CN101065458B - 用于高的氮化硅对氧化硅去除速率比率的抛光组合物及方法 - Google Patents
用于高的氮化硅对氧化硅去除速率比率的抛光组合物及方法 Download PDFInfo
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- CN101065458B CN101065458B CN2005800408876A CN200580040887A CN101065458B CN 101065458 B CN101065458 B CN 101065458B CN 2005800408876 A CN2005800408876 A CN 2005800408876A CN 200580040887 A CN200580040887 A CN 200580040887A CN 101065458 B CN101065458 B CN 101065458B
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- H—ELECTRICITY
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
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- H—ELECTRICITY
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Abstract
本发明提供一种化学-机械抛光组合物,包括阳离子磨料、阳离子聚合物、羧酸和水。本发明还提供使用上述抛光组合物化学-机械抛光基底的方法。所述抛光组合物显示出氮化硅去除对氧化硅去除的选择性。
Description
技术领域
本发明涉及抛光组合物和使用该组合物抛光基底的方法。
背景技术
作为隔离半导体器件的各元件的方法,大量关注集中在浅槽隔离(shallow trench isolation)(STI)工艺,其中在硅基底上形成氮化硅层,通过蚀刻或光刻法形成浅槽,并沉积介电层以填充该槽。由于以这种方式形成的槽或线的深度的变化,一般必须在基底顶部上沉积过量的介电材料以确保完全填充所有槽。
然后一般地通过化学-机械平面化工艺除去过量的介电材料(例如,氧化物)以暴露氮化硅层。当氮化硅层暴露时,暴露于化学-机械抛光系统的最大面积的基底包含氮化硅,其然后必须被抛光以获得高度平坦且均匀的表面。通常,过去的实践着重于对氧化物抛光优先于氮化硅抛光的选择性。因此,由于在氮化硅层暴露时总抛光速率已下降,在化学-机械平面化工艺的过程中氮化硅层用作停止层。然而,由于在下一代器件中氧化物线宽度变得越来越小,在一些情况下,期望使用具有氮化硅对氧化物抛光的选择性的抛光系统,以最小化在基底表面上形成的氧化物线的缺陷。
用于平面化或抛光基底表面的组合物和方法是本领域公知的。抛光组合物(也称为抛光浆料)一般地包含在液体载体中的磨料并通过将表面与充满着抛光组合物的抛光垫接触而施用于表面。一般的磨料包括二氧化硅、氧化铈、氧化铝、氧化锆和氧化锡。例如,美国专利5,527,423描述了一种通过将表面与抛光浆料接触而化学-机械抛光金属层的方法,所述抛光浆料包含在水性介质中的高纯度细金属氧化物颗粒。抛光组合物一般与抛光垫(例如,抛光布或盘)一起使用。合适的抛光垫描述在美国专利6,062,968、6,117,000和6,126,532中,其公开了具有开孔多孔网络的烧结聚氨酯抛光垫的使用,和在美国专利5,489,233中,其公开了具有表面结构或图案的固体抛光垫的使用。代替悬浮于抛光组合物中或除了悬浮于抛光组合物中之外,磨料可以引入抛光垫中。美国专利5,958,794公开了固定磨料的抛光垫。
已知若干种用于包含低介电常数材料(例如,氧化物)的基底的化学-机械抛光组合物。例如,美国专利6,043,155公开了用于无机和有机绝缘膜的基于氧化铈的浆料,具有二氧化硅相对氮化硅抛光的选择性。美国专利申请公开2002/0168857A1公开了一种制造半导体器件的方法,其中二氧化硅沉积在用槽图案化的氮化硅膜上,且然后进行两段式化学-机械抛光工艺以选择地去除覆盖的二氧化硅,从而留下填满二氧化硅的槽。由此,本领域仍需要对氮化硅相对下伏介电成分的抛光具有相反选择性的抛光组合物和方法。
本发明提供这样的组合物和方法。本发明的这些和其它优点以及另外的发现特征将由这里提供的发明描述变得明晰。
发明内容
本发明提供一种化学-机械抛光组合物,包括:(a)阳离子磨料,(b)选自由以下构成的组的阳离子聚合物:(1)0.1ppm至50ppm阳离子均聚物,(2)0.1ppm至50ppm阳离子共聚物,该阳离子共聚物包含至少一种阳离子单体和至少一种非离子单体,其中至少一种阳离子单体以摩尔计占阳离子共聚物的超过50%,和(3)0.1ppm至200ppm阳离子共聚物,该阳离子共聚物包含至少一种阳离子单体和至少一种非离子单体,其中至少一种阳离子单体以摩尔计占共聚物的50%或更少,以及(c)水,其中抛光组合物的pH值为7或更少。本发明进一步提供一种化学-机械抛光基底的方法,包括(i)将基底与抛光垫和化学-机械抛光组合物接触,该化学-机械抛光组合物包括:(a)阳离子磨料,(b)选自由以下构成的组的阳离子聚合物:(1)0.1ppm-50ppm的阳离子均聚物,(2)0.1ppm-50ppm的阳离子共聚物,该阳离子共聚物包括至少一种阳离子单体和至少一种非离子单体,其中所述至少一种阳离子单体以摩尔计占阳离子共聚物的超过50%,和(3)0.1ppm-200ppm的阳离子共聚物,该阳离子共聚物包括至少一种阳离子单体和至少一种非离子单体,其中所述至少一种阳离子单体以摩尔计占共聚物的50%或更少,以及(c)水;(ii)相对于基底移动抛光垫,在其之间具有所述化学-机械抛光组合物,以及(iii)研磨基底的至少一部分来抛光基底。
具体实施方式
本发明提供化学-机械抛光组合物,其包括(a)阳离子磨料,(b)阳离子聚合物(例如,均聚物或共聚物),和(c)水。该抛光组合物期望地容许在平面化包含氮化硅和二氧化硅的基底的过程中选择性去除氮化硅优先于二氧化硅。
该抛光组合物包含阳离子磨料。在本发明的范围内,阳离子磨料包括在抛光组合物的pH下具有正表面电荷的磨料颗粒。磨料颗粒的表面电荷可随pH变化。期望的阳离子磨料为阳离子金属氧化物磨料。优选,阳离子金属氧化物磨料选自二氧化铈、氧化铝、氧化锆、二氧化钛、掺杂的硅石、及其混合物。更优选,磨料为二氧化铈或氧化锆。最优选,磨料为二氧化铈。
阳离子金属氧化物磨料可以通过任意适宜的方法制备。用于制备在本发明的范围内有用的阳离子金属氧化物磨料颗粒的适宜方法包括火成法和水热法。在火成法中可由挥发性前体(例如,金属卤化物)通过在高温火焰(H2/空气或H2/CH4/空气)中前体的水解和/或氧化制造热解金属氧化物以制备所关心的金属氧化物。热解金属氧化物可由非挥发性前体通过将该前体溶解或分散在适宜的溶剂例如水、醇或基于酸的溶剂中来制备。可使用微滴产生器将包含前体的溶液喷射到高温火焰中,并随后可收集金属氧化物。一般的微滴产生器包括双流体雾化器、高压喷雾喷嘴和超声雾化器。
阳离子金属氧化物磨料可以是掺杂的硅石,例如,氧化铝-掺杂的硅石。通常地,通过共发烟(co-fuming)法制备氧化铝-掺杂的硅石,其中将四氯化硅和氯化铝的混合物进行气相水解,由此形成包含氧化铝和二氧化硅的复合颗粒。通常地,在硅石颗粒的等电点之上的pH(例如,pH 3.5或更高)时,硅石颗粒具有负的或阴离子的表面电荷。合适的第二种金属氧化物(例如,氧化铝)的存在使掺杂的硅石颗粒变为阳离子性。期望地,0.01重量%或更多(例如,0.2重量%或更多,或0.3重量%或更多)的第二种金属氧化物存在于掺杂的硅石颗粒中。优选地,2重量%或更少(例如,1.5重量%或更少,或1重量%或更少)的第二种金属氧化物存在于掺杂的硅石颗粒中。氧化铝-掺杂的硅石的实例为可以从Degussa获得的MOX 80和MOX 170产品(两者皆包含1%氧化铝)。
如上所述,阳离子金属氧化物磨料可以通过水热法制备。在水热法中,具有与期望的金属氧化物相同的氧化水平的金属盐(例如,硝酸盐)溶于水中,用碱(例如,氢氧化铵)处理,并经历高温和高压状态。水热法将金属盐转化为相应的金属氧化物。
或者,在水热法中,具有比期望的金属氧化物低的氧化水平的金属盐可与氧化剂一起使用。例如,美国专利5,389,352公开了制备氧化铈的方法,该方法包括形成由水溶性的三价铈盐和氧化剂组成的水溶液,然后将该溶液作为液相老化一段时间,在该过程中三价铈盐氧化为氧化铈颗粒。
在水热法过程中,包含第二种金属盐的掺杂剂可以加入到第一金属盐中,以制备包含第二金属化合物的掺杂金属氧化物。优选的掺杂剂选自镍、钴、锰、铁、铝、铬和锌。在水热法进行过程中,任意适宜量的第二金属盐可以加入到第一金属盐中。如果需要掺杂剂,在水热法过程中,一般1ppm或更多(例如,10ppm或更多,或50ppm或更多,或甚至100ppm或更多)的掺杂剂可加入到第一金属盐中。优选地,在水热法过程中,10000ppm或更少(例如,5000ppm或更少1000ppm或更少,或500ppm或更少)的掺杂剂可以加入到第一金属盐中。
阳离子磨料颗粒的期望的平均粒度(典型地,围绕颗粒的最小球体的平均粒径)为至少10nm或更大(例如,10-1000nm)。优选地,磨料颗粒的平均粒度为50nm或更大(例如,50至500nm,或甚至50至300nm)。更优选地,磨料颗粒的平均粒度为1000nm或更少(例如,800nm或更少,或500nm或更少,或甚至300nm或更少)。
阳离子磨料可以任意适宜的量存在于抛光组合物中。阳离子磨料存在于抛光组合物中的量一般为0.001重量%或更多(例如,0.005重量%或更多,或0.01重量%或更多),基于液体载体和溶解或悬浮其中的任何组分的重量。阳离子磨料存在于抛光组合物中的量优选为5重量%或更少(例如,2重量%或更少,或1重量%或更少),基于液体载体和溶解或悬浮其中的任何组分的重量。更优选地,阳离子磨料存在于抛光组合物中的量为0.01重量%-1重量%。
磨料期望地悬浮于抛光组合物中,更具体地,悬浮在抛光组合物的水组分中。当磨料悬浮于抛光组合物中时,磨料优选为胶体稳定的。术语胶体是指磨料颗粒在液态载体中的悬浮液。胶体稳定是指悬浮液随时间的保持。在本发明的范围内,如果当磨料置于100ml量筒并不搅动放置2小时时,量筒底部50ml中的颗粒浓度([B],单位为g/ml)与量筒上部50ml中的颗粒浓度([T],单位为g/ml)之间的差除以磨料组合物中颗粒的起始浓度([C],单位为g/ml)小于或等于0.5(即,{[B]-[T]}/[C]≤0.5),则磨料被认为是胶体稳定的。[B]-[T]/[C]的值期望小于或等于0.3,且优选小于或等于0.1。
所述抛光组合物包含阳离子聚合物。阳离子聚合物可以为任意适宜的阳离子聚合物。阳离子聚合物可以为阳离子均聚物或阳离子共聚物。阳离子聚合物的目的是,对于包括二氧化硅和氮化硅的基底,与氮化硅的去除速率相比降低二氧化硅的去除速率,这是通过本发明的抛光组合物可实现的。不希望受到任何特别理论的束缚,认为阳离子聚合物优先地吸附在二氧化硅表面上。认为阳离子聚合物在二氧化硅表面上形成保护膜来抑制所述抛光组合物与二氧化硅表面的接触,由此在有利地不显著影响氮化硅去除速率的同时降低二氧化硅的去除速率。
阳离子均聚物可以是任意适宜的基本上由阳离子单体重复单元组成的阳离子均聚物。例如,阳离子聚合物可以是任意适宜的基本上由包括氮的阳离子重复单元组成的阳离子聚合物,该阳离子包括但不限于包含碱性胺基和季铵化胺基的单体。碱性胺基或季铵化胺基可以是非环式的或引入环结构中。为了改变阳离子聚合物的溶解度、粘度或其它物理参数,对阳离子聚合物通过烷基化、酰化、乙氧基化或其它化学反应进一步改性也是合适的。优选地,阳离子聚合物选自:聚乙烯亚胺、乙氧基化聚乙烯亚胺、聚二烯丙基二甲基卤化铵、聚(酰氨基胺)、聚(甲基丙烯酰氧乙基三甲基铵)氯化物、聚(甲基丙烯酰氧乙基二甲基苄基铵)氯化物、聚(乙烯基吡咯烷酮)、聚(乙烯基咪唑)、聚(乙烯基吡啶)和聚(乙烯基胺)。更优选地,阳离子聚合物为聚乙烯亚胺。
阳离子聚合物可以是任意适宜的基本上由包含锍基团的单体组成的阳离子均聚物。锍基团包含用三个碳原子取代的硫原子,硫原子带有正电荷。包含锍基团的阳离子聚合物和阳离子单体的非限制性实例公开在美国专利4,528,384中。
阳离子聚合物可以是任意适宜的基本上由包含鏻基团的单体组成的阳离子均聚物。鏻基团包含用四个碳原子取代的磷原子,磷原子带有正电荷。包含鏻基团的阳离子聚合物和阳离子单体的非限制性实例公开在美国专利5,439,617中。
阳离子均聚物可以是任意适宜的具有净正电荷的过渡金属低聚物。例如,铝化合物可以形成阳离子低聚物质例如″聚-氯化铝″,其是指一类可溶性铝制品,其中氯化铝已部分地与碱反应,且其包含一些铝的高阳离子性低聚物。过渡金属低聚物的其它非限制性实例可在,例如,“ComprehensiveOrganometallic Chemistry II”,E.W.Abelm,F.G.A.Stone,and G.Wilkinson,eds.,Pergamon Press(1995)中找到。
阳离子聚合物可以是包含至少一种阳离子单体和至少一种非离子单体的共聚物,其中至少一种阳离子单体以摩尔计占共聚物的超过50%或以摩尔计占共聚物的50%或者更少。阳离子和非离子单体可以是任意适宜的阳离子和非离子单体。
例如,阳离子单体可以是任意适宜的含氮的阳离子单体,包括但不限于包含碱性胺基和季铵化胺基的单体。碱性胺基或季铵化胺基可以是非环式的或引入环结构中。在本发明的范围内有用的阳离子单体的实例包括但不限于氮丙环、二烯丙基二甲基卤化铵、甲基丙烯酰氧乙基三甲基氯化铵、甲基丙烯酰氧乙基二甲基苄基氯化铵、2-氨基乙基甲基丙烯酸酯、N-(3-氨基丙基)甲基丙烯酸酯、乙烯基咪唑、乙烯基吡啶、乙烯基胺和酰氨基胺。阳离子单体可以包含锍和鏻基团。适于引入共聚物的锍基团和鏻基团可以是如上所述的。优选地,阳离子单体是氮丙环(ethyleneimine)。
非离子单体,例如,可以是任意适宜的非离子单体,包括但不限于乙烯、丙烯、环氧乙烷、环氧丙烷、苯乙烯、表氯醇、丙烯酰胺、和它们的混合物。
阳离子共聚物可以由任何合适的技术制备。例如,可以通过自由基、阳离子、阴离子或缩聚聚合制备共聚物。共聚物可以是无规共聚物、交替共聚物、周期共聚物、嵌段共聚物(例如,AB、ABA、ABC等)、接枝共聚物、或梳型共聚物。为了改变共聚物的溶解度、粘度或其它物理参数,可通过烷基化、酰化、乙氧基化或其它化学反应进一步改性阳离子共聚物。
阳离子聚合物(例如,阳离子均聚物或共聚物)可以具有任意适宜的平均分子量。优选地,阳离子聚合物的平均分子量为1,000道尔顿或更多(例如,5,000道尔顿或更多,或10,000道尔顿或更多,或50,000道尔顿或更多,或甚至100,000道尔顿或更多)。
阳离子聚合物在抛光组合物中的量取决于阳离子聚合物的本性。当阳离子聚合物是阳离子均聚物或包含至少一种阳离子单体和至少一种非离子单体的阳离子共聚物,其中阳离子单体以摩尔计占阳离子共聚物的超过50%时,则阳离子聚合物在抛光组合物中的量基于抛光组合物的总重量为0.1ppm至50ppm。一般地,阳离子聚合物的量为0.5ppm或更多(例如,1ppm或更多)。因此,阳离子聚合物在抛光组合物中的量可以是0.5ppm至45ppm(例如,1ppm至40ppm),或2ppm至35ppm(例如,3ppm至30ppm)。当阳离子聚合物是包含至少一种阳离子单体和至少一种非离子单体的阳离子共聚物,其中阳离子单体以摩尔计占阳离子共聚物的50%或更少时,则阳离子聚合物在抛光组合物中的量基于抛光组合物的总重量为0.1ppm至200ppm。在这样的实施方案中,一般地阳离子聚合物的量为0.1ppm至200ppm(例如,5ppm至200ppm),或10ppm至150ppm(例如,20ppm至100ppm)。如果阳离子聚合物在抛光组合物中的量太低,则观察不到由阳离子聚合物的添加产生的效果。如果阳离子聚合物在抛光组合物中的量太高,则发生抑制氮化硅的去除,由此氮化硅的去除相对二氧化硅去除的比率降低,并且对于基底的总抛光速率降至有用的水平之下。
本发明的阳离子均聚物和阳离子共聚物实现在包含氮化硅和氧化硅的基底的化学-机械抛光中氮化硅优先于氧化硅的去除的类似选择性。通常地,与包含阳离子均聚物的抛光组合物相比,需要使用在抛光组合物中较高浓度的阳离子共聚物以实现类似的抛光性能。尽管在抛光组合物中与阳离子均聚物相比较大量阳离子共聚物的使用的需要可能存在缺点,例如成本和供应要求,但在制造过程中具有较高的阳离子共聚物浓度的抛光组合物的配料中可实现的较高的精确度在一些情况下可是有利的。
抛光组合物的pH值为7或更少(例如,6或更少)。优选地,抛光组合物的pH为1或更多(例如,2或更多,3或更多)。更优选地,抛光组合物的pH值为4至7(例如,4至6)。抛光组合物任选地包含pH调节剂,例如,氢氧化钾、氢氧化铵、烷基氢氧化铵和/或硝酸。抛光组合物可任选地包含pH缓冲系统,例如,乙酸铵或柠檬酸二钠。许多这样的pH缓冲系统是本领域公知的。
抛光组合物任选地进一步包括羧酸。在抛光组合物中有用的羧酸包括单羧酸和二羧酸及其盐。羧酸可以进一步包含选自以下的官能团:羟基、羰基、卤素、胺和含氮的芳族杂环。优选地,羧酸选自乙酸、丙酸、丁酸、苯甲酸、甲酸、丙二酸、琥珀酸、酒石酸、乳酸、邻苯二甲酸、水杨酸、邻氨基苯甲酸、柠檬酸、乙醇酸、富马酸、月桂酸、丙酮酸、硬脂酸、氯乙酸、二氯乙酸、2-吡啶羧酸、2-哌啶羧酸、甘氨酸、丙氨酸、3-氨基丙酸、4-氨基丁酸、其衍生物、其盐、及其组合。
抛光组合物可以包含任意适宜量的羧酸,且当存在时一般地包括10ppm或更多(例如,10-1000ppm)。优选地,羧酸存在于抛光组合物中的量为1000ppm或更少(例如,800ppm或更少,或600ppm或更少)。
应能理解,上述羧酸可以盐(例如,金属盐、铵盐等)、酸或其部分盐的形式存在。例如,酒石酸盐包括酒石酸、及其单盐和双盐。此外,包括碱性官能团的羧酸可以碱性官能团的酸式盐形式存在。例如,甘氨酸包括甘氨酸及其一酸价盐。此外,一些羧酸可以同时作为酸和螯合剂(例如,某些氨基酸等)。
羧酸在抛光组合物中起到若干作用。羧酸与阳离子聚合物的联合通过乙酯二氧化硅去除赋予使用本发明抛光组合物观察到的对于氮化硅去除优先于二氧化硅去除的选择性。羧酸进一步起到缓冲系统的pH以及改善抛光组合物的胶体稳定性的作用。
抛光组合物任选地进一步包括一种或多种其它添加剂。这些添加剂包括任意适宜的表面活性剂和/或流变控制剂,包括粘度增强剂和凝结剂(例如,聚合物流变控制剂,如,举例来说,氨基甲酸酯聚合物),包含一个或多个丙烯酸类子单元(subunit)的丙烯酸酯(例如,乙烯基丙烯酸酯和苯乙烯丙烯酸酯)、和其聚合物、共聚物、和低聚物、及其盐。适宜的表面活性剂包括,例如,阳离子表面活性剂、阴离子表面活性剂、阴离子聚电解质、非离子表面活性剂、两性表面活性剂、氟化表面活性剂、其混合物等。
抛光组合物任选地进一步包括杀生物剂。杀生物剂可以是任意适宜的杀生物剂,例如,异噻唑啉酮杀生物剂。杀生物剂在抛光组合物中的量一般为1ppm至500ppm,且优选地为10ppm至200ppm。
可以通过任意合适技术制备所述抛光组合物,许多合适技术为本领域技术人员公知。可以通过间歇式或连续式工艺制备所述抛光组合物。通常地,可以通过任意的顺序将其组分组合制备所述抛光组合物。这里所用的术语“组分”包括单独的成分(例如,酸、碱等)和各成分(例如,酸、碱、表面活性剂等)的任意组合。
例如,阳离子磨料可以分散在水中。然后可加入阳离子均聚物或共聚物和任选的羧酸,并通过能够将组分引入抛光组合物中的任意方法混合。抛光组合物可以在使用前制备,刚好在使用之前(例如使用前1分钟内,或使用前1小时内,或使用前7天内),一种或多种组分如阳离子均聚物或共聚物加入到抛光组合物中。pH可以在任意适宜的时候调节。抛光组合物还可在抛光操作过程中在基底的表面上通过将组分混合而制备。
此外抛光组合物可以作为浓缩物提供,浓缩物在使用前用适量的水稀释。在该实施方案中,抛光组合物浓缩物可以包含阳离子磨料、阳离子均聚物或共聚物、羧酸和水,其量使得在用适量的水稀释浓缩物时,抛光组合物的每一组分存在于抛光组合物中的量处于上述的每一组分的适宜范围之内。例如,阳离子磨料、阳离子均聚物或共聚物、和羧酸可各自以2倍(例如,3倍、4倍或5倍)于上述各个组分浓度的量存在于浓缩物中,使得当用等量的水(例如,分别以2等份水、3等份水或4等份水)稀释时,每一组分存在于抛光组合物中的量处于上述各组分的范围之内。此外,本领域技术人员应明白,浓缩物可以包含存在于最终抛光组合物中的适当分数的水以确保阳离子均聚物或共聚物、任选的羧酸和其它适宜的添加剂至少部分地或完全地溶于浓缩物中。
本发明还提供化学-机械抛光基底的方法,包括(i)将基底与抛光垫和本文所述的化学-机械抛光组合物接触,(ii)相对于基底移动抛光垫片,在其中间有化学-机械抛光组合物,以及(iii)研磨基底的至少一部分以抛光基底。
本发明的方法可用于抛光任意适宜的基底,且尤其适用于抛光包含氮化硅和二氧化硅的基底。适宜的基底包括用于半导体工业的晶片。抛光组合物特别地适合于平面化或抛光已经过浅槽隔离(STI)处理的基底。STI处理一般地包括提供硅家底,其上沉积有氮化硅层。在光刻法后将槽蚀刻在包含氮化硅覆盖层的基底上,并且过量的二氧化硅沉积其上。然后将基底进行平面化直到氮化硅表面层被基本上去除,使得保留在槽中的二氧化硅与槽的边缘大致水平。期望地,在STI处理中使用本发明的抛光组合物进行平面化或抛光,优选地使得基本上去除氮化硅且将二氧化硅适当地平面化,而没有过度侵蚀槽内的二氧化硅。
本发明的抛光方法特别地适于与化学-机械抛光(CMP)设备结合使用。一般地,所述设备包括压板,其在使用时移动且具有由于轨道、线性或圆周运动产生的速度;抛光垫,其与压板接触,且随压板移动而移动;以及载体,其通过接触抛光垫表面并相对其移动而保持待抛光的基底。通过将基底与抛光垫和本发明的抛光组合物接触,然后相对于基底移动抛光垫片来进行基底的抛光,以研磨基底的至少一部分从而将基底抛光。
可用所述化学-机械抛光组合物与任意适宜的抛光垫(例如,抛光表面)来平面化或抛光基底。适宜的抛光垫包括,例如,纺织物和无纺织物抛光垫。此外,适宜的抛光垫可以包含任意适宜的不同密度、硬度、厚度、可压缩性、对压缩的回弹性和压缩模量的聚合物。适宜的聚合物包括,例如,聚氯乙烯、聚氟乙烯、尼龙、碳氟化合物、聚碳酸酯、聚酯、聚丙烯酸酯、聚醚、聚乙烯、聚酰胺、聚氨酯、聚苯乙烯、聚丙烯、其共形成产物、以及其混合物。
期望地,CMP设备进一步包括原位抛光终点检测系统,其许多是本领域已知的。在本领域已知有通过分析自工件表面反射的光或其它辐射来检查和监测抛光过程的技术。这种方法描述在例如美国专利5,196,353、美国专利5,433,651、美国专利5,609,511、美国专利5,643,046、美国专利5,658,183、美国专利5,730,642、美国专利5,838,447、美国专利5,872,633、美国专利5,893,796、美国专利5,949,927和美国专利5,964,643中。期望地,对待抛光工件的抛光过程进度的检查或监测使得能够确定抛光终点,即,确定什么时候终止对具体工件的抛光过程。
下列实施例进一步阐述本发明但是,当然,不应该认为是以任何方式限制它的范围。
在下面的实施例中,抛光实验通常地包括使用50.8cm(20英寸)直径的抛光工具,基底对抛光垫的向下压力27.6kPa(4psi),60rpm的压板速度,56rpm的载体速度,200mL/分钟的抛光组合物流速,以及使用同心槽形CMP垫的原位调节。
实施例1
该实施例表明用本发明平抛光组合物观测到的增加平均分子量为2000道尔顿的聚乙烯亚胺的量对氮化硅和二氧化硅层的去除速率的影响。
分别地用六种不同的抛光组合物(组合物1A-1F)将类似的氮化硅层和二氧化硅层抛光。组合物各自包含在pH 4.9下在水中的0.4重量%的二氧化铈和400ppm的4-氨基丁酸。组合物1A(对照)不包含另外的成分(例如,不含聚乙烯亚胺)。组合物1B-1F(本发明)进一步包含如表1给出的不同量的聚乙烯亚胺。在使用所述抛光组合物后,测定氮化硅(“氮化物”)和二氧化硅(“氧化物”)的去除速率,并计算选择性,定义为氮化硅对二氧化硅去除速率的比率。结果在表1中列出。
表1:增加聚乙烯亚胺的量对氮化硅和氧化硅去除速率的影响
抛光组合物 | 聚乙烯亚胺(ppm) | 氮化物速率(/分钟) | 氧化物速率(/分钟) | 选择性 |
1A(对照) | 无(对照) | 950 | 640 | 1.5 |
1B(本发明) | 1 | 970 | 310 | 3.1 |
1C(本发明) | 2 | 930 | 180 | 5.2 |
1D(本发明) | 4 | 920 | 90 | 10.2 |
1E(本发明) | 6 | 350 | 60 | 5.8 |
1F(本发明) | 10 | 24 | 10 | 2.4 |
从表1中所列数据显而易见的是,聚乙烯亚胺的量从无增加到4ppm导致的氮化硅去除速率可以忽略,而二氧化硅的去除速率降低约86%。定义为氮化硅对氧化硅去除速率比率的选择性从没有聚乙烯亚胺存在于抛光组合物中的1.5提高到4ppm聚乙烯亚胺存在于抛光组合物中的10.2。增加聚乙烯亚胺在抛光组合物中的量至10ppm导致对于两层的去除速率的明显降低。因此,该实施例的结果表明氮化硅和二氧化硅的去除速率与阳离子聚合物在本发明的抛光组合物中的量的相关性。
实施例2
该实施例表明用本发明的抛光组合物观测到的不同的阳离子聚合物对氮化硅和二氧化硅层的去除速率的影响。
六种不同的抛光组合物分别地用于化学-机械抛光类似的氮化硅层和二氧化硅层(组合物2A-2F)。组合物各自包含在pH 4.9下在水中的0.4重量%的二氧化铈和400ppm的4-氨基丁酸。组合物2A(对照)不包含另外的成分(例如,不含阳离子聚合物)。组合物2B(本发明)另外包含8.5ppm的聚乙烯亚胺(平均分子量为25,000道尔顿)。组合物2C(本发明)另外包含15ppm的聚二烯丙基二甲基氯化铵(平均分子量为60,000道尔顿)。组合物2D(本发明)另外包含10ppm的80%乙氧基化聚乙烯亚胺(平均分子量为50,000道尔顿)。组合物2E(发明)另外包含25ppm的聚酰氨基胺(平均分子量为1,000,000道尔顿)。在使用所述抛光组合物后,测定氮化硅(“氮化物”)和二氧化硅(“氧化物”)的去除速率,并计算选择性,定义为氮化硅对二氧化硅去除速率之比。结果在表2中列出。
表2:不同阳离子聚合物对氮化硅和二氧化硅去除速率的影响
抛光组合物 | 氮化物速率(/分钟) | 氧化物速率(/分钟) | 选择性 |
2A(对照) | 1012 | 558 | 1.8 |
2B(本发明) | 861 | 33 | 26 |
2C(本发明) | 876 | 65 | 13 |
2D(本发明) | 1023 | 85 | 12 |
2E(本发明) | 1200 | 156 | 7.7 |
从表2所列结果显而易见的是,同对照抛光组合物相比,所有本发明抛光组合物降低与氮化硅去除速率相比的氧化硅的去除速率,同时保持氮化硅的高去除速率。同对照抛光组合物相比,使用平均分子量为25,000道尔顿的聚乙烯亚胺(抛光组合物2B)显著地降低二氧化硅去除速率约17倍,同时降低氮化硅去除速率仅仅约15%。因此,该实施例的结果表明通过本发明的抛光组合物可实现的对氮化硅层和二氧化硅层的去除速率的影响。
实施例3
该实施例表明用本发明抛光组合物观测到的包含不同比例的阳离子单体和非离子单体的阳离子聚合物对氮化硅和二氧化硅层的去除速率的影响。
分别地用五种不同的抛光组合物(组合物3A、3B、3C、3D和3E)将类似的氮化硅层和二氧化硅层化学-机械抛光。组合物各自包含在水中的二氧化铈和丙烯酰胺与二烯丙基-二甲基氯化铵(“DADMAC”)的共聚物,其中DADMAC单元在共聚物中的摩尔分数不同。组合物3A包含20ppm的与丙烯酰胺的5摩尔%DADMAC共聚物。组合物3B包含20ppm的与丙烯酰胺的15摩尔%DADMAC共聚物。组合物3C包含20ppm的与丙烯酰胺的30摩尔%DADMAC共聚物。组合物3D包含20ppm的与丙烯酰胺的100摩尔%DADMAC共聚物(即,DADMAC均聚物)。组合物3E包含100ppm的与丙烯酰胺的30摩尔%DADMAC共聚物。在使用所述抛光组合物后,测定氮化硅(“氮化物”)和二氧化硅(“氧化物”)的去除速率,并计算选择性,定义为氮化硅对二氧化硅去除速率的比值。结果在表3中列出。
表3:阳离子聚合物对于氮化硅和二氧化硅去除速率的影响
抛光组合物 | 阳离子聚合物的量(ppm) | 阳离子单体摩尔% | 氮化物速率(/分钟) | 氧化物速率(/分钟) | 选择性 |
3A | 20 | 5 | 1008 | 2000 | 0.5 |
3B | 20 | 15 | 1005 | 1732 | 0.6 |
3C | 20 | 30 | 1009 | 851 | 1.2 |
3D | 20 | 100 | 497 | 56 | 8.9 |
3E | 100 | 30 | 1032 | 63 | 16.4 |
从表3所列结果显而易见的是,在共聚物中将阳离子单体的摩尔分数从5摩尔%提高到30摩尔%(抛光组合物3A-3C)导致氧化物去除速率约2.4倍的降低,同时对氮化物速率的影响可以忽略。同使用包括阳离子共聚物的组合物相比,使用相同量的相应阳离子均聚物(抛光组合物3D)降低氮化物的去除速率约2倍,但是将选择性提高至8.9。使用更大量(即,100ppm)的30摩尔%DADMAC-丙烯酰胺共聚物(抛光组合物3E)将选择比提高至16.4,而对氮化物速率的影响可以忽略。因此,该实施例的结果表明通过本发明的抛光组合物可实现的对氮化硅层和二氧化硅层的去除速率的影响。
Claims (14)
1.一种抛光包含氮化硅和氧化硅的基底的化学-机械抛光组合物,包括:
(a)阳离子磨料,
(b)选自以下的阳离子聚合物:
(1)0.1ppm-50ppm的阳离子均聚物,所述阳离子均聚物选自:聚乙烯亚胺、乙氧基化聚乙烯亚胺、聚二烯丙基二甲基卤化铵、聚(酰氨基胺)、聚(甲基丙烯酰氧乙基三甲基铵)氯化物、聚(甲基丙烯酰氧乙基二甲基苄基铵)氯化物、聚(乙烯基吡咯烷酮)、聚(乙烯基咪唑)、聚(乙烯基吡啶)、聚(乙烯基胺)以及聚氯化铝;
(2)0.1ppm-50ppm的阳离子共聚物,该阳离子共聚物包含至少一种阳离子单体和至少一种非离子单体,其中所述至少一种阳离子单体以摩尔计占阳离子共聚物的超过50%,且该阳离子单体选自:二烯丙基二甲基卤化铵、甲基丙烯酰氧乙基三甲基氯化铵、甲基丙烯酰氧乙基二甲基苄基氯化铵、2-氨基乙基甲基丙烯酸酯、N-(3-氨基丙基)甲基丙烯酸酯、乙烯基咪唑、乙烯基吡啶、乙烯基胺、酰氨基胺和氮丙环;和
(3)0.1ppm-200ppm的阳离子共聚物,该阳离子共聚物包括至少一种阳离子单体和至少一种非离子单体,其中所述至少一种阳离子单体以摩尔计占共聚物的50%或更少,且该阳离子单体选自:二烯丙基二甲基卤化铵、甲基丙烯酰氧乙基三甲基氯化铵、甲基丙烯酰氧乙基二甲基苄基氯化铵、2-氨基乙基甲基丙烯酸酯、N-(3-氨基丙基)甲基丙烯酸酯、乙烯基咪唑、乙烯基吡啶、乙烯基胺、酰氨基胺和氮丙环;以及
(c)水,
其中所述抛光组合物的pH值为7或更少。
2.权利要求1所述的抛光组合物,其中该阳离子磨料选自氧化铝、二氧化钛和掺杂的硅石。
3.权利要求1所述的抛光组合物,其中该阳离子磨料为二氧化铈。
4.权利要求1所述的抛光组合物,其中该阳离子磨料为氧化锆。
5.权利要求1所述的抛光组合物,其中该阳离子磨料的存在量为0.01重量%-1重量%。
6.权利要求1所述的抛光组合物,其中该阳离子聚合物为阳离子均聚物。
7.权利要求6所述的抛光组合物,其中聚乙烯亚胺在该抛光组合物中的存在量为0.1ppm-20ppm。
8.权利要求1所述的抛光组合物,其中该阳离子聚合物为阳离子共聚物。
9.权利要求1所述的抛光组合物,其中该阳离子聚合物具有的平均分子量为5000道尔顿或更多。
10.权利要求9所述的抛光组合物,其中该阳离子聚合物包括氮、锍基团、鏻基团、或其组合。
11.权利要求1所述的抛光组合物,其中所述pH为4至7。
12.权利要求1所述的抛光组合物,其中该抛光组合物进一步包括羧酸。
13.权利要求12所述的抛光组合物,其中该羧酸为氨基羧酸。
14.一种化学-机械抛光基底的方法,该方法包括:
(i)将基底与抛光垫和权利要求1-13中任一项的化学-机械抛光组合物接触,
(ii)相对于该基底移动该抛光垫,在其之间有所述化学-机械抛光组合物,以及
(iii)研磨该基底的至少一部分以抛光该基底。
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SG157354A1 (en) | 2009-12-29 |
WO2006052433A2 (en) | 2006-05-18 |
JP2008519466A (ja) | 2008-06-05 |
EP1831321A2 (en) | 2007-09-12 |
US20090137124A1 (en) | 2009-05-28 |
US7504044B2 (en) | 2009-03-17 |
JP5102040B2 (ja) | 2012-12-19 |
KR101117401B1 (ko) | 2012-02-29 |
US20060099814A1 (en) | 2006-05-11 |
EP1831321B1 (en) | 2015-06-24 |
TW200630472A (en) | 2006-09-01 |
US7846842B2 (en) | 2010-12-07 |
IL182797A0 (en) | 2007-08-19 |
MY160422A (en) | 2017-03-15 |
WO2006052433A3 (en) | 2006-08-31 |
IL182797A (en) | 2011-08-31 |
CN101065458A (zh) | 2007-10-31 |
KR20070085738A (ko) | 2007-08-27 |
MY149519A (en) | 2013-09-13 |
TWI323274B (en) | 2010-04-11 |
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