200919119 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㈣於二氧化⑧、銅等金屬以及低k材料 荨，面上形絲關掩膜，曝光制賴核乾式_以進行 形轉移。低溫快速的清洗技術是半導體晶片製造技術發展的重 方向。在對半導體晶片上之光阻進行化學清洗的過程中， 常會對晶絲材，尤其是金屬基材，造成嚴重的雜，因此將 致晶片良率顯著降低。現有技術中已公開之光阻清洗劑或多或少 地存在清洗效果不佳或晶片基材腐蝕的問題。 專利文獻W003104901揭露一種鹼性清洗劑，包含四 氧化銨(TMAH)、環τ石風(SFL)、水以及反-u.環己烧二胺四=酸 (CyDTA)。其使用方法係將晶片浸入該清洗劑中，在5〇〜7〇它下 浸泡20〜30分鐘，以除去金屬以及電介質基材上的光阻。該光阻 清洗劑對半導體晶基材的雜性略高，且清洗能力不足以致於 無法元全去除半導體晶片上之光阻。 ^專利文獻W004059700揭露一種驗性清洗劑，包含四甲基氫 氧化銨(ΤΜΑΗ)、N-曱基嗎啡琳-N-氧化物(MO)、水以及2-窥^笨 並咪唾(MBI)。其使用方法係將晶片浸入該清洗劑中，在下 浸泡15〜60分^|，以除去金屬和電介質基材上的光阻。該清洗劑 的使用溫度較尚，並且其清洗速度相對較慢，因此不利於提高 導體晶片的清洗效率。 ° 專利文獻JP1998239865揭露一種鹼性清洗劑，包含四甲基 200919119 鐵TMAH)、二甲基亞石風_S〇)、I3，·二甲基I咪唑烷酮 Hi及水。其使用方法係將晶片以該清洗劑中，在 阳下除去金屬和電介質基材上的之20叫11以上的厚膜光 阻。該h洗劑之較高的操作溫度會造成铸體晶片基材的雜。 气气㈣01215736揭露一種驗性清洗劑，包含四甲基 =方法係將晶片浸人該清洗劑中，在 阻。歸㈣讀高賴作溫度纽成半導體晶 用方法係將晶片浸入該清洗劑中，(在25’〜二等。其使 片基 的光阻。該清洗劑隨著清洗溫度的升^半導 材的腐钱明顯增強。 开问對早導體日日 【發明内容】 本發明之一範轉在於提供一種既且 對晶片基材具有脑刻性的光阻清^有=2洗功效’同時 之現有清洗料佳輕洗技術t 及二㈣包術醇及/或其衍生物、季錢氧化物以 其中’該μ醇及/或其衍生物的含 〇.1〜98·"%，更佳的為質量百分比5〜50%# j為質量百分比 物的含量較佳的為f量百分比⑽〜15%，^中該季銨氫氧化 0.5〜10% ;其中該二尹基亞礪的 f t為質量百分比 1 〜".98%，更佳的為質量百分比60〜95% 的為質量百分比 200919119 甲醇:、:苯甲:s以物較佳的選自苯wa)、二苯 衍生物能夠少；·種。苯甲醇或其 及氣氧根籽等__，細素原子以 氫氧Ξί^ί=較佳的選巧甲基氯氧化鞍、四乙基 氧化銨所組成之群組中的至少3基⑽化銨以及节基三甲基氫 表面共溶劑、水、 』中量為小於或等於質量百分比 為小於或等於質量百分比:，更：量較佳的 於或等_百分比15%，“為小 f t-^Γ； 畈-丙一醇早乙键以及二丙二醇單丁鍵所級成之群組。 該表面活性劑選自聚丙稀酸(PAA)、聚乙稀醇(pvg)、聚乙婦 200919119 吡咯烷酮(PVP)、聚氧乙烯醚(P〇E)以及聚石夕氧焼(p 群組中的至少一種。 、 其中該缓蝕劑係選自胺類、酚類、唑類、羧酸類、羧酸酯 t聚烧基酯類、多減脂類、酸酐類、膦酸類以及膦酸醋類緩 ，所組成之群組巾的至少—種。其中該胺類較佳的係選自一乙 醇胺(MEA)、二乙醇胺(DEA)、三乙醇胺(TEA)、異丙醇胺、甲基 甲基乙醇胺、經乙基乙二胺(AEEA)以及氨基乙基呱 秦(AEP)所+組成之群組；其中該酚類較佳的為對羥基苯酚、鄰苯 一酚或it苯三酚’·其中該唑類較佳的選自苯並三氮唑(Βτ甲 三氮嗤(ΤΤΑ)、苯並三氮唾三乙醇胺鹽、i·苯基々祕四 =(PMTA)、2_祕苯並料(_、2_祕苯並射(mbt)、2_ =本並^(ΜΒΟ)、二疏基嗟二嗤(DMTDA)以及2_氨基领 唾iAMTDA)戶斤組成之群組；其中該羧酸類較佳的為 本甲酸 '鄰苯二甲酸(PA)、海藻酸或沒食子酸 類較佳的為沒食子酸丙®旨；其中該聚烧基醋 ，幸乂佳的為3祕的聚己内酯或含縣的聚丙錢丨其 較佳的為葡萄糖或動旨；其中該酸酐類較佳“酐、 =酐j來贿絲騎_ ;其巾_麵較佳 T?； Λ ^f(HEDPA) ' 丁烷-1,2,4-三羧酸(PBTCA)。 / * 夂 π，之低·^刻性光阻清洗劑由上述成分簡單混合即可獲 ======^清洗溫度高 並且可 本毛明之低餘刻性光阻清洗劑其使用溫度範圍較大， 200919119 迅速除去金屬、金屬人& +人# 阻以及其他殘留物，^時^於^基材上之以上厚度的光 等具有較低的蝕q 夺十於一氧化矽、銅等金屬以及低k材料 刻速率，在半導體晶片清洗等微電子領域具有ί 【實施方式】 將本體實施例的方式進—步說明本發明，但並不因此 字本lx月限制在所述的實施例範圍之中。 實施例1〜32 表1 «兒月根據本發明之實施例1〜32的低银刻性光阻清洗 劑，依照表中所述之配方將各成分簡單混合均勻，即可獲得各 洗劑。 查丄蝕刻性光阻清洗劑實施例1〜32 實 二甲基 苯甲 醇及/或其衍生物 季銨氫氧化物 其他 施 例 亞碉>含 量wt% 含量 wt% 具體物質 含量 wt% 具體物質 含量 Wt% ~ _ 具體物質 1 1 98.99 苯甲醇 0.01 四甲基氫氧化銨 / / 2 99.98 0.01 苯甲醇 0.01 四甲基氫氧化銨 / / 3 2 2 二苯甲醇 1 四乙基氫氧化銨 95 水 4 75 10 三苯甲醇 5 四丙基氫氧化鍵 10 聚氧乙烯醚 5 1 0.01 鄰氨基苯甲醇 0.01 四丁基氫氧化錢 98.98 —乙基亞爾（ 6 95 1 對氨基笨甲醇 0.5 苄基三曱基氫氧 化銨 3.5 一乙醇胺 7 9.45 —-- 50 . 甲基苯甲醇 15 四甲基氫氧化銨 0.5 水 200919119 10 甲乙基亞砜 0.05 聚乙烯醇 15 二乙醇胺 8 60 1 二曱基苯甲醇 1 苄基三曱基氫氧 化銨 25 水 3 甲基颯 1 四甲基氫氧化敍 4 聚乙烯吡咯烷酮 5 三乙醇胺 9 32.9 10 間甲氧基苯甲醇 2 四丙基氫氧化錢 50 乙基礙 3 四丁基氫氧化銨 0.05 聚丙烯酸 2 苄基三甲基氫氧 化銨 0.05 異丙醇胺 10 44 40 對甲氧基苯甲醇 10 四甲基氫氧化敍 5 環丁砜 1 氨基乙基狐°秦 11 54 30 苄氧基苯曱醇 10 四甲基氫氧化锻 5 2-咪唑烷酮 1 苯並三氮唑 12 14 3 二苄氧基苯甲醇 2 四曱基氫氧化銨 80 1，3-二甲基-2-咪 吐烧酮 1 曱基苯並三氮唑 13 14 2 三苯甲醇 5 四曱基氫氧化敍 70 二乙二醇單曱醚 2 苄氧基苯曱醇 4 苯並三氮唑三乙 醇胺鹽 1 對曱氧基苯曱醇 2 乙二醇單曱醚 14 78 10 對氨基苯曱醇 5 四甲基氫氧化敍 5 乙二醇單乙醚 10 200919119 1 1-苯基-5-疏基四 氮唑 1 2-酼基苯並咪唑 15 89.99 5 二曱基苯甲醇 1 四甲基氫氧化銨 2 乙二醇單丁醚 2 1,3-二乙基-2-p米 唾烧酮 0.1 2-酼基苯並噻唑 16 77 10 間甲氧基苯甲醇 2 四甲基氫氧化銨 4 二乙二醇單乙醚 2 2-酼基苯並噁唑 2 聚乙烯吡咯烷酮 3 聚矽氧烷 17 60 15 甲基苯甲醇 8 四甲基氮氧化銨 15 二乙二醇單丁醚 2 二酼基噻二唑 18 35 30 對甲氧基苯曱醇 10 四甲基氫氧化銨 20 丙二醇單曱醚 5 2-氣基-5-疏基_ 1，3,4-嘆二吐 19 40 10 二甲基苯甲醇 5 四甲基氫氧化銨 40 二丙二醇單乙醚 5 含羧基的聚己内 酯 20 70 5 間甲氧基苯曱醇 5 四曱基氫氧化敍 10 丙二醇單乙醚 10 含羧基的聚丙交 酯 21 70 2 苄氧基苯曱醇 8 四丙基氮氧化敍 15 丙二醇單丁醚 11 200919119 2 曱基二乙醇胺 3 二甲基乙醇胺 22 77 10 對甲氧基苯甲醇 5 苄基三甲基氫氧 化銨 2 二丙二醇單曱醚 2 甲基颯 2 2-咪唑烷酮 2 羥乙基乙二胺 23 74 10 二甲基苯甲醇 3 四乙基氫氧化銨 12 二丙二醇單丁醚 1 對羥基苯酚 24 74 10 三苯甲醇 5 四丁基氫氧化銨 10 乙二醇單曱醚 1 鄰苯二酚 25 81.5 10 對甲氧基苯甲醇 3 四甲基氫氧化銨 5 二乙二醇單甲醚 0.5 沒食子酸 26 69 15 甲基笨曱醇 5 四甲基氫氧化銨 10 乙二醇單乙醚 0.5 笨甲酸 0.5 對氨基苯曱酸 27 85.6 10 間曱氧基苯曱醇 2 四曱基氫氧化錄 2 環丁砜 0.3 鄰苯二甲酸 0.05 馬來酸酐 0.05 連苯三酚 28 34.8 20 苄氧基苯甲醇 10 四甲基氫氧化敍 35 甲基颯 0.1 沒食子酸丙酯 0.1 葡萄糖 29 64.7 10 對氨基苯曱醇 5 四曱基氫氧化銨 20 乙基礙 12 200919119 r 30 74.85 二苯甲醇 31 59.9 三苯甲醇 32 24.85 鄰氨基苯甲酵 0.2 瓊脂 0.1 丙酸酐 四甲基氫氧化銨 10 2-_嗤院酮 0.05 2-膦酸丁烷-1，2,4-三羧酸 0.05 海藻酸 0.05 聚馬來酸酐 四曱基氫氧化銨 25 甲基颯 0.1 1,3-(經乙基）-2,4,6-三膦酸 四曱基氫氧化銨 60 乙二醇單甲醚 0.05 氨基三亞甲基膦 酸 0.05 己酸酐 0.05 2-膦酸丁烧-1，2,4·三羧酸甲 酯 效果實施例BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist cleaning agent for a cleaning agent, and particularly for semiconductor manufacturing technology. [Prior Art] - Semiconductors have been manufactured (4) in metals such as dioxide 8, copper, and low-k materials. The surface is covered with a mask, and the exposure is dried to form a shape. Low-temperature and fast cleaning technology is the focus of semiconductor wafer fabrication technology. In the process of chemically cleaning the photoresist on a semiconductor wafer, the crystal material, especially the metal substrate, is often severely mixed, so that the wafer yield is significantly reduced. The photoresist cleaning agents disclosed in the prior art have more or less problems of poor cleaning or wafer substrate corrosion. Patent document W003104901 discloses an alkaline cleaning agent comprising ammonium tetrachloride (TMAH), ring tauolite (SFL), water and trans-u. cyclohexane diamine tetra-acid (CyDTA). The method of use is to immerse the wafer in the cleaning agent and soak it for 5 to 30 minutes under 5 Torr to 7 Torr to remove the photoresist on the metal and the dielectric substrate. The photoresist cleaner has a slightly higher impurity to the semiconductor crystal substrate, and the cleaning ability is insufficient to completely remove the photoresist on the semiconductor wafer. ^ Patent document W004059700 discloses an illustrative cleaning agent comprising tetramethylammonium hydroxide (ΤΜΑΗ), N-mercapto-morphine-N-oxide (MO), water, and 2-pigmentation (MBI) . The method of use is to immerse the wafer in the cleaning agent and soak it under 15~60 minutes to remove the photoresist on the metal and dielectric substrates. The cleaning agent is used at a relatively high temperature and its cleaning speed is relatively slow, so that it is not advantageous for improving the cleaning efficiency of the conductor wafer. The patent document JP1998239865 discloses an alkaline cleaning agent comprising tetramethyl 200919119 iron TMAH), dimethyl sulfite _S 〇, I3, dimethyl I imidazolidone Hi and water. The method of use is to remove the thick film photoresist of 20 or more on the metal and dielectric substrate from the wafer in the cleaning agent. The higher operating temperatures of the h lotion can cause impurities in the cast wafer substrate. Gas (4) 01215736 discloses an anatary cleaning agent containing tetramethyl = method for immersing the wafer in the cleaning agent. (4) Reading the high temperature temperature of the semiconductor semiconductor method is to immerse the wafer in the cleaning agent, (in 25' ~ second, etc. It makes the base of the photoresist. The cleaning agent rises with the cleaning temperature The rot of the material is obviously enhanced. The problem is that the early conductor is invented. [Inventive content] One aspect of the present invention is to provide a photoresist having a brain engraving effect on a wafer substrate. The existing cleaning materials are light-washing technology t and two (four)-coated alcohols and/or derivatives thereof, and the monoxide oxides are contained therein. The content of the alcohol and/or its derivatives is 〇.1~98·"%, more Preferably, the mass percentage is 5 to 50%, and the content of the mass percentage is preferably a percentage of f (10) to 15%, and the quaternary ammonium hydroxide is 0.5 to 10%; wherein the ft. For mass percentage 1 ~ ".98%, better for mass percentage 60~95% for mass percentage 200919119 methanol:, : benzo: s is preferably selected from benzene wa), diphenyl derivatives can Less; · kind. Benzyl alcohol or its oxygenated seeds, etc. __, fine atomic atoms are hydroxy Ξ ^ 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Ammonium and the tribasic hydrogen surface co-solvent, water, medium amount is less than or equal to the mass percentage is less than or equal to the mass percentage: more: the amount is preferably at or equal to _ percentage 15%, "for small f T-^Γ; a group of 畈-propanol early B bonds and dipropylene glycol monobutyl bond. The surfactant is selected from the group consisting of polyacrylic acid (PAA), polyethylene glycol (pvg), and polyethyl bromide. 200919119 Pyrrolidone (PVP), polyoxyethylene ether (P〇E), and polyoxoquinone (at least one of the group of p.) wherein the corrosion inhibitor is selected from the group consisting of amines, phenols, azoles, and carboxylic acids. a carboxylic acid ester t-polyalkyl ester, a poly-lipid-reducing acid, an acid anhydride, a phosphonic acid, and a phosphonic acid vinegar, at least one of the group towels, wherein the amine is preferably selected from the group consisting of Ethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), isopropanolamine, methylmethylethanolamine, ethylethylenediamine (AEEA), and aminoethylhydrazine (AEP) a group consisting of: wherein the phenol is preferably p-hydroxyphenol, phthalophenone or it quinolol. The azole is preferably selected from the group consisting of benzotriazole (Βτ甲三三 ( ΤΤΑ), benzotriazoletriethanolamine salt, i. phenyl hydrazine secret four = (PMTA), 2 _ benzo benzoate (_, 2 _ benzo benzopyrene (mbt), 2 _ = Ben and ^ (ΜΒΟ a group consisting of disulfide quinone dioxime (DMTDA) and 2 _ amino-negative iAMTDA); wherein the carboxylic acid is preferably a formic acid 'phthalic acid (PA), alginic acid or gluten The acid is preferably a gallic acid C; wherein the polyalkyl vinegar is preferably a polycaprolactone of 3 secrets or a polypropylene ketone containing a county, preferably glucose or a kinetic purpose; Among them, the acid anhydride is preferably "anhydride, = anhydride j to bribe"; its towel surface is preferably T?; Λ ^f (HEDPA) 'butane-1,2,4-tricarboxylic acid (PBTCA). / * 夂π, the low-cut etching resistor can be obtained by simple mixing of the above components. ======^The cleaning temperature is high and the temperature range of the low-resistance photoresist can be used. Larger, 200919119 Quickly remove metal, metal & + people # resistance and other disabilities The light of the above thickness on the substrate has a low etching frequency, and the metal such as cerium oxide, copper, and the like, and the low-k material etch rate, which has ί in the field of microelectronics such as semiconductor wafer cleaning. MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the embodiments of the present invention, but is not limited to the scope of the embodiments described herein. Embodiments 1 to 32 Table 1 «Children's implementation according to the present invention In the low-silver photoresist cleaning agents of Examples 1 to 32, each of the ingredients was simply mixed uniformly according to the formulation described in the table to obtain each lotion.丄 丄 etch resist cleaning agent Examples 1 to 32 dimethyl benzyl benzyl alcohol and / or its derivatives quaternary ammonium hydroxide other examples of arsenic > content wt% content wt% specific substance content wt% specific substance Content Wt% ~ _ Specific substance 1 1 98.99 Benzyl alcohol 0.01 Tetramethylammonium hydroxide / / 2 99.98 0.01 Benzyl alcohol 0.01 Tetramethylammonium hydroxide / / 3 2 2 Diphenylmethanol 1 Tetraethylammonium hydroxide 95 Water 4 75 10 triphenylmethanol 5 tetrapropyl hydroxide bond 10 polyoxyethylene ether 5 1 0.01 o-aminobenzyl alcohol 0.01 tetrabutyl hydroxide money 98.98 - ethyl yar (6 95 1 p-amino benzyl alcohol 0.5 benzyl tri Mercapto ammonium hydroxide 3.5 monoethanolamine 7 9.45 —-- 50. Methylbenzyl alcohol 15 tetramethylammonium hydroxide 0.5 water 200919119 10 methyl ethyl sulfoxide 0.05 polyvinyl alcohol 15 diethanolamine 8 60 1 dimercaptobenzyl alcohol 1 Benzyltrimethylammonium hydroxide 25 water 3 methyl hydrazine 1 tetramethyl hydroxide 4 polyvinylpyrrolidone 5 triethanolamine 9 32.9 10 m methoxy benzyl alcohol 2 tetrapropyl hydroxide 50 thiophene 3 Butyl ammonium hydroxide 0.05 polyacrylic acid 2 benzyl Trimethylammonium hydroxide 0.05 Isopropanolamine 10 44 40 p-Methoxybenzyl alcohol 10 Tetramethyl hydrazide 5 Cyclobutane 1 Aminoethyl fox ° Qin 11 54 30 Benzyloxyphenyl decyl alcohol 10 Tetramethyl hydrogen Oxidized wrought 5 2-imidazolidinone 1 benzotriazole 12 14 3 Dibenzyloxybenzyl alcohol 2 Tetramethylammonium hydroxide 80 1,3-Dimethyl-2-imidolone 1 Mercaptobenzoyl Triazole 13 14 2 Triphenylmethanol 5 Tetramethylhydrazine Hydroxide 70 Diethylene glycol monoterpene ether 2 Benzyloxyphenyl sterol 4 Benzotriazole triethanolamine salt 1 Pair methoxy benzophenone 2 B Glycol monoterpene ether 14 78 10 p-aminophenyl decyl alcohol 5 tetramethyl hydroxide 5 ethylene glycol monoethyl ether 10 200919119 1 1-phenyl-5-mercaptotetrazol 1 2-mercaptobenzimidazole 15 89.99 5 Dimercaptobenzyl alcohol 1 Tetramethylammonium hydroxide 2 Ethylene glycol monobutyl ether 2 1,3-Diethyl-2-p misopropanone 0.1 2-mercaptobenzothiazole 16 77 10 Oxybenzyl alcohol 2 tetramethylammonium hydroxide 4 diethylene glycol monoethyl ether 2 2-mercaptobenzoxazole 2 polyvinylpyrrolidone 3 polyoxyalkylene 17 60 15 methyl benzyl alcohol 8 tetramethylammonium oxynitride 15 diethylene glycol Monobutyl ether 2 Dimercaptothiadiazole 18 35 30 p-methoxyphenyl decyl alcohol 10 tetramethylammonium hydroxide 20 propylene glycol monoterpene ether 5 2- carbyl-5-sulfo _ 1,3,4- sigh Two vomiting 19 40 10 dimethyl benzyl alcohol 5 tetramethylammonium hydroxide 40 dipropylene glycol monoethyl ether 5 carboxyl group-containing polycaprolactone 20 70 5 m-methoxyphenyl decyl alcohol 5 tetradecyl hydroxy hydroxide 10 propylene glycol single Ether 10 Carboxyl-containing polylactide 21 70 2 Benzyloxyphenyl decyl alcohol 8 Tetrapropyl nitroxides 15 Propylene glycol monobutyl ether 11 200919119 2 Mercapto diethanolamine 3 Dimethylethanolamine 22 77 10 p-Methoxy benzyl alcohol 5 benzyltrimethylammonium hydroxide 2 dipropylene glycol monoterpene ether 2 methyl hydrazine 2 2-imidazolidinone 2 hydroxyethyl ethylenediamine 23 74 10 dimethyl benzyl alcohol 3 tetraethyl ammonium hydroxide 12 dipropylene glycol Monobutyl ether 1 p-hydroxyphenol 24 74 10 triphenylmethanol 5 tetrabutylammonium hydroxide 10 ethylene glycol monoterpene ether 1 catechol 25 81.5 10 p-methoxybenzyl alcohol 3 tetramethylammonium hydroxide 5 Ethylene glycol monomethyl ether 0.5 gallic acid 26 69 15 methyl cuminol 5 tetramethylammonium hydroxide 10 ethylene glycol monoethyl ether 0.5 Acid 0.5 p-aminobenzoic acid 27 85.6 10 m-decyloxybenzoate 2 tetradecyl hydroxide 2 sulfolane 0.3 phthalic acid 0.05 maleic anhydride 0.05 pyrogallol 28 34.8 20 benzyloxybenzyl alcohol 10 four Methyl Hydroxide 35 Methyl hydrazine 0.1 Propionate propyl ester 0.1 Glucose 29 64.7 10 p-Aminophenyl decyl alcohol 5 Tetramethyl hydrazide 20 Ethyl block 12 200919119 r 30 74.85 Diphenylmethanol 31 59.9 Trityl methanol 32 24.85 anthranilic acid 0.2 agar 0.1 propionic anhydride tetramethylammonium hydroxide 10 2-_ oxazolone 0.05 2-phosphonic acid butane-1,2,4-tricarboxylic acid 0.05 alginic acid 0.05 polymaleic anhydride Tetramethylammonium hydroxide 25 methyl hydrazine 0.1 1,3-(ethyl)-2,4,6-triphosphonic acid tetradecyl ammonium hydroxide 60 ethylene glycol monomethyl ether 0.05 aminotrimethylene phosphonic acid Example of the effect of 0.05 hexanoic anhydride 0.05 2-phosphonic acid butadiene-1,2,4·tricarboxylate
表2說日腾比赫· 1 i及Ϊ發日狀健雌*阻清洗劑 1〜8的配方，依照表2所列成》及，、含量簡單混合均句，即可择 得各清洗劑。 X 表2對比清洗劑1以及本發明清洗| 4 1〜8 清洗 二甲基 苯甲醇及/或其衍生物 季錄氫氧化物 ~_____、 其他 13 200919119 劑 亞礙含 量wt% 含量 wt% 具體物質 含量 wt% 具體物質 含量 Wt% 具體物質 對比 1 94 / / 1 四曱基氫氧化銨 5 水 1 88 5 苯甲醇 2 四甲基氫氧化铵 5 水 2 82.9 10 苯曱醇 2 四曱基氫氧化敍 5 水 0.1 聚乙烯吡咯烷酮 10 水 3 66.9 10 笨甲醇 2 四曱基氫氧化銨 10 二乙二醇單甲醚 1 一乙醇胺 0.1 聚氧乙烯醚 8 水 4 79.7 10 苯甲醇 2 四曱基氫氧化銨 0.1 聚氧乙烯醚 0.2 鄰苯二甲酸 10 水 5 76.7 10 苯曱醇 3 四曱基氫氧化銨 0.1 聚氧乙烯醚 0.2 苯並三氮唑 10 水 2 一乙醇胺 6 73.7 10 苯曱醇 4 四曱基氫氧化铵 0.2 2-毓基苯並噻 σ坐 0.1 聚氧乙烯醚 7 62.7 13 苯曱醇 5 四甲基氫氧化銨 7 水 14 200919119 0.1 聚乙烯吡咯烷酮 10 一乙醇胺 1 2-M基苯並噻 口坐 1 笨並三氮唑 0.2 含羧基的聚己 内酯 " ~~~~~---- 8 水 0.3 苯並三氮唑 8 66.3 20 苯甲醇 2 四甲基氫氧化錢 0.1 聚乙烯吡咯烷酮 0.3 2-巯基苯並噻 〇坐 3 一乙醇胺 -—-----1Table 2 shows that the formula of Tengbie·1 i and the hair-like female anti-resistance cleaning agent 1~8 can be selected according to the simple and mixed formulas listed in Table 2, and the cleaning agent can be selected. . X Table 2 Comparison of cleaning agent 1 and cleaning of the present invention | 4 1~8 Cleaning of dimethyl benzyl alcohol and/or its derivatives, quaternary hydroxides ~_____, other 13 200919119 agents, hind content, wt%, wt%, specific substances Content wt% Specific substance content Wt% Specific substance comparison 1 94 / / 1 Tetramethylammonium hydroxide 5 Water 1 88 5 Benzyl alcohol 2 Tetramethylammonium hydroxide 5 Water 2 82.9 10 Benzohydrin 2 Tetradecyl hydroxide叙5 water 0.1 polyvinylpyrrolidone 10 water 3 66.9 10 stupid methanol 2 tetradecyl ammonium hydroxide 10 diethylene glycol monomethyl ether 1 monoethanolamine 0.1 polyoxyethylene ether 8 water 4 79.7 10 benzyl alcohol 2 tetradecyl hydroxide Ammonium 0.1 Polyoxyethylene ether 0.2 Phthalic acid 10 Water 5 76.7 10 Benzohydrin 3 Tetramethylammonium hydroxide 0.1 Polyoxyethylene ether 0.2 Benzotriazole 10 Water 2 Monoethanolamine 6 73.7 10 Benzophenone 4 Hydrazine-based ammonium hydroxide 0.2 2-mercaptobenzothiazepine 0.1 polyoxyethylene ether 7 62.7 13 phenyl decyl alcohol 5 tetramethylammonium hydroxide 7 water 14 200919119 0.1 polyvinylpyrrolidone 10 -ethanol 1 2-M-Benzylbenzothiophene 1 stupid and triazole 0.2 carboxyl-containing polycaprolactone" ~~~~~----8 water 03 benzotriazole 8 66.3 20 benzyl alcohol 2 Methyl hydroxide money 0.1 polyvinylpyrrolidone 0.3 2-mercaptobenzothiazepine 3 monoethanolamine------1
*將表2中之對比清洗劑丨以及本發明清洗劑丨〜8使用於清洗 ’並且败其對於金屬銅之_速率。測試方法以 /二如下.首先，將4x4cm空白銅晶片浸入清洗劑；接著， 85°c之範圍間利用恒溫振H緩慢振盡3G分鐘；然 離子水洗滌後以高純度氮4吹乾。若清洗溫度高於 探針儀以ΐ離子觸。最後’利用四極 兮望工白銅日曰片，月洗刖後表面電阻的變化，經計算後得到 料㈣劑對於金屬銅之侧速率，結果如表3所示。曼传 蝕刻速率&且測定其對於非金屬_的 TEOS日η二太 其條件如下：首先，將4χ—空白 日日片汉入>月洗劑，接著，在室溫至坑之範圍間利用恒溫 15 200919119 振盪器緩慢振盛30分鐘；然後’經去離子水洗滌後以高純度氮 氣吹乾。若清洗温度高於45°C ’先以異丙醇洗條晶片再以去離子 水洗務。最後，利用Nanospec6100測厚儀測定空白TE〇s曰片 /月洗荊後TEOS厚度的變化’經计算仔到該等清洗劑對於非金屬 TEOS之蝕刻速率，結果如表3所示。 、’ 表3對比清洗劑1以及本發明的低蝕刻性清洗劑對空白 銅严片以及空白TEOS晶片之蝕刻速^及^阻的清洗二果 清洗 清洗溫度 Cu，触刻速率 TEOS，蝕刻速 光阻清洗時間 光阻清洗 劑 (t) (A/min) 率（A/min) (min) 結果 對比 1 23 12.50 1.65 30 基本完全去除 1 23 0.82 0.12 —-- 30 完全去除 2 23 0.23 0.10 完全去除 3 30 0.86 0.15 25 完全去除 4 45 1.25 0.18 20 完全去除 5 45 1.56 0.21 15 完全去除 6 45 2.30 0.23 -—------ 15 完全去除 7 60 2.68 0.28 10 完全去除 8 85 2,35 ----- 0.32 5 完全去除 神、主it 果顯示’與對比清洗劑1相比，本發日月之低侧 有良好的清洗效力，且對於金屬銅和非金屬 TEOS具有低蝕刻性。 興 發明之i徵鄉!φ實祕’鱗望能更加清楚描述本 ΐϋίίί神’而並非以上述所揭露的較佳具體實施例來對 4月之範’加以限制。相反地，其目的是希望能涵蓋各種改變 200919119 f具相等性的安排於本發明所欲申請之專利範圍的 廣的解釋，以致使其應該根據上述的·作最寬 1卟犯的改變以及具相等性的安排。 200919119 【圖式簡單說明】 無 【主要元件符號說明】* The comparative cleaning agent 表 in Table 2 and the cleaning agent 丨 8 of the present invention were used for cleaning and defeated the rate of metal copper. The test method was as follows. First, a 4x4 cm blank copper wafer was immersed in a cleaning agent; then, a temperature of 85 ° C was used to slowly excite for 3 G minutes using a constant temperature vibration H; after washing with ionized water, it was blown dry with high purity nitrogen 4. If the cleaning temperature is higher than the probe, the ion is touched. Finally, using the four-pole 兮 白 白 白 白 , , , , , , , 白 白 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用The etch rate & and the TEOS η η for the non-metal _ is too low. The conditions are as follows: First, 4 χ - blank day slabs into the > month lotion, then, between room temperature and pit range The oscillator was shaken slowly for 30 minutes using a constant temperature 15 200919119; then it was washed with deionized water and dried with high purity nitrogen. If the cleaning temperature is higher than 45 ° C, the wafer is first washed with isopropyl alcohol and then washed with deionized water. Finally, the change in TEOS thickness after blank TE〇s/wet washing was measured using a Nanospec 6100 thickness gauge. The etching rate of the cleaning agent to the non-metallic TEOS was calculated. The results are shown in Table 3. 'Table 3 compares the cleaning agent 1 and the low etching cleaning agent of the present invention to the blank copper plate and the blank TEOS wafer. The etching speed and the resistance of the cleaning are cleaned by the cleaning temperature Cu, the etch rate TEOS, the etching speed Resistance cleaning time photoresist cleaner (t) (A/min) rate (A/min) (min) Result comparison 1 23 12.50 1.65 30 Basic complete removal 1 23 0.82 0.12 —-- 30 Complete removal 2 23 0.23 0.10 Complete removal 3 30 0.86 0.15 25 Complete removal 4 45 1.25 0.18 20 Complete removal 5 45 1.56 0.21 15 Complete removal 6 45 2.30 0.23 -------- 15 Complete removal 7 60 2.68 0.28 10 Complete removal 8 85 2,35 -- --- 0.32 5 Complete removal of God, the main result shows that 'the lower side of the hair has a good cleaning efficiency compared to the comparative cleaning agent 1, and has low etching properties for metallic copper and non-metallic TEOS. I am invented by I, and I am not able to limit the scope of April by the preferred embodiment disclosed above. Rather, its purpose is to cover a broad interpretation of the scope of the invention as claimed in the present invention, so that it should be based on the above-mentioned changes and Arrangement of equality. 200919119 [Simple description of the diagram] None [Key component symbol description]