TW593224B - Liquid composition for removing a photoresist and process for producing a semiconductor device - Google Patents
Liquid composition for removing a photoresist and process for producing a semiconductor device Download PDFInfo
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- TW593224B TW593224B TW091121292A TW91121292A TW593224B TW 593224 B TW593224 B TW 593224B TW 091121292 A TW091121292 A TW 091121292A TW 91121292 A TW91121292 A TW 91121292A TW 593224 B TW593224 B TW 593224B
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- photoresist
- liquid composition
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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
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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
- G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
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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
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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
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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
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Weting (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
593224 五、發明說明（1) 發明 背景 1 ·發 明領域 用 於微影術應用之光阻已用於 廣 泛 範 圍 之領域， 例如 1 如1C與LSI之積體電路、如LCD與] EL 裝 置之顯示 裝 置 印刷 電路板基質、微機械及DNA 晶 片 0 本 發明係關 於 一 種 光阻 移除用液體組成物，其用於 白 各 種 型 式之基質 移 除 光 阻。 2·相 關技藝說明 近 來使用許多型式之方法製造 含 矽 ( 如 多矽）之 半 導 體 裝置 及液晶顯示裝置。因此，對 此 方 法 需 要不腐蝕 矽 之 光 阻移 除用液體組成物。施加光阻 之 基 質 大 多包括石夕 ， 而 且 通常 因爲存在一層氧化砂而不易 腐 蝕 0 然 而，在多 數 情 形· 存在在基質接受長期處理後或在 減 少 氧 化物層厚度 之 處 理 後移 除光阻，因而在這些區域更 易 腐 蝕 矽 。爲了移 除 光 阻 ，迄 今已使用光阻移除用鹼性 液 體 組 成 物。例如， T0K 106 [商標名；TOKYO OHKA K0GY0有限公司製造]爲 含 院 醇 胺與 •二甲基亞®之溶液，及 EKC 265 [商標名 > EKC TECHNOLOGY有限公司製造]爲含 院 醇 胺 羥基胺、 兒 茶 酚 與水 之溶液。以上之含鹼化合物光 阻 移 除 用組成物 通 常 用 於移 除光阻之步驟。不含水之光 阻 移 除 用 液體組成 物 具 有 乾燥 蝕刻後殘留之含金屬成分無 法完 全 移 除之缺點 〇 提 議 以改 良以上缺點之含水之胺溶液 具 有 腐 蝕 矽、鋁與 鋁 合金 之缺 點。在使用含羥基胺之液體 -3- 組 成 物 時 ，在含水時 抑 制 593224 五、發明說明（2) 矽等之腐鈾。然而，含羥基胺之液體組成物具有羥基胺昂 貴、易於分解之趨勢、及無法有效防止腐蝕之缺點，除非 大量使用羥基胺。 發明槪要 本發明之目的爲克服以上光阻移除用液體組成物之缺點 ，及提供可易於在短時間內移除基質上之光阻層、蝕刻後 殘留在基質上之部份光阻層、及蝕刻與去灰後殘留在基質 上之光阻殘渣，而不腐蝕各種型式之材料，特別是矽之光 阻移除用液體組成物，使得可製造高精確電路配線。 本發明人廣泛硏究以完成此目的之結果發現，包括胺化 合物與胺聚合物之光阻移除用液體組成物可自光阻移除殘 渣，不腐鈾各種型式之材料，而卫呈現優良之性質。本發 明已基於這些知識而完成。 本發明提供一種包括胺化合物與胺聚合物之光阻移除用 液體組成物；一種包括胺化合物、胺聚合物與水之光阻移 除用液體組成物。同時，本發明提供一種製造半導體裝置 之方法，其包括以上述液體組成物自具有矽之基質移除光 阻。 圖式之簡要說明 第1圖顯示半導體裝置之一部份在以氧電漿去灰處理後 之正切面圖。 第2圖顯示一部份之橫切面圖，其中多矽暴露於測試基 質上。 593224 五、發明說明（3) ! 較佳具體實施例之說明593224 V. Description of the invention (1) Background of the invention 1 · Field of invention Photoresist for lithography applications has been used in a wide range of fields, such as 1 integrated circuits such as 1C and LSI, such as LCD and] EL device display The present invention relates to a liquid composition for removing photoresist, which is used for removing photoresist of various types of substrates. 2. Description of related technologies Recently, many types of methods have been used to manufacture semiconductor devices and liquid crystal display devices containing silicon (such as polysilicon). Therefore, a liquid composition for photoresistance removal which does not corrode silicon is required for this method. Most of the photoresist-applied substrates include stone, and it is usually not easy to corrode because of the presence of a layer of oxidized sand. However, in most cases, the photoresist is removed after the substrate is subjected to a long-term treatment or after the oxide layer thickness is reduced. Silicon is more susceptible to corrosion in these areas. In order to remove the photoresist, a basic liquid composition for photoresist removal has been used so far. For example, T0K 106 [Trade name; manufactured by TOKYO OHKA K0GY0 Co., Ltd.] is a solution containing melamine and dimethylimide®, and EKC 265 [brand name> EKC TECHNOLOGY Co., Ltd.] is melamine containing hydroxyl A solution of amine, catechol and water. The above-mentioned alkali-containing compound photoresist removing composition is generally used in the step of removing photoresist. The liquid composition for non-aqueous photoresist removal has the disadvantages that the metal-containing components remaining after the etching cannot be completely removed. 〇 The proposed aqueous amine solution to improve the above disadvantages has the disadvantage of corroding silicon, aluminum, and aluminum alloys. When using liquid hydroxyl-3-containing composition containing hydroxylamine, it inhibits 593224 when it contains water. 5. Description of the invention (2) Corrosive uranium such as silicon. However, the hydroxylamine-containing liquid composition has disadvantages that the hydroxylamine is expensive, tends to be easily decomposed, and cannot prevent corrosion effectively unless the hydroxylamine is used in a large amount. It is an object of the present invention to overcome the disadvantages of the above liquid composition for photoresist removal, and to provide a photoresist layer on a substrate that can be easily removed in a short time, and a portion of the photoresist layer remaining on the substrate after etching. And photoresist residues left on the substrate after etching and ash removal without corrosive to various types of materials, especially the liquid composition for photoresist removal of silicon, making it possible to manufacture highly accurate circuit wiring. As a result of extensive research by the inventors to accomplish this purpose, it was found that the liquid composition for photoresist removal including amine compounds and amine polymers can remove residues from the photoresist, does not corrode various types of uranium materials, and Wei appears excellent The nature. The present invention has been completed based on this knowledge. The present invention provides a liquid composition for removing photoresist comprising an amine compound and an amine polymer; and a liquid composition for removing photoresist comprising an amine compound, an amine polymer and water. Meanwhile, the present invention provides a method for manufacturing a semiconductor device, which includes removing the photoresist from a substrate having silicon with the liquid composition. Brief Description of the Drawings Fig. 1 shows a tangential view of a part of a semiconductor device after being ash-treated with an oxygen plasma. Figure 2 shows a cross-sectional view of a portion with polysilicon exposed on the test substrate. 593224 V. Description of the invention (3)! Description of the preferred embodiment
本發明係關於一種用於自基質移除光阻之組成物，其爲 IThe present invention relates to a composition for removing photoresist from a substrate, which is I
包括胺化合物及胺聚合物之液體組成物。以包括胺化合物 · I 、胺聚合物與水之液體組成物可更有效地完成光阻移除。 用於本發明之胺聚合物具有250或更大之重量平均分子 量。氮原子可存在於任何側鏈及主鏈。雖然對分子量並無 指定上限，具有過大分子量之胺聚合物趨於具有混合胺化 合物之困難。胺聚合物可爲任何自由胺型式及鹽型式，而 春 且可依照目的而選擇。自由胺型式或有機酸鹽型式之胺聚 合物較佳。 胺聚合物之指定實例包括聚乙二亞胺、聚乙烯胺、聚烯 丙胺、聚鳥胺酸、聚離胺酸、聚烯丙基縮二胍基烯丙胺、 聚烯丙基胺甲醯基胍基烯丙胺、聚烯丙胺共聚物、聚 二烯丙胺、與聚二烯丙胺共聚物。在本發明中，胺聚化合 物並未特別地限制且不限於以上化合物。胺聚化合物可單 獨地或以二或更多種之組合使用。 聚乙二亞胺、聚乙烯胺與聚烯丙胺較佳，因爲這些聚合 春 物易於得到且易於使用。以上聚合物之結構式圖示地示於 以下。Liquid composition including amine compound and amine polymer. A liquid composition including an amine compound · I, an amine polymer, and water can more effectively complete photoresist removal. The amine polymer used in the present invention has a weight average molecular weight of 250 or more. The nitrogen atom can be present in any side chain and backbone. Although there is no upper limit on the molecular weight, amine polymers having excessive molecular weights tend to have difficulty in mixing amine compounds. The amine polymer can be any free amine type and salt type, and spring can be selected according to the purpose. Amine polymers of free amine type or organic acid salt type are preferred. Specified examples of amine polymers include polyethyleneimine, polyvinylamine, polyallylamine, polyguanine, polylysine, polyallylbiguanidylallylamine, polyallylamine formamyl Guanyl allylamine, polyallylamine copolymer, polydiallylamine, and polydiallylamine copolymer. In the present invention, the amine polymer compound is not particularly limited and is not limited to the above compounds. The amine polymer compound may be used alone or in a combination of two or more. Polyethyleneimine, polyvinylamine and polyallylamine are preferred because these polymeric springs are readily available and easy to use. The structural formula of the above polymer is shown graphically below.
聚乙二亞胺 593224 五、發明說明（4)Polyethylene diimide 593224 V. Description of the invention (4)
聚乙烯胺 在本發明中，胺聚合物不限於上述聚合物且可使用任何 聚合物，只要聚合物爲具有胺基之結構。任何型式之胺基 爲有效的，如一級胺基、二級胺基、三級胺基、與四級銨 基。不同型式之胺基可組合存在。例如，商業聚乙二亞胺 [NIPPON SHOKUBAI有限公司製造]爲35% —級胺、35%二級 胺與30%三級胺之混合物，而且可有效地使用。 通常，矽被胺化物腐蝕。腐蝕可藉胺聚合物防止。此機 制估計如下。在矽被腐蝕時，矽視爲以矽酸離子或胺之配 位化合物之形式溶離。在胺聚合物存在時，胺聚合物在表 面配位或以相對陽離子之形式在表面形成鈍化狀態，並且 抑制矽之溶離。 胺聚合物不僅抑制矽腐蝕且亦呈現抑制其他電線材料腐 蝕之效果。特別地，胺化合物可在鋁及鋁合金上有效地作 用。 用於本發明之胺化合物之實例包括烷胺、烷醇胺、多胺 、羥基胺、環形胺、與四級銨化合物。 593224 五、發明說明（5) 烷胺之實例包括一級胺，如甲胺、乙胺、正丙胺、異丙 胺、正丁胺、二級丁胺、異丁胺、三級丁胺、戊胺、2 -胺 基戊烷、3 -胺基戊烷、1 -胺基-2 -甲基丁烷、2 -胺基-2 -甲 基丁烷、3 -胺基-2 -甲基丁烷、4 -胺基-2 -甲基丁烷、己胺 、5 -胺基-2 -甲基戊烷、庚胺、辛胺、壬胺、癸胺、十一 碳胺、十二碳胺、十三碳胺、十四碳胺、十五碳胺、十六 碳胺、十七碳胺、與十八碳胺；二級胺，如二甲胺、二乙 胺、二丙胺、二異丙胺、二丁胺、二異丁胺、二-二級丁 胺、二-三級丁胺、二戊胺、二己胺、二庚胺、二辛胺、 二壬胺、二癸胺、甲基乙基胺、甲基丙基胺、甲基異丙基 胺、甲基丁基胺、甲基異丁基胺、甲基二級丁基胺、甲基 三級丁基胺、甲基三級丁基胺、甲基戊基胺、甲基異戊基 胺、乙基丙基胺、乙基異丙基胺、乙基丁基胺、乙基異丁 基胺、乙基二級丁基胺、乙胺、乙基異戊基胺、丙基丁基 胺、與丙基異丁基胺；及三級胺，如三甲胺、三乙胺、三 丙胺、三丁胺、三戊胺、二甲基乙基胺、甲基二乙基胺、 甲基二丙基胺、N-亞乙基甲基胺、N-亞乙基乙基胺、N-亞 乙基丙基胺、與N -亞乙基丁基胺。 烷醇胺之實例包括乙醇胺、N-甲基乙醇胺、N-乙基乙醇 胺、N-丙基乙醇胺、N-丁基乙醇胺、二乙醇胺、異丙醇胺 、N•甲基異丙醇胺、N-乙基異丙醇胺、N-丙基異丙醇胺、 2-胺基丙-1-醇、N-甲基-2-胺基丙-1-醇、N-乙甲基-2-胺 基丙-1-醇、1-胺基丙-3-醇、N-甲基-1-胺基丙-3-醇、N- 593224 五、發明說明（6) 乙基-1 -胺基丙-3-醇、1 -胺基丁 - 2-醇、N -甲基-1 -胺基丁 -2-醇、N -乙基-1 -胺基丁 - 2-醇、2-胺基丁 - 1 -醇、N-甲基 -2-胺基丁 - 1 ·醇、N-乙基-2-胺基丁 -1 -醇、3-胺基丁 -1 -醇、N_甲基-3-胺基丁 -1-醇、N_乙基-3-胺基丁 -1-醇、1-胺基-4-丁 - 4-醇、N -甲基-1-胺基丁 - 4-醇、N -乙基-1-胺 基丁 - 4-醇、1-胺基-2-甲基丙-2-醇、2 -胺基-2-甲基丙-1 -醇、1 -胺基戊-4 -醇、2 -胺基-4 -甲基戊-1 -醇、2 -胺基 己-1 -醇、3 -胺基庚-4 -醇、1 -胺基辛-2 -醇、5 -胺基辛-4 -醇、1 -胺基丙-2，3 -二醇、2 -胺基丙-1，3 -二醇、叁（氧基 甲基）胺基甲烷、1,2 -二胺基丙-3-醇、1，3-二胺基丙- 2-醇、2-(2-胺基乙氧基）乙醇、N-亞乙基乙醇胺、N-亞乙 基乙氧基乙醇胺、N-羥基甲基乙醇胺、N-羥基甲基乙二胺 、N，N’-貳（羥基甲基）乙二胺、與N-羥基甲基丙醇胺。 多胺之實例包括乙二胺、丙二胺、伸丙二胺、伸丁二胺 、1 , 3 -二胺基丁烷、2，3 -二胺基丁烷、伸戊二胺、2，4 -二 胺基戊烷、伸己二胺、伸庚二胺、伸辛二胺、伸壬二胺、 N-甲基乙二胺、N，N-二甲基乙二胺、三甲基乙二胺、N-乙 基乙二胺、N，N-二乙基乙二胺、三乙基乙二胺、1，2, 3-三 胺基丙烷、肼、叁（2 -胺基乙基）胺、四（胺基甲基）甲 烷、二伸乙三胺、三伸乙四胺、四伸乙五胺、七伸乙八胺 、九伸乙十胺、二氮雙環十一碳烯、聚乙二亞胺、聚乙烯 胺、與聚烯丙胺。 羥基胺之實例包括羥基胺、N -甲基羥基胺、N -乙基羥基 593224 五、發明說明（7) 胺、與N，N -二乙基羥基胺。 環形胺之實例包括吡咯、2-甲基吡咯、3-甲基败咯、2-乙基吡咯、3 -乙基吡咯、2,3 -二甲基吡咯、2,4 -二甲基吡 略、3,4 -二甲基卩比略、2,3,4 -三甲基η比略、2,3, 5 -三甲基 吡咯、2 -吡咯啉、3 -吡咯啉、吡咯啶、2 -甲基吡咯啶、3 -甲基吡咯啶、吡唑、咪唑、1，2，3 -三唑、1，2，3，4 -四唑、 六氫吡啶、2 -甲六氫吡啶、3 -甲六氫吡啶、4 -甲六氫吡啶 、2,4 -二甲六氫吡啶、2,6 -二甲六氫吡啶、3,5 -二甲六氫 吡啶、哌啶、2 -甲基哌啶、2，5 -二甲基哌啶、2，6 -二甲基 峨D定、與嗎啉。 四級銨化合物之實例包括氫氧化四甲銨、氫氧化四乙銨 、氫氧化四丙銨、氫氧化四丁銨、膽驗氫氧化物、與乙醯 基膽驗氫氧化物。 用於本發明之胺不限於以上化合物且可使用任何化合物 ，只要此化合物爲胺化合物。 以上之胺中’，甲胺、乙胺、丙胺、丁胺、乙醇胺、Ν -甲 基乙醇胺、Ν-乙基乙醇胺、二乙醇胺、異丙醇胺、2- ( 2-胺基乙氧基）乙醇、乙二胺、丙二胺、丁二胺、二伸乙三 胺、哌D定、與嗎啉較佳。 用於本發明之胺聚合物亦爲胺化合物。因此，胺聚合物 可作爲胺化合物。在此情形，胺聚合物可單獨使用。胺化 合物可單獨地或以二或更多種之組合使用。 本發明之光阻移除用液體組成物更可包括有機溶劑。用 593224 五、發明說明（8) jPolyvinylamine In the present invention, the amine polymer is not limited to the above-mentioned polymers and any polymer may be used as long as the polymer has a structure having an amine group. Any type of amine group is effective, such as primary, secondary, tertiary, and quaternary ammonium. Different types of amine groups can be present in combination. For example, commercial polyethylene diimide [manufactured by NIPPON SHOKUBAI Co., Ltd.] is a 35% -grade amine, a mixture of 35% secondary amine and 30% tertiary amine, and can be effectively used. Usually, silicon is corroded by amides. Corrosion can be prevented by amine polymers. This mechanism is estimated as follows. When silicon is corroded, silicon is considered to dissolve in the form of silicic acid ions or amine complexes. In the presence of the amine polymer, the amine polymer is coordinated on the surface or forms a passivation state on the surface in the form of a relatively cation, and suppresses the dissolution of silicon. Amine polymers not only inhibit the corrosion of silicon, but also exhibit the effect of inhibiting the corrosion of other wire materials. In particular, amine compounds can be effectively used on aluminum and aluminum alloys. Examples of the amine compound used in the present invention include alkamines, alkanolamines, polyamines, hydroxylamines, cyclic amines, and quaternary ammonium compounds. 593224 5. Description of the invention (5) Examples of alkylamines include primary amines, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, secondary butylamine, isobutylamine, tertiary butylamine, pentylamine, 2-aminopentane, 3-aminopentane, 1-amino-2-methylbutane, 2-amino-2 -methylbutane, 3-amino-2 -methylbutane, 4-amino-2-methylbutane, hexylamine, 5-amino-2-methylpentane, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, ten Tricarbonamine, tetradecylamine, pentacarbonamine, hexadecylamine, heptacarbonamine, and octadecylamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, Dibutylamine, diisobutylamine, di-secondary butylamine, di-tertiary butylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, methylethyl Methylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methylisobutylamine, methyl secondary butylamine, methyl tertiary butylamine, methyltertiary butylamine Methylamine, methylpentylamine, methylisopentylamine, ethylpropylamine, ethylisopropylamine, ethylbutylamine, ethyl Isobutylamine, ethyl secondary butylamine, ethylamine, ethyl isoamylamine, propylbutylamine, and propyl isobutylamine; and tertiary amines, such as trimethylamine, triethylamine, Tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine, methyldipropylamine, N-ethylenemethylamine, N-ethyleneethylamine, N-ethylenepropylamine and N-ethylenebutylamine. Examples of alkanolamines include ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, isopropanolamine, N • methylisopropanolamine, N -Ethylisopropanolamine, N-propylisopropanolamine, 2-aminoprop-1-ol, N-methyl-2-aminoprop-1-ol, N-ethylmethyl-2- Aminoprop-1-ol, 1-aminoprop-3-ol, N-methyl-1-aminoprop-3-ol, N-593224 5. Description of the invention (6) Ethyl-1 -amino Prop-3-ol, 1-aminobut-2-ol, N-methyl-1 -aminobut-2-ol, N-ethyl-1 -aminobut-2-ol, 2-amino Butan-1-ol, N-methyl-2-aminobut-1-ol, N-ethyl-2-aminobut-1-ol, 3-aminobut-1-ol, N-methyl -3-aminobut-1-ol, N-ethyl-3-aminobut-1-ol, 1-amino-4-but-4-ol, N-methyl-1-aminobut- 4-alcohol, N-ethyl-1-aminobut-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1 -Aminopent-4-ol, 2-amino-4 -methylpent-1 -ol, 2-aminohex-1 -alcohol, 3-aminoheptan-4 -alcohol, 1 -aminooctyl- 2-alcohol, 5-aminooctyl-4 -alcohol, 1-aminopropyl-2,3-diol, 2-amine Propane-1,3-diol, tris (oxymethyl) aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2- (2 -Aminoethoxy) ethanol, N-ethyleneethanolamine, N-ethyleneethoxyethanolamine, N-hydroxymethylethanolamine, N-hydroxymethylethylenediamine, N, N'-fluorene (hydroxyl Methyl) ethylenediamine, and N-hydroxymethylpropanolamine. Examples of polyamines include ethylenediamine, propylenediamine, propylenediamine, butylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentylenediamine, 2, 4-Diaminopentane, hexamethylene diamine, hexamethylene diamine, octyl diamine, hexamethylene diamine, N-methylethylenediamine, N, N-dimethylethylenediamine, trimethyl Ethylenediamine, N-ethylethylenediamine, N, N-diethylethylenediamine, triethylethylenediamine, 1,2,3-triaminopropane, hydrazine, tris (2-aminoethyl) ) Amine, tetrakis (aminomethyl) methane, ethylenediamine, triethylenetetraamine, tetraethylenepentaamine, heptaethyleneamine, nonaneethylenedecaamine, diazabicycloundecene , Polyethyleneimine, polyvinylamine, and polyallylamine. Examples of the hydroxylamine include hydroxylamine, N-methylhydroxylamine, N-ethylhydroxyl 593224 5. Description of the Invention (7) Amine, and N, N-diethylhydroxylamine. Examples of cyclic amines include pyrrole, 2-methylpyrrole, 3-methylpyrrole, 2-ethylpyrrole, 3-ethylpyrrole, 2,3-dimethylpyrrole, 2,4-dimethylpyrrole , 3,4-Dimethylpyridine, 2,3,4-Trimethyleta ratio, 2,3,5-Trimethylpyrrole, 2-Pyrroline, 3-Pyrroline, Pyrrolidine, 2 -Methylpyrrolidine, 3-methylpyrrolidine, pyrazole, imidazole, 1,2,3-triazole, 1,2,3,4-tetrazole, hexahydropyridine, 2-methylhexahydropyridine, 3 -Methylhexahydropyridine, 4-methylhexahydropyridine, 2,4-dimethylhexahydropyridine, 2,6-dimethylhexahydropyridine, 3,5-dimethylhexahydropyridine, piperidine, 2-methyl Piperidine, 2,5-dimethylpiperidine, 2,6-dimethylformidine, and morpholine. Examples of the quaternary ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, bile hydroxide, and acetamyl bile hydroxide. The amine used in the present invention is not limited to the above compounds and any compound may be used as long as the compound is an amine compound. Among the above amines, methylamine, ethylamine, propylamine, butylamine, ethanolamine, N-methylethanolamine, N-ethylethanolamine, diethanolamine, isopropanolamine, 2- (2-aminoethoxy) Ethanol, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, piperidine, and morpholine are preferred. The amine polymers used in the present invention are also amine compounds. Therefore, amine polymers can be used as amine compounds. In this case, the amine polymer may be used alone. The amine compound may be used alone or in a combination of two or more. The liquid composition for removing photoresist according to the present invention may further include an organic solvent. Use 593224 V. Description of Invention (8) j
I 於本發明之有機溶劑並未特別地限制，只要有機溶劑與上I 述胺聚合物及胺化合物之混合物相容。溶於水之有機溶劑 較佳。有機溶劑之實例包括醚系溶劑，如乙二醇、乙二醇 單甲醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙 醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、丙 二醇單丁醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二 醇單丁醚、二乙二醇二甲醚、與二丙二醇二甲醚；醯胺系 溶劑，如甲醯胺、單甲基甲醯胺、二甲基甲醯胺、單乙基 甲醯胺、二乙基甲醯胺、乙醯胺、單甲基乙醯胺、二甲基 乙醯胺、單乙基乙醯胺、二乙基乙醯胺、N-甲基吡咯啶酮 、與N -乙基吡咯啶酮；醇系溶劑，如甲醇、乙醇、異丙醇 、乙二醇、與丙二醇；亞珮系溶劑，如二甲基亞颯；珮系 溶劑，如二甲颯、二乙礪、與四甲颯；咪唑B定嗣溶劑，如 1，3_二甲基-2-咪唑啶酮、1，3 -二乙基-2-咪唑啶酮、與 1，3-二異丙基-2-咪唑啶酮；內酯系溶劑，如γ-丁內酯與 δ-戊內酯；及胺氧化物溶劑，如三甲胺氧化物與甲基嗎啉 〇 這些溶劑中，二甲基亞颯、Ν，Ν -二甲基亞颯、Ν，Ν -二甲 基甲醯胺、Ν，Ν-二甲基乙醯胺、Ν -甲基吡咯啶酮、二乙二 醇單甲醚、二乙二醇單丁醚、二丙二醇單甲醚、二丙二醇 單丁醚、與丙二醇較佳，因爲這些溶劑易於得到且具有高 沸點。 在本發明之光阻移除用液體組成物中，可視情況地使用 -10- 593224 五、發明說明（9) 抗腐蝕劑。抗腐蝕劑之實例包括以磷酸、羧酸、胺、肟、 乙炔、芳族羥基化合物、三唑化合物、與糖醇化合物爲主 之抗腐蝕劑。這些抗腐蝕劑中，以芳族羥基化合物、糖醇 化合物與三唑化合物爲主之抗腐蝕劑由於易於使用而廣爲 使用。 以磷酸爲主之抗腐蝕劑之實例包括1，2 -丙二胺四亞甲基 膦酸與羥基乙烷膦酸。以羧酸爲主之抗腐蝕劑之實例包括 乙二胺四乙酸、二羥基乙基甘胺酸、硝基乙酸、草酸、檸 檬酸、丙二酸、與酒石酸。以胺爲主之抗腐蝕劑之實例包 括二吡啶、四苯基卟啉、啡啉、與2，3 -吡啶二醇。以肟爲 主之抗腐蝕劑之實例包括二甲基乙二醛二肟與二苯基乙二 醛二肟。以乙炔爲主之抗腐蝕劑之實例包括苯基乙炔與 2, 5 -二甲基-3-己炔-2, 5 -二醇。 以芳族羥基化合物爲主之抗腐蝕劑之實例包括酚、甲苯 酚、二甲酚、兒茶酚、三級丁基兒茶酚、間苯二酚、氫醌 、五倍子酚、1，2，4 -苯三醇、柳醇、對羥基苄醇、鄰羥基 苄醇、對羥基苯乙醇、對胺基酚、間胺基酚、二胺基酚、 2-胺間苯二酚、對羥基苯甲酸、鄰羥基苯甲酸、2,4-二羥 基苯甲酸、2,5 -二羥基苯甲酸、3，4-二羥基苯甲酸、3，5-二羥基苯甲酸、與五倍子酸。以糖醇化合物爲主之抗腐蝕 劑之實例包括葡萄糖醇、木糖醇與para tinit。以三唑爲 主之抗腐蝕劑之實例包括苯并三唑、胺基三唑與胺基四唑 。以上化合物可單獨地或以二或更多種之組合使用。 -11- 593224 五、發明說明（1〇) 在本發明中，胺化合物以0 · 1至95重量％範圍之量使用 ;胺聚合物以0.0001至95重量％範圍之濃度使用；及有 機溶劑以〇至99重量％範圍之量使用。 有機溶劑之量並未特別地限制，而且依照組成物之黏度 與比重及蝕刻與去灰條件而適當地決定。在本發明之組成 物中，抗腐蝕劑之量並未特別地限制。抗腐蝕劑之量在0 至30重量％之範圍，而且較佳爲15重量％或更少。 在本發明中，水之量並未特別地限制，而且依照蝕刻與 去灰條件而適當地決定。水之量通常在〇至50重量％之範 圍。在完全無水時，於許多情形中矽蝕刻爲極少，而且胺 聚合物之功能無法有效地呈現。然而，在許多半導體製程 中，在移除光阻後進行以水淸洗，而且在淸洗中形成胺聚 合物‘與水之混合物。因此，含胺聚合物之光阻移除用液體 組成物在液體組成物混合水時具有抑制腐蝕之優點。 以本發明之光阻移除用液體組成物移除光阻之溫度通常 在常溫至150°C之範圍。特別地，移除可在70°C或更低之 溫度進行。在考慮侵蝕材料時，較低溫較佳。 至於用於本發明之基質材料，可使用半導體配線材料， 如矽、非晶矽、多矽、矽氧化物膜、氮化矽膜、銅、銅合 金、鋁、鋁合金、金、鉑、銀、鈦、鈦一鎢合金、氮化鈦 、鎢、鉬、钽化合物、鉻、氧化鉻、鉻合金、與ITO (銦 -錫合金）；複合半導體，如鎵-砷混合物、鎵一磷混合 物與銦-磷混合物；介電材料，如緦-鉍-鉅混合物；及 -12- 593224 五、發明說明（11 ) 玻璃，如用於LCD基質之玻璃。特別地，包括裸矽、非晶 矽與多矽之基質爲有效的。 - 製造半導體裝置之方法包括以光阻膜在基質上形成指定 圖樣，藉蝕刻移除基質上膜之不必要部份，及使用以上之 光阻移除用液體組成物移除光阻。在必要時，在蝕刻後可 進行去灰處理，而且可使用以上之液體組成物移除去灰形 成之殘渣。 在上述去灰處理中，例如，藉由在電漿中產生之氧電漿 之燃燒反應將由有機巨分子組成之光阻轉化成C0與C02且 移除。 爲了在應用本發明之光阻移除用液體組成物後之淸洗處 理，可使用如醇或水之有機溶劑。淸洗溶劑並未特別地限 制。 實例 本發明更特別地參考以下實例而敘述。然而，本發明 不受實例限制。 實例1至7及比較例1與2 將在絕緣膜上形成之具有非晶矽（a - S i )膜之玻璃基質塗 以光阻，然後將光阻膜顯影。在乾燥蝕刻步驟後形成電路 。使用所得之基質進行光阻移除性質之測試。測量非晶矽 之蝕刻速率。 在40°C將以上之基質浸入具有表1所示組成物之光阻移 除用液體組成物中。在指定時間後，將基質取出，以水淸 -13- 593224 五、發明說明（12 ) 洗，以氮氣吹乾然後以光學顯微鏡觀察。由結果得到移除 光阻所需之時間。爲了測量非晶矽之蝕刻速率，以緩衝氟 酸移除氧化物層然後進行測量。使用光學厚度計得到非晶 矽之蝕刻速率。 結果不於表1。 -14- 593224 五、發明說明（13 ) 表1The organic solvent in the present invention is not particularly limited as long as the organic solvent is compatible with the above-mentioned mixture of the amine polymer and the amine compound. Water-soluble organic solvents are preferred. Examples of the organic solvent include ether-based solvents such as ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether; ammonium amine series Solvents such as formamidine, monomethylformamide, dimethylformamide, monoethylformamide, diethylformamide, acetamide, monomethylacetamide, dimethylacetamide Ammonium amine, monoethylacetamide, diethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone; alcohol solvents such as methanol, ethanol, isopropanol, and ethylene glycol , And propylene glycol; fluorene-based solvents, such as dimethyl sulfene; fluorene-based solvents, such as dimethylamine, diethylpyrene, and tetramethyl fluorene; imidazole B, fluorene solvents, such as 1,3-dimethyl-2- Imidazolidone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone; lactone-based solvents such as γ-butyrolactone and δ-valerolactone Esters; and amine oxidation Solvents such as trimethylamine oxide and methylmorpholine. Among these solvents, dimethylsulfinium, N, N-dimethylsulfinium, N, N-dimethylformamidine, N, N-dimethylformamide Ethylamine, N-methylpyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, and propylene glycol are preferred because these solvents are easy Obtained and has a high boiling point. In the liquid composition for removing photoresist of the present invention, it may be used as appropriate -10- 593224 V. Description of the invention (9) Anticorrosive. Examples of the anticorrosive agent include anticorrosive agents based on phosphoric acid, carboxylic acid, amine, oxime, acetylene, aromatic hydroxy compound, triazole compound, and sugar alcohol compound. Among these anticorrosive agents, anticorrosive agents mainly composed of aromatic hydroxy compounds, sugar alcohol compounds, and triazole compounds are widely used because they are easy to use. Examples of phosphoric acid-based anticorrosives include 1,2-propanediaminetetramethylenephosphonic acid and hydroxyethanephosphonic acid. Examples of carboxylic acid-based anticorrosives include ethylenediaminetetraacetic acid, dihydroxyethylglycine, nitroacetic acid, oxalic acid, citric acid, malonic acid, and tartaric acid. Examples of amine-based anticorrosives include dipyridine, tetraphenylporphyrin, phenanthroline, and 2,3-pyridinediol. Examples of oxime-based anticorrosives include dimethylglyoxaldioxime and diphenylglyoxaldioxime. Examples of the acetylene-based anticorrosive include phenylacetylene and 2, 5-dimethyl-3-hexyne-2, 5-diol. Examples of the anticorrosive agent mainly composed of aromatic hydroxy compounds include phenol, cresol, xylenol, catechol, tertiary butyl catechol, resorcinol, hydroquinone, gallophenol, 1,2,4 -Pyrotriol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, 2-amine resorcinol, p-hydroxybenzoic acid , O-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and gallic acid. Examples of the anticorrosive agent based on sugar alcohol compounds include glucosyl alcohol, xylitol and para tinit. Examples of triazole-based anticorrosives include benzotriazole, aminotriazole, and aminotetrazole. The above compounds may be used alone or in a combination of two or more. -11- 593224 V. Description of the invention (10) In the present invention, the amine compound is used in an amount ranging from 0.1 to 95% by weight; the amine polymer is used in a concentration ranging from 0.0001 to 95% by weight; and the organic solvent is used It is used in an amount ranging from 0 to 99% by weight. The amount of the organic solvent is not particularly limited, and is appropriately determined in accordance with the viscosity and specific gravity of the composition and the conditions of etching and ashing. The amount of the anticorrosive agent in the composition of the present invention is not particularly limited. The amount of the anticorrosive agent is in the range of 0 to 30% by weight, and preferably 15% by weight or less. In the present invention, the amount of water is not particularly limited, and is appropriately determined in accordance with the etching and ashing conditions. The amount of water is usually in the range of 0 to 50% by weight. When completely anhydrous, silicon is etched very rarely in many cases, and the function of the amine polymer cannot be effectively exhibited. However, in many semiconductor processes, washing with water is performed after removing the photoresist, and an amine polymer 'mixed with water is formed in the washing. Therefore, the liquid composition for removing the photoresist of the amine-containing polymer has the advantage of suppressing corrosion when the liquid composition is mixed with water. The temperature at which the photoresist is removed by the liquid composition for photoresist removal of the present invention is usually in the range of ordinary temperature to 150 ° C. In particular, removal can be performed at a temperature of 70 ° C or lower. When considering aggressive materials, lower temperatures are preferred. As the matrix material used in the present invention, semiconductor wiring materials such as silicon, amorphous silicon, polysilicon, silicon oxide film, silicon nitride film, copper, copper alloy, aluminum, aluminum alloy, gold, platinum, silver , Titanium, titanium-tungsten alloy, titanium nitride, tungsten, molybdenum, tantalum compounds, chromium, chromium oxide, chromium alloy, and ITO (indium-tin alloy); composite semiconductors, such as gallium-arsenic mixtures, gallium-phosphorus mixtures, and Indium-phosphorus mixtures; dielectric materials, such as osmium-bismuth-macro mixtures; and -12-593224 V. Description of the invention (11) Glass, such as glass for LCD substrates. In particular, substrates including bare silicon, amorphous silicon, and polysilicon are effective. -A method for manufacturing a semiconductor device includes forming a specified pattern on a substrate with a photoresist film, removing unnecessary portions of the film on the substrate by etching, and removing the photoresist using the liquid composition for photoresist removal above. If necessary, the ashing treatment may be performed after the etching, and the residue formed by the ashing may be removed using the above liquid composition. In the above ashing treatment, for example, a photoresist composed of organic macromolecules is converted into C0 and C02 and removed by a combustion reaction of an oxygen plasma generated in the plasma. For the washing treatment after applying the liquid composition for photoresist removal of the present invention, an organic solvent such as alcohol or water may be used. The washing solvent is not particularly limited. Examples The present invention is described more specifically with reference to the following examples. However, the present invention is not limited by the examples. Examples 1 to 7 and Comparative Examples 1 and 2 A glass substrate having an amorphous silicon (a-Si) film formed on an insulating film was coated with a photoresist, and the photoresist film was developed. A circuit is formed after the dry etching step. The obtained substrate was used to test the photoresist removal property. Measure the etch rate of amorphous silicon. The above substrate was immersed in a liquid composition for removing photoresist having the composition shown in Table 1 at 40 ° C. After the specified time, the substrate is taken out, washed with water -13-593224 V. Description of the invention (12), blown dry with nitrogen and observed with an optical microscope. The result is the time required to remove the photoresist. To measure the etch rate of amorphous silicon, the oxide layer was removed with buffered hydrofluoric acid and then measured. An optical thickness meter was used to obtain the etch rate of the amorphous silicon. The results are not in Table 1. -14- 593224 V. Description of the invention (13) Table 1
非晶矽之光阻移除時間及蝕刻速率* 組成物 胺聚合物 水 光阻移 a-Si 之 (重量％) (重量％) (重量％) 除時間 蝕刻速率 (秒） (A/min) 實例1 EA 36， HMEA 1， PEI(Mw 10,000) 35 20 56 DMSO 20，葡萄糖醇5 3 實例2 EA 39.5,HMEA 0.1, PEI(Mw 1,800) 35 30 61 DMAC 19.9，葡萄糖醇5 0.5 實例3 EA 37， PEI(Mw 1,800) 35 45 58 DGME 20，葡萄糖醇5 3 實例4 EA 39.5， PEI(Mw 70,000) 35 45 40 NMP 20.葡萄糖醇5 0.5 實例5 EA 40， PEI(Mw 10,000) 35 60 54 PG 19,葡萄糖醇5 1 實例6 MEA 29.9, HMEA 0.1, PEI(Mw 10,000) 35 30 32 NMP 28，葡萄糖醇5 3 實例7 EDA 20, PAA(Mw 3,000) 35 45 30 DMAC 38，葡萄糖醇5 2 比較例1 EA 39， HMEA 1， DMSO 20，葡萄糖醇5 - 35 20 142 比較例2 EA 40， PG 20， 一 35 60 125 葡萄糖醇5 *註 EA :乙醇胺 HMEA : N-羥基甲基乙醇胺 DMSO :二甲基亞楓 DMAC :二甲基乙醯胺 DGME :二乙二醇單甲醚 NMP : N-甲基吡咯啶酮 MEA甲基乙醇胺 PG :丙二醇 -15- 593224 五、發明說明（14 ) EDA :乙二胺 PEI (Mw 10,000):聚乙二亞胺（平均分子量：1〇,〇〇〇) PEI (Mw Γ，800 ):聚乙二亞胺（平均分子量：1，800 ) PEI (Mw 70,000):聚乙二亞胺（平均分子量：70,000 ) 實例8至1 4及比較例3與4 爲了製備半導體裝置，使用光阻膜作爲遮罩進行乾燥蝕 刻，並且形成鋁合金（A1-Cu)配線。在氧電漿之去灰處理 後，得到半導體裝置。所得半導體裝置之一部份之正切面 圖示於第1圖。在半導體裝置中，在矽基質1上形成氧化 物膜2及在氧化物膜2上形成鋁合金配線5。光阻6之殘 渣殘留在其側壁上。存在鈦3與氮化鈦4作爲屏障層。 在70t將第1圖所示之半導體裝置浸入具有表2所示組 成物之光阻移除用液體組成物中1 5分鐘。然後自液體組 成物取出裝置，以超純水淸洗，乾燥及以電子顯微鏡（SEM) 觀察。光阻6殘渣移除及鋁配線5腐蝕之評估結果示於表 2。依照以下標準評估使用SEM之觀察結果： A :殘渣完全移除。 B :殘渣殘留。 C :發現腐蝕。 亦在7(TC測量用於以上測試之組成物之裸矽蝕刻速率。Removal time and etch rate of photoresist of amorphous silicon * (% by weight) (% by weight) (% by weight) of amine polymer water photoresist (a / Si) divided by time (A / min) Example 1 EA 36, HMEA 1, PEI (Mw 10,000) 35 20 56 DMSO 20, Glucitol 5 3 Example 2 EA 39.5, HMEA 0.1, PEI (Mw 1,800) 35 30 61 DMAC 19.9, Glucitol 5 0.5 Example 3 EA 37 , PEI (Mw 1,800) 35 45 58 DGME 20, Glucitol 5 3 Example 4 EA 39.5, PEI (Mw 70,000) 35 45 40 NMP 20. Glucitol 5 0.5 Example 5 EA 40, PEI (Mw 10,000) 35 60 54 PG 19, Glucitol 5 1 Example 6 MEA 29.9, HMEA 0.1, PEI (Mw 10,000) 35 30 32 NMP 28, Glucitol 5 3 Example 7 EDA 20, PAA (Mw 3,000) 35 45 30 DMAC 38, Glucitol 5 2 Compare Example 1 EA 39, HMEA 1, DMSO 20, Glucitol 5-35 20 142 Comparative Example 2 EA 40, PG 20,-35 60 125 Glucitol 5 * Note EA: Ethanolamine HMEA: N-hydroxymethylethanolamine DMSO: Di Methylacetomethyl DMAC: Dimethylacetamide DGME: Diethylene glycol monomethyl ether NMP: N-methylpyrrolidone MEA methyl Ethanolamine PG: Propylene glycol-15-593224 V. Description of the invention (14) EDA: Ethylenediamine PEI (Mw 10,000): Polyethyleneimine (average molecular weight: 10,000) PEI (Mw Γ, 800): Polyethyleneimine (average molecular weight: 1,800) PEI (Mw 70,000): Polyethyleneimine (average molecular weight: 70,000) Examples 8 to 14 and Comparative Examples 3 and 4 In order to prepare semiconductor devices, a photoresist film was used Dry etching is performed as a mask, and an aluminum alloy (A1-Cu) wiring is formed. After the ash removal of the oxygen plasma, a semiconductor device was obtained. A tangential view of a part of the obtained semiconductor device is shown in FIG. 1. In a semiconductor device, an oxide film 2 is formed on a silicon substrate 1 and an aluminum alloy wiring 5 is formed on the oxide film 2. Residue of the photoresist 6 remains on its side wall. Titanium 3 and titanium nitride 4 are present as the barrier layer. The semiconductor device shown in Fig. 1 was immersed in the liquid composition for removing photoresist having the composition shown in Table 2 at 70 t for 15 minutes. The device was then removed from the liquid composition, washed with ultrapure water, dried, and observed with an electron microscope (SEM). The evaluation results of the photoresist 6 residue removal and aluminum wiring 5 corrosion are shown in Table 2. The observation results using SEM were evaluated according to the following criteria: A: The residue was completely removed. B: Residue remains. C: Corrosion was found. The bare silicon etch rate of the composition used for the above tests was also measured at 7 ° C.
-16- 593224 五、發明說明（15 ) ，表2 裸矽之光阻移除時間及蝕刻速率* 組成物 (重量％) 胺聚合物 (重量％) 水 (重量％) 光阻移 除時間 (秒） 裸Si之 蝕刻速率 (A/min) 實例8 EA 60， DGME 20, CA 2 PEI(Mw 10,000) 3 15 A 69 實例9 EA 60, DGME 22.9, CA 2 PEI(Mw 10,000) 0.5 15 A 129 實例10 EA 61, DMAC 20, BT 0.02,CA 1.98 PEI(Mw 600) 2 15 A 115 實例11 EA 58, DGBE 20, BuCA 2 PAA(Mw 3,000) 2 18 A 30 實例12 DGBE 50, CA 2 PEI(Mw 600) 28 20 A 25 實例13 EA 36, DPME 40 ?^(从〜1,000)-50%甲酸酯 2 22 B 30 實例14 AEE 79, CA 5 PAA(Mw 5,000) 1 15 A 32 比較例3 EA 60, DGME 23, CA2 — 15 C 650 比較例4 AEE 75, CA 5, HA 5 - 15 B 600 *註 EA :乙醇胺 DGME :二乙二醇單甲醚 CA :兒茶酚 -17- 593224 五、發明說明（16 ) DMAC :二甲基乙醯胺 BT :苯并三唑 BuCA : 4-三級丁基兒茶酚 DGBE :二乙二醇單丁醚 DPME :二丙二醇單甲醚 AEE :胺基乙氧基乙醇 HA :羥基胺. EDA :乙二胺 PEI(Mw 10,000):聚乙二亞胺（平均分子量：10,000 ) PEI(Mw 600):聚乙二亞胺（平均分子量：600 ) PAA(Mw 3,000) ··聚烯丙胺（平均分子量：3,000 ) PVA(Mw 1,000)- 50%甲酸酯：聚乙烯胺之50%甲酸鹽（平均 分子量：1，000 ) PAA(Mw 5,000):聚嫌丙胺（平均分子量：5,000) 實例15至20及比較例5與6 使用具有在S i 02上形成之低溫多矽（p - S i )之結構之玻璃 基質（其用於薄層電晶體製備）進行光阻移除測試。第2 圖顯示一部份之橫切面圖，其中多矽暴露於測試基質上。 在一層Si02 10 (其形成於玻璃基質11上）上形成一層低 溫多矽9。在一層低溫多矽9上形成絕緣層7。光阻8之 殘渣殘留在絕緣層7上。在某些部份無絕緣層且下層直接 接觸光阻移除用液體組成物。使用以上之基質進行光阻移 除測試及多矽鈾刻速率測量。-16- 593224 5. Description of the invention (15), Table 2 Photoresist removal time and etching rate of bare silicon * Composition (wt%) Amine polymer (wt%) Water (wt%) Photoresist removal time ( Seconds) Etching rate of bare Si (A / min) Example 8 EA 60, DGME 20, CA 2 PEI (Mw 10,000) 3 15 A 69 Example 9 EA 60, DGME 22.9, CA 2 PEI (Mw 10,000) 0.5 15 A 129 Example 10 EA 61, DMAC 20, BT 0.02, CA 1.98 PEI (Mw 600) 2 15 A 115 Example 11 EA 58, DGBE 20, BuCA 2 PAA (Mw 3,000) 2 18 A 30 Example 12 DGBE 50, CA 2 PEI ( Mw 600) 28 20 A 25 Example 13 EA 36, DPME 40? (From ~ 1,000) -50% formate 2 22 B 30 Example 14 AEE 79, CA 5 PAA (Mw 5,000) 1 15 A 32 Comparative Example 3 EA 60, DGME 23, CA2 — 15 C 650 Comparative Example 4 AEE 75, CA 5, HA 5-15 B 600 * Note EA: Ethanolamine DGME: Diethylene glycol monomethyl ether CA: Catechol-17-593224 5 Explanation of the invention (16) DMAC: Dimethylacetamide BT: Benzotriazole BuCA: 4-Tributylbutylcatechol DGBE: Diethylene glycol monobutyl ether DPME: Dipropylene glycol monomethyl ether AEE: Amine Ethylethoxyethanol HA: Hydroxylamine. EDA: Ethylenediamine PEI (Mw 10,000): Ethylenediimide (average molecular weight: 10,000) PEI (Mw 600): Polyethyleneimine (average molecular weight: 600) PAA (Mw 3,000) · Polyallylamine (average molecular weight: 3,000) PVA (Mw 1,000)-50 % Formate: 50% formate of polyvinylamine (average molecular weight: 1,000) PAA (Mw 5,000): poly (propylamine) (average molecular weight: 5,000) Examples 15 to 20 and Comparative Examples 5 and 6 A photoresist removal test was performed on a glass substrate of a low temperature polysilicon (p-Si) structure formed on Si 02 (which is used for the preparation of thin-film transistors). Figure 2 shows a cross-sectional view of a portion with polysilicon exposed on the test substrate. A layer of low temperature polysilicon 9 is formed on a layer of Si02 10 (which is formed on the glass substrate 11). An insulating layer 7 is formed on a layer of low-temperature polysilicon 9. The residue of the photoresist 8 remains on the insulating layer 7. There is no insulating layer in some parts and the lower layer is in direct contact with the liquid composition for photoresist removal. Use the above substrate for photoresistance removal test and polysilicon etch rate measurement.
-18- 593224 五、發明說明（17 ) 在40°C將以上之基質浸入具有表3所示組成物之光阻移 除用液體組成物中。在指定時間後，將基質取出，以水淸 洗，以氮氣吹乾然後以光學顯微鏡觀察。由結果得到移除 光阻所需之時間。爲了測量非晶矽之鈾刻速率，以緩衝氟 酸移除氧化物層然後進行測量。使用光學厚度計得到非晶 石夕之f虫刻速率。 結果不於表3。 -19- 593224 五、發明說明（is) 表3 多矽之光阻移除時間及蝕刻速率* 組成物 (重量％) 胺聚合物 (重量％) 水 (重量％) 光阻移 除時間 (秒） p-Si 之 蝕刻速率 (A/min) 實例15 EA 5, NMP 74.9, PEI(Mw 10,000) 0.1 20 90 6 實例16 EA 5, HMEA 0.1, MEA 10, DMAC 44.4, 葡萄糖醇5 PEI(Mw 1,800) 0.5 35 45 7 實例17 EA 18, DGBE 60.99, 木糖醇1 PAA(Mw 3,000) 0.01 20 45 15 實例18 EA 69.5, NMP 28 PEI(Mw 70,000) 0.5 2 20 2 實例19 MEA 12, HMEA 1, DMAC 46.5， 葡萄糖醇5 PEI(MW 10,000) 0.5 35 60 5 實例20 PA 12, DGME 70 PAA(Mw 10,000) 2 16 45 6 實例21 MO 35, DEH 5, DMAC 19.95, PAA(Mw 3,000) 0.05 35 45 17 比較例4 EA 70, NMP 28 - 2 20 78 比較例5 EA 20， DGBE 39,木糖醇1 - 20 45 235 *註 EA :乙醇胺 NMP : N-甲基吡咯啶酮 HMEA : N,羥基甲基乙醇胺 MEA :甲基乙醇胺 DMAC :二甲基乙醯胺 DGBE :二乙二醇單丁醚 PA : 1-胺基-2-丙酮 -20 - 593224 五、發明說明（19 ) DGME :二乙二醇單甲醚 M0 :嗎啉 DEH ··二乙基羥基胺 EDA :乙二胺 PEI (Mw 10,000 ):聚乙二亞胺（平均分子量：1〇,〇〇〇) PEI (Mw 1，800):聚乙二亞胺（平均分子量：1，800 ) PEI (Mw 3,000):聚乙二亞胺（平均分子量：3,000 ) PEI (Mw 70,000):聚乙二亞胺（平均分子量：70,000 ) PAA (Mw 10,000):聚烯丙胺（平均分子量：1〇,〇〇〇) PAA (Mw 3,000):聚烯丙胺（平均分子量：3,000 ) NMP : N-甲基？咯啶酮 PG :丙二醇 本發明之效罢 茲歸納本發明之優點，可使用本發明之光阻移除用液體 組成物在短時間內移除光阻而不腐蝕配線材料，特別是矽 。更特別地，在使用本發明之光阻移除用液體組成物時， 可無關矽型式（如裸矽、非晶矽與多矽）而有效地防止矽 腐蝕及可自包含矽之基質移除光阻而不腐蝕。 熟悉此技藝者更應了解，以上之說明爲本發明之較佳具 體實施例，及可在本發明進行各種變化及修改而不背離其 精神與範圍。 主要元件之對照表 1 矽基質 -21 - 593224 五、發明說明（20) 2 氧化物膜 3 鈦 4 氮化鈦 5 配線 6 光阻 7 絕緣層 8 光阻 9 低溫多矽 10 二氧化5夕 11 玻璃基質 -22--18- 593224 V. Description of the invention (17) The above substrate was immersed in a liquid composition for photoresistance removal having the composition shown in Table 3 at 40 ° C. After the specified time, the substrate was removed, washed with water, dried with nitrogen and then observed with an optical microscope. The result is the time required to remove the photoresist. To measure the uranium etch rate of amorphous silicon, the oxide layer was removed with buffered hydrofluoric acid and then measured. An optical thickness meter was used to obtain the fetching rate of the amorphous stone. The results are not in Table 3. -19- 593224 V. Description of the invention (is) Table 3 Polysilicon photoresist removal time and etching rate * Composition (wt%) Amine polymer (wt%) Water (wt%) Photoresist removal time (seconds) ) Etching rate of p-Si (A / min) Example 15 EA 5, NMP 74.9, PEI (Mw 10,000) 0.1 20 90 6 Example 16 EA 5, HMEA 0.1, MEA 10, DMAC 44.4, Glucitol 5 PEI (Mw 1,800 ) 0.5 35 45 7 Example 17 EA 18, DGBE 60.99, Xylitol 1 PAA (Mw 3,000) 0.01 20 45 15 Example 18 EA 69.5, NMP 28 PEI (Mw 70,000) 0.5 2 20 2 Example 19 MEA 12, HMEA 1, DMAC 46.5, Glucitol 5 PEI (MW 10,000) 0.5 35 60 5 Example 20 PA 12, DGME 70 PAA (Mw 10,000) 2 16 45 6 Example 21 MO 35, DEH 5, DMAC 19.95, PAA (Mw 3,000) 0.05 35 45 17 Comparative Example 4 EA 70, NMP 28-2 20 78 Comparative Example 5 EA 20, DGBE 39, Xylitol 1-20 45 235 * Note EA: Ethanolamine NMP: N-methylpyrrolidone HMEA: N, hydroxymethyl Ethanolamine MEA: methylethanolamine DMAC: dimethylacetamide DGBE: diethylene glycol monobutyl ether PA: 1-amino-2-acetone-20-593224 5. Description of the invention (19) DGME: diethylene glycol Alcohol M0 :? DEH ·· Diethylhydroxylamine EDA: Ethylenediamine PEI (Mw 10,000): Polyethylenediimine (average molecular weight: 10,000) PEI (Mw 1,800): Polyethyleneimine (average Molecular weight: 1,800) PEI (Mw 3,000): Polyethyleneimine (average molecular weight: 3,000) PEI (Mw 70,000): Polyethyleneimine (average molecular weight: 70,000) PAA (Mw 10,000): Polyallylamine ( Average molecular weight: 10,000) PAA (Mw 3,000): Polyallylamine (average molecular weight: 3,000) NMP: N-methyl? Pyrrolidone PG: propylene glycol The effects of the present invention are summarized. The photoresist removal liquid composition of the present invention can be used to remove the photoresist in a short time without corroding the wiring material, especially silicon. More specifically, when using the liquid composition for photoresist removal of the present invention, it can effectively prevent silicon corrosion and can be removed from a silicon-containing substrate regardless of the silicon type (such as bare silicon, amorphous silicon, and polysilicon). Photoresist without corrosion. Those skilled in the art should further understand that the above description is a preferred specific embodiment of the present invention, and that various changes and modifications can be made in the present invention without departing from the spirit and scope thereof. Comparison table of main components 1 Silicon substrate-21-593224 V. Description of the invention (20) 2 Oxide film 3 Titanium 4 Titanium nitride 5 Wiring 6 Photoresistor 7 Insulating layer 8 Photoresistor 9 Low temperature polysilicon 10 May 12 Glass matrix-22-
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| US7879782B2 (en) | 2005-10-13 | 2011-02-01 | Air Products And Chemicals, Inc. | Aqueous cleaning composition and method for using same |
| KR100718527B1 (en) * | 2006-04-12 | 2007-05-16 | 테크노세미켐 주식회사 | Stripper composition for negative photoresist |
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| JP3236220B2 (en) * | 1995-11-13 | 2001-12-10 | 東京応化工業株式会社 | Stripper composition for resist |
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