CN103339719A - 被覆Pd的铜球焊线 - Google Patents

被覆Pd的铜球焊线 Download PDF

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Publication number
CN103339719A
CN103339719A CN2012800074911A CN201280007491A CN103339719A CN 103339719 A CN103339719 A CN 103339719A CN 2012800074911 A CN2012800074911 A CN 2012800074911A CN 201280007491 A CN201280007491 A CN 201280007491A CN 103339719 A CN103339719 A CN 103339719A
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China
Prior art keywords
palladium
copper
gold
layer
ball bonding
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CN2012800074911A
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CN103339719B (zh
Inventor
高田满生
山下勉
执行裕之
桑原岳
冈崎纯一
齐藤茂
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Tanaka Denshi Kogyo KK
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Tanaka Denshi Kogyo KK
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Abstract

本发明提供一种球焊用被覆钯的铜线，其能够提高对铝电极的接合可靠性。本发明的球焊用被覆钯的铜线中，在钯中间层表面形成包含厚度为5nm以下的极薄层的金层，在含氢的不活泼气氛中进行热处理，中间层的钯侵入到金极薄层，通过微细的金相和钯相进行三维生长的层岛混合模式生长，形成金-钯混杂层。在热处理过程中，钯吸收氢，在热处理后进行骤冷，由此使上述混杂层的钯稳定化，在熔融焊球形成时尽快熔化，随着被覆线端面的金到达端面的钯熔化，均匀微细地分散到熔融焊球表面层，抑制与铝的接合界面中的铝的氧化。

Description

被覆Pd的铜球焊线
技术领域
本发明涉及用于将半导体元件上的电极和电路布线基板的布线以球焊连接的被覆Pd的铜线。
背景技术
现在，作为以球焊接合半导体元件上的电极与外部端子之间的焊线，主要使用线径为15～30μm左右的金线。但是，随着近年的金锭价格的高涨，代替目前的高纯度4N系(纯度为99.99质量％以上)的金线而利用线径为10～25μm左右的铜线备受瞩目。
考虑将该铜线也用于与金线同样的利用领域，例如，在安装关系中，除了使用现行的引线框的QFP(Quad Flat Packaging)之外，还对在使用基板、聚酰亚胺胶带等的BGA(Ball Grid Array)、CSP(Chip ScalePackaging)等新形态中的应用进行了研究，并要求使以球焊进行接合时的环性、接合性、批量生产使用性等得以进一步提高的焊线。
另外，构成铜线的焊线接合对象的材质也与金线的情况相同，在硅基板上的布线、电极材料中，除了以往的铝(Al)合金衬垫外，适合于更微细布线的高纯度的铜(Cu)也被付诸实用化。此外，大多情况下，在引线框上实施银(Ag)镀敷、金(Au)镀敷、以及镍(Ni)镀敷后的钯(Pd)镀敷等，并且在树脂基板、胶带等上实施铜(Cu)布线，并在其上实施金(Au)等贵金属元素及其合金的膜。对应上述各种接合对象，要求提高铜(Cu)线的接合性、接合部可靠性。
最初考虑高纯度3N～6N系(纯度为99.9质量％以上～纯度99.9999质量％以上)的铜(Cu)线的利用。但是，铜线具有易氧化的缺点。因此，提出了在Cu、Cu-Sn等芯材的外周设置0.002～0.5μm的Pd、Pd-Ni、Pd-Co等的被覆层而能够改良耐腐蚀性和强度的结构(参照专利文献1)。进而，还提出对该钯(Pd)层被覆金(Au)等贵金属层的焊线(参照专利文献2～专利文献4)。
但是，在想要将这些铜线用于放置在80℃～200℃的高温下的环境的半导体用途的情况下，即使能够对铝(Al)等衬垫顺利地进行球焊，铝(Al)的氧化物也会从衬垫与线的接合界面生长而剥离接合界面。
另外，与此相对，只要能够使钯(Pd)分散到衬垫与线的接合界面，就能够抑制铝(Al)氧化物的生长(非专利文献1)。
现有技术文献
专利文献
专利文献1：日本实开昭60-160554号公报
专利文献2：日本特开昭62-97360号公报
专利文献3：日本特开2005-167020号公报
专利文献4：WO2011-13527号公报
专利文献5：日本专利第3024584号公报
非专利文献
非专利文献1：2006年7月SEI技术述评(SEIテクニカルレビユ一)第169号P47-51、“混合焊线的开发(「ハイブリツドボンデイングワイヤ一の開発」)”改森信悟等2人、
发明内容
发明所要解决的课题
一直以来就已知被覆钯的铜线，其本身主要用于防止易被氧化的铜芯材的氧化和对被覆钯的引线框进行楔形焊接，但是，仅设置这样的钯被覆层，还会使钯在熔融焊球形成时进入到芯材的铜中，无法使重要的焊球表面层分散所需浓度的钯。
由于原材料钯的价格昂贵，因此这些钯被覆层通常较薄，价格昂贵的钯(Pd)被覆层在铜(Cu)的芯材中所占的比例少至二十分之一以下，因此在形成铜(Cu)焊球的同时，钯(Pd)会扩散到铜(Cu)中，无法使钯(Pd)均匀微细地分散于熔融焊球的外侧。
此外，专利文献4记载的被覆钯的铜线是用于进行与钯被覆引线框的楔形接合的线，其在钯被覆层的表面形成具有3～80nm的厚度且包含金和钯的合金层。
但是，即使如此地进行钯的合金化，也还是会扩散到芯材的铜中，无法形成熔融焊球表面的钯分散层。
用于解决课题的方法
本发明人等想要发明出以下结构，即，将熔点比芯材的铜(Cu)低的金(Au)配置于芯材的铜(Cu)的外侧，以金(Au)为引子使芯材的铜(Cu)先熔化，使熔点比铜(Cu)高的钯(Pd)后熔化，由此能够形成使钯(Pd)均匀微细地分散于熔融焊球外侧的结构。因此，在钯(Pd)上形成金(Au)的被覆层后，实施适中程度的热处理而不使金(Au)和钯(Pd)合金化，利用所谓的层岛混合模式(Stranski-Krastanov)生长，使钯(Pd)三维生长到金(Au)的被覆层中，形成混杂有金(Au)和钯(Pd)的混杂层。
已知利用该层岛混合型的生长所形成的组织在极薄的金属层中产生，形成从基底金属生长出的岛结构，有损表面层的平坦性(专利文献5)。在本发明的方案中利用该层岛混合模式生长而形成的组织成为以下结构：形成于钯被覆层上的金层极薄，钯三维生长在厚度数nm以下的金层中，形成混杂微细的钯相和金相的结构。
金(Au)和钯(Pd)以原始全部的比例完全进行混合，晶格只有约4.9％的微小差异，因此，(Au)/钯(Pd)两层的密合性良好，在金(Au)层极薄的情况下，可以利用层岛混合模式生长而使钯(Pd)基底层析出到金(Au)层表面。
但是，该混杂有金(Au)和钯(Pd)的混杂层不稳定，金(Au)和钯(Pd)的纯度越高，越容易合金化。因此，为了使该混杂有金(Au)和钯(Pd)的混杂层稳定化，本发明人等使氢气在高温与钯(Pd)表面接触，使氢原子吸收到钯(Pd)中，从而使该混杂层更为稳定化。如果在热处理后进行骤冷的水溶液中混入乙醇等醇，则醇热分解产生的氢原子进入到骤冷后的钯(Pd)表层，因此更优选。
本发明人等通过适当调整连续拉丝后的最终热处理，从而使利用上述层岛混合模式生长的热处理与对铜(Cu)焊线的伸长率和拉伸强度进行调质处理的最终退火同时进行，接着短时间的最终热处理以该状态对线进行液冷，由此能够可靠地保持更稳定的混杂有金(Au)和钯(Pd)的混杂层的结构。
进而，本发明人等通过适当调整连续拉丝后的最终热处理，从而使利用上述层岛混合模式生长的热处理、使氢原子吸收到钯(Pd)中的高温处理、和对铜(Cu)焊线的伸长率和拉伸强度进行调质处理的最终退火同时进行，接着短时间最终热处理以该状态对线进行液冷，由此可靠地保持更稳定化的混杂有金(Au)和钯(Pd)的混杂层的结构。
本发明的目的在于解决上述课题，具体而言，其特征在于以下的技术方案。
(1)本发明的球焊用被覆铜线，其特征在于，其是包含芯材和中间被覆层且被表面被覆的线径为10～25μm的球焊用被覆铜线，上述芯材包含铜(Cu)或铜合金，上述中间被覆层包含钯(Pd)，在该球焊用被覆铜线中，上述中间被覆层为纯度99质量％以上的钯(Pd)，再在该中间层上形成金(Au)的最上层，在该中间被覆层的与芯材相反侧的接合界面上具有利用热生长而混杂有上述钯(Pd)和纯度99.9质量％以上的金(Au)的、利用扫描电子显微镜观察到的剖面的平均厚度为5nm以下的混杂层，且对该混杂层的钯表面进行氢扩散处理。
本发明的球焊用被覆铜线的具体的方案如下。
(2)根据上述(1)所述的球焊用被覆铜线，其中，上述混杂层剖面的平均厚度为3nm以下。
(3)根据上述(1)所述的球焊用被覆铜线，其中，上述混杂层剖面的平均厚度为1nm以下。
(4)根据上述(1)所述的球焊用被覆铜线，其中，对上述钯(Pd)进行了湿式镀敷。
(5)根据上述(1)所述的球焊用被覆铜线，其中，上述混杂层为如下：对经强拉丝加工的被覆有金(Au)和钯(Pd)的铜线，利用层岛混合模式生长，使钯(Pd)三维生长到金(Au)的被覆层中，形成混杂有金(Au)和钯(Pd)的混杂层。
(6)根据上述(1)所述的球焊用被覆铜线，其中，上述混杂层是对经强拉丝加工的被覆有金(Au)和钯(Pd)的铜线在450℃～700℃的含氢的不活泼气氛下进行而成的。
(7)根据上述(1)所述的球焊用被覆铜线，其中，在室温下对上述金(Au)进行磁控溅射。
(8)根据上述(1)所述的球焊用被覆铜线，其中，中间被覆层为经湿式镀敷的钯(Pd)。
(9)根据上述(1)所述的球焊用被覆铜线，其中，上述芯材的铜(Cu)为纯度99.999质量％以上的铜(Cu)。
(10)根据上述(1)所述的球焊用被覆铜线，其中，上述芯材的铜(Cu)为纯度99.9999质量％以上的铜(Cu)。
(11)根据上述(1)所述的球焊用被覆铜线，其中，上述芯材的铜合金包含0.1～500质量ppm的磷(P)和剩余部分的铜(Cu)。
(12)根据上述(1)所述的球焊用被覆铜线，其中，上述芯材的铜合金以0.5～99质量ppm的总量含有0.5～99质量ppm的锆(Zr)、0.5～99质量ppm的锡(Sn)、0.5～99质量ppm的钒(V)、0.5～99质量ppm的硼(B)及0.5～99质量ppm的钛(Ti)中的至少1种，并且剩余部分包含纯度99.9质量％以上的铜(Cu)。
(13)根据上述(1)所述的球焊用被覆铜线，其中，上述芯材的铜合金以0.5～99质量ppm的总量含有0.5～99质量ppm的锆(Zr)、0.5～99质量ppm的锡(Sn)、0.5～99质量ppm的钒(V)、0.5～99质量ppm的硼(B)及0.5～99质量ppm的钛(Ti)中的至少1种，并且含有0.1～500质量ppm的磷(P)，且剩余部分包含纯度99.9质量％以上的铜(Cu)。
发明效果
根据本发明，第一焊接的熔融焊球形成时，首先以易熔化的金(Au)为引子使芯材的铜(Cu)熔化，接着与铜(Cu)相接的钯(Pd)熔化，最后使吸藏有氢原子的表面的钯(Pd)熔化，由此能够使钯(Pd)均匀微细地分散到衬垫上的与铝(Al)界面相接的熔融焊球的表面。
此外，本发明通过适当调整纯度99.9质量％以上的金(Au)的膜厚和最终热处理，从而能够形成混杂有金(Au)和钯(Pd)的混杂层而并非金(Au)和钯(Pd)的合金层。
进而，通过在最终热处理中导入氢气，从而使露出金(Au)表面层的钯(Pd)与氢分子反应，使氢原子吸收到钯(Pd)内，可以更可靠地使混杂有金(Au)和钯(Pd)的混杂层稳定化。
本发明的线结构中，在第一焊接的熔融焊球形成时，首先，在层岛混合模式结构的最表层中熔点最低(1064℃)的金(A)开始熔化，随着混杂在相同层中的钯流动，对从中间层的钯层露出至线端面的铜芯材的表面进行覆盖。
铜(Cu)的熔点比金(Au)、钯(Pd)高(1085℃)，但其线端面与熔化的金(Au)直接接触而迅速地熔化，换言之，以熔化的金(Au)为引子而迅速地熔化，形成焊球。
线的结构中熔点最高的(1555℃)钯(Pd)在铜先熔化的期间在铜的周围暂且以薄鞘状残留，在形成铜的熔融焊球的期间，钯边熔化边进入并扩散到铜焊球中，另一方面，利用吸藏的氢原子使随着先熔化的金(Au)到达线端面的混杂层的钯稳定化，最终熔化而不发生合金化，并在焊球表面附近偏析，维持较高的钯(Pd)浓度。
本发明的焊线具有上述的结构，因此即使在高温放置很长时间也不会在线与衬垫的焊接接合界面产生铝氧化物等，长时间的高温稳定性优异。
具体实施方式
本发明的被覆铜线中，超极薄的表面层的理论厚度的上限为10nm，该上限优选为8nm，上限更优选为7nm以下。在此，“理论厚度”是指：由于难以对此种超极薄的全部表面层进行直接测定，因此由连续拉丝前的干式镀敷时的表面层的厚度按比例计算而求出。
求出“理论厚度”时的比例常数是焊线的连续拉丝结束后的线径除以连续拉丝开始前的线的直径而得的值。实际厚度可以用高倍率的扫描电子显微镜直接观察，以理论厚度来看，厚度为纳米级，因此只能得到大致的平均膜厚。厚度越薄，越易发生金(Au)和钯(Pd)的层岛混合模式生长。相反，如果厚度过厚，则金(Au)彼此间的相互作用比金(Au)和钯(Pd)的相互作用更强，钯(Pd)无法从金(Au)表面露出，无法使氢原子吸收到钯(Pd)内。
从均镀性以及与中间被覆层的接合性的观点出发，超极薄的金(Au)表面层可以利用溅射法进行涂布。利用溅射法涂布后的金(Au)等即使纯度在99.9质量％以上，也会因气体分子的碰撞而变成硬质，均镀性较佳。金(Au)等的表面层在进行冷间连续拉丝时会进入到进一步成为硬质的钯(Pd)析出物的微细凹凸的接合界面内部，被牢固地接合到冷间拉丝中。
另外，利用溅射法涂布后的金(Au)等的超极薄的表面层不能够成为线材的圆周方向的剖面形状为几何学上均匀的圆形的膜，因熔融焊球形成时的表面张力而迅速吸收到芯材的铜(Cu)中，消除表面层的不均匀性，形成圆球状的熔融焊球。
芯材的特别优选的形态如下：芯材含有1～80质量ppm的磷(P)，剩余部分包含纯度99.999质量％以上的铜(Cu)。这是由于，磷(P)即便微量也会使铜线的重结晶温度上升，具有加固线自身的强度的效果。在此，“纯度99.999质量％以上”是指磷(P)和铜(Cu)以外的金属的杂质元素小于0.001质量％且除去了铜(Cu)中存在的氧、氮、碳等气体状元素的情况。如果芯材中含有规定量的磷(P)，则在第一焊接中熔化的铜焊球逐渐凝固的过程中，发挥出铜(Cu)焊球的脱氧作用。如果铜(Cu)的纯度为99.999质量％以上，则磷(P)以1质量ppm以上的范围发挥脱氧作用，如果磷(P)为80质量ppm以下的范围，则不会在拉丝时使铜(Cu)芯材加工硬化。利用该磷<P>的脱氧效果，即使具有氧化成芯材的铜(Cu)的部分，也会由于磷(P)在熔融焊球的表面层附近发生浓缩而使铜(Cu)的氧化被分开消去，由此能够在熔融焊球形成时不受芯材的铜(Cu)氧化后的部分的影响。
中间层包含钯(Pd)。钯(Pd)的熔点(1554℃)高于铜(Cu)的熔点(约1085℃)或添加了微量元素的铜合金的熔点中的任一者。因此，在芯材的铜(Cu)或铜合金形成球状的熔融焊球的最初阶段，钯(Pd)成为薄皮而防止其从熔融焊球的侧面氧化。
钯中间层的纯度并不那么影响熔融焊球的圆球性，无论薄厚均不会形成偏芯，从进行连续拉丝的方面出发，需要纯度99质量％以上的钯(Pd)。对中间层的厚度进行适当确定，钯(Pd)中间层越厚，越倾向于使铜(Cu)或铜合金的芯材的劣化变缓。
钯(Pd)中间被覆层的形成方法可以利用干式镀敷、湿式镀敷。干式镀敷可以利用溅射法、离子镀法、真空蒸镀等。从避免杂质混入的观点出发，优选干式镀敷，为了得到剖面均匀的圆形形状，可以采用湿式镀敷。
由于铜(Cu)的纯度高，因此为了维持其纯度，钯(Pd)的电解镀浴也优选为不含卤素离子、硫酸离子的氨型水溶液或氰基系水溶液。此外，高分子化合物、金属盐的光泽剂会给熔融焊球的圆球性带来不良影响，因此优选不含有高分子化合物、金属盐的光泽剂作为膜成分。电解镀到铜(Cu)等芯材的膜利用之后的连续拉丝进行强压缩加工，因此对于膜性状而言膜成分最为重要。这是由于，如果膜成分中存在硫(S)，则在熔融焊球的形成时混入到铜(Cu)中，可能会使熔融焊球加工硬化。
作为钯(Pd)电解镀浴，可以利用二亚硝基二氨钯(Pd(NH3)2(NO2)2)、亚硝酸铵和硝酸钾、或二亚硝基二氨钯(Pd(NH3)2(NO2)2)、硝酸铵和氨水的弱碱性氨型水溶液、Pd(NH3)2(COO)2和(NH4)2HPO4的中性氨型水溶液(美国专利第S4715935号)等。在使用二亚硝基二胺钯的浴中，pH值越高，存在析出物的粒径越大的倾向。在对钯(Pd)进行干式镀敷的情况下，为了防止溅射膜等的异常析出，优选使铜(Cu)的纯度为比99.99质量％更高的99.999质量％以上。
另外，为了对在熔融焊球的形成时金(Au)表面极薄层熔入到铜(Cu)芯材的时机进行调整，也可以在镀钯(Pd)之前实施钯(Pd)、铂(Pt)、镍(Ni)等的触击电镀(strike plating)(极薄镀敷)。
在利用电弧放电的熔融焊球的形成中，各被覆层中的金属的熔点非常重要。高纯度的铜(Cu)的芯材占据焊线的大部分，因此铜(Cu)的熔点(约1085℃)成为基准。已知芯材的高纯度的铜(Cu)在还原性气氛中利用电弧放电而成为完全的圆球形状。
此外，还已知被覆有钯(Pd)的高纯度铜(Cu)的芯材也在非氧化性气氛中利用电弧放电而成为圆球形状。钯(Pd)的熔点(约1555℃)比铜(Cu)的熔点(约1085℃)高，因此在非氧化性气氛中铜(Cu)向着变成圆球形状的趋势被牵引成圆球形状。
但是，当高纯度的金(Au)的焊线无论在何种气氛下利用电弧放电而形成熔融焊球时，均能得到圆球状的熔融焊球，但是，将高纯度的金(Au)直接被覆于高纯度铜(Cu)的芯材的焊线变成长枪状，无法得到圆球形状的焊球。由于金(Au)的熔点(约1064℃)比铜(Cu)的熔点(约1085度)低，因此在铜(Cu)逐渐形成球状的熔融焊球的阶段，低熔点的金(Au)表面层比铜(Cu)更快地熔解，快速地包覆线端面，而高熔点的钯(Pd)则成为障碍。其结果：低熔点的金(Au)优先向铜(Cu)中扩散，逐渐吸收到熔融铜(Cu)中，之后钯(Pd)逐渐熔化。铜(Cu)中的微量添加元素对熔化现象几乎不构成影响。
由此，在一般的被覆钯的铜线中，最表层的金(Au)层的厚度给熔融焊球的圆球性带来影响，本发明中，如上述那样先熔化的金(Au)会促进线端面中铜(Cu)的熔解，本发明的金(Au-钯(Pd)混杂层为数nm的级别，且金(Au)的量为微量，因此其影响得到抑制，不会给熔融焊球的圆球性带来不良影响。
对于钯(Pd)中间层的湿式镀敷而言，由于不含有流平剂、光泽剂等，因此存在析出成不规则粒状的倾向。此外，对于其干式镀敷而言，存在沿着高纯度的铜(Cu)的芯材的晶面析出成层状的倾向。在任一情况下，线剖面均不成完全的圆轮形状，但只要使表面层的厚度为1nm以上就足以。
高纯度的金(Au)等的表面层不仅是利用溅射来进行均镀，在溅射中使线边围绕轴中心旋转边移动，或者在溅射中使线进行往复移动，或者从线的两侧进行溅射，从而可以在中间被覆层上以均匀的厚度析出高纯度的金(Au)。高纯度的金(Au)等的表面层的展延性良好，因此可以按照金刚石模具的模孔形状连续拉丝加工至最终线径。在连续拉丝加工中填埋金(Au)等的表面层与中间被覆层的界面的间隙，即使在钯(Pd)中间层的湿式镀敷中存在异常析出等，也不会机械性地刺破表面层而析出，焊线的表面被金-(Au)等整面地被覆。
连续拉丝可以是在冷却液中进行的湿式拉丝。这是由于，最表层的被覆层薄，因此在干式拉丝中可能会因伴随强压缩作用的热而使超极薄的表面层的金(Au)向铜(Cu)的芯材中扩散而消失。为了降低金刚石模具与金(Au)的摩擦阻力，除了将添加有市售的表面活性剂的金属润滑液用水、醇等稀释液稀释来使用以外，也可以在只含有乙醇、甲醇或异丙醇的水溶液等溶液中进行连续拉丝。
实施例1
以下，对实施例进行说明。
以从表1中记载的铜(Cu)锭拉丝加工至500μm的线径的铜线作为芯材，在该线表面利用通常的方法析出2.0μm的钯(Pd)中间层的电解镀膜。该钯(Pd)镀敷浴使用在中性的二硝基二胺合钯浴中添加10gW/l的磷酸盐而成的镀敷浴，所得的钯(Pd)的纯度为99％。接着，在室温磁控溅射纯度99.99质量％的金(Au)，析出0.08μm。另外，镀层厚度用俄歇电子能谱(Auger electron spectroscopy，AES)进行测定。
之后，将该被覆铜线进行模口拉丝至最终径17μm。金(Au)的理论膜厚度为0.0027μm。接着，除去加工形变，实施规定的最终热处理直至伸长率值达10％左右。对于最终热处理条件，在5％氢+氮气氛下以8m/秒的速度通过700℃的长度50cm的热处理炉，在10％乙醇性水溶液(20℃)中进行冷却。
[表1]
铜芯材的组成
实施例2
将在与实施例1相同的条件下制得的被覆铜线以5m/秒的速度通过5％氢+氮气气氛下600℃的热处理炉，并在纯水(40℃)中进行冷却。
〔比较例1〕
利用纯金镀敷(Electroplating Engineers of Japan Ltd.制造的AUTRONEX series GVC-S)浴使纯度99质量％的金(Au)析出0.0027μm(理论膜厚0.0027μm)，以5m/秒的速度通过氮气气氛下550℃的热处理炉，除此以外，与实施例1进行同样地操作。
〔比较例2〕
除了将最终热处理条件设定为以8m/秒的速度通过5％氢+氮气气氛下800℃的热处理炉以外，与实施例2进行同样地操作。
将以上的实施例及比较例的线的制造条件示于表2。
[表2]
实施例及比较例的制造条件
Figure BDA00003611788800111
对以上的实施例及比较例的线材，在铝电极上进行焊接及缝接合，进行了高温可靠性评价、接合强度性评价、轴上偏芯评价。
它们的接合条件、试验条件及评价结果如下所示。
焊线的连接使用市售的自动线焊机(K&S公司制造的超声波热压接线焊机“MAXμm Ultra(商品名)”)，进行焊球/缝接合。熔融焊球使用Maxμm plus Copper Kit，使用以流量0.5(l/min)供给的包含4体积％的氢气和剩余部分为氮气的混合气体，在气体气氛中利用电弧放电在线尖端制作焊球。
将其与硅基板上的0.8μm铝(Al-0.5％Cu)电极膜接合，将线另一端缝接合于镀敷有4μm银(Ag)的200℃的引线框(材质为42合金、膜厚为150μm)上。毛细管使用SPT公司制造的产品，对于与熔融焊球有关的线焊机的设定值，将EFO Fire Mode设为Bal Size，FAB Size按照使实际的熔融焊球径达到线径的2倍的方式进行调整。按照使压接径达到线径的2.5倍的方式调整焊接时的接合条件。
高温可靠性评价
使用在上述的条件进行焊接且第一接合部焊接于铝(Al-0.5％Cu)电极膜、第二接合部焊接于镀敷有银(Ag)的引线框的样品。该样品的第一接合部的衬垫形状由90μm见方构成，并以100μm间距进行配置。此外，对于邻接的第一接合部按照使一部分通电的方式设计电路。在焊接后，用包含卤素的市售的密封树脂进行树脂模压后，对剩余的焊接缺陷(タイバ一)等进行切断，之后，在温度175℃固化2小时，最终在温度220℃的高温加热炉中放置任意时间。对于电阻，使用KEITHLEY公司制造的制品名“Source meter(型号2004)”，用专用的IC插座和专门构建的自动测定系统进行测定。测定方法用所谓的直流四端子法进行测定。从测定用探针向邻接的外部导线间(选择IC芯片上的衬垫发生短路的一对)流通一定的电流，并对探针间的电压进行测定。对于电阻，对100对(200管脚(ピン)外部导线在放置前和放置后进行电阻测定，将电阻的上升率为20％以上的情况设为“不良”。对于好坏判定，将各样品的不良率达到50％的时间较长的情况设为良好。如果时间在200小时以上，则判断无实用上的大问题，标记为“◎”，如果时间为150小时以上且小于200小时，则标记为“○”，在时间为100小时以上～小于150小时时，标记为“△”，在时间小于100小时时，标记为“×”。
这些结果如表3所示。
[表3]
高温可靠性评价结果
Figure BDA00003611788800131
接合强度性评价
接合强度性评价如下：不使用上述的铝(Al-0.5％Cu)电极膜而将线两端球焊/缝焊接合于镀敷有4μm银(Ag)的200℃的引线框(材质为42合金、膜厚为150μm)上。对3920根线进行焊接，将不压接次数为0～1根设为“◎”、2～3本设为“○”、4～20根设为“△”、21本以上设为“×”。
这些结果如表4所示。
[表4]
接合强度性评价结果
Figure BDA00003611788800141
轴上偏芯评价
轴上偏芯评价如下：使用K&S公司制造的超声波热压接线焊机“MAXμm Ultra(商品名)”，将Loop Parameter设为FAB Mode，连续地制作FAB，并实施了评价。对于焊接，连续地焊接到镀敷有厚度4μm的银(Ag)的200℃的引线框上，不使用铝(Al-0.5％Cu)电极膜。另外，关于与其他线焊接有关的设定值，与上述的铝(Al-0.5％Cu)电极膜的损坏评价同样地进行。对于判定，观察200个接合前的熔融焊球形状，对轴上偏芯和尺寸精度是否良好等进行判定。对于相对于线的焊球位置的偏芯为5nm以上的个数进行测定，在偏芯为1个以下的情况下，由于焊球形成良好，因此标记为“◎”；在偏芯为2～4个时，判断为无实用上的大问题，标记为“○”；在偏芯为5～9个的情况下，标记为“△”；在偏芯为10个以上的情况下，标记为“×”。
它们的结果如表5所示。
[表5]
轴上偏芯评价结果
Figure BDA00003611788800151
根据以上各表的评价结果，如表2所示，实施例1与实施例2在热处理条件及冷却条件上存在差异，混合层的厚度几乎没有差异，在评价上略有降低。与此相对，比较例1在混杂层的厚度上无差异，由于在热处理气氛中没有添加氢，因此未得到好结果。此外，由于Au被覆方法为Au镀敷，因此，与湿式镀敷相比，膜的密合性和致密性低，在局部存在不均匀的膜厚，由于含有大量添加剂、pH调节材料等杂质，因此未得到好结果。
此外，比较例2由于热处理温度过高，因此混杂层的厚度肥大而大大超出本发明范围，无法得到效果。
即、理解为混杂层的厚度是确定的并且氢添加效果很大。
产业上的可利用性
本发明的球焊用被覆铜线能够维持由高纯度铜芯材带来的低电阻性、廉价等性质，并且在高温气氛中对铝电极具有高接合可靠性，能够广泛应用于各种用途中。

Claims (14)

1.一种球焊用被覆铜线，其特征在于，其是包含芯材和中间被覆层的且被表面被覆的线径为10～25μm的球焊用被覆铜线，所述芯材包含铜(Cu)或铜合金，所述中间被覆层包含纯度为99质量％以上的钯(Pd)，
在该球焊用被覆铜线中，通过在含氢气氛中对作为最上层的纯度99.9质量％以上的金(Au)层进行热处理，由此钯(Pd)从所述中间层热生长到该金(Au)层中而露出于该金(Au)层表面，并形成该钯(Pd)被氢扩散处理后的、利用扫描电子显微镜观察到的剖面的平均厚度为5nm以下的金(Au)-钯(Pd)混杂层。
2.根据权利要求1所述的球焊用被覆铜线，其特征在于，所述混杂层剖面的平均厚度为3nm以下。
3.根据权利要求1所述的球焊用被覆铜线，其特征在于，所述混杂层剖面的平均厚度为1nm以下。
4.根据权利要求1所述的球焊用被覆铜线，其中，对所述钯(Pd)进行了湿式镀敷。
5.根据权利要求1所述的球焊用被覆铜线，其中，所述混杂层为如下：对经强拉丝加工的被覆有金(Au)和钯(Pd)的铜线，利用层岛混合生长，使钯(Pd)三维生长到金(Au)的被覆层中，形成混杂有金(Au)和钯(Pd)的混杂层。
6.根据权利要求1所述的球焊用被覆铜线，其中，所述混杂层是对经强拉丝加工的被覆有金(Au)和钯(Pd)的铜线在450℃～700℃的含氢的不活泼气氛下进行而成的。
7.根据权利要求1所述的球焊用被覆铜线，其中，在室温下对所述金(Au)进行磁控溅射。
8.根据权利要求1所述的球焊用被覆铜线，其中，中间被覆层为经湿式镀敷的钯(Pd)。
9.根据权利要求1所述的球焊用被覆铜线，其特征在于，所述芯材的铜(Cu)为纯度99.999质量％以上的铜(Cu)。
10.根据权利要求1所述的球焊用被覆铜线，其特征在于，所述芯材的铜(Cu)为纯度99.9999质量％以上的铜(Cu)。
11.根据权利要求1所述的球焊用被覆铜线，其特征在于，所述芯材的铜合金包含0.1～500质量ppm的磷(P)和剩余部分的铜(Cu)。
12.根据权利要求1所述的球焊用被覆铜线，其特征在于，所述芯材的铜合金以0.5～99质量ppm的总量含有0.5～99质量ppm的锆(Zr)、0.5～99质量ppm的锡(Sn)、0.5～99质量ppm的钒(V)、0.5～99质量ppm的硼(B)及0.5～99质量ppm的钛(Ti)中的至少1种，并且剩余部分包含纯度为99.9质量％以上的铜(Cu)。
13.根据权利要求1所述的球焊用被覆铜线，其特征在于，所述芯材的铜合金以0.5～99质量ppm的总量含有0.5～99质量ppm的锆(Zr)、0.5～99质量ppm的锡(Sn)、0.5～99质量ppm的钒(V)、0.5～99质量ppm的硼(B)及0.5～99质量ppm的钛(Ti)中的至少1种，并且含有0.1～500质量ppm的磷(P)，且剩余部分包含纯度为99.9质量％以上的铜(Cu)。
14.根据权利要求1所述的球焊用被覆铜线，其特征在于，所述芯材的铜合金以0.5～99质量ppm的总量含有0.5～99质量ppm的锆(Zr)、0.5～99质量ppm的锡(Sn)、0.5～99质量ppm的钒(V)、0.5～99质量ppm的硼(B)及0.5～99质量ppm的钛(Ti)中的至少1种，并且含有1～80质量ppm的磷(P)，且剩余部分包含纯度为99.9质量％以上的铜(Cu)。
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CN106415830A (zh) * 2015-05-26 2017-02-15 日铁住金新材料股份有限公司 半导体装置用接合线
CN111276459A (zh) * 2015-05-26 2020-06-12 日铁新材料股份有限公司 半导体装置用接合线
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CN105132735A (zh) * 2015-08-22 2015-12-09 汕头市骏码凯撒有限公司 一种微电子封装用超细铜合金键合丝及其制备方法
CN106486449A (zh) * 2015-08-28 2017-03-08 田中电子工业株式会社 球焊用金分散铜线
CN106486449B (zh) * 2015-08-28 2018-09-21 田中电子工业株式会社 球焊用金分散铜线
CN106486450A (zh) * 2015-09-02 2017-03-08 田中电子工业株式会社 球焊用钯被覆铜线
CN107039295A (zh) * 2015-11-02 2017-08-11 田中电子工业株式会社 球焊用贵金属被覆铜线
CN108474058A (zh) * 2016-01-15 2018-08-31 贺利氏材料新加坡私人有限公司 经涂覆的线材
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CN109402445A (zh) * 2018-11-09 2019-03-01 上海理工大学 一种抗氧化铜基合金键合引线及其制备方法
CN115803856A (zh) * 2021-06-25 2023-03-14 日铁新材料股份有限公司 半导体装置用接合线
CN115803856B (zh) * 2021-06-25 2023-08-18 日铁新材料股份有限公司 半导体装置用接合线

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