CN102346383B - 一种光刻胶的清洗液 - Google Patents

一种光刻胶的清洗液 Download PDF

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CN102346383B
CN102346383B CN201010246706.8A CN201010246706A CN102346383B CN 102346383 B CN102346383 B CN 102346383B CN 201010246706 A CN201010246706 A CN 201010246706A CN 102346383 B CN102346383 B CN 102346383B
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刘兵
彭洪修
孙广胜
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Anji microelectronic technology (Shanghai) Limited by Share Ltd
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Abstract

本发明公开了一种低蚀刻性的适用与较厚光刻胶清洗的清洗液。这种低蚀刻性的光刻胶清洗液含有(a)氢氧化钾，(b)吡咯烷酮类溶剂，(c)砜类溶剂，(d)季戊四醇，(e)醇胺，(f)间苯二酚，(g)苯并三氮唑类腐蚀抑制剂。这种低蚀刻性的光刻胶清洗剂可以用于除去金属、金属合金或电介质基材上的光刻胶和其它残留物，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

一种光刻胶的清洗液
技术领域
本发明涉及半导体工艺中一种清洗液，具体的涉及一种低刻蚀性的较厚光刻胶清洗液。
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，曝光后进行图形转移，在得到需要的电路图形之后，进行下一道工序之前，需要剥去残留的光刻胶。例如，在晶圆微球植入工艺(bumpingtechnology)中，需要光刻胶形成掩膜，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。其中其常用的强碱主要是无机金属氢氧化物(如氢氧化钾等)和有机氢氧化物如四甲基氢氧化胺等。
如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；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。又例如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。
由此可见，寻找更为有效的金属腐蚀抑制剂和溶解更多光刻胶的溶剂体系是该类光刻胶清洗液努力改进的优先方向。
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剂。
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(a)氢氧化钾，(b)吡咯烷酮类溶剂，(c)砜类溶剂，(d)季戊四醇，(e)醇胺，(f)间苯二酚，(g)苯并三氮唑类腐蚀抑制剂。
其中，所述的氢氧化钾在清洗液中质量百分比较佳为0.1～6％；所述的吡咯烷酮类溶剂在清洗液中质量百分比较佳为1～90％；所述的砜类溶剂在清洗液中质量百分比较佳为1～90％；所述的季戊四醇在清洗液中质量百分比较佳为0.1～15％；所述的醇胺在清洗液中质量百分比较佳为0.1～55％；所述的间苯二酚在清洗液中质量百分比较佳为0.01～10％；所述的苯并三氮唑类腐蚀抑制剂在清洗液中质量百分比较佳为0.1～5％；
本发明中所述的吡咯烷酮类溶剂为N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-羟乙基吡咯烷酮和N-环己基吡咯烷酮。
本发明中所述的砜类溶剂为砜和亚砜。所述的亚砜较佳的为二甲基亚砜；所述的砜较佳的为环丁砜、二甲基砜和2，4-二甲基环丁砜。
本发明中所述的醇胺为单乙醇胺、二乙醇胺、三乙醇胺、正丙醇胺、异丙醇胺、2-(二乙氨基)乙醇、乙基二乙醇胺和二甘醇胺中的一种或几种。醇胺的存在有利于提高氢氧化钾和季戊四醇在体系中的溶解度，并有利于金属微球的保护。
本发明中所述的苯并三氮唑类腐蚀抑制剂为苯并三氮唑、甲基苯并三氮唑、1-羟基苯并三氮唑、5-羧基苯并三氮唑和/或它们的钾盐中的一种或多种。
本发明中的低蚀刻性光刻胶清洗液，可以在室温至90℃下清洗100μm以上厚度的光刻胶，而且由于其中含有的间苯二酚、苯并三氮唑类腐蚀抑制剂和醇胺，可以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。吡咯烷酮类溶剂、砜类溶剂和季戊四醇的复合溶剂体系，有利于提高光刻胶的去除效率。具体方法如下：将含有光刻胶的半导体晶片浸入本发明中的低蚀刻性的光刻胶清洗剂，在室温至90℃下浸泡合适的时间后，取出洗涤后用高纯氮气吹干。
本发明的清洗液经上述成分简单混合均匀即可制得。本发明的清洗液可在较大的温度范围内使用，一般在室温到90℃范围内。本发明所用试剂及原料均市售可得。
本发明的积极进步效果在于：
(1)本发明的光刻胶清洗液，可适用于较厚(厚度大于100μm)光刻胶的清洗，同时对Cu(铜)等金属具有较低的蚀刻速率。
(2)本发明中的低蚀刻性光刻胶清洗液，可以在室温至90℃下清洗光刻胶。
(3)配方中采用的醇胺溶剂，提高了氢氧化钾和季戊四醇在体系中的溶解度，并有利于金属微球的保护。
(4)配方中采用的吡咯烷酮类溶剂、砜类溶剂和季戊四醇的复合溶剂体系，进一步提高了光刻胶的去除能力。
(5)配方中采用的间苯二酚/苯并三氮唑类腐蚀抑制剂，有效地抑制了铜、锡、铅等金属的腐蚀。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。
实施例1～31
表1给出了本发明的适用于较厚光刻胶清洗液的实施例1～31，按表中配方，将各组分混合均匀，即可制得各实施例的清洗液。
表1本发明实施例1～31的组分和含量
效果实施例
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25～90℃下浸泡15～120分钟，然后取出半导体晶片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2所示。
表2实施例7～30对晶圆清洗情况
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2可以看出，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，同时对金属微球和金属铜等有较好的腐蚀抑制作用。

Claims (6)

1.一种光刻胶清洗液，其由：
(a)氢氧化钾，
(b)吡咯烷酮类溶剂，
(c)砜类溶剂
(d)季戊四醇，
(e)醇胺，
(f)间苯二酚，以及
(g)苯并三氮唑类腐蚀抑制剂组成，其中，
所述的氢氧化钾的含量为质量百分比0.1～6％，所述的吡咯烷酮类溶剂的含量为质量百分比1～90％，所述的砜类溶剂的含量为质量百分比1～90％，所述的季戊四醇的含量为质量百分比0.1～15％，所述的醇胺的含量为质量百分比0.1～55％，所述的间苯二酚的含量为质量百分比0.01～10％，所述的苯并三氮唑类腐蚀抑制剂的含量为质量百分比0.1～5％。
2.如权利要求1所述的清洗液，其特征在于：所述的吡咯烷酮类溶剂选自N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-羟乙基吡咯烷酮和N-环己基吡咯烷酮中的一种或多种。
3.如权利要求1所述的清洗液，其特征在于：所述的砜类溶剂为砜和/或亚砜。
4.如权利要求1所述的清洗液，其特征在于：所述的醇胺选自单乙醇胺、二乙醇胺、三乙醇胺、正丙醇胺、异丙醇胺、2-(二乙氨基)乙醇、N-乙基二乙醇胺和二甘醇胺中的一种或多种。
5.如权利要求1所述的清洗液，其特征在于：所述的苯并三氮唑类腐蚀抑制剂选自苯并三氮唑、甲基苯并三氮唑、1-羟基苯并三氮唑、5-羧基苯并三氮唑和它们的钾盐中的一种或多种。
6.如权利要求3所述的清洗液，其特征在于：所述的亚砜为二甲基亚砜；所述的砜为环丁砜、二甲基砜和/或2，4-二甲基环丁砜。
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