CN104205314A - 半导体装置及其制造方法 - Google Patents

半导体装置及其制造方法 Download PDF

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Publication number
CN104205314A
CN104205314A CN201380015809.5A CN201380015809A CN104205314A CN 104205314 A CN104205314 A CN 104205314A CN 201380015809 A CN201380015809 A CN 201380015809A CN 104205314 A CN104205314 A CN 104205314A
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Prior art keywords
copper cash
electrode pad
semiconductor device
copper
semiconductor element
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CN201380015809.5A
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CN104205314B (zh
Inventor
伊藤慎吾
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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Abstract

本发明的半导体装置具有：搭载于基板的半导体元件；以铝为主要成分、设置于半导体元件的电极焊盘；将设置于基板的连接端子和电极焊盘连接、以铜为主要成分的铜线；和封装半导体元件和铜线的封装树脂。该半导体装置在大气中以200℃加热16小时时，在铜线与电极焊盘的接合部形成有含有选自钯和铂中的任意的金属的阻挡层。

Description

半导体装置及其制造方法
技术领域
本发明涉及半导体装置及其制造方法。
背景技术
近年来，作为代替金线的接合线，提出了铜线。
在专利文献1中记载了一种利用铜的接合线将半导体元件的电极和引线连接导出的半导体装置，在接合线与电极的接合界面形成有铜－铝系金属间化合物。根据专利文献1的记载，通过在铜球与铝电极的界面形成CuAl2层，形成铜球与电极密接的状态，因此从耐蚀性等方面考虑，能够提高可靠性。
现有技术文献
专利文献
专利文献1：日本特开昭62－265729号公报
发明内容
发明所要解决的课题
但是，通过进一步对铜线与铝焊盘的接合部进行热处理，Cu从铜线向CuAl2层扩散，形成Cu组成比比CuAl2高的合金层。根据本发明的发明人的见解可知，Cu组成比比CuAl2高的合金层容易被卤素腐蚀，容易断线。
本发明是鉴于上述情况而完成的，通过抑制铜从铜线向铜线与电极焊盘的接合部扩散，抑制Cu组成比比CuAl2高的合金层的生长，提高高温高湿环境下的连接可靠性。
解决课题的技术方案
根据本发明，提供一种半导体装置，其具有：
搭载于基板的半导体元件；
以铝为主要成分、设置于上述半导体元件的电极焊盘；
将设置于上述基板的连接端子和上述电极焊盘连接，以铜为主要成分的铜线；
封装上述半导体元件和上述铜线的封装树脂，
在大气中以200℃加热16小时时，在上述铜线与上述电极焊盘的接合部形成含有选自钯和铂中的任意的金属的阻挡层。
另外，根据本发明，提供一种半导体装置，其具有：
搭载于基板的半导体元件；
以铝为主要成分、设置于上述半导体元件的电极焊盘；
将设置于上述基板的连接端子和上述电极焊盘连接、以铜为主要成分的铜线；和
封装上述半导体元件和上述铜线的封装树脂，
上述铜线含有选自钯和铂中的任意的金属，
上述铜线与上述电极焊盘的上述接合部中钯和铂的含量，相对于上述铜线与上述电极焊盘的接合部以外的部分中上述铜线中的钯和铂的含量大于1。
另外，根据本发明，提供一种半导体装置的制造方法，其包括：
将设置有以铝为主要成分的电极焊盘的半导体元件搭载于设置有连接端子的基板的工序；
利用以铜为主要成分的铜线，将上述连接端子和上述电极焊盘连接的工序；和
利用封装树脂封装上述半导体元件和上述铜线的工序，
在利用封装树脂封装的上述工序之后，在大气中以200℃加热16小时时，在上述铜线与上述电极焊盘的接合部形成含有选自钯和铂中的任意的金属的阻挡层。
发明效果
根据本发明，制成在铜线与电极焊盘的接合部处于高温高湿的环境时、形成了含有选自钯和铂中的任意的金属的阻挡层这样的半导体装置，由此能够抑制Cu组成比相比于铜线与电极焊盘的接合部中的CuAl2高的合金层的生长，能够提高高温高湿环境下的连接可靠性。
另外，根据本发明，铜线含有选自钯和铂中的任意的金属，铜线与电极焊盘的接合部中钯和铂的含量相对于铜线与电极焊盘的接合部以外的部分中铜线中的钯和铂的含量大于1，从而能够抑制Cu组成比比铜线与电极焊盘的接合部中的CuAl2高的合金层的生长，能够提高高温高湿环境下的连接可靠性。
附图说明
通过以下阐述的优选实施方式和与其对应的以下的附图，上述的目的和其它目的、特征和优点更为明确。
图1是示意性地表示实施方式的半导体装置的截面图。
图2是关于实施方式的半导体装置，放大了铜线与电极焊盘的接合部的图。
具体实施方式
以下，利用附图对本发明的实施方式进行说明。其中，在所有的附图中，对相同的构成要素标注相同的符号，适当地省略说明。
图1是示意性地表示本实施方式的半导体装置10的截面图。该半导体装置10具有具备芯片焊盘部3a和内引线部3b的引线框3作为基板，该半导体装置10还具有：搭载于芯片焊盘部3a的半导体元件1；以铝(Al)为主要成分、设置于半导体元件1的电极焊盘6；将设置于基板的连接端子(内引线部3b)和电极焊盘6连接、以铜(Cu)为主要成分的铜线4；和封装半导体元件1和铜线4的封装树脂5。该半导体装置10在大气中以200℃加热16小时时，如图2所示，在铜线4与电极焊盘6的接合部7、更详细而言在铜线4与CuAl合金层7a之间，形成有含有选自钯(Pd)和铂(Pt)中的任意的金属的阻挡层7b。另外，铜线含有选自钯和铂中的任意的金属，铜线与电极焊盘的接合部中钯和铂的含量相对于铜线与电极焊盘的接合部以外的部分中铜线中的钯和铂的含量大于1。
作为半导体元件1，没有特别限定，例如可以列举集成电路、大规模集成电路、固体摄像元件等。
作为引线框3，没有特别限制，可以代替引线框3使用电路基板。具体而言，可以使用双列直插式封装体(DIP)、带引线的塑料芯片载体(PLCC)、四面扁平封装体(QFP)、小外形四面扁平封装体(LQFP)、J形引线小外形封装体(SOJ)、薄型小外形封装体(TSOP)、薄型四面扁平封装体(TQFP)、带载封装体(TCP)、球栅阵列(BGA)、芯片尺寸封装体(CSP)、四方扁平无引脚封装体(QFN)、小外形无引线封装体(SON)、引线框·BGA(LF－BGA)、模塑阵列封装体类型的BGA(MAP－BGA)等现有公知的半导体装置中使用的引线框或电路基板。
半导体元件1可以是多个半导体元件叠层而成的元件。该情况下，第1段的半导体元件可以隔着膜粘合剂、热固型粘合剂等的芯片粘结材料固化体2与芯片焊盘部3a粘合。第2段以后的半导体元件可以通过绝缘性的膜粘合剂等依次叠层。然后，在各层的适当的位置，预先利用前工序形成电极焊盘6。
电极焊盘6中的Al的含量相对于电极焊盘6整体优选为98质量％以上。作为电极焊盘6中所含的Al以外的成分，可以列举铜(Cu)、硅(Si)等。通过在下层的铜电路端子的表面形成通常的钛系阻挡层，进一步使用将Al蒸镀、溅射、无电解镀等通常的半导体元件的电极焊盘的形成方法，可以制作电极焊盘6。
铜线4用于将引线框3和搭载于引线框3的芯片焊盘部3a的半导体元件1电连接。在铜线4的表面自然地或工艺上不可避免地形成有氧化膜。在本发明中，铜线4也包括具有这样在铜线表面形成的氧化膜的铜线。
铜线4的直径在30μm以下，进一步优选在25μm以下且在15μm以上。如果为该范围，铜线前端的球形状稳定，能够提高接合部分的连接可靠性。另外，由于铜线自身的硬度，能够降低导线的塑变。
铜线4中的铜的含量优选为铜线4整体的98～99.9质量％，更优选为98.5～99.7质量％，进一步优选为98.7～99.3质量％。作为铜线4，优选使用含有向电极焊盘的扩散速度慢的选自Pd和Pt中的任意的金属的铜线，更优选使用掺杂了选自Pd和Pt中的任意的金属的铜线。通过向电极焊盘的扩散速度慢的Pd和Pt，能够抑制铜线4的Cu扩散到电极焊盘6，能够得到良好的连接可靠性。
从良好的高温保存特性的观点出发，铜线4中的Pd和Pt的含量的合计相对于铜线4整体优选为0.1质量％以上，更优选为0.3质量％以上，进一步优选为0.5质量％以上。另一方面，为了抑制铜线4的硬度上升、抑制接合性降低，优选为2质量％以下，更优选为1.5质量％以下，进一步优选为1质量％以下。另外，铜线4中的Pd和Pt的合计量的范围相对于铜线4整体优选为0.1～2质量％，更优选为0.3～1.5质量％，进一步优选为0.5～1质量％。
铜线4中可以含有Pd或Pt中的任一种，此时，优选铜线4中的Pd的含量相对于铜线4整体为0.5～1质量％，或者铜线4中的Pt的含量相对于铜线4整体为0.5～1质量％。在上述范围内时，能够兼备优异的可靠性和接合操作性。
另外，推测掺杂在铜线4中的选自Pd和Pt中的任意的金属以在Cu中固溶的状态存在。
铜线4中，通过在作为芯线的铜中掺杂0.001质量％～0.003质量％的Ba、Ca、Sr、Be、Al或稀土金属，能够进一步改善接合强度。
铜线4使用如下所述得到铜线：将掺杂有选自Pd和Pt中的任意的金属的铜合金在熔解炉中铸造，将其铸块进行辊压延，进一步使用模具进行伸长线加工，实施一边连续地扫掠铜线一边进行加热的后热处理，从而得到铜线。
在铜线4与电极焊盘6的接合部7中，在铜线4的前端形成铜球4a。
半导体装置10可以在铜线4与电极焊盘6的接合部7形成有含有Cu和Al的CuAl合金层7a，也可以在大气中以200℃加热16小时时形成CuAl合金层7a。CuAl合金层7a包括Cu和Al的含量为各种值的合金层，Cu为铜线4所含的主要成分，Al为电极焊盘6所含的主要成分。CuAl合金层7a是通过接合时的加热或封装后的热处理使得电极焊盘6中的Al和铜球4a中的Cu扩散而产生的区域，主要含有Cu和Al。在此，所谓主要含有Cu和Al是指：相对于CuAl合金层7a整体，Cu的含量和Al的含量的合计大于50质量％，优选为80质量％以上，更优选为90质量％以上，进一步优选为95质量％以上。
CuAl合金层7a具体包括CuAl2层、和Cu含量比CuAl2层多的层。在CuAl合金层7a中，与Cu含量多的层相比，CuAl2层在CuAl合金层7a中所占的比例高。CuAl合金层7a的厚度例如可以为0.2～5μm。
阻挡层7b是含有选自Pd和Pt中的任意的金属的层，还可以含有Cu。具体而言，阻挡层7b中的Pd和Pt的质量比例优选为铜线4中的Pd和Pt的质量比例的1.1～2倍，更优选为1.2～1.8倍。
阻挡层7b在铜线4与电极焊盘6的接合部7中如下所述形成。
通过对铜线4与电极焊盘6的接合部7进行热处理，铜线4中的扩散速度快的Cu扩散到电极焊盘6。另一方面，铜线4中的扩散速度慢的选自Pd和Pt中的任意的金属滞留在CuAl合金层7a上，接着被浓缩，之后形成阻挡层7b。
由此，能够抑制铜线4中的Cu扩散到电极焊盘6。另外，由于能够抑制进一步扩散到CuAl合金层7a，因此能够抑制在CuAl合金层7a中Cu含量比CuAl2层多的层生长，并且能够减少Cu含量比CuAl2层多的层因封装树脂5产生的卤素被腐蚀而产生的断线。
阻挡层7b可以在将半导体装置10在大气中以200℃加热16小时时在CuAl合金层7a与铜线4之间形成，也可以预先在半导体装置10中形成阻挡层7b。
形成阻挡层7b的理由的详细情况尚不是很清楚，但可以推测如下。
可以认为：通过提高铜线4中的扩散速度慢的Pd和Pt的浓度，在铜线4与电极焊盘6接合后，能够增加滞留在接合部7附近的Pd和Pt的量，容易形成阻挡层7b；或者，封装树脂5的175℃的弹性模量为500MPa以上15000MPa以下，由此在封装时和封装后，能够降低铜线4与电极焊盘6的界面所受到的应力，并且能够适当地限制铜线4的移动，因此防止接合部因应力而被破坏，更容易形成阻挡层；或者是这两者的结合等的理由。
阻挡层7b的厚度优选为0.01～3μm，更优选为0.05～2μm。
接合部7在与电极焊盘6的界面中，优选底面平坦。
另外，在半导体装置10中，接合部7中Pd和Pt的含量比铜线4的接合部7以外的部分中的Pd和Pt的含量高。具体而言，优选铜线4与电极焊盘6的接合部7中Pd和Pt的含量相对于铜线4与电极焊盘6的接合部7以外的部分中铜线4中的Pd和Pt的含量大于1，从高温保存特性的观点出发，更优选为1.3以上。所谓“接合部7中Pd和Pt的含量”可以是接合部7的任意区域的含量，但更优选为铜线4与电极焊盘6的界面附近的Pd和Pt的含量。
作为使接合部7中Pd和Pt的含量高于铜线4的接合部7以外的部分中Pd和Pt的含量的方法，例如可以列举：使用Pd和Pt浓度高的铜线4的方法；使用175℃的弹性模量为500MPa以上15000MPa以下的封装树脂的方法等。其机理的详细情况尚不清楚，但可以认为Pd和Pt向电极焊盘6的扩散速度慢，因此在铜线4与电极焊盘6接合后，从铜线4向电极焊盘6扩散的Pd和Pt容易滞留在接合部7。另外，可以认为利用上述弹性模量的封装树脂5，在封装时和封装后，能够降低铜线4与电极焊盘6的界面受到的应力，并且能够适当地限制铜线4的移动，因此防止接合部因应力而被破坏，提高Pd和Pt的含量。
封装树脂5是固化型树脂的固化物，具体而言，更优选使含有(A)环氧树脂和(B)固化剂的环氧树脂组合物固化而得到的固化物。
封装树脂5的175℃的弹性模量优选为500MPa以上15000MPa以下，更优选为800以上5000以下。由此，能够降低铜线4与电极焊盘6的界面受到的应力，并且能够适当地限制铜线4的移动，因此更容易形成阻挡层，能够提高高温保存特性。
作为(A)环氧树脂，是在1个分子内具有2个以上环氧基的单体、低聚物、聚合物全部，其分子量、分子结构没有特别限定，例如可以列举联苯型环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂、四甲基双酚F型环氧树脂等双酚型环氧树脂、茋型环氧树脂；苯酚线型酚醛型环氧树脂、甲酚线型酚醛型环氧树脂等线型酚醛型环氧树脂；三酚甲烷型环氧树脂、烷基改性三酚甲烷型环氧树脂等多官能环氧树脂；具有亚苯基骨架的苯酚芳烷基型环氧树脂、具有亚联苯基骨架的苯酚芳烷基型环氧树脂等芳烷基型环氧树脂；二羟基萘型环氧树脂、将二羟基萘的二聚体缩水甘油醚化后得到的环氧树脂等萘酚型环氧树脂；异氰脲酸三缩水甘油酯、异氰脲酸单烯丙基二缩水甘油酯等含三嗪核的环氧树脂；二环戊二烯改性苯酚型环氧树脂等有桥环状烃化合物改性苯酚型环氧树脂，它们可以单独使用1种，也可以并用2种以上。
另外，上述联苯型环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂、四甲基双酚F型环氧树脂等双酚型环氧树脂、茋型环氧树脂优选具有结晶性的树脂。
作为环氧树脂(A)，优选使用含有选自下述式(1)所示的环氧树脂、下述式(2)所示的环氧树脂和下述式(3)所示的环氧树脂中的至少1种的环氧树脂。
〔式(1)中，Ar1表示亚苯基或亚萘基，在Ar1为亚萘基时，缩水甘油醚基可以与α位、β位中的任意位置结合，Ar2表示亚苯基、亚联苯基和亚萘基中的任一个基团，R5和R6分别独立地表示碳原子数1～10的烃基，g为0～5的整数，h为0～8的整数，n3表示聚合度，其平均值为1～3。〕
〔式(2)中，存在的多个R9分别独立地表示氢原子或碳原子数1～4的烃基，n5表示聚合度，其平均值为0～4。〕
〔式(3)中，存在的多个R10和R11分别独立地表示氢原子或碳原子数1～4的烃基，n6表示聚合度，其平均值为0～4。〕
(A)环氧树脂的含量相对于环氧树脂组合物整体优选为3质量％以上，更优选为5质量％以上，进一步优选为8质量％以上。由此能够降低因粘度上升导致的丝线破断的危险。另外，环氧树脂(A)的含量相对于环氧树脂组合物整体优选为18质量％以下，更优选为13质量％以下，进一步优选为11质量％以下。这样，能够降低因吸水率增加导致的耐湿可靠性下降等的危险。
作为(B)固化剂，例如可以大致分为加聚型的固化剂、催化剂型的固化剂、缩合型的固化剂这三类。
作为加聚型的固化剂，例如可以列举二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、间苯二甲胺(MXDA)等脂肪族多胺、二氨基二苯基甲烷(DDM)、间苯二胺(MPDA)、二氨基二苯砜(DDS)等芳香族多胺，除此以外还可以列举包括双氰胺(DICY)、有机酸二酰肼的多胺化合物；包括六氢邻苯二甲酸酐(HHPA)、甲基四氢邻苯二甲酸酐(MTHPA)等脂环族酸酐、偏苯三酸酐(TMA)、均苯四酸酐(PMDA)、二苯甲酮四甲酸(BTDA)等芳香族酸酐等的酸酐；线型酚醛树脂、聚乙烯基苯酚等酚醛树脂系固化剂；多硫化物、硫酯、硫醚等聚硫醇化合物；异氰酸酯预聚物、嵌段化异氰酸酯等异氰酸酯化合物；含有羧酸的聚酯树脂等有机酸类等。
作为催化剂型的固化剂，例如可以列举苄基二甲基胺(BDMA)、2,4,6－三(二甲基氨基甲基)苯酚(DMP－30)等叔胺化合物；2－甲基咪唑、2－乙基－4－甲基咪唑(EMI24)等咪唑化合物；BF3配位化合物等路易斯酸等。
作为缩合型的固化剂，例如可以列举甲阶型酚醛树脂；含有羟甲基的尿素树脂之类的尿素树脂；含有羟甲基的三聚氰胺树脂之类的三聚氰胺树脂等。
在这些树脂中，从耐燃性、耐湿性、电特性、固化性、保存稳定性等的平衡的观点出发，优选酚醛树脂系固化剂。酚醛树脂系固化剂是指在一个分子内具有2个以上酚羟基的单体、低聚物、聚合物全部，其分子量、分子结构没有特别限定，例如可以列举苯酚线型酚醛树脂、甲酚线型酚醛树脂、双酚线型酚醛树脂等线型酚醛树脂；三酚甲烷型酚醛树脂等多官能型酚醛树脂；萜烯改性酚醛树脂、二环戊二烯改性酚醛树脂等改性酚醛树脂；具有选自亚苯基骨架和亚联苯基骨架中的任意骨架的苯酚芳烷基树脂、具有选自亚苯基和亚联苯基骨架中的任意骨架的萘酚芳烷基树脂等芳烷基型树脂；双酚A、双酚F等双酚化合物等，这些树脂可以单独使用1种，也可以并用2种以上。
作为(B)固化剂，优选使用选自下述式(4)所示的化合物中的至少1种的固化剂。
〔式(4)中，Ar3表示亚苯基或亚萘基，在Ar3为亚萘基时，羟基可以与α位、β位中的任意位置结合，Ar4表示亚苯基、亚联苯基和亚萘基中的任一个基团，R7和R8分别独立地表示碳原子数1～10的烃基，i为0～5的整数，j为0～8的整数，n4表示聚合度，其平均值为1～3。〕
(B)固化剂的含量在环氧树脂组合物中优选为2质量％以上，更优选为3质量％以上，进一步优选为6质量％以上。这样，能够得到充分的流动性。另外，(B)固化剂的含量在环氧树脂组合物中优选为15质量％以下，更优选为11质量％以下，进一步优选为8质量％以下。这样，能够降低因吸水率增加导致的耐湿可靠性下降等的危险。
另外，作为(B)固化剂使用酚醛树脂系固化剂时，作为环氧树脂与酚醛树脂系固化剂的配合比率，优选总环氧树脂的环氧基数(EP)与总酚醛树脂系固化剂的酚羟基数(OH)的当量比(EP)/(OH)为0.8～1.3。当量比在该范围内时，引起环氧树脂组合物的固化性降低或树脂固化物的物性降低等的危险小。
另外，在形成封装树脂5的环氧树脂组合物中可以含有(C)填充材料以及根据需要的(D)中和剂和/或(E)固化促进剂。
作为(C)填充材料，可以使用通常的半导体封装用环氧树脂组合物所使用的材料。例如，可以列举熔融球状二氧化硅、熔融破碎二氧化硅、结晶二氧化硅、滑石、氧化铝、钛白、氮化硅等无机填充材料，有机硅粉末、聚乙烯粉末等有机填充材料，其中，特别优选熔融球状二氧化硅。这些填充材料可以单独使用1种，也可以并用2种以上。另外，作为(C)填充材料的形状，为了抑制环氧树脂组合物的熔融粘度升高、进一步提高填充材料的含量，优选尽可能为正球状、且粒度分布宽。另外，填充材料可以利用偶联剂进行表面处理。另外，可以根据需要利用环氧树脂或酚醛树脂等预先对填充材料进行处理后使用，作为处理的方法，有：使用溶剂进行混合后将溶剂除去的方法；直接添加到填充材料中，使用混合机进行混合处理的方法等。
从环氧树脂组合物的填充性、半导体装置的可靠性的观点出发，(C)填充材料的含量相对于环氧树脂组合物整体优选为65质量％以上，更优选为75质量％以上，进一步优选为80质量％以上。这样，能够获得低吸湿性、低热膨胀性，因此能够降低耐湿可靠性变得不充分的危险。另外，在考虑成形性时，(C)填充材料的含量相对于环氧树脂组合物整体优选为93质量％以下，更优选为91质量％以下，进一步优选为86质量％以下。这样，能够降低流动性下降、在成形时出现填充不良等、或者由于高粘度化导致半导体装置内的导线塑变等的不良情况的危险。
(D)中和剂可以使用将由于作为环氧树脂组合物或其固化体的封装树脂5的加热产生的酸性的腐蚀性气体中和的物质。由此，能够抑制铜线4与半导体元件1的电极焊盘6的接合部7的腐蚀(氧化劣化)。具体而言，作为(D)中和剂，可以使用碱性金属盐，特别是选自含钙元素的化合物、含铝元素的化合物和含镁元素的化合物中的至少1种。
作为上述含钙元素的化合物，可以列举碳酸钙、硼酸钙、硅酸钙等，其中，从杂质的含量、耐水性和低吸水率的观点出发，优选碳酸钙，更优选通过二氧化碳反应法合成的沉降性碳酸钙。
作为上述含铝元素的化合物，可以列举氢氧化铝、勃姆石等。其中，优选氢氧化铝，在氢氧化铝中，更优选利用2阶段拜耳法合成的低钠氢氧化铝。
作为上述含镁元素的化合物，可以列举水滑石、氧化镁、碳酸镁等，其中，从杂质的含量和低吸水率的观点出发，优选下述式(5)所示的水滑石。
MaAlb(OH)2a+3b－2c(CO3)c·mH2O       (5)
〔式(5)中，M表示至少包括Mg的金属元素，a、b、c为分别满足2≤a≤8、1≤b≤3、0.5≤c≤2的数，m为0以上的整数。〕
作为具体的水滑石，可以列举Mg6Al2(OH)16(CO3)·mH2O、Mg3ZnAl2(OH)12(CO3)·mH2O、Mg4.3Al2(OH)12.6(CO3)·mH2O等。
作为(D)中和剂的含量，优选相对于环氧树脂组合物整体为0.01～10质量％。通过将(D)中和剂的含量设定为0.01质量％以上，能够充分发挥添加中和剂的效果，能够更可靠地防止铜线4与电极焊盘6的接合部7的腐蚀(氧化劣化)，能够使半导体装置的高温保存特性提高。另外，通过将(D)中和剂的含量设定为10质量％以下，能够使吸湿率降低，由此存在耐焊裂缝性提高的倾向。特别是在作为防腐剂使用碳酸钙或水滑石时，从与上述同样的观点出发，其含量优选相对于环氧树脂组合物整体为0.05～2质量％。
(E)固化促进剂只要是能够促进环氧树脂的环氧基与固化剂(例如酚醛树脂系固化剂的酚羟基)的交联反应的物质即可，能够使用通常的半导体封装用环氧树脂组合物所使用的固化促进剂。例如，可以列举1,8－二氮杂双环(5,4,0)十一碳烯-7等的二氮杂双环烯烃及其衍生物；三苯基膦、甲基二苯基膦等有机膦类；2-甲基咪唑等咪唑化合物；四苯基鏻·四苯基硼酸酯等四取代鏻·四取代硼酸酯；膦化合物与醌化合物的加合物等，它们可以单独使用1种，也可以并用2种以上。
(E)固化促进剂的含量相对于环氧树脂组合物整体优选为0.05质量％以上，更优选为0.1质量％以上。这样，能够降低引起固化性下降的危险。另外，(E)固化促进剂的含量相对于环氧树脂组合物整体优选为1质量％以下，更优选为0.5质量％以下。这样，能够降低引起流动性下降的危险。
在用于形成封装树脂5的环氧树脂组合物中，可以根据需要进一步适当配合氢氧化锆等防铝腐蚀剂；氧化铋水合物等无机离子交换体；γ－环氧丙氧基丙基三甲氧基硅烷、3－巯基丙基三甲氧基硅烷、3－氨基丙基三甲氧基硅烷等偶联剂；碳黑、铁丹等着色剂；硅橡胶等低应力成分；巴西棕榈蜡等天然蜡、合成蜡、硬脂酸锌等高级脂肪酸及其金属盐类或石蜡等脱模剂；氢氧化铝、氢氧化镁、硼酸锌、钼酸锌、磷腈等阻燃剂、抗氧化剂等各种添加剂。
用于形成封装树脂5的环氧树脂组合物可以使用通过如下方法获得的组合物：利用混合机等在15℃～28℃将上述的各成分进行混合，之后，进一步将得到的混合物利用辊、捏合机、挤出机等混炼机进行熔融混炼、冷却后粉碎而得到的组合物等，根据需要适当调节分散度和/或流动性等而得到的组合物。
接着，对本实施方式的半导体装置10的制造方法的一个例子进行说明。
首先，通过公知的半导体制造工艺，将半导体元件1的最上层的保护膜8的一部分开口，形成电极焊盘6。保护膜8由SiN等绝缘膜形成。接着，再通过公知的后工序工艺，将具有电极焊盘6的半导体元件1设置于引线框3上的芯片焊盘部3a，通过铜线4将电极焊盘6与内引线部3b导线接合。
接合例如以以下的顺序进行。首先，在铜线4的前端形成规定直径的铜球4a(其中，图2以接合后的形状进行图示)。接着，使铜球4a相对于电极焊盘6上表面实质上垂直地下降，一边使铜球4a与电极焊盘6接触，一边施加超声波振动。
由此，铜球4a的底部与电极焊盘6接触，形成接合面。
另外，引线框3的内引线部3b与半导体元件1可以通过导线的逆结合(wire reverse bonding)进行接合。在逆结合中，首先在半导体元件1的电极焊盘6上接合形成于铜线4的前端的球，切断铜线4，形成点焊用的凸点。接着，使形成于导线的前端的球与引线框3的经过金属镀的内引线部3b接合，与半导体元件的凸点进行点焊。利用逆结合时，与正结合相比，能够降低半导体元件1上的导线高度，因此能够降低半导体元件1的接合高度。
接着，利用传递模塑、压缩模塑、注射模塑等现有的成形方法，将固化型树脂(例如上述的环氧树脂组合物)固化成形，封装半导体元件1、铜线4和内引线部3b，以80℃～200℃左右的温度、用10分钟～24小时左右的时间进行后固化。后固化更优选以150℃～200℃进行2～16小时。之后，可以将通过封装树脂5封装的半导体元件1搭载于电子机器等上。
这样制得的半导体装置10中，接合部7中Pd和Pt的含量相对于铜线4中的Pd和Pt的含量大于1。另外，对于半导体装置10，在利用封装树脂5封装的工序之后在大气中以200℃进行16小时的加热后，在铜线4与电极焊盘6的接合部7形成含有选自Pd和Pt中的任意的金属的阻挡层7b。即，接合部7中Pd和Pt的含量相对于铜线4中的Pd和Pt的含量大于1，另外在形成阻挡层7b的半导体装置10中，由于制造工艺或使用时接合部7的热量，Cu优先从铜球4a扩散到电极焊盘6，在接合部7形成CuAl合金层7a，并且，铜球4a中的Pt、Pd或它们两者不扩散到电极焊盘6而残留在CuAl合金层7a上。由此，能够防止铜线4中的Cu向CuAl合金层7a进一步扩散，能够抑制CuAl合金层7a的生长。因此，根据本发明，即使在接合后采用高温高热工艺的情况、或者使用环境在高温下的情况(例如，设置于汽车等的发动机周边的情况)下，也能够维持高的连接可靠性。
以上，参照附图对本发明的实施方式进行了说明，但这些是本发明的例示，也可以采用上述以外的各种构成。
例如，本发明涉及一种半导体装置，其具有：搭载于基板的半导体元件；以铝为主要成分、设置于上述半导体元件的电极焊盘；将设置于上述基板的连接端子与上述电极焊盘连接、以铜为主要成分的铜线；和封装上述半导体元件和上述铜线的封装树脂，上述铜线中的钯和铂的合计量相对于上述铜线整体为0.1重量％以上2重量％以下。
实施例
下面，基于实施例和比较例更具体地说明本发明，但本发明不限定于以下的实施例。
制造例1～5
使用混合器，以15～28℃将表1所示的各成分混合，接着以70℃～100℃进行辊混炼。冷却后进行粉碎，得到环氧树脂组合物。其中，表1中的各成分的详细信息如下。另外，表1中的单位为质量％。
＜(A)环氧树脂＞
环氧树脂－OCN：EOCN－1020－55、日本化药株式会社制、环氧当量200
Br化环氧树脂：EPICLON152－S、DIC Corporation制、环氧当量359
环氧树脂－2：NC3000P、日本化药株式会社制、环氧当量276
环氧树脂－3：YX4000K、三菱化学株式会社制、环氧当量185
＜(B)固化剂＞
固化剂－PN：PR－HF－3、住友电木株式会社制、羟基当量105
＜(C)填充材料＞
熔融球状二氧化硅：FB－820、电气化学工业株式会社制、平均粒径26.5μm、105μm以上的颗粒1％以下
＜(D)中和剂＞
水滑石：DHT－4A(注册商标)(在上述式(5)中，a为4.3，b为2，c为1的水滑石)、协和化学工业株式会社制
＜(E)固化促进剂＞
三苯基膦：TPP、北兴化学工业株式会社制
＜其他成分＞
偶联剂：γ－环氧丙氧基丙基三甲氧基硅烷
着色剂：碳黑
脱模剂：巴西棕榈蜡
[表1]
通过以下的方法测定制造例1～5中得到的环氧树脂组合物的物性。将其结果表示在表1中。
＜旋流长度(SF)＞
使用低压传递成型机(Kohtaki Precision Machine Co.，Ltd生产，“KTS-15”)，在基于EMMI－1－66的旋流长度测定用模具中，以模具温度175℃、注入压力6.9MPa、固化时间120秒的条件，分别注入制造例1～4的环氧树脂组合物，测定流动长度(单位：cm)。
＜胶凝时间(GT)＞
在加热到175℃的热板上，使制造例1～4的环氧树脂组合物分别熔融，之后一边利用刮刀搅拌一边测定直到固化的时间(秒)。
＜杂质量的测定＞
使用低压传递成型机(Kohtaki Precision Machine Co.，Ltd生产，“KTS-15”)，以模具温度175℃、注入压力7.5MPa、固化时间2分钟的条件，形成的试验片。在175℃、8小时的后固化之后进行微粉碎，向5g的粉碎品中加入50ml的蒸馏水，加入到Teflon(注册商标)衬里的容器中，进行125℃、20小时的处理，通过离子色谱分析，对处理后的上清液进行定量。
实施例1～11、比较例1～6
将具有铝制电极焊盘(Al纯度99.9质量％、厚度1μm的铝焊盘)的TEG(TEST ELEMENT GROUP)芯片(3.5mm×3.5mm)接合在352针BGA(基板为厚度0.56mm、双马来酰亚胺·三嗪树脂/玻璃布基板、封装体尺寸为30mm×30mm、厚度1.17mm)的芯片焊盘部，使用表2、3所示的铜线以间距80μm进行线接合，使得TEG芯片的铝制电极焊盘与基板的电极焊盘形成菊花链连接。将其利用低压传递成形机(TOWA制“Y系列”)，以模具温度175℃、注入压力6.9MPa、固化时间2分钟的条件，如表2、3所示，使用制造例1～5中的任一种环氧树脂组合物进行封装成形，制作352针BGA封装体。将该封装体在175℃、4小时的条件下进行后固化，之后得到半导体装置。
其中，表2、3中铜线的详细信息如下。
Pd掺杂1：铜纯度98.99质量％、Pd含量1质量％的铜线(直径25μm)
Pd掺杂2：铜纯度99.49质量％、Pd含量0.5质量％的铜线(直径25μm)
Pt掺杂：铜纯度98.99质量％、Pt含量1质量％的铜线(直径25μm)
裸线：铜纯度99.99质量％、不含Pd和Pt中的任一种的铜线(直径25μm)
Pd包覆：在铜纯度99.99质量％的表面包覆有50nm的Pd的铜线(直径25μm)
＜TEM分析＞
对于实施例1～11和比较例1～6的半导体装置，利用透射型电子显微镜(TEM)解析铜线与电极焊盘的接合部的结构。
在实施例1～11、比较例1～6的半导体装置中，确认了在铜线与铝焊盘之间形成了厚度为0.3μm的仅由CuAl2层构成的CuAl合金层。
在实施例1～11、比较例1～6的半导体装置中，在铜线与铝焊盘之间没有确认到阻挡层，但利用透射型电子显微镜(TEM)的元素分析进行解析时，在实施例1～11中，确认了相对于铜线中的Pd、Pt的质量比例，铜线与CuAl合金层之间的Pd、Pt的质量比例提高到1.02～1.08倍。
另外，在大气中以200℃对实施例1～11和比较例1～6的半导体装置加热16小时，利用TEM对铜线与电极焊盘的接合部的结构进行解析时，在实施例1～6、11的半导体装置中，确认了在厚度0.3μm的CuAl2层与铜线之间形成了厚度0.05～0.2μm的由Cu/Pd构成的阻挡层。另外，在TEM的元素分析中，确认了该阻挡层中的Pd质量比例相对于铜线中的Pd质量比例增加到1.2～1.3倍。
另外，在实施例7～10的半导体装置中，确认了在厚度0.3μm的CuAl2层与铜线之间形成了厚度0.1～0.2μm的由Cu/Pt构成的阻挡层。在TEM的元素分析中，确认了该阻挡层中的Pt质量比例相对于铜线中的Pt质量比例增加到1.2～1.4倍。
另外，在比较例1～6的半导体装置中，确认了在铜线与铝焊盘之间形成的CuAl2层的厚度为0.4μm，在CuAl2层与铜线之间进一步形成了厚度0.1μm的Cu9Al4层。在铜线中没有掺杂、只在表面包覆时，在大气中以200℃加热16小时时，没有形成阻挡层。
＜耐湿性和高温保存特性＞
对于实施例1～11、比较例1～6的半导体装置，进行半导体装置的HAST(不饱和耐湿性试验)和HTSL(高温保存试验)。将其结果表示在表2、3中。表2、3中的单位为小时(hour)。
具体而言，HAST基于IEC68－2－66进行实施。试验条件是，将温度设为130℃和140℃，以85％RH、施加电压20V进行处理，调查产生不良的时间。
另外，就HTSL而言，以175℃进行处理，调查产生不良的时间。
另外，在HAST和HTSL中，不良的判定使用制作的10个封装体进行评价，将处理后的电阻值相对于初始电阻超过1.2倍的封装体所产生的时间作为不良时间。
[表2]
[表3]
在实施例的半导体装置中，能够看到优异的高温耐湿特性和高温保存特性，特别是通过使用Pd或Pt的掺杂量为优选的范围0.1～2质量％、更优选的范围0.3～1.5质量％、进一步优选的范围0.5质量％以上1质量％以下的铜线，不受形成封装树脂的环氧树脂组合物的卤素量的影响，能够兼备稳定的可靠性和接合操作性。
该申请主张以2012年3月22日提出的日本专利申请特愿2012－066161为基础的优先权，在此引用其公开的全部内容。

Claims (8)

1.一种半导体装置，其特征在于，具有：
搭载于基板的半导体元件；
以铝为主要成分、设置于所述半导体元件的电极焊盘；
将设置于所述基板的连接端子和所述电极焊盘连接、以铜为主要成分的铜线；和
封装所述半导体元件和所述铜线的封装树脂，
在大气中以200℃加热16小时时，在所述铜线与所述电极焊盘的接合部形成有含有选自钯和铂中的任意的金属的阻挡层。
2.如权利要求1所述的半导体装置，其特征在于：
在大气中以200℃加热16小时时形成的所述阻挡层的厚度为0.01～3μm。
3.如权利要求1或2所述的半导体装置，其特征在于：
在大气中以200℃加热16小时时，在所述阻挡层与所述电极焊盘之间形成有铜和铝的合金层。
4.一种半导体装置，其特征在于，具有：
搭载于基板的半导体元件；
以铝为主要成分、设置于所述半导体元件的电极焊盘；
将设置于所述基板的连接端子和所述电极焊盘连接、以铜为主要成分的铜线；和
封装所述半导体元件和所述铜线的封装树脂，
所述铜线含有选自钯和铂中的任意的金属，
所述铜线与所述电极焊盘的接合部中钯和铂的含量相对于所述铜线中的钯和铂的含量大于1。
5.如权利要求1～4中任一项所述的半导体装置，其特征在于：
所述铜线中的铜含量相对于所述铜线整体为98～99.9质量％。
6.如权利要求1～5中任一项所述的半导体装置，其特征在于：
所述基板为引线框或电路基板。
7.一种半导体装置的制造方法，其特征在于，包括：
将设置有以铝为主要成分的电极焊盘的半导体元件搭载于设置有连接端子的基板的工序；
利用以铜为主要成分的铜线，将所述连接端子和所述电极焊盘连接的工序；和
利用封装树脂封装所述半导体元件和所述铜线的工序；
在利用封装树脂封装的所述工序之后，在大气中以200℃加热16小时时，在所述铜线与所述电极焊盘的接合部形成有含有选自钯和铂中的任意的金属的阻挡层。
8.如权利要求7所述的半导体装置的制造方法，其特征在于：
在利用所述封装树脂封装的所述工序中，使用环氧树脂组合物封装成形后，以150℃～200℃进行2～16小时的后固化。
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