CN101578394B - 通过无电镀形成金属薄膜的镀敷物及其制造方法 - Google Patents

通过无电镀形成金属薄膜的镀敷物及其制造方法 Download PDF

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CN101578394B
CN101578394B CN2008800013818A CN200880001381A CN101578394B CN 101578394 B CN101578394 B CN 101578394B CN 2008800013818 A CN2008800013818 A CN 2008800013818A CN 200880001381 A CN200880001381 A CN 200880001381A CN 101578394 B CN101578394 B CN 101578394B
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plating
metal
copper
forms
metallic film
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CN101578394A (zh
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矢部淳司
伊藤顺一
日角义幸
关口淳之辅
伊森彻
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JX Nippon Mining and Metals Corp
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Nippon Mining and Metals Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C18/31—Coating with metals
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
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    • 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
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  • Electrochemistry (AREA)
  • Chemically Coating (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Physical Vapour Deposition (AREA)
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Abstract

本发明涉及一种镀敷物以及该镀敷物的制造方法。所述镀敷物是能够通过无电镀而形成超微细配线的、具有以薄且均匀的膜厚形成的籽晶层的镀敷物，而且，在形成籽晶层前能够消除形成阻挡层和催化剂金属层这二层的烦杂。本发明的镀敷物，是在基材上形成具有无电镀的催化活性的金属(A)与能够与无电镀液中含有的金属离子置换镀敷的金属(B)的合金薄膜，并在该合金薄膜上通过无电解置换和还原镀而形成了金属薄膜的镀敷物，该具有催化活性的金属(A)与该能够置换镀敷的金属(B)的合金薄膜，是使该金属(A)为5原子％～40原子％的组成，该通过无电解置换和还原镀而形成的金属薄膜是厚度为10nm以下、电阻率为10μΩ·cm以下的金属薄膜。优选所述金属(B)对金属薄膜的金属具有阻挡功能。

Description

通过无电镀形成金属薄膜的镀敷物及其制造方法
技术领域
本发明涉及通过无电镀形成了金属薄膜的镀敷物及其制造方法。
特别是涉及通过无电镀形成了金属薄膜来作为形成ULSI超微细铜配线(大马士革铜配线)时的籽晶层(晶种层；seed layer)的镀敷物及其制造方法。
背景技术
作为ULSI超微细铜配线(大马士革铜配线)的铜的成膜方法，无电镀铜法作为代替现行的溅射法、电镀铜法的方法被寄予厚望。
以往，在半导体晶片之类的镜面上进行无电镀铜的场合，析出的镀膜难以得到充分的密着性。另外，镀敷的反应性低，也难以在基板整个面上进行均匀的镀敷。以往，例如在采用无电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、密着力不充分的问题。
本发明者们已发现，在无电镀铜液中添加重均分子量(Mw)小的水溶性含氮聚合物作为添加剂，另一方面在镀液浸渍前使催化剂金属附着于被镀物的基板上，或者预先在最表面将催化剂金属成膜后，浸渍在镀液中，借助于氮原子使聚合物吸附在该催化剂金属上，由此抑制镀层的析出速度，并且结晶非常地微细化，能够在晶片之类的镜面上形成膜厚15nm以下的均匀薄膜(专利文献1)。另外，本发明者们在上述发明的实施例中还显示出：预先在最表面将催化剂金属成膜后，浸渍在镀液中，借助于氮原子使聚合物吸附在该催化剂金属上，由此抑制镀层的析出速度，并且结晶非常地微细化，能够在晶片之类的镜面上形成膜厚6nm以下的均匀薄膜。
专利文献1：日本专利申请2007-064348号
发明内容
在这样的方法中，即在大马士革铜配线形成中，在成膜出催化剂金属层后通过无电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，在成膜出铜籽晶层之前形成阻挡层和催化剂金属层这二层的层，因此判明不能够将膜厚增厚的超微细配线难以适用于实际工序的问题。
本发明的目的是提供消除在铜籽晶层成膜前形成这样的两层的烦杂，而且能够形成超微细配线的、能够以薄而均匀的膜厚成膜出籽晶层的预处理技术，还提供含有利用该技术通过无电镀以薄而均匀的膜厚形成的籽晶层的镀敷物、以及提供制造该镀敷物的方法。
本发明者们潜心进行研究的结果发现，通过将具有无电镀的催化活性的金属与具有阻挡功能并且能够与无电镀液中的金属离子置换的金属进行合金化，形成为兼具阻挡功能和催化能力的单一的层，再通过并用无电解置换和还原镀，能够薄而均匀地形成在其上面形成的铜籽晶层的膜厚。从而完成了本发明。
即，本发明是如下的发明。
一种镀敷物，是在基材上形成了具有无电镀的催化活性的金属(A)与能够与无电镀液中含有的金属离子置换镀敷的金属(B)的合金薄膜，并在该合金薄膜上通过无电解置换和还原镀而形成了金属薄膜的镀敷物，其特征在于，该具有催化活性的金属(A)与该能够置换镀敷的金属(B)的合金薄膜，是使具有催化活性的金属(A)为5原子％～40原子％的组成；该通过无电解置换和还原镀而形成的金属薄膜，是厚度为10nm以下、电阻率为10μΩ·cm以下的金属薄膜。
根据[1]所述的镀敷物，其特征在于，通过无电解置换和还原镀而形成的金属薄膜的厚度为10nm以下、电阻率为5μΩ·cm以下。
根据[1]或[2]所述的镀敷物，其特征在于，还在上述金属薄膜上通过镀敷而形成了配线部。
根据[1]～[3]的任一项所述的镀敷物，其特征在于，合金薄膜与通过无电解置换和还原镀而形成的金属薄膜的界面的氧浓度，采用俄歇电子光谱法进行分析为1原子％以下。
根据[3]或[4]所述的镀敷物，其特征在于，具有催化活性的金属(A)是选自铂、金、银、钯中的至少一种金属；能够置换镀敷的金属(B)是选自铁、镍、钴、钨、铌、锡、镁、铝、锌、铅中的至少一种金属；在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是包含选自金、银、铜、镍、钴、铁、锡中的至少一种金属的薄膜；配线部是铜或以铜为主成分的合金。
根据[5]所述的镀敷物，其特征在于，能够置换镀敷的金属(B)，对通过无电解置换和还原镀而形成的金属薄膜的金属具有防止扩散的阻挡功能。
根据[5]或[6]所述的镀敷物，其特征在于，具有催化活性的金属(A)是选自铂、钯中的至少一种金属；能够置换镀敷的金属(B)是选自钨、铌中的至少一种金属；在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜或以铜为主成分的合金薄膜；配线部是铜或以铜为主成分的合金。
根据[5]～[7]的任一项所述的镀敷物，其特征在于，具有催化活性的金属(A)是钯；能够置换镀敷的金属(B)是钨；在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜；配线部是铜。
根据[1]～[8]的任一项所述的镀敷物，其特征在于，通过无电解置换和还原镀而形成的金属薄膜是大马士革铜配线用籽晶层。
根据[1]～[9]的任一项所述的镀敷物，其特征在于，合金薄膜是通过溅射而形成的。
一种半导体元件，其特征在于，在构成中包含[1]～[10]的任一项所述的镀敷物。
一种溅射靶，为了形成[10]所述的镀敷物的合金薄膜而使用。
一种镀敷物的制造方法，是在基材上形成具有无电镀的催化活性的金属(A)与能够与无电镀液中含有的金属离子置换镀敷的金属(B)的合金薄膜，在该合金薄膜上通过无电解置换和还原镀而形成金属薄膜的镀敷物的制造方法，其特征在于，该具有催化活性的金属(A)与该能够置换镀敷的金属(B)的合金薄膜，是使具有催化活性的金属(A)为5原子％～40原子％的组成；该通过无电解置换和还原镀而形成的金属薄膜，是厚度为10nm以下、电阻率为10μΩ·cm以下的金属薄膜。
根据[13]所述的镀敷物的制造方法，其特征在于，通过无电解置换和还原镀而形成的金属薄膜的厚度为10nm以下、电阻率为5μΩ·cm以下。
根据[13]或[14]所述的镀敷物的制造方法，其特征在于，还在上述金属薄膜上通过镀敷而形成配线部。
根据[13]～[15]的任一项所述的镀敷物的制造方法，其特征在于，合金薄膜与通过无电解置换和还原镀而形成的金属薄膜的界面的氧浓度，采用俄歇电子光谱法进行分析为1原子％以下。
根据[15]或[16]所述的镀敷物的制造方法，其特征在于，具有催化活性的金属(A)是选自铂、金、银、钯中的至少一种金属；能够置换镀敷的金属(B)是选自铁、镍、钴、钨、铌、锡、镁、铝、锌、铅中的至少一种金属；在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是包含选自金、银、铜、镍、钴、铁、锡中的至少一种金属的薄膜；配线部是铜或以铜为主成分的合金。
根据[17]所述的镀敷物的制造方法，其特征在于，能够置换镀敷的金属(B)，对通过无电解置换和还原镀而形成的金属薄膜的金属具有防止扩散的阻挡功能。
根据[17]或[18]所述的镀敷物的制造方法，其特征在于，具有催化活性的金属(A)是选自铂、钯中的至少一种金属；能够置换镀敷的金属(B)是选自钨、铌中的至少一种金属；在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜或以铜为主成分的合金薄膜；配线部是铜或以铜为主成分的合金。
根据[17]～[19]的任一项所述的镀敷物的制造方法，其特征在于，具有催化活性的金属(A)是钯；能够置换镀敷的金属(B)是钨；在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜；配线部是铜。
根据[13]～[20]的任一项所述的镀敷物的制造方法，其特征在于，通过无电解置换和还原镀而形成的金属薄膜是大马士革铜配线用籽晶层。
根据[13]～[21]的任一项所述的镀敷物的制造方法，其特征在于，通过溅射而形成合金薄膜。
根据本发明，采用无电镀法在基材上的阻挡金属层上形成籽晶层的场合，重要的是预备性地形成具有无电镀的催化活性的金属与能够与无电镀液中含有的金属离子置换镀敷的金属的具有特定组成的合金薄膜，由此在该合金薄膜上通过无电解置换和还原镀而形成铜等的金属薄膜时，不侵蚀成为基底的上述预备薄膜表面，能够以充分薄、均匀的膜厚且以优异的密着性成膜出在该合金薄膜上形成的铜等的金属薄膜层。另外，在上述预形成的合金薄膜与其上的无电镀层的界面，能够成为实质上不含有氧的状态。
此外，通过使能够与上述无电镀液中含有的金属离子置换镀敷的金属，为对通过无电镀而形成的金属薄膜的金属具有防止扩散的阻挡功能的金属，上述合金薄膜能够成为兼具阻挡功能和催化能力的单一的层，能够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，能够进一步薄膜化。
具体实施方式
本发明是涉及在通过无电镀形成金属薄膜时，预先在基材上形成具有无电镀的催化活性的金属(A)与能够与无电镀液中含有的金属离子置换镀敷的金属(B)的合金薄膜，通过并用无电镀液的还原反应和与无电镀液中含有的金属离子的置换反应而形成金属薄膜(籽晶层)的方法以及所得到的形成了籽晶层的镀敷物的发明。
在本发明中，无电镀可并用还原型镀敷和置换型镀敷。
通过置换镀敷，上述合金薄膜表面的氧化物在置换镀敷的过程中被除去，而且，由于同时地引起还原镀，因此能够使形成具有所期望的导电性的籽晶层所必需的膜厚均匀地减薄。
其结果，能够使籽晶层的厚度为10nm以下、并且电阻率为10μΩ·cm以下。通过将籽晶层的膜厚减薄，能够适用于线宽度为数十纳米水平的大马士革铜配线。
另外，通过上述的作用，采用俄歇电子光谱法(AES)分析合金薄膜与铜等的通过无电解置换和还原镀而形成的金属薄膜的界面的氧浓度，结果为1原子％以下(检测极限以下)。另一方面，在使用置换镀敷不作用的钽作为具有阻挡功能的金属的场合，在界面可显著地检测出氧。
在界面存在氧的场合，具有配线的电阻升高，或阻挡功能降低等的不良影响。
作为具有无电镀的催化活性的金属(A)，可举出铂、金、银、钯等，使用选自这些金属中的至少一种以上的金属，但其中优选使用铂、钯，特别优选钯。另外，也可以使用含有两种以上的具有催化活性的金属的合金。在本发明中，所谓上述具有无电镀的催化活性，是指具有将无电镀液中的铜等的金属离子还原从而形成镀膜的反应的催化能力。
作为能够与无电镀液中所含的金属离子置换镀敷的金属(B)，可举出铁、镍、钴、钨、铌、锡、镁、铝、锌、铅。另外，通过使金属(B)为对通过无电解置换和还原镀而形成的金属薄膜的金属具有阻挡功能的金属，能够使上述合金薄膜成为兼具阻挡功能和催化能力的单一的层，能够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，能够进一步薄膜化，因此优选。作为该具有阻挡功能的金属(B)，可举出钨、铌，使用选自这些金属中的至少一种以上的金属，但特别优选钨。
能够与无电镀液中所含有的金属离子置换镀敷的金属(B)与具有无电镀的催化活性的金属(A)的合金薄膜中的组成，一般优选金属(A)的组成比为5原子％～40原子％。当金属(A)少于5原子％时，与镀液的还原反应相比，置换反应变为优势，侵蚀被镀材料，不能够形成均匀的薄膜。而且，在金属(B)是上述具有阻挡功能的金属的场合，由于膜不均匀，因此产生膜厚极端地薄的部分，导致阻挡功能的降低。另外，当多于40原子％时，金属(A)混入到镀膜中，使电阻值升高，导致信号的延迟。另外，还产生膜的成本增高的问题。
上述合金薄膜，优选使用含有上述金属(A)和金属(B)的溅射合金靶，通过溅射而在基材上形成。上述组成的合金薄膜，能够使用与所希望的合金薄膜的组成大致相同的组成的含有金属(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。
作为在本发明中形成合金薄膜的基材，优选半导体晶片，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，能够谋求基材的清洁、润湿性提高。
通过无电解置换和还原镀而形成的金属薄膜，是通过无电镀液中含有的金属离子与金属(B)的置换反应，以及金属(A)作为将无电镀液的金属离子还原的催化剂发挥作用，无电镀液中含有的金属离子以金属形式析出从而形成的。作为该金属薄膜，可举出包含金、银、铜、镍、钴、铁、锡中的至少一种金属的薄膜，优选是铜薄膜或以铜为主成分的合金的薄膜，特别优选铜薄膜。
作为使用本发明的阻挡兼催化剂层(合金薄膜)进行无电解置换和还原镀时采用的无电镀方法，可以采用一般的方法。同样地，使用的镀液也可以使用一般的镀液。
作为使用本发明的阻挡兼催化剂层(合金薄膜)进行无电解置换和还原镀时采用的无电镀铜方法，可以采用一般的方法。同样地，使用的镀铜液也可使用一般的无电镀铜液。
无电镀铜液，通常含有铜离子、铜离子的配位剂、还原剂和pH调节剂等。
作为无电镀铜液的还原剂，考虑到甲醛水(formalin)对人体和环境的不良影响，优选使用乙醛酸。另外，次膦酸虽然在铜上不显示还原作用，但在钯等的催化剂金属上显示较高的还原作用，因此具有提高借助于催化剂金属的初期的镀敷反应性的效果。另外，这些还原剂不含有作为在半导体用途中希望避免的杂质的钠。
因此，作为还原剂更优选的是同时地使用乙醛酸和次膦酸。通过该并用，镀敷反应性比单独地使用乙醛酸的情况高，其结果，能够得到可在难以引起镀敷反应的半导体晶片之类的镜面上，在更低温下均匀镀敷的无电镀铜液。由于镀敷反应性变高，因此可在更低温下镀敷，而且，通过为更低温，液体稳定性增大，并且析出的铜粒子容易变得细而均匀。
乙醛酸的浓度，优选在镀液中为0.005～0.5摩尔/L，更优选为0.01～0.2摩尔/L。当浓度不到0.005摩尔/L时，不引起镀敷反应，当超过0.5摩尔/L时，镀液变得不稳定而分解。
次膦酸的浓度，优选在镀液中为0.001～0.5摩尔/L，更优选为0.005～0.2摩尔/L。当浓度不到0.001摩尔/L时，看不到上述的效果，当超过0.5摩尔/L时，镀液变得不稳定而分解。
在本发明中作为无电镀铜液的铜离子源，可以使用一般所使用的所有铜离子源，例如，可举出硫酸铜、氯化铜、硝酸铜等。另外，作为铜离子的配位剂，也可以使用一般所使用的所有配位剂，例如，可举出乙二胺四乙酸、酒石酸等。
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，本发明中的无电镀铜液，优选在pH 10～14下使用，更优选在pH 12～13下使用。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，本发明中的无电镀铜液，从浴稳定性和铜的析出速度的观点考虑，优选在浴温40～90℃下使用。
在本发明中使用无电镀铜液进行镀敷的场合，将被镀材料浸渍在镀浴中。被镀材料是成膜出如上所述的合金薄膜的材料。
本发明的通过无电解置换和还原镀而制造的金属薄膜的厚度，更优选为3～10nm。
本发明的通过无电解置换和还原镀而制造的金属薄膜，镀膜薄、膜厚均匀。因此作为大马士革铜配线用籽晶层使用的场合，在线宽度100nm以下的微细的孔、沟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、缝等缺陷的半导体晶片。
本发明的镀敷物，能够在通过无电镀而形成的金属薄膜上，进而通过镀敷来设置配线部。镀敷可使用电镀或无电镀。
配线部优选是铜或以铜为主成分的合金，更优选是铜。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，没有特别限定，例如可以使用含有硫酸铜和硫酸作为主成分、含有氯、聚乙二醇、二硫化双(3-磺丙基)二钠、烟鲁绿等作为微量成分的液体。另外，作为用于埋入的无电镀铜液，例如可以使用日本特开2005-038086号公报所述的铜配线埋入用镀液。
本发明的镀敷物，具有在基材上形成的上述特定的合金薄膜，在该合金薄膜上具有通过无电解置换和还原镀而形成的作为籽晶层发挥作用的金属薄膜。上述特定的合金薄膜，如已述那样可成为兼具催化能力和阻挡功能的单一的层，因此不需要形成通常膜厚为数十纳米的阻挡层。这样，在本发明的镀敷物上，能够使合金薄膜成为兼具阻挡功能和催化能力的单一的层，该作为籽晶层发挥作用的金属薄膜的膜厚为10nm以下，因此通过采用常规方法在该金属薄膜上镀敷成为配线部的金属，能够制成可适用于线宽度为数十纳米水平的大马士革铜配线的半导体元件。进而，上述作为籽晶层发挥作用的金属薄膜的电阻率为10μΩ·cm以下，因此其后的电镀初期的均匀成膜变得容易。上述金属薄膜的电阻率优选为5μΩ·cm以下。
实施例
以下通过实施例对本发明进行说明，但本发明不被这些实施例限定。
实施例1
在半导体基板上，使用由作为具有无电镀的催化活性的金属的钯、和作为能够与无电镀液中含有的金属离子置换镀敷的金属的钨形成的溅射合金靶，制造表1所表示的组成的膜厚10nm的合金薄膜，采用无电镀法在该合金薄膜上形成了镀铜薄膜。另外，通过无电镀来形成铜膜时，使用以下组成的镀液，在pH 12.5(调节剂：氢氧化钾)、50℃×30～40秒的条件下实施。
镀液组成
硫酸铜             0.02摩尔/L
乙二胺四乙酸盐     0.21摩尔/L
乙醛酸             0.03摩尔/L
次膦酸             0.09摩尔/L
2，2’-联二吡啶    20mg/L
关于得到的镀铜薄膜的膜厚、电阻率、铜有无向合金薄膜中扩散、具有无电镀的催化活性的金属(A)有无向镀铜薄膜中扩散、镀铜薄膜剥离后有无孔进行评价。另外，通过AES深度分布测定确认镀敷时的铜薄膜与合金薄膜的界面的氧化状态(氧含量)。
另外，对于带有线宽度为90nm、纵横尺寸比为4的沟图案的半导体基板，成膜出上述的溅射合金薄膜以及无电镀铜薄膜后，将其作为籽晶层通过电镀铜进行配线的埋入。
再者，通过电镀埋入配线时，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    0.25摩尔/L
硫酸      1.8摩尔/L
盐酸      10毫摩尔/L
微量添加剂(聚乙二醇、二硫化双(3-磺丙基)二钠、烟鲁绿)
通过得到的镀铜膜的劈开截面SEM观察，对线宽度90nm沟部的埋入性进行了评价。
结果示于表1。
实施例2～7、比较例1～3
除了将实施例1中的合金薄膜的组成如表1所记载的那样改变以外，与实施例1同样地制造合金薄膜，进行无电镀，并进行了评价。
结果示于表1。
本发明中表示数值范围的“以上”和“以下”均包括本数。
Figure G2008800013818D00121

Claims (27)

1.一种镀敷物，是在基材上形成了具有无电镀的催化活性的金属(A)与能够与无电镀液中含有的金属离子置换镀敷的金属(B)的合金薄膜，并在该合金薄膜上通过无电解置换和还原镀而形成了金属薄膜的镀敷物，其特征在于，
该具有催化活性的金属(A)与该能够置换镀敷的金属(B)的合金薄膜，其组成为具有催化活性的金属(A)为5原子％～40原子％；
该通过无电解置换和还原镀而形成的金属薄膜，是厚度为10nm以下、电阻率为10μΩ·cm以下的金属薄膜，
具有催化活性的金属(A)是选自铂、金、银、钯中的至少一种金属；
能够置换镀敷的金属(B)是选自铁、镍、钴、钨、铌、锡、镁、铝、锌、铅中的至少一种金属；
在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是包含选自金、银、铜、镍、钴、铁、锡中的至少一种金属的薄膜。
2.根据权利要求1所述的镀敷物，其特征在于，通过无电解置换和还原镀而形成的金属薄膜的厚度为10nm以下、电阻率为5μΩ·cm以下。
3.根据权利要求1所述的镀敷物，其特征在于，还在所述金属薄膜上通过镀敷而形成了配线部。
4.根据权利要求2所述的镀敷物，其特征在于，还在所述金属薄膜上通过镀敷而形成了配线部。
5.根据权利要求1～4的任一项所述的镀敷物，其特征在于，合金薄膜与通过无电解置换和还原镀而形成的金属薄膜的界面的氧浓度，采用俄歇电子光谱法进行分析为1原子％以下。
6.根据权利要求3或4所述的镀敷物，其特征在于，合金薄膜与通过无电解置换和还原镀而形成的金属薄膜的界面的氧浓度，采用俄歇电子光谱法进行分析为1原子％以下，配线部是铜或以铜为主成分的合金。
7.根据权利要求1～4的任一项所述的镀敷物，其特征在于，能够置换镀敷的金属(B)，对通过无电解置换和还原镀而形成的金属薄膜的金属具有防止扩散的阻挡功能。
8.根据权利要求3或4所述的镀敷物，其特征在于，
具有催化活性的金属(A)是选自铂、钯中的至少一种金属；
能够置换镀敷的金属(B)是选自钨、铌中的至少一种金属；
在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜或以铜为主成分的合金薄膜；
配线部是铜或以铜为主成分的合金。
9.根据权利要求1或2所述的镀敷物，其特征在于，
具有催化活性的金属(A)是选自铂、钯中的至少一种金属；
能够置换镀敷的金属(B)是选自钨、铌中的至少一种金属；
在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜或以铜为主成分的合金薄膜。
10.根据权利要求3或4所述的镀敷物，其特征在于，
具有催化活性的金属(A)是钯；
能够置换镀敷的金属(B)是钨；
在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜；
配线部是铜。
11.根据权利要求1或2所述的镀敷物，其特征在于，
具有催化活性的金属(A)是钯；
能够置换镀敷的金属(B)是钨；
在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜。
12.根据权利要求1～4的任一项所述的镀敷物，其特征在于，通过无电解置换和还原镀而形成的金属薄膜是大马士革铜配线用籽晶层。
13.根据权利要求1～4的任一项所述的镀敷物，其特征在于，合金薄膜是通过溅射而形成的。
14.一种半导体元件，其特征在于，在构成中包含权利要求1～4的任一项所述的镀敷物。
15.一种镀敷物的制造方法，是在基材上形成具有无电镀的催化活性的金属(A)与能够与无电镀液中含有的金属离子置换镀敷的金属(B)的合金薄膜，并在该合金薄膜上通过无电解置换和还原镀而形成金属薄膜的镀敷物的制造方法，其特征在于，
该具有催化活性的金属(A)与该能够置换镀敷的金属(B)的合金薄膜，其组成为具有催化活性的金属(A)为5原子％～40原子％；
该通过无电解置换和还原镀而形成的金属薄膜，是厚度为10nm以下、电阻率为10μΩ·cm以下的金属薄膜，
具有催化活性的金属(A)是选自铂、金、银、钯中的至少一种金属；
能够置换镀敷的金属(B)是选自铁、镍、钴、钨、铌、锡、镁、铝、锌、铅中的至少一种金属；
在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是包含选自金、银、铜、镍、钴、铁、锡中的至少一种金属的薄膜。
16.根据权利要求15所述的镀敷物的制造方法，其特征在于，通过无电解置换和还原镀而形成的金属薄膜的厚度为10nm以下、电阻率为5μΩ·cm以下。
17.根据权利要求15所述的镀敷物的制造方法，其特征在于，还在所述金属薄膜上通过镀敷而形成配线部。
18.根据权利要求16所述的镀敷物的制造方法，其特征在于，还在所述金属薄膜上通过镀敷而形成配线部。
19.根据权利要求15～18的任一项所述的镀敷物的制造方法，其特征在于，合金薄膜与通过无电解置换和还原镀而形成的金属薄膜的界面的氧浓度，采用俄歇电子光谱法进行分析为1原子％以下。
20.根据权利要求17或18所述的镀敷物的制造方法，其特征在于，合金薄膜与通过无电解置换和还原镀而形成的金属薄膜的界面的氧浓度，采用俄歇电子光谱法进行分析为1原子％以下，配线部是铜或以铜为主成分的合金。
21.根据权利要求15～18的任一项所述的镀敷物的制造方法，其特征在于，能够置换镀敷的金属(B)，对通过无电解置换和还原镀而形成的金属薄膜的金属具有防止扩散的阻挡功能。
22.根据权利要求17或18所述的镀敷物的制造方法，其特征在于，
具有催化活性的金属(A)是选自铂、钯中的至少一种金属；
能够置换镀敷的金属(B)是选自钨、铌中的至少一种金属；
在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜或以铜为主成分的合金薄膜；
配线部是铜或以铜为主成分的合金。
23.根据权利要求15或16所述的镀敷物的制造方法，其特征在于，
具有催化活性的金属(A)是选自铂、钯中的至少一种金属；
能够置换镀敷的金属(B)是选自钨、铌中的至少一种金属；
在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜或以铜为主成分的合金薄膜。
24.根据权利要求17或18所述的镀敷物的制造方法，其特征在于，
具有催化活性的金属(A)是钯；
能够置换镀敷的金属(B)是钨；
在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜；
配线部是铜。
25.根据权利要求15或16所述的镀敷物的制造方法，其特征在于，
具有催化活性的金属(A)是钯；
能够置换镀敷的金属(B)是钨；
在合金薄膜上通过无电解置换和还原镀而形成的金属薄膜是铜薄膜。
26.根据权利要求15～18的任一项所述的镀敷物的制造方法，其特征在于，通过无电解置换和还原镀而形成的金属薄膜是大马士革铜配线用籽晶层。
27.根据权利要求15～18的任一项所述的镀敷物的制造方法，其特征在于，通过溅射而形成合金薄膜。
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EP2067878B1 (en) 2017-03-22
EP2067878A1 (en) 2009-06-10
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US8394508B2 (en) 2013-03-12
JPWO2009016979A1 (ja) 2010-10-14
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