CN108026492A - 用于光刻法中的光刻胶清洁组合物及其用于处理衬底的方法 - Google Patents

用于光刻法中的光刻胶清洁组合物及其用于处理衬底的方法 Download PDF

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CN108026492A
CN108026492A CN201680052243.7A CN201680052243A CN108026492A CN 108026492 A CN108026492 A CN 108026492A CN 201680052243 A CN201680052243 A CN 201680052243A CN 108026492 A CN108026492 A CN 108026492A
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mass
mixture
organic solvent
photoresist
water
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CN108026492B (zh
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R·L-K·常
G·E·帕里斯
陈秀美
李翊嘉
刘文达
陈天牛
L·M·马兹
R·L·C·洛
孟令人
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Versum Materials US LLC
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Abstract

本文公开了用于剥离膜厚度为3‑150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)季铵氢氧化物、(b)水溶性有机溶剂的混合物、(c)至少一种腐蚀抑制剂和(d)水，及用该光刻胶清洁组合物处理衬底的方法。

Description

用于光刻法中的光刻胶清洁组合物及其用于处理衬底的方法
相关专利申请的交叉引用
本专利申请要求2015年8月5日提交的美国临时专利申请序列号62/201,352的利益，其通过引用完全并入。
背景技术
本发明涉及用于光刻法中以剥离厚光刻胶图案的光刻胶清洁组合物及使用该光刻胶清洁组合物处理衬底的方法。本发明的光刻胶清洁组合物合适地在半导体器件如IC和LSI的生产中特别地应用于形成凸点(bump)或柱或再分配层(RDL)。它也可以在半导体器件如IC和LSI的生产中，在蚀刻过程如Bosch蚀刻过程之后用于在硅或玻璃衬底上硅通孔(TSVs)的形成。
在最近几年，随着半导体器件如IC和LSI的高度集成及芯片尺寸的减小，已经需要减小金属布线的大小和以高精度对齐衬底上具有20μm或更大高度的作为连接端子(微凸电极(minute salient electrode))的凸点或柱。将来，随着芯片尺寸的进一步减小，金属布线和凸点的高精度将变得甚至更为必要。
凸点形成通过例如在衬底上提供金属薄膜，通过光刻技术在金属薄膜上形成厚的光刻胶图案，在衬底的光刻胶图案-未覆盖区域(即，金属薄膜-暴露区域)上提供导电层以形成凸点、柱或RDL和然后除去光刻胶图案来完成。
光刻胶图案可以是厚膜，通常膜厚度为约3-150μm，且光刻胶可以是正性作用光刻胶材料，因为用于负性作用光刻胶材料的许多常用剥离化学物质可能严重地蚀刻或损伤衬底材料如铜、镍、铜或镍与各种金属的合金、锡-银合金(也称为各种组成的SAC)、TiN或其它钝化材料如SiN、聚酰亚胺、BCB等等。
由于光刻胶图案可能是厚的，通常膜厚度为约3-150μm，光刻胶可以是负性作用光刻胶材料(鉴于对镀覆的抗性、图案形状性能等)。与由正性作用光刻胶材料形成的光刻胶图案相比，通常更困难的是除去由负性作用材料形成的光刻胶图案，且因此相对于厚的正性作用光刻胶材料，甚至更困难的是除去由负性作用光刻胶材料形成的厚光刻胶图案。
此外，厚光刻胶图案由于其大的膜厚度，可能在形成过程中变形或塌陷。在这种情况下，有必要中断后续过程并通过从衬底全部除去变形的光刻胶图案和重复用于形成光刻胶图案的步骤而完成返工(re-work)。
凸点形成后光刻胶图案的除去或为返工而除去光刻胶图案通常在一罐光刻胶清洁组合物中进行以快速和完全地剥离光刻胶图案(固化的材料)。重要的是光刻胶清洁组合物不腐蚀金属薄膜而同时清除光刻胶，但重要的是完全除去光刻胶。另外，在衬底上形成凸点时，退化的膜有可能在光刻胶图案与凸点之间的界面处形成。因此有必要防止金属膜的腐蚀和保护凸点免于腐蚀或保护不希望被光刻胶清洁组合物除去的任何存在的其它材料。
JP-A-08-301911描述了用于凸点形成的作为图案形成材料的辐射敏感树脂组合物并在第[0032]和[0043]段中公开了作为用于剥离光固化图案的剥离液体的季铵、二甲亚砜和水的混合物(具体地，0.5质量％的四甲基氢氧化铵的二甲亚砜溶液(包含1.5质量％的水))。但是，这种剥离液体存在的问题使得其花费时间来将从衬底剥离的光固化图案溶解在剥离液体中且生产量是低的。而且，这种剥离液体导致在这些应用中使用的各种金属衬底的高度蚀刻。
JP-A-10-239865描述了作为用于剥离形成凸点的负性作用光刻胶的剥离液体的包含特定量的二甲亚砜、1,3-二甲基-2-咪唑啉酮、四烷基氢氧化铵和水的制剂。如以上JP-A-08-301911中的情况一样，JP-A-10-239865也存在花费时间来将从衬底剥离的光固化图案溶解在剥离液体中和生产量低的问题。还重要的是，这种剥离液体导致在这些应用中使用的各种金属衬底的高度蚀刻。此外，JP-A-10-239865中的剥离液体包含作为必要组分的1,3-二甲基-2-咪唑啉酮。这一化合物引起变色或Cu的腐蚀。
在光刻技术领域中，JP-A-2001-324823、JP-A-07-028254等公开了包含季铵氢氧化物和水溶性有机溶剂如二甲亚砜的剥离液体。但是，它们都没有描述完全除去适合用于形成厚图案(用于形成凸点)的难以除去的厚的正性或负性作用光刻胶。
其它已知的组合物可以剥离掉光刻胶，但也腐蚀金属和待清洁的衬底上存在的其它材料。需要的是良好地清洁且导致很少或没有衬底上的金属和/或钝化材料的腐蚀的组合物。
发明内容
本发明的目的是提供能够不仅从衬底剥离厚的光刻胶图案(其可以用于凸点形成)的光刻胶清洁组合物，以及使用该光刻胶清洁组合物处理衬底的方法。
本发明的一个方面中提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)0.5-5或0.5-4或0.5-3或1-5或1-4或1-3或1-2或1.5-3或1.8-2.3或1.25-4.5质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)60-97.5或60-96或73-98或75-96或90-96或89-95或78-85或64-69或80.5-82.5或82-97.5或80-83或85-96或89-94或85-97.5或86-97或91-96质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，所述水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物；(c)0.5-15或0.5-14或0.5-12或0.5-10或10.5-15或11-14或11-13或10-20或0.5-5或0.5-4或0.5-3或1-10或1-5或1-4或1-3或3-4质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物；和(d)0.5-25或0.5-10或1-10或1-8或1-7或2-5或1-5或1-2或3-7或4-6质量％的水。
注意，在本文中任何提及“包含”、“含有”、“具有”等之处，它包括“基本上由…组成”和“由…组成”。
在本发明的另一方面中，本发明提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)0.5-5或0.5-4或0.5-3或1-5或1-4或1-3或1-2或1.5-3或1.8-2.3或1.25-4.5质量％的至少一种季铵氢氧化物，如四甲基氢氧化铵和/或四乙基氢氧化铵或任何其它的季铵氢氧化物(其可以选自以下所列的那些)，或者其混合物；(b)60-97.5或60-96或73-98或75-96或90-96或89-95或78-85或64-69或80.5-82.5或82-97.5或80-83或85-96或89-94或85-97.5或86-97或91-96质量％的水溶性有机溶剂与至少一种(或者两种或更多种)另外的有机溶剂的混合物，所述水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物，所述至少一种另外的有机溶剂选自丙二醇、其它二醇类(glycols)、二醇类(diols)、三醇类、环状醇类、四氢糠醇、二丙二醇甲基醚、其它二醇醚类、γ-丁内酯、γ-戊内酯、二甲基乙酰胺、单乙醇胺或其它烷醇胺类(通常C1-C6烷醇胺，如二乙醇乙胺)、氨基丙基吗啉及其混合物；(c)0.5-15或0.5-14或0.5-12或0.5-10或10.5-15或11-14或11-13或10-20或0.5-5或0.5-4或0.5-3或1-10或1-5或1-4或1-3或3-4质量％的至少一种腐蚀抑制剂，其选自邻苯二酚、叔丁基邻苯二酚、苯甲酸铵、邻氨基苯甲酸、苯甲酸、水杨酸、柠檬酸、没食子酸、单-或二-羟基苯甲酸、聚乙烯亚胺(PEI)、二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物，或者任何腐蚀抑制剂的混合物；和(d)0.5-25或0.5-10或1-10或1-7或2-5或1-5或1-2或3-7或4-6质量％的水。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)0.5-5或0.5-4或0.5-3或1-5或1-4或1-3或1-2或1.5-3或1.8-2.3或1.25-4.5质量％的至少一种季铵氢氧化物，其选自四甲基氢氧化铵或四乙基氢氧化铵及其混合物；(b)60-97.5或60-96或73-98或75-96或90-96或89-95或78-85或64-69或80.5-82.5或82-97.5或80-83或85-96或89-94或85-97.5或86-97或91-96质量％的水溶性有机溶剂与至少一种另外的有机溶剂的混合物，该水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物，该至少一种另外的有机溶剂选自丙二醇、四氢糠醇、二丙二醇甲基醚、其它二醇醚类、γ-丁内酯、γ-戊内酯、二甲基乙酰胺、单乙醇胺或氨基丙基吗啉及其混合物；(c)0.5-15或0.5-14或0.5-12或0.5-10或10.5-15或11-14或11-13或10-20或0.5-5或0.5-4或0.5-3或1-10或1-5或1-4或1-3或3-4质量％的至少一种腐蚀抑制剂，其选自邻苯二酚、叔丁基邻苯二酚、苯甲酸铵、邻氨基苯甲酸、苯甲酸、水杨酸、柠檬酸、没食子酸、单或二羟基苯甲酸、聚乙烯亚胺(PEI)或者其混合物和/或二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物；和(d)0.5-25或0.5-10或1-10或1-8或1-7或2-5或1-5或1-2或3-7或4-6质量％的水。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)0.5-5或0.5-4或0.5-3或1-5或1-4或1-3或1-2或1.5-3或1.8-2.3或1.25-4.5质量％的一种或多种季铵氢氧化物；(b)60-97.5或60-96或73-98或75-96或90-96或89-95或78-85或64-69或80.5-82.5或82-97.5或80-83或85-96或89-94或85-97.5或86-97或91-96质量％的二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物及选自丙二醇、四氢糠醇、二丙二醇甲基醚、其它二醇醚、γ-丁内酯、γ-戊内酯、二甲基乙酰胺、单乙醇胺、二乙醇胺、氨基丙基吗啉或其它溶剂或者其混合物的至少一种另外的有机溶剂；(c)0.5-15或0.5-14或0.5-12或0.5-10或10-20或10.5-15或11-14或11-13或0.5-5或0.5-4或0.5-3或1-10或1-5或1-4或1-3或3-4质量％的二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物及选自邻苯二酚、叔丁基邻苯二酚、苯甲酸铵、邻氨基苯甲酸、苯甲酸、水杨酸、柠檬酸、没食子酸、单或二羟基苯甲酸、聚乙烯亚胺(PEI)或者其混合物的至少一种另外的腐蚀抑制剂；和(d)0.5-25或0.5-10或1-10或1-8或1-7或2-5或1-5或1-2或3-7或4-6质量％的水。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)0.5-5或1-5或1.25-4.5质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)82-97.5或85-96或89-94质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，该水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物；(c)1-5或1-4或1-3质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物；和(d)1-10或1-8或1-7质量％的水。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)0.5-5或1-5或1.25-4.5质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)水溶性有机溶剂的混合物，其包含80-96或83-94或87-92质量％的二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物及1-4或2-3或2质量％的至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂；(c)1-5或1-4或1-3质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物；和(d)1-10或1-8或1-7质量％的水。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)0.5-5或1-5或1.25-4.5质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)82-97.5或85-96或89-94质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，该水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物；(c)1-5或1-4或1-3质量％的两种或更多种腐蚀抑制剂的混合物，其中包含PEI；和(d)1-10或1-8或1-7质量％的水。在该光刻胶清洁组合物中，所述PEI可以以1-2或1质量％存在。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)0.5-5或1-5或1.25-4.5质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)水溶性有机溶剂的混合物，其包含80-96或83-94或87-92质量％的二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物及1-4或2-3或2质量％的至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂；(c)1-5或1-4或1-3质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物，其中包含PEI；和(d)1-10或1-8或1-7质量％的水。在该光刻胶清洁组合物中，所述PEI可以以1-2或1质量％存在。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)0.5-5或1-5或1-2质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)85-97.5或86-97或91-96质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，该水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物；(c)1-10或1-5或3-4质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物；和(d)1-10或1-5或1-2质量％的水。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)0.5-5或1-5或1-2质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)水溶性有机溶剂的混合物，其包含35-50或38-45或41-44质量％的二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物及45-58或48-54或50-52质量％的另外的有机溶剂或者两种或更多种另外的有机溶剂；(c)1-10或1-5或3-4质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物；和(d)1-10或1-5或1-2质量％的水。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)1-5或1.5-3或1.8-2.3质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)78-85或80-83或80.5-82.5质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，该水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物；(c)10.5-15或11-14或11-13质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物；和(d)1-10或3-7或4-6质量％的水。光刻胶清洁组合物可以包含胺或烷醇胺作为另外的有机溶剂。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)1-5或1.5-3或1.8-2.3质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)59-84或65-81或63-67质量％的二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物及1-20或1-15或2-15质量％的至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂；(c)10.5-15或11-14或11-13质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物；和(d)1-10或3-7或4-6质量％的水。在任何方面中，光刻胶清洁组合物可以包含胺或烷醇胺作为另外的有机溶剂。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)1-5或1.5-3或1.8-2.3质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)78-85或80-83或80.5-82.5质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，该水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物；(c)10-20或5-14.5或7-12或9-11质量％的二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物及0.5-5或1-4或1-3质量％的至少一种另外的腐蚀抑制剂或者两种或更多种另外的腐蚀抑制剂的混合物；和(d)1-10或3-7或4-6质量％的水。光刻胶清洁组合物可以包含胺或烷醇胺作为另外的有机溶剂。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)1-5或1.5-3或1.8-2.3质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)59-84或65-81或63-67质量％的二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物及1-20或1-15或2-15质量％的至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂；(c)10-20或5-14.5或7-12或9-11质量％的二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物及0.5-5或1-4或1-3质量％的至少一种另外的腐蚀抑制剂或者两种或更多种另外的腐蚀抑制剂的混合物；和(d)1-10或3-7或4-6质量％的水。光刻胶清洁组合物可以包含胺或烷醇胺作为另外的有机溶剂。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)1-5或1.5-3或1.8-2.3质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)64-69质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，该水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物，该至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂包含烷醇胺，通常C1-C6烷醇胺，例如单乙醇胺；(c)10.5-15或11-14或11-13质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物；(d)1-10或3-7或4-6质量％的水。
在单独的或与其它方面结合的本发明任何方面中，水溶性有机溶剂可以包含二甲亚砜和选自丙二醇、四氢糠醇、二丙二醇甲基醚、其它二醇醚、γ-丁内酯、γ-戊内酯、二甲基乙酰胺、单乙醇胺和氨基丙基吗啉及其混合物的至少一种另外的有机溶剂。在单独的或与其它方面结合的本发明任何方面中，光刻胶清洁组合物可以包含选自四甲基氢氧化铵或四乙基氢氧化铵及其混合物的季铵氢氧化物。
本发明的另一方面提供了用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，其包含(a)1-3质量％的季铵氢氧化物，如四甲基氢氧化铵或四乙基氢氧化铵；(b)90-95质量％的二甲亚砜及1-6质量％的选自丙二醇、四氢糠醇、二丙二醇甲基醚、其它二醇醚、γ-丁内酯、γ-戊内酯、二甲基乙酰胺、单乙醇胺和氨基丙基吗啉及其混合物的至少一种另外的有机溶剂；(c)0.5-3质量％的选自邻苯二酚、叔丁基邻苯二酚、苯甲酸铵、邻氨基苯甲酸、苯甲酸、水杨酸、柠檬酸、没食子酸、单或二羟基苯甲酸、聚乙烯亚胺(PEI)或者其混合物的至少一种腐蚀抑制剂；和(d)2-5质量％的水。
在单独的或与其它方面结合的本发明任何方面中，另外的有机溶剂选自丙二醇、其它二醇类、二醇类、三醇类、环状醇类、四氢糠醇、二丙二醇甲基醚、其它二醇醚、γ-丁内酯、γ-戊内酯、二甲基乙酰胺、单乙醇胺或其它烷基烷醇胺(如二乙醇乙胺、氨基丙基吗啉)及其混合物。在本发明的任何方面中，至少一种腐蚀抑制剂选自邻苯二酚、叔丁基邻苯二酚、苯甲酸铵、邻氨基苯甲酸、苯甲酸、水杨酸、柠檬酸、没食子酸、单或二羟基苯甲酸、聚乙烯亚胺(PEI)、二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物，或者任何腐蚀抑制剂的混合物。
在本发明的任何方面中，腐蚀抑制剂(单独地或与其它方面结合)可以包含PEI，其可以以1-2或1质量％存在。在任何方面中，组分(b)(单独地或与本发明的其它方面结合)可以包含丙二醇和/或二甲亚砜。在其它方面中，单独地或与本发明的其它方面结合，组分(b)可以包含甘醇或二丙二醇甲基醚。
在光刻胶清洁组合物的一个方面中，组分(c)(单独地或与本发明的其它方面结合)选自邻苯二酚、叔丁基邻苯二酚、苯甲酸铵、邻氨基苯甲酸、苯甲酸、水杨酸、柠檬酸、没食子酸、单或二羟基苯甲酸、聚乙烯亚胺(PEI)或者其混合物；或者其中组分(c)(单独地或与本发明的其它方面结合)选自邻苯二酚、叔丁基邻苯二酚、没食子酸、单-或二-羟基苯甲酸或者其混合物；或者其中组分(c)(单独地或与本发明的其它方面结合)选自邻苯二酚、叔丁基邻苯二酚、单-或二-羟基苯甲酸或者其混合物；或者其中组分(c)(单独地或与本发明的其它方面结合)选自邻苯二酚、叔丁基邻苯二酚或者其混合物；或者其中组分(c)(单独地或与本发明的其它方面结合)选自柠檬酸、聚乙烯亚胺(PEI)或者其混合物。在根据任何前述实施方式的光刻胶清洁组合物中，单独地或与本发明的其它方面结合，其中光刻胶图案可以是使用正性或负性作用光刻胶组合物(其在用辐射照射时聚合)形成的光固化图案。
在本发明的其它方面中，腐蚀抑制剂(单独地或与本发明的其它方面结合)包含或进一步包含DEHA，或其中腐蚀抑制剂包含或进一步包含PEI。在本发明的其它方面中，单独地或与本发明的其它方面结合，其中另外的有机溶剂包含或进一步包含丙二醇，或进一步包含烷醇胺，如单乙醇胺。
在本发明的其它方面中，任何实施方式的或任何方法中使用的光刻胶清洁组合物，单独地或与其它方面结合，可以不含酰胺类，或不含内酰胺类，或不含咪唑啉酮类，或不含砜类，或不含醚类，或不含烷醇胺类，或不含羟胺类，或不含酸类。在另一方面中，本发明的任何方法中使用的本发明的任何组合物，单独地或与其它方面结合，可以具有9、或大于9.5、或9.5-12.5、或9.5-13、或10-12、或10.5-11.5、或11-12.5的pH。
而且，在另外的方面中，本发明提供用于处理衬底的方法，包括在其上具有金属薄膜的衬底上形成膜厚度为3-150μm的光刻胶图案，在金属薄膜-暴露区域或光刻胶图案未覆盖区域上提供导电层，和使所述光刻胶图案与光刻胶清洁组合物接触以使用本文中公开的任何光刻胶清洁组合物剥离光刻胶图案。
在本发明的其它方面中，本发明提供了用于处理衬底的方法，包括以下步骤：在其上具有金属薄膜的衬底上形成膜厚度为3-150μm的光刻胶图案，在金属薄膜-暴露区域或光刻胶图案未覆盖区域上提供非导电钝化层，使光刻胶图案与本文中公开的任何光刻胶清洁组合物接触以剥离光刻胶图案。
在本发明的其它方面中，提供了用于处理衬底的方法，包括在其上具有金属薄膜的衬底上形成膜厚度为3-150μm的光刻胶图案，在金属薄膜-暴露区域或光刻胶图案未覆盖区域上提供导电层，和使光刻胶图案与本文中公开的任何光刻胶清洁组合物接触以剥离和溶解光刻胶图案。
在该方法的其它方面中，光刻胶图案是使用正性或负性作用光刻胶组合物形成的光固化图案，该组合物在用辐射照射时聚合。
本发明的其它方面提供了用于处理衬底的方法，包括在其上具有金属薄膜的衬底上形成膜厚度为3-150μm的光刻胶图案，使所述光刻胶图案与本文中所述的任何光刻胶清洁组合物接触以剥离和溶解光刻胶图案，而不在金属薄膜-暴露区域或光刻胶图案未覆盖区域上提供导电层。
本发明的其它方面(单独地或与其它方面结合)提供了本发明的用于处理衬底的方法，其中光刻胶图案可以是使用正性或负性作用光刻胶组合物形成的光固化图案，该组合物在用辐射照射时聚合。
本发明的清洁组合物和方法提供以下的一种或多种益处：改善的其中光刻胶清洁组合物的组分的剥离性和溶解性及光刻胶在光刻胶清洁组合物中的溶解性，以及对Cu和其它金属的低腐蚀速率和钝化材料或衬底上存在的其它材料的低腐蚀。
具体实施方式
本发明的光刻胶清洁组合物用于剥离膜厚度为3-150μm的光刻胶图案，该光刻胶图案在其上具有金属薄膜的衬底上形成。光刻胶清洁组合物中的组分(a)可以是选自四甲基氢氧化铵(TMAH)或四乙基氢氧化铵(TEAH)或者其混合物的季铵氢氧化物。在替代的实施方式中，季铵氢氧化物可以是或可以包括四乙基氢氧化铵(TEAH)。在另一实例中，组合物可以包括四甲基氢氧化铵(TMAH)。在其它实例中，组合物可以包括以下的一种或多种：TEAH、TMAH、二甲基二丙基氢氧化铵、四丙基氢氧化铵、苄基三甲基氢氧化铵、二甲基二乙基氢氧化铵和/或四丁基氢氧化铵。在另外的实例中，组合物可以包括TEAH、TMAH、二甲基二丙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵或其组合。组分(a)的另外的实例包括四丙基氢氧化铵、四丁基氢氧化铵、甲基三丙基氢氧化铵和甲基三丁基氢氧化铵。组分(a)可以单独地使用或以其两种或更多种的混合物使用。
作为组分的一种或多种季铵化合物的总量可以是(a)本发明光刻胶清洁组合物中的0.5-5或0.5-4或0.5-3或1-5或1-4或1-3或1-2或1.5-3或1.8-2.3或1.25-4.5质量％。
作为组分(b)的水溶性有机溶剂的混合物可以包含二甲亚砜(DMSO)、环丁砜或二甲基砜中的一种或多种及与水混溶的至少一种有机溶剂。另外的有机溶剂可以选自丙二醇、四氢糠醇、二丙二醇甲基醚、其它二醇醚、γ-丁内酯、γ-戊内酯、二甲基乙酰胺、单乙醇胺和氨基丙基吗啉。
在一些实施方式中，本发明的光刻胶清洁组合物不含某些有机溶剂或另外的有机溶剂，其可以包括任意组合的以下任何一种或多种：胺类(不同于季铵化合物)、烷醇胺类、酰胺类、吗啉类、内酰胺类、咪唑类、咪唑啉酮类、砜类、酮类、酸类、醇类(例如，单醇类、二醇类、三醇类)、酯类、亚胺类和/或醚类。在一些实施方式中，组合物或另外的有机溶剂不是环丁砜和/或N-甲基-2-吡咯烷酮和/或其它N-烷基-吡咯烷类和/或其它吡咯烷类，和/或组合物不含环丁砜和/或N-甲基-2-吡咯烷酮和/或其它N-烷基-吡咯烷类和/或其它吡咯烷类。换句话说，作为一个实例，组合物可以是不含“烷醇胺”的，或者作为另外的实例，可以进一步包含另外的一种或多种溶剂(其是不含“醇”的和/或不含“二醇”的)。刚刚描述的任何组分可以代用于刚刚所列的实例中，如不含“酮”的和不含“咪唑”的，以描述本发明的任何方法中使用的任何光刻胶组合物。
作为本发明中的组分(b)，可以使用二甲亚砜(DMSO)、环丁砜或二甲基砜中的一种或多种与选自丙二醇、四氢糠醇、二丙二醇甲基醚、其它二醇醚、γ-丁内酯、γ-戊内酯、二甲基乙酰胺、单乙醇胺或其它烷醇胺和氨基丙基吗啉的一种或多种另外的有机溶剂的混合溶剂。作为本发明中的组分(b)，可以使用二甲亚砜和丙二醇的混合溶剂。可以使用二甲亚砜和甘醇的混合溶剂。还可以使用二甲亚砜和甘醇和烷醇胺的混合溶剂。
在一些实施方式中，二甲亚砜(DMSO)、环丁砜或二甲基砜中的一种或多种与一种或多种另外的水溶性有机溶剂的混合比率优选大于2:1，或大于5:1，或大于10:1，或大于15:1，或大于20:1，或大于25:1，或大于30:1，或大于35:1，或大于40:1，或大于45:1。组分(b)可以以三种或更多种有机溶剂的混合物使用。二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物中的一种或多种在光刻胶剥离剂(光刻胶清洁组合物)中可以以80-96或83-94或87-92或90-95质量％存在且溶剂的余量可以以光刻胶剥离剂组合物的1-4或2-3或2或1-6质量％存在。在替代的实施方式中，二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物中的一种或多种可以以58-84或65-81或63-67质量％存在且溶剂的余量可以以光刻胶清洁组合物的1-10或1-5或1.5-3质量％存在。
在替代的实施方式中，二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物中的一种或多种的质量％与另外的有机溶剂的质量％的比率可以小于1:2。在一些实施方式中，二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物中的一种或多种的质量％与另外的有机溶剂的质量％的比率为约1:0.9-1.5。在一些实施方式中，二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物中的一种或多种可以是35-50或38-45或41-44质量％且另外的有机溶剂可以是光刻胶清洁组合物的45-58或48-54或50-52质量％。在替代的实施方式中，二甲亚砜(DMSO)、环丁砜或二甲基砜中的一种或多种可以以34-59或35-53或40-50质量％的量存在且另外的有机溶剂可以是以光刻胶清洁组合物的40-65或46-60或48-55质量％存在的一种或多种溶剂。
另外的一种或多种溶剂可以选自以上所列的溶剂或它们可以是一种或多种二醇醚和/或一种或多种二醇。如果二醇醚和二醇在清洁组合物中与二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物一起使用，二醇醚可以以所存在的二醇量的大于15:1，或大于20:1，或大约25:1的量使用。
溶剂，组分(b)的总量可以是本发明的光刻胶清洁组合物的60-97.5或60-96或73-98或75-96或90-96或89-95或78-85或64-69或80.5-82.5或82-97.5或80-83或85-96或89-94或85-97.5或86-97或91-96质量％。
在一些实施方式中，溶剂组分(b)总量可以是光刻胶清洁组合物的78-85或64-69或80-83或82-97.5或80.5-82.5或85-96或89-94或85-97.5或86-97或91-96质量％。
作为组分(c)的腐蚀抑制剂的量可以是0.5-15或0.5-14或0.5-12或0.5-10或10.5-15或11-14或11-13或0.5-5或0.5-4或0.5-3或1-10或1-5或1-4或1-3或3-4质量％。腐蚀抑制剂减少金属薄膜或钝化材料或介电材料的腐蚀。腐蚀抑制剂可以选自邻苯二酚、叔丁基邻苯二酚、苯甲酸铵、邻氨基苯甲酸、苯甲酸、水杨酸、柠檬酸、没食子酸、单-或二-羟基苯甲酸、聚乙烯亚胺(PEI)或者其混合物。在一些实施方式中，优选的腐蚀抑制剂是4-羟基苯甲酸(4BHA)、或2,4-二羟基苯甲酸、或3,4-二羟基苯甲酸或3,5-二羟基苯甲酸，或者柠檬酸，其与聚乙烯亚胺(PEI)组合。在替代的实施方式中，光刻胶清洁组合物包含DEHA(作为至少一种腐蚀抑制剂)和甘醇(作为至少一种另外的有机溶剂)且可以进一步包含胺或烷醇胺。
在任何实施方式中，腐蚀抑制剂可以包含或可以另外进一步包含羟胺或其酸式盐，例如，二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物，其量为2-20或10-20或5-14.5或5-15或7-12或8-12或9-11质量％或约10质量％。二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物可以单独地作为腐蚀抑制剂使用或可以在一种或多种另外的腐蚀抑制剂之外使用。二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物可以以上面对于一种或多种腐蚀抑制剂所描述的量使用。在包含二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物的一些实施方式中，光刻胶清洁组合物可以包含60-94质量％的溶剂。该溶剂可以包含59-84或65-81或63-67质量％的二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物且1-10或1-5或1-4质量％可以是另外的有机溶剂。
作为组分(d)的水的量在本发明的光刻胶清洁组合物中可以是0.5-25或0.5-10或1-10或1-8或1-7或2-5或1-5或1-2或3-7或4-6质量％的水。
在DIW中稀释清洁组合物至5质量％后在室温下使用pH计测量时，清洁组合物的pH应当大于9，或大于9.5或为9.5-12.5或10-12或10.5-11.5或11-12.5。
光刻胶清洁组合物可能还包括以下任选添加剂中的一种或多种(只要这些添加剂没有不利地影响组合物的剥离和清洁性能，也不损伤下层的衬底表面)：表面活性剂、螯合剂、化学改性剂、染料、杀生物剂和/或其它添加剂，其量基于组合物的总重量高达总共5重量％。代表性添加剂的一些实例包括炔属醇及其衍生物、炔属二醇(非毒性烷氧基化和/或自身乳化炔属二醇表面活性剂)及其衍生物，及螯合剂如β-二酮类、β-酮亚胺类、苹果酸(mallic acid)和酒石酸基酯以及二酯类及其衍生物，及叔胺类、二胺类和三胺类。在替代的实施方式中，本发明的光刻胶清洁组合物可以不含任何该段落中单独地或总体地列出的添加剂。例如，清洁组合物可以不含表面活性剂和/或螯合剂和/或化学改性剂和/或染料和/或杀生物剂和/或胺和/或炔属醇，等。
对于厚的光刻胶图案(其是在本发明的方法中待通过本发明的光刻胶清洁组合物剥离和溶解的目标)，可以采用用于形成厚图案(用于形成凸点)的任何光刻胶组合物。
光聚合型负性作用光刻胶组合物和化学扩增型负性作用光刻胶组合物目前主要用于这类用于形成厚图案的光刻胶组合物。本发明的光刻胶清洁组合物相对于上述当前主要使用的光刻胶组合物应当表现出其有利的效果，但不限于此。预期本发明的光刻胶清洁组合物相对于用于i-射线的正性作用光刻胶组合物和化学扩增型正性作用光刻胶组合物也表现出其有利的效果。
在前述的各种光刻胶组合物中，据说光聚合型负性作用光刻胶组合物(其在照射时聚合且在碱中可能变成不溶性的)在光刻过程中最难以剥离和难以溶解在清洁溶液中。本发明的光刻胶清洁组合物可以有效地剥离且在许多情况中溶解这样的光聚合型负性作用光刻胶组合物。
光聚合型负性作用光刻胶组合物的实例包括含有聚合物组分(如(甲基)丙烯酸酯、环状含烷基(甲基)丙烯酸酯和苯乙烯基聚合物)、聚合引发剂、溶剂和交联剂作为主要组分的组合物。
化学扩增型负性作用光刻胶组合物的实例包括含有聚合物组分(如酚醛树脂)、交联剂、光酸产生剂和溶剂作为组成组分的组合物。
本发明的光刻胶清洁组合物的用途的实施方式及使用光刻胶清洁组合物处理衬底的方法的实施方式将在下面描述，但本发明不限于此。例如，描述了负性作用光刻胶涂层，但可以相反地使用正性作用光刻胶。
负性作用光刻胶涂层液体(其在照射时聚合且可能在碱中变成不溶性的)通过已知方法(如旋涂方法和滚涂方法)涂布(在涂层步骤中)在其上具有金属薄膜的衬底上，和然后干燥(其可以是在干燥步骤中)以形成光刻胶层。
金属薄膜的实例包括Cu、Cu合金、Al、Al合金、Ni、Au、Pd、TI、V、Cr和合金或者其分层结构，包括TiCu合金、TiCuNi合金和Cr:Cu或Cu:Ni:Au分层材料。金属薄膜的形成(在形成步骤中)通过例如CVD气相沉积方法、溅射方法、电镀方法等完成，但不限于此。
然后，光刻胶层通过掩模图案照射(在照射步骤中)并选择性地暴露。在以上负性作用光刻胶中，曝光的区域通过光聚合进行固化以变成光固化的区域。(对于正性作用光刻胶，未曝光的区域被固化。)辐射的类型包括紫外线、可见光、远紫外线、X射线、电子束等。辐射源包括低压汞蒸气灯、高压汞蒸气灯、超高压汞蒸气灯、KrF、ArF和F2准分子激光器。
之后，进行显影(在显影步骤中)，从而光刻胶层的未暴露区域被除去以形成膜厚度为3-150μm的光刻胶图案(光固化图案)。(对于正性作用光刻胶，暴露的区域被除去。)显影可以通过常用方法进行。在前述负性作用光刻胶中，碱性水溶液用作显影液。其具体实例包括氢氧化钠、氢氧化钾、碳酸钠、硅酸钠、偏硅酸钠、氨水、乙胺、正丙胺、二乙胺、二正丙胺、三乙胺、甲基二乙基胺、二甲基乙醇胺、三乙醇胺、四甲基氢氧化铵、四乙基氢氧化铵、吡咯、哌啶、1,8-二氮杂双环[5.4.0]-7-十一烯和1,5-[4.3.0]-5-壬烷。显影时间没有特别的限制，但通常为约30-360秒。常规方法可以用于显影，如浸渍法、浆板法和喷射法。
然后，衬底上的光刻胶未覆盖区域(金属薄膜暴露区域；即未照射区域)填充导电金属以形成导电层(凸点形成)。对于填充导电金属，尽管可以利用任意方法，但主要使用电镀方法。因此形成具有所需高度的凸点。凸点通常具有20μm或更大的高度。作为用于凸点形成的导电金属，使用任意金属如Cu、Cu合金、Al、Al合金、Ni、Au和焊料。本发明的光刻胶清洁组合物对于防止使用Cu或焊料作为导电金属的衬底的腐蚀是特别有效的。
在凸点形成过程中，光刻胶图案厚厚地形成，且因此不可避免的是，与形成薄膜图案的情况相比，图案易于引起其形状的变形，如塌陷和变形。如果在凸点形成完成之前的光刻胶图案形成过程中引起变形和塌陷，则有必要从衬底除去这种变形的光刻胶图案并再次从头涂布衬底用于凸点形成("返工")。
本发明的光刻胶清洁组合物在凸点已经形成后除去光刻胶图案方面或在除去变形的光刻胶图案用于返工过程方面是特别有效的。
也就是说，本发明的光刻胶清洁组合物在凸点形成后与光刻胶图案接触或者可与变形的光刻胶图案接触用于返工过程(其中凸点还未形成)，由此除去这些图案。
在光刻胶清洁组合物与光固化图案接触中，优选的是将衬底完全浸入光刻胶清洁组合物槽中。通过将衬底与光刻胶清洁组合物接触，光固化图案从衬底剥离而同时被部分溶解，且进一步在本发明中，它表现出良好的清洁以使得如此剥离掉的固化图案快速地溶解。尽管固化的图案从衬底剥离，如果剥离的固化图案保留在光刻胶清洁组合物槽中而没有快速溶解，则存在着剥离的光固化图案或其残留物再粘附到衬底或清洁槽中处理的后续衬底上的风险。
本发明的光刻胶清洁组合物允许光固化图案从衬底完全剥离且甚至在图案由负性作用光聚合光刻胶形成(其迄今为此被认为是难以完全除去的或花费长时间来除去，且在图案是厚的(例如，3-150μm)时甚至更难改除去)时被溶解。本发明表现出如从衬底的快速剥离的效果。而且，本发明能够有效地防止衬底上金属薄膜和凸点(导电层)的腐蚀。此外，本发明可以防止在凸点和光刻胶图案之间的界面处形成退化的膜。
衬底的浸渍时间可以是足以从衬底剥离光刻胶图案的时间且没有特别的限定，但通常为约10秒至20分钟。处理温度优选为约25-90℃，且特别地为40-80℃。在本发明的光刻胶清洁组合物中，固化的材料可以在约5-60分钟的时间内完全溶解。
另外，在本发明的方法中，在将其上具有光固化图案的衬底与本发明的光刻胶清洁组合物接触之前，衬底可以与臭氧的水溶液和/或过氧化氢的水溶液接触。此外，在本发明的方法中，其上具有光固化图案的衬底可以以循环的方式与以下接触：(1)臭氧水溶液或过氧化氢溶液，(2)一种或多种本文所述的光刻胶清洁组合物，(3)用DIW清洗，和(4)将步骤1-3重复1-10次。或者，可以仅将步骤2和3重复1-10次而不将衬底与臭氧水溶液或过氧化氢溶液接触。这一循环过程重复多达1-10次以实现衬底的完全清洁。
实施例
本发明下面参照以下实施例详细地描述，但不应理解为本发明限于这些实施例。包括在以下实施例中的在整个申请中的所有量以质量％计，除非另外指明。
光刻胶清洁组合物的制备
以下表格中显示的光刻胶清洁组合物通过在室温下搅拌板上的玻璃烧杯中组合所述量的单个组分来制备。
表格中用于相应组分的缩略词具有以下含义：
4BHA:4-羟基苯甲酸
DIW:去离子水
DMSO:二甲亚砜
PG:丙二醇
PEI:聚乙烯亚胺
TBC:叔丁基邻苯二酚
TMAH:四甲基氢氧化铵
组合物的pH通过在去离子水(DIW)中稀释组合物至5质量％后使用pH计在室温下测量该组合物来测定。
铝和铜及钝化材料的腐蚀(蚀刻)速率通过使用金属和钝化材料的空白芯片测试。如果蚀刻速率高于约则测试设定为持续20分钟，或如果蚀刻速率低于约则测试设定为60分钟。以计的厚度测量在时间0、3、5、10和20分钟或者0、10、20、40和60分钟后一式三份地进行。本文中报告了蚀刻速率的数值平均。金属厚度测量使用ResMap Four Point探针进行。钝化材料的膜厚度测量使用Filmtek椭率计。
清洁测试如下进行。具有预先固化和显影的光刻胶且其上早已形成微凸点的测试芯片从Fraunhofer IZM,Germany获得。一些芯片具有50μm的凸点直径，其它芯片具有25μm的凸点直径。具有50μm的凸点直径的芯片在各芯片中具有110、150、300和600μm的凸点间距。具有25μm的凸点直径的芯片在各芯片中具有55、75、150和300μm的凸点间距。芯片具有两种类型的金属堆叠以形成凸点：(a)Cu和SnAg及(b)Cu、Ni和SnAg。用于所有芯片的衬底具有50nm Ti和300nm Cu的涂层。光刻胶是AZ IPS-528，50μm厚。各2”x 2”的衬底块在500ml玻璃烧杯中浸入330ml的实施例清洁溶液中2-10分钟，同时溶液在搅拌板上以300rpm搅拌。溶液加热并记录温度。温度是～40-65℃。在浸渍后，衬底在环境下用DI水清洗3分钟并用氮气干燥。处理的衬底使用SEM照相且照片目视检查并使用以下等级分级：
√√√√＝完全清洁
√√√＝意指少量残留物
√√＝意指部分清洁
√＝意指很少至没有清洁
*TMAH是25质量％水溶液
*Al(4％Cu)
如以上详细描述的，通过使用本发明的光刻胶清洁组合物，有可能不仅从衬底剥离用于形成凸点的厚光刻胶图案，而且在光刻胶清洁组合物中溶解剥离的光刻胶图案而不引起对衬底的再粘附。而且，有可能提高生产效率。

Claims (20)

1.一种用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，所述组合物包含(a)0.5-5质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)60-97.5质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，所述水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物；(c)0.5-15质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物；和(d)0.5-25质量％的水。
2.根据权利要求1所述的光刻胶清洁组合物，所述组合物包含(a)0.5-5质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)82-97.5质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，所述水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物；(c)1-5质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物；和(d)1-10质量％的水。
3.根据权利要求1所述的光刻胶清洁组合物，其中(b)包含80-96质量％的所述二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物，及1-4质量％的所述至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂；且所述(c)占1-5质量％；和所述(d)占1-10质量％。
4.根据权利要求2所述的光刻胶清洁组合物，其中所述(c)包含两种或更多种腐蚀抑制剂的混合物，该混合物包含PEI。
5.根据权利要求1所述的光刻胶清洁组合物，其中所述(b)包含80-96质量％的二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物，及1-4质量％的至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂；其中所述(c)是1-10质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物，该混合物包含PEI；和所述(d)是1-10质量％。
6.根据权利要求1所述的光刻胶清洁组合物，其中所述(b)包含35-50质量％的二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物及45-58质量％的另外的有机溶剂或者两种或更多种另外的有机溶剂；所述(c)是1-10质量％；和所述(d)是1-10质量％。
7.根据权利要求1所述的光刻胶清洁组合物，其中所述(a)是1-5质量％；所述(b)是78-85质量％；所述(c)是10.5-15质量％；和所述(d)是1-10质量％。
8.根据权利要求1所述的光刻胶清洁组合物，其中所述(a)是1-5质量％；所述(b)是59-84质量％的二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物及1-20质量％的至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂；所述(c)是10.5-15质量％；和所述(d)是1-10质量％。
9.一种用于剥离膜厚度为3-150μm的光刻胶图案的光刻胶清洁组合物，所述组合物包含(a)1-5质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)78-85质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，所述水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物；(c)10-20质量％的二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物及0.5-5质量％的至少一种另外的腐蚀抑制剂或者两种或更多种另外的腐蚀抑制剂的混合物；和(d)1-10质量％的水。
10.根据权利要求8所述的光刻胶清洁组合物，其中所述(c)是10-20质量％的二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物及0.5-5或1-4或1-3质量％的至少一种另外的腐蚀抑制剂或者两种或更多种另外的腐蚀抑制剂的混合物。
11.根据权利要求8所述的光刻胶清洁组合物，其中所述(b)是64-69质量％的包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物的有机溶剂与包含烷醇胺的至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物。
12.根据权利要求1所述的光刻胶清洁组合物，其中所述(b)是75-96质量％的包含二甲亚砜的水溶性有机溶剂与至少一种另外的有机溶剂的混合物，所述至少一种另外的有机溶剂选自丙二醇、四氢糠醇、二醇醚、γ-丁内酯、γ-戊内酯、二甲基乙酰胺、单乙醇胺和氨基丙基吗啉及其混合物；所述(c)是0.5-5质量％的至少一种腐蚀抑制剂，其选自邻苯二酚、叔丁基邻苯二酚、苯甲酸铵、邻氨基苯甲酸、苯甲酸、水杨酸、柠檬酸、没食子酸、单-或二-羟基苯甲酸、聚乙烯亚胺(PEI)或者其混合物；和所述(d)是0.5-10质量％。
13.根据权利要求1所述的光刻胶清洁组合物，其中所述(a)包含1-3质量％的季铵氢氧化物，其选自四甲基氢氧化铵或四乙基氢氧化铵及其混合物；所述(b)是90-96质量％的二甲亚砜及至少一种选自丙二醇、四氢糠醇、二醇醚、γ-丁内酯、γ-戊内酯、二甲基乙酰胺、单乙醇胺和氨基丙基吗啉及其混合物的另外的有机溶剂；和所述(c)是0.5-4质量％的至少一种腐蚀抑制剂，其选自邻苯二酚、叔丁基邻苯二酚、苯甲酸铵、邻氨基苯甲酸、苯甲酸、水杨酸、柠檬酸、没食子酸、单或二羟基苯甲酸、聚乙烯亚胺(PEI)或者其混合物；和所述(d)是2-5质量％。
14.根据权利要求13所述的光刻胶清洁组合物，其中所述(b)是90-95质量％的二甲亚砜及1-6质量％的至少一种选自丙二醇、四氢糠醇、二丙二醇甲基醚、γ-丁内酯、γ-戊内酯、二甲基乙酰胺、单乙醇胺和氨基丙基吗啉或其混合物的另外的有机溶剂；和所述(c)是0.5-3质量％。
15.根据权利要求1所述的光刻胶清洁组合物，其中所述至少一种腐蚀抑制剂选自邻苯二酚、叔丁基邻苯二酚、苯甲酸铵、邻氨基苯甲酸、苯甲酸、水杨酸、柠檬酸、没食子酸、单或二羟基苯甲酸、聚乙烯亚胺(PEI)、二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物，或者任何所述腐蚀抑制剂的混合物。
16.一种用于处理衬底的方法，所述方法包括在其上具有金属薄膜的衬底上形成膜厚度为3-150μm的光刻胶图案，在金属薄膜-暴露区域或光刻胶图案未覆盖区域上提供导电层，和使所述光刻胶图案与光刻胶清洁组合物接触以剥离和溶解所述光刻胶图案，该光刻胶清洁组合物包含(a)0.5-5质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)60-97.5质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，所述水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物；(c)0.5-15质量％的至少一种腐蚀抑制剂或者两种或更多种腐蚀抑制剂的混合物；和(d)0.5-25质量％的水。
17.根据权利要求16所述的用于处理衬底的方法，其中所述(b)是82-97.5质量％；所述(c)是1-5质量％；和所述(d)是1-10质量％。
18.根据权利要求17所述的用于处理衬底的方法，其中所述(c)包含两种或更多种腐蚀抑制剂的混合物，该混合物包含PEI。
19.根据权利要求16所述的用于处理衬底的方法，其中所述(b)包含35-50质量％的二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物及45-58质量％的另外的有机溶剂或者两种或更多种另外的有机溶剂；所述(c)是1-10质量％；和所述(d)是1-10质量％。
20.一种用于处理衬底的方法，所述方法包括在其上具有金属薄膜的衬底上形成膜厚度为3-150μm的光刻胶图案，在金属薄膜-暴露区域或光刻胶图案未覆盖区域上提供导电层，和使所述光刻胶图案与光刻胶清洁组合物接触，所述光刻胶清洁组合物包含(a)1-5质量％的至少一种季铵氢氧化物或者两种或更多种季铵氢氧化物的混合物；(b)78-85质量％的水溶性有机溶剂与至少一种另外的有机溶剂或者两种或更多种另外的有机溶剂的混合物，所述水溶性有机溶剂包含二甲亚砜(DMSO)、环丁砜或二甲基砜或者其混合物；(c)10-20质量％的二乙基羟胺(DEHA)、羟胺或二丙基羟胺或者其盐或其混合物及0.5-5质量％的至少一种另外的腐蚀抑制剂或者两种或更多种另外的腐蚀抑制剂的混合物；和(d)1-10质量％的水。
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