CN1165978C - 安装结构、制作安装结构的方法 - Google Patents

安装结构、制作安装结构的方法 Download PDF

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Publication number
CN1165978C
CN1165978C CNB001065696A CN00106569A CN1165978C CN 1165978 C CN1165978 C CN 1165978C CN B001065696 A CNB001065696 A CN B001065696A CN 00106569 A CN00106569 A CN 00106569A CN 1165978 C CN1165978 C CN 1165978C
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China
Prior art keywords
elutriation
mounting structure
film
adhesive layer
conductive adhesive
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CNB001065696A
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CN1274950A (zh
Inventor
天見和由
竹沢弘辉
白石司
别所芳宏
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Abstract

借助于利用在至少部分导电填料上具有防淘析膜的导电粘合剂而构造安装结构的导电粘合剂层，提高了绝缘可靠性和抗硫化可靠性。

Description

安装结构、制作安装结构的方法
本发明涉及到用来安装诸如半导体器件之类的电子元件的安装结构及其制作方法以及用来制作安装结构的导电粘合剂。
迄今，在将半导体器件安装到电路板的输入/输出端子电极上的过程中，常常采用借助于焊接的金属丝键合方法。然而，近年由于半导体器件封装件尺寸的减小和连接端子数目的增大，各个连接端子之间的间距变得越来越小，使得越来越难于用常规的焊接技术来执行安装。
因此，近年提出了一种方法，其中诸如集成电路芯片之类的半导体器件被直接安装在电路板的输入/输出端子电极上，以便适应尺寸的减小并有效地利用安装区域。
首先，半导体器件面朝下安装在电路板上的倒装芯片安装方法，由于除了连接之后有高的机械强度之外，还能够在半导体器件与电路板之间建立集中的电连接，而被认为是一种有用的方法。
作为上述倒装芯片安装方法的一种连接材料，提出或实际使用了一种采用导电粘合剂的系统。
由于下面二个原因，考虑到可靠性的改进和环境保护措施二者，此方法是一种有前景的方法。
首先，由于导电粘合剂包含诸如环氧树脂之类的树脂材料，故比之焊料亦即金属材料，建立了一种能够抵抗外力或热应力的柔软的连接，从而改善了可靠性。
其次，由于导电粘合剂主要包含作为导电成分的银颗粒，故能够进行不使用铅的清洁的安装。
另一方面，对于诸如芯片元件或封装件元件之类的电子元件被安装在印刷板上的常规结构，也提出了一种结构，其中考虑到可靠性的改善和环境保护措施而使用了导电粘合剂。
于是，考虑到可靠性的改善和将来环境保护的措施，采用导电粘合剂的安装结构就将是一种有前景的方法。
然而，采用导电粘合剂的安装结构有下列二方面的问题，从而妨碍了其实际应用。
第一个问题是离子迁移引起的绝缘可靠性下降。离子迁移是一种电解作用，并且是一种当水之类的电解质出现在施加有电压的电极之间时，通过下列4个步骤在电极之间发生的绝缘击穿现象。
步骤1)正电极金属的淘析和离化，
步骤2)离化的金属由于电压的施加而向负电极迁移，
步骤3)迁移到负电极的金属离子淀积，
步骤4)重复步骤1)至3)。
通过这样一种离子迁移现象，金属枝状生长在电极之间，且电极最终被金属搭桥，从而引起绝缘击穿。
用作导电粘合剂的导电填料材料的银，具有被淘析的倾向，故易于引起离子迁移。而且，根据近年电子设备的尺寸和重量的进一步减小，排列在半导体器件、电子元件或电路板上的电极的间距变得越来越小，从而更增大了离子迁移的可能性。为此，为了用导电粘合剂实际进行安装，解决离子迁移的问题是至关重要的。
通常，为了抑制离子迁移，提出了下列3种方法。
提议1)制作具有合金(银-铜、银-钯之类)的导电填料，
提议2)用环氧树脂之类的绝缘树脂密封导电粘合剂，
提议3)借助于将诸如离子交换树脂或螯合剂之类的离子捕获剂加入到导电粘合剂中，将淘析的金属离子捕获并将其形成为不溶解的物质。
然而，这些提议牵涉到下列缺点。在提议1)中，填料金属非常昂贵，从而提高了导电粘合剂的生产成本。在提议2)中，密封步骤的加入必须增加步骤数目并大量安装额外的设备，从而提高生产成本。在提议3)中，金属离子从导电填料中的淘析降低了导电填料的接触性质，从而增大了连接电阻。
这样，虽然上述提议产生了抑制离子迁移的效果，但它们牵涉到其它的问题，致使除了特别的领域外，难以实际应用这些提议。第二个问题是由于硫化作用而增大了连接电阻。硫化作用是一种金属由于与诸如硫化氢或二氧化硫之类的含硫的弱酸性气体发生反应而改变成具有较低电导率的称为金属硫化物的物质的现象。硫化作用看来是通过下列步骤发生的，虽然其很多部分仍然未解决。
步骤1)金属在弱酸性气氛中的淘析和离化，
步骤2)由于硫离子与金属离子的反应而产生金属硫化物。
如上所述，导电填料主要由作为主要成分的银组成。但由于银极易被硫化，故当银被硫化时，导电粘合剂的体电阻率增大，从而连接电阻增大。目前尚未报道此问题的解决方法，因而不可能将采用导电粘合剂的安装结构用来生产可能使用在诸如硫化氢或二氧化硫浓度相当高的温泉或火山附近之类的环境中的电子元件。因此，采用导电粘合剂的安装结构的应用领域极为有限。
于是，本发明的主要目的是，即使在诸如非常潮湿的条件或含有硫的气体气氛之类的比较严厉的条件下，也能够保持采用导电粘合剂的安装结构的可靠性。
为了达到上述目的，简单地说，本发明提供了一种安装结构，它包含电气结构和排列在所述电气结构上的导电粘合剂层，其中所述导电粘合剂层包含导电填料和排列在至少部分所述导电填料上的防淘析膜。由于这一构造，本发明的安装结构即使在高温和高湿度环境下，仍然呈现良好的绝缘可靠性。这是由于防淘析膜即使在高温和高湿度条件下也防止了导电填料中的金属的淘析，从而基本上防止了离子迁移反应。而且，本发明的安装结构不引起导电填料的硫化作用，且即使处于含硫的气体中仍然呈现良好的连接可靠性。这是由于防止了导电填料的淘析而能够基本上防止硫化反应。本发明所用的防淘析膜可以例如由热凝树脂、热塑树脂、金属醇盐之类制成。热凝树脂的具体例子包括酚醛树脂、尿素树脂、三聚氰胺树脂、呋喃树脂、不饱和聚酯树脂、苯二甲酸二烯丙酯、环氧树脂、硅酮树脂、聚酰亚胺树脂等。热塑树脂的具体例子包括氯乙烯树脂、偏二氯乙烯树脂、聚苯乙烯、AS树脂、ABS树脂、异丁烯树脂、聚乙烯、离子聚合物、甲基戊烯树脂、异质同晶共聚物、氟树脂、聚酰胺、聚酰亚胺、聚酰胺-酰亚胺、聚亚胺酯、聚碳酸酯、聚酯、聚缩醛、改性聚亚苯基氧化物、聚砜、聚亚苯基硫化物等。金属醇盐的具体例子包括四乙氧化硅、三丁氧化铝、四丁氧化钛等。
此处，若安装结构还包含排列在所述电气结构上的另一个电气结构，且所述导电粘合剂层将所述电气结构电连接到所述其它的电气结构，则由于导电填料的离子迁移反应或硫化作用对连接电阻的影响明显而使本发明特别有效。
具体地说，若至少部分所述导电填料被暴露在所述导电粘合剂层的表面上，且所述防淘析膜被排列在至少所述导电填料的所述暴露的部分上，则足够了。更具体地说，若所述导电粘合剂层具有大量的彼此连通并与所述导电粘合剂层的表面连通的孔；至少部分所述导电填料被暴露于所述孔的内表面；且所述防淘析膜至少排列在暴露于所述孔的所述内表面的所述导电填料上，则足够了。这一构造使防淘析膜能够被选择性地仅仅形成在与导电粘合剂层的表面连通且易于淘析的部分导电填料上。这有下列优点。
若防淘析膜被排列在包含在电连接中的部分填料上，则防淘析膜在某些情况下引起导电障碍。因此，若防淘析膜出现在这一部分，则进行诸如从外部沿导电方向对其压缩之类的处理，以便击破这部分上的防淘析膜以确保导电。相反，若防淘析膜仅仅被选择性地排列在淘析易于发生的部分，则仅仅有有限数量的必须建立导电的部分填料上的防淘析膜，从而更加改进导电。
而且，防淘析膜最好是不溶于水的，因为这样即使在高温和高湿度条件下，防淘析膜也不会淘析，且防淘析作用也更不易于降低，从而能够长时间保持抑制离子迁移反应的作用和抑制导电填料硫化的作用。
能够用于本发明的不溶于水的防淘析膜可以例如由热凝树脂、热塑树脂、金属醇盐之类制成。热凝树脂的具体例子包括酚醛树脂、尿素树脂、三聚氰胺树脂、呋喃树脂、不饱和聚酯树脂、苯二甲酸二烯丙酯树脂、环氧树脂、硅酮树脂、聚酰亚胺树脂等。热塑树脂的具体例子包括氯乙烯树脂、偏二氯乙烯树脂、聚苯乙烯、AS树脂、ABS树脂、异丁烯树脂、聚乙烯、离子聚合物、甲基戊烯树脂、异质同晶共聚物、氟树脂、聚酰胺、聚酰亚胺、聚酰胺-酰亚胺、聚碳酸酯、改性聚亚苯基氧化物、聚亚苯基硫化物等。金属醇盐的具体例子包括四乙氧化硅、三丁氧基金属铝、四丁氧化钛等。
防淘析膜最好是不溶于含有硫化氢或氧化硫的水溶液中，因为这样防硫化反应的作用可以更大。这是由于即使硫化氢或氧化硫以水溶液的形式凝聚在防淘析膜的表面上，防淘析膜也不淘析，致使防淘析作用不太可能发生下降。
不溶于含有硫化氢或氧化硫的水溶液的防淘析膜，可以例如由热凝树脂、热塑树脂、金属醇盐之类制成。热凝树脂的具体例子包括酚醛树脂、三聚氰胺树脂、呋喃树脂、不饱和聚酯树脂、苯二甲酸二烯丙酯树脂、环氧树脂、硅酮树脂、聚酰亚胺树脂等。热塑树脂的具体例子包括氯乙烯树脂、偏二氯乙烯树脂、聚苯乙烯、AS树脂、ABS树脂、异丁烯树脂、聚乙烯、离子聚合物、甲基戊烯树脂、异质同晶共聚物、氟树脂、聚酰胺、聚酰亚胺、聚酰胺-酰亚胺、聚碳酸酯、改性聚亚苯基氧化物、聚亚苯基硫化物等。金属醇盐的具体例子包括四乙氧化硅、三丁氧基金属铝、四丁氧化钛等。
此处，术语“在含有硫化氢或氧化硫的水溶液中或在水中的不溶解性”被用来表示满足下列条件。亦即，若防淘析膜由树脂制成，则上述不溶解性被定义为一种性质，使24小时后吸收的水或水溶液的量小于或等于0.5％重量比。若防淘析膜由络合物制成，则上述不溶解性被定义为一种性质，使其溶解性(溶解于100克水中的络合物的重量)小于1×10-5克。
防淘析膜最好包含金属络合物。此金属络合物是一种由金属与络合剂反应而产生的配位化合物。这一反应在室温下快速进行。因此，借助于使导电填料能够与络合剂接触而进行导电填料表面上的络合物膜的制作。形成在填料表面上的金属络合物具有金属与络合剂之间的极强的配位键，致使金属络合物稳定并具有与金属的极紧密的接触。这进一步提高了防淘析作用，从而产生更好的改善抗离子迁移性质的作用和更好的改善抗硫化反应性质的作用。此处，用来制作金属络合物的络合剂的配合基可以例如是氨基乙酰基、氨基羧基、链烷醇胺基、β-双酮基、β-酮酯基、聚胺基、咪唑基等。其中，最好采用键合到苯环的氨基羧基或咪唑基，因为这样金属络合物膜将不溶于水且不溶于含有硫化氢或氧化硫的水溶液，从而进一步增大抑制离子迁移的效果和抑制硫化反应的效果。这种络合剂的例子包括邻氨基苯甲酸、2-氨基哌啶、棓酰镓酸、黄原酸钾、吡喃、喹啉酸、铜铁灵、4-氯-3-甲基-5-硝基苯磺酸、水杨醛肟、二安替比林基代甲烷、二乙基氨荒酸、p-二甲基氨基若丹明亚甲基苯、二甲基乙二肟、草酸、辛可宁酸、N-肉桂酰基-N-苯胲、硫代乙酰胺、巯萘剂、硫脲、四苯基硼酸、三甲基苯基铵、1-亚硝基-2-萘酚、黄硝、新铜铁灵、铋硫酮II、p-烃基苯基砷酸、8-烃基-7-碘-5-喹啉磺酸、连苯三酚、1-吡咯二硫代羧酸、苯基砷酸、phenylthiodantoic酸、苯基荧光酮、α-糠偶酰二肟、香木鳖碱、联苯胺、N-苯甲酰基-N-苯胲、α-苯偶姻肟、苯[f]喹啉、2-硫醇苯噻唑、若丹明B等。
而且，防淘析膜不仅仅局限于金属络合物，可以进一步包含树脂成分。简言之，若防淘析膜具有能够防止淘析的功能就足够了。
此处，若导电填料包含银，则由于银是一种易于引起离子迁移和硫化反应的物质，故本发明的效果，亦即抑制离子迁移的效果和抑制硫化作用的效果，将是突出的。
能够应用本发明的上述安装结构的例子包括其上安装有电子元件的电路板、其上倒装芯片安装有半导体器件的电路板、等等。
本发明的粘合剂含有导电填料，且至少部分导电填料具有防淘析膜。利用这种构造，本发明的用导电粘合剂安装的安装结构呈现良好的绝缘可靠性，即使在高温和高湿度环境下也不引起离子迁移。而且，呈现良好的连接可靠性，即使在含有硫的气体中也不引起导电填料的硫化。
此处，关于防淘析膜的组分，最好是不溶于水的，最好还不溶于含有硫化氢或氧化硫的水溶液，最好包含金属络合物，且最好包含树脂成分。而且，导电粘合剂最好包含银。
本发明还提供了一种制作安装结构的方法，所述方法包含在电气结构上制作导电粘合剂层的步骤，所述导电粘合剂层包含导电填料；以及在所述导电粘合剂层硬化之后在所述导电填料上制作与所述导电粘合剂层的表面连通的防淘析膜的步骤。用此制作方法生产的安装结构能够呈现改善抗离子迁移性质的效果以及改善抗硫化反应性质的效果，同时又借助于形成防淘析膜而很好地保持电气结构的导电。而且，由于防淘析膜在导电粘合剂层硬化之后制作在导电填料上，故防淘析膜不进入导电粘合剂层的电连接位置以对其导电状态产生不利的作用，致使能够确保良好的导电。
以这种方式制作防淘析膜的一种方法是制作络合物的工艺。制作络合物的这一工艺能够执行下列功能。例如用浇注络合剂的方法进行络合工艺。这种络合工艺可以用现有的设备来进行，从而免去了新的设备投资并仅仅少量增加生产成本。此处，若络合膜被制作在各个导电填料之间的接触点上或导电填料与电极金属之间的接触点上，则由于络合物通常是绝缘的而可能使导电粘合剂的电导率和安装结构的电学特性有某种程度的退化。相反，若采用本发明的生产方法，则导电粘合剂层硬化之后，导电填料被形成在络合物中以确保其导电，致使仅仅不涉及到导电的位置能够形成在络合物中，同时照原保持各个导电填料之间的上述接触点以及导电填料与其它电气结构之间的接触点电连接于导电粘合剂层。因此，能够有效地制作防淘析膜，同时确保安装结构的电学特性，从而得到低的连接电阻。此处，在此工艺中，由于络合剂选择性地与金属部分反应，故防淘析膜不形成在不需要络合过程的位置处，亦即导电粘合剂层的树脂成分(粘合剂树脂之类)的位置处或电气结构的表面(板的表面之类)。而且，根据本发明的方法，由于络合工艺在使用任意导电粘合剂制造安装结构之后进行，故本发明能够用于使用任何类型导电粘合剂的安装结构，致使其经济效益高。
可以用本发明生产的安装结构的具体例子包括用所述导电粘合剂层将另一个电气结构电连接于所述电气结构的安装结构、电子元件被安装在电路板上的安装结构、以及半导体器件被倒装芯片安装在电路板上的安装结构。确切地说，若本发明被用于由诸如芯片阻器之类的芯片元件制成的电子元件被安装在电路板上的安装结构，则可以执行下列功能。
若上述电子元件被安装，则它们的连接位置被暴露，致使能够在完成安装结构之后，用诸如络合工艺之类的工艺，同时在安装结构的所有元件的连接位置上制作防淘析膜。因此，能够缩短制作防淘析膜所需的时间。此处，若用络合工艺制作防淘析膜，则由于络合剂选择性地与金属部分反应，故络合膜(防淘析膜)不形成在不需要制成络合物的部分上，亦即板的表面上、元件的表面上等等。
从最佳实施例的下列详细描述中，本发明的上述和进一步目的将变得明显，在所附权利要求中精确地表明了本发明的上述和进一步目的，本技术领域的熟练人员在参照附图将本发明付诸实际时将回忆起本说明书未曾触及的大量其它的优点，在这些附图中，
图1是根据本发明第一最佳实施例的导电粘合剂的主要部分的放大图；
图2是根据本发明第二最佳实施例的倒装芯片安装结构的剖面图；
图3是根据本发明第三最佳实施例的芯片元件安装结构的平面图；
图4是用根据本发明第四最佳实施例的方法制造的电路板的平面图；
图5(A)和5(B)是用根据第四实施例的方法制造的导电粘合剂层的剖面图；以及
图6是抗硫化反应性质评估中所用的测试样品的平面图。
以下参照附图来描述本发明的最佳实施例。
(第一实施例)
在第一实施例中，本发明被用于导电粘合剂。图1是根据此实施例的导电粘合剂1的主要部分的放大图。导电粘合剂1的特征是导电粘合剂1本身的结构。亦即，导电粘合剂1包括具有防淘析膜3的导电填料2以及有机粘合剂4，其中的导电填料2与有机粘合剂4被混合并分散。
防淘析膜3可以例如由诸如尿烷树脂、氯乙烯树脂、偏二氯乙烯树脂、聚苯乙烯之类的热塑树脂制成，或由诸如酚醛树脂、尿素树脂、三聚氰胺树脂之类的热凝树脂制成。有机粘合剂3可以由例如环氧树脂制成，或由诸如醋酸乙烯树脂、丙烯树脂、苯氧基树脂之类的另一种树脂制成。而且，有机粘合剂3可以由金属络合物制成。
导电填料可以由例如银(Ag)、金(Au)、Ag涂敷的Cu、Cu-Ag合金、铜(Cu)、镍(Ni)、Ag-Pd合金之类制成。但考虑到体电阻率和材料成本，银(Ag)是最佳的。
(第二实施例)
在本实施例中，本发明被用于半导体器件的倒装芯片安装结构。参照图2，根据本实施例的安装结构包括作为电气结构例子的电路板5以及作为另一种电气结构的例子的半导体器件6。半导体器件6包括IC板7和排列在IC板7的表面上的凸块电极8。电路板5包括排列在电路板5的表面上的输入/输出端子电极9。而且，由第一实施例中所述的导电粘合剂1制成的导电粘合剂层1A，被排列在输入/输出端子9上，并在输入/输出端子9和凸块电极8之间由导电粘合剂层1A建立电连接。而且，密封树脂10被排列在半导体器件6与电路板5之间的间隙中，从而完成倒装芯片安装结构。
(第三实施例)
在本实施例中，本发明被用于芯片元件的安装结构。参照图3，本安装结构被构造成在组成电气结构的一个例子的电路板11的电极12的表面上，安装组成另一个电气结构的例子的芯片电阻器13、芯片线圈14和芯片电容器15。而且，由第一实施例所述的导电粘合剂1制成的导电粘合剂层1A，被排列在电极12上，并在电极12与芯片元件13、14、15之间由导电粘合剂层1A建立电连接。
(第四实施例)
上述第一到第三实施例所述的导电粘合剂1和安装结构的特征是，包含在导电粘合剂1中或导电粘合剂层1A中的导电填料2预先具有防淘析膜3。相反，本实施例的特征是，在电气结构上制作导电粘合剂层之后，在包含在导电粘合剂层中的导电填料上制作防淘析膜。在本实施例中，如图4所示，作为其一个例子，本发明被用于具有梳状电极形状的导电粘合剂层17、18用丝网印刷方法制作在作为电气结构的例子的电路板16上的电气结构。但不用多说，本发明也能够用于在电路板上安装各种电子元件的过程中制作在电路板上的导电粘合剂层。以下描述本实施例的生产方法。
首先，在电路板16上，用相似于常规的不具有防淘析膜的导电粘合剂制作导电粘合剂层17、18。
接着，借助于将络合剂混合到溶剂中而制备络合溶液。此处，络合溶液中的混合比率以及溶剂的种类，可以根据导电填料2的表面态和后续工艺中制作的防淘析膜3的厚度改变，致使其混合比率和溶剂种类不受特别的限制。
然后，将电路板16浸入络合溶液中并从中拉起，随之以热处理。通过这一工艺，由金属络合物制成的防淘析膜3，借助于溶剂的蒸发而被制作在导电填料2的表面上。
以下参照图5来详细描述制得的防淘析膜3的形状。构成导电粘合剂层17和18的导电粘合剂1，由导电填料2、有机粘合剂4以及各种各样的添加剂组成。借助于加热和硬化这样构成的导电粘合剂1而制作导电粘合剂层17和18。在这一工艺过程中，导电填料2之外的大多数组分(有机粘合剂等)被加热蒸发。因此，在加热和硬化工艺之后，由于这些组分的蒸发而在导电粘合剂层17和18中形成大量的孔19(见图5(A))。
这些孔19中的大多数彼此连通，并与导电填料2的表面连通。因此，暴露于这些孔19的内表面的导电填料2就被暴露于外部环境。因此，导电填料2易于从这一位置淘析。
当具有这种结构特征的导电粘合剂层17和18被浸入络合溶液中时，络合溶液到达彼此连通的孔19的底部处暴露的导电填料2的表面位置。因此，若用加热络合溶液的方法制作防淘析膜(金属络合物膜)3，则防淘析膜3被制作在孔19中，从而在孔19的底部暴露的导电填料2的表面位置被防淘析膜3覆盖。于是，防淘析膜3可以选择性地仅仅形成在易于淘析的导电填料2的表面位置上，致使防淘析膜3不形成在各个导电填料2之间的导电位置处或待要在导电填料2与另一个电气结构之间建立电连接的位置处。
接着，解释上述各个实施例的例子。
首先，描述第一实施例(导电粘合剂)的例子。
(例1)
此例子的特征是，第一实施例所示的导电粘合剂1的防淘析膜3由尿烷树脂制成。
接着描述生产本例子的导电粘合剂1的方法。首先，0.5％重量比的尿烷树脂被溶解并混合在95.5％重量比的异丙醇中，以制备此树脂的醇溶液。此处，尿烷树脂在24小时后具有大约0.8％的水吸收，并具有容易吸附水和含有硫化氢或氧化硫的水溶液的性质。待要制备的树脂的醇溶液中的混合比以及溶剂的种类，可以根据导电填料2的表面态和待要制作的防淘析膜3的厚度变化，致使它们不特别局限于上述的条件。
然后，将由银(Ag)制成的导电填料2加入到制得的醇树脂溶液中，随之以充分的搅拌。当导电填料2的表面被醇树脂溶液湿润时，从醇树脂溶液中取出导电填料2，随之以在100℃的炉子中干燥大约30分钟，以便充分地蒸发溶剂的异丙醇。通过这一工艺，由尿烷树脂制成的防淘析膜3被制作在导电填料2的表面上。这一干燥工艺的温度和时间也可以根据溶液中的树脂浓度和加工的导电填料2的数量而改变，致使它们不特别局限于上述的工艺条件。
借助于分散和混合92％重量比的其上这样制作防淘析膜3的导电填料2、7％重量比的由具有热凝性质的环氧树脂制成的有机粘合剂4、以及1％重量比的添加剂(分散剂、紧密接触性质改进剂等)，来制备本例子的导电粘合剂。
(例2)
此例子的特征是，例1所述的导电粘合剂1的防淘析膜3由尿素树脂制成，而不是由尿烷树脂制成。尿素树脂的水吸收小于0.5％重量比/24小时，并是一种在本发明中定义为不溶于水和不溶于含有硫化氢或氧化硫的水溶液的树脂。其它条件，亦即导电粘合剂材料的构造条件、生产方法等，与例1相同。
(例3)
此例子的特征是，例1所述的导电粘合剂1的防淘析膜3由氟树脂制成，而不是由尿烷树脂制成。氟树脂的水吸收小于0.01％重量比/24小时，并是一种在本发明中定义为不溶于水和不溶于含有硫化氢或氧化硫的水溶液的树脂。其它条件，亦即导电粘合剂材料的构造条件、生产方法等，与例1相同。
(例4)
此例子的特征是，例1所述的导电粘合剂1的防淘析膜3由含有二乙醇胺的金属络合物制成。
下面描述此实施例的导电粘合剂1的生产方法。首先，10％重量比的构成络合剂的二乙醇胺被溶解并混合在90％重量比的双异丙醇中，以制备络合剂的醇溶液。二乙醇胺与金属反应产生的金属络合物是一种离子性物质，极容易溶于水并具有容易吸附水和含有硫化氢或氧化硫的水溶液的性质。
此处，待要制备的络合剂溶液中的混合比以及溶剂的种类，可以根据导电填料2的表面态和待要制作的防淘析膜3的厚度变化，致使它们不特别局限于上述的条件。
然后，将导电填料2加入到制得的络合剂溶液中，随之以充分的搅拌。当导电填料2的表面被络合剂溶液湿润时，从络合剂溶液中取出导电填料2，随之以在100℃的炉子中干燥大约30分钟，以便充分地蒸发溶剂的异丙醇。通过这一工艺，二乙醇胺与导电填料2在导电填料2的表面上发生反应，由这一金属络合物制成的防淘析膜3就被制作在导电填料2的表面上。
这一干燥工艺的温度和时间也可以根据络合剂溶液中的络合剂浓度和加工的导电填料2的数量而改变，致使它们不特别局限于上述的工艺条件。
借助于分散和混合92％重量比的其上这样制作防淘析膜3的导电填料2、7％重量比的由环氧树脂制成的有机粘合剂4、以及1％重量比的添加剂(分散剂、紧密接触性质改进剂等)，来制备本例子的导电粘合剂。
(例5)
此例子的特征是，例4的导电粘合剂1的防淘析膜3由o-氨基苯甲酸制成，而不是由二乙醇胺的金属络合物制成。
二乙醇胺的金属络合物是一种离子性物质，并可溶于水和含有硫化氢或氧化硫的水溶液。相反，o-氨基苯甲酸组成的金属络合物是非离子性的，并且是一种在本发明中定义为不溶于水和不溶于含有二氧化硫或硫化氢的水溶液的金属络合物。
(比较例1)
根据上述例1-5，制备了比较例1的导电粘合剂。
借助于分散并混合92％重量比的由银(Ag)制成的导电填料2、7％重量比的由环氧树脂制成的有机粘合剂4、以及1％重量比的添加剂(分散剂、紧密接触性质改进剂等)，来构成这一导电粘合剂。
利用这样制备的例1-5以及比较例1的导电粘合剂1，制作了导电粘合剂层，并根据下列方法进行评估和测量。
(1)抗离子迁移性质的评估(水液滴测试)
水液滴测试是一种在短时间内以简单的方式评估材料的迁移性质的测试方法。此测试方法的细节如下。相似于第四实施例所述的电路板的结构的构造，被用作测试样品。亦即，再次参照图4，用丝网印刷方法在电路板16上制作具有梳状电极形状的导电粘合剂层17和18。此处，陶瓷衬底被用作电路板16。导电粘合剂层17和18排列成彼此相对，电极之间分隔预定的距离(400微米)，使电极的顶端交替排列。平时，在导电粘合剂层17与18之间不能流动电流。
将去离子水滴在这样制备的导电粘合剂层17和18上，在二个导电粘合剂层17和18之间施加DC电压(1V)。测量由二个导电粘合剂层17和18之间的短路造成的电流流动之前的时间，以便根据短路之前的时间长度来评估抗离子迁移性质。
(2)抗硫化反应性质的评估
参照图6，在由玻璃环氧树脂制成的电路板19上制作镀金的电极20，并用丝网印刷方法在镀金的电极20上制作由导电粘合剂1制成的导电粘合剂层21。再用安装装置将具有3216尺寸的0Ω电阻器(端子镀层为SnPb焊料)22安装在导电粘合剂层21上。然后，在150℃的炉子中对电路板19进行30分钟加热，以便硬化导电粘合剂层21。对于这样制备的样品，测量其初始连接电阻，然后将电路板19置于充满硫化氢的密封槽中，从而借助于测量连接电阻的改变而评估抗硫化反应性质。在温度为40℃、湿度为90％、硫化氢浓度为3ppm的条件下进行测试，测试的时间为96小时。
表1示出了进行上述评估和测量的结果。
表1
    防淘析膜 迁移测试(秒)     硫化测试(mΩ)
  初始   96小时后
 例1     尿烷树脂     550     38     56
 例2     尿素树脂     840     38     55
 例3     氟树脂     948     36     40
 例4     二乙醇胺Ag     1116     36     38
 例5     o-氨基苯甲酸Ag     1232     36     36
 例16     o-氨基苯甲酸Ag     1229     30     30
 比较例1     无     86     30     98
对于例1-5的导电粘合剂1，比之比较例1，发现下列情况。亦即，在抗离子迁移性质的评估中，电流开始流动之前的时间比比较例1更长，从而证实了抗离子迁移性质得到了改善。同样，在抗硫化反应性质的评估中，测试之前和之后的连接电阻的改变比比较例1小，从而证实了抗硫化反应性质得到了改善。
而且，借助于对各个例子进行比较，证实了下列情况。亦即，借助于将防淘析膜3由树脂制成的例1-3与防淘析膜3由金属络合物制成的例4和5进行比较，证实了例4和5具有更好的抗离子迁移性质。这看来是由于防淘析膜3对导电填料2的粘合强度由于络合物与导电膜2的直接化学反应以形成由金属络合物制成的防淘析膜3而得到了提高。
而且，借助于对各个例子进行比较，无论在具有由树脂制成的防淘析膜3的例子1-3中，还是在具有由金属络合物制成的防淘析膜3的例子4和5中，都有下列情况。亦即，具有由本发明中定义为不溶于水和不溶于含有硫化氢或氧化硫的水溶液的材料制作的防淘析膜3的例子2、3、5，比之具有由其它材料制成的防淘析膜3的例子1和4，表现出了抗离子迁移性质评估中的改善以及抗硫化反应性质评估中的改善。而且，在具有由被上述定义定义为不可溶解的材料制作的防淘析膜3的例子2与3之间，发现溶解度较低的那一个具有更高的评估结果。
下面描述第二实施例的例子(半导体器件的倒装芯片安装结构)。
(例6)
此例子的特征是，用防淘析膜3由尿烷树脂制成的例1的导电粘合剂1，将半导体器件6倒装芯片安装在电路板5上(唯一的不同是有机粘合剂由具有热塑性的环氧树脂制成)。
亦即，用熟知的方法将例1所述的导电粘合剂1转换到半导体器件6的凸块电极8上。然后，在被转换的导电粘合剂1与电路板5的输入/输出端子电极9对准的情况下，将半导体器件6倒装芯片安装在电路板5上。然后，在导电粘合剂1被硬化之后，进行电学测试。若得到好的结果，则在电路板5与半导体器件6之间的间隙中提供由环氧树脂制成的密封树脂10并进行硬化，以便将连接位置密封起来，从而完成倒装芯片安装结构。
(例7)
此例子的特征是，用防淘析膜3由尿素树脂制成的例2的导电粘合剂1构成倒装芯片安装结构。除了导电粘合剂1之外，此倒装芯片安装结构的构造和制造方法与例6相同。
(例8)
此例子的特征是，用防淘析膜3由氟树脂制成的例3的导电粘合剂1构成倒装芯片安装结构。除了导电粘合剂1之外，此倒装芯片安装结构的构造和制造方法与例6相同。
(例9)
此例子的特征是，用防淘析膜3由含有二乙醇胺的金属络合物制成的例4的导电粘合剂1构成倒装芯片安装结构。除了导电粘合剂1之外，此倒装芯片安装结构的构造和制造方法与例6相同。
(例10)
此例子的特征是，用防淘析膜3由含有o-氨基苯甲酸的金属络合物制成的例5的导电粘合剂1构成倒装芯片安装结构。除了导电粘合剂1之外，此倒装芯片安装结构的构造和制造方法与例6相同。
(比较例2)
根据上述例6-10，制造了比较例2的倒装芯片安装结构。
此倒装芯片安装结构被制作成具有相似于使用比较例1的导电粘合剂的例6-10的安装结构。
用下列方法，在如上所述制造的例6-10和比较例2的倒装芯片安装结构上进行可靠性测试。
亦即，对于这些倒装芯片安装结构，借助于测量连接电阻在高温和高湿度环境(85℃，85％)下通过实际使用时的电流(10mA)时的变化而进行抗离子迁移性质的评估。同样，借助于测量连接电阻在硫化氢气氛(40℃，90％，硫化氢浓度为3ppm)下通过实际使用时的电流(10mA)时的变化而进行抗硫化反应性质的评估。结果示于表2。
表2
    防淘析膜 迁移测试(小时)     硫化测试(mΩ)
  初始   96小时后
 例6     尿烷树脂     2240     16     26
 例7     尿素树脂     3564     16     25
 例8     氟树脂     4158     15     21
 例9     二乙醇胺Ag     5007     16     19
 例10     o-氨基苯甲酸Ag     5878     16     16
 例17     o-氨基苯甲酸Ag     5880     12     12
 比较例2     无     647     49     165
对于例6-10的倒装芯片安装结构，比之比较例2，发现下列情况。亦即，在抗离子迁移性质的评估中，电流开始流动之前的时间比比较例2更长，从而证实了抗离子迁移性质得到了改善。同样，在抗硫化反应性质的评估中，测试之前和之后的连接电阻的改变小于比较例2的，从而证实了抗硫化反应性质得到了改善。
而且，借助于对各个例子进行比较，证实了下列情况。亦即，借助于将防淘析膜3由树脂制成的例6-8与防淘析膜3由金属络合物制成的例9和10进行比较，证实了例9和10具有更好的抗离子迁移性质。
而且，借助于对各个例子进行比较，无论在具有由树脂制成的防淘析膜3的例子6-8中，还是在具有由金属络合物制成的防淘析膜3的例子9和10中，都有下列情况。亦即，具有由本发明中定义为不溶于水和不溶于含有硫化氢或氧化硫的水溶液的材料制作的防淘析膜3的例子7、8、10，比之具有由其它材料制成的防淘析膜3的例子6和9，表现出了抗离子迁移性质评估中的改善以及抗硫化反应性质评估中的改善。而且，在具有由被上述定义定义为不可溶解的材料制作的防淘析膜3的例子7和8之间，发现溶解度较低的那一个具有更高的评估结果。
这样，例子6-10(倒装芯片安装结构)就产生了相似于例1-5(导电粘合剂)的效果。
此处，在例子6-10中，用具有由热塑性环氧树脂制成的有机粘合剂4的导电粘合剂1，在半导体器件6与电路板5之间建立了电连接。但按与第一实施例相同的方式，利用热凝性环氧树脂，不用说也产生相似的效果。
而且，在例6-10中，恐怕防淘析膜3有可能妨碍各个连接位置处的电连接(导电填料2与凸块电极8之间、各个电学填料2之间、导电填料2与输入/输出端子电极9之间)。但由于在执行倒装芯片安装过程中，电路板5与半导体器件6被加压键合，故在加压位置(连接位置)处的防淘析膜3被加压键合工艺击破，从而在连接位置处建立直接的电连接，致使防淘析膜3不妨碍连接。
下面描述第三实施例(芯片元件安装结构)的例子。
(例11)
此例子的目的是利用例1的导电粘合剂制造的芯片元件安装结构。此处，在例1中，采用由尿烷树脂制成的防淘析膜3。此芯片元件安装结构包括安装在借助于在由玻璃环氧树脂衬底制成的电路板11(30mm×60mm，厚度为1.6mm)上镀金(Au)而制作的电极12上的5个芯片电阻器13(3216尺寸，镀SnPb)、2个芯片线圈14(直径为8mm，高度为4mm)、以及4个芯片电容器15(3216尺寸，镀SnPb)。
用下列方法来制造这一芯片元件安装结构。首先，将导电粘合剂1丝网印刷在电路板11的电极12上。然后，利用现有的元件安装设备，将芯片元件13、14、15安装在电极12上，随之以在炉子中于150℃下加热30分钟以硬化导电粘合剂1。
(例12)
此例子的特征是，用例2的导电粘合剂1构成芯片元件安装结构。此处，在例2中，防淘析膜3由尿素树脂制成。除了导电粘合剂1之外，此芯片元件安装结构的构造和制造方法与例11相同。
(例13)
此例子的特征是，用例3的导电粘合剂1构成芯片元件安装结构。此处，在例3中，防淘析膜3由氟树脂制成。除了导电粘合剂1之外，此芯片元件安装结构的构造和制造方法与例11相同。
(例14)
此例子的特征是，用例4的导电粘合剂1构成芯片元件安装结构。此处，在例4中，防淘析膜3由含有二乙醇胺的金属络合物制成。除了导电粘合剂1之外，此芯片元件安装结构的构造和制造方法与例11相同。
(例15)
此例子的特征是，用例5的导电粘合剂1构成芯片元件安装结构。此处，在例5中，防淘析膜3由含有o-氨基苯甲酸的金属络合物制成。除了导电粘合剂1之外，此芯片元件安装结构的构造和制造方法与例11相同。
(比较例3)
根据上述例11-15，制造了比较例3的芯片元件安装结构。
此芯片元件安装结构使用比较例1的导电粘合剂，被制作成具有相似于例11-15的安装结构。
用相似于例6-10和比较例2中所用的方法，在例11-15的芯片元件安装结构上和在如上所述制造的比较例3的芯片元件安装结构上，进行可靠性测试。结果示于表3。
表3
    防淘析膜   迁移测试(小时)       硫化测试(mΩ)
  初始   96小时后
例11     尿烷树脂     2040     24     40
例12     尿素树脂     3099     25     39
例13     氟树脂     4011     24     29
例14     二乙醇胺Ag     4996     23     26
例15     o-氨基苯甲酸Ag     5463     24     24
例18     o-氨基苯甲酸Ag     5475     21     21
比较例3     无     650     21     102
对于例10-15的芯片元件安装结构，比之比较例3，发现下列情况。亦即，在抗离子迁移性质的评估中，电流开始流动之前的时间比比较例3更长，从而证实了抗离子迁移性质得到了改善。同样，在抗硫化反应性质的评估中，测试之前和之后的连接电阻的改变小于比较例3的，从而证实了抗硫化反应性质得到了改善。
而且，借助于对各个例子进行比较，证实了下列情况。亦即，借助于将防淘析膜3由树脂制成的例11-13与防淘析膜3由金属络合物制成的例14和15进行比较，证实了例14和15具有更好的抗离子迁移性质。
而且，借助于对各个例子进行比较，无论在具有由树脂制成的防淘析膜3的例子11-13中，还是在具有由金属络合物制成的防淘析膜3的例子14和15中，都有下列情况。亦即，具有由本发明中定义为不溶于水和不溶于含有硫化氢或氧化硫的水溶液的材料制作的防淘析膜3的例子12、13、15，比之具有由其它材料制成的防淘析膜3的例子11和14，表现出了抗离子迁移性质评估中的改善以及抗硫化反应性质评估中的改善。而且，在具有由被上述定义定义为不可溶解的材料制作的防淘析膜3的例子12和13之间，发现溶解度较低的那一个具有更高的评估结果。
这样，例子11-15(芯片元件安装结构)就产生了相似于例1-5(导电粘合剂)和例6-10(倒装芯片安装结构)的效果。
下面描述本发明第四实施例的例子。
(例16)
制备了电路板6(见图4)，其结构相似于为例1-5的评估和测量而制备的电路板。然后，利用比较例1(常规例子)的导电粘合剂，在此电路板6上制作导电粘合剂层17和18。导电粘合剂层17和18的制造方法相似于例1-5和比较例1的样品。
而且，借助于将10％重量比的o-氨基苯甲酸与90％重量比的异丙醇混合，制备了络合剂溶液。此处，络合剂溶液中的混合比率以及溶剂的种类可以根据导电填料2的表面态和后续工艺中制作的防淘析膜3的厚度而改变，致使其混合比率和溶剂的种类不特别局限于此。
将上述电路板16浸入络合剂溶液30秒钟并从中拉出，随之以在100℃下干燥30分钟，以便在包含在导电粘合剂层17和18中的导电填料2上形成由金属络合物制成的防淘析膜3并使异丙醇蒸发。这就完成了图4所示的测试样品。
这样制备的测试样品的结构相似于作为第一实施例的例子的例1-5中制备的测试样品。于是，为了在此例子与例1-5之间进行比较，根据相似于例1-5的方法，进行了评估测试。其结果一起示于上述的表1中。
结果证实，在抗离子迁移性质的评估中，根据此例的生产方法制备的安装结构具有相似于预先在导电填料2上制作防淘析膜3的例1-5的安装结构的性质。同样，在抗硫化反应性质的评估中，证实连接电阻完全没有增大，还证实连接电阻的绝对值小于例1-5的最大值。
(例17)
制备了构造相似于比较例2的倒装芯片安装结构。但在此阶段，半导体器件6与电路板5之间的间隙未被密封树脂10密封。在此情况下，用注射器将相似于例1所用的络合剂注入到半导体器件6与电路板5之间的间隙中，随之以在100℃下干燥30分钟，以便在导电填料2的表面上形成由金属络合物制成的防淘析膜3并使溶剂蒸发。
然后，将密封树脂10注入到半导体器件6与电路板5之间的间隙中，从而完成倒装芯片安装结构的测试样品。
这样制备的测试样品的结构相似于作为第二实施例的例子的例6-10中制备的测试样品。于是，为了在此例子与例6-10之间进行比较，根据相似于例6-10的方法，进行了评估测试。其结果一起示于上述的表2中。
结果证实，在抗离子迁移性质的评估中，根据此例的生产方法制备的倒装芯片安装结构具有相似于预先在导电填料2上制作防淘析膜3的例6-10的安装结构的性质。同样，在抗硫化反应性质的评估中，证实连接电阻完全没有增大，还证实连接电阻的绝对值小于例6-10的最大值。
(例18)
制备了构造相似于比较例3的芯片元件安装结构。然后，将此芯片元件安装结构浸入相似于例16所用的络合剂溶液中30秒钟并从中拉出，随之以在100℃下干燥30分钟，以便在包含在导电粘合剂层21中的导电填料2上形成由金属络合物制成的防淘析膜3并使异丙醇蒸发。这就完成了图6所示的测试样品。
这样制备的测试样品的结构相似于作为第三实施例的例子的例11-15中制备的测试样品。于是，为了在此例子与例11-15之间进行比较，根据相似于例11-15的方法，进行了评估测试。其结果一起示于上述的表3中。
结果证实，在抗离子迁移性质的评估中，根据此例的生产方法制备的芯片元件安装结构具有相似于预先在导电填料2上制作防淘析膜3的例11-15的安装结构的性质。同样，在抗硫化反应性质的评估中，证实连接电阻完全没有增大，还证实连接电阻的绝对值小于例11-15的最大值。
如上所述，本发明产生了一种抗离子迁移性质或抗硫化反应性质优越于常规安装结构的安装结构。而且，若本发明被用于诸如倒装芯片安装结构或芯片元件安装结构之类的安装结构，则绝缘可靠性得到改善，从而使得有可能减小各个电极等等之间的间距并节省安装结构的空间。而且，由于本发明改善了抗硫化反应的可靠性，故本发明可以被用于可能用在诸如温泉或火山附近的含有大量硫的气体气氛中的产品中，从而完全能够预计其应用范围将进一步扩大。
虽然参照最佳实施例已经描述了本发明，但可以对最佳实施例的各个元件的组合和安排作出各种各样的改变和修正而不超越所附权利要求所规定的本发明的构思与范围。

Claims (13)

1.一种安装结构，它包含电路板和排列在所述电路板上的导电粘合剂层，其中所述导电粘合剂层包含导电填料，其中部分所述导电填料被暴露在外部环境中，且仅在所述导电填料的该部分上设置防淘析膜。
2.根据权利要求1的安装结构，包含设置在所述电路板上的电子器件，所述导电粘合剂层在所述电路板与所述电子器件之间建立电连接。
3.根据权利要求1的安装结构，其中所述导电粘合剂层具有大量彼此连通并与所述导电粘合剂层的表面连通的孔；至少部分所述导电填料被暴露于所述孔的内表面；且所述防淘析膜至少被排列在暴露于所述孔的所述内表面的所述导电填料上。
4.根据权利要求1的安装结构，其中所述防淘析膜包含不溶于水的物质。
5.根据权利要求1的安装结构，其中所述防淘析膜包含不溶于含有硫化氢或氧化硫的水溶液的物质。
6.根据权利要求1的安装结构，其中所述防淘析膜包含金属络合物。
7.根据权利要求1的安装结构，其中所述防淘析膜包含树脂组分。
8.根据权利要求1的安装结构，其中所述导电填料包含银。
9.根据权利要求2的安装结构，其中所述电子器件是半导体器件。
10.一种生产安装结构的方法，所述方法包含下列步骤：
在电路板上制作导电粘合剂层，所述导电粘合剂层含有导电填料；以及
在所述导电粘合剂层被硬化之后，在与所述导电粘合剂层的表面连通的所述导电填料上制作防淘析膜。
11.根据权利要求10的生产安装结构的方法，其中在所述导电粘合剂层被硬化之后，通过在所述导电粘合剂层中形成络合物来制作所述防淘析膜。
12.根据权利要求10的生产安装结构的方法，所述方法包括以下步骤：
在设置于所述电路板上的所述导电粘合剂层和电子器件之间建立电连接。
13.根据权利要求12的生产安装结构的方法，其中所述电子器件是半导体器件。
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