TW501939B - Composition and method for rendering halogen-containing gas harmless - Google Patents

Composition and method for rendering halogen-containing gas harmless Download PDF

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TW501939B
TW501939B TW90112833A TW90112833A TW501939B TW 501939 B TW501939 B TW 501939B TW 90112833 A TW90112833 A TW 90112833A TW 90112833 A TW90112833 A TW 90112833A TW 501939 B TW501939 B TW 501939B
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halogen
gas
pesticide
based gas
patent application
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TW90112833A
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Chinese (zh)
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Yuji Hayasaka
Hitoshi Atobe
Yoshio Furuse
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Showa Denko Kk
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B01D53/685—Halogens or halogen compounds by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/304—Linear dimensions, e.g. particle shape, diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/306—Surface area, e.g. BET-specific surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/202—Single element halogens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0216—Other waste gases from CVD treatment or semi-conductor manufacturing

Abstract

The present invention intends to provide a cheap agent and a cheap method of harm removal which exhibits high harm-removing ability per unit volume for harmful halogen-containing gas such as that contained in the exhaust gas from the etching or cleaning step durng the manufacturing process of a semiconductor device. The invention is characterized in that halogen-containing gas is removed using a harm-removing agent comprising iron oxide, an alkaline earth metal compound and activated carbon. In addition, when the exhaust gas contains halogen gas such as chlorine, etc or a gas such as sulfur dioxide, the gas is rendered harmless by using a harm removing agent comprising activated carbon or zeolite.

Description

501939 A7 _ B7 五、發明説明（1 ) 〔發明之所屬技術領域〕 (請先閲讀背面之注意事項再填寫本頁) 本發明係有關鹵素系氣體之除害劑鹵素系氣體之除害 方法及其所使用半導體裝置之製造方法，在半導體裝置步 驟，由乾蝕刻步驟及淸淨步驟予以排出含有鹵素系氣體使 排氣無害化。 〔習知技術〕 於半導體裝置之製造步驟之乾触刻，例如由氟化碳系 氣體、六氟化硫、氯化氫等之鹵化氫、三氯化硼、氯氣等 之鹵素氣體選1種以上之氣體，與因應該蝕刻氣體爲目的 而添加由氧、氮、氫、氬或氨等選1種以上之氣體，將 Si〇2、Si、SiW、SiN、Al、GaAs、 GaAs、GaP、I nP等之被蝕刻材使蝕刻。依蝕刻 裝置予以排出的排氣，除前述蝕刻氣體之外，以蝕刻經生 成之鹵化矽、鹵化鎢、鹵化羰基、四氟化硫、或反生成之 二氧化碳等之氣體。 經濟部智慧財產局員工消費合作社印製 以往，由半導體裝置之製造步驟，予以排出含有此等 之鹵素系氣體使排氣無害化爲手段，係爲人所知的濕式法 及乾式法之二法。不過，濕式法之設備複雜，吸收液之後 處理及操作性均係有問題，再者爲排氣洗淨苛性鈉或碳酸 鈉打之鹼性水溶液，雖有鹵素系氣體與鹼性水溶液反應生 成的固形物，但堵塞由處理裝置之排氣線上等之問題而仍 未予採用著。 另一方面乾式法係可容易爲改善濕式法之問題點，經 本紙張尺度適用中國國家標準（CNS ) A4規格Τ^Ϊ0Χ297公釐) ~ " 麵4· 501939 A7 __B7 五、發明説明（2 ) 予以提出多數的除害劑及除害方法之建議等。 其方法當爲可舉出例如 (1)使四氧化三鐵附著於鹼石灰之表面上的除害劑 之使用方法（日本特開平6 — 2 2 1 3號公報）。 (2 )使與活性碳接觸後，再與氧化鐵接觸的方法（ 曰本特開平6 — 3 19 9號公報）。 (3)氧化鐵與錳化合物爲主成分之除害劑及與除害 劑接觸後使金屬氧化物爲氣體接觸活性碳之方法（日本特 開平6 — 1 9 8 1 2 8號公報）。 (4 )將氫氧化緦爲主成分之除害劑，此再使用於含 水之除害劑的方法（日本特開平7 - 2 7 5 6 4 5號公報 )° (5 )將四氧化三鐵爲主成分之除害劑，此再使用於 含水之除害劑的方法（日本特開平7 — 2 7 5 6 4 6號公 報）。 (6 )使用使活性碳之鋁酸之鹼性金屬鹽或四烷基銨 鹽載持的除害劑之方法（日本特開平4 — 2 1 0 2 3 6號 公報）等，無論任一種之方法，大槪將均以氧化鐵、鹼性 金屬及鹼土類金屬化合物、活性碳及有效成分載持活性碳 之除害劑使含有鹵素系氣體乾式蝕刻排氣成無害化。 但是其中第（6 )項之除害劑，例如與活性碳比較， 雖然氯、三氯化硼等係有同等的除害能力，但鹵化氫、氟 化矽等之除害能力較高，不過實際上經予以處理乾式蝕刻 本紙張尺度賴t酬家標準（CNS ) A4驗（210X 297^^7" ~ "" -5- (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 經濟部智慧財產局員工消費合作社印製 501939 A7 ___B7_ 五、發明説明（4) 〔發明欲解決之課題〕 本發明係在此種背景下完成者，本發明係提供對於鈾 刻及淸淨排氣所包含有害的鹵素系氣體在每單位容積之除 害能力高，且廉價之除害劑及除害方法爲課題。 〔爲解決課題而採用的手段〕 本發明人等，爲解決前述的課題經精心檢討結果，將 以特定的比例含有特定的氧化鐵與鹼土類金屬化合物及活 性碳之除害劑，尤其爲具有鹵化氫之除害能力的高除害劑 ，發現能解決前述之課題，以至完成本發明。本發明表示 如下的（1 )〜（2 2 )項之鹵素系氣體之除害劑、鹵素 系氣體之除害方法及採用該除害方法之半導體裝置之製造 方法。 (1 )由r -氫氧化氧化鐵〜氧化鐵而成之群組選出 的氧化鐵1 0〜4 0質量％，將鹼土類金屬化合物含有 2 0〜8 0質量％及含有活性碳1 〇〜4 0質量％爲其特 徵之鹵素系氣體之除害劑。 (2 )前述鹼土類金屬化合物係由鎂、鈣、緦及鋇之 氧化物、氫氧化物及碳酸鹽而成的群組選出之至少1種之 如上述（1 )項記載的鹵素系氣體之除害劑。 (3 )前述活性碳之比表面積係5 Ό 0 m 2/ g以上之 如上述（1 )項記載的鹵素系氣體之除害劑。 (4 )前述除害劑係含硫酸鈣之如上述（1 )項記載 的鹵素系氣體之除害劑。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 -7- 501939 A7 B7 五、發明説明（5 ) (請先閲讀背面之注意事項再填寫本頁) (5 )前述硫酸鈣之含有量，對於氧化鐵、鹼土類金 屬化合物及活性碳之合計的量1，係於0〜0·2之範圍 如上述（4 )項記載的鹵素系氣體之除害劑。 (6 )前述除害劑之粒徑各各係1 0 0 μ m以下，將 氧化鐵、鹼土類金屬化合物、活性碳及硫酸鈣之粉末配合 後係使造粒成粒狀品如上述（1 )項記載的鹵素系氣體之 除害劑。 (7 )前述除害劑之粒徑係0 · 5〜1 0 m m之範圍 之粒狀品，如上述（6 )項記載的鹵素系氣體之除害劑。 (8 )前述鹵素系氣體係由鹵素、鹵化氫、鹵化矽、 鹵化鎢、鹵化羰基、氟化硫、氯化砷、氯化磷、三氯化鋁 及三氯化硼而成之群體選出的至少1種之氣體如上述（1 )項記載的鹵素系氣體之除害劑。 (9 )使含有鹵素系氣體之氣體與上述（1 )〜（8 )項之任一項記載之除害劑接觸爲其特徵之鹵素系氣體之 除害方法。 經濟部智慧財產局員工消費合作社印製 (1 0 )前述鹵素系氣體，係由鹵、鹵化氫、鹵化矽 、鹵化鎢、鹵化羰基、氟化硫、氯化砷、氯化磷、三氯化 鋁及三氯化硼而成之群組選出的至少1種之氣體，如上述 (9)項記載之鹵素系氣體之除害方法。 (1 1 )含有以使含有鹵素系氣體之氣體與由活性碳 而成的除害劑接觸的步驟，接著於該步驟後使以上述（1 )〜（8)項之任一種記載的除害劑與步驟接觸，爲其特 徵之鹵素系氣體之除害方法。 本紙張尺度適用中國國家標準(CNS ) Α4· ( 210X 297公釐） -8 - 501939 A7 B7 五、發明説明（6) (請先閲讀背面之注意事項再填寫本頁} (1 2 )即述活性碳之比表面積係5 0 〇m2/g以上 ，粒徑係0 · 5〜1 0mm之範圍之如上述（1 1)項記 載的鹵素系氣體之除害方法。 (13)包含前述鹵素系氣體係由包含鹵氣體，再者 鹵化氫、鹵化矽、鹵化鎢、鹵化羰基、氟化硫、氯化砷、 氯化磷、三氯化鋁及三氯化硼而成之群組選出的至少1種 之氣體之如上述（1 1 )或（1 2 )項記載的鹵素系氣體 之除害方法。 (1 4 )包含以使含有鹵素系氣體之氣體，與如上述 (1 )〜（8 )之任何一項所記載的除害劑接觸的步驟， 接著在該步驟之後，使與由沸石而成的除害劑接觸的步驟 ，爲其特徵之鹵素系氣體之除害方法。 (1 5 )前述沸石係指合成沸石及/或天然沸石，其 粒徑係0 · 5〜1 0mm之範圍之如上述（1 4)項記載 的鹵素系氣體之除害方法。 (16)前述合成沸石係MS-5A及/或MS- 1 3X之如上述（1 5 )項記載的鹵素系氣體之除害方法 經濟部智慧財產局員工消費合作社印製 〇 (1 7)前述鹵素系氣體，係由包含二氧化硫，再者 鹵化氫、鹵化矽、鹵化鎢、鹵化羰基、氟如硫黃、氯如砷 、氯化磷、三氯化鋁及三氯化硼而成之群組選出的至少1 種之氣體之如上述（1 4 )〜（1 6 )之任一項記載的鹵 素系氣體之除害方法。 (1 8 )前述被處理中的鹵素系氣體之濃度，係1 0 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -Q - 501939 A7 _B7 . 五、發明説明（7) vol%以下之如上述（9) 、 （ 11)及（14)之任 一項記載的鹵素系氣體之除害方法。 (1 9 ) 一種半導體裝置之製造方法，其特徵在於， 具有含採用由氟化碳、六氟化硫、鹵素、鹵化氫及三氯化 硼而成化合物群組選出的至少1種之氣體，作爲蝕刻氣體 或淸淨氣體之蝕刻步驟或淸淨步驟，與將由該等之步驟予 以排出鹵素系氣體使與接觸並除害的步驟之上述（1 )〜 (8 )之任一項記載的除害劑。 (2 0 )前述除害步驟，係包含使由活性碳而成的除 害劑接觸的步驟之如上述（1 9 )項記載的半導體裝置之 製造方法。 (2 1 )前述除害步驟，係含使與由沸石而成除害劑 接觸的步驟之如上述（1 9 )項記載的半導體裝置之製造 方法。 (2 2 )由蝕刻步驟或淸淨步驟予以排出的氣體中之 鹵素系氣體之濃度，係1 Ονο 1%以下之如上述（1 9 )〜（2 1 )之任一項記載的半導體裝置之製造方法。 〔發明之實施形態〕 於半導體裝置之製造步驟，例如由乾蝕刻步驟予以排 出含鹵素系氣體之排氣之乾式除害法。將排氣隨著載氣引 導除害筒予以塡充各種除害劑’與除害劑接觸予以無害化 僅將氣體排出系外。將其除害筒之終點當爲檢測方法，將 若與齒素系氣體全面接觸時色相全變色的ρ Η試驗紙或 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐)' ----------f (請先閲讀背面之注意事項再填寫本頁) 訂 線一 經濟部智慧財產局員工消費合作社印製 -10- 501939 A7 _____ B7__ 五、發明説明（8 ) (請先閲讀背面之注意事項再填寫本頁) P Η指示劑等載持於氧化鋁、矽膠等之載體上的色相檢測 劑與除害筒成整體化的除害裝置通常被廣泛於使用。因此 ’前述之以往技術之（1 )〜（6 )所表示，以往之除害 劑及除害方法，無論如何鹵化氫之除害能力都低，首先爲 鹵化氫全漏其終點檢測劑全變色，儘管無論如何其他之鹵 素系氣體之能力充分地保持著，但除害筒之頻度變多，結 果係產生成本高之問題。對於此，若本發明的除害劑及除 害方法征服者，除害劑之交換頻度變少，廉價之乾鈾刻排 氣可能成爲無害化，可解決有關半導體裝置之製造步驟之 問題。 以下，就本發明詳細而言。 經濟部智慧財產局員工消費合作社印製 對於本發明之半導體裝置之製造步驟，如將乾蝕刻舉 例說明，係由如氟化碳氣體、六氟化硫、鹵素、鹵化氫或 三氯化硼之氣體予以選擇1種以上之触刻，因應其目的係 由氧氣體、氮氣體、氫氣體、氬氣體及氦等選擇1種以上 之氣體添加，將被鈾刻材料（S i 0 2、S i、S i W、 SiN、Al、GaAs、GaP、InP 等）使飩刻之 際，依其蝕刻裝置予以排氣之排之排廢氣，前述蝕刻之其 他，以蝕刻生成之鹵化矽v鹵化鎢、氯化鋁、四氟化硫、 鹵化羰基等之鹵素系氣體與此等加以分解生成之鹵化氫、 二氧化硫等含有之氣體，本發明係將除害包含此等氣體之 排氣之除害劑、除害方法及其採用半導體裝置之製造方法 〇 - 本發明使用除害劑及除害方法當爲可除害之氣體，可 本紙張尺度適用中國國家標準（CNS ) A4規格（~ ~ -11 - 501939 Α7 Β7 五、發明説明（ιί (請先閲讀背面之注意事項再填寫本頁) 、BC 13、S i C 14、Si Br4等之氣體係有效，但 HC 1或S i F4等之氣體，幾乎未有效一事係爲公知。不 過，如前述，將活性碳與氧化鐵予以組合之除害劑或將活 性碳與鹼土類金屬予以組合之除害劑，其除害效果幾乎未 能提升。 如以上，本發明之鹵素系氣體之除害劑所包含氧化鐵 、鹼土類金屬化合物及活性碳之各各之效果，以單獨或二 分系未能發揮，依使用氧化鐵、鹼土類金屬化合物及活性 碳之三成系配合而混合成除害劑，始發揮鹵素系氣體之除 害效果。 經濟部智慧財產局員工消費合作社印製 再者，將除害劑之氧化鐵及鹼土類金屬化合物與鹵素 系氣體使反應生成鐵及鹼土類金屬之鹵素化合物，除氟化 合物以外幾乎係潮解性化合物，幾乎將未含氟原子之鹵素 系氣體爲除害時，其潮解性化合物，屢次發生除害筒成爲 堵塞原因。因而，本發明之除害劑由於添加硫酸鈣，幾乎 將未含氟原子之鹵素系氣體爲除害時，亦可使不潮解之除 害劑。不過，若將與氟素系氣體共存者，爲防止該氟化物 之潮解性，不一定是添加硫酸鈣可受到限制。 :其次就本發明所使用之除害劑之原料氧化鐵、鹼土類 金屬化合物、活性碳而言。 氧化鐵係由r — F e〇〇H ( r —氫氧化氧化鐵）及 r — F e 2〇3 ( r —氧化二鐵）成群中至少選1種之化合 物，並7 — F e〇〇Η爲宜。亦即，r — F e〇〇Η及 r 一 F e 2 Ο 3例如α — F e 2 Ο 3與其他之氧化鐵比較作爲 本紙張尺度適用中.國國家標準（ CNS ) Α4規格（210X297公釐） -14- 501939 A7 _ B7 五、發明説明（id 其次就本發明之除害劑之製造方法而言。 按照本發明鹵素系氣體之除害方法，使用含有前述之 氧化鐵、鹼土類金屬化合物及活性碳以特定之比例之除害 劑係爲其特徵。此除害劑配合氧化鐵、鹼土類金屬化合物 及活性碳之含有比例，氧化鐵係1 0〜4 0質量％、鹼土 類金屬化合物係2 0〜8 0質量％、活性碳係1 0〜4 0 質量％者爲佳，係宜爲氧化鐵1 5〜3 5質量％、鹼土類 金屬化合物3 0〜7 0質量％、活性碳1 5〜3 5質量％ ，係更宜爲氧化鐵係2 0〜3 0質量％、鹼土類金屬化合 物係4 0〜6 0質量％、活性碳係2 0〜3 0質量％者爲 佳。此配合比例，係爲將各成分之特性做最大限之活用之 配合比例。 再者，就本發明之除害劑以前述質量％配合氧化鐵、 鹼土類金屬化合物及活性碳之其他，必要可因應添加硫酸 鈣。含有硫酸鈣之比例，對於氧化鐵、鹼土類金屬化合物 及活性碳之合計質量爲1，0〜0' 2之範圍爲好，係宜 爲0 . 0 5〜0 · 1之範圍者爲佳。如此濃度過低者即失 去效果，過高者氧化鐵、鹼土類金屬化合物及活性碳之總 量相對的降低，硫酸鈣之效果亦因使飽和將使鹵素系氣體 效率好面變成不能除害。 本發明之除害劑，將氧化鐵、鹼土類金屬化合物及活 性碳或在此添加硫酸鈣之粉末使混合者雖然使充分發揮效 果，但作爲粒狀品的爲宜。造粒按照前述配合比例，係不 用粘合劑，雖然只有水也可充分造粒，但原料之粒子徑多 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) 訂 經濟部智慧財產局員工消費合作社印製 -16- 501939 A7 ___ B7_ 五、發明説明（ 少粗之情形與水共同添加粘合劑亦可。若得粘合劑而不給 予影響除害劑之性能，即不受限定其種類與量。 本發明製造使用粒狀之除害劑，各原料配合後，加適 量之水混練，將混練物造粒作爲粒狀品。此粒狀品之調製 必要以混練機混合及造粒雖然同時進行係便宜，但將混合 與造粒即使分開進行亦可。例如使用Henschel混合器或縱型 攪拌器、混合與造粒雖然可同時進行，但原料之混合使用 Henschel混合器或V型混合機進行，其次，將造粒使用皿型 造粒機或轉鼓式製錠機（drum Pelletizer )進行亦可。 其次爲提高造粒品之硬度與爲使水分蒸發，在空氣式 氮等之惰性氣體之氣流中，以1 0 0〜1 5 0 °C乾燥3〜 5小時。乾燥品之水分量以風環乾燥機，1 1 〇 °C，2〜 3小時使乾燥之減量若在1質量％以下雖然可達成目的， 但以最後製品，寧可水分多以含有機好》尤其以C 1 2、 S〇2爲除害劑使發揮效果之情形亦有。 將本發明之除害劑作爲造粒品爲理由，係爲提高乾蝕 刻排氣與除害劑之接觸機會，如除害劑之粒徑過大參與鹵 素系氣體之吸附擴散之表面積相對的變小，擴散速度變遲 。相反之，如除害劑之粒徑過小者參與吸附擴散之表面積 相對的變大，雖然擴散速度變快，但歆處理之瓦斯量如變 多，差壓亦變大，除害筒（裝置）之緊密化等招致障礙。 因此，即使粒錠狀、錠片狀、球狀亦可，尤其因有多孔性 爲宜，其粒徑係0 · 5〜10mm之範圍，係宜爲1〜5 m m之範圍較好。 本紙張ϋ適用中國國家標準（CNS ) Α4規格< 210X 297公羡) " ~ -17· (請先閲讀背面之注意事項再填寫本頁) 、1Τ 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 501939 A7 __ _ B7 五、發明説明（β 其次就使用本發明之除害劑鹵素系氣體之除害方法而 言。本發明之除害劑雖然可使用固定層、移動層、流動層 ，但一般上以固定層使用。本發明之除害劑單獨塡充於除 害筒或於同一除害筒以活性碳或沸石一齊以必要之比例塡 充，或以各種分別之除害筒塡充使用亦可。又本發明之除 害劑及活性碳或沸石之塡充層長度及除害筒之大小（容積 及其斷面積）因應其除害對象鹵素系氣體之量（濃度及其 此等之組成比），乾式蝕刻排氣之流量，可容許設置空間 ，可容許壓力損失等予以決定。 除害劑之斷面積作爲筒內之線速度（L V )，予以決 定如成爲0 · l m〜1 〇 m/m i η之範圍爲宜，雖然排 氣之接觸（處理）壓力並未特予限制，但鹵素系氣體包含 乾蝕刻排氣如考慮以真空泵予以排氣係- 1 〇〜2 0 kP a之範圍，宜爲係5〜5 kP a之範圍較佳。排氣之 處理溫度亦尤其不必要加熱式冷却以常溫（2 0〜3 0 t： )即可。又，鹵素系氣體雖然所包含乾蝕刻排氣中之水分 無給左乾燥狀態無論在濕潤狀態均可，但鹵素系氣體係因 腐蝕性氣體若未結露之濃度亦可。 本發明之除害劑雖然被適用於乾蝕刻排氣流量及其鹵 素系氣體濃度並未特予限定，但予以決定排氣流量與其鹵 素系氣體濃度之關係。雖然如過於超薄係對於經濟上不利 ’如過於超濃依鹵素系氣體之種類而異，但依其反應及吸 附熱使除害筒之溫度上昇，又反應所生成之Η 2 0之濃度亦 變過濃’由其Η 2 0在筒內及配管內結露筒及配管之腐蝕、 本紙張適用中國國家標準( CNS ) A4規格（210X297公釐)~'' (請先閲讀背面之注意事項再填寫本頁} 訂 線·_ -18 - 501939 A7 ___B7_ 五、發明説明（ 除害劑之潮解等之問題，其濃度，係因在1 〇 V 0 1 %以 下爲佳，宜爲5νο1%以下，更宜爲2νο1%以下即 可。 本發明之除害方法予以滿足前述之條件於除害筒之_ 素系氣體將所包含乾式蝕刻排氣以氮氣體載氣同件，本發 明之除害劑及活性碳或沸石由於使接觸，將鹵素系氣體固 定（反應式吸附）於各除害劑使無害化。 圖1係表币本發明所實施除害裝置之一例。1〜4係 蝕刻系統，由蝕刻氣體供應裝置1，依予以供應蝕刻氣體 與真空泵3 ’於蝕刻室- 2內予以減壓使發生等離子體， 係將蝕刻室- 2內之被蝕刻材使蝕刻裝置。由蝕刻系統1 〜4之蝕刻排氣依真空泵3及真空泵排除用氮氣體4(蝕 刻排氣之載氣）予以排氣。又5〜9係除害系統，由除害 筒入口 5將含前述鹵素系氣體之排氣導入除害筒6內，因 應除害對象氣體，予以塡充如本發明之除害劑、活性碳、 沸石依使接觸’將鹵素系氣體以物理的（吸附）或化學的 (鹵化合物）使固定於本發明之除害劑、活性碳、沸石。 予以無害化之排氣經過除害筒出口 7，使通過氣體檢出器 8 ’確認鹵素系氣體有無漏氣，由排氣出口 9通過排氣導 管予以放出大氣。除害筒之限界能力（終點檢測）可由氣 體偵測器8得知。氣體偵測器8已塡充由鹵素系氣體使變 色之色相檢測劑之容器（內部之色相檢測劑之變色由外部 監視可能之容器）即使與除害筒成一體型亦可。 其次就本發明朝除害劑與活性碳或沸石之除害筒之塡 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 Χ297公釐） "一 -19- (請先閲讀背面之注意事項再填寫本頁) 訂 線表 經濟部智慧財產局員工消費合作社印製 501939 A7 _B7___ 五、發明説明（li 充方法而言。 對於本發明之除害劑若使含有一定量之水，雖然幾乎 有害之鹵素系氣體，尤其使提升C 1 2、S〇2之除害能力 ，但當爲乾蝕刻排氣之除害劑並非實用。亦即，乾蝕刻好 晶圓（被蝕刻劑）之搬送，前處理，蝕刻等作爲一循環（ one cycle)係斷續的運轉圖案（乾淸淨亦斷續的運轉）， 予以導入除害筒之排氣，不含鹵素系氣體之只有載氣（氮 素）氣體之時間，係存在行爲。因此除害劑中之水分與其 排氣接觸予以脫水儘管對於除C 1 2、S 0 2以外之鹵素系 氣體乃有這樣之除害能力，但除害劑爲降低C1 2、S 〇2 之除害能力傳達終點，不得已進行除害筒之交換。 因此欲使不受到氮氣體載氣之影響的除害方法，於本 發明之除害劑係幾乎不使含水分，且由於被處理之C 1 2及 S〇2或加水分解使生成S 0 2含有成分氣體情形，與不含 此等情形（如實施例表示即有少量並未予限定）之乾蝕刻 排氣之除害方法成爲有必要。 雖然依被處理氣體之C 1 2及S 〇2或加水分解生成 S 0 2之成分氣體，但幾乎不含排氣之情形，如圖2表示將 本發明之除害劑1 〇單獨經予以塡充除害筒6，由於以氮 氣體載氣將引導彼處理氣體使接觸於除害劑，可將被處理 氣體中之鹵素系氣體使除害。不過，例如將鋁以C 1 2使乾 蝕刻之排氣，因含有C 1 2已使乾燥備有本發明之除害劑， 如前述係有不充分之除害能力。此處將其排氣首先使 c 1 2吸附容量之較多活性碳接觸後，朝C 1 2之活性碳之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公^ 一 -20- (請先閱讀背面之注意事項再填寫本頁) ,ιτ 經濟部智慧財產局員工消費合作社印製 501939 A7 ____B7_ 五、發明説明（d (請先閲讀背面之注意事項再填寫本頁) 吸附過程或以蝕刻步驟而生成，以活性碳未能予以除害 H C 1氣體之除害能力由於使高價本發明之除害劑接觸， 含有C 1 2之乾蝕刻排氣之除害，與各各單獨之情形比較使 提高除害能力。亦即，如圖3表示活性碳1 1與本發明之 除害劑1 0之順序經予以塡充之除害筒6 (如即有活性碳 1 1與本發明之除害劑1 0之順序即使分別之除害筒亦可 )，將含有C1 2之乾蝕刻排氣，依藉於導入除害筒入口 5 ，予以達成已提高之除害能力之除害方法。活性碳以與本 發明之除害劑1 0之比例，因應乾蝕刻排氣中之C 1 2與其 他之鹵素系氣體之組成比經過決定即可。雖然使用本發明 之除害方法可舉出活性碳之種類如椰穀碳系、石碳系、木 碳系等宜爲比表面積係5 0 0m2/g以上，更宜爲比表面 積係1 0 0 0 m 2 / g以上，對氣體吸附，必要之細孔分布 將持有2 0人前後Peak椰榖活性碳較佳。 經濟部智慧財產局員工消費合作社印製 又將矽或矽氧化膜使用S F 6予以蝕刻排氣，S F 6使 起因於S F4或S OF2等之氣體，亦即，將加水分解生成 SO 2含有氣體。已被乾燥僅以本發明之除害劑，S i F4 或S 0F2等之化合物中之氟元素當爲C a F2，又硫黃元 素以C a S 0 3予以固定本發明之除害劑。不過，尤其， SF4或S〇F2等之化合物的生成量多時Ca S〇3之生 成量亦變多，一旦固定之硫黃元素與鹵化氫之反應以S〇2 等再生。因此，含有S 0 2之乾蝕刻排氣之情形，依使與本 發明之除害劑接觸後，再使與沸石接觸，由於各各單獨可 提高除害能力。亦即，如圖4表示本發明之除害劑1 〇與 本紙張尺度適用中國國家標準(tNS ) A4規格（210X297公釐) " -21 - 501939 A7 _______B7 五、發明説明（β 沸石1 2之順序予以塡充除害筒6 (若以本發明之除害劑 1 0與沸石1 2之順序，即使分別之除害筒亦可），由於 將含有S〇2 (亦含SF 4或s〇F2)之乾蝕刻排氣使導 入除害筒入口 5 ’予以達成提高除害能力之除害方法。本 發明之除害劑1 0與沸石1 2之比例，因應乾蝕刻排氣中 之S〇2 (亦含SF4或S〇F2)與其他之鹵素系氣體之 組成比若經過決定即可。雖然可舉出本發明之所使用沸石 之種類如天然及合成沸石（MS - 5A、MS — 1 3X) ，係宜爲合成沸石，並宜爲S 〇2吸附容量大之MS — 1 3 X較佳。 如以上所說明’鹵素系氣體包含乾鈾刻排氣之除害方 法，單獨塡充本發明之除害劑或活性碳或與沸石2層予以 塡充之除害筒，依據將該排氣使通氣係有可能使提高每單 位容積之除害能力之除害方法，本發明若依照半導體裝置 製造步驟中之蝕刻步驟或在淸淨步驟將含有鹵素系氣體之 排氣之好效率即可使無害化。 其次就使用前述之鹵素系氣體之除害劑及除害方法將 含除害步驟半導體裝置之製造方法而言。 本發明以蝕刻氣體或淸淨氣體，依據由氟化碳、六氟 化硫、鹵、鹵化氫及三氯化硼所成化合物群選出至少使用 1種氣體飩刻步驟或淸淨步驟，與由此等之步驟予以排出 含有鹵素系氣體之氣體，與前述之除害劑使接觸具有除害 步驟係半導體裝置之製造方法。 LSI或TFT等之半導體裝置之製造過程，使用 本紙張尺度適用中國國家標準（CNS ) A4規格（210/297公餐1 ~^ (請先閲讀背面之注意事項再填寫本頁) 訂 線赢 經濟部智慧財產局員工消費合作社印製 -22- 501939 A7 ___B7 五、發明説明（20 (請先閲讀背面之注意事項再填寫本頁) C VD法、濺鍍法或蒸鍍法等使形成薄膜或厚膜，爲了使 形成電路圖等進行蝕刻。又對於形成薄膜或厚膜之裝置， 爲除去裝置內壁，冶具等所堆積不要之堆積物而進行淸淨 。此種不要之堆積物如生成者，即爲形成粒子發生之原因 ，爲製造優質之膜係有必要隨時除去。 氟、氯及溴等使用鹵素氣體之蝕刻步驟，例如日本特 開平4 一 3 1 4 3 3 1號公報所述，可進行等離子體（ Plasma )蝕刻等之乾触刻條件。由此鈾刻步驟予以排出氣體 中於前述鹵素氣體之其他，作爲分解生成物，雖然如生成 出鹵化氫、鹵化矽、鹵化鎢或鹵化羰基之氣體，但由於使 用本發明之除害劑，可將此等之化合物無害化。又，例如 將氯氣體使用作爲蝕刻氣體時，來反應之氯氣體係有予以 排出出來。此種情形，處理本發明之除害劑前，由如前述 由活性碳使接觸成除害劑，氯氣體亦可效果的除害。 經濟部智慧財產局員工消費合作社印製 又使用氟化碳或氟化硫黃等之氣體之蝕刻步驟，例如 日本特開平4— 1 2 1 3 7 9號公報所述，可進行等離子 體蝕刻等乾飩刻條件。此情形雖然亦相同生成出如鹵化氫 、鹵化矽、鹵化鎢或鹵化羥基之氣體，但依使用本發明之 除害劑，此等之化合物可使無害化。又使用氟化硫黃之蝕 刻情形，係令生成分解生成物的二氧化硫情形。此際，如 前述處理本發明之除害劑後，由沸石依使接觸成除害劑、 二氧化硫亦可效果的除害。 以下，由實施例及比較例雖然依本發明詳細說明，但 本發明對於此等實施例並未予限定。 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐)~ • 23 - 501939 A7 __B7_ 五、發明説明（ (除害劑之調製例） 如表1表示使用各試驗除害劑之各種原料。 經濟部智慧財產局員工消費合作社印製 〔表1〕 試驗用除害劑之原料名稱 平均粒子徑 (/zm) 比表面積 (m2/g) 製造廠商 (購入廠商） 酸化鐵 a -Fe2〇3 <1 25 純正化學(股） a -FeOOH <1 70 戶田工業(股） γ -Fe2〇3 <1 20 戶田工業(股） T -FeOOH <1 60 石原techno(股） Fe3〇4 <1 5 純正化學(股） 鹼土類金屬化合物 氫氧化鈣 Ca(OH) 5 15 吉澤石灰工業(股） 氫氧化緦 Sr(〇H)2 <1 — 純正化學(股） 活性碳 椰穀系活性碳 (Y-180C) — 1000-1500 味精 fine teohno(股） 媒碳系活性碳 (F-17C) — 1000〜1500 味精fine techno(股） 活性氧化鋁(r-Ai2〇3) 5 200 水澤化學(股） 天然沸石 50 一 Knimine工業(股） 硫酸鈣(CaS〇4) 1 ' — 純正化學(股） 表1表示使用原料物質，例如表3、4、5表示在試 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 麵24 - 501939 A7 B7 五、發明説明（2$ (請先閲讀背面之注意事項再填寫本頁) 驗條件下，各物質配合以Henschel mixer混合，添加水造粒 後，以1 1 0 °C 3小時進行乾燥處理，以篩劃分、調製 粒徑0 · 8 5〜2 · 8 m m之粒狀品。 (市販除害劑及吸附劑） 使用本試劑之前述調製以外之除害劑如表2的表示使 用。 經濟部智慧財產局員工消費合作社印製 〔表2〕 市販除害劑及吸附劑之種類 粒子徑(mm) 比表面積(m2/g) 製造廠商(購入廠商） 椰榖活性碳 0.5 〜3·0 >1100 味精fine techno(股） Υ-10 沸石 1.0 〜2.0 — Union昭和(股） MS-3A 沸石 1.0-2.0 — Union昭和(股） MS-4A 沸石 1.0 〜2.0 — Union昭和(股） MS-5A 沸石 1.0 〜2.0 — Union昭和(股） MS-13X 活性氧化鋁(r -) 1.0-2.0 210 水澤化學(股） 驗碳 1.5 〜3.5 一 純正化學(股） NaOH添附活性碳 2.0 〜5.0 >1100 味精fine techno(股） YN-4 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 25 - 501939 A7 B7 五、發明説明（23 (除害例） (請先閲讀背面之注意事項再填寫本頁) 使用與圖1表示者相同原理之裝置，表3、4之各試 驗條件實施本發明法。亦即，於壓克力製筒（內徑7 0 111111\筒長1〇〇〇111111)，塡充使用試驗除害劑5 5 〇 mm之層高（容量17 3m£)，於壓克力製除害筒將氮氣 體稀釋及載氣排氣（模擬）使通氣。此際以 被處理氣體之流量 :0.751/min 被處理氣體中之除害對象（鹵素）氣體濃度 ：1 .Ovol% 被處理氣體之純速度 1.85m/min 以任何試驗亦分析被處理氣體及處理氣體中之除害對象（ 鹵素）濃度，氣體檢測管法或純水吸收離子色譜法。該能 力係除害筒出口處理氣體中之除害對象（鹵素）氣體濃度 將體積百萬分之1 ( lVolppm)予以檢驗出終點（除害劑之 能力界限）爲時刻，由以往通氣之各除害對象（鹵素系） 氣體之摩爾（m ο 1)量與由除害劑之塡充量，表示除害 劑每單位容積之鹵素系氣體之摩爾（mo 1 )數。 經濟部智慧財產局員工消費合作社印製 除害劑（吸附劑）能力（mol/L-劑）= (C/100 X Q X T) + (R X V/1000) C:除害筒入口排氣中除害對象氣體濃度（v 〇 1%) Q :排氣濃度（L /m i η ) 丁 ：將排氣到終點所通氣時間（m i η ) R :氣體係數（試驗溫度及壓力之補正係數） V :除害劑（吸附劑）之塡充量（) ^紙張尺度適用中國國家標準( CNS ) A4規格< 210X297公釐） ~ " 賺26· 501939 Α7 Β7 五、發明説明（ 再者，與圖1表示相同原理之實裝置或者如表示後述 之實施例實施本發明之試驗。亦即，由實際之乾蝕刻步驟 將予以排出含有鹵素系氣體之排氣，以往之除害方法及活 性碳或沸石與本發明之除害劑予以組合實施與除害方法比 較試驗。此際，除害能力之界限設置除害筒出口整體型之 檢測器內之色相檢測劑變色爲終點，其能力以相同蝕刻條 件，相同容積除害劑（筒）相對的比較。亦即，將乾蝕刻 排氣中之鹵素系氣體可除害時間（實際上供應蝕刻氣體之 蝕刻延長時間）或其間與晶圓（被蝕刻材）處理張數（蝕 刻批張數X蝕刻次數）比較，確認其能力。 (實施例1〜5 ) 實施例1〜5如表3之表示試驗條件，於氧化鐵（r —Fe〇〇H、r — Fe2〇3)、鹼土類金屬化合物、活 性碳之三成分系及其三成分系中，添加硫酸鈣調整除害劑 ，實施試驗。結果如表3表示試驗結果，就S i F 4之除害 能力，亦就H C 1之除害能力而言，能得充分高能力。 (比較例1〜5 ) 比較例1〜5如表4所表示之試驗條件，調整τ 一 F eOOH、r — F e2〇3以外各種氧化鐵、鹼土類金屬 化合物、活性碳之三成分系之除害劑及改變r 一 F e 00 Η、鹼土類金屬化合物、活性碳之三成分系各原 料之配合比以調整之除害劑，實施試驗。結果如表4表示 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X297公釐） (請先閱讀背面之注意事項再填寫本頁) Γ 經濟部智慧財產局員工消費合作社印製 -27- 501939 A7 B7 五、發明説明（ 之S式驗結果’就S i F4、HC 1之任一個而言其除害能力 與本發明之除害劑比較亦成較低結果。 (比較例6〜1 0 ) 比較例6〜1 〇如表5所表示之試驗條件，將各種氧 化鐵之單獨除害劑調製’實施試驗。結果如表5所表示之 試驗結果，就H C 1之除害能力而言雖然可得僅γ — F e Ο Ο Η之高能力’但S i F 4之除害能力即使在任何之 氧化鐵亦不能得充分之能力。 (比較例1 1〜1 5 ) 比較例1 1〜1 5如表5所表示之試驗條件，依調整 驗土類金屬化合物單獨、活性碳單位及氧化鐵（7 — F e Ο〇Η )、鹼土類金屬化合物、活性碳之二者必居其 一以二成分系之除害劑，實施試驗，結果如表5所表示之 謂式驗結果，S i F 4之除害能力之任一個亦不能大幅的改善 〇 (比較例1 6〜2 4 ) 比較例1 6〜2 4如表6所表不之試驗條件，用活性 氧化鋁、天然沸石、合成沸石、鹼碳、氫氧化鈉添附活性 碳之市面出售之除害劑，實施相同之試驗。結果如表6所 表示之試驗結果，無論那個H C 1及S i F 4之除害能力與 本發明之除害劑比較亦都較低。 本紙張尺度適财目@家鮮（CNS )八4祕（210X297公釐) '一^ " -28- (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 501939 A7 B7 五、發明説明（2$ (請先閲讀背面之注意事項再填寫本頁) 又，對此等之市販除害劑就C 1 2之除害能力而言，活 性碳（椰榖活性碳、N a Ο Η添附活性碳）最高，關於 SO 2之除害能力，天然沸石、合成沸石（MS — 5Α、 MS — 1 3X)高，其中MS — 13X亦能得最高能力。 (實施例6 ) 用與圖1所表示的相同原理之實裝置，實施本發明之 試驗。其塡充方法，如圖3所示將活性碳（有機鹼添附活 性碳與本發明之除害劑以7 : 3之比率將塡充2層，以比 較裝置之有機添附活性碳單獨（1 〇 〇%)塡充。塡充了 此等各各有效容積1 3 0 L之除害筒。 此等之除害筒，將聚一矽以同一條件下，使用HB I* 50SCCM、Cl2 50SCCM之蝕刻氣體，將蝕 刻之乾蝕刻排氣，用氮氣體載體2 0 S L Μ引導前述除害 筒進行試驗。與結果設置除害筒整體型至色相檢測器變色 之拖延蝕刻時間比較，以比較裝置之除害方法2 〇 〇小時 ’有機鹼添附活性碳與本發明之除害劑組合裝置除害方法 經濟部智慧財產局員工消費合作社印製 係5 0 0小時，本發明之除害方法表示2 · 5倍之除害能 力。 (實施例7 ) 以圖1所表示的與相同原理之實裝置，實施本發明之 試驗。其塡充方法’如圖3所表示活性碳（椰榖活性碳） 與本發明之除害劑以7 : 3之比率塡充2層，將以比較裝 本紙張尺度適用中爾國家系準（CN7) A4規格（2^(^297公釐）~ ： -29- 501939 A7 B7_ 五、發明説明（2$ 置之有機鹼添附活性碳單獨（1 0 0%)塡充2層，此等 塡充各各有效容積1 3 0 L之除害筒。 此等之除害筒，將鉛在同一蝕刻條件下，使用B C 1 3 50SCCM、C12 100SCCM、Ar 10 0 S C C Μ之蝕刻氣體，將蝕刻之乾蝕刻排氣用氮氣體載體 2 0 S LM，於前述除害筒引導進行試驗。與將結果設置 除害筒整體比型至色相檢測器變色之拖延蝕刻時間比較， 比較裝置之除害方法4 8 0小時，椰穀活性碳再本發明之 除害劑，組合裝置之除害方法係9 5 0小時，本發明之除 害方法表示約2倍之除害能力。 (實施例8 ) 以圖1所表示的與相同原理之實裝置，實施本發明的 試驗。其塡充方法，如圖2所表示單獨（1 0 0%)塡充 本發明之除害劑。以比較裝置將有機鹼添附活性碳單獨（ 1 0 0%)塡充。此等塡充各各有效容積1 3 0 L之除害 筒。於此等之除害筒，將聚-矽在同一蝕刻條件下使用 Η B r 20SCCM、HC1 200SCCM、He 200SCCM、SF6 5SCCM之鈾刻氣體之乾飩刻 排氣用氮氣體載氣2 0 S LM，引導前述除害筒進行試驗 。與將結果設置整體化型至色相檢測器變色之拖延蝕刻時 間比較，以比較裝置之除害方法7 0 0小時，塡充本發明 之除害劑裝置之除害方法係3 5 〇 〇小時，本發明之除害 方法表示5倍之除害能力。 氏張尺度適用中國國家標準（CNS ) A4規格< 2l〇X297公釐） (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 -30- 501939 A7 B7 五、發明説明（ (實施例9 ) 如圖4所表示本發明之除害劑與沸石以5 : 5之比率 塡充2層，以比較裝置之有機鹼添附活性碳單獨（1 0 〇 %)塡充。塡充此等各各有效體積1 3 0 L之除害筒。此 等之除害筒，將矽在同一蝕刻條件下使用HC 1 700 SCCM、SF6 700SCCM之蝕刻氣體，將蝕刻之 乾蝕刻排氣用氮氣體載氣2 0 S LM引導前期除害筒進行 試驗。將結果於除害筒設置整體化型至色相檢測器變色如 與矽晶圓處理張數比較，對於比較裝置之20，〇〇〇， 將本發明之除害劑與沸石組合裝置成4 2，0 0 〇張，本 發明之除害方法表示約2倍之除害能力。 (請先閱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 本紙張尺·度適用中國國家標準（CNS ) A4規格（210X297公釐） -31 - 501939 A7 B7 五、發明説明（23 睞-Hnli (琴 i/l_) *R雜修盤ώίοο ντ s s ΟΤ501939 A7 _ B7 V. Description of the invention (1) [Technical field to which the invention belongs] (Please read the notes on the back before filling out this page) The present invention is a halogen-based gas pesticide and its method In the manufacturing method of the semiconductor device used therein, in the semiconductor device step, the halogen-containing gas is discharged from the dry etching step and the cleaning step to make the exhaust gas harmless. [Know-how] Dry contact engraving in the manufacturing steps of semiconductor devices, for example, select one or more kinds of halogen gas such as carbon fluoride gas, sulfur hexafluoride, hydrogen chloride, hydrogen halide, boron trichloride, chlorine gas, etc. Gas, and one or more gases selected from oxygen, nitrogen, hydrogen, argon, or ammonia are added for the purpose of etching gas, and Si02, Si, SiW, SiN, Al, GaAs, GaAs, GaP, I nP Wait for the etching material to etch. Except for the aforementioned etching gas, the exhaust gas discharged by the etching device is used to etch the generated silicon halide, tungsten halide, halogenated carbonyl group, sulfur tetrafluoride, or reversely generated carbon dioxide gas. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the past, semiconductor devices were manufactured to exhaust the halogen-containing gases to make the exhaust gas harmless. This method is known as the wet method and the dry method. law. However, the equipment of the wet method is complicated, and there are problems in the post-treatment and absorption of the absorption solution. Furthermore, the alkaline aqueous solution of caustic soda or sodium carbonate is used for exhaust gas cleaning. Although the halogen-based gas reacts with the alkaline aqueous solution, But it is still not used due to the problem of clogging the exhaust line of the processing device. On the other hand, the dry method can easily improve the problem of the wet method. According to the paper size, the Chinese National Standard (CNS) A4 specification (T ^ Ϊ0 × 297 mm) is applicable. &Quot; Surface 4 · 501939 A7 __B7 V. Description of the invention (2 ) Provide suggestions for most pesticides and methods. The method may be, for example, (1) a method of using a pesticide that attaches ferric tetroxide to the surface of soda lime (Japanese Patent Application Laid-Open No. 6-2 2 13). (2) A method of contacting with activated carbon and then contacting with iron oxide (Japanese Patent Application Laid-Open No. 6-3 19 9). (3) Pesticides containing iron oxide and manganese compounds as main components, and a method of contacting metal oxides with gas after contacting them with activated carbon (Japanese Laid-Open Patent Publication No. 6-198 8 1 2 8). (4) A method in which thorium hydroxide is used as a main ingredient, and this is used again for water-containing pesticides (Japanese Patent Laying-Open No. 7-2 7 5 6 4 5) ° (5) Ferric oxide The method of using pesticides containing water as the main ingredient (Japanese Patent Application Laid-Open No. 7-2 7 5 6 4 6). (6) A method of using a pesticide supported on an alkaline metal salt or a tetraalkylammonium salt of aluminate of activated carbon (Japanese Patent Application Laid-Open No. 4-2 1 0 2 36), etc. In the method, the osmium will dry the exhaust gas containing halogen-based gas by using iron oxide, alkaline metal and alkaline earth metal compounds, activated carbon, and active ingredient-containing pesticides as harmless. However, compared with activated carbon, for example, the pesticide of item (6), although chlorine, boron trichloride, etc. have the same ability to kill, but hydrogen halide, silicon fluoride, etc. have higher ability to kill, but In fact, the size of this paper is treated by dry etching (CNS) A4 inspection (210X 297 ^^ 7 " ~ " " -5- (Please read the precautions on the back before filling this page) Ordering economy Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau and printed by the Consumer Cooperative of the Ministry of Economics and the Ministry of Economic Affairs. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 501939 A7 ___B7_ V. Description of the invention It is an object to provide a low-cost pesticide and a method for eliminating harmful halogen-based gases contained in uranium engraving and plutonium exhaust gas per unit volume. [Means for Solving the Problems] The present invention People and others, in order to solve the aforementioned problems, after careful review, they will contain specific iron oxides and alkaline earth metal compounds and activated carbon pesticides in a specific ratio, especially those with a high ability to remove hydrogen halides. It is found that the above-mentioned problems can be solved, and the present invention has been completed. The present invention shows the following (1) to (2 2) of the halogen-based gas pesticides, halogen-based gas detoxification methods, and the use of the same Method for manufacturing a semiconductor device: (1) 10 to 40 mass% of iron oxide selected from the group consisting of r-iron hydroxide hydroxide to iron oxide, and an alkaline earth metal compound containing 20 to 80 mass % And a halogen-based gas pesticide containing activated carbon 10 to 40% by mass. (2) The alkaline earth metal compound is composed of oxides, hydroxides, and carbonic acid of magnesium, calcium, scandium, and barium. At least one selected from the group consisting of salts is a halogen-based gas pesticide as described in (1) above. (3) The specific surface area of the activated carbon is 5 Ό 0 m 2 / g or more as described above ( 1) Pesticides for halogen-based gases according to item 1). (4) The above-mentioned pesticides are calcium-sulfate-containing pesticides for halogen-based gases as described in item (1) above. This paper applies Chinese national standards (CNS) ) A4 size (210X297mm) (Please read the notes on the back before filling This page) Order-7- 501939 A7 B7 V. Description of the invention (5) (Please read the precautions on the back before filling this page) (5) The content of the aforementioned calcium sulfate, for iron oxide, alkaline earth metal compounds and activity The total amount of carbon 1 is in the range of 0 to 0 · 2, and is a halogen-based gas pesticide as described in the above item (4). (6) The particle size of each of the foregoing pesticides is 100 μm Hereinafter, a powder of iron oxide, an alkaline earth metal compound, activated carbon, and calcium sulfate is used as a pesticide for the halogen-based gas described in the item (1) above to form a granulated product. (7) The particle size of the above-mentioned pesticide is a granular product in the range of 0.5 to 10 mm, and is a halogen-based gas pesticide as described in the above item (6). (8) The aforementioned halogen-based gas system is selected from the group consisting of halogen, hydrogen halide, silicon halide, tungsten halide, carbonyl halide, sulfur fluoride, arsenic chloride, phosphorus chloride, aluminum trichloride, and boron trichloride. At least one kind of gas is a pesticide of the halogen-based gas described in the above item (1). (9) A method of detoxifying a halogen-based gas, which is characterized in that a gas containing a halogen-based gas is brought into contact with the pesticide described in any one of the above (1) to (8). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (10) The aforementioned halogen-based gases are composed of halogen, hydrogen halide, silicon halide, tungsten halide, halogenated carbonyl, sulfur fluoride, arsenic chloride, phosphorus chloride, and trichloride. At least one kind of gas selected from the group consisting of aluminum and boron trichloride is the halogen-based gas elimination method described in (9) above. (1 1) A step of bringing a gas containing a halogen-based gas into contact with a pesticide made of activated carbon, and after this step, the method described in any one of (1) to (8) above The agent is in contact with the step, and is a method of detoxifying a halogen-based gas. This paper size applies to Chinese National Standard (CNS) Α4 · (210X 297 mm) -8-501939 A7 B7 V. Description of the invention (6) (Please read the precautions on the back before filling this page) (1 2) The specific surface area of activated carbon is 500 m2 / g or more, and the particle size is in the range of 0.5 to 10 mm. The halogen-based gas detoxification method described in the above item (11). (13) The halogen-based gas is included. The gas system is at least selected from the group consisting of halogen gas, hydrogen halide, silicon halide, tungsten halide, carbonyl halide, sulfur fluoride, arsenic chloride, phosphorus chloride, aluminum trichloride, and boron trichloride. One type of gas is a method for removing harmful halogens as described in (1 1) or (1 2) above. (1 4) A gas containing a halogen-based gas and (1) to (8) The step of contacting the pesticide described in any one of the following paragraphs), followed by the step of contacting the pesticide with a zeolite after this step, is a method of detoxifying a halogen-based gas. (1 5 ) The aforementioned zeolite refers to a synthetic zeolite and / or a natural zeolite, and the particle size thereof is in the range of 0.5 to 10 mm as described in the above item (1 4). (16) Harmful method of halogen-containing gas contained in the aforementioned synthetic zeolite MS-5A and / or MS-1 3X as described in (1 5) above, employee of Intellectual Property Bureau, Ministry of Economic Affairs Printed by a consumer cooperative. (17) The aforementioned halogen-based gases are composed of sulfur dioxide, in addition to hydrogen halides, silicon halides, tungsten halides, halogenated carbonyls, fluorine such as sulfur, chlorine such as arsenic, phosphorus chloride, and aluminum trichloride. A method for removing harm of at least one gas selected from the group consisting of boron trichloride and boron trichloride as described in any one of (1 4) to (16) above. (1 8) The concentration of halogen-based gas in the system is 10. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -Q-501939 A7 _B7. V. Description of the invention (7) The above vol% is as above (9 ), (11), and (14) The halogen-based gas detoxification method according to any one of (1) and (19) A method for manufacturing a semiconductor device, comprising: using a carbon fluoride or sulfur hexafluoride; , Halogen, hydrogen halide, and boron trichloride, at least one selected from the group of compounds, The removal step described in any one of (1) to (8) above, as an etching step or a cleaning step of an etching gas or a purge gas, and a step in which a halogen-based gas is to be discharged from these steps and brought into contact with and detoxified. (2 0) The aforementioned detoxification step is a method for manufacturing a semiconductor device as described in the above item (19) including a step of contacting a pesticide made of activated carbon. (2 1) The aforementioned detoxification The step is a method for manufacturing a semiconductor device as described in the above item (19), which includes a step of contacting a pesticide made of zeolite. (2 2) The concentration of the halogen-based gas in the gas discharged in the etching step or the decontamination step is equal to or less than 1% and less than 1% of the semiconductor device according to any one of (1 9) to (2 1) above. Production method. [Embodiments of the Invention] In the manufacturing steps of the semiconductor device, for example, a dry-type detoxification method in which a halogen-containing gas is exhausted from a dry etching step. The exhaust gas is guided with the carrier gas to guide the harm-removing cylinder to be filled with various pesticides. The contact with the pesticide is rendered harmless, and only the gas is discharged out of the system. The end point of the detoxification tube is regarded as the detection method. The ρ Η test paper or the paper size that is completely changed in color when it comes into full contact with the tooth gas is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) '- --------- f (Please read the notes on the back before filling out this page) Order 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy-10-501939 A7 _____ B7__ V. Description of the Invention (8) (Please read the precautions on the back before filling in this page) P Η Indicators such as hue detection agents supported on alumina, silicone, and other carriers are integrated with the harm removal device, which is usually used widely. Therefore, as indicated in (1) to (6) of the foregoing prior art, the conventional pesticides and methods of harming have a low ability to remove hydrogen halides. First, the hydrogen halves completely, and the endpoint detection agent is completely discolored. Although the ability of other halogen-based gases is sufficiently maintained in any case, the frequency of the harm-removing tube becomes more, resulting in a problem of high cost. In this regard, if the pesticides and methods for conquering the present invention are conquered, the exchange frequency of the pesticides will be reduced, and the cheap dry uranium engraved exhaust gas may become harmless, which can solve the problems related to the manufacturing steps of semiconductor devices. Hereinafter, the present invention will be described in detail. The manufacturing process for the semiconductor device of the present invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as dry etching, is made of a material such as carbon fluoride gas, sulfur hexafluoride, halogen, hydrogen halide, or boron trichloride. Select one or more types of gas to be etched. Depending on the purpose, select one or more types of gas such as oxygen gas, nitrogen gas, hydrogen gas, argon gas, and helium to add, and it will be engraved by uranium (S i 0 2, S i , Si W, SiN, Al, GaAs, GaP, InP, etc.), when engraving, the exhaust gas exhausted by its etching device, the other etching mentioned above, the silicon halide v tungsten halide generated by etching, Halogen-based gases such as aluminum chloride, sulfur tetrafluoride, and halogenated carbonyl groups are decomposed with these contained gases such as hydrogen halide and sulfur dioxide. The present invention is a pesticide for removing exhaust gas containing these gases, Disinfection method and manufacturing method using semiconductor device 〇- The present invention uses pesticides and disinfestation methods as degassable gases. The paper size can be applied to Chinese National Standard (CNS) A4 specification (~ ~ -11- 501939 Α7 Β7 Five Description of invention (ιί (please read the notes on the back before filling this page), gas systems such as BC 13, Si C 14, Si Br4 are effective, but gases such as HC 1 or Si F4 are almost ineffective It is well-known. However, as mentioned above, the harmful effect of a pesticide that combines activated carbon and iron oxide or a combination of activated carbon and alkaline earth metals has hardly improved. As described above, the present invention The effects of each of the iron oxide, alkaline earth metal compounds, and activated carbon contained in the halogen-based pesticides cannot be exerted individually or in a dichotomy, and the combination of iron oxide, alkaline earth metal compounds, and activated carbon is used in combination. The pesticides are mixed into pesticides, and the harmful effects of halogen-based gases are exerted. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the iron oxides and alkaline-earth metal compounds of pesticides are reacted with halogen-based gases to produce iron. Alkaline earth metal halogen compounds, except for fluorine compounds, are almost deliquescent compounds. When halogen-based gases that do not contain fluorine atoms are used as harmful compounds, their deliquescent compounds are repeatedly Occurrence of the harm-removing cartridge becomes the cause of clogging. Therefore, the addition of calcium sulfate to the harm-removing agent of the present invention can also make non-deliquescent pesticides when the halogen-based gas that does not contain fluorine atoms is used as the harm-removing agent. In the case of coexistence with a fluorine-based gas, in order to prevent the deliquescent property of the fluoride, the addition of calcium sulfate may not necessarily be restricted. Secondly, iron oxide, an alkaline earth metal compound, and activated carbon are used as raw materials of the pesticide used in the present invention. In terms of iron oxides, at least one kind of compound is selected from the group consisting of r — F e〇〇H (r — iron oxide hydroxide) and r — F e 2 03 (r — iron oxide), and 7 — F e〇〇Η is suitable. That is, r — F e〇〇Η and r — F e 2 〇 3 such as α — F e 2 〇 3 compared with other iron oxides as the paper standard applicable. National standards (CNS) A4 specification (210X297 mm) -14- 501939 A7 _ B7 V. Description of the invention (id Secondly, in terms of the manufacturing method of the pesticide of the present invention. According to the method for detoxifying a halogen-based gas according to the present invention, it is characterized by using a pesticide containing aforesaid iron oxide, an alkaline earth metal compound, and activated carbon in a specific ratio. This pesticide contains iron oxide, alkaline earth metal compounds, and activated carbon. The iron oxide is 10 to 40% by mass, the alkaline earth metal compound is 20 to 80% by mass, and the activated carbon is 10 to 4. 0% by mass is preferred, and the system is preferably iron oxides 15 to 35% by mass, alkaline earth metal compounds 3 0 to 70% by mass, and activated carbon 15 to 35% by mass, more preferably the iron oxides 2 0 to 30% by mass, alkaline earth metal compounds based on 40 to 60% by mass, and activated carbon based on 20 to 30% by mass are preferred. This blending ratio is the blending ratio that makes full use of the characteristics of each component. In addition, the pesticide of the present invention is blended with iron oxide, an alkaline earth metal compound, and activated carbon in the aforementioned mass%, and calcium sulfate may be added as necessary. The proportion of calcium sulfate is preferably in the range of 1, 0 to 0 '2 for the total mass of iron oxide, alkaline earth metal compound, and activated carbon, and more preferably in the range of 0.5 to 0 · 1. If the concentration is too low, the effect will be lost, and if the concentration is too high, the total amount of iron oxide, alkaline earth metal compounds and activated carbon will be relatively reduced. The effect of calcium sulfate will also saturate the halogen-based gas with high efficiency, which cannot be eliminated. The pesticide according to the present invention is preferably a granular product in which iron oxide, an alkaline earth metal compound, and activated carbon or a powder in which calcium sulfate is added to the mixture so that the effect is fully exhibited. Granulation is in accordance with the aforementioned mixing ratio, and no binder is used. Although only granules can be fully granulated with water, the particle size of the raw materials is large. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) " (Please Read the notes on the back before filling this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives -16-501939 A7 ___ B7_ V. Description of the invention (If it is less coarse, add a binder with water. If you have The binder does not affect the performance of the pesticide, that is, the type and amount are not limited. The invention uses a granular pesticide, and after mixing each raw material, it is mixed with an appropriate amount of water, and the mixed product is granulated as Granular products. The preparation of this granular product requires mixing with a kneader and granulation. Although it is cheap to carry out at the same time, mixing and granulation can be performed separately. For example, using a Henschel mixer or vertical mixer, mixing and granulation Although granulation can be performed at the same time, mixing of raw materials can be performed using a Henschel mixer or a V-type mixer. Second, granulation can be performed using a dish-type granulator or a drum Pelletizer. Secondly, in order to increase the hardness of the granulated product and to evaporate moisture, it is dried at 100 to 150 ° C for 3 to 5 hours in an air stream of an inert gas such as air-type nitrogen. Dryer, 1 10 ° C, 2 to 3 hours to reduce the drying loss if the mass is below 1% by mass, although the purpose can be achieved, but the final product is better to contain more water than to contain the machine. Especially C 1 2, S〇2 There are also cases where the pesticide is effective. The reason why the pesticide of the present invention is used as a granulated product is to increase the chance of contact between the dry etching exhaust gas and the pesticide. For example, if the particle size of the pesticide is too large, The surface area for the absorption and diffusion of halogen-based gases is relatively small, and the diffusion speed becomes slower. On the contrary, if the particle size of the pesticide is too small, the surface area involved in adsorption and diffusion becomes relatively large. Although the diffusion speed becomes faster, If the amount of gas increases, the differential pressure also increases, and obstacles such as the compaction of the harm removal tube (device) cause obstacles. Therefore, even pellets, tablets, and balls can be used, especially because of its porosity. The particle size is in the range of 0 · 5 to 10 mm, and is preferably in the range of 1 to 5 mm. The paper is better. This paper is applicable to China National Standard (CNS) Α4 specifications < 210X 297 public envy) " ~ -17 · (Please read the notes on the back before filling out this page), 1T Printed by the Employees 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed 501939 A7 __ _ B7 V. Description of the invention (β Secondly, in terms of the method for harm elimination using the halogen-based gas of the present invention. Although the pesticide of the present invention can use a fixed layer, a moving layer, and a flowing layer, it is generally It can be used in a fixed layer. The pesticide of the present invention can be filled in the harm-removing tube alone or in the same harm-reducing tube with activated carbon or zeolite together at the necessary ratio, or it can be charged with various separate harm-reducing tubes. In addition, the length of the filling layer of the pesticide and activated carbon or zeolite of the present invention and the size (volume and cross-sectional area) of the harm-removing cylinder are based on the amount of halogen-based gas (concentration and its composition ratio) to be harmed. The flow rate of the dry etching exhaust gas is determined by allowable installation space, allowable pressure loss, etc. The cross-sectional area of the pesticide is determined as the linear velocity (LV) in the cylinder, such as 0 · lm ~ 1 0 m / mi. The range of η is Although the contact (treatment) pressure of the exhaust gas is not specifically limited, the halogen-based gas contains dry etching exhaust gas. If the exhaust system is considered to be exhausted by a vacuum pump, the range is from 1 to 20 kPa, preferably from 5 to The range of 5 kP a is better. The processing temperature of the exhaust gas is especially unnecessary. Heating cooling can be performed at normal temperature (20 to 30 t:). In addition, although the halogen-based gas contains no moisture in the dry etching exhaust gas, The left dry state can be used in the wet state, but the halogen-based gas system can be used if the concentration of the corrosive gas is not condensed. Although the pesticide of the present invention is suitable for the dry etching exhaust flow rate and its halogen-based gas concentration, It is specifically limited, but it determines the relationship between the exhaust gas flow rate and the concentration of its halogen-based gas. Although it is not economically beneficial if it is too thin, it depends on the type of halogen-based gas if it is too thick, but it depends on the reaction and the heat of adsorption. The temperature of the harm reduction tube rises, and the concentration of Η20 generated by the reaction also becomes too thick. From this Η20, dew condensation of the tube and piping in the tube and piping, this paper applies the Chinese National Standard (CNS) A4 Specifications (210X297 male ^) ~ '' (Please read the notes on the back before filling out this page} Threading__ -18-501939 A7 ___B7_ V. Description of the Invention (The problem of deliquescence of pesticides, etc., the concentration is due to 1 〇 V 0 1% or less is preferred, preferably 5νο1% or less, and more preferably 2νο1% or less. The detoxification method of the present invention satisfies the aforementioned conditions. The detoxification cylinder contains a dry etching gas exhausted by a pure gas The nitrogen gas carrier gas is the same. Because the pesticide of the present invention and activated carbon or zeolite are brought into contact, the halogen-based gas is fixed (reactively adsorbed) to each pesticide to make it harmless. Figure 1 An example of implementing a harm removal device. 1 ~ 4 series etching system, the etching gas supply device 1 supplies the etching gas and the vacuum pump 3 'according to the pressure in the etching chamber-2 to reduce the pressure to generate plasma, and the etching material in the etching chamber-2 is used to etch Device. The etching exhaust gas from the etching systems 1 to 4 is exhausted according to the vacuum pump 3 and the vacuum pump exhaust nitrogen gas 4 (the carrier gas for the etching exhaust gas). In addition, the 5 ~ 9 series of detoxification systems introduce the exhaust gas containing the aforementioned halogen-based gas into the detoxification cylinder 6 through the inlet 5 of the detoxification cylinder, and are filled with the pesticide and activated carbon according to the present invention in accordance with the gas to be detoxified. The zeolite is contacted to fix the halogen-based gas to the pesticide, activated carbon, or zeolite of the present invention by physical (adsorption) or chemical (halogen compound). The detoxified exhaust gas passes through the outlet 7 of the detoxification cylinder, passes through the gas detector 8 ', and confirms whether there is a leak of the halogen-based gas, and the exhaust gas is discharged to the atmosphere through the exhaust duct through the exhaust duct. The limit capability (end point detection) of the hazard killer can be known by the gas detector 8. The gas detector 8 has a container filled with a hue detection agent for discoloration with a halogen-based gas (a container for which the discoloration of the hue detection agent inside can be monitored from the outside), even if it is integrated with the harm reduction cartridge. Secondly, the Chinese paper standard (CNS) A4 (210 x 297 mm) is applied to the paper size of the cartridge for the pesticide and activated carbon or zeolite of the present invention. &Quot; 一 -19- (please read the note on the back first) Please fill in this page again) Ordering table Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 501939 A7 _B7___ V. Invention description (for charging method) For the pesticide of the present invention, if it contains a certain amount of water, although almost Harmful halogen-based gas, in particular, enhances the ability of C 1 2 and S 2 to eliminate harmful substances, but it is not practical to use a pesticide for dry etching exhaust. That is, the dry-etched wafer (the etchant) is transported. Pretreatment, etching, etc. are used as a one-cycle intermittent operation pattern (dry and intermittent operation), and the exhaust of the harm removal cylinder is introduced. The only carrier gas (nitrogen that does not contain halogen-based gases) is nitrogen. The time of the gas) is a behavior. Therefore, the moisture in the pesticide will be dehydrated in contact with its exhaust gas. Although halogen-based gases other than C 1 2 and S 0 2 have such a harmful effect, but the pesticide In order to reduce C1 2, S 〇2 The end point of the harmful power transmission must be exchanged. Therefore, in order to eliminate the harmful effects of the nitrogen gas carrier gas, the pesticide in the present invention hardly contains water, and because of the processed C 1 2 and S〇2 or hydrolytic decomposition to generate S 0 2 containing component gases, and dry etching gas exhaustion methods that do not contain such cases (as shown in the examples, there is a small amount is not limited) become necessary. Although it depends on C 1 2 and S 〇2 of the gas to be treated or the component gas of S 0 2 when it is decomposed to water, but there is almost no exhaust gas, as shown in FIG. 2, the pesticide 1 〇 of the present invention is separately treated. Filling the detoxification cylinder 6, since the other processing gas is guided by the nitrogen gas carrier gas to contact the pesticide, the halogen-based gas in the gas to be processed can be used for detoxification. However, for example, aluminum is dry-etched with C 1 2 The exhaust gas has been dried with the pesticide of the present invention because it contains C 1 2, as described above, it has insufficient harm removal ability. Here, the exhaust gas is first made to absorb more activated carbon with a capacity of c 1 2 After contacting, the paper size of C 1 2 activated carbon is applicable to China Home Standard (CNS) A4 Specification (210X297 public ^ I-20- (Please read the notes on the back before filling this page), ιτο printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 501939 A7 ____B7_ V. Description of the invention (d ( Please read the precautions on the back of the page before filling in this page) Adsorption process or generated by etching steps, which cannot be harmed by activated carbon HC 1 gas Detoxification ability Because the high-priced pesticide of the present invention is in contact, it contains C 1 The removal of the dry etching exhaust gas in 2 makes it possible to improve the removal ability compared with each case. That is, the order of activated carbon 11 and the pesticide 10 of the present invention is shown in FIG. 3 Detoxification cylinder 6 (if the order of activated carbon 11 and the pesticide 10 of the present invention is even a separate detoxification cylinder), the dry etching containing C1 2 will be exhausted, depending on the introduction of the detoxification cylinder At the entrance 5, the method for achieving the improved capability of harm elimination shall be given. The ratio of activated carbon to the pesticide 10 of the present invention may be determined in accordance with the composition ratio of C 1 2 and other halogen-based gases in the dry etching exhaust gas. Although the detoxification method of the present invention can be cited as the type of activated carbon, such as coconut grain carbon, stone carbon, wood carbon, etc., the specific surface area is preferably 500 m2 / g or more, and the specific surface area is 100 Above 0 m 2 / g, for gas adsorption, the necessary pore distribution will hold Peak Coconut activated carbon around 20 people. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and using silicon or silicon oxide film to etch and exhaust SF 6, which causes gases such as S F4 or S OF2, that is, decomposes water to generate SO 2 containing gas . The fluorine element in a compound such as Si F4 or S 0F2, which has been dried, is treated as Ca F2, and the sulfur compound is fixed with Ca S 0 3 as the pesticide of the present invention. However, in particular, when the amount of compounds such as SF4 or SOF2 is large, the amount of Ca S03 produced also increases. Once the reaction of the fixed sulfur element and hydrogen halide is regenerated with S02 or the like. Therefore, in the case of the dry etching exhaust gas containing S 0 2, it is possible to improve the detoxifying ability by contacting the zeolite after contacting with the pesticide of the present invention. That is, as shown in FIG. 4, the pesticide 1 of the present invention and the paper size are applicable to the Chinese National Standard (tNS) A4 specification (210X297 mm) " -21-501939 A7 _______B7 V. Description of the invention (β zeolite 1 2 The order is to fill the harm-removing cylinder 6 (if the order of the pesticide 10 and zeolite 12 of the present invention, even separate harm-reducing cylinders are possible), because it will contain S〇2 (also contains SF 4 or s 〇F2) The dry etching exhaust gas is introduced into the inlet 5 of the harm removal cylinder to achieve a method for improving the harm removal ability. The ratio of the pesticide 10 to the zeolite 12 of the present invention corresponds to S in the dry etching exhaust gas. The composition ratio of 〇2 (also containing SF4 or SOF2) and other halogen-based gases may be determined. Although the types of zeolites used in the present invention such as natural and synthetic zeolites (MS-5A, MS- 1 3X), which is preferably synthetic zeolite, and MS—1 3 X with a large S02 adsorption capacity is preferred. As explained above, the halogen-based gas contains dry uranium etched exhaust gas, which is separately charged. The pesticide or activated carbon of the present invention or a pesticide cartridge filled with two layers of zeolite is used to vent the exhaust system based on the exhaust gas. It is possible to make a detoxification method capable of improving the detoxification ability per unit volume. The present invention can render harmless if the etching efficiency in the semiconductor device manufacturing step or the decontamination step is based on the high efficiency of exhaust gas containing a halogen-based gas. Secondly, with regard to the manufacturing method of a semiconductor device containing a detoxification step using the aforementioned halogen-based gas detoxifier and detoxification method. The present invention uses an etching gas or a purge gas according to the methods of carbon fluoride, sulfur hexafluoride, Compounds of halogens, hydrogen halides, and boron trichloride are selected by using at least one gas engraving step or decontamination step, and a gas containing a halogen-based gas is discharged through these steps, and brought into contact with the aforementioned pesticide The steps for removing harmful substances are the manufacturing methods of semiconductor devices. For the manufacturing process of semiconductor devices such as LSI or TFT, this paper size is applicable to Chinese National Standard (CNS) A4 specifications (210/297 meals 1 ~ ^ (Please read the back Please fill in this page for the matters needing attention) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the staff consumer cooperative -22- 501939 A7 ___B7 V. Description of the invention (20 (Please read the note on the back first) Please fill in this page for details) C VD method, sputtering method or vapor deposition method to form a thin film or thick film, etc., to etch a circuit diagram, etc. For devices that form a thin film or thick film, in order to remove the inner wall of the device, Clean up unnecessary deposits. Such unwanted deposits, such as producers, are the reason for the formation of particles. It is necessary to remove them at any time in order to produce high-quality films. Fluorine, chlorine, bromine, and other halogen gases are used. The etching step is, for example, described in Japanese Unexamined Patent Publication No. 4 1 3 1 4 3 31, and dry contact etching conditions such as plasma etching can be performed. In the uranium etching step, the other halogen gas in the exhaust gas is used as a decomposition product. Although hydrogen halide, silicon halide, tungsten halide, or carbonyl halide gas is generated, it is possible to use the pesticide of the present invention. These compounds are rendered harmless. When a chlorine gas is used as an etching gas, for example, a chlorine gas system reacting is discharged. In this case, prior to the treatment of the pesticide of the present invention, the contact with the activated carbon as a pesticide as described above, chlorine gas can also effectively kill the pesticide. Etching steps printed by employees ’cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and using gases such as carbon fluoride or sulfur fluoride, as described in Japanese Unexamined Patent Publication No. 4-1 2 1 3 7 9 and plasma etching etc. Dry engraved conditions. In this case, although gases such as hydrogen halide, silicon halide, tungsten halide, or hydroxyl halide are generated in the same manner, these compounds can be rendered harmless according to the use of the pesticide of the present invention. Sulfur fluoride etching is also used, which is the case of sulfur dioxide that generates decomposition products. In this case, after the pesticide of the present invention is treated as described above, the zeolite can be contacted to form a pesticide, and sulfur dioxide can also effectively kill the pesticide. Hereinafter, although examples and comparative examples are described in detail according to the present invention, the present invention is not limited to these examples. This paper size applies to Chinese national standards (CNS> A4 size (210X297mm) ~ • 23-501939 A7 __B7_ V. Description of the invention ((Examples of pesticide preparation)) Table 1 shows the various raw materials used in each test pesticide Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Table 1] Raw material name of the pesticide used in the test Average particle diameter (/ zm) Specific surface area (m2 / g) Manufacturer (purchased manufacturer) Ferric acid a -Fe203 < 1 25 Pure Chemistry (stock) a -FeOOH < 1 70 Toda Industry Co., Ltd. γ -Fe2〇3 < 1 20 Toda Industry Co., Ltd. T -FeOOH < 1 60 Ishihara techno (share) Fe3〇4 < 1 5 Pure chemical (shares) Alkaline earth metal compounds Calcium hydroxide Ca (OH) 5 15 Yoshizawa lime industry (shares) Samarium hydroxide Sr (〇H) 2 < 1 — Pure chemical activated carbon Coconut activated carbon (Y-180C) — 1000-1500 MSG fine teohno (share) Activated carbon (F-17C) — 1000 ~ 1500 MSG fine techno (share ) Activated alumina (r-Ai2〇3) 5 200 Mizusawa Chemical Co., Ltd. Natural zeolite 50 Knimine Industrial Co., Ltd. Calcium Sulfate (CaS〇4) 1 '— Pure Chemistry (Plant) Table 1 shows the use of raw materials, such as Tables 3, 4, and 5 indicate trials (please read the precautions on the reverse side before filling out this page) This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) Surface 24-501939 A7 B7 V. Invention Instructions (2 $ (please read the precautions on the back before filling this page). Under the test conditions, each substance is mixed with a Henschel mixer. After adding water to granulate, it is dried at 110 ° C for 3 hours and divided by sieve. 5. Prepare granular products with a particle size of 0 · 8 5 ~ 2 · 8 mm. (Commercially available pesticides and adsorbents) Use pesticides other than the preparations described above as shown in Table 2. Intellectual Property Bureau, Ministry of Economic Affairs Printed by employee consumer cooperatives [Table 2] Seeds of pesticides and adsorbents sold by the city Particle diameter (mm) Specific surface area (m2 / g) Manufacturer (purchased by manufacturer) Coconut activated carbon 0.5 ～ 3 · 0 > 1100 MSG fine techno (share) (-10 Zeolite 1.0 ～ 2.0 — Union Showa (share) MS -3A zeolite 1.0-2.0 — Union Showa (share) MS-4A zeolite 1.0 ～ 2.0 — Union Showa (share) MS-5A zeolite 1.0 ～ 2.0 — Union Showa (share) MS-13X activated alumina (r-) 1.0- 2.0 210 Mizusawa Chemical Co., Ltd. Carbon test 1.5 ～ 3.5 A pure chemical chemistry (share) NaOH supplemented activated carbon 2.0 ～ 5.0 > 1100 MSG fine techno (share) YN-4 This paper size applies Chinese National Standard (CNS) A4 specification ( 210X297mm) 25-501939 A7 B7 V. Description of the invention (23 (Except for harm) (please read the precautions on the back before filling this page) Use the same principle as shown in Figure 1, each of Tables 3 and 4 The method of the present invention is carried out under test conditions. That is, in an acrylic cylinder (inner diameter 7 0 111 111 \ cylinder length 100 000 111 111), the test height of the test pesticide 5 500 mm (capacity 17 3 m) is used. £), dilute the nitrogen gas and exhaust the carrier gas in the acrylic harm killer (simulation) Ventilation. At this time, the flow rate of the processed gas: 0.751 / min. The target gas (halogen) gas concentration in the processed gas: 1. Ovol%. The pure speed of the processed gas is 1.85m / min. The processed gas is also analyzed by any test. Decontamination target (halogen) concentration in gas, gas detection tube method or pure water absorption ion chromatography. The capability is that the concentration of the target gas (halogen) in the processing gas at the outlet of the pesticide removal tube is 1 ppm by volume (lVolppm). The end point (the capacity limit of the pesticide) is the time. Harmful object (halogen-based) The molar amount (m ο 1) of the gas and the tritium charge from the pesticide represent the mole (mo 1) of the halogen-based gas per unit volume of the pesticide. Ability of printed pesticides (adsorbent) by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (mol / L-agent) = (C / 100 XQXT) + (RXV / 1000) Gas concentration (v 〇1%) Q: Exhaust gas concentration (L / mi η) D: Ventilation time from exhaust to the end point (mi η) R: Gas coefficient (correction coefficient of test temperature and pressure) V: Elimination of harm Charge amount of sorbent (adsorbent) (^ Paper size applies to Chinese National Standard (CNS) A4 specifications < 210X297 mm) ~ " Earn 26 · 501939 Α7 B7 V. Description of the invention (Further, the actual device with the same principle as that shown in Fig. 1 or the embodiment described later is used to implement the test of the present invention. That is, the actual test In the dry etching step, the exhaust gas containing halogen-based gas will be exhausted. The conventional method of detoxification and the combination of activated carbon or zeolite with the pesticide of the present invention are used to perform a comparative test with the method of detoxification. In this case, the limit of the detoxification ability Set the color change of the hue detector in the detector of the integral type of the cartridge as the end point. Its ability is compared with the same etching conditions and the same volume of the pesticide (cylinder). That is, the halogen in the dry etching exhaust gas is compared. The degassing time of the gas (actually the extension time of the etching gas supply) or the time between the processing time of the wafer (the material to be etched) (the number of etching batches and the number of etchings) is compared to confirm its ability. (Examples 1 to 5 ) Examples 1 to 5 show the test conditions as shown in Table 3. In the three-component system of iron oxide (r-FeOOH, r-Fe203), alkaline earth metal compounds, and activated carbon, and the three-component system, add Calcium sulfate was used to adjust the pesticide, and the test was performed. The results are shown in Table 3. The harm removal ability of S i F 4 and the harm removal ability of HC 1 were sufficiently high. (Comparative Examples 1 to 5) The test conditions of Comparative Examples 1 to 5 are shown in Table 4, and the three components of iron oxides, alkaline earth metal compounds, and activated carbon other than τ-F eOOH and r-F e203 are adjusted and changed. r One F e 00 Η, three components of alkaline earth metal compounds, activated carbon are the pesticides adjusted by the mixing ratio of each raw material, and the test is carried out. The results are shown in Table 4. This paper indicates that the Chinese paper standard (CNS) A4 specification is applicable to this paper size. (210 X297 mm) (Please read the notes on the back before filling out this page) Γ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -27- 501939 A7 B7 V. Description of the invention Either F4 or HC 1 has a lower harmful effect compared with the pesticide of the present invention. (Comparative Examples 6 to 10) Comparative Examples 6 to 10 The test conditions shown in Table 5, Various iron oxides were prepared as individual pesticides and tested. As shown in the test results shown in Table 5, in terms of the HC 1 detoxification ability, although only γ — F e 〇 〇 Η high capacity can be obtained, but the detoxification ability of S i F 4 is not even in any iron oxide. (Comparative Example 1 1 ~ 1 5) Comparative Example 1 1 ~ 1 5 The test conditions shown in Table 5 are adjusted according to the test of soil metal compounds alone, activated carbon units and iron oxide (7-F e 〇〇Η), alkaline earth metal compounds, activated carbon must be one of the two-component pesticides, the test is carried out, the results are shown in Table 5, the results of the formula test, S i F 4 of the harm None of the capabilities can be improved significantly. (Comparative Examples 16 to 24) Comparative Examples 16 to 24 The test conditions shown in Table 6 use activated alumina, natural zeolite, synthetic zeolite, alkali carbon, Commercially available pesticides with activated carbon added to sodium hydroxide were subjected to the same test. The results are shown in the test results shown in Table 6. Regardless of which H C 1 and S i F 4 have lower harmfulness compared with the pesticide of the present invention, they are also low. This paper is suitable for financial items @ 家 鲜 （CNS） 八 4 秘 （210X297mm） '一 ^ " -28- (Please read the precautions on the back before filling this page) Order the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed 501939 A7 B7 V. Description of the invention (2 $ (please read the precautions on the back before filling this page) Also, for these market-supplied pesticides, in terms of the detoxifying ability of C 1 2榖 Activated carbon and Na a 0 Η attached activated carbon) are the highest. Regarding the harmful ability of SO 2, natural zeolite and synthetic zeolite (MS-5A, MS-1 3X) are high, among which MS-13X also has the highest capacity. Example 6) The experiment of the present invention was carried out using a real device with the same principle as that shown in FIG. 1. As a filling method, as shown in FIG. 3, activated carbon (organic base is added with activated carbon and the pesticide of the present invention to The ratio of 7: 3 is filled with 2 layers, and the organically-added activated carbon of the comparison device is separately charged (100%). These are filled with each of the harmless cylinders with an effective volume of 130 L. These Pesticide tube, under the same conditions, using HB I * 50SCCM, Cl2 50SCCM etching gas, will etch Dry-etching the exhaust gas, and using a nitrogen gas carrier 2 0 SL Μ to guide the aforesaid harm-removing cylinder for testing. Compared with the result of setting the delaying etching time of the whole type of the harm-reducing cylinder to the hue detector discoloration, to compare the device's harm-reduction method 2 Hour 'organic base attached activated carbon and the pesticide combination device of the present invention Detoxification method 500 hours by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the detoxification method of the present invention shows 2.5 times the ability of detoxification (Example 7) The test of the present invention was carried out using the actual device shown in Fig. 1 with the same principle. The charging method 'as shown in Fig. 3 activated carbon (coconut activated carbon) and the pesticide of the present invention Fill 2 layers at a ratio of 7: 3, and apply the standard of the Chinese National Standard (CN7) A4 (2 ^ (^ 297mm)) to the paper size of comparison paper: -29- 501939 A7 B7_ V. Description of the invention (2 $ of organic alkali-attached activated carbon alone (100%) is filled with 2 layers, and these are filled with each effective volume of 130 L. each of the harmless cylinders. These harmless cylinders, the lead in the same Under the etching conditions, using BC 1 3 50SCCM, C12 100SCCM, Ar 10 0 SCC Μ The gas, dry etching exhaust gas nitrogen gas carrier 20 S LM, was guided in the aforesaid detoxification tube to conduct a test. Compared with the delayed etching time of setting the result of the entire detoxification tube type to the hue detector's discoloration, comparison device The method of removing harmful substances is 480 hours, and the method of removing harmful carbon from coconut grain activated carbon of the present invention is 950 hours. The method of removing harmful substances of the present invention is about 2 times of the harmful ability. (Embodiment 8) The actual device shown in Fig. 1 was used to carry out the test of the present invention. The charging method is as shown in FIG. 2 (100%) for charging the pesticide of the present invention alone. The organic base was supplemented with activated carbon alone (100%) with a comparative device. These are filled with harm-removing cylinders each having an effective volume of 130 L. In these detoxification cylinders, poly-silicon was used under the same etching conditions for the dry etching of uranium-etched gases such as Br 20SCCM, HC1 200SCCM, He 200SCCM, and SF6 5SCCM. Nitrogen carrier gas for exhaust gas 2 0 S LM , Guide the aforementioned harm removal tube for testing. Compared with the delayed etching time of setting the integrated type to the hue detector's discoloration, comparing the device's detoxification method with 700 hours, the detoxification method with the pesticide device of the present invention is 35,000 hours. The detoxification method of the present invention shows 5 times the detoxification ability. The Zhang scale is applicable to China National Standard (CNS) A4 < 2l0X297mm) (Please read the notes on the back before filling out this page) Order printed by the Intellectual Property Bureau's Consumer Cooperatives -30-501939 A7 B7 V. Description of the invention ((Example 9) as shown in the figure The pesticide and zeolite of the present invention represented by 4 are filled in two layers at a ratio of 5: 5, and charged with activated carbon alone (100%) in a comparison device. Fill each of these effective volumes 1 3 0 L detoxification cylinders. In these detoxification cylinders, silicon is used under the same etching conditions using HC 1 700 SCCM, SF6 700SCCM etching gas, and the dry etching exhaust gas is nitrogen gas carrier gas 2 0 S LM Guide the pre-harmicide cartridge to conduct the test. Set the integrated type in the harm-removal cartridge until the color detector changes color, as compared with the number of silicon wafer processing sheets. For a comparison device of 20,000, the pesticide of the present invention will be used. 42,000 sheets are combined with zeolite, and the detoxification method of the present invention represents about 2 times the detoxification capacity. (Please read the precautions on the back before filling this page) Order the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed paper scale · degrees apply to Chinese National Standard (CNS) A4 Specifications (210X297 mm) -31-501939 A7 B7 V. Description of the invention (23 Favors-Hnli (琴 i / l_) * R Miscellaneous repair tray FREE οο ντ s s ΟΤ

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〔1撇〕 試驗結果 SiF4除害能力 (mol/1-劑） ο 寸 O 寸 o 寸 〇 CO o HC1除害能力 (mol/1-劑） ON cn o m csi m 試驗條件 除害劑 比表面積 (m2/g) 270 csi ON CO csi OO CM ...............< ，丨丨丨丨丨丨丨·Η vr) CO 高密度 (g/ml) 0.66 1 0.72 i ! 0.73 1_ 0.70 1 1 0.60 調製除害劑之組成及 驟s 5 ^ 1 ^ 倍歡 藏 te 1111α a -FeOOH/Ca(OH)2/AC(Y-180C) (25 / 50 / 25 ) a -Fe2〇3/Ca(OH)2/AC(Y-180C) (25 / 50 / 25 ) Fe〇3〇4/Ca(OH)2/AC( Y-180C) (25 / 50 / 25 ) T -FeOOH/Ca(OH)2/AC(Y-180C) (5 / 90 / 5 ) r -FeOOH/Ca(OH)2/AC(Y-180C) (45 / 10 / 45 ) ΛΛ 蒙 rH CM 00 寸 LO (請先閲讀背面之注意事項再填寫本頁)[1 skimming] Test results SiF4 harm removal ability (mol / 1-agent) ο inch O inch o inch 〇CO o HC1 harm removal ability (mol / 1-agent) ON cn om csi m Test conditions Specific surface area of the pesticide ( m2 / g) 270 csi ON CO csi OO CM ............... < 丨 丨 丨 丨 丨 丨 丨 Η vr) CO high density (g / ml) 0.66 1 0.72 i! 0.73 1_ 0.70 1 1 0.60 Modulate the composition and steps of pesticides a -Fe2〇3 / Ca (OH) 2 / AC (Y-180C) (25/50/25) Fe〇3〇4 / Ca (OH) 2 / AC (Y-180C) (25/50/25) T -FeOOH / Ca (OH) 2 / AC (Y-180C) (5/90/5) r -FeOOH / Ca (OH) 2 / AC (Y-180C) (45/10/45) ΛΛ 蒙 rH CM 00 inch LO (Please read the notes on the back before filling this page)

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XU-SS 00 01 丨 λ 磐起、艇鵷屋 寸丨ΝΑ 醒#1胺銮藤ΗοβΝ <N Csl CO Csl 本紙張尺度適用中國國家標準（CNS ) A4規格（21 OX297公釐） 35- 501939 A7 _B7_ 五、發明説明（ 〔發明之效果〕 (請先閲讀背面之注意事項再填寫本頁) 如以上說明，將本發明之特定的氧化鐵、鹼土類金屬 化合物及活性碳以含有特定之比例之除害劑，尤其鹵化氫 之除害能力係高除害劑，由半導體裝置步驟予以排出含有 鹵素系氣體，可效果的除害排氣。又其排氣即使氯等之鹵 素氣體或含有二氧化硫黃等之氣體之情形，亦與由活性碳 或沸石成除害劑使組合若使用本發明之除害方法，將此等 氣體可無害化。 〔圖面之簡單說明〕 〔圖1〕含有本發明之鹵素系氣體之排氣之除害方法 係表示1實施形態之槪略圖。 〔圖2〕含有本發明之鹵素系氣體之排氣之除害方法 係表示1實施形態之槪略圖。 〔圖3〕由本發明之除害劑與活性碳成除害劑使組合 之除害方法，係表示1實施形態之槪略圖。 經濟部智慧財產局員工消費合作社印製 〔圖4〕由本發明之除害劑與沸石成除害劑使組合之 除害方法’係表示1實施形態之槪略圖。 〔符號之說明〕 1 蝕刻氣體供應裝置 2 蝕刻室 3 真空泵 4 真空泵排除氮氣體 本紙張尺度適用中國國家標準（asJS ) A4規格（210X 297公釐） -36 - 501939 A7 B7 五、發明説明（34 5 除害筒入口 6 除害筒 7 除害筒出口 8 氣體檢出器 9 排氣出口 10 除害劑 11 除害劑（活性碳） 12 除害劑（沸石） (請先閲讀背面之注意事項再填寫本頁) 訂 秦· 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -37-XU-SS 00 01 丨 λ Pan Qi, Boat House House 丨 ΝΑ ## 1amine 銮 藤 Η βΝ < N Csl CO Csl This paper size applies to China National Standard (CNS) A4 specification (21 OX297 mm) 35- 501939 A7 _B7_ V. Description of the invention ([Effects of the invention] (Please read the notes on the back before filling this page) As explained above, the specific iron oxide, alkaline earth metal compounds and activated carbon of the present invention are contained in a specific proportion Pesticides, especially hydrogen halides, are highly pesticides, which are discharged from the semiconductor device in a step containing halogen-based gases, which can effectively eliminate harmful gases. In addition, even the halogen gas such as chlorine or sulfur dioxide is contained in the exhaust gas. In the case of gas such as yellow, it is also used in combination with an active carbon or zeolite as a pesticide to make the gas harmless if the method for harm elimination of the present invention is used. [Simplified description of the drawing] [Figure 1] Contains this The detoxifying method of the exhaust gas of the halogen-based gas according to the invention is a schematic diagram showing the first embodiment. [Fig. 2] The detoxifying method of the exhaust gas containing the halogen-based gas of the present invention is a schematic diagram of the first embodiment. 3 The method for removing harmful substances from the combination of the pesticide and activated carbon of the present invention is a schematic diagram showing the implementation form 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Figure 4] The zeolite-based pesticide removal method "is a schematic diagram of the embodiment 1. [Explanation of symbols] 1 Etching gas supply device 2 Etching chamber 3 Vacuum pump 4 Vacuum pump excludes nitrogen gas This paper applies Chinese national standards (asJS ) A4 size (210X 297mm) -36-501939 A7 B7 V. Description of the invention (34 5 Pesticide inlet 6 Pesticide outlet 7 Pesticide outlet 8 Gas detector 9 Exhaust outlet 10 Pesticide 11 Removal Pesticides (activated carbon) 12 Pesticides (zeolite) (Please read the precautions on the back before filling out this page) Order Qin · Ministry of Economic Affairs Intellectual Property Bureau Employees' Cooperatives Printed on paper This paper applies Chinese National Standard (CNS) A4 Specifications (210X297 mm) -37-

Claims (1)

501939^_ f参 JE* A8 年月 e ^ Be 如· 7· 29補充I _§8 六、申請專利範圍 第901 12833號專利申請案 中文申請專利範圍修正本 民國91年7月29日修正 1 · 一種鹵素系氣體之除害劑，其特徵在於： 含有由7* -氫氧化氧化鐵及r -三氧化二鐵所成群選 出之氧化鐵10〜4 0質量％、鹼土金屬化合物2 〇〜 8 0質量％及活性碳1 0〜4 0質量％。 2 ·如申請專利範圍第1項之鹵素系氣體之除害劑， 其中該鹼土金屬化合物係由鎂、鈣、緦及鋇之氧化物、氫 氧化物及碳酸鹽所成群選出的至少1種。 3 ·如申請專利範圍第1項之鹵素系氣體之除害劑， 其中係該活性碳之比表面積爲5 0 0 m 2/ g以上。 4 .如申請專利範圍第1項之鹵素系氣體之除害劑， 其中該除害劑係含有硫酸鈣。 5 ·如申請專利範圍第4項之鹵素系氣體之除害劑， 其中相對於氧化鐵、鹼土金屬化合物及活性碳之總質量1 ，該硫酸鈣之含量係於〇〜〇 · 2之範圍內。 6 ·如申請專利範圍第1項之鹵素系氣體之除害劑， 其中該除害劑爲將粒徑各於1 〇 〇 // m以下之氧化鐵、鹼 土金屬化合物、活性碳及硫酸鈣之粉末摻合後造粒所成之 粒狀物。 7 ·如申請專利範圍第6項之鹵素系氣體之除害劑， 其中該除害劑爲粒徑於〇 . 5〜1 0 m m之範圍內之粒狀 物0 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） I- - V—-------- ΛΤ I-----0^-- (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 501939 Α8 Β8 C8 D8 01.7.2 9 六、申請專利範圍 ----------— (請先聞讀背面之注意事項再填寫本頁) 8 .如申請專利範圍第1項之鹵素系氣體之除害劑， 其中該鹵素系氣體爲由鹵素、鹵化氫、鹵化砂、鹵化鎢、 鹵化羰基、氟化硫、氯化砷、氯化磷、三氯化銀及三氯化 硼所成群選出的至少1種氣體。 9 . 一種鹵素系氣體之除害方法，其特徵在於： 使含有鹵素系氣體之氣體與如申請專利範圍第1〜8 項中任一項之除害劑接觸。 1 〇 .如申請專利範圍第9項之鹵素系氣體之除害方 法，其中該鹵素系氣體爲由鹵素、鹵化氫、鹵化矽、鹵化 鎢、鹵化羰基、氟化硫、氯化砷、氯化磷、三氯化鋁及三 氯化硼所成群選出的至少1種氣體。 1 1 · 一種鹵素系氣體之除害方法，其特徵在於： 包含使含有鹵素系氣體之氣體與由活性碳而成的除害 劑接觸的步驟，繼而與如申請專利範圍第1〜8項中任一· 項之除害劑接觸的步驟。 經濟部智慧財產局員工消費合作社印製 1 2 .如申請專利範爵第1 1項之鹵素系氣體之除害 方法，其中該活性碳之比表面積係5 0 0 m 2 / g以上，粒 徑係於0 . 5〜1 0 m m之範圍內。 1 3 ·如申請專利範圍第1 1項或第1 2項之鹵素系 氣體之除害方法，其中該鹵素系氣體係包含鹵素氣體，並 再包含由鹵化氫、鹵化砂、鹵化鎢、鹵化羰基、赢化硫、 氯化砷、氯化磷、三氯化鋁及三氯化硼所成群選出的至少 1種氣體。 14 _ 一種鹵素系氣體之除害方法，其特徵在於： 本紙張尺度適用中國國家標準(CNS ) A4規格（210X297公ΤΤΙ ' "" A8 B8 C8 D8 501939 翁—瘦允丨 六、申請專利範圍 包含使含有鹵素系氣體之氣體與如申請專利範圍第1 〜8項中任一項之除害劑接觸的步驟，繼而與由沸石所成 的除害劑接觸的步驟。 1 5 ·如申請專利範圍第1 4項之鹵素系氣體之除害 方法，其中該沸石係合成沸石及/或天然沸石，其粒徑係 於0.5〜10mm之範圍內。 1 6 ·如申請專利範圍第1 5項之鹵素系氣體之除害 方法，其中該合成沸石係MS - 5 A及/或MS -1 3 X。 1 7 ·如申請專利範圍第1 4〜1 6項中任一項之鹵 素系氣體之除害方法，其中該鹵素系氣體係包含二氧化硫 ，並再包含由鹵化氫、鹵化矽、鹵化鎢、鹵化羰基、氟化 硫、氯化砷、氯化磷、三氧化鋁及三氯化硼所成群選出的 至少1種氣體。 1 8 ·如申請專利範圍第9、1 1及1 4項中任一項 之鹵素系氣體之除害方法，其中該被處理氣體中鹵素系氣 體之濃度係1 0 v ο 1 %以下。 1 9 · 一種半導體裝置之製造方法，其特徵在於具有 下述步驟： 蝕刻步驟或淸潔步驟：使用由氟化碳、六氟化硫、鹵 素、鹵化氫及三氯化硼所成化合物群選出的至少1種氣體 ，以作爲蝕刻氣體或淸淨氣體；以及 除害步驟：使由此等步驟排出之含鹵素系氣體之氣體 與如申請專利範圍第1〜8項中任一項之除害劑接觸。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） i 訂 Αν (請先聞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 501939501939 ^ _ fRefer to JE * A8 month e ^ Be such as · 7 · 29 Supplement I _§8 VI. Application for Patent Scope No. 901 12833 Patent Application Chinese Application for Patent Scope Amendment July 29, 1991 Amendment 1 · A halogen-based gas pesticide, which is characterized in that it contains 10 to 40% by mass of iron oxide selected from the group of 7 * -iron hydroxide and r-iron trioxide, and alkaline earth metal compounds 〇 ~ 80 mass% and activated carbon 10 to 40 mass%. 2. The halogen-based gas pesticide as described in item 1 of the patent application range, wherein the alkaline earth metal compound is at least one selected from the group consisting of oxides, hydroxides and carbonates of magnesium, calcium, thallium and barium. . 3. The halogen-based gas pesticide according to item 1 of the patent application scope, wherein the specific surface area of the activated carbon is more than 500 m 2 / g. 4. The halogen-based gas pesticide according to item 1 of the patent application scope, wherein the pesticide contains calcium sulfate. 5. If the halogen-based gas pesticide of item 4 of the patent application scope, wherein the content of the calcium sulfate is in the range of 0 to 0.2 with respect to the total mass of iron oxide, alkaline earth metal compound and activated carbon. . 6. The halogen-based gas pesticide according to item 1 of the scope of patent application, wherein the pesticide is an iron oxide, alkaline earth metal compound, activated carbon, and calcium sulfate each having a particle size of less than 1000 // m. Granules formed by powder blending. 7 · The halogen-based gas pesticide as described in item 6 of the scope of patent application, wherein the pesticide is a granular material having a particle size in the range of 0.5 to 10 mm. 0 This paper uses Chinese national standards. (CNS) A4 specification (210X297mm) I--V —-------- ΛΤ I ----- 0 ^-(Please read the notes on the back before filling this page) Order the Ministry of Economy Printed by the Intellectual Property Bureau's Consumer Cooperatives 501939 Α8 Β8 C8 D8 01.7.2 9 VI. Scope of Patent Application ------------ (Please read the notes on the back before filling out this page) 8. Pesticide for halogen-based gas in the scope of patent application item 1, wherein the halogen-based gas is composed of halogen, hydrogen halide, sand halide, tungsten halide, carbonyl halide, sulfur fluoride, arsenic chloride, phosphorus chloride, trichloride At least one gas selected from the group consisting of silver carbide and boron trichloride. 9. A method for harm elimination of a halogen-based gas, comprising contacting a gas containing a halogen-based gas with a pesticide as described in any one of claims 1 to 8 of the scope of patent application. 10. The method for removing halogen-based gas according to item 9 of the scope of the patent application, wherein the halogen-based gas is composed of halogen, hydrogen halide, silicon halide, tungsten halide, halogenated carbonyl group, sulfur fluoride, arsenic chloride, chloride At least one gas selected from the group consisting of phosphorus, aluminum trichloride, and boron trichloride. 1 1 · A halogen-based gas detoxification method, comprising: a step of contacting a gas containing a halogen-based gas with a pesticide made of activated carbon, and then contacting a gas-containing pesticide as described in items 1 to 8 of the scope of patent application Steps in contact with pesticides of any of the items. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 12. For example, the method for harm elimination of halogen-based gases according to item 11 of the patent application, where the specific surface area of the activated carbon is more than 500 m 2 / g, and the particle size It is in the range of 0.5 to 10 mm. 1 3 · If the method of detoxifying a halogen-based gas according to item 11 or 12 of the scope of the patent application, the halogen-based gas system contains a halogen gas, and further includes hydrogen halide, sand halide, tungsten halide, and halogenated carbonyl group. , At least one selected from the group consisting of sulfur, arsenic chloride, phosphorus chloride, aluminum trichloride, and boron trichloride. 14 _ A method for harm elimination of halogen-based gases, which is characterized by: This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 male ΤΤΙ '" " A8 B8 C8 D8 501939 Weng Shouyun 丨 6. Patent application The scope includes a step of contacting a gas containing a halogen-based gas with a pesticide as described in any one of claims 1 to 8, and then a step of contacting a pesticide made of zeolite. 1 5 · If applied The method for removing halogen-based gases in the scope of the patent No. 14 wherein the zeolite is a synthetic zeolite and / or a natural zeolite, and the particle size thereof is in the range of 0.5 to 10 mm. A method for detoxifying a halogen-based gas, wherein the synthetic zeolite is MS-5 A and / or MS-1 3 X. 1 7 · As in the halogen-based gas of any one of claims 1 to 16 A method for detoxification, wherein the halogen-based gas system includes sulfur dioxide, and further comprises hydrogen halide, silicon halide, tungsten halide, halogenated carbonyl group, sulfur fluoride, arsenic chloride, phosphorus chloride, aluminum trioxide, and boron trichloride. At least 1 gas selected in groups. 1 8 · A method for detoxifying a halogen-based gas according to any one of items 9, 11, 11 and 14 of the scope of application for a patent, wherein the concentration of the halogen-based gas in the treated gas is 10 v ο 1% or less. 1 9 · A method for manufacturing a semiconductor device, comprising the following steps: an etching step or a cleaning step: using at least 1 selected from the group consisting of carbon fluoride, sulfur hexafluoride, halogen, hydrogen halide, and boron trichloride A gas as an etching gas or a purge gas; and a detoxification step: contacting the halogen-containing gas discharged from these steps with a pesticide such as any one of claims 1 to 8 of the scope of patent application. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) i Order Αν (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 501939 A8 B8 C8 D8 六、申請專利範圍 2 0 .如申請專利範圍第1 9項之半導體裝置之製造 方法，其中該除害步驟係包含與由活性碳而成的除害劑接 觸的步驟。 2 1 .如申請專利範圍第1 9項之半導體裝置之製造 方法，其中該除害步驟係包含與由沸石而成除害劑接觸的 步驟。 2 2 .如申請專利範圍第1 9〜2 1項中任一項之半 導體裝置之製造方法，其中由蝕刻步驟或淸潔步驟所排出 的氣體中之鹵素系氣體濃度係ΙΟνο1%以下。 ' (請先聞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 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 4 _A8 B8 C8 D8 VI. Patent application scope 20. For the method of manufacturing a semiconductor device according to item 19 of the patent application scope, wherein the harm removal step includes a step of contacting a pesticide made of activated carbon. 2 1. The method for manufacturing a semiconductor device according to item 19 of the scope of patent application, wherein the detoxification step includes a step of contacting a pesticide made of zeolite. 2 2. The method for manufacturing a semiconductor device according to any one of claims 19 to 21, wherein the concentration of the halogen-based gas in the gas discharged by the etching step or the cleaning step is 10% or less. '(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 4 _
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