CN103160219B - 各向异性导电膜组合物、各向异性导电膜和半导体装置 - Google Patents

各向异性导电膜组合物、各向异性导电膜和半导体装置 Download PDF

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CN103160219B
CN103160219B CN201210544591.XA CN201210544591A CN103160219B CN 103160219 B CN103160219 B CN 103160219B CN 201210544591 A CN201210544591 A CN 201210544591A CN 103160219 B CN103160219 B CN 103160219B
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conductive film
anisotropic conductive
film composition
formula
composition
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CN103160219A (zh
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柳·阿伦
金南柱
朴憬修
朴永祐
徐准模
薛庆一
鱼东善
崔贤民
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Guo Dujianduansucai
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Daiichi Woolen Co ltd
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Abstract

本申请公开了一种各向异性导电膜组合物和包含该组合物的各向异性导电膜以及半导体装置，所述组合物包含由式1表示的氢化双酚A型环氧单体或由式2表示的氢化双酚A型环氧低聚物；该组合物呈现了优异的防潮性和耐热性并在低温下可快速固化。[式1][式2]

Description

各向异性导电膜组合物、各向异性导电膜和半导体装置
技术领域
本发明涉及利用氢化双酚A型环氧单体和锍固化剂作为阳离子固化体系的各向异性导电膜组合物，以及包含该组合物的各向异性导电膜。更具体地，本发明涉及各向异性导电膜组合物和包含该组合物的各向异性导电膜，该组合物坚硬并呈现出优异的防潮性和耐热性，因而适用于各向异性导电膜，特别适用于玻璃覆晶（COG）。
背景技术
通常，各向异性导电膜（ACF）是指膜状粘合剂，其中导电颗粒，如包括镍或金颗粒的金属颗粒或者金属涂覆的聚合物颗粒，分散于诸如环氧树脂的树脂中。各向异性导电膜表示具有电各向异性和粘附性质的聚合物层，其在膜的厚度方向上呈现出导电性质并在膜的表面方向上呈现出绝缘性质。这种各向异性导电膜广泛用于将液晶显示器（LCD）面板或印刷电路板电连接到带载封装（TCP）上。
当各向异性导电膜设于要连接的电路板之间且在特定条件下受到加热和压制时，电路板的电路端子通过导电颗粒电连接且绝缘粘合用树脂填充在相邻电路端子之间的间隔内以使导电颗粒彼此隔离，从而在电路端子之间获得高绝缘性能。
主要使用可热固化的树脂作为用于各向异性导电膜的绝缘树脂。可热固化的树脂在加热固化时会放热，而通过消除施加的加热温度和放热而升高的温度，可热固化的树脂温度在固化终止时会下降。因此，由于温差引起体积变化，可热固化的树脂经历了固化收缩。当固化收缩发生时，各向异性导电膜在尺寸稳定性上受损，引起不良率增加。具体地，通常用作可热固化树脂的环氧树脂呈现出优异的粘附强度、耐热性和防潮性，但具有非常高的结合温度和相当长的结合时间，造成膜成型后不良率增加的可能性。因此，进行了各种尝试以开发出以在低温快速固化的可快速低温固化的各向异性导电膜。
同时，玻璃覆晶（COG）是在其上形成有薄膜电路的玻璃基底上安装芯片的芯片安装技术，使得IC直接安装于液晶显示器的液晶玻璃板上。用于COG的各向异性导电膜需要具有至少30MPa或更高的粘附强度并具有连接电阻，以便不仅在最初而且甚至 在可靠性测试后都能安全地支持驱动IC和面板。然而，用于COG的常规各向异性导电膜在固化后具有低模量且容易受热湿影响，从而使其难于生产出可靠连接的产品。
韩国专利公开文本第10-2011-0074320号（公布于2011年6月30日）公开了一种可快速低温固化的各向异性导电膜组合物，该组合物包含环己烷环氧树脂，该树脂具有环己烷和环氧环彼此直接相连的结构。因此，环氧环的结合强度实际低于其他普通的环氧树脂，且由固化剂的酸蚀造成的开环比其他环氧树脂发生得更快。因此，各向异性导电膜组合物可以在低温下快速固化。然而，各向异性导电膜组合物在固化后具有低模量，因此，与薄膜覆晶（COF）、玻璃覆膜（FOG）和外引线焊接（OLB）相比，因其低可靠性而不适用于COG，在COG中面板结合至硬驱动IC上。
日本专利公开文本第2001-261780号（公布于2001年9月26日）公开了一种包含氢化双酚A型环氧树脂的环氧树脂组合物。然而，该环氧树脂组合物为可UV固化的而不是可热固化的，且在90°C下受到约2小时的初次固化然后在140°C下受到4小时的二次固化。因此，该环氧树脂组合物不适用于ACF，ACF在150°C至170°C下需要固化5秒。而且，该公开文本中的环氧树脂组合物在柔性和粘附性之间提供了优异的平衡，而本发明的各向异性导电膜组合物在固化后提供了坚硬的结构。
作为广泛研究解决前述问题的结果，本发明的发明人开发出可快速低温固化的各向异性导电膜组合物和包含该组合物的各向异性导电膜，该组合物非常坚硬，呈现出优异的耐热性和防潮性并适用于COG。
发明内容
本发明旨在提供一种用于玻璃覆晶（COG）的各向异性导电膜组合物和包含该组合物的各向异性导电膜，所述组合物坚硬并呈现出优异的防潮性和耐热性，且具有改善的连接可靠性。
此外，本发明旨在提供一种各向异性导电膜组合物和包含该组合物的各向异性导电膜，所述组合物在低温下可快速固化。
本发明的一个方面提供一种各向异性导电膜组合物，所述各向异性导电膜组合物包含：（a）由式1表示的氢化双酚A型环氧单体或由式2表示的氢化双酚A型环氧低聚物；（b）锍固化剂；（c）粘合剂树脂；和（d）导电颗粒。
[式1]
[式2]
其中n为1至50的整数。
在一个实施方式中，基于100重量份的所述各向异性导电膜组合物，所述各向异性导电膜组合物包含：（a）1至50重量份由式1表示的所述氢化双酚A型环氧单体或由式2表示的所述氢化双酚A型环氧低聚物；（b）1至20重量份的所述锍固化剂；（c）20至60重量份的所述粘合剂树脂；和（d）10至50重量份的所述导电颗粒。
在一个实施方式中，所述锍固化剂（b）为芳族锍盐。
在一个实施方式中，所述芳族锍盐由通式3表示。
[通式3]
其中R1选自由氢、烷基、烷氧基、甲氧羰基和乙氧羰基组成的组中；R2选自由甲基、乙基、丙基和丁基组成的组中；且R3选自由硝基苄基、二硝基苄基、三硝基苄基和萘基甲基组成的组中。
在一个实施方式中，所述芳族锍盐由通式5表示。
[通式5]
其中R1选自由羟基、组成的组中，R5选自由芳族烃、取代的芳族烃、脂肪族烃、取代的脂肪族烃、羧基和磺酰基组成的组中；R2选自由氢和C1至C6烷基组成的组中。
在一个实施方式中，所述粘合剂树脂（c）包含芴环氧树脂。
在一个实施方式中，所述各向异性导电膜组合物具有120°C或更高的玻璃化转变温度。
在一个实施方式中，所述各向异性导电膜组合物用于COG。
本发明的另一个方面提供一种各向异性导电膜，所述各向异性导电膜包含由式1表示的氢化双酚A型环氧单体或由式2表示的氢化双酚A型环氧低聚物，且在150°C至170°C下固化5至10秒时具有70%或更高的固化率；并具有120°C或更高的玻璃化转变温度：
[式1]
[式2]
其中n为1至50的整数。
在一个实施方式中，所述各向异性导电膜在150°C下固化5至10秒时具有70%或更高的固化率，并具有120°C或更高的玻璃化转变温度。
在一个实施方式中，所述各向异性导电膜用于COG。
根据本发明的又一方面，提供一种半导体装置，所述半导体装置包括：布线基底；和半导体芯片，其中所述半导体装置通过所述各向异性导电膜连接。
在下文中，本发明将详细叙述。
本发明的一个方面提供一种各向异性导电膜组合物，所述各向异性导电膜组合物包含：（a）由式1表示的氢化双酚A型环氧单体或由式2表示的氢化双酚A型环氧低聚物；（b）锍固化剂；（c）粘合剂树脂；和（d）导电颗粒。
[式1]
[式2]
其中n为1至50的整数。
由式1表示的氢化的双酚A型环氧单体或由式2表示的氢化双酚A型环氧低聚物与 双酚A型环氧树脂相比形成了致密的结构，因此非常坚硬。而且，不像韩国专利公开文本第10-2011-0074320号中公开的环己烷环氧树脂那样，氢化双酚A型环氧单体或氢化双酚A型环氧低聚物具有线性伸长结构，因此呈现更加坚硬的性质。因此，各向异性导电膜组合物具有优异的防潮性和耐热性以及改善的连接可靠性。
基于100重量份的所述各向异性导电膜组合物，由式1表示的氢化双酚A环氧单体或由式2表示的氢化双酚A环氧低聚物的含量为1至50重量份，优选5至30重量份。在该范围内，可形成更加坚硬的具有优异的防潮性和耐热性的各向异性导电膜组合物。
所述锍固化剂可包括本领域通常使用的任何锍固化剂，而没有特别的限制。
所述锍固化剂的实例可包括由通式4或5表示的锍盐：
[通式4]
其中R1选自由苄基、取代的苄基、苯甲酰甲基、取代的苯甲酰甲基、烯丙基、取代的烯丙基、烷氧基、取代的烷氧基、芳氧基和取代的芳氧基组成的组中；R2和R3各自独立地与R1相同或选自由氟、氯、溴、羟基、羧基、巯基、氰基、硝基和由叠氮基取代的C1至C18直链的、支链的或环状的烷基组成的组中。R1和R2，R1和R3，或R2和R3可彼此结合成环状结构。
[通式5]
其中R1选自由羟基、组成的组中，R5选自由芳族烃、取代的芳族烃、脂肪族烃、取代的脂肪族烃、羧基和磺酰基组成的组中；R2选自由氢和C1至C6烷基组成的组中。
通式5的实例可包括，
所述锍固化剂可包括芳族锍盐，由于热活化能在产生阳离子中的高效率，考虑到为实现膜的快速低温固化，优选由通式3表示的芳族锍盐：
[通式3]
其中R1选自由氢、烷基、烷氧基、甲氧羰基和乙氧羰基组成的组中；R2选自由甲基、乙基、丙基和丁基组成的组中；R3选自由硝基苄基、二硝基苄基、三硝基苄基和萘基甲基组成的组中。
所述锍固化剂使所述各向异性导电膜组合物充分地实现快速低温固化。
基于100重量份的所述各向异性导电膜组合物，所述锍固化剂的含量为1至20重量份，优选1至10重量份。在该范围内，所述各向异性导电膜组合物可充分地实现低温快速固化并防止在室温或更低温度下的固化。
所述粘合剂树脂可包括本领域通常使用的任何粘合剂树脂，具体地只要该树脂不会阻碍氢化双酚A型环氧单体或低聚物的固化。粘合剂树脂的实例可包括聚酰亚胺树脂、聚酰胺树脂、苯氧基树脂、环氧树脂、聚甲基丙烯酸酯树脂、聚丙烯酸酯树脂、聚氨酯树脂、聚酯树脂、聚酯氨基甲酸乙酯树脂、聚乙烯醇缩丁醛树脂、苯乙烯-丁烯-苯乙烯（SBS）树脂及其环氧改性物、苯乙烯-乙烯-丁烯-苯乙烯（SEBS）树脂及其改性物和丙烯腈丁二烯橡胶（NBR）及其氢化化合物，这些粘合剂树脂可单独使用或作为混合物使用。
进一步，优选使用可热固化的环氧树脂作为粘合剂树脂，例如，具有90g/eq至5,000g/eq环氧当量和至少两个环氧基的环氧树脂。
可热固化的环氧树脂可为选自由双酚环氧树脂、酚醛环氧树脂、缩水甘油基环氧树脂、脂肪族环氧树脂、脂环族环氧树脂和芳族环氧树脂组成的组中的至少一种，但不限于此。进一步地，在室温下为固态的环氧树脂和在室温下为液态的环氧树脂可组 合使用，且可向该组合中进一步加入柔性环氧树脂。
在室温下为固态的环氧树脂的实例可包括苯酚酚醛环氧树脂、甲酚酚醛环氧树脂、具有二环戊二烯骨架的环氧树脂、双酚A或F型环氧树脂和改性的环氧树脂，但不限于此。在室温下为液态的环氧树脂的实例可包括双酚A型环氧树脂、双酚F型环氧树脂或它们的混合环氧树脂，不限于此。
柔性环氧树脂的实例可包括二聚酸改性的环氧树脂、具有丙二醇骨架的环氧树脂和氨基甲酸乙酯改性的环氧树脂。芳族环氧树脂可为选自由萘树脂、蒽树脂和芘树脂组成的组中的至少一种，但不限于此。
此外，芴环氧树脂可用作粘合剂树脂。当粘合剂树脂包括芴环氧树脂时，所述膜组合物可易于获得高玻璃化转变温度并具有优异的耐久性。
考虑到膜形成的便利，所述粘合剂树脂可具有高的重均分子量，但没有特别的限制。例如，所述粘合剂树脂具有5,000g/mol至150,000g/mol的重均分子量，优选10,000g/mol至80,000g/mol。在该范围内，所述粘合剂树脂具有与膜组合物其他组分之间的优异的相容性并利于膜的形成。
基于100重量份的所述各向异性导电膜组合物，所述芴环氧树脂的含量为0至30重量份，优选1至15重量份。
基于100重量份的所述各向异性导电膜组合物，所述粘合剂树脂的含量为20至60重量份，优选30至50重量份。
所述导电颗粒的可包括金属颗粒，或者涂覆有如金或银的金属的有机或无机颗粒。进一步地，所述导电颗粒可包括绝缘导电颗粒以确保导电颗粒过量使用时的电绝缘。所述导电颗粒的实例可包括金属颗粒，例如，Au、Ag、Ni、Cu和Pb颗粒；碳颗粒；金属涂覆的树脂颗粒，例如，涂覆有Au、Ag、Ni等的聚乙烯、聚丙烯、聚酯、聚苯乙烯、聚乙烯醇及其改性树脂颗粒；和通过进一步涂覆有绝缘颗粒而绝缘的导电颗粒。
基于100重量份的所述各向异性导电膜组合物，所述导电颗粒的含量为10至50重量份，优选20至40重量份。在该范围内，所述膜组合物可确保足够的导电性，且可防止由于导电颗粒过量造成的电短路。
所述各向异性导电膜组合物可进一步包括合适的溶剂。所述溶剂与所述氢化双酚A型环氧单体或低聚物、所述锍固化剂、所述粘合剂树脂和所述导电颗粒均匀地混合，降低了组合物的粘性，同时利于膜的形成。
所述溶剂可包括本领域通常使用的任何溶剂。例如，所述溶剂可包括甲苯、二甲苯、丙二醇单甲醚乙酸酯、苯、丙酮、甲乙酮、四氢呋喃、二甲基甲醛和环己酮。
所述各向异性导电膜组合物可进一步包括添加剂，如阻聚剂、抗氧化剂、热稳定 剂、固化促进剂和偶联剂。这种添加剂可包括本领域通常使用的的任何添加剂。
所述阻聚剂的实例可包括氢醌、氢醌单甲醚、对苯醌、吩噻嗪及它们的混合物。
所述抗氧化剂和热稳定剂的实例可包括四-亚甲基-(3,5-二-叔-丁基-4-氢化肉桂酸)甲烷、3,5-双(1,1-二甲基乙基)-4-羟基苯丙酸巯基二-2,1-乙二基酯、十八烷基3,5-二-叔-丁基-4-羟基氢化肉桂酸酯（所有这些都可以购自Ciba）、和2,6-二-叔-丁基-对-甲酚。
固化促进剂的实例可包括固体咪唑固化促进剂、固体胺固化促进剂和液体胺固化促进剂。
偶联剂的实例可包括乙烯基三氯硅烷、乙烯基三甲氧基硅烷、3-缩水甘油醚氧丙基三甲氧基硅烷、3-甲基丙烯酰氧丙基三甲氧基硅烷、2-氨乙基-3-氨丙基甲基二甲氧基硅烷和3-脲丙基三乙氧基硅烷。
所述各向异性导电膜组合物由于固化后的高模量、高玻璃化转变温度和坚硬性质优选用于COG。
本发明的另一个方面提供一种各向异性导电膜组合物，所述组合物在150°C至170°C下固化5至10秒时具有70%或更高的固化率，且具有120°C或更高的玻璃化转变温度。
本发明的另一个方面提供一种各向异性导电膜，所述膜在150°C固化5至10秒时具有70%或更高的固化率，且具有120°C或更高的玻璃化转变温度。
当用于在前述条件下的目的时，具有70%或更高固化率的各向异性导电膜在可靠性测试后可使最初的物理性质保持优异的程度，且具有120°C或更高玻璃化转变温度的各向异性导电膜在连接后不会严重变形以防止连接中短路的发生。
在一个实施方式中，所述各向异性导电膜包含由式1表示的氢化双酚A型环氧单体或由式2表示的氢化双酚A型环氧低聚物。
[式1]
[式2]
其中n为1至50的整数。
至于根据本发明的各向异性导电膜的形成方法，本文没有特别限制，可以使用本领域通常使用的任何方法。
在各向异性导电膜的形成方法中不涉及任何特殊的仪器或设备。例如，各向异性导电膜可通过以下方法制造：将粘合剂树脂溶解并液化于有机溶剂中，将剩余组分加入溶液中并搅拌一段时间，将混合物施加于隔离膜上至合适的厚度，例如，10μm至50μm，并干燥一段时间以挥发有机溶剂。
本发明的又一个方面提供一种通过所述各向异性导电膜连接的半导体装置。
所述半导体装置可包括布线基底、附着在布线基底的芯片安装表面上的各向异性导电膜和安装在膜上的半导体芯片。
至于本发明所用的布线基底和半导体芯片，本文没有特别的限制，可使用本领域通常已知的任何布线基底和半导体芯片。
如上所述，本发明提供一种各向异性导电膜组合物和包含该组合物的各向异性导电膜，所述组合物包含氢化双酚A型环氧单体或低聚物而具有坚硬的性质。具体地，本发明提供一种适于COG的各向异性导电膜组合物和包含该组合物的各向异性导电膜，所述组合物坚硬并具有120°C或更高的玻璃化转变温度。
进一步地，本发明提供一种各向异性导电膜组合物和包含该组合物的各向异性导电膜，所述组合物包含锍固化剂以在低温下快速固化°具体地，本发明提供一种在150°C至170°C固化5至10秒时具有70%或更高固化率的各向异性导电膜组合物，和包含该组合物的各向异性导电膜。
此外，本发明提供一种各向异性导电膜组合物和包含该组合物的各向异性导电膜，所述组合物具有优异的防潮性和耐热性而不易被温度或湿度损坏，而具有高连接可靠性。
具体实施方式
下文将参考以下实施例、对比例和实验例更详细地阐述本发明。这些实施例仅为了说明性目的而提供，并非以任何解释的方式限制本发明。
此处未包括的细节将易于本领域技术人员验证并评价，省略了该细节的说明。
实施例1
包含氢化双酚A型环氧单体的各向异性导电膜组合物的制备
将14重量份的氢化双酚A型环氧单体（式1中）、40重量份的双酚A型环氧树脂（YP-50，Kukdo Chemical Co.，Ltd.）、2重量份的多环含芳环的环氧树脂（HP4032D，Dainippon Ink & Chemicals）、5重量份的对苯二甲酸二环氧丙酯环氧树脂（EX-711， Nagase ChemteX）、4重量份的干二氧化硅（R812，Degussa）、5重量份的锍阳离子固化剂（SI-60L，Samshin Chemicals）、29重量份的涂覆有镍的聚合物颗粒和1重量份的γ-缩水甘油醚氧丙基三甲氧基硅烷（KBM403，Shin-Etsu Chemical）混合形成各向异性导电膜组合物。将这些组分与100重量份作为溶剂的PGMA混合，接着进行涂覆并干燥。
实施例2
包含芴环氧树脂的各向异性导电膜组合物的制备
将3重量份的芴BPA树脂（FX-293,，Shin Nippon Steel Corp.）、11重量份的氢化双酚A型环氧单体（式1中）、40重量份的双酚A环型氧树脂（YP-50，Kukdo Chemical Co.，Ltd.）、2重量份的多环含芳环的环氧树脂（HP4032D，Dainippon Ink & Chemicals）、5重量份的对苯二甲酸二环氧丙酯环氧树脂（EX-711，Nagase ChemteX）、4重量份的干二氧化硅（R812，Degussa）、5重量份的锍阳离子固化剂（SI-60L，Samshin Chemicals）、29重量份的涂覆有镍的聚合物颗粒和1重量份的γ-缩水甘油醚氧丙基三甲氧基硅烷（KBM403，Shin-Etsu Chemical）混合形成各向异性导电膜组合物。将这些组分与100重量份作为溶剂的PGEMA混合，接着进行涂覆并干燥。
实施例3
包含氢化双酚A型环氧低聚物的各向异性导电膜组合物的制备
除了使用14重量份的氢化双酚A型环氧低聚物（式2中）代替14重量份的氢化双酚A型环氧单体（式1中）之外，用与实施例1相同的方法制备各向异性导电膜组合物。
实施例4
包含氢化双酚A型环氧单体和氢化双酚A型环氧低聚物的各向异性导电膜组合物的制备
除了使用10重量份的氢化双酚A型环氧单体（式1中）和4重量份的氢化双酚A型环氧低聚物（式2中）代替14重量份的氢化双酚A型环氧单体（式1中）之外，用与实施例1相同的方法制备各向异性导电膜组合物。
对比例1
各向异性导电膜组合物的制备
除了使用16重量份的多环含芳环的环氧树脂（HP4032D，Dainippon Ink & Chemicals）代替14重量份的氢化双酚A型环氧单体（式1中）和2重量份的多环含芳环环氧树脂（HP4032D，Dainippon Ink & Chemicals）之外，用与实施例1相同的方法制备各向异性导电膜组合物。
对比例2
各向异性导电膜组合物的制备
除了使用19重量份的对苯二甲酸二环氧丙酯环氧树脂（EX-711，Nagase ChemteX）代替3重量份的芴BPA树脂（FX-293，ShinNippon Steel Corp.）、11重量份的氢化双酚A型环氧单体（式1中）和5重量份的对苯二甲酸二环氧丙酯环氧树脂（EX-711，NagaseChemteX）之外，用与实施例2相同的方法制备各向异性导电膜组合物。
实施例5
各向异性导电膜的制备
将实施例1至4和对比例1和2中制备的各组合物施加于白色隔离膜上并在80°C的干燥机内干燥，从而制得具有20μm厚度的各向异性导电膜。
实验例1
实施例5的各向异性导电膜固化率的评价
将具有2,000μm2隆起焊盘面积和厚度的氧化铟锡（ITO）电路的玻璃基底与具有2,000μm2隆起焊盘面积和0.7mm厚度的芯片结合，并用实施例5得到的每个各向异性导电膜来回压制，接着在170°C和90MPa压制并加热5秒，从而制备一个各向异性导电膜的样品。当用晶片剪切机分离芯片后，刮掉留在玻璃基底上的各向异性导电膜，并利用IR评价固化率。定义1,540至1,480cm-1范围内的峰为苯环吸收以及930至889cm-1范围内的峰为环氧环吸收，用下列等式计算固化率。
T(x)=E(x)/B(x)
E：环氧环吸收 
B：苯环吸收 
T：环氧环吸收对苯环吸收的光谱强度比
x=100：100%固化的样品
0：0%固化的样品
?：未知反应速率样品
固化率={(T(?)–T(0))/(T(100)–T(0))}×100(%)
固化率结果列于表1中。
表1
  实施例1 实施例2 实施例3 实施例4 对比例1 对比例2
固化率（%） 82 81 80 82 64 71
实验例2
实施例5的各向异性导电膜玻璃化转变温度的评价
将实施例5得到的每个各向异性导电膜形成具有60μm厚度的三层膜，然后在190°C固化1小时，切成30mm×5mm的样品，接着用DMA进行玻璃化转变温度的评价。
玻璃化转变温度的结果列于表2中。
表2
  实施例1 实施例2 实施例3 实施例4 对比例1 对比例2
玻璃化转变温度（Tg，°C) 132 141 137 135 147 121
实验例3
实施例5的各向异性导电膜连接可靠性的评价
为了评价实施例5得到的每个各向异性导电膜的连接可靠性，每个各向异性导电膜的电阻测量如下。
（1）样品的制备
将具有2,000μm2隆起焊盘面积和厚度的氧化铟锡（ITO）电路的玻璃基底与具有2,000μm2隆起焊盘面积和1.7mm厚度的芯片结合，并用实施例5得到的每个各向异性导电膜来回压制，接着在170°C和90MPa压制并加热5秒，从而制备每个各向异性导电膜的5个样品。
（2）初始连接电阻的测量
对每个完全连接的样品的连接电阻进行5次的测量，并计算平均连接电阻。
（3）可靠性测试后连接电阻的测量
在测量初始连接电阻后，每个样品在85°C和85%湿度的高温高湿条件经过100小时、250小时和500小时后，接着进行连接电阻的测量和平均连接电阻的计算。
各样品的平均初始连接电阻和可靠性测试后的平均连接电阻列于表3中。
表3
  实施例1 实施例2 实施例3 实施例4 对比例1 对比例2
初始连接电阻（Ω） 0.52 0.48 1.5 0.63 11.8 1.0
可靠性测试后的连接电阻(Ω) 1.6 1.4 2.9 1.8 62.9 11.3
如表3所示，根据对比例1的膜电阻在高温和高湿条件下的可靠性测试后与初始电阻相比增长了约5.33倍。根据对比例2的膜增长了约11.3倍。然而，根据实施例1的膜增长了约3.07倍，而根据实施例2的膜增长了约2.9倍。
因此，利用由式1表示的氢化双酚A型环氧单体制备的各向异性导电膜与常规各向异性导电膜相比具有紧密和坚硬的性质，从而具有优异的耐热性和防潮性以及更好的可靠性。
尽管本文提供了一些实施方式，但对本领域技术人员来说显然仅是以说明的方式提供了这些实施方式，且可以作出各种修改、变化、改动和等效实施方式，而不背离本发明的精神和范围。因此，本发明的范围应该仅受到所附权利要求的限制。

Claims (11)

1.一种各向异性导电膜组合物，所述各向异性导电膜组合物包含：
由式1表示的氢化双酚A型环氧单体或由式2表示的氢化双酚A型环氧低聚物；
锍固化剂；
粘合剂树脂；和
导电颗粒；
其中n为1至50的整数，
且所述粘合剂树脂包含芴环氧树脂。
2.根据权利要求1所述的各向异性导电膜组合物，其中基于100重量份的所述各向异性导电膜组合物，所述各向异性导电膜组合物包含1至50重量份由式1表示的所述氢化双酚A型环氧单体或由式2表示的所述氢化双酚A型环氧低聚物；1至20重量份的所述锍固化剂；20至60重量份的所述粘合剂树脂；和10至50重量份的所述导电颗粒。
3.根据权利要求1所述的各向异性导电膜组合物，其中所述锍固化剂包含芳族锍盐。
4.根据权利要求3所述的各向异性导电膜组合物，其中所述芳族锍盐由通式3表示：
其中R1选自由氢、烷基、烷氧基、甲氧羰基和乙氧羰基组成的组中；R2选自由甲基、乙基、丙基和丁基组成的组中；且R3选自由硝基苄基、二硝基苄基、三硝基苄基和萘基甲基组成的组中。
5.根据权利要求3所述的各向异性导电膜组合物，其中所述芳族锍盐由通式5表示：
其中R1选自由羟基、组成的组中，R5选自由芳族烃、取代的芳族烃、脂肪族烃、取代的脂肪族烃、羧基和磺酰基组成的组中；R2选自由氢和C1至C6烷基组成的组中。
6.根据权利要求1至5的任一项所述的各向异性导电膜组合物，其中所述各向异性导电膜组合物具有120℃或更高的玻璃化转变温度。
7.根据权利要求1至5的任一项所述的各向异性导电膜组合物，其中所述各向异性导电膜组合物用于玻璃覆晶。
8.一种各向异性导电膜，所述各向异性导电膜包含由式1表示的氢化双酚A型环氧单体或由式2表示的氢化双酚A型环氧低聚物、粘合剂树脂和锍固化剂，所述各向异性导电膜在150℃至170℃固化5至10秒时具有70％或更高的固化率并在190℃固化1小时后用DMA评价时具有120℃或更高的玻璃化转变温度；
其中n为1至50的整数，且所述粘合剂树脂包含芴环氧树脂。
9.根据权利要求8所述的各向异性导电膜，其中所述各向异性导电膜在150℃固化5至10秒时具有70％或更高的固化率，并具有120℃或更高的玻璃化转变温度。
10.根据权利要求8或9所述的各向异性导电膜，其中所述各向异性导电膜用于玻璃覆晶。
11.一种半导体装置，所述半导体装置包括：
布线基底；
附着在布线基底的芯片安装表面上的各向异性导电膜；和
安装在所述各向异性导电膜上的半导体芯片，
其中所述各向异性导电膜包含权利要求1至7的任一项所述的各向异性导电膜组合物或权利要求8至10的任一项所述的各向异性导电膜。
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