[go: up one dir, main page]

TW200424760A - Photoresist remover composition - Google Patents

Photoresist remover composition Download PDF

Info

Publication number
TW200424760A
TW200424760A TW092127124A TW92127124A TW200424760A TW 200424760 A TW200424760 A TW 200424760A TW 092127124 A TW092127124 A TW 092127124A TW 92127124 A TW92127124 A TW 92127124A TW 200424760 A TW200424760 A TW 200424760A
Authority
TW
Taiwan
Prior art keywords
photoresist
photoresist remover
remover composition
compound
patent application
Prior art date
Application number
TW092127124A
Other languages
Chinese (zh)
Other versions
TWI228640B (en
Inventor
Wei-Yong Kim
Seok-Il Yoon
Sam-Young Cho
Soon-Hee Park
Woo-Shik Cheon
Original Assignee
Dongjin Semichem Co Ltd
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
Application filed by Dongjin Semichem Co Ltd filed Critical Dongjin Semichem Co Ltd
Publication of TW200424760A publication Critical patent/TW200424760A/en
Application granted granted Critical
Publication of TWI228640B publication Critical patent/TWI228640B/en

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only
    • G03F7/425Stripping 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
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/30Imagewise removal using liquid means
    • G03F7/32Liquid compositions therefor, e.g. developers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only
    • G03F7/423Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only
    • G03F7/426Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/3105After-treatment
    • H01L21/311Etching the insulating layers by chemical or physical means
    • H01L21/31127Etching organic layers
    • H01L21/31133Etching organic layers by chemical means

Landscapes

  • 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)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (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

200424760 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 導電層上形成一個光阻圖案,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 用一電漿離子餘刻氣體與一物質層(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) zuu4^4760 發明說明, 果。缺而,化光阻膜可發揮較佳的去除效 半導""種去除劑組成卻對量產丨·0^以上D㈣ 2^用以取代_的鋼線金屬膜造成相當程度的侵 伴㈣/由於經胺的毒性高’因而需開發-種符合環 保的新型光阻去除劑。200424760 发明 Description of the invention (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and the drawings) [Technical field to which the invention belongs] The present invention refers to a photoresist remover composition, especially 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 photoresist pattern is formed on the conductive layer of the semiconductor substrate, and the portion of the conductive layer that is not covered by this pattern is etched away to form a conductive 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 is performed by a gas-solid reaction generated by a plasma ion post-etch gas and a matter layer, such as a conductive layer. 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. Recently proposed photoresist removal with hydroxylamine and aminoethoxyethanol 0 Continued page (If the description page of the invention is insufficient, please note and use the continued page) zuu4 ^ 4760 Invention description, fruit. However, the photoresist film can play a better removal effect. Semi-conductive " " kinds of remover composition but mass production 丨 · 0 ^ above D㈣ 2 ^ steel wire metal film to replace _ to a considerable extent Accompanied by / Due to the high toxicity of amines, it is necessary to develop a new type of environmentally friendly photoresist remover.

近來提出的另—種含有㈣胺及二甘醇單烧基喊的 先阻去除·成’幾乎錢味及毒性,且對大部份硬化 =光阻職㈣良好时除效果H賴去除劑組 將乾㈣或離子移植期間接觸過電⑽刻氣體 〔離子束的光阻膜去除乾淨。因此,需開發—種能去除 乾蝕刻及離子移植製程轉化的光阻膜。Recently, another kind of pre-resistance removal that contains ammonium amine and diethylene glycol monoalcohol group has almost money taste and toxicity, and it is effective for most hardening = photoresistance. Remove the photoresist film that has been exposed to dry etching or ion implantation during the ion implantation [ion beam. Therefore, it is necessary to develop a photoresist film capable of removing dry etching and ion implantation process conversion.

如岫所述,使用光阻去除劑難以去除業已經過離子 ^植加工的光。尤其,對於在製造極大型積體電路 守已、、、工過阿劑夏離子移植製程而形成源極/汲極區的光 U阻膜來說’更難以去除。在離子移植製程巾,光阻膜表 面主要疋因冋劑量和鬲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, 致使光阻膜表面因為膜内留存溶劑,造成光阻劑殘留物 的產生,從而爆裂(pop)。習用拋光處理的半導體晶圓, 20是在200 °c以上的溫度進行。就這製程而言,留存在光 阻4彳中的溶劑應已被蒸發及排放到外面。然而,經過高 劑量離子移植的光阻表面,因為表面上存有一道硬化 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- 200424760 發明說明®胃 是被熱所形成,因此,屬於雜質離子的摻雜劑(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 二曱基乙醯胺(DMAc),N,N-二曱基曱醯胺(DMF),N-曱 基四氫砒咯(NMP),二曱基亞砜(DMS0),卡必醇(carbitol) 乙酸酯,與曱氧醋酸基丙烷(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ME A,一丙醇胺,與曱基戊基乙醇之類的 -9- 200424760 有機胺化合物,和b)諸如Ν·曱基乙醯胺(MAC),Ν,Ν_ 一曱基乙醯fec(DMAc),二曱基甲酿胺(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,與队甲基_Ν-乙基丙醯胺 5 (美國第4,770,713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ι,3-二甲基_2-味峻炫 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(ΜΕΑ), 一乙醇胺(DEA),與三乙醇胺(TEA)以及乙二胺之類的 烷醇胺的乙烯氧化物,和b)諸如磺烷(sulf〇rane)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 丁基鍵(曰本第昭和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)丨,弘二甲基_2咪 唑烷基酮(日本第昭和63_2〇8〇43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 一胺,,、氫σ比唆,與苄胺之類的胺,b)諸如DMAc,, 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_,二甘醇二烧基 ^ 丫 丁内酉曰,與1二甲基-2-味峻烧基酮所構成之群 -10- 200424760 發明說明@胃 組中選用的溶劑,和C) DMSO (日本第昭和6心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)諸如二甘醇單烷 基醚,DMAc,NMP,與DMSO之類的無質子極性溶劑, 5和〇磷酸酯界面活性劑(日本第平成4-124668號專利 申請公報);一種含有下列的光阻去除劑組成:a)丨,弘二 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號專利申請公報);以及一種含有下列的光阻去 10除劑組成· a) MEA,b) DMSO ,和c)鄰一苯二酚(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11〇到140〇c的高溫下處理,所以光阻 15劑易被烘培。但是,前述的光阻去除劑卻無法將供培的 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d)抗腐蝕劑(日本第平成6-266119 號專利申凊公報);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) 諸如2-曱胺基乙醇之類的氨基醇,和匀水(日本第平成 200424760 發明說明,續頁 7-6961 8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(曰本第平成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)乙二醇單烷基醚,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, W水,c)酸離解常數(pKa)為7β5到13的胺,句水溶 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)。 然而,這些光阻去除劑組成也無法完全去除在乾蝕 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 姓0 20 【發明内容】 本發明之目的在於提供一種光阻去除劑組成,盆可 輕易及迅速去除在乾_、拋光、或離子移植加工期間 轉化和硬化的綠膜,以及進行該加卫期間從底部金屬 -12- 200424760 膜蝕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:(a) 20到60 wt% (重量百分比)的一種 水溶性有機溶劑,⑻10到45 wt%的水,(c) 5到15 wt% 的一種烷基胺或醇胺,(d) 0.1到1〇 wt%的醋酸,(e) 〇 〇1 到5 wt%的一種將化合物(oxime),⑴1到1 〇 wt%的一種 含有二或三個經基的有機酚化合物,和(g) 〇·5到5 wt〇/〇 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1的光阻去 除劑組成之後的掃瞄電子顯微相片。 20【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 口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、乾蝕刻、拋光(ashing)、或離子 -13- 200424760 發明說明 移植加工期間硬化的光阻膜,以及進行該加工期間從底 部金屬膜蝕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 烷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,烷基胺或 醇胺的含量宜為5到15 wt% (重量百分比)。如果烷基胺 或醇胺的含量低於5 wt%,便難以完全去除在乾蝕刻或 10拋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 會遭受過度腐餘。 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10 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- 200424760 劑即會受到乾蝕刻及拋光加工期間所產生之金屬副產品 的嚴重變性,以致去除效果不佳。另外,如果含水量超 過45 wt%,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, 5 大部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: 化學結構式1 (OH)m 10 其中m是2或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。 羥基胺與水的氫離子起反應而導致的羥基離子會在光阻 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酚化合物的含量宜為1到 10 wt/〇。如果這有機酚化合物的含量低於^ ,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k性的光阻劑便無法去除乾淨,致使底部金屬薄膜遭 到嚴重4又姓。反之,如果含量超過wt%,這組成的製 -15- 200424760 發明說明,1 賣Μ 造價格即高昂。As described in 岫, it is difficult to remove light that has been ion-implanted using photoresist removers. In particular, it is even more difficult to remove a photo-resistance film for the source / drain region that has been formed during the fabrication of very large-scale integrated circuits. In the ion implantation process, the surface of the photoresist film is mainly hardened by the dose of radon and the reaction heat of the 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 to pop on the surface of the photoresist film because of the solvent remaining in the film. For conventional polishing semiconductor wafers, 20 is performed at a temperature above 200 ° C. For this process, the solvent remaining in the photoresist should be evaporated and discharged to the outside. However, photoresist surfaces that have undergone high-dose ion implantation cannot do so because of a hardened layer on the surface. Hardened layers due to bursting are difficult to remove. In addition, since the hardened layer -8- 200424760 Invention Note® The stomach is formed by heat, so dopants, which are impurity ions, may be replaced and enter the molecular structure of the photoresist, causing a crosslinking reaction. 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 difluorenylacetamide (DMAc), N, N-difluorenylfluorenamine (DMF), N-fluorenyltetrahydrofluorene (NMP), difluorenyl A polar solvent such as sulfoxide (DMS0), carbitol acetate, and trioxoacetate (U.S. Patent No. 4,617,251); a photoresist remover consisting of the following two components: a ) Organic compounds such as ME A, monopropanolamine, -9-200424760, and fluorenylpentylethanol, and b) such as N. fluorenylacetamide (MAC), Ν, Ν_ monomethylacetamidine fec (DMAc), dimethyl methylamine (dmf), N, N-diethylacetamide (DEAc), N, N-dipropylacetamide (DpAc), N, N_dimethyl Protonamide, Ν, Ν-diethylbutyramine, and methylamine N-ethylpropylamine 5 (U.S. Patent No. 4,770,713); a solvent containing one of the following two components Photoresist remover composition: a) such as monoethanolamine MEA) and other organic amine compounds, and b) such as ι, 3-dimethyl_2-weijunxionone (DMI), and 1,3-dimethyl · tetrahydroxypyrimidone (Germany No. 3,828,513 Aprotic polar solvents such as Patent Application Bulletin); a 10 containing the following photoresist remover composition: a) such as monoethanolamine (MEA), monoethanolamine (DEA), and triethanolamine (TEA) and ethylenediamine Ethylene oxide of alkanolamine, and b) stone wind compounds such as sulforane, and c) such as diethylene glycol monoethyl ether and diethylene glycol monobutyl bond Patent Application Publication No. 62-49355) such as ethylene 15 glycol monoalkyl ether; a composition containing the following photoresist remover; a) water-soluble amines such as MEA and DEA, and b) 丨, Hongji Methyl_2imidazolidinone (Japanese Patent Application Publication No. 63_20088); a positive photoresist remover composition containing: a) such as MEA, ethylene monoamine, and hydrogen σ ratio 唆, With amines such as benzylamine, b) polar solvents such as DMAc, 20 and DMSO, and c) surfactants (Japan's No. And Patent Application Publication No. 63-21343); a positive photoresist remover composition comprising: a) a nitrogen-containing organic hydroxyl compound such as MEA b) more than two kinds of diethylene glycol monoethyl ether, diethylene glycol Diolyl alcohol ^ butyl butadiene, said a group consisting of 1 dimethyl-2-weishenyl ketone -10- 200424760 Description of the invention @solvent selected in the solvent, and C) DMSO (Japan Showa 6 Heart 42653 Patent Application Gazette) 'A composition containing the following positive photoresist remover a) Organic amine compounds such as MEA, b) Diethylene glycol monoalkyl ethers, DMAc, NMP, and Aprotic polar solvents such as DMSO, 5 and 0 phosphate ester surfactants (Japanese Patent Application Publication No. Hei 4-124668); a photoresist remover composition comprising: a) 丨, dimethyl-2- Imidazolidinone (DMI), b) dimethylsulfinium (DMs0) ', and c) a water-soluble organic amine compound such as MEA (Japanese Patent Application Publication No. 4-350660); and The composition of the following photoresist remover 10 a) MEA, b) DMSO, and c) catechol (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 the recent semiconductor device manufacturing process, since the substrate including the 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 photoresist supplied for cultivation. 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, and d) anticorrosive (Japanese Patent Application Publication No. 6-266119); a composition containing the following photoresist remover ... Polar solvents such as GBL 'DMF, DMAc, and NMP, b) Amino alcohols such as 2-amidoethanol, and homogenized water (Japanese Patent No. Heisei 200424760 Description of Invention, Continued 7-6961 Patent No. 8 Application Bulletin); a composition containing the following remover: a) an amino alcohol such as MEA, b) water, and c) butyl diethylene glycol (Japanese Patent Application Publication No. 8-123043); Contains the following photoresist remover composition: a) alkanolamine and alkoxyalkyl 5 amine 'b) ethylene glycol monoalkyl ether, c) sugar alcohol, d) quaternary ammonium hydroxide, and e) water (Japanese Patent Application Publication No. Hei 8-262746); a composition containing the following remover: a)-more than one such as MEA and AE Alkanolamines such as E, b) hydroxylamine, c) diethylene glycol monoalkyl ether, d) sugar (sorbitol), and e) water (Japanese Patent Application Publication No. 9-152721) ); And a photoresist remover composition comprising: a) hydroxylamine, W water, c) amines having an acid dissociation constant (pKa) of 7β5 to 13, water-soluble organic solvents, and e) an anticorrosive (Japan Heisei 9_96911 Patent Application Gazette). However, these photoresist remover compositions cannot completely remove the photoresist film converted and hardened during the 15-etching, polishing, and ion implantation processes, or light converted from metal by-products etched from the bottom metal film during the process. Resistive film. In addition, they are not environmentally friendly, and they cannot completely prevent the intrusion of the bottom metal wire during the photoresist removal process. [Summary of the Invention] The object of the present invention is to provide a photoresist removal composition, which can easily and easily Quickly remove the green film converted and hardened during the dry, polishing, or ion implantation process, and the photoresist film converted from the metal by-products etched away from the bottom metal-12-200424760 film during this guarding. 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: (a) 20 to 60 wt% (weight percent) of a water-soluble organic solvent, 10 to 45 wt% water, ( c) 5 to 15 wt% of an alkylamine or alcohol amine, (d) 0.1 to 10 wt% of acetic acid, and (e) 0.001 to 5 wt% of an oxime, 1 to 10%. wt% of an organic phenol compound containing two or three radicals, and (g) a triazole compound of 0.5 to 5 wt% / 〇10. [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 1 at a temperature of 65 ° C. [Embodiment] The present invention will be described in detail below. The present invention refers to a photoresist remover composition comprising an alkylamine or an alcoholamine, acetic acid, and an oximized substance. The photoresist remover composition of the present invention can easily and quickly remove photoresist films hardened during hard-baking, dry etching, ashes, or ions. Photoresist film converted from metal by-products etched away from the film. In addition, the photoresist remover can also minimize the corrosion of the bottom metal wires during photoresist removal. 5 The alkylamine or 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 alkylamine or alcoholamine is preferably 5 to 15% by weight (% by weight). 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 from 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 -14-200424760 will be severely denatured by metal by-products generated during the dry etching and polishing process, resulting in poor removal effect. In addition, if the water content exceeds 45 wt%, the relative content of the alkylamine and the water-soluble organic solvent is reduced, so that the bottom metal wire may be eroded. In addition to the denatured photoresist, most of the normal photoresist The removal effect is also not good. The organic phenol compound containing two or three hydroxyl groups is preferably a compound represented by the following chemical structural formula 1: Chemical structural formula 1 (OH) m 10 wherein m is 2 or 3. 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 are denatured by metal by-products etched from the bottom metal film. The hydroxyl ions caused by the reaction of hydroxyl amines with the hydrogen ions of water will provide a permeable space between the photoresist 15 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 phenol compound containing two or three hydroxyl groups is preferably 1 to 10 wt / 0. If the content of the organic phenol compound is less than ^, the k-type photoresist, which is severely affected by metal by-products generated during dry etching and ion implantation processing, cannot be removed cleanly, resulting in severe damage to the bottom metal film. Conversely, if the content exceeds wt%, the composition of this composition is described in the invention.

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),Ν-甲基砒咯 烷酮(ΝΜΡ),二甲基乙醯胺(DMAc),和二甲基曱醯胺 5 (DMF)。考慮到對光阻劑的溶解性,防止光阻劑的重澱 積,以及廢溶劑因快速生物降解而易於處理等因素,較 宜採用二甲基亞颯(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。The water-soluble organic solvent is preferably one or more organic solvents selected from the group consisting of: dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), dimethylacetamide ( DMAc), and dimethylamidamine 5 (DMF). Considering the solubility of the photoresist, the prevention of re-deposition of the photoresist, and the ease of disposal of the waste solvent due to rapid biodegradation, it is more appropriate to use dimethylsulfinium (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.

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),甲苯三唑(TT),羧基苯 並三唑(CBT),和含有苯並三唑(BT)及甲苯三唑(TT)的二 組分(two-component)三嗤化合物。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)及曱苯三唑(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- 200424760 發明說明 使用時變得不方便。 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NGiga DRAM (動The triazole compound is preferably one or more compounds selected from the group consisting of: benzotriazole (BT), toltriazole (TT), carboxybenzotriazole (CBT), and benzotriazole Two-component trifluorene compounds of azole (BT) and toltriazole (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 with a two-component triazole compound containing 20 benzotriazole (BT) and benzotriazole (TT), the mixing ratio should be 1: 1, so Can effectively prevent the side pitting of the side wall of the photoresist film. 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 -16-200424760 Invention Description It becomes inconvenient to use. 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 produce NGiga DRAM (active

態隨機存取記憶體)以上極大型積體電路半導體時,把所 用銅線的腐餘減至最低程度。 效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及比鮫範例1到2 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。State random access memory) to minimize the corrosion of the copper wire used in semiconductors with very large integrated circuit semiconductors. The present invention will be described in detail with reference to the following examples. 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 and comparative examples are based on weight. Examples Examples 1 to 5 and 鲛 Examples 1 to 2 Examples 1 to 5 and Comparative Examples 1 to 2 consist of the photoresist and resist remover compositions shown 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 三曱胺 10 - 12 15 - 30 35 乙醇胺 - 15 - 5 - • 化合物 乙醛 0.5 - - 3.5 - - - 丙酮 - 3 - - 0.5 - • 丁酮 - - 1 - - - • 水 31 28 45 33 30 20 醋酸 2 5 7 1 10 - 一 有機酚化 鄰笨二酚 8 - 10 - 5 - - -17- 200424760 合物 間苯二紛 - 5 - 10 - - - 甲酚 - 備 - - - 9 25 水溶性有 機溶劑 DMSO 1} 48 41 - - - - - DMAc 2) - - 20 35 - - - NMP 3) - - - - 45 - 20 DMF 4) - - - - - 31 - 三唑化合 物 BT 5) 0.5 3.0 5.0 - - - - Cobratec928 6) - - -2.5 - - - - CBT 7) - - - - 2.5 - 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。Table 1 Contents (wt%) Examples Comparative Examples 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--- Acetone-3--0.5-• Methyl ketone--1---• Water 31 28 45 33 30 20 Acetic acid 2 5 7 1 10-Monoorganophenolated o-diphenol 8-10-5---17- 200424760 Benzodibenzoate-5-10---Cresol-Preparation---9 25 Water-soluble organic solvent DMSO 1} 48 41-----DMAc 2)--20 35---NMP 3)- ---45-20 DMF 4)-----31-Triazole compound BT 5) 0.5 3.0 5.0----Cobratec928 6)---2.5----CBT 7)----2.5-Test Examples For each of the photoresist remover compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 2, (1) a photoresist removal test and (2) a copper corrosion 5 test were performed, respectively. The results shown in Tables 2 and 3 below are the results.

(1)光阻劑去除試驗 樣本A的ϋ備 在一由下往上澱積一道1000 Α厚之鎢膜和一道700 A厚之一氮化鈦膜的8吋矽晶圓的表面上,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 註) 0 DMSO:二甲基亞 2) DMAc :二曱基乙醯 3) NMP ·· N-甲基砒咯烷酮 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)(1) The photoresist removal test sample A was prepared on the surface of an 8-inch silicon wafer with a 1000 A thick tungsten film and a 700 A thick titanium nitride film deposited from the bottom up. 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. Place a patterned mask on top of the photoresist film to note) 0 DMSO: dimethylmethylene 2) DMAc: dimethylacetin 3) NMP ·· N-methylpyrrolidone 4) DMF: dimethylformamide 5) BT .. Benzotriazole (Cobratec 99, PMC) 6) CBT: Carboxybenzotriazole (Cobratec CBT, PMC) 7) Cobratec 928: Contains benzotriazole and toluene Triazole triazole compound (PMC)

-18 - 發明說明 後即施用紫外線。以一種2.38%的氫氧化四曱銨(TMAH) 顯心/容液在21 QC的溫度上顯影6〇秒鐘後,再在120 的加熱板上將光阻圖案樣本硬烘焙1〇〇秒鐘。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 供售的M318)而以SF0/C12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。 it阻劑去险謎.給 在65。(:的溫度下把樣本A浸入各光阻去除劑組成 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 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。 (2)銅腐#試驗 樣本B的·借^ 製備在半導體封裝製程中所用的鋼導線架。 銅腐蝕試驗 在65 °C的溫度下把樣本B浸入各光阻去除劑組成 ZUU4Z4/60-18-Description of the invention UV is applied immediately. After developing with a 2.38% tetramethylammonium hydroxide (TMAH) cardio / capacitor solution at 21 QC for 60 seconds, the photoresist pattern samples were hard-baked for 100 seconds on a 120 hot plate. . Using the photoresist pattern formed on the sample as a photomask, dry etching equipment (M318 supplied by Hitachi) was used to etch the tungsten and titanium nitride films not masked by the SF0 / C12 mixed gas. In a second, a metal line pattern is formed. It resists the mystery. Give at 65. The sample A was immersed in the composition of each photoresist remover at the temperature of (.). Then the sample was taken out, rinsed with ultrapure water, and then dried with nitrogen. Observe the pattern sidewall and line pattern surface with a scanning electron microscope (SEM). The photoresist residue was evaluated based on the following criteria. The results are shown in Table 2. The photoresist residue on the pattern sidewall and line pattern surface was completely removed. △ • The photoresist residue on the pattern sidewall and the line pattern surface was removed more than 8000 / 〇, but a small amount remained. X: The photoresist residue on the pattern sidewall and the line pattern surface was not mostly (2) 铜 腐 # Test sample B · Borrow ^ Prepare the steel lead frame used in the semiconductor packaging process. Copper corrosion test Dipping sample B into each photoresist remover at 65 ° C to make up ZUU4Z4 / 60

中。接著取出樣太,田 ..m α 用超純水沖洗,再以氮氣使其乾燥。 ^掃猫電子顯微鏡樣本表面,並以下列標準來評估腐 餘度。表3所_者即為其結果。 〇:鋼表面上無腐蝕。 5 △:銅表面上有部份腐蝕。 Χ:整個鋼表面上受到嚴重腐蝕。 10 表2 :光阻去除劑組成的光阻去除效率in. Then take out the sample, rinse ..m α with ultrapure water, and then dry it with nitrogen. ^ Scan the surface of a cat's electron microscope sample and use the following criteria to evaluate the degree of decay. Those in Table 3 are the results. 〇: No corrosion on the steel surface. 5 △: There is some corrosion on the copper surface. X: Severe corrosion on the entire steel surface. 10 Table 2: Photoresist removal efficiency consisting of photoresist removal agent

如表2所示,範例1到5的組成展現出優良的光阻 去除效率,而比較範例1到2的習用組成則展現出不佳 的光阻去除效率。 表 金屬線腐蝕試驗 〜---^ 類別 範例As shown in Table 2, the compositions of Examples 1 to 5 exhibited excellent photoresist removal efficiency, while the conventional compositions of Comparative Examples 1 to 2 exhibited poor photoresist removal efficiency. Table Metal Wire Corrosion Test ~ --- ^ Category Example

___^浸潰時間(分鐘) 5 --—- — 10 20 1 U 〇 〇 2 '^δ δ ~~ 〇 3 〇 〇 Δ 4 〇 〇 △ δ 〇~ 〇 〇 Δ X 2 〇 — _ X -20- 發明說明®頁 如表3所示,範例丨到5的組成在金屬線腐蝕試驗 中展現出良好的結果,而比較範例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丨的光阻去除劑組成之 岫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-41〇〇)之後 的掃瞄電子顯微相片。這試驗係在樣本A所用的65 cc 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 有的光阻劑。 從第一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。 從第三圖可看出在施用比較範例1的習用光阻去除 劑組成之後,側壁上仍留有光阻劑。 如前所述,本發明的光阻去除劑組成可輕易去除在 乾#刻、拋光、或離子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 餘減至最低程度。另外,後續的清洗製程亦可只用水處 理,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,倶屬本發明申請專利範圍。 -21- 200424760 發明說明續頁 【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瞒電子 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。___ ^ Dip time (minutes) 5 ------10 20 1 U 〇〇2 '^ δ δ ~~ 〇3 〇〇Δ 4 〇〇 △ δ 〇 ~ 〇〇Δ X 2 〇 — _ X -20 -Description of the invention® page is shown in Table 3. The compositions of Examples 丨 to 5 show good results in the wire corrosion test, while the conventional compositions of Comparative Examples 1 to 2 show poor corrosion resistance over time. . The first and second pictures are the application examples of the photoresist remover composition and subsequent scanning electron micrographs, while the third picture is the application of the comparative example 1 photoresist remover composition (available from Hitachi) s-41〇) after scanning electron micrographs. This test was carried out at a temperature of 65 cc used in Sample A. From the first figure, the photoresist existing on the side wall before applying the photoresist remover can be seen. It can be seen from the first figure that all the photoresist agents have been removed with the photoresist remover composition of Example 丨. It can be seen from the third figure that after the composition of the conventional photoresist remover of Comparative Example 1 was applied, the photoresist remained on the sidewall. As mentioned above, the composition of the photoresist remover of the present invention can easily remove the photoresist film hardened during the dry-etching, polishing, or ion implantation process, and the metal by-products etched from the bottom metal film during the process can be changed. Photoresist film, and can minimize the corrosion of the bottom metal line during photoresist removal. In addition, subsequent cleaning processes can also be treated with water only, without using 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 are not in violation of the spirit of the present invention fall into the scope of patent application of the present invention. -21- 200424760 Description of the invention continued [Simplified description of the figure] The first figure is a photomicrograph of a concealed electron before the application of a photoresist remover composition. 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.

-22--twenty two-

Claims (1)

200424760 拾、申請專利範圍 1 · 一種光阻去除劑組成,其包括(a) 20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,0·ι到1〇 wt%的 醋酸,(e) 〇·〇1到5 wt%的一肟化合物,(f) 1到10 wt0/〇 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·乙酸肪,丙嗣將,和丁調肪。 4·如申請專利範圍第1項所述之光阻去除劑組成, 15 其中該含有二或三個羥基的有機酚化合物是種以下列化 學結構式1所表示的酚化合物: 化學結構式1 (〇H)m 其中m是2或3。 20 5·如申請專利範圍第1項所述之光阻去除劑組成, 其中該三唾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 1—1續次頁(申纟R專利轮圍頁不敷使用時’請註記並使用續頁) -23- 200424760 苯並三唑(CBT),和含有苯並三唑及甲苯三唑的一種二組 分三嗤化合物。 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:二甲基亞 (DMSO),N-甲基砒咯烷酮(NMP),二甲基乙醯胺 (DMAc),和二甲基曱醯胺(DMF)。200424760 Patent application scope 1 · A photoresist remover composition comprising (a) 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) 0.001 to 5 wt% monooxime compound, (f) 1 to 10 wt0 / An organic phenol compound containing two or three hydroxyl groups, and (g) a triazole compound of 0.5 to 5 wt%. 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: . 4. The composition of the photoresist remover as described in item 1 of the scope of the patent application, 15 wherein the organic phenol compound containing two or three hydroxyl groups is a phenol compound represented by the following chemical structural formula 1: Chemical structural formula 1 ( OH) m where m is 2 or 3. 20 5. The photoresist remover composition as described in item 1 of the scope of patent application, wherein the trisial compound is one or more compounds selected from the group consisting of: benzotriazole (BT), toluene Triazole (ττ), carboxyl 1-1 continuation sheet (when the application of the R patent is insufficient, please note and use the continuation sheet) -23- 200424760 benzotriazole (CBT), and benzotriazole containing A two-component trifluorene compound of azole and toltriazole. 6. The photoresist remover composition as described in 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: dimethylsulfite (DMSO) , N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), and dimethylacetamide (DMF). -24--twenty four-
TW092127124A 2002-09-30 2003-09-30 Photoresist remover composition TWI228640B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020020059552A KR100862988B1 (en) 2002-09-30 2002-09-30 Photoresist Remover Composition

Publications (2)

Publication Number Publication Date
TW200424760A true TW200424760A (en) 2004-11-16
TWI228640B TWI228640B (en) 2005-03-01

Family

ID=32040946

Family Applications (1)

Application Number Title Priority Date Filing Date
TW092127124A TWI228640B (en) 2002-09-30 2003-09-30 Photoresist remover composition

Country Status (5)

Country Link
KR (1) KR100862988B1 (en)
CN (1) CN1682155B (en)
AU (1) AU2003265098A1 (en)
TW (1) TWI228640B (en)
WO (1) WO2004029723A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI851333B (en) * 2023-07-10 2024-08-01 關東鑫林科技股份有限公司 Resist layer removing composition and method for removing resist layer using the same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050032657A1 (en) * 2003-08-06 2005-02-10 Kane Sean Michael Stripping and cleaning compositions for microelectronics
TWI300580B (en) * 2004-11-04 2008-09-01 Nec Lcd Technologies Ltd Method of processing substrate and chemical used in the same (1)
ATE484774T1 (en) * 2005-08-13 2010-10-15 Techno Semichem Co Ltd PHOTORESIST REMOVAL COMPOSITION FOR SEMICONDUCTOR MANUFACTURING
WO2010118916A1 (en) * 2009-04-16 2010-10-21 Basf Se Organic photoresist stripper composition
KR102012464B1 (en) * 2013-09-06 2019-08-20 동우 화인켐 주식회사 Resist stripper composition and method of manufacturing flat panel display devices using the same

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05259066A (en) * 1992-03-13 1993-10-08 Texas Instr Japan Ltd Positive photoresist removing liquid and manufacture of semiconductor device
JPH07130700A (en) * 1993-10-29 1995-05-19 Sanyo Electric Co Ltd Manufacture of semiconductor device
US6500605B1 (en) * 1997-05-27 2002-12-31 Tokyo Electron Limited Removal of photoresist and residue from substrate using supercritical carbon dioxide process
JP4308959B2 (en) * 1998-02-27 2009-08-05 関東化学株式会社 Photoresist stripping composition
US6432209B2 (en) * 1998-03-03 2002-08-13 Silicon Valley Chemlabs Composition and method for removing resist and etching residues using hydroxylazmmonium carboxylates
JP3477390B2 (en) * 1999-01-22 2003-12-10 花王株式会社 Release agent composition
KR100286860B1 (en) * 1998-12-31 2001-07-12 주식회사 동진쎄미켐 Photoresist Remover Composition
US6562726B1 (en) * 1999-06-29 2003-05-13 Micron Technology, Inc. Acid blend for removing etch residue
KR100363271B1 (en) * 2000-06-12 2002-12-05 주식회사 동진쎄미켐 Photoresist remover composition
US6777380B2 (en) * 2000-07-10 2004-08-17 Ekc Technology, Inc. Compositions for cleaning organic and plasma etched residues for semiconductor devices
KR100742119B1 (en) * 2001-02-16 2007-07-24 주식회사 동진쎄미켐 Photoresist Remover Composition
KR100416657B1 (en) * 2001-06-26 2004-01-31 동부전자 주식회사 Method for manufacturing a contact hole of semiconductor device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI851333B (en) * 2023-07-10 2024-08-01 關東鑫林科技股份有限公司 Resist layer removing composition and method for removing resist layer using the same

Also Published As

Publication number Publication date
TWI228640B (en) 2005-03-01
KR20040028382A (en) 2004-04-03
KR100862988B1 (en) 2008-10-13
CN1682155A (en) 2005-10-12
AU2003265098A1 (en) 2004-04-19
CN1682155B (en) 2010-05-26
WO2004029723A1 (en) 2004-04-08

Similar Documents

Publication Publication Date Title
JP4819429B2 (en) Compositions and methods for removing residues
KR100700998B1 (en) Composition for removing residue from substrate and method of use thereof
US6103680A (en) Non-corrosive cleaning composition and method for removing photoresist and/or plasma etching residues
JP2001523356A (en) Non-corrosive compositions for resist stripping and cleaning
TWI752528B (en) Cleaning composition for semiconductor substrates
JP2002523546A (en) Non-corrosive stripping and cleaning compositions
JP3514435B2 (en) Photoresist stripping solution and photoresist stripping method using the same
TWI247976B (en) Resist and etching by-product removing composition and resist removing method using the same
JP3255623B2 (en) Stripper composition for resist
TWI228640B (en) Photoresist remover composition
JP2004526981A (en) Photoresist remover composition
JP4229552B2 (en) Photoresist stripping composition and photoresist stripping method using the same
JP2004533010A (en) Resist remover composition
JP2001222118A (en) Rinsing solution for photolithography and method for treating substrate with same
JP3976160B2 (en) Treatment liquid after ashing and treatment method using the same
JP2005535784A (en) Cleaning liquid
JP3476367B2 (en) Resist stripping composition and resist stripping method using the same
KR100742119B1 (en) Photoresist Remover Composition
US8399391B2 (en) Photoresist residue removal composition
KR100378551B1 (en) Resist remover composition
JP2005070230A (en) Resist stripping composition and resist stripping method
KR20020019813A (en) Photoresist remover composition comprising ammonium fluoride

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees