CN103871544A - 各向异性导电膜、用于该膜的组合物和半导体装置 - Google Patents

各向异性导电膜、用于该膜的组合物和半导体装置 Download PDF

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CN103871544A
CN103871544A CN201310675107.1A CN201310675107A CN103871544A CN 103871544 A CN103871544 A CN 103871544A CN 201310675107 A CN201310675107 A CN 201310675107A CN 103871544 A CN103871544 A CN 103871544A
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conductive film
anisotropic conductive
composition
solid content
free radical
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CN103871544B (zh
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申炅勋
金奎峰
徐贤柱
申颍株
林佑俊
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Guo Dujianduansucai
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Cheil Industries Inc
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Abstract

本发明提供了各向异性导电膜、用于各向异性导电膜的组合物和半导体装置，所述各向异性导电膜具有1）100MPa至300MPa的所述膜固化后40℃下的储能模量，和2）80℃至90℃的所述膜的DSC（差示扫描量热仪）曲线中的峰值点。

Description

各向异性导电膜、用于该膜的组合物和半导体装置
技术领域
本发明涉及用于各向异性导电膜的组合物和使用该组合物制备的各向异性导电膜。
背景技术
各向异性导电膜为在制造例如液晶显示器、个人电脑和移动通信设备等电子产品中用于将例如半导体装置的小电器元件电连接到基板或用于将基板彼此电连接的材料。
随着近来向大面板和精细互连线发展的趋势，连接基板变薄，并且电路连接部分与芯片、多层陶瓷芯片（MLCC）或通孔等之间的距离减小，引起严重的温度偏差。此外，印刷电路板（PCB）的每个图案的热耗散也引起温度偏差。
常规的各向异性导电膜通过顾及温度偏差而具有改善的高温特性以确保可加工性。然而，在这种情况下，由于PCB的收缩/膨胀很有可能遭遇接合故障或偏差，并且由于在高温使用接合设备会存在关于设备操作的问题。例如，韩国专利第0727741号公开了可快速固化的各向异性导电粘合剂在改善流动性和可靠性的同时能够使粘合强度随时间的降低率和连接电阻随时间的增长率最小化。然而，这种各向异性导电粘合剂在180℃或更高的高温下用作接合的粘合剂，因此会遭遇接合故障或关于设备操作的问题。
此外，即使在接合设备的有效温度尽量提高的情况下，该接合设备有时也不能达到根据PCB的类型的期望的接合温度。
为了解决由于在高温接合引起的诸如接合故障和偏差的问题，需要能够在低温（例如，在约130℃的接合温度）接合的各向异性导电膜。
发明内容
本发明的一个方面提供了各向异性导电膜和组合物，所述各向异性导电膜和组合物能够在低温接合以解决由于在高温接合引起的接合故障、偏差和关于设备操作的问题。
本发明的一个方面提供了各向异性导电膜，所述各向异性导电膜具有1）100MPa至300MPa的所述膜固化后40℃下的储能模量，和2）80℃至90℃的所述膜的DSC（差示扫描量热仪）曲线中的峰值点。
本发明的另一个方面提供了用于各向异性导电膜的组合物，所述组合物包含（A）热塑性树脂；（B）第一自由基可聚合材料；（C）第二自由基可聚合材料；（D）二氧化硅；（E）有机过氧化物；和（F）导电颗粒，其中，所述（B）第一自由基可聚合材料以固含量计的重量和所述（C）第二自由基可聚合材料以固含量计的重量之和（B+C）与所述（A）热塑性树脂以固含量计的重量和所述（D）二氧化硅以固含量计的重量之和（A+D）的比例（B+C）/（A+D）在0.20至0.45的范围内。
本发明的又一个方面提供了半导体装置，所述半导体装置包括：具有第一电极的第一连接元件；具有第二电极的第二连接元件；和前述各向异性导电膜或由前述组合物制备的各向异性导电膜，所述各向异性导电膜放置在所述第一连接元件和所述第二连接元件之间并将所述第一电极连接至所述第二电极。
根据本发明的实施方式的各向异性导电膜或组合物放置在第一连接元件和第二连接元件之间并经主压缩时，在120℃至200℃接合温度的宽范围内的接合条件下呈现优异的粘合力和连接可靠性。
此外，根据本发明的实施方式的各向异性导电膜或组合物即使在可靠性检测后也具有低的粘合强度降低率和低的连接电阻增长率。
附图说明
图1为描述根据本发明的一个实施方式的膜的储能模量根据温度变化的图。
图2显示了根据本发明的一个实施方式的膜的DSC曲线。
图3为根据本发明的一个实施方式的半导体装置的截面图，该半导体装置包括通过根据一个实施方式的各向异性导电粘合剂膜彼此连接并分别包含第一电极70和第二电极80的第一连接元件50和第二连接元件60。这里，当各向异性导电粘合剂膜在具有第一电极70的第一连接元件50与具有第二电极80的第二连接元件60之间压缩时，第一电极70和第二电极80通过各向异性导电粘合剂膜中的导电颗粒40彼此电连接。
具体实施方式
本发明的一个实施方式提供了各向异性导电膜，该各向异性导电膜具有1）100MPa至300MPa的该膜固化后40℃下的储能模量，和2）80℃中90℃的该膜的DSC（差示扫描量热仪）曲线中的峰值点。
储能模量可在固化各向异性导电膜后在40℃下测量，并且固化可通过如下方法实现，例如在热压机上放置各向异性导电膜并在30MPa的负荷下在190℃加热该膜15分钟。储能模量可使用本领域中已知的任何设备（例如DMA（动态机械分析仪）（TAInstruments））测量。
普通的各向异性导电膜具有400MPa至2000MPa的固化后40℃下的储能模量。然而，如果各向异性导电膜的储能模量超过300MPa，各向异性导电膜在固化后就会呈现强的粘性，从而在互连基板和芯片之间的界面引起粘合性劣化。此外，由于粘结剂系统显著地影响储能模量的增加，所以具有高储能模量的各向异性导电膜会因粘结剂系统的高硬度和高玻璃化转变温度而不能在低温工艺中呈现足够的流动性。如果该膜具有小于100MPa的储能模量，则会在固化后的长期耐久性方面存在问题。因此，当各向异性导电膜具有100MPa至300MPa的膜固化后40℃下的储能模量时，能够各向异性导电膜与互连的基板或芯片之间确保良好的初始粘合性和连接可靠性，并在低温工艺中确保流动性。通过基本上在具有±2℃误差范围的40℃，即在40℃±2℃的温度范围内，优选在40℃±1℃的温度范围内，测量该膜的储能模量，而获得40℃下的储能模量。因此，例如，具有100MPa至300MPa的38℃下的储能模量的各向异性导电膜也在本发明的保护范围内。
此外，根据实施方式的各向异性导电膜具有80℃至90℃的该膜的DSC（差示扫描量热仪）曲线中的峰值点。如本文所用，术语“DSC曲线中的峰值点”是指各向异性导电膜在DSC曲线中具有最大热通量时的温度。如果该膜在DSC曲线中具有小于80℃的峰值点，则该膜使低温下的接合可行，但是由于根据上述工艺的预固化而很有可能遭遇接合故障。如果该膜在DSC曲线中具有大于90℃的峰值点，则该膜不能实现充分的固化以在低温固化时呈现其特性。
在本发明中，各向异性导电膜具有120℃至200℃的主压缩温度，优选130℃至190℃。根据本发明的各向异性导电膜使得在如此宽的温度范围内的主压缩成为可能，从而实现低温下或高温下的快速固化。主压缩可在120℃至200℃的温度在2.0MPa至6.0MPa的负荷下进行3秒至7秒，优选在3.0MPa至5.0MPa的负荷下进行3秒至6秒。
本发明的各向异性导电膜可有利地用于将软膜覆晶（COF）或集成电路（IC）等接合到印刷电路板（PCB）或柔性印刷电路板（FPCB），但不限于此。
根据本发明，各向异性导电膜可包含：（A）热塑性树脂；（B）第一自由基可聚合材料；（C）第二自由基可聚合材料；和（D）二氧化硅，其中，（B）第一自由基可聚合材料以固含量计的重量和（C）第二自由基可聚合材料以固含量计的重量之和（B+C）与（A）热塑性树脂以固含量计的重量和（D）二氧化硅以固含量计的重量之和（A+D）的比例（B+C）/（A+D）在0.20至0.45的范围内。热塑性树脂可包括选自由丙烯腈丁二烯共聚物、丙烯酸酯改性的氨基甲酸乙酯树脂和丙烯酰类（acryl）共聚物组成的组中的至少一种。当比例（B+C）/（A+D）在0.20至0.45的范围内时，各向异性导电膜可确保低温工艺中足够的流动性和固化后的长期可靠性。各向异性导电膜可进一步包含有机过氧化物和导电颗粒。各向异性导电膜可进一步包含二氧化钛。
本发明的另一个实施方式提供了用于各向异性导电膜的组合物，该组合物包含（A）热塑性树脂；（B）第一自由基可聚合材料；（C）第二自由基可聚合材料；（D）二氧化硅；（E）有机过氧化物；和（F）导电颗粒，其中，（B）第一自由基可聚合材料以固含量计的重量和（C）第二自由基可聚合材料以固含量计的重量之和（B+C）与（A）热塑性树脂以固含量计的重量和（D）二氧化硅以固含量计的重量之和（A+D）的比例（B+C）/（A+D）在0.20至0.45的范围内。
当比例（B+C）/（A+D）在0.20至0.45的范围内时，上述组合物可确保低温工艺中足够的流动性和固化后的长期可靠性。
热塑性树脂可包括选自由丙烯腈丁二烯共聚物、丙烯酸酯改性的氨基甲酸乙酯树脂和丙烯酰类共聚物组成的组中的至少一种。
上述组合物可包含8wt%至20wt%以固含量计的丙烯酰类共聚物。上述组合物可包含3wt%至8wt%以固含量计的二氧化硅。
上述组合物可进一步包含二氧化钛。
本发明的再一个实施方式提供了半导体装置，该装置包括：具有第一电极的第一连接元件；具有第二电极的第二连接元件；和在第一连接元件和第二连接元件之间放置并将第一电极电连接至第二电极的根据本发明的各向异性导电粘合剂膜。
参见图3，根据本发明的一个实施方式的半导体装置包括具有第一电极70的第一连接元件50；具有第二电极80的第二连接元件60；和包含导电颗粒40的各向异性导电膜10。当放置在具有第一电极70的第一连接元件50和具有第二电极80的第二连接元件60之间的各向异性导电膜10压缩时，第一电极70和第二电极80通过导电颗粒40彼此连接。在一个实施方式中，第一连接元件和第二连接元件在材料、厚度、大小和互连性方面可具有相似的结构。第一连接元件和第二连接元件可具有约20μm至约100μm的厚度。在另一个实施方式中，第一连接元件和第二连接元件在材料、厚度、大小和互连性方面可具有不同的结构和功能。第一连接元件或第二连接元件可由玻璃、PCB（印刷电路板）、fPCB、COF、TCP和ITO玻璃等形成，但不限于此。第一电极或第二电极可为凸出电极或平面电极。当第一电极和第二电极为凸出电极时，这些电极可具有约2.50μm至约10μm的高度(H)、约50μm至约120μm的宽度(W)和约50μm至约110μm的电极间的间隙(G)。优选地，上述电极具有2.50μm至约9μm的高度(H)、约50μm至约100μm的宽度(W)和约60μm至约90μm的间隙(G)。
当第一电极和第二电极为平面电极时，这些电极可具有约
Figure BDA0000435048180000051
至约
Figure BDA0000435048180000052
的厚度。
第一电极或第二电极可由ITO、铜、硅和IZO等形成，但不限于此。
优选地，平面电极具有至
Figure BDA0000435048180000054
的厚度，凸出电极具有6μm至10μm的高度。在这种情况下，当绝缘层具有4μm至12μm的厚度时，粘合剂膜可呈现足够的粘合性。更优选地，平面电极具有
Figure BDA0000435048180000055
的厚度，凸出电极具有8μm的高度。在这种情况下，绝缘层具有6μm至10μm的厚度。
本发明的另一个实施方式提供了用于制造半导体装置的方法，该方法包括：在具有第一电极的第一连接元件上放置各向异性导电膜，然后进行预压缩；并在预压缩的各向异性导电膜上放置具有第二电极的第二连接元件，然后进行主压缩，其中，各向异性导电膜具有1）100MPa至300MPa的膜固化后40℃下的储能模量，和2）80℃至90℃的膜的DSC（差示扫描量热仪）曲线中的峰值点。预压缩可在30℃至70℃的温度在1.0MPa至5.0MPa的负荷下进行1秒至5秒，主压缩可在120℃至200℃的温度在2.0MPa至6.0MPa的负荷下进行3秒至7秒。
接下来，将更详细地说明根据本发明的各向异性导电粘合剂组合物的各个组分。
（A）热塑性树脂
热塑性树脂为起到用于形成各向异性导电粘合剂膜基质作用的粘结剂系统，并可包括选自普通热塑性树脂中的至少一种。例如，热塑性树脂可包括选自聚氨基甲酸乙酯树脂、丙烯腈树脂、丙烯酰类树脂、丁二烯树脂、聚酰胺树脂、烯烃树脂和硅氧烷树脂中的至少一种。优选地，热塑性树脂选自聚氨基甲酸乙酯树脂、丙烯酸树脂和丁二烯树脂中。更优选地，热塑性树脂选自丙烯酸酯改性的氨基甲酸乙酯树脂、丙烯腈丁二烯共聚物和丙烯酰类共聚物中的至少一种。
具体地，根据本发明的各向异性导电粘合剂组合物在流动性和粘合性方面可包含丙烯酸酯改性的氨基甲酸乙酯树脂作为热塑性树脂组分。这里，丙烯酸酯改性的氨基甲酸乙酯树脂在各向异性导电粘合剂组合物中以固含量计的含量可为20wt%至60wt%。优选地，丙烯酸酯改性的氨基甲酸乙酯树脂在各向异性导电粘合剂组合物中以固含量计的含量可为25wt%至55wt%。
作为粘结剂系统，丙烯酸酯改性的氨基甲酸乙酯树脂具有低的玻璃化转变温度，从而改善了流动性并使分子链中的氨基甲酸乙酯基团呈现高的粘合性。具体地，当用于各向异性导电膜时，丙烯酸酯改性的氨基甲酸乙酯树脂可通过改善固化性能而降低连接工艺的温度。
丙烯酸酯改性的氨基甲酸乙酯树脂的实例可包括二异氰酸酯、多元醇、二元醇和丙烯酸酯，但不限于此。
二异氰酸酯可包括芳族的、脂族的和脂环族的二异氰酸酯和它们的组合。具体地，二异氰酸酯可为选自由四亚甲基-1,4-二异氰酸酯、六亚甲基-1,6-二异氰酸酯、亚环己基-1,4-二异氰酸酯、亚甲基双(4-环己基异氰酸酯)、异佛尔酮二异氰酸酯、4,4-亚甲基双(环己基二异氰酸酯)和它们的混合物组成的组中的至少一种。
多元醇可包括在分子链中具有两个或更多个羟基的聚酯多元醇、聚醚多元醇和聚碳酸酯多元醇等。聚酯多元醇可通过二羧酸化合物和二元醇化合物的缩合得到。这里，二羧酸化合物的实例可包括丁二酸、戊二酸、间苯二甲酸、己二酸、辛二酸、壬二酸、癸二酸、十二烷二羧酸、六氢邻苯二甲酸、间苯二甲酸、对苯二甲酸、邻苯二甲酸、四氯邻苯二甲酸、1,5-萘二羧酸、富马酸、马来酸、衣康酸、柠康酸、中康酸和四氢邻苯二甲酸等。二元醇化合物的实例可包括乙二醇、丙二醇、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、新戊二醇、二乙二醇、二丙二醇、三乙二醇、四乙二醇、二丁二醇、2-甲基-1,3-戊二醇、2,2,4-三甲基-1,3-戊二醇和1,4-环己烷二甲醇等。聚醚多元醇的实例可包括聚乙二醇、聚丙二醇和聚四乙二醇等。聚醚多元醇可具有400g/mol至10,000g/mol范围内的重均分子量，优选400g/mol至3,000g/mol的重均分子量。聚碳酸酯多元醇可包括聚碳酸亚烷基酯和硅氧烷衍生的聚碳酸酯多元醇等。
二元醇的实例包括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、新戊二醇、二乙二醇、二丙二醇、三乙二醇、四乙二醇、二丁二醇、2-甲基-1,3-戊二醇、2,2,4-三甲基-1,3-戊二醇和1,4-环己烷二甲醇等。
丙烯酸酯可包括丙烯酸羟基酯或丙烯酸胺基酯。
通过上述四种组分的加成聚合反应，以使二异氰酸酯的基团（NCO）与羟基（OH）的摩尔比（NCO/OH）在1.04至1.6的范围内并且多元醇基于排除丙烯酸酯的三种组分的总量的含量为70wt%或更小，然后通过丙烯酸羟基酯或丙烯酸胺基酯与所制备的氨基甲酸乙酯的任一个末端二异氰酸酯以0.1至2.1的摩尔比反应，可制备丙烯酸酯改性的氨基甲酸乙酯树脂。此外，剩余的异氰酸酯基可与乙醇反应以产生最终的丙烯酸酯改性的氨基甲酸乙酯树脂。这里，加成聚合反应可通过本领域已知的任何普通的加成聚合方法进行。这里，加成聚合反应可使用锡类催化剂在90℃的反应温度和1atm的反应压力下进行5小时，但不限于此。
丙烯酸酯改性的氨基甲酸乙酯树脂呈现两个玻璃化转变温度（Tg），至少一个玻璃化转变温度可为0℃或更高。
也就是说，丙烯酸酯改性的氨基甲酸乙酯起到粘结剂系统的作用，该系统通过相混合作为软链段的多元醇和作为硬链段的二异氰酸酯而获得，并具有0℃或更高的单个玻璃转化温度，或至少一个为0℃或更高的两个玻璃转化温度，以使膜在室温形成。此外，丙烯酸酯改性的氨基甲酸乙酯树脂通过末端丙烯酸酯基团使得与固化系统中的丙烯酰基进行固化反应成为可能而起到固化系统的作用，从而提供优异的粘合强度和高的连接可靠性。
丙烯酸酯改性的氨基甲酸乙酯树脂可具有1,000g/mol至100,000g/mol的重均分子量，优选10,000g/mol至50,000g/mol。
在一些实施方式中，丙烯酸共聚物可用作热塑性树脂。
在一些实施方式中，通过聚合丙烯酰类单体，例如丙烯酸乙酯、丙烯酸甲酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸己酯、氧基（oxyl）丙烯酸酯、丙烯酸十二烷基酯、丙烯酸月桂酯、甲基丙烯酸酯、它们的改性的丙烯酸酯；丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、醋酸乙烯酯和它们的改性的丙烯酸单体等，可制备丙烯酸共聚物，但不限于此。丙烯酸共聚物可具有50℃至120℃的玻璃化转变温度（Tg）。在该玻璃化转变温度的范围内，上述组合物具有优异的连接可靠性并使膜有效地形成。
此外，丙烯酸共聚物实质上包含羟基或羧基，以具有1mg KOH/g至100mg KOH/g的酸值，并且可选地进一步包含环氧基或烷基。在这个范围内，上述粘合剂组合物在确保优异的连接可靠性的同时可呈现充足的粘合性。
具体而言，丙烯酸共聚物可具有90℃的玻璃化转变温度和3.4mgKOH/g的酸值，以实现强的膜特性，并可仅起到粘结剂的作用。由于氨基甲酸乙酯粘结剂具有较低的玻璃化转变温度，所以随着丙烯酸共聚物的玻璃化转变温度的提高，用作粘结剂的丙烯酸共聚物在连接可靠性方面具有更多的优点。然而，具有过高的玻璃化转变温度的丙烯酸共聚物是易损坏的，从而使其难以实现有效的膜形成。
丙烯酸共聚物在上述组合物中的含量可为8wt%至20wt%，优选10wt%至18wt%。
在一些实施方式中，丙烯腈丁二烯共聚物可用作热塑性树脂。
丙烯腈丁二烯共聚物的实例可包括(甲基)丙烯酸酯-丁二烯共聚物、(甲基)丙烯酸酯-丙烯腈-丁二烯-苯乙烯共聚物和羧基改性的丙烯腈-丁二烯共聚物等，但不限于此。这些物质可单独使用，或作为它们的混合物使用。优选地，热塑性树脂为能够改善树脂混合物的稳定性、通过极性提高的粘合性、耐湿性和耐热性等的羧基改性的丙烯腈-丁二烯橡胶。
在一个实施方式中，热塑性树脂为具有2,000g/mol至200,000g/mol重均分子量的羧基改性的丙烯腈-丁二烯橡胶，优选具有3,000g/mol至200,000g/mol重均分子量的羧基改性的丙烯腈-丁二烯橡胶。在这种情况下，丙烯腈-丁二烯橡胶含有10wt%至60wt%（优选20wt%至50wt%）的丙烯腈和1wt%至20wt%的羧基。
丙烯腈-丁二烯共聚物在上述组合物中的含量可为1wt%至10wt%，优选2wt%至8wt%。在这个范围内，上述组合物未经受相分离，并确保了良好的连接可靠性。
在用于各向异性导电膜的组合物中，基于用于上述膜的组合物的以固含量计的总重，热塑性树脂的含量可为50wt%至80wt%，优选55wt%至77wt%。
（B）自由基可聚合材料1
自由基可聚合材料1为固化系统的组分，并通过自由基固化反应用来确保彼此接合的各层之间的粘合性和连接可靠性。
自由基可聚合材料1含有至少一个乙烯基并包含可以单体形式、低聚物形式或它们的组合使用的丙烯酸酯、甲基丙烯酸酯和马来酰亚胺化合物。丙烯酸酯（甲基丙烯酸酯）的实例可包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸异丙酯、丙烯酸4-羟丁酯、丙烯酸异丁酯、二丙烯酸乙二醇酯、二丙烯酸二乙二醇酯、三丙烯酸酯三羟甲基丙烷、四丙烯酸四羟甲基甲烷酯、2-羟基-1,3-二丙烯酰氧基丙烷、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、丙烯酸二环戊烯酯、丙烯酸三环癸酯和三(丙烯酰氧基乙基)异氰酸酯等，但不限于此。这些物质可单独使用或以它们的组合使用。
在上述组合物中，基于用于上述膜的组合物的以固含量计的总重，自由基可聚合材料1的含量为约2wt%至约15wt%，优选约4wt%至约12wt%。
（C）自由基可聚合材料2
自由基可聚合材料2也为固化系统的组分，并通过与自由基可聚合材料1一起的自由基固化反应用来确保彼此结合的各层之间的粘合性和连接可靠性。
自由基可聚合材料2在分子中含有至少一个乙烯基，并包含可以单体形式、低聚物形式或它们的组合使用的丙烯酸酯、甲基丙烯酸酯和马来酰亚胺化合物。自由基可聚合材料2与自由基可聚合材料1不同。自由基可聚合材料2的实例可包括单(甲基)丙烯酸-1,6-己二醇酯、(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、(甲基)丙烯酸-2-羟丁酯、(甲基)丙烯酸-2-羟基-3-苯基丙氧酯、(甲基)丙烯酸-1,4-丁二醇酯、2-羟基烷基(甲基)丙烯酰磷酸酯、(甲基)丙烯酸-4-羟基环己酯、单(甲基)丙烯酸新戊二醇酯、二(甲基)丙烯酸三羟甲基乙烷酯、二(甲基)丙烯酸三羟甲基丙烷酯、三(甲基)丙烯酸季戊四醇酯、五(甲基)丙烯酸二季戊四醇酯、六(甲基)丙烯酸季戊四醇酯、六(甲基)丙烯酸二季戊四醇酯、二(甲基)丙烯酸甘油酯、(甲基)丙烯酸叔氢糠酯（t-hydrofurfuryl(meth)acrylate）、(甲基)丙烯酸异癸酯、(甲基)丙烯酸-2-(2-乙氧基乙氧基)乙酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸-2-苯氧基乙酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸十三烷基酯、乙氧基化的(甲基)丙烯酸壬基苯酚酯、二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸二乙二醇酯、二(甲基)丙烯酸三乙二醇酯、二(甲基)丙烯酸四乙二醇酯、聚二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸-1,3-丁二醇酯、二(甲基)丙烯酸三丙二醇酯、乙氧基化的双酚A二(甲基)丙烯酸酯、二(甲基)丙烯酸环己烷二甲醇酯、(甲基)丙烯酸苯氧基-叔-二醇酯（phenoxy-t-glycol(meth)acrylate）、磷酸-2-甲基丙烯酰氧基乙酯、二(甲基)丙烯酸二羟甲基三环癸烷酯、三羟甲基丙烷苯甲酸丙烯酸酯、(甲基)丙烯酸芴酯和酸性磷氧乙基(甲基)丙烯酸酯（acid phosphoxyethyl(meth)acrylate）等，但不限于此。
在上述组合物中，基于用于上述膜的组合物的以固含量计的总重，自由基可聚合材料2的含量可为约2wt%至约15wt%，优选约4wt%至约12wt%。在自由基可聚合材料2的这个含量范围内，上述组合物在可靠性和总体流动性方面呈现优异的性质，并可防止主压缩后连接可靠性的增加。
（D）二氧化硅
在上述组合物中，基于用于上述膜的组合物的以固含量计的总重，二氧化硅的含量可为3wt%至8wt%。在二氧化硅的这个含量范围内，通过将储能模量提高到预定水平或更高水平，组合物可允许有效地调节树脂挤出速率并改善可靠性。此外，各向异性导电粘合剂膜具有良好的初始压痕性质（initial indentation properties），因而可呈现电特性。此外，当二氧化硅具有1nm至30nm范围内的粒径时，二氧化硅向膜提供触变特性，并在预压缩和主压缩时可控制流动性。优选地，组合物含有气相二氧化硅。
（E）有机过氧化物
有机过氧化物起固化剂的作用，当加热或暴露于光时产生自由基。
鉴于高的连接温度、时间和保存的稳定性，有机过氧化物可选自酮过氧化物、过氧化缩酮、氢过氧化物、二烷基过氧化物、二酰基过氧化物、过氧化酯、过氧化碳酸酯或它们的组合中，但不限于此。
这样的有机过氧化物的实例包括叔丁基过氧化月桂酸酯、1,1,3,3-叔甲基丁基过氧化-2-乙基己酸酯、2,5-二甲基-2,5-二(2-乙基己酰基过氧化)己烷、1-环己基-1-甲基乙基过氧化-2-乙基己酸酯、2,5-二甲基-2,5-二(间甲苯酰基过氧化)己烷、叔丁基过氧化异丙基单碳酸酯、叔丁基过氧化-2-乙基己基单碳酸酯、叔己基过氧化苯甲酸酯、叔丁基过氧化醋酸酯、二枯基的过氧化物、2,5-二甲基-2,5-二（叔丁基过氧化）己烷、叔丁基枯基过氧化物、叔己基过氧化新癸酸酯、叔己基过氧化2-乙基己酸酯、叔丁基过氧化2-2-乙基己酸酯、叔丁基过氧化异丁酸酯、1,1-双(叔丁基过氧化)环己烷、叔己基过氧化异丙基单碳酸酯、叔丁基过氧化-3,5,5-三甲基己酸酯、叔丁基过氧化新戊酸酯、枯基过氧化新癸酸酯、二异丙基苯氢过氧化物、枯烯氢过氧化物、异丁基过氧化物、2,4-二氯苯甲酰过氧化物、3,5,5-三甲基己酰过氧化物、辛酰过氧化物、月桂酰过氧化物、硬脂酰过氧化物、琥珀酰过氧化物、过氧化苯甲酰、3,5,5-三甲基己酰过氧化物、苯甲酰过氧化甲苯、1,1,3,3-四甲基丁基过氧新癸酸酯、1-环己基-1-甲基乙基过氧化新癸酸酯、二正丙基过氧化二碳酸酯、二异丙基过氧化碳酸酯、双(4-叔丁基环己基)过氧化二碳酸酯、二-2-乙氧基甲氧基过氧化二碳酸酯、二(2-乙基己基过氧化)二碳酸酯、二甲氧基丁基过氧化二碳酸酯、二(3-甲基-3-甲氧基丁基过氧化)二碳酸酯、1,1-双(叔己基过氧化)-3,3,5-三甲基环己烷、1,1-双(叔己基过氧化)环己烷、1,1-双(叔丁基过氧化)-3,3,5-三甲基环己烷、1,1-(叔丁基过氧化)环十二烷、2,2-双(叔丁基过氧化)癸烷、叔丁基三甲基甲硅烷基过氧化物、双(叔丁基)二甲基甲硅烷基过氧化物、叔丁基三烯丙基甲硅烷基过氧化物、双(叔丁基)二烯丙基甲硅烷基过氧化物和三(叔丁基)芳基甲硅烷基过氧化物等，但不限于此。
有机过氧化物在40℃至100℃优选具有5至15的半衰期。在有机过氧化物的半衰期的这个范围内，上述组合物在室温存储过程中不会遭遇任何问题，并适于快速固化。
在上述组合物中，有机过氧化物的含量为1wt%至8wt%，优选1.5wt%至5wt%。在有机过氧化物的这个含量范围内，组合物呈现优异的压缩特性和可再加工性，并且不会遭遇气泡的产生。
（F）导电颗粒
各向异性导电粘合剂组合物包含导电颗粒，以在电路连接时改善导电性。
导电颗粒可为选自包括Au、Ag、Ni、Cu、Pd、Al、Cr、Sn、Ti和Pb的至少一种的金属颗粒；碳颗粒；包括苯代三聚氰胺、聚乙烯、聚酯、聚苯乙烯和聚乙烯醇的至少一种的树脂或用金属颗粒镀或涂布的上述改性树脂的颗粒；和通过在金属涂布的聚合物树脂颗粒上进一步涂布绝缘颗粒而获得的绝缘的导电颗粒中的至少一种。
导电颗粒的尺寸可根据待应用的电路的间距确定，并且根据预期的应用在0.1μm至30μm的范围内。优选地，导电颗粒具有0.5μm至15μm的颗粒尺寸。
导电颗粒的含量可为1wt%至10wt%。在这个范围内，导电颗粒可在保持绝缘性质的同时保留固有的导电性。导电颗粒的含量优选为2wt%至8wt%，更优选为3wt%至6wt%。
根据本发明的各向异性导电粘合剂组合物可进一步包含添加剂，例如阻聚剂、抗氧化剂和热稳定剂等，以提供另外的性质而不劣化基本的性质。添加剂在上述组合物中以固含量计的含量可为0.01wt%至10wt%，但不限于此。
阻聚剂可选自由氢醌、氢醌单甲醚、对-苯醌、吩噻嗪和它们的混合物组成的组。抗氧化剂可为酚类或羟基肉桂酸酯物质。例如，抗氧化剂可为四-(亚甲基-(3,5-二-叔丁基-4-羟基肉桂酸酯)甲烷和3,5-双(1,1-二甲基乙基)-4-羟基-苯丙酸硫醇二-2,1-乙二基酯等。
本发明提供了使用本发明的各向异性导电粘合剂组合物制备的各向异性导电粘合剂膜。不需要特定的仪器和设备形成各向异性导电膜。例如，通过在例如甲苯的有机溶剂中溶解各向异性导电粘合剂组合物，在不引起导电颗粒粉碎的速度下搅拌混合物一定时段，将混合物涂布到离型膜上至合适的厚度（例如10μm至50μm），并将混合物干燥足够的时间以蒸发甲苯，可获得各向异性导电膜。
接下来，将参照一些实施例更详细地阐述本发明。应理解提供这些实施例仅用于说明，而非以任何方式解释为限制本发明。
为了清楚起见，将省略对本领域普通技术人员来说明显的细节说明。
实施例
实施例1至3：各向异性导电组合物和各向异性导电膜的制备
以表1中列出的量共混丙烯腈丁二烯共聚物、丙烯酸酯改性的氨基甲酸乙酯树脂1和2、丙烯酰类共聚物、自由基可聚合材料1和2、有机过氧化物、二氧化钛、二氧化硅和导电颗粒，然后在防止导电颗粒被粉碎的同时用行星式混合器在25℃搅拌60分钟。将所得混合物涂布在经硅氧烷离型表面处理的聚乙烯基膜上以形成35μm厚的膜。使用铸刀形成膜，然后在60℃干燥5分钟，从而制备实施例1至3的每个各向异性导电膜。
对比例1至4：各向异性导电组合物和各向异性导电膜的制备
除了表1中显示的组分的量之外，以与实施例相同的方式制备各向异性导电膜。
在这些实施例和对比例中，各个组分按表1中显示的量加入。
表1
E1 E2 E3 CE1 CE2 CE3 CE4
1）丙烯腈丁二烯共聚物 5 5 5 5 10 20 5
2）丙烯酸酯改性的氨基甲酸乙酯树脂1 30 25 25 40 20 30 30
3）丙烯酸酯改性的氨基甲酸乙酯树脂2 18 28 25 11 13 16 30
4）丙烯酰类共聚物 10 15 15 5 30 10 10
5）自由基可聚合材料1 10 7 7 15 3 5 3
6）自由基可聚合材料2 15 10 10 15 7 10 10
7）有机过氧化物 5 3 4 5 3 3 5
8）二氧化钛 1 1 1 1 1 1 1
9）二氧化硅 3 3 5 10 2 3
10）导电颗粒 3 3 3 3 3 3 3
总计 100 100 100 100 100 100 100
40℃下的储能模量（MPa） 100 200 300 50 500 200 200
DSC曲线中的峰值点（℃） 83 88 85 82 85 93 75
（B+C）/（A+D） 0.38 0.22 0.23 0.49 0.12 0.19 0.17
A=1）+2）+3）+4），D=9），B=5），C=6）
1）丙烯腈丁二烯共聚物：溶解于甲苯/甲乙酮中至25vol%（体积百分比）的丙烯腈丁二烯共聚物（1072CGX，Zeon Chemical有限公司）
2）丙烯酸酯改性的氨基甲酸乙酯树脂1：使用二丁基锡二月桂酯作为催化剂在60wt%的多元醇和溶解于甲乙酮中至50vol%的摩尔比为0.5的甲基丙烯酸羟基酯/异氰酸酯的条件下通过在90℃和1atm加成聚合5小时，而制备的聚氨基甲酸乙酯丙烯酸酯（重均分子量：25,000g/mol）
3）丙烯酸酯改性的氨基甲酸乙酯树脂2：使用二丁基锡二月桂酯作为催化剂在60wt%的多元醇和溶解于甲乙酮中至50vol%的摩尔比为1的丙烯酸羟基酯/异氰酸酯的条件下通过在90℃和1atm加成聚合5小时，而制备的聚氨基甲酸乙酯丙烯酸酯树脂（重均分子量28,000g/mol）
4）丙烯酰类共聚物：溶解于甲苯/甲乙酮中至45vol%并具有90,000～120,000的重均分子量的丙烯酸树脂（AOF7003，Aekyung Chemical有限公司）
5）自由基可聚合材料1：丙烯酸4-羟丁酯
6）自由基可聚合材料2：丙烯酸四氢糠酯
7）有机过氧化物：过氧化月桂酰
8）二氧化钛：TiO2
9）导电颗粒：具有5μm颗粒尺寸的导电颗粒
10）二氧化硅：气相二氧化硅
实验例：测量40℃下的储能模量、初始粘合强度、初始连接电阻和可靠性测试后的连接电阻
实施例和对比例中制备的各向异性导电膜的40℃下的储能模量、初始粘合强度、初始连接电阻和可靠性测试后的连接电阻测量如下。
（1）40℃下的储能模量
将35μm厚的各向异性导电膜放在热压机上，并将0.2mm厚的硅橡胶放在该膜上，并在190℃和30MPa经加热和压缩15分钟以固化上述连接材料，然后去除离型膜。
然后，在以10℃/分钟的速度从﹣40℃升温到200℃的同时使用动态机械分析仪（DMA）（TA Instruments）测量该膜在40℃下的储能模量。
（2）初始粘合强度和初始连接电阻
为了测量实施例和对比例中制备的各向异性导电膜的粘合强度和连接电阻，将每个膜放在PCB（间距：200μm，端子宽度：100μm，端子之间的距离：100μm，端子高度：35μm）和COF膜（间距：200μm，端子宽度：100μm，端子之间的距离：100μm，端子高度：8μm）之间，并在以下条件下连接。
1）预压缩；50℃，1秒，1.0MPa
2）主压缩；130℃，3秒，3.0MPa（条件1），190℃，3秒，4.0MPa（条件2）
使用万能测试机(UTM)（Hounsfield型号H5KT）通过以下方法测量压缩的膜对于PCB或COF膜的粘合强度：1）将测力传感器安装到测试机之后，2）将夹具提供到测试机，和3）用夹具夹住样品在50mm/分钟的拉伸测试速度下以90°的剥离方式测量粘合强度。
通过施加1mA的测试电流使用电阻测试仪2000Multimeter（Keithley有限公司）用4探针法测量连接电阻。
（3）可靠性测试后的连接电阻
为了评估膜的可靠性，将膜样品在85℃和85%RH下置于室中500小时，然后通过与上面相同的方法测量连接电阻，并计算平均值。
测量结果显示于表2中。
表2
Figure BDA0000435048180000131
Figure BDA0000435048180000141
虽然已经公开了一些实施方式，但是本领域的技术人员明白这些实施方式仅以说明的方式给出，在不背离本发明的精神和范围的情况下可进行各种修改、改变、变化和等效的实施方式。本发明的范围应仅由所附权利要求书限定。

Claims (13)

1.一种各向异性导电膜，具有1）100MPa至300MPa的所述膜固化后40℃下的储能模量，和2）80℃至90℃的所述膜的差示扫描量热仪曲线中的峰值点。
2.根据权利要求1所述的各向异性导电膜，其中，所述各向异性导电膜具有120℃至200℃的主压缩温度。
3.根据权利要求1所述的各向异性导电膜，其中，所述各向异性导电膜用于将软膜覆晶接合到印刷电路板。
4.根据权利要求1至3的任一项所述的各向异性导电膜，其中，所述各向异性导电膜包含：（A）热塑性树脂、（B）第一自由基可聚合材料、（C）第二自由基可聚合材料和（D）二氧化硅。
5.根据权利要求4所述的各向异性导电膜，其中，所述（B）第一自由基可聚合材料以固含量计的重量和所述（C）第二自由基可聚合材料以固含量计的重量之和（B+C）与所述（A）热塑性树脂以固含量计的重量和所述（D）二氧化硅以固含量计的重量之和（A+D）的比例（B+C）/（A+D）在0.20至0.45的范围内。
6.根据权利要求4所述的各向异性导电膜，其中，所述热塑性树脂包括选自由丙烯腈丁二烯共聚物、丙烯酸酯改性的氨基甲酸乙酯树脂和丙烯酰类共聚物组成的组中的至少一种。
7.根据权利要求4所述的各向异性导电膜，其中，所述各向异性导电膜进一步包含有机过氧化物和导电颗粒。
8.一种用于各向异性导电膜的组合物，包含：（A）热塑性树脂；（B）第一自由基可聚合材料；（C）第二自由基可聚合材料；（D）二氧化硅；（E）有机过氧化物；和（F）导电颗粒，其中，所述（B）第一自由基可聚合材料以固含量计的重量和所述（C）第二自由基可聚合材料以固含量计的重量之和（B+C）与所述（A）热塑性树脂以固含量计的重量和所述（D）二氧化硅以固含量计的重量之和（A+D）的比例（B+C）/（A+D）在0.20至0.45的范围内。
9.根据权利要求8所述的用于各向异性导电膜的组合物，其中，所述热塑性树脂包括选自由丙烯腈丁二烯共聚物、丙烯酸酯改性的氨基甲酸乙酯树脂和丙烯酰类共聚物组成的组中的至少一种。
10.根据权利要求9所述的用于各向异性导电膜的组合物，其中，基于所述组合物的以固含量计的总重，所述丙烯酰类共聚物的含量为8wt%至20wt%。
11.根据权利要求8所述的用于各向异性导电膜的组合物，其中，基于所述组合物的以固含量计的总重，所述二氧化硅的含量为3wt%至8wt%。
12.根据权利要求8至11任一项所述的用于各向异性导电膜的组合物，其中，所述组合物进一步包含二氧化钛。
13.一种半导体装置，包括：
具有第一电极的第一连接元件；
具有第二电极的第二连接元件；和
根据权利要求1至7任一项所述的各向异性导电膜、或由根据权利要求8至12任一项所述的组合物制备的各向异性导电膜，所述各向异性导电膜放置在所述第一连接元件和所述第二连接元件之间并将所述第一电极连接至所述第二电极。
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