CN103155130A - Ag-Au-Pd三元合金接合线 - Google Patents

Ag-Au-Pd三元合金接合线 Download PDF

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CN103155130A
CN103155130A CN2011800490005A CN201180049000A CN103155130A CN 103155130 A CN103155130 A CN 103155130A CN 2011800490005 A CN2011800490005 A CN 2011800490005A CN 201180049000 A CN201180049000 A CN 201180049000A CN 103155130 A CN103155130 A CN 103155130A
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quality
partalloy
ternary alloy
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CN103155130B (zh
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千叶淳
手岛聪
小林佑
安德优希
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Tanaka Denshi Kogyo KK
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Tanaka Denshi Kogyo KK
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Abstract

本发明的目的是提高用于在高温和高湿度环境中使用的半导体的接合线键合至铝焊点的可靠性。解决方式是一种用于半导体装置的Ag-Au-Pd三元合金接合线，所述接合线由4-10质量％的具有99.999质量％以上的纯度的金，2-5质量％的具有99.99质量％以上的纯度的钯和剩余质量％的具有99.999质量％以上的纯度的银制成。这种用于半导体的接合线包含15-70重量ppm的氧化性非贵金属元素，并且在通过模具连续拉伸之前经过热退火，且在通过模具连续拉伸之后经过热回火，并且这种接合线在氮氛中进行球焊。在铝焊点与线之间的界面处的Ag2Al金属间化合物层与Ag-Au-Pd三元合金线之间的腐蚀由Au2Al和富Pb层抑制。

Description

Ag-Au-Pd三元合金接合线
技术领域
本发明涉及一种由Ag-Au-Pd三元合金制成的接合线，所述接合线适合用于将半导体装置中使用的基板如IC芯片电极与外部引出引线连接，并且尤其是涉及一种Ag-Au-Pd三元合金接合线，所述接合线在高温条件下如在机动车辆中或在高速装置中使用。
背景技术
传统上，作为半导体装置中将IC芯片电极连接至外部引出引线的金线，因为高可靠性的原因，广泛使用由掺杂有痕量的另一种金属元素制成的高纯金制成的具有99.99质量％以上的纯度的金线。这种纯金线的使用是使得线的一端通过采用超声波辅助热键合法连接至IC芯片电极上的纯铝(Al)焊点或铝合金焊点，并且另一端连接至电路板上的外部引线等，并且其后用树脂密封电路以制得半导体装置。这样的纯铝(Al)焊点和铝合金焊点通常通过真空沉积形成。
日本专利申请公布H09-272931中公开了另一种Ag-Au-Pd三元合金接合线“一种用于半导体装置的金合金细线，其特征在于由以下各项组成：10-60重量％的Ag和0.005-0.8％的Mn，加上与以上元素组合的总计0.005-5重量％的选自Cu、Pd和Pt中的至少一种元素和总计0.0002-0.03重量％的选自Ca、Be、La、Ce和Y中的至少一种元素，并且余量是金和不可避免的杂质。”
同样，日本专利申请公布2000-150562公开了“一种用于键合半导体装置的金合金细线，所述金合金细线由含有以下各项的金合金制成：1至50重量％的Ag、0.8至5重量％的Pb、0.1-2重量ppm的Ti，加上1-50重量ppm的选自Ca、Be和La中的一种或多种，以及由金和不可避免的杂质组成的剩余部分。开发像这些的接合线作为金线的备选，并且预期能够减少昂贵的金(Au)的消费并能够在大气环境中形成熔球。”
然而，在由具有超过60％的银(Ag)含量的Ag-Au-Pd合金制成的接合线的情况下，已有的经验是当将其在自然大气中球焊时，一些氧化物在熔球的表面中析出，导致熔球与目标如铝合金焊点的键合不良。这些氧化物来源于天然Ag中含有的氧化性非贵金属元素或不可避免的杂质，并且当这种微量加入的元素和不可避免的杂质在熔球的表面析出时，它们与大气中的氧结合并生成氧化物。
当银的含量超过60％时，接合线自身的硬度变得增大很多，以至于对成形后的接合线进行最终退火成为共同的惯例。例如，在日本专利申请公布H03-74851(下文中称为“IP公布1”)中公开了“由Ag-Pd合金、Au-Ag-Pd合金等制成的线，所述线已经在比各自的重结晶温度高的温度下进行了热处理”，并且日本专利申请公布2010-171378公开了一种用于制造由金-银-钯合金制成的线的方法，由清洁并且烘干线的表面以及接下来的退火组成，所述线并拉制为0.050mm-0.010mm的线直径，并且含有8.00-30.00重量％的金和66.00-90.00重量％的银以及0.01-6.00重量％的钯，所述方法包括清洁并干燥线表面并且之后退火。
然而，在由Ag-Au-Pd三元合金制成的接合线的情况下，存在的事实是银(Ag)的含量越大，从空气中引入的氧越多，以使得表面张力变的十分弱，以致熔球的形状变得不稳定，并且也带来上述氧化物的析出，只可能通过超声波楔入键合的方式获得连接。
因为树脂密封的半导体装置开始用于其中尽管升高温度的苛刻条件下仍需要高可靠性的车载装置IC，以及用于工作温度升高为非常高的用于高频波的IC和高亮度LED，已经完成最终退火的由Ag-Au-Pd三元合金制成的接合线在这样的高温条件下不能够保持它们的性能。因为这些原因，事实是Ag-Au-Pd三元合金接合线还未投入使用。
现有技术公布
[IP公布1]日本专利申请公布H03-74851
[IP公布2]日本专利申请公布H09-272931
[IP公布3]日本专利申请公布2000-150562
发明概述
本发明要解决的问题
考虑到要提供一种Ag-Au-Pd三元合金的接合线而提供本发明，所述接合线能够与铝焊点建立持久的球焊连接，甚至当在其中使用所述线的树脂密封的半导体装置要承受高温、高湿和高压的苛刻工作条件时仍然可以保持连接可靠性。
解决问题的方式
本发明的发明人将他们的注意力集中到由Ag-Au-Pd三元合金制成的接合线不与含有铜(Cu)的接合线一样容易受到氧化的事实，研究了将前者在高温条件下在氮氛中球焊在铝合金焊点上的连接持久性。他们发现在大气气氛下他们可以获得高球度的无空气球(FAB)，所述无空气球在氮氛下却没有完全封闭，并且甚至不需要使用氮气和氢气的混合气，并且甚至在形成熔球的过程中吹扫氮气就足够了。
本发明的发明人还将痕量的氧化性非贵金属元素加入至高纯Ag-Au-Pd三元合金中，并且通过在合金中均匀地分散添加剂，他们通过退火处理阻止Ag-Au-Pd三元合金中的晶粒粗大化，设计为将接合线通过模具连续拉伸后仍能够保持接合线中的拉伸结构，所述退火处理在拉伸中施加至线以消除成型应力
为了解决上述问题，本发明的用于半导体装置的Ag-Au-Pd三元合金接合线由具有99.99质量％以上的纯度的银(Ag)、具有99.999质量％以上的纯度的金(Au)和具有99.99质量％以上的纯度的钯(Pd)制成，并且这种三元合金接合线由4-10质量％的金(Au)、2-5质量％的钯和20-100质量ppm的氧化性非贵金属元素加上余量的银(Ag)组成，并且这种接合线在通过模具连续拉伸之前进行了热退火，并且在通过模具连续拉伸之后进行了热回火，并且适合用于在氮氛中球焊。
(Ag-Au-Pd三元合金)
本发明的Ag-Au-Pd三元合金是将由4-10质量％的金(Au)、2-5质量％的钯(Pd)加上余量的银(Ag)组成的固溶体充分均质化之后制成的合金。
在本发明的情况下，银(Ag)的含量为不少于84质量％，这是因为发现当含银合金线在氮氛中键合在纯铝(Al)焊点或铝合金焊点上时，在银(Ag)与铝(Al)之间形成很少的在天然大气中键合时形成的金属间化合物。
关于本发明，金(Au)不参与具有铝(Al)的金属间化合物在氮氛中的形成，并且在第一次键合时具有使得将熔球高度圆形压缩的效果。本发明为什么规定金(Au)的含量为4-10质量％的原因是：如果金超过10质量％，熔球当形成时的温度变得太高以至于氧化性非贵金属元素氧化物变得很容易形成，由此高球形度的FAB的获得变得困难，并且另一方面，如果小于4质量％，熔球变得太不稳定以至于很难保证FAB的球形度。金(Au)含量优选为6-9质量％。
在本发明中，钯具有阻止银(Ag)与铝(Al)之间金属间化合物的形成以及抑制当在高温和高湿度的条件下使用半导体装置时银(Ag)与铝(Al)之间的金属间化合物的劣化的效果。
在传统的Ag线的情况下，横跨这些元素之间的键合界面形成金属间化合物Ag2Al。
Ag2Al和球之间的键合界面在含水的环境中被腐蚀从而生成Ag和Ag2O3。
在由本发明的Ag-Au-Pd加上微量的添加元素制成的线的情况下，在Ag2Al与球之间形成Ag2Al和一层富Pd层，从而抑制Ag2Al的腐蚀。
如在图1的方案图中所示，在Ag线的情况下，横跨球与铝焊点之间的键合界面形成金属间化合物Ag2Al，并且在含水环境中容易受到腐蚀[参见图1的(A)]。
与此相反，如图1的(A)所示，在本发明的Ag-Au-Pd线的情况下，尽管横跨球与铝焊点之间的键合界面类似地形成金属间化合物Ag2Al，但Au与Pd彼此过于相容以至于在球面侧上形成Au2Al和富Pb层，从而减速铝的腐蚀，带来的结果是极大地提高了剪切强度(share strength)和HST可靠性。
为什么规定钯(Pd)是2-5质量％的原因是：如果它超过5质量％，在氮氛下形成熔球变得太硬，并且如果小于2质量％，不能保证抑制银(Ag)和铝(Al)之间的金属间化合物的劣化的效果。优选的是钯(Pd)含量为3-5质量％。
(氧化性非贵金属添加元素)
在本发明中，氧化性非贵金属添加元素的剂量是15-70质量ppm。根据本发明，要求银(Ag)的纯度为99.99质量％以上，并且不可避免杂质基本上含量为大约20ppm。这些不可避免的杂质和氧化性非贵金属添加元素一样均匀地分散在Ag-Au-Pd三元合金中，并且通过他们的磁通钉孔效应，他们履行他们的阻止Ag-Au-Pd三元合金晶粒粗大化的任务。氧化性非贵金属添加元素的主要作用是提高线的机械性能和在第一次键合时压缩球的圆度。
如果氧化性非贵金属添加元素的总量为以质量计70ppm以下，那么即使是当将Ag-Au-Pd三元合金在大气氛中退火时，也只会在合金表面出现将改变合金表面颜色的厚氧化物膜的少量出现。优选的是氧化性非贵金属元素的总量为20-60质量ppm，并且更优选20-50质量ppm。
氧化性非贵金属添加元素可以是钙(Ca)、稀土元素(Y、La、Ce、Eu、Gd、Nd和Sm)、铍(Be)、镁(Mg)、锡(Sn)、铟(In)和铋(Bi)。优选的候选是钙(Ca)和稀土元素，特别是镧(La)和铍(Be)。
(退火处理)
根据本发明的退火处理设计为消除Au-Ag-Pd三元合金拉线带来的成型应力，并且从而防止由应力引起的裂纹。需要的是氧化性非贵金属添加剂高度均匀地分散在Ag-Au-Pd三元合金中，以便将体系热处理的温度不会升高到Ag-Au-Pd三元合金的熔点附近(约1000摄氏度)。通常，热处理大致是在500摄氏度保持2小时，在600摄氏度保持30分钟或者在700摄氏度保持10分钟。当在退火后将合金拉成线时，在接合线中会形成拉伸结构。因此，期望的是在最终的连续拉伸之前进行退火处理。同时，如果重复进行退火处理，接合线的拉伸结构就会变得更加致密，所以优选的是进行两次或多次退火，但是这降低生产率，所以两次或者三次是最好的。
(热精炼热处理)
根据本发明的热精炼热处理设计为与在金线的情况下类似，以一定方式改变线以使得通过拉伸断裂强度试验机当将线拉长4％时会使其突然折断，并且这通过管式炉内的温度和拉线速度的控制实现。通常采用大约500摄氏度和2秒。
发明效果
如上所述，在氮氛中将本发明的Ag-Au-Pd合金接合线用于第一次键合，以使得纯铝(Al)和铝合金焊点上的熔球的键合性良好，并且也能够保证压缩球的圆形度，并且即使当将半导体装置在高温和高湿度环境中使用时，铝(Al)的金属间化合物在第一键合的键合界面将不会粗大化，从而保证了高键合可靠性。此外，用本发明的Ag-Au-Pd制造的接合线是机械脆弱的，以致未出现线弧高度内的倾斜和无规律性，并且减少了通过控制超声波键合的第二键合过程中键合强度上的无规律性。
发明实施方案
通过熔融铸造制备具有表1的左半边中所示的元素组成的Ag-Au-Pd合金，并且将10mm直径的线拉长至3mm直径并且在600摄氏度保温30分钟退火，并且接下来将线拉长到0.1mm直径并且在600摄氏度退火30分钟。此后，通过进行最终的湿式连续拉伸，发明人制备了由根据本发明的Ag-Au-Pd合金制成的20微米厚的接合线1-27(下文中称为发明线)以及用超出本发明组成范围的Ag-Au-Pd合金制成的接合线28-36(下文中称为比较线)。将这些发明线1-27和比较线28-36置于由Kulicke&Soffa制造的引线键合器(商品名：Maxμm Ultra)上，并且在吹扫氮气的气氛中键合在安装在半导体IC芯片中的50平方毫米的由Al加上0.5质量％的Cu制成的Al合金焊点上，其中制成38mm大的目标尺寸的FAB，键合时的操作条件为：加热温度为200摄氏度，线弧长度为5mm，线弧高度为220mm，压缩球的直径为48mm并且压缩球的高度为14mm，并且关于FAB球形度、压缩球圆形度、第一球剪切力和HAST可靠性进行评价。
[FAB球形度的评价方法]
通过线键合器在每一个组成的合金的情况下制备100个FAB，并且测量每一个FAB在X方向(垂直于金属线的纵向)和Y方向(金属线的纵向)上的长度，并且这些长度之间的差别是评价的基础。评价的结果在表1的右半边给出。
[压缩球圆形度的评价方法]
关于用于评价制备的IC芯片上每一种成分的合金进行一百次的键合，并且测量了每一个压缩球在X方向(垂直于超声波指向的方向)和Y方向(超声波指向的方向)上的长度，在这些长度之间的比的不规律性是评价的基础，并且结果在表1的右半边中给出。
[第一球剪切力的评价方法]
对于每一种合金成分，通过线键合器的方式在为这个目的特殊准备的IC芯片上进行一百次键合，并且通过Dage Corporation的产品名称“万能键合试验仪(BT)(型号：4000)”评价每一个第一压缩球的剪切强度。评价的结果在表1的右半边中给出。
[HAST可靠性的评价方法]
对于每一种合金成分，通过线键合器的方式在为这个目的特别制备的IC芯片(200插脚)上进行键合，并且用为这个目的特别制备的塑性树脂密封这个芯片，从而完成用于电阻测试的试样。将每一个试样在130摄氏度的温度、85％的湿度和2.2个大气压的压力的条件下置于高度加速寿命试验(HAST)中192小时，而后测量了电阻。电阻的测量通过KEITHLEYCORPORATION的产品名称“源表(型号2004)”借助于为这个目的特别制备的IC插孔在为这个目的特别构建的自动测量系统内的进行。测量的方式按照所谓的直流四端子法。使恒定电流从用于测量的探针流到相邻的外部引线探针(选择芯片上一对焊点短路)，并且测量探针之间的电压。
关于100对(200插脚)的外部引线，在HAST中保持之前和之后进行电阻的测量，并且评价电压升高率。该评价的结果在表1的右半边中给出。
[表1]
Figure BDA00003031112500081
Figure BDA00003031112500091
在表1的右半边中，关于FAB球形度，符号◎意指观察到的区别在1微米以下，○意指观察到的区别在2微米以下，并且△意指观察到的区别大于2微米。
在表1的右半边中，关于环形度稳定性，符号◎意指标准偏差的值小于0.8微米，○意指标准偏差值为0.8微米以上并且小于1.0微米，△意指标准偏差值为1.0微米以上并且小于1.5微米，并且×意指标准偏差值为1.5微米以上。
在表1的右半边中，关于第一球剪切力，符号◎意指剪切负荷为15gf以上，○意指剪切负荷为12gf以上，△意指剪切负荷为10gf以上，并且×意指剪切负荷或者小于10gf或者所述球被剪断。
在表1的右半边中，关于HAST可靠性，符号◎意指电阻值的增长率，即增量除以置于HAST中之前的电阻值，为20％以下，○意指其为50％以下，并且×意指其大于50％。
从表1的半边中示出的结果可以清楚地看到，本发明的线在熔球球形度、压缩球的环形度、第一球的键合性和HAST可靠性上是出色的，而比较例25-31中的每一种线都至少有一种所测试的性能不合格。
工业实用性
本发明的接合线用于在高温和高湿度环境中使用并且希望是更加廉价的这种IC组件，以及如，以及不容易使用Cu接合线的这些IC组件如叠层IC和低-k IC，或者由于车载高亮度LED用半导体设备。
附图概述
[图1]图1由显示Ag-Au-Pd三元合金线与铝焊点之间的键合界面的示意图(A)和显示Ag线与铝焊点之间的键合界面的示意图(B)组成。

Claims (7)

1.一种用于半导体装置的Ag-Au-Pd三元合金接合线，所述接合线由具有99.99质量％以上的纯度的银(Ag)、具有99.999质量％以上的纯度的金(Au)和具有99.99质量％以上的纯度的钯(Pd)制成，所述线由4-10质量％的所述金(Au)、2-5质量％的所述钯(Pd)、15-70质量ppm的氧化性非贵金属元素和余量％的所述银(Ag)组成，并且所述线在通过模具连续拉伸之前被热退火至少一次，并且所述线在通过所述模具连续拉伸之后被热回火，并且所述线适用于在氮氛中球焊。
2.如权利要求1所述的用于半导体装置的Ag-Au-Pd三元合金接合线，其特征在于所述线含有6-9质量％的所述金(Au)和3-5质量％的所述钯(Pd)。
3.如权利要求1所述的用于半导体装置的Ag-Au-Pd三元合金接合线，其特征在于所述氧化性非贵金属元素包括钙(Ca)。
4.如权利要求1所述的用于半导体装置的Ag-Au-Pd三元合金接合线，其特征在于所述氧化性非贵金属元素包括稀土元素。
5.如权利要求1所述的用于半导体装置的Ag-Au-Pd三元合金接合线，其特征在于所述氧化性非贵金属元素包括镧(La)。
6.如权利要求1所述的用于半导体装置的Ag-Au-Pd三元合金接合线，其特征在于所述线被热退火两次以上。
7.如权利要求1所述的用于半导体装置的Ag-Au-Pd三元合金接合线，其特征在于所述热退火在比进行所述热回火的温度高的温度进行。
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