CN101501154A - 粘合带、接合体和半导体封装件 - Google Patents

粘合带、接合体和半导体封装件 Download PDF

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Publication number
CN101501154A
CN101501154A CNA2007800292173A CN200780029217A CN101501154A CN 101501154 A CN101501154 A CN 101501154A CN A2007800292173 A CNA2007800292173 A CN A2007800292173A CN 200780029217 A CN200780029217 A CN 200780029217A CN 101501154 A CN101501154 A CN 101501154A
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Prior art keywords
adhesive tape
self adhesive
solder powder
resin
solidifying agent
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CNA2007800292173A
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CN101501154B (zh
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桂山悟
山代智绘
宫本哲也
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
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Abstract

本发明提供了一种粘合带101，其用于将导电组件电连接。所述粘合带101包括含有热固性树脂的树脂层132、焊料粉103和固化剂。焊料粉103和固化剂包含在树脂层132中，树脂层132的固化温度T1和焊料粉103的熔点T2满足T1≥T2+20℃，其中在焊料粉103的熔点T2下，树脂层132的熔融粘度为50Pa·s～5000Pa·s。

Description

粘合带、接合体和半导体封装件
技术领域
[0001]
本发明涉及粘合带、接合体和半导体封装件。
背景技术
[0002]
作为用于在导电组件(如电极)间提供连接的粘合带，已知的是含有焊料颗粒的粘合带(专利文件1)。专利文件1描述了一种各向异性导电膜(ACF)，其含有作为导电颗粒的焊料颗粒。
[0003]
在专利文件2中，描述了一种使用导电粘合剂的端子间连接方法，所述导电粘合剂含有导电颗粒，该导电颗粒由具有Sn/In组成的合金和环氧类树脂组分组成。
[0004]
专利文件3描述了制造粘合剂的方法，其通过以下工序进行：混合焊料球、助焊剂(flux agent，如苹果酸)和环氧树脂，然后将粘合剂涂布在其上形成有金属化图案的聚酰亚胺电路板上。
[0005]
[专利文件1]日本特开昭61-276873号公报
[专利文件2]日本特开2004-260131号公报
[专利文件3]日本特开平4-262890号公报
发明内容
本发明需要解决的问题
[0006]
然而，专利文件1的粘合带、专利文件2的导电粘合剂和专利文件3的粘合剂全都不能确保接合部分处稳定的低电阻率，因此，留有进一步改善连接可靠性的余地。
[0007]
因此，本发明的目的在于提供一种粘合带，其能够稳定地实现低电阻率，以及提供使用该粘合带的接合体和半导体封装。
解决问题的方法
[0008]
根据本发明，提供了一种将导电组件电连接的粘合带，其包括：
含有热固性树脂的树脂层；
焊料粉；和
固化剂，
其中，焊料粉和固化剂包含在树脂层中，
树脂层的固化温度T1和焊料粉的熔点T2满足式(1)：
T1≥T2+20℃      式(1)
其中固化温度T1定义为通过DSC以10℃/分钟的升温速度测量粘合带所获得的放热峰温度，且
在焊料粉的熔点T2下，树脂层的熔融粘度为50Pa·s～5000Pa·s。
[0009]
利用本发明的粘合带连接导电组件时，将粘合带设置在导电组件之间，然后在预设温度下将其加热。通过加热使焊料熔融，所熔融的焊料粉以自对准方式通过树脂层迁移至导电组件表面。由于相对金属而言，焊料具有良好的润湿性，其能够以自对准方式向导电组件表面迁移。由此，导电组件表面与焊料粉彼此接合，从而将导电组件电连接。
[0010]
由于难以控制树脂的固化行为，可以认为专利文件1中描述的粘合带不能成功将导电颗粒设置在导电组件之间，因此提高了接合电阻率。
相反，归因于其内包含的固化剂，本发明能够控制含有热固性树脂的树脂层的固化特性。由于在焊料粉熔点T2下，树脂层的熔融粘度被调节成50Pa·s或以上，加热下的熔融焊料能够通过树脂层移动，并集中在导电组件之间。
由于树脂层在焊料粉熔点T2下的熔融粘度调节成5000Pa·s或以下，因此能够成功防止焊料从导电组件之间的渗漏。
[0011]
专利文件2中描述的粘合剂和专利文件3中描述的粘合剂也同样难以有效地将焊料集中在导电组件之间，因此有时会增加接合电阻率。
相反，由于热固性树脂的固化温度T1和焊料粉的熔点T2满足T1≥T2+20℃，本发明容许焊料粉在加热下熔化，使其得以在固化前顺利地在树脂层中移动，焊料粉因此能够集中在导电组件之间。
另外，如上所述，由于树脂层在焊料粉熔点T2下的熔融粘度调节成50Pa·s或以上，容许加热下的熔融焊料粉在树脂层中移动，并集中在导电组件之间。
如上所述，由于树脂层在焊料粉熔点T2下的熔融粘度调节成5000Pa·s或以下，因此也能够成功防止包含在导电组件之间的焊料从导电组件之间的渗漏。
[0012]
由于本发明提供的粘合剂为带状，使其便于使用，从而简化导电组件之间的接合工序。
[0013]
相对于每100份除焊料粉以外所有组分的总重量，焊料粉含量优选为20重量份或更多。
通过将焊料粉含量调节成相对于每100份除焊料粉以外所有组分总重量的20重量份或更多，在集中在导电组件之间的焊料粉的作用下导电组件能够被确实地连接。
而且，焊料粉的平均粒径优选为1μm～100μm。
通过将焊料粉的平均粒径调节成1μm或更大，焊料粉能够确实地集中在导电组件的表面上。
通过将焊料粉的平均粒径调节成100μm或更小，可成功防止焊料粉与相邻的导电组件连接，从而防止相邻的导电组件出现短路。
[0014]
热固性树脂优选含有室温下为固体的环氧树脂和室温下为液体的环氧树脂。
其中，室温下为固体的环氧树脂优选含有固体三官能环氧树脂和甲酚酚醛清漆型环氧树脂；室温下为液体的环氧树脂优选为双酚A型环氧树脂或双酚F型环氧树脂。
通过将热固性树脂设置成含有室温下为固体的环氧树脂和室温下为液体的环氧树脂，树脂的熔融粘度可被随意设计。更具体地说，焊料粉熔点T2下的含有热固性树脂的树脂层的熔融粘度可容易地调节成50Pa·s～5000Pa·s。
[0015]
更优选固化剂为具有助焊活性(flux activity)的固化剂。
通过使树脂层包含具有助焊活性的活化剂(activating agent)，具有助焊活性的固化剂能够有效地迁移至导电组件和焊料之间的界面处。固化剂能够除去焊料粉表面的氧化层，从而提高焊料粉的润湿性。因此，能够确实地降低导电组件间的接触电阻率。
使用具有助焊活性的固化剂能够免除洗净助焊剂(flux cleaning)的工序，从而简化制造工序和节省成本。
[0016]
具有助焊的固化剂优选为含有羧基的固化剂。
[0017]
本发明还提供使用上述粘合带的接合体。更特别地，本发明的接合体例如具有导电组件对；和
粘合带，其设置在导电组件对之间用于将所述导电组件对电连接，其中所述粘合带为上文所述粘合带，且具有助焊活性的固化剂的50％或以上的羧基与热固性树脂反应。
一般当接合体在高温下存放时，含有热固性树脂和大量具有助焊活性的未反应的固化剂有时会导致导电组件的腐蚀。
相反，在本发明的接合体中，具有助焊活性的固化剂的50％或以上的羧基已与热固性树脂反应，即使例如接合体在高温下存放时，也能够防止导电组件出现腐蚀。
本发明的优势
[0018]
本发明提供了一种能够稳定地实现低电阻率的粘合带，还提供使用该粘合带的接合体和半导体封装。
附图说明
[0019]
通过下面优选的实施方式和附图，上述及其它目的、特征和优点将更清晰明确，其中：
[0020]
图1是一截面图，其示出了利用本实施方式的粘合带进行接合的方法；
图2是一截面图，其示出了利用本实施方式的粘合带进行接合的方法；
图3是一截面图，其示出了利用本实施方式的粘合带进行接合的方法；
图4是一截面图，其示出了本实施方式的半导体封装件的结构；
图5是一截面图，其示出了本实施方式的半导体封装件的结构；
图6是一截面图，其示出了本实施方式的半导体封装件的结构；
图7是一截面图，其示出了本实施方式的叠层(stack)的结构；
图8是一截面图，其示出了本实施方式的叠层的结构。
附图标记
[0021]
101 粘合带
103 焊料粉
105 第三基板
107 第二基板
109 第一基板
111 焊料区域
113 第一电极
115 第二电极
117 通孔
119 第三电极
121 第二电极
131 第二基材
132 树脂层
133 第一基材
135 第二电极
137 第一电极
139 第二阻焊层
141 第一阻焊层
143 间隙
151 第一半导体芯片
153 第二半导体芯片
155 安装基板
157 基板
159 配线
161 凸起电极
163 成型树脂(MOLDING RESIN)
165 凸起电极
167 树脂
169 配线
171 配线
本发明的最佳实施方式
[0022]
下面将参照附图说明本发明的实施方式。
[0023]
本发明的粘合带是将导电组件电连接的粘合带，其包括：
含有热固性树脂的树脂层；
焊料粉；和
固化剂，
其中，焊料粉和固化剂包含在树脂层中，
树脂层的固化温度T1和焊料粉的熔点T2满足式(1)：
T1≥T2+20℃        式(1)
其中固化温度T1定义为通过DSC以10℃/分钟的升温速度测量粘合带所获得的放热峰温度，且
树脂层在焊料粉的熔点T2下的熔融粘度为50Pa·s～5000Pa·s。
下面将更具体地描述上述各组分。
[0024]
粘合带的树脂层优选除热固性树脂外还含有热塑性树脂。从树脂的成膜特性和熔融粘度的角度考虑，优选为热塑性树脂和热固性树脂的混合体系。
[0025]
对于热塑性树脂没有特别限制，其中典型的实例包括苯氧树脂、聚酯树脂、聚氨酯树脂、聚酰亚胺树脂、硅氧烷改性的聚酰亚胺树脂、聚丁二烯、聚丙烯、苯乙烯-丁二烯-苯乙烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯共聚物、聚缩醛树脂、聚(乙烯醇缩丁醛)树脂、聚(乙烯醇缩乙醛)树脂、丁基橡胶、氯丁橡胶、聚酰胺树脂、丙烯腈-丁二烯共聚物、丙烯腈-丁二烯-丙烯酸共聚物、丙烯腈-丁二烯-苯乙烯共聚物、聚(乙酸乙烯酯)、尼龙和丙烯酸酯橡胶。它们可以单独地使用或两种或多种混合使用。
[0026]
作为热塑性树脂，具有腈基、环氧基、羟基和羧基的热塑性树脂可用于改善其与其它树脂的粘结性和相容性，其中丙烯酸酯橡胶一般可用作这种树脂。
[0027]
对于热固性树脂没有特别限制，其中一般使用环氧树脂、氧杂环丁烷树脂、酚醛树脂、(甲基)丙烯酸酯树脂、不饱和聚酯树脂、邻苯二甲酸二烯丙酯树脂、马来酰亚胺树脂。其中，优选使用具有优异的固化性、贮存稳定性以及固化后具有耐热性、耐湿性和耐化学性的环氧树脂。
[0028]
室温下为固体的环氧树脂或是室温下为液体的环氧树脂都可用作环氧树脂。而且，容许树脂中含有室温下为固体的环氧树脂或室温下为液体的环氧树脂两者。这种配置能够进一步提高对树脂的熔融行为的设计自由度。
[0029]
对于室温下为固体的环氧树脂没有特别限制，作为实例的有双酚A型环氧树脂、双酚S型环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、缩水甘油胺型环氧树脂、缩水甘油酯型环氧树脂、三官能环氧树脂和四官能环氧树脂。更具体地，其可含有固体三官能环氧树脂和甲酚酚醛清漆型环氧树脂。作为固体三官能环氧树脂和甲酚酚醛清漆型环氧树脂的实例可以是2-[4-(2，3-环氧基丙氧基)苯基]-2-[4[1，1-双[4-(2，3-环氧基丙氧基)苯基]乙基]苯基]丙烷和1，3-双[4-[1-[4-(2，3-环氧基丙氧基)苯基]-1-[4-[1-[4-(2，3-环氧基丙氧基)苯基]-1-甲基]乙基]苯基]苯氧基]-2-丙醇，它们在下述实施例中使用。
[0030]
室温下为液体的环氧树脂可为双酚A型环氧树脂或双酚F型环氧树脂。它们可组合使用。
[0031]
室温下为固体的环氧树脂可含有固体三官能环氧树脂和甲酚酚醛清漆型环氧树脂，室温下为液体的环氧树脂可为双酚A型环氧树脂或双酚F型环氧树脂。
[0032]
作为热塑性树脂和热固性树脂的混合体系的具体实例可以是设计成包含环氧树脂和丙烯酸酯橡胶的树脂。将粘合带设计成含有丙烯酸酯橡胶，可改善膜状粘合带的制造稳定性。而且，由于降低了粘合带的弹性模量和被粘物与粘合带的残余应力，还能够改善粘合带与被粘物的粘结性。
[0033]
对于本发明粘合带中热塑性树脂的含量，丙烯酸酯橡胶的含量例如被调节成基于除焊料粉以外粘合带其余各组分总量的10wt％～50wt％。将丙烯酸橡胶的含量调节成10wt％或更多，能够抑制成膜性的降低，抑制固化后粘合带的弹性模量的增加，从而进一步改善与被粘物的粘结性。另一方面，将丙烯酸酯橡胶的含量调节成50wt％或更少，能够抑制树脂的熔融粘度的增加，使焊料粉得以更确实地迁移到导电组件的表面。
[0034]
一般将作为热固性树脂的环氧树脂的含量调节成基于除焊料粉以外粘合带其余各组分总量的20wt％～80wt％。将环氧树脂的含量调节成20wt％或更多，能够更可靠地确保粘合后的弹性模量，从而进一步改善连接可靠性。另一方面，将环氧树脂的含量调节成80wt％或更少，能够进一步提高树脂的熔融粘度，从而抑制从被粘物中流出焊料粉导致连接可靠性的降低。
[0035]
作为热塑性树脂和热固性树脂的混合体系的另一实例可以是设计成包含环氧树脂和苯氧树脂的树脂。这样的配置能够更有利地实现固化后的耐热性和耐湿性。
作为环氧树脂的具体实例可以是以上所述的物质。
作为苯氧树脂的具体实例可以是双酚A型、双酚F型、双酚S型的苯氧树脂和具有芴骨架的苯氧树脂。
[0036]
为了改善粘合带的成膜性，一般将树脂中的苯氧树脂含量调节成基于除焊料粉以外粘合带其余各组分的总量的10wt％或更多，优选15wt％或更多。这样，能够确保苯氧树脂中含有的羟基导致的粘结性达到一个满意的程度。为了抑制树脂的熔融粘度的过度增加，并使焊料粉得以更确实地迁移至导电组件的表面，一般将苯氧树脂的含量调节成相对于除焊料粉以外粘合带其余各组分总量的50wt％或更少，优选40wt％或更少。
[0037]
如上所述，在本实施方式中，树脂层的固化温度T1和焊料粉的熔点T2满足下式：T1≥T2+20℃。
优选地，树脂层的固化温度T1是(焊料粉的熔点T2)+30℃或更高，更优选地，树脂层的固化温度T1是(焊料粉的熔点T2)+45℃或更高，且再更优选地，树脂层的固化温度T1是(焊料粉的熔点T2)+50℃或更高。
当满足下式：T1≥T2+20℃，加热下的熔融焊料粉得以在固化前顺利地在树脂层中移动。焊料粉因此能够集中在导电组件之间。
除了上述效果外，将树脂层的固化温度T1调节成(焊料粉的熔点T2)+30℃或更高，更优选调节成(焊料粉的熔点T2)+45℃或更高，再更优选调节成(焊料粉的熔点T2)+50℃或更高，还能够成功防止焊料粉将相邻的导电组件桥接(bridging)，由此防止相邻的导电组件出现短路。
另外，树脂层的固化温度T1是(焊料粉的熔点T2)+100℃或更低，更优选是(焊料粉的熔点T2)+80℃或更低。这样的配置，使熔融焊料粉得以在固化前顺利地在树脂层中移动。
[0038]
树脂层的固化温度T1定义为通过DSC(示差扫描热量计)以10℃/分钟的升温速度测量粘合带所获得的放热峰温度。
焊料粉的熔点T2定义为例如通过DSC以10℃/分钟的升温速度单独测量焊料粉时所获得的放热峰温度。
[0039]
在焊料粉的熔点T2下，树脂层的熔融粘度为50Pa·s～5000Pa·s。
由于在焊料粉的熔点T2下，树脂层的熔融粘度为50Pa·s或更多，因此加热下的熔融焊料粉得以在树脂层中移动，从而集中在导电组件之间。
特别优选在焊料粉的熔点T2下，树脂层的熔融粘度为100Pa·s或更多。将焊料粉熔点T2下的树脂层的熔融粘度调节成100Pa·s或更多，除了获得焊料粉集中在导电组件之间的效果外，在导电组件被用作基板上的电极的情况下，还能够抑制树脂层的膨胀以及焊料粉从上下连接基板漏出，从而防止出现与连接可靠性(如绝缘不良)相关的缺陷。
由于在焊料粉的熔点T2下，树脂层的熔融粘度为5000Pa·s或更少，因此能够成功防止焊料粉从导电组件之间渗漏。
在焊料粉的熔点T2下，树脂层的熔融粘度特别优选为4000Pa·s或更少。除了能够防止焊料粉从导电组件之间渗漏外，将焊料粉熔点T2下的树脂层的熔融粘度调节成4000Pa·s或更少，由于树脂层适当的流动性，能够确保对被粘物有足够的润湿性，从而获得足够的粘结性。
[0040]
使用频率0.1Hz、升温速度10℃/分钟的动态粘弹仪，利用100μm厚的粘合带样品可测量树脂层的熔融粘度。
[0041]
在本发明的粘合带中，例如无铅焊料可用作组成焊料粉的焊料。对于无铅焊料没有特别限制，但优选其为含有至少两种或多种元素的合金，所述元素选自Sn、Ag、Bi、In、Zn和Cu组成的组。其中，考虑到熔点和机械特性，优选含Sn的合金例如为Sn-Bi合金、Sn-Ag-Cu合金和Sn-In合金。
[0042]
为了确保粘合带粘合过程中树脂有足够的流动性，一般将焊料粉的熔点T2调节成100℃或更高，更优选130℃或更高。为了抑制接合期间设置在被粘物(如基板和芯片)上的元件的劣化，一般将焊料粉的熔点T2调节成250℃或更低，更优选230℃或更低。
[0043]
可根据导电组件的表面积和导电组件之间的距离设定焊料粉的平均粒径，优选将其调节成1μm～100μm。为了使焊料粉确实地集中在导电组件的表面，一般将焊料粉的平均粒径调节成5μm或更多，更优选10μm或更多。为了在导电组件表面选择性地形成焊料区域，以及确保粘合带在要求具有导电性的区域以外的区域(如电极形成区域)的绝缘性，一般将焊料粉的平均粒径调节成100μm或更少，更优选50μm或更少。一般可通过激光衍射散射法测量焊料粉的平均粒径。
通过将焊料粉的平均粒径调节成1μm或更多，焊料粉得以确实地集中在导电组件的表面上。
通过将焊料粉的平均粒径调节成100μm或更少，可成功防止焊料粉桥接相邻的导电组件，从而防止相邻的导电组件出现短路。
[0044]
为了改善连接可靠性，基于100重量份粘合带各组分(不包括焊料粉)，本发明粘合带中焊料粉的含量为20重量份或更多，更优选40重量份或更多。为了改善粘合带的成膜性，基于100重量份粘合带中各组分(不包括焊料粉)，焊料粉的含量为250重量份或更少，更优选230重量份或更少。
[0045]
在本发明的粘合带中，基于100重量份粘合带各组分(不包括焊料粉)，焊料粉的含量为20重量份或更多，同时焊料粉的平均粒径可以是1μm～100μm。这样，得以进一步改善在导电组件表面选择性形成焊料区域、确保粘合带在要求具有导电性的区域以外的区域(如电极形成区域)的绝缘性和粘合带的成膜性之间的平衡。
[0046]
本发明中使用的具有助焊活性的固化剂是能够减少焊料粉表面的氧化膜以使导电组件之间电接触的化合物，其具有可与树脂接合的官能团。作为含有环氧树脂的树脂，具有助焊活性的固化剂可具有羧基和与环氧基反应的基团。与环氧基反应的基团的实例可以是羧基、羟基和氨基等。
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为了除去接合过程中焊料粉表面的氧化膜，可根据焊料粉的种类，适当地选择和使用具有助焊活性的固化剂。
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具有助焊活性的固化剂是具有例如羧基的化合物。含羧基的化合物的实例可以是羧酸，如直链或支链烷基羧酸、芳香族羧酸等。
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作为烷基羧酸的具体实例，可以是下式(1)所示的化合物：
HOOC-(CH2)n-COOH (1)
在上式(1)中，n是0～20的整数，包括两个端点值。
考虑到助焊活性、接合期间的脱气(out gas)、以及固化后粘合带的弹性模量和玻璃化转变温度之间的平衡，式(1)中的n优选为4～10，包括两个端点值。将n定义为4或更多，能够防止由于环氧树脂交联的距离短而导致固化后粘合带的弹性模量的增加，从而改善其与被粘物的粘结性。另一方面，将n定义为10或更少，能够防止由于环氧树脂交联的距离长而导致固化后粘合带的弹性模量的减少，从而进一步改善连接可靠性。
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作为式(1)所示的化合物的实例，例如可以是己二酸(HOOC-(CH2)4-COOH，n＝4)、癸二酸(HOOC-(CH2)8-COOH，n＝8)和n＝10的HOOC-(CH2)10-COOH。
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作为芳香族羧酸的具体实例可以是一个分子中具有至少两个酚羟基和一个分子中具有至少一个与芳香环直接连接的羧基的化合物。这些化合物例如可以是苯甲酸衍生物如2，3-二羟基苯甲酸、2，4-二羟基苯甲酸、龙胆酸(2，5-二羟基苯甲酸)、2，6-二羟基苯甲酸、3，4-二羟基苯甲酸、没食子酸(3，4，5-三羟基苯甲酸)和酚酞啉(2-[二(p-羟基苯基)甲基]苯甲酸)；萘酸衍生物如1，4-二羟基-2-萘酸、3，5-二羟基-2-萘酸、3，7-二羟基-2-萘酸和双酚酸。
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更特别地，具有助焊活性的固化剂可以是上述的癸二酸和龙胆酸，其中可以包含二者中之一或是其二者。
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在本发明的粘合带中，具有助焊活性的固化剂可以包含在焊料粉之外，其中，焊料粉和具有助焊活性的固化剂例如可独立地分散在树脂中，或者固化剂可以粘附在分散在树脂中的焊料粉表面。由于具有助焊活性的固化剂包含在焊料粉外，具有助焊活性的固化剂能够在接合过程中有效地迁移到焊料和被粘物中导电物质之间的界面处，使焊料能够与导电组件直接接触。这样，能够改善连接可靠性。由于具有助焊活性的固化剂包含在树脂中，固化剂能够与树脂接合，从而提高弹性模量或Tg。
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为了提高助焊活性，一般将本发明粘合带中具有助焊活性的固化剂的含量调节成基于除焊料粉以外粘合带中各组分总含量的0.1wt％或更多，更优选1wt％或更多。为了降低接合过程中树脂的熔融粘度，一般将具有助焊活性的固化剂的含量调节成基于除焊料粉以外粘合带中各组分总含量的30wt％或更少，更优选10wt％或更少。
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再更特别地，在本发明粘合带包含环氧树脂的情况中，一般将具有助焊活性的固化剂的含量调节成粘合带中环氧树脂的50wt％，更优选30wt％或更少。通过调节，可以排除固化剂过量并改善固化性。
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本发明的粘合带还可在树脂中包含与具有助焊活性的固化剂不同的其他固化剂，或者可包含作为固化剂使用的树脂。
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对于固化剂没有特别限制，其实例可以是酚类、胺和硫醇，其中考虑到与环氧树脂的反应性和固化后的物理特性，酚类是优选的。
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对于酚类没有特别限制，然而，考虑到固化后粘合带的物理特性，优选双官能或多官能酚类。例如，可以是双酚A、四甲基双酚A、二烯丙基双酚A、双苯酚(biphenol)、双酚F、二烯丙基双酚F、三苯酚、四苯酚、苯酚酚醛清漆和甲酚酚醛清漆等，其中考虑到熔融粘度、与环氧树脂的反应性和固化后的物理特性，优选使用苯酚酚醛清漆和甲酚酚醛清漆。
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为了确实地将树脂固化，假设除焊料粉以外粘合带中各组分总含量为4100，一般将除具有助焊活性的固化剂以外的固化剂含量调节成5wt％或更多，优选10wt％或更多。为了改善接合过程中树脂的流动性，假设除焊料粉以外粘合带中各组分总含量为100，一般将固化剂含量调节成40wt％或更少，优选30wt％或更少。
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本发明的粘合带还可含有固化催化剂。通过包含固化催化剂，树脂可在粘合带的制造过程中更确实地进行固化。
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可根据树脂的种类适当地选择固化剂，其中一般使用熔点为150℃或更高的咪唑化合物。咪唑化合物熔点太低会不利地使树脂在焊料粉迁移至电极表面之前固化，还可能导致连接不稳定，使粘合带的贮存稳定性变差。因此，咪唑的熔点优选为150℃或更高。熔点150℃或更高的咪唑化合物的实例可以是2-苯基羟基咪唑、2-苯基-4-甲基羟基咪唑、2-苯基-4，5-二羟基咪唑和2-苯基-4-甲基咪唑。对于咪唑化合物的熔点的上限没有特别限制，其可取决于粘合带的粘合温度适当地选择。
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为了使环氧树脂更有效地作为固化催化剂，从而改善粘合带的固化性，假设除焊料粉以外粘合带中其余各组分的总含量为100，固化催化剂的含量一般为0.001wt％或更多，优选0.01wt％或更多。固化催化剂的含量一般为5wt％或更少。这样，可进一步改善粘合带的贮存稳定性。
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本发明的粘合带可进一步含有硅烷偶联剂。含有硅烷偶联剂，可进一步提高粘合带与被粘物的粘结性。硅烷偶联剂的实例可以是环氧硅烷偶联剂和含芳香环的氨基硅烷偶联剂，其中含有它们其中之一足以。也可以含有它们两者。假设除焊料粉以外粘合带中其余各组分的总含量为100，硅烷偶联剂的含量一般约为0.01～5wt％。
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本发明的粘合带可含有上述组分以外的组分。例如，可适当地加入各种添加剂，以提高各种特性包括相容性、稳定性和可加工性等。
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接下来，将说明本发明粘合带的制造方法。粘合带可通过如下工序制得：将树脂、焊料粉和具有助焊活性的固化剂以及任何其它任选的添加剂混合，使焊料粉和具有助焊活性的固化剂分散在树脂中，将由此所得的分散体涂布在可剥离的基材上(如聚酯薄片)，在预设温度下干燥涂层而制得。
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所得的膜状粘合带具有包含在树脂中的焊料粉和具有助焊活性的固化剂。将粘合带设置在被粘物之间，然后将其加热，树脂层中的焊料粉会以自对准方式迁移到被粘物中的导电组件表面，由此形成金属接合。
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以下将参照图1更详细地描述使用本发明的粘合带进行粘合的方法。
从下至上依次层叠第一基板109、粘合带101、第二基板107、粘合带101和第三基板105。这样，设置在第一基板109表面的第一电极(导电组件)113和设置在第二基板107表面的第二电极(导电组件)115彼此相对。同样，设置在第二基板107表面的第二电极(导电组件)121和设置在第三基板105表面的第三电极(导电组件)119彼此相对。
在第二基板107中，通孔(via)可以被预定物质填充，或者是贯通孔(through-hole)。
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然后在预设温度的加热下将叠层粘合。通过此工序，形成接合体。可以根据焊料粉103的种类和包含在粘合带101中树脂的种类设定粘合温度。
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粘合温度定义为高于焊料粉103的熔融温度且能够使树脂层132保持熔化的温度。考虑到这点，粘合温度一般设定为高于100℃，优选120℃或更高。考虑到树脂在粘合温度下优选具有低熔融粘度，粘合温度一般为250℃或更低，优选200℃或更低。而且，从扩大树脂熔融粘度低的区域考虑，粘合温度优选较低。
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为了使流动的焊料粉103更有效地迁移到电极表面，优选在粘合过程中在预定压力下对叠层施压。为了更确实地形成焊料区域111，施加的压力一般为0MPa或以上，优选1MPa或以上。即使打算向粘合带施加的压力为0MPa，也可向粘合带施加相当于粘合带上设置的元件重量的预定压力。为了进一步改善连接可靠性，一般将压力调节成20MPa或更少，优选10MPa或更少。
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粘合带101中树脂层132在加热下熔化。而且粘合带101中的焊料粉103也熔化。熔融焊料粉103以自对准方式从树脂层132向设置在各基板上的电极迁移。由于焊料粉103与电极的相对区域自对准，焊料区域111分别形成于第一电极113和第二电极115之间以及第二电极121和第三电极119之间。
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而且，包含在树脂中具有助焊活性的固化剂(未示出)也有效地迁移到焊料粉103和电极之间的界面处，同时从焊料粉103表面除去氧化膜，使焊料区域111和各电极直接通过金属进行接合，从而电连接。然后，通过叠层的冷却，粘合带中的树脂固化，由此通过焊料区域111维持电极间的接合状态。
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如上所述，使用带状粘合带101时可简单地仅需要在预定的单一温度下进行加热，且带状粘合带101易于将基板粘合。然而，粘合所需的加热不局限于在单一温度下加热，一般可以是分段固化，即在150℃下加热100秒，接着在200℃下加热100秒，或者在180℃下热压10秒，然后在200℃的烘箱中后固化10分钟。由于电极和包含在粘合带101中的焊料通过组成焊料粉103的焊料颗粒的金属接合而连接，因此可维持低的接触电阻率和高的连接可靠性。
在所形成的接合体中，优选包含在粘合带101中具有助焊活性的固化剂的50％或更多的羧基与热固性树脂反应。
特别是，优选包含在粘合带101中具有助焊活性的固化剂的70％或更多的羧基与热固性树脂反应。
通过使包含在粘合带101中具有助焊活性的固化剂的50％或更多，优选70％或更多的羧基与热固性树脂反应，即使在高温下贮存接合体，也可防止导电组件出现腐蚀。
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反应率可如下进行测量。
在置换了氮气的烘箱中180℃下固化粘合带10分钟，对未固化的粘合带进行IR测定。
通过下式计算出固化度，固化前在约1600cm-1出现属于羧基的峰强度定义为(A)，固化后出现的峰强度定义为(B)：
固化度(％)＝{1-(B)/(A)}×100
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本发明的粘合带被设计成与被粘物之间具有优异的粘结性，且导电组件之间具有优异的电连接可靠性。例如，本发明的粘合带可涂布到电子器件，使电子器件或电子部件间彼此接合，由此将它们电连接。作为电子器件的实例一般可以是计算机、手机、电子游戏机、各种通讯器具和测量器具。
即使被粘物中导电组件的接合面积很细小，本发明的粘合带也能够提供确实的接合，且优选适于在半导体封装中连接基板和芯片等。
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例如，本发明的粘合带用于在半导体封装中将基板彼此连接。
涂布了粘合带的半导体封装一般被设计成依次层叠有第一基板、粘合带和第二基板，其中设置在第一基板上的第一电极和设置在第二基板上的第二电极通过粘合带中的焊料区域进行连接。
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粘合后，粘合带具有树脂和贯穿树脂的焊料区域。具有助焊活性的固化剂可以残留在树脂中，或不残留在树脂中。
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如以下实施例所述，焊料区域具有从粘合带内部向第一电极和第二电极扩大的形状。由于粘合带两面的焊料区域直径的增加，这样使焊料区域与粘合带中的树脂之间具有优异的粘结性，确保第一电极和第二电极与焊料区域之间大的接触面积。
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当本发明的粘合带用于接合基板时，可以对第一基板和第二基板设置阻焊剂，或不设置阻焊剂。
图2的截面图描述了没有设置阻焊剂的基板的接合方法。
如图2所示，在第一基材133和第二基材131中分别设有第一电极(导电组件)137和第二电极(导电组件)135。通过在基板之间设置本发明的粘合带101，以及通过在预定温度下将其加热，树脂层132能够将基板彼此连接，同时，使焊料粉以自对准方式迁移到第一电极137和第二电极135的表面，从而通过焊料区域111将电极连接。
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图3的截面图描述了设置了阻焊剂的基板的接合方法。图3示出的基本构造类似于图2所示出的，不同的是第一基材133和第二基材131分别设置有第一阻焊层141和第二阻焊层139，且第一电极137和第二电极135分别包埋在第一阻焊层141和第二阻焊层139中。在第一电极137和第二电极135相对区域的预定位置处，设有间隙143，其贯穿第一阻焊层141和第二阻焊层139。
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在接合这些基材的工序中，在基板间设置本发明的粘合带101，在预定温度下将其加热。通过此工序，焊料粉以自对准方式迁移到第一电极137和第二电极135从间隙143露出的表面，将间隙143填充。由此通过焊料区域111而形成互连。
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本发明的粘合带可在半导体封装中接合半导体芯片。
图4和图5的截面图示出了通过粘合带接合了半导体芯片的半导体封装(接合体)的结构。
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在图4中，第二半导体芯片153、粘合带101和第一半导体芯片151依次层叠，其中作为第二半导体芯片153导电组件的电极(未示出)和作为第一半导体芯片151导电组件的电极(未示出)通过粘合带101中的焊料区域101连接。设置在第二半导体芯片153背面的电极和芯片安装基板(安装基板155)的电极通过配线159连接。第一半导体芯片151、第二半导体芯片153和配线159用成型树脂163包封。在安装基板155背面设有多个凸起电极161。
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图5示出的基本构造类似于图4所示出的，其中在图5中，第二半导体芯片153通过倒装芯片接合法利用凸起电极165与安装基板155连接，其中第一半导体芯片151设置在安装基板155和第二半导体芯片153之间。
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在图4和图5中，第一半导体芯片151和第二半导体芯片153利用本发明的粘合带101接合。因此，与通过凸起电极接合芯片的情况比较，能够减少封装件的厚度。通过使用粘合带101，可通过简单的工序将芯片接合，且芯片的电极能够以高度可靠和稳定的方式进行连接。
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当在另一基板上安装半导体封装件的基板时，本发明的粘合带也可用于接合基板。例如，可以在PC板等上进行半导体封装件的二次安装。
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图6的截面图示出了这种半导体封装件(接合体)的结构。在图6中，其上装有半导体芯片(第一半导体芯片151和第二半导体芯片153)的第一基板(安装基板155)和其上装有安装基板155的第二基板(安装基板157)通过粘合带101接合。基板157一般为PC板。第一半导体芯片151和第二半导体芯片153之间填充有树脂167。第一半导体芯片151和第二半导体芯片153设有的电极(未示出)分别通过配线169和配线171与安装基板155上的电极(未示出)连接。
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由于图6示出的安装基板155和基板157是通过粘合带101接合的，设置于基板的电极能够高度可靠和稳定的接合。使用粘合带101能够降低基板之间的距离，由此整体地将封装件薄化。
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上述参照附图说明的本发明的实施方式仅用于举例说明，还可以使用上述以外的各种不同结构。
[实施例]
[0090]
(制造粘合带)
制造40μm厚、含有树脂、焊料粉和具有助焊活性的固化剂的粘合带(实施例1～18)。另外，制造40μm厚、含有树脂、焊料粉和具有助焊活性的固化剂的粘合带(比较例1～4)作为比较例。
[0091]
各组分的混合比在表1至表4和表13中示出，其以重量份表示。在各实施例和比较例中，基于表1至表4和表13中示出的混合比，将各组分溶解在芳香族烃类溶剂(如甲苯和二甲苯)、酯类有机溶剂(如乙酸乙酯和乙酸丁酯)或酮类有机溶剂(如丙酮和甲乙酮)中，然后将获得的清漆涂布在聚酯薄片上，在有机溶剂挥发的温度下将其干燥。
Figure A200780029217D00251
Figure A200780029217D00261
Figure A200780029217D00271
Figure A200780029217D00281
Figure A200780029217D00301
Figure A200780029217D00311
Figure A200780029217D00321
[0096]
在各实施例和比较例中，树脂的固化温度T1、焊料粉的熔点T2和树脂层焊料粉熔点T2下的熔融粘度在表5～8和表14中示出。
[0097]
[表5]
 
实施例1 实施例2 实施例3 实施例4 实施例5
树脂层的固化温度(T1) 196 202 189 204 200
焊料粉的熔点(T2) 138 138 138 138 138
树脂层的熔融粘度 430 350 660 450 490
T1-T2 58 64 51 66 62
[0098]
[表6]
 
实施例6 实施例7 实施例8 实施例9 实施例10
树脂层的固化温度(T1) 206 186 196 196 196
焊料粉的熔点(T2) 138 138 138 138 118
树脂层的熔融粘度 550 740 810 1110 520
T1-T2 68 48 58 58 78
[0099]
[表7]
 
实施例11 实施例12 实施例13 实施例14
树脂层的固化温度(T1) 197 196 194 198
焊料粉的熔点(T2) 138 138 138 138
树脂层的熔融粘度 270 150 110 3870
T1-T2 59 58 56 60
[0100]
[表8]
 
比较例1 比较例2 比较例3 比较例4
树脂层的固化温度(T1) 132 192 204 144
焊料粉的熔点(T2) 138 138 138 138
树脂层的熔融粘度 1340 34 6580 7630
T1-T2 -6 54 66 6
[0101]
实施例1～18获得成膜性良好的粘合带。
[0102]
(评价基板之间的接合)
如图2所示，使用实施例1～18和比较例1～4中获得的粘合带，不使用阻焊剂将基板接合。在此所用的基板为厚0.4mm的FR-4，其具有12μm厚镀覆Ni/Au的铜箔(第一电极、第二电极)、电路的宽度/间距(width/space)为300μm/100μm、上下电路重叠宽度为100μm，其中在基板之间设置粘合带，在基板的上表面设置200μm厚的硅橡胶，使压力得以均匀地施加，通过在2MPa和220℃下热压600秒进行接合。
[0103]
如图3所示，使用实施例1～18和比较例1～4获得的粘合带，将设有阻焊剂的基板接合。在此所用的基板为厚0.4mm的FR-4，其具有12μm厚镀覆Ni/Au的铜箔(第一电极、第二电极)、12μm厚的阻焊剂(从电路的上表面开始量度的厚度(第一电极、第二电极))、电路的宽度/间距为300μm/100μm、上下电路重叠宽度为100μm，其中在基板之间设置粘合带，在基板的上表面设置200-μm厚的硅橡胶，使压力得以均匀地施加，通过在2MPa和220℃下热压600秒进行接合。
[0104]
获得的接合体的相邻端子间的接触电阻值通过四端子法对12个位点进行测量而得以测定，取其平均值作为测定值。在表9～表12和表15中，测定值为30mΩ或更小的评价为＂○＂，测定值为30mΩ或更大的评价为＂×＂。
测量粘合带中具有助焊活性的固化剂的羧基与热固性树脂的反应率。反应率的测量方法类似于上述实施方式中所述的。
[0105]
观察各实施例和比较例中10个端子的截面，如图7和图8所示，在观察位点中显示形成了焊料导电柱的评价为＂○＂，一个位点都不能观察到导电柱的评价为＂×＂。
[0106]
图7的截面图示出了扫描电子显微镜(SEM)观察下的实施例1的叠层，其没有阻焊剂。如图7所示，焊料的厚度为2μm，证明其具有良好的焊料接合性。
[0107]
图8的截面图示出了SEM观察下的实施例1的叠层，其具有阻焊剂。如图8所示，端子间的间距约18μm。焊料的厚度为18μm，证明其具有良好的焊料接合性。发现连接电极的焊料区域具有在两个电极侧直径扩大的形状。
[0108]
[表9]
Figure A200780029217D00351
[0109]
[表10]
Figure A200780029217D00352
[0110]
[表11]
[0111]
[表12]
Figure A200780029217D00362
Figure A200780029217D00371
Figure A200780029217D00381
[0113]
[表14]
 
实施例15 实施例16 实施例17 实施例18
树脂层的固化温度(T1) 208 212 210 213
焊料粉的熔点(T2) 138 138 138 138
树脂层的熔融粘度 130 140 150 170
T1-T2 70 74 72 75
[0114]
[表15]
Figure A200780029217D00391
[0115]
使用实施例的粘合带可将连接电阻率降至低水平。
相反，使用比较例的粘合带会将连接电阻率不适宜地提高。
已证明本发明能够稳定地实现低电阻率。
[0116]
(评价铜互连表面的润湿性)
在实施例1所述的粘合带中，所使用的各种焊料粉和具有助焊活性的固化剂如表1中所列。对具有助焊活性的固化剂和焊料粉所用的材料组合以及它们在铜互连表面的润湿效果进行评价。
[0117]
使用Sn/Pb、Sn/Bi、Sn/Zn/Bi和Sn/Ag/Cu作为焊料粉。对于各焊料粉，使用龙胆酸和癸二酸作为具有助焊活性的固化剂，其能够作为环氧树脂的固化催化剂。结果，上述组合中的任何一个都能够成功确保一定程度的润湿性。Sn/Bi和癸二酸的组合显示出最好的润湿性。
[0118]
(考察焊料粉的粒径)
改变粘合带中焊料粉的粒径，评价其对铜电路表面润湿性的影响。在实施例1所述的粘合带中，焊料粉的平均粒径在12μm、20μm和35μm之间变化。设定除焊料粉以外的组分总含量为100，焊料粉的添加量为20wt％。在没有设置阻焊剂的基板之间设置粘合带，然后在2MPa和220℃下进行热压600秒。发现所有粒径都能确保对铜互连表面的润湿性。按照润湿性的从高到低的顺序，粒径为35μm、20μm和12μm。

Claims (11)

1.一种粘合带，其用于将导电组件电连接，所述粘合带包括：
含有热固性树脂的树脂层；
焊料粉；和
固化剂，
其中，所述焊料粉和固化剂包含在树脂层中，
所述树脂层的固化温度T1和焊料粉的熔点T2满足式(1)：
T1≥T2+20℃              式(1)
其中所述固化温度T1定义为通过DSC以10℃/分钟的升温速度测量所述粘合带所获得的放热峰温度，且
树脂层在焊料粉的熔点T2下的熔融粘度为50Pa·s～5000Pa·s。
2.如权利要求1所述的粘合带，其中基于100重量份的除所述焊料粉以外的所有组分的总重量，所述焊料粉的含量为20重量份或更多。
3.如权利要求2所述的粘合带，其中所焊料粉的平均粒径为1μm～100μm。
4.如权利要求1所述的粘合带，其中所述热固性树脂含有室温下为固体的环氧树脂和室温下为液体的环氧树脂。
5.如权利要求4所述的粘合带，其中所述室温下为固体的环氧树脂含有固体三官能环氧树脂和甲酚酚醛清漆型环氧树脂，且
所述室温下为液体的环氧树脂为双酚A型环氧树脂或双酚F型环氧树脂。
6.如权利要求1所述的粘合带，其中所述固化剂是具有助焊活性的固化剂。
7.如权利要求6所述的粘合带，其中所述具有助焊的固化剂是含有羧基的固化剂。
8.如权利要求1所述的粘合带，其中包含在所述树脂中的所述焊料粉在加热下以自对准方式向所述导电组件表面迁移。
9.接合体，其包括：
导电组件对；和
粘合带，其设置在所述导电组件对之间以用于将所述导电组件对电连接，
其中所述粘合带为权利要求7所述的粘合带，且
所述具有助焊活性的固化剂的50％或以上的羧基已与所述热固性树脂发生反应。
10.半导体封装件，其包括：
芯片安装基板；和
层积在所述芯片安装基板一面上的第一半导体芯片和第二半导体芯片，
其中所述第一半导体芯片和第二半导体芯片是用权利要求1所述的粘合带粘合的。
11.半导体封装件，其包括：
其上安装有半导体芯片的第一基板；和
其上安装有所述第一基板的第二基板，
其中，所述第一基板和第二基板是用权利要求1所述的粘合带粘合的。
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