CN100475996C - 高温无铅焊料用组合物、生产方法及元件 - Google Patents
高温无铅焊料用组合物、生产方法及元件 Download PDFInfo
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- CN100475996C CN100475996C CNB018232760A CN01823276A CN100475996C CN 100475996 C CN100475996 C CN 100475996C CN B018232760 A CNB018232760 A CN B018232760A CN 01823276 A CN01823276 A CN 01823276A CN 100475996 C CN100475996 C CN 100475996C
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- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
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Abstract
一种无铅焊料(130),它包含一种含银2wt%-18wt%、含铋98wt%-82wt%的银铋合金。所述合金的固相线不低于262.5℃、液相线不高于400℃。所述合金还可以包含一种氧亲和力高于该合金的化学元素。
Description
技术领域
本发明涉及无铅焊料领域。
背景技术
多数已知的芯片(die)连接方法都是采用高铅焊料将集成电路中的半导体芯片连接在引线框上以形成机械连接、并使芯片和引线框之间能够进行热传导和电传导。尽管大多数高铅焊料价格相对低廉而且显示出多种良好的物理化学性能,但是基于环境和职业保健方面的观点,铅在固定芯片和其它焊料中的应用已经得到了更多研究。因此,目前人们已采取了多种措施,用无铅芯片连接组合物来代替含铅焊料。
例如,一种方法是如美国专利US5150195、US5195299、US5250600、US5399907和US5386000所述的,使用聚合物粘合剂(如环氧树脂或氰酸酯树脂)将芯片固定在基底上。如美国专利US5612403所述,在低于200℃的温度下,聚合物粘合剂一般在较短的时间内就会凝固,甚至会在凝固后保持结构上的柔性,因而能将集成电路的芯片固定在柔性的基底上。但是,很多聚合物粘合剂往往会发生树脂流失,这将潜在地导致芯片同基底之间的电接触不希望地减弱,甚至会造成芯片部分或完全地脱落。
为了防止树脂流失方面的至少一些问题的发生,Mitani等人的专利US5982041中指出可以使用含硅氧烷树脂的芯片连接粘合剂。尽管这种粘合剂有助于加强线路的连接、也有助于增强树脂密封层与半导体晶片、基底、封装、和/或引线框之间的结合,至少有某些这类粘合剂在凝固过程中需要高能辐射源,这会显著增加芯片连接工艺的成本。
作为另一种选择,Dietz等人的专利US4459166中记载了一种含有高铅硼硅酸盐玻璃的玻璃胶,从而避免了高能固化步骤。然而,多数含高铅硼硅酸盐玻璃的玻璃胶都需要425℃或更高的温度才能将芯片持久地固定在基底上。而且,玻璃胶在加热和冷却过程中常常易于结晶,这会降低粘结层的粘合质量。
还有另一种方法,是使用多种高熔点的焊料来将芯片固定在基底或引线框上。将芯片焊接在基底上有很多优点,包括工艺比较简单、不需要使用溶剂、在某些情况下成本比较低。在本领域中,有多种高熔点焊料是已知的。但是,所有或几乎所有的这些焊料都具有一个或者多个缺点。例如,大多数金共晶合金(如Au-20%Sn,Au-3%Si,Au-12%Ge和Au-25%Sn)比较昂贵并且其机械性能并不理想。作为另一种选择,J合金(Ag-10%Sb-65%Sn,见例如在Olsen等人的专利US4170472中记载的)可以应用于多种高熔点焊料。但是J合金的固相线为228℃,而且其机械性能也较差。
尽管在本领域中,已知了许多方法和组合物可以用于焊料和芯片连接组合物中,但是它们全部或者几乎全部都存在一种或多种缺点。因此,仍然需要提供改良的组合物或方法以应用于焊料、特别是无铅焊料。
发明内容
本发明涉及包括一种含银铋合金的焊料的方法、组合物和器件,该银铋合金含银2wt%-18wt%,含铋98wt%-82wt%。所述焊料的固相线不低于265.2℃,液相线不高于400℃。
本发明的一个主题是,所述合金中的银含量为2wt%-7wt%、铋含量为98wt%-93wt%,或银含量为7wt%-18wt%、铋含量为93wt%-82wt%,或银含量为5wt%-9wt%、铋含量为95wt%-91wt%。所述组合物中还可以包含一种具有高于该合金的氧亲和力的化学元素,优选元素包括Al、Ba、Ca、Ce、Cs、Hf、Li、Mg、Nd、P、Sc、Sr、Ti、Y和Zr。所述元素的浓度一般介于大约10ppm和大约1000ppm之间。
本发明的另一主题是,所述的焊料的热传导率至少为9W/m K,在1秒钟后的润湿平衡状态下对湿润的Ag的润湿力大约为0.2mN。所述组合物可以制造成多种形状,包括线材、带材、预型件、球状或锭。
本发明进一步的主题是,一种含有利用所述组合物而连结到一个表面上的半导体芯片的电子元件,其中特别考虑的半导体芯片包括硅、锗和砷化镓芯片。而且,芯片的至少一部分或者该器件表面的一部分要用银金属化。特别优选的方案是,该表面包含一个银金属化的引线框。进一步地,所述的焊料以半导体芯片上许多凸点的形式应用于区域阵列电子封装中,以起到芯片同封装基底(一般称为倒装晶片)或印刷线路板(即一般所说的电路板上的晶片)之间的电连接的作用。作为另一种选择,所述焊料可以以许多焊球的形式使用,以连接封装和基底(一般称为球栅阵列,同时还存在许多变化)或者将芯片连接到基底或印刷线路板上。
本发明的进一步的主题还有制造焊料组合物的方法,该方法包括使该组合物中铋和银的含量分别为98wt%-82wt%和2wt%-18wt%的步骤。在另外步骤中,银和铋在至少960℃的温度下熔化以形成固相线不低于262.5℃、液相线不高于400℃的合金。该方法还包括:任意添加具有氧亲和力高于该合金的氧亲和力的化学元素,。
通过下述本发明优选实施方案的详细描述以及附图,本发明的各种目的、特征、实现方式和优点将更加明确。
附图说明
图1是一个示例性的电子设备的垂直截面示意图。
详细描述
发明人发现在其它期望的性能中,几乎很意外地,所述的组合物很适合作为用于多种芯片固定的高铅焊料的替代品。特别是,所述组合物为无铅合金,其固相线不低于260℃(优选不低于262.5℃)、液相线不高于400℃。
本发明主题的特别优选方案是,所述组合物为二元合金,该二元合金可以用作焊料并且含有2wt%-18wt%的银和98wt%-82wt%的铋。作为制备该组合物的一种优选方法,将适当称量(上述的)的一次装填量的纯金属装在耐火或耐热容器(如石墨坩埚)中,于真空或惰性气氛(如氮气或氦气)中加热至960℃-1000℃直至形成液态溶液。然后进行搅拌并且使其在一段充足的时间内保持该温度,以确保两种金属完全混合、熔化。随后将熔化的混合物或熔体迅速倒入模子,冷却至环境温度使其凝固,再使用包括将坯料加热至大约190℃的常规挤压工艺将其制成线材,或者先将矩形板坯在225℃-250℃的温度之间进行退火,而后在同样温度下进行热轧从而制成带材。作为另一种选择,带材可以经挤压,随后轧制成更薄的尺寸。熔化步骤也可以在空气中进行,只要在混合物倒入模子之前将形成的渣清除即可。
本发明主题的另一方面,特别是当期望更高的液线温度时,所述的组合物中的合金可以包括7wt%-18wt%的银和93wt%-82wt%的铋。另一方面,当期望较低的液线温度时,所述组合物中的合金可以包括2wt%-7wt%的银和98wt%-93wt%的铋。但是一般认为,大多数芯片方法可以使用的组合物含银5wt%-10wt%、含铋95wt%-90wt%。
特别值得重视的是,所述的组合物可以用作无铅焊料,这种无铅焊料还完全不含已知无铅焊料中的常用主要成份Sn。而且,虽然一般认为对于本发明的主题来说,特别适合的组合物是二元合金,但同样值得重视的是作为替代的组合物可以包括三元、四元或更多元的合金。
例如,特别适合的作为替代的组合物可以包含一种或多种氧亲和力高于该合金(不含该化学元素)的氧亲和力的化学元素。特别适合的化学元素包括Al、Ba、Ca、Ce、Cs、Hf、Li、Mg、Nd、P、Sc、Sr、Ti、Y和Zr,而且这些化学元素在该合金中的浓度处于大约10ppm至大约1000ppm之间。尽管不希望限于特定的原理或机理,但具有高于合金的氧亲和力的元素会还原金属氧化物,而我们已知这些金属氧化物能够增加正在熔化和已熔化焊料的表面张力。因而,在焊接过程中减少金属氧化物的量一般可以降低熔化的焊料的表面张力,从而显著增强焊料的润湿能力。
在另一个例子中,可以加入一种或多种金属以提高无铅焊料的热机械性能(如热传导率、热膨胀系数、硬度、粘度范围、延展性等)。特别适合的金属包括铟、锡、锑、锌和镍。但是,结合此处的教导,除了上述金属之外的许多金属也适于应用,只要这些金属能够提高至少一种热机械性能。因此,其他所述金属还包括铜、金、锗和砷。因此,特别适合的合金可以含有Ag2wt%-18wt%、Bi98wt%-82wt%和含量为0.1wt%-5.0wt%的第三元素。特别适合的第三元素包括下述元素中的至少一种:Au、Cu、Pt、Sb、In、Sn、Ni、Ge和/或Zn。因此,根据第三元素的具体含量,应当认识到,该合金的固相线应不低于230℃,更优选的是不低于248℃,最优选的是不低于258℃,液相线不高于400℃。这类合金特别可以用于固定芯片(例如,将半导体芯片固定在基底上)。因此,本发明还提出一种电子器件,它包含一个利用一种材料而连接在一个表面上的半导体芯片,所述材料包括含有所述的三元(或多元)合金的组合物。对于该三元合金的制备方法,也适用于上面所概述的相同理由。一般而言,应当在二元合金或二元合金成份中加入适当量的第三元素。
应当进一步重视的是,为了提高一种或多种物理化学或热机械性能而加入的化学元素或金属,可以使用任意的顺序进行添加,只要合金中的所有组分充分完全地(即每种组分至少95%)熔化,同时,添加的顺序并不局限于本发明所述的。同样地,应引起注意的是,当希望银和铋能够在熔化步骤前就结合时,银和铋也可以分别熔化,随后将熔化的银和铋混合。可以增加一个进一步延长的加热步骤,该加热温度应高于银的熔点,这样可以确保各组分充分完全地熔化和混合。特别应当重视的是,当含有一种或多种的添加元素时,该合金的固相线可能降低。因此,含有这些添加合金的合金的固相线在260-255℃、255-250℃、250-245℃、245-235℃范围内甚至更低。
关于该合金的热传导率,根据本发明所述的组合物的传导率应不低于5W/mK,更优选的是不低于9W/mK,最优选的是不低于15W/mK。而且,较适合的组合物应包括一种焊料,该焊料在1秒钟后的润湿平衡状态下对湿润的银的润湿力应高于0.1mN,更优选的是高于0.2mN,最优选的是高于0.3mN。此外,所述组合物的特定形状对本发明并不关键。但是,该组合物优选制造成线材、带材或球状(焊料凸点)。
在各种其它用途中,所述组合物(例如制成线材的)可以用于将第一种材料粘结到第二种材料上。例如,所述组合物(和含有所述组合物的材料)可以应用于电子器件以将半导体芯片(例如硅、锗或砷化镓芯片)粘结到引线框上,如图1所述。图中,电子器件100包括一个镀敷了银层112的引线框110。第二银层122沉积在半导体芯片120上(例如在背面银金属化)。芯片和引线框通过它们各自的银层被所述的组合物130(此处例如含有下述合金的焊料,该合金包括2wt%-18wt%的银和98wt%-82wt%的铋,并且其固相线不低于262.5℃、液相线不高于400℃)连结在一起。最适合的芯片固定方法是,所述组合物加热至高于该特定合金液相线40℃的温度,保持15秒,温度最好不高于430℃,时间不超过30秒。焊接过程可以在还原气氛(例如氢气或合成气体)中进行。
另一方面,本发明所述的组合物还可以用于除芯片固定之外的许多焊接过程。事实上,对于随后的焊接步骤在低于所述组合物熔点的温度下进行的所有、或几乎所有的分步焊料应用方法而言,所述的组合物都特别适用。而且,当需要用无铅焊料来代替高铅焊料、希望固相线温度高于260℃时,所述的组合物可以作为焊料使用。其它特别优选的用途包括,在热交换器的部件连接中使用所述焊料作为非熔化的分隔球或电/热互联。
实施例
由于不同材料的热膨胀系数的差异,焊点常常要承受剪切负荷。因此,特别要求连结这些材料的合金具有低剪切模量以及由此产生的良好的耐热机械疲劳性。例如,在固定芯片时,低剪切模量和良好的耐热机械疲劳性有助于避免芯片产生裂纹,特别是当相对较大的芯片粘结在固体载体上时。
基于已知的纯金属的弹性模量、Ag和Bi表现出部分的固态互溶性和Ag-Bi体系不含金属间相或中间相这几点,本发明所述的Ag-Bi合金在室温下的剪切模量在13-16GPa范围内(假定室温时的剪切模量是一种可以加和的性能-即下述的混合物规则)。所述合金室温时的剪切模量所处的13-16GPa范围同Au-25%Sb和Au-20%Sn合金的25GPa(使用同样的假设、用相同的方法计算得出)、J合金(Ag-10%Sb-65%Sn)的21GPa以及J合金的测量值22.3GPa相比,是尤其有利的。
用Ag-89%Bi合金粘结在引线框上的硅芯片构成的检测组件,在1500次热老化循环后并没有直观的失效迹象,这就进一步证实了所述Ag-Bi合金的剪切模量的计算值和观测值都很低。
在测试组件中和多种其它芯片固定应用中,焊料一般要么被制备成薄片放置在芯片和要焊接在一起的基底之间。随后加热使焊料熔化以形成焊点。或者可以将基底加热,随后将薄片状、线状、熔化的或其它形式的焊料放置在加热的基底上,以此在放置芯片处产生焊料熔滴,从而形成焊点。
对于区域阵列封装,所述焊料可以制备成球状、小型预型件、用焊料粉制成的膏或其它形式,从而形成该用途通常需要的多个焊点。或者,所述焊料可以用于包括用电镀液进行镀敷、从固态或液态蒸发、用类似喷墨打印机的喷嘴进行印制、或者通过溅射法而形成一系列焊料凸点以形成焊点。
优选方法是,将焊料球放置在封装上的接点上,使用焊剂或者焊膏(焊料粉在液态载体中)使其保持在适当的位置上,直到经加热而粘结在封装上。加热温度为能使焊球熔化、或者当使用低熔点组合物的焊膏时,该温度可以低于焊料的熔点。使用焊剂或焊膏将固定了焊球的封装在基底上排列成区域阵列,随后加热以形成焊点。
优选的将半导体芯片固定在封装上或印刷线路板上的方法包括,将焊膏通过通孔掩模层印制、焊料通过掩模层蒸发或将焊料镀敷到导电接点阵列上,以形成焊料凸点。由这种工艺制成的凸点或柱状物要么具有均匀的组成因而整个凸点或柱状物在加热时能熔化而形成焊点,或者这些凸点和柱状物的组成在垂直于半导体芯片表面的方向上是不均匀的因而每个凸点或柱状物仅有一部分会熔化。
因此,关于无铝焊料的详细的具体实施方案和应用已经公开。但是很明显,除了已经述及的那些以外,本领域技术人员在不脱离本发明内容的情况下还可能作出许多改进。因此,本发明的主题由权利要求确定,不受其它限制。而且,在解释说明书和权利要求时,所有的用语都应该用与上下文一致的、尽可能达到最大范围的方式来解释。特别是,词语“包含”应当被解释为用不排它的方式提到元素、成分或步骤,也就是说,文中所提到的元素、成分或步骤可以存在、被使用或者与其它未明确提及的元素、成分或步骤结合。
Claims (18)
1.一种焊料组合物,它含有:
一种包含下述二元合金的焊料,该合金含有2重量%-18重量%的Ag和98重量%-82重量%的Bi,其中该合金的固相线不低于262.5℃、液相线不高于400℃,
该组合物还含有一种氧亲和力高于该合金的氧亲和力的化学元素,其浓度为10ppm-1000ppm,
其中各组分百分含量之和等于100重量%。
2.如权利要求1所述的组合物,其中所述的合金中Ag含量为2重量%-7重量%,Bi含量为98重量%-93重量%。
3.如权利要求1所述的组合物,其中所述的合金中Ag含量为7重量%-18重量%,Bi含量为93重量%-82重量%。
4.如权利要求1所述的组合物,其中所述的合金中Ag含量为5重量%-10重量%,Bi含量为95重量%-90重量%。
5.如权利要求1所述的组合物,其中所述的焊料的热导率不低于9W/mK。
6.如权利要求1所述的组合物,其中所述的焊料在1秒钟后的润湿平衡状态下润湿Ag的润湿力为0.2mN。
7.如权利要求1所述的组合物,其中所述的化学元素选自下列元素:Al、Ba、Ca、Ce、Cs、Hf、Li、Mg、Nd、P、Sc、Sr、Ti、Y和Zr。
8.如权利要求1所述的组合物,其中所述的合金被制造成下述中的至少一种:线材、带材、预型件、阳极、球、糊和蒸发块。
9.一种电子器件,它包含一个使用含有权利要求1所述组合物的材料而连结在一个表面上的半导体芯片。
10.如权利要求9所述的电子器件,其中半导体芯片的至少一部分用Ag金属化。
11.如权利要求9所述的电子器件,其中所述表面的至少一部分用Ag金属化。
12.如权利要求9所述的电子器件,其中所述的表面包含一个Ag金属化的引线框。
13.制备焊料组合物的方法,包括提供Ag和Bi,其中Ag的量为Ag和Bi总重量的2重量%-18重量%和Bi的量为98重量%-82重量%;在至少960℃的温度下将Ag和Bi熔化,形成其固相线不低于262.5℃、液相线不高于400℃的二元合金。
14.如权利要求13所述的方法,其中在所述熔化Ag和Bi的步骤前增加混合Ag和Bi的步骤。
15.如权利要求13所述的方法,还包括加入一种氧亲和力高于该合金的氧亲和力的化学元素。
16.如权利要求13所述的方法,其中Ag的加入量为2重量%-7重量%,Bi的加入量为98重量%-93重量%。
17.如权利要求13所述的方法,其中Ag的加入量为7重量%-18重量%,Bi的加入量为93重量%-82重量%。
18.如权利要求13所述的方法,其中Ag的加入量为5重量%-10重量%,Bi的加入量为95重量%-90重量%。
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PCT/US2001/017491 WO2002097145A1 (en) | 2001-05-28 | 2001-05-28 | Compositions, methods and devices for high temperature lead-free solder |
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JP (1) | JP2004533327A (zh) |
KR (1) | KR100700233B1 (zh) |
CN (1) | CN100475996C (zh) |
AT (1) | ATE351929T1 (zh) |
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JP5093373B2 (ja) | 2011-03-08 | 2012-12-12 | 住友金属鉱山株式会社 | Pbフリーはんだペースト |
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CN101745752B (zh) * | 2009-12-17 | 2011-12-14 | 北京有色金属研究总院 | 一种纳米增强铋基无铅高温焊料及其制备方法 |
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DE60126157T2 (de) | 2007-12-13 |
DE60126157D1 (de) | 2007-03-08 |
ATE351929T1 (de) | 2007-02-15 |
EP1705258A2 (en) | 2006-09-27 |
WO2002097145A1 (en) | 2002-12-05 |
EP1399600B1 (en) | 2007-01-17 |
WO2002097145B1 (en) | 2004-05-27 |
EP1399600A1 (en) | 2004-03-24 |
KR100700233B1 (ko) | 2007-03-26 |
CN1507499A (zh) | 2004-06-23 |
EP1399600A4 (en) | 2005-05-04 |
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JP2004533327A (ja) | 2004-11-04 |
EP1705258A3 (en) | 2007-01-17 |
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