CN102056954A - 抗反射涂层组合物 - Google Patents
抗反射涂层组合物 Download PDFInfo
- Publication number
- CN102056954A CN102056954A CN200980120871.4A CN200980120871A CN102056954A CN 102056954 A CN102056954 A CN 102056954A CN 200980120871 A CN200980120871 A CN 200980120871A CN 102056954 A CN102056954 A CN 102056954A
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- CN
- China
- Prior art keywords
- acid
- mercaptan
- imide
- coating composition
- antireflection coating
- 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
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- 239000008199 coating composition Substances 0.000 title claims description 62
- 239000002253 acid Substances 0.000 claims description 80
- 239000000203 mixture Substances 0.000 claims description 72
- 239000000463 material Substances 0.000 claims description 59
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 54
- 238000010521 absorption reaction Methods 0.000 claims description 53
- 239000011248 coating agent Substances 0.000 claims description 52
- 238000000576 coating method Methods 0.000 claims description 52
- 239000000126 substance Substances 0.000 claims description 52
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 29
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000005260 corrosion Methods 0.000 claims description 21
- 230000007797 corrosion Effects 0.000 claims description 21
- 150000003949 imides Chemical class 0.000 claims description 20
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
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- 125000003118 aryl group Chemical group 0.000 claims description 12
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- 150000003839 salts Chemical class 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
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- 150000007513 acids Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
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- 239000011324 bead Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000001393 microlithography Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
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- UIMAOHVEKLXJDO-UHFFFAOYSA-N (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;triethylazanium Chemical compound CCN(CC)CC.C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C UIMAOHVEKLXJDO-UHFFFAOYSA-N 0.000 description 1
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- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
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Abstract
本发明公开了抗反射涂层和有关的聚合物。
Description
技术领域
本发明涉及一种新的抗反射涂层组合物,以及其用于通过在反射性基材和光致抗蚀剂涂层之间形成该新的抗反射涂层组合物的薄层而进行图像处理的用途。这种组合物特别可用于通过光刻技术制造半导体器件。
背景技术
光致抗蚀剂组合物在缩微平版印刷工艺中用于制造小型化电子元件,例如制造计算机芯片和集成电路。通常,在这些工艺中,首先向基材,例如用于制造集成电路的硅晶片,施涂光致抗蚀剂组合物的薄涂膜。然后烘烤已涂布的基材,以蒸发光致抗蚀剂组合物中的任何溶剂并将涂层固定到基材上。基材的已烘烤的涂布表面接下来经历对辐射的成像式曝光。
这种辐射曝光在已涂布表面的曝光区域中引起化学转变。可见光、紫外(UV)光、电子束和X射线辐射能是当今在缩微平版印刷工艺中通常使用的辐射类型。在该成像式曝光之后,用显影剂溶液处理已涂布的基材,以溶解和去除光致抗蚀剂的已辐射曝光区域或未曝光区域。
半导体器件小型化的趋势已经导致使用对越来越短的波长的辐射敏感的新光致抗蚀剂,并且也已经导致使用复杂的多级体系以克服与这样的小型化有关的难题。
在光刻法中使用高吸收性的抗反射涂层是减少光从高反射性基材背反射所产生的问题的一种途径。背反射率的两个主要缺点是薄膜干涉效应和反射性刻痕。薄膜干涉或驻波导致由光致抗蚀剂薄膜中的总光强度随光致抗蚀剂厚度改变而变化所引起的临界线宽尺寸变化。当光致抗蚀剂在含有表面形态特征的基材上形成图案时,反射性刻痕变得严重,所述表面形态特征使经过光致抗蚀剂薄膜的光散射,导致线宽变化,以及在极端情况下,形成光致抗蚀剂完全损失的区域。
在其中需要进一步减少或消除线宽变化的情况下,使用底部抗反射涂层提供消除反射率的最佳解决方案。在采用光致抗蚀剂涂布之前和在曝光之前,将底部抗反射涂层施涂于基材。将光致抗蚀剂成像式曝光和显影。曝光区域中的抗反射涂层然后通常在气态等离子体中加以蚀刻,由此将光致抗蚀剂图案转印到基材上。与光致抗蚀剂相比,抗反射薄膜的蚀刻速率应较高,使得在蚀刻工艺期间在没有过量的光致抗蚀剂薄膜损失的情况下蚀刻抗反射薄膜。抗反射涂层在曝光波长下也必须具有恰当的吸收指数和折射率(已知称为‘k’和‘n’),以获得所需平版印刷性能。
必要的是具有底部抗反射涂层,其在低于300nm的曝光下工作良好。这种抗反射涂层需要具有高蚀刻速率和以恰当的折射率而是充分吸收性的,以用作抗反射涂层。
发明内容
发明概述
本发明描述一种抗反射涂层组合物,其含有新的没有芳族发色团的聚合物,所述聚合物可应用于在高NA平版印刷法中的抗反射涂层材料中。因为聚合物主链和不存在连接到聚合物上的芳族发色团,所以该材料具有超高的蚀刻速率。
本发明的抗反射涂层组合物包括不含芳族发色团的聚合物、酸产生剂和任选的交联剂,其中该聚合物包括衍生自氨基塑料的结构单元和衍生自二醇、三醇、二硫醇、三硫醇、其它多元醇、二酸、三酸、其它多元酸、二酰亚胺、二酰胺、酰亚胺-酰胺或其混合物的结构单元,其中所述二醇、二硫醇、三醇、三硫醇、二酸、三酸、二酰亚胺、二酰胺或酰亚胺-酰胺任选地含有一个或多个氮和/或硫原子或含有一个或多个烯烃(alkene)基团,以改进在可用于IC制造的波长下的吸收率和获得用于抗反射材料的高的n值。
本发明还涉及一种不含芳族发色团的聚合物,其包括衍生自氨基塑料的结构单元和衍生自二醇、三醇、二硫醇、三硫醇、其它多元醇、二酸、三酸、其它多元酸、二酰亚胺或其混合物的结构单元,其中所述二醇、二硫醇、三醇、三硫醇、二酸、三酸、二酰亚胺、二酰胺或酰亚胺-酰胺任选地含有一个或多个氮和/或硫原子或含有一个或多个烯烃基团。
本发明还涉及一种涂布的基材,包括基材,在该基材上具有由在此公开的抗反射涂层组合物形成的抗反射涂层,其中当在193nm下测量时,该抗反射涂层具有0.01≤k<0.35的吸收参数(k)。另外,本发明还涉及一种成像的方法,包括a)采用在此公开的抗反射涂层组合物涂布基材并烘烤基材;b)在抗反射涂层上涂布和烘烤光致抗蚀剂薄膜;c)成像式曝光该光致抗蚀剂;d)将光致抗蚀剂中的图像显影;e)任选地,在曝光步骤之后烘烤基材。另外,本发明还涉及一种在基材上形成抗反射薄膜和对曝光波长敏感的光致抗蚀剂薄膜的方法,包括a)在基材上形成抗反射薄膜,其中该抗反射薄膜由本发明的抗反射涂层组合物形成,其中抗反射涂层组合物中的二醇、三醇、二硫醇、三硫醇、二酸、三酸、二酰亚胺、二酰胺或酰亚胺-酰胺以这样的方式选择,使得抗反射涂层组合物中的聚合物的吸收最大值低于光致抗蚀剂的曝光波长和其中曝光波长在抗反射涂层组合物中聚合物的吸收谱带的吸收最大值和长波长侧的吸收最小值之间,导致对于抗反射薄膜的折射率的反常色散贡献,其提高抗反射薄膜的折射率‘n’和降低抗反射薄膜的吸收参数‘k’;和b)在抗反射薄膜上形成光致抗蚀剂薄膜。在有些情况下,可以选择所述二醇、三醇、二硫醇、三硫醇、其它多元醇、二酸、三酸、其它多元酸、二酰亚胺、二酰胺或酰亚胺-酰胺,使得抗反射涂层组合物中聚合物的吸收最大值低于光致抗蚀剂的曝光波长,和其中曝光波长在抗反射涂层组合物中聚合物的吸收谱带的半高度和长波长侧的吸收最小值之间。
附图说明
图1采用以下含义举例说明反常色散的原理:
Ca:Cauchy相关性
Exλ:曝光λ(高n低k区域)
ab:吸收谱带
ha:半测量值
图2显示色散曲线,其显示涂层实施例2的反常色散效应,由分光椭圆光度法测量。wa表示波长。
发明详述
本发明描述一种抗反射涂层组合物,其含有新的没有芳族发色团的聚合物,所述聚合物可应用于在高NA平版印刷法中的抗反射涂层材料中。因为聚合物主链和不存在连接到聚合物上的芳族发色团,所以该材料具有超高的蚀刻速率。
本发明的抗反射涂层组合物包括不含芳族发色团的聚合物、酸产生剂和任选的交联剂,该聚合物包括衍生自氨基塑料的结构单元和衍生自二醇、三醇、二硫醇、三硫醇、其它多元醇、二酸、三酸、其它多元酸、二酰亚胺、二酰胺、酰亚胺-酰胺或其混合物的结构单元,其中所述二醇、二硫醇、三醇、三硫醇、二酸、三酸、二酰亚胺、二酰胺或酰亚胺-酰胺任选地含有一个或多个氮和/或硫原子或含有一个或多个烯烃基团,以改进在可用于IC制造的波长下的吸收率和获得用于抗反射材料的高的n值。
本发明还涉及一种不含芳族发色团的聚合物,其包括衍生自氨基塑料的结构单元和衍生自二醇、三醇、二硫醇、三硫醇、其它多元醇、二酸、三酸、其它多元酸、二酰亚胺或其混合物的结构单元,其中所述二醇、二硫醇、三醇、三硫醇、二酸、三酸、二酰亚胺、二酰胺或酰亚胺-酰胺任选地含有一个或多个氮和/或硫原子或含有一个或多个烯烃基团。
本发明还涉及一种涂布的基材,包括基材,在该基材上具有由在此公开的抗反射涂层组合物形成的抗反射涂层,其中当在193nm下测量时,该抗反射涂层具有0.01≤k<0.35的吸收参数(k)。另外,本发明还涉及一种成像的方法,包括a)采用在此公开的抗反射涂层组合物涂布基材并烘烤基材;b)在抗反射涂层上涂布和烘烤光致抗蚀剂薄膜;c)成像式曝光该光致抗蚀剂;d)将在光致抗蚀剂中的图像显影;e)任选地,在曝光步骤之后烘烤基材。
本发明还涉及一种涂布的基材,包括基材,在该基材上具有由在此公开的抗反射涂层组合物形成的抗反射涂层,其中当在193nm下测量时,该抗反射涂层具有0.01≤k<0.35的吸收参数(k)。另外,本发明还涉及一种成像的方法,包括a)采用在此公开的抗反射涂层组合物涂布基材并烘烤基材;b)在抗反射涂层上涂布和烘烤光致抗蚀剂薄膜;c)成像式曝光该光致抗蚀剂;d)将在光致抗蚀剂中的图像显影;e)任选地,在曝光步骤之后烘烤基材。另外,本发明还涉及一种在基材上形成抗反射薄膜和对曝光波长敏感的光致抗蚀剂薄膜的方法,包括a)在基材上形成抗反射薄膜,其中该抗反射薄膜由本发明的抗反射涂层组合物形成,其中抗反射涂层组合物中的二醇、三醇、二硫醇、三硫醇、二酸、三酸、二酰亚胺、二酰胺或酰亚胺-酰胺以这样的方式选择,使得抗反射涂层组合物中的聚合物的吸收最大值低于光致抗蚀剂的曝光波长和其中曝光波长在抗反射涂层组合物中聚合物的吸收谱带的吸收最大值和长波长侧的吸收最小值之间,导致对于抗反射薄膜的折射率的反常色散贡献,其提高抗反射薄膜的折射率‘n’和降低抗反射薄膜的吸收参数‘k’;和b)在抗反射薄膜上形成光致抗蚀剂薄膜。在有些情况下,可以选择所述二醇、三醇、二硫醇、三硫醇、其它多元醇、二酸、三酸、其它多元酸、二酰亚胺、二酰胺或酰亚胺-酰胺,使得抗反射涂层组合物中聚合物的吸收最大值低于光致抗蚀剂的曝光波长,和其中曝光波长在抗反射涂层组合物中聚合物的吸收谱带的半高度和长波长侧的吸收最小值之间。
如在此使用的,芳族发色团是指含有在环结构中仅含有碳原子的发色团的芳烃;例如苯基、萘基等。
二醇、三醇、二硫醇、三硫醇、二酸、三酸和二酰亚胺的实例包括例如
本发明的聚合物可借助酸产生剂自交联。
氨基塑料可以被两个或更多个烷氧基取代,可以基于氨基塑料例如甘脲-醛树脂、三聚氰胺-醛树脂、苯并胍胺-醛树脂和脲-醛树脂。醛的实例包括甲醛、乙醛等。在有些情况下,三个或四个烷氧基是有用的。单体型烷基化甘脲-甲醛树脂是一个实例。一个实例为具有以下结构的四(烷氧基烷基)甘脲
其中R8各自为(CH2)n-O-(CH2)m-CH3,R11各自为氢或C1-C6烷基,n为1至4,和m为0至3。
((A)中的数字指示用于化合物命名的原子编号)
四(烷氧基甲基)甘脲的实例可以包括例如四(甲氧基甲基)甘脲、四(乙氧基甲基)甘脲、四(正丙氧基甲基)甘脲、四(异丙氧基甲基)甘脲、四(正丁氧基甲基)甘脲和四(叔丁氧基甲基)甘脲,取代的四(烷氧基甲基)甘脲,例如7-甲基四(甲氧基甲基)甘脲、7-乙基四(甲氧基甲基)甘脲、7-(异-或正-)丙基四(甲氧基甲基)甘脲、7-(异-或仲-或叔-)丁基四(甲氧基甲基)甘脲、7,8-二甲基四(甲氧基甲基)甘脲、7,8-二乙基四(甲氧基甲基)甘脲、7,8-二(异-或正-)丙基四(甲氧基甲基)甘脲、7,8-二(异-或仲-或叔-)丁基四(甲氧基甲基)甘脲、7-甲基-8-(异-或正-)丙基四(甲氧基甲基)甘脲等。四(甲氧基甲基)甘脲可以以商标POWDERLINK购自Cytec Industries(例如POWDERLINK 1174)。其它实例包括甲基丙基四甲氧基甲基甘脲和甲基苯基四甲氧基甲基甘脲。
其它氨基塑料可以以商标CYMEL购自Cytec Industries和以商标RESIMENE购自Monsanto Chemical Co.。也可以使用其它胺和酰胺的缩合产物,例如如下化合物的醛缩合物:三嗪、二嗪、二唑、胍、胍亚胺和这样的化合物的烷基-和芳基-取代的衍生物,包括烷基-和芳基-取代的三聚氰胺。这样的化合物的一些实例为N,N′-二甲基脲、苯甲酰脲(benzourea)、双氰胺、甲酰缩胍胺、乙酰胍胺、氰尿二酰胺、2-氯-4,6-二氨基-1,3,5-三嗪、6-甲基-2,4-二氨基、1,3,5-三嗪、3,5-二氨基三唑、三氨基嘧啶、2-巯基-4,6-二氨基-嘧啶、3,4,6-三(乙基氨基)-1,3,5-三嗪、三(烷氧基羰基氨基)三嗪、N,N,N′,N′-四甲氧基甲脲等。
其它可能的氨基塑料包括具有以下结构的化合物:
包括其类似物和衍生物,例如在Tosoh的日本公开专利申请(Kokai)号1-293339中找到的那些,以及醚化氨基树脂,例如甲基化或丁基化三聚氰胺树脂(分别为N-甲氧基甲基-或N-丁氧基甲基-三聚氰胺)或甲基化/丁基化甘脲,例如可以在Ciba Specialty Chemicals的加拿大专利号1 204 547中找到的那些。各种三聚氰胺和脲树脂可以以商品名Nicalacs(Sanwa Chemical Co.),Plastopal(BASF AG),或Maprenal(Clariant GmbH)商购。必要时,上述氨基塑料也可以在本发明中用作交联剂。
其它交联剂类型包括
和其衍生物。
本发明聚合物的重复单元的一个实例为
其中Z为二醇、三醇、二硫醇、三硫醇、其它多元醇、二酸、三酸、其它多元酸、二酰亚胺、二酰胺、酰亚胺-酰胺或其混合物的残基;X为-OR3、-O(O=C)R3
其中R3为氢、未取代或取代的烷基、未取代或取代的烯烃、未取代或取代的炔烃或未取代或取代的在环内任选具有一个或多个氮和/或硫原子的6-元环;R4和R5各自独立地为R3,或R4和R5与它们所连接到的原子一起形成未取代或取代的在环内任选具有一个或多个氮和/或硫原子的5-或6-元环;和R11各自为氢或C1-6烷基。
重复单元的其它实例包括
本发明的聚合物可以通过本领域中已知的任何标准聚合方法,特别是缩聚技术来制备。该聚合物可以使用溶液、乳液、本体、悬浮聚合等合成。典型地,在升高的温度下和任选在酸存在下,氨基塑料与二醇、三醇、二硫醇、三硫醇或其混合物缩合,以得到本发明的聚合物。氨基塑料对二醇、三醇、二硫醇、三硫醇、其它多元醇、二酸、三酸、其它多元酸、二酰亚胺或其混合物的一般比例为1∶2至约3∶1,进一步为约1∶1.5至约2.5∶1。
本发明使用的酸产生剂,优选热酸产生剂,是一种当被加热到高于90℃和低于250℃的温度时产生酸的化合物。酸与交联剂结合使聚合物交联。热处理之后抗反射涂层变得不溶于用于涂布光致抗蚀剂的溶剂中,并且此外也不溶于用于使光致抗蚀剂成像的碱性显影剂中。优选,热酸产生剂在90℃下,和更优选在高于120℃下,和甚至更优选在高于150℃下被活化。抗反射涂层被加热足够的时间长度以交联涂层。酸和热酸产生剂的实例为丁烷磺酸、三氟甲磺酸、九氟丁烷磺酸、甲苯磺酸硝基苄基酯,例如甲苯磺酸2-硝基苄基酯、甲苯磺酸2,4-二硝基苄基酯、甲苯磺酸2,6-二硝基苄基酯、甲苯磺酸4-硝基苄基酯;苯磺酸酯,例如4-氯苯磺酸2-三氟甲基-6-硝基苄基酯、4-硝基苯磺酸2-三氟甲基-6-硝基苄基酯;酚磺酸酯,例如4-甲氧基苯磺酸苯酯;有机酸的烷基铵盐,例如10-樟脑磺酸三乙基铵盐等。
热酸产生剂优于游离酸,但是在该新的抗反射组合物中也可以使用游离酸,因为如果聚合物要在溶液中发生交联,则抗反射溶液的搁置稳定性可能将随时间受到所述酸的存在的影响。热酸产生剂仅在基材上加热抗反射薄膜时被活化。另外,可以使用热酸和游离酸的混合物。尽管对于聚合物的有效交联,热酸产生剂是优选的,但是也可以使用包括聚合物和交联剂的抗反射涂层组合物,其中加热使聚合物交联。游离酸的实例在不受限制的情况下为强酸,例如磺酸。例如甲苯磺酸、三氟甲磺酸或这些物质的混合物的磺酸是优选的。
新的组合物可以进一步含有光酸产生剂,其实例在不受限制的情况下为盐、磺酸酯化合物、硝基苄基酯、三嗪等。优选的光酸产生剂为羟基酰亚胺的盐和磺酸酯,特别是二苯基碘盐、三苯基锍盐、二烷基碘盐、三烷基锍盐及其混合物。组合物中可以使用一种或多种交联催化剂。
用于涂层组合物的溶剂的实例包括醇、酯、乙二醇二甲醚、醚、二醇醚、二醇醚酯、酮、内酯、环酮及其混合物。这样的溶剂的实例包括但不限于丙二醇甲醚、丙二醇甲醚乙酸酯、环己酮、2-庚酮、3-乙氧基-丙酸乙酯、丙二醇甲醚乙酸酯、乳酸乙酯、γ-戊内酯、3-甲氧基丙酸甲酯及其混合物。溶剂通常以约40至约99wt%的量存在。在某些情况下,添加内酯溶剂可用于辅助抗反射涂层组合物当在层状体系中使用时的流动特性。当存在时,内酯溶剂构成溶剂体系的约1至约10%。γ-戊内酯是一种有用的内酯溶剂。
本发明组合物中聚合物的量可以在相对于组合物的固体部分为约100wt%至约1wt%之间变化。当使用时,本发明组合物中交联剂的量可以在相对于组合物的固体部分为0wt%至约50wt%之间变化。本发明组合物中酸产生剂的量可以在相对于组合物的固体部分为0.1wt%至约10wt%之间变化。
本发明组合物可以任选包括通常在抗反射涂层组合物中存在的额外的材料,例如单体染料、低级醇、表面流平剂、粘合促进剂、消泡剂等,条件是性能不受负面影响。
因为组合物被涂布在基材上并且进一步经历干法蚀刻,所以可以预见该组合物具有充分低的金属离子水平和纯度,使得半导体器件的性能不会受到不利影响。可以使用处理,例如使聚合物溶液或含有这种聚合物的组合物通过离子交换柱、过滤和萃取工艺,来降低金属离子浓度和减少颗粒。
抗反射涂层的光学特性对于曝光波长和其它所需平版印刷特性来加以优化。举例来说,该新的组合物的对于193nm曝光范围的吸收参数(k)为约0.1至约1.0,优选为约0.2至约0.75,更优选为约0.11至约0.35,如使用椭圆光度法所测量。折射率(n)的值为约1.25至约2.0,优选为约1.8至约2.0。由于该组合物在193nm下的良好吸收特性,所以可以使用大约20nm的非常薄的抗反射薄膜。当使用非芳族光致抗蚀剂,例如在193nm、157nm和更短波长下敏感的那些时,这一点是特别有利的,其中光致抗蚀剂薄膜是薄的并且必须用作抗反射薄膜的蚀刻掩模。
其上形成抗反射涂层的基材可以为半导体工业中通常使用的任一种。合适的基材不受限制地包括硅、涂有金属表面的硅基材、覆铜硅晶片、铜、涂有抗反射涂层的基材、铝、聚合物树脂、二氧化硅、金属、掺杂二氧化硅、氮化硅、氮氧化硅、氮化钛、钽、钨、铜、多晶硅、陶瓷、铝/铜混合物;砷化镓及其它这样的第III/V族化合物等。基材可以包括任何数目的由上述材料构成的层。
涂层组合物可以使用本领域技术人员公知的技术,例如浸渍、旋涂或喷涂,涂布在基材上。抗反射涂层的薄膜厚度为约0.01μm至约1μm。涂层可以在加热板或对流烘箱或其它公知加热方法上加热,以去除任何残余溶剂和如果需要,引发交联,和使抗反射涂层不溶解来防止抗反射涂层和光致抗蚀剂之间发生混合。优选的温度范围为约90℃至约250℃。如果温度低于90℃,则发生溶剂损失不足或交联量不足,而在高于300℃的温度下,组合物可能变得化学不稳定。然后将光致抗蚀剂薄膜涂覆在最上方的抗反射涂层之上并烘烤,以基本去除光致抗蚀剂溶剂。涂布步骤之后可以应用边胶清除剂,以使用本领域中公知的方法清洁基材边缘。
有两种光致抗蚀剂组合物,负性工作的和正性工作的。当负性工作光致抗蚀剂组合物对辐射成像式曝光时,曝光于辐射下的抗蚀剂组合物的区域变得较不溶于显影剂溶液(例如交联反应发生),而光致抗蚀剂涂层的未曝光区域仍然相对可溶于此类溶液。因此,用显影剂处理已曝光的负性工作抗蚀剂导致去除光致抗蚀涂层的未曝光区域和在涂层中产生负像,由此露出其上沉积光致抗蚀剂组合物的下层基材表面的所需部分。
另一方面,当正性工作光致抗蚀剂组合物对辐射成像式曝光时,曝光于辐射下的光致抗蚀剂组合物的那些区域变得更可溶于显影剂溶液(例如重排反应发生),而未曝光的那些区域仍然相对不可溶于显影剂溶液。因此,用显影剂处理已曝光的正性工作光致抗蚀剂引起去除涂层的已曝光区域和在光致抗蚀涂层中产生正像。同样露出下层表面的所需部分。
负性工作光致抗蚀剂和正性工作光致抗蚀剂组合物及其用途是本领域技术人员公知的。
连同通常以干燥形式制备的上述正性和负性光致抗蚀剂,193nm浸渍平版印刷法对于低至45nm节点和超出的节点来说是一种可行的解决方案。基于模拟,采用在193nm下的吸收性下层,低“k”BARC更适合于最佳基材反射率控制。另一方面,BARC薄膜需要足够薄,以在薄膜平版印刷法中对非常小的特征具有所需的蚀刻选择性。低薄膜厚度需要高n值用于BARC。本发明描述一种含有新的具有非芳族染料的聚合物的抗反射涂层组合物。与常规的193nm BARC,例如苯基或其衍生物相比,该染料在193nm下是吸收性较低的。通过合理选择染料,本发明利用了在吸收最大值λmax附近(不包括λmax)的反常色散效应。使用吸光率最大值低于曝光吸光率(193nm)的染料来实现超n值。理论上,高于由Cauchy相关性推算的值的n值被认为是高的,其覆盖高波长区域中的吸光率谱带的整一半。当使用中等强度的染料时,高n低k材料应理想地具有吸收最大值λmax,使得光化波长与处于吸收谱带的较高波长侧上的吸收谱带一半高度的波长λ+相同(图1)。从较短波长方向中的那个位置移动直至一半长度(λmax-λ-)的吸收最大值λmax推动曝光波长λ落入图1中指出的典型的高n低k区域。基于Kramers-Kronic关系式,折射率波动的幅度不仅由λmax的位置决定,而且受吸光率强度的影响。原则上,可以获得n值的几乎任何增量,只要染料具有对应于反常色散区域的极强的吸光率。有机BARC的低k要求限制n增加的幅度,并且增加了在染料选择和材料研发方面的挑战。发明人已经成功地将具有160-190nm,优选170-190nm的吸收最大值的染料,例如氰尿酸、烯烃、炔烃或酮,引入聚合物结构中。图2中示出通过使用椭圆光度法光谱学测定的基于涂层实施例2(得自合成实施例2的聚合物)的色散曲线的实例。假设材料是透明的,基于Cauchy相关性的推算在193nm下得到1.63的n值。材料的实际n值经测得为1.93。因此,0.30的折射率增量归因于色散效应,尽管曝光波长并不精确地处于最优的高n低k位置。
应提及的是,抗反射涂层中使用的光学指数与其纯净形式或其液体溶液形式中的有机化合物的吸收性能不同。涂层中的染料的吸收光谱可能由于化学和物理环境例如溶剂、添加剂和可能的化学反应的变化而偏移。在溶液中表现理想的染料可能不适合抗反射涂层。本发明已经采用各种精心选择的染料研究了许多低k的BARC材料,并且在此给出了所述结构。
在本发明中,可以选择抗反射涂层组合物中的二醇、三醇、二硫醇、三硫醇、二酸、三酸、二酰亚胺、二酰胺或酰亚胺-酰胺,使得用来在基材上形成抗反射薄膜的抗反射涂层组合物中的聚合物的吸收最大值低于光致抗蚀剂的曝光波长,和其中曝光波长在抗反射涂层组合物中聚合物的吸收谱带的吸收最大值和长波长侧的吸收最小值之间,导致对于抗反射薄膜的折射率的反常色散贡献,其提高抗反射薄膜的折射率‘n’和降低抗反射薄膜的吸收参数‘k’。在有些情况下,可以选择所述二醇、三醇、二硫醇、三硫醇、其它多元醇、二酸、三酸、其它多元酸、二酰亚胺、二酰胺或酰亚胺-酰胺,使得抗反射涂层组合物中聚合物的吸收最大值低于光致抗蚀剂的曝光波长,和其中曝光波长在抗反射涂层组合物中聚合物的吸收谱带的半高度和长波长侧的吸收最小值之间。在每种情况下,对于抗反射薄膜的折射率的反常色散贡献导致提高抗反射薄膜的折射率‘n’和降低抗反射薄膜的吸收参数‘k’。
本发明的方法包括用包括本发明聚合物的抗反射涂层组合物涂布基材,在足够的温度下将基材在加热板或对流烘箱或其它公知加热方法上加热足够的时间长度以去除涂层溶剂,和必要时使聚合物交联达到充分程度,使得涂层不可溶于光致抗蚀剂的涂层溶液或含水碱性显影剂。可以应用边胶清除剂,以使用本领域中公知的方法清洁基材边缘。加热温度为约70℃至约250℃。如果温度低于70℃,则可能发生溶剂损失不足或交联量不足,而在高于250℃的温度下,聚合物可能变得化学不稳定。然后将光致抗蚀剂组合物的薄膜涂覆在抗反射涂层之上并烘烤,以基本去除光致抗蚀剂溶剂。将光致抗蚀剂成像式曝光并在含水显影剂中显影,以去除已处理的抗蚀剂。可以在显影之前和曝光之后将任选的加热步骤引入方法中。将光致抗蚀剂涂布和成像的方法是本领域技术人员公知的,并且对于使用的抗蚀剂的具体类型加以优化。形成图案的基材然后可以在合适的蚀刻室中干法蚀刻,以去除抗反射薄膜的已曝光部分,其中剩余的光致抗蚀剂用作蚀刻掩模。本领域中已知各种气体用于蚀刻有机抗反射涂层,例如O2、Cl2、F2和CF4以及本领域中已知的其它蚀刻气体。本方法通常被称为双层法。
可以在抗反射涂层和光致抗蚀剂之间设置中间层来防止混合,并且预想所述中间层在本发明范围内。中间层为从溶剂流延的惰性聚合物,其中聚合物的实例为聚砜和聚酰亚胺。
另外,还预想一种多层体系,例如三层体系,或工艺也在本发明范围内。在例如三层工艺中,有机薄膜在基材上形成,抗反射薄膜在有机薄膜上形成,以及光致抗蚀剂薄膜在抗反射薄膜上形成。有机薄膜也可以用作抗反射薄膜。有机薄膜通过旋涂法等在基材上作为下部抗蚀剂薄膜形成。在通过旋涂法等施涂之后,有机薄膜然后可以或可以不采用加热或酸进行交联。在有机薄膜上形成抗反射薄膜,例如在此公开的那种,作为中间抗蚀剂薄膜。在通过旋涂等向有机薄膜施涂抗反射薄膜组合物之后,有机溶剂被蒸发,并进行烘烤,以便促进交联反应,以防止抗反射薄膜与上层的光致抗蚀剂薄膜混合。在形成抗反射薄膜之后,在其上形成光致抗蚀剂薄膜作为上部抗蚀剂薄膜。如对于形成抗反射薄膜一样,旋涂法可以用于形成光致抗蚀剂薄膜。在通过旋涂法等施涂光致抗蚀剂薄膜组合物之后,进行预烘烤。然后,使图案电路区域曝光,并进行曝光后烘烤(PEB)和利用显影剂显影,以获得抗蚀剂图案。
另外的三层抗蚀剂工艺为利用碳蚀刻掩模形成底层的那种工艺。在底层之上,通过使用含有硅原子的中间抗蚀剂层组合物形成中间层。在中间层之上,形成基于本发明的抗反射涂层组合物的抗反射层。最后,在抗反射层之上,通过使用光致抗蚀剂组合物的顶部抗蚀剂层组合物,形成顶层。在这种情况下,用于形成中间层的组合物的实例可以包括聚倍半硅氧烷基硅氧烷聚合物、四原硅酸酯玻璃(TEOS)等。然后通过旋涂这种组合物制备的薄膜,或通过CVD制备的SiO2、SiN或SiON的薄膜可以用作中间层。光致抗蚀剂组合物的顶部抗蚀剂层组合物优选包括没有硅原子的聚合物。包括没有硅原子的聚合物的顶部抗蚀剂层具有为包括含硅原子的聚合物的顶部抗蚀剂层提供优越分辨率的优点。然后以与上述双层抗蚀剂工艺相同的方式,根据标准程序曝光顶部抗蚀剂层的图案电路区域。随后,进行曝光后烘烤(PEB)和显影,以获得抗蚀剂图案,随后进行蚀刻和进一步的平版印刷工艺。
以下实施例提供制备和利用本发明组合物的方法的详细举例说明。但是这些实施例并不意图以任何方式限制或约束本发明的范围,并且不应被认为是在提供为实践本发明而必须排他性利用的条件、参数或数值。
具体实施方式
实施例
合成实施例1
将32g四甲氧基甲基甘脲、13g三-(2-羟乙基)氰尿酸和100g环己酮加入到具有温度计、冷水冷凝器和机械搅拌器的500mL烧瓶中。将反应混合物加热到80℃。在添加催化量的对-甲苯磺酸一水合物(0.14g)之后,将反应在这一温度下维持6.0小时。然后将反应溶液冷却至室温,获得大约30固体%的聚合物溶液。聚合物的平均分子量为约2000g/mol。
合成实施例2
将29g四甲氧基甲基甘脲、16g三-(2-羟乙基)氰尿酸和100g环己酮加入到具有温度计、冷水冷凝器和机械搅拌器的500mL烧瓶中。将反应混合物加热到80℃。在添加催化量的对-甲苯磺酸一水合物(0.14g)之后,将反应在这一温度下维持6.0小时。然后将反应溶液冷却至室温,获得大约30固体%的聚合物溶液。聚合物的平均分子量为约2000g/mol。
合成实施例3
将6.1g乙酸酐、13g三-(2-羟乙基)氰尿酸和120g环己酮加入到具有温度计、冷水冷凝器和机械搅拌器的500mL烧瓶中。将混合物加热到100℃,并且添加0.11g对-甲苯磺酸一水合物。16小时之后,将反应混合物冷却至80℃并添加32g四甲氧基甲基甘脲。该反应在这一温度下维持16.0小时。然后将反应溶液冷却至室温,获得聚合物溶液。
合成实施例4
将32g四甲氧基甲基甘脲、13g三-(2-羟乙基)氰尿酸、1.9g 1,4-二噻烷-2,5-二醇和100g环己酮加入到具有温度计、冷水冷凝器和机械搅拌器的500mL烧瓶中。将反应混合物加热到80℃。在添加催化量的对-甲苯磺酸一水合物(0.15g)之后,将反应在这一温度下维持6.0小时。然后将反应溶液冷却至室温,获得大约30固体%的聚合物溶液。
合成实施例5
将29.2g四甲氧基甲基甘脲、8g三-(2-羟乙基)氰尿酸、5.4g三聚硫氰酸和100g环己酮加入到具有温度计、冷水冷凝器和机械搅拌器的500mL烧瓶中。将反应混合物加热到80℃。在添加催化量的对-甲苯磺酸一水合物(0.15g)之后,将反应在这一温度下维持6.0小时。然后将反应溶液冷却至室温,获得大约30固体%的聚合物溶液。
合成实施例6
将29.2g四甲氧基甲基甘脲、16g三-(2-羟乙基)氰尿酸、9.6g异氰脲酸二烯丙基酯和100g环己酮加入到具有温度计、冷水冷凝器和机械搅拌器的500mL烧瓶中。将反应混合物加热到80℃。在添加催化量的对-甲苯磺酸一水合物(0.15g)之后,将反应在这一温度下维持6.0小时。然后将反应溶液冷却至室温,获得大约35固体%的聚合物溶液。
合成实施例A
将600g四甲氧基甲基甘脲、96g苯代乙二醇和1200g丙二醇单甲醚乙酸酯(PGMEA)加入到具有温度计、机械搅拌器和冷水冷凝器并被加热到85℃的2L夹套烧瓶中。在添加催化量的对-甲苯磺酸一水合物之后,将反应在这一温度下维持5小时。然后将反应溶液冷却到室温并过滤。将滤出液缓慢倾倒入蒸馏水中,同时搅拌以沉淀聚合物。过滤聚合物,将其用水充分洗涤并在真空烘箱中干燥(获得250g)。获得的聚合物具有约17,345g/mol的重均分子量和2.7的多分散性。
合成实施例B
将20g丁烷四羧酸二酸酐、20g(+)-L-酒石酸二甲基酯、1.0g苄基三丁基氯化铵和70g PGMEA加入到具有冷凝器、热控制器和机械搅拌器的烧瓶中。在氮气和搅拌下,将混合物加热到110℃。大约1-2小时之后获得透明溶液。将温度在110℃保持4小时。冷却至60℃之后,将40g PGMEA、60g乙腈、68g环氧丙烷和30g异氰脲酸三(2,3-环氧基丙基)酯与上述溶液混合。将反应在52℃下保持40小时。将反应溶液冷却至室温并缓慢倾倒入高速混合机中的大量水中。收集聚合物并将其用水充分洗涤。最后在真空烘箱中干燥聚合物。获得40g聚合物,其重均分子量(MW)为约32000g/mol。
涂层配方实施例1
将1.0g得自合成实施例1的聚合物溶液溶于7g丙二醇单甲醚乙酸酯/丙二醇单甲醚(PGMEA/PGME)70/30溶剂中,获得大约4wt%溶液。然后经由孔尺寸为0.2μm的微过滤器过滤混合物,将其涂布在硅晶片上并在200℃下烘烤90秒。将晶片提交用于使用分光椭率计评价光学参数。表1中列出193nm下的优化折射率“n”和吸收参数“k”。
涂层配方实施例2
将1.0g得自合成实施例2的聚合物溶液溶于7g PGMEA/PGME 70/30溶剂中,得到约4wt%溶液。然后经由孔尺寸为0.2μm的微过滤器过滤混合物,将其涂布在硅晶片上并在200℃下烘烤90秒。将晶片提交用于使用分光椭率计评价光学参数。表1中列出193nm下的优化折射率“n”和吸收参数“k”。
涂层配方实施例3
将1.0g得自合成实施例3的聚合物溶液溶于7g PGMEA/PGME 70/30溶剂中,得到约4wt%溶液。然后经由孔尺寸为0.2μm的微过滤器过滤混合物,将其涂布在硅晶片上并在200℃下烘烤90秒。将晶片提交用于使用分光椭率计评价光学参数。表1中列出193nm下的优化折射率“n”和吸收参数“k”。
涂层配方实施例4
将1.0g得自合成实施例4的聚合物溶液溶于7g PGMEA/PGME 70/30溶剂中,得到约4wt%溶液。然后经由孔尺寸为0.2μm的微过滤器过滤混合物,将其涂布在硅晶片上并在200℃下烘烤90秒。将晶片提交用于使用分光椭率计评价光学参数。表1中列出193nm下的优化折射率“n”和吸收参数“k”。
涂层配方实施例5
将1.0g得自合成实施例5的聚合物溶液溶于7g PGMEA/PGME 70/30溶剂中,得到约4wt%溶液。然后经由孔尺寸为0.2μm的微过滤器过滤混合物,将其涂布在硅晶片上并在200℃下烘烤90秒。将晶片提交用于使用分光椭率计评价光学参数。表1中列出193nm下的优化折射率“n”和吸收参数“k”。
涂层配方实施例6
将1.0g得自合成实施例6的聚合物溶液溶于7g PGMEA/PGME 70/30溶剂中,得到约4wt%溶液。然后经由孔尺寸为0.2μm的微过滤器过滤混合物,将其涂布在硅晶片上并在200℃下烘烤90秒。将晶片提交用于使用分光椭率计评价光学参数。表1中列出193nm下的优化折射率“n”和吸收参数“k”。
得自涂层配方实施例1至6的光学参数评价(在193nm下的n & k测量值)。
平版印刷配方实施例1
将2.2g得自合成实施例1的聚合物溶液和0.35g得自合成实施例A的聚合物固体溶于80g PGMEA/PGME(70/30)溶剂中,得到1.2wt%溶液。在聚合物溶液中加入0.35%十二烷基苯磺酸/三乙胺和1%九氟丁烷硫酸三苯基锍。然后经由孔尺寸为0.2μm的微过滤器过滤混合物。
平版印刷配方实施例1的平版印刷性能评价
使用AZT8 3472光致抗蚀剂(AZ Electronic Materials USA Corp.,Somerville,NJ的产品)评价得自平版印刷配方实施例1的抗反射涂层配方的性能。用AZ1C5D底部抗反射涂层组合物(AZ Electronic Materials USA Corp.,Somerville,NJ)涂布硅晶片,以形成60nm厚的薄膜。然后在上面涂布平版印刷配方实施例1的21nm厚的薄膜,并且将其在200℃下烘烤90秒。然后在上面涂布190nm厚的T83472光致抗蚀剂溶液薄膜,将其在115℃下烘烤60秒。然后在0.9σ的偶极子Y照明下,使用具有0.85NA的Nikon NSR-306D 193nm扫描仪以及PSM掩模,使晶片成像式曝光。在110℃下烘烤已曝光晶片60秒,在AZ300 MIF显影剂(可得自AZ Electronic Materials USA Corp.,Somerville,NJ)中显影30秒。然后在扫描电子显微镜下检查经清洁的晶片。线条和空白图案显示没有驻波,没有底脚(footing)和没有浮渣(scumming),表明底部抗反射涂层的功效。
平版印刷配方实施例2
将2.0g得自合成实施例1的聚合物溶液和0.3g得自合成实施例B的聚合物固体溶于3g γ-戊内酯和60g PGMEA/PGME 30/70溶剂,获得1.4wt%溶液。在聚合物溶液中加入1%十二烷基苯磺酸/三乙胺。然后经由孔尺寸为0.2μm的微过滤器过滤混合物。
平版印刷配方实施例2的平版印刷性能评价
使用T8 3472光致抗蚀剂(AZ Electronic Materials USA Corp.,Somerville,NJ的产品)评价得自平版印刷配方实施例2的抗反射涂层配方的性能。用AZ1C5D底部抗反射涂层组合物(AZ Electronic Materials USA Corp.,Somerville,NJ)涂布硅晶片并在200℃下烘烤90秒,以形成52nm厚的薄膜。然后在上面涂布23nm厚的平版印刷配方实施例1的薄膜。然后涂布190nm厚的T83472光致抗蚀剂溶液,将其在115℃烘烤60秒。然后在0.9σ的偶极子Y照明下,使用具有0.85NA的Nikon NSR-306D 193nm扫描仪以及PSM掩模,使晶片成像式曝光。在110℃下烘烤已曝光晶片60秒,在AZ300 MIF显影剂(可得自AZ Electronic Materials USA Corp.,Somerville,NJ)中显影30秒。然后在扫描电子显微镜下检查经清洁的晶片。线条和空白图案显示没有驻波,没有底脚和没有浮渣,表明底部抗反射涂层的功效。
平版印刷配方实施例3
将4.4g得自合成实施例2的聚合物溶液溶于5g γ-戊内酯和95g PGMEA/PGME 30/70溶剂中,获得1.2wt%溶液。在聚合物溶液中加入1%九氟丁烷硫酸三苯基锍。然后经由孔尺寸为0.2μm的微过滤器过滤混合物。
平版印刷配方实施例3的平版印刷性能评价
使用T8 3472光致抗蚀剂(AZ Electronic Materials USA Corp.,Somerville,NJ的产品)评价得自平版印刷配方实施例3的抗反射涂层配方的性能。用AZ1C5D底部抗反射涂层组合物(AZ Electronic Materials USA Corp.,Somerville,NJ)涂布硅晶片并将其在200℃下烘烤90秒,以形成60nm厚的薄膜。然后在上面涂布20nm厚的平版印刷配方实施例3的薄膜。然后涂布190nm厚的T83472光致抗蚀剂溶液,并将其在115℃烘烤60秒。然后在0.9σ的偶极子Y照明下,使用具有0.85NA的Nikon NSR-306D 193nm扫描仪以及PSM掩模,使晶片成像式曝光。在110℃下烘烤已曝光晶片60秒,在AZ300 MIF显影剂(可得自AZ Electronic Materials USA Corp.,Somerville,NJ)中显影30秒。然后在扫描电子显微镜下检查经清洁的晶片。线条和空白图案显示没有驻波,没有底脚和没有浮渣,表明底部抗反射涂层的功效。
上述本发明的说明书举例说明和描述了本发明。另外,公开内容仅显示和描述本发明的优选实施方案,但是如上所述,应理解本发明能够用于各种其它组合、改进和环境,以及能够在如在此表达的本发明构思范围内变化或改进,与上述教导和/或本领域技术人员的技术或知识相应。在上文描述的实施方案另外意图说明实践本发明的最佳方式,以及使其它本领域技术人员能够以这种或其它实施方案以及采用各种由本发明的特定应用或用途所需的改进形式应用本发明。因此,本说明书并不意图将本发明限于在此公开的形式。同样,希望所附的权利要求被视为包括替代的实施方案。
Claims (12)
1.一种抗反射涂层组合物,包括不含芳族发色团的聚合物、酸产生剂和任选的交联剂,其中该聚合物包括衍生自氨基塑料的结构单元和衍生自二醇、三醇、二硫醇、三硫醇、其它多元醇、二酸、三酸、其它多元酸、二酰亚胺、二酰胺、酰亚胺-酰胺或其混合物的结构单元,其中所述二醇、二硫醇、三醇、三硫醇、二酸、三酸、二酰亚胺、二酰胺或酰亚胺-酰胺任选含有一个或多个氮和/或硫原子或含有一个或多个烯烃基团。
5.权利要求1至4任一项的抗反射涂层组合物,其中该组合物进一步包括含芳族发色团的聚合物。
7.一种涂布的基材,包括基材,在该基材上具有由权利要求1至5任一项的抗反射涂层组合物形成的抗反射涂层,其中当在193nm下测量时,该抗反射涂层具有0.01≤k<0.35的吸收参数(k)。
8.一种成像方法,包括a)用权利要求1至5任一项的抗反射涂层组合物涂布基材并烘烤基材;b)在抗反射涂层上涂布和烘烤光致抗蚀剂薄膜;c)成像式曝光该光致抗蚀剂;d)将光致抗蚀剂中的图像显影;e)任选地,在曝光步骤之后烘烤基材。
9.一种在基材上形成抗反射薄膜和对曝光波长敏感的光致抗蚀剂薄膜的方法,包括:
a)在基材上形成抗反射薄膜,其中该抗反射薄膜由权利要求1至5任一项的抗反射涂层组合物形成,其中选择抗反射涂层组合物中的所述二醇、三醇、二硫醇、三硫醇、二酸、三酸、二酰亚胺、二酰胺或酰亚胺-酰胺,使得抗反射涂层组合物中聚合物的吸收最大值低于光致抗蚀剂的曝光波长,和其中曝光波长在抗反射涂层组合物中聚合物的吸收谱带的吸收最大值和长波长侧的吸收最小值之间,导致对于抗反射薄膜的折射率的反常色散贡献,其提高抗反射薄膜的折射率‘n’和降低抗反射薄膜的吸收参数‘k’;和
b)在抗反射薄膜之上形成光致抗蚀剂薄膜。
10.权利要求9的方法,其中该方法包括
a)在基材上形成抗反射薄膜,其中该抗反射薄膜由权利要求1至5任一项的抗反射涂层组合物形成,其中选择抗反射涂层组合物中的所述二醇、三醇、二硫醇、三硫醇、二酸、三酸、二酰亚胺、二酰胺或酰亚胺-酰胺,使得抗反射涂层组合物中聚合物的吸收最大值低于光致抗蚀剂的曝光波长,和其中曝光波长在抗反射涂层组合物中聚合物的吸收谱带半高度和长波长侧的吸收最小值之间,导致对于抗反射薄膜的折射率的反常色散贡献,其提高抗反射薄膜的折射率‘n’和降低抗反射薄膜的吸收参数‘k’;和
b)在抗反射薄膜之上形成光致抗蚀剂薄膜。
11.权利要求9或10的方法,其中所述二醇、三醇、二硫醇、三硫醇、二酸、三酸、二酰亚胺、二酰胺或酰亚胺-酰胺为权利要求3的那种。
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CN102056954B (zh) | 2013-07-03 |
KR20110042263A (ko) | 2011-04-26 |
JP5765854B2 (ja) | 2015-08-19 |
KR101536798B1 (ko) | 2015-07-14 |
US8329387B2 (en) | 2012-12-11 |
EP2300507B1 (en) | 2014-02-26 |
JP2011527461A (ja) | 2011-10-27 |
TW201002794A (en) | 2010-01-16 |
EP2300507A1 (en) | 2011-03-30 |
WO2010004378A1 (en) | 2010-01-14 |
US20100009297A1 (en) | 2010-01-14 |
MY155289A (en) | 2015-09-30 |
TWI510577B (zh) | 2015-12-01 |
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