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CN110325665B - 无电解镀敷工艺 - Google Patents

无电解镀敷工艺 Download PDF

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Publication number
CN110325665B
CN110325665B CN201880012615.2A CN201880012615A CN110325665B CN 110325665 B CN110325665 B CN 110325665B CN 201880012615 A CN201880012615 A CN 201880012615A CN 110325665 B CN110325665 B CN 110325665B
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China
Prior art keywords
electroless
nickel
plating
film
nickel plating
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CN201880012615.2A
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CN110325665A (zh
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加藤友人
渡边秀人
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Kojima Chemicals Co Ltd
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Kojima Chemicals Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L24/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by 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
    • 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
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    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
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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
    • 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
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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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    • C23C18/52—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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
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Abstract

本发明的目的在于提供一种无电解镀敷工艺，在铜材料的表面依次形成镀镍被膜和镀金被膜时能减少镀镍被膜的膜厚，且能够得到具有优异的封装特性的被膜。为了解决上述问题，提供一种无电解镀敷工艺，通过无电解镀敷法在铜材料的表面依次形成镀镍被膜和镀金被膜，该无电解镀敷工艺的特征在于，包括：通过无电解触击镀敷法在铜材料的表面形成镀镍被膜的工序、和通过还原型无电解镀敷法形成镀金被膜的工序。

Description

无电解镀敷工艺
技术领域
本发明涉及一种通过无电解镀敷法在铜材料的表面形成镀金被膜的无电解镀敷工艺。
背景技术
近年，一方面针对电子设备的高功能化和多功能化的要求增高，另一方面用于这些电子设备的树脂基板、陶瓷基板、晶片基板等电子电路基板也需要进一步轻薄短小化。由于为了应对该轻薄短小化需要高密度封装，因此需要能够实现高密度封装的表面处理技术。而且，在电子电路基板的技术领域中，确立了使用焊锡或引线接合(Wire bonding)的封装技术作为接合封装部件的技术。
为确保封装时的连接可靠性，对电子电路基板上的电路图案的封装部分即配线垫片，实施了镀敷处理作为表面处理。例如，在由低电阻的铜等金属形成的电路图案上，通过镀敷处理依次形成镀镍被膜和镀金被膜。以下，将依次形成镀镍被膜和镀金被膜的被膜记载为“Ni/Au被膜”。形成镀镍被膜是为了防止铜向镀金被膜扩散，形成镀金被膜是为了得到良好的封装特性。
而且，也已知在镀镍被膜和镀金被膜之间形成钯被膜的技术。以下，将依次形成镀镍被膜、镀钯被膜和镀金被膜的被膜记载为“Ni/Pd/Au被膜”。形成钯被膜是为了在热处理镀敷基板时防止镍向镀金被膜扩散。在镀镍被膜上形成镀钯被膜时，能够进行镀镍被膜的薄膜化。
作为上述镀敷处理，电解镀敷工艺是主流，但是对于电解镀敷工艺无法应对的情况，则适用无电解镀敷工艺。
以往，作为在铜表面形成Ni/Pd/Au被膜的无电解镀敷工艺，例如，专利文献1中如图10所示公开如下内容：对铜材料进行脱脂工序(步骤(以下记为“S”)11)及蚀刻(S12)，对铜材料的表面付与钯催化剂(S14)后，进行无电解镀镍(Ni)(S15)、无电解镀钯(Pd)(S16)和无电解镀金(Au)(S17)。专利文献1中虽没有记载，但是，一般会在蚀刻(S12)与付与钯催化剂处理(S14)之间进行去污(desmut)(S13)。为在无电解镀镍(S15)时进行镍析出，通常，必须进行付与钯催化剂处理(S14)。
在专利文献1公开的无电解镀镍(S15)中使用无电解镀镍液，该无电解镀镍液含有硫酸镍·6水合物22.5g/L(以镍进行换算为5g/L)、作为还原剂的次亚磷酸钠、作为络合物的苹果酸及琥珀酸、且含有作为稳定剂的铅盐、铋盐、硫化合物等，并且将pH调节为4.6，浴温调整为60～90℃。也可以使用二甲胺硼烷代替次亚磷酸钠作为还原剂。而且，通过无电解镀镍(S15)形成膜厚为0.1～15μm的镀镍被膜，通过无电解镀钯(S16)形成膜厚为0.001～2μm的镀钯被膜，通过无电解镀金(S17)形成膜厚0.001～1μm的镀金被膜。
Ni/Au被膜或Ni/Pd/Au被膜中，为了实现进一步高密度封装，期望镀镍被膜更进一步薄膜化
专利文献
专利文献1:日本特开2008-174774号公报
发明内容
发明所要解决的技术问题
但是，通过上述无电解镀镍(S15)形成膜厚例如为0.01μm以下的极薄的镀镍被膜的情况下，有时被覆不充分，在镀镍被膜的表面产生微小的凹部(孔)。而且，在进行后续的无电解镀金(S17)时，有时该凹部发生腐蚀从而产生贯穿镀镍被膜的贯通孔。该现象称为“镍局部腐蚀现象”。此时，存在Ni/Au被膜或Ni/Pd/Au被膜中无法得到优异的封装特性的不良情况。
本发明的课题是提供一种无电解镀敷工艺，该无电解镀敷工艺在铜材料的表面依次形成镀镍被膜和镀金被膜时能减少镀镍被膜的膜厚，且能够得到具有优异的封装特性的被膜。
用于解决课题的技术手段
本发明的无电解镀敷工艺是通过无电解镀敷法在铜材料的表面依次形成镀镍被膜和镀金被膜的工艺，其特征在于，具有：
通过无电解触击镀敷法在铜材料的表面形成镀镍被膜的工序，和
通过还原型无电解镀敷法形成镀金被膜的工序。
在本发明的无电解镀敷工艺中，优选：上述无电解触击镀敷法通过使用无电解触击镀镍液、且将所述铜材料浸渍于该无电解触击镀镍液中而进行，该无电解触击镀镍液含有：
以镍换算为0.002～1g/L的水溶性镍盐、
羧酸或其盐、和
选自二甲胺硼烷、三甲胺硼烷、肼、肼类衍生物中的1种以上的还原剂，
且该无电解触击镀镍液的pH调节至6～10、浴温调节为20～55℃。
而且，优选：所述无电解触击镀镍液是在将所述水溶性镍盐和所述羧酸或其盐和水混合进行搅拌从而制成含有镍络合物的水溶液后、通过在该水溶液中混合所述还原剂进行搅拌而制成的。
本发明的无电解镀敷工艺中，优选：形成所述镀镍被膜的工序是形成膜厚为0.005～0.3μm的镀镍被膜的工序。
并且，优选：本发明的无电解镀敷工艺是在铜材料的表面依次形成镀镍被膜、镀钯被膜和镀金被膜的工艺，在形成所述镀镍被膜的工序与形成所述镀金被膜的工序之间，具有通过还原型无电解镀敷法形成镀钯被膜的工序。
发明效果
本发明的无电解镀敷工艺中，通过采用无电解触击镀敷法，即使不进行在以往的无电解镀敷工艺中进行的钯催化剂赋予处理(S14)，也能够在铜材料的表面直接形成镀镍被膜。另外，即使膜厚很薄也能够确切地覆盖铜材料的表面，且能够形成对铜材料的密合性优异的镀镍被膜。因此，根据本发明的无电解镀敷工艺，能够实现镀镍被膜的薄膜化。而且，本发明的无电解镀敷工艺中，通过采用还原型无电解镀敷法，能够在不使之前已经形成的被膜的金属溶出的情况下形成镀金被膜或镀钯被膜。而且，根据本发明的无电解镀敷工艺，能够得到封装特性优异的Ni/Au被膜或Ni/Pd/Au被膜。
附图说明
图1是表示本实施方式的无电解镀敷工艺的流程图。
图2是通过实施例1的无电解镀敷工艺得到的镀镍被膜的SEM照片。
图3是通过比较例1的无电解镀敷工艺得到的镀镍被膜的SEM照片。
图4是通过比较例2的无电解镀敷工艺得到的镀镍被膜的SEM照片。
图5是表示针对通过实施例1和比较例1的无电解镀敷工艺得到的镀镍被膜进行低电压电解的结果的曲线图。
图6是表示通过实施例1和比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜的焊料扩展性的曲线图。
图7是表示通过实施例1和比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜的焊球剪切强度的曲线图。
图8是表示通过实施例1和比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜的引线接合强度的曲线图。
图9是表示通过实施例1和比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜的金引线断裂模式的曲线图。
图10是表示以往的无电解镀敷工艺的流程图。
具体实施方式
接下来，说明本发明的无电解镀敷工艺的实施方式。本实施方式的无电解镀敷工艺是在电极或配线等(其设于例如树脂基板、陶瓷基板、晶片基板等绝缘基材的表面)的铜材料表面通过无电解镀敷法依次形成镀镍被膜和镀金被膜的无电解镀敷工艺。具体来说，无电解镀敷工艺具有：通过无电解触击镀敷法在铜材料的表面形成镀镍被膜的工序，和通过还原型无电解镀敷法形成镀金被膜的工序。以下，针对通过在铜材料的表面依次形成镀镍被膜、镀钯被膜和镀金被膜从而在铜材料的表面形成Ni/Pd/Au被膜的无电解镀敷工艺，进行说明。
在本实施方式的无电解镀敷工艺中，如图1所示，首先，作为形成镀镍被膜之前的前处理，进行脱脂工序(S1)、蚀刻工序(S2)和去污工序(S3)。之后，通过无电解触击镀镍(Ni)工序(S4)在铜材料的表面形成镀镍被膜。接着，通过无电解镀钯(Pd)工序(S5)形成镀钯被膜，通过无电解镀金(Au)工序(S6)形成镀金被膜。在各个工序之后进行水洗处理。优选进行3次水洗处理。
1.脱脂工序(S1)
在脱脂工序(S1)中，通过将铜材料浸渍于酸性溶液中，从而除去附着于铜材料表面的油脂成分。
2.蚀刻工序(S2)
在蚀刻工序(S2)中，通过将实施了脱脂工序(S1)的铜材料浸渍于过硫酸类、过氧化氢类、硫醇类等蚀刻液中，从而除去形成于铜材料表面的铜氧化膜。
3.去污工序(S3)
在去污工序(S3)中，通过将完成蚀刻工序(S2)的铜材料浸渍于例如10％硫酸中，从而除去附着于铜材料表面的污物。
4.无电解触击镀镍工序(S4)
在无电解触击镀镍工序(S4)中，通过无电解触击镀敷法，在经过前处理的铜材料的表面形成镀镍被膜。无电解触击镀镍法是通过将已实施了去污工序(S3)的铜材料浸渍于无电解触击镀镍液中而进行的。
无电解触击镀镍液：
无电解触击镀镍液包含：水溶性镍盐；羧酸或其盐；和选自二甲胺硼烷、三甲胺硼烷、肼、肼类衍生物中的1种以上的还原剂。在本说明书中，所谓“1种以上”可以表示为仅1种，也可以是2种以上的多种。
水溶性镍盐：
作为用于无电解触击镀镍液的水溶性镍盐，可以举出例如，硫酸镍、氯化镍、碳酸镍、乙酸镍、次亚磷酸镍、氨基磺酸镍、柠檬酸镍等有机酸镍。上述水溶性镍盐可单独使用，也可以组合2种以上进行使用。本发明中，作为水溶性镍盐，最优选使用硫酸镍六水合物。
对于无电解触击镀镍液而言，优选水溶性镍盐的以镍换算的含量为0.002～1g/L的范围。该范围是在以往的无电解镀敷工艺的无电解镀镍(S15)中所使用的无电解镀镍液的镍浓度5g/L的1/5以下，是非常低的浓度。无电解触击镀镍液通过使水溶性镍盐的以镍换算的含量为上述范围，能够实现无电解触击镀敷法，能够在未付与钯催化剂的铜材料的表面直接形成镀镍被膜。
水溶性镍盐的以镍换算的含量不到0.002g/L时，析出速度过慢，因此为了得到所希望的膜厚的镀镍被膜需要增加浸渍时间，且不能满足工业生产率，故而不理想。另一方面，水溶性镍盐的以镍换算的含量超过1g/L时，析出速度过快，不能得到表面均匀的镀镍被膜，不理想。水溶性镍盐的以镍换算的含量更优选0.01～0.5g/L的范围，最优选0.03～0.1g/L的范围。
羧酸或其盐：
无电解触击镀镍液，包括羧酸或其盐。它们作为络合剂、pH调节剂来使用。作为羧酸，例如，单羧酸(甲酸、乙酸、丙酸、丁酸等)、二羧酸(草酸、丙二酸、琥珀酸、葡萄糖酸、己二酸、富马酸、马来酸、琥珀酸等)、三羧酸(乌头酸等)、羟基羧酸(柠檬酸、乳酸、苹果酸)、芳香族羧酸(苯甲酸、邻苯二甲酸、水杨酸等)、氧代羧酸(丙酮酸等)、以及氨基酸(精氨酸、天冬酰胺、天冬氨酸、半胱氨酸、谷氨酸、甘氨酸等)中的选择1种以上进行使用。
对于羧酸或其盐，优选以其总计为0.5～5g/L的范围进行使用，更优选0.8～2g/L的范围。对于本实施方式的无电解触击镀镍液而言，由于与以往的无电解镀敷工艺的无电解镀镍(S15)中所使用的无电解镀镍液相比镍含量低，所以将羧酸或其盐的含量设定得较低。羧酸或其盐也取决于其种类，但是含量不到0.5g/L时，无电解触击镀镍液中的镍离子的络合物形成变得不充分，会产生沉淀，因此不理想。另一方面，即使羧酸或其盐的含量超过5g/L，不仅不能获得特别的效果，更会造成资源的浪费，不理想。
还原剂：
无电解触击镀镍液含有选自二甲胺硼烷、三甲胺硼烷、肼、肼衍生物中的1种以上的还原剂。通过使用这些物质作为还原剂，无电解触击镀镍液能够在没有付与钯催化剂的铜材料的表面实现镍析出。出于人体的安全性的观点考虑，更优选二甲胺硼烷、三甲胺硼烷。
还原剂优选以2～10g/L的范围使用，更优选4～8g/L的范围。当上述还原剂的含量不到2g/L时，无法得到充分的还原作用，并且在铜表面不会析出镍，不理想。当上述还原剂的含量超过10g/L时，镍在除铜之外的表面(绝缘基材的表面)异常析出、或者发生无电解触击镀镍液的浴分解，因此不理想。
无电解触击镀镍液是通过在水中混合上述成分进行搅拌使其溶解而制成的。更优选：该无电解触击镀镍液是在将上述水溶性镍盐、上述羧酸或其盐和水混合进行搅拌而制成含有镍络合物的水溶液后、通过向该水溶液中混合上述还原剂进行搅拌而制成的溶液。对于以这种方式调制的无电解触击镀镍液，镍络合物能够长时间稳定存在，并且能够得到优异的浴稳定性。
无电解触击镀镍液除上述成分以外还可以含有硫酸盐、硼酸、氯化物盐等成分。
pH：
无电解触击镀镍液优选pH调节至6～10的中性区域。当pH低于6时，镍的析出速度降低，镀镍被膜的成膜性降低，并且在镀镍被膜的表面产生孔部、凹部(孔)，不理想。另一方面，当pH超过10时，镍的析出速度变得过快，镀镍被膜的膜厚难以控制，并且不能使析出的镍的结晶状态致密化，不理想。
浴温：
对于无电解触击镀镍液而言，优选将浴温调节至20～55℃。该范围是与以往的无电解镀镍(S15)中所使用的无电解镀镍液的浴温60～90℃相比较低的值。当浴温不满20℃时，镍的析出速度降低，镀镍被膜的成膜性降低，并且在镀镍被膜的表面产生孔部、凹部(孔)、或者发生没有镍析出的情况，不理想。另一方面，当浴温超过55℃时，无电解触击镀镍液的浴稳定性下降，无法实现无电解触击镀敷法，不理想。
膜厚：
镀镍被膜的膜厚可以通过在无电解触击镀镍液中的浸渍时间来进行调节。镀镍被膜的膜厚优选在能够防止铜扩散的范围内尽可能薄，优选0.005～0.3μm。当镀镍被膜的膜厚不到0.005μm时，铜材料的表面的被覆变得不充分，从而在镀镍被膜的表面产生细小的凹部，其结果，在进行随后的无电解镀金工艺(S6)时发生镍局部腐蚀现象、铜、镍扩散至镀金被膜表面，因而不理想。另一方面，虽然也可以形成膜厚超过0.3μm的镀镍被膜，但是镀镍被膜的柔软性降低，并且造成资源的浪费，因而不理想。
根据本实施方式的无电解触击镀镍工序(S4)，能够实现采用现有的无电解镀镍(S15)中难以完成的镀镍被膜的薄膜化，能够得到膜厚为0.005～0.3μm的镀镍被膜。进而，为了在确保良好的安装特性的同时实现薄膜化，通过无电解触击镀镍工序(S4)形成的镀镍被膜的膜厚更优选为0.007～0.1μm。
在本实施方式的无电解触击镀镍工序(S4)中，无电解触击镀镍液中所含的选自二甲胺硼烷、三甲胺硼烷、肼、肼衍生物中的1种以上物质作为还原剂来使用，能够在没有付与钯催化剂的铜材料的表面析出镍。而且，无电解触击镀镍液的镍含量低，且pH调节至6～10，浴温调节至20～55℃。由此，能够减缓镍的析出速度、实现无电解触击镀敷法，并且能够在铜材料的表面直接形成镀镍被膜。此时，由于镍的析出速度缓慢，所以能够使镍在铜材料的表面均匀地析出，其结果，能够得到膜厚均匀、且即使膜厚很薄也能够确实地覆盖铜材料表面的镀镍被膜。所得的镀镍被膜与根据现有的无电解镀敷工艺得到的镀镍被膜相比，对铜材料的密合性优，且防止铜扩散这样的阻隔特性优异。
对此，在根据以往的无电解镀敷工艺进行的无电解镀镍(S15)中，通过钯催化剂付与处理(S14)而付与在铜材料表面的钯作为催化剂使用，进行镍析出。因此，在铜材料表面的付与有钯催化剂的区域和没有付与钯催化剂的区域中，所形成的镀镍被膜的膜厚产生不均，难以得到膜厚均一的镀镍被膜。进而，用于无电解镀镍(S15)的无电解镀镍液由于镍含量、浴温都很高，使得镍的析出速度快，因此难以得到对铜材料的密合性优异的镀镍被膜。
根据本实施方式的无电解触击镀镍工序(S4)，使用二甲胺硼烷、三甲胺硼烷作为还原剂的情况下，能够得到由镍和硼的合金(镍-硼合金)构成的镀镍被膜。该镀镍被膜的硼含量非常少(例如0.1％以下)，实质上是由纯镍形成的镀镍被膜。另外，使用肼衍生物作为还原剂的情况下，能够得到由纯镍形成的镀镍被膜。
另外，在无电解触击镀镍工序(S4)中，上述无电解触击镀镍液中的水溶性镍盐的含量低，为0.002～1g/L。因此，即使不使用在以往的无电解镀敷工艺的无电解镀镍(S15)中所使用的铅盐、铋盐等稳定剂，也能够防止发生浴分解。另外，上述无电解触击镀镍液由于不含铅盐、铋盐等稳定剂，故而能够得到不含铅和铋等重金属的镀镍被膜。
5.无电解镀钯工序(S5)
无电解镀钯工序(S5)中，通过还原型无电解镀敷法，在上述镀镍被膜的表面形成镀钯被膜。在通过置换型无电解镀敷法形成钯被膜的情况下，会发生镍局部腐蚀现象、即镍溶出从而形成贯通镀镍被膜的贯通孔，因此采用还原型无电解镀敷法。
作为用于无电解镀钯工序(S5)的还原型无电解镀钯液，可以使用公知物。例如，能够使用包含0.001～0.1mol/L钯化合物、0.05～5mol/L胺化合物、0.01～0.1mol/L无机硫化合物、和0.05～1.0mol/L次亚磷酸或次亚磷酸化合物的还原型无电解镀钯液。或者，能够使用含有0.001～0.1mol/L甲酸或甲酸化合物代替上述次亚磷酸或次亚磷酸化合物的还原型无电解镀钯液。
无电解镀钯工序(S5)中，通过采用还原型无电解镀敷法，在形成镀钯被膜时能够防止从镀镍被膜中溶出镍。而且，本实施方式的无电解镀敷工艺中，根据无电解触击镀镍工序(S4)形成的镀镍被膜的膜厚均匀且平滑性优异，因此通过无电解镀钯工序(S5)能够形成具有均匀膜厚的镀钯被膜。
6.无电解镀金工序(S6)
无电解镀金工序(S6)中，根据还原型无电解镀敷法，在上述镀钯被膜的表面形成镀金被膜。通过置换型无电解镀敷法形成镀金被膜的情况下，钯溶出且产生贯通镀钯被膜的贯通孔，因此采用还原型无电解镀敷法。
作为用于无电解镀金工序(S6)的还原型无电解镀金液，可以使用公知物。例如，能够使用包含水溶性金化合物、柠檬酸或其盐、乙二胺四乙酸或其盐、作为还原剂的六亚甲基四胺、和具有碳原子数3个以上的烷基及3个以上氨基的链状聚胺的还原型无电解镀金液。
无电解镀金工序(S6)中，通过采用还原型无电解镀敷法，在形成镀金被膜时能够防止从镀钯被膜中溶出钯。而且，本实施方式的无电解镀敷工艺中，通过无电解镀钯工序(S4)形成的镀钯被膜具有均匀的膜厚，因此通过无电解镀金工序(S6)，能够形成具有均匀膜厚的镀金被膜。
无电解镀金工序结束后，进行水洗处理，使其干燥。如上所述，通过进行图1所示的无电解镀敷工艺，能够在铜材料的表面形成Ni/Pd/Au被膜。
在本实施方式的无电解镀敷工艺中，通过无电解触击镀镍工序(S4)，能够在没有付与钯催化剂的铜材料表面直接形成镀镍被膜。而且，即使膜厚很薄也能够确实地覆盖铜材料的表面，且能够形成对铜材料的密合性和阻隔特性优异的镀镍被膜。因此，能够实现镀镍被膜的薄膜化。
进而，由于能够使镀镍被膜的膜厚变薄，所以能够得到整体膜厚薄的Ni/Pd/Au被膜。另外，通过无电解触击镀镍工序(S4)，能够得到膜厚均匀且平滑性优异的镀镍被膜，因此在该被膜上形成的镀钯被膜及镀金被膜也能够另外以均匀的膜厚成膜，能够形成膜厚不均小的Ni/Pd/Au被膜。进一步，通过无电解触击镀敷法形成的镀镍被膜，不仅与铜材料的密合性优异，而且防止铜扩散这样的阻隔特性也优异，因此能够形成具有优异的封装特性的Ni/Pd/Au被膜。
另外，对于上述镀镍被膜而言，不仅膜厚薄、而且与通过以往的无电解镀镍(S15)形成的镀镍被膜不同，不含磷。从这方面考虑，上述镀镍被膜能够得到优异的柔软性，因此Ni/Pd/Au被膜能够得到优异的柔软性。
进一步，在本实施方式的无电解镀敷工艺中，与以往的无电解镀敷工艺不同，在无电解触击镀敷工序(S4)之前，不需要进行付与钯催化剂处理(S14)，因此能够减少工序的数量。
上述的本实施方式的无电解镀敷工艺，是在无电解触击镀镍工序(S4)之后进行无电解镀钯工序(S5)及无电解镀金工序(S6)的工艺。本实施方式的无电解镀敷工艺也可以是在无电解触击镀镍工序(S4)之后不进行无电解镀钯工序(S5)而是进行无电解镀金工序(S6)从而在铜材料的表面形成Ni/Au被膜的工艺。
以下，根据实施例等，具体地说明本发明。
实施例1
在本实施例的无电解镀敷工艺中，通过依次进行图1所示出的各工序S1～S6(全部6个工序)，在铜材料的表面形成Ni/Pd/Au被膜。依次进行上述的脱脂工序(S1)、蚀刻工序(S2)及去污工序(S3)之后，进行无电解触击镀镍工序(S4)。在无电解触击镀镍工序(S4)中，将铜材料浸渍于以下组成的无电解触击镀镍液中，在铜材料的表面形成镀镍被膜。无电解触击镀镍液是通过混合硫酸镍六水合物、DL-苹果酸和水进行搅拌而制成含有镍络合物的水溶液后，向其中添加二甲胺硼烷并且搅拌，从而制得。将铜材料浸渍于无电解触击镀镍液的期间，通过通气(aeration)对该无电解触击镀镍液进行搅拌。
(无电解触击镀镍液)
Figure BDA0002171197890000111
接着，进行无电解镀钯工序(S5)。将形成了镀镍被膜的铜材料浸渍于以下组成的还原型无电解镀钯液中，在镀镍被膜的表面形成镀钯被膜。
(还原型无电解镀钯液)
Figure BDA0002171197890000112
之后，进行无电解镀金工序(S6)。将形成了镀钯被膜的铜材料浸渍于以下组成的还原型无电解镀金液中，在镀钯被膜的表面形成镀金被膜。由此，在铜材料的表面形成Ni/Pd/Au被膜。
(还原型无电解镀金液)
Figure BDA0002171197890000121
比较例
[比较例1]
本比较例的无电解镀敷工艺中，进行以往的无电解镀敷工艺中进行的付与钯催化剂处理(S14)和无电解镀镍(S15)来代替无电解触击镀镍工序(S4)，除此以外，与实施例1的无电解镀敷工艺完全相同地进行，由此在铜材料的表面形成Ni/Pd/Au被膜。本比较例的无电解镀敷工艺的工序全部有7个工序。
在付与钯催化剂处理(S14)中，将已进行去污的铜材料浸渍于钯催化剂溶液(含有以钯换算为30mg/L的钯化合物和硫酸离子)中，使钯催化剂付与在铜材料的表面。
在无电解镀镍(S15)中，将已付与了钯催化剂的铜材料浸渍于以下组成的无电解镀镍液中。
(无电解镀镍液)
Figure BDA0002171197890000122
Figure BDA0002171197890000131
[比较例2]
本比较例的无电解镀敷工艺在无电解镀镍(S15)中使用以下组成的无电解镀镍液，除此以外，与比较例1完全相同地进行。本比较例的无电解镀敷工艺的工序全部有7个工序。
(无电解镀镍液)
Figure BDA0002171197890000132
[参考例1]
本参考例的无电解镀敷工艺在进行无电解镀镍(S15)之前没有进行付与钯催化剂处理(S14)，除此之外，与比较例1完全相同地进行。本参考例的无电解镀敷工艺的工序全部有6个工序。
[参考例2]
本参考例的无电解镀敷工艺在进行无电解镀镍(S15)之前没有进行付与钯催化剂处理(S14)，除此之外，与比较例2完全相同地进行。
<评价>
1.针对镀镍被膜的评价
首先，进行至实施例1的无电解镀敷工艺的无电解触击镀镍工序(S4)，或者进行至比较例1及比较例2的无电解镀敷工艺的无电解镀镍工序(S15)，由此，在铜材料的表面形成膜厚0.01μm的镀镍被膜。针对所得的镀镍被膜，进行以下评价。
1-1.镍析出性
在此，使用在绝缘基材上将30个直径为0.45mm的铜垫以30μm间隔配置为格子状的测试板。然后，进行至实施例1的无电解镀敷工艺的无电解触击镀镍工序(S4)、或者进行至比较例1及比较例2的无电解镀敷工艺的无电解镀镍工序(S15)，由此在铜垫的表面形成镀镍被膜。另一方面，在参考例1及参考例2的无电解镀敷工艺中，进行至无电解镀镍工序(S15)，但是在铜垫的表面完全没有析出镍、无法形成镀镍被膜。
通过金属显微镜(倍率1000倍)观察所得的镀镍被膜，计算出能够正常进行镍析出的铜垫的个数。此处，所谓正常进行镍析出，是指铜垫的整个表面被镀镍被膜覆盖，没有被覆盖的部分用金属显微镜无法确认。结果如表1所示。表1中的符号○、符号△及符号×的判断标准如下。
○：正常进行镍析出的铜垫为30个。
△：正常进行镍析出的铜垫为15～29个。
×：镍完全没有析出的铜垫为30个。
[表1]
实施例1 比较例1 比较例2 参考例1 参考例2
○ ○ △ × ×
如表1所示，将比较例1和参考例1进行比较的同时将比较例2和参考例2进行比较时，能够得知为了利用比较例1及比较例2的无电解镀镍(S15)中所用的无电解镀镍液形成镀镍被膜，在进行无电解镀镍(S15)之前必须进行付与钯催化剂处理(S14)。
而且，能够得知，虽然比较例1的无电解镀镍(S15)能够始终正常地进行镍析出，但是比较例2的无电解镀镍(S15)有时不能正常进行镍析出，镍析出性差。对此，能够得知，实施例1的无电解触击镀镍工序(S4)能够始终正常地进行镍析出，镍的析出性优异。
1-2表面形态
为评价在铜垫的表面形成的镀镍被膜的表面形态，用扫描电子显微镜(SEM)以5000倍及3万倍来拍摄镀镍被膜的表面，得到反射电子组成图像(COMPO图像)。结果在图2～图4中示出。图2表示通过实施例1的无电解触击镀镍工序(S4)得到的镀镍被膜的COMPO图像，图3表示通过比较例1的无电解镀镍(S15)得到的镀镍被膜的COMPO图像，图4表示通过比较例2的无电解镀镍(S15)得到的镀镍被膜的COMPO图像。图2(a)、图3(a)及图4(a)中的倍率是5000倍，图2(b)、图3(b)及图4(b)中的倍率是3万倍。
由图2～图4能够确认，相较于通过比较例1及比较例2的无电解镀镍(S15)得到的镀镍被膜，通过实施例1的无电解触击镀镍工序(S4)得到的镀镍被膜，黑色部分少。黑色部分表示镀镍被膜上存在原子序数小的碳等元素。由此可知，相较于通过比较例1及比较例2的无电解镀镍(S15)得到的镀镍被膜，通过实施例1的无电解触击镀镍工序(S4)得到的镀镍被膜是凹陷部分少且致密的膜。另外，通过比较例2的无电解镀镍(S15)得到的镀镍被膜，黑色部分特别多，因此认为凹陷部分多，不是致密的膜。
进一步地能够确认，通过比较例1及比较例2的无电解镀镍(S15)得到的镀镍被膜在表面存在大的凹凸，而相对于此，通过实施例1的无电解触击镀镍工序(S4)得到的镀镍被膜在表面不存在大的凹凸，仅存在细小的凹凸。由此能够得知，相较于通过比较例1及比较例2的无电解镀镍(S15)得到的镀镍被膜，通过实施例1的无电解触击镀镍工序(S4)得到的镀镍被膜，具有优异的平滑性。另外，比较例2的镀镍被膜存在特别多的大凹凸，因此认为其平滑性差。
由此可知，相较于比较例1及比较例2的无电解镀敷工艺的无电解镀镍(S15)，通过实施例1的无电解镀敷工艺的无电解触击镀镍工序(S4)，能够得到致密且平滑性优异的镀镍被膜。
1-3.表面元素分析
关于在铜垫的表面形成的镀镍被膜，通过俄歇电子分光分析装置(AugerElectron Spectroscopy)进行表面元素分析。如上所述，比较例2的镀镍被膜的性能差，因此只将实施例1及比较例1的镀镍被膜作为分析对象。
针对镀镍被膜，进行3次回流焊(Reflow)处理。回流焊处理是在230℃预热镀镍被膜后、于250℃加热来进行的。而且，在进行回流焊处理前、以及在进行回流焊处理使其自然冷却至常温后，进行表面元素分析。表面元素分析的测量条件为：加速电压10kV，探针电流值10nA，测量直径50μm，扫描范围30～2400eV。结果在表2中示出。表2中的数值是根据所得光谱的峰值强度比将元素进行定量化的数值(单位：原子％)。表2中的符号“-”表示完全没有检出该元素。
[表2]
Figure BDA0002171197890000161
对于通过实施例1的无电解触击镀镍工序(S4)得到的镀镍被膜，虽然认为含有来自二甲胺硼烷的硼元素，但是实际上没有检出硼元素，由此明确了实质上由纯镍组成。另一方面，如表2所示，通过比较例1的无电解镀镍(S15)得到的镀镍被膜由镍-磷合金构成，该镍-磷合金含有来自次亚磷酸钠的磷。
由表2可知，通过实施例1的无电解触击镀镍工序(S4)得到的镀镍被膜，即使在第2次的回流焊处理后铜也不会扩散至其表面，阻隔性能优异。另一方面，通过比较例1的无电解镀镍(S15)得到的镀镍被膜，虽然在第1次的回流焊处理后铜未扩散至其表面，但是在第2次的回流焊处理后铜扩散至其表面，认为阻隔性能差。
1-4.低电位电解
此处，用铜板代替上述测试板，在铜板的表面形成膜厚为0.01μm的镀镍被膜。而且，针对所得的镀镍被膜，在0.5体积％的硫酸溶液中于50mV进行低电位电解，评价阻隔特性。结果在图5中示出。图中的横轴是电解时间，纵轴是电流密度。电流密度的上升表示铜已经从铜材料(为镀镍被膜的下层)溶出。
如图5所示可知，相较于通过比较例1的无电解镀镍(S15)得到的镀镍被膜，通过实施例1的无电解触击镀镍工序(S4)得到的镀镍被膜，电流密度的上升小，因此，阻隔特性优异。
由上面的镍析出性、表面形态、表面元素分析及低电位电解的结果可知，相较于比较例1及比较例2的无电解镀敷工艺的无电解镀镍(S15)，实施例1的无电解镀敷工艺的无电解触击镀镍工序(S4)，镍析出性优异，并且能够得到致密、平滑、且阻隔特性优异的镀镍被膜。进而能够得知，对于通过实施例1的无电解镀敷工艺的无电解触击镀镍工序(S4)得到的镀镍被膜，相较于与其具有同样的膜厚、且通过比较例1及比较例2的无电解镀敷工艺的无电解镀镍(S15)得到的镀镍被膜，具有更优异的性能。
2.对Ni/Pd/Au被膜的评价
此处，使用下述测试板，即，在绝缘基材上配置有配线宽度/配线间隔(L/S)为30～100μm/30～100μm的铜的细微配线，且微细配线为直径0.45mm的铜垫以0.45μm间隔配置为格子状。针对该测试板，通过进行实施例1的无电解镀敷工艺的全部6个工序或者比较例1的无电解镀敷工艺的全部7个工序，在铜材料(微细配线及垫)的表面形成Ni/Pd/Au被膜。
在实施例1的无电解镀敷工艺中，得到由膜厚0.01μm的镀镍被膜、膜厚0.1μm的镀钯被膜、和膜厚0.1μm的镀金被膜所形成的Ni/Pd/Au被膜。在比较例1的无电解镀敷工艺中，得到由膜厚0.5μm的镀镍被膜、膜厚0.1μm的镀钯被膜、和膜厚0.1μm的镀金被膜所形成的Ni/Pd/Au被膜。进而，针对得到的Ni/Pd/Au被膜进行了以下评价。
2-1.焊料扩展性
在Ni/Pd/Au被膜的表面进行焊接，之后，进行焊料扩展性测试。使用千住金属工业株式会社的ECO SOLDER(注册商标)M770作为焊球，焊球直径D为700μm。焊料扩展测试中，使用了焊料回流炉(株式会社Japan Pulse技术研究所，PF-330)，预热温度230℃，回流温度250℃，并且使用了株式会社ASAHI化学研究所的AGF-780DS-AA作为助焊剂。然后，测定回流后的焊球的高度H(μm)，根据以下计算式计算扩展率S，求出其最大值、最小值及平均值。进一步，关于在进行焊接前于温度250℃进行了4小时热处理的Ni/Pd/Au被膜，也同样进行焊接扩展测试。结果在图6中示出。图6的“无热处理”，表示在实施例1或比较例1的无电解镀敷工艺后没有实施上述热处理而是进行焊接而成的Ni/Pd/Au被膜的焊料扩展测试的结果，“有热处理”表示在上述无电解镀敷工艺之后实施上述热处理后进行了焊接而成的Ni/Pd/Au被膜的结果。
扩展率S＝(D-H)/D×100(％)
由图6可知，在无热处理、有热处理的两种情况下，通过实施例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，与通过比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜相比，焊料扩展性优异。另外，比较无热处理和有热处理时，通过实施例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，平均值及最小值的差很小，相对于此，通过比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜的平均值大幅度下降。由此可知，对于通过实施例1的无电解镀敷工艺得到的Ni/Pd/Au被膜而言，抑制由热处理导致的铜和镍向镀金被膜的扩散的效果高，且即使进行了热处理时也能维持优异的焊料扩展性，具有优异的耐热性。
2-2.焊球剪切强度
在Ni/Pd/Au被膜的表面进行焊接，之后，测定焊球剪切强度。使用Dage公司制(Series 4000)焊球剪切测试器，在剪切高度20μm、剪切速度500μm/秒的条件下测定焊球剪切强度，求出其最大值、最小值及平均值。进一步，关于在实施焊接前于温度250℃进行了4小时热处理而成的Ni/Pd/Au被膜，也同样地测定了焊球剪切强度。结果在图7中示出。图7的“无热处理”，表示在实施例1或比较例1的无电解镀敷工艺后没有实施上述热处理而是进行焊接而成的Ni/Pd/Au被膜的焊球剪切强度，“有热处理”表示在上述无电解镀敷工艺之后实施上述热处理后进行焊接而成的Ni/Pd/Au被膜的结果。
由图7可知，在无热处理、有热处理的两种情况下，相较于通过比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，通过实施例1的无电解镀敷工艺得到的Ni/Pd/Au被膜尽管数值本身低，但具有优异的焊球剪切强度。另外，对无热处理与有热处理进行比较时，相对于通过实施例1的无电解镀敷工艺得到的Ni/Pd/Au被膜的平均值及最小值的差小，通过比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜在热处理前后的平均值及最小值大幅度下降。由此能够得知，相较于通过比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，通过实施例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，抑制由热处理所导致的铜和镍向镀金被膜扩散的效果较高，且即使进行热处理时也能维持优异的焊球剪切强度，具有优异的耐热性。
2-3.引线接合强度及断裂模式
将线线径25μm的金引线接合到Ni/Pd/Au被膜的表面后，用拉伸试验机测定金引线拉伸时的接合强度，即，引线接合强度。然后，求出其最大值、最小值及平均值。进一步，针对在进行焊接前于温度250℃进行4小时热处理的Ni/Pd/Au被膜，也同样地测定引线接合强度。结果在图8中示出。进一步，金引线断裂时的断裂模式在图9中示出。图8及图9的“无热处理”，表示在实施例1或比较例1的无电解镀敷工艺后没有实施上述热处理而进行焊接而成的Ni/Pd/Au被膜的引线接合强度或断裂模式，“有热处理”表示在上述无电解镀敷工艺之后实施了上述热处理后进行焊接而成的Ni/Pd/Au被膜的结果。
由图8能够得知，在无热处理、有热处理两种情况下，通过实施例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，与通过比较例1的无电解镀敷工艺得到无热处理的Ni/Pd/Au被膜具有同等水平的引线接合强度。另外，对无热处理与有热处理进行比较时，相对于通过实施例1的无电解镀敷工艺得到的Ni/Pd/Au被膜的平均值及最小值的差很小，通过比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜的平均值及最小值大幅度下降。
进一步，如图9所示，对于通过实施例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，在无热处理、有热处理的两种情况下，金引线断裂时的断裂模式全都是C模式。另一方面，对于通过比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，在无热处理的情况下全部为C模式，而在有热处理的情况下45％为C模式，55％为E模式。
根据上述结果能够得知，相较于通过比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，通过实施例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，抑制由热处理导致的铜和镍向镀金被膜扩散的效果高，且即使进行热处理时也能维持引线接合强度及断裂模式，具有优异的耐热性。
基于以上的焊料扩展性、焊球剪切强度、引线接合强度及断裂模式的结果能够得知，相较于通过比较例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，通过实施例1的无电解镀敷工艺得到的Ni/Pd/Au被膜，尽管镀镍被膜的膜厚是1/50，但具有同等以上的优异的封装特性。认为其原因在于，通过实施例1的无电解镀敷工艺的无电解触击镀镍工序(S4)所形成的镀镍被膜致密、平滑且阻隔性能优异。
产业上的可利用性
如以上说明所述，通过本发明的无电解镀敷工艺，能够在铜材料的表面形成Ni/Au被膜或Ni/Pd/Au被膜。所得的镀镍被膜即使膜厚很薄也能够确实地覆盖在铜材料的表面，因此通过本发明的无电解镀敷工艺能够实现镀镍被膜的薄膜化。所得的Ni/Au被膜或Ni/Pd/Au被膜即使镀镍被膜的膜厚很薄也能够获得优异的封装特性，因此，本发明的无电解镀敷工艺能够应对复杂的配线图案和窄间距配线，能够实现高密度封装。另外，对于所得的Ni/Au被膜或Ni/Pd/Au被膜而言，由于整体膜厚薄且柔软性优异，因此适合作为柔性基板。
进而，根据本发明的无电解镀敷工艺，即使不进行在以往的无电解镀敷工艺中进行的付与钯催化剂处理(S14)，也能够形成镀镍被膜，因此能够提高生产率。

Claims (1)

1.一种无电解镀敷工艺，是通过无电解镀敷法在铜材料的表面依次形成镀镍被膜、镀钯被膜和镀金被膜的无电解镀敷工艺，
其特征在于，包括：
通过无电解触击镀敷法在铜材料的表面形成镀镍被膜的工序、
通过还原型无电解镀敷法形成镀钯被膜的工序、和
通过还原型无电解镀敷法形成镀金被膜的工序，
所述无电解触击镀敷法通过使用下述无电解触击镀镍液、并将所述铜材料浸渍于该无电解触击镀镍液中而进行，
所述无电解触击镀镍液含有：
以镍换算为0.002~0.1g/L的水溶性镍盐、
羧酸或其盐、和
选自二甲胺硼烷、三甲胺硼烷、肼、肼类衍生物中的1种以上的还原剂，
所述无电解触击镀镍液不含铅盐和铋盐，
并且所述无电解触击镀镍液的pH调节为6~10、浴温调节为20~55°C，
形成所述镀镍被膜的工序形成膜厚为0.005~0.1μm的镀镍被膜，
所述无电解触击镀镍液是在将所述水溶性镍盐和所述羧酸或其盐和水混合进行搅拌从而制成含有镍络合物的水溶液后、通过向该水溶液中混合所述还原剂进行搅拌而制成的。
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