 110k c a 1/mo 1之反應熱。因此， 反應F2與NH3後製造NF3時，氫與氟之取代約產生一 3 30k c a 1/mo 1之反應熱，此熱的產生易造成n 一 F結合的切斷，爆炸等。更有降低收率乏不.理想點，造 成製造上的問題點。 本發明係於此背景下完成者，本發明係以提供一種於 基質（NH3)與Fa氣體相互反應後製造NF3之直接氟 化法中，於工業上可製造一種即經濟且安全又有效率之 NF3製造方法爲課題者。 本發明者爲解決該課題’進行精密硏討後結果發現， 於F 2氣體與n Η 3氣體相互反應後製造n F 3之方法中，-稀釋氣體之存在下，8 0 °C以下進行反應後可製造收率佳 之NF3者，進行完成本發明。本發明爲以下（1 )〜（ 1 3)所示2NF3製造方法及其用途者。 (1 )使氟氣體與氨氣相互以氣相反應後製造三氟化 尺度適用中_家標準（CNS ) A4規格（210x297公董〉 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 -5- 583137 A7 ______B7 五、發明説明（3) 氮之方法中，於稀釋氣體之存在下，_8 0°C以下進行反應 者爲特徵之三氟化氮的製造方法。 (2 )反應溫度爲5 〇°C以下之該（1 )所載三氟化 氮製造方法。 (3 )氟氣與氨氣之供給濃度以莫耳比爲1 : 1〜1 :2之該（1)或（2)所載三氟化氮製造方法。 (4 )分割供給氟氣及/或氨氣之該（1 )或（2 ) 所載之三氟化氮製造方法。 (5 )氟氣供給濃度爲3莫耳％以下之該（1 )或（ 2 )所載之三氟化氮製造方法。 (6 )氨氣供給濃度爲6莫耳％以下之該（1 )或（ 2)所載之三氟化氮製造方法。 (7 )稀釋氣體爲至少1種選自氮，氦，氬，六氟乙 烷及辛氟丙烷所成群之該（1 )或（2 )所載三氟化氮製 造方法者。 (8 )循環使用稀釋氣體之該（1 )或（2 )所載之 三氟化氮製造方法。 (9 )含處理未反應氟氣之步驟，該步驟係以鹼水溶 液及/或氧化鋁進行處理未反應氟氣之該（1 )或（2 ) 所載之三氟化氮製造方法者。 … - (1 0 )於8 0 °C以下進行該處理步驟之該（9 )所 載之三氟化氮製造方法。 (11)藉由該（1)〜（10)中任一所載製造方 法取得含三氟化氮者爲特徵之三氟化氮製品。 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） TfiT" ' ---------狀衣 ---- (請先閱讀背面之注意事項再填寫本頁)583137 Α7 Β7 V. Description of the invention (ο The present invention relates to a method for producing nitrogen trifluoride (hereinafter referred to as "NF3") by directly reacting a fluorine gas to fly F 2 in the gas phase with an ammonia gas (NQ3) and its method. Uses. In the prior art, N F 3 is used by users such as dry etching gas in the manufacturing process of semiconductor devices, and its manufacturing methods are generally divided into chemical methods and electrolytic methods. As examples of the chemical method, as known, there are: (1) a method of blow molding F 2 gas and N Η 3 gas in molten acid ammonium fluoride (Japanese Patent Publication No. 5 5-8 9 2 6), ( 2) A method for reacting a solid metal fluoride ammonium complex with F 2 gas (Japanese Patent Publication No. 60-71503), (3) A method for directly reacting F 2 gas with NH 3 gas (Japanese Patent Application Laid-Open No. 2-255513) ),Wait. In addition, examples of the electrolytic method are known: electrolyzing method using molten acid ammonium fluoride as an electrolyte, (4) using graphite as an anode, and (5) electrolytic method using nickel as an anode. In addition, in the report, Ruff is equal to the gas phase reaction of F 2 and N H3, and the yield is less than 5%, and NF3 is synthesized by chemical method (Z.anorg.allg.Chem. 1 97,3 95 ( 1 93 1)), Morrow et al. Also carried out the synthesis of NF 3 in the gas 1 phase (JLAmer.Chem.Soc.82.5301 (1960)) 〇 However, after using the first F 2 gas, the reaction matrix N 由 3 The synthetic direct fluorination method uses the highly reactive F 2 gas, so _____________________________ This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) _ 4-I ^ ------ --- ^-装 j — (Please read the notes on the back before filling out this page) Order. Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 583137 A7 B7 V. Invention Explanation (2) There is an explosion caused by the matrix and F 2 gas. Risk of corrosion. In addition, the heat of reaction of these reactions is extremely large ', the decomposition of NF3 occurs by the temperature rise in the reactor, and after the side reactions, N2, HF, NH4F are generated, and the yield decreases. In addition, Japanese Patent Application Laid-Open No. 2-2 5 5 5 1 3. The method described is to maintain the reactor temperature at 80 ~ 2 50 ° C in a heat medium, and use 2-3 times as much as NF 3 For those who use F 2 gas to make NF 3, the benchmark F 2 yield is poor, which causes problems in terms of poor economy. A direct fluorination method using F 2 gas replaces one fluorine in one matrix with approximately one hydrogen at 110 k c a 1 / mo 1. Therefore, when NF3 is produced after reacting F2 and NH3, the substitution of hydrogen and fluorine generates a reaction heat of about 3 30k c a 1 / mo 1, and the generation of this heat is likely to cause the cut off of the n-F bond, explosion, and the like. It is even more difficult to reduce the yield. It is an ideal point and causes manufacturing problems. The present invention was completed in this context. The present invention is to provide a direct fluorination method for producing NF3 after the substrate (NH3) and Fa gas react with each other. In the industry, an economical, safe and efficient method can be manufactured. The NF3 manufacturing method is the subject. In order to solve this problem, the present inventors conducted a precise discussion and found that in the method for producing n F 3 after the F 2 gas and the n Η 3 gas react with each other, the reaction is performed at a temperature below 80 ° C in the presence of a diluent gas. Those who can produce NF3 with good yield can complete the present invention. The present invention is a 2NF3 production method and uses thereof as shown in the following (1) to (1 3). (1) Fluoride gas and ammonia gas are reacted with each other in the gas phase to produce trifluoride scale. Applicable in China_Home Standard (CNS) A4 specification (210x297)> (Please read the precautions on the back before filling this page). Installation · -5--5-83137 A7 ______B7 V. Description of the invention (3) In the method of nitrogen, a method for producing nitrogen trifluoride characterized by those who carry out the reaction below -8 ° C in the presence of a diluent gas. (2) Reaction temperature The manufacturing method of nitrogen trifluoride contained in (1) below 50 ° C. (3) The supply concentration of fluorine gas and ammonia gas is (1) or (1) or ( 2) The manufacturing method of nitrogen trifluoride contained. (4) The manufacturing method of nitrogen trifluoride contained in (1) or (2) dividedly supplying fluorine gas and / or ammonia gas. (5) The concentration of fluorine gas supply is The manufacturing method of nitrogen trifluoride contained in (1) or (2) below 3 mole%. (6) The ammonia contained in (1) or (2) contained in ammonia at a concentration of 6 mole% or less Method for producing nitrogen fluoride. (7) The diluent gas is at least one selected from the group consisting of nitrogen, helium, argon, hexafluoroethane and octafluoropropane, and the nitrogen trifluoride contained in (1) or (2). Methodist (8) A method for producing nitrogen trifluoride contained in (1) or (2) using a diluent gas. (9) Containing a step of treating unreacted fluorine gas, which is a step of treating unreacted fluorine with an aqueous alkali solution and / or alumina. Those who manufacture the nitrogen trifluoride contained in (1) or (2).…-(1 0) Manufacture the nitrogen trifluoride contained in (9) in this process step below 80 ° C (11) Nitrogen trifluoride products characterized by those containing nitrogen trifluoride are obtained by the manufacturing method described in any one of (1) to (10). The paper standard is applicable to Chinese National Standard (CNS) A4 Specifications (210X297mm) TfiT " '--------- Ziyi ---- (Please read the precautions on the back before filling this page)
、1T 經濟部智慧財產局員工消費合作社印製 583137 A7 ____B7 —___ 五、發明説明（4) (1 2 )含有該（1 1 )所載三氟化氮製品之蝕刻氣 體。 (請先閱讀背面之注意事項再填寫本頁) (1 3 )含有該（1 1 )所載三氟化氮製品之洗淨氣 體。 亦即，本發明係「於氣相下反應氟氣與氨氣後製造三 氟化氮之方法中，於稀釋_氣體之存在下，8 0 °C以下進行 反應者爲特徵之三氟化氮製造方法」，「含有藉由該製造 方法取得之三氟化氮爲特徵之三氟化氮製品」以及「含有 該二氟化氮製品之鈾刻氣體及洗淨氣體」者。 〔發明實施之形態〕 以下，針對本發明進行詳細說明。 本發明係於稀釋氣體之存在下，以氣相，_ 8 0 t以下 使F2氣體與氨氣進行直接（無觸媒）反應製造NF3之 方法者，克服先行直接氟化反應之問題及課題，可於工業 上製造一種即經濟，且，安全又有效率之N F 3者。 經濟部智慧財產局員工消費合作社印製 如上述，利用F 2氣體之直接氟化法係使基質中1個 氫取代1個氟時，產生約—llOkca 1/mo 1之極 大反應熱者。 使F 2氣體與N Η 3氣體相互反應後製造N F 3時，僅r 氫與氟之取代下即產生約- 3 3 0k c a 1/mo 1之反 應熱，多半造成局部溫度變高。溫度高時，呈目的反應（ 下記式1 )以外受副反應（下記式2 )之支配。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 583137 A7 __ B7 _ 五、發明説明（5) 4NH3+3F2-NF3+3NH4F (式 1) 2NH3+3F2— N2+6HF (式 2) 因此，務必採取控制副反應（式2 )，選擇目的反應 (式1 )者。針對此課題，本發明者重覆進行精密硏討後 ’結果發現’反應溫度與副反應之關係密切。當反應溫度 爲8 0 °C以上時，如：1 1 〇 °C時，則副反應（式2 )以 支配性進行之，生成物爲氮與氟化氫者，而，目的物之 N F 3幾乎未產生，當溫度以8 0 °C以下則呈選擇性進行 目的反應（式1 )者。亦即，本發明之反應溫度爲8 0 °C 以下者，較佳者更以5 0 °C以下爲更理想。又，更進行冷 卻後，將更呈選擇性進行目的之反應（式1 )，惟，當反 應溫度過低時，則反應速度將下降有可能造成凝縮稀釋氣 體。因此，下限溫度限於一 3 0 °C以上者宜。 冷卻方法之例以利用外套式、旋管式等進行環循之方 法者宜。又，依不同情況，爲使反應器內溫度均勻，亦可 進行攪拌等動作，去除大反應熱後，預防局部溫度之上昇 者宜。 又，爲控制因反應熱所造成之局部溫度上昇，當原料 之F 2，N Η 3濃度很薄時，亦可一倂供給之，惟，當濃π 度高時以分割供給將可控制局部溫度之上昇較爲保險。分 割供給原料F 2氣體與Ν Η 3氣體之方法可使用如：由第 1原料氣體供給口使F 2氣體與Ν Η 3氣體流動，由第2 氣供給口流動Ν Η 3氣體之方法者。此分割供給可更有效 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） 77^~一 ' ---- I、--------— (請先閲讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局員工消費合作社印製 583137 A7 _B7 _ 五、發明説明（6) 控制反應溫度之局部上昇。 利用F 2氣體進行直接氧化氫反應者如上述將伴隨反 應產生極大反應熱，因此，做爲抑制此反應熱之方法有如 :以不活性氣體稀釋F 2氣體之方法或以不活性氣體稀釋 基質之N Η 3氣體之方法等被利用之。做爲稀釋氣體之例 者爲至少1種選自氮，氦，氬，六氟乙烷，及辛氟丙烷所 成群之不活性氣體者宜。較理想者以考量目的物之N F 3 (沸點：一 1 2 0 °C )與於與此等不活性氣體進行蒸餾步 驟下之分離，精製操作等後，比較N F 3後，其高沸點之 六氟乙烷（沸點··一 7 8 · 1 °C )與辛氟丙烷（沸點··— 3 6 · 7°C)由其分離成本面觀之較爲有利，更以辛氟丙 烷爲更佳者。 F2氣體及NH3氣體於導入反應器之前，先使任一 方，或兩者均以稀釋氣體進行稀釋後，再導入反應器者爲 較佳，若考量安全性，則F 2氣體與N Η 3氣體均以稀釋 氣體做成低濃度者宜。又，稀釋氣體與生成之NF3分離 後’進行回收後循環使用者宜。稀釋氣體之回收方法一般 使用藉由蒸餾分離之方法者。而，做爲稀釋氣體者以辛氟 丙烷使用時，目的物之N F 3由低沸份之蒸餾塔頂出脫， 稀釋氣體之辛氟丙烷由蒸餾塔殘留.物出脫後，於反應系被^ 循環使用之。 ， 實施本反應時，供給原料F 2氣體與Ν Η 3氣體時兩 者濃度以莫耳比爲1 : 1〜1 : 2者宜。又，分割供給上 述原料時，其反應全體所使用2F2氣體與ΝΗ3氣體之 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） _ q _ (請先閱讀背面之注意事項再填寫本頁) .裝· 訂 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 583137 A7 ___ B7 五、發明説明（7) 比仍以此範圍者宜。當NH3氣體爲F2氣體之莫耳比大 於2倍時，則務必設置爲回收未反應之氨氣體之設施爲不 經濟者。反之，小於1倍莫耳時，則未反應氟氣體量太大 ，安全性，經濟面均不理想。 又，F 2氣體供給濃度以3莫耳％以下者宜，N Η 3 氣體之供給濃度爲6莫耳％以下者宜。因此，被供給反應 器入口之氣體組成其反應基質（F2 + NH3)爲9莫耳 %以下，稀釋氣體爲9 1莫耳％以上者宜。使用上述F2 氣體之直接氟化法者由於使用極富反應性之F 2氣體。因 此，含氫之ΝΗ3接觸氟之後，將造成燃燒或爆炸之危險 。故，防止ΝΗ3與F2氣體之爆炸爲本發明之重要課題 者。本發明者進行硏討NH3氣體與F 2氣體之爆炸範圍 後，判定N Η 3爆炸範圍下限値可設定於6莫耳％以下爲 本反應之安全範圍者。又，將F2氣體及/或ΝΗ3氣體 由2處以上之氣體導入口進行分割供給於反應器後，可調 整反應器內之氣體濃度爲更安全之範圍者。 未反應F 2氣體於蒸餾步驟中進行濃縮等時，有安全 性問題存在，非得極力去除不可。因此，本發明N F 3製 造方法含處理未反應F 2氣體之步驟。做爲去除F 2氣體 之方法者有與鹼水溶液接觸之方法，·，如：接觸Κ〇Η水溶r 液之方法，或接觸氧化鋁後去除之方法者宜。處理溫度以 8 0 °C以下者宜，若爲8 0 °C以上則部份目的物之N F 3 將分解而不理想。 又，藉由F2氣體與NH3氣體之直接氟化反應製造 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -1〇 - (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T 583137 A7 ____B7 —___ V. Description of the Invention (4) (1 2) An etching gas containing the nitrogen trifluoride product contained in (1 1). (Please read the precautions on the back before filling this page) (1 3) The cleaning gas containing the nitrogen trifluoride product contained in (1 1). That is, the present invention is "a method for producing nitrogen trifluoride after reacting a fluorine gas and an ammonia gas in a gas phase, and it is characterized by nitrogen trifluoride in the presence of a dilution gas under 80 ° C "Manufacturing method", "containing nitrogen trifluoride products characterized by nitrogen trifluoride obtained by the manufacturing method" and "uranium-engraved gas and cleaning gas containing the nitrogen difluoride product". [Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The invention is a method for producing NF3 by direct (no catalyst) reaction between F2 gas and ammonia gas in the gas phase under _80 t in the presence of a diluent gas, which overcomes the problems and problems of the direct direct fluorination reaction, It can be used in industry to produce a kind of NF 3 which is economical, safe and efficient. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs As mentioned above, when the direct fluorination method of F 2 gas is used to substitute 1 hydrogen in the matrix for 1 fluorine, an extremely high reaction heat of about llOkca 1 / mo 1 is generated. When F 2 gas and N Η 3 gas are reacted with each other to produce N F 3, only the substitution of r hydrogen and fluorine produces a reaction heat of about -3 3 0k c a 1 / mo 1, which mostly causes the local temperature to become high. When the temperature is high, other than the intended reaction (Expression 1 below), it is dominated by side reactions (Expression 2 below). This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm> 583137 A7 __ B7 _ V. Description of the invention (5) 4NH3 + 3F2-NF3 + 3NH4F (Formula 1) 2NH3 + 3F2— N2 + 6HF (Formula 2 ) Therefore, it is necessary to take control of the side reaction (Eq. 2) and select the target reaction (Eq. 1). In response to this problem, the inventors repeatedly conducted precise discussions and found that the reaction temperature is closely related to the side reaction. When When the reaction temperature is 80 ° C or higher, such as: 1 10 ° C, the side reaction (Formula 2) is dominant, and the product is nitrogen and hydrogen fluoride, and the target substance NF 3 is hardly produced. When the temperature is below 80 ° C, the objective reaction (formula 1) is selectively carried out. That is, the reaction temperature of the present invention is below 80 ° C, preferably 50 ° C or less. Ideally, after further cooling, the objective reaction (formula 1) will be carried out more selectively. However, when the reaction temperature is too low, the reaction speed will decrease, which may cause condensation and dilution of the gas. Therefore, the lower limit temperature is limited to one. Above 30 ° C is preferred. Examples of cooling methods are jacket and coil. It is advisable to perform the circulation method. In addition, according to different situations, in order to make the temperature in the reactor uniform, operations such as stirring can be performed, and after removing the large reaction heat, it is appropriate to prevent local temperature rise. The local temperature rise caused by heat can be supplied at a time when the F 2, N Η 3 concentration of the raw material is very thin, but when the concentration π is high, the partial temperature increase can be controlled to control the increase in local temperature. The method of separately supplying the raw material F 2 gas and Ν Η 3 gas can be used, for example, a method of flowing F 2 gas and Ν Η 3 gas through the first raw material gas supply port and flowing Ν Η 3 gas through the second gas supply port. .This split supply can be more effective. This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 77 ^ ~ 一 '---- I 、 --------— (Please read first Note on the back, please fill in this page again), 11 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, 583137 A7 _B7 _ V. Description of the invention (6) Control the local rise in reaction temperature. Those who use F 2 gas for direct hydrogen oxidation reaction, such as The above will be accompanied by a great response Therefore, as a method for suppressing this reaction heat, methods such as: diluting F 2 gas with inert gas or diluting N Η 3 gas with inert gas are used. As examples of diluting gas, At least one inert gas selected from the group consisting of nitrogen, helium, argon, hexafluoroethane, and octafluoropropane. Ideally, NF 3 (boiling point: -120 ° C) is taken into consideration After separating and purifying the inert gas with these inactive gases, and comparing with NF 3, the high boiling point of hexafluoroethane (boiling point ·· -7 8 · 1 ° C) and octafluoropropane ( Boiling point ··· 3 6 · 7 ° C) It is more advantageous in terms of its separation cost, and octafluoropropane is more preferred. Before the F2 gas and NH3 gas are introduced into the reactor, either or both of them are diluted with a diluent gas before it is introduced into the reactor. If safety is considered, F 2 gas and N Η 3 gas It is advisable to use diluent gas to make low concentration. In addition, it is preferable that the diluent gas is separated from the generated NF3 and recycled after recycling. The method of recovering the diluent gas is generally a method of separation by distillation. However, when dichloromethane is used as the diluent gas, the NF 3 of the target substance is removed from the top of the distillation column with a low boiling point, and the octafluoropropane of the diluent gas is removed from the distillation column. ^ Recycle it. In carrying out this reaction, it is preferable that the concentration of both the F 2 gas and the N 3 gas when the raw materials are supplied is in a molar ratio of 1: 1 to 1: 2. In addition, when the above raw materials are divided and supplied, the paper size of the 2F2 gas and ΝΗ3 gas used in the whole reaction is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ q _ (Please read the precautions on the back before filling in this Page). Binding and printing printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 583137 A7 ___ B7 V. Description of the invention (7) It is better to be in this range. When the molar ratio of NH3 gas to F2 gas is more than two times, it is necessary to set up a facility for recovering unreacted ammonia gas as uneconomical. Conversely, when it is less than 1 mole, the amount of unreacted fluorine gas is too large, and the safety and economic aspects are not ideal. The supply concentration of F 2 gas is preferably 3 mol% or less, and the supply concentration of N Η 3 gas is preferably 6 mol% or less. Therefore, the gas supplied to the inlet of the reactor constitutes a reaction matrix (F2 + NH3) of 9 mol% or less, and a diluent gas of 91 mol% or more is preferred. The direct fluorination method using the above-mentioned F2 gas is due to the use of the highly reactive F2 gas. Therefore, the exposure of NH 3 containing hydrogen to fluorine will cause a danger of burning or explosion. Therefore, preventing the explosion of NH3 and F2 gas is an important subject of the present invention. After discussing the explosion range of NH3 gas and F2 gas, the inventors determined that the lower limit of N Η 3 explosion range can be set to 6 mol% or less as the safe range of this reaction. In addition, after the F2 gas and / or NH3 gas are divided and supplied to the reactor from two or more gas introduction ports, the gas concentration in the reactor can be adjusted to a safer range. When the unreacted F 2 gas is concentrated in the distillation step, there are safety issues, and it must be removed as much as possible. Therefore, the method for producing N F 3 of the present invention includes a step of treating unreacted F 2 gas. As a method for removing F 2 gas, there is a method of contacting with an alkaline aqueous solution. For example, a method of contacting a KOH water-soluble solution or a method of removing it after contacting alumina. The processing temperature is preferably below 80 ° C. If it is above 80 ° C, N F 3 of some objects will decompose, which is not ideal. In addition, it is manufactured by the direct fluorination reaction of F2 gas and NH3 gas. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -1〇-(Please read the precautions on the back before filling this page)
583137 A7 B7 -—------------- 五、發明説明（8) N F3之步驟中，如該（式1 )所示產生NH4F之副產 物。因此，做爲反應之形式者’以利用反應器2基取代之 方式進行回收副產物之N H 4 F後，再行利用者宜。 又，藉由本發明製造方法取得之N F 3可於半導體裝 置製造步驟之餓刻步驟ΐ做爲纟虫刻氣體之使用者。另外亦 可於半導體裝置製造步驟之洗淨步驟中做爲洗淨氣體之使 用。LS I ，TFT爲半導體裝置之製造流程中，利用 C V D法，濺射法或蒸鍍法等形成薄膜或厚膜後，爲形成 電路模型進行蝕刻。又，形成薄膜，厚膜之裝置中，爲去 除堆積於裝置內壁，治具等不必要堆積物，而進行洗淨。 此仍若產生不必要堆積物將造成脫落之原因，因此，欲製 造良質膜，務必隨時去除設堆積物者。 其中，使用N F 3之蝕刻方法可於等離子蝕刻，微波 蝕刻等各種乾蝕刻條件下進行之，亦可以適當比例混合 NF3與He ，N2，Ar等不活性氣體或HC 1 ，〇2， Η 2等氣體後使用之。 〔實施例〕 以下，藉由實施例及比較例進行本發明更詳細之說明 ’而，本發明並不僅限於此。 … 一 (實施例1 ) 使用內徑約4 0 m m 0，長約5 0 0 m m之因科鎳合 金6 0 〇型反應器（以外套式進行冷媒循環冷卻方式，反 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閎讀背面之注意事項再填寫本頁) 裝-583137 A7 B7 ----------------- V. Description of the invention (8) In the step of N F3, NH4F is produced as a by-product as shown in (formula 1). Therefore, as the reaction form, it is better to use it after recovering N H 4 F, which is a by-product, by using the 2-group substitution of the reactor. In addition, the N F 3 obtained by the manufacturing method of the present invention can be used as a user of the engraving gas in the starving step of the manufacturing step of the semiconductor device. It can also be used as a cleaning gas in the cleaning step of the semiconductor device manufacturing step. LS I, TFT is a semiconductor device manufacturing process. After forming a thin film or thick film by CVD method, sputtering method or evaporation method, etc., it is etched to form a circuit model. Further, in the apparatus for forming a thin film or a thick film, cleaning is performed to remove unnecessary deposits such as jigs and the like accumulated on the inner wall of the apparatus. If there is still an unnecessary deposit, it will cause the fall off. Therefore, if you want to make a good film, you must remove the deposit at any time. Among them, the etching method using NF 3 can be performed under various dry etching conditions such as plasma etching, microwave etching, etc., and NF 3 and He, N 2, Ar and other inert gases or HC 1, 02, Η 2 and the like can be mixed in an appropriate ratio. Use it after gas. [Examples] Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. However, the present invention is not limited thereto. … (Example 1) Inco nickel alloy 600 reactor with an inner diameter of about 40 mm 0 and a length of about 500 mm (in the form of a jacket-type refrigerant circulation cooling method, the paper size is applicable to China) Standard (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page) Pack-
、1T 經濟部智慧財產局員工消費合作社印製 -11 - 583137 A7 B7 五、發明説明（9) (請先閲讀背面之注意事項再填寫本頁} 應器以F 2氣體於溫度4 0 0 °C下實施不動態化處理）後 ，供給氬爲2 9 5 8 N L / h ί (由N Η 3供給線及F 2 供給線各等量）之同時設定溫度於5 °C，再供給Ν Η 3氣 體〇.701NL/hr及F2氣體爲〇·526NL/ h 後，進行反應之。反應器入口之NH3濃度爲 2 . 28莫耳％，F2濃度爲1 · 7 1莫耳％者。反應開 始2小時後，進行測定於碘化鉀水溶液所反應生成氣體中 之氟化氫及未反應氟氣體濃度，藉由氣體層析法進行組成 分析，其分析値如以下表1所示，F 2基準之N F 3收率 爲6 9%。表中之ND代表未檢出者。 〔表1〕Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -11-583137 A7 B7 V. Description of the invention (9) (Please read the precautions on the back before filling this page} The reactor should be F 2 gas at temperature 4 0 0 ° After the non-dynamic processing is performed under C), the argon supply is 2 9 5 8 NL / h ί (by N Η 3 supply line and F 2 supply line each equal amount), the temperature is set at 5 ° C, and then Ν Η The reaction was carried out after 3 gas of 0.701NL / hr and F2 gas of 0.526NL / h. The NH3 concentration at the reactor inlet is 2.28 mole%, and the F2 concentration is 1.71 mole%. Two hours after the start of the reaction, the concentrations of hydrogen fluoride and unreacted fluorine gas in the reaction gas produced by the potassium iodide aqueous solution were measured, and the composition was analyzed by gas chromatography. The analysis is shown in Table 1 below, and the NF on the F 2 basis 3 yield is 6 9%. ND in the table represents those not detected. 〔Table 1〕
反應生成氣體 分析結果 未反應NH3 ND 未反應F2 0.03 3NL/hr NF3 0.121NL/hr HF ND 經濟部智慧財產局員工消費合作社印製 (實施例2 ) 利用內徑4 Omm0，長度5 0 〇mm之因科鎳合金 6 0 0型反應器（電熱器加熱方式，’反應器以F 2氣體於π 溫度4 0 0 °C下進行靜態化處理）後，除反應溫度爲7 0 t：之外，與實施例1同條件，操作下進行反應，分析。分 析結果如表2所示，F 2基準之N F 3收率約爲4 2 %者 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 12 - 583137 A7 B7 五、發明説明（10) _ 〔表 2〕 反應生成氣體 分析結果 . 未反應NH3 ND 未反應F2 0.1 12NL/hr NF3 0.075NL/hr HF 0.042NL/hr (比較例1 ) 利用相同於實施例2之反應器後，反應溫度爲1 5 0 °C之外與實施例1同條件，操作下進行反應，分析之。分 析結果如表3所示，顯示反應溫度於8 0 °C以上之高溫時 ’完全未產生NF3，呈該（式2 )之反應進行之。 (請先閱讀背面之注意事項再填寫本頁) 裝- 訂 經濟部智惡財產局員工消費合作社印製 施以 ο 器 實 〇應 ( 6 反 〔表3〕 反應生成氣體 分析結果 未反應NH3 ND 未反應F2 ND NF3 ND HF 0.701NL/hr 例3 ) 內徑4 Omm0，長度5 0 Omm之因科鎳合金 型反應器（以外套式進行冷媒循環冷卻方式）做爲 使用，以N Η 3之供給做爲2分割方式，由反應器 -線 -13- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 583137 A7 B7 五、發明説明（1) 之入口部及中央部2處供給之外，與«施例1同條件，操 作下進行反應，.分析。分析結果如表4所示，F 2基準之 N F 3收率約7 6 %者。Analysis result of reaction generated gas Unreacted NH3 ND Unreacted F2 0.03 3NL / hr NF3 0.121NL / hr HF ND Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Example 2) Using an inner diameter of 4 mm and a length of 50 mm Inco nickel alloy 600 reactor (heater heating method, 'the reactor is statically treated with F 2 gas at π temperature 4 0 ° C), except that the reaction temperature is 7 0 t: The reaction was performed under the same conditions as in Example 1 and analyzed. The analysis results are shown in Table 2. The yield of NF 3 based on the F 2 benchmark is about 4 2%. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 12-583137 A7 B7 V. Description of the invention ( 10) _ [Table 2] Analysis results of reaction generated gas. Unreacted NH3 ND Unreacted F2 0.1 12NL / hr NF3 0.075NL / hr HF 0.042NL / hr (Comparative Example 1) After using the same reactor as in Example 2, The reaction temperature was 150 ° C and the same conditions as in Example 1 were used. The reaction was performed under operation and analyzed. The results of the analysis are shown in Table 3. It was shown that when the reaction temperature was higher than 80 ° C, NF3 was not generated at all, and the reaction of (Formula 2) proceeded. (Please read the precautions on the back before filling out this page) Packing-Order Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs, and apply it to the device. 0 Response (6 Reverse [Table 3] Analysis of reaction gas generation without reaction NH3 ND Unreacted F2 ND NF3 ND HF 0.701NL / hr Example 3) Inco nickel alloy reactor with inner diameter of 4 Omm0 and length of 50 Omm (refrigerant circulation cooling method with jacket type) is used. N Η 3 The supply is divided into 2 ways, from the reactor-line-13- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 583137 A7 B7 V. Description of the invention (1) There are 2 entrance and central parts Except for the supply, the reaction was performed under the same conditions as in Example 1 and analyzed. The analysis results are shown in Table 4. The yield of N F 3 based on F 2 was about 76%.
〔表4〕 反應生成氣體 分析結果 未反應NH3 ND 未反應F 2 0.01 INL/hr NFs 0.133NL/hr HF ND (比較例2 ) 除NH3氣體爲〇 · 3〇NL/hr ，F2氣體爲 1 · 〇5NL/hr ，做爲稀釋氣體之氨氣爲3 · 67 N L / h r之外，與實施例1同條件，操作下，進行反應 ，分析。分析結果如表5所示，當1莫耳之F 2氣體時’ NH3氣體爲1倍莫耳以下其未反應F2氣體大量溢出’ 極不理想。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本纸張尺度適用中國國家標準（CNS ) A4規格（210、x297公釐） -14- 583137 A7 _ B7五、發明説明（θ[Table 4] Analysis results of reaction gas generation Unreacted NH3 ND Unreacted F 2 0.01 INL / hr NFs 0.133NL / hr HF ND (Comparative Example 2) Except for NH3 gas, 0.30NL / hr, F2 gas was 1 · 〇5NL / hr, except that the ammonia gas used as the diluent gas is 3.67 NL / hr, under the same conditions as in Example 1, under the same conditions, the reaction was performed and analyzed. The analysis results are shown in Table 5. When 1 mole of F 2 gas is used, the amount of unreacted F 2 gas that overflows when the NH 3 gas is 1 mole or less is extremely unsatisfactory. (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy applies the Chinese National Standard (CNS) A4 specifications (210, x297 mm) -14- 583137 A7 _ B7 V. Description of the invention (θ
_ 〔表 5〕 反應生成氣體 分析結果 未反應NH3 ND 未反應F 2 0.825NL/hr NFs 〇.〇.49NL/hr HF ND (比較例3 ) 除ΝΗ3氣體爲1 · 5 8NL/hr ，F2氣體爲 〇 . 526NL/hr ，稀釋氣體之氦氣爲36 . 7NL / h r之外，與實施例1同條件，操作下進行反應，分析 。分析結果如表6所示，當1莫耳之F2氣體時，NH3 氣體爲2倍莫耳以上，其未反應NH3大量溢出，極不理 想者。 (請先閲讀背面之注意事項再填寫本頁) -訂 經濟部智慧財產局員工消費合作社印製_ [Table 5] Analysis results of reaction gas generation Unreacted NH3 ND Unreacted F 2 0.825NL / hr NFs 0.049NL / hr HF ND (Comparative Example 3) Except for NH 3 gas, it is 1.5 8NL / hr, F2 gas It was 0.526NL / hr, and the helium gas of the diluent gas was outside of 36.7NL / hr. The reaction was performed and analyzed under the same conditions as in Example 1. The analysis results are shown in Table 6. When 1 mole of F2 gas is used, the NH3 gas is more than twice the mole, and its unreacted NH3 overflows in a large amount, which is extremely undesirable. (Please read the notes on the back before filling out this page)-Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
〔表6〕 反應生成氣體 分析結果 未反應N Η 3 〇.867NL/hr 未反應f2 0.010NL/hr NFs 0.1 1 9 N L / h r HF ND 〔發明效果〕 如以上說明，根據本發明於稀釋氣體之存在下，以氣 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 7^5 - — 583137 A7 B7 五、發明説明（ 相，8 0 °C以下使F 2氣體與N Η 3氣體相互反應後，可 製造先行技術上所不易製造收率佳之N F 3者。且，以本 發明方法所製造之N F 3可做爲蝕刻氣體或洗淨氣體之使 用者。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -16- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐）[Table 6] Analysis result of reaction generated gas Unreacted N Η 3 0.867NL / hr unreacted f2 0.010NL / hr NFs 0.1 1 9 NL / hr HF ND [Effect of the invention] As explained above, according to the present invention, the dilution gas In the presence of paper, the Chinese national standard (CNS) A4 specification (210X297 mm) is applied to the paper size. 7 ^ 5-583137 A7 B7 V. Description of the invention (phase, below 80 ° C, F 2 gas and N Η 3 After the gases react with each other, it is possible to manufacture NF 3 which is not easy to produce in the prior art and has a good yield. Moreover, the NF 3 manufactured by the method of the present invention can be used as an etching gas or a cleaning gas user. (Please read the back Note: Please fill in this page again.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -16- This paper size applies to China National Standard (CNS) Α4 specification (210 × 297 mm)