CN1902550B - 形成硬掩模用涂布型氮化膜的组合物 - Google Patents
形成硬掩模用涂布型氮化膜的组合物 Download PDFInfo
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- CN1902550B CN1902550B CN2004800391122A CN200480039112A CN1902550B CN 1902550 B CN1902550 B CN 1902550B CN 2004800391122 A CN2004800391122 A CN 2004800391122A CN 200480039112 A CN200480039112 A CN 200480039112A CN 1902550 B CN1902550 B CN 1902550B
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- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- PQJYOOFQDXGDDS-ZCXUNETKSA-N dinonyl (z)-but-2-enedioate Chemical compound CCCCCCCCCOC(=O)\C=C/C(=O)OCCCCCCCCC PQJYOOFQDXGDDS-ZCXUNETKSA-N 0.000 description 1
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- 238000007922 dissolution test Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- AYEFIAVHMUFQPZ-UHFFFAOYSA-N propane-1,2-diol;prop-2-enoic acid Chemical compound CC(O)CO.OC(=O)C=C AYEFIAVHMUFQPZ-UHFFFAOYSA-N 0.000 description 1
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- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
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- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/06—Coating on selected surface areas, e.g. using masks
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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Abstract
本发明的课题在于提供一种在半导体器件制造的光刻工艺中可作为掩模使用的下层膜,其不与光致抗蚀剂层发生混合、可以利用旋涂法来形成。本发明通过提供下述组合物而解决了上述课题,即,一种形成在半导体器件的制造中使用的下层膜的组合物,其特征在于,含有平均粒径为1~1000nm的金属氮化物粒子和有机溶剂,上述金属氮化物粒子含有选自钛、硅、钽、钨、铈、锗、铪、镓中的至少一种元素。
Description
技术领域
本发明涉及一种在半导体器件的制造中使用的光致抗蚀剂图形的形成方法,其包括在半导体基板和光致抗蚀剂之间形成含有金属氮化物粒子的下层膜的工序。
另外,本发明涉及一种形成下层膜的组合物,其用于形成在半导体器件的制造中使用的光致抗蚀剂图形的形成中所使用的含有金属氮化物粒子的下层膜。另外,涉及使用了该形成下层膜的组合物的含有金属氮化物粒子的下层膜的形成方法、以及由该形成下层膜的组合物形成的含有金属氮化物粒子的下层膜。
背景技术
一直以来,在半导体器件的制造中,人们都是利用使用了光致抗蚀剂的光刻进行微细加工的。上述微细加工为,通过在硅晶片基板等的半导体基板上形成光致抗蚀剂膜,在该光致抗蚀剂膜上透过描绘有半导体器件的图形的掩模图形、照射紫外线等的活性光线,进行显影,以所获得的光致抗蚀剂图形作为保护膜来将基板进行蚀刻处理,由此在基板表面形成对应于上述图形的微细凹凸的加工法。
另外,在这样的加工法中,有时在半导体基板与光致抗蚀剂之间,形成防反射膜、平坦化膜等由有机物质构成的下层膜、有机下层膜。在这种情况下,以光致抗蚀剂图形为保护膜,首先,通过蚀刻来除去有机下层膜,然后,进行半导体基板的加工。有机下层膜的蚀刻一般通过干蚀刻来进行,但是,此时存在下述问题:不仅是有机下层膜,而且光致抗蚀剂也被蚀刻,其膜厚减少。因此,作为有机下层膜,倾向于使用由干蚀刻产生的除去速度很大的物质。但是,由于光致抗蚀剂也由与有机下层膜同样的有机物质构成,因此,很难抑制光致抗蚀剂的膜厚的减少。
近年,随着加工尺寸的微细化的进展,人们逐渐在研究薄膜光致抗蚀剂的使用。这是因为考虑到,在不改变膜厚而减小光致抗蚀剂图形的尺寸的情况下,光致抗蚀剂图形的纵横比(高度/宽度)变大,光致抗蚀剂图形发生破坏等。另外,光致抗蚀剂,其膜厚越薄,解像性越大。因此,优选以薄膜的形式使用光致抗蚀剂。但是,在使用光致抗蚀剂和有机下层膜的情况下,如上所述,在除去有机下层膜时,存在光致抗蚀剂膜厚减少的问题。因此,在使光致抗蚀剂形成薄膜的情况下,存在不能确保作为半导体基板加工用的保护膜(由光致抗蚀剂和有机下层膜构成)的充分膜厚的问题。
另一方面,作为半导体基板与光致抗蚀剂之间的下层膜,人们使用作为硬掩模已知的含有无机物质构成的膜。在这种情况下,光致抗蚀剂(有机物质)与硬掩模(无机物质),它们的构成成分存在很大差异,因此它们利用干蚀刻进行除去的速度,很大地依赖于干蚀刻使用的气体种类。另外,通过适当选择气体种类,可以在不伴随着光致抗蚀剂膜的厚度大幅度减少的情况下、利用干蚀刻来除去硬掩模(下层膜)。因此可以认为,在使用光致抗蚀剂和硬掩模的情况下,即使光致抗蚀剂是薄膜,也可以确保作为半导体基板加工用保护膜(由光致抗蚀剂和硬掩模构成)的充分的膜厚。
一直以来,硬掩模使用CVD装置、真空蒸镀装置和溅射装置等,利用蒸镀法来形成。与此相对,光致抗蚀剂、有机下层膜是利用旋涂装置等向半导体基板上的涂布和其后的烘烤(以下称作旋涂法)来形成的。旋涂法与蒸镀法相比,装置等很简单。因此,需求不利用蒸镀法,而是利用旋涂法可形成的硬掩模。
另外,已知含有无机物质的某种下层膜(例如,参考专利文献1、专利文献2、专利文献3)。
专利文献1:特开2001-53068号公报
专利文献2:特开2001-242630号公报
专利文献3:特开2003-177206号公报
发明内容
本发明是鉴于上述现状而完成的发明。本发明的目的在于提供用于利用旋涂法来形成硬掩模的形成下层膜的组合物。另外,提供可以利用旋涂法来形成的、与上层涂布、形成的光致抗蚀剂不发生混合的下层膜。另外,提供可以作为下述膜来使用的下层膜,所述膜为:利用旋涂法形成的、减少曝光照射光从基板向形成于半导体基板上的光致抗蚀剂的反射的下层防反射膜;用于使具有凹凸的半导体基板平坦化的平坦化膜;防止加热烘烤等时由半导体基板产生的物质所导致的光致抗蚀剂层的污染的膜等。另外,提供使用了形成下层膜的组合物的光刻用下层膜的形成方法、和光致抗蚀剂图形的形成方法。
本发明,作为第1观点,是一种形成在半导体器件的制造中使用的下层膜的组合物,含有平均粒径为1~1000nm的金属氮化物粒子和有机溶剂;
作为第2观点,是一种形成在半导体器件的制造中使用的下层膜的组合物,含有平均粒径为1~1000nm的金属氮化物粒子、有机材料和有机溶剂;
作为第3观点,是如第1观点或第2观点所述的形成下层膜的组合物,上述金属氮化物粒子含有选自钛、硅、钽、钨、铈、锗、铪、镓中的至少一种元素;
作为第4观点,是如第1观点或第2观点所述的形成下层膜的组合物,上述金属氮化物粒子为选自氮化钛、氮氧化钛、氮化硅、氮氧化硅、氮化钽、氮氧化钽、氮化钨、氮氧化钨、氮化铈、氮氧化铈、氮化锗、氮氧化锗、氮化铪、氮氧化铪、氮化铯、氮氧化铯、氮化镓、氮氧化镓中的至少一种金属氮化物的粒子;
作为第5观点,是如第2观点所述的形成下层膜的组合物,上述有机材料为选自聚合物、交联性化合物和吸光性化合物中的至少一种成分;
作为第6观点,是一种形成在半导体器件的制造中使用的下层膜方法,是通过将第1观点~第5观点的任一项所述的形成下层膜的组合物涂布在半导体基板上、进行烘烤来进行的;
作为第7观点,是如第6观点所述的形成下层膜的方法,上述烘烤是在烘烤温度为80℃~300℃,烘烤时间为0.5~10分钟的条件下进行的;
作为第8观点,是一种在半导体器件的制造中使用的下层膜,是通过将第1观点~第5观点的任一项所述的形成下层膜的组合物涂布在半导体基板上、在烘烤温度为80℃~300℃,烘烤时间为0.5~10分钟的条件下进行烘烤来形成的;
作为第9观点,一种在半导体器件的制造中使用的光致抗蚀剂图形的形成方法,包括以下工序:将第1观点~第5观点的任一项所述的形成下层膜的组合物涂布在半导体基板上、进行烘烤来形成下层膜的工序,在该下层膜上形成光致抗蚀剂层的工序,对由下层膜和光致抗蚀剂层被覆的半导体基板进行曝光的工序,在曝光后进行显影的工序;
作为第10观点,是如第9观点所述的光致抗蚀剂图形的形成方法,上述曝光是利用248nm、193nm或157nm的波长的光进行的。
本发明是用于形成含有金属氮化物粒子的下层膜的形成下层膜的组合物。通过本发明,可以提供一种下层膜,其不与光致抗蚀剂混合,具有很慢的干蚀刻速度。
利用本发明获得的含有金属氮化物粒子的下层膜,可以使干蚀刻工序时的半导体基底基板的加工变得容易。另外,通过使用本发明获得的含有金属氮化物粒子的下层膜,可以减少通过干蚀刻来除去下层膜时的光致抗蚀剂的膜厚的减少量。
具体实施方式
本发明的形成下层膜的组合物含有金属氮化物粒子和有机溶剂。另外,本发明的形成下层膜的组合物含有金属氮化物粒子、有机材料和有机溶剂。另外,还可以含有碳粒子、氧化硅粒子和氧化钛等的无机物粒子。
本发明的形成下层膜的组合物中的固体成分的比例,例如为0.1~70%质量,或者为0.5~50%质量,或者为1~40质量%,或者为10~30质量%。这里所谓固体成分是指,从形成下层膜的组合物的全体成分中除去有机溶剂成分后的成分。
在本发明的形成下层膜的组合物中使用金属氮化物粒子和有机材料的情况下,作为其含量,在固体成分中,以金属氮化物粒子计,例如为40~99.9质量%,例如为50~99.5质量%,或者为60~99质量%,或者为70~90质量%。在固体成分中,以有机材料计,例如为0.1~60质量%,例如为0.5~50质量%,或者为1~40质量%,或者为10~30质量%。
本发明的形成下层膜的组合物,在含有碳粒子、氧化硅粒子和氧化钛等的无机物的粒子的情况下,作为其含量,在固体成分中,为30质量%或其以下,或者为20质量%或其以下。
作为本发明的形成下层膜的组合物中含有的金属氮化物粒子,可以列举出例如,氮化钛、氮氧化钛、氮化硅、氮氧化硅、氮化钽、氮氧化钽、氮化钨、氮氧化钨、氮化铈、氮氧化铈、氮化锗、氮氧化锗、氮化铪、氮氧化铪、氮化铯、氮氧化铯、氮化镓、氮氧化镓等的金属氮化物的粒子。优选氮化钛、氮氧化钛、氮化硅、氮氧化硅的粒子。
作为所使用的金属氮化物粒子的粒径,只要可以在半导体基板上形成下层膜,就没有特别的限定,但是,以平均粒径计,为1000nm或其以下,优选为1nm~1000nm,特别优选为1nm~100nm。在这种情况下,如果平均粒径大于1000nm,则在利用蚀刻来除去下层膜时需要长时间。另外,下层膜的平滑性受损。进而,粒子向溶剂的分散性降低,粒子沉降,形成下层膜的组合物的保存稳定性变得不充分。平均粒径,是将金属氮化物粒子涂布在半导体基板上,进行干燥,然后利用扫描型电子显微镜(SEM)测定20个粒子的尺寸(粒径),以平均值的形式计算出的。另外,在粒子为椭圆形等的情况下,以其长径和短径的平均值作为该粒子的尺寸。
在本发明的形成下层膜的组合物中,这些金属氮化物粒子有时只使用一种,有时将2种或其以上组合使用。
在本发明的形成下层膜的组合物中,作为有机材料,没有特别的限定。可采用迄今为止为了形成设置在光致抗蚀剂的下层的膜而一直使用的有机材料。即,可使用防反射膜用的有机材料、平坦化用的有机材料和阻挡层用的有机材料等。
作为有机材料,可使用例如聚合物、交联性化合物、吸光性化合物、表面活性剂、高分子分散剂、交联催化剂、粘结辅助剂和流变调节剂等,它们可以适当组合使用。另外,对于它们的含量,可以适当选择使用。
作为有机材料使用的聚合物,对其种类没有特别限定。可以使用聚酯、聚苯乙烯、聚酰亚胺、丙烯酸聚合物、甲基丙烯酸聚合物、聚乙烯醚、苯酚线型酚醛清漆、萘酚线性酚醛清漆、聚醚、聚酰胺、聚碳酸酯等聚合物。优选使用具有作为吸光部位发挥功能的苯环、萘环、蒽环、三嗪环、喹啉环和喹喔啉环等芳香环结构的聚合物。
作为这样的聚合物,可以列举出例如,含有丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸苯酯、丙烯酸萘酯、甲基丙烯酸蒽酯、甲基丙烯酸蒽基甲酯、苯乙烯、羟基苯乙烯、苄基乙烯基醚、N-苯基马来酰亚胺等加成聚合性单体作为其结构单元的加成聚合类聚合物;苯酚线型酚醛清漆、萘酚线性酚醛清漆等缩聚类聚合物。另外,可以列举出美国专利第6323310号说明书所述的由三嗪化合物(商品名Cymel303、Cymel1123)制造的聚合物。
进而,还可以列举出具有下述(a)~(e)结构单元中的至少一种的聚合物,这样的聚合物可参照例如美国专利第5919598号、第5919599号和第6156479号来进行制造。
另外,作为聚合物,可以使用不具有芳香环结构的聚合物。作为这样的聚合物,可以列举出例如,仅含有丙烯酸烷基酯、甲基丙烯酸烷基酯、乙烯基醚、烷基乙烯基醚、丙烯腈、马来酰亚胺、N-烷基马来酰亚胺、马来酸酐等不具有芳香环结构的加成聚合性单体作为其结构单元的加成聚合类聚合物。
在作为聚合物使用加成聚合类聚合物的情况下,该聚合物可以是均聚物,也可以是共聚物。在加成聚合类聚合物的制造中使用加成聚合性单体。作为这样的加成聚合性单体,可以列举出丙烯酸、甲基丙烯酸、丙烯酸酯化合物、甲基丙烯酸酯化合物、丙烯酰胺化合物、甲基丙烯酰胺化合物、乙烯基化合物、苯乙烯化合物、马来酰亚胺化合物、马来酸酐和丙烯腈等。
作为丙烯酸酯化合物,可以列举出丙烯酸甲酯、丙烯酸乙酯、丙烯酸正己酯、丙烯酸异丙酯、丙烯酸环己酯、丙烯酸苄酯、丙烯酸苯酯、丙烯酸蒽基甲酯、丙烯酸-2-羟基乙酯、丙烯酸-3-氯-2-羟基丙酯、丙烯酸-2-羟基丙酯、丙烯酸-2,2,2-三氟乙酯、丙烯酸-2,2,2-三氯乙酯、丙烯酸-2-溴乙酯、丙烯酸-4-羟基丁酯、丙烯酸-2-甲氧基乙酯、丙烯酸四氢糠酯、丙烯酸-2-甲基-2-金刚烷酯、5-丙烯酰氧基-6-羟基降冰片烯-2-羧酸-6-内酯、3-丙烯酰氧基丙基三乙氧基硅烷和丙烯酸缩水甘油酯等。
作为甲基丙烯酸酯化合物,可以列举出,甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正己酯、甲基丙烯酸异丙酯、甲基丙烯酸环己酯、甲基丙烯酸苄酯、甲基丙烯酸苯酯、甲基丙烯酸蒽基甲酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯、甲基丙烯酸-2,2,2-三氟乙酯、甲基丙烯酸-2,2,2-三氯乙酯、甲基丙烯酸-2-溴乙酯、甲基丙烯酸-4-羟基丁酯、甲基丙烯酸-2-甲氧基乙酯、甲基丙烯酸四氢糠酯、甲基丙烯酸-2-甲基-2-金刚烷酯、5-甲基丙烯酰氧基-6-羟基降冰片烯-2-羧酸-6-内酯、3-甲基丙烯酰氧基丙基三乙氧基硅烷、甲基丙烯酸缩水甘油酯、甲基丙烯酸-2-苯基乙酯、甲基丙烯酸羟基苯酯、甲基丙烯酸溴代苯酯等。
作为丙烯酰胺化合物,可以列举出丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-苄基丙烯酰胺、N-苯基丙烯酰胺、N,N-二甲基丙烯酰胺、N-蒽基丙烯酰胺等。
作为甲基丙烯酰胺化合物,可以列举出甲基丙烯酰胺、N-甲基-甲基丙烯酰胺、N-乙基-甲基丙烯酰胺、N-苄基-甲基丙烯酰胺、N-苯基-甲基丙烯酰胺、N,N-二甲基-甲基丙烯酰胺和N-蒽基-甲基丙烯酰胺等。
作为乙烯基化合物,可以列举出乙烯醇、2-羟基乙基乙烯基醚、甲基乙烯基醚、乙基乙烯基醚、苄基乙烯基醚、乙烯基乙酸、乙烯基三甲氧基硅烷、2-氯乙基乙烯基醚、2-甲氧基乙基乙烯基醚、乙烯基萘和乙烯基蒽等。
作为苯乙烯化合物,可以列举出苯乙烯、羟基苯乙烯、氯代苯乙烯、溴代苯乙烯、甲氧基苯乙烯、氰基苯乙烯和乙酰基苯乙烯等。
作为马来酰亚胺化合物,可以列举出马来酰亚胺、N-甲基马来酰亚胺、N-苯基马来酰亚胺、N-环己基马来酰亚胺、N-苄基马来酰亚胺、N-羟基乙基马来酰亚胺等。
在作为聚合物、使用缩聚类聚合物的情况下,作为这样的聚合物,可以列举出例如,二元醇类化合物与二羧酸类化合物的缩聚聚合物。作为二元醇类化合物,可以列举出二甘醇、1,6-己二醇、丁二醇等。作为二羧酸类化合物,可以列举出琥珀酸、己二酸、对苯二甲酸、马来酸酐等。另外,还可以列举出例如,聚均苯四酰亚胺、聚(对苯二甲酰对苯二胺)、聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯等聚酯、聚酰胺、聚酰亚胺。
作为本发明的形成下层膜的组合物的有机材料使用的聚合物的分子量,以重均分子量计,例如为1000~1000000,或为3000~300000,或例如为5000~200000,或为10000~100000。
作为本发明的形成下层膜的组合物的有机材料使用的交联性化合物,对其种类没有特别限制。作为交联性化合物,可以列举出三聚氰胺化合物、取代脲化合物、含有环氧基的聚合物类交联性化合物等。作为交联性化合物,优选列举出具有两个或其以上的被羟基甲基或烷氧基甲基取代的氮原子的含氮化合物。是具有两个或其以上被羟基甲基、甲氧基甲基、乙氧基甲基、丁氧基甲基和己基氧基甲基等基团取代的氮原子的含氮化合物。具体来说,可以列举出,六甲氧基甲基三聚氰胺、四甲氧基甲基苯胍胺、1,3,4,6-四(丁氧基甲基)甘脲、1,3,4,6-四(羟基甲基)甘脲、1,3-双(羟基甲基)脲、1,1,3,3-四(丁氧基甲基)脲、1,1,3,3-四(甲氧基甲基)脲、1,3-双(羟基甲基)-4,5-二羟基-2-咪唑啉酮和1,3-双(甲氧基甲基)-4,5-二甲氧基-2-咪唑啉酮等的含氮化合物。作为交联性化合物,还可以列举出,三井サイテック(株)制甲氧基甲基型三聚氰胺化合物(商品名サイメル300、サイメル301、サイメル303、サイメル350)、丁氧基甲基型三聚氰胺化合物(商品名マイコ—ト506、マイコ—ト508)、甘脲化合物(商品名サイメル1170、パウダ—リンク1174)等化合物、甲基化脲树脂(商品名UFR65)、丁基化脲树脂(商品名UFR300、U-VAN10S60、U-VAN10R、U-VAN11HV)、大日本インキ化学工业(株)制脲/甲醛类树脂(高缩合型、商品名ベッカミンJ-300S、ベッカミンP-955、ベッカミンN)等市售的化合物。
作为交联性化合物,还可以使用下述聚合物,即,使用N-羟基甲基-丙烯酰胺、N-甲氧基甲基-甲基丙烯酰胺、N-乙氧基甲基-丙烯酰胺、N-丁氧基甲基-甲基丙烯酰胺等的被羟基甲基或烷氧基甲基取代的丙烯酰胺化合物或甲基丙烯酰胺化合物制造出的聚合物。作为这种聚合物,可以列举出例如,聚(N-丁氧基甲基-丙烯酰胺)、N-丁氧基甲基-丙烯酰胺与苯乙烯的共聚物、N-羟基甲基-甲基丙烯酰胺与甲基丙烯酸甲酯的共聚物、N-乙氧基甲基-甲基丙烯酰胺与甲基丙烯酸苄酯的共聚物、和N-丁氧基甲基-丙烯酰胺与甲基丙烯酸苄酯与甲基丙烯酸-2-羟基丙基酯的共聚物等。
作为本发明的形成下层膜的组合物的有机材料使用的吸光性化合物,对其种类并无特别限制。
通过选择吸光性化合物的种类、添加量,可调整由本发明的形成下层膜的组合物形成的下层膜的折射率、衰减系数等特性。作为这样的吸光性化合物,优选使用对在下层膜上设置的光致抗蚀剂层中的感光成分的感光特性波长区域的光具有高吸收能力的化合物。吸光性化合物可仅使用1种,也可组合使用2种或其以上。
作为吸光性化合物,可以使用例如苯基化合物、二苯甲酮化合物、苯并三唑化合物、偶氮化合物、萘化合物、蒽化合物、蒽醌化合物、三嗪化合物、三嗪三酮化合物和喹啉化合物等。可以使用苯基化合物、萘化合物、蒽化合物、三嗪化合物和三嗪三酮化合物等。
作为吸光性化合物,优选使用具有至少1个羟基、氨基或羧基的苯基化合物;具有至少1个羟基、氨基或羧基的萘化合物;具有至少1个羟基、氨基或羧基的蒽化合物。
作为具有至少1个羟基、氨基或羧基的苯基化合物,可以列举出苯酚、溴代苯酚、4,4’-磺酰基二苯酚、叔丁基苯酚、双酚、苯甲酸、水杨酸、羟基间苯二甲酸、苯基乙酸、苯胺、苄胺、苄醇、肉桂醇、苯基丙氨酸、苯氧基丙醇等。
作为具有至少1个羟基、氨基或羧基的萘化合物,可以列举出1-萘甲酸、2-萘甲酸、1-萘酚、2-萘酚、1-氨基萘、萘基乙酸、1-羟基-2-萘甲酸、3-羟基-2-萘甲酸、3,7-二羟基-2-萘甲酸、6-溴-2-羟基萘、2,6-萘二甲酸等。
作为具有至少1个羟基、氨基或羧基的蒽化合物,可以列举出9-蒽甲酸、9-羟基甲基蒽、1-氨基蒽等。
另外,作为吸光性化合物,也优选使用三嗪三酮化合物。作为三嗪三酮化合物,可以列举出式(1)所示的化合物:
其中,式中X表示(f)~(l)的基团。
作为本发明的形成下层膜的组合物的有机材料使用的交联催化剂,可以列举出,酸化合物或酸发生剂。
作为酸化合物,可以列举出对甲苯磺酸、三氟甲磺酸、对甲苯磺酸吡啶鎓、水杨酸、樟脑磺酸、磺基水杨酸、柠檬酸、苯甲酸、羟基苯甲酸等酸化合物。另外,作为酸化合物,可以使用芳香族磺酸化合物。作为芳香族磺酸化合物的具体例,可以列举出,对甲苯磺酸、对甲苯磺酸吡啶鎓、磺基水杨酸、4-氯苯磺酸、4-羟基苯磺酸、苯二磺酸、1-萘磺酸和1-萘磺酸吡啶鎓等。作为酸发生剂,可以列举出2,4,4,6-四溴环己二烯酮、2-硝基苄基甲苯磺酸酯、双(4-叔丁基苯基)三氟甲磺酸碘鎓、三苯基三氟甲磺酸锍、苯基-双(三氯甲基)-s-三嗪、苯偶姻甲苯磺酸酯和N-羟基琥珀酰亚胺三氟甲烷磺酸酯等。酸化合物和酸发生剂可以单独使用,也可以将两种或其以上组合使用。
作为本发明的形成下层膜的组合物的有机材料使用的高分子分散剂,可以使用例如聚氧乙烯烷基醚类、聚氧乙烯烷基苯基醚类、聚乙二醇二酯类、山梨糖醇的环氧乙烷加成物类、山梨糖醇的环氧丙烷加成物类、山梨糖醇的环氧乙烷·环氧丙烷混合加成物类、多亚乙基多胺的环氧乙烷加成物类、多亚乙基多胺的环氧丙烷加成物类、多亚乙基多胺的环氧乙烷·环氧丙烷混合加成物类、壬基苯基醚福尔马林缩合物的环氧乙烷加成物类、聚(甲基)丙烯酸盐类、含有羧基的不饱和单体与其他乙烯基化合物的共聚物盐类、聚(甲基)丙烯酸的部分烷基酯或其盐类、聚苯乙烯磺酸盐类、萘磺酸盐的福尔马林缩合物类、多亚烷基多胺类、失水山梨糖醇脂肪酸酯类、脂肪酸改性聚酯类、聚酰胺、叔胺改性聚氨酯类和叔胺改性聚酯类等。它们可以单独使用,也可以将两种或其以上组合使用。
作为本发明的形成下层膜的组合物的有机材料使用的表面活性剂,可以列举出例如,聚氧乙烯月桂基醚、聚氧乙烯十八烷基醚、聚氧乙烯油基醚等的聚氧乙烯烷基醚类;聚氧乙烯辛基苯酚醚、聚氧乙烯壬基苯酚醚等的聚氧乙烯烷基芳基醚类,聚氧乙烯·聚氧丙烯嵌段共聚物类;失水山梨糖醇单月桂酸酯、失水山梨糖醇单棕榈酸酯、失水山梨糖醇单硬脂酸酯、失水山梨糖醇三油酸酯、失水山梨糖醇三硬脂酸酯等的失水山梨糖醇脂肪酸酯类;聚氧乙烯失水山梨糖醇单月桂酸酯、聚氧乙烯失水山梨糖醇单棕榈酸酯、聚氧乙烯失水山梨糖醇单硬脂酸酯、聚氧乙烯失水山梨糖醇三硬脂酸酯等的聚氧乙烯失水山梨糖醇脂肪酸酯类等的非离子类表面活性剂;商品名工フトップEF301、EF303、EF352((株)ト—ケムプロダクツ制)、商品名マガファックF171、F173、R-08、R-30(大日本インキ(株)制)、フロラ—ドFC430、FC431(住友スリ—エム(株)制)、商品名アサヒガ—ドAG710、サ—フロンS-382、SC-101、SC-102、SC-103、SC-104、SC-105、SC-106(旭硝子(株)制)等的氟类表面活性剂;有机硅氧烷聚合物KP341(信越化学工业(株)制)等。这些表面活性剂的添加量,在形成下层膜的组合物的固体成分中,通常为小于等于0.5%质量,优选为小于等于0.2质量%。这些表面活性剂可以单独添加,也可以将2种或其以上组合添加。
作为本发明的形成下层膜的组合物的有机材料使用的粘结辅助剂,可以列举出例如,三甲基氯硅烷、二甲基乙烯基氯硅烷、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、二甲基乙烯基乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、二苯基二甲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的硅氮烷类;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、γ-甲基丙烯酰氧基丙基三甲氧基硅烷等的硅烷类,苯并三唑、苯并咪唑、吲唑、咪唑、2-巯基苯并咪唑、2-巯基苯并噁唑、尿唑、硫尿嘧啶、硫尿嘧啶等的杂环化合物;1,1-二甲基脲、1,3-二甲基脲等的脲化合物。
作为本发明的形成下层膜的组合物的有机材料使用的流变调节剂,可以列举出例如,苯二甲酸二甲酯、苯二甲酸二乙酯、苯二甲酸二异丁酯、苯二甲酸丁酯异癸酯等的苯二甲酸衍生物;己二酸二正丁酯、己二酸二异辛酯、己二酸辛酯癸酯等的己二酸衍生物;马来酸二正丁酯、马来酸二乙酯、马来酸二壬酯等的马来酸衍生物;油酸甲酯、油酸丁酯、油酸四氢糠酯等的油酸衍生物;硬脂酸正丁酯、硬脂酸甘油酯等的硬脂酸衍生物。
作为本发明的形成下层膜的组合物的有机材料,优选组合使用聚合物和交联性化合物。在这种情况下,聚合物在有机材料中的比例为20~90质量%,或者为30~60质量%,交联性化合物的比例为10~80质量%,或者为40~70质量%。
另外,作为本发明的形成下层膜的组合物的有机材料,优选组合使用聚合物、交联性聚合物和交联催化剂。在这种情况下,聚合物在有机材料中的比例为20~90质量%,或者为30~60质量%,交联性化合物的比例为5~75质量%,或者为30~65质量%,交联性催化剂的比例为0.1~5质量%,或者为0.5~3质量%。
作为本发明的形成下层膜的组合物中的有机溶剂,没有特别的限制,可以使用各种有机溶剂。可以使用例如,乙二醇单甲醚、乙二醇单乙醚、甲基溶纤剂乙酸酯、乙基溶纤剂乙酸酯、二甘醇单甲醚、二甘醇单乙醚、丙二醇、丙二醇单甲醚、丙二醇单甲醚乙酸酯、丙二醇丙基醚、丙二醇丙基醚乙酸酯、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-二甲基甲酰胺、N-二甲基乙酰胺、二甲基亚砜和N-甲基吡咯烷酮等。这些有机溶剂可以单独使用或将2种或其以上组合使用。
下面,对本发明的形成下层膜的组合物的使用进行说明。
在半导体器件的制造中使用的基板(例如,硅/二氧化硅被覆基板、氮化硅基板、玻璃基板、硅晶片基板、ITO基板、聚酰亚胺基板、低介电常数材料(low-k材料)被覆基板等)上,利用旋涂装置、涂层装置等的适当的涂布方法来涂布本发明的形成下层膜的组合物,然后,通过烘烤来形成下层膜。作为烘烤的条件,可以从烘烤温度为80℃~300℃或者150℃~250℃,烘烤时间为0.5~10分钟或1~5分钟中适当选择。作为下层膜的膜厚,例如为1~1000nm、或者10~500nm、或者50~100nm。
然后,在该下层膜上形成光致抗蚀剂层。作为光致抗蚀剂层的膜厚,为50~10000nm。在本发明中,作为涂布、形成在下层膜的上层的光致抗蚀剂,没有特别的限定,可以使用常用的负型光致抗蚀剂、正型光致抗蚀剂中的任一种。例如,含有线型酚醛清漆树脂和1,2-萘醌二叠氮基磺酸酯的正型光致抗蚀剂、含有具有通过酸分解来提高碱溶解速度的基团的粘合剂和光酸发生剂的化学放大型抗蚀剂、含有通过酸分解来提高光致抗蚀剂的碱溶解速度的低分子化合物和碱可溶性粘合剂和光酸发生剂的化学放大型光致抗蚀剂、含有具有通过酸分解来提高碱溶解速度的基团的粘合剂和通过酸分解来提高光致抗蚀剂的碱溶解速度的低分子化合物和光酸发生剂的化学放大型光致抗蚀剂等,可以列举出例如,シプレ—社制商品名APEX-E、住友化学工业(株)制商品名PAR710、信越化学工业(株)制商品名SEPR430等。
然后,对由含有金属氮化物粒子的下层膜和光致抗蚀剂层被覆的该基板,通过预先设置的掩模,用i线、KrF准分子激光器、ArF准分子激光器和F2准分子激光器等光进行曝光。在曝光后,根据需要进行曝光后加热(post exposure bake),然后,通过使用碱性水溶液等的显影液进行显影,依据设定的图形,将光致抗蚀剂进行部分的除去。
作为光致抗蚀剂的显影液,可以列举出例如,氢氧化钠、氢氧化钾等的碱金属氢氧化物的水溶液;氢氧化四甲基铵、氢氧化四乙基铵、胆碱等的氢氧化季铵盐的水溶液;乙醇胺、丙醇胺、乙二胺等的胺水溶液等的碱性水溶液。作为显影液,可以使用常用的2.38质量%的氢氧化四甲基铵水溶液。进而,也可以在这些显影液中添加表面活性剂等。作为显影的条件,温度可以从5~50℃、时间可以从0.1~5分钟中适当选择。
然后,将除去了光致抗蚀剂的部分的下层膜利用干蚀刻进行除去,露出半导体基板。干蚀刻优选使用氯类气体。在利用氯类气体进行干蚀刻中,很难除去光致抗蚀剂(有机物质),但是本发明的下层膜(无机物质)被快速除去。因此,可以以薄膜的形式使用光致抗蚀剂。
干蚀刻,有时与氯类气体一起使用四氟甲烷、全氟环丁烷(C4F8)、全氟丙烷(C3F8)、三氟甲烷、一氧化碳、氩、氢、氮、氨、氧、氮、六氟化硫、二氟甲烷、三氟化氮和三氟化氯等气体来进行。
然后,将含有已构图化的光致抗蚀剂和下层膜的膜作为保护膜,进行半导体基板的加工。半导体基板的加工优选利用四氟甲烷等的氟类气体的干蚀刻来进行。本发明的下层膜是硬掩模,这是因为其不易被氟类气体的干蚀刻所除去。
另外,有时在涂布、形成光致抗蚀剂之前,在本发明的下层膜的上层,涂布、形成防反射膜层。作为这里使用的防反射膜组合物,没有特别限制,可以从迄今为止在光刻工艺中惯用的防反射膜组合物中任意选择使用。另外,可以利用惯用的方法,例如利用旋涂、涂层进行涂布以及进行烘烤来形成防反射膜。作为防反射膜组合物,可以列举出例如,以吸光性化合物、树脂和溶剂为主成分的防反射膜组合物,以具有通过化学键连接的吸光性基团的树脂、交联剂和溶剂为主成分的防反射膜组合物,以吸光性化合物、交联剂和溶剂为主成分的防反射膜组合物,以具有吸光性的高分子交联剂和溶剂为主成分的防反射膜组合物等。这些防反射膜组合物根据需要还可以含有酸成分、酸发生剂成分、流变调节剂等。作为吸光性化合物,只要是对设置在防反射膜的上面的光致抗蚀剂中的感光成分的感光特性波长区域中的光具有高的吸收能的化合物,就可以使用,可以列举出例如,二苯甲酮化合物、苯并三唑化合物、偶氮化合物、萘化合物、蒽化合物、蒽醌化合物、三嗪化合物等。作为树脂,可以列举出聚酯、聚酰亚胺、聚苯乙烯、线型酚醛清漆树脂、聚缩醛树脂、丙烯酸树脂等。作为具有通过化学键连接的吸光性基团的树脂,可以列举出具有所谓蒽环、萘环、苯环、喹啉环、喹喔啉环、噻唑环的吸光性芳香环结构的树脂。
由本发明的形成下层膜的组合物形成的含有金属氮化物粒子的下层膜,另外,随着在光刻工艺中使用的光的波长的不同,有时对该光有吸收,在这样的情况下,可以作为具有防止来自基板的反射光的效果的层而起作用。进而,本发明的下层膜还可作为下述层使用:用于防止基板与光致抗蚀剂之间的相互作用的层、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影响的层、防止在加热烘烤时由基板生成的物质向上层光致抗蚀剂的扩散的层。
下面,通过实施例对本发明进行更具体的说明,但本发明并不限定于此。
实施例
合成例1
在27.91g丙二醇单甲醚中溶解20.93g甲基丙烯酸-2-羟基丙酯和6.98g甲基丙烯酸苄酯,在反应液中通氮气30分钟,然后升温至70℃。将反应溶液保持在70℃,同时添加0.3g偶氮双异丁腈,在氮气气氛下,在70℃搅拌24小时,由此得到甲基丙烯酸-2-羟基丙酯与甲基丙烯酸苄酯的共聚物溶液。对得到的聚合物进行GPC分析,结果重均分子量为15000(标准聚苯乙烯校正)。
合成例2
在30g乳酸乙酯中溶解30g丙烯酸-2-羟基乙酯,在反应液中通氮气30分钟,升温至70℃。将反应溶液保持在70℃,同时添加0.3g偶氮双异丁腈,在氮气气氛下,在70℃搅拌24小时,由此得到聚(2-羟基乙基)丙烯酸酯的溶液。对得到的聚合物进行GPC分析,结果重均分子量为9800(标准聚苯乙烯校正)。
实施例1
向7g丙二醇单甲基醚乙酸酯中,分散2.7g氮氧化钛粒子(平均粒径100nm、(株)アルバック·コ—ポレ—トセンタ—制),加入0.3g聚氧乙烯失水山梨糖醇单月桂酯。然后,使用孔径5μm的聚乙烯制微孔过滤器进行过滤,调制形成下层膜的组合物的溶液。
实施例2
向7.5g含有以30质量%分散的氮氧化钛粒子(平均粒径100nm、(株)アルバック·コ—ポレ—トセンタ—制)的丙二醇单甲基醚乙酸酯的溶液中,加入5g含有0.75g合成例1中获得的聚合物的溶液、1.15g六甲氧基甲基三聚氰胺、0.012g对甲苯磺酸吡啶鎓、0.77g丙二醇单甲醚和8.66g二甲基亚砜,制成30质量%溶液。然后,使用孔径0.2μm的聚乙烯制微孔过滤器进行过滤,配制出形成下层膜的组合物的溶液。
比较例1
在10g含有5g合成例1得到的聚合物的溶液中,加入1.15g六甲氧基甲基三聚氰胺、0.012g对甲苯磺酸吡啶鎓、0.77g丙二醇单甲醚和8.66g二甲基亚砜,制成30质量%溶液。然后使用孔径0.05μm的聚乙烯制微孔过滤器进行过滤,配制出不含有金属氮化物粒子的形成下层膜的组合物溶液。
比较例2
在10g含有5g合成例2得到的聚合物的溶液中,加入1.15g六甲氧基甲基三聚氰胺、0.012g对甲苯磺酸吡啶鎓、0.77g丙二醇单甲醚和8.66g二甲基亚砜,制成30质量%溶液。然后使用孔径0.05μm的聚乙烯制微孔过滤器进行过滤,配制出不含有金属氮化物粒子的形成下层膜的组合物溶液。
向光致抗蚀剂的溶剂的溶出试验
通过旋涂,将实施例1和2得到的形成下层膜的组合物的溶液分别涂布在硅晶片基板上。在电热板上在205℃烘烤1分钟,形成下层膜(膜厚460nm)。将这些下层膜浸渍在光致抗蚀剂所使用的溶剂中,例如乳酸乙酯、以及丙二醇单甲醚,确认不溶于这些溶剂中。
与光致抗蚀剂的混合试验
将实施例1和2得到的形成下层膜的组合物的溶液通过旋涂分别涂布于硅晶片基板上。在电热板上在205℃烘烤5分钟,形成下层膜(膜厚450nm)。在这些下层膜的上层上,通过旋涂而涂布市售的光致抗蚀剂溶液(シプレ—社制,商品名APEX-E等)。在电热板上在90℃加热1分钟,形成光致抗蚀剂层。在对光致抗蚀剂进行曝光后,在90℃进行1.5分钟的曝光后加热。使光致抗蚀剂显影后,测定下层膜的膜厚,确认下层膜与光致抗蚀剂不发生混合。
干蚀刻速度的试验
将实施例1、2和比较例1、2所得到的形成下层膜的组合物的溶液分别通过旋涂而涂布在硅晶片基板上。在电热板上在205℃烘烤5分钟,形成下层膜(各膜厚为450nm)。然后使用日本サイエンティフィック制RIE系统ES401,在使用CF4作为干蚀刻气体的条件下,测定它们的干蚀刻速度。干蚀刻速度以每单位时间的下层膜的膜厚的减少量的形式来计算。
结果如表1所示。选择性表示为,设光致抗蚀剂的干蚀刻速度为1.00时的下层膜的干蚀刻速度。另外,表中A1表示甲基丙烯酸-2-羟基丙酯与甲基丙烯酸苄酯的共聚物,A2表示聚(2-羟基乙基)丙烯酸酯,B1表示氮氧化钛。
表1
确认由实施例1、2的形成下层膜的组合物得到的含有金属氮化物粒子的下层膜的蚀刻速度,与比较例1的不含有金属氮化物粒子的下层膜小。
以上表明,不依赖于聚合物的有无,通过导入金属氮化物粒子,可以获得具有很小蚀刻速度的含有金属氮化物粒子的下层膜。
含有金属氮化物粒子的下层膜的干蚀刻速度需要具有比光致抗蚀剂更小的干蚀刻速度的必要性在于,在对下层膜上形成的光致抗蚀剂进行显影、然后利用干蚀刻对半导体基底基板进行加工的工序中,通过使含有金属氮化物粒子的下层膜的干蚀刻速度比半导体基底加工基板的干蚀刻速度更小,可以使光致抗蚀剂薄膜化,并且可以将图形正确地转印至基板上。
Claims (6)
1.一种形成在半导体器件的制造中使用的下层膜的组合物,含有:
(i)平均粒径为1~1000nm的金属氮化物粒子,
(ii)有机材料,所述有机材料选自聚合物、交联性化合物、吸光性化合物、表面活性剂、高分子分散剂、交联催化剂、粘结辅助剂、流变调节剂以及它们的组合,和
(iii)有机溶剂,
所述形成下层膜的组合物中的固体成分的比例为0.1~70质量%,所述固体成分是指,从形成下层膜的组合物的全体成分中除去有机溶剂成分后的成分,且在固体成分中金属氮化物粒子的含量为40~99.9质量%。
2.如权利要求1所述的形成下层膜的组合物,上述金属氮化物粒子含有选自钛、硅、钽、钨、铈、锗、铪和镓中的至少一种元素。
3.如权利要求1或2所述的形成下层膜的组合物,上述金属氮化物粒子为选自氮化钛、氮氧化钛、氮化硅、氮氧化硅、氮化钽、氮氧化钽、氮化钨、氮氧化钨、氮化铈、氮氧化铈、氮化锗、氮氧化锗、氮化铪、氮氧化铪、氮化铯、氮氧化铯、氮化镓和氮氧化镓中的至少一种金属氮化物的粒子。
4.一种在半导体器件的制造中使用的下层膜的形成方法,是通过将权利要求1~3的任一项所述的形成下层膜的组合物旋转涂布在半导体基板上、进行烘烤来进行的,上述烘烤是在烘烤温度为80℃~300℃,烘烤时间为0.5~10分钟的条件下进行的。
5.一种在半导体器件的制造中使用的光致抗蚀剂图形的形成方法,包括以下工序:将权利要求1~3的任一项所述的形成下层膜的组合物旋转涂布在半导体基板上,在烘烤温度为80℃~300℃,烘烤时间为0.5~10分钟的条件下进行烘烤来形成下层膜的工序;在上述下层膜上形成光致抗蚀剂层的工序;对由上述下层膜和上述光致抗蚀剂层被覆的半导体基板进行曝光的工序;在曝光后进行显影光致抗蚀剂层的工序;将除去了光致抗蚀剂的部分的下层膜利用干蚀刻进行除去的工序。
6.如权利要求5所述的光致抗蚀剂图形的形成方法,上述曝光是利用248nm、193nm或157nm的波长的光进行的。
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