CN103703168B - 焊料包覆球及其制造方法 - Google Patents

焊料包覆球及其制造方法 Download PDF

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CN103703168B
CN103703168B CN201380002311.5A CN201380002311A CN103703168B CN 103703168 B CN103703168 B CN 103703168B CN 201380002311 A CN201380002311 A CN 201380002311A CN 103703168 B CN103703168 B CN 103703168B
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solder
coated ball
solder layer
quality
ball
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CN103703168A (zh
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浅田贤
西村绚子
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Proterial Ltd
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Hitachi Metals Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
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    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
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    • B23K35/24—Selection of soldering or welding materials proper
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    • B23K35/264—Bi as the principal constituent
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    • C22C12/00—Alloys based on antimony or bismuth
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Abstract

本发明的实施方式的焊料包覆球（10A）具有：球状的芯（11）和以包覆芯（11）的方式形成的焊料层（12），焊料层（12）含有Sn和Bi，Bi含有率为45质量％以上65质量％以下，并且，Bi的含有率在内侧高、在外侧低。其他的焊料包覆球（10B）在芯（11）与焊料层（12）之间还具有Ni镀层（13）。

Description

焊料包覆球及其制造方法
技术领域
本发明涉及半导体封装的输入输出端子所使用的焊料包覆球及其制造方法。
背景技术
焊料包覆球主要用于连接电气、电子机器的部件。具体而言，焊料包覆球例如被用于部件周围具有引线端子的QFP（四边扁平封装，Quard Flat Package）、或比较小型且可以具有多管脚的BGA（球形阵列封装，Ball Grid Array）和CSP（芯片尺寸封装，Chip Size Package）等的半导体封装的输入输出端子。焊料包覆球具有在例如直径为50μm～1.5mm左右的由金属或树脂形成的微小球的表面上设置有含铅（Pb）的焊料层的结构。
近年来，含铅的焊料由于环境问题被替换为无铅焊料（无Pb焊料）。例如，在专利文献1和专利文献2中公开了具有不含铅的锡－银（Sn－Ag）系焊料层的焊料包覆球。但是，锡－银系的焊料层存在熔点高（例如220℃）的问题。
因此，在专利文献3中公开了具有锡－铋（Sn－Bi）二元系的焊料层的焊料包覆球。根据专利文献3，锡－铋二元系的焊料层的Bi含有率，在最内周为15.0质量％～22.0质量％、在最外周为29.0质量％～44.0质量％，由此能够将焊料层的熔点降到140℃。
现有技术文献
专利文献
专利文献1：日本特开2004－114123号公报
专利文献2：日本特开2004－128262号公报
专利文献3：日本特开2007－46087号公报
发明内容
发明所要解决的技术问题
但是，根据本发明的发明人的研究，专利文献3所记载的技术中存在以下的问题。
根据图7所示的锡－铋二元系的相图可以理解，即使为Bi的含有率低的组成，也是在140℃出现液相。但是，为了使专利文献3所记载的组成范围的焊料层完全成为熔融状态（液相），需要加热到超过200℃的温度，因此，在专利文献3的实施例中，在220℃进行再流平。另外，由于专利文献3所记载的组成范围含有较多的成为固液共存状态的组成，因此如果不加热到超过200℃的温度，熔融状态就会变得不稳定，固化后的焊料层的结构容易变得不均匀。即，当在160℃以下的温度对专利文献3所记载的焊料包覆球进行再流平时，固化后的焊料层的结构变得不均匀，结果存在机械特性的偏差增大的问题。另外，如专利文献3所述，为了使Bi浓度在焊料层的外侧高，需要一边进行镀敷一边向镀液补充Bi，镀液中的Bi浓度的管理困难。
本发明是鉴于上述技术问题而完成的发明，其目的在于提供一种能够在160℃以下的温度进行再流平的焊料包覆球及其制造方法。
用于解决技术问题的技术手段
本发明的实施方式的焊料包覆球具有球状的芯、和以包覆上述芯的方式形成的焊料层，上述焊料层含有Sn和Bi，Bi含有率为45质量％以上65质量％以下，并且，Bi的含有率在内侧高、在外侧低。上述焊料层由实质上只含有Sn和Bi的二元系合金形成。在此，所谓“实质上只含有Sn和Bi”是指，只要不对熔点造成无法获得本发明的效果的程度的影响，可以含有其他元素。
在某个实施方式中，以10℃／分钟的升温速度测定的DSC曲线中的终止温度为160℃以下。此时，起始温度优选为135℃以上。
在某个实施方式中，上述焊料包覆球在上述芯与上述焊料层之间还具有Ni镀层。此时，优选上述芯由铜形成。
本发明的实施方式的焊料包覆球的制造方法是用于制造上述任一实施方式所述的焊料包覆球的方法，该方法包括：准备球状的芯的工序；和在以垂直轴为中心旋转的镀槽内的镀液中，利用镀敷法在上述芯上形成焊料层的工序。
发明效果
根据本发明的实施方式，提供一种具有能够在160℃以下的温度进行再流平的焊料层的焊料包覆球及其制造方法。
附图说明
图1的（a）和（b）是本发明的实施方式的焊料包覆球10A和10B的截面示意图。
图2是示意地表示本发明的实施方式的焊料包覆球的制作中所使用的、高速旋转镀敷装置100的结构的图。
图3的（a）、（b）和（c）是分别表示本发明的实施方式的实施例的焊料包覆球A、B和C的DSC曲线的图。
图4的（a）和（b）是分别表示比较例的焊料包覆球D和E的DSC曲线的图。
图5的（a）和（b）是表示焊料包覆球A的截面SEM像（组成像）的图。
图6是表示利用旋转滚筒法制作的焊料包覆球的截面SEM像（组成像）的图。
图7是锡－铋的二元系的相图。
具体实施方式
下面参照附图，对本发明的实施方式的焊料包覆球及其制造方法进行说明。
图1（a）和（b）表示本发明的实施方式的焊料包覆球10A和10B的截面示意图。
图1（a）所示的焊料包覆球10A具有：球状（ball状）的芯11、和以包覆芯11的方式形成的焊料层12。焊料层12含有Sn和Bi，Bi含有率为45质量％以上65质量％以下，并且Bi的含有率在内侧高、在外侧低。焊料层12由实质上只含有Sn和Bi的二元系合金形成。芯11由金属或树脂形成。金属例如为铜（Cu）或含铜的合金、不锈钢（SUS）。芯11的直径例如为50μm以上1.5mm以下。
图1（b）所示的焊料包覆球10B，在芯11的表面还具有镀层13，在镀层13上具有焊料层12，在这一点上与焊料包覆球10A不同。镀层13例如为镍（Ni）镀层。镀层13的厚度例如为0.1μm以上4μm以下。例如，对在由铜（Cu）形成的芯11上直接形成有焊料层12的焊料包覆球10A进行再流平时，有时会在芯11与焊料层12的界面生成Cu6Sn5的金属间化合物，导致落下冲击性降低。通过设置镀层13，能够防止生成上述的金属间化合物。
在实质上只含有Sn和Bi的二元系合金中，Bi含有率为45质量％以上65质量％以下的组成接近共晶组成（Bi的含有率为58质量％，参照图7），成为固液共存状态的温度范围窄，为139℃以上160℃以下。因此，不仅能够在160℃以下的温度进行再流平，而且能够得到均匀且稳定的熔融状态，因此固化后（接合后）的焊料层的结构的均匀性高、机械特性的偏差小。本发明的实施方式的焊料包覆球10A和10B所具有的焊料层12，优选以10℃／分钟的升温速度测定的DSC曲线中的终止温度为160℃以下，起始温度为135℃以上。
Bi的含有率在内侧（芯11侧）高、在外侧低的这样的Bi的浓度分布容易形成。在镀液中，Sn由于阳极的溶解随时补充到镀液中，而Bi在镀敷的初期添加后，如果不补充，随着镀敷的进行，镀液中的Sn的存在比率就会增大（Bi的存在比率下降）。因此，本发明的实施方式的焊料包覆球10A和10B具有比专利文献3所记载的焊料包覆球容易制造的优点。
本发明的实施方式的焊料包覆球的制造方法是用于制造上述的焊料包覆球的方法，优选包括：准备球状的芯的工序；和在以垂直轴（铅直轴）为中心旋转的镀槽内的镀液中，利用镀敷法在芯上形成焊料层的工序。
一边使镀槽以垂直轴为中心旋转一边进行镀敷的工序，例如可以使用图2所示的高速旋转镀敷装置100实施。
高速旋转镀敷装置100具有被垂直延伸的旋转轴1支撑的、能够水平旋转的圆筒状的镀槽7。镀槽7具有：圆盘状的底部7a、与底部7a连接且以将底部7a扩张的方式连接的倾斜部7b、与倾斜部7b连接且具有阴极的第一圆筒部7c、和与第一圆筒部7c连接且内径比第一圆筒部7c小的第二圆筒部7d。镀槽7的上表面被与底部7a平行的平板状的上盖6覆盖，与第二圆筒部7d连接。旋转轴1例如为电动机的轴，支撑镀槽底部7a，并能够使镀槽7旋转。当然，也可以进行正旋转和反旋转两者（例如，最大转速1000rpm）。
镀敷装置100在镀槽7的第一圆筒部7c设置有阴极。在被镀物5与阴极接触时，被镀物5被通电，形成镀层。配置于第一圆筒部7c的阴极例如可以使用钛、黄铜、不锈钢、铜等。
上盖6在其中央部具有用于将阳极3插入镀槽7内的开口部。在此，阳极3使用锡（Sn）。镀敷装置100具有未图示的直流电源，向第一圆筒部7c的阴极与阳极3之间施加电压。控制施加电压，使得施加电流值或电压保持一定。另外，也可以以使电流密度保持一定的方式进行控制，但操作繁琐。
上盖6的开口部由圆筒部件8包围。圆筒部件8用于防止在镀槽7的高速旋转时或反转时镀液4飞散。
另外，上盖6抑制在镀槽7的高速旋转时镀槽7的中心部的镀液面的变动。因此，能够防止阳极3的整体或大部分从镀液4露出，因此能够形成具有均匀膜厚和良好外观的镀层。
另外，镀槽7在内周部具有倾斜部7b，因此受到离心力的被镀物5向倾斜部7b上堆积。由此，能够防止被镀物5滞留在镀槽7的底部，能够容易地使被镀物5与第一圆筒部7c的阴极接触。另外，在第一圆筒部7c上具有内径比第一圆筒部7c小的第二圆筒部7d，因此能够有效地使被镀物5与第一圆筒部7c的阴极接触。倾斜部7b的倾斜角α大于0°小于90°，可以根据被镀物5的量和镀槽7的旋转速度等适当设定。例如，α为45°。另外，优选第二圆筒部7d的内径为与倾斜部7b的最小内径同等的程度。
下面，例示几个实验结果，对本发明的实施方式的焊料包覆球10A及其制造方法进行详细说明。
在以下的实验例中，使用图2所示的高速旋转镀敷装置100，制作具有焊料层12的焊料包覆球10A。其中，镀敷装置100的镀槽7的外周为180mm，旋转速度为350rpm。作为镀液4，可以使用甲磺酸类的镀液（例如，大和化成研究所销售）。镀液含有甲磺酸Sn、甲磺酸Bi、甲磺酸和表面活性剂。另外也可以使用专利文献3所记载的镀液等公知的镀液。各自的浓度根据形成的焊料层12的组成调节。另外，在开始镀敷之后，不追加甲磺酸Bi，调节电压使得施加电流保持一定，形成Bi的含有率在内侧高、在外侧低的焊料层。作为芯11，使用直径为560μm的铜球。焊料层12的厚度约为20μm。
图3（a）、（b）和（c）分别表示本发明的实施方式的实施例的焊料包覆球A、B和C的DSC曲线。焊料包覆球A具有含有53质量％的Bi的Sn－Bi二元系焊料层，焊料包覆球B具有含有45质量％的Bi的Sn－Bi二元系焊料层，焊料包覆球C具有含有65质量％的Bi的Sn－Bi二元系焊料层。图4（a）和（b）表示比较例的焊料包覆球D和E的DSC曲线。焊料包覆球D具有含有18质量％的Bi的Sn－Bi二元系焊料层，焊料包覆球E具有含有79质量％的Bi的Sn－Bi二元系焊料层。
DSC的测定使用SII NanoTechnology Inc.生产的差示扫描量热计DSC6220。试样为40mg的焊料包覆球，使用铝制的坩埚。升温速度为10℃／分钟，测定温度范围为100℃～250℃，取样间隔为0.2秒。载气使用氩。
如图3（a）所示，在Bi的含有率为53质量％的焊料包覆球A的DSC曲线中，起始温度（熔解开始温度）为137.4℃，终止温度（熔解结束温度）为144.8℃。这样，由于焊料层12的组成接近共晶组成（Bi为58质量％），因而熔解峰尖锐，能够得到可以在160℃以下的温度充分再流平的、均质的焊料层12。
另外，如图3（b）所示，在Bi的含有率为45质量％的焊料包覆球B的DSC曲线中，起始温度为136.9℃，终止温度为153.3℃。这样，即使Bi的含有率为45质量％，熔解峰也是尖锐的，能够得到可以在160℃以下的温度充分再流平的、均质的焊料层12。
另外，如图3（c）所示，在Bi的含有率为65质量％的焊料包覆球C的DSC曲线中，起始温度为136.9℃，终止温度为159.8℃。这样，即使Bi的含有率为65质量％，熔解峰也是尖锐的，能够得到可以在160℃以下的温度充分再流平的、均质的焊料层12。
另一方面，在图4（a）所示的、Bi的含有率为18质量％的焊料包覆球D的DSC曲线中，起始温度为138.0℃，非常低，但终止温度为185.2℃，超过160℃。另外，在图4（b）所示的、Bi的含有率为79质量％的焊料包覆球E的DSC曲线中，起始温度为136.9℃，非常低，但终止温度为195.8℃，远远超过160℃。这样，在远远偏离共晶组成时，焊料层在160℃以下的温度不完全熔解，并且固化后的结构也容易变得不均匀。
因此，为了得到能够在160℃以下的温度再流平的、均质的焊料层12，优选Bi的含有率为45质量％以上。另一方面，优选Bi的含有率为65质量％以下，并且，由于Bi含有量少时熔点变得更低，因此进一步优选Bi的含有率低于58质量％（Bi含有率比共晶组成低）。从图7的相图可知，成为与Bi的含有率为45质量％的合金相同熔点的Bi的含有率超过65质量％，但Bi的含有率过大时，出现焊料的接合强度的偏差增大等的问题。可以认为这是由于Bi的含有率超过共晶组成时，Bi的熔融状态变得不稳定，使焊料层12熔融固化后的结构变得不均匀。特别是在Bi的含有率超过65质量％时，机械特性的偏差变大。
图5（a）和（b）表示上述焊料包覆球A的截面的由SEM得到的组成像。图5（a）是图5（b）的放大图。图6表示按照专利文献3记载的旋转滚筒法制作的焊料包覆球的截面SEM像（组成像）。
由图5（a）、（b）与图6的比较可知，采用滚筒镀敷法时，在焊料层内形成“孔（空隙）”（图6），而通过使用高速旋转镀敷装置，能够得到没有“孔”的致密的焊料层12（图5（a）和（b））。
另外，在图5（a）和（b）中，较亮的点在内侧分布多，由此可知，相比Sn为重元素的Bi的含有率在内侧（芯侧）增高。通常，在SEM的组成像中，观察为轻元素较暗、重元素较亮。
这样，在使用高速旋转镀敷装置时，能够容易地制造具有致密的焊料层的实施例的焊料包覆球。
产业上的可利用性
本发明适合用于半导体封装的输入输出端子所使用的焊料包覆球及其制造方法。
符号说明
10A、10B：包覆球；11：芯；12：焊料层；13：镀层（Ni镀层）。

Claims (4)

1.一种焊料包覆球，其特征在于：
所述焊料包覆球具有球状的芯、和以包覆所述芯的方式形成的焊料层，
所述焊料层为含有Sn和Bi的二元系焊料层，Bi含有率为45质量％以上65质量％以下，余量为Sn，并且，Bi的含有率在内侧高、在外侧低。
2.如权利要求1所述的焊料包覆球，其特征在于：
以10℃/分钟的升温速度测定的DSC曲线中的终止温度为160℃以下。
3.如权利要求1或2所述的焊料包覆球，其特征在于：
所述芯与所述焊料层之间还具有Ni镀层。
4.一种焊料包覆球的制造方法，用于制造权利要求1～3中任一项所述的焊料包覆球，其特征在于，包括：
准备球状的芯的工序；和
在以垂直轴为中心旋转的镀槽内的镀液中，利用镀敷法在所述芯上形成焊料层的工序。
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