CN109794848A - 具有cmp抛光垫用的高uv透明度的脂肪族uv固化的聚氨基甲酸酯光学终点检测窗口 - Google Patents
具有cmp抛光垫用的高uv透明度的脂肪族uv固化的聚氨基甲酸酯光学终点检测窗口 Download PDFInfo
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- CN109794848A CN109794848A CN201811264918.1A CN201811264918A CN109794848A CN 109794848 A CN109794848 A CN 109794848A CN 201811264918 A CN201811264918 A CN 201811264918A CN 109794848 A CN109794848 A CN 109794848A
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- Prior art keywords
- cmp
- methyl
- aliphatic
- cycloaliphatic
- carbamate
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
- C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
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Abstract
本发明提供化学机械(CMP)抛光垫,用于抛光选自包括所述CMP抛光垫的半导体衬底的衬底,并且具有一个或多个终点检测窗口,所述窗口为具有两个(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体或其环脂肪族氨基甲酸酯寡聚物与脂肪族引发剂的反应混合物的固化产物,所述(甲基)丙烯酸酯端基经由环脂肪族二氨基甲酸酯键合至平均分子量为450至2,000的聚醚、聚碳酸酯或聚酯链,其中所述氨基甲酸酯大分子单体中的总异氰酸酯含量在3.3至10重量%范围内,并且进一步地,其中,所述组合物包括小于5重量%的未反应的(甲基)丙烯酸酯单体,并且大体上不含未反应的异氰酸酯。无论其硬度或缺乏硬度,所述终点检测窗口在潮湿时均具有出色耐用性。
Description
本发明涉及用于紫外(UV)透明终点检测窗口的调配物,具有一个或多个终点检测窗口的化学机械抛光垫(CMP抛光垫),以及使用所述CMP抛光垫进行CMP抛光的方法。更具体来说,本发明涉及一种包括具有两个(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体或其环脂肪族氨基甲酸酯寡聚物与脂肪族引发剂,如光引发剂或热引发剂,如偶氮双异丁腈(AIBN)的反应混合物的组合物,所述(甲基)丙烯酸酯端基经由环脂肪族二氨基甲酸酯键合至聚醚、聚碳酸酯或聚酯链,并且关于一种具有一个或多个终点检测窗口的CMP抛光垫,所述终点检测窗口为反应混合物的固化产物,以及制造和使用所述CMP抛光垫的方法。
化学机械平坦化或化学机械抛光(CMP)通常用于平坦化包括集成电路和其它电子装置衬底(如半导体晶片)的导电、半导电和介电材料的多个薄层中的一个或多个。平坦化适用于去除非所期望的表面形貌和表面缺陷,如粗糙表面、聚结材料、晶格损伤、划痕和污染的层或材料。在常规CMP中,衬底安装在载体组件上并且定位成与CMP设备中的抛光垫接触。当垫通过外部驱动力相对于衬底移动(例如旋转)时,载体组件通过将其压靠在CMP抛光垫上而向衬底施加受控压力。与此同时,在晶片和CMP抛光垫之间提供的抛光介质(例如浆料)用于通过垫表面和抛光介质的化学和机械作用抛光和平坦化衬底表面。
CMP抛光中存在的一个挑战为确定何时将衬底抛光至所需程度。已研发出用于确定抛光终点的原位方法。原位光学终点指向技术可分为两种基本类别:(1)在单一波长下监测反射光信号,如来自激光源的光,或(2)从多个波长监测反射光信号。用于光学终点指向的典型波长包含可见光谱(例如400至700nm)、紫外光谱(300至400nm)和红外光谱(例如700至1000nm)中的波长。在监测光信号时,衬底的反射率会随衬底表面处的组分从一种材料变化成另一种材料而改变。然后使用这种反射率变化来检测CMP抛光终点。例如,已经使用光谱仪来获取光谱的可见范围内的反射光的强度光谱,同时使用整个光谱来检测抛光终点。为了适应这些光学终点测量技术,CMP抛光垫已研发成具有终点检测窗口。然而,常规的含聚合物终点检测窗口在曝露于波长为300至425nm的光之后经常展现出非所希望的降解。此外,用于CMP抛光垫的已知终点检测窗口材料在低于400nm的波长下具有低透射率。因此,仍然需要在低于400nm的波长下具有足够透射率,并且在曝露于低于400nm的波长的此类辐射后不会过度降解的终点检测窗口材料。
降低抛光缺陷(如微划痕或颤痕)的低透射率问题的一种解决方案为使用更具脂肪族性的窗口材料。例如,美国专利第7,927,183号,Fukuda等人,公开了一种抛光垫,其中CMP抛光垫的的至少一个窗口部分在波长为300至400nm的整体范围内展现出30%或更大的透光率。Fukuda终点检测窗口材料包括芳香环密度为2重量%或更小的聚氨基甲酸酯树脂。此类含脂肪族异氰酸酯的聚氨基甲酸酯材料可在宽光谱提供改良的透光率。不幸的是,Fukuda中所公开的脂肪族聚氨基甲酸酯终点检测窗口缺乏所需CMP抛光垫应用所需的必要耐用性。特定来说,在从含有植入或放置呈制品中的塞子的窗口材料的模制品切下的CMP抛光垫中,刮削本身会磨损并且损坏窗口表面。此外,刮削的替代方案,如将单独的窗口形成和放置在适于接收其的垫中的凹槽中,已证明实施起来为耗时的并且可能会导致窗口与垫的粘着问题。另外,聚氨基甲酸酯窗口材料通过CMP抛光垫调节而磨损,所述抛光垫调节使用调节盘在垫表面中形成微观纹理以进行抛光。
本发明人致力于提供一种用于CMP抛光垫中的耐用终点检测窗口材料,其在300至400nm下具有可接受的紫外(UV)透射率,同时不会在垫调节中遭受磨损,其改进使用中的窗和垫之间的粘着性,并且使得能够对软垫和硬垫进行快速窗口定制,而无需刮削形成窗口。
发明内容
在本发明的一个方面,终点检测窗口组合物包括具有两个(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体或其环脂肪族氨基甲酸酯寡聚物与脂肪族引发剂,如脂肪族光引发剂或脂肪族热引发剂的反应混合物,所述(甲基)丙烯酸酯端基经由环脂肪族二氨基甲酸酯键合至聚醚、聚碳酸酯或聚酯链,其中氨基甲酸酯大分子单体中的总反应和未反应的异氰酸酯含量在3.3至10重量%,或优选4至9重量%范围内,并且进一步地,其中,所述组合物包括小于5重量%,或优选小于2重量%的未反应的(甲基)丙烯酸酯单体,并且进一步大体上不含未反应的异氰酸酯。
根据本发明的终点检测窗口组合物,其中线性环脂肪族氨基甲酸酯大分子单体的环脂肪族二氨基甲酸酯含有C6至C18,或优选C10至C16环脂肪族基团,优选亚甲基二环己基或二环己基。
根据本发明的终点检测窗口组合物,其中引发剂为光引发剂,优选樟脑醌或其它脂肪族引发剂。
根据本发明的终点检测窗口组合物,其中引发剂的量以反应混合物的总固体重量计,在0.05至0.5重量%,或优选0.08至0.15重量%范围内。
1.在本发明的第二方面,用于抛光选自磁性衬底、光学衬底和半导体衬底中的至少一者的衬底的化学机械(CMP)抛光垫包括CMP抛光垫,优选聚氨基甲酸酯泡沫垫,其具有一个或多个终点检测窗口,其为具有两个(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体或其环脂肪族氨基甲酸酯寡聚物与脂肪族引发剂,优选光引发剂,如樟脑醌的反应混合物的固化产物,所述(甲基)丙烯酸酯端基经由环脂肪族二氨基甲酸酯键合至聚醚、聚碳酸酯或聚酯链,其中氨基甲酸酯大分子单体中的总(反应和未反应的)异氰酸酯含量在3.3至10重量%,或优选4至9重量%范围内,并且进一步地,其中,所述组合物包括小于5重量%,或优选小于2重量%的未反应的(甲基)丙烯酸酯单体,并且大体上不含未反应的异氰酸酯。
2.根据如上述第1项中的本发明的CMP抛光垫,其中线性环脂肪族氨基甲酸酯大分子单体的环脂肪族二氨基甲酸酯含有C6至C18,或优选C10至C16环脂肪族基团,优选亚甲基二环己基或二环己基。
3.根据如上述第1项或第2项中任一项中的本发明的化学机械抛光垫,其中线性环脂肪族氨基甲酸酯大分子单体的环脂肪族二氨基甲酸酯为聚合二醇的活性氢与环脂肪族二异氰酸酯的反应产物,所述环脂肪族二异氰酸酯选自1,4-环己烷二异氰酸酯、4,4′-二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯,或优选亚甲基双环己基异氰酸酯(4,4′-二环己基甲烷二异氰酸酯)。
4.根据如上述第1、2或3项中任一项中的本发明的化学机械抛光垫,其中线性环脂肪族氨基甲酸酯大分子单体包括具有平均分子量为450至2,000,或优选为600至1500的聚醚、聚碳酸酯或聚酯链的聚合二醇的氨基甲酸酯。
5.根据如第4项中的本发明的化学机械抛光垫,其中聚合二醇的氨基甲酸酯包括聚丙二醇的氨基甲酸酯;聚乙二醇;聚丁二醇;含有聚碳酸酯基团的二醇,如脂肪族聚碳酸酯的二醇,例如聚(三亚甲基碳酸酯)的二醇;或其嵌段共聚物或混合物。
6.根据如第1、2、3、4或5项中任一项中的本发明的化学机械抛光垫,其中具有两个(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体包括两至十个或优选2至4个环脂肪族二氨基甲酸酯基团,并且重均分子量为1,000至10,000,或优选1,100至8,000。
7.根据如上述第1、2、3、4、5或6项中任一项中的本发明的化学机械抛光垫,其中具有两个(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体以酯化形式含有羟基官能的(甲基)丙烯酸烷酯。
8.根据如上述第7项中的本发明的化学机械抛光垫,其中羟基官能的(甲基)丙烯酸烷酯选自丙烯酸C1至C4羟烷酯、甲基丙烯酸C1至C4羟烷酯或甘油(甲基)丙烯酸酯,优选甲基丙烯酸C1至C4羟烷酯,如甲基丙烯酸羟乙酯。
9.根据如上述第1、2、3、4、5、6、7或8项中任一项中的本发明的化学机械抛光垫,其中(甲基)丙烯酸酯端基的量在以具有两个(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体的总重量计,4至19重量%,或优选7至15重量%,或更优选9至14重量%范围内。
10.根据如上述第1、2、3、4、5、6、7、8或9项中任一项中的本发明的化学机械抛光垫,其中反应混合物进一步包括含叔胺的共引发剂或促进剂,优选N-甲基二乙醇胺或三亚乙基二胺。
11.根据如上述第1至10项中任一项中的本发明的化学机械抛光垫,其中脂肪族引发剂的量在以反应混合物的总固体重量计,0.05至0.5重量%,或优选0.08至0.15重量%范围内。
12.根据如上述第1至11项中任一项中的本发明的化学机械抛光垫,其中一个或多个终点检测窗口的肖氏D硬度ASTM D2240-15(2015)为20至70或优选20到55。
在本发明的第三方面,制得如上述第1至12项中任一项中的CMP抛光垫的方法包括:形成反应混合物;提供具有一个或多个孔或开口的CMP抛光垫,每个孔或开口具有适于装配终点检测窗口的厚度和外部尺寸,优选地,通过冲压或冲孔其中的开口;将CMP抛光垫放置在平坦表面上,其抛光表面朝上在密封背衬上,所述密封背衬选自可去除的带,如含氟聚合物或聚四氟乙烯衬里的带、带有压敏粘合剂的玻璃板和/或位于CMP抛光垫下方的真空;用反应混合物填充一个或多个开口中的每一个,使得反应混合物与CMP抛光垫的抛光表面齐平1mm以内;在填充的开口上放置透明的平坦膜或玻璃板,或提供惰性的低氧环境,如氮气;并且用紫外(UV)光或发出包括UV光的光的光源固化反应混合物,如持续1至30分钟或优选2至15分钟的时段。
根据前一段所述的制备本发明CMP抛光的方法,其中形成反应混合物包括:干燥聚合二醇;优选在加热至65至85℃的同时,使环脂肪族二异氰酸酯与聚合二醇以1.9∶1至3.2∶1,或优选1.98∶1至2.5∶1的摩尔比反应,以形成线性环脂肪族氨基甲酸酯大分子单体;然后,优选在加热至65至85℃的同时,使羟基官能的(甲基)丙烯酸烷酯与线性环脂肪族氨基甲酸酯大分子单体以0.98∶1至1.4∶1,或优选0.999∶1至1.12∶1的摩尔比反应,以形成具有(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体。
根据前两段所述的制备本发明CMP抛光的方法,其中形成反应混合物进一步包括:优选在不存在任何光或UV辐射的情况下,混合具有(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体与一种或多种引发剂,优选光引发剂,或更优选光引发剂和共引发剂或促进剂,直至得到均相反应混合物。
除非另有指示,否则温度和压力条件为环境温度和标准压力。所述的所有范围均为包括性的并且可加以组合。
除非另有指示,否则含有圆括号的任何术语均替代地指完整术语以及每种替代形式的组合,如同圆括号不存在以及术语没有其一般。因此,术语“(聚)异氰酸酯”是指异氰酸酯、聚异氰酸酯或其混合物。
所有范围均为包括性的并且可加以组合。例如,术语“50至3000cPs的范围,或100或更大cPs”将包含50至100cPs、50至3000cps和100至3000cPs中的每一个。
如本文所用,术语“ASTM”是指宾夕法尼亚州西康舍霍肯ASTM国际组织(ASTMInternational,West Conshohocken,PA)的出版物。
如本文所用,术语“氨基甲酸酯(carbamate)”是指氨基甲酸酯(urethane)或(-RNCOOR′-)基团,其为异氰酸酯基团RNCO与醇R′OH的反应产物。
如本文所用,除非另有指示,否则术语“分子量”或“平均分子量”是指如由其制造商报告的给定材料的配方重量。平均分子量是指针对给定材料中的分子分布,例如聚合物分布报告的分子量。
如本文所用,术语“(甲基)丙烯酸酯端基的量”是指具有这种(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体中存在的“CH2=CHCOO-”或“CH2=CH(CH3)COO-”基团的以重量%为单位的量。
如本文所用,术语“NCO含量”、“%NCO”或“异氰酸酯含量”是指与羟基官能的(甲基)丙烯酸烷酯反应,以在其上形成(甲基)丙烯酸酯端基之前的给定的线性环脂肪族氨基甲酸酯大分子单体中,未反应或游离的异氰酸酯基团的量。
如本文所用,术语反应混合物的“化学计量”是指NCO基团的摩尔当量与给定反应混合物中OH基团的摩尔当量数的比。
如本文所用,术语“反应的异氰酸酯”意指形成氨基甲酸酯并且在氨基甲酸酯中包含NCO部分但不包含异氰酸酯或聚合物二醇的相应烃基或活性氢取代基的任何异氰酸酯基团或其含量。如本文所用,术语“未反应的异氰酸酯”是指二异氰酸酯中的NCOH部分或其含量,其未与活性氢反应。
如本文所用,术语“聚氨基甲酸酯”是指来自双官能或多官能异氰酸酯的聚合产物,例如聚醚脲、聚异氰脲酸酯、聚氨基甲酸酯、聚脲、聚氨基甲酸酯脲、其共聚物和其混合物。
如本文所用,术语“半导体晶片”意图涵盖半导体衬底,如未图案化的半导体或具有图案的半导体衬底;半导体装置;用于各种互连水平的各种封装体,包含单芯片晶片或多芯片晶片;发光二极管(LED)的衬底或需要焊接连接的其它组件。
如本文所用,术语“半导体衬底”定义为意指包括半导体材料的任何构造。半导体衬底包括半导体装置和具有包括半导体装置的有源或可操作部分的一个或多个半导体层或结构的任何衬底。
如本文所用,术语“半导体装置”是指其上有至少一个已经或正在制造的微电子装置的半导体衬底。
如本文所用,术语“肖氏D硬度”与“肖氏A硬度”是如根据ASTM D2240-15(2015),“橡胶特性的标准测试方法-硬度计硬度”,在给定时段后测量的给定材料的硬度值。在分别配备有D或A探针的Rex Hybrid硬度测试仪(伊利诺伊州比弗洛格罗夫的Rex Gauge公司(Rex Gauge Company,Inc.,Buffalo Grove,IL))上测量硬度。针对每个硬度测量堆栈并且重组四个样品;在测试之前,使用ASTM D2240-15(2015)中概述的方法,通过将测试的每个样品在23℃下在50%相对湿度下放置5天来加以调节,以提高硬度测试的可重复性。
如本文所用,术语“SG”或“比重”是指根据本发明的抛光垫或层的矩形切口的重量/体积比。
如本文所用,术语“固体”意指除了水或胺的外的任何材料,其在使用条件下不会挥发,无论其物理状态如何。因此,在使用条件下不挥发的液体反应物被认为成“固体”。
如本文所用,术语“大体上不含未反应的异氰酸酯”意指给定的组合物包括2,000ppm或更小,或优选1,000ppm的任何异氰酸酯基团。
如本文所用,术语“损耗角正切”(tanδ)意指给定材料的值G″/G′,如上述通过DMA所测定。损耗角正切(tanδ)的峰值对应于给定材料的Tg或玻璃转移温度。
如本文所用,给定材料的术语“Tg”或“玻璃转移温度”是指所述材料的损耗角正切在DMA测试中达至峰值所处的温度切割样品,宽6.5mm,长36mm。根据ASTM D5279-13“塑料的标准测试方法:动态机械特性:扭转”(2013),使用ARES G2拉伸流变仪或RheometricScientific RDA3(均来自TA仪器(TA instruments))。分隔间隙为20mm。仪器分析参数设定为100g预载0.2%应变,振荡速度为10rads/sec,并且升温速率为3℃/min,-100℃至150℃。
如本文所用,如本文中和所附权利要求书中使用的给定波长下的关于终点检测窗口的术语“透射率%(DPT)”或“双通透射率”或“DPT”使用下式测定:DPT=(IWSi-IWD)÷(IAsi-IAD)
其中IWsi、IWD、IAsi和IAD使用Verity SP2006光谱干涉仪,包括SD1024F光谱仪、氙气闪光灯和3mm光纤电缆通过以下测量:放置3mm光纤电缆的发光表面抵靠(和垂直于)原点处的终点检测窗口的第一面,引导光通过窗口的厚度TW并且在原点处测量通过窗口厚度TW反射回的光的强度,从大体上平行于第一面的抵靠终点检测窗口的第二面定位的表面;其中IWSi为从原点穿过窗口的光强度的测量值,并且从抵靠窗口的第二面放置的硅覆盖晶片的表面反射通过窗口返回至原点;其中IWD为从原点穿过窗口并且从黑体表面反射并且通过窗口返回至原点的光强度的测量值;其中IASi为从原点穿过与终点检测窗口的厚度TW相等的空气厚度,从与3mm光纤电缆的发光表面垂直放置的硅覆盖晶片的表面反射并且通过空气厚度反射回原点的光强度的测量值;并且其中IAD为在3mm光纤电缆的发光表面处从黑体反射的光强度的测量值。
如本文所用,术语“400nm下的透射率%”或为对于具有400nm波长的光的终点检测窗口所展现出的透射率%。
如本文所用,和所附权利要求书中的术语“抛光介质”涵盖含有颗粒的抛光溶液和含非颗粒的抛光溶液,如无磨料和反应性液体抛光溶液。
如本文所用,术语“UV截止”定义为在200nm至800nm范围内从零透射率至最高透射率的梯度中的半最大值处的波长。
如本文所用,术语“窗口变色”是由加速的UV稳定性测量来测量。对于所述测量,设定为6mm直径的窗口材料的特定直径区域曝露于高强度的UV-A光持续较短时间,峰值强度为365nm。选择强度和持续时间以对应于典型垫寿命期间窗口的UV曝露。例如,如果曝光强度为330+/-30mW/cm2(365nm下),那么45秒曝光对应于典型的垫寿命(在CMP抛光中使用的闪光灯闪光约6,000,000次)。根据分析物窗口的UV曝光区域的窗口透射率与未曝光窗口的透射率的比来测量变色。
如本文所用,术语“重量%”表示重量百分比。
根据本发明,当湿润时,具有(甲基)丙烯酸酯端基的自由基或UV固化的线性环脂肪族聚氨基甲酸酯大分子单体的终点检测窗口在300至400nm的波长下提供高透光率%。在将本发明的终点检测窗口浇铸在CMP抛光垫样品中并且进行调节后,相对柔软的终点检测窗口显示出优异UV透射率。CMP抛光垫的调节通常磨损垫表面并且预期在调节时在其表面上形成纹理时降低终点检测窗口的透明度。在含有光引发剂的UV可固化树脂和热引发剂固化的终点检测窗口中均观测到改进的对垫调节的终点检测窗口响应。此外,本发明的终点检测窗口材料易于作为流体处理并且可分配到CMP抛光垫中的孔中并且在原位固化而不会使终点检测窗口材料变形,如通过在孔下方放置不粘或可移动胶带然后固化。
本发明人已发现,本发明的终点检测窗口的硬度可低于先前的预期,因为其在湿调节下保持不变;本发明的终点检测窗口在湿调节和整个湿CMP抛光时保持耐用。本发明的反应混合物能够形成终点检测窗口,其足够耐用以用于硬化学机械抛光(CMP抛光)垫,如肖氏D硬度ASTM D2240-15(2015)为40至90的垫。由本发明的反应混合物产生较硬(较高Tg)终点检测窗口,所述反应混合物具有在大分子单体链中含有重复碳酸酯基团的聚合二醇的环脂肪族二氨基甲酸酯或较短链的聚合二醇,其以1∶1 NCO∶OH摩尔比升高%NCO。此外,反应混合物能够形成用于软CMP抛光垫的较软(低Tg)终点检测窗口,其肖氏A硬度ASTM D2240-15(2015)将为较好的硬度量度)。由本发明的反应混合物产生较软的终点检测窗口,所述反应混合物包括具有聚醚基团的多元醇次单元或较高分子量,例如1,200或更高的较长链聚合二醇,其以1∶1 NCO∶OH摩尔比降低%NCO。
根据本发明,线性环脂肪族氨基甲酸酯大分子单体中的(甲基)丙烯酸酯端基包含脂肪族丙烯酸酯或甲基丙烯酸酯,其含有比其芳族对应物要少的不饱和度,同时还为改进与聚氨基甲酸酯CMP抛光垫的兼容性的氨基甲酸酯。脂肪族(甲基)丙烯酸酯端基含有有限的不饱和官能团,如双键、羰基或芳香环,并且因此提供光学透明性和良好UV透明度。
根据本发明,通过在配方中使用最少量的异氰酸酯和甲基丙烯酸酯来改进UV光谱的较低波长下的透射率(较低透明度损失(λUV0)),以实现完全固化的终点检测窗口。这可通过将二醇∶异氰酸酯摩尔比设定在优选的1∶2以避免游离的NCO基团,并且通过将异氰酸酯∶(甲基)丙烯酸酯的摩尔比设定为优选的1∶1来实现。然后,最终极限由1∶2二醇∶异氰酸酯摩尔比可能的最低%NCO界定,其通过选择可用的最高二醇分子量来决定;结果为较软终点检测窗口。因此,已发现相对较软的终点检测窗口足够耐用以经受CMP抛光条件,即使对于如氧化物去除的硬垫应用亦为如此。
用于形成根据本发明的线性环脂肪族氨基甲酸酯大分子单体的混合物包括脂肪族聚合二醇,如聚丙二醇,含聚碳酸酯的二醇或聚四甲基乙二醇,其用脂肪族异氰酸酯封端,如4,4′-亚甲基二环己基二异氰酸酯(H12MDI)、异佛尔酮二异氰酸酯(IPDI),任选地超过异氰酸酯。本发明的线性环脂肪族氨基甲酸酯大分子单体经羟基官能的(甲基)丙烯酸烷酯进一步封端,如选自C1至C4丙烯酸羟烷酯、C1至C4甲基丙烯酸羟烷酯或甘油(甲基)丙烯酸酯的一种,优选C1至C4甲基丙烯酸羟烷酯,优选甲基丙烯酸羟乙酯(HEMA)。(甲基)丙烯酸酯可过量存在。然后将调配物用脂肪族光引发剂,如樟脑醌固化,并且优选亦用叔胺基共引发剂或促进剂,如N-甲基二乙醇胺固化。
本发明的反应混合物不含或大体上不含(小于10,000ppm,以反应混合物的总固体重量计)芳族二异氰酸酯或聚异氰酸酯。芳族二异氰酸酯或聚异氰酸酯在400nm或更小的波长下损害由其制得的聚氨基甲酸酯的透射率%。
在根据本发明的用于制得终点检测窗口的反应混合物中,如上文第1至12项中任一项所述,经由改变二醇的分子量处于450至2000g/mol之间,或优选600至1500可调节机械特性。如果太高,那么反应混合物太软,不会完全固化,如粘性所示;如果太低,那么在所得终点检测窗口中透明度较低,因为反应混合物将需要更多的异氰酸酯,因此需要更多的环脂肪族二异氰酸酯。
根据本发明的线性环脂肪族氨基甲酸酯,聚合二醇选自聚碳酸酯二醇,如聚酯二醇与碳酸亚烷酯的任何反应产物,例如聚己内酯多元醇与碳酸亚烷酯的任何反应产物;通过使碳酸亚乙酯与二醇或二醇反应并且使所得反应混合物与有机二羧酸反应得到的聚酯聚碳酸酯多元醇,和通过二醇或聚醚二醇化合物与碳酸亚烷酯的酯交换反应得到的聚碳酸酯多元醇,和(B)(ii)三醇为三羟甲基丙烷(TMP)、具有1至4个丙氧基的丙氧基化三羟甲基丙烷或具有2至6个丙氧基的丙氧基化甘油,优选TMP。
优选地,为了控制具有(甲基)丙烯酸酯端基并且限制多分散性的线性环脂肪族氨基甲酸酯大分子单体的结构,用于制得根据本发明的反应混合物的环脂肪族二异氰酸酯与聚合二醇的反应性较低并且需要一些加热来与聚合二醇进行反应。
根据本发明,(甲基)丙烯酸酯基团的量应足够高,以确保含有其和线性环脂肪族氨基甲酸酯的混合物保持可流动。同时,(甲基)丙烯酸酯基团的量应保持足够低,使得游离(甲基)丙烯酸酯基团不会在终点检测窗口中终结。当较多的异氰酸酯可用于反应和封端时,使用较多的(甲基)丙烯酸酯。
本发明提供一种制造根据本发明的CMP抛光垫的方法,包括:提供具有抛光表面的CMP抛光层;以分开形式由本发明的反应混合物原位形成如上文第1至12项中任一项中的终点检测窗口;在抛光层中提供化学机械抛光垫;其中终点检测窗口经模制以实现其所需尺寸。
根据本发明的终点检测窗口为无气体或无气泡的,并且大体上不含水或优选不含水。因此,在制备线性环脂肪族氨基甲酸酯预聚物之前,将聚合二醇在真空烘箱中干燥。脱气或避免气泡为不必要的,因为反应混合物在两个板或两个密封表面之间在压力下固化,这两个板或两个密封表面与其在其中反应的CMP抛光垫的底部和顶部齐平。
本发明的化学机械抛光垫可进一步包括与抛光层相接的至少一个附加层,如子垫。所述附加层可以具有比所述的CMP抛光垫的抛光层略小的开口或孔,所述开口或孔与抛光垫中的孔洞、孔或开口同心或具有相同中心点,以使得能够进行光学检测同时提供终点检测窗口可搁置并且与的相接的架。优选地,使用粘合剂将抛光层与至少一个附加层相接。粘合剂可选自压敏粘合剂、热熔粘合剂、接触粘合剂和其组合。优选地,粘合剂为热熔粘合剂或压敏粘合剂。更优选地,粘合剂为热熔粘合剂。更优选地,粘合剂是热熔粘合剂。
根据本发明,抛光衬底的方法包括:提供选自磁性衬底、光学衬底和半导体衬底中的至少一者的衬底;提供化学机械(CMP)抛光垫,其具有如上文第1至12项中任一项中的终点检测窗口;在CMP抛光垫的抛光层的抛光表面与衬底之间产生动态接触,以抛光衬底的表面;并且用研磨调节剂调节抛光垫的抛光表面。
更特定来说,本发明提供一种包括以下的抛光衬底的方法:提供具有台板、光源和光传感器的化学机械抛光装置;提供至少一个衬底;提供如上文第1至12项中任一项中的化学机械抛光垫;将化学机械抛光垫安装至台板上;任选地,在抛光表面与衬底之间的界面处提供抛光介质;在抛光表面与衬底之间产生动态接触,其中至少一些材料从衬底去除;并且通过从光源透射光通过终点检测窗口并且通过分析入射在光传感器上的通过终点检测窗口从衬底表面反射回的光来确定抛光终点。
根据本发明,使用终点检测窗口的方法具体为,经由CMP抛光垫用光束照射衬底通过终点检测窗口,并且监测光束反射产生的信号干涉来检测抛光终点的方法。例如通常使用白色LED或白光作为光束,其使用具有波长为300至800nm的光的卤素灯或氘灯。在此类方法中,经由监测晶片表面层厚度的变化,通过知晓表面不均匀的近似深度来确定终点。当这种厚度变化等于不平坦的厚度时,CMP过程结束。因此,通过从光源透射光通过终点检测窗口并且通过分析入射在光电传感器上的通过终点检测窗口从衬底表面反射回的光来确定CMP抛光终点。作为通过这种光学构件和所述方法中使用的抛光垫检测抛光终点的方法,已经提出了各种方法和抛光垫。
在抛光期间,光束经引导通过窗口到达晶片表面,在那里其反射并且通过窗口返回至检测器(例如分光亮度计)。基于返回信号,可以确定衬底表面的特性(例如其上的膜的厚度)以用于终点检测。
本发明的化学机械抛光垫的抛光层具有适于抛光衬底的抛光表面。优选地,所述抛光表面适于抛光选自磁性衬底、光学衬底和半导体衬底中的至少一者的衬底。更优选地,抛光表面适于抛光半导体衬底。
本发明的化学机械抛光垫的抛光层优选由包括选自以下的聚合物的聚合物材料制成:聚碳酸酯、聚砜、尼龙、聚醚、聚酯、聚苯乙烯、丙烯酸类聚合物、聚甲基丙烯酸甲酯、聚氯乙烯、聚氟乙烯、聚乙烯、聚丙烯、聚丁二烯、聚乙烯亚胺、聚氨基甲酸酯、聚醚砜、聚酰胺、聚醚酰亚胺、聚酮、环氧树脂、硅氧烷、EPDM和其组合。优选地,抛光层包括聚氨基甲酸酯。所属领域普通技术人员将理解,选择具有适用于给定抛光操作的化学机械抛光垫的厚度的抛光层。优选地,抛光层的平均厚度为20至150密耳(更优选30至125密耳;最优选40至120密耳)。
优选地,抛光表面具有选自穿孔和凹槽中的至少一者的宏观纹理。穿孔可以从抛光表面部分地延伸或一直延伸穿过抛光层的厚度。优选地,凹槽布置在抛光表面上,使得在抛光期间化学机械抛光垫旋转时,至少一个凹槽扫过经抛光的衬底的表面。优选地,抛光表面具有宏观纹理,所述宏观纹理包含选自由弯曲凹槽、线性凹槽和其组合组成的群组的至少一个凹槽。
优选地,本发明的化学机械抛光垫的抛光层具有适于抛光衬底的抛光表面,其中抛光表面具有包括在其中形成的凹槽图案的宏观纹理。优选地,凹槽图案包括多个凹槽。更优选地,凹槽图案选自凹槽设计。优选地,凹槽设计选自由同心凹槽(可以为圆形或螺旋形)、弯曲凹槽、交叉影线凹槽(例如布置在垫表面上的X-Y网格)、其它常规设计(例如六边形、三角形)、轮胎胎面型图案、不规则设计(例如分形图案)和其组合。更优选地,凹槽设计选自随机槽、同心槽、螺旋槽、交叉影线凹槽、X-Y栅格槽、六边形槽、三角形凹槽、分形凹槽和其组合组成的群组。最优选地,抛光表面具有形成在其中的螺旋槽图案。凹槽轮廓优选地选自具有直侧壁的矩形,或者凹槽截面可以呈“V”形、“U”形、锯齿形和其组合。
现将在以下非限制性实例中详细描述本发明:
在以下实例中,除非另有说明,否则所有的压力均为标准压力(101kPa)并且所有温度均为环境温度或室温(约22至23℃)。在实例中使用以下原材料:
H12MDI:亚甲基双(4-环己基异氰酸酯),又名二环己基甲烷-4,4′-二异氰酸酯;
HEMA;甲基丙烯酸羟乙酯;
聚合二醇1:线性羟基封端的脂肪族聚碳酸酯二醇,重均分子量为约650g/mol,以DesmophenTMC XP 2716(德国勒沃库森的科思创(Covestro AG,Leverkusen,DE))出售;
聚合二醇2:通过丙二醇与环氧丙烷反应产生的线性聚(丙二醇)(PPG),其中丙二醇作为引发剂,1,000MW(重均分子量);(以VoranolTM220-110,密歇根州米德兰的陶氏化学公司,陶氏聚氨基甲酸酯(Dow Polyurethanes,The Dow Chemical Company,Midland,MI)(陶氏)出售);
聚合二醇3:线性聚(丙二醇)(PPG),1,200MW(重均分子量);(以VoranolTM220-094(陶氏)出售);和,
聚合二醇4:线性聚(丙二醇)(PPG),2,000MW(重均分子量);(以VoranolTM220-056(陶氏)出售。
实例1:使用所示材料制得反应混合物。首先通过混合PPG与异氰酸酯组分合成预聚物,加热至80℃,并且使其反应4小时。在合成预聚物后,将HEMA添加至预聚物中,并且通过涡旋混合器以1000RPM混合30秒将两种材料混合,然后置于80℃的烘箱中使其反应24小时。通过傅里叶变换红外(Fourier Transform Infrared;FTIR)光谱法监测反应进程,其中不存在指示完成的NCO峰。二醇∶异氰酸酯和异氰酸酯∶甲基丙烯酸酯的比率列于下表1中。
表1:窗口反应混合物
向含(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体的每一种中添加以紫外线固化树脂的总重量计,0.1重量%樟脑醌和0.2重量%N-甲基二乙醇胺,以形成反应混合物。将每种反应混合物混合直至溶解,然后倒入安装在玻璃板上的金属模具中。然后将每种反应混合物夹在玻璃板和另一玻璃板之间,以防止空气与反应混合物接触。然后将每种反应混合物曝露于来自金属卤化物灯泡的光,强度为105mW/cm2,持续5分钟。随后将所得的板用于透射测试。
透射率测试:将以前一段落中公开的方式制成的每块板从UV固化的板上切成5.12cm×5.12cm(2″×2″)的正方形。从每个切割的正方形中冲孔出直径为1.28cm(0.5″)的圆。测试冲孔圆的透射率,每个正方形中留有空孔用作气隙参考。使用DH-2000TM光源(佛罗里达州达尼丁的海洋光学(Ocean Optics,Dunedin,FL])测试并且测量通过每个冲孔圆的光或辐射的透射率。使用以下等式计算每个冲孔圆或“窗口”的归一化透射率T(λ):
在上面的等式中,T黑暗,空气为没有窗口的“暗”信号(使用空间隔物),设置为零透射点。Tsi,空气为具有硅晶片的透射率,所述硅晶片用作覆盖空间隔物的反射镜。所述值归一化为100%透射率值。T黑暗,窗口为黑暗中窗口的测量值,其反映窗口表面的反射光。TSi,窗口为通过具有硅背衬的窗口透射的光的测量值。透射率%越高越好。300nm下的可接受的透射率结果为10%或更好。
调节测试:准备小CMP抛光垫用于调节测试。以与上面的冲孔圆窗口类似的方式对抛光垫进行冲孔。每种25.6cm(10″)CMP抛光垫材料为由聚氨基甲酸酯泡沫制成的较大垫冲孔而成,其肖氏D硬度为65并且SG为0.95。根据其在小抛光垫中冲孔出1.28cm(0.5″)直径孔洞或孔。将压敏粘合剂(PSA)施加至每个小垫的背侧。然后将小垫PSA侧向下放至玻璃板上。用注射器将每种指定的反应混合物施加至小垫的孔上。然后,将第二玻璃板放置在每个小垫上。根据其使用与上文公开的用于制备板的相同的反应混合物固化方法。然后将含模制窗口的所得小垫从玻璃板去除并且施加至配备有aAK45TM调节盘(得克萨斯州奥斯汀的塞索尔(Saesol,Austin,TX))的ECOMETTM4迷你抛光器(伊利诺伊州布勒夫的标乐(Buehler,LakeBluff,IL))。所指示的小垫中的每一个以10和20分钟的时间间隔在180rpm和35.5N(8lbs)的下压力下调节。对于干透射测试,使每个小垫风干隔夜(约12小时)对于湿透射测试,将一滴水放在小垫中的干燥窗上,并且使表面浸泡5分钟。
表2:透射率%或透明度
如上述表2所示,与实例3中相比,在实例4中通过将二醇∶异氰酸酯比率降低至1∶2,透射率扩展至较低波长(λ)。比较实例2与实例1,看到相同趋势。实例4和实例2比较的表明,与PPG聚合二醇相比,脂肪族聚碳酸酯聚合二醇在300nm下提供改进的透射率。此外,通过将聚合二醇的分子量增加至1200并且保持1∶2二醇∶异氰酸酯比率,如在实例5中,材料的%NCO含量降低至4.8%并且透射率进一步扩展至约260nm。此外,实例1与实例3的材料中游离(甲基)丙烯酸酯基团的存在降低了透射率;将实例2与实例4分别与实例1与实例3进行比较。与实例6的窗口材料相比,发现聚合二醇的MW进一步增加并且因此%NCO降低,使得粘性材料指示不完全固化。这亦引起300nm下的透射率有所降低。
表3:调节和湿润对干燥的效果
如上表3中所示,并且尤其在实例3、实例4和实例5的较软终点检测窗口中,在干燥和湿润状态下调节后UV可固化样品的透射率显示出在湿润状态下透射率有所改进。在实例1中观测到相同的湿透射率。改进的透射率甚至产生类似于实例4的软终点检测窗口,其可预期缺乏耐用性并且在使用期间如经由磨损而丧失透射率。由于终点检测窗口在使用时将为湿的,因此湿透射率的增加将对应于用于终点检测的改进的窗口性能。
Claims (10)
1.一种化学机械(CMP)抛光垫,用于抛光选自包括所述CMP抛光垫的磁性衬底、光学衬底和半导体衬底中的至少一者的衬底,所述CMP抛光垫具有一个或多个终点检测窗,其为具有两个(甲基)丙烯酸酯端基的线性环脂肪族氨基甲酸酯大分子单体或其环脂肪族氨基甲酸酯寡聚物与脂肪族引发剂的反应混合物的固化产物,所述(甲基)丙烯酸酯端基经由环脂肪族二氨基甲酸酯键合至聚醚、聚碳酸酯或聚酯链,其中所述氨基甲酸酯大分子单体中的总异氰酸酯含量在3.3至10重量%范围内,并且进一步地,其中,所述组合物包括少于5重量%的未反应的(甲基)丙烯酸酯单体,并且大体上不含未反应的异氰酸酯。
2.根据权利要求1所述的化学机械(CMP)抛光垫,其中所述线性环脂肪族氨基甲酸酯大分子单体的所述环脂肪族二氨基甲酸酯含有C6至C18环脂肪族基团。
3.根据权利要求1所述的化学机械(CMP)抛光垫,其中所述线性环脂肪族氨基甲酸酯大分子单体的所述环脂肪族二氨基甲酸酯含有C10至C16环脂肪族基团。
4.根据权利要求1所述的化学机械(CMP)抛光垫,其中所述线性环脂肪族氨基甲酸酯大分子单体的所述环脂肪族二氨基甲酸酯为聚合二醇的活性氢与环脂肪族二异氰酸酯的反应产物,所述环脂肪族二异氰酸酯选自1,4-环己烷二异氰酸酯、4,4′-二环己基甲烷二异氰酸酯或异佛尔酮二异氰酸酯。
5.根据权利要求1所述的化学机械(CMP)抛光垫,其中所述线性环脂肪族氨基甲酸酯大分子单体包括具有平均分子量为450至2,000的聚醚、聚碳酸酯或聚酯链的聚合二醇的氨基甲酸酯。
6.根据权利要求5所述的化学机械(CMP)抛光垫,其中所述线性环脂肪族氨基甲酸酯大分子单体包括具有平均分子量为600至1,500的聚醚、聚碳酸酯或聚酯链的聚合二醇的所述氨基甲酸酯。
7.根据权利要求5所述的化学机械(CMP)抛光垫,其中所述聚合二醇包括聚丙二醇;聚乙二醇;聚丁二醇;含聚碳酸酯基团的二醇;或其嵌段共聚物或混合物。
8.根据权利要求1所述的化学机械(CMP)抛光垫,其中具有两个(甲基)丙烯酸酯端基的所述线性环脂肪族氨基甲酸酯大分子单体包括两至十个环脂肪族二氨基甲酸酯基团,并且重均分子量为1,000至10,000。
9.根据权利要求1所述的化学机械(CMP)抛光垫,其中具有两个(甲基)丙烯酸酯端基的所述线性环脂肪族氨基甲酸酯大分子单体以酯化形式含有羟基官能的(甲基)丙烯酸烷酯。
10.根据权利要求1所述的化学机械(CMP)抛光垫,其中所述脂肪族引发剂为光引发剂,并且所述光引发剂的量在以所述反应混合物的总固体重量计,0.05至0.5重量%,或优选0.08至0.15重量%范围内。
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