TW200300523A - Method of stripping resist and resist-stripping liquid - Google Patents

Method of stripping resist and resist-stripping liquid Download PDF

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Publication number
TW200300523A
TW200300523A TW091132407A TW91132407A TW200300523A TW 200300523 A TW200300523 A TW 200300523A TW 091132407 A TW091132407 A TW 091132407A TW 91132407 A TW91132407 A TW 91132407A TW 200300523 A TW200300523 A TW 200300523A
Authority
TW
Taiwan
Prior art keywords
photoresist stripping
photoresist
stripping solution
weight
stripping method
Prior art date
Application number
TW091132407A
Other languages
Chinese (zh)
Other versions
TWI311694B (en
Inventor
Hideki Shimizu
Hiroshi Matsunaga
Masaru Ohto
Kazuto Ikemoto
Original Assignee
Mitsubishi Gas Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2001338436A external-priority patent/JP2003140364A/en
Priority claimed from JP2001338438A external-priority patent/JP2003140365A/en
Application filed by Mitsubishi Gas Chemical Co filed Critical Mitsubishi Gas Chemical Co
Publication of TW200300523A publication Critical patent/TW200300523A/en
Application granted granted Critical
Publication of TWI311694B publication Critical patent/TWI311694B/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • H01L21/31138—Etching organic layers by chemical means by dry-etching

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  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

A method of stripping resist, wherein a circuit board with remaining resist is brought into contact with a resist stripper in an atmosphere of 2 vol. % or less oxygen. Preferably, the resist stripping is carried out after the remaining resist is pretreated with hydrogen peroxide. The method of stripping resist in the present invention is preferably carried out using a resist stripper comprising amine-containing compounds, solvents, strong bases and water.

Description

200300523 先前技術 用於光微影技術的利用之際的光阻體，已見使用 於如IC、LSI之積體電路，如LCD、EL元件之顯示 設備，印刷電路板、微機電、D N A晶片、微工廠等廣 泛領域。 向來，光阻體剝離液係使用包含有機鹼及水溶性 溶劑等之溶液。尤以有機鹼係以用胺化合物者爲多， 有例如烷醇胺與二甲亞楓之非水溶液，含烷醇胺、水 溶性有機溶劑及糖醇之水溶液，烷醇胺、羥基胺及兒 茶酚之水溶液等之使用。此類鹼性光阻體剝離液對於 含酚式羥基之化合物，含酯基之化合物構成的光阻體 之剝離非常有效。 此類光阻體剝離液通常係於室溫至1 〇 〇 °C之範圍，主 要使用於鋁、鋁合金等之不以銅爲主要成分之基板上 的光阻體剝離。 近年來，電阻較低之銅已開始用於配線材料。尤 其是已經多用作以LSI爲代表之半導體的配線材料。 又，與此平行，絕緣材料則係使用低介電膜。習知製 程係光阻體顯像、作乾式蝕刻後經去灰過程作光阻體 剝離。但是，去灰過程易於導致低介電膜表面之變 質，會傷及電路之功能。因而省卻去灰過程之製程受 到期待，但作乾式蝕刻後光阻體已有變質，習知以胺 化合物爲有效成分之光阻體剝離液，有不能充分剝離 光阻體之缺點。再者，含胺化合物之光阻體剝離液因 形成銅-胺錯化物，有易於腐飩銅配線之缺點。 200300523 發明之掲示 本發明之目的在提供，以不腐蝕銅，尤其是銅配 線，而含胺化合物之光阻體剝離液剝離光阻體之方 法。本發明之另一目的在提供，適用於上述光阻體剝 離方法的含有胺化合物之光阻體剝離液。 本發明人等精心探討銅配線基板用之光阻體剝離 液，結果發現，含有胺化合物、溶劑、強鹼及水之組 成物，可剝離光阻體而不腐蝕銅或銅合金。 本發明人等對於不腐蝕銅而可剝離光阻體之最適 條件作了精心探討。結果發現，一般雖有胺化合物會 腐蝕銅之說法，但溶解於光阻體剝離液之氧將銅氧 化，氧化之銅形成銅-胺錯化物而有銅腐蝕之發生， 亦即，溶解於剝離液之氧才是銅腐鈾之主要原因。 亦即，本發明提供一種光阻體剝離方法，其特徵 爲：使鈾刻後殘留有光阻膜之配線基板，在氧濃度2 體積％以下之環境氣體中接觸光阻體剝離液。本發明 之較佳樣態，係在以過氧化氫作前處理以後，接觸光 阻體剝離液。 又，本發明係在提供，適用於上述光阻體剝離方 法，含有胺化合物、溶劑、強鹼及水之光阻體剝離液。 發明之最佳實施形態 本發明之光阻體剝離液含有胺化合物、溶劑、強 鹼（任意成分）及水。 胺化合物有氨、單烷基胺、二烷基胺、三烷基胺、 烷醇胺、多胺、羥胺化合物，及環胺。 200300523 單烷基胺有例如甲胺、乙胺、正丙胺、異丙胺、 正丁胺、二級丁胺、異丁胺、三級丁胺、戊胺、2 -胺基戊烷、3-胺基戊烷、1-胺基-2-甲基丁烷、2-胺基 -2 -甲基丁烷、3 -胺基-2 -甲基丁烷、4 -胺基-2 -甲基丁 院、己胺、5 -胺基-2 -甲基戊院、庚胺、辛胺、壬胺、 癸胺、十一胺、十二胺、十三胺、十四胺、十五胺、 十六胺、十七胺、十八胺等；二烷基胺有例如二甲胺、 二乙胺、二丙胺、二異丙胺、二正丁胺、二異丁胺、 二（二級丁）胺、二（三級丁）胺、二戊胺、二己胺、二 庚胺、二辛胺、二壬胺、二癸胺、甲乙胺、甲丙胺、 甲異丙胺、甲正丁胺、甲異丁胺、甲二級丁胺、甲三 級丁胺、甲戊胺、甲異戊胺、乙丙胺、乙異丙胺、乙 正丁胺、乙異丁胺、乙二級丁胺、乙三級丁胺、乙異 戊胺、丙正丁胺、丙異丁胺等；三烷基胺有例如三甲 胺、三乙胺、三丙胺、三丁胺、三戊胺、二甲乙胺、 甲二乙胺、甲二丙胺等。 烷醇胺有乙醇胺、1-胺基-2-丙醇、N-(胺乙基）乙 醇胺、N -甲基乙醇胺、N -乙基乙醇胺、N -丙基乙醇胺、 N - 丁基乙醇胺、二乙醇胺、異丙醇胺、N -甲基異丙醇 胺、N -乙基異丙醇胺、N -丙基異丙醇胺、2 -胺丙-1 -醇、N -甲基-2 -胺丙-1 -醇、N -乙基-2 -胺丙-卜醇、1 -胺丙-3-醇、N -甲基-1-胺丙-3-醇、N -乙基-1-胺丙- 3-醇、卜胺丁 - 2 -醇、N -甲基-1 -胺丁 - 2 -醇、N -乙基-1 -胺丁 - 2 -醇、2 -胺丁 - 1 -醇、N -甲基-2 -胺丁 - 1 -醇、N -乙基-2 -胺丁 - 1-醇、N -甲基-3 -胺丁 - 1 -醇、N -乙基-3 - 200300523 胺丁 - 1 -醇、1 -胺丁 - 4 -醇、N -甲基-1 -胺丁 - 4 -醇、N -乙 基 - 1 - 胺丁 - 4 - 醇、 1 - 胺基 - 2 - 甲丙 - 2 - 醇、 2 - 胺基 - 2 -甲丙-1 -醇、1 -胺戊-4 -醇、2 -胺基-4 -甲戊-1 -醇、2 -胺己-1 -醇、3 -胺丁 - 4 -醇、1-胺辛-2 -醇、5 -胺辛-4 -醇、1 -胺丙-2，3 -二醇、2 -胺丙-1 , 3 -二醇、參（氧甲 基）胺甲烷、1，2 -二胺丙-3 -醇、1，3 -二胺丙-2 -醇、 2-(2 -胺乙氧基）乙醇等。 多胺有乙二胺、丙二胺、丁二胺、1，3 -二胺丁烷、 2，3 -二胺丁烷、戊二胺、2，4 -二胺戊烷、己二胺、 庚二胺、辛二胺、壬二胺、N -甲基乙二胺、N，N -二 甲基乙二胺、三甲基乙二胺、1，2，3 -三胺丙烷、肼、 參（2 -胺乙基）胺、四（胺甲基）甲烷、二乙三胺、三乙 四胺、四乙五胺、七乙八胺、九乙十胺、二疊氮雙環 十一烯、肼、二甲肼、甲肼、羥乙肼等。 羥胺化合物有羥胺、N -甲基羥胺、N -乙基羥胺、 N，N -二乙基羥胺。 環胺有吡略、2 -甲吡咯、3 -甲吡略、2 -乙吡咯、3 -乙吡咯、2，3 -二甲吡咯、2，4 -二甲吡咯、3 , 4 -二甲 吡咯、2，3，4 -三甲吡咯、2 , 3，5 -三甲吡咯、2 -吡咯 啉、3 -吡咯啉、吡咯啉、2 -甲吡咯啉、3 -甲吡略啉、 吡唑、咪唑、1 , 2，3 -***、1，2，3，4 -四唑、哌啶、 2-哌可啉、3-哌可啉、4-哌可_、2，4-二甲哌11定、2，6-二甲哌啶、3 , 5 -二甲哌啶、哌哄、2 -甲哌畊、2，5 -二甲哌畊、2，6 -二甲哌畊、嗎福啉等。 上述化合物中，較佳者爲至少一種選自乙醇胺、 200300523 1-胺基-2-丙醇、N-(胺乙基）乙醇胺、N-甲基乙醇胺、 · N -乙基乙醇胺、二乙醇胺、異丙醇胺、2 - ( 2 -胺乙氧 基）乙醇、乙二胺、丙二胺、丁二胺、二乙三胺、哌 哄、嗎福啉、三乙四胺、四乙五胺、五乙六胺之群組 的化合物。 強鹼之較佳者爲至少一種選自氫氧化四甲銨、氫 氧化四乙銨、氫氧化四丙銨、氫氧化四丁銨、氫氧化 膽鹼、氫氧化乙醯膽鹼之群組的化合物，更佳者爲氫 氧化四甲銨及氫氧化膽鹼。 · 溶劑係以可與上述胺化合物相溶者爲較佳，有乙 二醇、乙二醇單***、乙二醇單丁醚、二乙二醇單甲 醚、二乙二醇單***、二乙二醇單丁醚、丙二醇單甲 醚、丙二醇單***、丙二醇單丁醚、二丙二醇單甲醚、 二丙二醇單***、二丙二醇單丁醚、二乙二醇二甲 醚、二丙二醇二甲醚等之醚系溶劑；甲醛、單甲基甲 醛、二甲基甲醛、單乙基甲醛、二乙基甲醛、乙醯胺、 單甲基乙醯胺、二甲基乙醯胺、單乙基乙醯胺、二乙 · 基乙醯胺、N -甲基 咯烷酮、N -乙基吡咯烷酮等之醯 胺系溶劑；甲醇、乙醇、異丙醇、乙二醇、丙二醇等 之醇系溶劑；二甲亞楓等之亞楓系溶劑；二甲砸、二 乙楓、雙（2-羥楓）、四亞甲碾等之珮系溶劑；1,3 -二 甲基-2-咪唑啶酮、1，3-二乙基-2-咪唑啶酮、1，3 -二 異丙基-2 -咪唑啶酮等之咪唑啶酮系溶劑；及τ - 丁內 酯、6 -戊內酯等之內酯系溶劑等。 其中，二甲亞楓、Ν,Ν -二甲基甲醯胺、N，N -二甲 200300523 基乙醯胺、N -甲基吡咯烷酮、二乙二醇單甲醚、二乙 二醇單丁醚、二丙二醇單甲醚、二丙二醇單丁醚、丙 二醇因易於取得，且沸點高容易使用而爲較佳。又， 亦可使用上述胺化合物作爲溶劑。 爲不腐蝕銅而剝離光阻體，光阻體剝離液係以含 胺化合物5至9 5重量％，溶劑3至8 5重量％，強鹼 0.0 1至5重量％，水1至2 5重量％爲較佳，以含胺化 合物1 0至4 0重量％，溶劑5 0至8 0重量％，強鹼0 . 1 至3重量％，水5至2 0重量％爲更佳。本發明之光阻 體剝離液，在無損於本發明之效果的範圍，可含習用 之山梨糖醇、兒茶酹等抗蝕劑、界面活性劑等添加 物。 光阻體剝離液之製造方法無特殊限制，可用習知 方法製造。 本發明中光阻體之剝離係於蝕刻後，較佳者爲在 去灰前，使殘留之光阻體與含胺化合物、溶劑、強鹼 (任意成分）及水之光阻體剝離液於20至6(TC接觸1 至3 0分鐘。接觸通常係將殘留有光阻體之基板浸泡 於光阻體剝離液。- 例如，泛用之含有酚式羥基之光阻體，經乾式蝕 刻而表面變質。習知光阻體剝離液係藉胺化合物與酚 式羥基形成鹽，氧化產生之羰基經胺化合物加成反應 以剝離光阻體。但是，去除經變質之光阻體的能力 差。此時，藉由使用含強鹼之光阻體剝離液，可加強 與酚式羥基形成鹽之能力及來自乾式蝕刻之鹵素去 -10- 200300523 除功能，並可賦予水解之功能。 如上述，溶入光阻體剝離液之氧係銅及銅合金腐 蝕之主要原因。腐蝕作用在光阻體剝離液中鹼成分 (胺化合物+強鹼）含量3 %以上，且光阻體剝離操作 環境氣體氧濃度高時更爲顯著。因此，本發明中係於 氧濃度2體積％以下，較佳者爲1體積％以下之環境 氣體中進行，以有效抑制銅及銅合金之腐蝕。低氧環 境氣體可藉使用氮、氬、氫等而得，較佳者爲氮。更 佳者爲，氧濃度2體積％以下之環境氣體中，以氮、 氬、氫等氣體吹入光阻體剝離液趕出溶解之氣體，維 持光阻體剝離液中溶氧量於3 ppm以下，進行光阻體 剝離操作，即可更有效抑制銅及銅合金之腐蝕。又， 亦可於使用前將光阻體剝離液脫氣。如此，本發明之 光阻體剝離方法，在去除具有銅膜或銅合金膜之基板 上的殘留光阻體時有效。 又，本發明人等更發現，剝離經變質之光阻體時， 過氧化氫之前處理有效。藉由過氧化氫之前處理，經 變質之光阻體表面氧化，分子量下降，促進羰基之形 成。因此光阻體之去除變得容易。 過氧化氫前處理係蝕刻後，光阻體剝離液處理 前，使配線基板與過氧化氫濃度0 . 5重量％以上，較 佳者爲1至1 0重量％之溶液，於2 0至6 0 °C例如以浸 泡等方法接觸1至3 0分鐘。溶液有水溶液等。過氧 化氫溶液中亦可加入螯合劑、界面活性劑等添加劑。 經過氧化氫前處理之配線基板可以直接，或以水等淸 -11 - 200300523 洗之後，作上述之光阻體剝離。 以下參照實施例說明本發明，但本發明絕不限於 以下實施例。 實施例1至6及比較例1、2200300523 Photoresist when the previous technology is used in the photolithography technology has been used in integrated circuits such as ICs and LSIs, display devices such as LCD and EL elements, printed circuit boards, micro-electromechanical, DNA chips, Micro factories and other fields. Conventionally, a photoresist stripping solution is a solution containing an organic base, a water-soluble solvent, and the like. In particular, organic bases are mostly amine compounds, such as non-aqueous solutions of alkanolamine and dimethyl sulfoxide, aqueous solutions containing alkanolamine, water-soluble organic solvents and sugar alcohols, alkanolamine, hydroxylamine and children Use of an aqueous solution of theophylol. Such alkaline photoresist stripping solution is very effective for stripping photoresist composed of phenolic hydroxyl group-containing compounds and ester group-containing compounds. This type of photoresist stripping solution is usually in the range of room temperature to 1000 ° C. It is mainly used for stripping photoresist on substrates such as aluminum and aluminum alloys without copper as the main component. In recent years, copper having lower resistance has been used for wiring materials. In particular, it has been widely used as a wiring material for semiconductors typified by LSI. In parallel to this, a low dielectric film is used as the insulating material. The conventional process is to develop a photoresist body, dry it, and remove the photoresist body through a ashing process after dry etching. However, the ash removal process easily leads to the deterioration of the surface of the low-dielectric film, which may damage the function of the circuit. Therefore, the process of omitting the ash removal process is expected, but the photoresist has been deteriorated after dry etching. It is known that the photoresist stripping solution using an amine compound as an active ingredient has the disadvantage that the photoresist cannot be fully peeled off. In addition, the photoresist stripping solution containing an amine compound has the disadvantage of easily corroding copper wiring because it forms a copper-amine complex. 200300523 Presentation of the invention The object of the present invention is to provide a method for stripping a photoresist with a photoresist stripping solution containing an amine compound without corroding copper, especially copper wiring. Another object of the present invention is to provide a photoresist body peeling liquid containing an amine compound, which is suitable for the above-mentioned photoresist body peeling method. The present inventors have carefully studied a photoresist stripping solution for a copper wiring board, and found that a composition containing an amine compound, a solvent, a strong alkali, and water can strip the photoresist without corroding copper or a copper alloy. The present inventors have carefully studied the optimum conditions of the peelable photoresist without corroding copper. It was found that although there is a general statement that amine compounds corrode copper, the oxygen dissolved in the stripping solution of the photoresist oxidizes copper, and the oxidized copper forms copper-amine complexes and copper corrosion occurs, that is, it dissolves in stripping Liquid oxygen is the main reason for copper rot. That is, the present invention provides a method for stripping a photoresist, which is characterized in that a wiring substrate with a photoresist film remaining after uranium etching is brought into contact with the photoresist stripping solution in an ambient gas having an oxygen concentration of 2% by volume or less. A preferred aspect of the present invention is that it comes into contact with the photoresist stripping solution after pretreatment with hydrogen peroxide. The present invention also provides a photoresist stripping solution containing an amine compound, a solvent, a strong base, and water, which is suitable for the photoresist stripping method. Best Mode for Carrying Out the Invention The photoresist stripping solution of the present invention contains an amine compound, a solvent, a strong base (optional component), and water. The amine compound includes ammonia, monoalkylamine, dialkylamine, trialkylamine, alkanolamine, polyamine, hydroxylamine compound, and cyclic amine. 200300523 Monoalkylamines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, secondary butylamine, isobutylamine, tertiary butylamine, pentylamine, 2-aminopentane, 3-amine Pentane, 1-amino-2-methylbutane, 2-amino-2 -methylbutane, 3-amino-2 -methylbutane, 4-amino-2 -methylbutane Hexylamine, Hexylamine, 5-amino-2-methylpentylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentaamine, ten Hexaamine, heptaamine, octadecylamine, etc .; dialkylamines include, for example, dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, diisobutylamine, and di (secondary butyl) amine , Di (tertiary butyl) amine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, methylethylamine, methylpropylamine, methylisopropylamine, methyl-n-butylamine, methyliso Butylamine, Methylbutylamine, Methyl tertiary butylamine, Methylpentylamine, Methylisoamylamine, Ethylpropylamine, Ethylisopropylamine, Ethylbutylamine, Ethylisobutylamine, Ethylbutylamine, Ethyl tertiary Butylamine, ethylisoamylamine, propyl-n-butylamine, propylisobutylamine, etc .; trialkylamines are, for example, trimethylamine, triethylamine , Tripropylamine, tributylamine, pentyl amine, dimethyl amine, methyl diethylamine, dipropylamine and the like A. Alkanolamines are ethanolamine, 1-amino-2-propanol, N- (aminoethyl) ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diamine Ethanolamine, isopropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropanol-1, alcohol, N-methyl-2- Aminopropan-1-ol, N-ethyl-2 -aminopropan-l-ol, 1-aminoprop-3-ol, N-methyl-1-aminoprop-3-ol, N-ethyl-1- Amine 3-ol, Pubuta-2-ol, N-Methyl-1-Amine-2-Alcohol, N-Ethyl-1-Amine-2-Alcohol, 2-Amine-1- Alcohol, N-methyl-2 -aminobutane-1 -alcohol, N -ethyl-2 -aminobutane-1 -alcohol, N -methyl-3 -aminobutane-1 -alcohol, N -ethyl-3 -200300523 Amine-1, Amine-1, Amine-4, A-1, N-methyl-1, Amine-4, A-1, N-ethyl-1, Amine-4, A-1, Amine -2-Methylpropane-2-alcohol, 2-Amine-2-Methylpropane-1-alcohol, 1-Aminepent-4-ol, 2-Amine-4-Methylpentane-1-alcohol, 2-Amine Hexyl-1 -alcohol, 3-aminobutane-4 -alcohol, 1-aminooctane-2 -alcohol, 5-aminooctane-4 -alcohol, 1 -amine propane-2,3-diol, 2-aminopropane- 1, 3 -diol, ginseng (oxymethyl ) Amine methane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2- (2-aminoethoxy) ethanol, and the like. Polyamines are ethylenediamine, propylenediamine, butylenediamine, 1,3-diaminebutane, 2,3-diaminebutane, pentanediamine, 2,4-diaminepentane, hexamethylenediamine, Heptanediamine, octanediamine, nonanediamine, N-methylethylenediamine, N, N-dimethylethylenediamine, trimethylethylenediamine, 1,2,3-triaminepropane, hydrazine, Ginseng (2-aminoethyl) amine, tetrakis (aminemethyl) methane, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, heptaethylene octaamine, nonaethylenedecaamine, diazodicycloundecene , Hydrazine, dimethyl hydrazine, methyl hydrazine, isethizine, etc. The hydroxylamine compounds are hydroxylamine, N-methylhydroxylamine, N-ethylhydroxylamine, and N, N-diethylhydroxylamine. Cyclic amines are pyrilex, 2-methylpyrrole, 3-methylpyrrole, 2-ethylpyrrole, 3-ethylpyrrole, 2,3-dimethylpyrrole, 2,4-dimethylpyrrole, 3,4-dimethylpyrrole , 2, 3, 4-trimethylpyrrole, 2, 3, 5-trimethylpyrrole, 2-pyrroline, 3-pyrroline, pyrroline, 2-methylpyrroline, 3-methylpyrroline, pyrazole, imidazole, 1,2,3-triazole, 1,2,3,4-tetrazole, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-dimethylpiperidine , 2,6-dimethylpiperidine, 3, 5-dimethylpiperidine, piperazine, 2-methylpiperidine, 2,5-dimethylpiperidine, 2,6-dimethylpiperidine, morpholine, etc. . Of the above compounds, at least one selected from the group consisting of ethanolamine, 200300523 1-amino-2-propanol, N- (aminoethyl) ethanolamine, N-methylethanolamine, N-ethylethanolamine, diethanolamine, Isopropanolamine, 2- (2-amineethoxy) ethanol, ethylenediamine, propylenediamine, butanediamine, diethylenetriamine, piperazine, morpholine, triethylenetetramine, tetraethylenepentamine , Pentaethylenehexaamine group of compounds. The strong base is preferably at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, and acetylcholine hydroxide. Compounds, more preferred are tetramethylammonium hydroxide and choline hydroxide. · The solvent is preferably compatible with the above amine compounds. Ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and two Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether Ether-based solvents; formaldehyde, monomethyl formaldehyde, dimethyl formaldehyde, monoethyl formaldehyde, diethyl formaldehyde, acetamidamine, monomethylacetamide, dimethylacetamide, monoethyl Ethylamine, diethylacetamidamine, N-methylpyrrolidone, N-ethylpyrrolidone, and other amine solvents; methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, and other alcohol-based solvents ； Small maple solvents such as dimethyl acer, etc .; stilbene series solvents such as dimethyl para, diethyl maple, bis (2-hydroxymaple), tetramethylene mill, etc .; 1,3-dimethyl-2-imidazolidine Ketones, 1,3-diethyl-2-imidazolidone, 1,3-diisopropyl-2-imidazolidone, and other imidazolidone-based solvents; and τ-butyrolactone, 6-valerolactone The lactone-based solvent. Among them, dimethylphosphine, Ν, Ν-dimethylformamide, N, N-dimethyl200300523 methylacetamide, N-methylpyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monobutylene Ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, and propylene glycol are preferable because they are easily available and have a high boiling point and are easy to use. Moreover, you may use the said amine compound as a solvent. In order to peel off the photoresist without corroding copper, the photoresist stripping solution is based on an amine-containing compound 5 to 95% by weight, a solvent 3 to 85% by weight, a strong base 0.01 to 5% by weight, and water 1 to 25% by weight. % Is more preferred, 10 to 40% by weight of the amine-containing compound, 50 to 80% by weight of the solvent, 0.1 to 3% by weight of the strong base, and 5 to 20% by weight of water is more preferred. The photoresist stripping solution of the present invention may contain additives such as conventional sorbitol, catechin and other resists, surfactants and the like within a range that does not impair the effects of the present invention. The manufacturing method of the photoresist stripping solution is not particularly limited, and it can be manufactured by a conventional method. In the present invention, the stripping of the photoresist is performed after etching, and it is preferable to remove the remaining photoresist and the photoresist stripping solution containing an amine compound, a solvent, a strong alkali (optional component) and water before removing the ash. 20 to 6 (TC contact for 1 to 30 minutes. Contact is usually to immerse the substrate with the photoresist in the photoresist stripping solution.-For example, the photoresist containing phenolic hydroxyl groups is widely used, dry etching Surface deterioration. The conventional photoresist stripping solution is based on the formation of a salt by an amine compound and a phenolic hydroxyl group, and the carbonyl group produced by the oxidation is subjected to an amine compound addition reaction to strip the photoresist. However, the ability to remove the deteriorated photoresist is poor. At this time By using a strong alkali-containing photoresist stripping solution, the ability to form salts with phenolic hydroxyl groups and the halogen removal from dry etching can be enhanced, and the function of hydrolysis can be imparted. As mentioned above, dissolve The main reason for the corrosion of the oxygen-based copper and copper alloy of the photoresist stripping solution. The corrosion acts on the photoresist stripping solution with an alkali component (amine compound + strong alkali) content of more than 3%, and the oxygen concentration of the ambient gas in the photoresist stripping operation. It is more significant at high times. In the present invention, it is performed in an environmental gas having an oxygen concentration of 2% by volume or less, preferably 1% by volume or less, to effectively inhibit the corrosion of copper and copper alloys. The low-oxygen environment gas can be used by nitrogen, argon, hydrogen, etc. Whereas, the preferred one is nitrogen. The more preferred one is that in an ambient gas having an oxygen concentration of 2% by volume or less, nitrogen, argon, or hydrogen is blown into the photoresist stripping solution to drive out the dissolved gas to maintain the photoresist The amount of dissolved oxygen in the stripping solution is less than 3 ppm, and the photoresist stripping operation can more effectively suppress the corrosion of copper and copper alloys. Also, the photoresist stripping solution can be degassed before use. Thus, the present invention The photoresist stripping method is effective for removing the remaining photoresist on a substrate having a copper film or a copper alloy film. Furthermore, the inventors have found that when the deteriorated photoresist is peeled off, it is treated before hydrogen peroxide. Effective. By pre-treatment with hydrogen peroxide, the surface of the photoresist undergoes oxidation, which reduces the molecular weight and promotes the formation of carbonyl groups. Therefore, the removal of the photoresist becomes easier. After the hydrogen peroxide pretreatment, the photoresist is peeled off Before liquid treatment, make The wiring substrate and a hydrogen peroxide concentration of 0.5% by weight or more, preferably a solution of 1 to 10% by weight, are contacted at 20 to 60 ° C, for example, by immersion for 1 to 30 minutes. The solution has an aqueous solution Etc. Additives such as chelating agents and surfactants can also be added to the hydrogen peroxide solution. The wiring substrate that has been pretreated with hydrogen oxide can be directly or after washing with water such as 淸 -11-200300523 to peel off the above photoresist. The present invention is described below with reference to examples, but the present invention is by no means limited to the following examples. Examples 1 to 6 and Comparative Examples 1 and 2

矽基板上依序積層有銅膜、SiN膜、Si 02系層間絕 緣膜、光阻膜之6吋晶圓，以乾式蝕刻設置通孔構 造。通孔構造抵達銅膜。將該基板於組成如下之光阻 體剝離液在7 0 °C浸泡3 0分鐘後，用水沖洗，以掃瞄 式電子顯微鏡觀察光阻體之剝離程度及銅膜之腐蝕 程度。結果列於表2。 而光阻體剝離液中之溶氧量係用N. T.(股）公司 製數位氧濃度計（型式D〇-5 5 0 9，檢測下限0 · 5 p p m ) 在氮氣環境下測出。A 6-inch wafer with a copper film, a SiN film, an Si 02-based interlayer insulation film, and a photoresist film was laminated in this order on a silicon substrate, and a through-hole structure was formed by dry etching. The via structure reaches the copper film. The substrate was immersed in a photoresist stripping solution having the following composition at 70 ° C for 30 minutes, then rinsed with water, and the degree of peeling of the photoresist and the degree of corrosion of the copper film were observed with a scanning electron microscope. The results are shown in Table 2. The dissolved oxygen content in the photoresist stripping solution was measured under a nitrogen environment using a digital oxygen concentration meter (type D0-5 509, lower detection limit 0 · 5 p p m) made by N.T.

_表 1_ 光阻體剝離液之組成 胺化合物 Μ__劑 蓮___ 丞 種類 重量％ 種類 重量％ 種類 雷量％ 實施例 1 ΕΑ 30 DMSO 60 ΤΜΑΗ 0.2 其餘 2 ΕΑ 25 ΝΜΡ 65 ΤΜΑΗ 1 其餘 3 1Α2Ρ 32 PG 61 ΤΜΑΗ 0.5 其餘 4 ΤΕΤΑ 18 DGME 72 CH 1 其餘 5 ΡΕΗΑ 30 DGBE 60 ΤΜΑΗ 2 其餘 6 ΑΕΕΑ 10 ΜΕΑ 80 CH 0.1 其餘 比較例 1 ΕΑ 30 DMSO 60 — — 其餘 2 ΕΑ 30 DMSO 60 ΤΜΑΗ 0.2 其餘 12- 200300523 EA :乙醇胺 1 A 2 P : 1 -胺基-2 -丙醇 TETA :三乙四胺 PEHA ：五乙六胺 AEEA ：胺乙基乙醇胺 TMAH:氫氧化四甲銨 C Η :氫氧化膽鹼 DMSO :二甲亞楓 Ν Μ P : Ν -甲基吡咯烷酮 PG :丙二醇 DGME :二乙二醇單甲醚 DGBE:二乙二醇單丁醚 MEA: Ν -甲基乙醇胺 表2 環境氣體氧濃度 光阻體剝離 銅腐蝕 溶氧濃度 (ppm) (ppm) 實施例1 500 良好 4τττ. iltr j \ w 0. 5以下 實施例2 200 良好 4rrr ιΐητ j \ \\ 0.6 實施例3 400 良好 4rrr. ww 1.3 實施例4 800 良好 /frrr 111! > ό 0. 5以下 實施例5 200 良好 te j\w 1.5 實施例6 400 良好 Arrc. ΎΠΤ > \ SN 0. 5以下 比較例1 500 無剝離 Ajrr ΤΤΤΓ J \ \\ 0. 5以下 比較例2 200000 良好 明顯 5.8 實施例7至1 2及比較例3、4 -13- 200300523 矽基板上依序積層有銅膜、S 1 N膜、S i ◦ 2系層間絕 緣膜、光阻膜之1 2吋晶圓，以乾式蝕刻設置通孔構 造。通孔構造抵達銅膜。將該基板於表3所示之液體 ~ 在6 (TC浸泡1 5分鐘作前處理，其次於表3所示之組 成的光阻體剝離液浸泡3 0分鐘。水沖洗後，以掃瞄 式電子顯微鏡觀察光阻體之剝離程度及銅膜之腐鈾 程度。結果列於表4。 _表 3_ 前處理 光阻體剝離液之組成 φ 雙氧水 胺化合物 溶 劑 強 驗 丞 濃度 添加物 種類 重量％ 種類 重量％ 種類 重量％ (重量％) (雷量 其餘 實施例 7 6 — EA 30 DMSO 60 TMAH 0.2 其餘 8 5 EDTA TETA 25 NMP 25 TMAH 1 其餘 (0.001) PG 40 9 3 — 1A2P 25 DMSO 65 TMAH 1.5 其餘 10 4 nh4f EA 18 DGME 72 CH 1 其餘 (0.001) 11 4 — PEHA 30 DGBE 60 TMAH 2 其餘 12 4 — AEEA 10 MEA 80 CH 0.1 其餘 比較例 3 — — EA 30 DMSO 60 TMAH 0.2 其餘 4 — 一 EA 25 NMP 65 TMAH 1 其餘_ 表 1_ Composition of photoresist stripping solution amine compound M__ 剂 莲 _ 丞 Species weight% Kind weight% Species lightning% Example 1 ΕΑ 30 DMSO 60 ΤΑΗ 0.2 The remaining 2 ΕΑ 25 NM 65 65 ΜΑΗ 1 The remaining 3 1Α2P 32 PG 61 ΤΜΑΗ 0.5 remaining 4 ΤΕΤΑ 18 DGME 72 CH 1 remaining 5 ΡΕΑΑ 30 DGBE 60 ΤΜΑΗ 2 remaining 6 ΑΕΑ 10 ΕΕ80 80 CH 0.1 remaining comparative example 1 ΕΑ 30 DMSO 60 —-remaining 2 ΕΑ 30 DMSO 60 ΤΜΑΗ 0.2 remaining 12-2003 EA: Ethanolamine 1 A 2 P: 1-Amine-2-Propanol TETA: Triethylenetetramine PEHA: Pentaethylenehexamine AAEA: Amine ethylethanolamine TMAH: Tetramethylammonium hydroxide C Η: Choline hydroxide DMSO : Dimethyl isocyanate NM P: Ν-methylpyrrolidone PG: Propylene glycol DGME: Diethylene glycol monomethyl ether DGBE: Diethylene glycol monobutyl ether MEA: Ν-methylethanolamine Table 2 Ambient gas oxygen concentration photoresist Bulk copper corrosion dissolved dissolved oxygen concentration (ppm) (ppm) Example 1 500 Good 4τττ.iltr j \ w 0.5 The following example 2 200 Good 4rrr ιrrητ j \ \\ 0.6 Example 3 400 Good 4rrr. Ww 1.3 Example 4 800 Good / frrr 111! ≫ ό 0.5 The following Example 5 200 Good te j \ w 1.5 Example 6 400 Good Arrc. ΎΠΤ > \ SN 0.5 The following Comparative Example 1 500 No peel Ajrr ΤΤΤΓ J \ \\ 0.5 or less Comparative Example 2 200000 Good and obvious 5.8 Examples 7 to 12 and Comparative Examples 3 and 4 -13- 200300523 A copper film, an S 1 N film, and Si i are sequentially laminated on a silicon substrate 2 It is a 12-inch wafer with interlayer insulation film and photoresist film. It has a through-hole structure with dry etching. The via structure reaches the copper film. The substrate was immersed in the liquid shown in Table 3 for 15 minutes at 6 ° C for 15 minutes, followed by 30 minutes of photoresist stripping solution with the composition shown in Table 3. After washing with water, the scanning method was used. The degree of peeling of the photoresist and the degree of uranium decay of the copper film were observed with an electron microscope. The results are shown in Table 4. _Table 3_ Composition of the pretreatment photoresist stripping solution φ Hydrogen amine compound solvent strong test 丞 Concentration type Additives% by weight Type % By weight Kind by weight (% by weight) (lightning remaining Example 7 6 — EA 30 DMSO 60 TMAH 0.2 remaining 8 5 EDTA TETA 25 NMP 25 TMAH 1 remaining (0.001) PG 40 9 3 — 1A2P 25 DMSO 65 TMAH 1.5 remaining 10 4 nh4f EA 18 DGME 72 CH 1 remaining (0.001) 11 4 — PEHA 30 DGBE 60 TMAH 2 remaining 12 4 — AEEA 10 MEA 80 CH 0.1 remaining Comparative Example 3 — — EA 30 DMSO 60 TMAH 0.2 remaining 4 — one EA 25 NMP 65 TMAH 1 remaining

EA :乙醇胺 1A2P ：卜胺基-2 -丙醇 TETA :三乙四胺 -14- 200300523 PEHA ：五乙六胺 A E E A :胺乙基乙醇胺 TMAH:氫氧化四甲銨 CH :氫氧化膽鹼 DMSO :二甲亞楓 Ν Μ P : N -甲基吡咯烷酮 PG :丙二醇 DGME:二乙二醇單甲醚 DGBE ：二乙二醇單丁醚 Μ E A : Ν -甲基乙醇胺 EDTA :乙二胺四醋酸 表4 環境氣體氧濃度 (ppm) 光阻體剝離 銅腐蝕 溶氧濃度 (ppm) 實施例7 200 良好 J \ SN 0. 5以下 實施例8 200 良好 Μ 0. 5以下 實施例9 200 良好 Μ J \ w 1.0 實施例10 200 良好 M J \ 0. 5以下 實施例11 200 良好 άτντ ΤΠΤ j\w 0. 5以下 實施例12 200 良好 J \ w 0. 5以下 比較例3 200 無剝離 無 J \ NN 0. 5以下 比較例4 200 無剝離 M J \ w 0. 5以下 由表2及表4之結果可知，利用本發明之剝離方 法，配線基板之光阻體剝離可無銅膜之腐蝕。又更以 過氧化氫作前處理，難以僅用光阻體剝離液時，亦可 -15- 200300523 輕易進行光阻體剝離。 . 實施例1 3至1 5及比較例5 具有厚度4 0 0埃之銅膜的矽基板，浸泡於組成如 下之光阻體剝離液，於5 0 °C測出銅膜之腐蝕速度。 結果列於表5。 光阻體剝離液組成 乙醇胺：45重量％ 二乙二醇單甲醚：20重量％ 水：3 2重量％ ® 山梨糖醇：3重量％ 表5 環境氣體條件 腐蝕速度(埃/分鐘） 實施例13 氮氣環境中 0.7 實施例14 處理中邊以氮氣吹入光阻體剝離液 0.3 實施例15 含1%氧之氮中 1 比較例5 空氣環境中 7 可知由於氧之影響，銅腐蝕速度大有變化。持續 供給空氣則銅繼續腐鈾。爲其防止必須斷絕氧源。 實施例1 6、1 7及比較例6 具有厚度4 0 0埃之銅膜的矽基板，浸泡於組成如 下之光阻體剝離液，於5 0 °C測出銅膜之腐蝕速度。 量測係於附有環境氣體氧濃度計之手套箱內進行。結 果列於表6。 光阻體剝離液組成 乙醇胺：4 0重量％ -16 - 200300523 二乙二醇單丁醚：38重量％ 水：20重量％ 兒茶酚：2重量％ 表6 環境氣體條件 腐蝕速度(埃/分鐘） 實施例16 氧濃度200 ppm之氮氣環境中 1.3 實施例17 光阻體剝離液脫氣後，氧濃度200 ppm之 0.5 氮氣環境中 比較例6 空氣環境中 2.0 實施例1 8及比較例7 具有厚度400埃之銅膜的矽基板，浸泡於組成如 下之光阻體剝離液，於5 0 °C測出銅膜之腐蝕速度。 量測係於附有環境氣體氧濃度計之手套箱內進行。 光阻體剝離液組成 乙醇胺：3 0重量％ N -甲基吡咯烷酮：5 5重量％ 水：1 0重量％ 兒茶酚：5重量％ 更於上述矽基板塗布光阻劑，形成圖型，施以乾 式飩刻後，以上述光阻體剝離液於5 (TC浸泡3 0分 鐘。邊以光學顯微鏡觀察，邊測出去除殘留光阻體所 需之時間。結果列於表7。 -17- 200300523 表7 環境氣體條件 腐蝕速度 (埃/分鐘） 光阻體去除時間 (分鐘） 實施例18 氮氣環境中 0.8 15 比較例7 空氣環境中 4.5 15 在氮氣中（低氧濃度環境氣體下）作光阻體剝離 處理，即可無光阻體剝離性之變化，而抑制銅之腐 蝕。 產業上之利用可能性 φ 利用本發明即可剝離乾式蝕刻後之光阻體而無銅 之腐蝕。藉此，以往無法用於具有銅配線之基板的處 理之光阻體剝離液變成可以使用。而且，經由過氧化 氫之前處理，難以剝離之光阻體也變得容易剝離。EA: Ethanolamine 1A2P: Ethyl-2-propanol TETA: Triethylenetetramine-14- 200300523 PEHA: Pentaethylenehexamine AEEA: Amine ethylethanolamine TMAH: Tetramethylammonium hydroxide CH: Choline hydroxide DMSO: Dimethyl isocyanate NM P: N-methylpyrrolidone PG: propylene glycol DGME: diethylene glycol monomethyl ether DGBE: diethylene glycol monobutyl ether M EA: Ν-methylethanolamine EDTA: ethylenediamine tetraacetic acid table 4 Ambient gas oxygen concentration (ppm) Photoresist stripping copper corrosion dissolved oxygen concentration (ppm) Example 7 200 Good J \ SN 0.5 The following example 8 200 Good M 0.5 The following example 9 200 Good M J \ w 1.0 Example 10 200 Good MJ \ 0. 5 The following Example 11 200 Good. τττ ΤΠΤ j \ w 0. 5 The following Example 12 200 Good J \ w 0. 5 The following Comparative Example 3 200 No peeling No J \ NN 0 5 or less Comparative Example 4 200 Non-stripping MJ \ w 0.5 or less From the results of Tables 2 and 4, it can be known from the results of Tables 2 and 4 that the photoresist of the wiring substrate can be peeled without corrosion of the copper film by using the peeling method of the present invention. It also uses hydrogen peroxide as a pre-treatment. When it is difficult to use only the photoresist stripping solution, you can easily peel the photoresist. Examples 13 to 15 and Comparative Example 5 A silicon substrate having a copper film having a thickness of 400 angstroms was immersed in a photoresist stripping solution having the following composition, and the corrosion rate of the copper film was measured at 50 ° C. The results are shown in Table 5. Photoresist stripping solution composition Ethanolamine: 45% by weight Diethylene glycol monomethyl ether: 20% by weight Water: 3 2% by weight ® Sorbitol: 3% by weight Table 5 Ambient gas conditions Corrosion rate (Angstroms / minute) Examples 13 0.7 in a nitrogen environment. Example 14 In the treatment process, the photoresist stripping solution was blown with nitrogen under nitrogen. 0.3 Example 15 In 1% oxygen in nitrogen 1 Comparative Example 5 In the air environment 7 It can be seen that due to the influence of oxygen, the copper corrosion rate is great. Variety. The continuous supply of air keeps the copper from decaying uranium. To prevent this, the source of oxygen must be cut off. Examples 16 and 17 and Comparative Example 6 A silicon substrate having a copper film with a thickness of 400 angstroms was immersed in a photoresist stripping solution having the following composition, and the corrosion rate of the copper film was measured at 50 ° C. The measurement was performed in a glove box with an ambient gas oxygen concentration meter. The results are shown in Table 6. Composition of photoresist stripping solution: ethanolamine: 40% by weight -16-200300523 diethylene glycol monobutyl ether: 38% by weight water: 20% by weight catechol: 2% by weight Table 6 Ambient gas conditions Corrosion rate (Angstroms / minute ) Example 16 1.3 in a nitrogen environment with an oxygen concentration of 200 ppm 1.3 Example 17 After degassing the photoresist stripping solution, 0.5 in an oxygen concentration of 200 ppm in a nitrogen environment Comparative Example 6 2.0 in an air environment Example 1 8 and Comparative Example 7 The silicon substrate with a copper film thickness of 400 angstroms was immersed in a photoresist stripping solution composed of the following, and the corrosion rate of the copper film was measured at 50 ° C. The measurement was performed in a glove box with an ambient gas oxygen concentration meter. Composition of photoresist stripping solution: ethanolamine: 30% by weight N-methylpyrrolidone: 55% by weight water: 10% by weight catechol: 5% by weight A photoresist is coated on the above silicon substrate to form a pattern, and After dry etching, the photoresist stripping solution was immersed in 5 ° C for 30 minutes. The time required to remove the remaining photoresist was measured while observing with an optical microscope. The results are shown in Table 7. -17- 200300523 Table 7 Ambient gas corrosion rate (Angstroms / minute) Photoresist removal time (minutes) Example 18 0.8 15 in nitrogen environment Comparative Example 7 4.5 15 in air environment Under nitrogen (under low oxygen concentration ambient gas) as light The resist peeling treatment can prevent the corrosion of copper without the change of the peelability of the resist. Industrial applicability φ The present invention can peel the resist after dry etching without the corrosion of copper. In the past, a photoresist stripping solution that could not be used for the treatment of a substrate with copper wiring has become available. In addition, a photoresist that is difficult to peel off can be easily peeled off by a pretreatment with hydrogen peroxide.

Claims (1)

200300523 拾、申請專利範圍 1. 一種光阻體剝離方法，其特徵爲：使蝕刻後殘留有 光阻膜之配線基板，在氧濃度2體積％以下之環境 氣體中，與光阻體剝離液接觸。 2. 如申請專利範圍第1項之光阻體剝離方法，其中邊 趕出上述光阻體剝離液中之溶解氣體，邊使配線基 板與光阻體剝離液接觸。 3. 如申請專利範圍第1項之光阻體剝離方法，其中將 光阻體剝離液脫氣後，使配線基板與光阻體剝離液 接觸。 4. 如申請專利範圍第1至3項中任一項之光阻體剝離 方法，其中在配線基板與光阻體剝離液接觸之前， 使殘留之光阻膜與過氧化氫接觸作前處理。 5. 如申請專利範圍第4項之光阻體剝離方法，其中過 氧化氫前處理，係使殘留之光阻膜與過氧化氫濃度 0.5重量％以上之溶液接觸。 6. 如申請專利範圍第1至5項中任一項之光阻體剝離 方法，其中光阻體剝離液中之溶氧濃度在3 ppm以 下。 7. 如申請專利範圍第1至6項中任一項之光阻體剝離 方法，其中光阻體剝離液含有胺化合物、溶劑、強 鹼及水。 8. 如申請專利範圍第7項之光阻體剝離方法，其中光 阻體剝離液含有胺化合物5至9 5重量％，溶劑3 至8 5重量％，強鹼0. 0 1至5重量％，及水1至2 5 200300523 重量％。 9. 如申請專利範圍第7或8項之光阻體剝離方法， 其中胺化合物係選自由乙醇胺、1-胺基-2-丙醇、 N -(胺乙基）乙醇胺、N -甲基乙醇胺、N -乙基乙醇 胺、二乙醇胺、異丙醇胺、2 - ( 2 -胺乙氧基）乙醇、 乙二胺、丙二胺、丁二胺、二乙三胺、哌阱、嗎 福啉、三乙四胺、四乙五胺及五乙六胺所組成族 群的至少一種。 10. 如申請專利範圍第7至9項中任一項之光阻體剝 離方法，其中強鹼係選自由氫氧化四甲銨、氫氧 化膽鹼、氫氧化四乙銨及氫氧化四丁銨所組成族 群的至少一種。 11. 如申請專利範圍第7至1 0項中任一項之光阻體剝 離方法，其中溶劑係選自由二甲亞碱、Ν,Ν -二甲 基甲醯胺、Ν，Ν -二甲基乙醯胺、Ν -甲基吡咯烷酮、 二乙二醇單甲醚、二乙二醇單丁醚、二丙二醇單甲 醚、二丙二醇單丁醚及丙二醇所組成族群的至少一 種。 1Ζ如申請專利範圍第7至1 1項中任一項之光阻體剝 離方法，其中配線基板具有銅膜或銅合金膜。 - 20-200300523 Patent application scope 1. A photoresist stripping method, characterized in that a wiring substrate with a photoresist film remaining after etching is brought into contact with a photoresist stripping solution in an ambient gas having an oxygen concentration of 2% by volume or less. . 2. For the photoresist stripping method according to item 1 of the patent application scope, in which the wiring substrate is brought into contact with the photoresist stripping solution while driving out the dissolved gas in the photoresist stripping solution. 3. The photoresist stripping method according to item 1 of the patent application scope, wherein after the photoresist stripping solution is degassed, the wiring substrate is brought into contact with the photoresist stripping solution. 4. The photoresist stripping method according to any one of claims 1 to 3, wherein before the wiring substrate is brought into contact with the photoresist stripping solution, the remaining photoresist film is brought into contact with hydrogen peroxide as a pretreatment. 5. The photoresist stripping method according to item 4 of the patent application, wherein the pretreatment of hydrogen peroxide is to contact the remaining photoresist film with a solution having a hydrogen peroxide concentration of 0.5% by weight or more. 6. The photoresist stripping method according to any one of claims 1 to 5, wherein the dissolved oxygen concentration in the photoresist stripping solution is less than 3 ppm. 7. The photoresist stripping method according to any one of claims 1 to 6, wherein the photoresist stripping solution contains an amine compound, a solvent, a strong alkali, and water. 8. The photoresist stripping method according to item 7 of the application, wherein the photoresist stripping solution contains an amine compound 5 to 95% by weight, a solvent 3 to 85% by weight, and a strong base 0.0 to 1 to 5% by weight. , And water 1 to 2 5 200300523% by weight. 9. The photoresist stripping method according to item 7 or 8 of the scope of patent application, wherein the amine compound is selected from the group consisting of ethanolamine, 1-amino-2-propanol, N- (aminoethyl) ethanolamine, N-methylethanolamine , N-ethylethanolamine, diethanolamine, isopropanolamine, 2- (2-amineethoxy) ethanol, ethylenediamine, propylenediamine, succindiamine, diethylenetriamine, piperidine, morpholine , Triethylenetetramine, tetraethylenepentamine and pentaethylenehexaamine. 10. The photoresist stripping method according to any one of claims 7 to 9, wherein the strong base is selected from the group consisting of tetramethylammonium hydroxide, choline hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. At least one of the ethnic groups formed. 11. The photoresist stripping method according to any one of claims 7 to 10, wherein the solvent is selected from the group consisting of dimethyl subbase, Ν, Ν-dimethylformamide, and Ν, Ν-dimethyl At least one of the group consisting of acetofluoramine, N-methylpyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, and propylene glycol. 1Z The method for peeling a photoresist according to any one of claims 7 to 11 of the scope of patent application, wherein the wiring substrate has a copper film or a copper alloy film. -20-
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