CN102197128A - 用于对多金属装置处理的含有葡糖酸的光致抗蚀剂清洗组合物 - Google Patents

用于对多金属装置处理的含有葡糖酸的光致抗蚀剂清洗组合物 Download PDF

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CN102197128A
CN102197128A CN2009801428748A CN200980142874A CN102197128A CN 102197128 A CN102197128 A CN 102197128A CN 2009801428748 A CN2009801428748 A CN 2009801428748A CN 200980142874 A CN200980142874 A CN 200980142874A CN 102197128 A CN102197128 A CN 102197128A
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alkanolamine
glyconic acid
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稻冈诚二
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Anwantuo Spcial Materials Co Ltd
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Abstract

本发明提供一种微电子光致抗蚀剂清洗组合物，其适合用于清洗多金属微电子装置，当存在运用水的后续冲洗步骤时，清洗不会产生实质性的或显著的电偶腐蚀。

Description

用于对多金属装置处理的含有葡糖酸的光致抗蚀剂清洗组合物
技术领域
本发明涉及一种微电子光致抗蚀剂清洗组合物，其适合用于清洗多金属微电子装置，当存在采用水的后续冲洗步骤时，清洗不会产生实质性的或显著的电偶腐蚀。本发明还涉及使用本发明的组合物清洗多金属微电子装置的方法。
背景技术
将现有能够获得的多种碱性光致抗蚀剂清洗组合物用于清洗多金属(例如Al/Mo或Al/Ti)微电子装置时，可以产生良好的清洗效果。然而，当采用后续常规的水冲洗步骤除去装置表面的清洗组合物时，会产生pH为9或更高的碱性水溶液，其一旦接触微电子装置的多金属叠层，即在两种或多种不同的金属之间形成动电电流，产生或加速电化学(电流的)腐蚀。因此，需要运用一个例如使用常规溶剂，通常为异丙醇的“中间”冲洗步骤。所述中间冲洗步骤有助于在清洗组合物中的碱性化合物接触水冲洗步骤中的水之前，将其从微电子装置上清除掉。所述中间冲洗步骤是可以省去的一个附加步骤。此外，需要提供一种用于多金属微电子装置的良好的清洗组合物，其产生良好的清洗效果同时保护金属不受电偶腐蚀。
发明概要
按照本发明，提供一种用于清洗多金属微电子装置的半水基碱性清洗组合物，所述组合物由以下组成：
(a)约10％～约35％的水；
(b)约5％～约15％的至少一种烷醇胺；
(c)约10％～约50％的选自N-甲基吡咯烷酮(pyrrolidinone)或N-甲基吡咯烷酮与环丁砜混合物的溶剂；
(d)约2％～约10％的葡糖酸或通过在水中的水解作用产生葡糖酸的化合物；
(e)约1％～约8％的至少一种式HO(CH2CH2O)nCH2CH2OH代表的寡甘醇，其中，n为1或大于1；和
(f)任选约10％～约40％的至少一种二甘醇单烷基醚，其中烷基含有1～4个碳原子；
其中百分比为基于组合物总重量的重量百分比，当烷醇胺的百分比等于或小于6％时，组合物中的N-甲基吡咯烷酮溶剂等于或大于20％，当烷醇胺的百分比等于或大于9％时，N-甲基吡咯烷酮可以等于或小于20％。本发明的清洗组合物特别有用于清洗多金属微电子装置，且可以抑制微电子装置中金属的电偶腐蚀。所述组合物可以在约50℃～约60℃的温度下用于清洗微电子装置，且不会对装置的金属带来任何显著性的或者实质性的电偶腐蚀。
发明内容
本发明的半水基(semi-aqueous)、碱性清洗组合物中具有约10％～约35％重量的水存在于组合物中。所述水可以是水本身或者组合物中另一组分的含水溶液中的水，或者是上述两种来源的混合物。组合物中水的优选量为约10％～约30％，进一步优选约15％～约30％，更进一步优选约18％～约25％重量。
至少一种烷醇胺可以是任何适当的烷醇胺，包括碳原子数为1～6，优选碳原子数1～4，进一步优选碳原子数1～3的烷醇胺。特别优选单异丙醇胺和二乙醇胺。本发明组合物中烷醇胺组分的量可以是约5％～约15％，优选约6％～约10％，更特别为约6％～约8％，更进一步特别为约6％～约7％。
本发明清洗组合物中所使用的溶剂可以是N-甲基吡咯烷酮或N-甲基吡咯烷酮与环丁砜混合物。本发明组合物中溶剂的量为，约0％～约20％的环丁砜和约10％～约30％的N-甲基吡咯烷酮。溶剂的总量为约10％～约50％，优选约20％～约50％，进一步优选约30％～约50％，更进一步优选约30％～约40％。当本发明组合物中烷醇胺的百分比等于或小于6％时，组合物中的N-甲基吡咯烷酮溶剂等于或大于20％，当烷醇胺的百分比等于或大于9％时，N-甲基吡咯烷酮可以等于或小于20％。
葡糖酸或通过水中的水解作用产生葡糖酸的化合物被用作组合物中的电偶腐蚀抑制剂组分。当使用葡糖酸时，其通常以50％的含水溶液使用，其含有50％的水作为组合物中允许存在的水的总量的一部分。作为通过水解作用产生葡糖酸的化合物的例子，可以列举葡糖酸δ-内酯。组合物中葡糖酸的总量以葡糖酸来计，为约2％～约10％，优选约2％～约6％，进一步优选约3％～约6％，最优选约3％。因此，当组合物中需要含有例如3％的葡糖酸时，需要使用6％的50％含水葡糖酸溶液。
已经发现本发明组合物中的葡糖酸是一种有效的电偶腐蚀抑制剂，然而葡糖酸不能与组合物中所使用的有机溶剂高度互溶。在制造本发明的清洗组合物时，组分中存在足够的水，因此互溶性不成问题。然而，在使用清洗组合物的过程中，水会蒸发，特别是在特别优选的约50℃～约60℃的温度下进行清洗时，发现产生相分离，清洗组合物变得浑浊。为了克服上述问题和缺陷，研究发现本发明的清洗组合物中必须含有至少一种式HO(CH2CH2O)nCH2CH2OH代表的寡甘醇组分，其中，n为1或大于1，优选1～4。所述组分的存在抑制或者防止相分离的发生，并且使得本发明清洗组合物保持葡糖酸组分的电偶腐蚀抑制特性。寡甘醇(oligoethylene glycol)组分优选二甘醇(diethylene glycol)，三甘醇(triethylene glycol)和四甘醇(tetraethylene glycol)。令人意外的是，所述寡甘醇组分可以抑制或防止上述相分离，并降低在本发明组合物中的电偶腐蚀抑制作用，因为乙二醇和甘油不具备抑制或防止上述相分离的作用和降低本发明组合物中的电偶腐蚀抑制作用。组合物中存在的至少一种寡甘醇组分的含量为约1％～约8％，优选约2％～约6％，进一步优选约3％～约5％，更进一步优选约5％。
本发明的清洗组合物任选具有至少一种二甘醇单烷基胺，其中烷基具有1～4个碳原子。若本发明组合物中含有至少一种二甘醇单烷基胺组分，且优选具有所述组分，其含量为约10％～约40％，优选约10％～约30％，进一步优选约20％～约30％，更进一步优选约25％～约28％。
本发明的清洗组合物可以在足以清洗多金属微电子装置的光致抗蚀剂和其他残余物，例如等离子体和蚀刻残余物的任何适宜的清洗温度和时间进行，特别是可以在约50℃～约60℃的温度下，约30～约60秒的时间内清洗所述多金属装置，且实施上述步骤后，甚至当清洗后的装置接受后续的水冲洗时，也可以抑制装置中金属的电偶腐蚀。
下述表1例示了本发明清洗组合物的实施例。在表1和下述表2中，使用了下述的缩写。百分比为重量百分比。
MIPA＝单异丙醇胺
DEA＝二乙醇胺
GLU＝葡糖酸-50％含水溶液
δ-LAC＝葡糖酸δ-内酯
SFL＝环丁砜
NMP＝N-甲基吡咯烷酮
DEG＝二甘醇
EG＝乙二醇
TEG＝四甘醇
CAR＝卡必醇(二甘醇单甲醚)
GLY＝甘油
表1
  组合物   A   B   C   D   E   F   G   H   I
  水   25   25   25   25   25   25   25   25   25
  MIPA   6   6   6   6   9   9   9   9
  DEA   7
  SFL   10   10   10   10   10   10   10   10
  NMP   20   20   20   20   15   15   20   20   40
  GLU   6   6   6   6   6   6   6   6
  δ-LAC   5
  TEG   5   5   3
  DEG   5   1   5   1   5   1
  CAR   28   28   32   28   34   30   29   25   20
使用具有AL/Ti双金属丝的TFT玻璃微电子衬底对上述组合物A～I进行评价。在约50℃～约60℃的温度条件下，将衬底置于清洗液中并保持约30～约60秒。随后将冲洗后的衬底浸渍于5％的清洗溶液(95％水)中并保持1～3分钟(用于模拟水冲洗的环境，没有任何中间冲洗)，然后评价任一电偶腐蚀的等级。上述所有组合物A～I彻底清洗衬底，而没有发现可见的电偶腐蚀的发生和浑浊的产生。
使用下述表2中的对比组合物AA～EE在相同测试条件下进行比较。
表2
  组合物   AA   BB   CC   DD   EE
  水   25   25   25   25
  MIPA   6   6   6   6   6
  SFL   10   10   10   10   10
  NMP   20   20   20   15   15
  GLU   6   6   6   6   6
  TEG   1   5
  EG   5
  GLY   5
  CAR   28   28   28   37   33
不含有葡糖酸的组合物AA具有显著的电偶腐蚀。组合物BB和CC，除-了将四甘醇替代为乙二醇和甘油外，其他与本发明组合物A和B相同。所述对比组合物BB和CC出现了不希望的浑浊和常见的葡糖酸相分离。对比组合物DD和EE均出现了显著的浑浊，导致相分离。所述对比组合物中低含量(6％)MIPA和低含量(15％)NMP的组合产生了上述结果，然而，本发明的下列类似组合物却未出现所述浑浊和相分离：其中，组合物中烷醇胺(MIPA)的百分比等于或小于6％且组合物中NMP溶剂的量等于或大于20％，或者烷醇胺(MIPA)的百分比等于或大于9％且NMP的量等于或小于20％。因此，本发明组合物中的MIPA或NMP溶剂的浓度必须在高的范围内，即，当组合物中烷醇胺的百分比等于或小于6％时，组合物中N-甲基吡咯烷酮溶剂的百分比等于或大于20％，当烷醇胺的百分比等于或大于9％时，N-甲基吡咯烷酮的百分比等于或小于20％。
本发明例示了具体的实施方式，在不偏离本发明公开思想的精神和范围的条件下，做出各种变更、修订和变化是可以理解的。因此，所述的变更、修订和变化均落在所附权利要求的精神和范围内。

Claims (8)

1.一种用于清洗多金属微电子装置的半水基、碱性清洗组合物，所述组合物由以下组成：
(a)约10％～约35％的水；
(b)约5％～约15％的至少一种烷醇胺；
(c)约10％～约50％的选自N-甲基吡咯烷酮或N-甲基吡咯烷酮与环丁砜混合物的溶剂；
(d)约2％～约10％的葡糖酸或通过在水中的水解作用产生葡糖酸的化合物；
(e)约1％～约8％的至少一种式HO(CH2CH2O)nCH2CH2OH代表的寡甘醇，其中，n为1或大于1；和
(f)任选约10％～约40％的至少一种二甘醇单烷基醚，其中烷基含有1～4个碳原子；
其中百分比为基于组合物总重量的重量百分比，且当烷醇胺的百分比等于或小于6％时，组合物中的N-甲基吡咯烷酮溶剂等于或大于20％，且当烷醇胺的百分比等于或大于9％时，N-甲基吡咯烷酮的量可以等于或小于20％。
2.根据权利要求1中所述的半水基、碱性清洗组合物，其由以下组成：
(a)约10％～约30％的水；
(b)约6％～约10％的至少一种烷醇胺；
(c)约20％～约50％的溶剂；
(d)约2％～约6％的葡糖酸或通过在水中的水解作用产生葡糖酸的化合物；
(e)约2％～约6％的式HO(CH2CH2O)nCH2CH2OH代表的寡甘醇，其中，n为1、2、3或4；和
(f)约20％～约30％的至少一种二甘醇单烷基醚。
3.根据权利要求2中所述的半水基、碱性清洗组合物，其中：
烷醇胺由单异丙醇胺组成；
寡甘醇由四甘醇组成；和
二甘醇单烷基醚由二甘醇单甲醚组成。
4.根据权利要求2中所述的半水基、碱性清洗组合物，其由以下组成：
15％～30％的水；
6％～8％的单异丙醇胺；
10％～30％的N-甲基比咯烷酮和0％～20％的环丁砜；
2％～6％的葡糖酸；
3％～5％的寡甘醇；和
20％～30％的二甘醇单甲醚。
5.根据权利要求1中所述的半水基、碱性清洗组合物，其由以下组成：
约28％的水；
约6％的单异丙醇胺；
约10％的环丁砜和20％的N-甲基吡咯烷酮；
约3％的葡糖酸；
约5％的四甘醇；和
约28％的二甘醇单甲醚。
6.根据权利要求1中所述的半水基、碱性清洗组合物，其由以下组成：
约25％的水；
约7％的二乙醇胺；
约40％的N-甲基比咯烷酮；
约5％的葡糖酸δ-内酯；
约3％的四甘醇；和
约20％的二甘醇单甲醚。
7.一种清洗多金属微电子装置的方法，其包括将权利要求1～6中任一项所述的清洗组合物与装置接触，并在一定温度下保持一定时间，以完成对装置的清洗。
8.根据权利要求7中所述的方法，其中，清洗在约50℃～约60℃的温度下进行。
CN2009801428748A 2008-10-28 2009-10-22 用于对多金属装置处理的含有葡糖酸的光致抗蚀剂清洗组合物 Pending CN102197128A (zh)

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