CN101187788A - 低蚀刻性较厚光刻胶清洗液 - Google Patents
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Classifications
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
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- G—PHYSICS
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- 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
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- 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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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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Abstract
本发明公开了一种低蚀刻性的适用于清洗较厚光刻胶的清洗液，其特征是含有氢氧化钾、二甲基亚砜、苯甲醇和乙醇胺。本发明的清洗液可以用于除去金属、金属合金或电介质基材上的光刻胶(光阻)和其它残留物，尤其适用于较厚(厚度大于100微米)光刻胶的清洗，同时对于Cu(铜)等金属具有较低的蚀刻速率，在半导体晶片清洗等微电子领域具有良好的应用前景。
Description
技术领域
本发明涉及一种低蚀刻性的适用于清洗较厚光刻胶的清洗液。
背景技术
在通常的半导体制造工艺中，通过在二氧化硅、Cu(铜)等金属以及低k材料等表面上形成光刻胶的掩膜，曝光后利用湿法或干法刻蚀进行图形转移。在晶圆微球植入工艺(bumping technology)中，也需要光阻材料(光刻胶)形成掩膜，该掩膜在微球成功植入后同样需要去除，但由于该光刻胶较厚，完全去除常较为困难。改善去除效果较为常用的方法是采用延长浸泡时间、提高浸泡温度和采用更富有攻击性的溶液，但这常会造成晶片基材的腐蚀和微球的腐蚀，从而导致晶片良率的显著降低。
因此，这一问题亟待解决。专利文献WO2006/056298A1利用由四甲基氢氧化铵(TMAH)、二甲基亚砜(DMSO)，乙二醇(EG)和水组成碱性清洗剂，用于清洗50～100微米厚的光刻胶，同时对金属铜基本无腐蚀。专利文献US2204/0074519A1利用由苄基三甲基氢氧化铵(BTMAH)、N-甲基吡咯烷酮(NMP)、乙二醇(EG)、腐蚀抑制剂、表面活性剂和稳定剂组成碱性清洗剂，用于清洗厚的负性光刻胶。专利文献US6040117利用由TMAH、二甲基亚砜(DMSO)、1，3’-二甲基-2-咪唑烷酮(DMI)和水等组成碱性清洗剂，将晶片进入该清洗剂中，于50～100℃下除去金属和电介质基材上的20μm以上的厚膜光刻胶。
US5962197利用丙二醇醚、吡咯烷酮、KOH和表面活性剂及微量的水组成碱性清洗剂用于清洗光刻胶。US5529887利用二乙二醇单烷基醚、乙二醇单烷基醚，碱金属氢氧化物和水及水溶性氟化物组成碱性清洗剂用于清洗光刻胶。
发明内容
本发明的目的是公开一种低蚀刻性的适用于清洗较厚光刻胶的清洗液。
本发明的清洗液，其特征是含有氢氧化钾、二甲基亚砜、苯甲醇和乙醇胺。
本发明中，所述的氢氧化钾的含量较佳的是质量百分比0.1-10％，更佳的是质量百分比0.1-3％；所述的二甲基亚砜的含量较佳的是质量百分比20-98.8％，更佳的是质量百分比50-98.4％；所述的苯甲醇的含量较佳的是质量百分比1-50％，更佳的是质量百分比1-30％；所述的乙醇胺的含量较佳的是质量百分比0.1-50％，更佳的是质量百分比0.5-30％。
本发明中，所述的清洗液还可含有金属缓蚀剂。所述的金属缓蚀剂的含量较佳的是质量百分比0-10％，更佳的是质量百分比0-3％。
本发明中，所述的金属缓蚀剂较佳的选自酚类，羧酸、羧酸酯类，2-巰基苯并噻唑类，苯并三氮唑类，酸酐类或膦酸、膦酸酯类缓蚀剂。
其中，所述的酚类较佳的为苯酚、1，2-二羟基苯酚、对羟基苯酚或连苯三酚；所述的羧酸、羧酸酯类较佳的为苯甲酸、对氨基苯甲酸、对氨基苯甲酸甲酯、邻苯二甲酸、邻苯二甲酸甲酯、没食子酸或没食子酸丙酯；所述的酸酐类较佳的为乙酸酐、己酸酐马来酸酐或聚马来酸酐；所述的磷酸、磷酸酯类较佳的为1，3-(羟乙基)-2，4，6-三膦酸。其中，优选的金属缓蚀剂为苯并三氮唑(BTA)和2-巰基苯并噻唑(MBT)。
本发明的清洗液由上面所述组分简单均匀混合即可制得。
本发明的积极进步效果在于：本发明的低蚀刻性较厚光刻胶清洗液含有苯甲醇和乙醇胺。苯甲醇可作为溶剂溶解氢氧化钾，同时对金属铜有较好的保护作用；乙醇胺可在对金属微球和金属微球下面的金属(UBM)表面形成一层保护膜，从而降低基材的腐蚀。本发明的清洗液可以用于除去金属、金属合金或电介质基材上的光刻胶(光阻)和其它残留物，尤其适用于较厚(厚度大于100微米)光刻胶的清洗，同时对于Cu(铜)等金属具有较低的蚀刻速率，在半导体晶片清洗等微电子领域具有良好的应用前景。
具体实施方式
下面通过实施例的方式进一步说明本发明，并不因此将本发明限制在所述的实施例范围之中。
实施例1～19低蚀刻性较厚光刻胶清洗液
表1给出了低蚀刻性较厚光刻胶清洗液实施例1～19的组成配方，按表中配方简单均匀混合各组分即可制得清洗液。
表1低蚀刻性较厚光刻胶清洗液实施例1～19
效果实施例1
表2给出了对比清洗液1～2和清洗液1～4的组分和含量。
表2 对比清洗液1～2和清洗液1～4的组分和含量
按表2的配方，将各组分均匀混合制得各清洗液。对比清洗液1不能形成均匀的溶液，说明KOH在二甲亚砜中的溶解度较小。对比清洗液2表明，加入苯甲醇能提高KOH在体系中的溶解度，能形成均匀的溶液。
将含有厚度为120um的光刻胶的半导体晶片分别浸入对比清洗液2和清洗液1～4浸泡之后，取出在高纯氮气下吹干。实验条件及测定的各清洗液的清洗效果如表3所示。
表3对比清洗液2和清洗液1～4对晶圆的清洗效果
| 清洗液 | 清洗温度/℃ | 清洗时间/min | 光刻胶去除效果 | 铜的腐蚀情况 | 金属微球腐蚀情况 |
| 对比2 | 65 | 120 | 完全去除 | 受到抑制 | 有腐蚀 |
| 1 | 65 | 120 | 完全去除 | 受到抑制，略差于对比清洗液2 | 受到抑制 |
| 2 | 65 | 120 | 完全去除 | 受到抑制 | 受到抑制 |
| 3 | 65 | 120 | 完全去除 | 进一步受到抑制 | 受到抑制 |
| 4 | 45 | 120 | 完全去除 | 进一步受到抑制 | 受到抑制 |
由表3可以看出，在碱(氢氧化钾)的存在下，未加入乙醇胺的情况下，金属微球的腐蚀较重(对比清洗液2)。加入乙醇胺后，金属微球腐蚀情况明显得到抑制(清洗液1～4)。这表明乙醇胺对金属微球具有腐蚀抑制作用。但乙醇胺的加入会引起Cu的腐蚀的加大(清洗液1)，故需在KOH、乙醇胺与苯甲醇的用量上作适当平衡(清洗液2～3)。
综上所述，本发明的低蚀刻性较厚光刻胶清洗液对较厚(厚度大于100微米)光刻胶有显著的清洗效果，且对金属铜有较好的保护作用；对金属微球具有明显的腐蚀抑制作用。
本发明所使用的原料和试剂均为市售产品。
Claims (17)
1.一种低蚀刻性较厚光刻胶清洗液，其特征是含有氢氧化钾、二甲基亚砜、苯甲醇和乙醇胺。
2.根据权利要求1所述的清洗液，其特征在于：所述的氢氧化钾的含量是质量百分比0.1-10％。
3.根据权利要求2所述的清洗液，其特征在于：所述的氢氧化钾的含量是质量百分比0.1-3％。
4.根据权利要求1所述的清洗液，其特征在于：所述的二甲基亚砜的含量是质量百分比20-98.8％。
5.根据权利要求4所述的清洗液，其特征在于：所述的二甲基亚砜的含量是质量百分比50-98.4％。
6.根据权利要求1所述的清洗液，其特征在于：所述的苯甲醇的含量是质量百分比1-50％。
7.根据权利要求6所述的清洗液，其特征在于：所述的苯甲醇的含量是质量百分比1-30％。
8.根据权利要求1所述的清洗液，其特征在于：所述的乙醇胺的含量是质量百分比0.1-50％。
9.根据权利要求8所述的清洗液，其特征在于：所述的乙醇胺的含量是质量百分比0.5-30％。
10.根据权利要求1所述的清洗液，其特征在于：所述的清洗液还含有金属缓蚀剂。
11.根据权利要求10所述的清洗液，其特征在于：所述的金属缓蚀剂的含量为质量百分比0-10％。
12.根据权利要求11所述的清洗液，其特征在于：所述的金属缓蚀剂的含量为质量百分比0-3％。
13.根据权利要求10所述的清洗液，其特征在于：所述的金属缓蚀剂选自酚类，羧酸、羧酸酯类，2-巰基苯并噻唑类，苯并三氮唑类，酸酐类或膦酸、膦酸酯类缓蚀剂。
14.根据权利要求13所述的清洗液，其特征在于：所述的酚类为苯酚、1，2-二羟基苯酚、对羟基苯酚或连苯三酚。
15.根据权利要求13所述的清洗液，其特征在于：所述的羧酸、羧酸酯类为苯甲酸、对氨基苯甲酸、对氨基苯甲酸甲酯、邻苯二甲酸、邻苯二甲酸甲酯、没食子酸或没食子酸丙酯。
16.根据权利要求13所述的清洗液，其特征在于：所述的酸酐类为乙酸酐、己酸酐、马来酸酐或聚马来酸酐。
17.根据权利要求13所述的清洗液，其特征在于：所述的磷酸、磷酸酯类为1，3-(羟乙基)-2，4，6-三膦酸。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009021400A1 (fr) * | 2007-08-10 | 2009-02-19 | Anji Microelectronics (Shanghai) Co., Ltd | Composition de nettoyage pour retirer une réserve |
| WO2009146606A1 (zh) * | 2008-06-06 | 2009-12-10 | 安集微电子科技(上海)有限公司 | 一种等离子刻蚀残留物清洗液 |
| WO2009155782A1 (zh) * | 2008-06-27 | 2009-12-30 | 安集微电子（上海）有限公司 | 一种光刻胶清洗剂 |
| CN102096345A (zh) * | 2009-12-11 | 2011-06-15 | 安集微电子（上海）有限公司 | 一种厚膜光刻胶清洗液及其清洗方法 |
| WO2014079145A1 (zh) * | 2012-11-22 | 2014-05-30 | 安集微电子科技(上海)有限公司 | 一种去除光刻胶的清洗液 |
| CN101685273B (zh) * | 2008-09-26 | 2014-06-04 | 安集微电子（上海）有限公司 | 一种去除光阻层残留物的清洗液 |
| CN107229191A (zh) * | 2016-03-25 | 2017-10-03 | 达兴材料股份有限公司 | 光致抗蚀剂脱除组合物及利用其的电子元件的制造方法 |
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| GB2369687B (en) * | 1997-11-21 | 2002-10-09 | Samsung Electronics Co Ltd | Method of manufacturing semiconductor devices |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009021400A1 (fr) * | 2007-08-10 | 2009-02-19 | Anji Microelectronics (Shanghai) Co., Ltd | Composition de nettoyage pour retirer une réserve |
| WO2009146606A1 (zh) * | 2008-06-06 | 2009-12-10 | 安集微电子科技(上海)有限公司 | 一种等离子刻蚀残留物清洗液 |
| CN102047184A (zh) * | 2008-06-06 | 2011-05-04 | 安集微电子科技(上海)有限公司 | 一种等离子刻蚀残留物清洗液 |
| CN102047184B (zh) * | 2008-06-06 | 2013-10-23 | 安集微电子科技(上海)有限公司 | 一种等离子刻蚀残留物清洗液 |
| WO2009155782A1 (zh) * | 2008-06-27 | 2009-12-30 | 安集微电子（上海）有限公司 | 一种光刻胶清洗剂 |
| CN101685273B (zh) * | 2008-09-26 | 2014-06-04 | 安集微电子（上海）有限公司 | 一种去除光阻层残留物的清洗液 |
| CN102096345A (zh) * | 2009-12-11 | 2011-06-15 | 安集微电子（上海）有限公司 | 一种厚膜光刻胶清洗液及其清洗方法 |
| WO2014079145A1 (zh) * | 2012-11-22 | 2014-05-30 | 安集微电子科技(上海)有限公司 | 一种去除光刻胶的清洗液 |
| CN107229191A (zh) * | 2016-03-25 | 2017-10-03 | 达兴材料股份有限公司 | 光致抗蚀剂脱除组合物及利用其的电子元件的制造方法 |
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