TWI228640B - Photoresist remover composition - Google Patents

Photoresist remover composition Download PDF

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Publication number
TWI228640B
TWI228640B TW092127124A TW92127124A TWI228640B TW I228640 B TWI228640 B TW I228640B TW 092127124 A TW092127124 A TW 092127124A TW 92127124 A TW92127124 A TW 92127124A TW I228640 B TWI228640 B TW I228640B
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photoresist
photoresist remover
compound
patent application
remover composition
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TW092127124A
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Chinese (zh)
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TW200424760A (en
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Wei-Yong Kim
Seok-Il Yoon
Sam-Young Cho
Soon-Hee Park
Woo-Shik Cheon
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Dongjin Semichem Co Ltd
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    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • 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

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

Abstract

The present invention relates to a photoresist remover composition, more particularly to a photoresist remover composition comprising (a) 20 to 60 wt% of a water-soluble organic solvent, (b) 10 to 45 wt% of water, (c) 5 to 15 wt% of an alkyl amine or an alcohol amine, (d) 0.1 to 10 wt% of acetic acid, (e) 0.01 to 5 wt% of an oxime compound, (f) 1 to 10 wt% of an organic phenol compound containing two or three hydroxyl groups, and (g) 0.5 to 5 wt% of a triazole compound. The photoresist remover composition of the present invention can easily and quickly remove a resist film hardened during the hard baking, dry etching, ashing, or ion implantation processes, and a resist film transformed by metallic byproducts etched from the bottom metal film during the process in a short time, and can minimize corrosion of the bottom metal wire during the resist removal process, so that it is very effective for a manufacturing process of semiconductor devices, such as integrated circuits, large-scale integrated circuits, and very large-scale integrated circuits.

Description

1228640 玖、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明） 【發明所屬之技術領域】 本發明係指一種光阻去除劑組成，尤指一種可在諸 如積體電路（1C)、大型積體電路（LSI)、和極大型積體電 路（VLSI)之類半導體裝置的製程期間去除光阻劑的光阻 5 去除劑組成。 【先前技術】 在一般的半導體裝置製造方面，會在半導體基板的 導電層上形成一^固光阻圖案’並將導電層未被這圖案遮 10 敝的部份蝕刻掉，據以形成一個導電層圖案。這製程會 重複進行數十次。等導電層圖案形成後，已被當作光罩 的光阻圖案便應使用光阻去除劑將其從導電層去除。然 而，由於在新近的極大型積體路半導體製程中，主要是 以乾蝕刻來形成導電層圖案，因而難以去除光阻劑。 15 不同於採用酸性液態化學物的濕蝕刻，乾蝕刻係利 用一電漿離子#刻氣體與一物質層（matter layer)，例如導 電層，所產生的氣體-固體反應來進行。由於乾蝕刻易於 控制，且可提供鮮明的圖案，因而在新近的蝕刻製程中 位居主導地位。然而，因為電漿蝕刻氣體中的離子及自 20 由基會與光阻膜起反應而使光阻膜迅速硬化，所以乾蝕 刻在去除光阻劑方面有其缺點。尤其，對鎢及一氮化鈦 製成的導電層進行乾蝕刻時，縱然採用各式各樣的化學 物，亦難去除側壁上轉化及硬化的光阻劑。 近來所提出的含有羥胺及氨基乙氧基乙醇的光阻去 0續次頁（發明說明頁不敷使用時，請註記並使用續頁） 1228640 10 15 20 發明說明，續頁 除劑組成對大部份的硬化光阻膜可發揮較佳的去除效 果。然而，這種去除劑組成卻對量產hGiga以上dram 半導體時用以取代鋁線的銅線金屬膜造成相當程度的侵 蝕。另外，由於羥胺的毒性高，因而需開發一種符合環 5 保的新型光阻去除劑。 近來提出的另一種含有烷醇胺及二甘醇單烷基醚的 光阻去除劑組成，幾乎無氣味及毒性，且對大部份硬化 的光阻膜能發揮良好的去除效果。然而，這種去除劑組 成也無法將乾蝕刻或離子移植期間接觸過電漿蝕刻氣體 或離子束的光阻膜去除乾淨。因此，需開發一種能去除 乾蝕刻及離子移植製程轉化的光阻膜。 如前所述，使用光阻去除劑難以去除業已經過離子 移植加工的光阻膜。尤其，對於在製造極大型積體電路 時已經過高劑量離子移植製程而形成源極/汲極區的光 阻膜來說，更難以去除。在離子移植製㈣，光阻膜表 面主要是因南劑量和高能量離子束的反應熱而硬化。另 外’如同時進行拋光製程時，光阻膜内的壓力就會增加， 致使光賴表面因為膜㈣存溶劑，造成光阻劑殘留物 的產生’從而爆裂（pGp)。f用抛光處理的半導體晶圓， 是在2〇G°C以上的溫度進行。就這製程而言，留存在光 阻劑中的溶賴已被祕及㈣餐面。_，經過高 劑量離子移植的綠表面，因為表面上存有—道硬化 層，所以無法如此。 因爆裂而硬化的層面難以去除 此外，由於硬化層 -8- 1228640 發明說明$賣胃 是被熱所形成，因此，屬於雜質離子的掺雜劑（dopants) 可能被取代而進入光阻劑的分子結構，造成交聯反應。 於是，反應的位置就被氧（02)電漿氧化。氧化的光阻劑 變成可說是另一種污染源的殘留物及粒子，以致減低極 5 大型積體電路的良率。 現已有人提出許多能有效去除硬化光阻層的乾及濕 製程。該等製程的其中一種即為二步驟式的拋光法 [Fujimura，曰本應用物理學會春季會議（Spring Meeting of the Japanese Society of Applied Physics)，簡報 IP-13， 10 第574頁，1989年]。然而，這方法的乾蝕刻製程複雜， 而需要大型設備，因而對良率不利。 另有人曾提出含有一種有機胺化合物及各式各樣有 機溶劑的光阻去除劑組成，其係在習用的濕清潔製程中 作為光阻去除劑。尤其，現已廣泛採用一種含有有機胺 15 化合物，特別是含有一乙醇胺（MEA)作為基本組分的光 阻去除劑組成。 舉例來說，曾有人提出一種含有下列的二組分的光 阻去除劑組成：a)諸如一乙醇胺（MEA)和2-(2-胺基乙 氧基）乙醇（AEE)之類的有機胺化合物，和b)諸如N，N-20 二甲基乙醯胺（DMAc)，N，N-二甲基甲醯胺（DMF)，N-甲 基四氫砒咯（NMP)，二曱基亞砜（DMS0)，卡必醇（carbitol) 乙酸酯，與甲氧醋酸基丙烷（美國第4,617,251號專利）之 類的極性溶劑；一種含有下列的二組分的光阻去除劑組 成：a)諸如MEA，一丙醇胺，與曱基戊基乙醇之類的 -9- 1228640 發明說明續頁 有機胺化合物，和b)諸如N-甲基乙醯胺（MAc)，Ν,Ν-二甲基乙醯胺（DMAc)，二甲基曱醯胺（DMF)，Ν，Ν-二乙 基乙醯胺（DEAc)，Ν，Ν-二丙基乙醯胺（dpac)，Ν，Ν-二甲 基丙醯胺，Ν，Ν-二乙基丁醯胺，與Ν-甲基乙基丙醯胺 5 (美國第4,77〇,713號專利）之類的醯胺溶劑；一種含有下 列的二組分的光阻去除劑組成：a)諸如一乙醇胺（ΜΕΑ) 之類的有機胺化合物，和b)諸如1，3-二甲基-2-咪唑烧 基酮（DMI)，與1，3-二甲基-四羥基嘧啶酮（德國第 3,828,513號專利申請公報）之類的無質子極性溶劑；一種 10 含有下列的光阻去除劑組成：a)諸如一乙醇胺（MEA)， 二乙醇胺（DEA)，與三乙醇胺（TEA)以及乙二胺之類的 烧醇胺的乙稀氧化物，和b)諸如續燒（sulforane)之類的 石風化合物，以及c)諸如二乙二醇單乙基醚與二乙二醇單 丁基醚（日本第昭和62-49355號專利申請公報）之類的乙 15二醇單烷基醚；一種含有下列的光阻去除劑組成：a)諸 如MEA與DEA之類的水溶性胺，和b) L3-二甲基2_咪 唑烷基酮（曰本第昭和63-208043號專利申請公報）；一 種含有下列的正型光阻去除劑組成：a)諸如Mea，乙 二胺，六氫吡啶，與苄胺之類的胺，b)諸如dmAc，nmp， 20與DMSO之類的極性溶劑，和c)界面活性劑（日本第昭 和63-21343號專利申請公報）；一種含有下列的正型光 阻去除劑組成·· a)諸如MEA之類的含氮有機羥基化合 物，b) —種以上從二乙二醇單乙基醚，二甘醇二烷基 醚，γ-丁内酯，與1，3-二曱基-2-咪唑烷基酮所構成之群 -10- 1228640 發明說明，續;1； 組中選用的溶劑，和c) DMSO (日本第昭和64-42653號 專利申請公報）；一種含有下列的正型光阻去除劑組成： a)諸如MEA之類的有機胺化合物，b)諸如二甘醇單烧 基醚，DMAc’NMP，與DMSO之類的無質子極性溶劑， 5和c)磷酸酯界面活性劑（曰本第平成4-124668號專利 申請公報）；一種含有下列的光阻去除劑組成：a) 13_二 甲基-2-咪唑烷基酮（DMI)，b)二甲基亞颯（DMS〇)，和 c)諸如MEA之類的水溶性有機胺化合物（日本第平成 4-350660號專利申凊公報）；以及一種含有下列的光阻去 10除劑組成：a)MEA，b)DMSO,和c)鄰一笨二酚（日本第 平成5-281753號專利申請公報）。這些光阻去除劑組成 均具有較佳的安全性，加工性，和光阻去除效率。 然而，就新近的半導體裝置製程而言，由於包括矽 晶圓的基板是在110到140 〇C的高溫下處理，所以光阻 15劑易被烘焙。但是，前述的光阻去除劑卻無法將烘焙的 光阻劑完全去除。因此，為去除烘焙的光阻劑，曾有人 提出含有水或羥胺化合物的光阻去除劑組成。舉例來 說，曾有人提出一種含有下列的光阻去除劑組成：a)羥 胺，b)烷醇胺，和c)水（日本第平成4 289866號專利 2〇申請公報）；一種含有下列的光阻去除劑：a)羥胺，b)鏈 烷醇胺，c)水，和句抗腐蝕劑（日本第平成6_266119 號專利申請公報）；一種含有下列的光阻去除劑組成：幻 諸如GBL，DMF , DMAc，和NMP之類的極性溶劑，b) 古如2甲胺基乙醇之類的氨基醇，和水（日本第平成 -11- 1228640 發明說明，續頁 7-69618號專利申請公報）；一種含有下列的去除劑組 成· a)諸如MEA之類的氨基醇，b)水，和c) 丁基二 乙二醇（日本第平成8-123043號專利申請公報）；一種含 有下列的光阻去除劑組成：a)鏈烷醇胺與烷氧基烷基 5胺’ b)乙一醇單燒基醚，c)糖醇，d)氫氧化季銨，和 e)水（曰本第平成8-262746號專利申請公報）；一種含 有下列的去除劑組成：a) —種以上諸如MEA和AEE之 類的鏈烷醇胺，b)羥胺，c)二甘醇單烷基醚，d)糖（山 梨糖醇）’和e)水（曰本第平成9-152721號專利申請公 10報）；以及一種含有下列的光阻去除劑組成：a)羥胺， b)水，c)酸離解常數（pKa)為7·5到13的胺，d)水溶 性有機溶劑，和e)抗腐蝕劑（日本第平成9_96911號專 利申請公報）。 ~ j而這些光阻去除劑組成也無法完全去除在乾餘 15刻、拋光、和離子移植加工期間轉化及硬化的光阻膜， 或進行該加工期間從底部金屬膜蝕刻掉之金屬副產品轉 化的光阻膜。另外，它們亦不符合環保，而且無法完全 防止底部金屬線在光阻去除加工過程中可能遭受的侵 ♦虫0 【發明内容】 本發明之目的在於提供—種光阻去除劑組成，其可 輕易及迅速去除在乾_、拋光、或離子移植加工期間 轉化和硬化的光阻膜，以及進行該加1期間從底部金屬 20 1228640 發明說明續頁 膜钱刻掉之金屬副產品轉化的光阻膜。此外，該光阻去 除劑組成亦可在光阻去除期間將底部金屬線，尤其是鋼 線的腐餘減至最低程度，而且符合環保。 為達成此目的，本發明提供一種含有下列各組分的 5光阻去除劑組成：U) 20到60 wt% (重量百分比）的一種 水溶性有機溶劑，（b) 10到45 wt%的水，（C) 5到15 wt0/〇 的一種烧基胺或醇胺，（d) 0.1到1〇 wt%的醋酸，⑷〇 〇1 到5 wt%的一種肟化合物（oxime)，（f) i到1〇 wt%的一種 含有二或三個羥基的有機酚化合物，和〇·5到5 wt% 10 的一種三唑化合物。 【圖示之簡單說明】 第一圖係一在施用光阻去除劑組成之前的掃瞄電子 顯微相片。 15 第二圖係一在65 °C溫度下施用範例1的光阻去除劑 組成之後的掃瞄電子顯微相片。 第三圖係一在65 °C溫度下施用比較範例i的光阻去 除劑組成之後的掃瞄電子顯微相片。 2〇【實施方式】 現將本發明詳予說明於後。 本發明係指一種含有烷基胺或醇胺，醋酸，及肟化 合物的光阻去除劑組成。本發明的光阻去除劑組成可輕 易及迅速去除在硬烘焙' 乾姓刻、拋光（ashing)、或離子 -13- 1228640 發明說明,_胃 移植加工期間硬化的光阻膜，以及進行該加工期間從底 部金屬膜敍刻掉之金屬副產品轉化的光阻膜。此外，該 光阻去除劑亦可在光阻去除期間將底部金屬線的腐蝕減 至最低程度。 5 院基胺或醇胺宜為從下列構成之群組中選用的一種 或以上化合物：乙胺，二甲胺，二乙胺，三甲胺，三乙 胺，乙醇胺，二乙醇胺，和三乙醇胺。另外，烧基胺或 醇胺的含量宜為5到15 wt% (重量百分比）。如果烧基胺 或醇胺的含量低於5 wt%，便難以完全去除在乾蝕刻或 10抛光加工期間轉化的側壁光阻聚合物。此外，如果含量 超過15 wt%，那麼由鋁或鋁合金製成的底部金屬薄膜就 會遭受過度腐蝕。 醋酸的含量宜為〇. 1到1 〇 wt%。如果醋酸的含量低 於〇·1 wt%，聚合物去除效率即減低。此外，如果含量超 15 過1 〇 wt%，底部金屬薄膜就會遭受過度腐蝕。 將化合物宜為從下列構成之群組中選用的一種或以 上之化合物：乙醛肟，丙酮肟，和丁酮肟。肟化合物的 含量宜為0·01到5 wt%。如果肟化合物的含量低於〇 〇1 wt%，剝離之側壁光阻聚合物的溶解效果就不佳。另外， 20如果含量超過5 wt%，那麼因為肟的高沸點，光阻劑的 低溫溶解解便減低。 本發明所用者宜為經由離子交換樹脂過濾出的純 水。更佳者是採用電阻係數在18 ΜΩ以上的超純水。含 水量宜為10到45 wt%。如果含水量低於1〇 wt%，光阻 -14- 1228640 發明說明胃 5 10 劏即會受到乾蝕刻及拋光加工期間所產生之金屬副產口 的嚴重變性，以致去除效果不佳。另外，如果含水量: 過45 wt°/〇，則因烷基胺與水溶性有機溶劑的相對含量減 低:以致底部金屬線可能遭侵蝕，而除了變性光阻劑外， 大。卩份正常光阻劑的去除效果也不佳。 含有二或三個羥基的有機酚化合物宜為下列化學結 構式1所表示的化合物：1228640 发明 Description of the invention (The description of the invention should state: the technical field, the prior art, the content, the embodiments, and the drawings of the invention are briefly explained. Refers to a photoresist 5 remover composition that can remove photoresist during the manufacturing process of semiconductor devices such as integrated circuits (1C), large scale integrated circuits (LSI), and very large scale integrated circuits (VLSI). [Previous technology] In general semiconductor device manufacturing, a solid photoresist pattern is formed on the conductive layer of the semiconductor substrate, and a portion of the conductive layer that is not covered by this pattern is etched away to form a conductive layer. Layer pattern. This process is repeated dozens of times. After the conductive layer pattern is formed, the photoresist pattern that has been used as a photomask should be removed from the conductive layer with a photoresist remover. However, it is difficult to remove the photoresist because the conductive layer pattern is mainly formed by dry etching in the recent semiconductor manufacturing process of very large integrated circuits. 15 Unlike wet etching using acidic liquid chemicals, dry etching uses a plasma-ion #etching gas and a matter layer, such as a conductive layer, to generate a gas-solid reaction. Because dry etching is easy to control and provides vivid patterns, it has dominated the recent etching process. However, because the ions in the plasma etching gas and the photoresist film react with the substrate to rapidly harden the photoresist film, dry etching has its disadvantages in removing the photoresist. In particular, when conducting a dry etching of a conductive layer made of tungsten and titanium nitride, it is difficult to remove the photoresist that is converted and hardened on the sidewalls, even if a variety of chemicals are used. The recently proposed photoresist containing hydroxylamine and aminoethoxyethanol is removed from the next page. (When the description page of the invention is insufficient, please note and use the continued page.) 1228640 10 15 20 Description of the invention. Part of the cured photoresist film can play a better removal effect. However, the composition of this remover caused considerable corrosion to the copper wire metal film used to replace aluminum wires in mass production of dram semiconductors above hGiga. In addition, due to the high toxicity of hydroxylamine, it is necessary to develop a new photoresist remover that complies with environmental protection. Recently, another photoresist remover composition containing alkanolamine and diethylene glycol monoalkyl ether has almost no odor and toxicity, and can exert a good removal effect on most hardened photoresist films. However, such a remover composition cannot remove a photoresist film that has been exposed to plasma etching gas or ion beam during dry etching or ion implantation. Therefore, it is necessary to develop a photoresist film capable of removing dry etching and ion implantation process conversion. As mentioned earlier, it is difficult to remove a photoresist film that has been ion-implanted using a photoresist remover. In particular, it is more difficult to remove a photoresist film that has undergone a high-dose ion implantation process to form a source / drain region when manufacturing a very large integrated circuit. In the ion implantation system, the surface of the photoresist film is hardened mainly by the south dose and the reaction heat of the high-energy ion beam. In addition, 'if the polishing process is performed at the same time, the pressure in the photoresist film will increase, which will cause the photoresist residue on the photoresist surface to burst (pGp). fSemiconductor wafers are polished at a temperature of 20G ° C or higher. As far as this process is concerned, the solvents left in the photoresist have been secreted and eaten with noodles. _, The green surface after high-dose ion implantation cannot be used because there is a hardened layer on the surface. The hardened layer is difficult to remove due to the burst. In addition, because the hardened layer-8-1228640 Invention Description $ Stomach is formed by heat, so dopants that are impurity ions may be replaced and enter the molecules of the photoresist Structure, causing cross-linking reactions. Then, the reaction site is oxidized by the oxygen (02) plasma. The oxidized photoresist becomes a residue and particles that can be said to be another source of pollution, which reduces the yield of extremely large integrated circuits. Many dry and wet processes have been proposed to effectively remove the hardened photoresist layer. One of these processes is a two-step polishing method [Fujimura, Spring Meeting of the Japanese Society of Applied Physics, Bulletin IP-13, 10 p.574, 1989]. However, the dry etching process of this method is complicated, and large equipment is required, which is disadvantageous to the yield. Others have proposed photoresist removers containing an organic amine compound and various organic solvents, which are used as photoresist removers in conventional wet cleaning processes. In particular, a photoresist remover composition containing an organic amine 15 compound, particularly monoethanolamine (MEA) as a basic component has been widely used. For example, a two-component photoresist remover composition has been proposed: a) Organic amines such as monoethanolamine (MEA) and 2- (2-aminoethoxy) ethanol (AEE) Compounds, and b) such as N, N-20 dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), N-methyltetrahydrofluorene (NMP), difluorenyl Polar solvents such as sulfoxide (DMS0), carbitol acetate, and methoxyacetoxypropane (U.S. Patent No. 4,617,251); a photoresist remover consisting of the following two components: a ) Such as MEA, monopropanolamine, and fluorenylpentyl ethanol-9-1228640 Description of the invention continued on organic amine compounds, and b) such as N-methylacetamide (MAc), N, N-di Methylacetamide (DMAc), dimethylampamide (DMF), N, N-diethylacetamide (DEAc), N, N-dipropylacetamide (dpac), N, N -Amine solvents such as dimethylpropylamine, N, N-diethylbutylamine, and N-methylethylpropylamine 5 (US Pat. No. 4,77,713); Photoresist remover composition containing the following two components: a) such as Organic amine compounds such as ethanolamine (MEA), and b) such as 1,3-dimethyl-2-imidazolyl ketone (DMI), and 1,3-dimethyl-tetrahydroxypyrimidone (Germany No. 3,828,513 Patent Application Gazette), aprotic polar solvents, etc .; a 10 containing the following photoresist remover composition: a) such as monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA) and ethylenediamine Ethoxylated amines, and b) stone wind compounds such as sulforane, and c) such as diethylene glycol monoethyl ether and diethylene glycol monobutyl ether (Japan Patent Application Publication No. Showa 62-49355) such as ethylene 15 glycol monoalkyl ether; a photoresist remover composition comprising: a) water-soluble amines such as MEA and DEA, and b) L3- Dimethyl 2-imidazolidinone (Japanese Patent Application Publication No. 63-208043); a positive photoresist remover composition containing: a) such as Mea, ethylenediamine, hexahydropyridine, and benzyl Amines such as amines, b) polar solvents such as dmAc, nmp, 20 and DMSO, and c) surfactants 63-21343 Patent Application Publication); a composition containing the following positive photoresist remover a) a nitrogen-containing organic hydroxyl compound such as MEA, b) more than one kind of diethylene glycol monoethyl ether, The group consisting of diethylene glycol dialkyl ether, γ-butyrolactone, and 1,3-difluorenyl-2-imidazolidinone -10- 1228640 Description of the invention, continued; 1; solvents selected in the group, And c) DMSO (Japanese Patent Application Publication No. 64-42653); a positive photoresist remover composition comprising: a) an organic amine compound such as MEA, and b) a diethylene glycol monoalkyl ether , DMAc'NMP, aprotic polar solvents such as DMSO, 5 and c) Phosphate ester surfactant (Japanese Patent Application Publication No. Hei 4-124668); a composition containing the following photoresist remover: a) 13_dimethyl-2-imidazolidinyl ketone (DMI), b) dimethylsulfinium (DMS〇), and c) water-soluble organic amine compounds such as MEA (Japanese Patent No. Hei 4-350660 Shenying Gazette); and a photoresist remover composition containing the following: a) MEA, b) DMSO, and c) o-dihydroxybenzene (Japan Heisei 5- Patent Application Gazette No. 281753). These photoresist remover compositions all have better safety, processability, and photoresist removal efficiency. However, in terms of a recent semiconductor device manufacturing process, since a substrate including a silicon wafer is processed at a high temperature of 110 to 140 ° C, the photoresist 15 is easily baked. However, the aforementioned photoresist removing agent cannot completely remove the baked photoresist. Therefore, in order to remove baked photoresist, a photoresist remover composition containing water or a hydroxylamine compound has been proposed. For example, a photoresist remover composition has been proposed that contains: a) hydroxylamine, b) alkanolamine, and c) water (Japanese Patent Application No. 4 289866, Japanese Patent Application Publication No. 20); Resistance remover: a) hydroxylamine, b) alkanolamine, c) water, Japanese anti-corrosive agent (Japanese Patent Application Publication No. 6_266119); a photoresist remover composition containing the following: such as GBL, DMF, DMAc, polar solvents such as NMP, b) amino alcohols such as 2-methylaminoethanol, and water (Japanese Patent Heisei-11-1228640 Invention Description, Continued Patent Application Publication No. 7-69618); Contains the following remover composition: a) an amino alcohol such as MEA, b) water, and c) butyl diethylene glycol (Japanese Patent Application Publication No. 8-123043); a photoresist removal containing Agent composition: a) alkanolamine and alkoxyalkyl 5 amine 'b) monoethanol ether of glycol, c) sugar alcohol, d) quaternary ammonium hydroxide, and e) water (Japanese Heisei 8- Patent Application Publication No. 262746); a composition containing the following remover: a)-more than one such as MEA and AEE Alkanolamine, b) hydroxylamine, c) diethylene glycol monoalkyl ether, d) sugar (sorbitol) 'and e) water (Japanese Patent Application Publication No. 9-152721, Japanese Patent Publication No. 10); and A photoresist remover composition comprising: a) hydroxylamine, b) water, c) an amine having an acid dissociation constant (pKa) of 7.5 to 13, d) a water-soluble organic solvent, and e) an anticorrosive agent (Japanese Heisei 9_96911 Patent Application Gazette). ~ j And these photoresist remover compositions cannot completely remove the photoresist film converted and hardened during the 15-minute dry, polishing, and ion implantation process, or the conversion of metal by-products etched from the bottom metal film during the process. Photoresist film. In addition, they are not environmentally friendly, and cannot completely prevent the invasion of the bottom metal wire during the photoresist removal process. [Abstract] The object of the present invention is to provide a photoresist removal composition, which can easily And quickly remove the photoresist film converted and hardened during the dry, polishing, or ion implantation process, and the photoresist film converted from the metal by-products engraved from the bottom metal film during the addition of the 1st. In addition, the composition of the photoresist remover can also minimize the corrosion of the bottom metal wire, especially the steel wire, during the photoresist removal, and is environmentally friendly. To achieve this, the present invention provides a 5 photoresist remover composition comprising: U) a water-soluble organic solvent of 20 to 60 wt% (weight percent), and (b) 10 to 45 wt% of water , (C) 5 to 15 wt0 / 0 of a benzyl amine or alcohol amine, (d) 0.1 to 10 wt% of acetic acid, 1001 to 5 wt% of an oxime (oxime), (f) i to 10 wt% of an organic phenol compound containing two or three hydroxyl groups, and 0.5 to 5 wt% 10 of a triazole compound. [Brief description of the diagram] The first image is a scanning electron micrograph before the composition of the photoresist remover is applied. 15 The second image is a scanning electron micrograph after applying the photoresist remover composition of Example 1 at 65 ° C. The third image is a scanning electron micrograph after applying the composition of the photoresist remover of Comparative Example i at a temperature of 65 ° C. 20 [Embodiment] The present invention will be described in detail below. The present invention refers to a photoresist removing agent composition comprising an alkylamine or an alcoholamine, acetic acid, and an oxime compound. The composition of the photoresist remover of the present invention can be easily and quickly removed in hard baking, dry, ashing, or ion-13-1228640. Description of the invention, _ photoresist film hardened during gastric transplantation process, and the process A photoresist film converted from metal by-products engraved from the bottom metal film during the period. In addition, the photoresist remover can also minimize the corrosion of the bottom metal wires during photoresist removal. 5 An aminoamine or an alcoholamine is preferably one or more compounds selected from the group consisting of ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, ethanolamine, diethanolamine, and triethanolamine. In addition, the content of the alkyl amine or the alcohol amine is preferably 5 to 15 wt% (weight percent). If the content of the alkylamine or alcoholamine is less than 5 wt%, it is difficult to completely remove the sidewall photoresist polymer converted during the dry etching or polishing process. In addition, if the content exceeds 15 wt%, the bottom metal film made of aluminum or aluminum alloy may suffer excessive corrosion. The content of acetic acid is preferably from 0.1 to 10 wt%. If the content of acetic acid is less than 0.1 wt%, the polymer removal efficiency is reduced. In addition, if the content exceeds 15 wt%, the bottom metal film will suffer excessive corrosion. The compound is preferably one or more compounds selected from the group consisting of acetaldehyde oxime, acetoxime, and butanone oxime. The content of the oxime compound is preferably from 0.01 to 5 wt%. If the content of the oxime compound is less than 0.01 wt%, the dissolution effect of the peeled sidewall photoresist polymer is not good. In addition, if the content of 20 exceeds 5 wt%, the low-temperature dissolution of the photoresist is reduced due to the high boiling point of the oxime. The present invention is preferably pure water filtered through an ion exchange resin. It is even better to use ultrapure water with a resistivity of 18 MΩ or more. The water content should be 10 to 45 wt%. If the water content is less than 10 wt%, the photoresist -14-1228640 Invention Description Stomach 5 10 劏 will be severely denatured by metal by-products produced during dry etching and polishing processes, resulting in poor removal. In addition, if the water content is more than 45 wt ° / 〇, the relative content of the alkylamine and the water-soluble organic solvent is reduced: so that the bottom metal wire may be eroded, except for the modified photoresist, which is large. The removal effect of the normal photoresist is also not good. The organic phenol compound containing two or three hydroxyl groups is preferably a compound represented by the following chemical structure formula 1:

化學結構式1 (〇H)m 其中m是2或3Chemical structural formula 1 (〇H) m where m is 2 or 3

含有二或三個羥基的有機酚化合物係用以去除乾蝕 刻’拋光和離子移植加工期間硬化的光阻膜，以及被底 部金屬薄膜所蝕刻出之金屬副產品予以變性的光阻膜。 每基胺與水的氫離子起反應而導致的經基離子會在光阻 15膜與半導體基板（substrate)之間提供一個可滲透的空 間。另外，含有二或三個羥基的有機酚化合物亦可防止 底部金屬薄膜不受光阻去除劑組成的侵蝕。 含有二或三個羥基的有機紛化合物的含量宜為1到 10 wt%。如果這有機盼化合物的含量低於1 wt%，受到 20 乾蝕刻及離子移植加工期間所產生之金屬副產品予以嚴 重變性的光阻劑便無法去除乾淨，致使底部金屬薄膜遭 到嚴重侵蝕。反之，如果含量超過10 wt%，這組成的製 -15- 1228640 造價格即高昂。 水溶性有機溶劑宜為從下列構成之群組中選用的一 種或以上之有機溶劑：二曱基亞砜（DMSO)，N-曱基砒咯 烷酮（NMP)，二曱基乙醯胺（DMAc)，和二甲基曱醯胺 5 (DMF)。考慮到對光阻劑的溶解性，防止光阻劑的重殿 積，以及廢溶劑因快速生物降解而易於處理等因素，較 宜採用二甲基亞砜（DMSO)或二甲基乙醯胺（DMAc)。此 種水溶性有機溶劑的含量宜為20到60 wt%。 採用含有二或三個羥基的有機酚化合物，即可有效 10 防止侵蝕。然而，底部金屬線薄膜之側壁或頂面的部份 侵蝕，或點蝕（pitting)，卻無法完全解決。如果讓含有二 或三個羥基的有機酚化合物與三唑化合物一起使用，即 可防止發生點蝕的問題。 三唑化合物宜為從下列構成之群組中選用的一種或 15 以上之化合物：苯並三唑（BT)，曱苯三唑（TT)，羧基苯 並三唑（CBT)，和含有苯並三唑（BT)及曱苯三唑（TT)的二 組分（two-component)三唾化合物。在這些化合物當中， 較宜者為含有苯並三唑（BT)及甲苯三唑（TT)的二組分三 唑化合物。尤其，如果讓含有羥基的芳基酚化合物與含 20 有苯並三唑（BT)及甲苯三唑（TT)的二組分三唑化合物一 起使用時，混合比宜為1 : 1，如此可較有效地防止光阻 膜側壁的側點蝕。三唑化合物的含量為0.5到5 wt%。如 果含量低於0.5 wt%，即無法有效防止點餘。反之，如果 含量超過5 wt%，光阻去除劑組成的黏性即增加，因而 -16- 丄22864〇 發明說明,_頁; 使用時變得不方便。Organic phenolic compounds containing two or three hydroxyl groups are used to remove photoresist films that are hardened during dry etching 'polishing and ion implantation, and photoresist films that have been denatured by metal by-products etched from the bottom metal film. Each base amine reacts with the hydrogen ions of the water to cause a base ion to provide a permeable space between the photoresist film and the semiconductor substrate. In addition, the organic phenol compound containing two or three hydroxyl groups can also prevent the bottom metal film from being attacked by the composition of the photoresist removing agent. The content of the organic compound containing two or three hydroxyl groups is preferably 1 to 10 wt%. If the content of the organic desired compound is less than 1 wt%, the photoresist severely denatured by metal by-products generated during dry etching and ion implantation processing cannot be removed, resulting in severe erosion of the bottom metal film. Conversely, if the content exceeds 10 wt%, the manufacturing cost of this composition is high. The water-soluble organic solvent is preferably one or more organic solvents selected from the group consisting of: difluorenylsulfoxide (DMSO), N-fluorenylpyrrolidone (NMP), difluorenylacetamide ( DMAc), and dimethylamidamine 5 (DMF). Considering the solubility of the photoresist, preventing heavy accumulation of the photoresist, and the ease of disposal of waste solvents due to rapid biodegradation, it is more appropriate to use dimethyl sulfoxide (DMSO) or dimethylacetamide (DMAc). The content of such a water-soluble organic solvent is preferably 20 to 60 wt%. Using organic phenolic compounds containing two or three hydroxyl groups can effectively prevent erosion. However, partial erosion or pitting of the sidewall or top surface of the bottom metal wire film cannot be completely solved. If an organic phenol compound containing two or three hydroxyl groups is used together with a triazole compound, the problem of pitting corrosion can be prevented. The triazole compound is preferably one or more compounds selected from the group consisting of: benzotriazole (BT), pyrenetriazole (TT), carboxybenzotriazole (CBT), and benzotriazole-containing compounds Two-component trisialic compounds of triazole (BT) and benzotriazole (TT). Among these compounds, a two-component triazole compound containing benzotriazole (BT) and toltriazole (TT) is preferred. In particular, if an arylphenol compound containing a hydroxyl group is used together with a two-component triazole compound containing 20 benzotriazole (BT) and toluenetriazole (TT), the mixing ratio should be 1: 1. The side pitting of the side wall of the photoresist film is effectively prevented. The content of the triazole compound is 0.5 to 5 wt%. If the content is less than 0.5 wt%, it is impossible to effectively prevent the margin. Conversely, if the content exceeds 5 wt%, the viscosity of the composition of the photoresist remover increases, so -16- 丄 22864〇 Description of the invention, _ page; It becomes inconvenient to use.

若在半導體置的製程巾使用本發明的光阻去除劑組 成，就可輕易在短時間内去除光阻膜。尤其，更可輕易 去除鎢及一氮化鈦膜轉化的光阻膜。另外，它也符合環 5保要求，可在去除光阻劑的進行期間將底部金屬線的腐 蝕減至最低程度。尤其，它能在量產1-Giga DRAM (動 怨隨機存取記憶體）以上極大型積體電路半導體時，把所 用銅線的腐蝕減至最低程度。 茲舉下列各範例將本發明詳予說明於後。然而，該 10等範例僅供瞭解本發明，不得用以限制本發明。除另有 規定外，下列各範例和比較範例的含量及混合比均以重 量為準。 範例 範例1到5及比較範例1到2 15 範例1到5及比較範例1到2的光阻去阻劑組成係 以下列表1所載列的組成及含量製備而成。If the photoresist removing agent of the present invention is used in a semiconductor process towel, the photoresist film can be easily removed in a short time. In particular, the photoresist film converted by tungsten and titanium nitride film can be easily removed. In addition, it also meets environmental protection requirements, which can minimize the corrosion of the bottom metal wire during the photoresist removal process. In particular, it can minimize the corrosion of copper wires used in mass production of very large integrated circuit semiconductors above 1-Giga DRAM (Random Access Memory). The following examples are given to explain the present invention in detail. However, these 10 examples are only for understanding the present invention and should not be used to limit the present invention. Unless otherwise specified, the contents and mixing ratios of the following examples and comparative examples are based on weight. Examples Examples 1 to 5 and Comparative Examples 1 to 2 15 The photoresist and resist remover compositions of Examples 1 to 5 and Comparative Examples 1 to 2 were prepared from the compositions and contents listed in Table 1 below.

表1 含量(wt%) 範例 比較範例 1 2 3 4 5 1 2 烧基胺或 醇胺 三甲胺 10 - 12 15 - 30 35 乙醇胺 - 15 - - 5 - - 化合物 乙醛 0.5 - - 3.5 - - • 丙_ - 3 - - 0.5 雄 - 丁酮 - - 1 - - - - 水 31 28 45 33 32 30 20 醋酸 2 5 7 1 10 - - 有機盼化 鄰苯二酚 8 - 10 - 5 - - -17- 1228640 發明說明$賣胃 合物 間笨二酚 - 5 - 10 - - - 曱酚 - - - - - 9 25 水溶性有 機溶劑 DMS0 1} 48 41 - - - - - DMAc 2) - - 20 35 - - - NMP 3) - - - - 45 - 20 DMF 4) - - - - - 31 - 三峻化合 物 BT 5) 0.5 3.0 5.0 - - - - Cobratec928 6) CBT 7) - - - 2.5 - - 註） 0 DMSO:二甲基亞 2) DMAc :二甲基乙醯 3) NMP : N-曱基砒咯烷酮 4) DMF :二甲基甲醯胺 5) BT :苯並三唑(Cobratec 99, PMC) 6) CBT ··羧基笨並三唑(Cobratec CBT，PMC) 7) Cobratec 928 :含有苯並三唑及甲苯三唑的三唑化合物(PMC) 測試範例 對於範例1到5和比較範例1到2所製備的各光阻 去除劑組成，分別進行（1)光阻劑去除試驗和（2)銅腐蝕 5 試驗。下列表2和3所示者即為其結果。 (1)光阻劑去除試驗 樣本A的製備 在一由下往上澱積一道1000 A厚之鎢膜和一道700 A厚之一氮化鈦膜的8忖石夕晶圓的表面上，先以旋轉塗 10 布法塗布一層常用的正型（positive type)光阻劑組成（三 菱公司供售的IS401)，使最終膜厚達到1.01 μπι。接著， 在一溫度為100 °C的加熱板上將這光阻膜預烘焙90秒 鐘。把一圖案光罩（patterned mask)置於光阻膜之上以 -18- 1228640 發明說明胃 後即％用紫外線。以一種2·38%的氫氧化四甲銨（tmah) 顯衫洛液在21 °C的溫度上顯影60秒鐘後，再在120 °C 的加熱板上將光阻圖案樣本硬烘焙丨〇〇秒鐘。以樣本上 所形成的光阻圖案作為光罩，採用乾蝕刻設備（日立公司 5供售的M318)而以SFVC12混合氣體對這光阻圖案未遮蔽 的鎢及一氮化鈦膜進行蝕刻35秒鐘，即形成一金屬線圖 案。 iL里劑去险 在65 °C的溫度下把樣本a浸入各光阻去除劑組成 1〇中。接著取出樣本，用超純水沖洗，再以氮氣使其乾燥。 利用掃瞄電子顯微鏡（SEM)觀察圖案側壁及線圖案表面 上的光阻劑殘留物，並以下列標準來評估光阻去除效 率。表2所載列者即為其結果。 〇·圖案側壁及線圖案表面上的光阻劑殘留物完全被 15 去除。 △ ••圖案側壁及線圖案表面上的光阻劑殘留物有8〇0/〇 以上被去除，但仍有少量留下。 x ·圖案側壁及線圖案表面上的光阻劑殘留物大部份 未被去除。 20 (2)銅腐蝕試驗 瘗_本B的掣借 製備在半導體封裝製程中所用的銅導線架。 銅腐餘試給 在65。(：的溫度下把樣本B浸入各光阻去除劑組成 -19- ^28640Table 1 Content (wt%) Example Comparative Example 1 2 3 4 5 1 2 Alkylamine or alcoholamine trimethylamine 10-12 15-30 35 Ethanolamine-15--5--Compound acetaldehyde 0.5--3.5--• • Propane_-3--0.5 Andro-butanone--1----Water 31 28 45 33 32 30 20 Acetic acid 2 5 7 1 10--Organic catechol 8-10-5---17 -1228640 Description of the invention $ Selling gastrointestinal resorcinol-5-10---Phenol-----9 25 Water-soluble organic solvent DMS0 1} 48 41-----DMAc 2)--20 35 ---NMP 3)----45-20 DMF 4)-----31-Sanjun Compound BT 5) 0.5 3.0 5.0----Cobratec928 6) CBT 7)---2.5--Note) 0 DMSO: dimethylimine 2) DMAc: dimethylacetamidine 3) NMP: N-fluorenylpyrrolidone 4) DMF: dimethylformamide 5) BT: benzotriazole (Cobratec 99, PMC) 6) CBT ·· Carboxybenztriazole (Cobratec CBT, PMC) 7) Cobratec 928: Triazole compound (PMC) containing benzotriazole and toltriazole Test Examples For Examples 1 to 5 and Comparative Example 1 To the composition of each photoresist remover prepared in 2, respectively, (1) photoresist removal test (2) Copper corrosion test. The results shown in Tables 2 and 3 below are the results. (1) Preparation of Photoresist Removal Test Sample A On the surface of an 8 ocher wafer where a 1000 A thick tungsten film and a 700 A thick titanium nitride film were deposited from the bottom up, first A spin coating 10 cloth method was used to coat a layer of a commonly used positive type photoresist composition (IS401 available from Mitsubishi Corporation) to achieve a final film thickness of 1.01 μm. Next, the photoresist film was prebaked for 90 seconds on a hot plate at a temperature of 100 ° C. A patterned mask is placed on top of the photoresist film. -18-1228640 Invention Description The stomach is treated with ultraviolet rays. After developing with a 2.38% tetramethylammonium hydroxide (tmah) solution at 21 ° C for 60 seconds, the photoresist pattern samples were hard-baked on a 120 ° C hot plate. 〇 seconds. Using the photoresist pattern formed on the sample as a photomask, dry etching equipment (M318 supplied by Hitachi 5) was used to etch the unmasked tungsten and titanium nitride film of this photoresist pattern with SFVC12 for 35 seconds The clock forms a metal wire pattern. iL solution remover Dip sample a into photoresist remover composition 10 at 65 ° C. Then remove the sample, rinse it with ultrapure water, and dry it with nitrogen. Scanning electron microscope (SEM) was used to observe the photoresist residue on the pattern sidewall and the line pattern surface, and the photoresist removal efficiency was evaluated according to the following criteria. Those listed in Table 2 are their results. 〇 · The photoresist residue on the pattern sidewall and line pattern surface is completely removed by 15. △ • The photoresist residue on the pattern sidewall and line pattern surface was removed more than 8000 / 〇, but a small amount remained. x • Most of the photoresist residue on the pattern sidewall and line pattern surface has not been removed. 20 (2) Copper corrosion test 的 _The borrowing of this B Preparation of copper lead frame used in the semiconductor packaging process. Copper rot test gave at 65. Composition of sample B immersed in each photoresist remover at a temperature of -19- ^ 28640

著取出樣本，用超純水沖洗，再以氮氣使其乾燥。 刊用掃瞄電子g§他 电卞”属喊鏡樣本表面，並以下列標準來評估 餘度。表3所載列者即為其結果。 5 〇：銅表面上無腐蝕。 △:銅表面上有部份腐蝕。 X.整個銅表面上受到嚴重腐蝕。Remove the sample, rinse it with ultrapure water, and dry it with nitrogen. Scanning electrons published by the journal "Gallium Electrode" belong to the sample surface of the mirror, and the margin is evaluated according to the following criteria. The results listed in Table 3 are the results. 5 〇: No corrosion on the copper surface. △: Copper surface Partial corrosion. X. Serious corrosion on the entire copper surface.

-20- 1228640 _ 發明說明續頁 如表3所示’範例1到5的組成在金屬線腐蝕試驗 中展現出良好的結果，而比車父範例1到2的習用組成則 隨著時間展現出不佳的耐腐蝕性。 第一及二圖分別是施用範例1的光阻去除劑組成之 5 前和之後的掃瞄電子顯微相片，而第三圖則是施用比較 範例1之光阻去除劑組成（日立公司供售的S-4100)之後 的知猫電子顯微相片。這試驗係在樣本A所用的65。匸 溫度下進行。 從第一圖可看出施用光阻去除劑之前在側壁上所存 10 有的光阻劑。 從第二圖可看出所有的光阻劑均已用範例丨的光阻 去除劑組成去除乾淨。 k第二圖可看出在施用比較範例丨的習用光阻去除 劑組成之後，側壁上仍留有光阻劑。 15 如前所述，本發明的光阻去除劑組成可輕易去除在 乾蝕刻、拋光、或離子移植加工期間硬化的光阻膜，以 及進行邊加工期間從底部金屬膜蝕刻掉之金屬副產品轉 變化的光阻膜，並可在光阻去除期間將底部金屬線的腐 钱減至最低程度。另外，後續的清洗製程亦可只用水處 ?0 I© ，不必用到諸如異丙醇或二甲基亞隻有機溶劑。 以上所舉實施例僅用以說明本發明而已，非用以限 制本發明之範圍。舉凡不違本發明精神所從事的種種修 改或變化，俱屬本發明申請專利範圍。 -21- 1228640 _ 發明說明$賣頁 【圖式簡單說明】 第一圖係一在施用光阻去除劑組成之前的掃瞄電子 顯微相片。 第二圖係一在65 °C溫度下施用範例1的光阻去除劑 5 組成之後的掃瞄電子顯微相片。 第三圖係一在65 °C溫度下施用比較範例1的光阻去 除劑組成之後的掃瞄電子顯微相片。 -22--20- 1228640 _ Description of the invention The continuation page is shown in Table 3. 'The compositions of Examples 1 to 5 showed good results in the wire corrosion test, while the conventional compositions of Carrier Examples 1 to 2 showed over time. Poor corrosion resistance. The first and second images are the scanning electron micrographs before and after applying the photoresist remover composition of Example 1, respectively, and the third image is the photoresist remover composition of Comparative Example 1, which was applied (supplied by Hitachi) Electron micrographs of the cat after S-4100). This test is based on 65 used in Sample A.进行 Perform at temperature. From the first figure, it can be seen that the photoresist existed on the side wall before the photoresist removal agent was applied. It can be seen from the second figure that all of the photoresist have been removed with the photoresist remover composition of Example 丨. The second figure shows that after applying the conventional photoresist remover composition of Comparative Example 丨, the photoresist remained on the sidewall. 15 As mentioned above, the composition of the photoresist remover of the present invention can easily remove the photoresist film hardened during dry etching, polishing, or ion implantation, and the metal by-products etched away from the bottom metal film during edge processing. Photoresist film, and can minimize the corruption of the bottom metal wire during photoresist removal. In addition, the subsequent cleaning process can also be performed with water only. It does not require the use of organic solvents such as isopropyl alcohol or dimethylene. The above embodiments are only used to illustrate the present invention, and are not intended to limit the scope of the present invention. Various modifications or changes that do not violate the spirit of the present invention are within the scope of the patent application of the present invention. -21- 1228640 _ Description of invention $ Selling page [Simplified description of the drawing] The first picture is a scanning electron micrograph before the composition of the photoresist remover is applied. The second image is a scanning electron micrograph after applying the photoresist remover 5 of Example 1 at 65 ° C. The third image is a scanning electron micrograph after the composition of the photoresist remover of Comparative Example 1 was applied at a temperature of 65 ° C. -twenty two-

Claims (1)

1228640 拾、申請專利範圍 1· 一種光阻去除劑組成，其包括⑷20到60 wt% (重 量百分比）的一水溶性有機溶劑，（b) 1〇到45 wt%的水， (c) 5到15 wt%的一烷基胺或醇胺，〇」到10 wt%的 醋酸，（e) 0·01到5 wt%的一肟化合物，（f) 1到1〇 wt% 5 的一種含有二或三個羥基的有機酚化合物，和（g) 0.5到 5 wt%的一種三唑化合物。 2·如申請專利範圍第1項所述之光阻去除劑組成， 其中該烧基胺或醇胺係從下列構成之群組中所選用的一 種或以上之化合物：乙胺，二甲胺，二乙胺，三甲胺， 10 三乙胺，乙醇胺，二乙醇胺，和三乙醇胺。 3·如申請專利範圍第1項所述之光阻去除劑組成， 其中該肟化合物係從下列構成之群組中所選用的一種或 以上之化合物：乙酸聘，丙酮將，和丁_两。 4·如申請專利範圍第1項所述之光阻去除劑組成， 15 其中该含有二或三個經基的有機紛化合物是種以下列化 學結構式1所表示的紛化合物： 化學結構式11228640 Patent application scope 1. A photoresist remover composition comprising 20 to 60 wt% (weight percent) of a water-soluble organic solvent, (b) 10 to 45 wt% water, (c) 5 to 15 wt% monoalkylamine or alcohol amine, 0 "to 10 wt% acetic acid, (e) 0.01 to 5 wt% monooxime compound, (f) 1 to 10 wt% 5 Or three hydroxy organic phenol compounds, and (g) 0.5 to 5 wt% of a triazole compound. 2. The photoresist remover composition according to item 1 in the scope of the patent application, wherein the alkyl amine or alcohol amine is one or more compounds selected from the group consisting of ethylamine, dimethylamine, Diethylamine, trimethylamine, 10 triethylamine, ethanolamine, diethanolamine, and triethanolamine. 3. The photoresist remover composition as described in item 1 of the scope of the patent application, wherein the oxime compound is one or more compounds selected from the group consisting of: acetic acid, acetone, and dioxane. 4. The composition of the photoresist remover as described in item 1 of the scope of the patent application, 15 wherein the organic compound containing two or three radicals is a chemical compound represented by the following chemical structural formula 1: Chemical structural formula 1 (〇H)m 其中m是2或3。 ) 5·如申請專利範圍第1項所述之光阻去除劑組成， 其中该二唑化合物係從下列構成之群組中所選用的一種 或以上之化合物：苯並三唑（BT)，甲苯三唑（ττ)，羧基 □續次頁（申請專利範圍頁不敷使用時，請註記並使用續頁） -23- 1228640 利纏 苯並三唑（CBT)，和含有苯並三唑及甲苯三唑的一種二組 分三σ坐化合物。 6.如申請專利範圍第1項所述之光阻去除劑組成，其中該水 溶性有機溶劑係從下列構成之群組中所選用的一種或以上之化合 5 物：二曱基亞 （DMSO)，Ν-曱基砒咯烷酮(ΝΜΡ)，二甲基乙醯胺 (DMAc)，和二曱基曱酿胺(DMF) 〇(〇H) m wherein m is 2 or 3. ) 5. The photoresist remover composition as described in item 1 of the scope of patent application, wherein the diazole compound is one or more compounds selected from the group consisting of: benzotriazole (BT), toluene Triazole (ττ), carboxyl □ Continued page (Please note and use the continuation page when the patent application page is not enough, -23-1228640 Lizenetriazole (CBT), and contains benzotriazole and toluene Triazole is a two-component trisigma compound. 6. The photoresist remover composition according to item 1 of the scope of the patent application, wherein the water-soluble organic solvent is one or more compounds 5 selected from the group consisting of: dithionyl (DMSO) , N-fluorenylpyrrolidone (NMMP), dimethylacetamide (DMAc), and dimethylfluorenamine (DMF). -24--twenty four-
TW092127124A 2002-09-30 2003-09-30 Photoresist remover composition TWI228640B (en)

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CN1682155A (en) 2005-10-12
TW200424760A (en) 2004-11-16

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