CN102073226B - 一种厚膜光刻胶清洗液及其清洗方法 - Google Patents

一种厚膜光刻胶清洗液及其清洗方法 Download PDF

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CN102073226B
CN102073226B CN200910199092.XA CN200910199092A CN102073226B CN 102073226 B CN102073226 B CN 102073226B CN 200910199092 A CN200910199092 A CN 200910199092A CN 102073226 B CN102073226 B CN 102073226B
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刘兵
彭洪修
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Abstract

本发明公开了一种厚膜光刻胶清洗液及其清洗方法。这种低蚀刻性厚膜光刻胶清洗液包含二甲基亚砜，氢氧化钾，芳基醇，醇胺，金属钾。本发明的光刻胶清洗液可以在较大的温度范围内(45～90℃)使用，用于除去半导体制造工艺中金属、金属合金或电介质等基材上的厚光刻胶，特别是适合用于除去厚度在100μm以上的高交联度的负性光刻胶。同时，该光刻胶清洗液对铜、锡、铅等金属具有极弱的腐蚀性，不会对晶片图案和基材造成损坏，在半导体晶片清洗等微电子领域具有良好的应用前景。

Description

一种厚膜光刻胶清洗液及其清洗方法
技术领域
本发明涉及一种低蚀刻性的光刻胶清洗液及其清洗方法。
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。
目前，光刻胶清洗液主要由极性有机溶剂、强碱和/或水等组成，通过将半导体晶片浸入清洗液中或者利用清洗液冲洗半导体晶片，去除半导体晶片上的光刻胶。
JP1998239865由四甲基氢氧化铵(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液，将晶片浸入该清洗液中，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。其对半导体晶片基材的腐蚀略高，且不能完全去除半导体晶片上的光刻胶，清洗能力不足。
US5529887由氢氧化钾(KOH)、烷基二醇单烷基醚、水溶性氟化物和水等组成碱性清洗液，将晶片浸入该清洗液中，在40～90℃下除去金属和电介质基材上的厚膜光刻胶。其对半导体晶片基材的腐蚀较高。
WO2006/056298A1利用由四甲基氢氧化铵(TMAH)、二甲基亚砜(DMSO)，乙二醇(EG)和水组成碱性清洗液，用于清洗50～100微米厚的光刻胶，同时对金属铜基本无腐蚀。
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液，将晶片进入该清洗液中，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。
综上所述，现有的光刻胶的清洗液对厚度较高的光刻胶，特别如厚度大于100μm的光刻胶的清洗能力不足，或者对半导体晶片图案和基材腐蚀性较强，存在较大的缺陷。
发明内容
本发明要解决的技术问题就是针对现有的厚膜光刻胶清洗液存在的清洗能力不足或者对半导体晶片图案和基材腐蚀性较强的缺陷，而提供一种对厚膜光刻胶清洗能力强且对半导体晶片图案和基材腐蚀性较低的光刻胶清洗液。
本发明解决上述技术问题所采用的技术方案是：一种用于厚膜光刻胶的清洗液，该清洗液包含二甲基亚砜，氢氧化钾，芳基醇，醇胺，金属钾。
本发明中，所述的二甲基亚砜的含量较佳的为质量百分比20～98.79％，更佳的为质量百分比35～98％。
本发明中，所述的氢氧化钾的含量较佳的为质量百分比0.1～10％，更佳的为质量百分比0.1～3％。
本发明中，所述的芳基醇较佳的为选自苯甲醇、苯乙醇、二苯甲醇、邻氨基苯甲醇、对氨基苯甲醇、甲基苯甲醇、二甲基苯甲醇、三甲基苯甲醇、邻苯二甲醇、间苯二甲醇、对苯二甲醇中的一种或多种，更佳的为选自苯甲醇、邻苯二甲醇和甲基苯甲醇中的一种或多种。所述的芳基醇的含量较佳的为质量百分比1～50％，更佳的为质量百分比1～30％。所述的芳基醇可以明显增加氢氧化钾在二甲基亚砜中的溶解度。
本发明中，所述的醇胺较佳的为选自乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺、甲基乙醇胺、甲基二乙醇胺、二甲基乙醇胺、二甘醇胺和羟乙基乙二胺中的一种或多种，更佳的为选自乙醇胺、二甘醇胺、三乙醇胺和甲基二乙醇胺中的一种或多种。所述的醇胺的含量较佳的为质量百分比0.1～50wt％，更佳的为质量百分比0.5～30wt％。
本发明中，所述的金属钾的含量较佳的为质量百分比0.01～5wt％，更佳的为质量百分比0.01～2wt％。金属钾的加入有利于除去其他组分中含有的微量水分，这有利于控制金属的腐蚀。同时金属钾与微量水生成的少量氢氧化钾，有利于提高溶液体系的碱性，这有利于光刻胶的去除。
本发明中的光刻胶清洗液，可以在较大的温度范围(45～90℃之间)内用于清洗除去半导体晶片上的厚膜光刻胶，特别是100μm以上厚度的光刻胶。清洗方法可参照如下步骤：将含有光刻胶的半导体晶片浸入清洗液中，在45～90℃下利用恒温振荡器缓慢振荡，然后经去离子水洗涤后用高纯氮气吹干。
本发明所用试剂及原料均市售可得。本发明中，所述的用于厚膜光刻胶的清洗剂由上面所述组分混合即可制得。
本发明的积极效果是：本发明采用芳基醇作为溶剂溶解氢氧化钾，芳基醇对金属铜有较好的保护作用；采用醇胺作为金属微球(bump)的保护剂；采用金属钾作为除水剂，既除去了溶液中微量的水，又加强了溶液的碱性。因此对厚膜光刻胶清洗能力强且对半导体晶片图案和基材腐蚀性较低。
具体实施方式
下面通过具体实施方式来进一步说明本发明。按照表中的组分配比均匀混合即可得到本发明的清洗液。
表1实施例1～25中的清洗剂的组分和含量
Figure G200910199092XD00041
Figure G200910199092XD00051
表2部分实施例和对比实施例配方
Figure G200910199092XD00052
注：NA是没有加入该组分。
为了进一步说明本发明的效果及原理，特配置了表2中的溶液，详见表2。需要特别说明的是在表2中对比例1’不能形成均匀的溶液，这说明KOH在二甲亚砜中的溶解度较小。对比例2’表明加入芳基醇即苯甲醇能提高KOH在体系中的溶解度，能形成均匀的溶液。为了进一步考察该类清洗液的清洗情况，本发明采用了如下技术手段：即将含有负性丙烯酸酯类光刻胶(厚度约为120微米，且经过曝光和刻蚀)的半导体晶片(凸点封装晶圆)浸入清洗剂中，在45～90℃下利用恒温振荡器以约60转/分的振动频率振荡15～120分钟，然后经去离子水洗涤后用高纯氮气吹干。光刻胶的清洗效果和清洗液对晶片的腐蚀情况如表3所示。
表3对比实施例和部分实施例的晶圆清洗情况
Figure G200910199092XD00053
腐蚀情况：◎基本无腐蚀；    清洗情况：◎完全去除；
          ○略有腐蚀；                ○少量残余；
          △中等腐蚀；                △较多残余；
          ×严重腐蚀。                ×大量残余。
从表3可以看出，对比例2’和对比例1’相比，芳基醇即苯甲醇除了能提高KOH在体系中的溶解度外，还有利于对金属铜腐蚀的抑制。对比例3’和对比例2’相比，可以看出醇胺的加入有利于对金属微球的保护。实施例26和对比例3’相比，由于金属钾的加入，除去了清洗液中的微量水，金属微球得到了更好的保护。其它进一步的测试表明本发明的清洗液对厚膜光刻胶具有良好的清洗效果，使用温度范围广，同时对金属铜等有较好的腐蚀抑制作用。

Claims (8)

1.一种厚膜光刻胶清洗液，其包含：二甲基亚砜，氢氧化钾，芳基醇，醇胺，金属钾，其中所述金属钾的质量百分含量为：0.01-2%。
2.如权利要求1所述清洗液，其特征在于，所述二甲基亚砜的质量百分含量为：20-98.79%；所述氢氧化钾的质量百分含量为：0.1-10%；所述芳基醇的质量百分含量为：1-50%；所述醇胺的质量百分含量为：0.1-50%。
3.如权利要求2所述清洗液，其特征在于，所述二甲基亚砜的质量百分含量为：35-98%；所述氢氧化钾的质量百分含量为：0.1-3%；所述芳基醇的质量百分含量为：1-30%；所述醇胺的质量百分含量为：0.5-30%。
4.如权利要求1所述清洗液，其特征在于，所述芳基醇为选自苯甲醇、苯乙醇、二苯甲醇、邻氨基苯甲醇、对氨基苯甲醇、甲基苯甲醇、二甲基苯甲醇、三甲基苯甲醇、邻苯二甲醇、间苯二甲醇和对苯二甲醇中的一种或多种。
5.如权利要求4所述清洗液，其特征在于，所述芳基醇为选自苯甲醇、邻苯二甲醇和甲基苯甲醇中的一种或多种。
6.如权利要求1所述清洗液，其特征在于，所述醇胺为选自乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺、甲基乙醇胺、甲基二乙醇胺、二甲基乙醇胺、二甘醇胺和羟乙基乙二胺中的一种或多种。
7.如权利要求6所述清洗液，其特征在于，所述醇胺为选自乙醇胺、二甘醇胺、三乙醇胺和甲基二乙醇胺中的一种或多种。
8.利用权利要求1～7任一项所述清洗液清洗厚膜光刻胶的清洗方法，其特征在于，所述清洗方法可参照如下步骤进行：将含有光刻胶的半导体晶片浸入清洗液中，在45～90℃下利用恒温振荡器缓慢振荡，然后经去离子水洗涤后用高纯氮气吹干。
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