CN111719064A - 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
CN111719064A
CN111719064A CN202010782102.9A CN202010782102A CN111719064A CN 111719064 A CN111719064 A CN 111719064A CN 202010782102 A CN202010782102 A CN 202010782102A CN 111719064 A CN111719064 A CN 111719064A
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China
Prior art keywords
bonding wire
wire
semiconductor device
bonding
mass
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Granted
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CN202010782102.9A
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CN111719064B (zh
Inventor
小田大造
江藤基稀
斋藤和之
榛原照男
大石良
山田隆
宇野智裕
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel and Sumikin Chemical Co Ltd
Nippon Steel Chemical and Materials Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B15/00—Layered products comprising a layer of metal
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    • C22C5/04—Alloys based on a platinum group metal
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    • C22C9/00—Alloys based on copper
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Abstract

提供一种半导体装置用接合线，该接合线是在表面具有Pd被覆层的Cu接合线，改善了在高温高湿环境中的球接合部的接合可靠性，适合于车载用装置。一种半导体装置用接合线，具有Cu合金芯材、和形成于所述Cu合金芯材的表面的Pd被覆层，所述接合线包含Ge，相对于线整体，Ge的浓度为0.011质量％以上1.5质量％以下。由此，能够提高在高温高湿环境下的球接合部的接合寿命，改善接合可靠性。Pd被覆层的厚度优选为0.015～0.150μm。当接合线还含有分别为0.011～1.2质量％的Ni、Ir、Pt中的1种以上时，能够提高在175℃以上的高温环境中的球接合部可靠性。另外，当在Pd被覆层的表面进一步形成包含Au和Pd的合金表皮层时，楔接合性改善。

Description

半导体装置用接合线
本申请是申请日为2015年9月17日、申请号为201580020010.4、发明名称为“半导体装置用接合线”的中国专利申请的分案申请。
技术领域
本发明涉及为了将半导体元件上的电极和外部引线(lead)等的电路布线板的布线连接而被利用的半导体装置用接合线。
背景技术
现在，作为将半导体元件上的电极与外部引线之间接合的半导体装置用接合线(以下称为接合线)，主要使用线径15～50μm左右的细线。接合线的接合方法一般为并用超声波的热压接方式，可使用通用接合装置、将接合线通到其内部而用于连接的毛细管工具等。接合线的接合工艺通过下述过程来完成：通过电弧热输入将线尖端加热熔融，利用表面张力形成球(FAB：Free Air Ball，无空气的球)后，使该球部压接接合于在150℃～300℃的范围内加热了的半导体元件的电极上(以下称为球接合)，接着，形成环(环路：loop)之后，将线部压接接合于外部引线侧的电极(以下称为楔接合)。作为接合线的接合对象的半导体元件上的电极可以使用在Si基板上形成了以Al为主体的合金膜的电极结构，而外部引线侧的电极可以使用施加了镀Ag层和/或镀Pd层的电极结构等。
迄今为止，接合线的材料以Au为主流，但以LSI用途为中心，替代为Cu的工作正在推进。另一方面，以近年来的电动汽车、混合动力汽车的普及为背景，在车载用装置用途中，对于从Au替代为Cu的需求也在提高。
关于Cu接合线，曾提出了使用高纯度Cu(纯度：99.99质量％以上)的Cu接合线(例如，专利文献1)。Cu与Au相比具有易氧化的缺点，存在接合可靠性、球形成性、楔接合性等较差的问题。作为防止Cu接合线的表面氧化的方法，曾提出了用Au、Ag、Pt、Pd、Ni、Co、Cr、Ti等金属被覆Cu芯材表面的结构(专利文献2)。另外，曾提出了在Cu芯材的表面被覆Pd，再将Pd被覆层表面用Au、Ag、Cu或它们的合金被覆的结构(专利文献3)。
在先技术文献
专利文献
专利文献1：日本特开昭61-48543号公报
专利文献2：日本特开2005-167020号公报
专利文献3：日本特开2012-36490号公报
发明内容
车载用装置与一般的电子设备相比，要求在严酷的高温高湿环境下的接合可靠性。特别是将线的球部与电极接合的球接合部的接合寿命成为最大的问题。曾提出了好几种评价高温高湿环境下的接合可靠性的方法，作为代表性的评价方法，有HAST(HighlyAccelerated Temperature and Humidity Stress Test)(高温高湿环境暴露试验)。在采用HAST来评价球接合部的接合可靠性的情况下，将评价用的球接合部暴露于温度为130℃、相对湿度为85％的高温高湿环境中，测定接合部的电阻值的经时变化、或测定球接合部的剪切强度的经时变化，由此评价球接合部的接合寿命。最近，在这样的条件下的HAST中变得要求100小时以上的接合寿命。
使用以往的具有Pd被覆层的Cu接合线与纯Al电极进行接合，1st接合设为球接合，2nd接合设为楔接合，用塑模树脂封装后，进行了上述HAST条件下的评价，结果可知有时球接合部的接合寿命低于100小时，车载用装置所要求的接合可靠性不充分。
本发明的目的是提供一种接合线，其是在表面具有Pd被覆层的Cu接合线，改善了高温高湿环境下的球接合部的接合可靠性，适合于车载用装置。
即，本发明的要旨如下。
(1)一种半导体装置用接合线，其特征在于，具有Cu合金芯材、和形成于所述Cu合金芯材的表面的Pd被覆层，
所述接合线包含选自Ga、Ge之中的1种以上的元素，相对于线整体，所述元素的浓度合计为0.011～1.5质量％。
(2)根据上述(1)所述的半导体装置用接合线，其特征在于，所述Pd被覆层的厚度为0.015～0.150μm。
(3)根据上述(1)或(2)所述的半导体装置用接合线，其特征在于，在所述Pd被覆层上还具有包含Au和Pd的合金表皮层。
(4)根据上述(3)所述的半导体装置用接合线，其特征在于，所述包含Au和Pd的合金表皮层的厚度为0.0005～0.050μm。
(5)根据上述(1)～(4)的任一项所述的半导体装置用接合线，其特征在于，所述接合线还包含选自Ni、Ir、Pt之中的1种以上的元素，相对于线整体，所述元素的浓度分别为0.011～1.2质量％。
(6)根据上述(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Cu合金芯材包含Pd，所述Cu合金芯材中所含有的Pd的浓度为0.05～1.2质量％。
(7)根据上述(1)～(6)的任一项所述的半导体装置用接合线，其特征在于，所述接合线还包含选自B、P、Mg之中的至少1种元素，相对于线整体，所述元素的浓度分别为1～100质量ppm。
(8)根据上述(1)～(7)的任一项所述的半导体装置用接合线，其特征在于，在测定所述接合线表面的晶体取向时所得到的测定结果中，所述接合线长度方向的晶体取向之中、相对于长度方向角度差为15度以下的晶体取向＜111＞的存在比率以面积率计为30～100％。
(9)根据上述(1)～(8)的任一项所述的半导体装置用接合线，其特征在于，在所述接合线的最表面存在Cu。
根据本发明，对于具有Cu合金芯材、和形成于Cu合金芯材的表面的Pd被覆层的半导体装置用接合线，通过接合线包含规定量的选自Ga、Ge之中的1种以上，能够提高在高温高湿环境下的球接合部的接合寿命，改善接合可靠性。
具体实施方式
本发明的接合线，其特征在于，具有Cu合金芯材、和形成于所述Cu合金芯材的表面的Pd被覆层，包含选自Ga、Ge之中的1种以上，相对于线整体，Ga、Ge的浓度合计为0.011～1.5质量％。本发明的接合线，能够改善车载用装置所要求的在高温高湿环境下的球接合部的接合可靠性。
详情在后面叙述，当使用本发明的接合线，通过电弧放电来形成球时，在接合线熔融、凝固的过程中，在球的表面形成Pd的浓度比球的内部高的合金层。当使用该球与Al电极进行接合，来实施高温高湿试验时，变为在接合界面Pd浓化了的状态。该Pd浓化而形成的浓化层能够抑制高温高湿试验中的接合界面的Cu、Al的扩散，使易腐蚀性化合物的生长速度下降。由此，本发明的接合线能够提高接合可靠性。
另外，在球的表面形成的Pd浓度高的合金层，抗氧化性优异，因此，能够减少在球形成时球的形成位置相对于接合线的中心发生偏移等的不良。
从使在温度为130℃、相对湿度为85％的高温高湿环境下的球接合部的接合寿命提高、改善接合可靠性的观点出发，相对于线整体，Ga、Ge的浓度合计为0.011质量％以上，优选为0.025质量％以上，更优选为0.031质量％以上，进一步优选为0.050质量％以上、0.070质量％以上、0.090质量％以上、0.100质量％以上、0.150质量％以上、或0.200质量％以上。当相对于线整体，Ga、Ge的浓度合计为0.100质量％以上时，能够应对对于更苛刻的接合可靠性的要求。
再者，在本发明的接合线单独含有Ge的情况下，相对于线整体，Ge的浓度优选为0.025质量％以上。
作为半导体装置的封装包(package)的塑模树脂(环氧树脂)，在分子骨架中含有氯(Cl)。在HAST评价条件即130℃、相对湿度85％的高温高湿环境下，分子骨架中的Cl水解而以氯离子(Cl-)的形式溶出。在将不具有Pd被覆层的Cu接合线与Al电极接合了的情况下，如果Cu/Al接合界面被置于高温下，则Cu和Al相互扩散，最终会形成金属间化合物Cu9Al4。Cu9Al4容易受到Cl等卤素的腐蚀，由于从塑模树脂溶出的Cl而进行腐蚀，导致接合可靠性的降低。在Cu线具有Pd被覆层的情况下，被覆有Pd的Cu线与Al电极的接合界面成为Cu/Pd浓化层/Al这样的结构，因此与不具有Pd被覆层的Cu线相比，虽然Cu9Al4金属间化合物的生成被抑制，但车载用装置所要求的高温高湿环境下的接合可靠性不充分。
对此，可以认为，如果如本发明那样使被覆有Pd的Cu接合线含有规定量的选自Ga、Ge之中的1种以上的元素，则有接合部中的Cu9Al4金属间化合物的生成被进一步抑制的倾向。在球接合部的FAB形成时，线中的Ga、Ge也向Pd被覆层扩散。可以认为，在球接合部中的Cu与Al界面的Pd浓化层中存在的Ga、Ge进一步提高抑制Cu和Al的相互扩散的效果，作为结果，抑制了在高温高湿环境下容易腐蚀的Cu9Al4的生成。另外，也有线中所含的Ga、Ge具有直接阻碍Cu9Al4形成的效果的可能性。
进而，使用含有规定量的选自Ga、Ge中的至少1种元素的被覆有Pd的Cu接合线形成球部，用扫描型电子显微镜(SEM：Scanning Electron Microscope)观察FAB，结果在FAB的表面观察到许多的直径(Ф)为数十nm左右的析出物。当通过能量色散型X射线分析(EDS：Energy Dispersive X-ray Spectroscopy)来分析析出物时，确认到Ga、Ge浓化了。从以上的状况来看，虽然详细的机理尚不明确，但是可认为由于FAB中所观察到的该析出物存在于球部与电极的接合界面，因此在温度为130℃、相对湿度为85％的高温高湿环境下的球接合部的接合可靠性格外提高了。
作为Ga、Ge的存在部位，优选是在Cu合金芯材中，但即使是包含于Pd被覆层和/或后述的包含Au和Pd的合金表皮层中，也能够获得充分的作用效果。向Cu合金芯材中添加Ga、Ge的方法，容易进行准确的浓度管理，线生产率、品质稳定性提高。另外，由于由热处理引起的扩散等，在Pd被覆层和/或合金表皮层中也含有一部分的Ga和/或Ge，因此各层界面的密着(密合)性优良化，能够进一步提高线生产率。
另一方面，从得到良好的FAB形状的观点、抑制接合线的硬质化从而得到良好的楔接合性的观点出发，相对于线整体，Ga、Ge的浓度合计为1.5质量％以下，优选为1.4质量％以下，更优选为1.3质量％以下、或1.2质量％以下。
本发明的接合线，有时在Pd被覆层的最表面存在Cu。当Cu的浓度变为30原子％以上时，线表面的抗硫化性下降，接合线的使用寿命下降，因而有时不适于实用。因此，在Pd被覆层的最表面存在Cu的情况下，优选Cu的浓度小于30原子％。在此，最表面是指在不实施溅射等的状态下，对于接合线的表面由俄歇电子能谱装置测定到的区域。
对于本发明的接合线，从更进一步改善车载用装置所要求的在高温高湿环境下的球接合部的接合可靠性的观点、抑制FAB的偏芯而得到更加良好的FAB形状的观点出发，Pd被覆层的厚度优选为0.015μm以上，更优选为0.02μm以上，进一步优选为0.025μm以上、0.03μm以上、0.035μm以上、0.04μm以上、0.045μm以上、或0.05μm以上。另一方面，从抑制FAB的缩孔、得到良好的FAB形状的观点出发，Pd被覆层的厚度优选为0.150μm以下，更优选为0.140μm以下、0.130μm以下、0.120μm以下、0.110μm以下、或0.100μm以下。
说明上述接合线的Cu合金芯材、Pd被覆层的定义。Cu合金芯材与Pd被覆层的边界以Pd浓度为基准来判定。将Pd浓度为50原子％的位置作为边界，将Pd浓度为50原子％以上的区域判定为Pd被覆层，将Pd浓度小于50原子％的区域判定为Cu合金芯材。其根据是因为，如果在Pd被覆层中Pd浓度为50原子％以上，则由Pd被覆层的结构能得到特性的改善效果。Pd被覆层可以包含单纯的Pd层的区域、Pd和Cu在线的深度方向具有浓度梯度的区域。在Pd被覆层中能形成具有该浓度梯度的区域的原因是因为，有时由于制造工序中的热处理等，Pd和Cu的原子进行扩散。进而，Pd被覆层也可以包含不可避免的杂质。
本发明的接合线，也可以在Pd被覆层上进一步形成包含Au和Pd的合金表皮层。由此，本发明的接合线能够进一步改善楔接合性。
说明上述接合线的包含Au和Pd的合金表皮层的定义。包含Au和Pd的合金表皮层与Pd被覆层的边界，以Au浓度为基准来判定。将Au浓度为10原子％的位置作为边界，将Au浓度为10原子％以上的区域判定为包含Au和Pd的合金表皮层，将Au浓度小于10原子％的区域判定为Pd被覆层。另外，即使是Pd浓度为50原子％以上的区域，如果存在10原子％以上的Au，则也判定为包含Au和Pd的合金表皮层。其根据是因为，如果Au浓度在上述的浓度范围，则能够由Au表皮层的结构期待特性的改善效果。包含Au和Pd的合金表皮层，为Au-Pd合金，包括以下两种情况，即，包含Au和Pd在线的深度方向具有浓度梯度的区域的情况、和不包含具有该浓度梯度的区域的情况。优选包含Au和Pd的合金表皮层包含具有该浓度梯度的区域。在包含Au和Pd的合金表皮层中能形成具有该浓度梯度的区域的原因是因为，由于制造工序中的热处理等，Au和Pd的原子进行扩散。进而，包含Au和Pd的合金表皮层也可以包含不可避免的杂质和Cu。
在本发明的接合线中，包含Au和Pd的合金表皮层能够与Pd被覆层进行反应来提高包含Au和Pd的合金表皮层、Pd被覆层、Cu合金芯材间的密着强度，抑制楔接合时的Pd被覆层和包含Au和Pd的合金表皮层的剥离。由此，本发明的接合线能够进一步改善楔接合性。当包含Au和Pd的合金表皮层的厚度小于0.0005μm时，不能得到上述的效果，当变得比0.050μm厚时，有时FAB形状发生偏芯。从得到良好的楔接合性的观点出发，包含Au和Pd的合金表皮层的厚度优选为0.0005μm以上，更优选为0.001μm以上、0.002μm以上、或0.003μm以上。从抑制偏芯、得到良好的FAB形状的观点出发，包含Au和Pd的合金表皮层的厚度优选为0.050μm以下，更优选为0.045μm以下、0.040μm以下、0.035μm以下、或0.030μm以下。再者，包含Au和Pd的合金表皮层能够采用与Pd被覆层的形成方法同样的方法来形成。
在本发明的接合线中，有时在包含Au和Pd的合金表皮层的最表面存在Cu。当Cu的浓度变为35原子％以上时，线表面的抗硫化性下降，接合线的使用寿命下降，因而有时不适于实用。因此，在Au表皮层的最表面存在Cu的情况下，优选Cu的浓度小于35原子％。在此，最表面是指在不实施溅射等的状态下，对于接合线的表面由俄歇电子能谱仪测定到的区域。
在作为半导体装置的封装包的塑模树脂(环氧树脂)中包含硅烷偶联剂。硅烷偶联剂具有提高有机物(树脂)与无机物(硅、金属)的密着性的作用，因此能够提高与硅基板、金属的密着性。进而，在要求在更高温下的可靠性的面向车载的半导体等要求高的密着性的情况下，可添加“含硫的硅烷偶联剂”。塑模树脂中所含的硫，在HAST中的温度条件即130℃左右下不会游离，但如果在175℃～200℃以上的条件下使用则会游离出来。而且，如果在175℃以上的高温下游离出的硫与Cu接触，则Cu的腐蚀变得剧烈，生成硫化物(Cu2S)、氧化物(CuO)。如果在使用Cu接合线的半导体装置中发生Cu的腐蚀，则特别是球接合部的接合可靠性会降低。
作为评价在175℃以上的高温环境下的球接合部的接合可靠性的手段，可采用HTS(High Temperature Storage Test)(高温放置试验)。对暴露于高温环境中的评价用的样品，测定球接合部的电阻值的经时变化、或测定球接合部的剪切强度的经时变化，由此评价球接合部的接合寿命。近年来，在车载用的半导体装置中，要求在175℃～200℃的HTS中的球接合部的可靠性提高。
本发明的接合线，优选：包含选自Ni、Ir、Pt之中的1种以上的元素，相对于线整体，所述元素的浓度分别为0.011～1.2质量％。通过接合线含有这些元素，球接合部的在高温环境下的接合可靠性之中的、在175℃以上的HTS中的成绩改善。当接合线中的这些成分的浓度分别小于0.011质量％时，不能得到上述的效果，当变得高于1.2质量％时，FAB形状发生恶化，并且接合线硬质化，线接合部的变形变得不充分，楔接合性的下降成为问题。另外，当接合线的Cu合金芯材包含Pd，且Cu合金芯材中所含有的Pd的浓度为0.05～1.2质量％时，能够得到与上述Ni、Ir、Pt同样的效果。进而，通过以上述含量范围含有Ni、Ir、Pt、Pd，能够提高环形成性、即降低在高密度安装中成为问题的倾斜(leaning)。这是因为，通过接合线包含这些元素，接合线的屈服强度提高，能够抑制接合线的变形。
另外，通过以上述含量范围含有Ni、Ir、Pt、Pd，能够进一步提高在温度为130℃、相对湿度为85％的高温高湿环境下的球接合部的接合寿命。可以认为，当如本发明那样被覆有Pd的Cu接合线含有Ni、Ir、Pt、Pd时，存在能够进一步抑制接合部中的Cu9Al4金属间化合物的生成的倾向。当添加有这些元素时，芯材的Cu与被覆层的Pd的界面张力下降，球接合界面的Pd浓化更有效地显现。因而，由Pd浓化层带来的抑制Cu和Al的相互扩散的效果进一步变强，作为结果，推定为在Cl的作用下容易腐蚀的Cu9Al4的生成量变少，球接合部的在高温高湿环境下的可靠性提高。
在本发明的接合线包含选自Ni、Ir、Pt之中的1种以上的元素的情况下，相对于线整体，所述元素的浓度分别更优选为0.02质量％以上、0.05质量％以上、0.1质量％以上、0.2质量％以上、0.3质量％以上、或0.5质量％以上。另外，在本发明的接合线中，在Cu合金芯材含有Pd的情况下，Cu合金芯材中所含有的Pd的浓度更优选为0.1质量％以上、0.2质量％以上、0.3质量％以上、或0.5质量％以上。再者，作为从接合线制品求出Cu合金芯材中所含有的Pd的浓度的方法，例如可举出使接合线的截面露出，对Cu合金芯材的区域进行浓度分析的方法；一边从接合线的表面向深度方向通过溅射等进行切削，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浓度变化的程度是每0.1μm小于10mol％的区域)进行浓度分析即可。关于Pd以外的元素，在从接合线制品求Cu合金芯材中所含有的元素的浓度时，也可以使用与上述同样的方法。关于浓度分析的方法在后面叙述。
本发明的接合线，通过进一步包含选自B、P、Mg之中的至少1种元素，且相对于线整体，所述元素的浓度分别为1～100质量ppm，能够改善高密度安装所要求的球接合部的压溃形状、即改善球接合部形状的圆形性。这是因为，通过添加所述元素，能够使球的晶体粒径微细化，能够抑制球的变形。当相对于线整体，所述元素的浓度小于1质量ppm时，不能得到上述的效果，当变得大于100质量ppm时，有时由于球硬质化，球接合时的芯片损伤成为问题，因而不适于实用。相对于线整体，所述元素的浓度分别更优选为3质量ppm以上、或5质量ppm以上。相对于线整体，所述元素的浓度分别更优选为95质量ppm以下、90质量ppm以下、85质量ppm以下、或80质量ppm以下。
对于Pd被覆层、包含Au和Pd的合金表皮层的浓度分析、Cu合金芯材中的Pd的浓度分析，一边从接合线的表面向深度方向通过溅射等进行切削一边进行分析的方法、或者使线截面露出从而进行线分析、点分析等的方法是有效的。用于这些浓度分析的解析装置，可以利用在扫描型电子显微镜或透射型电子显微镜中装备的俄歇电子能谱分析装置、能量色散型X射线分析装置、电子射线显微分析仪等。作为使线截面露出的方法，可以利用机械研磨、离子蚀刻法等。关于接合线中的Ga、Ge、Ni、Ir、Pt、B、P、Mg等的微量成分，可利用ICP发射光谱分析装置、ICP质谱分析装置来分析用强酸溶解接合线而得到的液体，作为接合线整体中所包含的元素的浓度来检测出。
当接合线的表面的、接合线长度方向的晶体取向之中、相对于长度方向角度差为15度以下的晶体取向＜111＞的存在比率以面积率计为30～100％时，能够提高环形成性、即提高在高密度安装中所要求的环的直进性，并且能够降低环的高度的偏差(波动)。如果表面晶体取向一致，则对于横向的变形，抗性变强，抑制横向的变形，因此能够抑制倾斜不良。因此，在一实施方式中，在测定接合线表面的晶体取向时所得到的测定结果中，所述接合线长度方向的晶体取向之中、相对于长度方向角度差为15度以下的晶体取向＜111＞的存在比率以面积率计为30～100％。从抑制倾斜不良的观点出发，以面积率计，上述晶体取向＜111＞的存在比率更优选为35％以上，进一步优选为40％以上。
(制造方法)
接着，说明本发明的实施方式涉及的接合线的制造方法。接合线是通过在制造出用于芯材的Cu合金后，加工成细线状，形成Pd被覆层、Au层，进行热处理而得到。也有时在形成Pd被覆层、Au层后，进行再次拉丝和热处理。对于Cu合金芯材的制造方法、Pd被覆层、包含Au和Pd的合金表皮层的形成方法、热处理方法进行详细说明。
芯材所使用的Cu合金，是通过将成为原料的Cu和添加的元素一起熔化，使其凝固而得到的。对于熔化，可以利用电弧加热炉、高频加热炉、电阻加热炉等。为了防止从大气中混入O2、H2等气体，优选在真空气氛或Ar、N2等惰性气氛中进行熔化。
在Cu合金芯材的表面形成Pd被覆层、Au层的方法，有镀敷法、蒸镀法、熔融法等。关于镀敷法，可以应用电解镀敷法、无电解镀敷法中的任何方法。被称为触击镀、闪镀的电解镀敷，其镀敷速度快，与基底的密着性也良好。用于无电解镀敷的溶液，可分类为置换型和还原型，在厚度薄的情况下仅采用置换型镀敷就足够了，但在厚度厚的情况下，在置换型镀敷之后阶段性地实施还原型镀敷是有效的。
在蒸镀法中，可以利用溅射法、离子镀法、真空蒸镀等物理吸附、和等离子体CVD等化学吸附。都是干式方法，在形成Pd被覆层、Au层之后不需要洗涤，不用担心洗涤时的表面污染等。
通过在Pd被覆层、Au层形成后进行热处理，Pd被覆层的Pd向Au层中扩散，能形成包含Au和Pd的合金表皮层。也可以不是在形成Au层后通过热处理来形成包含Au和Pd的合金表皮层，而是从最初就覆着包含Au和Pd的合金表皮层。
对于Pd被覆层、包含Au和Pd的合金表皮层的形成，在拉丝到最终线径然后进行形成的方法、和在形成于粗径的Cu合金芯材上后数次拉丝直到目标线径为止的方法中的任何方法都是有效的。在前者的在最终线径下形成Pd被覆层、包含Au和Pd的合金表皮层的情况下，制造、品质管理等很简便。在后者的将Pd被覆层、包含Au和Pd的合金表皮层与拉丝组合的情况下，在提高与Cu合金芯材的密着性方面是有利的。作为各形成法的具体例，可举出：对于最终线径的Cu合金芯材，一边使线在电解镀敷溶液中连续地扫掠通过一边形成Pd被覆层、包含Au和Pd的合金表皮层的方法；或者，将粗的Cu合金芯材浸渍在电解镀浴或无电解镀浴中来形成Pd被覆层、包含Au和Pd的合金表皮层，然后将线进行拉丝而达到最终线径的方法；等等。
在形成Pd被覆层、包含Au和Pd的合金表皮层后，有时进行热处理。通过进行热处理，在包含Au和Pd的合金表皮层、Pd被覆层、Cu合金芯材之间原子进行扩散，密着强度提高，因此能够抑制加工中的包含Au和Pd的合金表皮层、和Pd被覆层的剥离，在生产率提高方面是有效的。为了防止来自大气中的O2的混入，优选在真空气氛或Ar、N2等惰性气氛中进行热处理。
在对接合线实施的扩散热处理、退火热处理中，有时芯材的Cu在Pd被覆层和/或包含Au和Pd的表皮合金层中扩散从而到达接合线的最表面。也能够根据扩散热处理、退火处理的条件(热处理温度和时间)等来调整芯材的Cu的扩散的程度(接合线最表面的Cu的存在的有无、最表面的Cu浓度)。
在如前述那样使接合线中含有Ga、Ge时，不论采用使Cu芯材中含有这些元素的方法、和使这些元素覆着在Cu芯材或者线表面而含有的方法的哪种方法，都能够发挥上述本发明的效果。对于Ni、Ir、Pt、B、P、Mg也是同样的。
作为上述成分的添加方法，最简便的方法是预先向Cu的原材料中添加成分元素的方法。例如，在称量了高纯度的铜和上述成分元素之后，将其在高真空下或者氮气、氩气等惰性气氛下加热来熔化，由此可制作出添加有目标的浓度范围的上述成分的Cu合金锭。因此，在优选的一实施方式中，本发明的接合线的Cu合金芯材，包含选自Ga、Ge之中的1种以上的元素，并使得相对于线整体、所述元素的浓度合计为0.011～1.5质量％。该浓度合计的合适的数值范围如前所述。在另一优选的实施方式中，本发明的接合线的Cu合金芯材，包含选自Ni、Ir、Pt之中的1种以上的元素，并使得相对于线整体、所述元素的浓度分别为0.011～1.2质量％。该浓度的适合的数值范围如前所述。因此，在优选的一实施方式中，Cu合金芯材的Cu的纯度为3N以下(优选为2N以下)。以往的被覆有Pd的Cu接合线，从接合性(bondability)的观点出发，具有使用高纯度(4N以上)的Cu芯材而避免使用低纯度的Cu芯材的倾向。含有特定元素的本发明的接合线，特别适合于使用如上述那样Cu纯度低的Cu合金芯材的情况，从而实现了车载用装置所要求的在高温高湿环境中的球接合部的接合可靠性。在另一优选的实施方式中，本发明的接合线的Cu合金芯材，包含选自B、P、Mg中的1种以上的元素，并使得相对于线整体、上述元素的浓度分别为1～100质量ppm。该浓度的合适的数值范围如前所述。
也可通过在线制造工序的途中使上述成分覆着于线表面来含有。在该情况下，可以在线制造工序的任一时间点组入覆着步骤，可以反复进行多次覆着。可以组入到多个工序中。可以向Pd被覆前的Cu表面添加，可以向Pd被覆后的Pd表面添加，可以向Au被覆后的Au表面添加，可以组入到各被覆工序中。作为覆着方法，可以从(1)
Figure BDA0002620625410000131
Figure BDA0002620625410000132
(2)镀敷法(湿式)、(3)蒸镀法(干式)中选择。
在采用
Figure BDA0002620625410000133
的方法的情况下，首先用包含上述成分元素的水溶性化合物调制出适当浓度的水溶液。由此，能够将上述成分纳入线材料中。可以在线制造工序的任一时间点组入覆着步骤，可以反复进行多次覆着。可以组入到多个工序中。可以向Pd被覆前的Cu表面添加，可以向Pd被覆后的Pd表面添加，可以向Au被覆后的Au表面添加，可以组入到各被覆工序中。
在使用镀敷法(湿式)的情况下，镀敷法可以应用电解镀敷法、无电解镀敷法中的任何方法。在电解镀敷法中，除了通常的电解镀敷以外，还可以应用被称为闪镀的镀敷速度快且与基材的密着性也良好的镀敷法。用于无电解镀敷的溶液有置换型和还原型。一般而言，在镀层厚度较薄的情况下可应用置换型镀敷，在镀层厚度较厚的情况下可应用还原型镀敷，但是不论哪种都可以应用，只要按照想要添加的浓度来选择并调节镀液浓度、时间即可。电解镀敷法、无电解镀敷法均可以在线制造工序的任一时间点组入，可以反复进行多次。可以组入到多个工序中。可以向Pd被覆前的Cu表面添加，可以向Pd被覆后的Pd表面添加，可以向Au被覆后的Au表面添加，可以组入到各被覆工序中。
在蒸镀法(干式)中有溅射法、离子镀法、真空蒸镀法、等离子体CVD等。由于是干式的，因此不需要预处理和后处理，不用担心污染，这是优点。一般而言，蒸镀法存在作为目标的元素的添加速度慢的问题，但是由于上述成分元素的添加浓度比较低，因此是适合本发明的目的的方法之一。
各蒸镀法，可以在线制造工序的任一时间点组入，可以反复进行多次。可以组入到多个工序中。可以向Pd被覆前的Cu表面添加，可以向Pd被覆后的Pd表面添加，可以向Au被覆后的Au表面添加，可以组入到各被覆工序中。
在测定接合线表面的晶体取向时所得到的测定结果中，使接合线长度方向的晶体取向之中、相对于长度方向角度差为15度以下的晶体取向＜111＞的存在比率以面积率计成为30～100％的方法如下。即，可通过增大Pd被覆层形成后或Pd被覆层和Au表皮层形成后的加工率，来使线表面上的具有方向性的织构(沿拉丝方向晶体取向一致的织构)发达。具体而言，通过使Pd被覆层形成后或Pd被覆层和Au表皮层形成后的加工率成为90％以上，能够在测定接合线表面的晶体取向时所得到的测定结果中，使接合线长度方向的晶体取向之中、相对于长度方向角度差为15度以下的晶体取向＜111＞的存在比率以面积率计成为30％以上。在此，用“加工率(％)＝(加工前的线截面面积-加工后的线截面面积)/加工前的线截面面积×100”表示。
在测定线表面的晶体取向时，优选使用电子射线背散射衍射法(EBSD，ElectronBackscattered Diffraction)。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。
本发明并不被上述实施方式限定，能够在本发明的主旨的范围内进行适当变更。
实施例
以下一边示出实施例一边对本发明的实施方式涉及的接合线进行具体说明。
(样品)
首先，对样品的制作方法进行说明。成为芯材的原材料的Cu使用了纯度为99.99质量％以上且其余量由不可避免的杂质构成的Cu。Ga、Ge、Ni、Ir、Pt、Pd、B、P、Mg使用了纯度为99质量％以上且其余量由不可避免的杂质构成的材料。调配作为向芯材添加的元素的Ga、Ge、Ni、Ir、Pt、Pd、B、P、Mg，使得线或芯材的组成成为目标组成。关于Ga、Ge、Ni、Ir、Pt、Pd、B、P、Mg的添加，可以是用单质来进行调配，但是在为单质具有高熔点的元素、和/或添加量为极微量的情况下，也可以预先制作包含添加元素的Cu母合金来调配以使得成为目标的添加量。
芯材的Cu合金通过以下过程来制造出：向加工成直径为Ф3～6mm的圆柱形的碳坩埚中装填原料，使用高频炉，在真空中或者N2、Ar气体等惰性气氛下加热到1090～1300℃使其熔化后，进行炉冷。对所得到的Ф3～6mm的合金进行拉拔加工，加工到Ф0.9～1.2mm后，使用拉模连续地进行拉丝加工等，由此制作出Ф300～600μm的线。拉丝时使用市售的润滑液，拉丝速度设为20～150m/分。为了除去线表面的氧化膜，采用盐酸进行酸洗处理，然后，以覆盖芯材的Cu合金的表面整体的方式形成了厚1～15μm的Pd被覆层。进而，一部分的线在Pd被覆层上形成了厚0.05～1.5μm的包含Au和Pd的合金表皮层。对于Pd被覆层、包含Au和Pd的合金表皮层的形成，使用了电解镀敷法。镀液使用了市售的半导体用镀液。然后，通过反复进行200～500℃的热处理和拉丝加工，加工到直径20μm。在加工后，最终一边流通N2或者Ar气体一边进行了热处理以使得断裂伸长率成为约5～15％。热处理方法是一边使线连续地扫掠通过一边进行，一边流通N2或者Ar气体一边进行。线的输送速度设为20～200m/分，热处理温度设为200～600℃，热处理时间设为0.2～1.0秒。
通过调整Pd被覆层形成后或Pd被覆层和包含Au和Pd的合金表皮层形成后的加工率，来调整了在测定接合线表面的晶体取向时所得到的测定结果中的、接合线长度方向的晶体取向之中相对于长度方向角度差为15度以下的晶体取向＜111＞的存在比率(面积率)。
关于Pd被覆层、包含Au和Pd的合金表皮层的浓度分析，一边采用Ar离子从接合线的表面向深度方向溅射，一边使用俄歇电子能谱分析装置进行分析。被覆层和表皮合金层的厚度，从所得到的深度方向的浓度廓线(深度的单位是按SiO2换算)求出。将Pd的浓度为50原子％以上且Au的浓度小于10原子％的区域作为Pd被覆层，将处于Pd被覆层的表面的Au浓度为10原子％以上的范围的区域作为合金表皮层。将被覆层和合金表皮层的厚度以及组成分别记载于表1、表2中。Cu合金芯材中的Pd的浓度通过以下方法测定出：使线截面露出，采用在扫描型电子显微镜中装备的电子射线显微分析仪进行线分析、点分析等。作为使线截面露出的方法，利用了机械研磨、离子蚀刻法等。接合线中的Ga、Ge、Ni、Ir、Pt、B、P、Mg的浓度，是利用ICP发射光谱分析装置、ICP质谱分析装置来分析用强酸溶解接合线所得到的液体，作为接合线整体中所含有的元素的浓度来检测出。
在下述表中示出采用上述的步骤制作出的各样品的构成。表1是本发明例，表2是比较例。在表2中，脱离本发明范围的数值附带有下划线。
Figure BDA0002620625410000171
Figure BDA0002620625410000181
Figure BDA0002620625410000191
Figure BDA0002620625410000201
Figure BDA0002620625410000211
(评价方法)
将线表面作为观察面，进行了晶体组织的评价。作为评价方法，使用了电子射线背散射衍射法(EBSD，Electron Backscattered Diffraction)。EBSD法具有能够观察观察面的晶体取向、并图示相邻的测定点间的晶体取向的角度差这样的特征，即使是如接合线这样的细线，也能够比较容易且高精度地观察晶体取向。
在将如线表面那样的曲面作为对象来实施EBSD法的情况下需要注意。如果测定曲率大的部位，则难以进行高精度的测定。但是，通过将供测定的接合线在平面上固定成直线状，并测定该接合线的中心附近的平坦部，就能够进行高精度的测定。具体而言，可以设为如下那样的测定区域。周向的尺寸以线长度方向的中心为轴线设为线径的50％以下，线长度方向的尺寸设为100μm以下。优选将周向的尺寸设为线径的40％以下、线长度方向的尺寸设为40μm以下，如果这样的话，则由于缩短了测定时间而可提高测定效率。为进一步提高精度，优选测定3处以上来得到考虑了波动的平均信息。测定部位距离1mm以上以使得不接近为好。
表面晶体取向＜111＞的存在比率是通过将能够利用专用软件(例如，TSLソリューションズ公司制OIM analysis等)确定的全部晶体取向作为母集团(母群)，算出接合线长度方向的晶体取向之中、相对于长度方向角度差为15度以下的晶体取向＜111＞的面积率而求出的。
高温高湿环境或高温环境下的球接合部的接合可靠性，是通过制作接合可靠性评价用的样品，进行HAST和HTS评价，根据各试验中的球接合部的接合寿命而判定的。接合可靠性评价用的样品，是对于在一般的金属框上的Si基板上形成厚度0.8μm的Al-1.0％Si-0.5％Cu合金膜而形成的电极，利用市售的焊线机进行球接合，利用市售的环氧树脂进行封装而制作的。球是一边以0.4～0.6L/分钟的流量流通N2+5％H2气体一边进行形成，其大小设为Ф33～34μm的范围。
关于HAST评价，使用不饱和型压力锅蒸煮试验机，将制作出的接合可靠性评价用的样品暴露于温度130℃、相对湿度85％的高温高湿环境中，施加了7V的偏电压。球接合部的接合寿命设为每48小时就实施球接合部的剪切试验，剪切强度的值成为初始所得到的剪切强度的1/2的时间。高温高湿试验后的剪切试验，是通过酸处理来除去树脂从而使球接合部露出后进行的。
HAST评价的剪切试验机使用了DAGE公司制的试验机。剪切强度的值采用了随机选择的球接合部的10处位置的测定值的平均值。在上述的评价中，接合寿命如果低于96小时则判断为在实用上存在问题而标记为×，如果为96小时以上且低于144小时则判断为能够实用但稍有问题而标记为△，如果为144小时以上且低于288小时则判断为在实用上没有问题而标记为○，如果为288小时以上则判断为特别优异而标记为◎，都记载于表1的“HAST”栏中。
关于HTS评价，使用高温恒温器，将制作出的接合可靠性评价用的样品暴露于温度200℃的高温环境中。球接合部的接合寿命设为每500小时就实施球接合部的剪切试验，剪切强度的值成为初始所得到的剪切强度的1/2的时间。高温高湿试验后的剪切试验，是通过酸处理来除去树脂从而使球接合部露出后进行的。
HTS评价的剪切试验机使用了DAGE公司制的试验机。剪切强度的值采用了随机选择的球接合部的10处位置的测定值的平均值。在上述的评价中，接合寿命如果为500小时以上且低于1000小时则判断为能够实用但还需要改善而标记为△，如果为1000小时以上且低于3000小时则判断为在实用上没有问题而标记为○，如果为3000小时以上则判断为特别优异而标记为◎。
球形成性(FAB形状)的评价，是采取进行接合之前的球来进行观察，判定球表面有无气泡、本来为圆球的球有无变形。在发生了上述任一现象的情况下都判断为不良。关于球的形成，为了抑制熔融工序中的氧化，一边以0.5L/min的流量喷吹N2气体一边进行。球的大小设为34μm。对于1个条件观察50个球。观察时使用了SEM。对于球形成性的评价，在发生了5个以上的不良的情况下，判断为有问题而标记为×，如果不良为3～4个，则判断为能够实用但稍有问题而标记为△，当不良为1～2个时判断为无问题而标记为○，当没有发生不良时判断为优异而标记为◎，都记载在表1的“FAB形状”栏中。
线接合部中的楔接合性的评价，是在引线框的引线部分进行1000根的接合，根据接合部的剥离的发生频度来判定的。引线框使用了施加了厚1～3μm的镀Ag层的Fe-42原子％Ni合金引线框。在本评价中，设想比通常严格的接合条件，将台(stage)温度设定为比一般的设定温度域低的150℃。在上述的评价中，在发生了11个以上的不良的情况下，判断为有问题而标记为×，如果不良为6～10个，则判断为能够实用但稍有问题而标记为△，在不良为1～5个的情况下，判断为无问题而标记为○，在没有发生不良的情况下，判断为优异而标记为◎，都记载在表1的“楔接合性”栏中。
球接合部的压溃形状的评价，是从正上方观察进行接合而得到的球接合部，根据其圆形性来判定。接合对象使用了在Si基板上形成有厚度1.0μm的Al-0.5％Cu合金膜的电极。观察时使用光学显微镜，对于1个条件观察200处。将与圆球的偏差大的椭圆状的情况、在变形方面具有各向异性的情况判断为球接合部的压溃形状不良。在上述的评价中，在发生了6个以上的不良的情况下判断为有问题而标记为×，如果不良为4～5个则判断为能够实用但稍有问题而标记为△，在不良为1～3个的情况下判断为没有问题而标记为○，在全部得到了良好的圆形性的情况下判断为特别优异而标记为◎，都记载于表1的“压溃形状”栏中。
[倾斜]
对评价用的引线框，以环长度5mm、环高度0.5mm接合了100根。作为评价方法，从芯片水平方向观察线直立部，用通过球接合部的中心的垂线与线直立部的间隔最大时的间隔(倾斜间隔)进行了评价。在倾斜间隔小于线径的情况下，对于倾斜判断为良好，在倾斜间隔大于线径的情况下，由于直立部倾斜因此对于倾斜判断为不良。利用光学显微镜观察100根接合了的线，计数倾斜不良的根数。在发生了7个以上的不良的情况下判断为有问题而标记为×，如果不良为4～6个则判断为能够实用但稍有问题而标记为△，在不良为1～3个的情况下判断为没有问题而标记为○，在没有发生不良的情况下判断为优异而标记为◎，都记载于表1的“倾斜”栏中。
(评价结果)
表1中记载的本发明例1～107涉及的接合线，具有Cu合金芯材、和形成于Cu合金芯材的表面的Pd被覆层，接合线包含选自Ga、Ge之中的1种以上的元素，相对于线整体，所述元素的浓度合计为0.011～1.5质量％。由此确认出，本发明例1～107涉及的接合线在温度为130℃、相对湿度为85％的高温高湿环境下的HAST试验中能得到球接合部可靠性。
另一方面，表2中记载的比较例1～9，Ga和Ge的合计浓度脱离出下限，在HAST试验中没有得到球接合部可靠性。比较例1和比较例6，Pd被覆层的厚度脱离出合适范围的下限，FAB形状为×。比较例1、3、6、8，＜111＞晶体取向的面积率脱离本发明的合适范围，在倾斜方面为△。
关于在Pd被覆层上还具有包含Au和Pd的合金表皮层的本发明例，确认出：通过包含Au和Pd的合金表皮层的层厚为0.0005～0.050μm，能得到优异的楔接合性。
对于接合线还包含选自Ni、Ir、Pt、Pd之中的至少1种元素的本发明例，确认出：通过相对于线整体，Pd以外的所述元素的浓度分别为0.011～1.2质量％，且Cu合金芯材中所含有的Pd的浓度为0.05～1.2质量％，基于HTS评价的球接合部高温可靠性良好。
接合线还包含选自B、P、Mg之中的至少1种元素的本发明例，通过相对于线整体，所述元素的浓度分别为1～100质量ppm，球接合部的压溃形状良好。

Claims (32)

1.一种半导体装置用接合线，其特征在于，具有Cu合金芯材、和形成于所述Cu合金芯材的表面的Pd被覆层，
所述接合线包含Ge，相对于线整体，Ge的浓度为0.011质量％以上1.5质量％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，相对于所述线整体，Ge的浓度为0.025质量％以上。
3.根据权利要求1所述的半导体装置用接合线，其特征在于，相对于所述线整体，Ge的浓度为0.031质量％以上。
4.根据权利要求1所述的半导体装置用接合线，其特征在于，相对于所述线整体，Ge的浓度为0.050质量％以上。
5.根据权利要求1所述的半导体装置用接合线，其特征在于，相对于所述线整体，Ge的浓度为1.4质量％以下。
6.根据权利要求1所述的半导体装置用接合线，其特征在于，相对于所述线整体，Ge的浓度为1.3质量％以下。
7.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Pd被覆层的厚度为0.015μm以上0.150μm以下。
8.根据权利要求7所述的半导体装置用接合线，其特征在于，所述Pd被覆层的厚度为0.02μm以上。
9.根据权利要求7所述的半导体装置用接合线，其特征在于，所述Pd被覆层的厚度为0.025μm以上。
10.根据权利要求7所述的半导体装置用接合线，其特征在于，所述Pd被覆层的厚度为0.140μm以下。
11.根据权利要求7所述的半导体装置用接合线，其特征在于，所述Pd被覆层的厚度为0.130μm以下。
12.根据权利要求1所述的半导体装置用接合线，其特征在于，在所述Pd被覆层上还具有包含Au和Pd的合金表皮层。
13.根据权利要求12所述的半导体装置用接合线，其特征在于，所述包含Au和Pd的合金表皮层的厚度为0.0005μm以上0.050μm以下。
14.根据权利要求13所述的半导体装置用接合线，其特征在于，所述包含Au和Pd的合金表皮层的厚度为0.001μm以上。
15.根据权利要求13所述的半导体装置用接合线，其特征在于，所述包含Au和Pd的合金表皮层的厚度为0.002μm以上。
16.根据权利要求13所述的半导体装置用接合线，其特征在于，所述包含Au和Pd的合金表皮层的厚度为0.045μm以下。
17.根据权利要求13所述的半导体装置用接合线，其特征在于，所述包含Au和Pd的合金表皮层的厚度为0.040μm以下。
18.根据权利要求1所述的半导体装置用接合线，其特征在于，所述接合线还包含选自Ni、Ir、Pt之中的1种以上的元素，相对于线整体，所述元素的浓度分别为0.011质量％以上1.2质量％以下。
19.根据权利要求18所述的半导体装置用接合线，其特征在于，所述接合线还包含选自Ni、Ir、Pt之中的1种以上的元素，相对于线整体，所述元素的浓度分别为0.02质量％以上。
20.根据权利要求18所述的半导体装置用接合线，其特征在于，所述接合线还包含选自Ni、Ir、Pt之中的1种以上的元素，相对于线整体，所述元素的浓度分别为0.05质量％以上。
21.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Cu合金芯材包含Pd，所述Cu合金芯材中所含有的Pd的浓度为0.05质量％以上1.2质量％以下。
22.根据权利要求21所述的半导体装置用接合线，其特征在于，所述Cu合金芯材包含Pd，所述Cu合金芯材中所含有的Pd的浓度为0.1质量％以上。
23.根据权利要求21所述的半导体装置用接合线，其特征在于，所述Cu合金芯材包含Pd，所述Cu合金芯材中所含有的Pd的浓度为0.2质量％以上。
24.根据权利要求1所述的半导体装置用接合线，其特征在于，所述接合线还包含选自B、P、Mg之中的至少1种元素，相对于线整体，所述元素的浓度分别为1质量ppm以上100质量ppm以下。
25.根据权利要求24所述的半导体装置用接合线，其特征在于，所述接合线还包含选自B、P、Mg之中的至少1种元素，相对于线整体，所述元素的浓度分别为3质量ppm以上。
26.根据权利要求24所述的半导体装置用接合线，其特征在于，所述接合线还包含选自B、P、Mg之中的至少1种元素，相对于线整体，所述元素的浓度分别为5质量ppm以上。
27.根据权利要求24所述的半导体装置用接合线，其特征在于，所述接合线还包含选自B、P、Mg之中的至少1种元素，相对于线整体，所述元素的浓度分别为95质量ppm以下。
28.根据权利要求24所述的半导体装置用接合线，其特征在于，所述接合线还包含选自B、P、Mg之中的至少1种元素，相对于线整体，所述元素的浓度分别为90质量ppm以下。
29.根据权利要求1所述的半导体装置用接合线，其特征在于，在测定所述接合线表面的晶体取向时所得到的测定结果中，所述接合线长度方向的晶体取向之中、相对于长度方向角度差为15度以下的晶体取向＜111＞的存在比率为30％以上100％以下。
30.根据权利要求29所述的半导体装置用接合线，其特征在于，所述接合线长度方向的晶体取向之中、相对于长度方向角度差为15度以下的晶体取向＜111＞的存在比率为35％以上。
31.根据权利要求29所述的半导体装置用接合线，其特征在于，所述接合线长度方向的晶体取向之中、相对于长度方向角度差为15度以下的晶体取向＜111＞的存在比率为40％以上。
32.根据权利要求1～31的任一项所述的半导体装置用接合线，其特征在于，在所述接合线的最表面存在Cu。
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