CN108172523B - 芯材料和半导体封装体和凸块电极的形成方法 - Google Patents

芯材料和半导体封装体和凸块电极的形成方法 Download PDF

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CN108172523B
CN108172523B CN201711286173.4A CN201711286173A CN108172523B CN 108172523 B CN108172523 B CN 108172523B CN 201711286173 A CN201711286173 A CN 201711286173A CN 108172523 B CN108172523 B CN 108172523B
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solder
mass
core
core material
plating layer
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CN108172523A (zh
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西野友朗
近藤茂喜
服部贵洋
川崎浩由
六本木贵弘
相马大辅
佐藤勇
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Senju Metal Industry Co Ltd
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Senju Metal Industry Co Ltd
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    • H—ELECTRICITY
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    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/492—Bases or plates or solder therefor
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    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
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    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
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    • H01L23/49816—Spherical bumps on the substrate for external connection, e.g. ball grid arrays [BGA]
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Abstract

提供芯材料和半导体封装体和凸块电极的形成方法。该芯材料是将包含Sn和Bi的(Sn‑Bi)系软钎料合金在芯(12)的表面形成镀覆膜而得到的芯材料，其是软钎料镀覆层(16)中的Bi以规定范围的浓度比分布在软钎料镀覆层中的芯材料，是以Bi的浓度比在91.7～106.7％的规定范围内分布于软钎料镀覆层中的芯材料。软钎料镀覆层中的Bi是均匀的。因此，不会发生如下的情况：内周侧比外周侧更早发生熔融，在内周侧与外周侧产生体积膨胀差，使芯材料被弹飞。另外，软钎料镀覆层整体大致均匀地熔融，因此不会发生被认为是因熔融时机参差不齐而发生的芯材料的位置偏移，因此不存在伴随位置偏移等的电极间短路等担心。

Description

芯材料和半导体封装体和凸块电极的形成方法
技术领域
本发明涉及芯材料、具有使用了该芯材料的软钎料凸块的半导体封装体和凸块电极的形成方法。
背景技术
近年来，随着小型信息设备的发展，搭载的电子部件开始急速的小型化。电子部件为了应对由于小型化的要求而进行的连接端子的狭窄化、安装面积的缩小化而应用了在背面配置有电极的球栅阵列(BGA)。
应用了BGA的电子部件中，例如有半导体封装体。半导体封装体是用树脂密封具有电极的半导体芯片而构成的。半导体芯片的电极上形成有软钎料凸块。软钎料凸块通过将软钎料球接合于半导体芯片的电极而形成。应用了BGA的半导体封装体通过将加热熔融的软钎料凸块与印刷基板的导电性焊盘接合而搭载于印刷基板。近年来，为了应对进一步的高密度安装的要求，也开发了半导体封装体沿高度方向堆叠而成的三维高密度安装。
进行了三维高密度安装的半导体封装体为BGA，在半导体芯片的电极上载置软钎料球并进行了回流焊处理时，有时因半导体封装体的自重而使软钎料球被压碎。若发生这种状况，则存在如下的担心：软钎料从电极挤出，电极间彼此接触，发生电极间短路。
为了防止这种短路事故，提出了作为软钎料球不会因自重而被压碎或在软钎料熔融时变形的软钎料凸块。具体而言，提出了：使用由金属、树脂成型而成的球作为芯，将用软钎料覆盖该芯而得到的芯材料用作软钎料凸块。
作为覆盖芯的软钎料镀覆层，往往使用以Sn作为主成分的无铅软钎料。作为适宜例，可列举出包含Sn和Bi的Sn系软钎料合金(参照专利文献1和专利文献2)。
专利文献1中公开的芯材料如下得到：使用Cu球作为金属，将其作为芯而在其表面将包含Sn和Bi的Sn系软钎料合金形成为软钎料镀覆层。含有Bi的Sn系软钎料合金由于熔融温度为130～140℃这样较低的温度，因此出于对半导体封装体施加的热应力少等理由而用作镀覆组成。
专利文献1中，以软钎料镀覆层中所含的Bi的含量在内侧(内周侧)低并朝向外侧(外周侧)变高那样的浓度梯度进行了镀覆处理。
专利文献2也出于与专利文献1同样的理由而公开了：使用Cu球作为芯，在其上将包含Sn和Bi的Sn系软钎料合金形成镀覆膜而得到的软钎料凸块。专利文献2中以软钎料镀覆层中所含的Bi的含量在内侧(内周侧)高并向着外侧(外周侧)变低那样的浓度梯度进行了镀覆处理。
专利文献2的技术为与专利文献1完全相反的浓度梯度。认为这是因为，专利文献2的浓度控制比专利文献1的情况简单，容易制造。
现有技术文献
专利文献
专利文献1：日本特开2007-44718号公报
专利文献2：日本特许第5367924号公报
发明内容
发明要解决的问题
然而，将包含Sn和Bi的Sn系软钎料合金在Cu球的表面形成镀覆膜而得到的芯材料载置在半导体芯片的电极上并进行回流焊处理时，专利文献1和2中会发生如下的问题。
专利文献1中公开的技术是像这样具有Bi浓度在内周侧低并在外周侧变高那样的浓度梯度的软钎料镀覆层，但这种浓度梯度(内侧低、外侧高)的情况下，存在Bi熔融的时机在内周侧与外周侧稍微错开的担心。
熔融时机参差不齐时，会混合存在即使芯材料的外表面已开始熔融、在内周面侧的区域也尚未发生熔融这样的部分熔解，其结果，芯材料在发生了熔融的一侧略微发生位置偏移。在窄间距的高密度安装中，存在基于该位置偏移的软钎料处理造成致命缺陷的担心。
专利文献2的Bi的浓度梯度与专利文献1相反。此时也为了连接半导体封装体而进行基于回流焊的加热处理。像专利文献2那样以软钎料镀覆层中的Bi浓度在内周侧高、在外周侧低的状态加热熔融时，由于内周侧的Bi密度高，软钎料从内周侧的Bi区域开始熔融。即使内周侧的Bi区域熔融，外周侧的Bi区域也尚未开始熔融，因此内周侧的Bi区域侧快速发生体积膨胀。
因该体积膨胀在内外周侧的速度不同而在Bi的内周侧与外周侧(外部气体)产生压力差，Bi的外周侧开始熔融时，会发生因内周侧的体积膨胀所造成的压力差而将作为芯的Cu球弹飞那样的情况。必须避免这种情况的发生。
像这样具有由包含Sn和Bi的Sn系软钎料合金形成的软钎料镀覆层的Cu芯球在软钎料镀覆层中的Bi存在浓度梯度时会发生不良情况。
本发明是鉴于上述课题而做出的，其目的在于，提供特别是在芯表面具有电镀包含Sn和Bi的(Sn-Bi)系软钎料合金而形成的电镀软钎料镀覆层的芯材料，其中，软钎料镀覆层中所含的Bi以91.4～106.7％的规定范围的浓度比分布在软钎料镀覆层中。换言之，提供如下的芯材料和使用了该芯材料的半导体封装体，即，所述芯材料通过使Bi的浓度比处于规定范围内，从而软钎料镀覆层中的Bi浓度变得均匀(均等)，包括软钎料镀覆层中的内层、中间层和外层在内而在其整个区域中Bi浓度比处于规定范围内。
其中，提供在芯与(Sn-Bi)系软钎料合金的软钎料镀覆层之间施加镀Ni等基底镀覆层时在除去基底镀覆层以外的软钎料镀覆层中Bi均匀分布的芯材料。
另外，提供具有使用了这种芯材料的凸块的半导体封装体。
需要说明的是，本申请中使用的Bi浓度比(％)是指，软钎料镀覆层的规定区域中的Bi测量值(质量％)与目标的Bi含量(质量％)之比(％)、或Bi测量值的平均值(质量％)与目标的Bi含量(质量％)之比(％)。
另外，规定区域中的Bi含量也可以被称为该规定区域中的Bi浓度，因此本申请中使用的Bi浓度比(％)是指，软钎料镀覆层的规定区域中的测量得到的Bi浓度与目标的Bi浓度之比(％)、测量得到的Bi浓度的平均值与目标的Bi浓度之比(％)。
需要说明的是，关于软钎料镀覆层的Bi含量的测量，也可以对芯材料使用含氧酸等将软钎料镀覆层溶解，使用ICP-AES、ICP-MS等公知分析方法。
用于解决问题的方案
为了解决上述课题，第1项中记载的本发明的芯材料在芯表面具有电镀软钎料而成的包含Sn和Bi的(Sn-Bi)系软钎料合金的软钎料镀覆层，其特征在于，
前述芯由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质或它们的两种以上的合金、金属氧化物、或者金属混合氧化物形成，
如下表示上述软钎料镀覆层中所含的Bi的浓度比时，上述浓度比处于91.4～106.7％的范围内。
浓度比(％)＝Bi的测量值(质量％)/目标的Bi含量(质量％)
或者，
浓度比(％)＝Bi的测量值的平均值(质量％)/目标的Bi含量(质量％)
第2项中记载的本发明的芯材料在芯表面具有电镀软钎料而成的包含Sn和58质量％Bi的(Sn-58Bi)系软钎料合金的电镀软钎料镀覆层，其特征在于，
前述芯由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质或它们的两种以上的合金、金属氧化物、或者金属混合氧化物形成，
如下表示上述软钎料镀覆层中所含的Bi的浓度比时，上述浓度比处于91.4～108.6％的范围内。
浓度比(％)＝Bi的测量值(质量％)/目标的Bi含量(质量％)
或者，
浓度比(％)＝Bi的测量值的平均值(质量％)/目标的Bi含量(质量％)
此处，(Sn-58Bi)为(Sn-58重量％Bi)。
第3项中记载的本发明的芯材料在芯表面具有电镀软钎料而成的包含Sn和40质量％Bi的(Sn-40Bi)系软钎料合金的电镀软钎料镀覆层，
前述芯由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质或它们的两种以上的合金、金属氧化物、或者金属混合氧化物形成，
如下表示上述软钎料镀覆层中所含的Bi的浓度比时，上述浓度比处于90～107.5％的范围内。
浓度比(％)＝Bi的测量值(质量％)/目标的Bi含量(质量％)
或者，
浓度比(％)＝Bi的测量值的平均值(质量％)/目标的Bi含量(质量％)
此处，(Sn-40Bi)为(Sn-40重量％Bi)。
第4项中记载的本发明的芯材料在芯表面具有电镀软钎料而成的包含Sn和3质量％Bi的(Sn-3Bi)系软钎料合金的电镀软钎料镀覆层，其特征在于，
前述芯由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质或它们的两种以上的合金、金属氧化物、或者金属混合氧化物形成，
如下表示上述软钎料镀覆层中所含的Bi的浓度比时，上述浓度比处于90～106.7％的范围内。
浓度比(％)＝Bi的测量值(质量％)/目标的Bi含量(质量％)
或者，
浓度比(％)＝Bi的测量值的平均值(质量％)/目标的Bi含量(质量％)
此处，(Sn-3Bi)为(Sn-3重量％Bi)。
第5项中记载的本发明的芯材料为第1～4项中任一项所述的芯材料，前述芯材料的特征在于，自前述芯表面起依次具有选自Ni和Co中的1种以上元素的基底镀覆层和前述电镀软钎料镀覆层。
第6项中记载的本发明的芯材料为第1～5项中任一项所述的芯材料，其特征在于，使用了Cu球作为芯。
第7项中记载的本发明的芯材料为第1～5项中任一项所述的芯材料，其特征在于，使用了Cu柱作为芯。
第8项中记载的本发明的半导体封装体的特征在于，其为使用了第1～7项中任一项所述的芯材料的半导体封装体。
第9项中记载的本发明的凸块电极的形成方法的特征在于，包括：
将芯材料搭载在电极上的工序；和
对所搭载的前述芯材料进行加热，从而形成凸块电极的工序，
所述芯材料在芯表面具有电镀软钎料而成的包含Sn和Bi的(Sn-Bi)系软钎料合金的电镀软钎料镀覆层，
前述芯由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质或它们的两种以上的合金、金属氧化物、或者金属混合氧化物形成，
如下表示上述软钎料镀覆层中所含的Bi的浓度比时，上述浓度比处于91.4～106.7％的范围内。
浓度比(％)＝Bi的测量值(质量％)/目标的Bi含量(质量％)
或者，
浓度比(％)＝Bi的测量值的平均值(质量％)/目标的Bi含量(质量％)
对于软钎料镀覆层中的Bi，以相对于镀层厚度自其内周侧朝向外周侧且包括内周侧、外周侧在内而在其整个区域中其浓度分布均匀的方式进行了处理(其中，在芯上施加镀Ni等基底镀覆层时，不包括基底镀覆层)。
Sn系软钎料合金除了(Sn-Bi)系的软钎料合金之外还可以含有其它添加元素。作为能在(Sn-Bi)系软钎料合金中添加的元素，有Ag、Cu、Ni、Ge、Ga、In、Zn、Fe、Pb、Sb、Au、Pd、Co等之中的一种或两种以上的元素。例如，可以考虑(Sn-Bi-Cu-Ni)系软钎料合金、(Sn-Ag-Cu-Bi)系软钎料合金等。
该芯材料是将包含Sn和Bi的(Sn-Bi)系软钎料合金在芯的表面通过电镀软钎料形成镀覆膜而得到的芯材料，其是软钎料镀覆层中的Bi以规定范围的浓度比分布在软钎料镀覆层中的芯材料，是以Bi的浓度比在91.4～106.7％的规定范围内分布在软钎料镀覆层中的芯材料。关于浓度比(％)在后文中说明。
发明的效果
根据本发明的芯材料，电镀软钎料镀覆层中的Bi是均匀的，因此相对于软钎料镀覆层的膜厚包括Bi的内周侧、外周侧在内而在其整个区域中Bi浓度比处于规定范围内。因此，不会发生如下的情况：内周侧比外周侧更早发生熔融，在内周侧与外周侧产生体积膨胀差而芯材料被弹飞那样的情况。
另外，电镀软钎料镀覆层中的Bi是均匀的，因此在芯材料的整个面上大致均匀地熔融，因而软钎料镀覆层内的熔融时机几乎不产生时间差。其结果，不会发生因熔融时机的参差不齐而产生的芯材料的位置偏移，因此不存在伴随位置偏移等的电极间短路等的担心。因此，通过使用该芯材料，能够提供高品质的半导体封装体。此处，对于虽然膜厚能够均匀地控制、但浓度变得不均匀的电镀软钎料的问题，本发明通过控制Bi浓度比处于规定的范围内，从而能够得到具有均匀的电镀软钎料镀覆层的芯材料。
附图说明
图1为示出本发明的一个实施方式的Cu芯球的构成例的截面图。
图2为示出本发明的其它实施方式的Cu芯球的构成例的截面图。
图3为示出表示软钎料镀覆层中的Bi分布状态的Cu芯球的构成例的放大截面图。
图4为图3的进一步放大的截面图。
图5为放大地示出Sn和Bi的分布状态的主要部分的截面图(场发射型电子束微分析仪(FE-EPMA)照片)。
图6为实施例1中的电镀处理的镀液中的Bi浓度与软钎料镀覆层中所含有的Bi浓度的关系以Cu芯球直径为基准时的特性曲线图。
图7为示出测定芯材料的Bi的浓度分布的方法的一例的说明图。
图8为实施例2中的电镀处理的镀液中的Bi浓度与软钎料镀覆层中所含有的Bi浓度的关系以Cu芯球直径为基准时的特性曲线图。
附图标记说明
10 Cu芯球
12 Cu球
14 基底镀覆层
16 软钎料镀覆层
16a 内层
16b 中间层
16c 外层
17a～17c 切片(测量区域)
具体实施方式
实施例1
以下，详细说明本发明的适宜的实施方式。
本发明中，提供如下的芯材料和使用其的半导体封装体，即，所述芯材料是将包含Sn和Bi的Sn系软钎料合金在芯表面上通过电镀处理形成镀覆膜而得到的，其中，软钎料镀覆层中的Bi的分布均匀。
本发明的软钎料镀覆层的组成包含含有Sn和Bi的(Sn-Bi)系合金。关于Bi的含量，相对于合金整体的Bi量为0.1～99.9质量％的范围时，能将Bi的浓度比控制在91.4～106.7％的规定范围内，能够使软钎料镀覆层中的Bi分布均匀。
例如，(Sn-58Bi)系软钎料合金的情况下，作为目标值的Bi的分布以58质量％为目标值，作为允许范围，为52质量％(浓度比91.4％)～63质量％(浓度比108.6％)。
需要说明的是，允许范围是指，若在该范围内则能没有问题地进行凸块形成等软钎焊的范围。另外，浓度比(％)是指，测量值(质量％)与目标的含量(质量％)之比、或者测量值的平均值(质量％)与目标的含量(质量％)之比(％)。即，浓度比(％)可以如下表示。
浓度比(％)＝测量值(质量％)/目标的含量(质量％)
或者，
浓度比(％)＝测量值的平均值(质量％)/目标的含量(质量％)
另外，即使在包含Sn、Bi的二元电镀软钎料镀覆层中添加除此之外的添加元素，也能将Bi的浓度比控制在91.4～106.7％的规定范围内。
作为添加元素，可以考虑使用Ag、Cu、Ni、Ge、Ga、In、Zn、Fe、Pb、Sb、Au、Pd、Co等之中的一种或两种以上。
作为芯(核)，使用金属材料。芯的形状可以考虑球体等形状(柱状的柱、片状等)。本例中，对于使用为球体、特别是由Cu形成的球(以下称为Cu球)作为芯的Cu芯球的情况进行说明。
Cu球的粒径(球直径)也因BGA的尺寸等而异，以下的例子中为左右的球状，软钎料镀覆层的径向的单侧的厚度为20～100μm。Cu芯球的粒径根据所使用的电子部件的密度、尺寸而适当选择，可以使用1～1000μm的范围内的Cu球，根据使用的Cu球的粒径适当选择镀层厚度。进行镀覆处理的镀覆装置使用电镀装置。
接着，示出使用了Cu球的Cu芯球例。
图1为示出本发明的Cu芯球10的一例的截面图。为了便于说明，图示为夸大绘制。
Cu芯球10形成有Cu球12和在该例中夹着Ni基底镀覆层14由Sn系软钎料合金形成的软钎料镀覆层16。Ni基底镀覆层14发挥用于在Cu球12与软钎料镀覆层16之间防止由金属扩散导致的软钎料镀覆层16的组成变化的基底镀层的作用，为1～4μm左右的厚度。该Ni基底镀覆层14不是必需的组成，也可以如图2那样在Cu球12的表面直接形成软钎料镀覆层。需要说明的是，形成基底镀覆层14时，基底镀覆层14也可以由包含选自Ni、Co中的1种以上元素的层构成。
Cu球12中使用的Cu可以为纯铜、也可以为铜的合金。
使用以Cu为主成分的合金组成的Cu球12时，其纯度没有特别限定，从抑制由纯度降低导致的Cu芯球的电导率、热导率的劣化，并且根据需要抑制α射线量的观点出发，优选为99.9质量％以上。
作为芯，除了Cu之外，也可以由Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质或它们的两种以上的合金、金属氧化物、或者金属混合氧化物构成。
从控制焊点高度的观点出发，Cu球12的球形度优选为0.95以上、更优选为0.990以上。Cu球12的球形度不足0.95时，Cu球12为不规则形状，因此在凸块形成时形成高度不均匀的凸块，发生接合不良的可能性变高。进而，将Cu芯球10搭载于电极并进行回流焊时，若球形度低，则Cu芯球10发生位置偏移，自对准性也恶化。
此处，球形度表示距离完美圆球的偏差。球形度可以通过例如最小二乘中心法(LSC法)、最小区域中心法(MZC法)、最大内切中心法(MIC法)、最小外切中心法(MCC法)等各种方法求出。详细而言，球形度是指，将500个的各Cu球的直径除以长径时算出的算术平均值，值越接近作为上限的1.00，表示越接近完美圆球。长径的长度是指，利用MitutoyoCorporation制造的Ultra Quick Vision、ULTRA QV350-PRO测定装置测定得到的长度。
包含软钎料镀覆层16的Cu芯球10整体的直径优选为1～1000μm。处于该范围时，能够稳定地制造球状的Cu芯球10，另外，通过选择粒径，能够抑制电极端子间为窄间距时的连接短路。
有时将粒径为1～300μm左右的Cu芯球10的集合体称为“Cu芯粉末”。该Cu芯粉末有时以作为焊膏中的粉末用软钎料配混的状态来使用。
软钎料镀覆层16为软钎料合金，该例中包含Sn和Bi。
此时，如前述那样，关于软钎料镀覆层16中的Bi含量，相对于目标值的58质量％，作为允许范围，优选为53质量％(浓度比91.4％)～63质量％(浓度比108.6％)左右。
软钎料镀覆层16的厚度也因Cu球12的粒径而异，优选径向的单侧为100μm以下。例如，为粒径的Cu球12时，以50～70μm的厚度形成软钎料镀覆层16。这是为了确保充分的软钎料接合量。
作为镀液，使用有机酸、甲磺酸Bi和表面活性剂的混合液。镀液的浓度以在软钎料镀覆层形成中恒定的方式控制。
通过电镀形成包含Sn和Bi的Sn-Bi系软钎料合金组成的软钎料镀覆层时，Bi比Sn更优先地被导入至软钎料镀覆层中，因此存在电镀液中的Bi浓度与软钎料镀覆层中的Bi量不一致的问题，无法形成Bi的浓度分布均匀的软钎料合金镀覆层。因此，以图6的条件在阳极电极与阴极电极之间施加规定的直流电压，并且边摇动Cu球边将液体中的Bi浓度调整均匀地进行电镀处理。
关于基于该镀覆处理的软钎料镀覆层16的生成过程，参照图6来进一步详细说明。图6为电镀处理的镀液中的Bi浓度(曲线Lb)与软钎料镀覆层16中的Bi浓度(曲线La)的关系以Cu芯球直径为基准时的特性曲线图。
该例中，作为Cu球的初始值，为使用粒径215μm的Cu球的情况。逐一监测软钎料镀覆层16的厚度，该例中，采集软钎料镀覆层16的厚度逐次增加规定值时的Cu芯球10作为每一次的样品。采集的样品在清洗后进行干燥，然后测量粒径。
对于测量时机的Cu芯球的粒径成为目标值时的软钎料镀覆层中的Bi的含量依次进行测定时，得到图6曲线La那样的结果。根据该结果可知，即使软钎料镀覆层16依次增加规定厚度，此时的Bi的含量也呈现与之前的含量大致相同的值。曲线La的情况下，Bi的含量大致为58～60质量％。因此，根据图6曲线La可以理解，Bi的浓度分布相对于镀层厚度是均匀(均等)的，没有浓度梯度。
图3示出此时的Cu芯球10的截面图。根据将其放大而成的图4和进一步将其放大而成的图5，可以明确软钎料镀覆层16中Sn和Bi均匀混合存在并生长的过程。图5是使用FE-EPMA拍摄的。
即使软钎料镀覆层16的厚度生长，软钎料镀覆层16中的Bi的浓度也几乎维持相同状态，因此可以明确，是以软钎料镀覆层16中的Bi几乎均匀分布的状态生长(析出)的。以Bi浓度处于期望值内的方式以镀液中的Bi浓度均匀的状态进行镀覆处理。该例中，作为软钎料镀覆层16中的Bi的含量，以58质量％作为目标值，因此以达到目标值的方式控制镀液中的Bi浓度。
为了使软钎料镀覆层16中的Bi的浓度分布成为期望值，一边进行电压/电流控制一边进行镀覆处理。通过这种电镀处理，能够将软钎料镀覆层16中的Bi的分布维持在期望值。
实施例中，镀液中的Bi浓度在镀覆处理中大致为42～44质量％，这是因为，如上所述一边以软钎料镀覆层16中的Bi浓度为53～63质量％的方式随时调整镀液中的Bi浓度一边进行了镀覆处理。
作为曲线La示出的软钎料镀覆层16内的Bi浓度与作为曲线Lb示出的镀液中的Bi浓度不一致是因为，镀液中的Bi比镀液中的Sn更优先地被导入至软钎料镀覆层内。
为了确认软钎料镀覆层16中的Bi的浓度分布成为与目标值相应的值，进行了如下的实验。
(1)以下述条件制作软钎料镀覆层16的组成为(Sn-58)Bi的Cu芯球10。
·Cu球12的直径：250μm
·Ni基底镀覆层14的膜厚：2μm
·软钎料镀覆层16的膜厚：23μm
·Cu芯球10的直径：300μm
为了容易测定实验结果，作为Cu芯球10，制作具有其厚度较薄的软钎料镀覆层的Cu芯球。
镀覆方法通过电镀工艺以图6的条件制作。
(2)作为试样，准备10个形成有同一组成的(Sn-58Bi)系软钎料合金的软钎料镀覆层的Cu芯球10。使用它们作为试样A。
(3)将各个试样A1～A10用树脂密封。
(4)对于经密封的各试样A1～A10，与树脂一起进行研磨，观察各试样A1～A10的截面。观察设备使用日本电子株式会社制造的FE-EPMAJXA-8530F。
将试样A1的截面图示于图7。为了方便，软钎料镀覆层16之中自Cu球12的表面侧起分为内层16a、中间层16b和外层16c。内层16a设为自Cu球12的表面起至9μm为止，中间层16b设为9～17μm，并且外层16c设为17～23μm，从内层16a、中间层16b和外层16c，如图7所示在该例中以厚度5μm分别切取宽度为40μm的区域17a、17b、17c，通过定性分析进行Bi的浓度的测量。在总计10个视场中逐一对各内层16a、中间层16b和外层16c进行该操作。
将其结果总结于(表-1)。根据该(表-1)可知，在内层、中间层、外层，处于最小值53.29质量％(浓度比91.9％)、最大值60.97质量％(浓度比105.1％)的范围。如上所述，将Bi的允许范围设为53质量％(浓度比91.4％)～63质量％(浓度比108.6％)，但根据该实验结果的实测值能够允许至53.29质量％(浓度比91.9％)～60.97质量％(浓度比105.1％)的范围。
【表1】
此外，算出试样A1～A10的算术平均值，结果为：
内层区域17a＝57.46(质量％)(浓度比99.1％)
中间层区域17b＝56.32(质量％)(浓度比97.1％)
外层区域17c＝56.62(质量％)(浓度比97.6％)。
另外可知，像这样对内层、中间层、外层的各区域17a～17c进行算术平均时，软钎料镀覆层中的Bi处于上述53质量％～63质量％的允许范围内，因此成为大致目标值的Bi的浓度比。
对于与试样A分开制作的试样B～D也同样地进行这种测量操作，将其结果示于(表-2)。
【表2】
根据(表-2)的结果可知，虽然多少有些波动，但软钎料镀覆层16中的Bi浓度处于目标值的53～63质量％。
此外，将与这些试样A～D同批制造的Cu芯球分别抽取10个(例)，分别通过通常的回流焊处理接合于基板。
接合结果也一并示于(表-2)。
对于接合结果，所有样品均未测定到任何接合不良的情况判定为“良”，即便有1个样品在接合时发生位置偏移的情况和即便有1个样品在接合时Cu芯球10被弹飞的情况也都判定为“不良”。
均没有发生内周侧比外周侧更早熔融、在内周侧与外周侧产生体积膨胀差而使Cu芯球10被弹飞那样的情况，此外，软钎料镀覆层16整体大致均匀地熔融，因此没有发生被认为是因熔融时机的参差不齐而发生的芯材料的位置偏移，因此不存在伴随位置偏移等的电极间短路等的担心。因此，得到了完全没有发生接合不良的良好结果，判定为“良”。
实施例2
第二实施例是形成除了Sn、Bi之外还包含Cu和Ni的由(Sn-Cu-Bi-Ni)组成的四元Sn系软钎料合金的软钎料镀覆层16的例子。作为其目标值，其组成比如以下所述。
Bi：40质量％、Cu：0.5质量％、Ni：0.03质量％、Sn：余量。此时的Bi的分布的目标值为40质量％，允许范围为36质量％(浓度值90％)～43质量％(浓度比107.5％)。
具体而言，以下述条件制作软钎料镀覆层的组成根据上述表述为(Sn-40Bi-0.5Cu-0.03Ni)的Cu芯球。
·Cu球的直径：180μm
·Ni基底镀覆层的膜厚：2μm
·软钎料镀覆层的膜厚：33μm
·Cu芯球的直径：250μm
Cu芯球的制作方法利用与实施例1同样的电镀条件以镀液中的Bi浓度均匀的方式进行。
对于实验方法，除了将内层16a设为自Cu球的表面起至11μm为止、将中间层16b设为11～22μm、并且将外层16c设为22～33μm之外，与实施例1为相同的条件。
将测定得到的结果示于(表-2)的E～H。
根据(表-2)试样E～H的结果可知，此时的Bi的目标值为40质量％，此时的软钎料镀覆层16中的Bi的平均值为最小37.81质量％(浓度比94.5％)～最大41.33质量％(浓度比103.3％)(均为对于同一组成的软钎料合金测量10次而得到的平均值)，存在一些偏差，但是处于大致与目标值相应的值、即允许范围的36质量％(浓度值比90.0％)～43质量％(浓度值比107.5％))内。此外，在所有样品中，接合判定与实施例1同样地得到了完全没有发生接合不良的良好结果，因此判定为“良”。
图8与图6同样为电镀处理的镀液中的Bi浓度(曲线Lc)与软钎料镀覆层16中的Bi浓度(曲线Ld)的关系以Cu芯球直径为基准时的特性曲线图。
该例中，与实施例1同样地，作为Cu球的初始值，为使用粒径215μm的Cu球的情况。逐一监测软钎料镀覆层16的厚度，该例中，采集软钎料镀覆层16的厚度逐次增加规定值时的Cu芯球10作为每一次的样品。采集的样品在清洗后进行干燥，然后测量粒径。
对于测量时机的Cu芯球的粒径成为目标值时的软钎料镀覆层中的Bi的含量依次进行测定时，得到图8的曲线Lc那样的结果。根据该结果可知，即使软钎料镀覆层16依次增加规定厚度，此时的Bi的含量也呈现与之前的含量大致相同的值。曲线Lc的情况下，Bi的含量大致为40～42质量％。因此，根据曲线Lc可以理解，Bi的浓度分布相对于镀层厚度是均匀(均等)的，没有浓度梯度。软钎料镀覆层16内的Bi浓度(曲线Lc)与镀液中的Bi浓度(曲线Ld)不一致是因为，与图6同样地，镀液中的Bi比镀液中的Sn更优先地被导入至软钎料镀覆层内。
实施例3
实施例3中，针对形成了包含Ag且包含少量Bi的由(Sn-3Ag-0.8Cu-3Bi)组成的四元Sn系软钎料合金的软钎料镀覆层16的情况进行同样的测量。此时的Bi的分布的目标值为3质量％，允许范围为2.7质量％(浓度值比90.0％)～3.2质量％(浓度比106.7％)。
Cu芯球的制作方法与实施例1和实施例2相同。
关于所使用的Cu球和Cu芯球的直径、Ni基底镀覆层和软钎料镀覆层的膜厚等的规格和实验条件，除了软钎料镀覆层的组成以外，为与实施例1相同的条件。
将其结果示于(表-2)试样I～L。此时，作为目标值的Bi为3质量％，因此，如试样I～L所示虽然是2.81～3.08质量％(均为对于同一试样测量10次而得到的平均值)这样存在一些偏差(平均值的最小2.81质量％(浓度比93.7％)～最大3.08质量％(浓度比102.7％)的程度，但处于允许范围。因此，可知处于2.7质量％(浓度比90.0％)～3.2质量％(浓度比106.7％)。接合判定与实施例1同样地得到了完全没有发生接合不良的良好结果，因此判定为“良”。
将上述[实施例1]～[实施例3]的结果汇总于表-3。Bi的浓度比为91.4％～106.7质量％。
【表3】
需要说明的是，作为比较例，将以往周知的软钎料镀覆层中的Bi的分布具有浓度梯度时的实验结果示于上述(表-2)中。关于所使用的Cu球、Cu芯球的球直径、Ni基底镀覆层和软钎料镀覆层的膜厚等以及实验条件，除了下述电镀的方法之外，为与实施例1相同的条件。
比较例1
比较例1中，关于镀液，利用包含甲磺酸Sn、有机酸和表面活性剂的镀液进行电镀。此外，在镀覆膜厚为目标值的一半的阶段，进一步仅追加甲磺酸Bi。由此，一边使镀液中的甲磺酸Sn的浓度减少并使甲磺酸Bi的浓度增加一边进行了电镀处理。
其结果，形成了具有软钎料镀覆层中的Bi浓度在内侧低并朝向外侧逐渐变高的浓度梯度(内层0质量％、中层52.12质量％、外层100质量％)、作为软钎料镀覆层整体使Bi的含量成为目标值58质量％那样的软钎料镀覆层。
比较例2
比较例2中，利用包含甲磺酸Sn、甲磺酸Bi、有机酸和表面活性剂的镀液进行电镀。开始镀覆后，在阳极电极与阴极电极之间施加规定的直流电压，同时一边摇动Cu球一边进行电镀处理。
其结果，形成了呈现软钎料镀覆层中的Bi浓度在内侧高并朝向外侧逐渐变低的浓度梯度(内层70.7质量％、中层24.8质量％、外层3.8质量％)、作为软钎料镀覆层整体使Bi的含量成为目标值58质量％那样的软钎料镀覆层。
其结果，比较例1在接合时发生位置偏移，比较例2中Cu芯球被弹飞，因此均判定为“不良”。
如此改变软钎料镀覆层16内的Bi浓度时，发生了位置偏移、Cu芯球10的吹飞等现象。
本发明的在芯表面覆盖有软钎料镀覆层的材料中所含的Bi是均匀的。例如，在BGA那样的半导体封装体中可以使用本发明的芯材料作为软钎料凸块。作为芯，球是合适的，而且Cu等金属球是合适的。
需要说明的是，本发明的保护范围不限定于上述实施方式，在不超出本发明的主旨的范围内，包括对上述实施方式加以各种变更而成的技术方案。其形状也包括球体等形状(柱状的柱、片状等)。
例如，向上表面和底面的直径：1～1000μm、高度：1～3000μm的Cu制柱的表面上设置单侧1～4μm的Ni基底镀覆层、Fe基底镀覆层、Co基底镀覆层等，并在与实施例相同的条件下覆盖(Sn-Bi)系软钎料镀覆层而得到的Cu芯柱中，软钎料镀覆层中的Bi成为91.4～106.7％的规定范围的浓度比，与本申请实施例的Cu芯球同样地不会发生接合不良。
产业上的可利用性
本发明的芯材料可以用作BGA等那样的半导体封装体的接合材料。

Claims (11)

1.一种芯材料，其在芯表面具有电镀软钎料而成的包含Sn和Bi的Sn-Bi系软钎料合金的电镀软钎料镀覆层，其特征在于，
所述芯由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质或它们的两种以上的合金、金属氧化物、或者金属混合氧化物形成，
如下表示所述软钎料镀覆层中所含的Bi的浓度比时，所述浓度比处于91.4～106.7％的范围内，
浓度比(％)＝Bi的测量值(质量％)/目标的Bi含量(质量％)
或者，
浓度比(％)＝Bi的测量值的平均值(质量％)/目标的Bi含量(质量％)。
2.一种芯材料，其在芯表面具有电镀软钎料而成的包含Sn和58质量％Bi的Sn-58Bi系软钎料合金的电镀软钎料镀覆层，其特征在于，
所述芯由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质或它们的两种以上的合金、金属氧化物、或者金属混合氧化物形成，
如下表示所述软钎料镀覆层中所含的Bi的浓度比时，所述浓度比处于91.4～108.6％的范围内，
浓度比(％)＝Bi的测量值(质量％)/目标的Bi含量(质量％)
或者，
浓度比(％)＝Bi的测量值的平均值(质量％)/目标的Bi含量(质量％)。
3.一种芯材料，其在芯表面具有电镀软钎料而成的包含Sn和40质量％Bi的Sn-40Bi系软钎料合金的电镀软钎料镀覆层，其特征在于，
所述芯由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质或它们的两种以上的合金、金属氧化物、或者金属混合氧化物形成，
如下表示所述软钎料镀覆层中所含的Bi的浓度比时，所述浓度比处于90～107.5％的范围内，
浓度比(％)＝Bi的测量值(质量％)/目标的Bi含量(质量％)
或者，
浓度比(％)＝Bi的测量值的平均值(质量％)/目标的Bi含量(质量％)。
4.一种芯材料，其在芯表面具有电镀软钎料而成的包含Sn和3质量％Bi的Sn-3Bi系软钎料合金的电镀软钎料镀覆层，其特征在于，
所述芯由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质或它们的两种以上的合金、金属氧化物、或者金属混合氧化物形成，
如下表示所述软钎料镀覆层中所含的Bi的浓度比时，所述浓度比处于90～106.7％的范围内，
浓度比(％)＝Bi的测量值(质量％)/目标的Bi含量(质量％)
或者，
浓度比(％)＝Bi的测量值的平均值(质量％)/目标的Bi含量(质量％)。
5.根据权利要求1～4中任一项所述的芯材料，其特征在于，所述芯材料从所述芯表面起依次具有选自Ni和Co中的1种以上元素的基底镀覆层和所述电镀软钎料镀覆层。
6.根据权利要求1～4中任一项所述的芯材料，其特征在于，使用了Cu球作为芯。
7.根据权利要求5所述的芯材料，其特征在于，使用了Cu球作为芯。
8.根据权利要求1～4中任一项所述的芯材料，其特征在于，使用了Cu柱作为芯。
9.根据权利要求5所述的芯材料，其特征在于，使用了Cu柱作为芯。
10.一种半导体封装体，其特征在于，使用了权利要求1～9中任一项所述的芯材料作为软钎料凸块。
11.一种凸块电极的形成方法，其特征在于，包括：
将芯材料搭载在电极上的工序；和
对所搭载的所述芯材料进行加热，从而形成凸块电极的工序，
所述芯材料在芯表面具有电镀软钎料而成的包含Sn和Bi的Sn-Bi系软钎料合金的电镀软钎料镀覆层，
所述芯由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质或它们的两种以上的合金、金属氧化物、或者金属混合氧化物形成，
如下表示所述软钎料镀覆层中所含的Bi的浓度比时，所述浓度比处于91.4～106.7％的范围内，
浓度比(％)＝Bi的测量值(质量％)/目标的Bi含量(质量％)
或者，
浓度比(％)＝Bi的测量值的平均值(质量％)/目标的Bi含量(质量％)。
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