CN103339718B - Sn合金隆起物的制造方法 - Google Patents

Sn合金隆起物的制造方法 Download PDF

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Publication number
CN103339718B
CN103339718B CN201280006685.XA CN201280006685A CN103339718B CN 103339718 B CN103339718 B CN 103339718B CN 201280006685 A CN201280006685 A CN 201280006685A CN 103339718 B CN103339718 B CN 103339718B
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layer
alloy
bulge
manufacture method
composition
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CN103339718A (zh
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八田健志
增田昭裕
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Abstract

本发明提供一种容易控制Sn合金隆起物的组成的Sn合金隆起物的制造方法。本发明的Sn合金隆起物的制造方法为由Sn与其他一种或两种以上的金属的合金形成的Sn合金隆起物的制造方法，其具有如下工序：通过电解电镀，在形成于基板（1）上的保护层开口部（2a）内的电极焊盘（3）上形成Sn层（4a）；通过电解电镀，在Sn层（4a）上层叠Sn与其他金属的合金层（4b）；及去除保护层（2）后，熔融Sn层（4a）与层叠的合金层（4b）来形成Sn合金隆起物（5）。

Description

Sn合金隆起物的制造方法
技术领域
本发明涉及一种在将电子部件封装于基板的倒装芯片封装等时合适的Sn合金隆起物的制造方法。
背景技术
当前，在将电子部件封装于印制电路板等时，多采用通过使用了隆起物的倒装芯片封装来进行表面封装的方法。作为形成上述隆起物的方法，例如通过电解电镀，在形成于基板上的保护层（レジスト）开口部内的电极焊盘上形成焊锡层，并在去除保护层后进行回流，从而熔融焊锡层来形成大致球状的隆起物。
近年来，含有铅（Pb）的焊锡材料从环境方面考虑不优选，因此正在推进着用于接合电子部件的焊锡的无铅化，关于隆起物的材料也正研究着以Sn为主成分的Sn-Ag或Sn-Cu二元系焊锡或者Sn-Ag-Cu三元系焊锡等。例如，专利文献1中记载有在基材上形成Sn-Ag-Cu三元系薄膜的方法，该方法将基材浸渍于含有Sn化合物、Ag化合物及Cu化合物的电镀浴中，并通过电镀来形成。并且，专利文献2中提出有进行Sn-Ag合金电镀，接着进行Sn-Cu合金电镀，然后使所获得的多层合金电镀层回流的Sn-Ag-Cu焊锡合金的形成方法。
专利文献1：日本特开2006-291323号公报
专利文献2：日本特开2003-342784号公报
上述以往的技术中留有以下课题。即，在通过近年来的微细化而细距化并成为高纵横尺寸比图案的保护层的开口部（通孔）形成镀合金时、使用Su-Ag-Cu合金电镀液时或进行基于Sn-Ag与Sn-Cu的电镀液的双层电镀时，在开口部的底部抑制Ag或Cu的析出，因此存在越是底部Ag或Cu越少，从而Sn大量析出的不良情况。因此，在开口部的高度方向上产生组成的偏差，其结果是存在难以控制Sn合金隆起物的组成的问题。尤其，若重复多次电解电镀则电镀液中的酸浓度变高从而粘度升高，Ag更难以在底部析出，因此难以在回流后获得稳定的组成。
发明内容
本发明是鉴于上述课题而完成的，其目的在于提供一种能够轻松控制Sn合金隆起物的高度方向上的组成的Sn合金隆起物的制造方法。
本发明为了解决上述课题而采用了以下结构。即，本发明的Sn合金隆起物的制造方法为由Sn与其他一种或两种以上的金属的合金形成的Sn合金隆起物的制造方法，其特征在于，具有如下工序：通过电解电镀，在形成于基板上的保护层开口部内的电极上形成Sn层；通过电解电镀，在所述Sn层上层叠Sn与所述其他金属的合金层；及去除所述保护层后，熔融所述Sn层与所述合金层来形成Sn合金隆起物。
该Sn合金隆起物的制造方法中，通过电解电镀在电极上形成Sn层，并通过电解电镀在该Sn层上层叠Sn与所述其他金属（所述另一种或两种以上的金属）的合金层，因此在电镀合金层时，通过预先形成的Sn层来减小开口部的深度，从而能够抑制高度方向的其他金属的组成偏差。另外，根据熔融Sn层与合金层来作为Sn合金隆起物时的目标组成，所层叠的合金层中的其他金属设定为高于仅进行Sn与其他金属的合金电镀时的组成，从而能够进行Sn合金隆起物的组成控制。
并且，本发明的Sn合金隆起物的制造方法，其特征在于，具有如下工序：所述其他金属为Ag，通过电解电镀，在所述Sn层上形成Sn-Ag层来作为所述合金层；及去除所述保护层后，熔融所述Sn层与所述Sn-Ag层来形成Sn-Ag隆起物，以此来作为所述Sn合金隆起物。即，该Sn合金隆起物的制造方法中，通过电解电镀，在Sn层上形成Sn-Ag层，且使Sn层与Sn-Ag层熔融，因此能够形成降低因Ag析出导致的高度方向的Ag组成偏差的Sn-Ag合金隆起物。
并且，本发明的Sn合金隆起物的制造方法，其特征在于，具有如下工序：所述其他金属为两种金属，通过电解电镀，在所述Sn层上层叠与所述两种中的一种的合金层及Sn与所述两种中的另一种的合金层这两层；及去除所述保护层后，熔融所述Sn层与两层层叠的所述合金层来形成Sn合金隆起物。即，该Sn合金隆起物的制造方法中，通过电解电镀，在Sn层上层叠Sn与所述两种中的一种的合金层、及Sn与所述两种中的另一种的合金层这两层，因此在对合金层的两层进行电镀时，通过预先形成的Sn层来减小开口部的深度，从而能够抑制高度方向的两种金属的组成偏差。
另外，本发明的Sn合金隆起物的制造方法，其中，具有如下工序：所述两种中的一种金属为Ag且另一种金属为Cu，通过电解电镀，在所述Sn层上形成Sn-Ag层与Sn-Cu层这两层；及去除所述保护层后，熔融所述Sn层、所述Sn-Ag层及所述Sn-Cu层来形成Sn-Ag-Cu隆起物，以此来作为所述Sn合金隆起物。即，该Sn合金隆起物的制造方法中，通过电解电镀，在Sn层上形成Sn-Ag层与Sn-Cu层这两层，且使Sn层、Sn-Ag层及Sn-Cu层熔融，因此能够形成降低因Ag或Cu的析出导致的高度方向的Ag或Cu的组成偏差的Sn-Ag-Cu合金隆起物。
根据本发明，得到以下效果。即，根据本发明所涉及的Sn合金隆起物的制造方法，通过电解电镀在电极上形成Sn层，并通过电解电镀在该Sn层上层叠Sn与其他金属的合金层，因此能够抑制高度方向的其他金属的组成偏差，并能够控制熔融各层而形成的隆起物的组成。由此，根据本发明的Sn合金隆起物的制造方法，能够获得适应于高纵横尺寸比图案的组成均匀性较高的Sn合金隆起物，并能够适应于细距化。
附图说明
图1是在本发明所涉及的Sn合金隆起物的制造方法的第1实施方式中，以工序顺序表示制造工序的简要的主要部分截面图。
图2是在本发明所涉及的Sn合金隆起物的制造方法的第2实施方式中，以工序顺序表示制造工序的简要的主要部分截面图。
图3是在本发明所涉及的Sn合金隆起物的制造方法的实施例中，表示回流剖面的曲线图。
具体实施方式
以下，参考图1对本发明所涉及的Sn合金隆起物的制造方法的第1实施方式进行说明。
第1实施方式中的Sn合金隆起物的制造方法为由Sn与Ag等其他一种或两种以上的金属的合金形成的Sn合金隆起物的制造方法，其如图1所示，具有如下工序：通过电解电镀，在形成于基板1上的保护层2的开口部2a内的电极焊盘3上形成Sn层4a；通过电解电镀，在Sn层4a上层叠Sn与所述其他金属的合金层4b；及去除保护层2后，通过回流处理熔融Sn层4a与层叠的合金层4b来形成Sn合金隆起物5。
例如，若对所述其他金属为Ag的情况进行说明，则如图1的（a）所示，首先通过电解电镀在形成于基板1上的保护层2的开口部2a内的电极焊盘3上形成Sn层4a。该Sn层4a例如形成至开口部2a的深度的一半。上述基板1为半导体晶圆、印制电路板或散热基板等，表面上图案形成有保护层2，且以1.0以上的高纵横尺寸比图案设置有隆起物用的开口部2a。
并且，上述电极焊盘3例如为将Cu电镀膜3a与Ni电镀膜3b进行层叠的金属膜。上述开口部2a例如设为深度：120μm、开口直径：70μm，且设为纵横尺寸比为1.7的高纵横尺寸比图案。另外，隆起物间距也可为一百几十μm的细距。
接着，如图1的（b）所示，通过电解电镀在Sn层4a上形成Sn-Ag层即合金层4b。该Sn-Ag层即合金层4b形成为与Sn层4a相同的高度且填补开口部2a的剩余一半部分。即，以埋入由Sn层4a抬高而实际的纵横尺寸比减小的开口部2a的方式形成合金层4b（Sn-Ag层）。
另外，根据熔融Sn层4a与合金层4b来作为Sn合金隆起物时的目标组成，所层叠的合金层4b中的所述其他金属设定为高于仅进行Sn与其他金属的合金电镀时的组成，从而能够进行Sn合金隆起物的组成控制。即，第1实施方式中，使Sn-Ag层即合金层4b对应于回流处理后与Sn层4a熔融的Sn合金隆起物的Ag组成，与仅以Sn-Ag电镀形成Sn合金隆起物时相比，将Ag组成设定得更高。例如，设为Sn合金隆起物的目标的Ag组成为2.5wt%时，在与Sn层4a相同高度的Sn-Ag层（合金层4b）中，将Ag组成设定为5wt%。
接着，去除上述保护层2，如图1的（c）所示，通过回流处理熔融Sn层4a与合金层4b（Sn-Ag层），形成Sn-Ag隆起物来作为大致球状的Sn合金隆起物5。另外，作为回流处理，例如使用热风式的回流炉，在以去除氧化膜为目的涂布有助熔剂的状态下且在氮气气氛下对隆起物表面进行加热。
如此第1实施方式的Sn合金隆起物制造方法中，通过电解电镀在电极焊盘3上形成Sn层4a，并通过电解电镀在该Sn层4a上层叠Sn与其他金属的合金层4b，因此在电镀合金层4b时，通过预先形成的Sn层4a来减小开口部2a的深度，从而能够抑制高度方向上的所述其他金属的组成偏差。由此，容易控制回流处理后的Sn合金隆起物5的组成。
尤其，在第1实施方式中，通过电解电镀在Sn层4a上形成Sn-Ag层即合金层4b，熔融Sn层4a与合金层4b（Sn-Ag层），因此通过Ag析出，能够降低高度方向的Ag组成的偏差，并形成控制了Ag组成的Sn-Ag合金隆起物。
接着，参考图2对本发明所涉及的Sn合金隆起物的制造方法的第2实施方式进行说明。另外，在以下的实施方式的说明中，对在上述实施方式中说明的相同构成要件附加相同符号，并省略其说明。
第2实施方式与第1实施方式的不同点在于，第1实施方式中，在Sn层4a上形成Sn与一种金属（Ag）的合金层4b并通过回流处理形成Sn合金隆起物，相对于此，第2实施方式中，所述其他金属为两种金属，且为以Sn与两种金属的合金形成的Sn合金隆起物的制造方法，如图2所示，通过电解电镀在Sn层4a上层叠Sn与所述两种中的一种的第1合金层24b及Sn与所述两种中的另一种的第2合金层24c这两层，将此作为进行回流处理的点。
例如，作为第2实施方式，若对所述两种中的一种金属为Ag并且另一种金属为Cu的情况进行说明，则如图2的（a）所示，首先通过电解电镀在形成于基板1上的保护层2的开口部2a内的电极焊盘3上形成Sn层4a。接着，如图2的（b）所示，通过电解电镀在Sn层4a上层叠形成Sn-Cu层即第1合金层24b与Sn-Ag层即第2合金层24c这两层。
这些Sn-Cu层即第1合金层24b及Sn-Ag层即第2合金层24c形成为填补开口部2a的剩余一半部分。例如，上述各层的厚度以Sn层4a:第1合金层24b（Sn-Cu层）:第2合金层24c（Sn-Ag层）=1:1:3的比率形成。
另外，根据熔融Sn层4a、第1合金层24b及第2合金层24c来作为Sn合金隆起物25时的目标组成，第1合金层24b及第2合金层24c中的所述两种金属设定为高于仅进行Sn与所述两种金属的合金电镀时的组成，从而能够进行Sn合金隆起物的组成控制。
即，第2实施方式中，使第1合金层24b（Sn-Cu层）及第2合金层24c（Sn-Ag层）对应于回流处理后熔融的Sn合金隆起物的Ag组成及Cu组成，与仅以Sn-Ag-Cu电镀形成Sn合金隆起物时相比，将Ag组成及Cu组成设定得更高。例如，设为Sn合金隆起物25的目标的组成为Sn-3Ag-0.5Cu（质量%）时，将第1合金层24b（Sn-Cu层）的Cu组成设定为2.5wt%，将第2合金层24c（Sn-Ag层）的Ag组成设定为5wt%。
接着，去除上述保护层2，如图2的（c）所示，通过回流处理熔融Sn层4a、第1合金层24b及第2合金层24c并形成Sn-Ag-Cu隆起物来作为大致球状的Sn合金隆起物25。另外，在Sn层4a上以第1合金层24b（Sn-Cu层）、第2合金层24c（Sn-Ag层）的顺序进行层叠，但相反地以第2合金层24c（Sn-Ag层）、第1合金层24b（Sn-Cu层）的顺序来进行层叠也无妨。
如此在第2实施方式的Sn合金隆起物的制造方法中，通过电解电镀在Sn层4a上层叠Sn与所述两种中的一种的第1合金层24b及Sn与所述两种中的另一种的第2合金层24c这两层，因此在电镀第1合金层24b时，通过预先形成的Sn层4a来减小开口部2a的深度，并且在对第2合金层24c进行电镀时，通过第1合金层24b来进一步减小开口部2a的深度，从而能够抑制高度方向的所述两种金属的组成偏差。
尤其，在第2实施方式中，通过电解电镀在Sn层4a上形成Sn-Ag层的第1合金层24b与Sn-Cu层的第2合金层24c这两层，并熔融Sn层4a、第1合金层24b及第2合金层24c，因此能够降低基于Ag或Cu的析出的高度方向的Ag或Cu的组成偏差，并形成控制了Ag组成及Cu组成的Sn-Ag-Cu合金隆起物。
实施例
接着，关于本发明所涉及的Sn合金隆起物的制造方法，说明通过根据上述实施方式制作的实施例进行评价的结果。
作为基板，使用直径12英寸（30.48cm）的晶圆，在其表面图案形成保护层，该保护层以200μm间距形成开口直径80μm、开口部的厚度为120μm的高纵横尺寸比图案的开口部。首先，作为与第1实施方式对应的实施例1，利用Sn电镀液及Sn-Ag电镀液的新溶液，通过以下条件进行电解电镀。
即，以Sn电镀为厚度：60μm、Sn-Ag电镀为厚度：60μm来进行双层电镀，并层叠Sn层与合金层（Sn-Ag层）。此时，将条件设定成回流后的Sn合金隆起物中的Ag组成成为2.5wt%来进行电解电镀。即，将电镀液中的Ag浓度调整为仅以Sn-Ag电镀来形成Sn合金隆起物时的两倍。
并且，去除保护层后进行回流处理，形成实施例1的Sn合金隆起物。此时的回流处理用热风式的回流炉来实施，以去除隆起物表面的氧化膜为目的在隆起物表面涂布助熔剂，并在氮气气氛下（氧浓度100ppm以下）以图3所示的回流剖面条件来实施。
并且，作为比较例1，仅以Sn-Ag电镀在与实施例1同样的高纵横尺寸比图案的开口部以厚度：120μm形成Sn-Ag层的单层，并以与实施例1相同的回流处理来形成Sn合金隆起物。此时，将条件设定成回流后的Sn合金隆起物中的Ag组成成为2.5wt%来进行电解电镀。并且，作为实施例2及比较例2，用对约1000片晶圆进行电镀处理后的Sn-Ag电镀液以分别与实施例1及比较例1相同的条件实施电解电镀，并以与上述相同的回流处理来形成Sn合金隆起物。另外，将这些溶液中的Ag浓度设定为与实施例1及比较例1的条件相等的浓度。
对于这些实施例1、2及比较例1、2的Sn合金隆起物，以XRF（X射线荧光分析）测定Ag组成的结果，平均隆起物组成为实施例1：2.5wt%、比较例1：2.5wt%、实施例2：2.4wt%及比较例2：2.0wt%。如此，在使用新溶液的电解液的实施例1及比较例1中可获得设为目标的Ag组成，相对于此，使用相当于对1000片晶圆进行电镀处理后的电镀液时，在比较例2中Ag组成低于设为目的的组成，而在实施例2中基本维持了设为目标的Ag组成。
接着，作为与第2实施方式对应的实施例3，使用Sn电镀液、Sn-Cu电镀液及Sn-Ag电镀液的新溶液，通过以下条件进行电解电镀。即，使用与实施例1相同的晶圆，以Sn电镀为厚度成为24μm且膜中Cu组成成为2.5wt%的条件、Sn-Cu电镀为厚度成为24μm且膜中Ag组成成为5wt%的条件、及Sn-Ag电镀为厚度成为72μm的条件来进行三层电镀，并以使回流处理后的Sn合金隆起物的组成成为Sn-3Ag-0.5Cu的方式实施电解电镀。并且，去除保护层后进行回流处理，形成实施例2的Sn合金隆起物。
并且，施加相当于对约1000片晶圆进行电镀处理后的电解后，通过相同条件实施上述电镀处理。以XRF测定这些回流处理后的Sn合金隆起物中的Ag组成时，平均隆起物组成未受到电解的影响，为恒定。
另外，本发明的技术范围并非限定于上述实施方式及上述实施例，在不脱离本发明宗旨的范围内能够进行各种变更。
例如，如上述第2实施方式，优选在Sn层上层叠第1合金层24b（Sn-Cu层）与第2合金层24c（Sn-Ag层）这两层并以回流处理熔融它们来形成Sn-Ag-Cu三元系的隆起物，但在Sn层上层叠Sn与两种金属即Ag及Cu的合金层来作为Sn-Ag-Cu层，再以回流处理熔融它们来形成Sn-Ag-Cu三元系的隆起物也无妨。
符号的说明
1-基板，2-保护层，2a-开口部，3-电极焊盘（电极），4a-Sn层，4b-合金层，5、25-Sn合金隆起物，24b-第1合金层，24c-第2合金层。

Claims (2)

1.一种Sn合金隆起物的制造方法，其为由Sn与两种金属的合金形成的Sn合金隆起物的制造方法，其特征在于，具有如下工序：
通过电解电镀，在形成于基板上的保护层的开口部内的电极上形成Sn层；通过电解电镀，在所述Sn层上层叠Sn与所述两种金属中的一种的合金层及Sn与所述两种金属中的另一种的合金层这两层；及去除所述保护层后，熔融所述Sn层与两层层叠的所述合金层来形成Sn合金隆起物。
2.根据权利要求1所述的Sn合金隆起物的制造方法，其特征在于，具有如下工序：
所述两种金属中的一种金属为Ag且另一种金属为Cu，通过电解电镀，在所述Sn层上形成Sn-Ag层与Sn-Cu层这两层；及去除所述保护层后，熔融所述Sn层、所述Sn-Ag层及所述Sn-Cu层来形成Sn-Ag-Cu隆起物，以此来作为所述Sn合金隆起物。
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