CN102112660A - 通过非电解镀形成铜薄膜的镀件 - Google Patents

通过非电解镀形成铜薄膜的镀件 Download PDF

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CN102112660A
CN102112660A CN2009801303460A CN200980130346A CN102112660A CN 102112660 A CN102112660 A CN 102112660A CN 2009801303460 A CN2009801303460 A CN 2009801303460A CN 200980130346 A CN200980130346 A CN 200980130346A CN 102112660 A CN102112660 A CN 102112660A
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copper
metal
plating
electroless plating
film
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CN102112660B (zh
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伊藤顺一
矢部淳司
关口淳之辅
伊森彻
山越康广
仙田真一郎
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JX Nippon Mining and Metals Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Abstract

本发明的目的是提供一种镀件，其中，与在钨、钼等的单质金属上进行非电解镀铜的情况相比，使在大马士革铜配线等上的通过非电解镀铜形成籽晶层时的成膜均匀性和粘附性提高，进而消除在铜籽晶层成膜之前的形成阻挡层和催化剂金属层这两层的烦杂，能够进行超微细配线的形成，以薄且均匀的膜厚形成籽晶层。该镀件的特征在于，在基材上形成有包含金属B和金属A的防止铜扩散用阻挡合金薄膜，所述金属B能够与非电解镀铜液中所含的铜离子进行置换镀，并且对铜具有阻挡性，所述金属A在pH10以上的非电解镀铜液中的离子化倾向比金属B小；该防止铜扩散用阻挡合金薄膜具有所述金属A为15原子％～35原子％的组成，在其上通过使用了pH10以上的非电解镀铜液的非电解镀而形成有铜薄膜。

Description

通过非电解镀形成铜薄膜的镀件
技术领域
本发明涉及通过非电解镀形成了铜薄膜的镀件。尤其是涉及通过非电解镀形成铜薄膜来作为形成ULSI超微细铜配线(大马士革铜配线)时的籽晶层(晶种层；seed layer)的镀件。
背景技术
作为ULSI微细铜配线(大马士革铜配钱)的铜的成膜方法，非电解镀铜法被期待着作为代替现行的溅射法、电镀铜法的方法。
以往，在如半导体晶片那样的镜面上进行了非电解镀铜的场合，析出的镀膜难以获得充分的粘附性。并且，镀敷的反应性低，也难以在基板全面上进行均匀的镀敷。以往，例如在采用非电解镀法在氮化钽等的阻挡金属层上形成铜籽晶层的场合，存在难以均匀地形成镀层、粘附力不充分的问题。另外，在钨、钼等的金属单质上采用非电解镀法形成铜籽晶层来作为阻挡金属层的场合，也存在难以均匀地形成镀层、粘附力不充分的问题。因此，为了在氮化钽等的阻挡金属层上采用非电解镀法均匀地形成铜籽晶层，在镀敷前需要催化剂给予工序。
本发明者们已发现：在非电解镀铜液中加入作为添加剂的重均分子量(Mw)小的水溶性含氮聚合物，另一方面，使被镀件的基板在浸渍镀液前附着催化剂金属，或者预先在最表面成膜出催化剂金属后，使其浸渍在镀液中，借助于氮原子使该催化剂金属上吸附聚合物，由此可抑制镀层的析出速度，并且晶体非常地微细化，能够在如晶片那样的镜面上形成膜厚为15nm以下的均匀的薄膜(专利文献1)。另外，本发明者们还在上述发明的实施例中示出：预先在最表面成膜出催化剂金属后，使其浸渍在镀液中，借助于氮原子使该催化剂金属上吸附聚合物，由此可抑制镀层的析出速度，并且晶体非常地微细化，能够在如晶片那样的镜面上形成膜厚6nm以下的均匀的薄膜。
这样的方法，即在大马士革铜配线形成中，在成膜出催化剂金属后通过非电解镀设置铜籽晶层的场合，必须与催化剂金属层分开地预先形成用于防止铜扩散的阻挡层，因此，在成膜出铜籽晶层前将形成阻挡层和催化剂金属层这两层的层，因此判明了不能够增厚膜厚的超微细配线难以应用于实际工序的问题。
现有技术文献
专利文献1：日本特开2008-223100号公报
发明内容
本发明的目的在于提供一种镀件，其中，与在上述的钨、钼等的单质的金属上进行非电解镀铜的情况相比，使通过非电解镀铜形成籽晶层时的成膜均匀性和粘附性提高，进而消除在铜籽晶层成膜前的形成上述两层的烦杂，能够进行超微细配线的形成，以薄且均匀的膜厚成膜出籽晶层。
本发明者们潜心进行研究的结果发现：通过形成下述合金薄膜，在该合金薄膜上使用pH10以上的非电解镀铜液进行了非电解镀铜时的成膜均匀性和粘附性，与在上述的钨、钼等的单质金属上进行了非电解镀铜的情况相比提高，而且，能够消除在铜籽晶层成膜前的形成上述两层的烦杂，所述合金薄膜包含金属B和金属A，所述金属B能够与非电解镀铜液中所含的铜离子进行置换镀，并且对铜具有阻挡性，所述金属A在pH10以上的非电解镀铜液中的离子化倾向比金属B小，从而完成了本发明。
即，本发明如下。
(1)一种镀件，其特征在于，在基材上形成有包含金属B和金属A的防止铜扩散用阻挡合金薄膜，所述金属B能够与非电解镀铜液中所含的铜离子进行置换镀，并且对铜具有阻挡性，所述金属A在pH10以上的非电解镀铜液中的离子化倾向比金属B小；该防止铜扩散用阻挡合金薄膜具有所述金属A为15原子％～35原子％的组成，在其上通过使用了pH10以上的非电解镀铜液的非电解镀而形成有铜薄膜。
(2)根据上述(1)所述的镀件，其特征在于，上述金属B是钨或钼，上述金属A是选自镍、钴、锡中的至少一种金属。
(3)根据上述(1)或(2)所述的镀件，其特征在于，通过上述非电解镀形成的铜薄膜的膜厚为10nm以下，电阻率为10μΩ·cm以下。
根据本发明，在基材上形成包含能够与含于非电解镀铜液中的铜离子进行置换镀、并且对铜具有阻挡性的金属B、和在pH10以上的非电解镀铜液中的离子化倾向比金属B小的金属A，并具有特定的组成的防止铜扩散用阻挡合金薄膜，在其上通过使用pH10以上的非电解镀铜液的非电解镀形成铜薄膜，由此与在钨、钼等的单质金属上进行非电解镀铜的情况相比，能够提高铜薄膜的成膜均匀性、粘附性。并且，可以形成为在防止铜扩散用阻挡合金薄膜与其上面的非电解镀铜层的界面实质上不含氧的状态，能够降低铜薄膜的电阻。
此外，上述合金薄膜，即使在其上不设置催化剂金属层，也能够通过非电解镀铜来形成成膜均匀性、粘附性优异的铜籽晶层，因此可以消除在大马士革铜配线形成中的形成阻挡层和催化剂金属层这二层的烦杂，进而能够薄膜化。
具体实施方式
本发明涉及一种镀件，其中，在基材上形成有包含金属B和金属A、并具有特定的组成的防止铜扩散用阻挡合金薄膜，所述金属B能够与非电解镀铜液中所含的铜离子进行置换镀，并且对铜具有阻挡性，所述金属A在pH10以上的非电解镀铜液中的离子化倾向比金属B小，在该防止铜扩散用阻挡合金薄膜上，通过使用了pH10以上的非电解镀铜液的非电解镀而形成有铜薄膜。
作为能够与含于非电解镀铜液中的铜离子进行置换镀并且对铜具有阻挡性的金属B，可举出钨和钼，使用这些金属中的任一种，但其中优选钨。
作为金属B使用钨、钼的场合，作为在pH10以上的非电解镀铜液中的离子化倾向比钨、钼小的金属A，可举出镍、钴、锡、镁、铝、锌等，优选镍、钴、锡，更优选镍、钴。镍、钴的熔点比较高，能够使用粉末原料与钨、钼合金化，并且，作为靶电极材料是有用的。
向钨、钼等的单质金属上非电解镀铜的场合，首先，开始钨、钼与铜的置换镀，但由于置换的开始是不均匀的，因此，在全面上引起置换反应之前，在先通过置换而析出的铜上进行还原反应，还原镀膜也覆盖不引起置换镀的部分。由于在置换未反应部分上形成还原镀膜的期间成为残留间隙的形态，因此可以认为粘附性变差。在形成为上述金属A与金属B的合金薄膜的场合，通过在其上使用pH10以上的非电解镀铜液进行非电解镀铜，变得容易引起金属B与铜的置换镀。此外可以认为，由于金属B的离子化倾向比金属A高，因此引起局部电池腐蚀，金属B进行溶解，由于其影响而进行置换反应，置换未反应部分减少，粘附性和成膜均匀性提高。
能够与含于非电解镀铜液中的铜离子进行置换镀并且对铜具有阻挡性的金属B、与在pH10以上的非电解镀铜液中的离子化倾向比金属B小的金属A在防止铜扩散用阻挡合金薄膜中的组成，优选：金属A的组成比为15原子％以上、35原子％以下，更优选为25原子％以下。金属A小于15原子％时，如上述那样置换未反应部分增多，铜的析出变得不均匀，铜膜的粘附性降低。另外，当大于35原子％时，金属A向铜膜中扩散，电阻上升。
上述合金薄膜可以采用形成薄膜的公知的方法形成，但优选使用含有上述金属A和金属B的溅射合金靶，在基材上通过溅射来形成。上述组成的合金薄膜，可以使用含有与所希望的合金薄膜的组成大致相同的组成的金属A和金属B的溅射靶形成。
合金薄膜的膜厚优选为3～20nm，更优选为5～15nm。
本发明中作为形成合金薄膜的基材，优选半导体晶片，可以通过实施酸处理、碱处理、表面活性剂处理、超声波清洗或将它们组合的处理，来谋求基材的清洁化、润湿性提高。
通过非电解镀铜形成的铜薄膜，反应初期主要通过含于非电解镀铜液中的铜离子与金属B的置换反应，使含于非电解镀铜液中的铜离子作为金属析出从而形成。
在本发明中，在反应初期通过置换镀形成铜薄膜，由此在置换镀的过程中上述合金薄膜表面的氧化物被除去。并且，通过上述的作用，由俄歇电子能谱法(AES)分析上述合金薄膜与铜薄膜的界面的氧浓度，可成为1原子％以下(检测极限以下)。在界面存在氧的场合，存在配线的电阻上升、阻挡功能降低等的不良影响。
另外，其结果，可以使铜薄膜的厚度为10nm以下，且电阻率为10μmΩ·cm以下。通过减薄籽晶层的膜厚，能够应用于线宽度为数十nm水平的大马士革铜配线。
作为本发明中的使用防止铜扩散用阻挡合金薄膜进行非电解镀铜时采用的非电解镀铜方法，可以采用一般的方法。同样地使用的镀铜液也可以使用一般的pH10以上的非电解镀铜液。
非电解镀铜液通常含有铜离子、铜离子的络合剂、还原剂和pH调节剂等。
作为非电解镀铜液的还原剂，考虑到福尔马林对人体和环境的不良影响，优选使用乙醛酸。
乙醛酸的浓度，在镀液中优选为0.005～0.5mol/L，更优选为0.01～0.2mol/L。浓度低于0.005mol/L时不引起镀敷反应，当超过0.5mol/L时镀液变得不稳定而进行分解。
本发明中作为非电解镀铜液的铜离子源，可以使用一般所使用的全部的铜离子源，例如，可举出硫酸铜、氯化铜、硝酸铜等。非电解镀铜液中的铜离子源的浓度优选为0.005～0.1mol/L。另外，作为铜离子的络合剂，也可以使用一般所使用的全部络合剂，例如，可举出乙二胺四乙酸、酒石酸等。非电解镀铜液中的络合剂的浓度优选为0.02～0.5mol/L。
作为其他的添加剂，可以使用在镀液中一般所使用的添加剂，例如2，2′-联二吡啶、聚乙二醇、亚铁氰化钾等。
另外，本发明中的非电解镀铜液，优选以pH10～14来使用，更优选以pH12～13来使用。作为pH调节剂，可以使用氢氧化钠、氢氧化钾等的一般所使用的pH调节剂，但在半导体用途中希望避免钠、钾等的碱金属的场合，优选使用氢氧化四甲基铵。
另外，本发明中的非电解镀铜液，从镀浴稳定性和铜的析出速度的观点考虑，优选在40～90℃的浴温下使用。
在本发明中使用非电解镀铜液进行镀敷的场合，将被镀材料浸渍在镀浴中，被镀材料是形成了如上述那样的合金薄膜的材料。
通过本发明的非电解镀而制成的铜薄膜的厚度更优选为3～10nm。
通过本发明的非电解镀而制成的铜薄膜，镀膜薄、膜厚均匀。因此，在用作为大马士革铜配线用籽晶层的情况下，在配线宽度为100nm以下的微细的通孔(vias)和沟槽(trenches)内也能够形成膜厚均匀的薄膜籽晶层，其结果能够得到不发生孔隙、缝等缺陷的半导体晶片。
本发明的镀件，在通过非电解镀形成的铜薄膜上，还可以通过镀敷来设置配线部，镀敷可以采用电镀或非电解镀。
配线部优选是铜或以铜为主成分的合金，更优选铜。电镀铜液，只要是一般在大马士革铜配线埋入用途中使用的组成即可，没有特别的限定，例如可以使用：含有作为主要成分的硫酸铜以及硫酸、作为微量成分的氯、聚乙二醇、二硫代双(3-磺丙基)二钠、烟鲁绿等的液体。另外，作为在埋入时使用的非电解镀铜液，可以使用例如国际公开第2005/038086号小册子所记载的铜配线埋入用镀液。
本发明的镀件，具有形成于基材上的上述特定的合金薄膜，在其上具有作为通过非电解镀形成的籽晶层发挥作用的铜薄膜。通过形成为上述特定的合金薄膜，如已叙述那样，可以在其上通过非电解镀铜来设置成膜均匀性、粘附性好的铜籽晶层，因此可以成为能够进行非电解镀并具有阻挡功能的单一的层，不需要形成催化剂金属层和通常膜厚为数十nm的阻挡层这两层。这样，在本发明的镀件中，通过形成为特定的合金薄膜，可以成为能够进行非电解镀并具有阻挡功能的单一的层，可以使作为该籽晶层发挥作用的铜薄膜的膜厚为10nm以下，因此通过在该铜薄膜上采用常规方法进行成为配线部的金属镀，能够制成为可适用于线宽度为数十nm水平的大马士革铜配线的半导体元件。此外，作为上述籽晶层发挥作用的铜薄膜的电阻率可以为10μΩ·cm以下，其后的电镀初期的均匀成膜变得容易。
实施例
以下通过实施例来说明本发明，但本发明不被这些实施例限定。
实施例1
使用溅射合金靶在半导体基板上形成膜厚为10nm的合金薄膜，并采用非电解镀法在该合金膜上形成了镀铜薄膜。所述溅射合金靶包含能够与含于非电解镀铜液中的铜离子进行置换镀、并且对铜具有阻挡性的金属B和在pH10以上的非电解镀铜液中的离子化倾向比金属B小的金属A，所述金属B为钨，所述金属A为镍。使用上述溅射合金靶形成的该合金薄膜的组成、和通过非电解镀形成的镀铜薄膜的膜厚示于表1。
再者，利用非电解镀进行的铜膜的形成，使用以下组成的镀液，在pH12.5(调节剂：氢氧化钾)、50℃×30～40秒的条件下实施。
镀液组成
硫酸铜             0.02mol/L
乙二胺四乙酸盐     0.21mol/L
乙醛酸             0.03mol/L
2，2′-联二吡啶    20mg/L
关于得到的镀铜薄膜的膜厚、有无孔径为10nm以上的孔、电阻率、铜有无向合金薄膜中扩散、镀铜薄膜与合金薄膜的界面的氧化状态(氧含量)、镀铜薄膜的粘附性进行了评价。膜厚通过截面TEM观察来确认。有无孔是通过表面SEM观察来确认。电阻率是由采用四探针法进行的表面电阻测定、以及通过截面TEM观察进行的膜厚测定结果来算出。铜有无扩散以及界面的氧化状态是通过AES深度分布测定来判断。镀铜薄膜的粘附性，是通过实施使用玻璃纸带(cellophane tape)(CT24，Nichiban公司制)的胶带剥离试验，利用手指肚使带与镀面粘附后，剥离带，确认膜有无剥离。评价规定为：O：镀膜没有剥离、X：镀膜有剥离。结果归纳于表1。
另外，对带有线宽度90nm、纵横尺寸比为4的沟槽图案的半导体基板，形成上述的溅射合金薄膜和非电解镀铜薄膜后，将其作为籽晶层，通过电镀铜来进行配线的埋入。
再者，通过电镀进行的配线的埋入，使用以下组成的镀液，在25℃×60秒、电流密度1A/dm2下实施。
硫酸铜    0.25mol/L
硫酸      1.8mol/L
盐酸      10mmol/L
微量添加剂(聚乙二醇、二硫代双(3-磺丙基)二钠、烟鲁绿)
由得到的镀铜膜的截面TEM观察来评价线宽度为90nm的沟槽部埋入性。判断有无孔和缝，规定为：O：没有孔和缝，X：有孔或缝。
结果示于表1。
实施例2～3、比较例1～3
除了将实施例1中的合金薄膜的组成变成如表1所记载的那样以外，与实施例1同样地制作合金薄膜，进行非电解镀，并进行评价。
结果示于表1。

Claims (3)

1.一种镀件，其特征在于，在基材上形成有包含金属B和金属A的防止铜扩散用阻挡合金薄膜，所述金属B能够与非电解镀铜液中所含的铜离子进行置换镀，并且对铜具有阻挡性，所述金属A在pH10以上的非电解镀铜液中的离子化倾向比金属B小；该防止铜扩散用阻挡合金薄膜具有所述金属A为15原子％～35原子％的组成，在其上通过使用了pH10以上的非电解镀铜液的非电解镀而形成有铜薄膜。
2.根据权利要求1所述的镀件，其特征在于，所述金属B是钨或钼，所述金属A是选自镍、钴、锡中的至少一种金属。
3.根据权利要求1或2所述的镀件，其特征在于，通过所述非电解镀形成的铜薄膜的膜厚为10nm以下，电阻率为10μΩ·cm以下。
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US8283051B2 (en) 2012-10-09
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EP2309025B1 (en) 2012-09-26
US20110129688A1 (en) 2011-06-02
KR101254407B1 (ko) 2013-04-15
CN102112660B (zh) 2013-07-10
JPWO2010016358A1 (ja) 2012-01-19
TWI390080B (zh) 2013-03-21
EP2309025A1 (en) 2011-04-13
KR20110038731A (ko) 2011-04-14
TW201012967A (en) 2010-04-01

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