CN103173143B - 各向异性导电膜和半导体器件 - Google Patents

各向异性导电膜和半导体器件 Download PDF

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Publication number
CN103173143B
CN103173143B CN201210567731.5A CN201210567731A CN103173143B CN 103173143 B CN103173143 B CN 103173143B CN 201210567731 A CN201210567731 A CN 201210567731A CN 103173143 B CN103173143 B CN 103173143B
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Prior art keywords
conductive film
anisotropic conductive
acrylate
resin
fluorenes
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CN201210567731.5A
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CN103173143A (zh
Inventor
韩在善
金显昱
南宫贤熺
徐辰瑛
郑光珍
鱼东善
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Daiichi Woolen Co ltd
Cheil Industries Inc
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Daiichi Woolen Co ltd
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    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/482—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of lead-in layers inseparably applied to the semiconductor body
    • H01L23/4827—Materials
    • H01L23/4828—Conductive organic material or pastes, e.g. conductive adhesives, inks
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    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/156—Material
    • H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H01L2924/15788—Glasses, e.g. amorphous oxides, nitrides or fluorides

Abstract

本申请公开了一种各向异性导电膜和半导体器件。所述膜使用了阴离子可固化化合物的芴取代生成物和实质上同阴离子可固化化合物可混合的自由基可固化化合物的芴取代生成物，从而实现了芴取代生成物的可混合性。更确切地说，所述各向异性导电膜包含了芴取代的苯氧树脂和同芴取代的苯氧树脂可混合的芴取代的丙烯酸酯，显示了低温下的快速固化性能以及高储能模量，实现了高可靠性。

Description

各向异性导电膜和半导体器件
技术领域
本发明涉及一种使用可阴离子固化化合物的芴取代生成物和可自由基固化化合物的芴取代生成物以获得可阴离子固化化合物和可自由基固化化合物的可混合性的各向异性导电膜。
更具体地说，本发明涉及一种含有芴取代的苯氧树脂和芴取代的丙烯酸酯以具有可混合性、低温下的快速固化性能和高储能模量的各向异性导电膜，从而实现高可靠性。
背景技术
近年来，基于各向异性导电膜在电子元件或半导体器件同基板端子间连接应用的连接方法已被广泛采用。这种各向异性导电连接方法广泛用于平板显示器的平板制造中载带封装(TCP)端子和玻璃基板的透明电极间的连接、驱动集成电路和挠性印刷电路(FPC)板端子间的连接以及驱动集成电路和透明电极间的连接。特别地，各向异性导电连接有可能成为未来的封装方法，它具有替代覆晶封装中焊球连接的可能性，其应用范围正在不断扩展。
当各向异性导电膜用于在高温下粘结驱动集成电路和透明电极时，由于构成驱动集成电路的硅片和其上形成透明电极的玻璃之间热膨胀系数的差异，粘结后进行的热固化时产生了严重变形。这种变形导致最终产品中缺陷的形成。因此，需要开发一种在低温下较短时间内进行固化的各向异性导电膜。
另一方面，各向异性导电膜在热和压力下粘结时发生膨胀且在粘结后收缩。膨胀和收缩的结果产生了气泡，妨碍了粘合剂组合物的充分填充，在膜中留下了空隙。一定数量气泡的生成导致了各向异性导电膜较差的粘着强度，致使含有各向异性导电膜作为连接材料的半导体器件无法长时间使用。这导致半导体器件的低可靠性。
为了解决上述问题，开发在低温下进行快速固化的高可靠性各向异性导电膜受到广泛关注。
涉及本发明的现有技术有例如韩国专利No.10-0642445 B1，其公开日期为2006 年11月2日。
所述现有技术涉及一种用于各向异性导电粘合剂的树脂组合物，其中使用了羟基被其它官能团取代了的环氧树脂和可自由基聚合树脂，后者实质上同被取代前的环氧树脂不能混合。上述现有技术的意义在于使两种几乎不相容的树脂相互间可混合。除这个意义外，仍然存在缓慢的低温固化性能和较低的可靠性问题。
发明内容
本发明的发明人进行了认真努力的研究来解决上述提到的问题。结果，发明人成功开发出一种含有芴取代的苯氧树脂和芴取代的丙烯酸酯的各向异性导电膜，以实现低温下的快速固化性能和高可靠性。
本发明的一个目的是提供一种使用可阴离子固化化合物的芴取代生成物和可自由基固化化合物的芴取代生成物以获得可阴离子固化化合物和可自由基固化化合物的可混合性的各向异性导电膜。
本发明的另一个目的是提供一种含有芴取代的苯氧树脂和芴取代的丙烯酸酯以具有可混合性、低温下的快速固化性能和高储能模量的各向异性导电膜，从而实现高可靠性。
本发明的一个方面提供一种各向异性导电膜。在一个实施例中，所述各向异性导电膜含有芴取代的苯氧树脂和芴取代的丙烯酸酯。
在一个实施例中，所述各向异性导电膜含有：
a)苯氧树脂，所述苯氧树脂包括芴取代的苯氧树脂；和
b)可自由基聚合树脂，所述可自由基聚合树脂包括芴取代的丙烯酸酯。
在一个实施例中，基于100重量份的所述各向异性导电膜的固体含量，所述各向异性导电膜含有：
a)20至60重量份的苯氧树脂，所述苯氧树脂包括芴取代的苯氧树脂；和
b)40至80重量份的可自由基聚合树脂，所述可自由基聚合树脂包括芴取代的丙烯酸酯。
在一个实施例中，基于100重量份的所述各向异性导电膜固体含量，所述各向异性导电膜含有：
a)5至50重量份的所述芴取代的苯氧树脂；和
b)5至40重量份的所述芴取代的丙烯酸酯。
在一个实施例中，所述各向异性导电膜进一步包含丙烯酸改性的环氧树脂。
在一个实施例中，所述各向异性导电膜进一步包含聚氨酯丙烯酸酯。
在一个实施例中，所述各向异性导电膜在160℃和3MPa下按压5秒后经测量具有700gf/cm或更高的粘着强度。
在一个实施例中，所述各向异性导电膜具有60至200gf/mm2的抗张强度。
本发明的另一个方面提供了一种含有苯氧树脂和可自由基聚合树脂的各向异性导电膜，其具有a)在160℃和3MPa下按压5秒后经测量具有700gf/cm或更高的粘着强度，和b)在固化度为90%或更高的情况下1000MPa或更高的储能模量。
本发明的另一个方面提供了一种半导体器件。在一个实施例中，所述半导体器件包括布线基板和半导体芯片，其中布线基板通过所述各向异性导电膜同半导体芯片相连接。
具体实施方式
下面将详细描述本发明的实施例。未包括在这里的申请内容可以被本领域技术人员认知并理解，因此省略了其描述。并且在这里，数量词“一个”及其词组并不排除多数形式。
在一个实施例中，各向异性导电膜含有，
a)苯氧树脂，所述苯氧树脂包括芴取代的苯氧树脂；和
b)可自由基聚合树脂，所述可自由基聚合树脂包括芴取代的丙烯酸酯。
a)苯氧树脂
本发明使用的苯氧树脂其特征在于包括芴取代的苯氧树脂。
芴取代的苯氧树脂
芴取代的苯氧树脂没有特别限制，只要其是用芴取代了的即可。
本领域中已知的任何苯氧树脂都可以没有限制地用于本发明，芴取代的苯氧树脂也是如此。
适用于本发明的优选的苯氧树脂的例子包括双酚A型苯氧树脂。
b)可自由基聚合树脂
本发明使用的可自由基聚合树脂其特征在于包括芴取代的丙烯酸酯。
芴取代的丙烯酸酯
本发明使用的芴取代的丙烯酸酯没有特别限制，只要其是用芴取代了的即可。
适用于本发明的芴取代的丙烯酸酯的非限定性实例包括芴取代的环氧（甲基）丙烯酸酯和芴取代的聚氨酯（甲基）丙烯酸酯。
本领域中已知的任何可自由基聚合树脂都可以没有限制地用于本发明，芴取代的丙烯酸酯也是如此。
适用于本发明的可自由基聚合树脂的非限定性实例包括丙烯酸酯、甲基丙烯酸酯和马来酰亚胺化合物。其单体、低聚物或组合也可使用。
丙烯酸酯和甲基丙烯酸酯
适用于本发明的丙烯酸酯和甲基丙烯酸酯的实例包括但不限于丙烯酸甲酯、丙烯酸乙酯、丙烯酸异丙酯、丙烯酸异丁酯、二丙烯酸乙二醇酯、二丙烯酸二乙二醇酯、三甲醇丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、四羟甲基甲烷四丙烯酸酯、2-羟基-1,3-二丙烯酰氧丙烷、2,2-双[4-(丙烯酰氧基聚甲氧基)苯基]丙烷、2,2-双[4-(丙烯酰氧基聚乙氧基)苯基]丙烷、二环戊烯丙烯酸酯、三环癸基丙烯酸酯和三(丙烯酰氧乙基)异氰脲酸酯。这些丙烯酸酯和甲基丙烯酸酯可以单独或以其两种或更多种的混合物形式使用。
还可以使用具有磷酸酯结构的丙烯酸酯或甲基丙烯酸酯、异氰脲酸酯类丙烯酸酯或双酚A型环氧丙烯酸酯树脂来提高所述各向异性导电膜的粘着强度和室温稳定性。
马来酰亚胺
本发明使用的马来酰亚胺化合物可以是其分子中含有至少两个马来酰亚胺基团的化合物。这样的马来酰亚胺化合物的例子包括但不限于1-甲基-2,4-双马来酰亚胺基苯、N,N’-间-亚苯基双马来酰亚胺、N,N’-对-亚苯基双马来酰亚胺、N,N’-间-甲次苯基双马来酰亚胺、N,N’-4,4-亚联苯基双马来酰亚胺、N,N’-4,4-(3,3’-二甲基亚联苯)双马来酰亚胺、N,N’-4,4-(3,3’-二甲基二苯基甲烷)双马来酰亚胺、N,N’-4,4-(3,3’-二乙基二苯基甲烷)双马来酰亚胺、N,N’-4,4-二苯基甲烷双马来酰亚胺、N,N’-4,4-二苯 基丙烷双马来酰亚胺、N,N’-4,4-二苯醚双马来酰亚胺、N,N’-3,3-二苯砜双马来酰亚胺、2,2-双(4-(4-马来酰亚胺基苯氧基)苯基)丙烷、2,2-双(3-s-丁基-4-s-(4-马来酰亚胺基苯氧基)苯基)丙烷、1,1-双(4-(4-马来酰亚胺基苯氧基)苯基)癸烷、4,4’-亚环己基双(1-(4-马来酰亚胺基苯氧基)-2-环己苯和2,2-双(4-(4-马来酰亚胺基苯氧基)苯基)六氟丙烷。这些马来酰亚胺化合物可以单独或以其两种或更多种的混合物的形式使用。
基于100重量份的所述各向异性导电膜固体含量，优选包含20至60重量份的本发明使用的苯氧树脂。
基于100重量份的所述各向异性导电膜固体含量，本发明使用的苯氧树脂中芴取代的苯氧树脂的含量优选为5至50重量份。在此范围内，可获得高可靠性。
基于100重量份的所述各向异性导电膜固体含量，包含40至80重量份的本发明使用的可自由基聚合树脂。
基于100重量份的所述各向异性导电膜固体含量，本发明使用的可自由基聚合树脂中的芴取代的丙烯酸酯的含量为5至40重量份。在此范围内，可以获得足够的低温快速固化性能。
本发明的各向异性导电膜除成分a)和b)之外还可以包含固化引发剂和导电颗粒。
固化引发剂
本发明使用的固化引发剂没有特别限制，可以是本领域中经常使用的任何一种。本发明适用的固化引发剂的非限定性实例包括过氧化物和偶氮引发剂。
过氧化物引发剂
本发明适用的过氧化物引发剂的实例包括但不限于过氧化苯甲酰、过氧化月桂酰、过氧化月桂酸叔丁酯、1,1,3,3-四甲基丁基过氧-2-己酸乙酯和氢过氧化枯烯。
偶氮引发剂
本发明适用的偶氮基引发剂的实例包括但不限于2,2’-偶氮双(4-甲氧基-2,4-二甲基戊腈)、二甲基2,2’-偶氮双(2-丙酸甲酯)和2,2’-偶氮双(N-环己基-2-丙酸甲酯)。
导电颗粒
本发明使用的导电颗粒没有特别限制，可以是本领域中经常使用的种类。
作为可用于本发明的导电颗粒的非限定性实例，可以例如为金属颗粒，包括Au、Ag、Ni、Cu和焊料颗粒；碳颗粒；以金属包括例如Au、Ag和Ni电镀和涂覆的树脂颗粒，包括例如聚乙烯、聚丙烯、聚酯、聚苯乙烯、聚乙烯醇及其改性树脂的颗粒；和在金属涂覆的聚合物树脂颗粒上通过进一步涂覆绝缘颗粒所获得的绝缘（insulated）导电颗粒。
导电颗粒的粒径可以藉由采取的电路间距来确定并根据实际应用在2至30μm的范围内。
基于100重量份的所述各向异性导电膜固体含量,本发明使用的导电颗粒优选含有0.1至10重量份。如果导电颗粒的含量小于0.1重量份，在连接过程中端子间的位置未对准可能造成端子的连接面积减小，带来连接不良的危险。同时，如果导电颗粒的含量超过10重量份，可能形成绝缘不良的危险。
在另一个实施例中，本发明的各向异性导电膜除成分a)和b)之外进一步包含环氧或苯氧树脂。
适用于本发明的环氧或苯氧树脂的实例包括但不限于酚醛(novolac)型环氧树脂、表卤代醇改性的环氧树脂、丙烯酸改性的环氧树脂、乙烯基改性的环氧树脂、表卤代醇改性的苯氧树脂、丙烯酸改性的苯氧树脂和乙烯基改性的苯氧树脂。
表卤代醇改性的环氧树脂可以通过分子上含有羟基基团的环氧树脂同表卤代醇进行反应来制备。丙烯酸改性的环氧树脂可以通过分子上含有羟基基团的环氧树脂同丙烯酸单体进行反应来制备。乙烯基改性的环氧树脂可以通过分子上含有羟基基团的环氧树脂同乙烯基单体进行反应来制备。
另一方面，环氧树脂可以是用橡胶树脂对环氧分子进行改性的产物。例如，对环氧树脂进行改性的橡胶树脂可以选自由丁二烯聚合物、丙烯酸聚合物、聚醚尿烷橡胶、聚酯尿烷橡胶、聚酰胺尿烷橡胶、硅酮橡胶、二聚酸、硅酮树脂及其混合物组成的组中。
这些环氧和苯氧树脂可以单独或以其两种或更多种的混合物的形式使用。
可以用橡胶树脂改性的环氧树脂的实例包括：双酚A型树脂、双酚F型树脂、双酚AD型树脂、双酚S型树脂、烯化氧加合物，其卤化物（例如四溴双酚型环氧树脂）和氢化产物（例如氢化双酚型环氧树脂）；以及脂环族环氧树脂、脂环链环氧树脂及其卤化物和氢化产物。
用于改性环氧树脂的市售商品的实例包括：KD-1011、KD-1012和KD-1014，所有这些都可以从Kukdo Chemical Co.,Ltd.获得；以及EP-5100R、EP-5200R和EP-5400R，所有这些都可以从ADEKA获得。
基于100重量份的所述各向异性导电膜固体含量，环氧或苯氧树脂的含量优选在0至40重量份的范围内，更优选10至40重量份。在此范围内，可以确保芴取代的苯氧树脂和芴取代的丙烯酸酯间更好的可混合性，并可获得各向异性导电膜的高粘合度和可靠性。
在另一个实施例中，本发明的各向异性导电膜还包含聚氨酯丙烯酸酯。
适用于本发明的聚氨酯丙烯酸酯可通过异氰酸酯、丙烯酸酯、多羟基化合物和/或二醇的聚合反应来制备。
对于异氰酸酯，可以使用例如芳香族二异氰酸酯、脂肪族二异氰酸酯、脂环族二异氰酸酯或其组合。特别地，异氰酸酯可选自但不限于由异佛尔酮二异氰酸酯(IPDI)、四亚甲基-1,4-二异氰酸酯、环己烷-1,6-二异氰酸酯、二苯基甲烷二异氰酸酯、亚环己基-1,4-二异氰酸酯、亚甲基双(4-环己基异氰酸酯)、二异氰酸二甲苯酯、氢化二苯基甲烷二异氰酸酯、萘二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯及其混合物组成的组中。优选芳香族异氰酸酯。
丙烯酸酯可以为例如氢化丙烯酸酯或氨化丙烯酸酯，但不限于此。
多羟基化合物或二醇可以为例如乙二醇、丙二醇、己二醇、新戊二醇、二甘醇、三甘醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、二丙二醇、二丁二醇、2-甲基-1,3-戊二醇、2,2,4-三甲基-1,3-戊二醇或1,4-环己烷二甲醇，但不限于此。
聚合反应没有特别限制，可以通过本领域已知的任何适合的方法进行。例如，聚合反应可以通过在90℃且1atm下，60wt%的多羟基化合物同羟基（甲基）丙烯酸酯和异氰酸酯（摩尔比1:1）以50%体积百分比的甲乙酮作为溶剂且在作为催化剂的二丁基锡二丙烯酸酯存在下反应5小时来进行。
在另一个实施例中，各向异性导电膜具有60至200gf/mm2的抗张强度。
根据本发明的各向异性导电膜的抗张强度优选在60至200gf/mm2的范围内，更优选100至200gf/mm2。在此范围内，当预压后需要重做时，无需切割就可以剥离。
对于抗张强度的测量方法没有特别限制。抗涨强度可以通过本领域中常用的任何适合的方法进行测量。
例如，在各向异性导电膜被切割成尺寸为约1.0mm（宽度）×约10mm（长度）的样品后，通过万能试验机(UTM)(H5K-T,Hounsfield)测量样品的抗涨强度。
本发明各方面提供了一种含有苯氧树脂和可自由基聚合树脂的各向异性导电膜，其具有a)在160℃和3MPa下按压5秒后经测量具有700gf/cm或更高的粘着强度，和b)在固化度为90%或更高的情况下1000MPa或更高的储能模量。
对于粘着强度的测量方法没有特别限制。粘着强度可以通过本领域中常用的任何适合的方法进行测量。
例如，各向异性导电膜在160℃和3MPa下按压5秒后，通过剥离强度测试仪(H5KT,Tinius Olsen)以90°的剥离角度、50mm/min的剥离速度测量剥离强度。
各向异性导电膜的粘着强度优选700gf/cm或更高。如果粘着强度小于700gf/cm，包含各向异性导电膜作为连接材料的半导体器件很难长时间使用，即半导体器件具有较短的使用寿命。
各向异性导电膜的储能模量定义为在90%或更高的固化度下测量的值。90%或更高的固化度是指各向异性导电膜实质上完全固化的时刻。
对于储能模量的测量方法没有特别限制。储能模量可以通过本领域中常用的任何适合的方法进行测量。
例如，当各向异性导电膜片叠加在一起直到总厚度达到100μm并在150℃的热风烘箱中保持2小时后，通过动态机械分析仪(DMA)(Q800,TA)来测量层压制件的储能模量。
各向异性导电膜的储能模量优选1000MPa。如果储能模量低于1000MPa，不能有效控制热收缩和热膨胀，造成低可靠性的风险。
对于本发明各向异性导电膜的成型方法没有特别限制。
本领域中常用的任何适合的方法都可以没有限制地用来成型各向异性导电膜。
制备各向异性导电膜不需要特别的装置或设备。例如，可通过将粘结剂树脂溶解在有机溶剂中，向溶液中加入其它成分，搅拌混合物一段时间，将混合物涂覆到离型膜上至适合的厚度（例如10至50μm）并以足以蒸发有机溶剂的时间干燥该混合物来获得各向异性导电膜。
本发明提供了一种包含各向异性导电膜作为连接材料的半导体器件。
半导体器件可以包括布线基板、附着在布线基板表面上的各向异性导电膜以及安装在膜上的半导体芯片。
本发明使用的布线基板和半导体芯片的种类没有特别限制。布线基板和半导体芯片可以是本领域已知的。
半导体器件的制造方法没有特别限制。半导体器件可以通过本领域中已知的任何适合的方法来制造。
下面将通过下述实例包括对比例和实验例对本发明进行更详细地解释。这些实例仅以说明的目的提供，不能以任何方式解释为对本发明的限制。
实例
实例1
含有芴取代的苯氧树脂和芴取代的丙烯酸酯的各向异性导电膜的制备
以要制备的各向异性导电膜固体含量为100重量份计，
1)47重量份芴取代的苯氧树脂（FX293,New Japan Chemical），
2)35重量份芴取代的丙烯酸酯（BPF-022,Hannong Chemicals Inc.），
3)5重量份导电颗粒（NIEYB00375,Sekisui），
4)3重量份粘结助剂（KBM-403,Shinetsu），和
5)10重量份胶囊型咪唑固化剂（HXA-3941,Asahi Kasei）用以制备各向异性导电膜组合物。
组合物在室温（25℃）下以不使导电颗粒破碎的速率搅拌。将所得溶液薄薄地涂覆于经硅酮脱模剂处理过的聚对苯二甲酸乙二醇酯(PET)基膜表面并用70℃的热风干燥5分钟形成30μm厚的膜。使用铸刀(casting knife)用以膜的成型。
实例2
含有芴取代的苯氧树脂、芴取代的丙烯酸酯和环氧树脂的各向异性导电膜的制备
此各向异性导电膜的制备方法同实例1的方法相同，只是芴取代的苯氧树脂的用量为32重量份，芴取代的丙烯酸酯的用量为25重量份，及环氧树脂（SG-80H,Nagase）的用量为25重量份。
实例3
含有芴取代的苯氧树脂、芴取代的丙烯酸酯、环氧树脂和聚氨酯丙烯酸酯的各向异性导电膜的制备
以要制备的各向异性导电膜固体含量为100重量份计，
1)20重量份芴取代的苯氧树脂，
2)10重量份芴取代的丙烯酸酯，
3)20重量份环氧树脂(SG-80H,Nagase)，
4)10重量份聚氨酯丙烯酸酯
5)12重量份可自由基聚合树脂(80MFA,Kyoeisha Chemical Co.,Ltd.)，
6)5重量份导电颗粒(NIEYB00375,Sekisui)，
7)3重量份粘结助剂(KBM403,Shinetsu)，和
8)10重量份过氧化物引发剂(BPO/LPO,Dongsung Highchem)用于制备各向异性导电膜组合物。
以实例1所述相同的制备过程使用上述组合物来成型各向异性导电膜。
[对比例1-4]
不含有芴取代的苯氧树脂和芴取代的丙烯酸酯的各向异性导电膜的制备
对比例1
此各向异性导电膜以实例1所述相同的方法制备，只是不使用芴取代的苯氧树脂和芴取代的丙烯酸酯，而分别使用37重量份的BPA苯氧树脂(PKHH,Union Carbide)和45重量份的环氧树脂(SG-80H,Nagase)。
对比例2
此各向异性导电膜以实例3所述相同的方法制备，只是不使用芴取代的苯氧树脂和芴取代的丙烯酸酯，而分别使用45重量份的聚氨酯丙烯酸酯和37重量份的可自由基聚合树脂。
对比例3
此各向异性导电膜以对比例1所述相同的方法制备，只是BPA苯氧树脂为32重量份，环氧树脂为25重量份及使用25重量份的可自由基聚合树脂(80MFA,Kyoeisha Chemical Co.,Ltd.)。
对比例4
此各向异性导电膜以对比例2所述相同的方法制备，只是聚氨酯丙烯酸酯为25重量份，可自由基聚合树脂为25重量份并使用32重量份BPA苯氧树脂(PKHH,Union Carbide)。
对比例5
含有芴取代的苯氧树脂但不含有芴取代的丙烯酸酯的各向异性导电膜的制备
此各向异性导电膜以对比例4所述相同的方法制备，只是以芴取代的苯氧树脂代替BPA苯氧树脂。
实例1至3和对比例1至5制备的各向异性导电膜组合物的成分含量以重量份示于表1和2中。
表1
  成分   实例1   实例2   实例3
  BPA苯氧树脂   -   -   -
  芴取代的苯氧树脂   47   32   20
  可自由基聚合树脂   -   -   12
  聚氨酯丙烯酸酯   -   -   10
  芴取代的丙烯酸酯   35   25   10
  环氧树脂   -   25   20
  导电颗粒   5   5   5
  粘结助剂   3   3   3
  过氧化物引发剂   -   -   10
  胶囊型咪唑固化剂   10   10   -
  总计   100   100   100
表2
  成分   对比例1   对比例2   对比例3   对比例4   对比例5
  BPA苯氧树脂   37   -   32   32   -
  芴取代的苯氧树脂   -   -   -   -   32
  可自由基聚合树脂   -   37   25   25   25
  聚氨酯丙烯酸酯   -   45   -   25   25
  芴取代的丙烯酸酯   -   -   -   -   -
  环氧树脂   45   -   25   -   -
  导电颗粒   5   5   5   5   5
  粘结助剂   3   3   3   3   3
  过氧化物引发剂   -   10   -   10   10
  胶囊型咪唑固化剂   10   -   10   -   -
  总计   100   100   100   100   100
实验例1
苯氧树脂和丙烯酸酯间可混合性评价
实例1至3和对比例1至5制备的每种各向异性导电膜组合物在调糊机中搅拌，25℃下保持1小时，涂覆到其上具有脱模层的聚对苯二甲酸乙二醇酯(PET)膜上。用肉眼观察脱模层上形成的膜的均匀性。
当膜非常均匀时可混合性评价为“优”，膜一般均匀时为“良”，膜不均匀时为“差”。
实验例2
抗张强度测量
实例1至3和对比例1至5制备的每种各向异性导电膜都切割成尺寸为1.0mm（宽度）×10mm（长度）的样品。使用万能试验机(UTM)(H5K-T,Hounsfield)来测量样品的抗张强度。
实验例3
固化后储能模量测量
实例1至3和对比例1至5制备的每种各向异性导电膜的多个层叠加在一起直至总厚度达到100μm并在150℃的热风烘箱中保持2小时。之后，使用动态机械分析仪(DMA)(Q800,TA)测量40℃时层压制件的储能模量。
实验例4
初始粘着强度和可靠粘着强度测量
实例1至3和对比例1至5制备的每种各向异性导电膜通过在160℃和3MPa下按压5秒钟连接至具有200个或更多铜回路（线宽=100μm，间距=100μm，厚度=18μm）的挠性印刷电路(FPC)来制备样品。
样品的初始粘着强度通过剥离强度测试仪(H5KT,Tinius Olsen)以90°的剥离角度和50mm/min的剥离速度进行测量。
对于高温和高湿度可靠性评价，样品在85℃的温度下和85%的相对湿度下保持100小时。其后，样品的可靠粘着强度通过上述相同方法进行测量。
实验例5
初始连接电阻和可靠连接电阻测量
实例1至3和对比例1至5制备的每种各向异性导电膜通过在160℃和3MPa下按压5秒钟连接至具有200个或更多铜回路（线宽=100μm，间距=100μm，厚度=18μm）的挠性印刷电路(FPC)来制备样品。
样品的初始连接电阻通过4探头测量方法(ASTM F43-64T)进行测量。
对于高温和高湿度可靠性的评价，样品在85℃的温度下和85%的相对湿度下保持500小时。其后，样品的可靠连接电阻根据ASTM D117进行测量。
表3和4显示了实验例1至5的测量结果
表3
  物理性能   实例1   实例2   实例3
  可混合性   优   优   优
  抗张强度(gf/mm2)   150   140   150
  储能模量(MPa)   1200   1400   2000
  粘着强度(gf/cm)   720   760   820
  连接电阻(Ω)   0.8   0.9   0.8
  可靠粘着强度(gf/cm)   610   540   630
  可靠连接电阻(Ω)   1.1   1.2   0.9
表4
  物理性能   对比例1   对比例2   对比例3   对比例4   对比例5
  可混合性   良   良   差   差   良
  抗张强度(gf/mm2)   120   90   40   46   120
  储能模量(MPa)   1500   1200   800   600   800
  粘着强度(gf/cm)   520   580   无法评价   无法评价   640
  连接电阻(Ω)   1.2   1.5   无法评价   无法评价   1.2
  可靠粘着强度(gf/cm)   340   330   无法评价   无法评价   420
  可靠连接电阻(Ω)   4.4   5.8   无法评价   无法评价   2.0
根据上述测量结果，可以证实使用芴取代的苯氧树脂和芴取代的丙烯酸酯制备的各向异性导电膜显示出优秀的可混合性、高抗张强度和高储能模量。另外，实例1至3的膜在低温快速固化条件下可有效地连接，证明其在可靠粘着强度、可靠连接电阻以及初始粘着强度和初始连接电阻方面具有优秀的物理性能。 
对比例1、2和5的膜显示了良好的可混合性，但在低温快速固化条件下不能有效连接，显示了其较低的粘着强度。特别是，上述膜在可靠粘着强度和可靠连接电阻方面显示出较差的物理性能。通过这些结果，可以确定当这些膜连接至半导体膜时，很难在保持膜的可靠性的前提下长时间使用这些膜。
另一方面，对比例3和4的膜显示了较差的可混合性，在低温快速固化条件下实质上无法连接，显示了其非常低的粘着强度。因此，无法评价这些膜的粘着强度和连接电阻。
因此，芴取代的苯氧树脂和芴取代的丙烯酸酯在各向异性导电膜制备中的联合使用证明可以实现膜的低温快速固化性能和高可靠性。此外，适量添加环氧树脂和/或聚氨酯丙烯酸酯证明有助于实现各向异性导电膜优秀的物理性能。
根据上述内容显而易见，本发明的各向异性导电膜由于加入了芴取代的苯氧树脂 和芴取代的丙烯酸酯，在低温下可快速固化且高度可靠。
更确切地说，本发明的各向异性导电膜使用了阴离子可固化化合物的芴取代生成物和实质上同阴离子可固化化合物可混合的自由基可固化化合物的芴取代生成物，从而实现了芴取代生成物的可混合性。
此外，本发明的各向异性导电膜包含了芴取代的苯氧树脂和同芴取代的苯氧树脂可混合的芴取代的丙烯酸酯，显示了低温下的快速固化性能以及高储能模量，实现了高可靠性。
虽然提供了一些实例，但对于本领域技术人员来说显而易见的是，实例仅以解释说明性的方式给出，可以对其作出各种修改、变化、改动和等效的实例而不背离本发明的精神和范围。本发明的范围应该仅以附带的权利要求进行限定。

Claims (12)

1.一种各向异性导电膜，包含
a)苯氧树脂，所述苯氧树脂包括芴取代的苯氧树脂；和
b)可自由基聚合树脂，所述可自由基聚合树脂包括芴取代的丙烯酸酯，
其中所述可自由基聚合树脂进一步包括选自由具有磷酸酯结构的丙烯酸酯或甲基丙烯酸酯、异氰脲酸酯类丙烯酸酯、双酚A型环氧丙烯酸酯树脂和马来酰亚胺组成的组中的化合物；且
所述各向异性导电膜进一步包含环氧树脂和聚氨酯丙烯酸酯。
2.根据权利要求1的各向异性导电膜，其中，基于100重量份的所述各向异性导电膜的固体含量，所述各向异性导电膜包含
a)20至60重量份的所述苯氧树脂，所述苯氧树脂包括所述芴取代的苯氧树脂；和
b)40至80重量份的所述可自由基聚合树脂，所述可自由基聚合树脂包括所述芴取代的丙烯酸酯。
3.根据权利要求2的各向异性导电膜，其中基于100重量份的所述各向异性导电膜的固体含量，所述各向异性导电膜包含5至50重量份的芴取代的苯氧树脂和5至40重量份的芴取代的丙烯酸酯。
4.根据权利要求1至3中任一项的各向异性导电膜，进一步包含丙烯酸改性的环氧树脂。
5.根据权利要求1至3中任一项的各向异性导电膜，其中所述各向异性导电膜在160℃和3MPa下按压5秒后经测量具有700gf/cm或更高的粘着强度。
6.根据权利要求1至3中任一项的各向异性导电膜，其中所述各向异性导电膜具有60gf/mm2至200gf/mm2的抗张强度。
7.一种含有苯氧树脂和可自由基聚合树脂的各向异性导电膜，其中所述膜具有
a)在160℃和3MPa下按压5秒后经测量具有700gf/cm或更高的粘着强度，和
b)在固化度为90％或更高的情况下1,000MPa或更高的储能模量，
其中所述苯氧树脂包括芴取代的苯氧树脂，且所述可自由基聚合树脂包括芴取代的丙烯酸酯，
其中所述可自由基聚合树脂进一步包括选自由具有磷酸酯结构的丙烯酸酯或甲基丙烯酸酯、异氰脲酸酯类丙烯酸酯、双酚A型环氧丙烯酸酯树脂和马来酰亚胺组成的组中的化合物；且
所述各向异性导电膜进一步包含环氧树脂和聚氨酯丙烯酸酯。
8.根据权利要求7的各向异性导电膜，其中基于100重量份的所述各向异性导电膜的固体含量，所述各向异性导电膜包含5至50重量份的所述芴取代的苯氧树脂。
9.根据权利要求7的各向异性导电膜，其中基于100重量份的所述各向异性导电膜的固体含量，所述各向异性导电膜包含5至40重量份的芴取代的丙烯酸酯。
10.根据权利要求7至9中任一项的各向异性导电膜，进一步包含丙烯酸改性的环氧树脂。
11.根据权利要求7至9中任一项的各向异性导电膜，其中所述各向异性导电膜具有60gf/mm2至200gf/mm2的抗张强度。
12.一种半导体器件，包含
a)布线基板；
b)附着在所述布线基板表面上的各向异性导电膜；和
c)安装在所述膜上的半导体芯片；
其中所述各向异性导电膜是根据权利要求1至11中任一项所述的膜。
CN201210567731.5A 2011-12-23 2012-12-24 各向异性导电膜和半导体器件 Expired - Fee Related CN103173143B (zh)

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