CN105981164A - 半导体装置用接合线 - Google Patents

半导体装置用接合线 Download PDF

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Publication number
CN105981164A
CN105981164A CN201580005634.9A CN201580005634A CN105981164A CN 105981164 A CN105981164 A CN 105981164A CN 201580005634 A CN201580005634 A CN 201580005634A CN 105981164 A CN105981164 A CN 105981164A
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China
Prior art keywords
alloy
layer
coating
line
epidermis
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Granted
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CN201580005634.9A
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CN105981164B (zh
Inventor
山田隆
小田大造
大石良
宇野智裕
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Nippon Steel & Sumitomo New Materials Co.,Ltd.
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Kanae Co Ltd
Nippon Micrometal Corp
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    • 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
    • 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
    • B23K35/0227—Rods, wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

本发明提供一种半导体装置用接合线，其具有在Cu合金芯材的表面的以Pd为主成分的被覆层、和在该被覆层的表面的包含Au和Pd的表皮合金层，该半导体装置用接合线能够进一步改善镀Pd引线框上的2nd接合性，并且能够实现在高湿加热条件下也优异的球接合性。一种半导体装置用接合线，具有在Cu合金芯材的表面的以Pd为主成分的被覆层、和在该被覆层的表面的包含Au和Pd的表皮合金层，将线最表面中的Cu浓度设为1～10at％，在芯材中含有总计为0.1～3.0质量％的范围的元素周期表第10族的金属元素，由此能够实现2nd接合性的改善和高湿加热条件下的优异的球接合性。进而，优选表皮合金层的Au的最大浓度为15at％～75at％。

Description

半导体装置用接合线
技术领域
本发明涉及为连接半导体元件上的电极和外部连接端子而使用的半导体装置用接合线。
背景技术
半导体元件上的电极与外部连接端子之间使用半导体用接合线(以下也称为“接合线”。)连接。为使接合线与作为半导体元件的硅芯片上的电极接合，进行并用超声波的热压接方式的球接合。另一方面，在将接合线与引线、焊盘(land)等的外部连接端子连接时，一般进行所谓的2nd接合，即，不形成球部而将接合线直接与电极接合。
作为接合线，以往主要使用线径15～50μm左右、材质为高纯度4N(4-Nine，纯度为99.99质量％以上)的Au(金)的Au接合线(金接合线)。
但是，伴随着近来的资源价格的高涨，作为Au接合线的原料的金的价格也猛涨，正在研究采用Cu(铜)作为代替Au的低成本的线坯料。但是，Cu与Au相比容易氧化，因此单纯的Cu接合线难以长期保管，2nd接合特性也并不良好。另外，在这样的单纯的Cu接合线的顶端形成球部时，必须设为还原气氛以使得球部不氧化。
因此，为了解决Cu接合线的氧化这样的课题，曾提出了在Cu线表面被覆了贵金属的Cu接合线的方案。在专利文献1中，公开了在高纯度Cu极细线的表面被覆了Au、Pd等贵金属的Cu接合线。
在Cu线表面被覆有贵金属的Cu接合线，由于抑制了Cu接合线的氧化，因此线的长期保管、2nd接合特性优异。特别是在Cu线表面被覆了Pd的Cu接合线，在线顶端形成球部时球部氧化这样的担心得到大幅改善，即使不使用危险的气体即氢气而仅是使用纯氮气来使球部周边为氮气气氛，也能够形成圆球的球部。
在先技术文献
专利文献
专利文献1：日本特开昭62-97360号公报
发明内容
目前为止的引线框的表面一般被镀银，与此相对，最近正在推进使用镀Pd的引线框。当为在Cu线表面被覆了Pd的Cu接合线时，发现了下述新的问题，即，虽然对目前为止的镀银引线框而言没有显现化，但是对镀Pd的引线框的2nd接合性不充分的情况变多。关于在镀Pd层之上施加了镀Au层的引线框也是同样的。在为解决这样的问题而进行研究的过程中，本发明人等发现，通过使用在Cu线表面被覆Pd，且在该Pd被覆层的表面具有包含Au和Pd的合金层的接合线，能将该问题减轻一些。但是，对于2nd接合性要求进一步改善。特别是要求改善剥离(peeling)、即2nd接合状态的接合线的接合部剥离的现象。另外，伴随由细间距带来的细线化，要求进一步改善2nd接合的鱼尾状(鱼的臀鳍)的压接部对称性。本发明的第1目的是，在具有Pd被覆层的Cu线中，进一步改善对在镀Pd的引线框或者在镀Pd层上施加了镀Au层的引线框的2nd接合性、2nd接合的鱼尾(鱼的臀鳍)状的压接部对称性。
另外，对于Cu接合线的长期可靠性，即使是在最多地被利用的加热试验即干燥气氛下的高温保管评价中没有发生特别的问题的情况，当进行高湿加热评价时，有时也发生不良。作为一般的高湿加热评价，已知PCT试验(压力锅蒸煮试验)。其中，饱和型的PCT试验作为比较严格的评价经常被使用，代表性的试验条件是在温度121℃、相对湿度100％RH(Relative Humidity)、两个大气压下进行。在具有Pd被覆层的Cu线中，虽然能够降低高湿加热评价中的不良，但是作为高湿加热评价进行更严格的HAST试验(High AcceleratedTemperature and humidity Stress Test：高加速温湿度应力试验)(温度130℃、相对湿度85％RH(Relative Humidity)、5V)时，可知与Au线相比不良的发生率仍很高。本发明的第2目的是在具有Pd被覆层的Cu线中，进一步降低高湿加热评价中的不良。
本发明人等发现，对于具有以Cu为主成分的芯材、在该芯材的表面的以Pd为主成分的被覆层、和在该被覆层的表面的包含Au和Pd的表皮合金层的接合线，通过使以Cu为主成分的芯材中含有规定量的元素周期表第10族的金属元素，并且使线最表面的Cu浓度为1at％以上，能够进一步改善对于镀有Pd的引线框或者在镀Pd层上施加了镀Au层的引线框的2nd接合性、2nd接合的鱼尾状(鱼的臀鳍)的压接部对称性。
本发明人等还发现，通过使以Cu为主成分的芯材中含有规定量的元素周期表第10族的金属元素，即使在如HAST试验那样的苛刻的高湿加热评价中也能够减少不良的发生。
本发明是基于上述见解而完成的，其要旨如下。
(1)一种半导体装置用接合线，其特征在于，包含：
芯材，其以Cu为主成分，含有总计为0.1～3.0质量％的元素周期表第10族的金属元素；
设置于该芯材表面的以Pd为主成分的被覆层；和
设置于该被覆层表面的包含Au和Pd的表皮合金层，
线最表面的Cu浓度为1～10at％。
(2)根据(1)所述的半导体装置用接合线，其特征在于，
所述元素周期表第10族的金属元素为选自Ni、Pd和Pt中的一种以上。
(3)根据(1)或(2)所述的半导体装置用接合线，其特征在于，
所述元素周期表第10族的金属元素包含Ni。
(4)根据(1)～(3)的任一项所述的半导体装置用接合线，其特征在于，
上述以Pd为主成分的被覆层的厚度为20～90nm，
上述包含Au和Pd的表皮合金层的厚度为0.5～40nm，Au的最大浓度为15～75at％。
(5)根据(1)～(4)的任一项所述的半导体装置用接合线，其特征在于，上述芯材还含有Au，芯材中的Ni、Pd、Pt、Au的总计含量超过0.1质量％且为3.0质量％以下。
(6)根据(1)～(5)的任一项所述的半导体装置用接合线，其特征在于，上述接合线还含有P、B、Be、Fe、Mg、Ti、Zn、Ag、Si中的1种以上，这些元素在线整体中所占的浓度的总计为0.0001～0.01质量％的范围。
(7)根据(1)～(6)的任一项所述的半导体装置用接合线，其特征在于，在上述芯材与上述被覆层的边界部、以及上述被覆层与上述表皮合金层的边界部具有扩散区域。
(8)根据(1)～(7)的任一项所述的半导体装置用接合线，其特征在于，在对与上述接合线的线轴垂直的方向的芯材截面(以下称为“垂直截面”。)测定晶体取向所得到的结果中，线长度方向的晶体取向之中、相对于线长度方向角度差为15°以下的晶体取向＜100＞的取向比率为30％以上。
本发明，通过对于具有以Cu为主成分的芯材、设置于该Cu合金芯材的表面的以Pd为主成分的被覆层、和设置于该被覆层表面的包含Au和Pd的表皮合金层的半导体装置用接合线，使以Cu为主成分的芯材中含有规定量的元素周期表第10族的金属元素，并且使线最表面的Cu浓度为1～10at％，能够进一步改善对于镀有Pd的引线框或者在镀Pd层上施加了镀Au层的引线框的2nd接合性。另外，通过使以Cu为主成分的芯材中含有规定量的元素周期表第10族的金属元素，对于接合线与电极之间的球接合部，能够实现在高湿加热条件下也优异的球接合性。
具体实施方式
以下就本发明的优选的实施方式来详细说明本发明。以下关于浓度、厚度、比率所示出的值只要没有另行明示就都表示平均值。
本发明的半导体装置用接合线，其特征在于，包含：以Cu为主成分、含有总计为0.1～3.0质量％的元素周期表第10族的金属元素的芯材、设置于该芯材表面的以Pd为主成分的被覆层、和设置于该被覆层表面的包含Au和Pd的表皮合金层，线最表面的Cu浓度为1～10at％。
首先，对于以Cu为主成分、含有总计为0.1～3.0质量％的元素周期表第10族的金属元素的芯材(以下称为“Cu合金芯材”。)进行说明。
由于Cu容易被氧化，因此对于由Cu构成的接合线而言，长期保管和2nd接合特性差，但如果在Cu合金芯材的表面形成以Pd为主成分的被覆层，则能够抑制Cu合金芯材的氧化，因此前述的长期保管和2nd接合特性优异。
另外，使用在表面具有Pd被覆层的Cu线在Al电极上进行球接合的情况下，在线顶端形成了球时，会在熔融了的球表面形成Pd浓化层。由于这样地在球表面形成有Pd浓化层，因此在Al电极上进行了球接合时，与没有Pd被覆层的Cu线对比，在高湿加热评价中的不良减少。
但是，对于在Cu芯材上设置有Pd被覆层的Cu接合线的长期可靠性，作为高湿加热评价进行HAST试验(High Accelerated Temperature and humidity Stress Test)(温度130℃、相对湿度85％RH(Relative Humidity)、5V)时，与Au线相比不良的发生率仍然高。
本发明人等发现：对于在球接合时所形成的球表面的Pd浓化层，并不总是在整个球表面形成Pd浓化层，有时Pd浓化层仅形成于球的侧面，而在球的顶端部未形成Pd浓化层。而且，在球顶端部未形成Pd浓化层的情况下，高湿加热评价中的不良发生频率增大。其原因是Cu接合线中含有的Pd量不充分。因此，作为使Pd量增加的手段，可考虑到使以Pd为主成分的被覆层较厚，但如后述那样从芯片损伤降低等的观点出发，Pd被覆层的厚度存在合适的上限，在使该被覆层较厚来使Pd量增加方面存在限度。
在球顶端部未形成Pd浓化层的状况下在Al电极上进行球接合时，以Cu为主成分的芯材在球顶端部的表面露出，该部分与Al电极直接接触而形成接合部。该情况下，在高湿加热评价试验中，在Cu/Al接合界面(Cu接合线与Al电极的接合界面)，Cu-Al系的金属间化合物生长出来，该Cu-Al系的金属间化合物，与密封树脂中所含有的氯等的气体成分或离子等引起腐蚀反应。作为其结果，成为高湿加热评价试验中的不良的原因。
与此相对，在本发明中，使用以Cu为主成分、含有规定量的元素周期表第10族的金属元素的Cu合金芯材。可以认为，由此，Cu合金芯材中的元素周期表第10族的金属元素在球接合时扩散或浓化至接合界面，对Cu和Al的相互扩散造成影响，因此使腐蚀反应延迟。接合界面附近的元素周期表第10族的金属元素的作用，可考虑到阻碍腐蚀反应物移动的阻挡功能、控制Cu、Al的相互扩散以及金属间化合物的生长等的功能等。在本发明中，Cu合金芯材中的元素周期表第10族的金属元素优选为选自Ni、Pd和Pt中的一种以上。在优选的一实施方式中，Cu合金芯材含有作为元素周期表第10族的金属元素的Ni。例如，在Cu合金芯材中，作为元素周期表第10族的金属元素，可以单独地含有Ni，也可以组合地含有Ni；以及，Pd和Pt中的一方或两方。在另一优选的实施方式中，Cu合金芯材含有作为元素周期表第10族的金属元素的、Pd和Pt中的一方或两方。
如果Cu合金芯材中的元素周期表第10族的金属元素的浓度总计为0.1质量％以上，则能够充分控制接合界面中的Cu、Al的相互扩散，在作为苛刻的高湿加热评价试验的HAST试验中接合部的寿命也提高至380小时以上。作为这里的接合部的评价，在HAST试验后将树脂开封并除去，其后通过牵拉(pull)试验来评价接合部的断裂状况。从充分获得上述的HAST试验可靠性的改善效果的观点出发，Cu合金芯材中的元素周期表第10族的金属元素的浓度总计为0.1质量％以上，优选为0.2质量％以上，更优选为0.3质量％以上、0.4质量％以上、0.5质量％以上、或者0.6质量％以上。另外，从获得在低温接合中与Al电极的初期的接合强度良好，在HAST试验中的长期可靠性、对BGA(Ball Grid Array)、CSP(Chip SizePackage)等的基板、带(tape)等的接合的量产余裕度(margin)优异的接合线、降低芯片损伤的观点出发，Cu合金芯材中的元素周期表第10族的金属元素的浓度总计为3.0质量％以下，优选为2.5质量％以下、或者2.0质量％以下。当Cu合金芯材中的元素周期表第10族的金属元素的浓度总计超过3.0质量％时，需要以低载荷进行球接合以使得不发生芯片损伤，与电极的初期的接合强度降低，作为结果，有时HAST试验可靠性恶化。本发明的接合线，通过使Cu合金芯材中的元素周期表第10族的金属元素的浓度的总计在上述合适的范围，HAST试验中的可靠性进一步提高。例如，能够实现HAST试验的直至不良发生为止的寿命超过450小时的接合线。这有时相当于以往的Cu接合线的1.5倍以上的长寿命化，也能够应对在苛刻环境中的使用。再者，作为由接合线制品求出在Cu合金芯材中含有的上述元素的浓度的方法，例如可举出使接合线的截面露出，对于Cu合金芯材的区域进行浓度分析的方法；一边采用溅射等从接合线的表面向深度方向削，一边对Cu合金芯材的区域进行浓度分析的方法。例如，在Cu合金芯材包含具有Pd浓度梯度的区域的情况下，对接合线的截面进行线分析，对不具有Pd浓度梯度的区域(例如，向深度方向的Pd浓度变化的程度为每0.1μm小于10mol％的区域、Cu合金芯材的轴心部)进行浓度分析即可。对于浓度分析的方法在后面进行叙述。
在本发明中，可以使Cu合金芯材进一步含有Au。当使Cu合金芯材进一步含有Au时，再结晶温度上升，防止了拉丝加工中的动态再结晶，因此加工组织变得均匀，调质后的晶粒尺寸变得比较均匀。由此线的断裂伸出率提高，在进行接合时能够形成稳定的线环(线环路：wire loop)。在进一步含有Au的情况下，优选确定含量以使得芯材中的Ni、Pd、Pt、Au的总计含量超过0.1质量％且为3.0质量％以下。从下限来看，芯材中的Ni、Pd、Pt、Au的总计含量更优选为0.2质量％以上、0.3质量％以上、0.4质量％以上、0.5质量％以上、或者0.6质量％以上，从上限来看，该总计含量更优选为2.5质量％以下、或者2.0质量％以下。
优选：本发明的接合线还含有选自P、B、Be、Fe、Mg、Ti、Zn、Ag、Si中的1种以上的元素，这些元素在线整体中所占的浓度的总计为0.0001～0.01质量％的范围。由此，能够实现更良好的球形状。从下限来看，这些元素的浓度的总计更优选为0.0003质量％以上、0.0005质量％以上、或0.001质量％以上，从上限来看，这些元素的浓度的总计更优选为0.009质量％以下、或者0.008质量％以下。在本发明的接合线含有这些元素的情况下，这些元素可以包含在Cu合金芯材中，也可以包含在后述的被覆层、表皮合金层中。
Cu合金芯材中含有的成分，除了以元素周期表第10族的金属元素为首的上述成分以外，余量为Cu以及不可避免的杂质。在优选的一实施方式中，Cu合金芯材的Cu纯度为3N以下(优选为2N以下)。在以往的Pd被覆的Cu接合线中，从接合性的观点出发，存在使用高纯度(4N以上)的Cu芯材、而避免使用低纯度的Cu芯材的倾向。与此相对，具有Cu合金芯材、设置于该Cu合金芯材表面的以Pd为主成分的被覆层、和设置于该被覆层的表面的包含Au和Pd的表皮合金层、且线最表面的Cu浓度为1～10at％的本发明的接合线，在使用如上述那样Cu纯度比较低的Cu合金芯材的情况下，特别理想地实现了对于镀Pd的引线框或者在镀Pd层上施加了镀Au层的引线框的2nd接合性的进一步的改善、和如HAST试验那样的苛刻的高湿加热评价中的优异的球接合性。
接着，对以Pd为主成分的被覆层进行说明。
如前所述为了抑制Cu合金芯材的氧化，在Cu合金芯材的表面形成的以Pd为主成分的被覆层的厚度优选为20～90nm。如果被覆层的厚度为20nm以上，则抑制氧化的效果变得充分，2nd接合性和FAB形状变得良好，因而优选。再者，所谓FAB形状，意指圆球性、偏芯的有无、以及气孔的有无。被覆层的厚度更优选为25nm以上、或者30nm以上。另外，如果被覆层的厚度为90nm以下，则在芯片损伤降低的同时FAB形状变得良好，而且在球部的表面产生直径数μm大小的气泡的情况较少，因而优选。被覆层的厚度更优选为85nm以下、或者80nm以下。
在此，以Pd为主成分的被覆层中除了Pd以外所含有的元素，是Pd的不可避免的杂质、和构成被覆层内侧的芯材的成分、构成被覆层的表面侧的表皮合金层的元素。这是因为通过后述的热处理，有时在芯材与被覆层之间、表皮合金层与被覆层之间产生各层的构成元素的相互扩散的缘故。即，着眼于被覆层来看，是因为有时构成芯材的元素以及构成表皮合金层的元素向被覆层扩散的缘故。因此，在一实施方式中，本发明的接合线在芯材与被覆层的边界部、以及被覆层与表皮合金层的边界部具有扩散区域。因此，在本发明中，芯材与被覆层的边界设定在Pd浓度为50at％的位置，被覆层与表皮合金层的边界设定在Au为10at％的位置，将这些边界之间的厚度作为被覆层的厚度。
以Pd为主成分的被覆层中的Pd的最大浓度，从能够享有本发明的效果的观点出发，优选为60at％以上，更优选为70at％以上、80at％以上、或者90at％以上。被覆层中的Pd的最大浓度优选为100at％，但对于使用包含规定量的元素周期表第10族的金属元素的Cu合金芯材并且线最表面的Cu浓度为1～10at％的本发明的接合线而言，即使是被覆层中的Pd的最大浓度低于100at％，例如为99.9at％以下、99.8at％以下、99.7at％以下、99.6at％以下、99.5at％以下、99.0at％以下、98.5at％以下、98at％以下、97at％以下、96at％以下、或者95at％以下的情况，也能够达到所期望的效果。
对于本发明的接合线，Pd被覆层中的Pd的浓度为99.0at％以上的区域的厚度可以为40nm以下，例如可以为35nm以下、30nm以下、25nm以下、20nm以下、15nm以下、10nm以下、或者5nm以下。
接着，对包含Au和Pd的表皮合金层进行说明。
如前所述，当仅仅是在Cu合金芯材的表面具有以Pd为主成分的被覆层的构成时，在镀Pd引线框上不能确保良好的2nd接合性。在本发明中，在以Pd为主成分的被覆层的表面进一步形成包含Au和Pd的表皮合金层。包含Au和Pd的表皮合金层的厚度优选为0.5～40nm。如果线的最表面的区域为Au与Pd的合金层，则在将线2nd接合于镀Pd引线框上时，构成线的最表面的表皮合金层中的Au向镀Pd引线框上的Pd中优先地扩散，在接合线与镀Pd引线框这两者之间容易形成合金层。因此，与镀Pd引线框的2nd接合性提高。另外，在闪镀Au的镀Pd引线框上也同样确认到2nd接合性提高，该情况可以认为是引线框上的极薄闪镀层的Au与表皮合金层中Au的相互的密着性促进效果所致。从改善对于镀Pd引线框或者在镀Pd层上施加了镀Au层的引线框的2nd接合性的观点出发，表皮合金层的厚度优选为0.5nm以上，更优选为1nm以上、2nm以上、或者3nm以上。另一方面，当表皮合金层的厚度过厚时，有时FAB形状恶化，另外，高价格的Au的使用量增加、成本提高，因此表皮合金层的厚度优选为40nm以下，更优选为35nm以下、或者30nm以下。
另外，通过使具有上述被覆层以及上述表皮合金层的线的Cu合金芯材中含有元素周期表第10族的金属元素，与在未被覆有Pd的裸Cu中含有元素周期表第10族的金属元素的情况相比，除了上述的接合可靠性提高以外，HAST评价结果也进一步提高。可以认为这是因为，在球表面所形成的Pd浓化层中，通过线表面的被覆层的Pd与在Cu合金芯材中含有的元素周期表第10族的金属元素这两者组合，Pd浓化层中的元素周期表第10族的金属元素的合计浓度上升，促进了控制在接合界面处的Cu、Al的相互扩散以及金属间化合物的生长等的功能的缘故。
在以往的被覆有Pd的Cu线中，Pd层与毛细管内壁的滑动阻力高，在接合工作时有时Pd被刮削。在反复进行接合的过程中，削屑等异物附着于毛细管，其量变多时就必须更换毛细管。与此相对，通过进一步具有包含Au和Pd的表皮合金层，线最表面的摩擦阻力变低。另外，如前所述，通过对芯材添加元素周期表第10族的金属元素能够保持适度的强度。由于这些效果，毛细管内壁与线的滑动阻力下降，能够进行顺畅的接合工作，即使反复进行接合，也能够将由异物向毛细管的附着所致的污染抑制为较少，毛细管寿命提高。另外，作为毛细管内壁与线的滑动阻力下降的结果，环稳定性、倾斜特性提高。
进而，可以认为，表皮合金层中含有的Au元素，提高在球表面稳定形成由线表面的被覆层的Pd和Cu合金芯材中的元素周期表第10族的金属元素这两者形成的Pd浓化层的作用，另外，促进电极的Al从接合界面向球的方向扩散的现象，促进仅是元素周期表第10族的金属元素时会变慢的接合界面处的相互扩散速度，促进对腐蚀的抗性高的金属间化合物的生长。
从改善对镀有Pd的引线框或者在镀Pd层之上施加了镀Au层的引线框的2nd接合性的观点出发，包含Au和Pd的表皮合金层中的Au的最大浓度优选为15at％以上。表皮合金层中的其余量为Pd以及不可避免的杂质。再者，在表皮合金层的最表面，如后述那样Cu浓化了。从改善对于镀有Pd的引线框等的2nd接合性的观点出发，表皮合金层中的Au的最大浓度更优选为20at％以上，进一步优选为25at％以上、30at％以上、35at％以上、或者40at％以上。从特别地改善对于镀Pd的引线框或者在镀Pd层之上施加了镀Au层的引线框的2nd接合性的观点出发，Au的最大浓度优选为40at％以上。另一方面，当Au的最大浓度超过75at％时，在线顶端形成球部时包含Au和Pd的表皮合金层中的Au优先地熔融，因此形成走形的球部的危险性增加，有时FAB形状变得不良。与此相对，如果表皮合金层中的Au的最大浓度为75at％以下，则在线顶端形成球部时，没有仅Au优先地熔融而形成走形的球部的危险性，不会损害球部的圆球性、尺寸精度，因而优选。从提高球部的圆球性、尺寸精度的观点出发，表皮合金层中的Au的最大浓度优选为75at％以下，更优选为70at％以下，进一步优选为65at％以下、60at％以下、或者55at％以下。从提高球部的圆球性、尺寸精度、实现特别良好的FAB形状的观点出发，Au的最大浓度优选为55at％以下。
本发明的接合线，其特征是，线最表面的Cu浓度为1～10at％。所谓线最表面，意指包含Au和Pd的表皮合金层的表面。线最表面的Cu浓度变高的区域(以下，称为“Cu浓化部”。)，其厚度优选为2～9nm。Cu浓化部的厚度规定为从线最表面到Cu浓度变为线最表面的Cu浓度的一半的位置的厚度。
如前所述，对于具有以Cu为主成分的芯材、和在该芯材的表面的以Pd为主成分的被覆层、以及在该被覆层的表面的包含Au和Pd的合金层的接合线，通过在以Cu为主成分的芯材中含有规定量的元素周期表第10族的金属元素，并且将线最表面的Cu浓度设为规定的范围，能够进一步改善对镀有Pd的引线框或者在镀Pd层上施加了镀Au层的引线框的2nd接合性，并且提高2nd接合的鱼尾状(鱼的尾鳍)的压接部的对称性。关于该作用，通过将上述特定的Cu合金芯材、与线最表面的Cu浓化部/包含Au和Pd的表皮合金层/以Pd为主成分的被覆层这样的被覆结构组合来使用，可得到显著的改善效果。可以认为这是因为，由上述特定的Cu合金芯材、和表皮合金层、以及Cu浓化部的组合产生的协同作用发挥效力，因此2nd接合性被进一步改善，2nd接合中的线变形的对称性提高了。
Cu具有在包含于其他的金属中的情况下在高温下由于晶粒内扩散、晶界扩散等而容易扩散的性质。在具有Cu合金芯材、和在其表面的以Pd为主成分的被覆层、以及进而在被覆层的表面的包含Au和Pd的表皮合金层的本发明中，当如后所述进行扩散热处理、退火热处理时，芯材的Cu在被覆层、表皮合金层中扩散，能够使Cu到达表皮合金层的最表面。线最表面中的上述Cu的状态，可以想到表面浓化或表面偏析了，但一部分Cu发生氧化、或在表皮合金层的包含Au和Pd的合金中上述浓度范围的Cu发生部分固溶也无妨。
在Cu芯材的表面仅具有以Pd为主成分的被覆层的以往的被覆有Pd的Cu接合线中，如前所述，存在使用高纯度(4N以上)的Cu芯材、避免使用低纯度的Cu芯材的倾向。在这样的以往的被覆有Pd的Cu接合线中，当Cu在线最表面浓化时，观察到FAB形状变得不良的现象。FAB形状，是指圆球性、偏芯的有无、以及缩孔的有无。另外，关于2nd接合性，也观察到不充分的性能进一步降低的现象。与此相对，在本发明作为对象的包含以Cu为主成分、且含有规定量的元素周期表第10族的金属元素的特定的Cu合金芯材、和设置于该Cu合金芯材的表面的以Pd为主成分的被覆层、以及设置于该被覆层的表面的包含Au和Pd的表皮合金层的半导体装置用接合线中，未出现由Cu在线最表面浓化所致的性能的降低，相反地，首次发现：通过使线最表面含有1at％以上的Cu，能够大幅度改善对镀有Pd的引线框的2nd接合性、特别是剥离性。从能够更进一步改善2nd接合性的观点出发，在本发明的接合线中，线最表面的Cu浓度优选为1.5at％以上，更优选为2at％以上、2.5at％以上、或者3at％以上。
但是，当表皮合金层的表面、即线最表面的Cu浓度过高时，2nd接合性和FAB形状变得不良，而且线表面变得容易氧化，有时发生随着时间经过品质降低这样的问题。从实现良好的2nd接合性和FAB形状的观点、抑制线表面的氧化从而抑制品质的经时劣化的观点出发，在本发明的接合线中，线最表面的Cu浓度为10at％以下，优选为9.5at％以下、或者9at％以下。
作为包含Au和Pd的表皮合金层的形成方法，优选：在Cu合金芯材的表面被覆Pd，进而在Pd被覆层的表面覆着Au，其后将线进行热处理从而使Pd和Au相互扩散，形成包含Au和Pd的表皮合金层。通过进行扩散，以使被覆层的Pd扩散到达表皮合金层的表面，并使表面中的Pd浓度变为25at％以上，由此使表皮合金层表面的Au浓度变为75at％以下。例如，通过在Cu合金芯材的表面被覆Pd，并实施了镀Au之后，进行拉丝，在200μm以及100μm的线直径下进行共计2次的适当的热处理，由此最终线直径下的表面中的Pd浓度变为25at％以上。此时，形成从表皮合金层的最表面向线的中心Pd浓度逐渐增大的浓度梯度。由此，能够使表皮合金层中的Au的最大浓度成为15at％～75at％。在这里，将Au浓度成为10at％的位置定义为表皮合金层与以Pd为主成分的被覆层的边界。
再者，通过使Pd向表皮合金层中扩散的上述热处理，Cu合金芯材与以Pd为主成分的被覆层之间也引起相互扩散。其结果是，有时在Cu合金芯材与被覆层的边界附近形成从表面侧向中心Pd浓度逐渐减少、并且Cu浓度增大的区域，或者在上述边界部形成20nm厚以下的PdCu金属间化合物层，但在本发明中哪一种情况都称为扩散区域。
对本发明的线的成分组成的评价方法进行说明。
在被覆层、表皮合金层的浓度分析、Cu合金芯材中的Ni、Pd、Pt、Au的浓度分析时，以下方法是有效的：一边采用溅射等从接合线的表面向深度方向削除一边进行分析的方法，或者，使线截面露出来进行线分析、点分析等的方法。前者在表皮合金层、被覆层薄的情况下较有效，但当变厚时，会过于花费测定时间。后者的在截面中的分析，在表皮合金层、被覆层厚的情况下较有效，另外，优点是在截面整体中的浓度分布、多个位置处的再现性的确认等比较容易，但在表皮合金层、被覆层薄的情况下精度降低。也可以倾斜研磨接合线，来扩大表皮合金层、被覆层、芯材以及它们的边界部中的扩散区域的厚度来进行测定。
对于截面而言，线分析比较简便，但在想要提高分析的精度时，使线分析的分析间隔较狭窄、或进行集中于界面附近的想要观察的区域的点分析也是有效的。
在这些浓度分析中使用的解析装置，可以采用在扫描型电子显微镜(SEM)或者透射型电子显微镜(TEM)中所装备的俄歇电子能谱分析(AES)装置、能量色散型X射线分析(EDX)装置、电子射线显微分析仪(EPMA)等。作为使线截面露出的方法，可以采用机械研磨、离子蚀刻法等。特别是使用了AES装置的方法，空间分辨率高，因此对最表面的薄的区域的浓度分析很有效。
对于接合线中的P、B、Be、Fe、Mg、Ti、Zn、Ag、Si的分析，可以利用ICP发射光谱分析装置和/或ICP质量分析装置分析将接合线用强酸溶解而得到的液体，作为接合线整体中所含的元素浓度来检测出。另外，对于平均组成的调查等，也可以采用下述方法：用酸等从表面部阶段性地溶解下去，由其溶液中所含的浓度求出溶解部位的组成；等等。
对于在被覆层与芯材的边界形成的PdCu化合物，通过利用EPMA、EDX装置、AES装置、TEM等，对线的研磨截面在夹有芯材与被覆层的界面的情况下进行线分析，能够得知扩散区域的厚度、组成等。
以下将与接合线的线轴垂直的方向的芯材截面称为“垂直截面”。对于垂直截面，通过测定晶体取向，能够评价线长度方向的晶体取向之中、相对于线长度方向角度差为15°以下的晶体取向＜100＞的取向比率。在本发明中，优选：在芯材的垂直截面中，线长度方向的晶体取向之中、相对于线长度方向角度差为15°以下的晶体取向＜100＞的取向比率为30％以上。通过使芯材具有这样的结晶组织，在能够抑制倾斜不良的同时，在球接合时所形成的球部软质化，球接合中的芯片损伤降低。另外，由于线软质化，因此能够改善2nd接合性。从抑制倾斜不良的观点、降低芯片损伤的观点、更进一步改善2nd接合性的观点出发，上述晶体取向＜100＞的取向比率更优选为35％以上，进一步优选为40％以上、45％以上、50％以上、或者55％以上。
在上述芯材的垂直截面中所观察到的晶体取向，能够利用设置于TEM观察装置中的微小区域X射线法或者电子背散射衍射法(EBSD，Electron BackscatteredDiffraction)等进行测定。其中，EBSD法具有能够观察观察面的晶体取向、并图示在相邻的测定点间的晶体取向的角度差这样的特征，即使是如接合线那样的细线，也能够比较简便且精度良好地观察晶体取向，因而更优选。另外，相对于线长度方向角度差为15°以下的晶体取向＜100＞的取向比率，在利用微小区域X射线法时，能够以各晶体取向的X射线强度为基础以晶体取向的体积比率的形式求出，另外，在利用EBSD法时，可从上述观察到的晶体取向直接算出。为了算出垂直截面的取向比率，观察了在与接合线的拉丝方向垂直的方向上的接合线截面的全部区域。对于晶体取向比率的计算方法，为了将不能够测定晶体取向的部位、或者即使能够测定取向解析的可靠性也低的部位等排除在外来进行计算，将在测定区域内以专用软件所设定的可靠度为基准能够鉴定出的晶体取向的面积作为总体(母集团)。如果采用上述任一种方法得到的厚度、组成在本发明的范围内，就能够得到本发明的作用效果。
本发明的半导体装置用接合线的线径虽也取决于半导体装置的所期望的设计，但可以为10～80μm的范围，通常为10～50μm的范围。
接着，对于本发明的半导体装置用接合线的制造方法进行说明。
首先，按照Cu合金芯材的组成，将高纯度的Cu(纯度99.99％以上)和添加元素原料作为起始原料进行称量后，将其在高真空下或者氮气、Ar气等惰性气氛下进行加热熔化，由此得到含有规定的成分、且其余量为Cu和不可避免的杂质的直径约2～10mm的锭。供本发明的接合线的制造使用的锭，是以Cu为主成分、含有总计为0.1～3.0质量％的元素周期表第10族的金属元素的、直径约2～10mm的铜合金锭。该铜合金锭可以含有的其他成分，同所说明的本发明的接合线中的铜合金芯材中的其他成分一样，这些成分的含量的合适的范围也同前面所述的一样。将该铜合金锭进行锻造、轧制、拉丝，从而制作出要形成被覆层的直径约0.3～1.5mm的铜合金线。本发明也提供这样的供半导体装置用接合线使用的铜合金锭以及铜合金线。
作为在Cu合金芯材的表面形成以Pd为主成分的被覆层的方法，可以利用电解镀敷、无电解镀敷、蒸镀法等，但在工业上最优选的是利用能够稳定地控制膜厚的电解镀敷。采用这些方法在Cu合金芯材表面形成以Pd为主成分的被覆层之后，在上述被覆层的表面形成包含Au和Pd的表皮合金层。形成表皮合金层的方法可以是任何的方法，但优选：形成上述被覆层后，进而在该被覆层的表面形成作为表皮层的Au膜，并且为了使覆着的Au变为包含Au和Pd的合金层，通过热处理来使Pd扩散以使得Pd到达Au的表面。作为该方法，通过在一定的炉内温度下在电炉中使线在一定的速度下连续地扫掠通过来促进合金化的方法，能够切实地控制合金的组成和厚度，因而优选。再者，作为在上述被覆层的表面形成Au膜的方法，可以利用电解镀敷、无电解镀敷、蒸镀法等，但由于上述的理由，在工业上最优选的是利用电解镀敷。对于在Cu合金芯材的表面覆着被覆层以及表皮合金层的阶段，最优选的是在拉丝到最终的Cu合金芯材的直径之后进行，但也可以在Cu合金芯材的拉丝途中阶段、拉丝到规定的线径的时间点进行覆着，其后拉丝到最终线径为止。在这样的情况下，可得到直径约100～700μm的多层线来作为中间制品，所述多层线包含以Cu为主成分、含有总计为0.1～3.0质量％的元素周期表第10族的金属元素的芯材、设置于该芯材表面的以Pd为主成分的被覆层、和设置于该被覆层表面的以Au为主成分的表皮层(优选是包含Au和Pd的表皮合金层)。被覆层以及表皮合金层也可以在锭的阶段来进行覆着。
在用于表皮合金层的合金化的加热时，考虑原料的污染，将炉内的气氛设为氮气、Ar气等惰性气氛，进而，与以往的接合线的加热法不同，将气氛中所含有的氧气浓度设为5000ppm以下。如果使惰性气体中混入至少500ppm的氢气等还原性气体，则防止线原料的污染的效果进一步提高，因而更优选。另外，炉内的适当的温度、使线扫掠通过的速度根据线的组成而不同，但当将炉内温度大约设为210℃～700℃的范围、将使线扫掠通过的速度设为例如20～40m/min左右时，能够实现稳定的操作，并得到稳定品质的接合线，因而优选。用于表皮合金层的合金化的加热，当在拉丝到最终的芯材直径后进行时，能够兼作为拉丝后的线的退火，因而优选。当然，也可以在拉丝到中间阶段的直径的时候进行用于表皮合金层的合金化的加热。通过如以上那样进行加热，Cu合金芯材的Cu在被覆层、表皮合金层中扩散，能够使Cu到达表皮合金层的最表面。通过在上述适合的范围内适当选择加热温度和时间，能够使线最表面的Cu浓度在1～10at％的范围。
为了将表皮合金层的厚度和上述被覆层的厚度各自地控制，与单纯的一次的热处理相比，在Cu合金芯材的表面被覆Pd后实施热处理，进而覆着Au后实施热处理是有效的。该情况下，具有以下优点：相对于各自的热处理条件的炉内温度、线的扫掠通过速度能够各自地设定。
在形成表皮合金层、被覆层后的加工工序中，根据目的选择、灵活运用辊轧制、模锻、模拉丝等。通过加工速度、压下率或者模减面率等来控制加工组织、位错、晶界的缺陷等，这对表皮合金层、被覆层的结构、密着性等也带来影响。
加工后的热处理工序，要求以最终的线直径来进行，但仅这样的话难以得到期望的合金层、被覆层的厚度、Au的最大浓度、表面的Cu浓度。该情况下，在加工的途中实施2至3次热处理工序是有效的。
特别是Au和Pd，熔点、加工容易度(强度)都不同，因此在加工度低的阶段进行热处理，从而遍及线全周来形成AuPd的合金层很重要。另外，为了使Cu在表面浓化，不是单纯地提高热处理温度，而是特意使由惰性气体填充的热处理炉中的氧气浓度高一些很有效。但是，当氧气浓度过高时会担心Cu合金芯材中的Cu氧化，因此期望氧气浓度为0.2％～0.7％，这以外的热处理可使氧气浓度下降至ppm级。
为了形成所期望的组成以及膜厚的被覆层、表皮合金层、Cu向最表面浓化的Cu浓化部，由初期形成的膜厚、多个热处理条件等，利用Fick定律等通常的相互扩散知识来估算是有效的。为了进一步提高精度，以上述估算为基础试制线一次左右，通过表面解析求得实际的扩散现象来调整热处理装置等的条件，由此即使是不同的膜厚、组成也容易应对。
对于Cu合金芯材的垂直截面中的线长度方向的晶体取向之中、相对于线长度方向角度差为15°以下的晶体取向＜100＞的取向比率，能够通过在最终拉丝后进行的热处理的条件来控制。即，当使热处理温度为比较低的温度、例如350～550℃时，会引起用于除去加工应变的再结晶(一次再结晶)，但粗大的晶粒的生长(二次再结晶)被抑制为较少。一次再结晶晶粒的＜100＞晶体取向的比例多，但二次再结晶晶粒的＜100＞晶体取向的比例少。因此，能够使Cu合金芯材的垂直截面中的、线长度方向的晶体取向之中、相对于线长度方向角度差为15°以下的晶体取向＜100＞的取向比率成为30％以上。
实施例
作为接合线的原材料，为了制造Cu合金芯材准备了纯度为99.99质量％以上的Cu，作为添加元素准备了Ni、Pd、Pt、Au、P、B、Be、Fe、Mg、Ti、Zn、Ag、Si，为用于被覆层形成，准备了纯度为99.99质量％以上的Pd，为用于表皮合金层形成，准备了纯度为99.99质量％以上的Au。将Cu和添加元素的原料作为起始原料进行称量后，将其在高真空下进行加热熔化，由此得到了直径10mm左右的铜合金锭。其后，将该锭进行锻造、轧制、拉丝来制作出直径500μm的Cu合金线。接着，实施电解镀敷，使得在Cu合金线表面形成1～3μm厚的Pd被覆层、在被覆层的表面形成0.05～0.2μm厚的Au表皮层，从而得到多层线。将Pd被覆层、AuPd表皮合金层的最终厚度记载于表1、表2。在这里，芯材与被覆层的边界设定为Pd浓度为50at％的位置，被覆层与表皮合金层的边界设定为Au浓度为10at％的位置。其后，以拉丝速度为100～700m/min、模减面率为8～30％来进行连续拉丝加工，形成为表1、表2中记载的最终线径。表皮合金层的厚度、Au最大浓度、表面Cu浓度、被覆层的厚度，是通过在拉丝加工之间实施2次至3次热处理来控制的。此时的条件是：在线直径为200～250μm时，温度500～700℃、速度10～70m/min；在线直径为70～100μm时，温度450～650℃、速度20～90m/min；在最终线径较细的情况下，进而线直径为40～70μm时，温度300～500℃、速度30～100m/min。其后，以最终线径、表1、表2的温度、30～120m/min的速度来实施了热处理。另外，为了使Cu扩散至表面，当为仅1次的热处理时将热处理炉中的氧气浓度设定为0.2～0.7％而高于通常。如果可能的话，该热处理在最后进行为好，其理由是因为，如果Cu出现到表面后反复进行拉丝加工，则变得容易发生Cu的氧化。在这以外的热处理中，使热处理炉中的氧气浓度小于0.2％，由此一边抑制表皮合金层的过量的氧化，一边控制了稳定的厚度、组成等。这样地进行，得到了直径为15～25μm的接合线。
被覆层、表皮合金层的浓度分析、Cu合金芯材中的Ni、Pd、Pt、Au的浓度分析，一边从接合线的表面向深度方向采用Ar离子进行溅射一边使用AES装置进行分析。被覆层以及表皮合金层的厚度，由得到的深度方向的浓度廓线图(深度的单位是按SiO2换算的)来求出的。对于元素分布的观察，也通过EPMA、EDX装置等进行了分析。将Pd的浓度为50at％以上、且Au的浓度小于10at％的区域作为被覆层，将处于被覆层表面的Au浓度为10at％以上的范围的区域作为表皮合金层。将被覆层和表皮合金层的厚度以及组成分别记载于表1、表2。接合线中的P、B、Be、Fe、Mg、Ti、Zn、Ag、Si的浓度利用ICP发射光谱分析装置和ICP质量分析装置等进行了测定。
对于接合线的连接，使用了市售的自动焊线机。在即将接合前，通过电弧放电在接合线的顶端制作出球部，进行选择使得其直径成为接合线的直径的1.7倍。球部制作时的气氛设为氮气。
作为接合线的接合的对象，分别使用了在Si芯片上形成的厚度1μm的Al电极、和表面镀Pd的引线框的引线。将制作的球部与加热至260℃的上述电极进行球接合后，将接合线的母线部与加热至260℃的上述引线进行2nd接合，再次制作球部，由此连续地反复进行接合。环长为3mm和5mm这两种，环高度为0.3mm和0.5mm这2种。
关于接合线的2nd接合性，是对余裕度(margin)、剥离、强度、鱼尾对称性进行了评价。关于余裕度，在使2nd接合时的载荷从20gf开始以10gf为一刻度提高到90gf、使超声波从60mA开始以10mA为一刻度提高到120mA的56种条件下实施连续接合100根，计数能够连续接合的条件。能够连续接合的条件，为40种以上时记为◎，为30种以上且小于40种时记为○，小于30种时记为×。对于剥离，观察100根已被2nd接合的状态的接合线的接合部，将接合部剥离了的情形统计为NG。对于鱼尾对称性，观察100根已被2nd接合的状态的接合线的接合部，评价其对称性。测量从鱼尾状压接部的中央到左端的长度、到右端的长度，将其差为10％以上的情形统计为NG。关于剥离和鱼尾对称性，NG为0个时记为◎、为1～10个时记为○、为11个以上时记为×。关于强度，在2nd接合部正上方捏住已被2nd接合的状态的接合线，向上方提拉直至切断为止，读取在其切断时所得到的断裂载荷。由于强度被线径支配，因此利用了强度/线抗拉强度的比率。该比率若为85％以上则为良好，因此记为◎，为70～85％时判断为没有问题，记为○，为55～70％时判断为有时发生不良情况，记为△，为55％以下时判断为不良，记为×，都记载于表3、表4的“2nd接合强度”栏中。
关于接合线的1st接合性(球接合性)，是对HAST试验、球形状、FAB形状、芯片损伤进行了评价。为了评价HAST试验中的球接合部的健全性，对于实施了接合的半导体装置，放置在温度130℃、相对湿度85％RH(Relative Humidity)、5V这样的高温高湿炉中，每隔48小时取出进行评价。作为评价方法，是测定电阻，将电阻上升了的情形记为NG。直至变为NG为止的时间，为480小时以上时记为◎，为384小时以上且小于480小时时记为○，小于384小时时记为×。
对于球形状，用光学显微镜观察100个球接合部，将接近于圆形的球接合部记为OK，将成为花瓣状的球接合部记为NG，计数其数量。对于FAB形状，在引线框上制作100根FAB，用SEM进行了观察。圆球状的形状记为OK，偏芯、缩孔记为NG，计数其数量。关于球形状和FAB形状，NG为0个时记为◎、为1～5个时记为○、为6～10个时记为△，为11个以上时记为×。◎和○为合格，△为合格但稍微品质不良。
在芯片损伤的评价中，将20个球接合部进行截面研磨，若电极产生了裂纹则判断为不良，不良为4个以上时记为×、为3个以下时记为△、为1～2个时记为○，如果未观察到裂纹则判为良好，记为◎，都记载在表3、表4的“芯片损伤”栏中。○和◎为合格，△为合格但稍微品质不良。
关于倾斜评价，对于环长：3mm和5mm、环高度：0.3mm和0.5mm的各个情况，在进行接合后各试样都用光学显微镜观察100根的环，仅0～2根的环被观察到倾斜不良时，为良好，记为◎，仅3～4根的环被观察到倾斜不良时，为没有实用上的问题的水平，记为○，5～7根的环被观察到倾斜不良时，记为△，若8根以上的环被观察到倾斜不良，则为低劣，记为×，都记载于表3、表4的“倾斜”栏中。△、○、◎为合格。
在芯材的垂直截面所观察到的相对于线长度方向角度差为15°以下的晶体取向＜100＞的取向比率，在用EBSD法观察观察面的晶体取向的基础上来算出。EBSD测定数据的解析利用了专用软件(TSL制OIM analysis等)。在计算时，选择接合线的全区域，各试样都各观察3个视场。芯材的垂直截面中的相对于线长度方向角度差为15°以下的晶体取向＜100＞的取向比率，记入表3、表4的“垂直截面”的“晶体取向＜100＞”栏中。
在表2中，脱离本发明范围的数值附带有下划线。
本发明例1～35，在评价的所有的品质指标中都实现了合格水平的品质实际成绩。
比较例1，由于线最表面的Cu浓度小于下限，因此2nd接合的剥离以及鱼尾对称性为不良，被覆层的厚度超过理想范围的上限，因此芯片损伤和FAB形状虽为合格但稍微品质不良。比较例2，由于线最表面的Cu浓度小于下限，因此2nd接合的剥离和鱼尾对称性为不良，由于被覆层的厚度小于理想范围的下限，因此FAB形状虽为合格但稍微品质不良。比较例3和比较例7，由于作为必需元素的添加元素1的添加量小于下限，因此高湿加热条件下的球接合性(HAST评价)为不良，而且，2nd接合的余裕度以及强度为不良，由于被覆层的厚度小于理想范围的下限，因此FAB形状虽为合格但稍微品质不良。比较例4，由于线最表面的Cu浓度小于下限，因此2nd接合的剥离以及鱼尾对称性为不良，由于表皮合金层的厚度以及Au的最大浓度超过理想范围的上限，因此FAB形状虽为合格但稍微品质不良。
比较例5，线最表面的Cu浓度超过本发明的上限，2nd接合的余裕度以及强度和FAB形状为不良。
再者，比较例5，由于＜100＞晶体取向脱离本发明的合适范围，因此倾斜是△的结果，虽然为合格的范围但性能稍低。
使用高纯度(4N以上)的Cu芯材、且作为必需元素的添加元素1的添加量小于下限的比较例6，2nd接合的剥离以及鱼尾对称性为不良。

Claims (8)

1.一种半导体装置用接合线，其特征在于，包含：
芯材，其以Cu为主成分，含有总计为0.1质量％以上3.0质量％以下的元素周期表第10族的金属元素；
设置于该芯材表面的以Pd为主成分的被覆层；和
设置于该被覆层表面的包含Au和Pd的表皮合金层，
线最表面的Cu浓度为1at％以上10at％以下。
2.根据权利要求1所述的半导体装置用接合线，其特征在于，
所述元素周期表第10族的金属元素为选自Ni、Pd和Pt中的一种以上。
3.根据权利要求1或2所述的半导体装置用接合线，其特征在于，
所述元素周期表第10族的金属元素包含Ni。
4.根据权利要求1～3的任一项所述的半导体装置用接合线，其特征在于，
所述以Pd为主成分的被覆层的厚度为20nm以上90nm以下，
所述包含Au和Pd的表皮合金层的厚度为0.5nm以上40nm以下，Au的最大浓度为15at％以上75at％以下。
5.根据权利要求1～4的任一项所述的半导体装置用接合线，其特征在于，所述芯材还含有Au，芯材中的Ni、Pd、Pt、Au的总计含量超过0.1质量％且为3.0质量％以下。
6.根据权利要求1～5的任一项所述的半导体装置用接合线，其特征在于，所述接合线还含有P、B、Be、Fe、Mg、Ti、Zn、Ag、Si中的1种以上，这些元素在线整体中所占的浓度的总计为0.0001质量％以上0.01质量％以下的范围。
7.根据权利要求1～6的任一项所述的半导体装置用接合线，其特征在于，在所述芯材与所述被覆层的边界部、以及所述被覆层与所述表皮合金层的边界部具有扩散区域。
8.根据权利要求1～7的任一项所述的半导体装置用接合线，其特征在于，在对与所述接合线的线轴垂直的方向的芯材截面即垂直截面测定晶体取向所得到的结果中，线长度方向的晶体取向之中、相对于线长度方向的角度差为15°以下的晶体取向＜100＞的取向比率为30％以上。
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