200923077 九、發明說明： 【發明所屬之技術領域】 並且特別地，本發明係關於 阻之清洗液。200923077 IX. Description of the invention: [Technical field to which the invention pertains] And in particular, the present invention relates to a cleaning liquid for resisting.
本發明係關於一種清洗液， 低Ί虫刻性並能適用於清洗較厚光 【先前技術】 Ο 1 ^ ^ 式刻姓進行_轉移。在/ f光後彻濕式或乾 :去 形 要去除，但由於該光阻較厚，完全去 而 方法是採用延長浸泡時間、提高i泡溫度和採 腐二ίϊ導ίί方法常會造成晶片基材的腐飯和微球的 腐餘進而‘致日日片良率的顯著降低。 此’這:問題亟待解決。於專利文獻w〇2〇〇6/〇5 二利=，氫氧化銨(難H)、二甲基亞 Γ^ίΓί^Τ f 50"00 m甘 ^ 扪用卞基二曱基虱氧化銨(BTMAH)、N- …、乙二醇、腐钱抑制劑、表面活性劑以及穩 疋別組成’用於清洗厚的負 g US_0117中，利用四甲基氫氧化銨、二甲基亞砜 =唾烧啡Μίμχ及水雜錢性清洗劑，將晶#置入該清洗 =阻於賴t下除去金屬和電介質基材上的2啊以上之厚 於專利文獻US5%2197中，利用丙二義、σ比洛烧酮、魏 化_(1观）、表面利蝴以及微量的水喊祕清洗劑，〗以清 200923077 【發明内容】 本發明 阻之清洗魏侧性並細料洗較厚光 胺。 /、 3辽虱化鉀、二甲基亞砜、苯甲醇以及乙醇 至的的含量的是品質百分比0.1% 人旦私/+ 、 口口貝百刀比〇」％至3%，·所述的二甲灵g磁的 ====至嶋，更佳的是^百分比 鄕更H，fi的^義含餘佳的是品質百分比1%至 佳的是百分比1%至Μ %;所述的乙_的含量較 Γ 分比αΐ%至5G%，更佳的是品質百分比G.5%至30 本毛月之，月洗液進一步包含金屬緩姓。 0%, 1〇〇/0, 本發明中，所述的金屬缓蝕劑較佳的選自由酚類、 綾酸、羧 酸酯類 、2-騎基苯並噻唑類、苯並三氮 及膦酸酯類緩蝕劑所組成之群組。 、_ - ” 3者膦酸以 其中，上述之紛類較佳的為笨紛、1 2_ __ 2=苯;盼以魏、?，触=酸： 沒食子酸或沒ίΐί丙:;甲:述二::佳 酐馬聚馬來酸酐；上述之魏、她旨類較佳^ = (技乙基)-2,4,6调酸。其中，較佳的金屬緩_為笨^三氮唾 200923077 (BTA)和2-巯基苯並噻唑(MBT)。 本發明之清洗液，H由上述成分簡單柄混合即可獲得。 ，較於先前，，本發明之低侧性較厚細清洗 细作可作為溶綱溶解氫氧化鉀，同時對金屬 的保護作用，·乙醇胺可在對金屬微球和金屬微球下面的 護臈’進而降低基材的賴。本發明的清洗 H = 屬、金屬合金或電介質基材上的練和直他殘 ，，尤其_較厚(厚度大於⑽微米)光_清洗了同日^ 對於銅等金屬具她_侧速率，在半報⑼清洗等微電子 領域具有良好的應用前景。 ·' 關於本發明之優點與精神可以藉由以下的發明詳述 步的瞭解。 【實施方式】 下面通過實施例的方式進一步說明本發明，並不因此將本發 明限制在所述的實施例範圍之中。 實施例1〜19低钱刻性較厚光阻清洗液 於表1中標示實施例1〜19之低蝕刻性較厚光阻清洗 液的組成配方，按照表1之配方簡單均勻混合各成分即可 獲得此清洗液。 兔厚光阻清洗液實施例1〜19 I 實施例 氫氧化鉀 二甲基亞砜 笨甲醇 乙醇胺 金屬緩腐劑 wt% wt% I wt% wt% wt% 具體物質 200923077The invention relates to a cleaning liquid, low mites and can be used for cleaning thicker light [Prior Art] Ο 1 ^ ^ type _ transfer. After /f light, it is wet or dry: the shape is removed, but because the photoresist is thicker, the method is to use the extended soaking time, increase the i-bubble temperature and the method of etching. The rot of rice and the rot of the microspheres in turn led to a significant reduction in the yield of the sun. This 'this: the problem needs to be solved. In the patent document w〇2〇〇6/〇5 二利=, ammonium hydroxide (difficult H), dimethyl hydrazine ^ Γ Τ Τ Τ f 50 " 00 m 甘 ^ 卞 卞 曱 曱 虱 虱 虱(BTMAH), N-..., ethylene glycol, rot, inhibitor, surfactant, and stable composition 'used in cleaning thick negative g US_0117, using tetramethylammonium hydroxide, dimethyl sulfoxide = Saliva Μμμχ and water miscellaneous cleaning agent, put crystal # into the cleaning = resisting the 赖t to remove the metal and dielectric substrate 2 ah or more thicker than the patent document US 5% 2197, using Bingyiyi , σ piroxime, Weihua _ (1 view), surface blemishes and traces of water shouting secret cleaning agent, 〗 〖Qing Qing 200923077 [Invention] The invention prevents the cleaning of the Wei side and the fine material wash thicker light amine. /, 3 content of potassium, dimethyl sulfoxide, benzyl alcohol and ethanol to the content of the quality of 0.1% of the human private / +, mouth Bai Bai knife than 〇 "% to 3%, · said The dimethyl sulphide g magnetic ==== to 嶋, more preferably ^ 鄕 鄕 H, fi 义 含 是 是 是 是 是 是 品质 品质 品质 品质 品质 品质 品质 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; The content of B_ is more than αΐ% to 5G%, and more preferably the percentage of quality is G.5% to 30% of the month. The monthly lotion further contains a metal slow surname. 0%, 1〇〇/0, in the present invention, the metal corrosion inhibitor is preferably selected from the group consisting of phenols, citric acid, carboxylic acid esters, 2-radylbenzothiazoles, benzotriazoles and A group consisting of phosphonate inhibitors. , _ - ” 3 of the phosphonic acid, among which the above-mentioned varieties are better, idiot, 1 2_ __ 2 = benzene; hope to Wei,?, touch = acid: gallic acid or no ΐ 丙 :: A :Section 2:: Jia anhydride male poly maleic anhydride; the above-mentioned Wei, her purpose class is better ^ = (technical ethyl)-2,4,6 acid adjustment. Among them, the preferred metal slow _ is stupid ^ three Nitrogen saliva 200923077 (BTA) and 2-mercaptobenzothiazole (MBT). The cleaning solution of the present invention, H is obtained by simple stalk mixing of the above components. Compared with the prior art, the low side of the present invention is thick and fine. It can be used as a solute to dissolve potassium hydroxide and protect the metal at the same time. · Ethanolamine can protect the substrate from the underside of the metal microspheres and the metal microspheres. The cleaning of the present invention H = genus, metal On the alloy or dielectric substrate, the practice and straightness, especially _ thicker (thickness greater than (10) micron) light _ cleaning the same day ^ for copper and other metals with her _ side rate, in the semi-report (9) cleaning and other microelectronics field Good application prospects. 'The advantages and spirit of the present invention can be understood by the following detailed description of the invention. The present invention is further described by way of example, and is not intended to limit the invention to the scope of the embodiments described herein. Examples 1 to 19 low-light-etching thick photoresist cleaning liquids are shown in Table 1 in Example 1~ The composition of the low-etching thicker photoresist cleaning liquid of 19 can be obtained by simply and uniformly mixing the components according to the formula of Table 1. Rabbit thick photoresist cleaning liquid Examples 1 to 19 I Example potassium hydroxide II Methyl sulfoxide stupid methanol ethanolamine metal retarder wt% wt% I wt% wt% wt% specific substance 200923077
1 0.1 98.8 1 0.1 \ \ 2 10 20 50 15 5 1,2-二羥基笨酚 3 0.1 20 19.9 50 10 苯並三氮唑 4 1 71 21 5.5 L5 對羥基苯酚 5 0.2 98.4 1 0.2 0.2 對氨基苯甲酸 6 7 34 40 13 6 苯甲酸 7 3 39 20 30 8 連苯三酚 8 1 50 30 18 1 對氨基苯甲酸甲酯 9 1.6 68.3 15 15 0.1 鄰苯二甲酸 10 0.8 69.1 20 10 0,1 鄰苯二甲酸甲酯 11 2 70 20 7.5 0.5 沒食子酸 12 0.5 86.4 10 3 0.1 沒食子酸丙酯 13 0.5 93.3 5 0.5 0.7 乙酸酐 14 1.5 78.4 10 10 0.1 己酸酐 15 1.5 78.4 10 10 0.1 馬來酸酐 2009230771 0.1 98.8 1 0.1 \ \ 2 10 20 50 15 5 1,2-dihydroxyindophenol 3 0.1 20 19.9 50 10 benzotriazole 4 1 71 21 5.5 L5 p-hydroxyphenol 5 0.2 98.4 1 0.2 0.2 p-aminobenzene Formic acid 6 7 34 40 13 6 Benzoic acid 7 3 39 20 30 8 Pyrogallol 8 1 50 30 18 1 Methylparaben 9 1.6 68.3 15 15 0.1 Phthalic acid 10 0.8 69.1 20 10 0,1 Methyl phthalate 11 2 70 20 7.5 0.5 Gallic acid 12 0.5 86.4 10 3 0.1 Propionate gallate 13 0.5 93.3 5 0.5 0.7 Acetic anhydride 14 1.5 78.4 10 10 0.1 Hexanoic anhydride 15 1.5 78.4 10 10 0.1 Horse Anhydride 200923077
ί)ί)
表2標示了對比清洗液1〜2以及渣、味 次〜先液1〜4的成分和含量 表2 對比清洗液1〜2和洛冰达ί , 清洗液 氫氧化鉀 wt% 二甲亞石 wt% 對比1 1 99 對比2 1 91 1 1 85 2 1 80 3 1 83 4 2 62 笨甲醇 Wt% \ 8 12 7 20 乙醇胺 wt% \ 緩飯劑 8 15 笨並三氮嗤 2-毓基笨並噻唑 主依恥表2的配方，將各成分均勻混合以獲得各清洗液。對比 =^液1無法幵>成均勻的溶液，說明了氳氧化鉀在二甲亞礙中的 浴解度較小。對比清洗液2則說明了加入苯曱醇能提高氫氧化鉀 在溶液中的溶解度，能形成均勻的溶液。 將包含厚度為120um之光阻的半導體晶片分別浸入，」比清洗 200923077 液2和清洗液κ4浸泡，之後取出 件及測定出各清洗液的清洗效果如表3所示祕下人乾實_ 清洗效果 清洗液Table 2 shows the composition and content of the comparative cleaning solution 1~2 and the slag, the taste times ~ the first liquid 1~4. Table 2 Comparison cleaning liquid 1~2 and Luo Bingda, cleaning liquid potassium hydroxide wt% dimethyl sulphite Wt% Comparison 1 1 99 Comparison 2 1 91 1 1 85 2 1 80 3 1 83 4 2 62 Stupid methanol Wt% \ 8 12 7 20 Ethanolamine wt% \ Slowing rice 8 15 Stupid and triazine 嗤 2-毓 base stupid The thiazole was mainly formulated according to the formula of Table 2, and the ingredients were uniformly mixed to obtain each cleaning liquid. Contrast = ^ liquid 1 can not be 幵 > into a uniform solution, indicating that the potassium bromide in the dimethyl sulphate bath solution is less. Comparing the cleaning solution 2 shows that the addition of phenylhydroxide can increase the solubility of potassium hydroxide in the solution and form a uniform solution. The semiconductor wafer containing the photoresist having a thickness of 120 um is immersed separately, and is immersed in the cleaning liquid 2 and the cleaning liquid κ4, and then the parts are taken out and the cleaning effect of each cleaning liquid is determined as shown in Table 3. Effect cleaning solution
清洗溫度/°C 清洗時間/min 光阻去除效果 銅的腐蝕情況 金屬微球腐蝕情況 對比2 65 120 完全去除 受到抑制 有腐餘 65 完全去除 觉到抑制，略差 於對比清洗液2 受到抑制Cleaning temperature / °C Cleaning time / min Photoresist removal effect Copper corrosion Corrosion of metal microspheres Comparison 2 65 120 Complete removal Suppressed Corrosion 65 Complete removal Suppression is suppressed, slightly worse than Contrast cleaning solution 2 Suppressed
由表3可以看出，在存在氫氧 下(如對比清洗液2所示），對金屬微球的腐乙力醇^情況 後(如清洗液W所示），金屬微 重。加入乙醇胺 明乙醇胺對金屬微球具有腐咖作用制产 銅金屬的雜加大(如清洗液！所 ；加人會弓丨起 以及苯甲醇的用量上作適當平衡(如清洗液二=)化鉀、乙醇胺 綜上所述，本發明之低綱性較厚光 於100微米)光阻有顯著的清洗效果，且 / /乂厚(厚度大 用；對金屬微球具有明顯的腐蝕抑制作用:屬銅有較好的保護作 本發明所使用的原料和試劑均為市售產品。 藉由以上較佳具體實_之料， 主此更加清楚描述本 200923077 ί 二月之特徵/、精神，而並非以上述所揭露的較佳具體實 本發明之範_加以限制。相反地，其目的是希望能喊各種改^ 及具相等性的安排於本發明所欲申請之專利範圍的範疇内。g 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。 11 200923077 【圖式簡單說明】 無 【主要元件符號說明】It can be seen from Table 3 that in the presence of hydrogen and oxygen (as shown by the comparative cleaning solution 2), the metal microspheres are slightly heavier after the corrosion of the metal microspheres (as indicated by the cleaning solution W). Adding ethanolamine and ethanolamine to the metal microspheres has the effect of rotting coffee to produce copper metal (such as cleaning solution! Addition of people will bow up and the appropriate amount of benzyl alcohol (such as cleaning solution 2 =) In view of potassium and ethanolamine, the low-profile and thicker light of the present invention has a significant cleaning effect on the photoresist, and//the thickness is large (the thickness is large; the metal microsphere has obvious corrosion inhibition effect: Copper is better protected. The raw materials and reagents used in the present invention are all commercially available products. With the above preferred materials, the characteristics and spirit of this 200923077 ί February are more clearly described. It is not intended to limit the scope of the invention as disclosed in the foregoing. The purpose of the invention is to limit the various modifications and equivalents to the scope of the claimed invention. Therefore, the scope of the patent application scope of the present invention should be construed broadly so that it may be construed in the light of the description of the invention. Piece Legend]