CN102113096A - 化学机械研磨用研磨液以及使用了该研磨液的基板的研磨方法 - Google Patents

化学机械研磨用研磨液以及使用了该研磨液的基板的研磨方法 Download PDF

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Publication number
CN102113096A
CN102113096A CN2009801304406A CN200980130440A CN102113096A CN 102113096 A CN102113096 A CN 102113096A CN 2009801304406 A CN2009801304406 A CN 2009801304406A CN 200980130440 A CN200980130440 A CN 200980130440A CN 102113096 A CN102113096 A CN 102113096A
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China
Prior art keywords
cmp
substrate
lapping liquid
quality
palladium
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南久贵
税所亮太
小野裕
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Resonac Corp
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Hitachi Chemical Co Ltd
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Publication of CN102113096A publication Critical patent/CN102113096A/zh
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    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
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Abstract

本发明的化学机械研磨用研磨液含有1，2，4-三唑、磷酸类、氧化剂以及磨粒。本发明的研磨方法是以下研磨方法：其是一边向基板与研磨布之间供给化学机械研磨用研磨液，一边用上述研磨布研磨上述基板的基板的研磨方法，其中上述基板是具有钯层的基板，上述化学机械研磨用研磨液是含有1，2，4-三唑、磷酸类、氧化剂以及磨粒的化学机械研磨用研磨液。

Description

化学机械研磨用研磨液以及使用了该研磨液的基板的研磨方法
技术领域
本发明涉及化学机械研磨用研磨液以及使用了该化学机械研磨用研磨液的基板的研磨方法。
背景技术
近年来，随着半导体集成电路(LSI)的高集成化、高性能化，开发了新的微细加工技术。化学机械研磨(CMP)法也是其中之一，成为在LSI制造工序、特别是在多层配线形成工序中的层间绝缘膜层的平坦化、金属插塞(plug)形成、埋入式配线形成中频繁使用的技术(例如，参照专利文献1)。
化学机械研磨中使用的金属用的研磨液通常含有氧化剂以及固体磨粒，根据需要还可以进一步添加氧化金属溶解剂、保护膜形成剂(金属防蚀剂)。据认为研磨的基本机理是：首先利用氧化剂将金属层表面氧化，然后将该氧化层利用固体磨粒切去(磨削去)。
堆积在沟(凹部)上的金属表面的氧化层不太接触研磨垫(pad)，达不到利用固体磨粒来切去的效果，但对堆积在接触研磨垫的凸部上的金属层表面的氧化层，可以进行切去。因此，可以在进行化学机械研磨的同时，除去凸部上的金属层而使基板表面平坦化(例如，参照非专利文献1)。
另一方面，随着半导体元件的高集成化，要求多引脚化、窄间距化，进一步要求薄型安装化。而且，半导体元件与配线基板间的配线延迟或噪声的防止也成为重要的课题。因此，半导体元件与配线基板的连接方式，一直以来广泛采用倒装片安装方式来代替以往的以引线接合作为主体的安装方式。
并且，在该倒装片安装方式中，广泛使用在半导体元件的电极端子上形成凸起电极、通过该凸起电极与形成在配线基板上的连接端子一并接合的焊料凸块连接法。
作为化学机械研磨用研磨液，已知有将由形成在基板上的氮化钛或氮化钽等构成的层作为研磨对象，并添加了保护膜形成剂、有机酸的研磨液(参照专利文献2)。
另外，关于对由铜构成的层使用化学机械研磨的尝试，例如已知有使用添加了2-喹啉羧酸的研磨液的方法(参照专利文献3)。此外，关于对镍层使用化学机械研磨的尝试，例如已知有使用添加了磨粒、有机酸、氧化剂的研磨液作为HDD磁头用研磨液的方法(参照专利文献4)。
钯一般与铂、钌等一起被分类为“贵金属”。关于对这种贵金属层使用化学机械研磨的尝试，例如已知有使用以下研磨液的方法：添加了硫化合物的研磨液，添加了二酮、含氮杂环化合物或者两性离子化合物之中的任一种的研磨液，添加了铂族系金属的氧化物的研磨液(参照专利文献5、6、7)。
现有技术文献
专利文献
专利文献1：美国专利第4944836号公报
专利文献2：日本特许第3780767号公报
专利文献3：日本特许第3192968号公报
专利文献4：日本特开2006-297501号公报
专利文献5：国际公开第01/44396号小册子
专利文献6：美国专利第6527622号说明书
专利文献7：日本特开平11-121411号公报
非专利文献
非专利文献1：Journal of Electrochemical Society，第138卷11号(1991年发行)，3460～3464页。
发明内容
发明所要解决的课题
但是，迄今为止未对使用化学机械研磨来研磨钯进行研究。根据本发明人们的见解表明，使用上述专利文献2、3、4的研磨液，不仅难以氧化且无法研磨硬度高的钯。另外，使用上述专利文献5、6、7的研磨液，虽然能研磨铂或钌，但即使用同样的研磨液研磨钯，研磨也无法进行。
因此，本发明的目的在于提供一种与使用了以往的研磨液的情况相比，至少使钯层的研磨速度更提高的化学机械研磨用研磨液，以及使用了该化学机械研磨用研磨液的研磨方法。
用于解决课题的手段
本发明还提供一种含有1，2，4-三唑、磷酸类、氧化剂以及磨粒而形成的化学机械研磨用研磨液。
根据本发明的化学机械研磨用研磨液，与使用以往的研磨液的情况相比，至少使钯层的研磨速度更提高，可以用所需的研磨速度进行研磨。
作为氧化剂，氧化剂优选选自由过氧化氢、高碘酸、高碘酸盐、碘酸盐、溴酸盐以及过硫酸盐所组成的组中的至少一种；作为磨粒，优选选自由氧化铝、二氧化硅、氧化锆、二氧化钛以及二氧化铈所组成的组中的至少一种。
磨粒的浓度以化学机械研磨用研磨液的总量为基准优选为0.1～10质量％。通过将化学机械研磨用研磨液中的磨粒的浓度设定在该范围，可以在保持切去作用的同时，抑制粒子凝聚沉降。
上述的化学机械研磨用研磨液作为钯研磨用化学机械研磨用研磨液是特别有用的。
本发明还提供一种研磨方法，其是一边向基板与研磨布之间供给化学机械研磨用研磨液，一边用上述研磨布研磨上述基板的基板的研磨方法，其中基板是具有钯层的基板，化学机械研磨用研磨液是含有1，2，4-三唑、磷酸类、氧化剂以及磨粒的化学机械研磨用研磨液。
发明的效果
根据本发明的化学机械研磨用研磨液以及使用该化学机械研磨用研磨液的研磨方法，与使用以往的研磨液的情况相比，至少使钯层的研磨速度更提高，可以用所需的研磨速度进行研磨。
附图说明
图1是表示具有凸起电极的基板的制造方法的第1实施方式的剖面图。
图2是表示具有凸起电极的基板的制造方法的第2实施方式的剖面图。
图3是表示具有凸起电极的基板的制造方法的第3实施方式的剖面图。
图4是表示第3实施方式的具体例子的剖面图。
具体实施方式
以下，对用于实施本发明的最好的方式进行详细说明。
(1，2，4-三唑)
化学机械研磨用研磨液含有1，2，4-三唑。据认为1，2，4-三唑与后述的磷酸一起对钯形成配位化合物，这里形成的配位化合物由于容易研磨，因此推定是可以得到良好的研磨速度的物质。另外，若是含氮化合物，则被认为可以与钯形成配位化合物，但根据本发明人们的研究可知，若是1，2，4-三唑以外的化合物，则无法提高对钯层的研磨速度。例如，若是结构类似的1，2，3-三唑、3-氨基-1，2，4-三唑，则难以获得对钯层的良好的研磨速度。
1，2，4-三唑的添加量相对于研磨液的总质量优选为0.001～20质量％。该含量若在0.001质量％以上，则具有化学机械研磨钯层的研磨速度变大的倾向，作为下限值，更优选在0.01质量％以上，特别优选在0.05质量％以上。另外，若超过20质量％，则具有钯层的研磨速度饱和的倾向，作为上限值，更优选在15质量％以下，进一步优选在12质量％以下，特别优选在10质量％以下。
(磷酸类)
化学机械研磨用研磨液含有磷酸类。据认为磷酸类通过将由后述的氧化剂氧化的金属进行配位和/或溶解来促进金属膜的研磨，推定其具有作为对钯的氧化金属溶解剂的功能。
作为具有作为对钯的氧化金属溶解剂的功能的化合物，被认为有各种无机酸、有机酸等，但根据本发明人的研究，若是磷酸类以外的酸，则难以获得对钯的良好的研磨速度。
所谓的磷酸类是表示磷酸以及具有磷酸骨架的其它的类似化合物群(磷酸、磷酸衍生物、焦磷酸、焦磷酸衍生物、多磷酸、多磷酸衍生物等)，也包括它们的盐。作为磷酸类的具体的例子，可以列举出：磷酸、连二磷酸、亚磷酸、次磷酸、焦磷酸、三聚偏磷酸、四聚偏磷酸、焦亚磷酸、多磷酸等。另外，作为磷酸类的盐的例子，是磷酸类的阴离子与阳离子的盐，作为阳离子的例子，有锂、钠、钾、铷、铯、铍、镁、钙、锶、钡、钛、锆、钒、铬、锰、铁、钴、镍、铜、银、钯、锌、铝、镓、锡、铵等的离子。它们的盐可以是具有一个金属和2个氢的一代盐、具有2个金属和1个氢的二代盐、具有3个金属的三代盐之中的任一种，也可以是酸性盐、碱性盐、中性盐之中的任一种。这些磷酸类可以单独使用1种也可以将2种以上混合使用。
上述磷酸类的添加量相对于研磨液的总重量优选为0.001～20质量％。该含量若在0.001质量％以上，则具有化学机械研磨钯层的研磨速度变高的倾向，作为下限值，更优选在0.01质量％以上，特别优选在0.02质量％以上。另外，若超过20质量％，则具有钯层的研磨速度饱和的倾向，作为上限值，更优选在15质量％以下，特别优选在10质量％以下。另外，除了如后述的钯层以外，在研磨具有镍层、基底金属层等的基板时，上述添加量也是优选的。
(氧化剂)
化学机械研磨用研磨液中含有的氧化剂是对作为层形成用等在基板中使用的金属的氧化剂。作为氧化剂，可以列举出：过氧化氢(H2O2)、高碘酸、高碘酸盐、碘酸盐、溴酸盐、过硫酸盐等，其中特别优选过氧化氢。它们可以单独使用1种，或者2种以上混合使用。
氧化剂的添加量相对于研磨液的总质量优选为0.05～20质量％，更优选为0.1～15质量％，特别优选为0.1～10质量％。该配合量若在0.05质量％以上，则金属的氧化充分，且具有钯层的研磨速度变高的倾向，若在20质量％以下，则具有研磨面上难以生成皲裂的倾向。此外，过氧化氢通常可以过氧化氢水的形式来获得。因此，使用过氧化氢作为氧化剂时，使其换算成实际浓度后在上述含量范围内。另外，除了如后述的钯层以外，在研磨具有镍层、基底金属层等的基板时，上述添加量也是优选的。
(磨粒)
作为磨粒，具体可以列举出：热解法氧化铝(fumed alumina)、过渡型氧化铝、热解法二氧化硅(fumed silica)、胶体二氧化硅(也称为胶态二氧化硅)、氧化锆、二氧化钛、二氧化铈等，其中优选热解法氧化铝、过渡型氧化铝、热解法二氧化硅、胶体二氧化硅，从保持高速研磨速度的同时能抑制研磨损伤的观点考虑，更优选胶体二氧化硅。
磨粒的添加量相对于研磨液的总质量优选为0.1质量％～10质量％，更优选为0.2质量％～8.0质量％的范围。该添加量若在0.1质量％以上，则可以得到物理的切去作用，具有化学机械研磨钯层的研磨速度变高的倾向。另外，若在10质量％以下，则具有抑制粒子凝聚沉降的倾向。另外，即使添加超过10质量％的量，也有可能未见随着添加的量增加而使研磨速度相应地增加。这种倾向有可能根据钯层的研磨速度而显著可见。
从平坦性以及能够抑制研磨后残留在被研磨面上的损伤的观点考虑，磨粒的一次粒径优选在300nm以下，更优选在200nm以下，特别优选在150nm以下，极其优选在100nm以下。另外，作为一次粒径的下限，没有特别的限制，但从能获得充分的物理的切去作用的观点考虑，更优选在1nm以上，特别优选在3nm以上，极其优选在5nm以上。
这里，上述一次粒径是指平均一次粒径，是指能由BET比表面积算出的粒子的平均直径。具体地说，首先将磨粒在800℃(±10℃)下干燥1小时而得到灼烧残留成分。然后，将该灼烧残留成分用研钵(磁性、100ml)细细地捣碎，制成测定用试样。接着，使用BET比表面积测定装置(例如，Yuasa-Ionics株式会社制造，商品名：UTOSORB 6)，对测定用试样的BET比表面积V(单位：nm2/g)进行测定，将通过式：D＝6/(ρ·V)求得的值D(nm)作为平均一次粒径。此外，上述式中的ρ表示粒子的密度(单位：g/nm3)，在粒子为胶体二氧化硅时，ρ＝0.022。
磨粒的平均二次粒径优选为5～500nm。从提高平坦性的观点考虑，上述平均二次粒径的上限值优选在300nm以下，更优选在200nm以下，特别优选在100nm以下。另外，从能确保研磨粒子产生的力学反应层(氧化层)除去能力，并加速研磨速度的观点考虑，上述平均二次粒径的下限值更优选在5nm以上，特别优选在10nm以上。
化学机械研磨用研磨液中的研磨粒子的一次粒径可以使用透射型电子显微镜(例如株式会社日立制作所制造的S4700)进行测定。
作为具体的测定方法，例如，将含有上述的两种无机磨粒的复合粒子与其它的成分进行混合来制成研磨液，抽取适量的该研磨液。关于抽取量，其是考虑磨粒浓度来决定的，例如磨粒浓度为1质量％时抽取0.2cc左右。将抽取的研磨液进行干燥，进行观察。
另外，上述研磨粒子的平均二次粒径是指化学机械研磨用研磨液中的研磨粒子的二次粒径，例如可以使用光衍射散射式粒度分布计(例如，COULTER Electronics公司制造的COULTER N4SD)来进行测定。
(金属防蚀剂)
在化学机械研磨用研磨液中，也可以进一步添加金属防蚀剂。金属防蚀剂是抑制金属层的刻蚀，提高凹陷变形(dishing)特性的化合物。
作为金属防蚀剂，具体地说，例如可以列举出：亚胺、唑、硫醇以及多糖类等，上述这些物质之中从兼顾金属层的刻蚀速度的抑制和金属层的研磨速度的观点考虑，优选含氮环状化合物。它们可以单独或者两种以上组合使用。
作为亚胺，具体可以列举出：双硫腙、亚铜试剂(2，2’-双喹啉)、新亚铜试剂(2，9-二甲基-1，10-菲绕啉)、浴铜灵(2，9-二甲基-4，7-二苯基-菲绕啉)以及双环己酮草酰二腙(cuprizone)等。
作为唑，具体可以列举出：苯并咪唑-2-硫醇、三嗪二硫醇、三嗪三硫醇、2-[2-(苯并噻唑基)]硫代丙酸、2-[2-(苯并噻唑基)]硫代丁酸、2-巯基苯并噻唑、1，2，3-三唑、2-氨基-1H-1，2，4-三唑、3-氨基-1H-1，2，4-三唑、3，5-二氨基-1H-1，2，4-三唑、苯并三唑、1-羟基苯并三唑、1-二羟丙基苯并三唑、2，3-二羧丙基苯并三唑、4-羟基苯并三唑、4-羧基-1H-苯并三唑、4-羧基-1H-苯并三唑甲酯、4-羧基-1H-苯并三唑丁酯、4-羧基-1H-苯并三唑辛酯、5-己基苯并三唑、[1，2，3-苯并三唑基-1-甲基][1，2，4-三唑-1-甲基][2-乙基己基]胺、甲苯基三唑、萘并三唑、双[(1-苯并三唑基)甲基]膦酸、四唑、5-氨基-四唑、5-甲基-四唑、1-甲基-5-巯基四唑、1-N，N-二甲基氨基乙基-5-四唑等。
作为硫醇，具体可以列举出：壬基硫醇以及十二烷基硫醇等。
作为多糖类，具体可以列举出：葡萄糖、纤维素等。
添加上述金属防蚀剂时，其配合量优选在不损害由1，2，4-三唑和磷酸带来的研磨速度提高效果的范围内，从谋求兼顾刻蚀抑制功能和研磨速度的观点考虑，所述配合量相对于研磨液是总质量优选为0.005～2.0质量％。从能获得更高的刻蚀性能的观点考虑，更优选在0.01质量％以上，进一步优选在0.02质量％以上。另外，从容易获得适合的研磨速度的观点考虑，更优选在1.0质量％以下，特别优选在0.5质量％以下。
(水溶性聚合物)
从能提高研磨后的平坦性的观点考虑，可以在化学机械研磨用研磨液中添加水溶性聚合物。从上述的观点考虑，水溶性聚合物的重均分子量优选在500以上，更优选在1500以上，特别优选在5000以上。重均分子量的上限没有特别的规定，但从溶解性的观点考虑，优选在500万以下。重均分子量不足500时，具有无法表现出高研磨速度的倾向。
此外，重均分子量可以通过凝胶渗透色谱法(GPC)使用标准聚苯乙烯的校正曲线进行测定，更具体地说可以用下述的条件进行测定。
使用仪器：日立L-6000型[株式会社日立制作所制作]
柱子：Gel-Pak GL-R420+Gel-Pak GL-R430+Gel-Pak GL-R440[日立化成工业株式会社商品名、共计3根]
洗提液：四氢呋喃
测定温度：40℃
流量：1.75ml/min
检测仪：L-3300RI[株式会社日立制作所制作]
作为重均分子量为500以上的水溶性聚合物，只要是不降低研磨液的成分的溶解性，且磨粒不会凝聚就行，没有特别的限制，具体可以列举出：多糖类、聚羧酸类化合物、乙烯基聚合物、乙二醇化合物等，它们可以单独或2种以上混合使用。作为上述聚羧酸类化合物，可以列举出聚羧酸或其盐、聚羧酸酯或其盐。
用作上述水溶性聚合物的多糖类的具体例子，例如可以列举出：褐藻酸、果胶酸、羧甲基纤维素、琼脂、凝胶多糖(curdlan)以及普鲁兰多糖(pullulan)等。另外，用作上述水溶性聚合物的聚羧酸类化合物的具体例子，例如可以列举出：聚天冬氨酸、聚谷氨酸、聚赖氨酸、聚苹果酸、聚甲基丙烯酸、聚甲基丙烯酸铵盐、聚甲基丙烯酸钠盐、聚酰胺酸、聚马来酸、聚衣康酸、聚富马酸、聚(对苯乙烯羧酸)、聚丙烯酸、聚丙烯酰胺、氨基聚丙烯酰胺、聚丙烯酸铵盐、聚丙烯酸钠盐、聚酰胺酸、聚酰胺酸铵盐、聚酰胺酸钠盐以及聚乙醛酸等聚羧酸，聚羧酸酯及其盐，以及它们的共聚物。
另外，用作上述水溶性聚合物的乙烯基聚合物的具体例子，可以列举出：聚乙烯醇、聚乙烯吡咯烷酮以及聚丙烯醛等。另外，也可以使用聚乙二醇等。
使用上述水溶性聚合物的化合物时，使用的基板为半导体集成电路用硅基板等时，由于由碱金属、碱土类金属、卤化物等产生的污染是不受欢迎的，因此优选酸或其铵盐。
上述水溶性聚合物的化合物之中，从可以实现高平坦化的观点考虑，优选普鲁兰多糖、聚苹果酸、聚甲基丙烯酸、聚丙烯酸、聚丙烯酰胺、聚乙烯醇以及聚乙烯吡咯烷酮、它们的酯以及它们的铵盐。
(pH)
从增加钯层的化学机械研磨速度的观点考虑，化学机械研磨用研磨液的pH优选为1～12。若pH在1以上或pH在6以下，则具有能确保规定的化学机械研磨的研磨速度的倾向，成为实用的研磨液。pH更优选为1～5，特别优选为1～4。
(研磨方法)
通过使用以上说明的化学机械研磨用研磨液，可以进行基板的研磨。即，本发明提供一种基板的研磨方法，其是一边向具有钯层的基板和研磨布之间供给含有1，2，4-三唑、磷酸类、氧化剂以及磨粒的化学机械研磨用研磨液，一边用研磨布研磨基板。
当使用该研磨方法时，优选的是：将基板的被研磨面按压在研磨定盘的研磨布上，在一边向被研磨面与研磨布之间供给本发明的化学机械研磨用研磨液、一边对基板的背面(与被研磨面相反的面)施加规定的压力的状态下，使基板相对于研磨定盘作相对转动，从而研磨被研磨面。
作为研磨装置，例如，可以使用具有定盘和保持基板的支持架(holder)的一般的研磨装置，所述定盘装有可改变转速的马达等并可贴附有研磨布(垫)。作为研磨布，可以使用一般的无纺布、发泡聚氨酯、多孔氟树脂等。作为研磨条件，为了不使基板飞出，优选定盘的旋转速度在200rpm以下的低转速。
向按压在研磨布上的基板施加的压力(研磨压力)优选为4～100kPa，从基板面内的均一性以及图案的平坦性的观点考虑，更优选为6～50kPa。通过使用本发明的化学机械研磨用研磨液，可以在低研磨压力下以高研磨速度研磨钯层。从研磨层的剥离、碎屑、小片化、裂化等的防止以及图案的平坦性的观点考虑，可以在低研磨压力下进行研磨是重要的。
在进行研磨期间，用泵等向研磨布连续供给化学机械研磨用研磨液。作为其供给量，优选的是使得研磨布的表面经常被研磨液覆盖。研磨结束后的基板优选在流水中充分洗涤，然后使用旋转式干燥等将附着在基板上的水滴掸落而使其干燥。
最能发挥化学机械研磨用研磨液的效果的基板是具有钯层(即含有钯的层)的基板。对以下基板也是适合的：在硅等半导体晶片上依次至少形成绝缘膜层、镍层(即含有镍的层)、钯层而成的基板。此外，在绝缘膜层与镍层之间也可以形成基底金属层。
作为形成钯层的材料，可以列举出选自钯、钯合金、其它的钯化合物之中的至少1种。
作为形成镍层的材料，可以列举出选自镍、镍合金、其它的镍化合物之中的至少1种。
基底金属层是防止导电性物质向层间绝缘膜扩散的层。作为形成基底金属层的材料，可以列举出：钽、钽合金、氮化钽等钽化合物；钛、钛合金、氮化钛等钛化合物；钨、氮化钨、钨合金等钨化合物等。
作为绝缘膜层，可以列举出SiO2膜、SiN膜等无机绝缘膜，有机硅酸盐玻璃、全芳香环系Low-k膜等Low-k膜等。
以下，参照附图来对使用化学机械研磨用研磨液的研磨方法进行说明。图1是表示具有凸起电极的基板的制造方法的第1实施方式的剖面图，在该制造方法的工序的一部分中使用上述研磨方法。
图1(a)中所示的基板具备硅晶片1、形成在硅晶片1上的具有凹凸的绝缘膜2和覆盖绝缘膜2的凹凸面的底阻挡金属(under barrier metal)层3。此外，该底阻挡金属层3相当于钯层。使用本发明的化学机械研磨用研磨液研磨这种基板的底阻挡金属层3。即，一边向底阻挡金属层3和研磨布之间供给含有1，2，4-三唑、磷酸类、氧化剂以及磨粒的化学机械研磨用研磨液，一边用研磨布研磨基板，从而使绝缘膜2的凸部露出。
通过这种研磨，可以除去形成在绝缘膜2的凸部上的底阻挡金属层3。图1(b)是表示用这种研磨得到的基板的剖面图。
然后，为了使形成在绝缘膜2的凹部上的底阻挡金属层3露出，在除去了底阻挡金属层3的绝缘膜2的凸部上用公知的方法形成抗蚀图案4。图1(c)是表示形成有抗蚀图案4的基板的剖面图。
接着，使用电镀法等方法，在形成有抗蚀图案4的基板的凹部上形成凸起电极5，使其从绝缘膜2的表面上突出。图1(d)是表示形成有凸起电极5的基板的剖面图。最后，通过除去抗蚀图案4，可以得到在硅晶片1上形成有凸起电极5的基板。图1(e)是表示如此得到的具有凸起电极的基板的剖面图。此外，作为凸起电极5，一般使用金、银、铜、镍或焊料等材料。
图2是表示具有凸起电极的基板的制造方法的第2实施方式的剖面图，在该制造方法的工序的一部分中也使用上述研磨方法。但是，图2中，仅示出了使用研磨方法前的基板(图2(a))、和最终得到的具有凸起电极的基板(图2(b))，其间的化学机械研磨、抗蚀图案形成、凸起电极形成、抗蚀图案除去的各工序按照与第1实施方式同样的方式进行。
图2(a)中所示的基板具备：硅晶片1、形成在硅晶片1上的具有凹凸的绝缘膜2、覆盖绝缘膜2的凹凸面的基底金属膜6和形成在基底金属膜6上的底阻挡金属层3。此外，该底阻挡金属层3相当于钯层。另外，基底金属膜6的形成是以抑制底阻挡金属层3的成分向硅晶片1扩散、提高硅晶片1和底阻挡金属层3的密合性(粘附性)为目的来进行的。
使用本发明的化学机械研磨用研磨液研磨这种基板的底阻挡金属层3以及基底金属膜6。即，一边向底阻挡金属层3和研磨布之间供给含有1，2，4-三唑、磷酸类、氧化剂以及磨粒的化学机械研磨用研磨液，一边用研磨布研磨基板，使绝缘膜2的凸部露出。通过这种研磨，除去形成在绝缘膜2的凸部上的底阻挡金属层3以及基底金属膜6。然后，对如此得到的基板通过与第1实施方式同样地进行抗蚀图案形成、凸起电极形成、抗蚀图案除去，可以得到图2(b)所示的在硅晶片1上形成有凸起电极5的基板。
图3是表示具有凸起电极的基板的制造方法的第3实施方式的剖面图，在该制造方法的工序的一部分中也使用上述研磨方法。但是，图3中，仅示出了使用研磨方法前的基板(图3(a))、和最终得到的具有凸起电极的基板(图3(b))，其间的化学机械研磨、抗蚀图案形成、凸起电极形成、抗蚀图案除去的各工序按照与第1实施方式同样的方式进行。
图3(a)中所示的基板具备：硅晶片1、形成在硅晶片1上的具有凹凸的绝缘膜2、覆盖绝缘膜2的凹凸面的基底金属膜6、形成在基底金属膜6上的第1底阻挡金属层3b、和形成在第1底阻挡金属层3b上的第2底阻挡金属层3a。此外，该第1底阻挡金属层3b或第2底阻挡金属层3a相当于钯层。
使用本发明的化学机械研磨用研磨液研磨这种基板的第1底阻挡金属层3b、第2底阻挡金属层3a以及基底金属膜6。即，一边向第2底阻挡金属层3a和研磨布之间供给含有1，2，4-三唑、磷酸类、氧化剂以及磨粒的化学机械研磨用研磨液，一边用研磨布研磨基板，从而使绝缘膜2的凸部露出。通过这种研磨，除去形成在绝缘膜2的凸部上的第1底阻挡金属层3b、第2底阻挡金属层3a以及基底金属膜6。然后，对如此得到的基板通过与第1实施方式同样地进行抗蚀图案形成、凸起电极形成、抗蚀图案除去，可以得到图3(b)所示的在硅晶片1上形成有凸起电极5的基板。
将图3中的第1底阻挡金属层作为镍层、第2底阻挡金属层作为钯层的例子(屏障下金属由2层构成的结构)显示在图4中。
图4(a)中所示的基板是在设置于硅基板11上的绝缘膜12的凹凸部上依次形成基底金属层15、镍层14以及钯层13而成的。使用本发明的化学机械研磨用研磨液研磨钯层13、镍层14以及基底金属层15，如图4(b)所示，可以使绝缘膜12的凸部露出。
作为使用化学机械研磨用研磨液的研磨方法的其它例子，可以列举出含有以下工序的研磨方法：将存在于绝缘膜12的凸部上的钯层13进行研磨使镍层14露出的第1研磨工序，和将存在于绝缘膜层1的凸部上的镍层14、基底金属层15、以及埋入绝缘膜12的凹部的钯层13的一部分进行研磨而使绝缘膜的凸部露出的第2研磨工序；上述2种研磨工序之中，至少在第1研磨工序中使用化学机械研磨用研磨液。
实施例
以下，通过实施例说明本发明。此外，本发明并不受这些实施例限制。
(研磨液的制备方法)
制备实施例1～5以及比较例1～16中使用的化学机械研磨用研磨液，使其相对于研磨液质量含有表1所示的磨粒10质量％、30％过氧化氢水10质量％、表1所示的氧化金属溶解剂0.5～5质量％、表1所示的金属防蚀剂0～0.5质量％，其余为纯水。使用这些金属用研磨液在下述的研磨条件下进行基板的研磨。
(液状特性评价)
测定温度：25±5℃
pH：使用电气化学计器株式会社制造的型号PHL-40进行测定。
(化学机械研磨条件)
研磨装置：台式研磨装置(株式会社Nano Factor制造)
研磨液流量：11mL/分
基板：用溅射法形成了厚度为0.3μm的钯膜的硅基板。
研磨垫：具有独立气泡的发泡聚氨酯树脂(Rohm and Haas Japan株式会社制造，型号IC1000)
研磨压力：29.4kPa
基板与研磨定盘的相对速度：25m/分钟
研磨液的供给量：11mL/分钟
研磨时间：1分钟
洗涤：用流水将研磨后的晶片充分洗涤，然后除去水滴，使其干燥。
(研磨品评价项目)
研磨速度：由电阻值换算研磨前后的膜厚差来求出上述条件下研磨和洗涤后的钯膜的研磨速度。
将实施例1～5以及比较例1～16中的钯研磨速度(PdRR)示在表1中。
[表1]
Figure BDA0000046478510000141
下面对表1中所示的结果进行详细说明。在实施例1中，添加了与比较例4、7～16同样的氧化剂、氧化金属溶解剂，但进一步添加0.5质量％的1，2，4-三唑作为配位剂、10质量％的二次粒径为0.3μm的α氧化铝作为磨粒。氧化剂为过氧化氢水，氧化金属溶解剂为磷酸。实施例1显示出钯研磨速度为67nm/分钟，是比比较例4、7～16高的值。
在实施例2中，添加了与比较例4、7～16同样的氧化剂、氧化金属溶解剂，但进一步添加了0.5质量％的1，2，4-三唑作为配位剂、10质量％的二次粒径为42nm的胶体二氧化硅作为磨粒。氧化剂为过氧化氢水，氧化金属溶解剂为磷酸。实施例2显示出钯研磨速度为40nm/分钟，是比比较例4、7～16高的值。
在实施例3中，添加了与比较例4、7～16同样的氧化剂、氧化金属溶解剂，但进一步添加了0.5质量％的1，2，4-三唑作为配位剂、2质量％的二次粒径为42nm的胶体二氧化硅作为磨粒。氧化剂为过氧化氢水，氧化金属溶解剂为磷酸。磷酸的添加量为1质量％。实施例3显示出钯研磨速度为36nm/分钟，是比比较例4、7～16高的值。
在实施例4中，添加了与比较例1～16同样的氧化剂，但进一步添加了0.5质量％的1，2，4-三唑作为配位剂、1质量％的多磷酸作为氧化金属溶解剂、2质量％的二次粒径为42nm的胶体二氧化硅作为磨粒。氧化剂为过氧化氢水。实施例4显示出钯研磨速度为34nm/分钟，是比比较例1～16高的值。
在实施例5中，添加了与比较例1～16同样的氧化剂，但进一步添加了0.5质量％的1，2，4-三唑作为配位剂、1质量％的焦磷酸作为氧化金属溶解剂、2质量％的二次粒径为42nm的胶体二氧化硅作为磨粒。氧化剂为过氧化氢水。实施例5显示出钯研磨速度为31nm/分钟，是比比较例1～16高的值。
产业上的利用可能性
根据本发明的化学机械研磨用研磨液以及使用了该化学机械研磨用研磨液的研磨方法，与使用了以往的研磨液的情况相比，至少使钯层的研磨速度也提高，可以用所需的研磨速度进行研磨。
符号说明
1硅晶片、2，12绝缘膜、3底阻挡金属层、3a第2底阻挡金属层3b第1底阻挡金属层、4抗蚀图案、5凸起电极、6，15基底金属膜11硅基板、13钯层、14镍层。

Claims (9)

1.一种化学机械研磨用研磨液，其含有1，2，4-三唑、磷酸类、氧化剂以及磨粒。
2.根据权利要求1所述的化学机械研磨用研磨液，其中所述氧化剂选自由过氧化氢、高碘酸、高碘酸盐、碘酸盐、溴酸盐以及过硫酸盐所组成的组中的至少一种。
3.根据权利要求1或2所述的化学机械研磨用研磨液，其中所述磨粒选自由氧化铝、二氧化硅、氧化锆、二氧化钛以及二氧化铈所组成的组中的至少一种。
4.根据权利要求1～3任一项所述的化学机械研磨用研磨液，其中所述磨粒的浓度以化学机械研磨用研磨液的总量为基准为0.1～10质量％。
5.根据权利要求1～4任一项所述的化学机械研磨用研磨液，其是用作钯研磨用。
6.一种研磨方法，其是一边向基板与研磨布之间供给化学机械研磨用研磨液，一边用所述研磨布研磨所述基板的基板的研磨方法，其中所述基板是具有钯层的基板，所述化学机械研磨用研磨液是含有1，2，4-三唑、磷酸类、氧化剂以及磨粒的化学机械研磨用研磨液。
7.根据权利要求6所述的研磨方法，其中所述氧化剂选自由过氧化氢、高碘酸、高碘酸盐、碘酸盐、溴酸盐以及过硫酸盐所组成的组中的至少一种。
8.根据权利要求6或7所述的研磨方法，其中所述磨粒选自由氧化铝、二氧化硅、氧化锆、二氧化钛以及二氧化铈所组成的组中的至少一种。
9.根据权利要求6～8任一项所述的研磨方法，其中所述磨粒的浓度以化学机械研磨用研磨液的总量为基准为0.1～10质量％。
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CN107020574A (zh) * 2016-02-01 2017-08-08 中国砂轮企业股份有限公司 化学机械研磨修整器及其制造方法

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