CN1578932A - 剥离抗蚀剂的方法 - Google Patents
剥离抗蚀剂的方法 Download PDFInfo
- Publication number
- CN1578932A CN1578932A CNA028216881A CN02821688A CN1578932A CN 1578932 A CN1578932 A CN 1578932A CN A028216881 A CNA028216881 A CN A028216881A CN 02821688 A CN02821688 A CN 02821688A CN 1578932 A CN1578932 A CN 1578932A
- Authority
- CN
- China
- Prior art keywords
- resist stripping
- resist
- stripping composition
- stripping means
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
- H01L21/31138—Etching organic layers by chemical means by dry-etching
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Abstract
在本发明的抗蚀剂剥离方法中,在氧气比例为2%体积或更低的氛围中,使具有残留抗蚀剂层的布线基质与抗蚀剂剥离组合物接触。优选在用过氧化氢预处理残留的抗蚀剂层之后除去抗蚀剂。在本发明的抗蚀剂剥离方法中优选使用含胺化合物、溶剂、强碱和水的抗蚀剂剥离组合物。
Description
技术领域
本发明涉及在半导体集成电路、液晶板、有机EL板、印刷电路板等的制造中使用的除去抗蚀剂的组合物与方法。
背景技术
在集成电路如IC和LSI、显示器件如LCD和EL器件、印刷电路板、微型机器、DNA芯片和微型装置的平版印刷生产中广泛使用光致抗蚀剂。
含有机碱和水溶性溶剂的溶液常规用作抗蚀剂剥离组合物。特别地,胺化合物常用作有机碱,和作为抗蚀剂剥离组合物,已使用例如含烷醇胺和二甲亚砜的非含水溶液;含烷醇胺、水溶性溶剂和糖醇的水溶液;含烷醇胺、羟胺和儿茶酚的水溶液。这些碱性抗蚀剂剥离组合物在除去包括含酚羟基化合物和含酯键化合物的抗蚀剂方面是相当有效的。
这些抗蚀剂剥离组合物已用于在室温-100℃下主要除去在非铜基质如铝和铝合金上的抗蚀剂。
最近,低电阻铜开始用作布线材料,特别地日益用作以LSI为代表的半导体用布线材料。同时,低介电层开始用作绝缘材料。在常规方法中,形成抗蚀剂,进行干蚀和灰化,然后除去。然而灰化工艺易于改变低介电层的表面性质,有损电路的功能。因此,要求不进行灰化工艺的方法。由于干蚀抗蚀剂其性质显著变化,所以不可能采用已知的含胺化合物作为有效成分的抗蚀剂剥离组合物来充分除去抗蚀剂。此外,由于含胺化合物的抗蚀剂剥离组合物产生铜胺络合物,因此容易腐蚀铜线。
发明公开
本发明的目的是提供在没有腐蚀铜,特别地铜线情况下,通过使用含胺化合物的抗蚀剂剥离组合物,除去抗蚀剂的方法。本发明另一目的是提供在除去抗蚀剂的方法中使用的含胺化合物的抗蚀剂剥离组合物。
本发明者对在除去铜线基质上的抗蚀剂进行了深入研究,结果发现,含胺化合物、溶剂、强碱和水的组合物,在没有腐蚀铜或铜合金的情况下,可除去抗蚀剂。
此外,本发明者深入研究了在没有腐蚀铜的情况下,除去抗蚀剂的最佳条件。结果,与胺化合物腐蚀铜的一般知识相反,本发明者发现,溶解在抗蚀剂剥离组合物内的氧气氧化铜,和氧化的铜被转化成可溶的铜胺络合物,促进铜的腐蚀,也就是说,已发现,溶解在抗蚀剂剥离组合物内的氧气是腐蚀铜的主要原因。
因此,本发明提供一种抗蚀剂剥离方法,它包括以下步骤:在含比例为2%体积或更低的氧气的氛围中,使在蚀刻后具有残留抗蚀剂的布线基质与抗蚀剂剥离组合物接触。在优选的实施方案中,在用过氧化氢预处理残留的抗蚀剂层之后进行与抗蚀剂剥离组合物的接触。
此外,本发明提供一种抗蚀剂剥离组合物,它包括胺化合物、溶剂、强碱和水,它可在以上的抗蚀剂剥离方法中使用。
实施本发明的最佳模式
抗蚀剂剥离组合物包括胺化合物、溶剂、强碱(任选组分)和水。
胺化合物的实例包括氨、单烷胺、二烷胺、三烷胺、烷醇胺、多胺、羟胺化合物和环胺。
单烷胺可包括甲胺、乙胺、正丙胺、异丙胺、正丁胺、仲丁胺、异丁胺、叔丁胺、戊胺、2-氨基戊烷、3-氨基戊烷、1-氨基甲基丁烷、2-氨基-2-甲基丁烷、3-氨基-2-甲基丁烷、4-氨基-2-甲基丁烷、己胺、5-氨基-2-甲基戊烷、庚胺、辛胺、壬胺、癸胺、十一烷胺、十二烷胺、十三烷胺、十四烷胺、十五烷胺、十六烷胺、十七烷胺和十八烷胺;二烷胺可包括二甲胺、二乙胺、二丙胺、二异丙胺、二正丁胺、二异丁胺、二仲丁胺、二叔丁胺、二戊胺、二己胺、二庚胺、二辛胺、二壬胺、二癸胺、甲基乙胺、甲基丙胺、甲基异丙胺、甲基正丁胺、甲基异丁胺、甲基仲丁胺、甲基叔丁胺、甲基戊胺、甲基异戊胺、乙基丙胺、乙基异丙胺、乙基正丁胺、乙基异丁胺、乙基仲丁胺、乙基叔丁胺、乙基异戊胺、丙基正丁胺和丙基异丁胺;和三烷胺可包括三甲胺、三乙胺、三丙胺、三丁胺、三戊胺、二甲基乙胺、甲基二乙胺和甲基二丙胺。
烷醇胺可包括包括乙醇胺、1-氨基-2-丙醇、N-(氨基乙基)乙醇胺、N-甲基乙醇胺、N-乙基乙醇胺、N-丙基乙醇胺、N-丁基乙醇胺、二乙醇胺、异丙醇胺、N-甲基异丙醇胺、N-乙基异丙醇胺、N-丙基异丙醇胺、2-氨基丙烷-1-醇、N-甲基-2-氨基丙烷-1-醇、N-乙基-2-氨基丙烷-1-醇、1-氨基丙烷-3-醇、N-甲基-1-氨基丙烷-3-醇、N-乙基-1-氨基丙烷-3-醇、1-氨基丁烷-2-醇、N-甲基-1-氨基丁烷-2-醇、N-乙基-1-氨基丁烷-2-醇、2-氨基丁烷-1-醇、N-甲基-2-氨基丁烷-1-醇、N-乙基-2-氨基丁烷-1-醇、3-氨基丁烷-1-醇、N-甲基-3-氨基丁烷-1-醇、N-乙基-3-氨基丁烷-1-醇、1-氨基丁烷-4-醇、N-甲基-1-氨基丁烷-4-醇、N-乙基-1-氨基丁烷4-醇、1-氨基-2-甲基丙烷-2-醇、2-氨基-2-甲基丙烷-1-醇、1-氨基戊烷-4-醇、2-氨基-4-甲基戊烷-1-醇、2-氨基己烷-1-醇、3-氨基庚烷-4-醇、2-氨基辛烷-2-醇、5-氨基辛烷-4-醇、1-氨基丙烷-2,3-二醇、2-氨基丙烷-1,3-二醇、三(氧甲基)氨基甲烷、1,2-二氨基丙烷-3-醇、1,3-二氨基丙烷-2-醇和2-(2-氨基乙氧基)乙醇。
多胺可包括乙二胺、丙二胺、三亚甲基二胺、四亚甲基二胺、1,3-二氨基丁烷、2,3-二氨基丁烷、五亚甲基二胺、2,4-二氨基戊烷、六亚甲基二胺、七亚甲基二胺、八亚甲基二胺、九亚甲基二胺、N-甲基乙二胺、N,N-二甲基乙二胺、三甲基乙二胺、N-乙基乙二胺、N,N-二乙基乙二胺、三乙基乙二胺、1,2,3-三氨基丙烷、肼、三(2-氨基乙基)胺、四(氨基甲基)甲烷、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、七亚乙基八胺、九亚乙基十胺、二氮杂双环十一碳烯、肼、二甲基肼、甲基肼和羟乙基肼。
羟胺化合物可包括羟胺、N-甲基羟胺、N-乙基羟胺和N,N-二乙基羟胺。
环胺可包括吡咯、2-甲基吡咯、3-甲基吡咯、2-乙基吡咯、3-乙基吡咯、2,3-二甲基吡咯、2,4-二甲基吡咯、3,4-二甲基吡咯、2,3,4-三甲基吡咯、2,3,5-三甲基吡咯、2-吡咯啉、吡咯烷、2-甲基吡咯烷、3-甲基吡咯烷、吡唑、咪唑、1,2,3-三唑、1,2,3,4-四唑、哌啶、2-甲基哌啶、3-甲基哌啶、4-甲基哌啶、2,4-二甲基哌啶、2,6-二甲基哌啶、3,5-二甲基哌啶、哌嗪、2-甲基哌嗪、2,5-二甲基哌嗪、2,6-二甲基哌嗪和吗啉。
在以上所述的胺化合物当中,优选至少一种选自下述的化合物:乙醇胺、1-氨基-2-丙醇、N-(氨基乙基)乙醇胺、N-甲基乙醇胺、N-乙基乙醇胺、二乙醇胺、异丙醇胺、2-(2-氨基乙氧基)乙醇、乙二胺、丙二胺、丁二胺、二亚乙基三胺、哌嗪、吗啉、三亚乙基四胺、四亚乙基五胺和五亚乙基六胺。
强碱优选至少一种选自下述物质中的化合物:四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵、氢氧化胆碱和氢氧化乙酰胆碱,其中更优选四甲基氢氧化铵和氢氧化胆碱。
溶剂优选可与胺化合物混溶,和其实例包括醚溶剂如乙二醇、乙二醇单乙醚、乙二醇单丁醚、二甘醇单甲醚、二甘醇单乙醚、二甘醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单丁醚、二丙二醇单甲醚、二丙二醇单乙醚、二丙二醇单丁醚、二甘醇二甲醚和二丙二醇二甲醚;酰胺溶剂如甲酰胺、单甲基甲酰胺、二甲基甲酰胺、单乙基甲酰胺、二乙基甲酰胺、乙酰胺、单甲基乙酰胺、二甲基乙酰胺、单乙基乙酰胺、二乙基乙酰胺、N-甲基吡咯烷酮和N-乙基吡咯烷酮;醇溶剂如甲醇、乙醇、异丙醇、乙二醇和丙二醇;亚砜溶剂如二甲亚砜;砜溶剂如二甲砜、二乙砜、双(2-羟基砜)和四亚甲基砜;咪唑烷酮溶剂如1,3-二甲基-2-咪唑烷酮、1,3-二乙基-2-咪唑烷酮和1,3-二异丙基-2-咪唑烷酮;和内酯溶剂如γ-丁内酯和δ-戊内酯。
在上述溶剂当中,优选二甲亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甘醇单甲醚、二甘醇单丁醚、二丙二醇单甲醚、二丙二醇单丁醚和丙二醇,这是因为它们容易获得且由于高沸点导致容易处理的性质所致。另外,上述胺化合物可用作溶剂。
为了在没有腐蚀铜线的情况下除去抗蚀剂,抗蚀剂剥离组合物优选含有5-95wt%的胺化合物,3-85wt%的溶剂,0.01-5wt%的强碱,和1-25wt%的水;更优选含有10-40wt%的胺化合物,50-80wt%的溶剂,0.1-3wt%的强碱,和5-20wt%的水。本发明的抗蚀剂剥离组合物可含有用量不负面影响本发明效果的常规添加剂,如表面活性剂和包括山梨醇和儿茶酚在内的抗腐蚀剂。
可毫无具体限制地通过常规已知的方法生产抗蚀剂剥离组合物。
在本发明中,通过在20-60℃下,使在蚀刻之后和优选在灰化之前的残留抗蚀剂,与抗蚀剂剥离组合物接触1-30分钟,其中所述抗蚀剂剥离组合物包括胺化合物、溶剂、强碱(任选的组分)和水。通常通过将具有残留抗蚀剂的基质浸渍在抗蚀剂剥离组合物内进行接触操作。
例如,广泛使用的含酚羟基的抗蚀剂因干蚀工艺而变化其表面性质。已知的抗蚀剂剥离组合物通过利用在胺化合物与酚羟基之间形成的盐,和胺化合物与通过氧化形成的羰基的加成反应,从而除去抗蚀剂,然而,对其性质显著变化的抗蚀剂的除去不那么有效。在这种情况下,使用含强碱的抗蚀剂剥离组合会提高与酚羟基形成盐的能力和除去在干蚀工艺中生成的卤素的能力,和还增加水解功能。
如上所述,溶解在抗蚀剂剥离组合物内的氧气是铜与铜合金腐蚀的主要原因。在3%或更高的碱含量(胺化合物+强碱)和在抗蚀剂除去操作中氛围的高氧气浓度下,腐蚀作用变得显著。因此,在本发明中,在2%体积或更小,优选1%体积或更小的氧气浓度下,除去抗蚀剂,以便有效防止铜与铜合金的腐蚀。通过使用氮气、氩气或氢气,优选使用氮气,实现低氧氛围。更优选地,为了有效防止铜与铜合金的腐蚀,在2%体积或更小的氧气浓度下,同时通过向其中吹入诸如氮气、氩气和氢气之类气体维持抗蚀剂剥离组合物内已溶解的氧气含量为3ppm或更小的情况下,除去抗蚀剂。可在使用之前除去抗蚀剂剥离组合物内的空气。如上所述,本发明的抗蚀剂剥离组合物可最有效地除去在具有铜层或铜合金层的基质上残留的抗蚀剂。
此外,本发明者发现,通过过氧化氢预处理可有效地除去其性能显著变化的抗蚀剂。用过氧化氢预处理会氧化其性能显著变化的抗蚀剂表面,降低分子量,从而促进羰基的形成。如上所述,这加速抗蚀剂的除去。
通过在蚀刻之后和用抗蚀剂剥离组合物处理之前,例如在20-60℃下,通过将布线基质浸渍在含0.5wt%或更高,优选1-10wt%过氧化氢的溶液中1-30小时,使布线基质与过氧化氢接触,从而进行用过氧化氢的预处理。过氧化氢溶液可以是水溶液。添加剂如螯合剂和表面活性剂可加入到过氧化氢溶液中。直接或在用水洗涤之后对用过氧化氢预处理的布线基质进行抗蚀剂除去操作。
通过参考下述实施例,更详细地解释本发明,其中实施例不应当解释为限制本发明的范围。
实施例1-6和对比实施例1与2
在具有按照以下所述顺序在硅基质上层压铜层、氮化硅层、二氧化硅层间绝缘层和抗蚀剂层的6英寸晶片上干蚀,形成通路孔结构。该通路孔结构到达铜层。在70℃下,将基质浸渍在具有以下所示配方的抗蚀剂剥离组合物中30分钟。在用水漂洗之后,在扫描电子显微镜下检验抗蚀剂的除去程度和铜层的腐蚀。结果见表2。
在氮气氛围内,用获自N.T.Corporation的数字氧气分析仪(DO-5509型号,检测下限为0.5ppm),测量抗蚀剂剥离组合物内溶解的氧气含量。
表1
抗蚀剂剥离组合物 | |||||||
胺化合物 | 溶剂 | 强碱 | 水 | ||||
种类 | wt% | 种类 | wt% | 种类 | wt% | ||
实施例 | |||||||
1 | EA | 30 | DMSO | 60 | TMAH | 0.2 | 平衡量 |
2 | EA | 25 | NMP | 65 | TMAH | 1 | 平衡量 |
3 | 1A2P | 32 | PG | 61 | TMAH | 0.5 | 平衡量 |
4 | TETA | 18 | DGME | 72 | CH | 1 | 平衡量 |
5 | PEHA | 30 | DGBE | 60 | TMAH | 2 | 平衡量 |
6 | AEEA | 10 | MEA | 80 | CH | 0.1 | 平衡量 |
对比实施例 | |||||||
1 | EA | 30 | DMSO | 60 | - | - | 平衡量 |
2 | EA | 30 | DMSO | 60 | TMAH | 0.2 | 平衡量 |
EA: 乙醇胺
1A2P: 1-氨基-2-丙醇
TETA: 三亚乙基四胺
PEHA: 五亚乙基六胺
AEEA: 氨基乙基乙醇胺
TMAH: 四甲基氢氧化铵
CH: 氢氧化胆碱
DMSO: 二甲亚砜
NMP: N-甲基吡咯烷酮
PG: 丙二醇
DGME: 二甘醇单甲醚
DGBE: 二甘醇单丁醚
MEA: N-甲基乙醇胺
表2
氛围中的氧气浓度(ppm) | 抗蚀剂的除去 | 铜的腐蚀 | 溶解的氧气浓度(ppm) | |
实施例 | ||||
1 | 500 | 良好 | 无 | 0.5或更低 |
2 | 200 | 良好 | 无 | 0.6 |
3 | 400 | 良好 | 无 | 1.3 |
4 | 800 | 良好 | 无 | 0.5或更低 |
5 | 200 | 良好 | 无 | 1.5 |
6 | 400 | 良好 | 无 | 0.5或更低 |
对比实施例 | ||||
1 | 500 | 未除去 | 无 | 0.5或更低 |
2 | 200000 | 良好 | 显著 | 5.8 |
实施例7-12和对比实施例3与4
在具有按照以下所述顺序在硅基质上层压铜层、氮化硅层、二氧化硅层间绝缘层和抗蚀剂层的12英寸晶片上干蚀,形成通路孔结构。该通路孔结构到达铜层。在60℃下,将基质浸渍在具有以下表3所示的溶液中15分钟,对基质进行预处理,然后,在70℃下,将基质浸渍在具有以下表3所示配方的抗蚀剂剥离组合物中30分钟。在用水漂洗之后,在扫描电子显微镜下检验抗蚀剂的除去程度和铜层的腐蚀。结果见表4。
表3
预处理 | 抗蚀剂剥离组合物 | ||||||||
过氧化氢 | 胺化合物 | 溶剂 | 强碱 | 水 | |||||
浓度(wt%) | 添加剂(wt%) | 种类 | wt% | 种类 | wt% | 种类 | wt% | ||
实施例 | |||||||||
7 | 6 | - | EA | 30 | DMSO | 60 | TMAH | 0.2 | 平衡量 |
8 | 5 | EDTA(0.001) | TETA | 25 | NMPPG | 2540 | TMAH | 1 | 平衡量 |
9 | 3 | - | 1A2P | 25 | DMSO | 65 | TMAH | 1.5 | 平衡量 |
10 | 4 | NH4F(0.001) | EA | 18 | DGME | 72 | CH | 1 | 平衡量 |
11 | 4 | - | PEHA | 30 | DGBE | 60 | TMAH | 2 | 平衡量 |
12 | 4 | - | AEEA | 10 | MEA | 80 | CH | 0.1 | 平衡量 |
对比实施例 | - | ||||||||
3 | - | - | EA | 30 | DMSO | 60 | TMAH | 0.2 | 平衡量 |
4 | - | - | EA | 30 | NMP | 65 | TMAH | 1 | 平衡量 |
EA: 乙醇胺
1A2P: 1-氨基-2-丙醇
TETA: 三亚乙基四胺
PEHA: 五亚乙基六胺
AEEA: 氨基乙基乙醇胺
TMAH: 四甲基氢氧化铵
CH: 氢氧化胆碱
DMSO: 二甲亚砜
NMP: N-甲基吡咯烷酮
PG: 丙二醇
DGME: 二甘醇单甲醚
DGBE: 二甘醇单丁醚
MEA: N-甲基乙醇胺
EDTA: 乙二胺四乙酸
表4
氛围中的氧气浓度(ppm) | 抗蚀剂的除去 | 铜的腐蚀 | 溶解的氧气浓度(ppm) | |
实施例 | ||||
7 | 200 | 良好 | 无 | 0.5或更低 |
8 | 200 | 良好 | 无 | 0.5或更低 |
9 | 200 | 良好 | 无 | 1.0 |
10 | 200 | 良好 | 无 | 0.5或更低 |
11 | 200 | 良好 | 无 | 0.5或更低 |
12 | 200 | 良好 | 无 | 0.5或更低 |
对比实施例 | ||||
3 | 200 | 未除去 | 无 | 0.5或更低 |
4 | 200 | 未除去 | 无 | 0.5或更低 |
从表2和4看出,采用本发明的抗蚀剂剥离方法,在铜层没有腐蚀的情况下可除去布线基质上的抗蚀剂。另外,通过用过氧化氢预处理,甚至当仅通过抗蚀剂剥离组合物难以除去抗蚀剂时,加速了抗蚀剂的除去。
实施例13-15和对比实施例5
在50℃下,将铜层为400埃厚的硅基质浸渍在具有下述配方的抗蚀剂剥离组合物中,测量铜层的腐蚀速度。结果见表5。
抗蚀剂剥离组合物
乙醇胺: 45wt%
二甘醇单甲醚:20wt%
水: 32wt%
山梨醇: 3wt%
表5
氛围条件 | 腐蚀速度(埃/分钟) | |
实施例 | ||
13 | 在氮气氛围中 | 0.7 |
14 | 在将氮气吹入抗蚀剂剥离组合物的同时处理 | 0.3 |
15 | 在含1%氧气的氮气中 | 1 |
对比实施例 | ||
5 | 在空气中 | 7 |
发现,铜的腐蚀速度大大地受到氧气的影响。若持续供应空气,则同样持续促进铜的腐蚀。因此,应当除去氧源,防止铜的腐蚀。实施例16和17与对比实施例6
在50℃下,将铜层为400埃厚的硅基质浸渍在具有下述配方的抗蚀剂剥离组合物中,测量铜层的腐蚀速度。在配有大气氧气分析仪的球状盒中进行测量。结果见表6。
抗蚀剂剥离组合物
乙醇胺: 40wt%
二甘醇单丁醚: 38wt%
水: 20wt%
儿茶酚: 2wt%
表6
氛围条件 | 腐蚀速度(埃/分钟) | |
实施例 | ||
16 | 在氮气氛围中 | 1.3 |
17 | 在抗蚀剂剥离组合物除去空气之后含200ppm氧气的氮气氛围中 | 0.5 |
对比实施例 | ||
6 | 在空气中 | 2.0 |
实施例18和对比实施例7
在50℃下,将铜层为400埃厚的硅基质浸渍在具有下述配方的抗蚀剂剥离组合物中,测量铜层的腐蚀速度。在配有大气氧气分析仪的球状盒中进行测量。抗蚀剂剥离组合物
乙醇胺: 30wt%
N-甲基吡咯烷酮: 55wt%
水: 10wt%
儿茶酚: 5wt%
在施加光致抗蚀剂、构图并干蚀之后,在50℃下,将硅基质浸渍在抗蚀剂剥离组合物中。测量除去残留抗蚀剂所要求的时间,并同时在光学显微镜下观察。结果见表7。
表7
氛围条件 | 腐蚀速度(埃/分钟) | 除去抗蚀剂的时间(分钟) | |
实施例 | |||
18 | 在氮气氛围中 | 0.8 | 15 |
对比实施例 | |||
7 | 在空气中 | 4.5 | 15 |
通过在氮气中进行抗蚀剂的除去(在低氧氛围中),可在没有影响抗蚀剂除去能力的情况下防止铜的腐蚀。
工业实用性
根据本发明,可在没有腐蚀铜的情况下除去干蚀之后的抗蚀剂。因此,本发明使得可能采用常规的抗蚀剂剥离组合物,而所述常规的抗蚀剂剥离组合物有损于具有图象的基质的处理。另外,可通过用过氧化氢预处理,容易地除去难以除去的抗蚀剂。
Claims (12)
1.一种抗蚀剂剥离方法,它包括下述步骤:
在含比例为2%体积或更低的氧气的氛围中,使在蚀刻后具有残留抗蚀剂层的布线基质与抗蚀剂剥离组合物接触。
2.权利要求1的抗蚀剂剥离方法,其中在从抗蚀剂剥离组合物中驱逐已溶解气体的同时,进行使布线基质与抗蚀剂剥离组合物接触的步骤。
3.权利要求1的抗蚀剂剥离方法,其中在使抗蚀剂剥离组合物脱气之后,进行使布线基质与抗蚀剂剥离组合物接触的步骤。
4.权利要求1-3任何一项的抗蚀剂剥离方法,其中在使布线基质与抗蚀剂剥离组合物接触之前,通过与过氧化氢接触对残留的抗蚀剂层进行预处理。
5.权利要求4的抗蚀剂剥离方法,其中通过使残留的抗蚀剂层与过氧化氢浓度为0.5wt%或更高的溶液接触,进行预处理。
6.权利要求1-5任何一项的抗蚀剂剥离方法,其中在抗蚀剂剥离组合物内,已溶解的氧气的浓度为3ppm或更低。
7.权利要求1-6任何一项的抗蚀剂剥离方法,其中抗蚀剂剥离组合物包括胺化合物、溶剂、强碱和水。
8.权利要求7的抗蚀剂剥离方法,其中抗蚀剂剥离组合物包括5-95wt%的胺化合物,3-85wt%的溶剂,0.01-5wt%的强碱和1-25wt%的水。
9.权利要求7或8的抗蚀剂剥离方法,其中胺化合物是至少一种选自下列化合物的化合物:乙醇胺、1-氨基-2-丙醇、N-(氨基乙基)乙醇胺、N-甲基乙醇胺、N-乙基乙醇胺、二乙醇胺、异丙醇胺、2-(2-氨基乙氧基)乙醇、乙二胺、丙二胺、丁二胺、二亚乙基三胺、哌嗪、吗啉、三亚乙基四胺、四亚乙基五胺和五亚乙基六胺。
10.权利要求7-9任何一项的抗蚀剂剥离方法,其中强碱是至少一种选自下列化合物的化合物:四甲基氢氧化铵、氢氧化胆碱、四乙基氢氧化铵和四丁基氢氧化铵。
11.权利要求7-10任何一项的抗蚀剂剥离方法,其中溶剂是至少一种选自下列化合物的化合物:二甲亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甘醇单甲醚、二甘醇单丁醚、二丙二醇单甲醚、二丙二醇单丁醚和丙二醇。
12.权利要求7-11任何一项的抗蚀剂剥离方法,其中布线基质具有铜层或铜合金层。
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- 2002-10-31 KR KR1020047006663A patent/KR20050042051A/ko not_active Application Discontinuation
- 2002-10-31 US US10/493,700 patent/US20040256358A1/en not_active Abandoned
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US20040256358A1 (en) | 2004-12-23 |
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