CN101689517B - 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
CN101689517B
CN101689517B CN2008800230881A CN200880023088A CN101689517B CN 101689517 B CN101689517 B CN 101689517B CN 2008800230881 A CN2008800230881 A CN 2008800230881A CN 200880023088 A CN200880023088 A CN 200880023088A CN 101689517 B CN101689517 B CN 101689517B
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Prior art keywords
copper
line
concentration
thickness
closing line
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CN101689517A (zh
Inventor
宇野智裕
木村圭一
寺嶋晋一
山田隆
西林景仁
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Nippon Micrometal Corp
Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Materials Co Ltd
Nippon Micrometal Corp
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Abstract

本发明的目的是提供材料费廉价且球接合性、热循环试验或软熔试验的可靠性优异、保管寿命也良好的也适应于窄间距用细线化的铜系接合线。本发明的半导体装置用接合线是具有以铜为主成分的芯材、和设置在所述芯材上的含有成分和组成的某一方或两方与所述芯材不同的金属M和铜的外层的接合线，其特征在于，所述外层的厚度为0.021～0.12μm。

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与线路板(引线框、基板、带等)的配线而使用的半导体装置用接合线及其接合线的连接方法。 
背景技术
现在，作为将半导体元件上的电极与外部端子之间进行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20～50μm左右的细线(接合线)。接合线的接合一般是超声波并用热压接方式，可使用通用接合装置、使接合线在其内部通过而用于连接的毛细管夹具等。在由电弧热输入将线端头加热熔融，借助于表面张力使之形成球后，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，然后，通过超声波压接使线直接接合在外部引线侧。 
近年，半导体组装的结构、材料、连接技术等在急速地多样化，例如，组装结构除了使用现行的引线框的QFP(Quad Flat Packaging)以外，使用基板、聚酰亚胺带等的BGA(Ball Grid Array)、CSP(Chip Scale Packaging)等的新形态也已实用化，需求进一步提高了环性、接合性、大批量生产使用性等的接合线。即使是这样的接合线的连接技术，除了现在主流的球/楔接合以外，在适合于窄间距化的楔/楔接合方面，为了在2处的部位直接将接合线接合，要求细线的接合性提高。 
成为接合线的接合对方的材质也在多样化，硅基板上的配线、电极材料，除了以往的铝合金以外，适合于更微细配线的铜也已实用化。另外，在引线框上施加Ag镀层、Pd镀层等，或在树脂基板、带等上施加铜配线，并在其上施加金等贵金属元素及其合金的膜的情形较多。要求相应于这样的种种的接合对方来提高线的接合性、接合部可靠性。 
迄今为止接合线的材料主要使用高纯度4N系(纯度＞99.99质量％)的金。然而，由于金价格高，因此期望得到材料费价廉的其他种类金属的接合线。 
在来自接合线技术的要求上，重要的是在进行球形成时形成圆球性良好的球，在其球部与电极的接合部得到充分的接合强度。另外，为了对应于接合温度的低温化、接合线的细线化等，也需要在线路板上的配线部楔形连接接合线的部位的接合强度、抗拉强度等。 
在高速注入高粘性的热固化环氧树脂的树脂封装工序中，接合线发生变形而与相邻线接触成为问题，而且，窄间距化、长线化、细线化也在发展中，要求尽管少也能够抑制树脂封装时的线变形。随着线强度的增加，虽然能够某种程度地控制这样的变形，但难以控制环，或不能解决接合时的强度降低等的问题，难以实用化。 
此外，连接接合线而组装出的半导体元件实际使用时的长期可靠性也很重要。尤其是装载在汽车上的半导体元件等，为了确保严格的安全性，要求在高温、高湿、热循环等苛刻的环境下的高的可靠性。即使是在这样的以往没有的苛刻的环境下，连接接合线的接合部也不劣化而必须维持高的可靠性。 
作为满足上述要求的线的特性，期望在接合工序中的环控制容易，而且对电极部、引线部的接合性也提高，抑制接合以后的树脂封装工序中的过剩的线变形，而且满足连接部的长期可靠性和在苛刻环境下的接合部稳定性等的综合特性。 
为了材料费廉价、导电性优异、球接合、楔接合等也提高，以铜为材料的接合线被开发，专利文献1等曾进行了公开。然而，对于铜接合线而言，由于线表面的氧化而导致接合强度降低、或树脂封装时容易发生线表面的腐蚀等，这些情况成为问题。这些问题也成为铜接合线的实用化未进行的原因。 
铜系接合线，在将线端头熔融形成球部时，为了抑制氧化，一边对线 端头喷射气体一边进行接合。现在，作为形成铜系接合线的球时的气氛气体，一般使用含有5体积％的氢的氮气。专利文献2公开了在将铜线与铜或铜合金引线框连接时，在5体积％H2+N2的气氛下进行连接的方法。另外，非专利文献1报道了：在形成铜接合线的球时，5体积％H2+N2气能够抑制球表面的氧化，因此相比于N2气是优选的。现在，作为在使用铜系接合线时所使用的气体，5体积％H2+N2气体已被标准化。 
作为防止铜接合线表面氧化的方法，专利文献3提出了使用金、银、铂、钯、镍、钴、铬、钛等贵金属、耐腐蚀性金属被覆了铜的接合线。另外，从球形成性、防止镀液劣化等的观点考虑，专利文献4提出了呈下述结构的接合线，所述结构具有以铜为主成分的芯材、在该芯材上形成的由铜以外的金属构成的异种金属层、和在该异种金属层上形成的由熔点比铜高的耐氧化性金属构成的被覆层。专利文献5提出了具有以铜为主成分的芯材、和在该芯材上具有含有成分或组成的一方或两方与芯材不同的金属和铜的外皮层，且该外皮层为厚度0.001～0.02μm的薄膜的接合线。 
专利文献1：日本特开昭61-99645号公报 
专利文献2：日本特开昭63-24660号公报 
专利文献3：日本特开昭62-97360号公报 
专利文献4：日本特开2004-64033号公报 
专利文献5：日本特开2007-12776号公报 
非专利文献1：“Copper Ball Bonding for Fine Pitch，High I/O Devices”：P.Devlin，Lee Levine，38th International Symposium on Microelectronics(2005)，P.320-324。 
发明内容
作为以往的单层结构的铜系接合线(是非被覆的铜系接合线，有时在线表面形成有薄的自然氧化膜层等。以下记为单层铜线。)的实用上的问题，可举出线表面容易氧化、容易引起接合强度的降低等。因此，作为防止铜接合线表面氧化的手段，可在线表面被覆贵金属或耐氧化性的金属。 
考虑半导体组装的高密度化、小型化、薄型化等的要求，本发明者们进行评价的结果判明：由与铜不同的金属被覆了铜接合线表面的结构的现有多层铜线(相对于将非被覆的铜线称为单层铜线，将由1层构成的被覆层被覆了的上述铜线作为多层铜线。以下记为现有多层铜线)，残留许多的如后所述的实用上的问题。 
在现有多层铜线的端头形成了球的场合，形成偏离了圆球的扁平球、或在球内部残留未熔融的线、或发生气泡等都成为问题。当在电极上接合这种不正常的球部时，成为引起接合强度降低、芯片损伤等的问题的原因。 
由现有多层铜线实施复杂的环控制时，担心下述情况：由于在被覆层与铜的界面发生剥离等，环形状变得不稳定；窄间距连接时相邻线发生电短路。 
在由现有多层铜线形成了球的场合，与使用单层铜线或现在主流的金接合线的场合相比，容易引起球接合部的形状不良和接合强度的降低等成为实用上的问题。具体的不良事例，有时形成偏离圆球的扁平球、或发生球相对于线倾斜地形成的偏芯等、或在球内部残留未熔融的线、或生成气泡(气孔)成为问题。当在电极上接合这种不正常的球部时，由于偏离线中心从而球产生变形的偏芯变形、作为偏离圆形的形状不良而产生椭圆变形、花瓣变形等，成为引起接合部从电极面剥出、接合强度降低、芯片损伤、生产管理上的不良情况等问题的原因。这种初期接合的不良，也有时诱发上述的长期可靠性降低。 
作业解决与现有多层铜线的球接合有关的不良情况的方法，专利文献4公开了外皮层的厚度为0.001～0.02μm。也记载了：在此的外皮层也包含浓度梯度的区域，外皮层与芯材的界面的金属M的浓度为10mol％以上。据本发明者们的评价，通过这样地将外皮层的厚度薄膜化，可观察到上述的球接合部的问题部分地得到改善，但在装载到汽车上的半导体元件等的用途中在新的环境下使用的场合，效果不一定充分，但已确认外皮层的厚度越减薄则扁平球的发生频度越增加。另外，还确认了通过薄膜化，线的楔接合的提高并不充分。而且已确认后述的长期可靠性产生问题。 
作为在新的苛刻环境下的评价，具体地进行了如下的试验，即连接了单层铜线的半导体的可靠性试验，其中，在热循环试验(TCT试验：Temperature Cycle Test)中，在楔接合部附近发生线断裂、其不良频度比金接合线高在最近开始成为问题。另外，在软熔(焊料软熔)工序中也担心同样地发生铜系线的接合部断裂的不良情况。这也是一种由热疲劳造成的线断裂，最近环境对策中急速实用化的无铅(Pb)焊料，由于熔点比现有的锡/铅焊料高，因此热应变开始成为问题。这些线断裂的原因是由于作为构成半导体的部件的封装树脂、引线框、硅芯片等的热膨胀差而导致的不良情况。为了适用于半导体工作时放热量增大，使用环境高温化、温度变化增大等，对于铜系接合线而言，改善在TCT试验中的线断裂今后变得更重要。 
本发明者们已确认：现有多层铜线，在TCT试验中的不良频度比单层铜线减少一些，另一方面，与金接合线进行比较，仍较差。例如即使是现有多层铜线，在上述的外皮层为厚度0.001～0.02μm的薄膜的场合，在TCT试验中的改善效果并不充分。 
单层铜线由于表面进行氧化，因此在大气中的保管寿命短成为使用中的问题。以往的金接合线，在使用前或使用途中可保管一个月左右。单层铜线在大气中只保管数日就发生楔接合性降低、球形状变得不稳定的问题。这成为使铜系接合线的作业性降低的主要原因。 
现有多层铜线，可期待比单层铜线延缓氧化的效果，但其效果根据外层或线表面附近的组成、结构、厚度等而大大不同。现有多层铜线的结构的合适化很重要。为了确保与金接合线同等的操作性，例如必须保障即使是在大气中保管2个月左右后楔接合性、环形状等也不劣化。这与单层铜线的保管寿命相比，必须提高数十倍的寿命，对于以铜为主体的材料，要求相当苛刻的条件。 
在与氧化相关的问题中，抑制形成球时的氧化也是铜线的重要课题。以往的单层铜线，在球形成用气体中，5体积％H2+N2气大多被作为标准气体使用。由于使用该5体积％H2+N2气，在工厂内供给该气体需要设置 专用配管的费用，混合气的操作费用也比较高。若以包含这些制造成本的总成本进行比较，则即使线材料使用铜，与金接合线相比甚至有成本优势少的情况。这样的气体费用也成为铜系接合线未普及的主要原因之一。另外，由于竟含有5体积％的氢气，因此安全管理变得严格，还担心作业性降低等。 
若只是纯N2气，则费用削减效果也大幅度提高，安全管理上的障碍也降低等等，对使用者来说优点大。然而，在大量生产中使用以往的单层铜线时，由于判断为使用困难，因此纯N2气并没有被实用化。迄今为止的现有多层铜线的场合也使用5体积％H2+N2气，这容易确保综合地稳定的生产率，若使用纯N2气，则存在发生上述的偏芯球、或球尺寸变得不稳定等的问题。若即使使用纯N2气也能够制造可得到高生产率、可靠性的现有多层铜线，则延缓铜系接合线普及的障碍降低，可期待加速实用化。 
本发明的目的是解决如上所述的现有技术的问题，提供除了以往的基本性能以外还谋求提高球接合性、减少热循环试验中的不良、改善线保管寿命的以铜为主体的半导体装置用接合线和上述接合线的线接合方法。 
本发明者们为了解决上述问题而潜心研究铜系接合线的结果发现，具有外层，并且以特定的外层厚度形成为特定的厚度范围是有效的。而且发现在效果上，控制外层和芯材等的组成、结构等较有效。 
本发明是基于上述见解而完成的研究，其要旨为以下的构成。 
权利要求1涉及的接合线，其特征在于，是具有以铜为主成分的芯材、和设置在该芯材上的含有成分和组成的某一方或两方与芯材不同的金属M和铜的外层的半导体装置用接合线，上述外层的厚度为0.021～0.12μm。 
另外，权利要求2涉及的接合线，其特征在于，在权利要求1中，构成上述外层的金属M以选自Au、Pd、Pt和Rh中的一种以上的元素为主成分。 
另外，权利要求3涉及的接合线，其特征在于，在权利要求1或2中，以上述铜为主成分的芯材含有选自P、B、Ir、Zr、Bi、Ti、Au、Ag、Sn和稀土类元素之中的一种以上的元素，该元素在线整体中所占的浓度总计 为0.0001～0.03mol％的范围。 
另外，权利要求4涉及的接合线，其特征在于，在权利要求1～3的任一项中，上述外层含有选自Bi、P、Se和Tl中的一种以上的元素，在上述外层的表面的该元素浓度总计为0.01～5mol％的范围。 
另外，权利要求5涉及的接合线，其特征在于，在权利要求1～4的任一项中，在上述外层与上述芯材之间具有扩散层。 
另外，权利要求6涉及的接合线，其特征在于，在权利要求1～5的任一项中，以相对于金属元素与碳、氧和氮的各元素的总计的浓度进行比较，上述外层的最表面的碳浓度为15～80mol％的范围，从表面向深度方向碳浓度为5～80mol％的范围的区域的厚度为0.0004～0.01μm。 
另外，权利要求7涉及的接合线，其特征在于，在权利要求1～6的任一项中，以相对于金属元素与碳、氧和氮的各元素的总计的浓度进行比较，上述外层的最表面的氧浓度为1～25mol％的范围，在该外层的表面氧浓度为0.2～25mol％的范围的区域的厚度为0.0005～0.007μm的范围。 
另外，权利要求8涉及的接合线，其特征在于，在权利要求1～7中，上述金属M相对于金属系元素的总计的浓度为10mol％以上的区域的厚度为0.03～0.2μm。 
另外，权利要求9涉及的接合线，其特征在于，在权利要求1～8的任一项中，在上述外层内，上述金属M相对于金属系元素的总计的浓度总计为90mol％以上的区域的厚度为0.004～0.07μm。 
另外，权利要求10涉及的接合线，其特征在于，在权利要求1～9的任一项中，在上述外层内，金属M相对于金属系元素的总计的浓度总计为96mol％以上的区域的厚度为0.002～0.06μm。 
另外，权利要求11涉及的接合线，其特征在于，在权利要求1～10的任一项中，在上述外层的最表面相对于金属系元素的总计的铜浓度为45mol％以下。 
另外，权利要求12涉及的接合线，其特征在于，在权利要求1～11的任一项中，在上述外层的表面相对于金属系元素的总计的铜浓度为1～ 30mol％的范围的区域的厚度为0.0005～0.008μm。 
另外，权利要求13涉及的接合线，其特征在于，在权利要求1～12的任一项中，铜以外的上述金属M在线整体中所占的浓度总计为0.05～3mol％的范围。 
另外，权利要求14涉及的线接合方法，是连接权利要求1～13的任一项所述的接合线的线接合方法，其特征在于，一边向线端头或其周围喷射纯度为99.95体积％以上的氮气一边产生电弧放电从而形成球部，将该球部接合。 
利用本发明的接合线能够减少在热循环试验中的不良。并且，能够提高球接合性。另外能够改善线保管寿命，其结果能够提供材料费价廉、球接合性、热循环试验或软熔试验的可靠性优异的保管寿命良好的也适应于窄间距用细线化等的铜系接合线。 
具体实施方式
对于接合线，研究由以铜为主成分的芯材和含有金属M的被覆层构成的接合线的结果判明：通过在线的表面附近含有金属M，能够期待楔接合性的提高等，但球的不稳定形成、在热循环试验或软熔工序中的楔接合部的断裂成为新的问题，并且保管寿命的改善效果不充分等等。因此，研讨对窄间距的小球接合、在热疲劳下的楔接合部的高可靠化、保管寿命的延长等的新的组装要求的对应，也能够与大量生产适应性的进一步提高、进而削减组装工艺费用的廉价气体下的连接稳定性的改善等对应的铜系接合线的结果发现：具有外层，且以特定的外层厚度形成为特定的厚度范围较有效。而且发现在效果上控制外层和芯材等的组成、结构等是有效的。 
即，优选是：具有以铜为主成分的芯材、和设置于该芯材上的含有成分和组成的一方或两方与芯材不同的金属M和铜的外层，且上述外层的厚度为0.021～0.12μm的接合线。只要是该接合线，则能得到在热循环试验(TCT试验)或软熔工序中抑制在楔接合部的断线的较高的效果。所谓在此的主成分是指铜浓度相对于铜与金属M的浓度的总计的比率为50％以 上。 
在TCT试验中通过重复温度的升降，产生起因于封装树脂、引线框、硅芯片的热膨胀差的热应变，在原来在强度上弱的楔接合部的附近诱发断裂或损伤。在接合线大大地变形的楔接合部，由于截面积缩小和加工时的晶格缺陷的导入等，一般地强度比线单质低下。而且，铜线由于楔接合界面的接合强度与金接合线相比相当地低，因此判明当重复进行拉伸和压缩时容易发生在该接合部附近的剥离、断线等。由于这样的因素，在铜系接合线的楔接合部，在TCT试验中的不良的发生成为比金接合线大的问题。 
只要外层的厚度是0.021～0.12μm的范围则在TCT试验中的楔接合部的可靠性提高的主要原因，认为是由于构成外层的金属M对与接合对方的粘附性的提高有效地作用的缘故。只要厚度是0.021μm以上，则外层在接合界面大致稳定而带来强度增加，因此在TCT试验中可得到高的可靠性，经验性地把握了如果厚度不到0.021μm则不能得到TCT试验中的充分的可靠性。其根据认为是由于在楔接合时外层与线同样大地受到变形，因此在残留在接合界面的外层薄的区域或不存在的区域等局部地发生，不能够确保能够耐受TCT试验的充分的界面强度的缘故。即使在这样的接合界面外层的存在不均匀，在很多的情况下对初期的接合强度的提高有效地作用，而在TCT试验的热过程中，拉伸、压缩方向的应变复杂地参与楔接合，因此不能够确保充分的耐性。另一方面，外层厚度超过0.12μm时，由于球部的表面平滑性的降低、高尔夫棒状的偏芯球的不良发生，因此球的形状、尺寸变得不稳定。只要是0.12μm以下，则能够满足难以兼具的球形成性和楔接合性二者。 
如果优选外层的厚度是0.025～0.095μm的范围，则能够减少在苛刻的热过程条件下的TCT试验中的不良，获得高的可靠性。如果更优选是0.03～0.85μm的范围，则能够进一步提高在苛刻的热过程条件下的TCT试验中的可靠性。 
TCT试验中的楔接合部的损伤也与引线框的材料关联，在引线框为铜合金的场合，热应变量大而容易产生损伤，而在为热膨胀系数小的42合金 的场合基本上不发生不良。如果考虑廉价的铜系引线框的使用量今后更加增加、面向要求高温可靠性的车载用半导体的用途的铜系接合线的应用等，则TCT试验中的铜系接合线的可靠性虽然报道事例尚少，但是是最近热门的课题。 
在只有TCT试验的判定中，担心以下情况：试样制作烦杂，评价时间长；根据接合线以外的引线框、封装树脂等的材料的选定情况，评价结果也不同；等等。因此作为提高评价效率的简便试验法，本发明者们考察了楔接合部的拉伸试验(以下称为楔接合的剥离试验)，已确认可得到与TCT试验同样的相关性。这是对沿楔接合部的正上方向提拉接合线的通常的剥离试验进行改良，将拉伸方向、速度等合适化的测定法。在该试验中的断裂延性高的接合线和连接试样，已确认了在TCT试验中直到发生不良为止的循环数多的倾向。楔接合的剥离试验，是能够定量地评价在TCT试验中不能得到的楔接合部的机械特性的有效的方法。 
所谓成为外层的主成分的金属M是铜以外的金属，优选是对接合线的接合性的改善有效果，还对防止铜的氧化有效的金属。例如，可举出Au、Pd、Pt、Rh、Ag、W、Mo、Cr和Ni等。其中，作为金属M，优选是Au、Pd、Pt和Rh中的至少一种金属。Au具有在与封装树脂的粘附性、对电极的接合性等方面实绩多、质量管理也容易等的优点。Pd和Pt比较容易使球形状稳定化，在TCT试验中的接合可靠性也能得到高的改善效果。Pd材料费比较便宜，与铜的粘附性也良好，因此作为外层的利用价值进一步提高。其中，在外层的主成分是Pd，该外层的厚度为0.021～0.12μ的场合，上述的TCT试验中的接合可靠性的改善效果显著，而且具有优异的线接合性、操作性等，因此可确认对在细线的条件下的批量生产合格率的提高也有利。 
芯材的主成分是铜，添加合金元素，根据铜合金中的成分、组成来改善特性。上述以铜为主成分的芯材，含有选自P、B、Ir、Zr、Bi、Ti、Au、Ag、Sn和稀土类元素中的一种以上的添加元素，通过在接合线整体中所占的该添加元素浓度总计为0.0001～0.03mol％的范围，TCT试验中的不良 率降低，楔接合的剥离试验中的断裂延伸率增加等的效果增大。尤其是在楔接合的剥离试验中，改善效果高。作为这些合金元素的作用，可认为通过在线制造、楔接合中控制芯材的加工和在再结晶中的织构的形成，从而对楔接合部附近的接合线的断裂延伸率的增加有效地作用。另外，在构成外层的金属M为Au、Pd、Pt和Rh的场合，通过球熔融，芯材中的该添加元素与金属M协同作用，因此具有使球变形时的圆度进一步提高的效果。对于这样的添加效果，与添加到不形成外层的以往的铜系接合线中的场合比较，发现外层与该添加元素并用的场合效果得到促进。如果该添加元素的浓度不到0.0001mol％，则有时上述的改善效果变小。当超过0.03mol％时，有时在球表面发生折皱状的凹坑，球形状变得不稳定。其中，在外层的金属M为Pd时，可确认可增大上述的芯材的合金化效果，能够与细线、粗线的线径无关系地稳定地确保剥离试验中的改善效果，进而提高球变形的圆度等。 
通过上述外层含有选自Bi、P、Se和Tl中的一种以上的元素，且在外层的表面的该元素浓度总计为0.01～5mol％的范围，能够使线表面的伤痕减少，结果毛细管的堵塞减少，可提高毛细管的更换寿命。这可认为含有上述元素的外层，膜质致密，表面硬化等产生影响。如果在外层的表面的该元素浓度不到0.01mol％，则有时上述的改善效果变小，当超过5mol％时，接合线与毛细管内壁的滑动阻力增加，有时环形状变得不稳定。 
对于本申请的线截面结构，基本上可区分成外层/芯材或外层/扩散层/芯材。在此，外层的边界定为构成外层的金属M的检测浓度的总计为50mol％的部位。因此，所谓本发明中所说的外层，是从构成外层的金属M的检测浓度的总计为50mol％部位开始的表面，即，构成外层的金属M的检测浓度的总计为50mol％以上的部位。其根据是因为发现上述检测浓度为50mol％以上的部位对被TCT试验、软熔耐性等高温环境下的接合界面的扩散现象所控制的线特性支配性地作用的缘故。虽然认为该浓度作为层边界浓度比较高，但是由于将50mol％以上的区域作为外层与线内部区别进行控制，因此不仅本发明的效果，而且对线综合特性的管理、整理也 起作用。对于这里的外层、扩散层中的浓度，使用将金属M和铜总计的浓度比率，使用表面附近的C、O、N、Cl、S等气体成分、非金属元素等除外而进行计算的浓度值。 
将外层与芯材的中间区作为扩散层，所谓扩散层是通过芯材的铜与外层的金属M相互扩散而形成的区域。本申请的扩散层的定义从性能等进行判断来看，为金属M的检测浓度的总计为10mol％以上、且不到50mol％的区域。这是因为在该浓度区，金属M的浓度低，外层与芯材两者起稍微不同的作用的缘故。更优选具有这样的扩散层的接合线。 
优选是下述的半导体装置用接合线：该接合线是在外层与芯材之间具有扩散层的接合线，具有设置在该芯材上的含有成分和组成的某一方或两方与芯材不同的金属M和铜的外层，上述外层的厚度为0.021～0.12μm，金属M的浓度为10mol％以上的区域的厚度为0.03～0.2μm。只要是该接合线，则初期的楔接合性进一步提高，而且更加提高在使用了无Pb的焊料的软熔工序中的楔接合部的可靠性，在此，所谓金属M的浓度为10mol％以上的区域，相当于将外层与扩散层合计的部位。 
在只是特定的厚度的外层时，有时难以同时地提高楔接合性和软熔特性，金属M的浓度为10mol％以上的区域的厚度，即，外层与扩散层合计的厚度起更重要的作用。可以认为这是因为在楔接合中由于接合线受到复杂的塑性变形，局部达到相当大的塑性变形量，因此不仅是外层，而且扩散层也在接合界面发挥功能的缘故。只要是该浓度区的厚度为0.03μm以上，则可以进一步减少铜系接合线在楔接合中经常成为问题的不粘不良(non-sticu failure)，也容易进一步提高批量生产合格率。另外，作为该浓度区的厚度为0.03μm以上的另外的效果，即使在软熔温度高的场合热应变增大，也能够进一步降低楔接合部的裂纹、断裂等。在软熔工序中，由于半导体元件暴露在以短时间温度上升和下降中，因此在被急热和急冷的楔接合部，要求与TCT试验稍微不同的可靠性。如果该浓度区的厚度超过0.2μm，则接合线的弯曲刚性增高，有时环形状的偏差增加。在此，如果使扩散层成为金属M的浓度为10mol％以上且不到50mol％的区域，则作 为只扩散层分离的厚度优选0.009～0.18μm的范围。如果优选金属M的浓度为10mol％以上的区域的厚度为0.04μm以上，则即使是在180℃以下的低温下线连接的试样，对提高软熔耐性也有效。其原因是在180℃以下的低温连接时，有时难以在初期得到充分的接合强度，与通常的250℃左右下的线连接相比，有时楔接合的耐性降低。 
更优选是下述的半导体装置用接合线：该接合线是在外层与芯材之间具有扩散层的接合线，具有设置在该芯材上的含有成分和组成的某一方或两方与芯材不同的金属M和铜的外层，上述外层的厚度为0.021～0.12μm，在外层内，金属M的浓度总计为90mol％以上的区域的厚度为0.004～0.07μm。只要是该接合线，则除了TCT试验中的接合性提高以外，还能够大幅度地提高将接合线放置在大气中时的保管寿命。 
作为保管事例，已确认该接合线即使在常温下在大气中放置30天以上也不发生线接合工序中的不粘不良。这与以往的单层铜线通过5天左右的大气放置而发生不粘不良比较，保管寿命也大幅度延长，若使用超过保管寿命的铜系接合线，则有时发生球接合或楔接合的不粘不良，或与其相关接合装置因错误而停止成为问题。在能够延长大气放置的优点上，可期待接合线的品质保障期间延长、通过线制品的卷数增加实用时的线更换频度改善等作业性提高。 
从在金属M的合计浓度为90mol％以上的区域，铜浓度不到10mol％来看，在上述区域中在外层内成为金属M的高浓度区。发现该高浓度区具有阻碍氧侵入内部、铜沿表面方向扩散的阻隔功能，更加提高该功能的浓度是90mol％以上。只要该浓度区的厚度为0.004μm以上，则该阻隔功能有效地发挥作用从而抑制氧化、硫化，由此能够在常温下将保管寿命提高到30天以上。另一方面当超过0.07μm时，由于球表面的凹凸增加或硬化，球接合部的形状劣化。如果优选该高浓度区是0.008～0.06μm的范围，则能够将保管寿命延长到更长时间。如果进一步优选该高浓度区是0.01～0.05μn的范围，则进一步提高保管寿命，能够抑制长期保管后的接合线的楔接合的不良。 
作为起因于线的氧化的问题，在组装工序中在高温下加速进行氧化成为问题。由于在接合工序中装载有半导体元件的台被加热到150～300℃，因此通过形成环而连接的线也被放置于高温下。端子数超过500针的多针系LSI，被连接的线的高温放置有时超过数十秒钟。也有时在接合后进一步在大气中放置数天，在初期进行氧化在品质上也不利。由于高温放置而导致线表面被氧化会成为使可靠性劣化、难以进行品质管理等不良原因。例如，由于线表面的氧化，封装树脂与线表面的粘附性发生变化，水分容易渗入其界面，有可能长期可靠性降低。 
只要是上述外层的厚度为0.021～0.12μm，在外层内金属M的浓度总计为96mol％以上的区域的厚度为0.002～0.06μm的半导体装置用接合线，则在线接合工序中被连接了的线对抑制装载在加热台上的期间的氧化有效。已发现仅管理外层的厚度难以降低高温氧化，外层的组成、尤其是金属M的浓度相当高的区域对抑制氧化发挥作用。如果在外层内有金属M为96mol％以上的高浓度的区域，则即使高温加热也可得到同时地抑制氧进入内部和铜在线表面扩散的高的效果。如果金属M为96mol％以上的区域的厚度为0.002μm以上，则能够抑制在台上的加热时间下的氧化，另一方面，如果该厚度超过0.06μm，则熔融、凝固了的球部的圆度变得不稳定，有可能生产率降低。如果优选金属M为96mol％以上的高浓度的区域的厚度为0.004～0.05μm，则即使用于功率系IC等的线径35μm以上的粗线，也能够得到抑制高温氧化的高的效果。该高纯度区域的位置不一定必须是最表面，通过存在于外层内就可得到效果。优选该高纯度区域位于外层的表面附近。具体地讲，通过位于比外层厚度的一半更靠表面的一侧，能够得到抑制高温氧化的显著的效果。 
为了适应于多样化的LSI组装结构、连接技术，即使是具有如上述的外层厚度0.021～0.12μm那样比较厚的外层的接合线，有时也要求滑动性、表面刮削、放送性(线抽出性)等的性能进一步提高。若毛细管的贯通孔与线表面的滑动性降低，则成为环形状产生偏差的原因。对于表面刮削，在环控制的过程中在线表面发生伤痕、刮削等，成为毛细管的孔堵塞的原 因，刮屑与相邻的线接触时会引起电短路不良，成为实用上的故障。若放送性降低，则从线轴放送线时引起线折曲等的变形，使其连接出的环形状的直线性降低，在放送性的降低显著的场合也有时线断裂、装置停止。通过进一步改善这样的表面性能，对窄间距连接、多段连接(Multi-tierbonding)等要求严格的环控制的最新的组装要求也可确保稳定的批量生产性。 
已发现为了改善这些滑动性、表面刮削、放送性等起因于线表面的特性，形成碳、氧等非金属元素在外层的表面浓化了的区域是有效的。只调整构成芯材、外层的金属系元素的成分、组成时难以应对。已确认这样的表面的非金属元素的影响与外层厚度也有关联。只要是上述的0.021～0.12μm的厚度的外层，则碳、氧等非金属元素的控制有效地发挥作用。虽然详细机理尚不清楚，但认为在厚度不到0.021μm的薄的场合，芯材的机械特性等的影响大，另一方面认为在0.12μm以上的相当厚时，外层的强度、金属组织等支配性地发挥作用，难以通过外层表面的非金属元素的控制来提高性能。 
限于碳、氧的浓度计算，将铜、金属M等的金属系元素与碳、氧和氮的各元素等的非金属系元素总计来算出浓度。与此相对，对于上述的外层、芯板等的金属M、铜的浓度计算，使用将表面附近的碳、氧等的非金属元素除外，只将金属系元素总计而计算出的浓度值。通过灵活使用这样的2种的浓度计算法，能够更明确与使用性能的关联性。碳、氧在表面浓化，其区域只存在于从最表面沿深度方向0.01μm以内的表面附近，在外层内部和芯材中不含有碳、氧。碳、氧造成影响的特性主要限于滑动性、表面刮削、退卷性等。已确认与作为上述的外层、芯材的主要构成的金属M、铜、一部分的合金化元素等相关地进行了说明的大部分的特性(TCT试验、软熔耐性、楔接合性、球接合性等)受金属M、铜的金属系元素的成分、组成支配，碳、氧的直接影响小。 
如果是上述外层的厚度为0.021～0.12μm，外层的最表面的碳浓度为15～80mol％的范围，从表面沿深度方向碳浓度为5～80mol％的区域(以 下记为碳浓化区)的厚度为0.0004～0.01μm的半导体装置用接合线，则能够提高线表面的滑动性使环形状稳定化、或抑制线的损伤、刮削。最表面的碳浓度的限定理由，是因为如果为15mol％以上则有助于滑动性改善的缘故。而超过80mol％时，线的接合性降低，有时连续接合性降低成为问题。碳浓度为5～80mol％的范围的碳浓化区，通过至少一部分作为有机膜存在，可期待具有使毛细管的贯通孔与线表面的摩擦降低的充分的缓冲功能。只要碳浓化区的厚度为0.0004μm以上，则能够得到提高滑动性的缓冲功能，当超过0.01μm时连续接合性降低，尤其是线径20μm以下的细线，不粘不良(Non-stick failure)成为问题。如果优选碳浓化区的厚度是0.0007～0.007μm的范围，则由于提高滑动性抑制线的损伤、刮削的效果、和扩大在楔接合中的制造极限的效果等，能够加快接合速度，更有助于提高生产率。 
作为上述的控制外层的表面碳浓度的方法，例如在线制造工序中，根据需要对拉线工序中的润滑液、拉线速度、洗涤和干燥时间等的调整、或退火工序中的防锈剂、润滑剂等的涂布、浸渍条件、洗涤和干澡等的调整进行选择、合适化是有效的。其中，在拉线、退火等工序的途中或最后在线表面涂布防锈剂、表面活性剂等是有效的。通过将涂布剂的条件(溶剂、溶媒、浓度、温度、浸渍时间和速度)、洗涤条件(温度、浸渍时间)、干燥条件(气体、温度、风量)等合适化，能够控制上述的外层表面的碳浓化区。对于防锈剂，根据外层的成分、组成等选择较多，但例如也可以利用三唑、苯并三唑、咪唑或它们的衍生物等铜用防锈剂。另外，在拉线工序的液槽内添加的润滑剂也有许多种，但在成分构成方面基本上是油、皂、表面活性剂等的混合，将那些主成分的选定、配合比例等合适化很重要。从工序的追加、修正的观点进行分类的话，为了进行再现性、精度高的浓度管理，可分成新追加以表面碳浓度的控制为着重点的工序的情况、和为了使制造成本优先而不增加工序而通过现行的线制造工序的一些改进、条件变更等来应对的情况。任一种方法都通过综合地将工艺合适化而能够形成所希望的碳浓度的区域。 
线的放送性是基本的使用性能之一，在多层铜线中的支配因素残留很多不明之处。通常以一边对200～3000m的长的线施加某种程度的张力，一边卷绕在线轴上的状态出厂。将该线轴安装在接合装置上，一边使线轴旋转来放出线，一边进行连续接合。若放送性降低，则在形成环时发生圆弧状的翘曲不良、塑性变形成“ㄑ”字形的弯折不良等，环的直线性降低、或线断裂等成为问题。相反地若使放送性优先而使卷绕张力过弱，则发生卷崩开，发生卷绕在线轴上的线全体不能使用的另外的问题。 
作为使多层铜线的放送性降低的主要的因素，卷绕在线轴上的状态的线的咬入、卷崩开、线粘着等成为原因的情况较多。发现为了抑制这样的不良，控制外层的表面氧浓度有效。通过控制外层的表面氧化，在卷取于线轴上的线的外层接触的界面附近，一边抑制外层彼此的金属接合，一边微妙地调整线的滑动、摩擦等，由此放送性提高。另一方面，当氧化膜太过于牢固时，存在损害作为多层铜线优点的接合性的危险性，因此氧的浓度、膜厚等的管理很重要。例如，即使只形成单一的氧化膜也难以综合性地改善放送性，将最表面和深度方向的氧浓度合适化有效。此外，由于根据多层铜线的外层厚度，表面氧的合适条件发生变化，因此综合性地将外层厚度、氧的表面浓度、深度方向的氧浓度等合适化很重要。 
如果是上述外层的厚度为0.021～0.12μm，外层的最表面的氧浓度为1～25mol％的范围，在该外层的表面氧浓度(以下记为氧浓化区)为0.2～25mol％的范围的区域的厚度为0.0005～0.007μm的范围的半导体装置用接合线，则能够同时地实现线从线轴放出的放送性的提高、环直线性的提高和线接合性的提高等。这是因为当最表面的氧浓度不到1mol％时，引起外层彼此的粘接不良(烧接不良)，当超过25mol％时细线等的接合性降低的缘故。这是因为氧浓度为0.2～25mol％氧浓化区，对抑制外层彼此的接触部的咬入、粘接不良等有效地发挥作用，如果氧浓化区不到0.0005μm，则提高放送性的效果小，当超过0.007μm时接合性降低的缘故。 
作为上述的控制外层的表面氧浓度的方法，调整在线制造工序中的外层的氧化有效。例如，根据需要将拉线工序中的洗涤、干燥等的调整、退 火工序中的热过程、气氛气体的流量、退火时间、冷却时的气氛等的调整进行选择、合适化是有效的。此外，通过将退火工序与拉线工序组合，综合性地将工艺合适化，对形成所希望的氧浓度的区域有利。其中，在退火工序中将加热条件(炉内温度分布、牵引速度)、冷却条件(气体种类、流量、保护性)等合适化对控制外层表面的氧浓化区有效。此外，通过按拉线→退火→拉线→退火的顺序进行，将上述的退火条件、拉线条件的合适组合，能够提高深度方向的氧浓度分布控制中的再现性。从工序的追加、修正的观点进行分类时，为了进行再现性、精度高的浓度管理，可分成新追加以控制表面的氧浓度为着重点的工序的情况、和为了使制造成本优先而不增加工序，通过现行的线制造工序的一些改进、条件变更等来应对的情况。 
只要是构成外层的铜以外的金属M在线整体中所占的浓度总计为0.05～3mol％的范围的接合线，则除了提高TCT试验中的长期可靠性以外，通过抑制球部的硬化，对接合强度的增加、向球外周扫出铝电极材料(铝飞射不良)的降低、芯片损伤的降低等有利。铜系接合线端头的球部硬度高，变形时的加工硬化也高，因此，在接合时铝电极被扫出，诱发与相邻的电极的短路不良，或对接合部正下方的芯片造成损伤，这些往往成为实用上的课题。通过抑制金属M在线整体中所占的浓度使其低，即使金属M在球中固溶，也能够抑制硬化的程度。在此，只要是金属M在线整体中所占的浓度总计为3mol％以下，则通过抑制球的硬化，便能够得到降低铝扫出的效果，进一步优选是2mol％以下，这样进一步抑制扫出，可得到良好的接合。当不到0.05mol％时，有时难以在批量生产工序中稳定地实现将上述的外层的厚度保持在0.021～0.12μm的范围。 
更优选是下述的半导体装置用接合线：该接合线是在外层与芯材之间具有扩散层的接合线，具有设置在该芯材上的含有成分和组成的某一方或两方与芯材不同的金属M和铜的外层，上述外层的厚度为0.021～0.12μm，外层的最表面的铜浓度为0.5～45mol％。只要是该接合线，则能够得到减少球接合部的偏芯不良的充分的效果。由此，即使是球接合部间隔窄的窄 间距连接，也能够进一步提高批量生产率。所谓在此的最表面的浓度，是表面深度为2nm左右的区域中的浓度。 
当外层的最表面的铜浓度超过45mol％时，由于电弧放电的分布、扩展变得不均匀，只将接合线的一侧优先地熔融，由此有时在球形成时引起芯偏移。对于电弧放电，最表面的影响大，铜与金属M由于电子放出等不同，因此有时球形状根据线最表面的铜浓度而发生变化。如果该铜浓度为0.5mol％以上，则能够得到减少偏芯不良的效果。优选最表面的铜浓度为0.5～30mol％，若这样则即使是球直径相对于线径为2倍以下的小球也能够更有效地抑制异形、花瓣状等的不良形状。进一步优选最表面的铜浓度为0.5～20mol％，若这样则由于小球的圆球度进一步提高，因此对窄间距连接有利。 
通过为上述外层的厚度为0.021～0.12μm，在上述外层的表面铜浓度为1～30mol％的范围的区域(以下记为铜浓化区)的厚度为0.0005～0.008μm的半导体装置用接合线，在球形成时能够抑制偏芯，并且能够减少球头部的缩孔和球表面的微小凹凸等，通过球压接形状的稳定化和球接合强度的偏差降低，能够提高大量生产率。可认为通过在线表面具有铜浓化了的区域，具有电弧放电的扩展稳定化，并且以短时间促进球部熔融、凝固中的铜与金属M的混合的效果。只要是在上述外层的表面铜浓度为1～30mol％的范围的区域，便可期待上述效果。铜浓度为该浓度范围的区域的厚度为0.0005μm以上，能够得到抑制缩孔和微小凹凸等的效果。当超过0.008μm时发生芯偏移，有球形状稍微不稳定的可能性。 
对于该铜浓化区的构成，也可以含有金属M与铜的合金或铜氧化物。此外，在形成了后者的铜氧化物的场合，由于该铜浓化区与上述的氧浓化区的至少一部分重复，因此能够得到兼具抑制球形成时的缩孔和微小凹凸和改善放送性的高的效果。该铜浓化区的位置不一定必须是最表面，通过存在于外层内也能得到效果。优选该铜浓化区位于外层的表面附近，具体地讲，通过位于比外层厚度的1/4更靠表面的一侧，能够得到抑制高温氧化的显著的效果。例如，通过在外层的最表面形成碳浓化区，在其下层形 成该铜浓化区，能够得到兼具良好的球形成和抑制线表面的损伤、刮削的高的效果。 
对于外层、扩散层、芯材等的浓度分析，采用溅射等从接合线的表面一边沿深度方向挖下一边进行分析的方法、或线截面的线分析或点分析有效。前者在外层薄的情况下有效，而当变厚时过于花费测定时间。后者的在截面的分析，在外层厚的情况下有效，另外，在整个截面的浓度分布、在数个地方的再现性的确认等比较容易是其优点，但在外层薄的情况下精度降低。也能够将接合线斜向研磨使扩散层的厚度扩大来进行测定。在截面，线分析比较简便，但在欲提高分析的精度时，使线分析的分析间隔窄，或进行集中在界面附近的想要观察的区域的点分析也有效。这些浓度分析所使用的解析装置，可以利用电子束显微分析法(EPMA)、能量分散型X射线分析法(EDX)、俄歇光谱分析法(AES)、透射电镜(TEM)等。尤其是AES法，由于空间分辨率高，因此对最表面的薄的区域的浓度分析有效。另外，对于平均组成的调查等，也可从表面部阶段性地溶解于酸等中，由在该溶液中含有的浓度求出溶解部位的组成；等等。 
在外层中除了浓度梯度以外，还含有以铜和金属M为主体的金属间化合物相也有效。即，由以铜为主体的芯材和金属M的外层构成，在外层的内部含有具有铜的浓度梯度的部位和具有铜和金属M的金属间化合物一层以上的接合线，由于金属间化合物相使接合线的强度、弹性模量等的机械特性增加，因此对环直线性的提高、封装时的线流的抑制等更有效。 
在制造本发明的接合线时，需要在芯材的表面形成外层的工序、控制外层、扩散层、芯材等的结构的加工·热处理工序。首先，为控制外层、芯材的组成、厚度，在形成上述的外层的工序中，在形成外层的初期阶段的厚度、组成的管理首先是重要的。 
在铜的芯材的表面形成外层的方法，有镀覆法、蒸镀法、熔融法等。镀覆法可以采用电解镀法、无电解镀法的某一种方法制造。被称作薄镀、触击镀的电解镀，镀覆速度快，与基底的粘附性也良好。无电解镀使用的溶液被分类成置换型和还原型，在膜薄的场合只利用置换型镀覆便足够， 而在形成厚的膜的场合，在置换型镀覆之后阶段性地实施还原型镀覆有效。对于无电解法，装置等简便，且容易，但比电解法需要时间。 
蒸镀法可以利用溅射法、离子镀法、真空蒸镀等的物理吸附以及等离子CVD等的化学吸附。任一种方法都是干式，不需要膜形成后的洗涤，不担心洗涤时的表面污染等。 
对于实施镀覆或蒸镀的阶段，按目标的线径形成金属M的膜的方法、和在粗径的芯材上形成膜后，进行多次拉线直到目标线径的方法的任一种方法都有效。前者的在最终径下的膜形成，制造、品质管理等简便，后者的膜形成与拉线的组合对提高膜与芯材的粘附性有利。作为各形成法的具体例，可以采用在电解镀溶液中一边连续地对线牵引一边在目标的线径的铜线上进行膜形成的方法，或者将粗的铜线浸渍在电解或无电解的镀浴中形成膜后，将线拉伸达到最终径的方法等。 
在形成外层后的加工工序中，根据目的对辊轧制、模锻、模拉线等进行选择、灵活运用。根据加工速度、压下率或模减面率等控制加工组织、位错、晶界的缺陷等也对外层的结构、粘附性等带来影响。 
在热处理工序中，在外层与芯材的界面助长铜与金属M的相互扩散。根据目的实施1次或多次热处理是有效的。为了以外层和扩散层的结构得到所希望的膜厚、组成，要求以严格的精度控制％级的浓度、nm级的膜厚等的制造技术。热处理工序被分类成刚形成膜后的退火、在加工途中的退火、在最终径下的最终退火，对它们进行选择、灵活运用很重要。 
只单纯地加热了线的话，并不能够控制外层的表面和内部的铜的分布。即使原样地使用在通常的线制造中使用的在最终线径下的消加工应力退火，由于外层与芯材的粘附性降低而导致环控制变得不稳定，或难以控制线纵向的外层的均质性、在线截面中的外层、扩散层等的分布。因此，热处理的定时、温度、速度、时间等的控制很重要。 
通过将加工与热处理组合而控制扩散的进行度，能够控制所希望的膜厚、组成、结构。由于热处理之前的加工过程关系到外层与芯材的界面的组织等，因此也对在热处理下的扩散行为带来影响。根据在哪个加工阶段 进行热处理，最终的外皮层、扩散层的组成、厚度等发生变化。在一例中，在加工途中实施中间退火后，对线进行拉线，在最终径下实施最终退火的工序中制作的接合线，与不实施中间退火的工序进行比较，已确认外层、扩散层的组织、浓度梯度发生变化。 
作为热处理法，通过对线一边连续地进行牵引一边进行热处理，而且不使作为一般的热处理的炉内温度为一定，而在炉内形成温度倾斜(温度梯度)，容易批量生产具有作为本发明特征的外层和芯材的接合线。具体的事例有局部地导入温度倾斜的方法、在炉内使温度变化的方法等。在抑制接合线的表面氧化的场合，一边向炉内通入N2、Ar等的惰性气体一边进行加热也有效。 
对于温度倾斜的方式，在炉入口附近的正的温度倾斜(相对于线的牵引方向温度上升)、在稳定温度区域、炉出口附近的负的温度倾斜(相对于线的牵引方向温度下降)等在多个区域使温度带有倾斜是有效果的。由此，在炉入口附近不产生外层与芯材的剥离等而使粘附性提高，在稳定温度区域促进铜与金属的扩散，形成所希望的浓度梯度，此外，通过在炉出口附近抑制在表面上的铜的过剩的氧化，能够改善所得的接合线的接合性、环控制性等。为了得到这样的效果，优选将在出入口的温度梯度设置为10℃/cm以上。 
对于使温度变化的方法，将炉内分割成多个区域，通过在各区域进行不同的温度控制来形成温度的分布也有效。例如，将炉内分割成3个区以上，独立地进行温度控制，通过使炉的两端比中央部的温度低，可得到与温度倾斜的场合同样的改善效果。另外，为了抑制接合线的表面氧化，通过使炉出口侧成为铜氧化速度慢的低温，能够得到楔接合部的接合强度的上升。 
另外，熔融法是使外层或芯材的某一方熔融而铸入的方法，具有下述优点：通过以1～50mm左右的粗径连接外层和芯材后进行拉线生产率优异；外层的合金成分设计比镀覆、蒸镀法容易，强度、接合性等的特性改善也容易；等等。在具体的工序中，可分成在预先制作的芯材的周围铸入熔融 了的金属M形成外层的方法、和通过使用预先制作的金属M的中空圆柱，并向其中央部铸入熔融了的铜或铜合金从而形成芯材的方法。优选在后者的中空圆柱的内部铸入铜的芯材，此法能够在外层中容易地稳定形成铜的浓度梯度等。在此，只要使预先制作的外层中含有少量的铜，则容易的控制在外层表面的铜浓度。另外，熔融法也能够省去用于使铜向外层扩散的热处理作业，但通过为了调整外层内的铜的分布而实施热处理估计更加改善特性。 
此外，利用这样的熔融金属的场合，也能够通过连铸来制造芯材和外层的至少一方。采用该连铸法，与上述的铸入方法相比，工序被简化，而且也能够使线径细、提高生产率。 
作为本发明涉及的具有外层和芯材的现有多层铜线的接合方法，形成球时的保护气体即使使用纯N2气，也可确认有良好的球接合性。即，是使用具有以铜为主成分的芯材、和设置在该芯材上的含有成分和组成的某一方或两方与芯材不同的金属M和铜的外层，上述外层的厚度为0.021～0.12μm的接合线，一边向线端头或其周围喷射纯度为99.95体积％以上的N2气一边产生电弧放电来形成球部，将该球部进行接合的方法。该接合方法通过使用廉价的纯N2气体代替作为标准气体的5体积％H2+N2气，能够降低操作费用，促进铜系接合线的实用化。 
用于本发明涉及的多层铜接合线的球形成的保护气体，即使使用标准的5体积％H2+N2气也能够得到良好的接合特性，此外即使使用纯N2气体也能够得到同样的良好的特性。在外层的厚度为0.021μm以下的较薄的场合，使用纯N2气时发心偏芯球是个问题。另外，当超过0.12μm时，使用纯N2气时在球表面发生褶皱状的突起或微小孔等，难以得到平滑的球表面。当这样的外层的厚度为0.021～0.12μm时，使用纯N2气体时的球形成性良好，这也成为选定该厚度的一个优点。在上述外层的厚度的范围中若为0.035μm以上，则圆球度进一步提高，纯N2的纯度为99.95体积％以上的理由是在工业上能够廉价地得到的N2气的保证浓度的范围，是能够形成良好的球的缘故。 
通常认为通过混入5体积％H2气，对电弧放电的稳定化、抑制熔融的球的氧化有效果。与其相对，在纯N2气体中，将接合线熔融形成球时，在单层铜线或即使是现有多层铜线但外层薄的场合，电弧放电变得不稳定，或由于铜的氧化优先地进行，因此球形状变得不稳定。另一方面认为如果外层是本发明的范围，则即使是在纯N2气体中，表面附近的金属M也能够使电弧放电稳定化，以及通过外层优先地熔融起保护的作用能够抑制球的氧化。根据接合条件，也已确认出在纯N2气下接合的球的接合强度比5体积％H2+N2气的情况高的情况。 
此外，在纯N2气体下的球形成，除了上述的外层的厚度以外，也有根据构成外层的金属M的种类而变动的倾向。其中，在构成外层的金属M以选自Au、Pb、Pt和Rh中的一种以上为主成分的场合，已确认在使用纯N2气体的球形成中，圆球度的提高、球尺寸的稳定化比较容易。 
实施例 
以下对实施例进行说明。 
作为接合线的原材料，芯材所使用的铜使用了纯度为约99.99质量％以上的高纯度的材料，外层的Au、Pt、Pd、Rh和Ag的材料准备了纯度为99.9质量％以上的原料。 
将细到某个线径的铜系接合线作为芯材，为了在该线表面形成不同的金属M的层，进行电解镀法、无电解镀法、蒸镀法、熔融法等，为了形成浓度梯度也实施了热处理。利用了：以最终的线径形成外层的情形、和以某个线径形成外层后再通过拉线加工弄细到最终线径的方法。电解镀液、无电解镀液使用按半导体用途市售的镀液，蒸镀采用溅射法。预先准备直径约30～2500μm的接合线，通过蒸镀、镀覆等对该线表面被覆，拉线达到最终径的15～50μm，最后实施了热处理使得消除加工应力、且延伸率值为5～20％的范围。拉线速度在5～100m/分的范围而进行。根据需要在拉线液中加入少量的市售的铜拉线用润滑剂。根据需要在摸拉线到线径为30～100μm后，实施扩散热处理后再实施拉线加工。 
在利用熔融法的场合，采用了在预选制作的芯材的周围铸入熔融了的金属的方法、和在预先制作的中空圆柱的中央部铸入熔融了的铜或铜合金的方法。其后，进行铸造、辊轧制、模拉线等的加工和热处理，制造出接合线。 
对于本发明例的线的热处理，一边连续地对线牵引一边进行加热。利用了局部地导入温度倾斜的方式、在炉内使温度变化的方式等。例如，利用了按照能够将炉内温度分三部分进行控制的方式进行改造了的热处理炉。炉内温度设定在200～700℃的范围，线牵引速度在10～500mm/分的范围进行调整。在温度分布的一例中，从线的插入口朝向出口获得高温→中温→低温、或中温→高温→低温的分布，各加热长度也进行了管理。线牵引速度等也与温度分布一起进行了合适化。为了抑制氧化，热处理的气氛也利用了N2、Ar等的惰性气体。气体流量在0.0002～0.004m3/分的范围进行调节，也用于炉内的温度控制。作为进行热处理的定时，按对拉线后的铜线实施热处理后形成镀层的情况、和进行接线后和镀层形成后的2次热处理的情况的2种类准备了试样。 
在控制外层表面的氧浓化区的场合，将热处理工序中加热条件(炉内温度分布、牵引速度)、冷却条件(气体种类、流量、保护性)等进行了合适化。例如，为了控制在炉内和出入口附近的气氛，气体流入口设为2处以上，通过调整各注入口的位置、流入方向、气体流量等，来调节炉内的氧分压、温度分布等。气体流量在0.0002～0.004m3/分的范围进行调节。此外，由于有时在炉的出口附近的余热区域线被加热而被氧化，因此也注意了加热区之后的冷却区中的气氛控制。 
在控制外层表面的碳浓化区的场合，在上述的热处理后连续地进行浸渍在少量含有防锈剂、表面活性剂等的溶液中的涂布、洗涤、干燥。在此的涂布液，使用了在蒸馏水中混合数种的总计为1～20体积％的浓度范围的防锈剂、表面活性剂的溶液。洗涤利用了以蒸馏水为基本，根据需要加有一部分的醇的液体。在需要提高除去过剩地附着的涂布剂的效果的场合，将涂布液加热到30～50℃的温度范围。对于干燥，是对线喷射干燥空气或 N2气。另外，根据需要在拉线直到线径30～100μm后，实施上述的热处理和涂布工序后，再实施拉线加工，以最终线径再次实施了热处理和涂布工序。作为该二次的热处理所带来的效果之一，最表面的碳浓度被抑制为较低，并且对控制深度方向的碳浓度的分布有效。 
线表面的膜厚测定采用AES深度分析，晶界的浓化等元素分布的观察采用AES、EPMA等进行面分析、线分析。采用AES深度分析时，一边由Ar离子进行溅射一边沿深度方向进行测定，深度的单位按SiO2换算而表示出。接合线中的金属M的浓度采用ICP分析、ICP质量分析等进行测定。 
接合线的连接使用市售的自动焊线机进行球/楔接合。由电弧放电在线端头制作球，将该球接合在硅基板上的电极膜上，在引线端子上楔接合线的另一端。为抑制球形成时氧化而使用的保护气体使用了标准的5体积％H2+N2气、和纯N2气。除了球形状的评价以外，基本上利用了作为标准气体的5体积％H2+N2气。气体流量在0.0003～0.005m3/分的范围调节。 
作为接合对方，使用了作为硅基板上的电极膜材料的、厚度1μm的Al合金膜(Al-1质量％Si-0.5质量％Cu膜、Al-0.5质量％Cu膜)。另一方面，楔接合的对方使用了表面镀Ag(厚度：1～4μm)的引线框、或镀Au层/镀Ni层/Cu的电极结构的树脂基板。 
有关球形成性，为抑制氧化而使用的保护气体为标准的5体积％H2-N2气(纯度5N以上，高压气瓶供给)、和纯N2气(纯度4N，集中配管供给)，在该情形下进行了比较。初期球形状的评价中，球径/线径的比例为1.7～2.0的范围。由扫描型电子显微镜(SEM)或光学显微镜观察接合前的球30个，对表面性状、形状、尺寸精度等进行了评价。若发生异常形状的球为3个以上则为不良并且需要改善，用×符号表示，在异常形状的球为2个以下，但表面的凹凸大或球位置相对于接合线的芯偏移显著的个数为5个以上的场合，用△符号表示，芯偏移为2～4个、其程度也小，判断为没有实用上的大问题时用○符号表示，芯偏移不到1个且尺寸精度也良好的场合，球形成性良好，用◎符号表示，标记于表2中的「球形成性」栏中。 
压接球部的接合形状的判定，观察500个被接合了的球，对形状的圆度、尺寸精度等进行评价，按形成初期球径/线径的比例为1.9～2.2的通常尺寸的球的情况、和形成比例为1.5～1.7的范围的小径球的情况这2种来分别进行评价。若偏离了圆的各向异性、花瓣状等不良球形状为5个以上则判断为不良，用×符号表示，若不良球形状为2～4个，根据需要希望改善用△符号表示，若不良球形状为1个以下则为良好，用○符号表示，标记于表2中的「球接合形状」的栏中。 
关于初期球的缩孔和压接球部的微小凹凸的评价，通过20个的初期球的端头部的SEM观察、和300个被接合了的球部来综合性地进行评价。缩孔为8个以上或发生了微小凹凸的接合部为30个以上的任一方都判断为不良，用×符号表示，如果缩孔为2～7个或发生了微小凹凸的球接合部为4～29个的范围，则根据需要希望改善，因此用△符号表示，如果未看到缩孔、且发生了微小凹凸的球接合部为3个以下则为良好，用○符号表示，标记于表2中的「缩孔、表面凹凸」的栏中。 
球接合部的Al扫出的评价，对球接合部进行SEM观察，采用两种方法确认，即，对在超声波施加方向评价Al扫出的程度的直接观察、和采用剪切试验除去球部，由残留在其剪切断裂面的Al电极的变形、残留量等判断Al电极的扫出的间接观察。基本上没有Al扫出，与金接合线的情况同等且良好的场合用◎符号表示，有扫出但变形量小的场合用○符号表示，扫出增多但基本上没有问题的场合用△符号表示，扫出显著因此需要改善的场合用×符号表示，标记于表2中的「Al膜的扫出」的栏中。 
对于接合工序中的环形状稳定性，使用线长为2mm的通用跨距和0.5mm的跨距2种来制作梯形环，利用投影机观察各500根的接合线，判断接合线的直线性、环高度的偏差等。线长度短、为0.5mm的梯形环的形成，为了避免对芯片端的接触，需要更严格的环控制。线长度为2mm、直线性、环高度等的不良为5根以上的场合，判断为有问题，用×符号表示，在线长度为0.5mm、不良为2～4根、以及线长度为0.5mm、不良为5根以上的场合，判断为需要改善，用△符号表示，在线长度为2mm、不良为 1根以下、以及线长度为2mm、不良为2～4根的场合，环形状比较良好，用○符号表示，在线长度为0.5mm、不良为1根以下的场合，判断为环形状稳定，用◎符号表示，标记于表2中的「环稳定性」的栏中。不良原因之一可设想到芯材与外周部的界面的粘附性不充分、在截面中的特性偏差等。 
线表面的损伤(伤痕)、刮削等的评价，通过被接合了的环的外观观察进行调查。形成线径25μm、线长2mm、环高度的目标值为200μm左右的梯形环，利用投影机观察1000根的线。损伤观察是以环的上侧为中心，刮削观察是对环整体评价尺寸为30μm以上的刮削进行评价。刮削为4根以上、损伤也显著的场合判断为有问题，用×符号表示，刮削为1～3根的范围但损伤的发生多、担心造成毛细管堵塞等的影响的场合，判断为需要改善，用△符号表示，刮削为1～3根的范围，没有发生视为问题的大的伤痕的场合，线表面比较良好，用○符号表示，没有发生刮削，损伤也不显著的场合，判断为稳定且良好，用◎符号表示，标记于表3中的「环的伤痕、刮削」的栏中。由于担心损伤、刮削的判断多少受观察者个人的判断的影响，因此由2名以上的观察者进行评价，由平均信息进行等级标记。 
对于接合在半导体元件上的线的表面氧化的评价，制作2个在QFP上连接有208根线的试样，主要由通过来自环上方的光线观察得出的环表面的颜色的变化来评价氧化状况。接合条件，按台温度为200℃，暴露在加热台上的时间为约2分钟进行统一。在线表面可看到氧化的线为20根以上的场合，用×符号表示，为6～19根的场合判断为对于严格的要求需要改善，用△符号表示，在位2～5根的场合判断为实用上没有问题的水平的氧化，用○符号表示，在为1根以下的场合，为良好，因此用◎符号表示，标记于表2中的「接合后被加热了的线表面的氧化」的栏中。 
放送性的评价，按线径20μm、跨距1～3mm、环高度150～300μm进行5000根的接合，统计发生翘曲、折曲等的不良、直线性降低的数量。直线性降低的不良数为20根以上的场合用×符号表示，在为10～19根的场合判断为对于严格的要求需要改善，用△符号表示，在为3～9根，其程度也 比较小的场合，判断为实用上没有问题的水平的氧化，用○符号表示，在为2根以下的场合，为良好，因此用◎符号表示，标记于表3中的「放送性」的栏中。 
线保管寿命的评价，使在常温下放置于大气中的接合线连接，由楔接合的不粘不良(non-stick failure)的次数进行评价。接合线以放入线轴箱中的状态保管在洁净室内。放置期间分为30天、60天从而进行了比较。接合条件，以在批量生产工序中使用的通常的接合条件、和稍微减少超声波输出而诱发不粘接的低接合条件这2种接合条件进行了比较。由于温度越低则接合越困难，因此将台温度设为180℃的低温，使用1000根的接合线评价不粘接发生频度。在通常的接合条件下产生3根以上的不粘接的情况下，由于需要改善，因此用×符号表示，在通常的接合条件下的不粘接为2根以下，且在低接合条件下的不粘接为5根以下的场合，用△符号表示，没有在通常的接合条件下的不粘接，且在低接合条件下的不粘接为2～4根的场合，由于大致良好，因此用○符号表示，在没有在通常接合条件下的不粘接、且在低接合条件下的不粘接为1根以下的场合，判断为保管寿命良好，用◎符号表示，标记于表2中的「楔接合性」的栏中。 
在TCT试验中，使用市售的TCT试验装置。温度过程采用以下两种条件：苛刻环境的标准条件(-55℃/30分～125℃/30分)、和极苛刻的条件(-55℃/30分～155℃/30分)。试验后进行电测定，对导电进行了评价。进行线数为400根的测定。在不良率为零的情况下，可靠性高，用◎符号表示，若为1％以下，则判断为没有实用上的大问题，用○符号表示，若为2～5％的范围，则用△符号表示，若超过5％则需要改善，用×符号表示，标记于表2中的「TCT试验」的栏中。 
楔接合的剥离试验，实施一边保持楔接合部的线插入角一边提拉接合线的测定。这作为TCT试验的加速评价来利用。已确认在该试验中的断裂延伸率越高的接合线，则对接合部的应力越具有良好的性能。若楔接合的剥离试验中的断裂延伸率为3％以上则为非常良好，用◎符号表示，若为1.5％以上且不到3％则为充分，用○符号表示，若为1％以上且不到1.5％ 则用△符号表示，若不到1％则判断为延伸率不充分，用×符号表示，标记于表2中的「楔接合的剥离试验」的栏中。 
在软熔耐性的评价中，将进行了线接合和树脂封装的半导体试样使用软熔炉实施10次的在260℃保持10秒钟、然后冷却到常温的热过程，关于试样，使用线接合的条件为在通常的温度即200℃下连接的情况、和在苛刻的条件即160℃的低温下连接的情况的2种试样分别进行了评价。软熔试验后进行电测定，评价导电。进行线数为400根的测定。在不良率为零的情况下可靠性高，用◎符号表示，若为1％以下则判断为没有实用上的大问题，用○符号表示，若为2～5％的范围则用△符号表示，若超过5％则需要改善，用×符号表示，标记于表2中的「软熔耐性」的栏中。 
毛细管寿命的评价，连接5万根的接合线后，由毛细管端头的污染、磨损等的变化来进行判断。若表面清洁则用○符号表示，在不粘物等少的情况下通常的操作中没有问题，因此用△符号表示，在不粘物的量、大小显著的情况下用×符号表示，标记于表2中的「毛细管寿命」的栏中。 
表1～3表示本发明涉及的铜接合线的评价结果和比较例。表1、2的实施例1～33、比较例C1～C9，没有实施使线外层表面的碳、氧浓化的处理，表1的金属M、铜等的浓度，将金属系元素的总计设为100mol％来表示浓度。表3的实施例B1～B33，是利用试样序号(SA1～SA33)与表1相同的线，实施了使碳、氧浓化的处理的情况。 
表3的碳、氧的浓度计算，将铜、金属M等的金属系元素与碳、氧和氮的非金属系元素的总计设为100mol％来算出浓度。对于表1和表3中试样序号相同的试样，已确认金属M以及铜元素等的金属系元素的浓度比例基本上是相同的分析值。对于由金属元素的浓度比例支配的表1中所示的性能，已确认在表3中试样序号相同的试样也能得到大致相同的评价结果。关于实施例B1～B33，在表3中表示出作为代表性的特性的TCT试验、剥离度验、软熔耐性、大气放置后的楔接合性的评价结果。另外，对于球形成性、球接合形状、Al膜的扫出行为、毛细管堵塞等的性能，已确认在实施例B1～B33中也得到与表1同样的结果。 
权利要求1涉及的接合线是实施例1～33、B1～B33，权利要求2涉及的接合线相当于实施例1～32、B1～B32，权利要求3涉及的接合线相当于实施例2、4、7、8、10、14、18、24、27、29、32、B2、B4、B7、B8、B10、B14、B18、B24、B27、B29、B32，权利要求4涉及的接合线相当于实施例3、18～20、24、31、B3、B18～B20、B24、B31，权利要求5涉及的接合线相当于实施例1～33、B1～B33，权利要求6涉及的接合线相当于实施例B1～B3、B5、B8～B15、B17、B19～B20、B22～B26、B29～B33，权利要求7涉及的接合线相当于实施例B1、B4～B6、B8～B18、B20、B22、B24～B33，权利要求8涉及的接合线相当于实施例2、3、5～18、20～30、32、33、B2、B3、B5～B18、B20～B30、B32、B33，权利要求9涉及的接合线相当于实施例1～3、5、7～16、19～24、26～33、B1～B3、B5、B7～B16、B19～B24、B26～B33，权利要求10涉及的接合线相当于实施例2、3、5、7～10、12～16、18～24、26～33、B2、B3、B5、B7～B10、B12～B16、B18～B24、B26～B33，权利要求11涉及的接合线相当于实施例1、2、5～9、12、14～17、19、21～23、25～33、B1、B2、B5～B9、B12、B14～B17、B19、B21～B23、B25～B33，权利要求12涉及的接合线相当于实施例1、2、4～12、15、19、21～23、26～33、B1、B2、B4～B12、B15、B19、B21～B23、B26～B33，权利要求13涉及的接合线相当于实施例2、3、5～20、22～26、28～33、B2、B3、B5～B20、B22～B26、B28～B33。比较例1～9、BC1～BC9表示不满足权利要求1的情况的结果。 
对于各权利要求的代表例，对评价结果的一部分进行说明。 
实施例1～33的多层铜接合线，通过本发明涉及的外层的厚度为0.021～0.12μm的范围，可确认在TCT试验中可靠性高。另一方面，没有外层的以往的单层铜线涉及的比较例1，或外层的厚度不到0.021μm的比较例2、4、6、8，即使是在标准条件的TCT试验中也确认不良。作为优选的事例，外层的厚度为0.025～0.095μm的范围的实施例2、3、6～18、21～23、26、28～30、33，即使是在极苛刻的条件的TCT试验中也能够将不良数抑制为不到1％，此外，外层的厚度为0.03～0.085μm的范围的实施例2、3、 6～16、22、23、26、28～30，已确认不发生不良，得到了高的可靠性。 
实施例1～32的多层铜接合线，通过本发明涉及的外层的厚度为0.021～0.12μm的范围，且构成外层的金属M以选自Au、Pd、Pt、Rh中的一种以上为主成分，与外层的主成分由Ag构成的实施例33进行比较，已确认综合性地改善TCT试验的可靠性、球形成性、接合形状等是比较容易的。 
比较例3、5、7、9，外层的厚度超过0.021μm，楔接合性良好，即使是通常径的球也形状良好，但小径球发生形状不良，因此有可能用途被限定。 
实施例2、4、7、8、10、14、18、24、27、29、32的多层铜接合线，通过本发明涉及的芯材以0.0001～0.03mol％的浓度范围含有选自P、B、Ir、Zr、Bi、Ti、Au、Ag、Sn或稀土类元素中的一种以上的元素，已确认楔接合的剥离试验中的断裂延伸率高。这暗示了综合地提高了楔接合的可靠性。 
实施例3、18～20、24、31的多层铜接合线，通过本发明涉及的外层含有选自Bi、P、Se、Tl中的一种以上的元素，且以其表面浓度为0.01～5mol％的范围而含有，已确认抑制了毛细管堵塞。由此，可延长毛细管的更换寿命，批量生产率提高。 
实施例B1～B3、B5、B8～B15、B17、B19～B20、B22～B26、B29～B33的多层铜接合线，通过本发明涉及的外层的厚度为0.021～0.12μm的范围，且上述外层的最表面的碳浓度为15～18mol％的范围，从表面沿深度方向碳浓度为15～80mol％的范围的区域的厚度为0.0004～0.01μm，提高线表面的滑动性，由此确认能够抑制线的损伤/刮削。优选该区域的厚度为0.0007～0.007μm的实施例B1～B3、B8、B10～B15、B17、B20、B22～B26、B29～B33，已确认抑制损伤、刮削的高的效果。 
实施例B1、B4～B6、B8～B18、B20、B22、B24～B33的多层铜接合线，通过本发明涉及的外层的厚度为0.021～0.12μm的范围，且上述外层的最表面的碳浓度为1～25mol％的范围，在该外层的表面氧浓度为0.2～25mol％的 范围的区域的厚度为0.0005～0.007μm的范围，线的放送性改善，由此确认能够减少通过接合形成环时的翘曲、折曲的良好结果。 
实施例2、3、5～18、20～30、32、33的多层铜接合线，通过本发明涉及的外层的厚度为0.021～0.12μm的范围，且金属M的浓度为10mol％以上的区域的厚度为0.03～0.2μm，已确认在软熔试验中可靠性高。优选该区域的厚度为0.04～0.2μm的实施例2、3、6～18、20、22～25、26～30、32、33，已确认即使是在低温下线连接了的试样软熔耐性也高。 
实施例1～3、5、7～16、19～24、26、33的多层铜接合线，通过本发明涉及的外层的厚度为0.021～0.12μm的范围，且金属M的浓度总计为90mol％以上的区域的厚度为0.004～0.07μm，已确认在大气中放置30天后的楔接合性良好，与没有外层的比较例1或外层的厚度不到0.021μm的比较例2、4、6、8进行比较，接合线的保管寿命也得到改善。优选该区域的厚度为0.008～0.06μm的实施例2、3、7～16、19、22～24、27～33，已确认放置60天后的楔接合性良好。 
实施例2、3、5、7～10、12～16、18～24、26～33的多层铜接合线，通过本发明涉及的外层的厚度为0.021～0.12μm的范围，且金属M的浓度总计为96mol％以上的区域的厚度为0.002～0.06μm，已确认即使在接合工序中被连接了的线在台上被加热，也能够抑制在高温下的氧化。 
实施例1、2、5～9、12、14～17、19、21～23、25～33的多层铜接合线，通过本发明涉及的外层的厚度为0.021～0.12μm的范围，且最表面的铜浓度为0.5～45mol％的范围，能够减少球接合时的偏芯，得到良好的接合形状。优选铜浓度为0.5～20mol％的实施例1、2、5、7、8、12、14～16、19、21、22、25、27、29、31、32，即使是小径球，接合形状也得到改善 
实施例1、2、4～12、15、19、21～23、26～33的多层铜接合线，通过本发明涉及的外层的厚度为0.021～0.12μm的范围，且在外层的表面相对于金属系元素的总计的铜浓度为1～30mol％的区域的厚度为0.0005～0.008μm，能够减少球头部的缩孔和表面的微小凹凸。 
实施例2、3、5～20、22～26、28～33的多层铜接合线，通过本发明涉及 的外层的厚度为0.021～0.12μm的范围，且铜以外的金属M的浓度总计为0.05～3mol％，能够得到降低球接合时Al扫出的效果。 
实施例1～33的多层铜接合线，通过本发明涉及的外层的厚度为0.021～0.12μm的范围，除了形成球时的保护气体为5体积％H2+N2的标准气体时可得到良好的球形状以外，已确认即使是使用纯N2气，球形状也大致为圆球且良好。 
本发明中表示数值范围的“以上”和“以下”均包括本数。 
表1 
Figure G2008800230881D00351
表2 
Figure G2008800230881D00361
表3 
Figure G2008800230881D00371

Claims (10)

1.一种半导体装置用接合线，具有：
以铜为主成分的芯材；和
设置在所述芯材上的、含有成分和组成的某一方或两方与所述芯材不同的金属M和铜、且作为所述金属M的检测浓度的总计为50mol％以上的部位的外层，
其特征在于，
所述外层其厚度为0.021～0.12μm，所述金属M以选自Au、Pd、Pt和Rh中的一种以上为主成分，
所述以铜为主成分的芯材含有选自P、B、Ir、Zr、Bi、Ti、Au和稀土类元素中的一种以上的元素，该元素在线整体中所占的浓度总计为0.0001～0.03mol％的范围。
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，所述外层的厚度为0.021～0.095μm。
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，所述外层含有选自Bi、P、Se和Tl中的一种以上的元素，在所述外层的最表面的该元素浓度总计为0.01～5mol％的范围。
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，在所述外层与所述芯材之间具有扩散层。
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，所述金属M相对于金属元素的总计的浓度为10mol％以上的区域的厚度为0.03～0.2μm。
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，在所述外层内，所述金属M相对于金属元素的总计的浓度总计为90mol％以上的区域的厚度为0.004～0.07μm。
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，在所述外层内，所述金属M相对于金属元素的总计的浓度总计为96mol％以上的区域的厚度为0.002～0.06μm。
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，所述外层的最表面的相对于金属元素的总计的铜浓度为0.5～45mol％。
9.根据权利要求1所述的半导体装置用接合线，其特征在于，在所述外层内，相对于金属元素的总计的铜浓度为1～30mol％的范围的区域的厚度为0.0005～0.008μm。
10.根据权利要求1所述的半导体装置用接合线，其特征在于，在线整体中所占的、铜以外的所述金属M相对于金属元素的总计的浓度总计为0.05～3mol％的范围。
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