200919118 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種 本發明係關於一種清洗劑，並且特別地， 用於半導體製造技術之光阻清洗劑。 【先前技術】 -般半導體製造過程雜二氧化砍、銅等金屬以及低 專表面上形成光阻的掩膜，經曝光後利用 导體阳片^技術發展的重要研究方向。在對 ϋ行化學清洗的過㈣，清洗财會對晶片基材，^是 基^ ’造成嚴㈣顧，因此將導致晶片良麵著降低 開之厚膜光阻清洗劑或多或少地存在清洗效果不佳ΐΐ 片基材腐蝕的問題。 Ν王次日日BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent, and in particular to a photoresist cleaning agent for semiconductor manufacturing technology. [Prior Art] - The general research direction of the development of semiconductors in the semiconductor manufacturing process, such as hetero-diode chopping, copper and other metals, and masks that form photoresist on the surface of the semiconductor. In the chemical cleaning of the ( (4), the cleaning of the financial resources of the wafer substrate, ^ is the base ^ 'caused strict (four) Gu, so will lead to the wafer surface with a reduced thickness of the film photoresist cleaner more or less present Poor cleaning effect 腐蚀 The problem of corrosion of the substrate. King of the next day
專利文獻JP1998239865揭露一種驗性清洗劑，包含 ，錄σ讀)、二碰_0)、π二甲1基上; 50〜⑽。C下除去金屬以及電介質基材上之以上 =。该清洗劑之較高的操作溫度會造成半導體晶絲材韻， 並且無法完全去除半導體晶片上之光阻，其清洗能力不足 _ ，獻US5529887揭露一種驗性清洗劑，包含氫氧化钾、 =基二醇單烧基_、水溶性氟化物以及水。其使用方法係將晶片 浸入該清洗劑中，在4〇〜9〇t：下除去金屬以及電介質基材上^尸 膜光阻。該清洗液對半導體晶片基材的腐蝕性較高。 予 專利文獻US5962197揭露一種驗性清洗劑’包含氫氧化_、 200919118 N-甲基吡咯烷酮_p)、丙二醇醚、水以及表面活性劑。其 將晶片浸入該清洗劑中’纟1〇5t下除去金眉以及電介質 的厚膜光阻。由於該清洗液使用溫度較高，導致半導體晶 月暴材的腐邊虫。 US2G_25976以及w〇細113486揭露一種驗性 A二受tf銨氫氧化物、水溶性有機溶劑、水、緩蝕劑以及 ^小於的氯氧化卸。其使用方法係在20〜机 下將曰曰片次入該清洗劑中，以除去金屬以及電介 光阻。該清洗液對厚膜光阻，特別是厚膜負光阻之i洗能“ 四氫獻種驗性清洗劑’包含氫氧化_、 膜光阻。該清洗液對半辦日H = 以及電4基材上的厚 全去除半賴則的略高’並且無法完 【發明内容】 餘性膜供清洗效果較佳’並且對基材腐 清洗劑清洗絲不錢縣洗雜中之現有 醇及氫氧化鉀、苯甲Patent document JP1998239865 discloses an illustrative cleaning agent comprising: recording σ read), two touches _0), π dimethyl 1 group; 50~(10). Remove the metal and the above on the dielectric substrate. The higher operating temperature of the cleaning agent causes the semiconductor crystal wire to be rhyme, and the photoresist on the semiconductor wafer cannot be completely removed, and the cleaning ability thereof is insufficient. U.S. Patent 5,529,887 discloses an anionic cleaning agent comprising potassium hydroxide and a base. A diol monoalkyl group, a water soluble fluoride, and water. The method of use is to immerse the wafer in the cleaning agent, and remove the metal and the photoresist film on the dielectric substrate at 4 〇 to 9 〇t:. The cleaning solution is highly corrosive to the semiconductor wafer substrate. U.S. Patent No. 5,962,197 discloses an exemplary cleaning agent' comprising hydroxide _, 200919118 N-methylpyrrolidone _p), propylene glycol ether, water, and a surfactant. It dipped the wafer into the cleaning agent to remove the golden eyebrow and the thick film photoresist of the dielectric at 纟1〇5t. Due to the high temperature of the cleaning solution, the surface of the semiconductor crystal is a rot. US 2G_25976 and 〇 113 113,486 disclose an oxime-removing of a Tf ammonium hydroxide, a water-soluble organic solvent, water, a corrosion inhibitor, and less than chlorine. The method of use is to remove the ruthenium into the cleaning agent under a 20~ machine to remove metal and dielectric photoresist. The cleaning solution for thick film photoresist, especially the thick film negative photoresist i wash "tetrahydrogen-providing cleaning agent" contains hydroxide _, film photoresist. The cleaning solution for half a day H = and electricity 4 The thickness of the substrate is slightly higher than that of the semi-rear, and it is not complete. [Inventive content] The residual film is better for cleaning effect> and the substrate rot cleaning agent is used to clean the existing alcohol in Potassium hydroxide, benzo
其中，該二甲其π rrT ⑽議，更佳的為〇佳的^質量百分比 含量較佳的為質量百八 95/° ’其中該氫氧化鉀的 1.〇5〜2.5%，·其中該苯^& .0^5%，更佳的為質量百分比 分比1〜3〇%，更佳的為質 H知生物的含量較佳的為質量百 巧貝里百分比5〜20%;其中該季錢氫氧化物 200919118 °·01^ ^ .其中該烷基醇胺的含量較佳的為口晳百八士1 γ0/ s 佳的為品質百分比5〜30%。仙的為叩貝百为比1〜35°/。，更 ^中上笨甲^醇及/或其衍生物較佳的為選自苯甲 苯曱醇、三苯甲醇 醇(ΒΑ) ίWherein, the dimethyl π rrT (10), more preferably 〇 good ^ mass percentage content is preferably one hundred and eighty 95 / ° 'where the potassium hydroxide is 1. 〇 5 ~ 2.5%, · which Benzene ^ & .0 ^ 5%, more preferably a percentage by mass of 1 to 3 〇%, more preferably a content of H known organisms is preferably 5 to 20% by mass of Baiqiao Baili; The season of the hydroxide hydroxide 200919118 ° · 01 ^ ^. The content of the alkyl alcohol amine is preferably phrasing babbles 1 γ0 / s better than the mass percentage of 5 to 30%. The fairy is a mussel for a ratio of 1 to 35 ° /. Further, it is preferably selected from the group consisting of benzhydryl alcohol and triphenylmethanol alcohol (ΒΑ) ί.
L 醇、二甲基笨甲醇、nm氨基苯甲醇、甲基苯甲 或其衍生物能夠在晶片基材矣而二畔^的至乂種。本甲酵 子以及氫離·素原 狀1二1=^_佳的為選自四甲基氮氧化錢、四乙 s二氧四種丁基氣氧化似及节基三甲基 (-ί叫二乙醇胺 胺以及經乙基乙二胺(ΑΕΕΑ)戶斤組成之敎中的甲基乙知 本發明中，該清洗劑進—步包合g ό 表面活性劑以及緩钱劑所組成之群組中的自=少_^:、溶劑、水、 其中，該雜有機赫_含量較 分比50%，更佳的為質量百分比5〜3〇% ;質:百 為小於或等於質量百分比·，更佳的為質量百^匕3〇里=的更佳的為”百纽一其; 於或等於質里百M1G%，更佳的為質量百分比_〜5%。、’，、、 其中，該極性有機共溶劑較佳的為選自 以及炫基二醇單炫基輯組成之群組中的至少 ^垸酮 較佳的為二乙基亞石風或甲乙基亞石風；其中該石風較佳的為^石^風 200919118 =„環丁硬；其中辦姚_較佳的為2_料細、以二 ;其懷基二醇單烧 的為、自乙一知单曱醚、乙二醇單乙醚、乙二醇單丁 =、:乙項單曱_EGME)、二乙二醇單⑽、二乙二醇單丁 ㈣醇早㈣、丙二醇單乙H醇單丁醚、二丙二醇單 甲知、—丙二醇單乙醚以及二丙二醇單丁_組成之群組。 醇rpiH絲面活性劑較佳的為選自聚_酸(嫩）、聚乙烯 烷(POS)所組成之群組中的至少一}種 Ο ' 乙 乙 ㈣魏侧較麵鱗自_、賴以及聚絲醋類緩 烯群組中的f少一種。其中該胺類較佳的為選自二 = )、三乙烯四胺(TETA)、五乙烯六胺(PEHA)、多。 ΪίΪ^ΑΧ)以及氨基乙基孤嘻(AEP)所組成之群組；其中触 的為選自雜二氮唾(BTA)、甲基苯並三氮4(TTA)、苯並 醇胺鹽、1_苯基_5_疏基四氮唾(PMTA)、2_疏基苯並味 (=1)、2-缝苯並嗟唾(MBT)、2_疏基苯並嚼唾_〇)、二魏 j一唑(DMTDA)以及2-氨基-5-巯基],3,㈣二唑(AMTDA)所 获盆組，其巾㈣絲賴較佳的為含羧基㈣己细旨或含 羧基的聚丙交酯。 本發明之厚膜光阻清洗劑藉由上述成分簡單混合即可獲得， =所及補均市售可得。本發日狀光阻清洗劑可在室 j 85 C之範_使用。其具體操作方法包含下述步驟：首先， !。„光阻的半導體晶片浸人清洗劑中；接著，在室溫至 恒溫_器、緩慢振i ;最後，經去離子水洗滌 曰人乾。封洗溫度高於45°c，應先以異丙醇洗滌 晶片再以去離子水洗務。 本毛明之明洗劑可有效除去金屬、金屬合金或電介質基材上 200919118 之wop111以上厚度的光阻以及其它殘留物，π拄掷认卜 銅等金屬以及低k㈣敎以:$留物8時對於二氧化石夕、 二 材科4具有較低的腐谢生，在半導靜日μ 專被電子倾具有良好的應財景。 械阳片 洗 【實施方式】 下面透過具體實施例的方式進一步 將本發明_在所描述的具體實_範财 J，但並不因此 實施例1〜18 照表③阻清洗劑，依 | J獲侍各清洗劑。 膏洗劑實^ij〜T8 C一::L alcohol, dimethyl benzyl alcohol, nm amino benzyl alcohol, methyl benzene or a derivative thereof can be entangled in the wafer substrate. The present invention is as follows: tetramethyl oxynitride, tetraethyl s-diox, tetrabutyl oxy-oxidation, and benzyl-methyl (- a diethanolamine and a methyl group in a hydrazine composed of ethylethylenediamine, in the present invention, the cleaning agent further comprises a group of g ό surfactant and a vaginal agent. In the self = less _ ^:, solvent, water, wherein, the hetero-organic content is 50%, more preferably 5 to 3 % by mass; quality: hundred is less than or equal to the mass percentage, More preferably, it is better for the quality of 100 匕 3 〇 = = "百百一一一; 于 or equal to the quality of 100 M1G%, better for the mass percentage _ ~ 5%., ',,, among them, Preferably, the polar organic co-solvent is at least fluorenone selected from the group consisting of leucodiol monodisperse, preferably diethyl slate or methyl ethyl slate; wherein the stone The wind is better for ^石^风200919118 = „环丁硬; among them, Yao _ is preferably 2_fine, two; its kiwi diol is single-burned, from Yiyi Zhidan, B Glycol monoethyl ether, B Alcohol monobutyl =,: B monoterpene _EGME), diethylene glycol mono (10), diethylene glycol monobutyl (tetra) alcohol early (four), propylene glycol monoethyl H alcohol monobutyl ether, dipropylene glycol monomethyl, propylene glycol A group consisting of diethyl ether and dipropylene glycol monobutyl. The alcohol rpiH silk activator is preferably at least one selected from the group consisting of poly-acid (nen) and polyvinyl alkane (POS), and the E-B (four) Wei side is more than the scale. And one of f in the group of polyketone sulfene. Among them, the amine is preferably selected from the group consisting of di-), triethylenetetramine (TETA), and pentaethylenehexamine (PEHA). ΪίΪ^ΑΧ) and a group consisting of aminoethyl guanidine (AEP); wherein the contact is selected from the group consisting of heterodiazepine (BTA), methylbenzotriazide 4 (TTA), benzoanilide, 1_phenyl_5_carbyltetrazole (PMTA), 2_sulfenylbenzoate (=1), 2-stained benzopyrene (MBT), 2_ thiophene and chewable 〇 , diwei j-azole (DMTDA) and 2-amino-5-mercapto], 3, (tetra) diazole (AMTDA) obtained from the basin, the towel (four) silk is preferably a carboxyl group (four) has a fine purpose or contains a carboxyl group Polylactide. The thick film photoresist cleaning agent of the present invention can be obtained by simply mixing the above components, and is available commercially. The present daytime photoresist cleaning agent can be used in the chamber j 85 C. The specific operation method includes the following steps: First, !. „The photoresist semiconductor wafer is immersed in the cleaning agent; then, at room temperature to constant temperature _, slow vibration i; finally, the dehydrated water is washed by deionized water. The sealing temperature is higher than 45 °c, should be different The propanol washes the wafer and then washes it with deionized water. The present invention can effectively remove the photoresist and other residues of the thickness of wop111 above 200919118 on metal, metal alloy or dielectric substrate, and π 拄 认 认And low k (four) 敎 to: $ 留 8 when there is a lower stagnation for the sulphur dioxide, the second physiology 4, in the semi-conducting static day μ dedicated to electronic tilt has a good financial situation. [Embodiment] Hereinafter, the present invention will be further exemplified in the specific embodiment, but the specific cleaning method described in the first embodiment is not used in the embodiment 1 to 18, and the cleaning agent is treated according to the method. Paste agent ^ij~T8 C one::
200919118 甲醇 氧化錢 石風 5 46.95 1.05 5 對氨基苯 甲醇 2 苄基三曱 基氫氧化 銨 35 甲基二乙 醇胺 10 二乙烯三 胺 10 水 6 43 2 6.5 甲基苯甲 3 四甲基氫 30 二甲基乙 5 甲乙基亞 颯 醇 氧化銨 醇胺 0.1 聚乙烯醇 0.4 三乙烯四 胺 苄基三曱 5 水 二曱基苯 曱醇 0.5 基氫氧化 録 乙基乙 二胺 50 曱基颯 7 40 1.4 1 1 四甲基氫 1 0.05 聚乙烯。比 σ各院酮 氧化敍 0.05 五乙烯六 胺 1 四丙基氮 氧化銨 1 三乙醇胺 30 乙基石風 8 43 3 10 間甲氧基 苯甲醇 1 四丁基氫 氧化銨 1 異丙醇胺 5 聚氧乙烯 0.5 苄基三甲 基氫氧化 4 甲基二乙 醇胺 0.5 多乙烯多 胺 10 200919118 兹 9 35 2 20 對甲氧基 苯曱醇 2.5 四甲基氫 氧化銨 10 一乙醇胺 27 環丁颯 0.5 氨基乙基 °瓜°秦 3 聚矽氧烷 10 50 2 10 苄氧基苯 甲醇 3 四甲基氫 氧化銨 20 三乙醇胺 13 2-咪唑烷 酮 2 苯並三氮 σ全 11 54 1.5 18 二苄氧基 苯曱醇 2 四甲基氫 氧化銨 18 甲基二乙 醇胺 6 1，3-二曱 基-2-咪唑 烷酮 0.5 甲基苯並 三氮唑 12 60 2 1 三苯曱醇 2 四曱基氫 氧化銨 25 二乙醇胺 1 U-二乙 基-2-咪唑 烷酮 1 苄氧基苯 甲醇 5 苯並三氮 。全三乙醇 胺鹽 1 對甲氧基 苯甲醇 2 丙二醇單 乙醚 13 68 2 15 對氨基苯 2 四甲基氫 10 二甲基乙 Ο L·, 乙三醇等， 200919118 醇單曱醚 1-苯基-5- 甲醇 甲基氫氧 化銨 甲基乙醇 胺 0.5 Μ基四氮 σ圭、 0.5 2-Μ基苯 並咪吐 0.5 乙二醇單 乙醚 14 72 2 8 二甲基苯 甲醇 2 四曱基氮 氧化銨 10 異丙醇胺 5 乙二醇單 丁醚 0.5 2-巯基苯 並σ塞吐 1 二乙二醇 單甲醚 15 70 2 間甲氧基 1 四曱基氫 15 一乙醇胺 0.8 2-巯基苯 並°惡。皇 K) 笨甲醇 氧化銨 0.1 聚乙烯吡 °各烧酮 0.1 聚氧乙烯 it 16 69 2 15 甲基苯甲 醇 2 四甲基氬 氧化敍 5 羥乙基乙 二胺 6 二乙二醇 單丁醚 1 二巯基噻 12 200919118 二吐 17 78 2 2 甲基苯甲 醇 2 四甲基氫 氧化銨 15 一乙醇胺 0.5 二丙二醇 單乙醚 0.5 2-氨基-5-酼基-1,3,4-噻二 σ坐 18 76 1.2 15 甲基苯甲 醇 2 四甲基氫 氧化銨 5 三乙醇胺 0.4 含羧基的 聚己内酯 0.4 含羧基的 聚丙交酯 效果實施例 表2說明對比清洗劑1〜3以及本發明之厚膜光阻清洗劑1〜5 的配方，依照表2所列成分及其含量簡單混合均勻，即可獲得各 清洗劑。 表2對比清洗劑1〜3以及本發明清洗劑1〜5 清 洗 劑 二甲 基亞 石風含 量 wt% 氫氧 化舒 含量 wt% 苯甲醇及/或其 衍生物 季銨氫氧化物 貌基醇胺 其他 含 量 wt % 具體物質 含 量 wt % 具體物質 含 量 wt % 具體物質 含 量 wt % 具體物質 13 200919118 對 比 1 60 / / / 10 四曱基氫 氧化銨 20 單乙 醇胺 10 水 對 比 2 68 2 / / / / 20 單乙 醇胺 10 水 對 比 3 59.9 0.1 / / 10 四甲基氫 氧化錄 20 單乙 醇胺 10 水 四甲基氫 氧化銨 單乙 醇胺 1 水 1 76.85 1.1 10 苯曱醇 1 10 0.0 5 聚氧乙稀 3 水 2 67.3 1.1 15 苯甲醇 3 四曱基氫 氧化銨 10 二乙 醇胺 0.1 聚氧乙烯 醚 0.5 2-酼基苯 並嗟tr坐 3 62.4 1.5 15 苯甲醇 2 四曱基氫 15 單乙 3 水 氧化銨 醇胺 0.1 聚氧乙烯 醚 0.5 氨基乙基 Ρ瓜嗪 14 200919118 59.9 15 苯甲醇 0.5 四曱基氫 氧化銨 20 58.5 1.2 15 苯甲醇 2200919118 Methanol Oxidation Qianshifeng 5 46.95 1.05 5 p-Aminobenzyl Alcohol 2 Benzyl Tridecyl Ammonium Hydroxide 35 Methyldiethanolamine 10 Diethylene Triamine 10 Water 6 43 2 6.5 Methylbenzene 3 Tetramethyl Hydrogen 30 2 Methyl ethyl 5-methyl decyl alcohol ammonium oxyhydroxide 0.1 polyvinyl alcohol 0.4 triethylene tetramine benzyl triterpene 5 water dimercapto phenyl decyl alcohol 0.5 hydroxy hydroxide ethyl ethyl diamine 50 曱 飒 7 40 1.4 1 1 tetramethylhydrogen 1 0.05 polyethylene. More than σ 院 ketone oxidation 0.05 pentaethylene hexamine 1 tetrapropylammonium oxynitride 1 triethanolamine 30 ethyl stone wind 8 43 3 10 m-methoxybenzyl alcohol 1 tetrabutylammonium hydroxide 1 isopropanolamine 5 poly Oxyethylene 0.5 benzyltrimethylhydroxide 4 methyldiethanolamine 0.5 polyethene polyamine 10 200919118 兹 9 35 2 20 p-methoxybenzoin 2.5 tetramethylammonium hydroxide 10 monoethanolamine 27 cyclobutanthine 0.5 amino Ethyl ° melon ° Qin 3 polyoxane 10 50 2 10 benzyloxybenzyl alcohol 3 tetramethylammonium hydroxide 20 triethanolamine 13 2-imidazolidinone 2 benzotriazole σ all 11 54 1.5 18 dibenzyloxy Benzophenone 2 tetramethylammonium hydroxide 18 methyldiethanolamine 6 1,3-dimercapto-2-imidazolidinone 0.5 methylbenzotriazole 12 60 2 1 triphenyl sterol 2 tetradecyl Ammonium hydroxide 25 Diethanolamine 1 U-Diethyl-2-imidazolidinone 1 Benzyloxybenzyl alcohol 5 Benzotriazole. All-triethanolamine salt 1 p-methoxybenzyl alcohol 2 propylene glycol monoethyl ether 13 68 2 15 p-aminobenzene 2 tetramethylhydrogen 10 dimethyl ethyl hydrazine L ·, ethoxytriol, etc., 200919118 Alcohol monoterpene ether 1-phenyl -5- Methanol methylammonium hydroxide methylethanolamine 0.5 decyl tetrazine σ, 0.5 2-mercaptobenzopyrazine 0.5 ethylene glycol monoethyl ether 14 72 2 8 dimethyl benzyl alcohol 2 tetradecyl oxynitride Ammonium 10 Isopropanolamine 5 Ethylene glycol monobutyl ether 0.5 2-Mercaptobenzo σ sep 1 Diethylene glycol monomethyl ether 15 70 2 m methoxy 1 Tetrahydrogen 15 Monoethanolamine 0.8 2-mercaptobenzene And ° evil.皇K) Stupid methanol ammonium oxide 0.1 Polyvinyl ketone Each ketone 0.1 Polyoxyethylene it 16 69 2 15 Methyl benzyl alcohol 2 Tetramethyl argon oxidation 5 Hydroxyethyl ethylene diamine 6 Diethylene glycol monobutyl ether 1 Dimercaptothiol 12 200919118 Dioxa 17 78 2 2 Methylbenzyl alcohol 2 Tetramethylammonium hydroxide 15 Monoethanolamine 0.5 Dipropylene glycol monoethyl ether 0.5 2-Amino-5-mercapto-1,3,4-thiazepine Sitting 18 76 1.2 15 methylbenzyl alcohol 2 tetramethylammonium hydroxide 5 triethanolamine 0.4 carboxyl group-containing polycaprolactone 0.4 carboxyl group-containing polylactide effect example Table 2 illustrates comparative cleaning agents 1 to 3 and the present invention The formula of thick film photoresist cleaning agent 1~5 can be obtained by simply mixing and mixing the ingredients listed in Table 2 and their contents. Table 2 Comparison of cleaning agents 1 to 3 and cleaning agent 1 to 5 of the present invention Cleaning agent dimethyl sulphur content wt% Hydroxide content wt% benzyl alcohol and/or its derivative quaternary ammonium hydroxide phenanthrenylamine Other content wt % Specific substance content wt % Specific substance content wt % Specific substance content wt % Specific substance 13 200919118 Comparison 1 60 / / / 10 Tetramethylammonium hydroxide 20 Monoethanolamine 10 Water contrast 2 68 2 / / / / 20 Monoethanolamine 10 Water Comparison 3 59.9 0.1 / / 10 Tetramethylhydroxide Record 20 Monoethanolamine 10 Water Tetramethylammonium hydroxide Monoethanolamine 1 Water 1 76.85 1.1 10 Benzohydrin 1 10 0.0 5 Polyoxyethylene 3 Water 2 67.3 1.1 15 benzyl alcohol 3 tetradecyl ammonium hydroxide 10 diethanolamine 0.1 polyoxyethylene ether 0.5 2-mercaptobenzopyrene tr sitting 3 62.4 1.5 15 benzyl alcohol 2 tetradecyl hydrogen 15 monoethyl 3 water ammonium oxide alcohol amine 0.1 polyoxyethylene ether 0.5 aminoethyl guanazhuzin 14 200919118 59.9 15 benzyl alcohol 0.5 tetradecyl ammonium hydroxide 20 58.5 1.2 15 benzyl alcohol 2
L 四曱基氫 氧化敍 20 早乙 醇胺 單乙 醇胺 0.5 苯並三氮 口坐 1.5 水 0.1 聚氧乙烯 醚 0.5 2-£t基苯 並噻唑 0.5 笨並三氮 cr圭 2 水 0.1 聚氧乙烯 醚 0.5 2-酿基本 並嗟嗤 0.5 苯並三氮 〇坐 0.2 含羧基的 聚己内酯 洗空之劑1〜3以及本發明清洗劑1〜5使用於清 工麵日日片，並且測疋其對於金屬銅之餘刻速率。測試方法以 及其條件如下··首先’將4x4cm空白鋼晶片浸入清洗劑；接著， 在室溫至85°C之範圍間利用恒溫振盪器緩慢振盪分鐘；然 後’經去離子水洗滌後以高純度氮氣吹乾，若清洗溫度高於 15 200919118 丙醇洗務晶片再以去離子水洗務’·最後，利用四極 二、主=空白銅晶片清洗前後表面電阻的變化，經計算後得到 該洗劑對於金屬銅之钱刻速率，結果如表3所示。 表”，比清洗劑1〜3和本發明清洗劑1〜5使用於清洗 二二卜基魏(TEC>S)晶片，並且測定其對於非金屬TE0S =刻，率。測試方法以及其條件如下：首先，將4χ_空白 ，洗劑;接著’在室溫至85〇c之範圍間利用恒溫 滅3〇分鐘，紐，經絲子水洗滌後以高純度氮 ，洗溫度高於45°c ’先以異丙醇洗務晶片再以去離子 水洗“，最後，利用NanospeC6100測厚儀測定空白TE〇s f 度的㈣，料算得職等清洗麟於非:屬 TEOS之姓刻速率，結果如表3所示。 表3對比清洗劑1〜3以及本發明清洗劑is對金屬$刻速率青洗狀況 清洗劑 清洗溫 度 (°C) 金屬銅的腐 ϋ情況 非金屬 TEOS的腐 蝕情況 光阻清洗 時間 (min) 光阻清洗 效果 晶片圖案的 腐餘情況 對比1 60 嚴重 略有腐触 90 ------ 部分去除 ~~- _ 略有腐蝕 對比2 60 嚴重 嚴重 60 --— 較少殘留 嚴重 對比3 60 嚴重 嚴重 90 — 部分去除 —一 — 略有腐蝕 1 30 良好 良好 75 '—-- 完全去除 良好 2 55 良好 良好 —------------ 45 ^--- 完全去除 良好 3 50 良好 良好 Γ ·— 30 ~~〜丨. 完全去除 良好 4 50 良好 良好 Γ -- 45 ---__ 完全去除 良好 5 85 良好 良好 20 '--*---- 完全去除 —- — 良好 ^ 16 200919118 劑1〜5^於"^^顯7^ ’與對比清洗齊U〜3相比，本發明之清洗 廣，同時對於子今属3具有良好的清洗效果，並且其使用溫度範圍 晶片圖案。、/屬鋼和非金屬TE〇S具有低蝕刻性，因此不損壞 發明具體實施例之詳述，係希望能更加清楚描述本 與精神’而並非以上述所揭露的較佳具體實施例來對 3» L ^彆加以限制。相反地，其目的是希望能涵蓋各種改變 及/、相荨性的安排於本發明所欲申請之專利範圍的範疇内。因 此，本發明所申請之專利範圍的範疇應該根據上述的說明作最寬 廣的解釋，以致使其涵蓋所有可能的改變以及具相等性的安排。、 17 200919118 【圖式簡單說明】 / '、、 【主要元件符號說明】L tetradecyl hydroxide hydrazine 20 early ethanolamine monoethanolamine 0.5 benzotriazine mouth 1.5 water 0.1 polyoxyethylene ether 0.5 2-£t benzothiazole 0.5 benzotriazine cr gui 2 water 0.1 polyoxyethylene ether 0.5 2-brewed basic 嗟嗤0.5 benzotriazole 0.22 carboxy-containing polycaprolactone emptying agent 1~3 and the cleaning agent 1~5 of the invention are used in the clearing surface of the day, and the 疋For the residual rate of metallic copper. The test method and its conditions are as follows: First, '4x4cm blank steel wafer is immersed in the cleaning agent; then, slowly shake the minute with a constant temperature oscillator between room temperature and 85 °C; then 'high purity after washing with deionized water Nitrogen is blown dry, if the cleaning temperature is higher than 15 200919118, the propanol cleaning wafer is washed with deionized water. Finally, the surface resistance of the front and back of the cleaning using the quadrupole and the main = blank copper wafer is calculated, and the lotion is obtained after calculation. The rate of metal copper engraving is shown in Table 3. Table", the cleaning agents 1 to 3 and the cleaning agents 1 to 5 of the present invention were used for cleaning the bismuth-containing (TEC > S) wafer, and the rate was measured for non-metal TEOS = engraving. The test method and its conditions are as follows : First, 4 χ _ blank, lotion; then 'with room temperature to 85 〇 c between the use of constant temperature for 3 〇 minutes, New Zealand, after washing with silk water with high purity nitrogen, wash temperature is higher than 45 ° c 'First wash the wafer with isopropyl alcohol and then wash it with deionized water. Finally, use the NanospeC6100 thickness gauge to measure the blank TE〇sf degree (4). It is expected to be cleaned by the grade: the TEOS surname rate, the result is as follows Table 3 shows. Table 3 Comparison of cleaning agents 1 to 3 and the cleaning agent of the invention is for metal engraving rate, green cleaning condition, cleaning agent cleaning temperature (°C), corrosion of metallic copper, corrosion of non-metallic TEOS, photoresist cleaning time (min) light Resistance to cleaning effect wafer pattern of corrosion comparison 1 60 severely slightly rotted 90 ------ partial removal ~~- _ slightly corroded contrast 2 60 severely severe 60 --- less residual serious contrast 3 60 serious Severe 90 - Partially removed - One - slightly corroded 1 30 Good good 75 '--- Completely removed well 2 55 Good good —------------ 45 ^--- Completely removed well 3 50 Good good Γ · — 30 ~~~丨. Completely removed well 4 50 Good good Γ -- 45 ---__ Completely removed well 5 85 Good good 20 '--*---- Completely removed --- Good ^ 16 200919118 Agent 1~5^ is compared with the comparison cleaning U~3, the cleaning of the invention is wide, and at the same time, it has a good cleaning effect for the subgenus 3, and its use temperature range wafer pattern . , / genus steel and non-metallic TE 〇 S have low etchability, and therefore do not damage the detailed description of the specific embodiments of the invention, it is intended to more clearly describe the present and the spirit of the present invention and not the preferred embodiment disclosed above 3» L ^ Do not limit. On the contrary, the intention is to cover the various modifications and/or the nature of the scope of the invention as claimed. Therefore, the scope of the patented scope of the invention should be construed as broadly construed as the , 17 200919118 [Simple description of the diagram] / ',, [Main component symbol description]