CN112745982B - 一种含有低聚皂化合物的晶圆切割液 - Google Patents

一种含有低聚皂化合物的晶圆切割液 Download PDF

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CN112745982B
CN112745982B CN202011598311.4A CN202011598311A CN112745982B CN 112745982 B CN112745982 B CN 112745982B CN 202011598311 A CN202011598311 A CN 202011598311A CN 112745982 B CN112745982 B CN 112745982B
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侯军
褚雨露
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Jiangsu Austrian Mstar Technology Ltd
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Abstract

一种含有低聚皂化合物的晶圆切割液，其属于光电子器件的表面精密加工领域。该切割液通过控制pH在8‑9，使切割产生硅碎屑表面具有负电荷，切割液中加入低聚皂化合物在溶液中电离形成负电荷基团，其同时还具有类似表面活性剂的两亲性结构，使其能够在晶圆表面形成定向排列的吸附层，其带有负电荷的基团朝外，与带有负电荷的硅碎屑之间形成斥力，从而阻挡硅碎屑与晶圆表面直接接触，避免了硅碎屑对晶圆造成的污染。

Description

一种含有低聚皂化合物的晶圆切割液
技术领域
本发明涉及一种含有低聚皂化合物的晶圆切割液，其属于光电子器件的表面精密加工领域。
背景技术
在半导体芯片制造流程中，半导体晶圆的切割工艺是指在半导体芯片电路制造工艺完成后，针对称之为切割道的区域进行切割而使半导体晶圆上整齐分布的芯片分隔开的一道工艺。在30倍显微镜下观察可以发现晶圆半导体是由许多个独立单元的集合体组成的。这些独立单元以行或列为单位，整齐排列且每行或每列之间有一“沟槽”状长条相间隔，这些“沟槽”称之为切割道。当切割工艺完成后，即可得到一颗颗独立的微小芯片。
通常一片半导体晶圆上集成了上千颗芯片，通过超薄金刚石刀片切割工艺将其分割成独立的芯片。在切割工艺过程中产生的残渣颗粒，例如硅残留物，会粘附到晶圆表面和晶圆侧壁上。这些残渣颗粒一旦与晶圆接触，则很难在随后的清洗工艺中去除。目前普遍使用的减少切割过程中残渣粘附的方法是将高纯度去离子水作为切割过程中的清洗剂，通过高压喷洒在切割区域和高速旋转的刀片上，借此将切割过程中产生的硅残渣去离子水冲走。然而，利用这种方法仅能够将较大颗粒冲走，仍有一些细小的硅残渣无法被冲走。
发明内容
为了解决上述技术问题，本发明提供一种含有低聚皂化合物的晶圆切割液，用于半导体晶圆切割制程，该切割液中通过低聚皂化合物的加入，使细小硅残渣容易清理。
本发明采用的技术方案为：一种含有低聚皂化合物的晶圆切割液，该切割液的组分及其质量分数如下：
Figure BDA0002868647110000011
Figure BDA0002868647110000021
余量为超纯水；
所述低聚皂化合物为低聚皂化合物A和/或低聚皂化合物B；
所述低聚皂化合物A的结构通式为：
Figure BDA0002868647110000022
其中：2≤n≤16
低聚皂化合物B的结构通式为：
Figure BDA0002868647110000023
其中：2≤m≤18。
所述表面活性剂为非离子表面活性剂或阴离子表面活性剂。
所述分散剂为马来酸/丙烯酸共聚物、马来酸/烯烃共聚物、改性聚丙烯酸钠盐、改性聚丙烯酸、阳离子聚乙烯胺亚胺、苯乙烯/丙烯酸共聚物、聚乙烯吡咯烷酮、羧甲基纤维素、羟丙基纤维素或羟乙基纤维素中的一种或几种；
所述非离子表面活性剂为烷基酚类表面活性剂、阴离子表面活性剂为仲烷磺酸盐类表面活性剂、脂肪醇硫酸盐类表面活性剂、仲烷基苯磺酸盐类表面活性剂。
所述有机酸类螯合剂为柠檬酸、葡萄糖酸、草酸、酒石酸、戊二酸、马来酸、苯二甲酸、富马酸或多聚羧酸螯合剂；
所述醇类增溶剂为1,2-丙二醇、甘油、1,3-丁二醇、异丙醇、季戊四醇、木糖醇、山梨醇；
所述抑菌剂为苯氧乙醇、苯酚、卡松或季铵盐型阳离子表面活性剂；
所述pH调节剂为氢氧化钾、氨水、三乙醇胺、单乙醇胺、二甘醇胺、四甲基氢氧化铵或三乙胺。
本发明的有益效果为：在硅晶圆切割过程中，刀片高速旋转与晶圆表面剧烈摩擦，由于使用的水为18兆欧超纯水，因此摩擦产生的静电荷可以在晶片上累积。切割产生的碎屑也会由于静电吸引而牢牢吸附在晶圆表面，导致后续无法清洗干净，因此在切割过程中将静电电荷释放掉是十分重要的。该切割液通过控制pH在8-9，使切割产生硅碎屑表面具有负电荷，切割液中加入低聚皂化合物在溶液中电离形成负电荷基团，其同时还具有类似表面活性剂的两亲性结构，使其能够在晶圆表面形成定向排列的吸附层，其带有负电荷的基团朝外，与带有负电荷的硅碎屑之间形成斥力，从而阻挡硅碎屑与晶圆表面直接接触，避免了硅碎屑对晶圆造成的污染。
附图说明
图1是实施例1中切割液的效果图(无颗粒残留)。
图2是对比例1中切割液的效果图(圈中有颗粒残留)
具体实施方式
下面通过具体实施例对本发明作进一步说明，但本发明并不受以下实施例所限定。
表1实施例1-10中组分及其质量百分比
Figure BDA0002868647110000031
Figure BDA0002868647110000041
实施例1-10的制备方法为：按比例将超纯水加入反应釜中，开动搅拌；按加入低聚皂类化合物，搅拌3分钟；再加入分散剂，搅拌5分钟；加入表面活性剂，搅拌5分钟；加入有机酸螯合剂，搅拌3分钟；加入醇类增溶剂，搅拌3分钟；加入抑菌剂，搅拌5分钟；最后加入pH调节剂，搅拌20分钟，至透明，即得晶圆切割液。
对比例1
Figure BDA0002868647110000042
对比例1的制备方法为在超纯水中依次按比例加入壬基酚局氧乙烯醚、氧化聚乙烯(分子量50万)、柠檬酸、乙二醇甲醚、苯氧乙醇、二甘醇胺，搅拌至透明即得。
对比例2
Figure BDA0002868647110000043
Figure BDA0002868647110000051
对比例2的制备方法为在超纯水中依次按比例加入仲烷基苯磺酸、羧甲基纤维素(分子量10万)、柠檬酸、乙二醇甲醚、苯氧乙醇、二甘醇胺，搅拌至透明即得。
实施例11颗粒残留检测
以下实施例的效果检测均采用以下方法：以Disco晶圆切割机切割12寸晶圆，切割液稀释倍数为3000倍，以金相显微镜观察切割后的晶圆表面是否有颗粒残留；取切割后的废水样品，以ICP检测其中金属离子含量。
表2实施例1-10与对比例1的颗粒残留结果
Figure BDA0002868647110000052
其中：ICP最低检出限为0.2ppm，低于检出限结果记为N.D.
切割后有无颗粒残留对比图如图1和图2所示，图1是实施例1中切割液切割后金相显微镜观察切割后的晶圆表面，图中可见晶圆表面干净无颗粒残留；图2是对比例1中切割液切割后的晶圆表面，图中圈出的部分有颗粒残留。

Claims (5)

1.一种含有低聚皂化合物的晶圆切割液，其特征在于：该切割液的组分及其质量分数如下：
低聚皂化合物 1.0-10.0%
分散剂 1.0-5.0%
表面活性剂 1.0-5.0%
有机酸螯合剂 0.5-2.0%
醇类增溶剂 2.0-5.0%
抑菌剂 0.1-0.5%
pH调节剂 0.1-2.0%
余量为超纯水；
所述低聚皂化合物为低聚皂化合物A和/或低聚皂化合物B；
所述低聚皂化合物A的结构通式为：
Figure 599026DEST_PATH_IMAGE002
，其中：2≤n≤16；
低聚皂化合物B的结构通式为：
Figure DEST_PATH_IMAGE003
，其中：2≤m≤18；
所述表面活性剂为非离子表面活性剂或阴离子表面活性剂；
所述分散剂为氧化聚乙烯，马来酸/丙烯酸共聚物、马来酸/烯烃共聚物、改性聚丙烯酸钠盐、改性聚丙烯酸、阳离子聚乙烯胺亚胺、苯乙烯/丙烯酸共聚物、聚乙烯吡咯烷酮、羧甲基纤维素、羟丙基纤维素或羟乙基纤维素中的一种或几种；分散剂的分子量为10-50万；
所述非离子表面活性剂为烷基酚类表面活性剂、阴离子表面活性剂为仲烷磺酸盐类表面活性剂、脂肪醇硫酸盐类表面活性剂、仲烷基苯磺酸盐类表面活性剂；
该切割液的pH值为8-9。
2.根据权利要求1所述的一种含有低聚皂化合物的晶圆切割液，其特征在于：所述有机酸类螯合剂为柠檬酸、葡萄糖酸、草酸、酒石酸、戊二酸、马来酸、苯二甲酸、富马酸或多聚羧酸螯合剂。
3.根据权利要求1所述的一种含有低聚皂化合物的晶圆切割液，其特征在于：所述醇类增溶剂为1,2-丙二醇、甘油、1,3-丁二醇、异丙醇、季戊四醇、木糖醇、山梨醇。
4.根据权利要求1所述的一种含有低聚皂化合物的晶圆切割液，其特征在于：所述抑菌剂为苯氧乙醇、苯酚、卡松或季铵盐型阳离子表面活性剂。
5.根据权利要求1所述的一种含有低聚皂化合物的晶圆切割液，其特征在于：所述pH调节剂为氢氧化钾、氨水、三乙醇胺、单乙醇胺、二甘醇胺、四甲基氢氧化铵或三乙胺。
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Publication number Priority date Publication date Assignee Title
CN102311863A (zh) * 2010-07-09 2012-01-11 气体产品与化学公司 晶片切割方法及用于该方法的组合物
CN104395448A (zh) * 2012-06-29 2015-03-04 出光兴产株式会社 水性加工液

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CN102311863A (zh) * 2010-07-09 2012-01-11 气体产品与化学公司 晶片切割方法及用于该方法的组合物
CN104395448A (zh) * 2012-06-29 2015-03-04 出光兴产株式会社 水性加工液

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