CN101085902B - 具有改进的终点检测能力、用来对二氧化硅和氮化硅进行化学机械抛光的组合物 - Google Patents
具有改进的终点检测能力、用来对二氧化硅和氮化硅进行化学机械抛光的组合物 Download PDFInfo
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- CN101085902B CN101085902B CN2007101098948A CN200710109894A CN101085902B CN 101085902 B CN101085902 B CN 101085902B CN 2007101098948 A CN2007101098948 A CN 2007101098948A CN 200710109894 A CN200710109894 A CN 200710109894A CN 101085902 B CN101085902 B CN 101085902B
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- hydroxide
- aqueous solution
- ammonium
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- ion
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- 239000000203 mixture Substances 0.000 title claims abstract description 51
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- 238000005498 polishing Methods 0.000 title claims abstract description 33
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 18
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 17
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000000126 substance Substances 0.000 title claims description 31
- 238000001514 detection method Methods 0.000 title claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 30
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- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims abstract description 16
- 238000005342 ion exchange Methods 0.000 claims abstract description 14
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- CPOUUWYFNYIYLQ-UHFFFAOYSA-M tetra(propan-2-yl)azanium;hydroxide Chemical compound [OH-].CC(C)[N+](C(C)C)(C(C)C)C(C)C CPOUUWYFNYIYLQ-UHFFFAOYSA-M 0.000 claims description 2
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
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Abstract
本发明提供了一种用来对半导体基板上的二氧化硅和氮化硅进行抛光的组合物的制备方法。该方法包括:对羧酸聚合物进行离子交换以减少氨;将0.01-5重量%离子交换的羧酸聚合物与以下组分混合起来:0.001-1重量%的季铵化合物、0.001-1重量%的邻苯二甲酸及其盐、0.01-5重量%的磨料和余量的水。
Description
技术领域
本发明涉及具有改进的终点检测能力、用来对二氧化硅和氮化硅进行化学机械抛光的组合物。
背景技术
在半导体工业中,制造集成电路的关键步骤是在下面的基板上选择性地形成和除去膜。这些膜由各种物质制成,可以是导电的或不导电的。导电的膜通常用于引线或引线连接。不导电的膜或介电膜用于一些领域,例如用作金属化层之间的层间电介质,或者作为相邻的电路元件之间的绝缘体。
通常的工艺步骤包括:(1)沉积膜,(2)使用光刻法和蚀刻法使所述膜的一些区域图案化,(3)沉积一层膜,填充所述蚀刻过的区域,(4)通过蚀刻法或化学机械抛光法(CMP)对所述结构进行平面化。通过多种众所周知的方法在基板上形成膜,所述方法包括例如通过溅射或蒸发进行的物理气相沉积(PVD)、化学气相沉积(CVD)、等离子辅助化学气相沉积(PECVD)。通过一些众所周知的方法除去膜,这些方法包括化学机械抛光、活性离子蚀刻(RIE)之类的干蚀刻、湿蚀刻、电化学蚀刻、蒸气蚀刻和喷雾蚀刻。
在除去膜的时候,极为重要的一点是在已经除去恰当的厚度之后停止该过程。换而言之,在除去膜的过程中,很重要的是要知道何时达到终点。在CMP中,通过在化学活性浆液的存在下,在施加大小受到控制的压力的条件下,使晶片对着抛光垫旋转(或者使抛光垫对着晶片旋转,或者二者都旋转),从半导体晶片上选择性地除去膜。膜的过度抛光会造成产率降低,而抛光不足会造成高成本的返工。因此,人们使用各种方法来检测达到所需的去除终点和应当停止抛光的时间。
现有技术中的适合对所有种类的膜进行CMP终点检测的方法包括以下类型的测量:(1)简单定时测量,(2)摩擦或电机电流测量,(3)电容测量,(4)光学测量,(5)声学测量,(6)电导性测量和(7)化学性质测量。具体来说,化学终点检测(例如Li等人的美国专利第6021679号)由于能够在抛光过程中进行实时和连续的分析,能够在抛光氮化物层的时候立刻检测出信号终点,而且响应时间快(通常小于1秒),还具有其它的优点,因此流行开来。
已经发现当使用包含氢氧化钾(KOH)的浆液,对其上具有氮化物终止膜(Si3N4)以及位于该氮化物膜之上的氧化物目标膜(SiO2)的基板进行化学机械抛光的时候,当达到氧化物/氮化物界面的时候会发生化学反应,生成氨气(NH3)。在抛光氧化物的时候,发生以下反应:
SiO2+2KOH+H2O→K2SiO3+2H2O
在抛光氮化物的时候,发生以下反应:
Si3N4+6KOH+3H2O→3K2SiO3+4NH3
生成的氨气溶解在浆液中,主要以NH3的形式而非NH4 +的形式存在。浆液中氨气的存在表明已经到达了下面的氮化物膜,而且对其进行了抛光,可以通过检测浆液中氨的含量来确定去除氧化物膜的终点。一旦达到该终点,便可停止抛光。
通常,为了检测和监测气体形式的氨,通过泵抽使来自抛光设备的浆液通过氨提取装置。可以分析和监测包含氨的气流,以检测目标膜的去除终点。气相化学分析,例如标准质谱法可以具有高灵敏度和快速的响应时间,这是终点检测所需的。不幸的是,在对浆液取样的时候,由浆液组成本身产生的任何残余的氨都会造成显著的影响,使得准确的终点检测极为困难。
因此,人们需要用于浅沟槽隔离工艺的对二氧化硅和氮化硅进行化学机械抛光的组合物和方法,所述组合物和方法具有改进的终点检测能力。
发明内容
在第一方面,本发明提供了一种用来对半导体基板上的二氧化硅和氮化硅进行抛光的组合物的制备方法,该方法包括:对羧酸聚合物进行离子交换以减少氨;将0.01-5重量%经过离子交换的羧酸聚合物与以下组分混合起来:0.001-1重量%的季铵化合物、0.001-1重量%的邻苯二甲酸及其盐、0.01-5重量%的磨料和余量的水。
在第二方面,本发明提供了一种对半导体基板上的二氧化硅和氮化硅进行化学机械抛光的方法,该方法包括:提供抛光垫和包含二氧化铈磨料的浆液;对将要用于所述浆液的羧酸聚合物的溶液进行离子交换,将该溶液中的氨含量减小到10ppb至2ppm;使用所述抛光垫和包含氨含量较少的羧酸聚合物溶液的浆液抛光所述基板。
附图说明
图1A显示了中心、中部和边缘管芯的晶片尺度均匀性(wafer scaleuniformity)保留程度的抛光后结果的平均值;
图1B显示了中心、中部和边缘管芯的晶片尺度均匀性保留程度的抛光后结果的平均值;
图2显示了使用各种终点检测技术获得的结果;
图3A显示了使用各种终点检测技术获得的平面化效率;
图3B显示了使用各种终点检测技术获得的平面化效率。
具体实施方式
所述组合物和方法提供了用于化学终点检测系统的改进的终点检测信号。具体来说,本发明的组合物和方法中减少了氨的含量,从而提高了化学终点检测系统的精确度。本发明有益地使用离子交换树脂来减小组合物中的氨含量,以减少任何来自浆液的氨污染物的影响。具体来说,对所述羧酸聚合物进行离子交换以减少二氧化铈基浆液中的氨含量。另外,所述组合物提供了出人意料的选择性,可选择除去二氧化硅而不影响氮化硅。所述组合物宜依赖于螯合剂或选择性增强剂,以便在浅沟槽隔离工艺中选择性抛光二氧化硅而不影响氮化硅。具体来说,所述组合物包含季铵化合物,以在使用的pH之下选择性抛光二氧化硅而不影响氮化硅。
本发明的季铵化合物具有以下结构:
式中R1、R2、R3和R4是碳链长度为包含1-15个碳原子的有机化合物。更佳的是,R1、R2、R3和R4的碳链长度为1-10。最佳的是,R1、R2、R3和R4的碳链长度包含1-5个碳原子。R1、R2、R3和R4的有机化合物是取代的或未取代的芳基、烷基、芳烷基或烷芳基。阴离子的例子包括硝酸根、硫酸根、卤离子(例如溴离子、氯离子、氟离子和碘离子)、柠檬酸根、磷酸根、草酸根、苹果酸根、葡糖酸根、氢氧根、乙酸根、硼酸根、乳酸根、硫氰酸根、氰酸根、磺酸根、硅酸根、高卤酸根(例如高溴酸根、高氯酸根和高碘酸根)、铬酸根和包含至少一种上述阴离子的混合物。
优选的季铵化合物包括:氢氧化四甲基铵、氢氧化四乙基铵、氢氧化四丙基铵、氢氧化四异丙基铵、氢氧化四环丙基铵、氢氧化四丁基铵、氢氧化四异丁基铵、氢氧化四叔丁基铵、氢氧化四仲丁基铵、氢氧化四环丁基铵、氢氧化四戊基铵、氢氧化四环戊基铵、氢氧化四己基铵、氢氧化四环己基铵、以及它们的混合物。最优选的季铵化合物是氢氧化四甲基铵。
所述组合物宜包含0.001-1重量%的季铵化合物,以选择性地除去二氧化硅而不影响氮化硅。较佳的是,所述组合物包含0.01-0.5重量%的季铵化合物。
除了季铵化合物以外,所述组合物宜包含0.001-1重量%的络合剂。较佳的是,所述组合物包含0.01-0.5重量%的络合剂。示例性的络合剂包括羰基化合物(例如乙酰丙酮酸盐等),简单的羧酸盐(例如乙酸盐、芳族羧酸盐等),包含一个或多个羟基的羧酸盐(例如甘醇酸盐、乳酸盐、葡糖酸盐、五倍子酸及其盐等),二羧酸盐、三羧酸盐和多羧酸盐(例如草酸盐、邻苯二甲酸盐、柠檬酸盐、琥珀酸盐、酒石酸盐、苹果酸盐、乙二胺四乙酸盐(例如EDTA钠盐)、它们的混合物等),包含一个或多个磺酸根和/或膦酸根的羧酸盐。另外,其它合适的络合剂包括例如二醇、三醇或多醇(例如乙二醇、邻苯二酚、连苯三酚、单宁酸等)和包含磷酸根的化合物(例如鏻盐和膦酸)。较佳的是,所述络合剂是邻苯二甲酸及其盐。优选的邻苯二甲酸盐包括邻苯二甲酸氢铵和邻苯二甲酸氢钾,以及它们的混合物。
较佳的是,所述新颖的抛光组合物包含约0.01-5重量%的羧酸聚合物。较佳的是,所述组合物包含约0.05-3重量%的羧酸聚合物。所述聚合物的数均分子量优选约为20000-1500000。另外,还可使用具有更高和更低数均分子量的羧酸聚合物的混合物。这些羧酸聚合物通常存在于溶液中,也可为水分散体的形式。上述聚合物的数均分子量通过GPC(凝胶渗透色谱法)测定。
所述羧酸聚合物由不饱和一元羧酸和不饱和二元羧酸形成。通常的不饱和一元羧酸单体包含3-6个碳原子,包括丙烯酸、低聚丙烯酸、甲基丙烯酸、巴豆酸和乙烯基乙酸。通常的不饱和二元羧酸包含4-8个碳原子,包括其酸酐,例如马来酸、马来酸酐、富马酸、戊二酸、衣康酸、衣康酸酐和环己烯二羧酸。另外,也可使用上述酸的水溶性盐。
另外可以使用包含共聚物和三元共聚物的羧酸,其中羧酸组分占聚合物的5-75重量%。通常这些聚合物是(甲基)丙烯酸和丙烯酰胺或甲基丙烯酰胺的聚合物;(甲基)丙烯酸和苯乙烯以及其它乙烯基芳族单体的聚合物;(甲基)丙烯酸烷基酯(丙烯酸或甲基丙烯酸的酯)和单羧酸或二羧酸,例如丙烯酸或甲基丙烯酸或衣康酸的聚合物;包含取代基的取代的乙烯基芳族单体和不饱和的单羧酸或二羧酸以及(甲基)丙烯酸烷基酯的聚合物,所述取代基包括例如:卤素(即氯、氟、溴),硝基,氰基,烷氧基,卤代烷基,羧基,氨基,氨基烷基;包含氮环的单烯键式不饱和单体(例如乙烯基吡啶、烷基乙烯基吡啶、乙烯基丁内酰胺、乙烯基己内酰胺)与不饱和单羧酸或二羧酸的聚合物;烯烃(例如丙烯、异丁烯或包含10-20个碳原子的长链烷基烯烃)与不饱和单羧酸或二羧酸的聚合物;乙烯醇酯(例如乙酸乙烯酯和硬脂酸乙烯酯)或乙烯基卤化物(例如乙烯基氟、乙烯基氯、偏二氟乙烯)或乙烯基腈(例如丙烯腈和甲基丙烯腈)与不饱和单羧酸或二羧酸的聚合物;烷基中包含1-24个碳原子的(甲基)丙烯酸烷基酯与不饱和单羧酸(例如丙烯酸或甲基丙烯酸)的聚合物。这仅仅是可用于本发明新颖的抛光组合物的各种聚合物中的一些例子。还可使用可生物降解聚合物、可光降解聚合物或可通过其它方式降解的聚合物。可生物降解的组合物的一个例子是包含聚(丙烯酸酯-共-2-氰基丙烯酸甲酯)链段的聚丙烯酸聚合物。
较佳的是,对本发明的羧酸聚合物进行离子交换,以减少会对检测氨的终点检测系统造成影响的氨的含量。具体来说,本发明的离子交换树脂中结合有阴离子性基团。这些阴离子性基团使得所述阳离子交换树脂能够从水溶液中吸收金属离子(例如Na+、K+、Ca2+、Fe3+等)和氨之类的可溶性阳离子。本发明的树脂能够将阳离子的浓度减小到10ppb至2ppm。更佳的是,本发明的树脂能够将阳离子浓度减小到50ppb至1ppm。最佳的是,本发明的树脂能够将阳离子浓度减小到小于100ppb至200ppb。这些离子交换树脂通常使用强酸进行再生,使吸附的离子脱附,用氢离子代替这些吸附的离子。优选的离子交换树脂包括购自美国宾夕法尼亚州费城罗门哈斯公司的离子交换树脂。优选的离子交换树脂是IRN-77。
本发明的阳离子交换树脂可以为以下物理形式:凝胶珠粒(例如球形凝胶珠粒)或大孔珠粒(包括网状珠粒)或凝胶或大孔树脂研细的树脂颗粒。这些研细的颗粒可使用已知的细研技术由体相聚合的或悬浮聚合的聚合物制得。
优选的离子交换树脂颗粒是通过对本领域众所周知作为离子交换树脂前体的悬浮聚合的交联共聚物珠粒进行官能化而制备的。凝胶共聚物珠粒在其均匀深度的外壳中带有其官能团。由于用来制备这些珠粒的官能化方法以均匀的速率渗透所述共聚物,所以无论珠粒的尺寸大小如何,所有珠粒的官能化层倾向于具有均匀的深度,只是最小的珠粒没有完全官能化,即没有完全磺化。因此无论珠粒尺寸的均匀性如何,扩散路径高度均匀。
适合用来制备交联的共聚物的单体包括单乙烯基芳族单体,例如苯乙烯、乙烯基甲苯、乙烯基萘、乙基乙烯基苯、乙烯基氯苯、氯代甲基苯乙烯等,以制备所述共聚物的单体的重量为基准计,所述单烯键芳族单体的含量可约为50-99.5摩尔%,优选约为80-99摩尔%;包含至少两个可以与所述单乙烯基单体聚合的活性乙烯基的多乙烯基单体,以制备所述共聚物的单体的重量为基准计,该多乙烯基单体的含量可约为0.5-50摩尔%,优选约为1-20摩尔%。合适的多乙烯基单体的例子包括二乙烯基苯、三羟甲基丙烷三甲基丙烯酸酯、二甲基丙烯酸乙二醇酯、二乙烯基甲苯、三乙烯基苯、二乙烯基氯代苯、邻苯二甲酸二烯丙酯、二乙烯基吡啶、二乙烯基萘、二丙烯酸乙二醇酯、二甲基丙烯酸新戊二醇酯、二甘醇二乙烯基醚、双酚A二甲基丙烯酸酯、季戊四醇四甲基丙烯酸酯和季戊四醇三甲基丙烯酸酯、二乙烯基二甲苯、二乙烯基乙基苯、二乙烯基砜、二乙烯基酮、二乙烯基硫、丙烯酸烯丙酯、马来酸二烯丙酯、富马酸二烯丙酯、琥珀酸二烯丙酯、碳酸二烯丙酯、丙二酸二烯丙酯、草酸二烯丙酯(diallyoxylate)、己二酸二烯丙酯、癸二酸二烯丙酯、酒石酸二烯丙酯、硅酸二烯丙酯、丙三羧酸二烯丙酯、乌头酸三烯丙酯、柠檬酸三烯丙酯、磷酸三烯丙酯、N,N’-亚甲基二丙烯酰胺、N.N’-亚甲基二甲基丙烯酰胺、N.N’-亚乙基二丙烯酰胺、三乙烯基萘、多乙烯基萘,以及二醇、甘油、季戊四醇、间苯二酚和二醇的单硫代和二硫代衍生物的多烯丙基醚和多乙烯基醚。所述单体混合物还可包含最高约5摩尔%的不会对制得的树脂基质的基本性质造成影响的其它乙烯基单体,例如丙烯腈、丁二烯、甲基丙烯酸和本领域已知的其它单体。在本发明的一个实施方式中,所述共聚物颗粒是丙烯酸酯共聚物颗粒。
一种所需的官能化形式是磺化,本发明能够提供部分磺化的树脂,相对于通过常规共聚物磺化形成的树脂,本发明的部分磺化的树脂在溶剂溶胀或非溶胀状态下对离子交换应用中加料和再生循环中的应力的耐受性都要好得多。
较佳的是,所述抛光组合物包含0.01-5重量%的磨料,以促进二氧化硅的去除。在此范围内,希望磨料的含量大于或等于0.1重量%。还希望在此范围内所需的磨料含量小于或等于3重量%。
所述磨料的平均粒度为50-200纳米(nm)。出于本说明书的目的,粒度表示磨料的平均粒度。更佳的是,优选使用平均粒度为80-150纳米的磨料。如果将磨料的粒度减小到小于或等于80纳米,则会提高抛光组合物的平面化能力,但是也会减小去除速率。
磨料的例子包括无机氧化物、无机氢氧化物、金属硼化物、金属碳化物、金属氮化物、聚合物颗粒、以及包含以上至少一种的混合物。合适的无机氧化物包括例如二氧化硅(SiO2)、氧化铝(Al2O3)、氧化锆(ZrO2)、二氧化铈(CeO2)、氧化锰(MnO2),或者包含上述氧化物中至少一种的组合。如果需要,也可使用这些无机氧化物的改良形式,例如涂敷了聚合物的无机氧化物颗粒和涂敷了无机化合物的颗粒。合适的金属碳化物、硼化物和氮化物包括例如碳化硅、氮化硅、碳氮化硅(SiCN)、碳化硼、碳化钨、碳化锆、硼化铝、碳化钽、碳化钛,或者包含上述金属碳化物、硼化物和氮化物中至少一种的组合。如果需要,还可使用金刚石作为磨料。其它磨料还可包括聚合物颗粒和涂敷的聚合物颗粒。优选的磨料是氧化铈。
所述化合物在包含余量的水的溶液中,在很宽的pH范围内都具有效果。该溶液有效的pH范围至少从4延伸到7。另外,所述溶液有益地依靠余量的去离子水来限制固有的杂质。本发明抛光液的pH值优选为4.5-6.8,更优选为5-6.5。用来调节本发明组合物的pH值的酸是例如硝酸、硫酸、盐酸、磷酸等。用来调节本发明组合物的pH值的碱的例子是例如氢氧化钾。
因此,本发明提供了对化学终点检测系统提供改进的终点检测信号的组合物和方法。具体来说,本发明的组合物和方法减少了氨的含量,从而提高了化学终点检测系统的精确度。本发明有益地使用离子交换树脂来减少组合物中的氨含量,以减少任何源自浆液氨污染物造成的影响。本发明提供了可用来在浅沟槽隔离工艺中对半导体晶片上的二氧化硅和氮化硅进行抛光的组合物和方法。具体来说,对所述羧酸聚合物进行离子交换,以减少二氧化铈基浆液中的氨含量。另外,所述组合物优选包含季铵化合物以提高选择性。具体来说,本发明提供了可用来对半导体晶片上的二氧化硅和氮化硅进行抛光的水性组合物,该组合物包含季铵化合物、邻苯二甲酸及其盐、羧酸聚合物、磨料和余量的水。所述组合物在4-7的pH范围内表现出特别高的选择性。注意,尽管本实施方式描述了减少羧酸聚合物中的氨含量,但是本发明不限于此。换而言之,可以根据需要对浆液的任意组成或组分,例如季铵化合物进行离子交换以减少任意的氨含量。
实施例
实施例1
所有实施例的溶液都包含1.8重量%的二氧化铈、0.18重量%的聚丙烯酸和0.21重量%的邻苯二甲酸氢钾。另外,本发明的实施例包含0.12重量%的季铵化合物,具体来说是包含氢氧化四甲基铵。可以通过将磨料包与化学试剂包混合起来制备所述浆液。所述磨料包是通过使用桨叶式混合器将聚丙烯酸浓缩物溶解在去离子水中,然后将二氧化铈浓缩物加入该聚丙烯酸溶液中来制备的。较佳的是,使用Amberlite IRN-77离子交换树脂对所述聚丙烯酸聚合物进行离子交换。所述离子交换树脂购自美国宾夕法尼亚州,Warrendale,Siemens WaterTechnologies。将所述羧酸聚合物溶液稀释至5%以减小溶液的粘度。通过泵抽使该溶液流过装填有所述阳离子交换树脂的柱子。溶液通过所述树脂床,流出时的pH值小于3,基本不含金属离子或铵之类的任何阳离子性物质。然后使用硝酸滴定所述二氧化铈-聚丙烯酸-水混合物。然后将所述混合物加入高剪切Kady研磨机中。所述化学试剂包是通过将所有余下的化学试剂以合适的量溶解在去离子水中,使用桨叶式混合器进行混合,并使用硝酸滴定至所需的最终pH值而制得的。所述最终浆液是通过将磨料包与化学试剂包混合起来,并滴定至所需的pH值而制得的。
图案化的晶片是具有HDP和LPCVD-SiN膜的购自Praesagus,Inc.的STI-MIT-864TM掩模(mask)。所述MIT-864掩模结构具有由4毫米×4毫米的特征结构组成的20毫米×20毫米的管芯(die)。所述掩模中的特征结构具有100微米的节距,密度各自为10-100%;50%的密度,节距为1-1000微米。此处50%密度定义为重复结构阵列中的间隔,其中间隔宽度/(间隔宽度+线路宽度)×100%=50%。例如如果间隔宽度+线路宽度=1000微米,则50%的间隔的宽度为500微米。在所有的测试中使用IC1010TM抛光垫。使用IC1010TM聚氨酯抛光垫(德国,Newark,Rohm and Haas Electronic Materials CMP Inc.),通过Applied Materials200毫米抛光机,在下压力=2.7psi、抛光溶液流速=85立方厘米/分钟、台板转速=123RPM、支架转速=44RPM的条件下对样品进行平面化。所述抛光溶液的pH值用硝酸调节到pH=6.1。所有的溶液包含余量的去离子水。使用得自Therma-Wave,Inc.的2600度量器具测量氧化物和氮化物膜的厚度。
如图1A、1B所示,图中显示了来自中心、中部和边缘管芯的抛光后结果,即晶片尺度均匀性的保留程度的信息。如图1A所示,管芯内的平均沟槽范围为如图1BB所示,管芯内的氮化物厚度范围为总沟槽(trench)氧化物损失反映出了凹陷和侵蚀的组合。
实施例2
本试验将使用化学终点数据与使用摩擦和光学数据分析终点显示稳健度(robustness)的结果相比较。化学终点检测系统是购自Eco Physics的Eco SystemsM17 N-EPD。所有其它的参数都与实施例1的参数相同。
如图2所示,化学终点的显示(“开/关”)最明了,使其可以高度工艺化。化学终点可以比摩擦终点或光学终点提前10-15秒确定。通过化学终点可以提高过度抛光范围(overpolish window)的置信水平和工艺稳健度。
实施例3
本试验将使用化学终点数据以及使用摩擦和光学数据分析平面化效率的结果相比较。化学终点检测系统与实施例2相同。所有其它的参数都与实施例1的参数相同。
如图3A、3B所示,使用化学终点的最优化的工艺显著提高了平面化效率。所述化学终点系统改进了氧化物清除置信水平,需要进行较短的过度抛光。
因此,本发明提供了用于化学终点检测系统的具有改进的终点检测信号的组合物和方法。具体来说,本发明的组合物和方法减少了氨,从而提高了化学终点检测系统的精确度。本发明有益地使用离子交换树脂减少所述组合物中的氨含量,以减少来自浆液的氨污染的影响。本发明还提供了可用来在浅沟槽工艺中对半导体晶片上的二氧化硅和氮化硅进行抛光的组合物。
Claims (10)
1.一种用来对半导体基板上的二氧化硅和氮化硅进行抛光的组合物的制备方法,该方法包括:
提供存在于水溶液中的羧酸聚合物;
使所述水溶液与离子交换树脂接触,从而从所述水溶液中除去可溶性阳离子和氨,提供存在于水溶液中的进行过离子交换的羧酸聚合物,所述水溶液的阳离子浓度为10ppb至2ppm;
将0.01-5重量%的进行过离子交换的羧酸聚合物与0.001-1重量%的季铵化合物、0.001-1重量%的邻苯二甲酸及其盐、0.01-5重量%的磨料和余量的水混合。
2.如权利要求1所述的方法,其特征在于,所述季铵化合物选自:氢氧化四甲基铵、氢氧化四乙基铵、氢氧化四丙基铵、氢氧化四异丙基铵、氢氧化四环丙基铵、氢氧化四丁基铵、氢氧化四异丁基铵、氢氧化四叔丁基铵、氢氧化四仲丁基铵、氢氧化四环丁基铵、氢氧化四戊基铵、氢氧化四环戊基铵、氢氧化四己基铵、氢氧化四环己基铵、以及它们的混合物。
3.如权利要求1所述的方法,其特征在于,所述邻苯二甲酸或邻苯二甲酸盐是邻苯二甲酸氢钾。
4.如权利要求1所述的方法,其特征在于,所述磨料是二氧化铈。
5.如权利要求4所述的方法,其特征在于,所述二氧化铈的平均粒度为50-200纳米。
6.如权利要求4所述的方法,其特征在于,所述二氧化铈的平均粒度为80-150纳米。
7.如权利要求1所述的方法,其特征在于,所述水溶液的阳离子浓度为100ppb至200ppb。
8.一种对半导体基板上的二氧化硅和氮化硅进行化学机械抛光的方法,该方法包括:
提供抛光垫;
提供浆液,所述浆液通过以下方式制得:
提供存在于水溶液中的羧酸聚合物;
使所述水溶液与离子交换树脂接触,从而从所述水溶液中除去可溶性阳离子和氨,提供存在于水溶液中的进行过离子交换的羧酸聚合物,所述水溶液的阳离子浓度为10ppb至2ppm;
将0.01-5重量%的进行过离子交换的羧酸聚合物与0.001-1重量%的季铵化合物、0.001-1重量%的邻苯二甲酸及其盐、0.01-5重量%的磨料和余量的水混合;
使用所述抛光垫和所述浆液抛光所述半导体基板。
9.如权利要求8所述的方法,其特征在于,所述方法还包括:通过监控浆液中的氨的含量来化学检测抛光终点并停止抛光。
10.如权利要求8所述的方法,其特征在于,所述浆液的pH值为4-7。
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US20090181475A1 (en) * | 2008-01-11 | 2009-07-16 | Novellus Systems, Inc. | Detecting the presence of a workpiece relative to a carrier head |
US8366959B2 (en) * | 2008-09-26 | 2013-02-05 | Rhodia Operations | Abrasive compositions for chemical mechanical polishing and methods for using same |
US8735293B2 (en) * | 2008-11-05 | 2014-05-27 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing composition and methods relating thereto |
CN102714132A (zh) | 2009-12-18 | 2012-10-03 | 睿纳有限责任公司 | 用于去除衬底层的方法 |
US8671685B2 (en) * | 2010-03-08 | 2014-03-18 | Tma Power, Llc | Microturbine Sun Tracker |
CN102464946B (zh) * | 2010-11-19 | 2015-05-27 | 安集微电子(上海)有限公司 | 一种化学机械抛光液及其应用 |
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US8808573B2 (en) * | 2011-04-15 | 2014-08-19 | Cabot Microelectronics Corporation | Compositions and methods for selective polishing of silicon nitride materials |
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