CN106164774A - 含有包含丙烯酰胺结构和丙烯酸酯结构的聚合物的光刻用抗蚀剂下层膜形成用组合物 - Google Patents
含有包含丙烯酰胺结构和丙烯酸酯结构的聚合物的光刻用抗蚀剂下层膜形成用组合物 Download PDFInfo
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- CN106164774A CN106164774A CN201580018433.2A CN201580018433A CN106164774A CN 106164774 A CN106164774 A CN 106164774A CN 201580018433 A CN201580018433 A CN 201580018433A CN 106164774 A CN106164774 A CN 106164774A
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Classifications
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
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- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
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- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
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- 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
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Abstract
本发明提供用于形成在从上层进行图案转印、基板加工时能够进行干蚀刻,在基板加工后能够利用碱性水溶液除去的抗蚀剂下层膜的抗蚀剂下层膜形成用组合物。本发明的解决方法是一种抗蚀剂下层膜形成用组合物,其特征在于,含有聚合物(A)、交联性化合物(B)和溶剂(C),所述聚合物(A)含有下述式(1)所示的结构单元和下述式(2)所示的结构单元,所述交联性化合物(B)具有至少2个选自封闭异氰酸酯基、羟甲基或碳原子数为1~5的烷氧基甲基中的基团,该聚合物(A)是该式(1)所示的单元结构与该式(2)所示的单元结构以摩尔百分比计为式(1)所示的单元结构:式(2)所示的单元结构=(25~60):(75~40)的比例进行共聚而得到的聚合物。
Description
技术领域
本发明涉及在半导体基板加工时有效的光刻用抗蚀剂下层膜形成用组合物、以及使用该抗蚀剂下层膜形成用组合物的抗蚀剂图案形成方法、以及半导体装置的制造方法。
背景技术
一直以来,在半导体器件的制造中,通过使用了光致抗蚀剂组合物的光刻来进行微细加工。前述微细加工为下述加工法:在硅晶片等被加工基板上形成光致抗蚀剂组合物的薄膜,在该薄膜上经由描绘有半导体器件图案的掩模图案来照射紫外线等活性光线,进行显影,将得到的光致抗蚀剂图案作为保护膜对硅晶片等被加工基板进行蚀刻处理。然而,近年来,随着半导体器件的高集成度化推进,所使用的活性光线也从KrF准分子激光(248nm)向ArF准分子激光(193nm)逐渐短波长化。与此相伴,活性光线从基板的漫反射、驻波的影响成为大问题。因此,在光致抗蚀剂与被加工基板之间设置防反射膜(底部抗反射涂层,Bottom Anti-Reflective Coating,BARC)的方法逐渐被广泛研究开来。例如,已经公开了含有包含丙烯酰胺结构的聚合物的感光性抗蚀剂下层膜形成用组合物(参照专利文献1)。
已经公开了含有具有羟基丙烯酰胺结构单元的聚合物的抗蚀剂下层膜形成用组合物(参照专利文献2)。
已经公开了含有包含羟基亚烷基甲基丙烯酰胺的结构单元和芳香族亚烷基甲基丙烯酸酯的结构单元的聚合物的防反射膜形成用组合物(参照专利文献3)。
今后,如果抗蚀剂图案的微细化推进,则产生分辨率的问题、抗蚀剂图案在显影后倒塌这样的问题,会逐渐期望抗蚀剂的薄膜化。因此,不容易获得对于基板加工而言充分的抗蚀剂图案膜厚,逐渐需要不仅使抗蚀剂图案、还有使在抗蚀剂与进行加工的半导体基板之间制成的抗蚀剂下层膜也具有作为基板加工时的掩膜的功能。作为这样的工艺用抗蚀剂下层膜,与以往的高蚀刻速率性(蚀刻速度快)的抗蚀剂下层膜不同,逐渐要求具有与抗蚀剂相近的干蚀刻速度的选择比的光刻用抗蚀剂下层膜、具有比抗蚀剂小的干蚀刻速度的选择比的光刻用抗蚀剂下层膜、具有比半导体基板小的干蚀刻速度的选择比的光刻用抗蚀剂下层膜。
已经公开了具有丙烯酰胺结构、利用碱性水溶液能够除去的有机硬掩膜层形成用组合物(参照专利文献4)。
现有技术文献
专利文献
专利文献1:国际申请小册子WO2005/111724
专利文献2:日本特开2009-025670
专利文献3:日本特开2001-027810
专利文献4:国际申请小册子WO2012/161126
发明内容
发明所要解决的课题
本发明的目的是提供用于半导体装置制造的光刻工艺的抗蚀剂下层膜形成用组合物。此外,本发明的目的在于,提供不发生与无机硬掩膜层的混合、可获得优异的抗蚀剂图案、具有与抗蚀剂相近的干蚀刻速度的选择比的光刻用抗蚀剂下层膜、具有比抗蚀剂小的干蚀刻速度的选择比的光刻用抗蚀剂下层膜、具有比半导体基板小的干蚀刻速度的选择比的光刻用抗蚀剂下层膜。此外,本发明的目的在于,在将248nm、193nm、157nm等波长的照射光用于微细加工时赋予抗蚀剂下层膜有效地吸收来自基板的反射光的性能。进而,本发明的目的在于,提供使用抗蚀剂下层膜形成用组合物的抗蚀剂图案的形成方法。而且,本发明的目的还在于,提供一种用于形成抗蚀剂下层膜的抗蚀剂下层膜形成用组合物,其在来自上层的图案转印、基板加工时能够干蚀刻,在基板加工后利用碱性水溶液能够除去。
用于解决课题的方法
本发明作为第1观点,是一种抗蚀剂下层膜形成用组合物,其特征在于,含有聚合物(A)、交联性化合物(B)和溶剂(C),所述聚合物(A)含有下述式(1)所示的结构单元和下述式(2)所示的结构单元,所述交联性化合物(B)具有至少2个选自封闭异氰酸酯基、羟甲基或碳原子数为1~5的烷氧基甲基中的基团,该聚合物(A)是该式(1)所示的单元结构与该式(2)所示的单元结构以摩尔百分比计为式(1)所示的单元结构:式(2)所示的单元结构=(25~60):(75~40)的比例进行共聚而得到的聚合物,
(式(1)、式(2)中,R1和R4分别表示氢原子或甲基,X1和X2分别表示NH基或氧原子,R2表示芳香族环,R3表示羟基或羧基,Y表示可被取代的碳原子数为1~10的烷基。)
作为第2观点,是根据第1观点所述的抗蚀剂下层膜形成用组合物,R2是苯环,
作为第3观点,是根据第1观点或第2观点所述的抗蚀剂下层膜形成用组合物,其以相对于所述聚合物(A)的质量为1~40质量%的比例含有交联性化合物(B),
作为第4观点,是根据第1观点~第3观点中任一项所述的抗蚀剂下层膜形成用组合物,其还含有交联催化剂,
作为第5观点,是一种半导体装置的制造方法,包括下述工序:在半导体基板上由第1观点~第4观点中任一项所述的抗蚀剂下层膜形成用组合物形成抗蚀剂下层膜的工序,在该抗蚀剂下层膜上形成抗蚀剂膜的工序,通过光或电子射线的照射和显影在抗蚀剂膜上形成抗蚀剂图案的工序,利用所形成的抗蚀剂图案来蚀刻抗蚀剂下层膜的工序,以及利用图案化了的抗蚀剂下层膜来加工半导体基板的工序,以及
作为第6观点,是一种半导体装置的制造方法,包括下述工序:在半导体基板上由第1观点~第4观点中任一项所述的抗蚀剂下层膜形成用组合物形成抗蚀剂下层膜的工序,在该抗蚀剂下层膜上形成无机硬掩膜层的工序,进一步在无机硬掩膜层上形成抗蚀剂膜的工序,通过光或电子射线的照射和显影在抗蚀剂膜上形成抗蚀剂图案的工序,利用所形成的抗蚀剂图案来蚀刻无机硬掩膜层的工序,利用图案化了的无机硬掩膜层来蚀刻抗蚀剂下层膜的工序,以及利用图案化了的抗蚀剂下层膜来加工半导体基板的工序。
发明效果
由本发明的抗蚀剂下层膜形成用组合物形成的抗蚀剂下层膜能够在不引起与在其上层的无机硬掩膜层混合的情况下形成良好的抗蚀剂图案形状。
此外,通过本发明的抗蚀剂下层膜形成用组合物,能够提供具有与抗蚀剂相近的干蚀刻速度的选择比、比抗蚀剂小的干蚀刻速度的选择比、比半导体基板小的干蚀刻速度的选择比的优异的抗蚀剂下层膜。
因此,由本发明的抗蚀剂下层膜形成用组合物获得的抗蚀剂下层膜,能够利用干蚀刻将转印到上层的无机硬掩膜层的抗蚀剂图案转印到抗蚀剂下层膜。进而转印在抗蚀剂下层膜的抗蚀剂图案能够利用干蚀刻进行半导体基板的加工。
进而,本发明的抗蚀剂下层膜形成用组合物能够赋予由其形成的抗蚀剂下层膜有效率地抑制来自基板的反射的性能,该抗蚀剂下层膜还能够一并具有作为曝光用光的防反射膜的效果。
因此,由本发明的光刻用抗蚀剂下层膜形成用组合物形成的抗蚀剂下层膜可以用作平坦化膜、抗蚀剂层的防污染膜、具有干蚀刻选择性的膜。由此能够容易且精度良好地进行半导体制造的光刻工艺中的抗蚀剂图案形成。
此外,本发明的光刻用抗蚀剂下层膜形成用组合物由于热稳定性高,因此对于由其形成的抗蚀剂下层膜而言,能够防止由在为了形成无机硬掩膜层的真空蒸镀时和/或烧成时的分解物引起的对上层膜污染,此外,能够使烧成工序的温度裕量有富余。
进而,由本发明的光刻用抗蚀剂下层膜形成用组合物形成的抗蚀剂下层膜在对半导体基板进行了加工后,能够利用碱性水溶液除去。
具体实施方式
本发明是一种抗蚀剂下层膜形成用组合物,其特征在于,含有聚合物(A)、交联性化合物(B)和溶剂(C),所述聚合物(A)含有下述式(1)所示的结构单元和下述式(2)所示的结构单元,所述交联性化合物(B)具有至少2个选自封闭异氰酸酯基、羟甲基或碳原子数为1~5的烷氧基甲基中的基团,该聚合物(A)是该式(1)所示的单元结构与该式(2)所示的单元结构以摩尔百分比计为式(1)所示的单元结构:式(2)所示的单元结构=(25~60):(75~40)的比例进行共聚而得到的聚合物。
本发明的抗蚀剂下层膜形成用组合物可以根据需要含有产酸剂、表面活性剂等添加剂。
该组合物的固体成分为0.1~70质量%、或0.1~60质量%。固体成分是从抗蚀剂下层膜形成用组合物中除去溶剂(C)后剩余成分的含有比例。
在固体成分中可以以1~99.9质量%、或1~99质量%、或50~98质量%的比例含有上述聚合物(A)。上述聚合物(A)的重均分子量可以处于例如1000~1000000、或1000~100000、或1000~50000的范围。
式(1)、式(2)中,R1和R4分别表示氢原子或甲基,X1和X2分别表示NH基或氧原子,R2表示芳香族环,R3表示羟基或羧基,Y表示可被取代的碳原子数为1~10的烷基。
作为前述芳香族环,可举出苯环、萘环、蒽环、联苯环等,但特别优选苯环。
作为前述烷基中的取代基,可举出羟基、羧基、卤素、硝基、氨基等。
作为前述碳原子数为1~10的烷基,可举出例如甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、1-甲基-环丙基、2-甲基-环丙基、正戊基、1-甲基-正丁基、2-甲基-正丁基、3-甲基-正丁基、1,1-二甲基-正丙基、1,2-二甲基-正丙基、2,2-二甲基-正丙基、1-乙基-正丙基、环戊基、1-甲基-环丁基、2-甲基-环丁基、3-甲基-环丁基、1,2-二甲基-环丙基、2,3-二甲基-环丙基、1-乙基-环丙基、2-乙基-环丙基、正己基、1-甲基-正戊基、2-甲基-正戊基、3-甲基-正戊基、4-甲基-正戊基、1,1-二甲基-正丁基、1,2-二甲基-正丁基、1,3-二甲基-正丁基、2,2-二甲基-正丁基、2,3-二甲基-正丁基、3,3-二甲基-正丁基、1-乙基-正丁基、2-乙基-正丁基、1,1,2-三甲基-正丙基、1,2,2-三甲基-正丙基、1-乙基-1-甲基-正丙基、1-乙基-2-甲基-正丙基、环己基、1-甲基-环戊基、2-甲基-环戊基、3-甲基-环戊基、1-乙基-环丁基、2-乙基-环丁基、3-乙基-环丁基、1,2-二甲基-环丁基、1,3-二甲基-环丁基、2,2-二甲基-环丁基、2,3-二甲基-环丁基、2,4-二甲基-环丁基、3,3-二甲基-环丁基、1-正丙基-环丙基、2-正丙基-环丙基、1-异丙基-环丙基、2-异丙基-环丙基、1,2,2-三甲基-环丙基、1,2,3-三甲基-环丙基、2,2,3-三甲基-环丙基、1-乙基-2-甲基-环丙基、2-乙基-1-甲基-环丙基、2-乙基-2-甲基-环丙基以及2-乙基-3-甲基-环丙基等。
可用于本发明的聚合物(A)的结构可以例示如下。
可用于本发明的交联性化合物(B)是具有封闭异氰酸酯基、羟甲基或碳原子数为1~5的烷氧基甲基中的至少2个基团的交联性化合物。
交联性化合物(B)以相对于聚合物(A)为1~40质量%、优选为1~30质量%的比例包含于抗蚀剂下层膜形成用组合物中。
前述封闭异氰酸酯基,是异氰酸酯基(-N=C=O)被适当的保护基团封闭而成的有机基团。
关于封闭异氰酸酯基,可以使异氰酸酯基与封端剂反应而形成封闭异氰酸酯基。
在与聚合物(A)中的羟基或羧基进行反应时,封端剂脱离,羟基或羧基与异氰酸酯基进行反应并形成交联结构。
作为封端剂,是指可与异氰酸酯反应的含有活性氢的化合物,可举出例如醇、酚、多环酚、酰胺、酰亚胺、亚胺、硫醇、肟、内酰胺、含有活性氢的杂环、含有活性亚甲基的化合物。
作为封端剂的醇可举出例如碳原子数为1~40的醇,可示例出甲醇、乙醇、丙醇、异丙醇、丁醇、戊醇、己醇、辛醇、氯乙醇、1,3-二氯-2-丙醇、叔丁醇、叔戊醇、2-乙基己醇、环己醇、月桂醇、乙二醇、丁二醇、三羟甲基丙烷、甘油、乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单丁基醚、二乙二醇单甲基醚、丙二醇单甲基醚、丙二醇单乙基醚、苯甲醇等。
作为封端剂的酚可举出例如碳原子数为6~20的酚类,可示例出苯酚、氯代苯酚、硝基苯酚等。
作为封端剂的酚衍生物可举出例如碳原子数为6~20的酚衍生物,可示例出对叔丁基苯酚、甲酚、二甲苯酚、间苯二酚等。
作为封端剂的多环酚可举出例如碳原子数为10~20的多环酚,它们是具有酚性羟基的芳香族稠环,可示例出羟基萘、羟基蒽等。
作为封端剂的酰胺可举出例如碳原子数为1~20的酰胺,乙酰苯胺、己酰胺、辛二酰胺、琥珀酰胺、苯磺酰胺、乙二酰胺等。
作为封端剂的酰亚胺可举出例如碳原子数为6~20的酰亚胺,可示例出环己烷二甲酰亚胺、环己烯二甲酰亚胺、苯二甲酰亚胺、环丁烷二甲酰亚胺、碳化二亚胺等。
作为封端剂的亚胺可举出例如碳原子数为1~20的亚胺,可示例出己烷-1-亚胺、2-丙烷亚胺、乙烷-1,2-亚胺等。
作为封端剂的硫醇可举出例如碳原子数为1~20的硫醇,可示例出乙硫醇、丁硫醇、苯硫酚、2,3-丁二硫醇等。
作为封端剂的肟可举出例如碳原子数为1~20的肟,可示例出丙酮肟、丁酮肟、环己酮肟、丙酮肟、甲基异丁基甲酮肟、甲基戊基甲酮肟、甲酰胺肟、乙醛肟、二乙酰单肟、二苯甲酮肟、环己酮肟等。
作为封端剂的内酰胺是例如碳原子数为4~20的内酰胺,可示例出ε-己内酰胺、δ-戊内酰胺、γ-丁内酰胺、β-丙内酰胺、γ-吡咯烷酮、月桂内酰胺等。
作为封端剂的含有活性氢的杂环化合物为例如碳原子数为3~30的含有活性氢的杂环化合物,可示例出吡咯、咪唑、吡唑、哌啶、哌嗪、吗啉、氮茚、吲哚、吲唑、嘌呤、咔唑等。
作为封端剂的含有活性亚甲基的化合物,是例如碳原子数为3~20的含有活性亚甲基的化合物,可示例出丙二酸二甲酯、丙二酸二乙酯、乙酰乙酸甲酯、乙酰乙酸乙酯、乙酰丙酮等。
具有至少2个封闭异氰酸酯基的交联性化合物(B),作为其具体例,可举出例如タケネート〔注册商标〕B-830、タケネートB-870N(三井化学(株)制)、VESTANAT〔注册商标〕B1358/100(エボニックデグサ社制)。
具有羟甲基或碳原子数为1~5的烷氧基甲基中的至少2个基团的交联性化合物(B)可举出三聚氰胺系、取代脲系或它们的聚合物系等。例如甲氧基甲基化甘脲、丁氧基甲基化甘脲、甲氧基甲基化三聚氰胺、丁氧基甲基化三聚氰胺、甲氧基甲基化苯胍胺、丁氧基甲基化苯胍胺、甲氧基甲基化脲、丁氧基甲基化脲、甲氧基甲基化硫脲、或甲氧基甲基化硫脲等化合物。此外,还可以使用这些化合物的缩合物。
作为本发明中为了促进上述交联反应的催化剂,可以配合对甲苯磺酸、三氟甲烷磺酸、对甲苯磺酸吡啶水杨酸、磺基水杨酸、柠檬酸、苯甲酸、羟基苯甲酸、萘甲酸等酸性化合物或/和2,4,4,6-四溴环己二烯酮、苯偶姻甲苯磺酸酯、2-硝基苄基甲苯磺酸酯、其他有机磺酸烷基酯等热产酸剂。配合量相对于全部固体成分为0.0001~20质量%,优选为0.0005~10质量%,优选为0.01~3质量%。
为了使本发明的抗蚀剂下层膜形成用组合物与光刻工序中被覆在上层的光致抗蚀剂的酸度一致,可以添加光产酸剂。作为优选的光产酸剂,可举出例如,双(4-叔丁基苯基)碘三氟甲烷磺酸盐、三苯基锍三氟甲烷磺酸盐等盐系光产酸剂类,苯基-双(三氯甲基)-均三嗪等含有卤素的化合物系光产酸剂类,苯偶姻甲苯磺酸酯、N-羟基丁二酰亚胺三氟甲烷磺酸酯等磺酸系光产酸剂类等。上述光产酸剂相对于全部固体成分为0.2~10质量%,优选为0.4~5质量%。
本发明的光刻用抗蚀剂下层膜形成用组合物中,除上述以外,可以根据需要进一步添加吸光剂、流变调节剂、粘接助剂、表面活性剂等。
作为进一步的吸光剂,可以优选使用例如“工业用色素的技术与市场”(CMC出版)、“染料便览”(有机合成化学协会编)中记载的市售的吸光剂,例如,C.I.分散黄1、3、4、5、7、8、13、23、31、49、50、51、54、60、64、66、68、79、82、88、90、93、102、114以及124;C.I.分散橙1、5、13、25、29、30、31、44、57、72以及73;C.I.分散红1、5、7、13、17、19、43、50、54、58、65、72、73、88、117、137、143、199以及210;C.I.分散紫43;C.I.分散蓝96;C.I.荧光增白剂112、135以及163;C.I.溶剂橙2以及45;C.I.溶剂红1、3、8、23、24、25、27以及49;C.I.颜料绿10;C.I.颜料棕2等。上述吸光剂通常以相对于光刻用抗蚀剂下层膜形成用组合物的全部固体成分为10质量%以下、优选为5质量%以下的比例进行配合。
添加流变调节剂的目的主要是提高抗蚀剂下层膜形成用组合物的流动性,特别是在烘烤工序中,提高抗蚀剂下层膜的膜厚均匀性和/或提高抗蚀剂下层膜形成用组合物向孔内部的填充性。作为具体例,可举出邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二己酯、邻苯二甲酸丁基异癸酯等邻苯二甲酸衍生物,己二酸二正丁酯、己二酸二异丁酯、己二酸二异辛酯、己二酸辛基癸酯等己二酸衍生物,马来酸二正丁酯、马来酸二乙酯、马来酸二壬酯等马来酸衍生物,油酸甲酯、油酸丁酯、油酸四氢糠基酯等油酸衍生物,或硬脂酸正丁酯、硬脂酸甘油酯等硬脂酸衍生物。相对于光刻用抗蚀剂下层膜形成用组合物的全部固体成分,这些流变调节剂通常以小于30质量%的比例进行配合。
添加粘接助剂的目的主要是提高基板或抗蚀剂与抗蚀剂下层膜的密合性,特别是为了使抗蚀剂在显影中不剥离。作为具体例,可举出三甲基氯硅烷、二甲基乙烯基氯硅烷、甲基二苯基氯硅烷、氯甲基二甲基氯硅烷等氯硅烷类,三甲基甲氧基硅烷、二甲基二乙氧基硅烷、甲基二甲氧基硅烷、二甲基乙烯基乙氧基硅烷、二苯基二甲氧基硅烷、苯基三乙氧基硅烷等烷氧基硅烷类,六甲基二硅氮烷、N,N’-双(三甲基甲硅烷基)脲、二甲基三甲基甲硅烷基胺、三甲基甲硅烷基咪唑等硅氮烷类,乙烯基三氯硅烷、γ-氯丙基三甲氧基硅烷、γ-氨基丙基三乙氧基硅烷、γ-(环氧丙氧基)丙基三甲氧基硅烷等硅烷类,苯并三唑、苯并咪唑、吲唑、咪唑、2-巯基苯并咪唑、2-巯基苯并噻唑、2-巯基苯并唑、尿唑、硫脲嘧啶、巯基咪唑、巯基嘧啶等杂环式化合物,1,1-二甲基脲、1,3-二甲基脲等脲,或硫脲化合物。相对于光刻用抗蚀剂下层膜形成用组合物的全部固体成分,这些粘接助剂通常以小于5质量%、优选以小于2质量%的比例进行配合。
为了不发生针孔、条纹等并进一步提高对不平整表面的涂布性,可以在本发明的光刻用抗蚀剂下层膜形成用组合物中配合表面活性剂。作为表面活性剂,可举出例如聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯十六烷基醚、聚氧乙烯油基醚等聚氧乙烯烷基醚类、聚氧乙烯辛基苯酚醚、聚氧乙烯壬基苯酚醚等聚氧乙烯烷基芳基醚类、聚氧乙烯-聚氧丙烯嵌段共聚物类、脱水山梨糖醇单月桂酸酯、脱水山梨糖醇单棕榈酸酯、脱水山梨糖醇单硬脂酸酯、脱水山梨糖醇单油酸酯、脱水山梨糖醇三油酸酯、脱水山梨糖醇三硬脂酸酯等脱水山梨糖醇脂肪酸酯类、聚氧乙烯脱水山梨糖醇单月桂酸酯、聚氧乙烯脱水山梨糖醇单棕榈酸酯、聚氧乙烯脱水山梨糖醇单硬脂酸酯、聚氧乙烯脱水山梨糖醇三油酸酯、聚氧乙烯脱水山梨糖醇三硬脂酸酯等聚氧乙烯脱水山梨糖醇脂肪酸酯类等非离子系表面活性剂、エフトツプEF301、EF303、EF352((株)トーケムプロダクツ制,商品名)、メガファックF171、F173、R-30、R-40、R-40LM(大日本インキ(株)制,商品名)、フロラードFC430、FC431(住友スリーエム(株)制,商品名)、アサヒガードAG710、サーフロンS-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子(株)制,商品名)等氟系表面活性剂、有机硅氧烷聚合物KP341(信越化学工业(株)制)等。这些表面活性剂的配合量相对于本发明的光刻用抗蚀剂下层膜形成用组合物的全部固体成分通常为2.0质量%以下,优选为1.0质量%以下。这些表面活性剂可以以单独形式添加,或者也可以以2种以上的组合的形式添加。
在本发明中,作为溶解上述聚合物和交联剂成分、交联催化剂等的溶剂(C),可以使用乙二醇单甲基醚、乙二醇单乙基醚、甲基溶纤剂乙酸酯、乙基溶纤剂乙酸酯、二乙二醇单甲基醚、二乙二醇单乙基醚、丙二醇、丙二醇单甲基醚、丙二醇单甲基醚乙酸酯、丙二醇单乙基醚、丙二醇单乙基醚乙酸酯、丙二醇丙基醚乙酸酯、甲苯、二甲苯、甲基乙基甲酮、环戊酮、环己酮、2-羟基丙酸乙酯、2-羟基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羟基乙酸乙酯、2-羟基-3-甲基丁酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯等。这些有机溶剂单独或组合2种以上来使用。
进而,可以混合丙二醇单丁基醚、丙二醇单丁基醚乙酸酯等高沸点溶剂而使用。这些溶剂中,丙二醇单甲基醚、丙二醇单甲基醚乙酸酯、乳酸乙酯、乳酸丁酯以及环己酮等对于流平性的提高是优选的。
用于本发明的抗蚀剂可以使用光致抗蚀剂、电子射线抗蚀剂等。
作为涂布于由本发明的光刻用抗蚀剂下层膜形成用组合物形成的抗蚀剂下层膜的上部的光致抗蚀剂,可以使用负型、正型中的任一种,有包含酚醛清漆树脂与1,2-重氮萘醌磺酸酯的正型光致抗蚀剂、包含具有通过酸进行分解从而提高碱溶解速度的基团的粘合剂与光产酸剂的化学增幅型光致抗蚀剂、包含碱溶性粘合剂与通过酸进行分解从而提高光致抗蚀剂的碱溶解速度的低分子化合物与光产酸剂的化学增幅型光致抗蚀剂、包含具有通过酸进行分解从而提高碱溶解速度的基团的粘合剂与通过酸进行分解从而提高光致抗蚀剂的碱溶解速度的低分子化合物与光产酸剂的化学增幅型光致抗蚀剂、骨架中具有Si原子的光致抗蚀剂等,可举出例如,ロームアンドハーツ社制,商品名APEX-E。
此外,作为涂布于由本发明的组合物形成的光刻用抗蚀剂下层膜的上部的电子射线抗蚀剂,可举出例如含有主链中包含Si-Si键且末端包含芳香族环的树脂和通过电子射线的照射而产生酸的产酸剂的组合物、或含有羟基被包含N-羧基胺的有机基团取代了的聚(对羟基苯乙烯)和通过电子射线的照射而产生酸的产酸剂的组合物等。在后者的电子射线抗蚀剂组合物中,由产酸剂产生的酸与聚合物侧链的N-羧基氨氧基通过电子射线照射发生反应,聚合物侧链分解为羟基且显示碱溶性而溶解于碱性显影液中,形成抗蚀剂图案。该通过电子射线的照射而产生酸的产酸剂可举出1,1-双[对氯苯基]-2,2,2-三氯乙烷、1,1-双[对甲氧基苯基]-2,2,2-三氯乙烷、1,1-双[对氯苯基]-2,2-二氯乙烷、2-氯-6-(三氯甲基)吡啶等卤代有机化合物,三苯基锍盐、二苯基碘盐等盐、硝基苄基甲苯磺酸酯、二硝基苄基甲苯磺酸酯等磺酸酯。
作为具有使用本发明的光刻用抗蚀剂下层膜形成用组合物而形成的抗蚀剂下层膜的抗蚀剂的显影液,可以使用氢氧化钠、氢氧化钾、碳酸钠、硅酸钠、偏硅酸钠、氨水等无机碱类,乙胺、正丙胺等伯胺类,二乙胺、二正丁胺等仲胺类,三乙胺、甲基二乙胺等叔胺类,二甲基乙醇胺、三乙醇胺等醇胺类,四甲基氢氧化铵、四乙基氢氧化铵、胆碱等季铵盐,吡咯、哌啶等环状胺类等碱类的水溶液。进而,也可以向上述碱类的水溶液中添加适当量的异丙醇等醇类、非离子系等表面活性剂而使用。其中,优选的显影液为季铵盐,进一步优选为四甲基氢氧化铵和胆碱。
接下来,针对本发明的抗蚀剂图案形成法进行说明,通过旋转器、涂布机等适当的涂布方法在精密集成电路元件的制造所使用的基板(例如硅/二氧化硅被覆基板、玻璃基板、ITO基板等透明基板)上涂布抗蚀剂下层膜形成用组合物,然后进行烘烤使其固化从而制成涂布型下层膜。在这里,作为抗蚀剂下层膜的膜厚,优选为0.01~3.0μm。此外,作为涂布后烘烤的条件,为在80~400℃下0.5~120分钟。然后,可以通过在抗蚀剂下层膜上直接涂布抗蚀剂或根据需要将1层~数层的涂膜材料在涂布型下层膜上成膜之后涂布抗蚀剂,通过规定的掩模进行光或电子射线的照射,进行显影、冲洗、干燥,从而得到良好的抗蚀剂图案。也可以根据需要进行光或电子射线的照射后加热(PEB:PostExposureBake)。而且,可以将通过前述工序显影除去了抗蚀剂的那部分抗蚀剂下层膜通过干蚀刻除去,在基板上形成期望的图案。
上述光致抗蚀剂中的曝光用光是近紫外线、远紫外线、或极紫外线(例如,EUV)等化学射线,可使用例如248nm(KrF激光)、193nm(ArF激光)、157nm(F2激光)等波长的光。对于光照射,只要是能够使光产酸剂产生酸的方法,就可以无特别限制地使用,曝光量采用1~2000mJ/cm2、或10~1500mJ/cm2、或50~1000mJ/cm2。
此外,电子射线抗蚀剂的电子射线照射可以使用例如电子射线照射装置进行照射。
在本发明中,可以经由下述工序来制造半导体装置:在半导体基板上由本发明的抗蚀剂下层膜形成用组合物形成该抗蚀剂下层膜的工序,在该抗蚀剂下层膜上形成抗蚀剂膜的工序,通过光或电子射线照射和显影而形成抗蚀剂图案的工序,利用所形成的抗蚀剂图案来蚀刻该抗蚀剂下层膜的工序,以及利用图案化了的抗蚀剂下层膜来加工半导体基板的工序。
今后,若抗蚀剂图案的微细化进行,就会逐渐产生分辨率的问题、抗蚀剂图案在显影后倒塌这样的问题,期望抗蚀剂的薄膜化。因此,不容易获得对基板加工充分的抗蚀剂图案膜厚,逐渐需要不仅使抗蚀剂图案、而且使在抗蚀剂与加工的半导体基板之间制成的抗蚀剂下层膜也具有作为基板加工时的掩模的功能的工艺。作为这样的工艺用的抗蚀剂下层膜,与现有的高蚀刻速率性抗蚀剂下层膜不同,要求具有与抗蚀剂相近的干蚀刻速度的选择比的光刻用抗蚀剂下层膜、具有比抗蚀剂小的干蚀刻速度的选择比的光刻用抗蚀剂下层膜、具有比半导体基板小的干蚀刻速度的选择比的光刻用抗蚀剂下层膜。此外,也可以赋予这样的抗蚀剂下层膜防反射能力,可以一并具有现有的防反射膜的功能。
另一方面,为了获得微细的抗蚀剂图案,也开始使用在抗蚀剂下层膜干蚀刻时使抗蚀剂图案与抗蚀剂下层膜比抗蚀剂显影时的图案宽度窄的工艺。作为这样的工艺用的抗蚀剂下层膜,与现有的高蚀刻速率性防反射膜不同,要求具有与抗蚀剂相近的干蚀刻速度的选择比的抗蚀剂下层膜。另外,也可以赋予这样的抗蚀剂下层膜防反射能力,可以一并具有现有的防反射膜的功能。
在那样的使用薄膜抗蚀剂的工艺中,利用蚀刻工艺将抗蚀剂图案转印到其下层膜,将该下层膜作为掩膜进行基板加工的工艺、或者重复进行“利用蚀刻工艺将抗蚀剂图案转印到其下层膜,进而使用不同的气体组成将转印在下层膜的图案转印到其下层膜”这样的历程,最终进行基板加工。本发明的抗蚀剂下层膜形成用组合物和由其形成的抗蚀剂下层膜对该工艺有效,在使用由本发明的组合物形成的抗蚀剂下层膜来加工基板时,相对于加工基板(例如,基板上的热氧化硅膜、氮化硅膜、多晶硅膜等)具有充分的蚀刻耐性。
在本发明中,在基板上形成本发明的抗蚀剂下层膜后,可以在抗蚀剂下层膜上直接涂布抗蚀剂或根据需要将1层~数层的涂膜材料在抗蚀剂下层膜上成膜之后涂布抗蚀剂。由此抗蚀剂的图案宽度变窄,即使在为了防止图案倒塌而薄薄地被覆抗蚀剂的情况下,也可以通过选择适当的蚀刻气体进行基板的加工。
即,可以经由下述工序来制造半导体装置:在半导体基板上由本发明的抗蚀剂下层膜形成用组合物形成抗蚀剂下层膜的工序,在该抗蚀剂下层膜上利用含有硅成分等的涂膜材料形成无机硬掩膜层的工序,进一步在无机硬掩膜层上形成抗蚀剂膜的工序,通过光或电子射线的照射和显影形成抗蚀剂图案的工序,利用抗蚀剂图案来蚀刻无机硬掩膜层的工序,利用图案化了的无机硬掩膜层来蚀刻抗蚀剂下层膜的工序,以及利用图案化了的抗蚀剂下层膜来加工半导体基板的工序。
在该由抗蚀剂下层膜形成用组合物在基板上形成抗蚀剂下层膜、在该抗蚀剂下层膜上形成无机硬掩膜层、在该无机硬掩膜层上形成抗蚀剂膜、通过曝光和显影形成抗蚀剂图案、将所形成的抗蚀剂图案转印到无机硬掩膜层上、将已经转印于无机硬掩膜层上的抗蚀剂图案转印到抗蚀剂下层膜上、利用该抗蚀剂下层膜进行半导体基板的加工的工艺中,本发明的抗蚀剂下层膜形成用组合物在以下方面是有利的。在该工艺中,无机硬掩膜层有通过包含有机聚合物或无机聚合物、和溶剂的涂布型的组合物进行的情况、和通过无机物的真空蒸镀进行的情况。在无机物(例如,氮氧化硅)的真空蒸镀中,蒸镀物堆积在抗蚀剂下层膜表面,此时抗蚀剂下层膜表面的温度有时会上升到400℃前后。对于该情况,本发明的光刻用抗蚀剂下层膜形成用组合物由于热稳定性高,因此对于由其形成的抗蚀剂下层膜而言,能够防止由为了形成无机硬掩膜而进行的真空蒸镀时、烧成时的分解物引起对上层膜的污染,此外,能够使烧成工序的温度裕量有富余。
此外,在考虑本发明的光刻用抗蚀剂下层膜形成用组合物作为防反射膜的效果的情况下,由于光吸收部位在骨架中,因此在加热干燥时没有向光致抗蚀剂中的扩散物,此外,光吸收部位具有充分大的吸光性能,因此防反射光效果好。
进而,本发明的光刻用抗蚀剂下层膜形成用组合物可以随着工艺条件变化而作为形成具有以下功能的膜的材料来使用:防止光反射的功能,以及防止基板与光致抗蚀剂的相互作用的功能、或防止光致抗蚀剂中使用的材料或对光致抗蚀剂进行曝光时生成的物质对基板的不良作用的功能。
因此,由本发明的光刻用抗蚀剂下层膜形成用组合物形成的抗蚀剂下层膜可以作为平坦化膜、抗蚀剂层的防污染膜、具有干蚀刻选择性的膜使用。由此,能够容易且精度良好地进行半导体制造的光刻工艺中的抗蚀剂图案形成。
而且,在加工半导体基板后,由本发明的组合物形成的抗蚀剂下层膜能够利用碱性水溶液除去。
实施例
作为重均分子量,记载的是利用凝胶渗透色谱法(GPC)测得的测定结果。
测定使用東ソー(株)制GPC装置,测定条件如下。
GPC柱:Shodex〔注册商标〕·Asahipak〔注册商标〕(昭和电工(株)制)
柱温:40℃
溶剂:N,N-二甲基甲酰胺(DMF)
流量:0.6mL/分
标准试样:聚苯乙烯(東ソー(株)制)
合成例1
将N-(4-羟基苯基)甲基丙烯酰胺20.0g(大阪有机化学工业株式会社制)、甲基丙烯酸甲酯(东京化成工业株式会社制)11.3g、2,2-偶氮二(异丁腈)(东京化成工业株式会社制)3.7g添加到丙二醇单甲基醚140.2g中使其溶解。将该溶液滴加到装有被加热至85℃的58.5g丙二醇单甲基醚的300mL的烧瓶中,滴加结束后进行约15小时搅拌。反应结束后,向该溶液中添加阳离子交换树脂(商品名:ダウエックス〔注册商标〕550A、ムロマチテクノス(株))45g、阴离子交换树脂(商品名:アンバーライト〔注册商标〕15JWET、オルガノ(株))45g,在室温下进行4小时离子交换处理,然后除去离子交换树脂。所得的聚合物的结构相当于式(A-1)所示的结构。聚合物中的N-(4-羟基苯基)甲基丙烯酰胺单元:甲基丙烯酸甲酯单元为50摩尔%:50摩尔%。聚合物溶液的聚合物含量(固体成分)为12.0%。对所得的化合物进行GPC分析,结果利用标准聚苯乙烯换算而得的重均分子量Mw为5,000。
合成例2
将N-(4-羟基苯基)甲基丙烯酰胺16.0g(大阪有机化学工业株式会社制)、甲基丙烯酸甲酯(东京化成工业株式会社制)21.1g、2,2-偶氮二(异丁腈)(东京化成工业株式会社制)4.3g添加到丙二醇单甲基醚165.5g中使其溶解。将该溶液滴加到装有被加热至85℃的68.9g丙二醇单甲基醚的300mL烧瓶中,滴加结束后进行约15小时搅拌。反应结束后,向该溶液中添加阳离子交换树脂(商品名:ダウエックス〔注册商标〕550A、ムロマチテクノス(株))42.0g、阴离子交换树脂(商品名:アンバーライト〔注册商标〕15JWET、オルガノ(株))42.0g,在室温下进行4小时离子交换处理,然后除去离子交换树脂。所得的聚合物的结构相当于式(A-1)所示的结构。聚合物中的N-(4-羟基苯基)甲基丙烯酰胺单元:甲基丙烯酸甲酯单元为30摩尔%:70摩尔%。聚合物溶液的聚合物含量(固体成分)为13.7%。对所得的化合物进行GPC分析,结果利用标准聚苯乙烯换算而得的重均分子量Mw为9,000。
比较合成例1
将N-(4-羟基苯基)甲基丙烯酰胺5.0g(大阪有机化学工业株式会社制)、甲基丙烯酸甲酯(东京化成工业株式会社制)0.7g、2,2-偶氮二(异丁腈)(东京化成工业株式会社制)0.7g添加到丙二醇单甲基醚25.5g中使其溶解。将该溶液滴加到装有被加热到85℃的10.6g丙二醇单甲基醚的100mL烧瓶中,滴加结束后进行约15小时搅拌。反应结束后,向该溶液中添加阳离子交换树脂(商品名:ダウエックス〔注册商标〕550A、ムロマチテクノス(株))6.4g、阴离子交换树脂(商品名:アンバーライト〔注册商标〕15JWET、オルガノ(株))6.4g,在室温下进行4小时离子交换处理,然后除去离子交换树脂。所得的聚合物的结构相当于式(A-1)所示的结构。聚合物中的N-(4-羟基苯基)甲基丙烯酰胺单元:甲基丙烯酸甲酯单元为80摩尔%:20摩尔%。聚合物溶液的聚合物含量(固体成分)为12.6%。对所得的化合物进行GPC分析,结果利用标准聚苯乙烯换算而得的重均分子量Mw为4,700。
比较合成例2
将N-(4-羟基苯基)甲基丙烯酰胺1.0g(大阪有机化学工业株式会社制)、甲基丙烯酸甲酯(东京化成工业株式会社制)5.1g、2,2-偶氮二(异丁腈)(东京化成工业株式会社制)0.7g添加到丙二醇单甲基醚27.1g中使其溶解。将该溶液滴加到装有被加热到85℃的11.3g丙二醇单甲基醚的100mL烧瓶中,滴加结束后进行约15小时搅拌。反应结束后,向该溶液中添加阳离子交换树脂(商品名:ダウエックス〔注册商标〕550A、ムロマチテクノス(株))6.8g、阴离子交换树脂(商品名:アンバーライト〔注册商标〕15JWET、オルガノ(株))6.8g,在室温下进行4小时离子交换处理,然后除去离子交换树脂。所得的聚合物的结构相当于式(A-1)所示的结构。聚合物中的N-(4-羟基苯基)甲基丙烯酰胺单元:甲基丙烯酸甲酯单元为10摩尔%:90摩尔%。聚合物溶液的聚合物含量(固体成分)为13.5%。对所得的化合物进行GPC分析,结果利用标准聚苯乙烯换算而得的重均分子量Mw为4,300。
实施例1
使由合成例1得到的聚合物溶液(以N-(4-羟基苯基)甲基丙烯酰胺单元:甲基丙烯酸甲酯单元为50摩尔%:50摩尔%的比例含有二者的聚合物的溶液)52.7g、封闭异氰酸酯系交联剂(デグザジャパン(株)制,商品名:VESTANAT〔注册商标〕B1358,基于异佛尔酮二异氰酸酯结构、被肟基保护的封闭多元异氰酸酯)1.6g、以及表面活性剂(DIC(株)制,商品名:メガファック〔注册商标〕R-40)0.06g溶解于丙二醇单甲基醚乙酸酯22.4g、丙二醇单甲基醚31.5g、γ-丁内酯11.2g中,调制在利用多层膜进行的光刻工艺中使用的抗蚀剂下层膜形成用组合物的溶液。
实施例2
使由合成例2得到的聚合物溶液(以N-(4-羟基苯基)甲基丙烯酰胺单元:甲基丙烯酸甲酯单元为30摩尔%:70摩尔%的比例含有二者的聚合物的溶液)3.9g、封闭异氰酸酯系交联剂(デグザジャパン(株)制,商品名:VESTANAT〔注册商标〕B1358,基于异佛尔酮二异氰酸酯结构、被肟基保护的封闭多元异氰酸酯)0.15g、以及表面活性剂(DIC(株)制,商品名:メガファック〔注册商标〕R-40)0.05g溶解于丙二醇单甲基醚乙酸酯1.8g、丙二醇单甲基醚2.8g、γ-丁内酯0.9g中,调制在利用多层膜进行的光刻工艺中使用的抗蚀剂下层膜形成用组合物的溶液。
比较例1
使由比较合成例1得到的聚合物溶液(以N-(4-羟基苯基)甲基丙烯酰胺单元:甲基丙烯酸甲酯单元为80摩尔%:20摩尔%的比例含有二者的聚合物的溶液)8.9g、封闭异氰酸酯系交联剂(デグザジャパン(株)制,商品名:VESTANAT〔注册商标〕B1358,基于异佛尔酮二异氰酸酯结构、被肟基保护的封闭多元异氰酸酯)0.3g、以及表面活性剂(DIC(株)制,商品名:メガファック〔注册商标〕R-40)0.001g溶解于丙二醇单甲基醚10.7g中,调制在利用多层膜进行的光刻工艺中使用的抗蚀剂下层膜形成用组合物的溶液。
比较例2
使由比较合成例2得到的聚合物溶液(以N-(4-羟基苯基)甲基丙烯酰胺单元:甲基丙烯酸甲酯单元为10摩尔%:90摩尔%的比例含有二者的聚合物的溶液)8.3g、封闭异氰酸酯系交联剂(デグザジャパン(株)制,商品名:VESTANAT〔注册商标〕B1358,基于异佛尔酮二异氰酸酯结构、被肟基保护的封闭多元异氰酸酯)0.3g、以及表面活性剂(DIC(株)制,商品名:メガファック〔注册商标〕R-40)0.001g溶解于丙二醇单甲基醚11.3g中,调制在利用多层膜进行的光刻工艺中使用的抗蚀剂下层膜形成用组合物的溶液。
(光致抗蚀剂在溶剂中的溶出试验)
使用旋转涂布机将由实施例1~2、和比较例1~2调制的抗蚀剂下层膜形成用组合物的溶液涂布在硅晶片上。在加热板上在240℃下进行1分钟烧成,形成抗蚀剂下层膜(膜厚0.20μm)。相对于作为在这些抗蚀剂下层膜的抗蚀剂中使用的溶剂的OKシンナー(商品名,东京应化工业(株),丙二醇单甲基醚:丙二醇单甲基醚乙酸酯以容积比计为7:3)进行浸渍试验。关于残膜率,将抗蚀剂下层膜分别放置在旋转涂布机上2000rpm的旋转下,分别滴加作为溶剂的OKシンナー60秒,然后立即使其以3000rpm进行30秒旋转。将结果示于表1。残膜率是利用(浸渍后的膜厚)/(浸渍前的膜厚)×100计算出的结果。
表1溶出试验后的残膜率(%)
(高低差(段差)被覆性的评价)
使用旋转涂布机将由实施例1~2、和比较例1~2调制的抗蚀剂下层膜形成用组合物的溶液涂布在高低差基板上。所使用的高低差基板((株)アドハ゛ンテック制)是高低差的高度为400nm、孔开口部直径/高度为120nm/120nm、被覆有氧化硅膜的基板。然后,用扫描型电子显微镜(SEM)观察在240℃下进行了60秒烘烤的试样的截面。将结果示于表2。将被覆得无孔隙(void)的情况判断为良好,将孔内观察到孔隙的情况判断为不良。
表2高低差被覆性的评价结果
产业上的可利用性
本发明提供用于形成下述抗蚀剂下层膜的抗蚀剂下层膜形成用组合物,所述抗蚀剂下层膜能够用于使用抗蚀剂下层膜形成用组合物形成抗蚀剂图案的方法中,而且,在从上层进行图案转印、基板加工时能够进行干蚀刻,在基板加工后能够利用碱性水溶液除去。
Claims (6)
1.一种抗蚀剂下层膜形成用组合物,其特征在于,含有聚合物(A)、交联性化合物(B)和溶剂(C),所述聚合物(A)含有下述式(1)所示的结构单元和下述式(2)所示的结构单元,所述交联性化合物(B)具有至少2个选自封闭异氰酸酯基、羟甲基或碳原子数为1~5的烷氧基甲基中的基团,该聚合物(A)是该式(1)所示的单元结构与该式(2)所示的单元结构以摩尔百分比计为式(1)所示的单元结构:式(2)所示的单元结构=(25~60):(75~40)的比例进行共聚而得到的聚合物,
式(1)、式(2)中,R1和R4分别表示氢原子或甲基,X1和X2分别表示NH基或氧原子,R2表示芳香族环,R3表示羟基或羧基,Y表示可被取代的碳原子数为1~10的烷基。
2.根据权利要求1所述的抗蚀剂下层膜形成用组合物,R2是苯环。
3.根据权利要求1或2所述的抗蚀剂下层膜形成用组合物,其以相对于所述聚合物(A)的质量为1~40质量%的比例含有交联性化合物(B)。
4.根据权利要求1~3中任一项所述的抗蚀剂下层膜形成用组合物,其进一步含有交联催化剂。
5.一种半导体装置的制造方法,包括下述工序:在半导体基板上由权利要求1~4中任一项所述的抗蚀剂下层膜形成用组合物形成抗蚀剂下层膜的工序,在该抗蚀剂下层膜上形成抗蚀剂膜的工序,通过光或电子射线的照射和显影在抗蚀剂膜上形成抗蚀剂图案的工序,利用所形成的抗蚀剂图案来蚀刻抗蚀剂下层膜的工序,以及利用图案化了的抗蚀剂下层膜来加工半导体基板的工序。
6.一种半导体装置的制造方法,包括下述工序:在半导体基板上由权利要求1~4中任一项所述的抗蚀剂下层膜形成用组合物形成抗蚀剂下层膜的工序,在该抗蚀剂下层膜上形成无机硬掩膜层的工序,进一步在无机硬掩膜层上形成抗蚀剂膜的工序,通过光或电子射线的照射和显影在抗蚀剂膜上形成抗蚀剂图案的工序,利用所形成的抗蚀剂图案来蚀刻无机硬掩膜层的工序,利用图案化了的无机硬掩膜层来蚀刻抗蚀剂下层膜的工序,以及利用图案化了的抗蚀剂下层膜来加工半导体基板的工序。
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WO2017191767A1 (ja) * | 2016-05-02 | 2017-11-09 | 日産化学工業株式会社 | 特定の架橋剤を含む保護膜形成組成物及びそれを用いたパターン形成方法 |
CN109563234B (zh) * | 2016-08-08 | 2022-08-23 | 日产化学株式会社 | 光固化性组合物及半导体装置的制造方法 |
JP7050784B2 (ja) | 2016-12-12 | 2022-04-08 | クラリアント・インターナシヨナル・リミテツド | 化粧料組成物、皮膚科学的組成物または医薬組成物におけるバイオベースのポリマーの使用 |
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