1320035 A7 __B7_ 五、發明説明（1) 發明技術領域 (請先閲讀背面之注意事項再填寫本頁) 本發明係有關全氟化碳之製造方法。更詳細地說，係 有關適用於製造半導體裝置之可抑制含氧化合物等不純物 生成的全氟化碳類之製造方法。 又’本發明係有關實質不含含氧化合物之高純度全氟 化碳類、含全氟化碳之氣體及其用途。 發明技術背景 目前，半導體裝置製造過程中，適用的蝕刻氣體或淸 潔氣體之一爲，目前所使用之全氟化碳類。 .又’近年來隨著電器或電子機器高性能化、小型化、 高密度配線化等，而有回路基板之電極微細化傾向。爲了 使蝕刻等方法能更高精準度形成回路圖型，而需使用極力 排除不純物之極高純度的蝕刻氣體。但，鈾刻氣體既使僅 含微量不純物下，仍會成爲使微細圖型成形時產生寬幅線 ，或增加高密度積成回路製品之缺陷的主要原因。 經濟部智慧財產局員工消費合作社印製 利用淸潔氣體去除附著物之過程中，爲了提供高純度 及品質之裝置，而需盡可能減少淸潔後半導體裝置製造過 程中所殘留之不純物，因此寄望提供實質不含不純物之高 純度淸潔氣體。 目前已有各種全氟化碳類之製造方法提案。例如有關 四氟甲烷之存在觸媒下使氯三氟甲烷與H F反應之方法（ 特公昭62—10211號公報）；存在觸媒下使二氯二 氟甲烷與HF反應之方法（特公昭42 — 3004號公報 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -4- 1320035 A7 ____B7__ 五、發明说明（2) (請先閱讀背面之注意事項再填寫本頁) ):有關六氟乙烷之以乙烷及/或乙烯爲原料的電解氟化 法：將四氟乙烯等熱分解之熱分解法；利用金屬氟化物使 乙炔、乙烯、乙烷等氟化之方法等。又，使碳氫化物或氫 氟化碳接觸氟氣而直接氟化之方法如，使三氟甲烷與氟氣 反應之方法（GB— 1， 116，9 2 0 ):使四氟乙烷 與氟氣反應之方法（專利第2947 1 58號公報；使六氟丙烯 與氟氣反應之方法（特公昭6 2 — 6 1572號公報）； 於B r F3或I F3中使碳（C)與F2反應之方法（特開 昭58 — 1 6 2 536號公報）等。又如，碳原子數3之 全氟化碳爲八氟丙烷時，利用氟氣使丙烷反應之直接氟化 法（EP-31519)等。 上述各種製造方法，直接氟化法因使用反應性極豐富 之氟氣，而有基質之有機化合物及氟氣產生爆炸或腐蝕等 危險性，又，因發熱而有造成C-C鍵斷裂'聚合、生成 碳（C )及增加體積與激烈反應或爆炸等副反應之危險性 〇 經濟部智慧財產局員工消費合作社印製 例如，利用直鏈狀碳氫化合物與氟氣反應之直接氟化 法合成全氟化碳時，會伴隨下列般非常大的反應熱。 c Η 4 + 4 F : C F,- —4 Η F (式 ι ) (Δ Η = -4 7 9kcal/m〇|) c 2 Η 6 + 6 F , c2 f6 + 6 Η F (式 2 ) (Δ Η = ~6 9 Okcal/mol) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 1320035 A7 B7 五、發明説明（3) (請先閲讀背面之注意事項再填寫本頁) 即，以C — F鍵取代C — H鍵時，會產生約—1 1〇 Kca l/m〇 1之反應熱。又，使丙烷（c3H8)與氟 氣反應之直接氨化法的ΔΗ約爲—8 8 0 Kcal/mol。 以甲烷爲原料時（式1 )，對甲烷1莫耳需使用4莫 耳氟氣，又’以乙烷爲原料時（式2)，對乙烷1莫耳需 使用6莫耳氟氣。此時會因基質之有機化合物的氫原子較 多，或所使用之氟量較多而增加反應熱，故曾有抑制直接 氟化法中激烈產生反應熱之方法。例如，以其他不活性氣 體（氮或氦等）稀釋氟氣之方法；以不活性氣體稀釋基質 之有機化合物的方法；將基質之有機化合物溶解於對氟爲 不活性之溶劑而爲低濃度的方法；低溫域下進行反應之方 法；利用氣相進行反應時以連續性少量氟接觸基質之有機 化合物般噴射反應器等裝置之方法等。 爲了解決上述直接氟化法之問題，本發明者們曾提案 適當控制直接氟化法之反應條件，而使工業上能安全，有 效率且符合經濟性製造全氟化碳類（專利第3067633號公 報）。 經濟部智慧財產局員工消費合作社印製 以所得全氟化碳類作爲半導體裝置製造過程等之淸潔 氣體或蝕刻氣體時，如上述般需爲盡量不含各種不純物之 高純度全氟化碳類。又，一般係利用蒸餾等方法使不純物 分離去除等。目前爲止，直接氟化法組合使用原料精製， 生成物蒸餾精製步驟等時，可去除不純物達某程度純度， 而得一定純度之全氟化碳類。 但，本發明者們硏究以上述直接氟化法製造全氟化碳 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ' -6- 1320035 A7 B7 五、發明説明（4) (請先閱讀背面之注意事項再填寫本頁) 類之方法的過程中發現，既使利用高精準度之蒸餾法等， 仍會殘留不純物成分，且很難有效去除該殘留不純物。又 ，分析該不純物時驗出全氟化二甲基醚、全氟化二甲基過 氧化物、全氟化甲基乙基醚等含氧化合物。因該含氧化合 物會與全氟化碳類形成共沸組成物或共沸樣混合物，故例 如利用蒸餾法時極難由全氟化碳類分離》因此，以混有高 濃度含氧化合物之全氟化碳類作爲半導體裝置製造用之蝕 刻氣體或淸潔氣體時，將無法符合極微細圖型成形時等之 要求。 經本發明者們針對抑制含氧化合物生成一事專心硏究 後發現，該含氧化合物係來自氟氣或氫氟化碳等反應原料 中所含微量之氧氣，因此，將反應溫度與反應條件控制於 —定範圍’且將反應原料中氧氣含量減至特定量以下時， 可有效抑制含氧化合物生成，而完成本發明。又，經本發 明者們調查的結果，目前尙無有關抑制來自原料中氧氣之 含氧化合物的全氟化碳類製造方法。 經濟部智慧財產局員工消費合作社印製 發明目的 爲了解決上述目前技術所伴隨之問題，本發明之目的 爲’提供一種抑制含氧化合物等不純物生成之高純度全氟 化碳類及其製造方法》又’本發明之目的爲，提供該高純 度全氟化碳類之用途。 發明槪要 本纸浪尺度適用中國國家揉準（CNS ) A4規格（210X297·公釐） 1320035 Α7 Β7 五、發明説明（6) 又，上述不純物可爲含氧化合物。 (請先閲讀背面之注意事項再填寫本頁) 全氟化碳類之製造方法可包含吸附去除含氧化合物之 步驟。 含氧化合物可利用活性碳吸附去除。 此時全氟化碳類較佳爲，四氟甲烷、六氟乙烷及八氟 丙烷中至少一種。 又，全氟化碳類所含之含氧化合物總量較佳爲5體積 P pm以下，更佳爲2體積p pm以下。 本發明之含全氟化碳氣體爲，含有上述全氟化碳類。 本發明之蝕刻氣體的特徵爲，由上述含全氟化碳類氣 體所形成。該全氟化碳類較佳爲四氟甲烷。 本發明之淸潔氣體的特徵爲，由上述含全氟化碳類氣 體所形成。又，該全氟化碳類較佳爲六氟乙烷或八氟丙烷 〇 發明具體說明 經濟部智慧財產局員工消費合作社印製 下面將具體說明本發明之全氟化碳類的製造方法及其 用途。 〔全氟化碳類之製造方法〕 本發明之全氟化碳類的製造方法爲，將有機化合物接 觸氟氣（F2)而製造八氣化碳類之方法中，係將反應系所 含氧氣含量控制於一定量以下之製造方法β又，必要時， 本發明之全氟化碳類的製造方法可於稀釋氣體存在下進行 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公楚) ' ---- -9- 1320035 A7 _B7 五、發明説明（7) (請先閲讀背面之注意事項再填寫本頁) (有機化合物） 本發明所使用之有機化合物並無特別限制，可爲已知 全氟化碳類製造時所使用之有機化合物。 該有機化合物較佳如，碳原子數6以下之脂肪族飽和 化合物’碳原子數6以下之脂肪族不飽和化合物中至少1 種。其中又以碳原子數6以下之脂肪族飽和化合物中至少 1種爲佳。 碳原子數6以下之脂肪族飽和化合物如，氟甲烷，二 氟甲烷、三氟甲烷、三氟乙烷、四氟乙烷、五氟乙烷、五 氟丙烷、六氟丙烷、七氟丙烷等氫氧化碳，又以其中選出 至少1種爲佳。 氣相中存在稀釋氣體下，以無觸媒方式使有機化合物 接觸氟氣時，有機化合物較佳爲，碳原子數4以下之氫氟 化碳。 經濟部智慧財產局員工消費合作社印製 該氫氧化碳如，二氟甲烷、三氟甲烷、四氟乙烷、五 氟乙烷、六氟丙烷、七氟丙烷等，又以其中選出至少1種 爲佳。 又以上述氫氟化碳數爲原料而得之四氟甲烷、六氟乙 烷、八氟丙烷等全氟化碳類爲佳。 (氟氣） 本發明所使用之氟氣可爲，利用氟化氫之電解法等已 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -10- 1320035 A7 B7 五、發明説明（8) 知方法製得之物，或市售之氟氣。 (请先閱讀背面之注意事項再填寫本頁) (稀釋氣體） 本發明所使用之稀釋氣體如，四氟甲烷、六氟乙烷、 八氟丙烷、氟化氫等。 該稀釋氣體可單獨使用或2種以上混用。其中又以氟 化氫爲佳’又’倂用氟化氫及其他稀釋氣體時，較佳爲含 豐富氟化氫之氣體’具體而言即，對全體稀釋氣體之氟化 氫較佳爲5 0體積％以上’更佳爲6 〇體積％以上。 (全氟化碳類之製造方法） 例如以四氟乙烷（CF3CH2F)、三氟甲烷（ 經濟部智慧財產局員工消費合作社印製 CHF 3 )作爲有機化合物原料，接觸氟氣而製造四氟甲烷 (CF4)、六氟乙烷（CF3CF3)時，原料中（有機 化合物及氟氣）存在氧氣時，會生成例如C F3〇C F3、 CF3OOCF3、CF3CF2OCF3等含氧化合物。又 ’該含氧化合物會與目的物形成共沸組成物或共沸樣混合 物’因此很難以已知方法，例如蒸餾法等由目的物分離。 本發明之全氟化碳類的製造方法中，將有機化合物接 觸氟氣（F 2)而製造全氟化碳類時，係使反應系所含氧氣 含量對進行有機化合物及氟氣之接觸反應時反應系內氣體 成分爲2體積％以下，又以1體積％以下爲佳，更佳爲 0 . 5體積％以下。 該「反應系」係指’進行有機化合物接觸氟氣之反應 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 - 1320035 A7 B7 五、發明説明（9) (請先閲讀背面之注意事項再填寫本頁) 容器內’有機化合物及氟氣所形成之反應原料及必要時添 加之稀釋氣體等所形成的反應溶液及氣相環境。又，係指 裝入原料起至反應結束之間，反應容器內反應溶液及氣相 環境，但不包含反應結束後萃取及精製步驟等。 氣相中存在稀釋氣體下，以無觸媒方式進行有機化合 物及氟氣之接觸反應時，氟氣原料所含之氧氣含量對氟氣 較佳爲1體積％以下，更佳爲0 . 6體積％以下，特佳爲 0 . 4體積％以下。 反應系所含氧氣少於2體積％時，可製得實質不含含 氧化合物之高純度全氟化碳類。又，氟氣中所含氧氣少於 1體積％時，可製得實質不含含氧化合物之高純度全氟化 碳類。 反應系所含氧氣大於2體積％時，會生成有影響力之 含氧化合物。 經濟部智慧財產局員工消費合作社印製 將反應系內及氟氣中氧氣含量控制於上述範圍之方法 爲，除了避免氧氣由外部混入反應容器般，以密閉系進行 反應外，需由有機化合物、氟氣或稀釋氣體等反應原料中 去除氧氣。又，將反應後部分氣體循環作爲稀釋氣體用時 ，又以降低氧氣由外部混入之可能性爲佳。去除有機化合 物、氟氣及稀釋氣體所含氧氣之方法可爲已知方法，例如 可對反應原料進行蒸餾或利用活性碳等吸附劑進行吸附等 分離出原料中不純物。 存在稀釋氣體下將有機化合物接觸氟氣時，可於將有 機化合物或氟氣裝入反應容器前以稀釋氣體稀釋反應基質 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） •12- 1320035 A 7 B7 五、發明説明（iih (有機化合物）、氟氣中任何一種或雙方。 其中又以裝入氟氣前以稀釋氣體稀釋爲佳。 (請先閲讀背面之注意事項再填寫本頁) 此時導入反應系內之氟氣量對反應系內氣體成分之合 計量較佳爲9體積％以下，更佳爲8體積％以下。連續進 行反應時較佳爲，將導入反應系內之氟氣量保持於該範圍 以下。又，反應系內氣體成分係指，反應系內氟氣、有機 化合物及稀釋氣體。 如上述般，使用氟氣製造全氟化碳類之直接氟化法因 使用反應性極豐富之氟氣，故會有高濃度的基質用有機化 合物，特別是含氫之化合物曝露於氟氣中，而造成的燃燒 或爆炸危險性。因此，使反應容器進料口之氟氣濃度爲9 體積％以下時，可使混合氣體濃度爲爆炸範圍外，而進行 工業上安全的氟氣及有機化合物反應。 本發明中，有機化合物接觸氟氣時之反應溫度爲 200至500 °C，又以300至450 °C爲佳。 經濟部智慧財產局員工消費合作社印製 反應溫度爲上述範圍時，可明顯減少來自氧氣所生成 之含氧化合物不純物。反應溫度超過5 0 0 °C時，既使將 反應系內氧氣（濃度）控制於2體積％以下，或將氟氣中 氧氣濃度控制於1體積％以下，仍會生成有影響力之含氧 化合物。因此，本發明較佳爲，將反應溫度控制於上述範 圍。又，控制反應溫度之區域除了反應容器內反應區外， 又以存在有機化合物、氟氣之部分利用例如熱電對等方法 ，將溫度確實控制於不超過5 0 0 °C爲佳。 本發明可明顯抑制含氧化合物混入，但對有機化合物 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 -13- 1320035 A7 B71320035 A7 __B7_ V. INSTRUCTIONS (1) Field of the Invention (Please read the note on the back and fill out this page.) The present invention relates to a method for producing perfluorocarbon. More specifically, it relates to a method for producing a perfluorocarbon which is suitable for producing a semiconductor device and which can suppress the formation of impurities such as oxygen-containing compounds. Further, the present invention relates to a high-purity perfluorocarbon-containing gas containing no oxygen-containing compound, a gas containing perfluorocarbon, and use thereof. BACKGROUND OF THE INVENTION Currently, one of suitable etching gases or cleaning gases in the manufacture of semiconductor devices is the perfluorocarbons currently used. In recent years, with the increase in performance, miniaturization, and high-density wiring of electric appliances and electronic devices, the electrode of the circuit board tends to be fine. In order to make the circuit pattern more precise by etching and the like, it is necessary to use an extremely high-purity etching gas for removing impurities. However, even if the uranium engraved gas contains only a trace amount of impurities, it will become a major cause of the formation of wide-width lines during the formation of fine patterns or the increase of defects in high-density integrated circuit products. In the process of using the cleaning gas to remove the deposits, the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs, in order to provide high-purity and high-quality devices, must minimize the impurities remaining in the manufacturing process of the semiconductor device after cleaning. It is expected to provide a high purity clean gas which is substantially free of impurities. There are various proposals for manufacturing methods for perfluorocarbons. For example, a method for reacting chlorotrifluoromethane with HF in the presence of tetrafluoromethane (Special Publication No. 62-10211); a method of reacting dichlorodifluoromethane with HF in the presence of a catalyst (Special Example 42) Circular 3004 This paper scale applies to China National Standard (CNS) Α4 specification (210X297 mm) -4- 1320035 A7 ____B7__ V. Invention description (2) (Please read the note on the back and fill out this page)): Related Electrolytic fluorination method using hexafluoroethane as a raw material of ethane and/or ethylene: a thermal decomposition method of thermally decomposing tetrafluoroethylene or the like; a method of fluorinating acetylene, ethylene, ethane or the like by using a metal fluoride. Further, a method of directly fluorinating a hydrocarbon or hydrofluorocarbon with fluorine gas, for example, a method of reacting trifluoromethane with fluorine gas (GB-1, 116, 9 2 0): using tetrafluoroethane with Method for reacting fluorine gas (Patent No. 2947 1 58; method for reacting hexafluoropropylene with fluorine gas (Japanese Patent Publication No. Sho 62-2-6572); carbon (C) in B r F3 or I F3 A method of F2 reaction (JP-A-58-166), etc. Another example is a direct fluorination method in which a propane reaction is carried out using a fluorine gas when the perfluorocarbon having a carbon number of 3 is octafluoropropane (EP) -31519), etc. In the above various production methods, the direct fluorination method uses a fluorine gas which is extremely reactive, and the organic compound of the matrix and the fluorine gas cause explosion or corrosion, and the CC bond is caused by heat. The risk of 'polymerization, carbon generation (C) and increased volume and side effects such as violent reaction or explosion. 〇 Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, for example, direct fluorine reaction using linear hydrocarbons and fluorine gas When synthesizing perfluorocarbons, it will be accompanied by the following very large reactions. c Η 4 + 4 F : CF, - 4 Η F (式 ι ) (Δ Η = -4 7 9kcal/m〇|) c 2 Η 6 + 6 F , c2 f6 + 6 Η F (Formula 2) (Δ Η = ~6 9 Okcal/mol) This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -5-1320035 A7 B7 V. Invention description (3) (Please read the note on the back first) Fill in this page) That is, when the C-H bond is substituted by the C-F bond, a heat of reaction of about -1 1〇Kca l/m〇1 is generated. Further, direct amination of propane (c3H8) with fluorine gas is achieved. The ΔΗ of the method is about -800 0 Kcal/mol. When methane is used as the raw material (formula 1), 4 moles of fluorine gas is used for methane 1 molar, and when ethane is used as raw material (formula 2), Ethane 1 mole requires 6 moles of fluorine gas. At this time, the organic compound of the matrix has a large number of hydrogen atoms, or the amount of fluorine used is increased to increase the heat of reaction, so it has been suppressed in the direct fluorination method. a method of generating heat of reaction, for example, a method of diluting fluorine gas with other inert gas (nitrogen or helium, etc.); a method of diluting an organic compound of a matrix with an inert gas; and dissolving the organic compound of the matrix A method in which a fluorine is an inactive solvent and a low concentration; a method in which a reaction is carried out in a low temperature region; a method in which a reactor is sprayed in a gas phase with a small amount of fluorine in contact with an organic compound like a substrate, and the like. The above-mentioned inventors have proposed to appropriately control the reaction conditions of the direct fluorination method, and to industrially manufacture perfluorocarbons safely, efficiently, and economically (patent No. 3067633). . In the case of a clean gas or an etching gas in which a perfluorocarbon is used as a semiconductor device manufacturing process, etc., the high-purity perfluorocarbons which do not contain various impurities as much as possible are required as described above. . Further, in general, impurities are separated and removed by a method such as distillation. Heretofore, when the direct fluorination method is used in combination with the raw material purification, the product distillation purification step, and the like, the impurities can be removed to a certain degree of purity, and a perfluorocarbon having a certain purity can be obtained. However, the inventors of the present invention have studied the production of perfluorocarbon by the above direct fluorination method. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210×297 mm) ' -6- 1320035 A7 B7 5. Invention Description (4 (Please read the precautions on the back and fill out this page.) In the process of the class, it was found that even with the high-precision distillation method, the impurities were still left, and it was difficult to effectively remove the residual impurities. Further, when the impurities were analyzed, oxygen-containing compounds such as perfluorinated dimethyl ether, perfluorinated dimethyl peroxide, and perfluorinated methyl ethyl ether were detected. Since the oxygen-containing compound forms an azeotropic composition or an azeotrope-like mixture with the perfluorocarbons, it is extremely difficult to separate from the perfluorocarbons by, for example, distillation. Therefore, a high concentration of oxygenated compounds is mixed. When a perfluorocarbon is used as an etching gas or a cleaning gas for manufacturing a semiconductor device, it cannot meet the requirements for molding in a very fine pattern. The inventors of the present invention have found that the oxygen-containing compound is derived from a trace amount of oxygen contained in a reaction raw material such as fluorine gas or hydrofluorocarbon, and is therefore controlled by the reaction temperature and the reaction conditions. When the range is 'and the oxygen content in the reaction raw material is reduced to a specific amount or less, the formation of an oxygen-containing compound can be effectively suppressed, and the present invention has been completed. Further, as a result of investigations by the present inventors, there is currently no method for producing a perfluorocarbon which suppresses oxygen compounds derived from oxygen in a raw material. In order to solve the problems associated with the prior art described above, the present invention aims to provide a high-purity perfluorocarbon which inhibits the formation of impurities such as oxygenates and a method for producing the same. Further, the object of the present invention is to provide the use of the high-purity perfluorocarbon. Summary of the invention This paper wave scale is applicable to China National Standard (CNS) A4 specification (210X297·mm) 1320035 Α7 Β7 5. Inventive Note (6) Further, the above impurities may be oxygenated compounds. (Please read the precautions on the back and fill out this page.) The method for producing perfluorocarbons may include the step of adsorbing and removing oxygenates. Oxygenates can be removed by adsorption with activated carbon. In this case, the perfluorocarbon is preferably at least one of tetrafluoromethane, hexafluoroethane and octafluoropropane. Further, the total amount of the oxygen-containing compound contained in the perfluorocarbon is preferably 5 vol or less, more preferably 2 pm or less. The perfluorocarbon-containing gas of the present invention contains the above perfluorocarbons. The etching gas of the present invention is characterized by being formed of the above-described perfluorocarbon-containing gas. The perfluorocarbon is preferably tetrafluoromethane. The cleaning gas of the present invention is characterized by being formed of the above-described perfluorocarbon-containing gas. Further, the perfluorocarbon is preferably hexafluoroethane or octafluoropropane. The invention specifically describes the manufacturing method of the perfluorocarbon of the present invention, which will be specifically described below. use. [Method for Producing Perfluorocarbons] The method for producing a perfluorocarbon according to the present invention is a method for producing an eight-gasified carbon by bringing an organic compound into contact with a fluorine gas (F2), and is a method for producing oxygen in the reaction system. The manufacturing method of the content controlled by a certain amount or less β, if necessary, the method for producing the perfluorocarbon of the present invention can be carried out in the presence of a diluent gas in accordance with the Chinese National Standard (CNS) Α4 specification (210Χ297 public) ' ---- -9- 1320035 A7 _B7 V. INSTRUCTIONS (7) (Please read the notes on the back and fill out this page) (Organic Compounds) The organic compounds used in the present invention are not particularly limited and may be Know the organic compounds used in the manufacture of perfluorocarbons. The organic compound is preferably at least one of an aliphatic unsaturated compound having 6 or less carbon atoms and an aliphatic unsaturated compound having 6 or less carbon atoms. Among them, at least one of the aliphatic saturated compounds having 6 or less carbon atoms is preferred. An aliphatic saturated compound having 6 or less carbon atoms such as fluoromethane, difluoromethane, trifluoromethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, pentafluoropropane, hexafluoropropane or heptafluoropropane It is preferable to select at least one of carbon. When the organic compound is brought into contact with the fluorine gas in a gas-free atmosphere in the absence of a catalyst, the organic compound is preferably a hydrogen fluoride having 4 or less carbon atoms. The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, prints the carbon oxycarbons such as difluoromethane, trifluoromethane, tetrafluoroethane, pentafluoroethane, hexafluoropropane, heptafluoropropane, etc., and at least one of them is preferably selected. . Further, perfluorocarbon such as tetrafluoromethane, hexafluoroethane or octafluoropropane obtained from the above-mentioned number of hydrofluorinated carbon atoms is preferred. (Fluorine gas) The fluorine gas used in the present invention may be an electrolytic method using hydrogen fluoride or the like. The paper has been applied to the Chinese National Standard (CNS) A4 specification (210×297 mm) -10- 1320035 A7 B7 5. Invention Description (8) ) Known methods, or commercially available fluorine gas. (Please read the precautions on the back side and fill out this page.) (Dilution gas) The diluent gas used in the present invention is, for example, tetrafluoromethane, hexafluoroethane, octafluoropropane, hydrogen fluoride or the like. The diluent gas may be used singly or in combination of two or more. In the case where hydrogen fluoride is preferred, and hydrogen fluoride and other diluent gases are used, it is preferably a hydrogen fluoride-rich gas. Specifically, the hydrogen fluoride for the entire diluent gas is preferably 50% by volume or more. 6 〇 vol% or more. (Manufacturing method of perfluorocarbons) For example, tetrafluoroethane (CF3CH2F) and trifluoromethane (CHF 3 printed by the Ministry of Economic Affairs and Intellectual Property Office employees' cooperatives) are used as raw materials for organic compounds, and fluorine gas is contacted to produce tetrafluoromethane. In the case of (CF4) or hexafluoroethane (CF3CF3), when oxygen is present in the raw material (organic compound and fluorine gas), an oxygen-containing compound such as C F3〇C F3, CF3OOCF3, CF3CF2OCF3 or the like is formed. Further, the oxygen-containing compound forms an azeotropic composition or an azeotrope-like mixture with the target product. Therefore, it is difficult to separate from the object by a known method such as distillation. In the method for producing a perfluorocarbon according to the present invention, when the organic compound is brought into contact with the fluorine gas (F 2 ) to produce a perfluorocarbon, the oxygen content in the reaction system is brought into contact with the organic compound and the fluorine gas. The gas component in the reaction system is preferably 2% by volume or less, more preferably 1% by volume or less, still more preferably 0.5% by volume or less. The term "reaction system" means 'the reaction of organic compounds in contact with fluorine gas. This paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) -11 - 1320035 A7 B7 V. Description of invention (9) (Read first Precautions on the back side Fill in the reaction solution and the gas phase environment of the reaction material formed by the organic compound and fluorine gas and the diluent gas added if necessary. Further, it means a reaction solution and a gas phase environment in the reaction vessel from the time when the raw material is charged to the end of the reaction, but does not include the extraction and purification steps after completion of the reaction. When the contact reaction between the organic compound and the fluorine gas is carried out in the absence of a catalyst in the presence of a diluent gas, the oxygen content of the fluorine gas raw material is preferably 1% by volume or less, more preferably 0.6% by volume. % or less, particularly preferably 0.4% by volume or less. When the oxygen contained in the reaction system is less than 2% by volume, a high-purity perfluorocarbon which is substantially free of an oxygen-containing compound can be obtained. Further, when the oxygen contained in the fluorine gas is less than 1% by volume, a high-purity perfluorocarbon which is substantially free of an oxygen-containing compound can be obtained. When the oxygen contained in the reaction system is more than 2% by volume, an influential oxygen-containing compound is formed. The method of controlling the oxygen content in the reaction system and the fluorine gas in the above range by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs is to prevent the oxygen from being externally mixed into the reaction vessel and to react in a closed system. Oxygen is removed from the reaction raw materials such as fluorine gas or diluent gas. Further, when a part of the gas after the reaction is circulated as a diluent gas, it is preferable to reduce the possibility of oxygen being mixed from the outside. The method of removing the oxygen contained in the organic compound, the fluorine gas, and the diluent gas may be a known method. For example, the reaction raw material may be distilled or adsorbed by an adsorbent such as activated carbon to separate impurities in the raw material. When the organic compound is exposed to fluorine gas in the presence of a diluent gas, the reaction substrate may be diluted with a diluent gas before the organic compound or fluorine gas is charged into the reaction vessel. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X297 mm). 12- 1320035 A 7 B7 V. INSTRUCTIONS (iih (organic compound), fluorine gas, either or both. It is better to dilute with a diluent gas before charging the fluorine gas. (Please read the precautions on the back and fill in In this case, the total amount of fluorine gas in the reaction system to be introduced into the reaction system is preferably 9% by volume or less, more preferably 8% by volume or less. Preferably, the reaction is carried out continuously into the reaction system. The amount of fluorine gas is kept below this range. Further, the gas component in the reaction system means fluorine gas, organic compound, and diluent gas in the reaction system. As described above, the direct fluorination method for producing perfluorocarbons using fluorine gas The use of highly reactive fluorine gas, there is a high concentration of organic compounds for the matrix, especially hydrogen-containing compounds exposed to fluorine gas, resulting in burning or explosion hazard. Therefore, when the concentration of the fluorine gas in the inlet of the reaction vessel is 9% by volume or less, the mixed gas concentration can be out of the explosion range, and the industrially safe fluorine gas and the organic compound are reacted. In the present invention, the organic compound is exposed to fluorine. The gas reaction temperature is 200 to 500 ° C, and it is preferably 300 to 450 ° C. When the printing reaction temperature of the Intellectual Property Bureau of the Intellectual Property Bureau of the Ministry of Economic Affairs is within the above range, the oxygenates generated from oxygen can be significantly reduced. When the reaction temperature exceeds 500 ° C, even if the oxygen (concentration) in the reaction system is controlled to 2% by volume or less, or the oxygen concentration in the fluorine gas is controlled to 1% by volume or less, an influential effect is generated. Oxygen-containing compound. Therefore, in the present invention, it is preferred to control the reaction temperature to the above range. Further, in addition to the reaction zone in the reaction vessel, the reaction temperature is controlled by the presence of an organic compound or a fluorine gas, for example, a thermoelectric equivalent. The method is preferably controlled to a temperature not exceeding 500 ° C. The present invention can significantly inhibit the incorporation of oxygen compounds, but the organic compound paper ruler Applicable Chinese National Standard (CNS) A4 size (210X297 mm> -13- 1320035 A7 B7
五、發明説明（A (請先閱讀背面之注意事項再填寫本頁) 接觸氟氣後，所得精製前之粗全氟化碳類所含的微量含氧 化合物，或所含氮、一氧化碳、二氧化碳等不純物較佳爲 ’利用活性碳等進行吸附去除步驟。 所使用之活性碳可爲已知活性碳，其中又以椰子殻碳 爲佳。又，可以液相、氣相進行吸附去除步驟，更佳爲液 相。 〔全氟化碳類〕 上述所得之全氟化碳類中所含的含氧化合物總量，對 精製前之粗全氟化碳類而言較佳爲5體積p pm以下，更 佳爲2體積p pm以下，特佳爲1體積p pm以下。利用 本發明之製造方法可於無需蒸餾、吸附等精製步驟下，得 到明顯減少含氧化合物含量之高純度全氟化碳類。 又’利用上述精製步驟可使含量較佳爲1體積P Pm 以下，更佳爲0.5體積ppm以下，特佳爲0.4 p pm以下，利用本發明之製造方法可極簡便地製得更進 一步減少含氧化合物含量之高純度全氟化碳類。 經濟部智慧財產局員工消費合作社印製 所使用之含氧化合物檢驗（分析）方法如，氣相色譜 (GC)之TCD法、F ID法及D ID法，又，可利用 氣相色譜質量分析計（GC- MS)等分析方法進行。 〔含全氟化碳類氣體及其用途〕 本發明之製造方法所製得的全氟化碳類因能充分減少 含氧化合物等不純物，故常溫下氣體狀化合物適用爲半導 本纸張尺度適用中國國家標準（CNS)A4規格（210X297公釐） -14- 1320035 A7 __B7_ 五、發明説明（1灸 體裝置製造步驟中’鈾刻步驟用之蝕刻氣體。又，常溫下 液體狀化合物可使用於冷卻溶劑等廣泛用途。 (請先閲讀背面之注意事項再填寫本頁) 具體而言即，適用爲LSI或TFT等半導體裝置之 製造過程中，利用CVD法、濺射法或蒸鍍法等形成薄膜 或厚膜後，回路圖型形成用之蝕刻氣體。 又’適用爲半導體裝置製造過程中，淸潔步驟用之淸 潔氣體。 以上述本發明所得之全氟化碳類作爲鈾刻氣體時，較 佳爲使用四氟甲烷，又，作爲淸潔氣體時，較佳爲使用六 氟乙烷或八氟丙烷。 具體而言即，對形成薄膜或厚膜之裝置進行去除裝置 內壁、夾具等所堆積之不要堆積物用的淸潔步驟》所生成 之不要堆積物係產生微片之原因，因此，爲了製造良質膜 需隨時去除，而本發明之全氟化碳類適用爲該淸潔氣體。 經濟部智慧財產局員工消費合作社印製 本發明含有高純度全氟化碳類之氣體爲，常溫下含有 上述全氟化碳類之氣體。又，該含有全氟化碳類之氣體可 單獨含有全氟化碳類，或另含適當之其他氣體。該其他氣 體如，H e、N e、A r等不活性氣體。又，該其他氣體 之含量並無特別限制，例如以本發明之高純度全氟化碳類 作爲蝕刻氣體或淸潔氣體時，會因蝕刻對象之化合物種類 、厚度等而異，又，可對應淸潔對象之附著量、厚度等而 作決定。 發明效果 本紙張尺度適用中國國家標隼（CNS) A4規格（210X 297公釐） -15- 1320035 A7 B7 五、發明説明（1¾ (請先閱讀背面之注意事項.再填寫本頁) 利用本發明之全氣化碳類製造方法可將反應系所含氧 氣含量控制於特定量以下，因此可得明顯抑制含氧化合物 等不純物生成之高純度全氟化碳類。又，本發明製造方法 所製得之全氟化碳類實質不含含氧化合物，因此適用爲半 導體裝置製造過程用等之蝕刻氣體或淸潔氣體。 實施例 下面將以實施例說明本發明，但非限於此例。 調製例1 存在氟化觸媒下，以氣相將氯仿（CHC 1 3)接觸氟 化氫（H F )，以進行氟化反應。其後利用已知之蒸餾法 精製，得粗三氟甲烷（CHF3)。對所得粗三氟甲烷進行 氣相色譜分析，得下列組成。 CHFj 97.2667 其他有機不純物 0.1126 經濟部智慧財產局員工消費合作社印製 氧氣 1.2081 氮氣 1.4126 單位：體積％ 又，其他不純物包含CHC 1 F2、CC 1 1^3等。 結果如表1所示。 調製例2 本紙張尺度適用中國國家標隼（CNS) A4規格（210X297公釐） -16 - 1320035 A7 B7 五、發明説明（ 對調製例1所得粗三氟甲烷重覆進行蒸餾後，對所得 三氟甲烷進行氣相色譜分析，得下列組成。 單位：體積％ (請先閲讀背面之注意事項再填寫本頁) CHF3 99.8288 其他有機不純物 0.0208 氧氣 0.0720 氮氣 0.0784 結果如表1所示。 調製例3 存在氟化觸媒下，以氣相將三氯化乙烯接觸氟化氫， 以進行氟化反應。其後利用已知之蒸餾法精製，得粗四氟 乙烷（CF3CH2F)。對所得粗四氟乙烷進行氣相色譜 分析，得下列組成。 經濟部智慧財產局員工消費合作社印製 CF3CH2F 其他有機不純物 氧氣 氮氣 97.0359 0.5124 1.3314 1.1203 單位：體積％ 又，其他不純物包含CF3CH3、CF3CHF C H F 2 C H F 2 等。 結果如表1所示。 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17- 1320035 A7 B7 五、發明説明（1客 調製例4 (請先閲讀背面之注意事項再填寫本頁) 對調製例3所得之粗四氟乙烷重覆進行蒸餾後，對所 得四氟乙烷進行氣相色譜分析，得下列組成。 CF3CH2F 99.9018 其他有機不純物 0.0088 氧氣 0.0402 氮氣 0.0492 單位：體積％ 結果如表1所示。 調製例'5 利用氟化氫之電解法製造氟氣。其後利用s U S汽缸 (經內面不動態化處理）進行取樣，去除氟後進行氣相色 譜分析，結果氟氣中氧氣濃度値如下所示。 經濟部智慧財產局員工消費合作社印製 氧氣 1.3825 單位：體積％ 其他係以氟爲主成分，另包含氮氣、氟化氫等。 調製例6 對原料例5進行精製（冷卻操作等）後，同原料5進 行分析，結果氟氣中氧氣濃度値如下所示。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18- 1320035 A7 B7 五、發明説明（ιέ 氧氣 0.3020 單位：體積％ 結果如表1所示。 (請先閱讀背面之注意事項再填寫本頁) 實施例1 將氮氣以30NL/hr流速供應內徑20.6 、長5 0 Omm之鎳鉻鐵合金6 0 0製反應器（電 熱器加熱方式，以氟氣及6 0 0 °C溫度對反應器進行不動 態化處理），同時升溫至42CKC後，以5 0NL/hr 流速供給氟化氫，再將該氮及氟化氫所形成之稀釋氣體流 動至支化氣流之一方，並以3.6NL/hr流速供給調 製例2所得之三氟甲烷。 接著將同上述之氮及氟化氫所形成的稀釋氣體流動主 支化氣流之另一方，並以3 . 9NL/h r流速供給調製 例6所得之氟氣以進行反應。 3小時後，利用氫氧化鉀水溶液及碘化鉀水溶液去除 反應出口氣體中的氟化氫及未反應氟氣，再進行氣相色譜 分析。結果去除氧及氮成分之有機物組成如下所示。 98.7992 經濟部智慧財產局員工消費合作社印製 CF^ CF3CF3 0.4808 其他 0.7200 單位：體積％ 該「其他」係指C3F8、CC1 F3等，又，含氧化 合物之C F3〇C F3及C F3〇OCF3的總量爲2體積 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） -19- 1320035 A7 B7 五、發明説明（合 p p m以下。 其後將利用氫氧化鉀水溶液及碘化鉀水溶液去除反應 出口氣體中氟化氫及未反應氟氣而得之氣體通過脫水劑， 冷卻的同時利用S U S汽缸收集，再以已知之蒸餾法蒸餾 精製，得四氟甲烷。利用氣相色譜及氣相色譜質量分析計 等進行有機物組成分析，結果如下所示。 CF3OCF3 CFjOOCFj 其他 CF. <0.2 體積 ρ p m <0.2 體積 p p m <2.0 體積 p p m >99.9997 體積 ％ (請先閲讀背面之注意事項再填寫本頁) 含氧化合物對總量爲0 結果如表2所不。 5體積p pm以下 經濟部智慧財產局員工消費合作社印製 實施例2 使用同實施例1之反應器，以3 0 N L / h r流速供 給氮氣的同時升溫至3 7 0°C，並以5 ONL/h r流速 供給氟化氫，其後將該氮及氟化氫所形成之稀釋氣體流動 至支化氣流之一方，並以3.9NL/hr流速供給調製 例6所得之氟氣以進行反應。 3小時後，利用氫氧化鉀水溶液及碘化鉀水溶液去除 反應出口氣體中氟化氫及未反應氟氣，再進行氣相色譜分 析。去除氧及氮成分之有機物組成分析結果如下所示。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -20- 1320035 A7 B7 五、發明説明（1¾ CF3CF3 98.4875 CF3CHF2 0.0025 CF4 0.7280 其他 0.7820 單位：體積％ 該「其他」係C3F 8爲主成分，又，含氧化合物之 CF3CF2OCF3、CF3OCF3 及 CF3OOCF3 的 總量爲1體積ppm以下。 其後將利用氫氧化鉀水溶液及碘化鉀水溶液去除反應 出口氣體中氟化氫及未反應氟氣而得之氣體通過脫水劑， 冷卻的同時利用S U S汽缸收集，再以已知之蒸餾法蒸餾 精製，得六氟乙烷（CF3CF3)。利用氣相色譜及氣相 色譜質量分析計等所得之有機物組成分析結果如下所示。 (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 CF3OCF3 <0.2 體積 p p m CF3OOCF3 <0.1 體積 p p m CF3CF2〇CF3 <0.1 體積 P P m 其他 <2.0 體積 p p m CFjCFj >99.9997 體積 ％ 結果如表2所示。 比較例1 使用同實施例1之反應器，以3 0 NL/h r供給氮 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -21- 1320035 A7 _B7_ 五、發明説明（ (請先閱讀背面之注意事項再填寫本頁) 氣的同時升溫至4 5 0°C，再以5 〇NL/h r供給氟化 氫，其後將該氮氣及氟化氫所形成之稀釋氣體流動至支化 氣流之一方，再以3 · 6NL/hr流速供給調製例1所 示以三氟甲烷爲主成分的氣體。接著將相同之稀釋氣體流 動至支化氣流之另一方，並以3.9NL/hr流速供給 調製例5所得之氟氣以進行反應。 3小時後，利用氫氧化鉀水溶液及碘化鉀水溶液去除 反應出口氣體中氟化氫及未反應氟氣，再進行氣相色譜分 析，去除氧及氮之有機物組成分析結果如下所示。 CF. 98.3618 cf3cf3 0.4988 其他 1.1123 CFsOCFs 0.0146( 146ppm) CF3OOCF3 0.01 25( 1 25ppm)單位：體積 ％ 經濟部智慧財產局員工消費合作社印製 原料中氧含量（濃度）之總量爲2%以上，故生成有 作爲量之含氧化合物不純物。 結果如表2所不。 比較例2 使用同實施例1之反應容器，以3 0 NL/h r流速供 給氟氣的同時升溫至4 3 Ot，再以5 ONL/h r流速 供給氟化氫，其後將該氮氣及氟化氫所形成之稀釋氣體流 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -22 - 1320035 A7 B7 五、發明説明（2ί) (請先閱讀背面之注意事項再填寫本頁) 動至支化氣流之一方，並以1 .8NL/hr流速供給以 調製例3所得之四氟乙烷爲主成分的氣體。其後將相同之 稀釋氣體流動至支化氣流之另一方，並以3 . 9 NL/hr流 速供給調製例5所得之氟氣以進行反應。 3小時後，利用氫氧化鉀水溶液及碘化鉀水溶液去除 反應出口氣體中氟化氫及未反應氟氣，再進行氣相色譜分 析，去除氧及氮成分之有機物組成分析結果如下所示β CF3CF3 97.1841 CF. 0.8920 其他 1.8920 CF3〇CF3 0.0133(133ppm) CF300CF3 0.0088(88ppm) CF3CF20CF3 0.0098(98ppm)單位：體積 ％ 經濟部智慧財產局員工消費合作社印製 其後將利用氫氧化鉀水溶液及碘化鉀水溶液去除反應 出口氣體中氟化氫及未反應氟氣之氣體通去脫水劑，冷卻 的同時利用S U S汽缸收集，再以已知之蒸餾法蒸餾精製 ’得六氟乙烷。利用氣相色譜及氣相色譜質量分析計等而 得之有機物組成分析結果如下所示。 CF3CF3 >99.9866 體積 ％ cf4 <0.4 體積 p p m 其他 <2.0 體積 ppm 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -23 - 1320035 A7 B7 五、發明説明（ CF3〇cf3 CF300CF3 CF3CF20CF3 2) 128體積p p 1體積P P m 1體積P P m C F3〇 C F3與目的物之六氟乙烷形成共沸混合物， 故不易分離。 結果如表2所示。 比較例3 除了同實施例1之反應器下，將反應溫度改爲5 2 0 °C外，其他同實施例1之條件及方法，進行氣相色譜分析 後，去除氧及氮成分之有機物組成分析結果如表2所示。 CF^ CFjCFj 其他 CF3〇CF3 CF300CF: 95.3548 1.6872 2.8945 0.0367 0.0268 單位：體積％ (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 結果如表2所示 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） -24- 1320035V. Description of the invention (A (please read the precautions on the back and fill in this page). After exposure to fluorine gas, the trace amount of oxygenated compounds contained in the crude perfluorocarbon before purification, or nitrogen, carbon monoxide and carbon dioxide. Preferably, the impurity is an adsorption removal step using activated carbon or the like. The activated carbon used may be a known activated carbon, wherein coconut shell carbon is preferred. Further, the adsorption removal step may be carried out in a liquid phase or a gas phase. Preferably, it is a liquid phase. [Perfluorocarbons] The total amount of oxygen-containing compounds contained in the perfluorocarbons obtained above is preferably 5 vol or less for the crude perfluorocarbon before purification. More preferably, it is 2 volume p pm or less, particularly preferably 1 volume p pm or less. By using the production method of the invention, high purity perfluorocarbon which can significantly reduce the oxygen content can be obtained without purification steps such as distillation or adsorption. Further, the content of the above-mentioned purification step can be preferably 1 volume P Pm or less, more preferably 0.5 volume ppm or less, and particularly preferably 0.4 p pm or less, and the production method of the present invention can be extremely easily produced. Reduce oxygen High-purity perfluorocarbons of the content of the compound. The oxygenate test (analysis) method used by the Ministry of Economic Affairs, Intellectual Property Office, and the Consumer Cooperatives, such as TCD, FID, and D for gas chromatography (GC). The ID method can be carried out by an analytical method such as a gas chromatography mass spectrometer (GC-MS). [Perfluorocarbon-containing gas and use thereof] The perfluorocarbon-based factor produced by the production method of the present invention It can fully reduce impurities such as oxygen compounds, so the gas-like compound at room temperature is suitable for semi-conductive paper scale. Applicable to China National Standard (CNS) A4 specification (210X297 mm) -14- 1320035 A7 __B7_ V. Invention description (1 moxibustion In the manufacturing process of the device, the etching gas used in the uranium engraving step. Further, the liquid compound at normal temperature can be used for a wide range of applications such as cooling solvents. (Please read the back note and then fill out this page.) Specifically, it is applicable. In the manufacturing process of a semiconductor device such as an LSI or a TFT, a thin film or a thick film is formed by a CVD method, a sputtering method, a vapor deposition method, or the like, and an etching gas for forming a circuit pattern is formed. In the process, the cleaning gas used in the cleaning step. When the perfluorocarbon obtained by the above invention is used as the uranium engraving gas, tetrafluoromethane is preferably used, and when it is used as the cleaning gas, it is preferably used. Specifically, the apparatus for forming a film or a thick film is formed by a cleaning step for removing a deposit of an inner wall of a device, a jig, or the like, and a non-stacking system generated by a cleaning step. For the reason of the film, therefore, in order to manufacture a good quality film, it is necessary to remove it at any time, and the perfluorocarbon of the present invention is suitable for the cleaning gas. The Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative, printed the present invention, which contains high-purity perfluorocarbons. The gas is a gas containing the above perfluorocarbon at normal temperature, and the perfluorocarbon-containing gas may contain a perfluorocarbon alone or another suitable gas. The other gas is an inert gas such as He, N e or Ar. In addition, the content of the other gas is not particularly limited. For example, when the high-purity perfluorocarbon of the present invention is used as an etching gas or a cleaning gas, it may be different depending on the type and thickness of the compound to be etched, and The amount of adhesion, thickness, etc. of the object to be cleaned is determined. Effect of the invention The paper scale is applicable to China National Standard (CNS) A4 specification (210X 297 mm) -15- 1320035 A7 B7 V. Invention description (13⁄4 (please read the note on the back. Fill in this page first). The method for producing a fully vaporized carbon can control the oxygen content of the reaction system to a specific amount or less, thereby obtaining a high-purity perfluorocarbon which significantly suppresses the formation of impurities such as an oxygen-containing compound. The perfluorocarbons are substantially free of oxygen-containing compounds, and are therefore suitable for etching gases or cleaning gases for semiconductor device manufacturing processes, etc. EXAMPLES Hereinafter, the present invention will be described by way of examples, but is not limited thereto. 1 In the presence of a fluorination catalyst, chloroform (CHC 13 ) is contacted with hydrogen fluoride (HF) in a gas phase for fluorination reaction, and then purified by a known distillation method to obtain crude trifluoromethane (CHF3). The crude trifluoromethane was analyzed by gas chromatography to obtain the following composition: CHFj 97.2667 Other organic impurities 0.1126 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed oxygen 1.2081 Nitrogen 1.4126 Single : % by volume, other impurities include CHC 1 F2, CC 1 1^3, etc. The results are shown in Table 1. Preparation Example 2 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -16 - 1320035 A7 B7 V. DESCRIPTION OF THE INVENTION (The crude trifluoromethane obtained in Preparation Example 1 was repeatedly subjected to distillation, and the obtained trifluoromethane was subjected to gas chromatography analysis to obtain the following composition. Unit: % by volume (Please read the back sheet first. Fill in this page again) CHF3 99.8288 Other organic impurities 0.0208 Oxygen 0.0720 Nitrogen 0.0784 The results are shown in Table 1. Preparation Example 3 In the presence of a fluorination catalyst, ethylene trichloride is contacted with hydrogen fluoride in a gas phase for fluorination. After purification by a known distillation method, crude tetrafluoroethane (CF3CH2F) is obtained. Gas chromatography analysis of the obtained crude tetrafluoroethane gives the following composition. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed CF3CH2F other organic impurities oxygen Nitrogen 97.0359 0.5124 1.3314 1.1203 Unit: vol% Further, other impurities include CF3CH3, CF3CHF CHF 2 CHF 2 , etc. The results are shown in Table 1. Applicable to China National Standard (CNS) A4 Specification (210X297 mm) -17- 1320035 A7 B7 V. Invention Description (1 guest modulation example 4 (please read the back note first and then fill in this page) After the crude tetrafluoroethane was repeatedly subjected to distillation, gas chromatography analysis of the obtained tetrafluoroethane gave the following composition: CF3CH2F 99.9018 Other organic impurities: 0.0088 Oxygen 0.0402 Nitrogen 0.0492 Unit: % by volume The results are shown in Table 1. Modification Example '5 A fluorine gas was produced by an electrolysis method of hydrogen fluoride. Thereafter, the s U S cylinder (not oscillating through the inner surface) was used for sampling, and the fluorine gas was removed for gas phase chromatography analysis. As a result, the oxygen concentration in the fluorine gas was as follows. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed oxygen 1.3825 Unit: vol% Others are mainly fluorine, and also contain nitrogen, hydrogen fluoride and so on. Preparation Example 6 After the raw material example 5 was purified (cooling operation, etc.), it was analyzed with the raw material 5, and as a result, the oxygen concentration 氟 in the fluorine gas was as follows. This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -18- 1320035 A7 B7 V. Invention Description (ιέ Oxygen 0.3020 Unit: vol% The results are shown in Table 1. (Please read the notes on the back first) Fill in this page again. Example 1 Nitrogen ferrochrome 60 0 reactor with an inner diameter of 20.6 and a length of 50 °m was supplied at a flow rate of 30 NL/hr (heater heating method, fluorine gas and temperature of 600 °C) The reactor was not kinetically treated. After heating to 42 CKC, hydrogen fluoride was supplied at a flow rate of 50 NL/hr, and the diluent gas formed by the nitrogen and hydrogen fluoride was flowed to one of the branched gas streams at 3.6 NL/hr. The flow rate was supplied to the trifluoromethane obtained in Preparation Example 2. Then, the diluent gas formed by the above nitrogen and hydrogen fluoride was flowed to the other of the main branched gas streams, and the fluorine gas obtained in Preparation Example 6 was supplied at a flow rate of 3.9 NL/hr. After 3 hours, the hydrogen fluoride and the unreacted fluorine gas in the reaction outlet gas were removed by an aqueous potassium hydroxide solution and a potassium iodide aqueous solution, and then analyzed by gas chromatography. As a result, the organic group of oxygen and nitrogen components was removed. 98.7992 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed CF^CF3CF3 0.4808 Other 0.7200 Unit: vol% The "Other" means C3F8, CC1 F3, etc., and C F3 〇C F3 and C of Oxygenated Compounds The total amount of F3〇OCF3 is 2 volumes. The paper size is applicable to China National Standard (CNS) A4 specification (2丨0X297 mm) -19- 1320035 A7 B7 V. Description of invention (in ppm or less. Potassium hydroxide will be used thereafter) The aqueous solution and the potassium iodide aqueous solution remove the hydrogen fluoride and the unreacted fluorine gas in the reaction outlet gas, and the gas obtained is passed through a dehydrating agent, and is collected by a SUS cylinder while being cooled, and then distilled and purified by a known distillation method to obtain tetrafluoromethane. The composition of the organic matter was analyzed by a gas chromatograph mass spectrometer, and the results are shown below. CF3OCF3 CFjOOCFj Other CF. <0.2 Volume ρ pm < 0.2 vol. < 2.0 vol. > 99.9997 vol% (Please read the back of the note first) Please fill in this page again) The total amount of oxygenated compounds is 0. The results are shown in Table 2. 5 volume p pm below Ministry of Economic Affairs Intellectual Property Bureau employee consumption Co-Printing Example 2 Using the reactor of the same example, the temperature was raised to 370 ° C while supplying nitrogen gas at a flow rate of 30 NL / hr, and hydrogen fluoride was supplied at a flow rate of 5 ONL/hr, after which the nitrogen was supplied. The diluent gas formed by the hydrogen fluoride was flowed to one of the branched gas streams, and the fluorine gas obtained in Preparation Example 6 was supplied at a flow rate of 3.9 NL/hr to carry out the reaction. After 3 hours, hydrogen fluoride and unreacted fluorine gas in the reaction outlet gas were removed by using an aqueous potassium hydroxide solution and a potassium iodide aqueous solution, followed by gas chromatography. The analysis results of the organic composition of the oxygen and nitrogen components were as follows. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) -20- 1320035 A7 B7 V. Invention description (13⁄4 CF3CF3 98.4875 CF3CHF2 0.0025 CF4 0.7280 Other 0.7820 Unit: vol% The "Other" is mainly C3F 8 Further, the total amount of the CF3CF2OCF3, CF3OCF3, and CF3OOCF3 of the oxygen-containing compound is 1 ppm by volume or less. Thereafter, the potassium hydroxide aqueous solution and the potassium iodide aqueous solution are used to remove the hydrogen fluoride and the unreacted fluorine gas in the reaction outlet gas to pass the dehydration. The agent was collected by a SUS cylinder while being cooled, and then distilled and purified by a known distillation method to obtain hexafluoroethane (CF3CF3). The results of analysis of the composition of the organic matter obtained by gas chromatography and gas chromatography mass spectrometry are shown below. (Please read the note on the back and fill out this page.) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Print CF3OCF3 <0.2 Volume ppm CF3OOCF3 <0.1 Volume ppm CF3CF2〇CF3 <0.1 Volume PP m Other <2.0 Volume ppm CFjCFj > 99.9997 vol% The results are shown in Table 2. Comparative Example 1 Using the same as in Example 1 Reactor, supplied with nitrogen at 30 NL/hr. Standard for Chinese paper (CNS) A4 size (210X297 mm) -21- 1320035 A7 _B7_ V. Invention description (Please read the notes on the back and fill in the form) Page) The gas is simultaneously heated to 405 ° C, and then hydrogen fluoride is supplied at 5 〇 NL / hr, after which the dilution gas formed by the nitrogen gas and hydrogen fluoride is flowed to one of the branched gas streams, and then 3 · 6 NL / hr The flow rate was supplied to a gas containing trifluoromethane as a main component as shown in Preparation Example 1. Then, the same diluent gas was flowed to the other of the branched gas streams, and the fluorine gas obtained in Preparation Example 5 was supplied at a flow rate of 3.9 NL/hr to carry out a reaction. After 3 hours, the potassium hydroxide aqueous solution and the potassium iodide aqueous solution were used to remove hydrogen fluoride and unreacted fluorine gas in the reaction outlet gas, and then analyzed by gas chromatography to remove oxygen and nitrogen. The composition analysis results are as follows: CF. 98.3618 cf3cf3 0.4988 Others 1.1123 CFsOCFs 0.0146 ( 146ppm) CF3OOCF3 0.01 25 ( 1 25ppm) Unit: vol % The total amount of oxygen (concentration) in the printed materials of the Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Association When it is 2% or more, an oxygen-containing compound impurity is produced as a quantity. The results are shown in Table 2. Comparative Example 2 Using the reaction vessel of the same example as in Example 1, the fluorine gas was supplied at a flow rate of 30 NL/hr while raising the temperature to 4 3 Ot, and hydrogen fluoride was supplied at a flow rate of 5 ONL/hr, and thereafter the nitrogen gas and hydrogen fluoride were formed. Diluted gas flow paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -22 - 1320035 A7 B7 V. Invention description (2ί) (Please read the note on the back and fill in this page) Move to branch One of the gas streams was supplied, and a gas containing the tetrafluoroethane obtained in Example 3 as a main component was supplied at a flow rate of 1.8 NL/hr. Thereafter, the same dilution gas was flowed to the other side of the branched gas stream, and the fluorine gas obtained in Preparation Example 5 was supplied at a flow rate of 3.9 NL/hr to carry out the reaction. After 3 hours, the potassium hydroxide aqueous solution and the potassium iodide aqueous solution were used to remove hydrogen fluoride and unreacted fluorine gas in the reaction outlet gas, and then analyzed by gas chromatography to remove the oxygen and nitrogen components. The composition analysis results are as follows: β CF3CF3 97.1841 CF. 0.8920 Others 1.8920 CF3〇CF3 0.0133 (133ppm) CF300CF3 0.0088(88ppm) CF3CF20CF3 0.0098(98ppm) Unit: vol% The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, will use the potassium hydroxide aqueous solution and the potassium iodide aqueous solution to remove hydrogen fluoride from the reaction outlet gas. The unreacted fluorine gas is passed through a dehydrating agent, and is collected by a SUS cylinder while being cooled, and then distilled to obtain hexafluoroethane by a known distillation method. The results of analysis of the composition of the organic matter obtained by gas chromatography, gas chromatography mass spectrometry, etc. are shown below. CF3CF3 >99.9866 vol% cf4 <0.4 vol. ppm Other <2.0 vol. ppm This paper scale applies to Chinese National Standard (CNS) Α4 Specification (210X297 mm) -23 - 1320035 A7 B7 V. Invention Description (CF3〇cf3 CF300CF3 CF3CF20CF3 2) 128 volume pp 1 volume PP m 1 volume PP m C F3〇C F3 forms an azeotrope with the hexafluoroethane of the target, so it is not easy to separate. The results are shown in Table 2. Comparative Example 3 In the same manner as in the reactor of Example 1, except that the reaction temperature was changed to 520 ° C, the conditions and methods of Example 1 were analyzed by gas chromatography to remove the organic components of oxygen and nitrogen components. The results of the analysis are shown in Table 2. CF^ CFjCFj Other CF3〇CF3 CF300CF: 95.3548 1.6872 2.8945 0.0367 0.0268 Unit: vol% (please read the notes on the back and fill out this page) The printed results of the Ministry of Economic Affairs Intellectual Property Office employees' cooperatives are shown in Table 2. Applicable to China National Standard (CNS) A4 specification (2丨0X297 mm) -24- 1320035
7 B 五、發明説明（2灸 經濟部智慧財產局員工消費合作社印製 表1 生成物 氧氣含量 (體積％ ) 調製例1 三氟甲烷 1.2081 調製例2 三氟甲烷 0.0720 調製例3 四氟乙烷 1.3314 調製例4 四氟乙烷 0.0402 調製例5 F 2 1.3825 調製例6 F 2 0.3020 表2 反應原料 反應 溫度 (°C ) 反應原料 中氧氣合 計濃度 (體積％) 全氟化碳類 中含氧化合 物濃度 (體積ppm) 精製後含 氧化合物 濃度 (體積ppm) 實施例1 調製例2 調製例6 420 0.3740 2以下 0.5以下 實施例2 調製例4 調製例6 370 0.3422 1以下 0.4以下 比較例1 調製例1 調製例5 450 2.5906 271 比較例2 調製例3 調製例5 430 2.7139 319 130 比較例3 調製例2 調製例6 520 0.3740 635 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -25- I32003S件：第91103190號專利申請案 中文說明書修正頁 申請曰期 91 年 2目22日 案 號 91103190 類 別 C/0^1 G ^/σο 以上各櫊由本局填註）7 B V. Description of Invention (2 Moxibustion Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Table 1 Product Oxygen Content (% by volume) Preparation Example 1 Trifluoromethane 1.2081 Preparation Example 2 Trifluoromethane 0.0720 Preparation Example 3 Tetrafluoroethane 1.3314 Preparation Example 4 Tetrafluoroethane 0.0402 Preparation Example 5 F 2 1.3825 Preparation Example 6 F 2 0.3020 Table 2 Reaction raw material reaction temperature (°C) Total concentration of oxygen in the reaction raw material (% by volume) Oxygenated compound in the perfluorocarbon type Concentration (ppm by volume) Oxygenate concentration after purification (volume ppm) Example 1 Preparation Example 2 Preparation Example 6 420 0.3740 2 or less 0.5 or less Example 2 Preparation Example 4 Preparation Example 6 370 0.3422 1 or less 0.4 or less Comparative Example 1 Preparation Example 1 Modulation Example 5 450 2.5906 271 Comparative Example 2 Modulation Example 3 Modulation Example 5 430 2.7139 319 130 Comparative Example 3 Modulation Example 2 Modulation Example 6 520 0.3740 635 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back and fill out this page) -25- I32003S: Patent Application No. 91103190, Revision of the Chinese Manual, Application for the Period, 91 Years, 2nd, 22nd Case No. 91103190 Category C/0^1 G ^/σο The above are filled in by this Council)
民國户牟3均 ||專利説明書 中 文 全氟化硪類之製造方法及其用途 發明 新型‘ 英 文民 牟 均 | | | | | | | | | | | | | | | | | | | | | | | | 全 全
Process for Producing Perfluorocarbons and Use-THereof 姓 名 ⑴大野博基 (2)大井敏夫 國 籍 (1)日本國神奈川縣川崎市川崎區扇町五之一 限公司内 昭和霜工股份有 發明 創作, 住、居所 (2)日本國神奈川縣川崎市川崎區扇町五之一 限公司内 昭和電工股份有 經濟部智祛对產馬員工消費合竹社印製 填請委員明示：不案修正後是否變更原實質内容 申請人 姓 名 (名稱） 國 籍 住、居所 (事務所） 代表人 姓 名 (1)昭和電工股份有限公司 昭和電工株式会社 (1)曰本 (1)日本國東京都港區芝大門一丁目一三番九號 1)大橋光夫 本纸張尺度適用中國國家標準（CNS ) A4規格（210X29·?公褒） 1320035 ο. 0 8 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（5 ) 本發明之全氟化碳類製造方法的特徵爲，使用有機化 合物與氟氣所形成之反應原料製造全氟化碳類時，係於 2 ◦ 0至5 0 0 °C下使有機化合物接觸氟氣，且使反應系 內氧氣對反應原料中氣體成份之含量爲2體積％以下，而 得降低不純物含量之全氟化碳類。 又以存在稀釋氣體下，將有機化合物接觸氟氣爲佳。 上述有機化合物較佳爲，碳原子數6以下之脂肪族飽 和化合物及/或碳原子數6以下之脂肪族不飽和化合物。 有機化合物更佳爲，碳原子數6以下之脂肪族飽和化 合物，又該有機化合物較佳爲氫氟化碳，特佳爲氟甲烷、 二氟甲烷、三氟甲烷、三氟乙烷、四氟乙烷、五氟乙烷' 五氟丙烷、六氟丙烷及七氟丙烷中所選出至少一種。 氣相中存在稀釋氣體下，以無觸媒方式使有機化合物 接觸氟氣之全氟化碳類製造方法中，有機化合物接觸氟氣 前’氟氣所含之氧氣對氟氣的含量較佳爲1體積％以下， 此時有機化合物較佳爲，碳原子數4以下之氫氧化碳，更 佳’爲二氟甲烷、三氟甲烷、三氟乙烷、四氟乙烷、五氟 乙烷、六氟丙烷及七氟丙烷中所選出至少1種。 導入反應系內之氟氣量對反應系內氣體成分合計量較 佳爲9體積％以下。 稀釋氣體較佳爲，四氟甲烷、六氟乙烷 '八氟丙烷及 氟化氫中所選出至少1種。 稀釋氣體含有氟化氫時，氟化氫對稀釋氣體全量之含 量較佳爲50體積％以上。 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X 297公釐） " ^ -8- (請先聞讀背面之注意事¥ •裝-- π寫本頁) 訂 kProcess for Producing Perfluorocarbons and Use-THereof Name (1) Ohno Boki (2) Osumi Minami Nationality (1) Nakagawa, Kawasaki-shi, Kawasaki-shi, Kawasaki-shi, Japan, one of the company's inventions, living and living (2) In the case of the Japanese company, the Kawasaki City, Kawasaki City, Kawasaki City, Japan, the company, the company, the Ministry of Economic Affairs, the Ministry of Economic Affairs, the Ministry of Economic Affairs, the Ministry of Health, the production of the employees, and the printing of the members of the company. (Name) Nationality residence, residence (office) Name of representative (1) Showa Denko Co., Ltd. Showa Denko Co., Ltd. (1) Sakamoto (1) No. 1 and 3, No.1, Chiba, Minato-ku, Minato-ku, Tokyo, Japan 1) Bridge Guangfu Paper Size Applicable to China National Standard (CNS) A4 Specification (210X29·?) 1320035 ο. 0 8 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printing 5, Invention Description (5) The whole of the present invention The method for producing a fluorinated carbon is characterized in that, when a perfluorocarbon is produced by using a reaction material formed of an organic compound and fluorine gas, it is at 2 ◦ 0 to 500 ° C. Organic compound contacting fluorine gas, and the inner oxygen content in the reaction system of the reaction feed gas component is 2% or less by volume, while reducing perfluorocarbons have content of impurities. Further, it is preferred to contact the organic compound with fluorine gas in the presence of a diluent gas. The above organic compound is preferably an aliphatic saturated compound having 6 or less carbon atoms and/or an aliphatic unsaturated compound having 6 or less carbon atoms. The organic compound is more preferably an aliphatic saturated compound having 6 or less carbon atoms, and the organic compound is preferably hydrofluorocarbon, particularly preferably fluoromethane, difluoromethane, trifluoromethane, trifluoroethane or tetrafluorocarbon. At least one selected from the group consisting of ethane, pentafluoroethane, pentafluoropropane, hexafluoropropane and heptafluoropropane. In the method for producing a perfluorocarbon in which a gaseous compound is exposed to a fluorine gas in a gas-free manner in a gas-free manner, the content of oxygen in the fluorine gas contained in the fluorine gas before the organic compound is exposed to the fluorine gas is preferably 1% by volume or less, in this case, the organic compound is preferably a carbon atom having 4 or less carbon atoms, more preferably 'difluoromethane, trifluoromethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, At least one selected from the group consisting of hexafluoropropane and heptafluoropropane. The amount of fluorine gas introduced into the reaction system is preferably 9% by volume or less based on the total amount of gas components in the reaction system. The diluent gas is preferably at least one selected from the group consisting of tetrafluoromethane, hexafluoroethane 'octafluoropropane and hydrogen fluoride. When the diluent gas contains hydrogen fluoride, the total amount of hydrogen fluoride to the diluent gas is preferably 50% by volume or more. This paper scale applies to the national standard (CNS) A4 specification (210X 297 mm) " ^ -8- (please read the note on the back first ¥•装-- π write this page)