CN107077071A - 包含具有亚芳基的聚合物的抗蚀剂下层膜形成用组合物 - Google Patents
包含具有亚芳基的聚合物的抗蚀剂下层膜形成用组合物 Download PDFInfo
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- CN107077071A CN107077071A CN201580055292.1A CN201580055292A CN107077071A CN 107077071 A CN107077071 A CN 107077071A CN 201580055292 A CN201580055292 A CN 201580055292A CN 107077071 A CN107077071 A CN 107077071A
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Abstract
本发明提供一种光刻工艺用抗蚀剂下层膜形成用组合物,所述光刻工艺用抗蚀剂下层膜形成用组合物具有下述特征:在高低差基板上的平坦化性能优异,向微细孔隙图案填埋的填埋性能良好,可使得成膜后的晶片表面平坦。其解决手段为包含含有下述式(1)表示的单元结构的聚合物和溶剂的抗蚀剂下层膜形成用组合物。
Description
技术领域
本发明涉及一种光刻工艺用抗蚀剂下层膜形成用组合物,所述光刻工艺用抗蚀剂下层膜形成用组合物具有下述特征:在高低差基板(stepped substrate)上的平坦化性能优异,向微细孔隙图案填埋的填埋性能良好,因此,可使得成膜后的晶片表面平坦。
背景技术
半导体器件的制造中,可进行基于光刻工艺的微细加工。已知在该光刻工艺中,用KrF准分子激光、ArF准分子激光等紫外线激光对基板上的抗蚀剂层进行曝光时,存在下述问题:由于因该紫外线激光在基板表面反射而产生的驻波的影响,导致无法形成具有所期望的形状的抗蚀剂图案。为了解决该问题,采用了在基板与抗蚀剂层之间设置抗蚀剂下层膜(防反射膜)的方案。而且,作为用于形成抗蚀剂下层膜的组合物,使用酚醛清漆树脂是已知的。例如,公开了含有具有将具有双酚基的化合物酚醛清漆化而得到的重复单元的树脂的光致抗蚀剂下层膜形成用材料(专利文献1)。
此外,公开了包含在聚合物的主链中具有3个或3个以上稠合而成的芳香族环的聚合物的、可旋涂的防反射膜组合物(专利文献2)。
另外,使用了利用了苯基萘基胺的酚醛清漆树脂(专利文献3)。
还提出了使用这样的聚合物作为分散剂的方案(专利文献4)。
现有技术文献
专利文献
专利文献1:日本特开2006-259249号
专利文献2:日本特表2010-528334号
专利文献3:国际公开WO2013/047516号小册子
专利文献4:国际公开WO2011/065395号小册子
发明内容
发明所要解决的课题
由于伴随着抗蚀剂图案的微细化而要求的抗蚀剂层的薄膜化,形成至少2层抗蚀剂下层膜、并使用该抗蚀剂下层膜作为掩模材料的光刻工艺也是已知的。作为形成前述至少2层的材料,可举出有机树脂(例如,丙烯酸树脂、酚醛清漆树脂)、硅树脂(例如,有机聚硅氧烷)、无机硅化合物(例如,SiON、SiO2)。此外,近年来,广泛应用了为了得到1个图案而进行2次光刻和2次蚀刻的双重图案化(double patterning)技术,在各工序中使用了上述的多层工艺。此时,需要在形成最初的图案后形成的有机膜上,使高低差平坦化的特性。
本发明提供一种光刻工艺用抗蚀剂下层膜形成用组合物,所述光刻工艺用抗蚀剂下层膜形成用组合物具有下述特征:在高低差基板上的平坦化性能优异,向微细孔隙图案填埋的填埋性能良好,因此,可使得成膜后的晶片表面平坦。
用于解决课题的手段
本发明中,作为第1观点,是一种抗蚀剂下层膜形成用组合物,其包含聚合物和溶剂,所述聚合物含有下述式(1)表示的单元结构,
(式(1)中,R1~R4各自独立地表示氢原子或甲基。X1表示可被烷基、氨基、或羟基取代的包含至少一个亚芳基的二价的有机基团。)
作为第2观点,是第1观点所述的抗蚀剂下层膜形成用组合物,其中,式(1)中,X1的定义中的亚芳基为亚苯基、亚联苯基、亚三联苯基、亚芴基、亚萘基、亚蒽基、亚芘基、或亚咔唑基,
作为第3观点,是第1观点所述的抗蚀剂下层膜形成用组合物,其中,式(1)中,X1为式(2)表示的有机基团,
〔式(2)中,A1表示亚苯基或亚萘基。A2表示亚苯基、亚萘基、或式(3)表示的有机基团。虚线表示连接键。〕
(式(3)中,A3及A4各自独立地表示亚苯基或亚萘基。虚线表示连接键。)
作为第4观点,是第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,其中,还包含交联剂,
作为第5观点,是第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,其中,还包含酸及/或产酸剂,
作为第6观点,是一种抗蚀剂下层膜,其形成于半导体基板上,其是由第1观点~第5观点中任一项所述的抗蚀剂下层膜形成用组合物的固化物形成的,
作为第7观点,是一种半导体器件的制造方法,其包括以下工序:在半导体基板上由第1观点~第5观点中任一项所述的抗蚀剂下层膜形成用组合物形成下层膜的工序;在其上形成抗蚀剂膜的工序;通过照射光或电子束、并显影而形成抗蚀剂图案的工序;利用所形成的抗蚀剂图案对该下层膜进行蚀刻的工序;以及,利用已图案化的下层膜对该半导体基板进行加工的工序,
作为第8观点,是一种半导体器件的制造方法,其包括以下工序:在半导体基板上由第1观点~第5观点中任一项所述的抗蚀剂下层膜形成用组合物形成下层膜的工序;在其上形成硬掩模的工序;进一步在其上形成抗蚀剂膜的工序;通过照射光或电子束、并显影而形成抗蚀剂图案的工序;利用所形成的抗蚀剂图案对硬掩模进行蚀刻的工序;利用已图案化的硬掩模对该下层膜进行蚀刻的工序;以及,利用已图案化的下层膜对该半导体基板进行加工的工序。
发明的效果
在将本发明中可使用的聚合物应用于光刻工艺用抗蚀剂下层膜的情况下,由于在高低差基板上的平坦化性能优异,向微细孔隙图案填埋的填埋性能良好,因此,成为使成膜后的晶片表面平坦化的抗蚀剂下层膜。
另外,得到的抗蚀剂下层膜为高硬度,而且,通过在光刻工艺中应用该抗蚀剂下层膜,可抑制形成的图案的扭摆(wiggling)。
具体实施方式
本发明是一种抗蚀剂下层膜形成用组合物,其包含聚合物和溶剂,所述聚合物含有式(1)表示的单元结构。
而且,可包含交联剂和酸,根据需要,可包含产酸剂、表面活性剂等添加剂。该组合物的固态成分为0.1~70质量%、或0.1~60质量%、或0.2~30质量%、或0.3~15质量%。此处,固态成分为从抗蚀剂下层膜形成用组合物中除去溶剂而得到的全部成分的含有比例。在固态成分中,可以以1~100质量%、或1~99.9质量%、或50~99.9质量%、或50~95质量%、或50~90质量%的比例含有上述聚合物。
本发明中可使用的聚合物的重均分子量为600~1000000、或600~200000、或1500~15000。
式(1)中,R1~R4各自独立地表示氢原子或甲基。X1表示可被烷基、氨基、或羟基取代的包含至少一个亚芳基的有机基团。
关于亚芳基,可优选使用由碳原子数6~40的芳基衍生的亚芳基。作为亚芳基,例如,可例举亚苯基、亚联苯基、亚三联苯基、亚芴基、亚萘基、亚蒽基、亚芘基、或亚咔唑基等。
作为烷基,可举出碳原子数1~10的烷基,例如,可举出甲基、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-甲基环丙基及2-乙基-3-甲基环丙基等。
作为氨基,可举出伯氨基、仲氨基、叔氨基,可优选使用仲氨基。
式(1)中,X1可使用式(2)表示的有机基团。
式(2)中,A1表示亚苯基或亚萘基。A2表示亚苯基、亚萘基、或式(3)表示的有机基团。需要说明的是,式(2)中,虚线表示连接键。
式(3)中,A3及A4各自独立地表示亚苯基或亚萘基。需要说明的是,式(3)中,虚线表示连接键。
本发明中可使用的聚合物是通过含有羟基甲基或甲氧基甲基的芳香族化合物、与芳香族化合物之间的缩合反应而形成的、芳香族亚甲基化合物的聚合物。对于该反应而言,例如,在酸催化剂(例如,对甲苯磺酸)的存在下,于100~150℃的温度进行10~20小时。作为该反应中使用的溶剂,例如,可举出丙二醇单甲基醚乙酸酯(PGMEA)等。
本发明中可使用的聚合物例如可示例如下。
本发明的抗蚀剂下层膜形成用组合物还可含有交联剂。作为前述交联剂,可优选使用具有至少两个形成交联的取代基的交联性化合物。例如,可举出具有羟甲基、甲氧基甲基等形成交联的取代基的、三聚氰胺系化合物、取代脲系化合物及酚系化合物。具体而言,为甲氧基甲基化甘脲、甲氧基甲基化三聚氰胺等化合物,例如,可举出四甲氧基甲基甘脲、四丁氧基甲基甘脲、六甲氧基甲基三聚氰胺。此外,作为取代脲系化合物,例如,可举出四甲氧基甲基脲、四丁氧基甲基脲。作为酚系化合物,例如,可举出四羟基甲基联苯酚、四羟基甲基联苯酚、四甲氧基甲基联苯酚、四甲氧基甲基双酚。
作为上述交联剂,可使用耐热性高的交联剂。作为耐热性高的交联剂,可优选使用在分子内含有具有芳香族环(例如,苯环、萘环)的形成交联的取代基的化合物。
作为这些化合物,可举出具有下述式(4)的部分结构的化合物、具有下述式(5)的重复单元的聚合物或低聚物。
上述式中,R11、R12、R13、及R14各自独立地表示氢原子或碳原子数1~10的烷基,这些烷基可使用上文中所例举的烷基。另外,n1表示1~2的整数,n2表示1~(6-n1)的整数,n3表示1~2的整数,以及,n4表示0~(4-n3)的整数。
关于式(4)及式(5)的化合物、聚合物、低聚物,可例举以下的式(6-1)~(6-27)。在以下的式中,Me表示甲基。
上述化合物可作为旭有机材工业(株)、本州化学工业(株)的制品而获得。例如,上述交联剂中,式(6-23)的化合物可作为本州化学工业(株)制3,3’,5,5’-四甲氧基甲基-4,4’-二羟基联苯、商品名TMOM-BP而获得。式(6-24)的化合物可作为旭有机材工业(株)、商品名TM-BIP-A而获得。
作为前述交联剂,另外,还可使用具有至少两个环氧基的化合物。作为这样的化合物,例如,可举出三(2,3-环氧丙基)异氰脲酸酯、1,4-丁二醇二缩水甘油基醚、1,2-环氧-4-(环氧乙基)环己烷、甘油三缩水甘油基醚、二乙二醇二缩水甘油基醚、2,6-二缩水甘油基苯基缩水甘油基醚、1,1,3-三[对(2,3-环氧丙氧基)苯基]丙烷、1,2-环己烷二甲酸二缩水甘油酯、4,4’-亚甲基双(N,N-二缩水甘油基苯胺)、3,4-环氧环己烷羧酸3,4-环氧环己基甲酯、三羟甲基乙烷三缩水甘油基醚、双酚-A-二缩水甘油基醚、(株)ダイセル制的エポリード〔注册商标〕GT-401、エポリードGT-403、エポリードGT-301、エポリードGT-302、セロキサイド〔注册商标〕2021、セロキサイド3000、三菱化学(株)制的1001、1002、1003、1004、1007、1009、1010、828、807、152、154、180S75、871、872、日本化药(株)制的EPPN201、EPPN202、EOCN-102、EOCN-103S、EOCN-104S、EOCN-1020、EOCN-1025、EOCN-1027、ナガセケムテックス(株)制的デナコール〔注册商标〕EX-252、デナコールEX-611、デナコールEX-612、デナコールEX-614、デナコールEX-622、デナコールEX-411、デナコールEX-512、デナコールEX-522、デナコールEX-421、デナコールEX-313、デナコールEX-314、デナコールEX-321、BASFジャパン(株)制的CY175、CY177、CY179、CY182、CY184、CY192、DIC(株)制的エピクロン200、エピクロン400、エピクロン7015、エピクロン835LV、エピクロン850CRP。作为前述具有至少两个环氧基的化合物,另外,还可使用具有氨基的环氧树脂。作为这样的环氧树脂,例如,可举出YH-434、YH-434L(新日化エポキシ制造(株)制)。
作为前述交联剂,另外,也可使用具有至少2个封端异氰酸酯基的化合物。作为这样的化合物,例如,可举出三井化学(株)制的タケネート〔注册商标〕B-830、タケネートB-870N、エボニックデグサ公司制的VESTANAT〔注册商标〕B1358/100。
作为前述交联剂,另外,也可使用具有至少2个乙烯基醚基的化合物。作为这样的化合物,例如,可举出戊二酸双(4-(乙烯基氧基甲基)环己基甲基)酯、三(乙二醇)二乙烯基醚、己二酸二乙烯基酯、二乙二醇二乙烯基醚、偏苯三酸1,2,4-三(4-乙烯基氧基丁基)酯、偏苯三酸1,3,5-三(4-乙烯基氧基丁基)酯、对苯二甲酸双(4-(乙烯基氧基)丁基)酯、间苯二甲酸双(4-(乙烯基氧基)丁基)酯、乙二醇二乙烯基醚、1,4-丁二醇二乙烯基醚、1,4-丁二醇二乙烯基醚、四乙二醇二乙烯基醚、新戊二醇二乙烯基醚、三羟甲基丙烷三乙烯基醚、三羟甲基乙烷三乙烯基醚、己二醇二乙烯基醚、1,4-环己二醇二乙烯基醚、四乙二醇二乙烯基醚、季戊四醇二乙烯基醚、季戊四醇三乙烯基醚及环己烷二甲醇二乙烯基醚。
可添加选自上述各种交联剂中的1种,也可组合2种以上而添加。对于前述交联剂的含有比例而言,相对于从本发明的抗蚀剂下层膜形成用组合物中除去后述的溶剂而得到的固态成分,例如为2质量%~60质量%。
本发明的抗蚀剂下层膜形成用组合物还可含有酸性化合物。前述酸性化合物作为促进交联反应的催化剂发挥作用,例如,可举出对甲苯磺酸、三氟甲磺酸、对甲苯磺酸吡啶鎓盐、水杨酸、樟脑磺酸、5-磺基水杨酸、4-氯苯磺酸、4-羟基苯磺酸、苯二磺酸、1-萘磺酸、柠檬酸、苯甲酸、羟基苯甲酸等磺酸化合物及羧酸化合物、盐酸、硫酸、硝酸、磷酸等无机酸。可代替上述酸性化合物而含有、或在含有上述酸性化合物的同时含有热产酸剂。前述热产酸剂也作为促进交联反应的催化剂发挥作用,例如,可举出三氟甲磺酸的季铵盐。可添加选自这些酸性化合物及热产酸剂中的1种,也可组合2种以上而添加。对于前述酸性化合物或热产酸剂的含有比例而言,相对于从本发明的抗蚀剂下层膜形成用组合物中除去后述的溶剂而得到的固态成分,例如为0.1质量%~20质量%。
本发明的抗蚀剂下层膜形成用组合物还可含有表面活性剂。作为前述表面活性剂,例如,可举出聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯鲸蜡基醚、聚氧乙烯油基醚等聚氧乙烯烷基醚类、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基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、山梨糖醇酐单月桂酸酯、山梨糖醇酐单棕榈酸酯、山梨糖醇酐单硬脂酸酯、山梨糖醇酐单油酸酯、山梨糖醇酐三油酸酯、山梨糖醇酐三硬脂酸酯等山梨糖醇酐脂肪酸酯类、聚氧乙烯山梨糖醇酐单月桂酸酯、聚氧乙烯山梨糖醇酐单棕榈酸酯、聚氧乙烯山梨糖醇酐单硬脂酸酯、聚氧乙烯山梨糖醇酐三油酸酯、聚氧乙烯山梨糖醇酐三硬脂酸酯等聚氧乙烯山梨糖醇酐脂肪酸酯类等非离子系表面活性剂、エフトップ〔注册商标〕EF301、エフトップEF303、エフトップEF352(三菱マテリアル電子化成(株)制)、メガファック〔注册商标〕F171、メガファックF173、メガファックR30、メガファックR-30N、メガファックR-40LM(DIC(株)制)、フロラードFC430、フロラードFC431(住友スリーエム(株)制)、アサヒガード〔注册商标〕AG710、サーフロン〔注册商标〕S-382、サーフロンSC101、サーフロンSC102、サーフロンSC103、サーフロンSC104、サーフロンSC105、サーフロンSC106(旭硝子(株)制)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)。可添加选自这些表面活性剂中的1种,也可组合2种以上而添加。对于前述表面活性剂的含有比例而言,相对于从本发明的抗蚀剂下层膜形成用组合物中除去后述的溶剂而得到的固态成分,例如为0.01质量%~5质量%。
本发明的抗蚀剂下层膜形成用组合物可通过将上述的各成分溶解于适当的溶剂中而制备,可以以均匀的溶液状态使用。作为这样的溶剂,例如,可举出乙二醇单甲基醚、乙二醇单乙基醚、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、丙二醇单丙基醚、丙二醇单甲基醚乙酸酯、丙二醇丙基醚乙酸酯、甲基溶纤剂乙酸酯、乙基溶纤剂乙酸酯、甲苯、二甲苯、甲基乙基酮、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、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮。对于这些有机溶剂而言,可使用1种或者也可以组合2种以上而使用。对于从前述组合物中除去有机溶剂而得到的固态成分的比例而言,例如为0.5质量%~30质量%,优选为0.8质量%~15质量%。
本发明中,作为使上述的聚合物及交联剂成分、交联催化剂等溶解的溶剂,可使用乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单丁基醚、乙二醇单异丙基醚、乙二醇甲基醚乙酸酯、乙二醇乙基醚乙酸酯、甲基溶纤剂乙酸酯、乙基溶纤剂乙酸酯、二乙二醇、二乙二醇单甲基醚、二乙二醇单乙基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇单乙基醚乙酸酯、丙二醇、丙二醇单甲基醚、丙二醇单丁基醚、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、二丙二醇单甲基醚、二丙二醇单乙基醚、三乙二醇二甲基醚、甲苯、二甲苯、苯乙烯、甲基乙基酮、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、1-辛醇、乙二醇、己二醇、1,3-丙二醇、1-甲氧基-2-丁醇、环己醇、二丙酮醇、糠醇、四氢糠醇、丙二醇、苯甲醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、γ-丁基内酯、丙酮、甲基异丙基酮、二乙基酮、甲基异丁基酮、甲基正丁基酮、乙酸异丙基酮、乙酸正丙酯、乙酸异丁酯、甲醇、乙醇、异丙醇、叔丁醇、烯丙醇、正丙醇、2-甲基-2-丁醇、异丁醇、正丁醇、2-甲基-1-丁醇、1-戊醇、2-甲基-1-戊醇、2-乙基己醇、1-辛醇、乙二醇、己二醇、1,3-丙二醇、1-甲氧基-2-丁醇、二丙酮醇、糠醇、四氢糠醇、丙二醇、苯甲醇、异丙基醚、1,4-二氧杂环己烷、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、1,3-二甲基-2-咪唑烷酮、二甲基亚砜、N-环己基-2-吡咯烷酮等。这些有机溶剂可单独使用,或者也可组合2种以上而使用。
接着,对使用本发明的抗蚀剂下层膜形成用组合物的抗蚀剂图案形成方法进行说明。利用旋涂机(spinner)、涂布器(coater)等适当的涂布方法,在可用于制造精密集成电路元件的基板(例如硅/二氧化硅被覆、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,制成涂布型下层膜。此处,作为抗蚀剂下层膜的膜厚,优选为0.01~3.0μm。另外,作为涂布后进行烘烤的条件,在80~350℃、或优选100~400℃进行0.5~120分钟、或优选0.3~10分钟。然后,在抗蚀剂下层膜上直接地、或根据需要在涂布型下层膜上涂布1层~数层的涂膜材料而形成膜后,涂布抗蚀剂,通过规定的掩模照射光或电子束,进行显影、漂洗、干燥,由此,可得到良好的抗蚀剂图案。根据需要,也可在照射光或电子束后进行加热(PEB:Post Exposure Bake)。而后,利用干法蚀刻,将已通过前述工序将抗蚀剂显影除去了的部分的抗蚀剂下层膜除去,可在基板上形成所期望的图案。
对于针对上述光致抗蚀剂的曝光用光而言,可使用近紫外线、远紫外线、或超紫外线(例如EUV,波长13.5nm)等化学射线,例如248nm(KrF激光)、193nm(ArF激光)、157nm(F2激光)等波长的光。对于光照射而言,只要是能从光产酸剂产生酸的方法,就可以没有特别限制地使用,使曝光量为1~2000mJ/cm2、或10~1500mJ/cm2、或50~1000mJ/cm2。
另外,对于电子束抗蚀剂的电子束照射而言,例如,可使用电子束照射装置进行照射。
作为具有使用本发明的光刻用抗蚀剂下层膜组合物形成的抗蚀剂下层膜的抗蚀剂的显影液,可使用氢氧化钠、氢氧化钾、碳酸钠、硅酸钠、偏硅酸钠、氨水等无机碱类、乙基胺、正丙基胺等伯胺类、二乙基胺、二正丁基胺等仲胺类、三乙基胺、甲基二乙基胺等叔胺类、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。此外,也可在上述碱类的水溶液中添加适当量的异丙醇等醇类、非离子系等的表面活性剂而使用。这些中优选的显影液是季铵盐,进一步优选的是四甲基氢氧化铵及胆碱。
另外,作为显影液,可使用有机溶剂。例如,作为例子,可举出乙酸甲酯、乙酸丁酯、乙酸乙酯、乙酸异丙酯、乙酸戊酯、乙酸异戊酯、甲氧基乙酸乙酯、乙氧基乙酸乙酯、丙二醇单甲基醚、乙二醇单乙基醚乙酸酯、乙二醇单丙基醚乙酸酯、乙二醇单丁基醚乙酸酯、乙二醇单苯基醚乙酸酯、二乙二醇单甲基醚乙酸酯、二乙二醇单丙基醚乙酸酯、二乙二醇单乙基醚乙酸酯、二乙二醇单苯基醚乙酸酯、二乙二醇单丁基醚乙酸酯、乙酸2-甲氧基丁酯、乙酸3-甲氧基丁酯、乙酸4-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、乙酸3-乙基-3-甲氧基丁酯、丙二醇单甲基醚乙酸酯、丙二醇单乙基醚乙酸酯、丙二醇单丙基醚乙酸酯、乙酸2-乙氧基丁酯、乙酸4-乙氧基丁酯、乙酸4-丙氧基丁酯、乙酸2-甲氧基戊酯、乙酸3-甲氧基戊酯、乙酸4-甲氧基戊酯、乙酸2-甲基-3-甲氧基戊酯、乙酸3-甲基-3-甲氧基戊酯、乙酸3-甲基-4-甲氧基戊酯、乙酸4-甲基-4-甲氧基戊酯、丙二醇二乙酸酯、甲酸甲酯、甲酸乙酯、甲酸丁酯、甲酸丙酯、乳酸乙酯、乳酸丁酯、乳酸丙酯、碳酸乙酯、碳酸丙酯、碳酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、丙酮酸丁酯、乙酰乙酸甲酯、乙酰乙酸乙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸异丙酯、2-羟基丙酸甲酯、2-羟基丙酸乙酯、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-甲氧基丙酸丙酯等。此外,也可在这些显影液中添加表面活性剂等。作为显影的条件,可从5~50℃的温度、10~600秒的时间的范围内适当选择。
本发明中,可经过以下工序而制造半导体器件:在半导体基板上由抗蚀剂下层膜形成用组合物形成抗蚀剂下层膜的工序;在其上形成抗蚀剂膜的工序;通过照射光或电子束、并显影而形成抗蚀剂图案的工序;利用所形成的抗蚀剂图案对该抗蚀剂下层膜进行蚀刻的工序;以及,利用已图案化的抗蚀剂下层膜对该半导体基板进行加工的工序。
将来,随着抗蚀剂图案的微细化的发展,产生分辨率的问题、抗蚀剂图案在显影后倒毁这样的问题,期望抗蚀剂的薄膜化。因此,难以得到对基板加工而言充分的抗蚀剂图案膜厚,变得需要下述工艺:不仅抗蚀剂图案作为基板加工时的掩模发挥功能,而且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模的功能。作为用于这样的工艺的抗蚀剂下层膜,与以往的高蚀刻速度性抗蚀剂下层膜不同,要求具有与抗蚀剂接近的干法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法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法蚀刻速度的选择比的光刻用抗蚀剂下层膜。另外,也可向这样的抗蚀剂下层膜赋予防反射功能,可兼具以往的防反射膜的功能。
另一方面,为了得到微细的抗蚀剂图案,在对抗蚀剂下层膜进行干法蚀刻时,比针对抗蚀剂图案和抗蚀剂下层膜进行抗蚀剂显影时的图案宽度更细的工艺也开始使用。作为用于这样的工艺的抗蚀剂下层膜,与以往的高蚀刻速度性防反射膜不同,要求具有与抗蚀剂接近的干法蚀刻速度的选择比的抗蚀剂下层膜。另外,也可向这样的抗蚀剂下层膜赋予防反射功能,可兼具以往的防反射膜的功能。
本发明中,在基板上形成本发明的抗蚀剂下层膜后,可在抗蚀剂下层膜上直接地、或根据需要在抗蚀剂下层膜上形成1层~数层的涂膜材料后,涂布抗蚀剂。由此,即使在抗蚀剂的图案宽度变窄、为了防止图案倒毁而较薄地被覆抗蚀剂的情况下,也可通过选择适当的蚀刻气体,而进行基板的加工。
即,可经过以下工序制造半导体器件:在半导体基板上由抗蚀剂下层膜形成用组合物形成该抗蚀剂下层膜的工序;在其上形成利用含有硅成分等的涂膜材料而得到的硬掩模或利用蒸镀而得到的硬掩模(例如,氮化氧化硅)的工序;进一步在其上形成抗蚀剂膜的工序;通过照射光或电子束、并显影而形成抗蚀剂图案的工序;利用所形成的抗蚀剂图案、用卤素系气体对硬掩模进行蚀刻的工序;利用已图案化的硬掩模、用氧系气体或氢系气体对该抗蚀剂下层膜进行蚀刻的工序;以及,利用已图案化的抗蚀剂下层膜、用卤素系气体对该半导体基板进行加工的工序。
对于本发明的光刻用抗蚀剂下层膜形成用组合物而言,在考虑作为防反射膜的效果的情况下,在骨架中引入光吸收部位,因此,在加热干燥时,不存在向光致抗蚀剂中扩散的扩散物,另外,由于光吸收部位具有足够大的吸光性能,因而防止反射光的效果高。
对于本发明的光刻用抗蚀剂下层膜形成用组合物而言,热稳定性高,防止因烧成时的分解物而导致的对上层膜的污染,另外,可使烧成工序的温度裕量(margin)有余裕。
此外,对于本发明的光刻用抗蚀剂下层膜材料而言,根据工艺条件不同,可作为具有下述功能的膜而使用:防止光的反射的功能,进而防止基板与光致抗蚀剂的相互作用的功能或防止在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。
实施例
下述合成例1~合成例8、比较合成例1中所示的重均分子量及多分散度基于利用凝胶渗透色谱法(以下,在本说明书中简称为GPC。)得到的测定结果。测定中使用東ソー(株)制GPC系统,测定条件如下所述。
GPC柱:TSKgel SuperMultipore〔注册商标〕Hz-N(東ソー(株))
柱温:40℃
溶剂:四氢呋喃(THF)
流量:0.35ml/分钟
标准试样:聚苯乙烯(東ソー(株))
(合成例1)
在氮气下,在300mL四颈瓶中添加α,α’-二羟基-1,3-二异丙基苯(28.79g,0.148mol,东京化成工业(株)制)、N-苯基-1-萘基胺(30.00g,0.1368mol,东京化成工业(株)制)、对甲苯磺酸一水合物(5.68g,0.029mol,东京化成工业(株)制),进而装入丙二醇单甲基醚乙酸酯(以下,在本说明书中有时也以PGMEA的简称而表示。)(150.43g,关东化学(株)制)并进行搅拌,进行升温直至确认到回流而使其溶解,引发聚合。16小时后,放置冷却至60℃,然后,在甲醇(1600g,关东化学(株)制)中进行再沉淀。将得到的沉淀物过滤,用减压干燥机于60℃干燥16小时,得到具有式(1-1)表示的结构单元的目标聚合物(38.6g)。得到的聚合物的利用GPC并按照聚苯乙烯换算而测得的重均分子量为2000。
(合成例2)
在氮气下,在500mL四颈瓶中添加α,α’-二羟基-1,3-二异丙基苯(37.33g,0.1921mol东京化成工业(株)制)、N,N’-二苯基-1,4-苯二胺(50.00g,0.1921mol,东京化成工业(株)制)、对甲苯磺酸一水合物(1.53g,0.008mol,东京化成工业(株)制),进而装入丙二醇单甲基醚乙酸酯(PGMEA)207.33g,关东化学(株)制)并进行搅拌,进行升温直至确认到回流而使其溶解,引发聚合。16小时后,放置冷却至60℃,然后,在甲醇(1600g,关东化学(株)制)中进行再沉淀。将得到的沉淀物过滤,用减压干燥机于50℃干燥16小时,得到具有式(1-2)表示的结构单元的目标聚合物(56.04g)。得到的聚合物的利用GPC并按照聚苯乙烯换算而测得的重均分子量为2700。
(合成例3)
在氮气下,在100mL四颈瓶中添加α,α’-二羟基-1,3-二异丙基苯(3.23g,0.017mol,东京化成工业(株)制)、N,N’-二-2-萘基-1,4-苯二胺(6.00g,0.017mol,东京化成工业(株)制)、对甲苯磺酸一水合物(0.50g,0.003mol,东京化成工业(株)制),进而装入丙二醇单甲基醚乙酸酯(PGMEA)22.70g,关东化学(株)制)并进行搅拌,进行升温直至确认到回流而使其溶解,引发聚合。16小时后,放置冷却至60℃,然后,在甲醇(800g,关东化学(株)制)中进行再沉淀。将得到的沉淀物过滤,用减压干燥机于60℃干燥16小时,得到具有式(1-3)表示的结构单元的目标聚合物(5.8g)。得到的聚合物的利用GPC并按照聚苯乙烯换算而测得的重均分子量为1700。
(合成例4)
在氮气下,在200mL四颈瓶中添加α,α’-二羟基-1,3-二异丙基苯(5.97g,0.031mol,东京化成工业(株)制)、N-苯基-1-萘基胺(3.37g,0.015mol,东京化成工业(株)制)、N,N’-二苯基-1,4-苯二胺(4.00g,0.015mol,东京化成工业(株)制)、对甲苯磺酸一水合物(0.25g,0.001mol,东京化成工业(株)制),进而装入丙二醇单甲基醚乙酸酯(PGMEA)31.70g,关东化学(株)制)并进行搅拌,进行升温直至确认到回流而使其溶解,引发聚合。16小时后,放置冷却至60℃,然后,在甲醇(1000g,关东化学(株)制)中进行再沉淀。将得到的沉淀物过滤,用减压干燥机于60℃干燥16小时,得到具有式(1-4)表示的结构单元的目标聚合物(7.1g)。得到的聚合物的利用GPC并按照聚苯乙烯换算而测得的重均分子量为2800。
(合成例5)
在氮气下,在100mL四颈瓶中添加α,α’-二羟基-1,3-二异丙基苯(6.65g,0.034mol,东京化成工业(株)制)、N-苯基-1-萘基胺(3.68g,0.017mol,东京化成工业(株)制)、2,2-联苯酚(3.00g,0.016mol,东京化成工业(株)制)、对甲苯磺酸一水合物(1.34g,0.007mol,东京化成工业(株)制),进而装入丙二醇单甲基醚乙酸酯(PGMEA)34.23g,关东化学(株)制)并进行搅拌,进行升温直至确认到回流而使其溶解,引发聚合。16小时后,放置冷却至60℃,然后,在甲醇(1000g,关东化学(株)制)中进行再沉淀。将得到的沉淀物过滤,用减压干燥机于60℃干燥16小时,得到具有式(1-5)表示的结构单元的目标聚合物(7.1g)。得到的聚合物的利用GPC并按照聚苯乙烯换算而测得的重均分子量为2800。
(合成例6)
在氮气下,在100mL四颈瓶中添加1,4-双(甲氧基甲基)苯(5.00g,0.030mol,东京化成工业(株)制)、N-苯基-1-萘基胺(3.23g,0.015mol,东京化成工业(株)制)、1-萘酚(2.04g,0.014mol,东京化成工业(株)制)、对甲苯磺酸一水合物(1.18g,0.006mol,东京化成工业(株)制),进而装入丙二醇单甲基醚乙酸酯(PGMEA)26.71g,关东化学(株)制)并进行搅拌,进行升温直至确认到回流而使其溶解,引发聚合。16小时后,放置冷却至60℃,然后,在甲醇(1000g,关东化学(株)制)中进行再沉淀。将得到的沉淀物过滤,用减压干燥机于60℃干燥16小时,得到具有式(1-6)表示的结构单元的目标聚合物(7.6g)。得到的聚合物的利用GPC并按照聚苯乙烯换算而测得的重均分子量为2000。
(合成例7)
在氮气下,在500mL四颈瓶中添加3-羟基二苯基胺(5.00g,0.324mol,东京化成工业(株)制)、1,4-苯二甲醇(44.76g,0.324mol,东京化成工业(株)制)、甲磺酸(6.23g,0.065mol,东京化成工业(株)制),进而装入丙二醇单甲基醚(以下,在本说明书中有时也简称为PGME而表示。)(206.11g,关东化学(株)制)并进行搅拌,进行升温直至确认到回流而使其溶解,引发聚合。17小时后,放置冷却至60℃,然后,在甲醇(3200g,关东化学(株)制)纯水(800g)的混合溶剂中进行再沉淀。将得到的沉淀物过滤,用减压干燥机于60℃干燥16小时,得到具有式(1-7)表示的结构单元的目标聚合物(62.9g)。得到的聚合物的利用GPC并按照聚苯乙烯换算而测得的重均分子量为3300。
(合成例8)
在氮气下,在200mL四颈瓶中添加2,2-联苯酚(5.00g,0.027mol,东京化成工业(株)制)、α,α’-二羟基-1,3-二异丙基苯(5.97g,0.031mol东京化成工业(株)制)、对甲苯磺酸一水合物(1.09g,0.006mol,东京化成工业(株)制),进而装入丙二醇单甲基醚乙酸酯(PGMEA)26.88g,关东化学(株)制)并进行搅拌,进行升温直至确认到回流而使其溶解,引发聚合。16小时后,放置冷却至60℃,然后,在水/甲醇=1/1(1000g,关东化学(株)制)中进行再沉淀。将得到的沉淀物过滤,用减压干燥机于60℃干燥16小时,得到具有式(1-8)表示的结构单元的目标聚合物(7.6g)。得到的聚合物的、利用GPC并按照聚苯乙烯换算而测得的重均分子量为3400。
(比较合成例1)
在氮气下,在100mL四颈瓶中添加咔唑(6.69g,0.040mol,东京化成工业(株)制)、9-芴酮(7.28g,0.040mol,东京化成工业(株)制)、对甲苯磺酸一水合物(0.76g,0.0040mol,东京化成工业(株)制),进而装入1,4-二氧杂环己烷(6.69g,关东化学(株)制)并进行搅拌,升温至100℃而使其溶解,引发聚合。24小时后,放置冷却至60℃,然后,添加氯仿(34g,关东化学(株)制)进行稀释,在甲醇(168g,关东化学(株)制)中进行再沉淀。将得到的沉淀物过滤,用减压干燥机于80℃干燥24小时,得到具有下述式(7-1)表示的结构单元的目标聚合物(9.37g)。得到的聚合物的利用GPC并按照聚苯乙烯换算而测得的重均分子量为2800。
(实施例1)
向合成例1中得到的聚合物2.0g中混合作为交联剂的商品名TMOM-BP(本州化学工业(株)制,式(6-23))0.4g、作为催化剂的对甲苯磺酸吡啶鎓0.05g、作为表面活性剂的商品名メガファックR-40LM(DIC(株)制)0.003g,使其溶解于PGMEA(丙二醇单甲基醚乙酸酯)16.71g和PGME(丙二醇单甲基醚)4.18g中而制成溶液。然后,使用孔径为0.10μm的聚乙烯制微滤器进行过滤,制备用于基于多层膜的光刻工艺的抗蚀剂下层膜形成用组合物。
(实施例2)
向合成例2中得到的聚合物2.0g中混合作为交联剂的商品名TMOM-BP(本州化学工业(株)制)0.4g、作为催化剂的苯酚磺酸吡啶鎓0.06g、作为表面活性剂的商品名メガファックR-40LM(DIC(株)制)0.004g,使其溶解于PGMEA14.70g、PGME4.44g和环己酮4.44g中而制成溶液。然后,使用孔径为0.10μm的聚乙烯制微滤器进行过滤,制备用于基于多层膜的光刻工艺的抗蚀剂下层膜形成用组合物。
(实施例3)
向合成例3中得到的聚合物2.0g中混合作为交联剂的商品名TMOM-BP(本州化学工业(株)制)0.4g、作为催化剂的苯酚磺酸吡啶鎓0.06g、作为表面活性剂的商品名メガファックR-40LM(DIC(株)制)0.004g,使其溶解于PGMEA13.31g、PGME4.44g和环己酮4.44g中而制成溶液。然后,使用孔径为0.10μm的聚乙烯制微滤器进行过滤,制备用于基于多层膜的光刻工艺的抗蚀剂下层膜形成用组合物。
(实施例4)
向合成例4中得到的聚合物2.0g中混合作为交联剂的商品名TMOM-BP(本州化学工业(株)制)0.4g、作为催化剂的苯酚磺酸吡啶鎓0.06g、作为表面活性剂的商品名メガファックR-40LM(DIC(株)制)0.004g,使其溶解于PGMEA15.52g和PGME6.65g中而制成溶液。然后,使用孔径为0.10μm的聚乙烯制微滤器进行过滤,制备用于基于多层膜的光刻工艺的抗蚀剂下层膜形成用组合物。
(实施例5)
向合成例5中得到的聚合物2.0g中混合作为交联剂的商品名TMOM-BP(本州化学工业(株)制)0.4g、作为催化剂的苯酚磺酸吡啶鎓0.06g、作为表面活性剂的商品名メガファックR-40LM(DIC(株)制)0.004g,使其溶解于PGMEA15.52g和PGME6.65g中而制成溶液。然后,使用孔径为0.10μm的聚乙烯制微滤器进行过滤,制备用于基于多层膜的光刻工艺的抗蚀剂下层膜形成用组合物。
(实施例6)
向合成例6中得到的聚合物2.0g中混合作为表面活性剂的商品名メガファックR-40LM(DIC(株)制)0.004g,使其溶解于PGMEA12.63g和PGME5.41g中而制成溶液。然后,使用孔径为0.10μm的聚乙烯制微滤器进行过滤,制备用于基于多层膜的光刻工艺的抗蚀剂下层膜形成用组合物。
(实施例7)
向合成例7中得到的聚合物2.0g中混合作为交联剂的商品名TMOM-BP(本州化学工业(株)制)0.3g、作为催化剂的苯酚磺酸吡啶鎓0.03g、作为表面活性剂的商品名メガファックR-40LM(DIC(株)制)0.004g,使其溶解于PGMEA12.60g和PGME8.40g中而制成溶液。然后,使用孔径为0.10μm的聚乙烯制微滤器进行过滤,制备用于基于多层膜的光刻工艺的抗蚀剂下层膜形成用组合物。
(实施例8)
向合成例8中得到的聚合物2.0g中混合作为交联剂的商品名TMOM-BP(本州化学工业(株)制)0.4g、作为催化剂的苯酚磺酸吡啶鎓0.06g、作为表面活性剂的商品名メガファックR-40LM(DIC(株)制)0.004g,使其溶解于PGMEA15.52g和PGME6.65g中而制成溶液。然后,使用孔径为0.10μm的聚乙烯制微滤器进行过滤,制备用于基于多层膜的光刻工艺的抗蚀剂下层膜形成用组合物。
(比较例1)
向比较合成例1中得到的聚合物20g中混合作为交联剂的四甲氧基甲基甘脲3.0g、作为催化剂的对甲苯磺酸吡啶鎓0.02g、作为表面活性剂的商品名メガファックR-40(DIC(株)制)0.006g,使其溶解于PGMEA16.71g和PGME4.18g中而制成溶液。然后,使用孔径为0.10μm的聚乙烯制微滤器进行过滤,制备用于基于多层膜的光刻工艺的抗蚀剂下层膜形成用组合物。
(耐热性的测定)
使用旋转涂布器,将实施例1~实施例8和比较例1中制备的抗蚀剂下层膜形成用组合物分别涂布于硅晶片上。在加热板上,于400℃烘烤90秒,形成抗蚀剂下层膜(膜厚0.2μm)。将这些抗蚀剂下层膜从硅晶片上削掉,得到粉末体。利用TG/DTA(BRUKER公司制TG-DTA2010SR)测定得到的粉末体的400℃时的热失重。将其结果示于表1。
[表1]
表1
(向孔隙基板填埋的填埋性和平坦化性)
为了评价材料的平坦化性和填埋性,利用ArF曝光机和干法蚀刻制成下述这样的晶片。在TEOS晶片上形成孔隙直径75nm、孔隙深度500nm、孔隙与孔隙的间隔为105nm的图案。使用旋转涂布器,在该TEOS晶片上,分别涂布实施例1~实施例8及比较例1中制备的抗蚀剂下层膜形成用组合物。在加热板上,于400℃将它们烘烤90秒,形成抗蚀剂下层膜(膜厚220nm)。接下来,用电子显微镜观察晶片的剖面,测定孔隙密集的区域的TEOS表面上的抗蚀剂下层膜的膜厚。另外,还测定了位于图案区域旁边的平坦的区域的膜厚。基于得到的测定值,利用以下的计算式,将平坦化性数值化。
平坦化性(%)={(平坦区域的膜厚)-(孔隙区域的膜厚)}/(平坦区域的膜厚)×100
将该平坦化性为20%以下的情况评价为良好,将高于20%的情况评价为不良。将测定结果示于表2。
[表2]
表2向孔隙基板填埋的填埋性和平坦化性
可知本发明的用于基于多层膜的光刻工艺的抗蚀剂下层膜形成用组合物具有可在其上层形成基于CVD法的硬掩模的耐热性。另外,对于本发明的抗蚀剂下层膜形成用组合物而言,75nm的微小的孔隙图案的填埋性能良好,与无图案的区域的膜厚差也非常小,因此可知,具有良好的平坦化性能。
产业上的可利用性
本发明的组合物可作为具有下述特征的光刻工艺用抗蚀剂下层膜形成用组合物使用:在高低差基板上的平坦化性能优异,向微细孔隙图案填埋的填埋性能良好,因此,可使得成膜后的晶片表面平坦。
Claims (8)
1.一种抗蚀剂下层膜形成用组合物,其包含聚合物和溶剂,所述聚合物含有下述式(1)表示的单元结构,
式(1)中,R1~R4各自独立地表示氢原子或甲基;X1表示可被烷基、氨基、或羟基取代的包含至少一个亚芳基的二价的有机基团。
2.根据权利要求1所述的抗蚀剂下层膜形成用组合物,其中,式(1)中,X1的定义中的亚芳基为亚苯基、亚联苯基、亚三联苯基、亚芴基、亚萘基、亚蒽基、亚芘基、或亚咔唑基。
3.根据权利要求1所述的抗蚀剂下层膜形成用组合物,其中,式(1)中,X1为式(2)表示的有机基团,
式(2)中,A1表示亚苯基或亚萘基;A2表示亚苯基、亚萘基、或式(3)表示的有机基团;虚线表示连接键,
式(3)中,A3及A4各自独立地表示亚苯基或亚萘基;虚线表示连接键。
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,其中,还包含交联剂。
5.根据权利要求1~4中任一项所述的抗蚀剂下层膜形成用组合物,其中,还包含酸及/或产酸剂。
6.一种抗蚀剂下层膜,其形成于半导体基板上,其是由权利要求1~5中任一项所述的抗蚀剂下层膜形成用组合物的固化物形成的。
7.一种半导体器件的制造方法,其包括以下工序:
在半导体基板上由权利要求1~5中任一项所述的抗蚀剂下层膜形成用组合物形成下层膜的工序;在其上形成抗蚀剂膜的工序;通过照射光或电子束并显影而形成抗蚀剂图案的工序;利用所形成的抗蚀剂图案对该下层膜进行蚀刻的工序;及利用已图案化的下层膜对该半导体基板进行加工的工序。
8.一种半导体器件的制造方法,其包括以下工序:
在半导体基板上由权利要求1~5中任一项所述的抗蚀剂下层膜形成用组合物形成下层膜的工序;在其上形成硬掩模的工序;进一步在其上形成抗蚀剂膜的工序;通过照射光或电子束并显影而形成抗蚀剂图案的工序;利用所形成的抗蚀剂图案对硬掩模进行蚀刻的工序;利用已图案化的硬掩模对该下层膜进行蚀刻的工序;及利用已图案化的下层膜对该半导体基板进行加工的工序。
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