CN112038312B - 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
CN112038312B
CN112038312B CN202010954614.9A CN202010954614A CN112038312B CN 112038312 B CN112038312 B CN 112038312B CN 202010954614 A CN202010954614 A CN 202010954614A CN 112038312 B CN112038312 B CN 112038312B
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Prior art keywords
bonding wire
wire
bonding
semiconductor device
concentration
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CN202010954614.9A
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CN112038312A (zh
Inventor
山田隆
小田大造
榛原照男
宇野智裕
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Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Nippon Steel and Sumikin Chemical Co Ltd
Nippon Steel Chemical and Materials Co Ltd
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Priority claimed from PCT/JP2015/066392 external-priority patent/WO2016189752A1/ja
Application filed by Nippon Steel and Sumikin Chemical Co Ltd, Nippon Steel Chemical and Materials Co Ltd filed Critical Nippon Steel and Sumikin Chemical Co Ltd
Priority to CN202010954614.9A priority Critical patent/CN112038312B/zh
Priority claimed from PCT/JP2015/076721 external-priority patent/WO2016189758A1/ja
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    • H—ELECTRICITY
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    • H01L24/42—Wire connectors; Manufacturing methods related thereto
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Abstract

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，适合于车载用设备。一种半导体装置用接合线，具有Cu合金芯材和形成于其表面的Pd被覆层，接合线含有合计为0.1～100质量ppm的As、Te、Sn、Sb、Bi、Se中的1种以上的元素。由此，能够提高高温高湿环境下的球接合部的接合寿命并改善接合可靠性。当Cu合金芯材还含有分别为0.011～1.2质量％的Ni、Zn、Rh、In、Ir、Pt、Ga、Ge中的1种以上时，能够提高在170℃以上的高温环境下的球接合部可靠性。另外，当在Pd被覆层的表面进一步形成含有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18日、申请号为201580002533.6、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等电路布线基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：FreeAir 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，外部引线侧的电极可以使用施加了镀Ag层、镀Pd层的电极结构等。
迄今为止，接合线的材料中Au是主流，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向Cu的替代的需求也在提高。
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，再将其表面用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
车载用设备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中开始要求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接合为球接合，2nd接合为楔接合，用环氧树脂封装后，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，车载用设备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，适合于车载用设备。
即，本发明的主旨如下。
(1)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，其特征在于，
所述接合线含有选自As、Te、Sn、Sb、Bi、Se中的至少1种以上的元素，相对于线整体，所述元素的浓度合计为0.1～100质量ppm，Sn≤10质量ppm、Sb≤10质量ppm、Bi≤1质量ppm。
(2)根据上述(1)所述的半导体装置用接合线，其特征在于，相对于线整体，选自As、Te、Sn、Sb、Bi、Se中的至少1种以上的元素的浓度合计为1～100质量ppm。
(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，所述Pd被覆层的厚度为0.015～0.150μm。
(4)根据上述(1)～(3)的任一项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。
(5)根据上述(4)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。
(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，所述接合线还含有选自Ni、Zn、Rh、In、Ir、Pt、Ga、Ge中的至少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％。
(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Cu合金芯材含有Pd，所述Cu合金芯材中所含的Pd的浓度为0.05～1.2质量％。
(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，所述接合线还含有选自B、P、Mg、Ca、La中的至少1种以上的元素，相对于线整体，所述元素的浓度分别为1～100质量ppm。
(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，在测定所述接合线表面的晶体取向而得到的测定结果中，相对于所述接合线长度方向角度差为15度以下的晶体取向＜111＞的存在比率以面积率计为30～100％。
(10)根据上述(1)～(9)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合金芯材表面的Pd被覆层的半导体装置用接合线，通过接合线含有合计为0.1～100质量ppm的选自As、Te、Sn、Sb、Bi、Se中的至少一种以上的元素，能够提高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，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，接合线含有合计为0.1～100质量ppm的选自As、Te、Sn、Sb、Bi、Se中的至少1种以上的元素。具有该特定的构成的本发明的接合线，能够改善车载用设备所要求的高温高湿环境下的球接合部的接合可靠性。
详细情况会在后面描述，如果使用本发明的接合线，通过电弧放电而形成球，则在接合线熔融、凝固的过程中，在球的表面形成与球的内部相比Pd的浓度高的合金层。如果使用该球与Al电极进行接合，实施高温高湿试验，则成为在接合界面Pd浓化的状态。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中的Cu、Al的扩散，使易腐蚀性化合物的生长速度降低，能够使高温高湿环境中的球接合部的接合可靠性格外地提高。
另外，形成于球表面的Pd浓度高的合金层，抗氧化性优异，因此在球形成时能够减少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，相对于接合线整体，选自As、Te、Sn、Sb、Bi、Se中的至少1种以上的元素的浓度合计为0.1质量ppm以上，优选为0.5质量ppm以上，更优选为1质量ppm以上，进一步优选为1.5质量ppm以上、2质量ppm以上、2.5质量ppm以上、或3质量ppm以上。
作为半导体装置的外壳的塑模树脂(环氧树脂)，分子骨架包含氯(Cl)。在HAST评价条件即130℃、相对湿度为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(洗脱)。在将不具有被覆层的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容易受到卤素的腐蚀，由于从塑模树脂溶出的氯化物而进行腐蚀，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，与不具有被覆层的Cu线相比，虽然Cu9Al4金属间化合物的生成被抑制，但车载用设备中所要求的高温高湿环境下的接合可靠性不充分。
与此相对，可以认为，如果如本发明那样被覆有Pd的Cu接合线含有规定量的选自As、Te、Sn、Sb、Bi、Se中的至少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。如果含有规定量的这些元素，则在形成球时，芯材的Cu与被覆层的Pd的界面张力降低，界面的润湿性优化，因而更显著地显现球接合界面的Pd浓化。因此，由Pd浓化层带来的抑制Cu和Al相互扩散的效果进一步增强，结果推测因Cl的作用而易腐蚀的Cu9Al4的生成量减少，球接合部的高温高湿环境下的接合可靠性格外提高。
在具有Cu合金芯材和形成于Cu合金芯材表面的Pd被覆层、进而根据需要在所述Pd被覆层表面具有包含Au和Pd的表皮合金层的本发明中，如果如后述那样进行扩散热处理、退火热处理，则芯材的Cu在被覆层、表皮合金层中通过晶界扩散等而扩散，能够使Cu到达线的最表面而使最表面存在Cu。因此，在本发明中，有时在接合线的最表面存在Cu。
如本发明那样在被覆有Pd的Cu接合线含有规定量的As、Te、Sn、Sb、Bi、Se的情况下，如果进而在接合线的最表面存在Cu，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。在被覆有Pd的Cu接合线含有规定量的As、Te、Sn、Sb、Bi、Se的情况下，如果进而在接合线的最表面存在Cu，则通过接合线中所含的As、Te、Sn、Sb、Bi、Se与Cu的相互作用，在FAB形成时会促进FAB表面的Pd浓化，球接合界面的Pd浓化会更显著地显现。由此，推定由Pd浓化层带来的抑制Cu和Al相互扩散的效果进一步增强，因Cl的作用而容易腐蚀的Cu9Al4的生成量减少，球接合部在高温高湿环境下的接合可靠性更进一步提高。
在利用俄歇电子能谱装置测定接合线的表面时，如果在表面检测出Cu，则可以说在最表面存在Cu，能够发挥上述效果。进而，如果相对于构成接合线最表面的金属元素，Cu浓度为1原子％以上，则能更切实地显现出所述高温高湿环境下的球接合部的接合可靠性的提高效果，因而优选。从使高温高湿环境下的球接合部的接合可靠性更进一步提高的观点出发，相对于构成接合线最表面的金属元素，Cu浓度更优选为1.5原子％以上，进一步优选为2原子％以上、2.5原子％以上、或3原子％以上。另外，从抑制线表面的抗氧化性和抗硫化性的降低、抑制接合线的使用寿命的减少的观点出发，相对于构成接合线最表面的金属元素，Cu浓度优选为50原子％以下，更优选为45原子％以下，进一步优选为40原子％以下、35原子％以下、或30原子％以下。
进而有下述倾向，即，由在表面存在Cu带来的上述效果，在芯材的Cu的纯度低的情况(例如3N以下)下呈现，特别是Cu的纯度为2N以下的情况下更显著地呈现。
由在接合线的最表面存在Cu带来的、球接合部在高温高湿环境下的接合可靠性提高的效果，是含有规定量的As、Te、Sn、Sb、Bi、Se的本发明的接合线所特有的。在不含有这些元素的一般的被覆有Pd的Cu接合线中，在球接合部的高温高湿环境下的接合可靠性方面得不到如本发明那样的提高效果。不仅如此，不含有这些元素的一般的被覆有Pd的Cu接合线，通过在接合线的最表面存在Cu，线表面的抗氧化性、抗硫化性降低，接合线的使用寿命降低。另外，较多地发生FAB的偏芯，球形状容易恶化。另外，可观察到楔接合性恶化的倾向。
由在接合线的最表面存在Cu带来的上述效果，在本发明的接合线中，Pd被覆层为最表面的情况、和包含Au和Pd的合金表皮层为最表面的情况下都同样地呈现出来。
在此，最表面是指在不实施溅射等的状态下，利用俄歇电子能谱装置测定到的接合线表面的区域。
另一方面，从得到良好的FAB形状、进而得到良好的球接合性的观点出发，线中的上述元素的浓度合计为100质量ppm以下，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。另外，在Sn、Sb浓度超过10质量ppm的情况、或者Bi浓度超过1质量ppm的情况下，FAB形状变得不良，因此通过设为Sn≤10质量ppm、Sb≤10质量ppm、Bi≤1质量ppm，能够更加改善FAB形状，因而优选。进而，通过将Se浓度设为4.9质量ppm以下，能够进一步改善FAB形状、楔接合性，因而更优选。
在使接合线中含有As、Te、Sn、Sb、Bi、Se时，不论采用使Cu芯材中含有这些元素的方法、使这些元素覆着于Cu芯材或线表面而含有的方法中的哪种方法都能够发挥上述本发明的效果。由于这些成分的添加量为极微量，因此添加方法的变化(variation)广，不论采用怎样的方法添加，只要含有指定的浓度范围的成分，就能够显现效果。
在本发明的接合线中，从更进一步改善车载用设备中所要求的高温高湿环境下的球接合部的接合可靠性的观点出发，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。
对上述接合线的Cu合金芯材、Pd被覆层的定义进行说明。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浓度低于50原子％的区域判定为Cu合金芯材。其根据是由于在Pd被覆层中如果Pd浓度为50原子％以上则可由Pd被覆层的结构得到特性的改善效果。Pd被覆层可以包含仅为Pd的层的区域、Pd和Cu在线的深度方向上具有浓度梯度的区域。在Pd被覆层中，具有该浓度梯度的区域形成的原因是有时通过制造工序中的热处理等，Pd和Cu的原子会扩散。在本发明中，浓度梯度是指在深度方向上的浓度变化的程度是每0.1μm为10mol％以上。进而，Pd被覆层可以包含不可避免的杂质。
本发明的接合线，可以在Pd被覆层的表面还具有包含Au和Pd的合金表皮层。由此，本发明的接合线能够进一步提高接合可靠性，并且能够改善楔接合性。
对上述接合线的包含Au和Pd的合金表皮层的定义进行说明。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浓度低于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，只要存在10原子％的Au，就判定是包含Au和Pd的合金表皮层。其根据是由于如果Au浓度为上述的浓度范围，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：包含Au和Pd在线的深度方向上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这两种情况。含有Au和Pd的合金表皮层优选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，具有该浓度梯度的区域形成的原因是由于通过制造工序中的热处理等，Au和Pd的原子扩散。进而，包含Au和Pd的合金表皮层可以含有不可避免的杂质和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被覆层反应从而提高包含Au和Pd的合金表皮层、Pd被覆层、Cu合金芯材之间的密合强度、抑制楔接合时的Pd被覆层、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改善楔接合性。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形成。
在作为半导体装置的外壳的塑模树脂(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，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℃左右不会游离，但如果在175℃以上(例如175℃～200℃)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170℃以上的高温环境下的球接合部的接合可靠性的方法，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中的球接合部的接合可靠性提高。
优选：本发明的接合线还包含选自Ni、Zn、Rh、In、Ir、Pt、Ga、Ge中的至少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％。通过本发明的接合线还含有这些元素，球接合部在高温环境下的接合可靠性之中，175℃以上的HTS中的成绩改善。从改善球接合部在高温环境下的接合可靠性(特别是175℃以上的HTS中的成绩)的观点出发，相对于线整体，所述元素的浓度分别优选为0.011质量％以上，更优选为0.020质量％以上，进一步优选为0.030质量％以上、0.050质量％以上、0.070质量％以上、0.090质量％以上、0.10质量％以上、0.15质量％以上、或0.20质量％以上。从得到良好的FAB形状的观点、抑制接合线的硬质化、抑制楔接合性的降低的观点出发，相对于线整体，所述元素的浓度分别优选为1.2质量％以下，更优选为1.1质量％以下。在本发明的接合线包含选自Ni、Zn、Rh、In、Ir、Pt、Ga、Ge中的多种元素的情况下，相对于线整体，这些元素的浓度合计优选为0.011～2.2质量％。从改善球接合部在高温环境下的接合可靠性(特别是175℃以上的HTS中的成绩)的观点出发，相对于线整体，所述元素的浓度合计优选为0.011质量％以上，更优选为0.020质量％以上，进一步优选为0.030质量％以上、0.050质量％以上、0.070质量％以上、0.090质量％以上、0.10质量％以上、0.15质量％以上、或0.20质量％以上。从得到良好的FAB形状的观点、抑制接合线的硬质化、抑制楔接合性的降低的观点出发，相对于线整体，所述元素的浓度合计优选为2.0质量％以下、1.8质量％以下、或1.6质量％以下。
另外，优选：在本发明的接合线中，Cu合金芯材包含Pd，Cu合金芯材中所含的Pd的浓度为0.05～1.2质量％。由此，能够得到与包含上述Ni、Zn、Rh、In、Ir、Pt、Ga、Ge的情况同样的效果。在本发明的接合线中，从改善球接合部在高温环境下的接合可靠性(特别是175℃以上的HTS中的成绩)的观点出发，Cu合金芯材中所含的Pd的浓度优选为0.05质量％以上，更优选为0.1质量％以上、0.2质量％以上、0.3质量％以上、0.4质量％以上、或0.5质量％以上。另外，从得到良好的FAB形状的观点、抑制接合线的硬质化、抑制楔接合性的降低的观点出发，Cu合金芯材中所含的Pd的浓度优选为1.2质量％以下，更优选为1.1质量％以下。本发明的接合线，通过以上述含量范围含有Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、Pd，能够提高环路形成性，即，能够减少在高密度安装中成为问题的倾斜(leaning)。这是因为，通过接合线含有这些元素，接合线的屈服强度提高，能够抑制接合线的变形的缘故。再者，作为从接合线制品求出Cu合金芯材中所含的Pd的浓度的方法，可举出例如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；一边通过溅射等从接合线的表面向深度方向削除，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(即向深度方向的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。关于浓度分析的方法在后面进行描述。
另外，通过以上述含量范围含有Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、Pd，本发明的接合线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，当本发明的接合线还含有规定量的Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、Pd时，具有接合部中的Cu9Al4金属间化合物的生成被进一步抑制的倾向。当还含有这些元素时，芯材的Cu与被覆层的Pd的界面张力更进一步降低，球接合界面的Pd浓化更显著地显现出。因此推定：由Pd浓化层带来的抑制Cu和Al相互扩散的效果进一步增强，其结果能够大幅度减少因Cl的作用而容易腐蚀的Cu9Al4的生成量，球接合部在高温高湿环境下的可靠性进一步提高。
优选：本发明的接合线还包含选自B、P、Mg、Ca、La中的至少1种以上的元素，相对于线整体，所述元素的浓度分别为1～100质量ppm。由此，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。可以认为这是由于通过添加上述元素，能够使球的结晶粒径微细化，能够抑制球的变形。从改善球接合部的压溃形状、即改善球接合部形状的圆形性的观点出发，相对于线整体，所述元素的浓度分别优选为1质量ppm以上，更优选为2质量ppm以上、3质量ppm以上、4质量ppm以上、或5质量ppm以上。从抑制球的硬质化、抑制球接合时的芯片损坏的观点出发，相对于线整体，所述元素的浓度分别优选为100质量ppm以下，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。在本发明的接合线包含选自B、P、Mg、Ca、La中的多种元素的情况下，相对于线整体，这些元素的浓度合计优选为1～100质量ppm。从改善球接合部的压溃形状、即改善球接合部形状的圆形性的观点出发，相对于线整体，所述元素的浓度合计优选为1质量ppm以上，更优选为2质量ppm以上、3质量ppm以上、4质量ppm以上、或5质量ppm以上。另外，从抑制球的硬质化、抑制球接合时的芯片损坏的观点出发，相对于线整体，所述元素的浓度合计优选为90质量ppm以下、80质量ppm以下、或70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分析装置，可以利用扫描型电子显微镜或透射型电子显微镜中所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。对于接合线中的As、Te、Sn、Sb、Bi、Se、Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、B、P、Mg、Ca、La等的微量分析，可以利用ICP发射光谱分析装置、ICP质量分析装置来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的浓度而检测出。
在本发明的优选的一实施方式中，在测定接合线表面的晶体取向而得到的测定结果中，相对于接合线长度方向角度差为15度以下的晶体取向＜111＞的存在比率以面积率计为30～100％。在该实施方式中，能够提高环路形成性、即提高在高密度安装中所要求的环路的直进性，并且能够降低环路高度的波动。这是由于如果表面晶体取向一致，则对横向变形的抗力增强，从而抑制横向的变形，因此能够抑制倾斜不良。从抑制倾斜不良的观点出发，上述晶体取向＜111＞的存在比率以面积率计更优选为35％以上，进一步优选为40％以上、45％以上、50％以上、或55％以上。
(制造方法)
接着，对本发明的实施方式涉及的接合线的制造方法进行说明。接合线是通过制造出用于芯材的Cu合金后，加工成细线状，形成Pd被覆层、Au层，进行热处理而得到的。也有时在形成Pd被覆层、Au层之后，进行再次拉丝和热处理。对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。
用于芯材的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。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，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，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，不需要形成Pd被覆层、Au层之后的清洗，不用担心洗涤时的表面污染等。
通过在形成Pd被覆层、Au层之后进行热处理，Pd被覆层的Pd向Au层中扩散，形成包含Au和Pd的合金表皮层。也可以从最初就覆着包含Au和Pd的合金表皮层，而不是在形成Au层之后通过热处理来形成包含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，在拉丝到最终线径为止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，在与Cu合金芯材的密合性提高这点上是有利的。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。
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，因此在能够抑制加工中的包含Au和Pd的合金表皮层、Pd被覆层的剥离、生产率提高这点上是有效的。为了防止从大气中混入O2，优选在真空气氛或Ar、N2等惰性气氛中进行热处理。
如前所述，通过调整对接合线实施的扩散热处理和/或退火热处理的条件，芯材的Cu通过晶界扩散等向Pd被覆层、包含Au和Pd的表皮合金层中扩散，能够使Cu到达接合线的最表面从而使最表面存在Cu。作为用于使最表面存在Cu的热处理，如上所述，可以使用用于形成包含Au和Pd的合金表皮层的热处理。在进行用于形成合金表皮层的热处理时，通过选择热处理温度和时间，能够使最表面存在Cu、或不使最表面存在Cu。进而，也能够将最表面的Cu浓度调整为规定的范围(例如，1～50原子％的范围)。也可以通过在形成合金表皮层时以外进行的热处理来使Cu向最表面扩散。
如前所述，在使接合线中含有As、Te、Sn、Sb、Bi、Se时，不论采用使Cu芯材中含有这些元素的方法、使这些元素覆着于Cu芯材或线表面而含有的方法中的哪种方法都能够发挥上述本发明的效果。对于Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、B、P、Mg、Ca、La也是同样的。
作为上述成分的添加方法，最简便的是预先添加到Cu合金芯材的起始材料中的方法。例如，将高纯度的铜和上述成分元素原料作为起始原料进行称量，然后将其在高真空下或氮气、氩气等惰性气氛下加热、熔化，从而制成添加有目标浓度范围的上述成分的锭，作为包含目标浓度的上述成分元素的起始材料。因此，在优选的一个实施方式中，本发明的接合线的Cu合金芯材包含选自As、Te、Sn、Sb、Bi、Se中的至少1种以上的元素，使得相对于线整体，上述元素的浓度总计为0.1～100质量ppm，且Sn≤10质量ppm、Sb≤10质量ppm、Bi≤1质量ppm。该浓度合计的优选的数值范围如前所述。在其他优选的一个实施方式中，本发明的接合线的Cu合金芯材包含选自Ni、Zn、Rh、In、Ir、Pt、Ga、Ge中的至少1种以上的元素，使得相对于线整体，上述元素的浓度合计为0.011～1.2质量％。该浓度的优选的数值范围如前所述。在优选的一个实施方式中，Cu合金芯材的Cu纯度为3N以下(优选为2N以下)。以往的被覆有Pd的Cu接合线，从接合性的观点出发，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。含有特定元素的本发明的接合线，特别适合于使用了如上述那样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。在其他优选的一个实施方式中，本发明的接合线的Cu合金芯材包含选自B、P、Mg、Ca、La中的至少1种以上的元素，使得相对于线整体，上述元素的浓度分别为1～100质量ppm。该浓度的优选的数值范围如前所述。
也可以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上述成分。在该情况下，可以在线制造工序的任一时间点编入该覆着步骤，可以反复编入多次。可以编入到多个工序中。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，也可以编入到各被覆工序中。作为覆着方法，可以从(1) (2)镀敷法(湿式)、(3)蒸镀法(干式)中选择。
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编入该覆着方法，可以反复编入多次。可以编入到多个工序中。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，也可以编入到各被覆工序中。
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，在镀层厚度薄的情况下可应用置换型镀敷，在镀层厚度厚的情况下可应用还原型镀敷，但是哪种都可以应用，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编入，可以反复编入多次。可以编入到多个工序中。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，也可以编入到各被覆工序中。
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，存在目标元素的添加速度慢的问题，但是上述成分元素的添加浓度比较低，因此它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编入，可以反复编入多次。可以编入到多个工序中。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，也可以编入到各被覆工序中。
使测定接合线表面的晶体取向时所得到的、相对于接合线长度方向角度差为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被覆层形成之后或形成Pd被覆层和Au表皮层之后的加工率，来使线表面上的具有方向性的织构(在拉丝方向上晶体取向一致的织构)发达。具体而言，通过使Pd被覆层形成之后或形成Pd被覆层和Au表皮层之后的加工率为90％以上，能够使测定接合线表面的晶体取向时所得到的、相对于接合线长度方向角度差为15度以下的晶体取向＜111＞的存在比率以面积率计为30％以上。在此，用“加工率(％)＝(加工前的线截面积-加工后的线截面积)/加工前的线截面积×100”表示。
在测定线表面的晶体取向时，优选采用电子背散射衍射方法(EBSD；ElectronBackscattered Diffraction)。EBSD法具有能够观察观察面的晶体取向，能够图示在相邻的测定点之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，也能够比较简便且高精度地观察晶体取向。
本发明并不被上述实施方式限定，可以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使用纯度为99.99质量％以上、且余量由不可避免的杂质构成的Cu。As、Te、Sn、Sb、Bi、Se、Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、Pd、B、P、Mg、Ca、La使用纯度为99质量％以上、且余量由不可避免的杂质构成的材料。调合作为向芯材添加的元素的As、Te、Sn、Sb、Bi、Se、Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、Pd、B、P、Mg、Ca、La，以使得线或芯材的组成成为目标组成。关于As、Te、Sn、Sb、Bi、Se、Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、Pd、B、P、Mg、Ca、La的添加，可以是采用单质来进行调合，但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，可以预先制作包含添加元素的Cu母合金，再进行调合以使得成为目标添加量。
芯材的Cu合金是通过下述过程来制造的，即，向加工成直径为φ3～6mm的圆柱形的碳坩埚中装填原料，使用高频炉在真空中或N2、Ar气体等惰性气氛中加热至1090～1300℃而使其熔化后，进行炉冷。对所得到的φ3～6mm的合金进行拉拔加工，加工至φ0.9～1.2mm之后，使用拉模连续地进行拉丝加工等，由此制作出φ300～600μm的线。在拉丝中使用市售的润滑液，拉丝速度设为20～150m/分钟。为了除去线表面的氧化膜，利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1～15μm厚度的Pd被覆层。进而，一部分线在Pd被覆层上形成了0.05～1.5μm厚度的包含Au和Pd的合金表皮层。关于Pd被覆层、包含Au和Pd的合金表皮层的形成，采用了电解镀敷法。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而加工到直径20μm。加工后一边流通N2或Ar气体一边进行热处理以使得最终断裂伸长率成为约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Ar气体一边进行。线的送给速度为20～200m/分钟，热处理温度为200～600℃，热处理时间设为0.2～1.0秒。
通过调整Pd被覆层形成之后或形成Pd被覆层和包含Au和Pd的合金表皮层之后的加工率，来调整了测定接合线表面的晶体取向时所得到的、相对于接合线长度方向角度差为15度以下的晶体取向＜111＞的存在比率(面积率)。
作为Pd被覆层、包含Au和Pd的合金表皮层的浓度分析，是一边采用溅射等从接合线的表面向深度方向切除一边实施俄歇电子能谱分析。从所得到的深度方向的浓度廓线，求出了Pd被覆层厚度、包含Au和Pd的合金表皮层厚度。
关于下述表1-5中记载的本发明例93～98，芯材使用了纯度为99.99质量％以上的Cu，通过在线制造工序的途中，采用电镀法使As、Te、Sn、Sb、Bi、Se覆着于线表面，从而含有这些元素。因此，在表1-5中设有“成分添加方法”栏，关于本发明例99～109，记载为“被覆层”。关于表1-1～表1-4的全部、以及表1-5的“成分添加方法”栏中记载为“芯材”的例子，都是使芯材中含有As、Te、Sn、Sb、Bi、Se。
关于下述表1-5中记载的本发明例99～109、比较例13、14，是使接合线的最表面存在Cu。因此，在表1-5中设有“线表面Cu浓度”栏，记载了利用俄歇电子能谱装置测定接合线的表面而得到的结果。通过选择接合线的热处理温度和时间，而使最表面含有规定浓度的Cu。关于表1-1～表1-4的全部、以及表1-5的“线表面Cu浓度”栏为空栏的例子，都设为不使最表面存在Cu的热处理条件，即使采用俄歇电子能谱装置也没有检测出Cu。
将采用上述的步骤制作出的各样品的构成示于表1-1～表1-5。
(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，采用了电子背散射衍射法(EBSD；Electron Backscattered Diffraction)。EBSD法具有能够观察观察面的晶体取向，并图示在相邻的测定点之间的晶体取向的角度差这一特征，即使是如接合线那样的细线，也能够比较简便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而实施EBSD法的情况下需要加以注意。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，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＜111＞取向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)确定的总晶体取向作为母集团，算出相对于接合线长度方向角度差为15度以下的晶体取向＜111＞的存在比率(面积率)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密封而制作的。球是一边以0.4～0.6L/分钟的流量流通N2+5％H2气体一边形成的，其大小设为φ33～34μm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5V的偏电压。球接合部的接合寿命设为每隔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×，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○，如果为288小时以上且低于384小时则判断为优异而标记◎，如果为384小时以上则判断为特别优异而标记◎◎，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隔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要求改善而标记△，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○，如果为3000小时以上则判断为特别优异而标记◎。
球形成性(FAB形状)的评价，是采取进行接合之前的球进行观察，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。关于球形成性的评价，在发生了5个以上的不良的情况下，判断为有问题，记为×符号；如果不良为3～4个，则能够实用但稍有问题，记为△符号；在不良为1～2个的情况下判断为无问题，记为○符号；在没有发生不良的情况下，判断为优异，记为◎符号，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，利用接合部的剥离发生频度来判定的。引线框使用了施加了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，记为×符号；如果不良为6～10个，则能够实用但稍有问题，记为△符号；在不良为1～5个的情况下，判断为无问题，记为○符号；在没有发生不良的情况下，判断为优异，记为◎符号，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了接合的球接合部，根据其圆球性来判定。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、变形具有异向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，发生了6个以上的不良的情况下判断为有问题而标记×，如果不良为4～5个则判断为能够实用但稍有问题而标记△，在不良为1～3个的情况下判断为没有问题而标记○，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◎，都记载于表1的“压溃形状”栏中。
[倾斜]
对评价用的引线框，以环路长度5mm、环路高度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×，如果不良为4～6个则判断为能够实用但稍有问题而标记△，在不良为1～3个的情况下判断为没有问题而标记○，在没有发生不良的情况下判断为优异而标记◎，都记载于表1的“倾斜”栏中。
(评价结果)
本发明例1～109涉及的接合线，具有Cu合金芯材和形成于Cu合金芯材表面的Pd被覆层，接合线含有选自As、Te、Sn、Sb、Bi、Se中的至少1种以上的元素，相对于线整体，上述元素的浓度合计为0.1～100质量ppm。由此确认到：本发明例1～109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试验中得到了球接合部可靠性。
另一方面，比较例1、2、4～6、11～14，上述元素浓度偏离出下限，在HAST试验中没有得到球接合部可靠性。比较例3、7～10，上述元素浓度偏离出上限，FAB形状不良。比较例1、3、5～10，＜111＞晶体取向的面积率脱离本发明的合适范围，倾斜为△。
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，确认到：通过使包含Au和Pd的合金表皮层的层厚为0.0005～0.050μm，可得到优异的楔接合性。
关于本发明例27～92、100、102、104～109，确认到：通过接合线还含有选自Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、Pd中的至少1种以上的元素，相对于线整体，Pd以外的上述元素的浓度分别为0.011～1.2质量％，Cu合金芯材中所含的Pd的浓度为0.05～1.2质量％，从而HTS评价中的球接合部高温可靠性良好。
本发明例28～92的一部分，通过接合线还含有选自B、P、Mg、Ca、La中的至少1种以上的元素，相对于线整体，上述元素的浓度分别为1～100质量ppm，从而FAB形状良好，并且楔接合性良好。
本发明例99～109，线含有As、Te、Sn、Sb、Bi、Se，并且在线的最表面存在Cu。由此，本发明例99、101、103、105、106、108、109，HAST评价结果为◎◎或◎，观察到了使最表面存在Cu的效果。本发明例100、102、104、107，进而线的Cu纯度低为2N以下，HAST评价结果全都为◎◎，非常良好。另一方面，这些本发明例，在楔接合性上观察到少许的降低。
比较例13、14，线不含As、Te、Sn、Sb、Bi、Se，另一方面，在线的最表面存在Cu，因此，不仅HAST评价是不良，HTS评价结果也是不良，FAB形状、压溃形状也为不良，而且楔接合性、倾斜也恶化了。

Claims (25)

1.一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，其特征在于，
所述接合线含有选自As、Te中的至少1种元素，相对于线整体，所述选自As、Te中的至少1种元素的浓度合计为100质量ppm以下，
相对于线整体，As元素的浓度为6.2质量ppm以上，或者，相对于线整体，Te元素的浓度大于2质量ppm。
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，相对于线整体，选自As、Te中的至少1种元素的浓度合计为80质量ppm以下。
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，相对于线整体，As元素的浓度为10质量ppm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，相对于线整体，As元素的浓度为12质量ppm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，相对于线整体，Te元素的浓度为2.5质量ppm以上。
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，相对于线整体，Te元素的浓度为3质量ppm以上。
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，作为所述接合线中所含的、相对于线整体的浓度合计为100质量ppm以下的元素，还包含选自Sn、Sb、Bi、Se中的至少1种元素，并且，在包含Sn的情况下，Sn≤10质量ppm，在包含Sb的情况下，Sb≤10质量ppm，在包含Bi的情况下，Bi≤1质量ppm。
8.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0.015～0.150μm。
9.根据权利要求8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。
10.根据权利要求8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0.03μm以上。
11.根据权利要求8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0.100μm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0.0005～0.050μm。
14.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0.001μm以上。
15.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0.002μm以上。
16.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0.030μm以下。
17.根据权利要求1所述的半导体装置用接合线，其特征在于，所述接合线还含有选自Ni、Zn、Rh、In、Ir、Pt、Ga、Ge中的至少1种元素，相对于线整体，所述选自Ni、Zn、Rh、In、Ir、Pt、Ga、Ge中的至少1种元素的浓度分别为0.011～1.2质量％。
18.根据权利要求17所述的半导体装置用接合线，其特征在于，相对于线整体，所述选自Ni、Zn、Rh、In、Ir、Pt、Ga、Ge中的至少1种元素的浓度分别为0.030质量％以上。
19.根据权利要求17所述的半导体装置用接合线，其特征在于，相对于线整体，所述选自Ni、Zn、Rh、In、Ir、Pt、Ga、Ge中的至少1种元素的浓度分别为0.050质量％以上。
20.根据权利要求17所述的半导体装置用接合线，其特征在于，相对于线整体，所述选自Ni、Zn、Rh、In、Ir、Pt、Ga、Ge中的至少1种元素的浓度分别为0.070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合金芯材含有Pd，所述Cu合金芯材中所含的Pd的浓度为0.05～1.2质量％。
22.根据权利要求1所述的半导体装置用接合线，其特征在于，所述接合线还含有选自B、P、Mg、Ca、La中的至少1种元素，相对于线整体，所述选自B、P、Mg、Ca、La中的至少1种元素的浓度分别为1～100质量ppm。
23.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而得到的测定结果中，相对于所述接合线长度方向角度差为15度以下的晶体取向＜111＞的存在比率以面积率计为30～100％。
24.根据权利要求23所述的半导体装置用接合线，其特征在于，所述晶体取向＜111＞的存在比率为50％以上。
25.根据权利要求1～24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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