CN106688085A - Cu柱、Cu芯柱、钎焊接头及硅穿孔电极 - Google Patents

Cu柱、Cu芯柱、钎焊接头及硅穿孔电极 Download PDF

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CN106688085A
CN106688085A CN201480081816.XA CN201480081816A CN106688085A CN 106688085 A CN106688085 A CN 106688085A CN 201480081816 A CN201480081816 A CN 201480081816A CN 106688085 A CN106688085 A CN 106688085A
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CN106688085B (zh
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川崎浩由
六本木贵弘
相马大辅
佐藤勇
川又勇司
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Senju Metal Industry Co Ltd
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Senju Metal Industry Co Ltd
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    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/53204—Conductive materials
    • H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
    • H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
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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
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Abstract

本发明提供维氏硬度低、且算术平均粗糙度小的Cu柱、Cu芯柱、钎焊接头及硅穿孔电极。本发明的Cu柱1的纯度为99.9％以上且99.995％以下，算术平均粗糙度为0.3μm以下，维氏硬度为20HV以上且60HV以下。Cu柱1在软钎焊温度下不熔融，能够确保一定的焊点高度(基板间的空间)，因此适用于三维安装、窄间距安装。

Description

Cu柱、Cu芯柱、钎焊接头及硅穿孔电极
技术领域
本发明涉及Cu柱、Cu芯柱、钎焊接头及硅穿孔电极。
背景技术
近年来，由于小型信息设备的发达，所搭载的电子部件正在迅速小型化。电子部件根据小型化的要求，为了应对连接端子的窄小化、安装面积的缩小化，正在应用在背面设置有电极的球栅阵列封装(以下称为“BGA”)。
利用BGA的电子部件中，例如有半导体封装体。半导体封装体中，具有电极的半导体芯片被树脂密封。半导体芯片的电极上形成有焊料凸块。该焊料凸块通过将焊料球接合于半导体芯片的电极而形成。利用BGA的半导体封装体通过利用加热而熔融了的焊料凸块与印刷基板的导电性焊盘接合，从而搭载于印刷基板。另外，为了应对进一步的高密度安装的要求，正在研究将半导体封装体在高度方向上堆叠而成的三维高密度安装。
然而，在进行了三维高密度安装的半导体封装体上应用BGA时，由于半导体封装体的自重，焊料球有时会被压碎。如果发生这样的情况，则变得无法保持基板之间的适当空间。
因此，研究了使用焊膏将Cu球电接合在电子部件的电极上的焊料凸块。使用Cu球而形成的焊料凸块在将电子部件安装于印刷基板时，即使半导体封装体的重量施加于焊料凸块，也能够利用在软钎料的熔点下不熔融的Cu球支撑半导体封装体。因而，不会因半导体封装体的自重而压碎焊料凸块。
然而，在使用了上述的Cu球的情况下存在如下问题。在Cu球中，由于基板间的焊点高度成为Cu球的球径，因此，为了实现所要求的焊点高度而Cu球的宽度变大，有时不能应对窄间距化安装。另外，通常在半导体封装体中，使用芯片接合用的软钎焊材料将半导体芯片接合于引线架的芯片焊盘电极部后，用树脂密封。在将该半导体封装体安装于印刷基板时，使用与芯片接合用的软钎焊材料不同的安装用的软钎焊材料。其理由是为了使芯片接合用的软钎焊材料不会因将半导体封装体安装于基板时的安装用的软钎焊材料的加热条件而熔出。这样，在芯片接合用的软钎焊材料与安装用的软钎焊材料使用不同的材料时，由于各基板的热膨胀系数产生差异，因此有时会因环境温度等的变化而导致在与焊料凸块的接合部产生应力(热应力)，TCT(温度循环试验)可靠性降低。
因此，近年来，开发了能够比焊料球窄间距化、且能够实现TCT可靠性提高的Cu柱。另外，在比较相同间距的Cu球与Cu柱时，由于柱形状比球形状更能够稳定地支撑电极间，因此在这一点上研究了Cu柱的采用。例如，专利文献1～5中记载了由铜、软钎料等形成的柱状的圆柱。专利文献6中记载了维氏硬度为55HV以下的、用于接合陶瓷基板和玻璃环氧基板的铜柱。
现有技术文献
专利文献
专利文献1:日本特开平7-66209号公报
专利文献2:日本专利第3344295号
专利文献3:日本特开2000-232119号公报
专利文献4:日本专利第4404063号
专利文献5:日本特开2009-1474号公报
专利文献6:日本特开2011-176124号公报
发明内容
发明要解决的问题
然而，根据上述专利文献1～6，虽然能够应对窄间距化安装、且能够抑制热应力，但对Cu柱的算术平均粗糙度完全没有公开。因此，在使用了专利文献1～6的Cu柱的情况下，有时会出现如下问题：将Cu柱排列于基板上时Cu柱的流动性会降低，或安装时的Cu柱与电极的密合性会降低等。
因此，本发明的目的在于，为了解决上述课题而提供维氏硬度低、且算术平均粗糙度小的Cu柱、Cu芯柱、钎焊接头及硅穿孔电极。
用于解决问题的方案
本发明人等对Cu柱进行了选定。发现若Cu柱的维氏硬度为20HV以上且60HV以下、且算术平均粗糙度为0.3μm以下，可得到用于解决本发明的课题的优选的Cu柱等。
在此，本发明如下所述。
(1)一种Cu柱，其纯度为99.9％以上且99.995％以下，算术平均粗糙度为0.3μm以下，维氏硬度为20HV以上且60HV以下。
(2)上述(1)所述的Cu柱，其α射线量为0.0200cph/cm2以下。
(3)上述(1)或(2)所述的Cu柱，其由上表面及底面的直径为1～1000μm、且高度为1～3000μm的柱体构成。
(4)上述(1)～(3)中任一项所述的Cu柱，其覆盖有助焊剂层。
(5)上述(1)～(3)中任一项所述的Cu柱，其覆盖有含有咪唑化合物的有机覆膜。
(6)一种Cu芯柱，其具备上述(1)～(4)中任一项所述的Cu柱和覆盖所述Cu柱的软钎料层。
(7)一种Cu芯柱，其具备上述(1)～(4)中任一项所述的Cu柱和覆盖所述Cu柱的镀层，该镀层包含选自Ni、Fe及Co中的一种以上元素。
(8)上述(7)所述的Cu芯柱，其还具备覆盖所述镀层的软钎料层。
(9)上述(6)～(8)中任一项所述的Cu芯柱，其α射线量为0.0200cph/cm2以下。
(10)上述(6)～(9)中任一项所述的Cu芯柱，其覆盖有助焊剂层。
(11)一种钎焊接头，其使用了上述(1)～(5)中任一项所述的Cu柱。
(12)一种硅穿孔电极，其使用了上述(1)～(5)中任一项所述的Cu柱。
(13)一种钎焊接头，其使用了上述(6)～(10)中任一项所述的Cu芯柱。
(14)一种硅穿孔电极，其使用了上述(6)～(10)中任一项所述的Cu芯柱。
发明的效果
根据本发明，由于Cu柱的维氏硬度为20HV以上且60HV以下，因此，能够提高耐落下冲击性，且能够保持基板之间的适当空间。另外，由于Cu柱的算术平均粗糙度为0.3μm以下，因此，能够提高将Cu柱排列于基板上时的流动性，且能够提高安装时的Cu柱与电极的密合性。
附图说明
图1是表示本发明的Cu柱的结构例的图。
图2是表示本发明的Cu芯柱的结构例的图。
图3是表示退火处理时的温度与时间的关系的图。
具体实施方式
以下更详细地说明本发明。在本说明书中，关于Cu柱的组成的单位(ppm、ppb、及％)，在没有特别指定的情况下表示相对于Cu柱的质量的比例(质量ppm、质量ppb、及质量％)。
图1所示的本发明的Cu柱1的纯度为99.9％以上且99.995％以下，算术平均粗糙度为0.3μm以下，维氏硬度为20HV以上且60HV以下。Cu柱1例如由圆柱形状构成。Cu柱1在软钎焊的温度下不会熔融，能够确保一定的焊点高度(基板之间的空间)，因此，能够适用于三维安装、窄间距安装。
·Cu柱的算术平均粗糙度：0.3μm以下
Cu柱1的算术平均粗糙度为0.3μm以下、更优选为0.2μm以下。在Cu柱1的算术平均粗糙度为0.3μm以下时，由于Cu柱1的晶粒的尺寸也变小，因此，能够使Cu柱1的表面更平滑(平坦)。由此，能够提高利用安装机等将Cu柱1排列于基板上时的Cu柱1的流动性，而且能够实现安装时的Cu柱1与基板上的电极的密合性的提高。
·维氏硬度为20HV以上且60HV以下
本发明的Cu柱1的维氏硬度优选为60HV以下。这是由于，维氏硬度为60HV以下时，对于来自外部的应力的耐久性变高，耐落下冲击性提高，而且变得不容易产生裂纹。另外，这是由于，在三维安装的凸块、接头的形成时赋予加压等辅助力的情况下，通过使用柔软性高的Cu柱1，能够降低引起电极压坏等的可能性。
另外，本发明的Cu柱1的维氏硬度至少需要大于一般的软钎料的维氏硬度10～20HV的值，优选为20HV以上。在Cu柱1的维氏硬度为20HV以上时，能够防止在三维安装时由于半导体芯片等的自重而使Cu柱1本身变形(压坏)，并保持基板之间的适当空间(焊点高度)。另外，由于如Cu柱状物(pillar)等那样不需要镀覆工序，因此能够通过使Cu柱1的维氏硬度为20HV以上来实现电极等的窄间距化。
在本实施例中，在制造Cu柱1后，通过促进制造的Cu柱1的晶体生长来制造维氏硬度为60HV以下的Cu柱1。作为促进Cu柱1的晶体生长的方法，例如，可列举出退火处理。如果对制造后的Cu柱1进行退火处理，则Cu组织重结晶化而晶粒生长，因此Cu柱1的柔软性提高。另一方面，在使用含有一定量的杂质的Cu柱1、例如纯度为3N、4N、4N5的Cu柱1时，所含有的杂质在Cu柱1表面抑制晶粒的过度生长，因此晶粒的尺寸被抑制在固定值以下。由此，能够提供兼备低维氏硬度、且低算术平均粗糙度这两个条件的Cu柱。
·U：5ppb以下、Th：5ppb以下
U和Th为放射性元素，为了抑制软错误而需要抑制它们的含量。为了将Cu柱1的α射线量设为0.0200cph/cm2以下，需要使U和Th的含量分别为5ppb以下。此外，从抑制现在或将来的高密度安装中的软错误的观点出发，U和Th的含量优选分别为2ppb以下。
·Cu柱的纯度：99.9％以上且99.995％以下
构成本发明的Cu柱1的纯度优选为99.9％以上且99.995％以下。如果Cu柱1的纯度为该范围，则能够在Cu中确保充分量的杂质元素的晶核，因此能够减小Cu柱1的算术平均粗糙度。另一方面，如果杂质元素少，则相应地成为晶核的杂质元素少，晶粒生长不会受到抑制，而是具有某种方向性地生长，因此Cu柱1的算术平均粗糙度变大。对Cu柱1的纯度的下限值没有特别限制，从抑制α射线量、抑制由纯度降低导致的Cu柱1的电导率、热导率劣化的观点出发，优选为99.9％以上。作为杂质元素，可列举出Sn、Sb、Bi、Zn、As、Ag、Cd、Ni、Pb、Au、P、S、In、Co、Fe、U、Th等。
·α射线量：0.0200cph/cm2以下
构成本发明的Cu柱1的α射线量为0.0200cph/cm2以下。这是在电子部件的高密度安装中软错误不会成为问题的水平的α射线量。从抑制进一步的高密度安装中的软错误的观点出发，α射线量更优选为0.0010cph/cm2以下。
·杂质元素的含量总计为1ppm以上
构成本发明的Cu柱1含有Sn、Sb、Bi、Zn、As、Ag、Cd、Ni、Pb、Au、P、S、In、Co、Fe、U、Th等作为杂质元素，杂质元素的含量总计为含有1ppm以上。需要说明的是，优选作为杂质元素的Pb和Bi的含量尽量低。
·Cu柱的上表面及底面的直径：1～1000μm，Cu柱的高度：1～3000μm
本发明的Cu柱1的上表面和底面的直径优选为1～1000μm，特别是用于细间距时更优选为1～300μm、进一步优选为1～200μm、最优选为1～100μm。而且，Cu柱1的高度L优选为1～3000μm，特别是用于细间距时更优选为1～300μm、进一步优选为1～200μm、最优选为1～100μm(参照图1)。Cu柱1的直径和高度L为上述范围时，使端子间为窄间距的安装成为可能，因此能够抑制连接短路，而且能够实现半导体封装体的小型化和高集成化。
另外，为了使本发明的Cu柱1的最外表面的算术平均粗糙度为0.3μm以下，可以在Cu柱1的最外表面覆盖软钎料镀层、Ni镀层、Fe镀层、Co镀层、含有咪唑化合物的有机覆膜层。若在本发明的Cu柱1上设置算术平均粗糙度为0.3μm以下的最外表面层，能够提高利用安装机等排列于基板上时的Cu柱1的流动性，实现安装时的Cu柱1与基板上的电极的密合性的提高，而且由于Cu柱1本身的维氏硬度为20HV以上且60HV以下，因此能够实现提高Cu柱1安装后的耐落下冲击性，解决保持基板之间的适当空间之类的本申请课题。
进而，在用助焊剂层覆盖本发明的Cu柱1或Cu芯柱的最外表面时，由于助焊剂层与软钎料层、Ni镀层相比有柔软性，因此不会对流动性带来较大影响，对于安装时的Cu柱1与基板上的电极的密合性，由于助焊剂层被电极挤压时，助焊剂层发生变形，因此所述密合性与助焊剂层的算术平均粗糙度无关，而是与Cu柱1或Cu芯柱本身的算术平均粗糙度有关。因而，只要用助焊剂覆盖的Cu柱1或Cu芯柱的算术平均粗糙度为0.3μm以下即可，即使用助焊剂层覆盖的Cu柱1或Cu芯柱的算术平均粗糙度超过0.3μm，排列于基板上时的Cu柱1的流动性也几乎不会恶化，能够实现安装时的Cu柱1与基板上的电极的密合性的提高，而且由于Cu柱1本身的维氏硬度为20HV以上且60HV以下，因此能够实现提高Cu柱1安装后的耐落下冲击性，解决保持基板之间的适当空间之类的本申请课题。
例如，通过利用由单一的金属或合金形成的金属层覆盖本发明的Cu柱1的表面，能够构成包含Cu柱1和金属层的Cu芯柱。如图2所示，Cu芯柱3具备Cu柱1和覆盖该Cu柱1的表面的软钎料层2(金属层)。关于软钎料层2的组成，在合金的情况下，只要是以Sn为主要成分的软钎料合金的合金组成即可，没有特别限制。另外，作为软钎料层2，也可以是Sn镀覆膜。例如，可列举出Sn、Sn-Ag合金、Sn-Cu合金、Sn-Ag-Cu合金、Sn-In合金、以及在它们中添加有规定的合金元素的合金。Sn的含量均为40质量％以上。另外，在没有特别指定α射线量的情况下，作为软钎料层2，还可以使用Sn-Bi合金、Sn-Pb合金。作为添加的合金元素，例如有Ag、Cu、In、Ni、Co、Sb、Ge、P、Fe等。其中，从落下冲击特性的观点出发，软钎料层2的合金组成优选为Sn-3Ag-0.5Cu合金。对软钎料层2的厚度没有特别限制，优选为单侧100μm以下就足够。通常为单侧20～50μm即可。
另外，在Cu芯柱中，可以在Cu柱1的表面与软钎料层2之间预先设置Ni镀层、Fe镀层、Co镀层等。由此，能够减少在向电极接合时Cu向软钎料中的扩散，能够抑制Cu柱1的Cu侵蚀。Ni镀层、Fe镀层、Co镀层等的膜厚通常为单侧0.1～20μm。
另外，在上述的Cu芯柱中，为了使Cu芯柱的α射线量为0.0200cph/cm2以下，软钎料层2的U和Th的含量分别为5ppb以下。另外，从抑制现在或将来的高密度安装中的软错误的观点出发，U和Th的含量优选分别为2ppb以下。
本发明的Cu芯柱还可以由Cu柱1、覆盖该Cu柱1的包含选自Ni、Fe及Co的一种以上元素的镀层(金属层)构成。另外，在构成Cu芯柱的镀层的表面，可以覆盖软钎料层。软钎料层可以采用与上述的软钎料层相同的物质。
本发明的Cu柱1或Cu芯柱3还能够用于接合电极间的钎焊接头的形成。在本例中，例如，将在印刷基板的电极上安装焊料凸块而成的结构称为钎焊接头。焊料凸块为在半导体芯片的电极上安装有Cu柱1的结构。
另外，本发明的Cu柱1或Cu芯柱3也可以在用于连接层叠的半导体芯片之间的电极的硅穿孔电极(through-silicon via：TSV)中使用。TSV如下制造：通过蚀刻在硅中开孔，在孔中依次形成绝缘层、位于其上的贯通导体，研磨硅的上下表面，使贯通导体在上下表面露出，从而制造。该工序中，以往采用通过镀覆法在孔中填充Cu等而形成贯通导体的方法，但在该方法中，由于将硅整面浸渍于镀液，因此会有杂质的吸附、吸湿的担心。因此，可以将本发明的柱直接沿高度方向插入到形成在硅中的孔而用作贯通导体。将Cu柱1插入到硅中时，可以通过焊膏等软钎焊材料接合，此外，将Cu芯柱插入到硅中时，也可以仅用助焊剂接合。由此，可以防止杂质的吸附、吸湿等的不良，也可以通过省略镀覆工序来减少制造成本、制造时间。
另外，也可以利用助焊剂层覆盖上述的Cu柱1、Cu芯柱的最外表面。上述的助焊剂层由包含防止Cu柱1、软钎料层等的金属表面的氧化并且作为在软钎焊时进行金属氧化膜的去除的活化剂发挥作用的化合物的一种或多种成分构成。例如，助焊剂层也可以利用由作为活化剂发挥作用的化合物和作为活化助剂发挥作用的化合物等组成的多个成分构成。
作为构成助焊剂层的活化剂，根据本发明中要求的特性而添加胺、有机酸、卤素化合物中任意者；多种胺的组合；多种有机酸的组合；多种卤素化合物的组合；单一或多种胺、有机酸、卤素化合物的组合。
作为构成助焊剂层的活化助剂，根据活化剂的特性而添加酯、酰胺、氨基酸中任意者；多种酯的组合；多种酰胺的组合；多种氨基酸的组合；单一或多种酯、酰胺、氨基酸的组合。
另外，助焊剂层也可以为了保护作为活化剂发挥作用的化合物等免受回流焊时的热的影响而包含松香、树脂。进而，助焊剂层也可以包含用于将作为活化剂发挥作用的化合物等固定于软钎料层的树脂。
助焊剂层也可以由包含单一或多种化合物的单一的层构成。另外，助焊剂层也可以由包含多种化合物的多个层构成。构成助焊剂层的成分以固体的状态附着于软钎料层的表面，但在使助焊剂附着于软钎料层的工序中，需要助焊剂为液态或气态。
因此，利用溶液涂布时，构成助焊剂层的成分需要可溶于溶剂，例如，形成盐时，存在在溶剂中变得不溶的成分。通过存在在液态的助焊剂中变得不溶的成分，形成沉淀物等的包含难溶解性成分的助焊剂变得难以均匀吸附。因此，一直以来，无法混合会形成盐那样的化合物来构成液态的助焊剂。
与此相对，在具备本发明的助焊剂层的Cu柱1、Cu芯柱中，逐层地形成助焊剂层并制成固体的状态，可以形成多层的助焊剂层。由此，即使在使用会形成盐那样的化合物的情况下，即使是在液态的助焊剂中无法混合的成分，也能够形成助焊剂层。
通过用作为活化剂发挥作用的助焊剂层覆盖容易氧化的Cu柱1、Cu芯柱的表面，可以在保管时等抑制Cu柱1的表面及Cu芯柱的软钎料层或金属层的表面的氧化。
此处，助焊剂与金属的颜色通常不同，Cu柱1等与助焊剂层的颜色也不同，因此可以利用色彩度例如亮度、黄色度、红色度确认助焊剂的吸附量。需要说明的是，也可以为了着色而在构成助焊剂层的化合物中混合色素。
也可以利用含有咪唑化合物的有机覆膜覆盖上述的Cu柱1。由此，通过Cu柱1的最外表面的Cu层与咪唑化合物结合，在Cu柱1的表面形成OSP覆膜(咪唑铜络合物)，可以抑制Cu柱1的表面氧化。
接着，对本发明的Cu柱1的制造方法的一个例子进行说明。准备作为材料的铜线，使准备的铜线通过模具而进行拉伸，然后，通过切断机以规定的长度切断铜线。如此，制作由圆柱形状构成的规定直径及规定长度(高度L)的Cu柱1。需要说明的是，Cu柱1的制造方法并不限定于本实施方式，也可以采用其它公知的方法。
在本实施例中，为了得到低算术平均粗糙度及低维氏硬度的Cu柱1，对于制作的Cu柱1实施退火处理。在退火处理中，在能够退火的700℃下将Cu柱1加热规定时间，然后，将加热的Cu柱1经过长时间进行缓冷。由此，能够进行Cu柱1的重结晶，能够促进缓慢的晶体生长。另一方面，由于Cu柱1所含有的杂质元素抑制晶粒的过度生长，因此不会引起Cu柱1的算术平均粗糙度的极度降低。
根据本实施方式，由于Cu柱1的维氏硬度为20HV以上且60HV以下，因此能够提高耐落下冲击性，且能够保持基板之间的适当空间。另外，由于Cu柱1的算术平均粗糙度为0.3μm以下，因此能够提高将Cu柱1排列在基板上时的流动性，且能够提高安装时的Cu柱1与电极的密合性。
实施例
以下说明本发明的实施例，但本发明并不限定于这些实施例。以下所示的实施例中，使用纯度不同的多个铜线来制作多个Cu柱，测定这些制作的各Cu柱的维氏硬度、算术平均粗糙度及α射线量。
·Cu柱的制作
准备纯度为99.9％、99.99％、99.995％的铜线。接着，使这些铜线通过模具，以使上表面及底面的直径为200μm的方式对铜线进行拉伸，然后，在长度(高度L)成为200μm的位置切断铜线，从而制作目标Cu柱。
·算术平均粗糙度
使用KEYENCE公司制造的激光显微镜(型号VK-9510/对应JISB0601-1994)进行Cu柱的算术平均粗糙度的评价(图像评价)。在本实施例中，以Cu柱的上表面的最平坦的部分为中心，在10×10μm的范围内进行测定。Cu柱的z轴上(高度方向)的测定间距为0.01μm。在这样的条件下，作为Cu柱的算术平均粗糙度Ra，测定任意10处的算术平均粗糙度Ra，使用它们的算术平均作为真实的算术平均粗糙度。
需要说明的是，算术平均粗糙度Ra也可以测定Cu柱的底面、周面，也可以使用将Cu柱的上表面、底面及周面的各测定值平均而得到的值作为测定值。另外，在上述例中，为了使Cu柱的表面平坦化而利用了超声波，但并不限定于此。例如，还可以使Cu柱浸渍于轻微溶解Cu柱的表面而促进平滑化加工的溶解性液体。作为液体，可以使用磺酸系(甲烷磺酸等)、羧酸系(草酸等)酸性溶液。
·维氏硬度
Cu柱的维氏硬度依照“维氏硬度试验-试验方法JIS Z2244”进行测定。装置使用明石制作所制造的微型维氏硬度试验器、AKASHI微小硬度计MVK-F 12001-Q。
·α射线量
α射线量的测定方法如下所述。α射线量的测定使用气流正比计数器的α射线测定装置。测定样品是将Cu柱铺满于300mm×300mm的平面浅底容器直至看不到容器的底而成的。将该测定样品放入α射线测定装置内，在PR-10气流下放置24小时，然后测定α射线量。
需要说明的是，测定中使用的PR-10气体(氩气90％-甲烷10％)是将PR-10气体填充于储气瓶中后经过了3周以上的气体。使用经过了3周以上的储气瓶是为了按照JEDEC(Joint Electron Device Engineering Council；电子器件工程联合委员会)中规定的JEDEC标准-电子材料中的阿尔法射线测量JESD221(JEDEC STANDARD-Alpha RadiationMeasurement in Electronic Materials JESD221)使得进入到气体储气瓶的大气中的氡不产生α射线。
·实施例1
将使用纯度99.9％的铜线制造的Cu柱放入碳制盘后，将该盘搬入至连续输送带式电阻加热炉中进行退火处理。将此时的退火条件示于图3。需要说明的是，为了防止Cu柱的氧化，使炉内为氮气气氛。室温为25℃。
作为退火条件，如图3所示，将从室温加热至700℃的升温时间设为60分钟，将在700℃下保持的保持时间设为60分钟，将从700℃冷却至室温的冷却时间设为120分钟。炉内的冷却是使用设置于炉内的冷却风扇进行的。接着，通过将实施了退火处理的Cu柱浸渍于稀硫酸中而进行酸处理。这是为了去除通过退火处理而在Cu柱表面上形成的氧化膜。将如此得到的Cu柱在有退火处理情况和无退火处理情况的维氏硬度、算术平均粗糙度及α射线量示于下述表1。
·实施例2
在实施例2中，对于利用纯度为99.99％的铜线制作的Cu柱，通过与实施例1同样的方法，进行退火处理并进行氧化膜去除处理。然后，测定得到的Cu柱的维氏硬度、算术平均粗糙度及α射线量。将这些的测定结果示于下述表1。
在实施例3中，对于利用纯度为99.995％的铜线制作的Cu柱，通过与实施例1同样的方法，进行退火处理并进行氧化膜去除处理。然后，测定得到的Cu柱的维氏硬度、算术平均粗糙度及α射线量。将这些的测定结果示于下述表1。
·比较例1
在比较例1中，分别测定利用纯度为99.9％的铜线制作的Cu柱的维氏硬度、算术平均粗糙度及α射线量。将这些的测定结果示于下述表1。
·比较例2
在比较例2中，分别测定利用纯度为99.99％的铜线制作的Cu柱的维氏硬度、算术平均粗糙度及α射线量。将这些的测定结果示于下述表1。
·比较例3
在比较例3中，分别测定利用纯度为99.995％的铜线制作的Cu柱的维氏硬度、算术平均粗糙度及α射线量。将这些的测定结果示于下述表1。
·比较例4
在比较例4中，分别测定利用纯度超过99.995％的铜线制作的Cu柱的维氏硬度、算术平均粗糙度及α射线量。将这些的测定结果示于下述表1。
·比较例5
在比较例5中，对于利用纯度超过99.995％的铜线制作的Cu柱，通过与实施例1同样的方法，进行退火处理并进行氧化膜去除处理。然后，测定得到的Cu柱的维氏硬度、算术平均粗糙度及α射线量。将这些的测定结果示于下述表1。
[表1]
如表1所示，实施例1中，Cu柱的算术平均粗糙度为0.10μm，实施例2中，Cu柱的算术平均粗糙度为0.17μm，实施例3中，Cu柱的算术平均粗糙度为0.28μm，实施例的算术平均粗糙度均为0.3μm以下。另外，实施例1中，Cu柱的维氏硬度为57.1，实施例2中，Cu柱的维氏硬度为52.9，实施例3中，Cu柱的维氏硬度为50.2，实施例的维氏硬度均为20HV以上且60HV以下。由这些结果可确认，通过对制造时的Cu柱实施退火处理，可得到具有低维氏硬度且低算术平均粗糙度的两个物性的Cu柱。
另一方面，在未对Cu柱实施退火处理的比较例1～4中，虽然Cu柱的算术平均粗糙度为0.3μm以下，但维氏硬度超过60HV，可确认不满足关于维氏硬度为20HV以上且60HV以下的条件。另外，比较例5中，虽然Cu柱的维氏硬度为20HV以上且60HV以下的范围内，但算术平均粗糙度超过0.3μm。由此，可确认即使在对制造时的Cu柱实施退火处理的情况下，使用高纯度的Cu柱时也不满足关于算术平均粗糙度为0.3μm以下的条件。
另外，实施例1～3的Cu柱中，Cu柱的α射线量小于0.0010cph/cm2，可确认其为满足＜0.0200cph/cm2、进而满足＜0.0010cph/cm2的结果。
接着，在上述的实施例1的退火处理后的Cu柱的表面覆盖包含Sn-3Ag-0.5Cu合金的软钎料镀层而制作Cu芯柱，将该Cu芯柱与制造Cu芯柱时使用的镀液直接采取于300cc的烧杯中放入超声波机照射超声波60分钟。超声波机使用市售的超声波清洗机(AS ONE公司制造的US-CLEANER)，在功率80W、频率40kHz的条件下进行。经过60分钟后用离子交换水进行清洗，然后使其热风干燥，分别测定制作的Cu芯柱的算术平均粗糙度及α射线量。与实施例1～3同样地，Cu芯柱的算术平均粗糙度为0.3μm以下。另外，对于在实施例1的Cu柱的表面覆盖有Ni镀层的Cu芯柱、在实施例1的Cu柱的表面依次覆盖有Ni镀层及软钎料镀层的Cu芯柱，在与前述相同的条件下进行超声波处理，分别测定算术平均粗糙度及α射线量，结果与实施例1～3同样地，Cu芯柱的算术平均粗糙度为0.3μm以下。另外，在任意情况下，α射线量均小于0.0010cph/cm2，可确认其为满足＜0.0200cph/cm2、进而满足＜0.0010cph/cm2的结果。
需要说明的是，在覆盖Fe镀层、Co镀层代替上述Ni镀层的情况下，与覆盖Ni镀层的Cu芯柱同样地，算术平均粗糙度为0.3μm以下。另外，α射线量也小于0.0010cph/cm2，可确认其为满足＜0.0200cph/cm2、进而满足＜0.0010cph/cm2的结果。
接着，在上述的实施例1的退火处理后的Cu柱的表面覆盖助焊剂而制作助焊剂涂层Cu柱，分别测定制作的助焊剂涂层Cu柱的算术平均粗糙度及α射线量。与实施例1～3同样地，在助焊剂涂层Cu柱中，算术平均粗糙度为0.3μm以下。进而，助焊剂涂层Cu柱中，α射线量也小于0.0010cph/cm2，可确认其为满足＜0.0200cph/cm2、进而满足＜0.0010cph/cm2的结果。
另外，对于在上述的Cu芯柱的表面覆盖有助焊剂的助焊剂涂层Cu芯柱，与助焊剂涂层Cu柱同样地，算术平均粗糙度为0.3μm以下。进而，助焊剂涂层Cu芯柱中，α射线量也小于0.0010cph/cm2，可确认其为满足＜0.0200cph/cm2、进而满足＜0.0010cph/cm2的结果。
此外，在实施例1的退火处理后的Cu柱的表面覆盖含有咪唑化合物的有机覆膜而制作OSP处理Cu柱，分别测定制作的OSP处理Cu柱的算术平均粗糙度及α射线量。与实施例1～3同样地，OSP处理Cu柱中，可确认算术平均粗糙度为0.3μm以下，α射线量为0.0010cph/cm2以下。
需要说明的是，本发明的柱在实施例和比较例中列举的是圆柱状的柱，但形状并不限定于圆柱，如果是三角柱体、四角柱体等直接与基板相接的上下表面由3边以上构成的柱体，也能够得到本发明的效果。

Claims (14)

1.一种Cu柱，其纯度为99.9％以上且99.995％以下，算术平均粗糙度为0.3μm以下，维氏硬度为20HV以上且60HV以下。
2.根据权利要求1所述的Cu柱，其α射线量为0.0200cph/cm2以下。
3.根据权利要求1或2所述的Cu柱，其由上表面及底面的直径为1～1000μm、且高度为1～3000μm的柱体构成。
4.根据权利要求1～3中任一项所述的Cu柱，其覆盖有助焊剂层。
5.根据权利要求1～3中任一项所述的Cu柱，其覆盖有含有咪唑化合物的有机覆膜。
6.一种Cu芯柱，其具备权利要求1～4中任一项所述的Cu柱和覆盖所述Cu柱的软钎料层。
7.一种Cu芯柱，其具备权利要求1～4中任一项所述的Cu柱和覆盖所述Cu柱的镀层，该镀层包含选自Ni、Fe及Co中的一种以上元素。
8.根据权利要求7所述的Cu芯柱，其还具备覆盖所述镀层的软钎料层。
9.根据权利要求6～8中任一项所述的Cu芯柱，其α射线量为0.0200cph/cm2以下。
10.根据权利要求6～9中任一项所述的Cu芯柱，其覆盖有助焊剂层。
11.一种钎焊接头，其使用了权利要求1～5中任一项所述的Cu柱。
12.一种硅穿孔电极，其使用了权利要求1～5中任一项所述的Cu柱。
13.一种钎焊接头，其使用了权利要求6～10中任一项所述的Cu芯柱。
14.一种硅穿孔电极，其使用了权利要求6～10中任一项所述的Cu芯柱。
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