CN104073178A - 包括导电粘合剂层的各向异性导电膜和半导体装置 - Google Patents

包括导电粘合剂层的各向异性导电膜和半导体装置 Download PDF

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Publication number
CN104073178A
CN104073178A CN201410125845.3A CN201410125845A CN104073178A CN 104073178 A CN104073178 A CN 104073178A CN 201410125845 A CN201410125845 A CN 201410125845A CN 104073178 A CN104073178 A CN 104073178A
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particle
adhesive layer
conductive
conductive film
anisotropic conductive
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CN201410125845.3A
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CN104073178B (zh
Inventor
朴憬修
权纯荣
金智软
朴永祐
韩在善
黃慈英
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Cheil Industries Inc
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Cheil Industries Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
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    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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Abstract

本文公开了各向异性导电膜，其包括含有导电颗粒和绝缘颗粒的导电粘合剂层，以及不含导电颗粒的绝缘粘合剂层。在该各向异性导电膜中，上述导电粘合剂层的导电颗粒和绝缘颗粒具有7.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2）的总颗粒密度（其中，d是以μm表示的该导电颗粒直径）。本文还公开了由所述各向异性导电膜连接的半导体装置。

Description

包括导电粘合剂层的各向异性导电膜和半导体装置
技术领域
本申请涉及各向异性导电膜和制造所述各向异性导电膜的方法，所述各向异性导电膜包括含有导电颗粒和绝缘颗粒的导电粘合剂层以及不含导电颗粒的绝缘粘合剂层，其中，所述导电粘合剂层的所述导电颗粒和所述绝缘颗粒具有7.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2）的总颗粒密度（其中，d是以μm表示的所述导电颗粒直径）。
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（例如包括镍颗粒或金颗粒的金属颗粒，或者金属涂覆的聚合物颗粒）分散在树脂中，并且该膜在z轴呈现导电性并在x-y平面的方向上呈现绝缘性。
当置于电路元件之间的该各向异性导电膜在预定条件下受到加热和压缩时，电路端子通过导电颗粒彼此电连接，并且绝缘粘合剂树脂填充相邻电路间的空间以使导电颗粒彼此独立，从而提供高的绝缘性能。各向异性导电膜通常用于液晶显示器（LCD）面板和带载封装（TCP）之间或印刷电路板和TCP之间以及类似的电连接。在电路连接过程中，各向异性导电膜布置在两个电路元件之间，并且被向其施加的热和压力压缩。此时，导电颗粒在两个电路元件之间移动，从而引起相应端子间导电颗粒较少被捕获以及相邻端子间导电颗粒的数目增加。结果，各向异性导电膜在相邻端子间电连接和绝缘性能方面糟受到损害。
根据显示器领域中尺寸大和厚度薄的近期趋势，电极和电路间隔已经逐渐变得微型化。具体地，为满足移动装置的高分辨率，该领域中要被连接的端子面积和端子间的距离逐渐减小。在这样的情况下，与现有技术相比，各向异性导电膜还需要在连接和绝缘方面具有最佳的性能。然而，普通的单层或多层结构的各向异性导电膜在精细电路端子的连接方面存在限制（例如，韩国专利申请第2010-0140773号和第2010-0138216号）。
关于确保精细电路端子的连接方面的各向异性导电膜的连接和绝缘性能的方法，可提出在提高导电颗粒的密度的同时，通过减小导电颗粒的尺寸而制备各向异性导电膜。然而，在这种情况下难以减少由于电路端子之间的狭窄间隙而出现的短路，并且导电颗粒减小的尺寸在处理元件的高度偏差方面产生了小的连接点和低的容量，从而产生了劣化的连接性能。
发明内容
为了解决现有技术中的上述问题而构思了本发明，本发明提供了各向异性导电膜和由所述各向异性导电膜连接的半导体装置，所述各向异性导电膜在连接如同高分辨率移动装置及类似物中具有小的端子面积和小的端子间距离的精细电路时能够确保连接和绝缘可靠性。
本发明的一个方面涉及各向异性导电膜，所述各向异性导电膜包括含有导电颗粒和绝缘颗粒的导电粘合剂层以及不含导电颗粒的绝缘粘合剂层，其中，所述导电粘合剂层的所述导电颗粒和所述绝缘颗粒具有7.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2）的总颗粒密度（其中，d是以μm表示的所述导电颗粒直径）。
本发明的另一个方面涉及各向异性导电膜，所述各向异性导电膜包括含有导电颗粒和绝缘颗粒的导电粘合剂层以及不含导电颗粒的绝缘粘合剂层，其中，所述导电粘合剂层的所述导电颗粒和所述绝缘颗粒以所述各向异性导电膜的总面积的80%或更大的总颗粒面积比存在。
在一些实施方式中，就固含量而言，基于所述导电粘合剂层的总重量，所述导电颗粒和所述绝缘颗粒的含量可为25wt%至60wt%。
在一些实施方式中，所述导电颗粒与所述绝缘颗粒的体积比可在1.5:1至1:3.5的范围内。
在一些实施方式中，所述导电颗粒可具有1μm至10μm的颗粒直径（d），优选1μm至5μm。
在一些实施方式中，所述导电粘合剂层可具有为所述导电颗粒直径的50%至150%的厚度。
在一些实施方式中，所述导电颗粒与所述绝缘颗粒的直径比可在1.2:1至1:1.2的范围内。
在一些实施方式中，所述绝缘粘合剂层可在所述导电粘合剂层的一个表面或两个表面上形成。
在一些实施方式中，所述导电颗粒可包括选自金属颗粒（包括Au、Ag、Ni、Cu、Pd、Al、Cr、Sn、Ti和Pb中的至少一种）；碳颗粒；和树脂颗粒或改性树脂颗粒（用所述金属颗粒涂布的所述树脂颗粒）中的至少一类颗粒。这里，所述树脂颗粒包括苯胍胺、聚乙烯、聚酯、聚苯乙烯和聚乙烯醇中的至少一种。
在一些实施方式中，所述导电颗粒或所述绝缘颗粒可具有在它表面上形成的突起。
在一些实施方式中，所述绝缘颗粒可为无机颗粒、有机颗粒或无机和有机颗粒的混合物，其中，所述无机颗粒可包括选自氧化硅（SiO2）、Al2O3、TiO2、ZnO、MgO、ZrO2、PbO、Bi2O3、MoO3、V2O5、Nb2O5、Ta2O5、WO3或In2O3中的至少一种；并且所述有机颗粒可包括选自丙烯酰类共聚物、苯并鸟嘌呤、聚乙烯、聚酯、聚苯乙烯、聚乙烯醇、聚氨酯和它们的改性树脂中的至少一种树脂。
在一些实施方式中，所述导电粘合剂层和所述绝缘粘合剂层的每个可包含粘结剂树脂和固化剂。在导电粘合剂层中，就固含量而言，基于所述导电粘合剂层的总重量，所述粘结剂树脂的含量可为10wt%至60wt%，并且所述固化剂的含量可为10wt%至40wt%。在所述绝缘粘合剂层中，就固含量而言，基于所述绝缘粘合剂层的总重量，所述粘结剂树脂的含量可为30wt%至80wt%，并且所述固化剂的含量可为20wt%至70wt%。
在一些实施方式中，所述绝缘粘合剂层与所述导电粘合剂层的厚度比可大于1/5且小于10。
在一些实施方式中，所述导电粘合剂层的所述导电颗粒和所述绝缘颗粒可以7.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2）的总颗粒密度存在，所述导电粘合剂层可具有为所述导电颗粒直径的50%至150%的厚度，并且所述导电颗粒和所述绝缘颗粒的中心可位于基本相同的平面上。
本发明的另一个方面涉及半导体装置，其包括：a）布线基板；b）粘附于所述布线基板的根据本发明实施方式的所述各向异性导电膜的所述导电粘合剂层和所述绝缘粘合剂层；以及c）安装在所述导电粘合剂层或所述绝缘粘合剂层上的半导体芯片。
在一些实施方式中，所述导电颗粒与所述绝缘颗粒的体积比在所述导电粘合剂层中可在1.5:1至1:3.5的范围内。
在一些实施方式中，所述导电粘合剂层可具有为所述导电颗粒直径的50%至150%的厚度。
在一些实施方式中，所述导电颗粒与所述绝缘颗粒的直径比可在1.5:1至1:1.5的范围内。
根据本发明的各向异性导电膜在精细电路的连接方面能够确保相邻端子间优异的电连接和稳定的绝缘。
在根据本发明的各向异性导电膜中，所述导电颗粒和所述绝缘颗粒被均匀地混合，使得在一个单独的层中存在的颗粒彼此邻近，以便上述颗粒的移动经热压缩达最小，从而在防止相邻端子间的短路的同时增加有助于端子间连接的有效颗粒的数目。
附图说明
图1为根据本发明的一个实施方式的各向异性导电膜的截面视图。
图2为普通的包括导电粘合剂层的各向异性导电膜的截面视图。
图3为根据本发明的另一个实施方式的各向异性导电膜的截面视图。
具体实施方式
在下文中将更详细地说明本发明的实施方式。为了清楚起见，将省略对本领域技术人员来说显而易见的细节说明。
本发明的一个实施方式涉及各向异性导电膜，包括含有导电颗粒和绝缘颗粒的导电粘合剂层，以及不含导电颗粒的绝缘粘合剂层，其中，导电粘合剂层的导电颗粒和绝缘颗粒具有7.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2）的总颗粒密度（其中，d是以μm表示的导电颗粒直径），由此各向异性导电膜可使导电颗粒的移动经热压缩达最小，从而在防止相邻端子间的短路的同时增加有助于端子间连接的有效颗粒的数目。
如文中使用，术语导电粘合剂层的导电颗粒和绝缘颗粒的“总颗粒密度”意指包括导电颗粒和绝缘颗粒的全部颗粒的密度。总颗粒密度可在7.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2）的范围内，具体为8.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2），更具体为9.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2）（其中，d是以μm表示的导电颗粒直径）。
当导电颗粒和绝缘颗粒的总颗粒密度在7.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2）的范围内时，能够防止当由粘合剂层中的粘结剂树脂等在导电粘合剂层中形成空间使导电颗粒在该空间中移动时，或者当导电颗粒未在粘合剂层内以单层排列并且可在粘合剂层中移动时，出现的连接性能和绝缘性能的劣化。
导电颗粒可具有1μm至10μm的直径（d），具体为1μm至5μm。
本发明的另一个实施方式涉及各向异性导电膜，其包括含有导电颗粒和绝缘颗粒的导电粘合剂层，以及不含导电颗粒的绝缘粘合剂层，其中，导电粘合剂层的导电颗粒和绝缘颗粒以各向异性导电膜的总面积的80%或更大的总颗粒面积比存在，由此使导电颗粒的移动经热压缩达最小，从而在防止相邻端子间的短路的同时增加位于端子间的有效导电颗粒的数目。
如文中使用，术语导电粘合剂层的导电颗粒和绝缘颗粒的“总颗粒面积比”意指x-y平面中导电颗粒和绝缘颗粒相对各向异性导电膜的总面积的总颗粒面积比。具体地，总颗粒面积比可为85%或更大，更具体为90%或更大，例如95%或更大。各向异性导电膜的z轴对应于在半导体芯片和布线基板之间压缩导电颗粒或绝缘颗粒的方向，因此，x-y平面的面积是垂直于压缩方向的平面的面积。
在导电颗粒和绝缘颗粒的总颗粒面积比的这个范围内，能够防止当由粘合剂层中的粘结剂树脂等在导电粘合剂层中形成空间使导电颗粒在该空间中移动时，或者当导电颗粒未在粘合剂层内以单层排列并且可在粘合剂层中移动时，出现的连接性能和绝缘性能的劣化。
就固含量而言，基于导电粘合剂层总重量，导电颗粒和绝缘颗粒的含量可为25wt%至60wt%。
在下文中，将参照附图说明本发明的示例性实施方式。应理解，下面的实施方式仅为了具体说明而提供，本发明并不限于此。
图1为根据本发明的一个实施方式的各向异性导电膜的截面视图。如图1中显示，根据本发明的一个实施方式的各向异性导电膜6包括绝缘粘合剂层3和导电粘合剂层2。根据这个实施方式，各向异性导电膜6可进一步包括基膜1。在这个实施方式中，导电颗粒4和绝缘颗粒5以单层排列，而在导电粘合剂层2内没有间隙，因此经连接基本保持不动。此外，由于导电颗粒4和绝缘颗粒5被非常均匀地混合而形成导电粘合剂层2，所以导电颗粒4和绝缘颗粒5提供了良好的分布轮廓（distribution profile）。这样，由于导电颗粒4和绝缘颗粒5以单层排列，而在导电粘合剂层2内没有间隙，所以能够减小由导电颗粒4在导电粘合剂层2内的移动引起的连接性能或绝缘性能的劣化。图3为根据本发明的另一个实施方式的各向异性导电膜的截面视图，其中，绝缘粘合剂层在导电粘合剂层的两个表面上形成。参见图3，根据这个实施方式的各向异性导电膜可包括分别在导电粘合剂层2的两个表面上形成的第一绝缘粘合剂层3'和第二绝缘粘合剂层3"。
另一方面，图2为普通的包括导电粘合剂层的各向异性导电膜的截面视图。在这个各向异性导电膜中，导电粘合剂层2提供了导电颗粒4可在其中移动的大间隙，由此端子上有效导电颗粒的数目经压缩而减少，从而引起连接性能和绝缘性能的劣化。
导电颗粒和绝缘颗粒的总颗粒密度例如可通过下面的方法计算。
首先，通过光学显微镜观察各向异性导电膜。这里，在调节显微镜的放大率的同时观察到约180μm×130μm（23,400μm2）的区域。计算这个区域中导电颗粒和绝缘颗粒的总数，并除以测量的面积以计算每μm2的颗粒密度。最终，从该结果获得每平方毫米（mm2）的总颗粒密度（颗粒）。
导电颗粒和绝缘颗粒的总颗粒面积比例如可通过下面的方法计算。
首先，通过光学显微镜观察各向异性导电膜。这里，在调节显微镜的放大率的同时观察到约180μm×130μm（23,400μm2）的区域。然后，使用图像分析程序（ImageAnalyzer,IMT i-Solution,产品名:i-Solution）计算导电颗粒和绝缘颗粒相对于总面积所占的面积，以获得导电颗粒和绝缘颗粒相对于总面积的颗粒面积比（百分比%）。
导电颗粒与绝缘颗粒的体积比可在1.5:1至1:3.5的范围内，优选1.2:1至1:3.2，更优选1:1至1:3。当体积比在1.5:1至1:3.5的范围内时，能够实现绝缘性能和连接性能两方面的改善。
导电粘合剂层可具有导电颗粒直径的50%至150%的厚度。根据本发明，导电颗粒或绝缘颗粒具有1μm至10μm范围内的直径，优选1μm至5μm。因此，导电粘合剂层可具有0.5μm至15μm范围内的厚度，优选0.5μm至7.5μm。在这个范围内，可抑制经热压缩的导电颗粒的移动，从而改善绝缘性能和连接性能。
导电颗粒与绝缘颗粒的直径比可在1.5:1至1:1.5的范围内。优选地，导电颗粒和绝缘颗粒具有基本相同的直径。
本发明的又一个实施方式涉及各向异性导电膜，其包括含有导电颗粒和绝缘颗粒的导电粘合剂层，以及不含导电颗粒的绝缘粘合剂层，其中，导电粘合剂层的导电颗粒和绝缘颗粒具有7.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2）的总颗粒密度（其中，d是以μm表示的导电颗粒直径），或者其中，导电粘合剂层的导电颗粒和绝缘颗粒以各向异性导电膜的总面积的80%或更大的总颗粒面积比存在，导电粘合剂层具有导电颗粒直径的50%至150%的厚度，并且导电颗粒和绝缘颗粒的中心基本位于相同的平面上。表述“导电颗粒和绝缘颗粒的中心基本位于相同的平面上”意指当导电颗粒的重心连接到绝缘颗粒的重心时基本上形成二维的平面。
在另一个实施方式中，导电粘合剂层的导电颗粒和绝缘颗粒可具有10.0×105/d2（颗粒）每平方毫米（mm2）的总颗粒密度，并且导电颗粒和绝缘颗粒的中心基本位于相同的平面上。
绝缘粘合剂层可在导电粘合剂层的一个表面或两个表面上形成。优选地，各向异性导电膜包括在导电粘合剂层的两个表面上形成的绝缘粘合剂层。
导电颗粒可包括选自金属颗粒（包括Au、Ag、Ni、Cu、Pd、Al、Cr、Sn、Ti和Pb中的至少一种）；碳颗粒；和树脂颗粒或改性树脂颗粒（用金属颗粒涂布的树脂颗粒）中的至少一类颗粒，但不限于此。这里，树脂颗粒包括苯胍胺、聚乙烯、聚酯、聚苯乙烯和聚乙烯醇中的至少一种。
导电颗粒或绝缘颗粒可具有在它的表面上形成的突起。
绝缘颗粒可为无机颗粒、有机颗粒或有机和无机颗粒的混合物，其中，无机颗粒可包括选自二氧化硅（SiO2）、Al2O3、TiO2、ZnO、MgO、ZrO2、PbO、Bi2O3、MoO3、V2O5、Nb2O5、Ta2O5、WO3或In2O3中的至少一种；并且有机颗粒可包括选自丙烯酰类共聚物、苯并鸟嘌呤、聚乙烯、聚酯、聚苯乙烯、聚乙烯醇、聚氨酯和它们的改性树脂中的至少一种树脂。有机和无机颗粒的混合物的一个实例可包括倍半硅氧烷颗粒。
绝缘粘合剂层与导电粘合剂层的厚度比可大于1/5且小于10。
优选地，绝缘粘合剂层与导电粘合剂层的厚度比大于2且小于8。在这个范围内，绝缘粘合剂层充分地填充相邻电路之间的空间，从而提供良好的绝缘和粘合性。
在根据本发明的各向异性导电膜中，导电粘合剂层和绝缘粘合剂层的每个可进一步包含粘结剂树脂和固化剂。
粘结剂树脂可选自由丙烯酸树脂、环氧树脂、氨基甲酸酯丙烯酸酯树脂、苯氧树脂、丙烯腈树脂、苯乙烯-丙烯腈树脂、丁二烯树脂、聚酰胺树脂、烯烃树脂、氨基甲酸酯树脂和硅酮树脂组成的组中。优选地，粘结剂树脂选自由丙烯酸树脂、环氧树脂和氨基甲酸酯丙烯酸酯树脂组成的组中。
丙烯酸树脂可为通过(甲基)丙烯酸酯单体的共聚反应制备的共聚物树脂，(甲基)丙烯酸酯单体选自由单(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-戊氧基丙酯（2-hydroxy-3-penyloxypropyl(meth)acrylate）、(甲基)丙烯酸1,4-丁二醇酯、2-羟烷基(甲基)丙烯酰基磷酸酯、(甲基)丙烯酸4-羟基环己基酯、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、(甲基)丙烯酸2-(2-乙氧基乙氧基)乙酯、(甲基)丙烯酸十八烷基酯、(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、乙氧基化的壬基苯酚(甲基)丙烯酸酯、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t-乙二醇酯（t-ethylene glycol di(meth)acrylate）、二(甲基)丙烯酸聚乙二醇酯、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-t-二醇酯(phenoxy-t-glycol(meth)acrylate)、2-甲基丙烯酰氧基乙基磷酸酯、二(甲基)丙烯酸二羟甲基三环癸烷酯、三羟甲基丙烷苯甲酸酯丙烯酸酯和芴(甲基)丙烯酸酯组成的组中，但不限于此。
环氧树脂可包括具有选自由双酚型、酚醛型、缩水甘油型和脂环族基团组成的组中的至少一种粘结结构的共聚物，但不限于此。例如，环氧树脂可包括双酚A或双酚F或改性的环氧树脂、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、二聚酸改性的环氧树脂、具有丙二醇骨架的环氧树脂或氨基甲酸酯改性的环氧树脂等。
氨基甲酸酯丙烯酸酯树脂可包括由二异氰酸酯、多元醇、二醇或丙烯酸酯单体制备的树脂。二异氰酸酯可包括选自由四亚甲基-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和4,4-亚甲基双(环己基二异氰酸酯)组成的组中的至少一种。多元醇的实例可包括聚酯多元醇、聚醚多元醇和聚碳酸酯多元醇，但不限于此。可通过二羧酸化合物和二元醇化合物的缩合得到多元醇。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。二元醇的实例可包括1,3-丙二醇、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。丙烯酸酯可为丙烯酸羟基酯或丙烯酸胺基酯。
粘结剂树脂在导电粘合剂层中的含量可为10wt%至60wt%，优选15wt%至40wt%。粘结剂树脂在绝缘粘合剂层中的含量可为30wt%至80wt%，优选40wt%至70wt%。在粘结剂树脂的这些含量范围内，粘合剂组合物可形成膜。粘结剂树脂可具有30,000g/mol至1,000,000g/mol的重均分子量，优选50,000g/mol至850,000g/mol。
对于固化剂，可使用本领域中已知的任何固化剂而无限制。固化剂的实例可包括咪唑、苯甲酰、酸酐、胺、酰肼、阳离子固化剂、潜伏性固化剂和它们的组合，但不限于此。
固化剂在导电粘合剂层中的含量可为10wt%至40wt%，优选15wt%至30wt%。此外，固化剂在绝缘粘合剂层中的含量可为20wt%至70wt%，优选35wt%至50wt%。在这个范围内，当在预定温度范围内加热时，固化剂使粘合剂组合物与粘结剂树脂一起固化，使得粘合剂组合物呈现粘合强度，并具有坚固的结构，从而改善可靠性。
本发明的另一个实施方式涉及半导体装置，包括a）布线基板；b）粘附于布线基板的根据本发明的实施方式的的各向异性导电膜的导电粘合剂层和绝缘粘合剂层；和c）安装在导电粘合剂层或绝缘粘合剂层上的半导体芯片。
在导电粘合剂层中，导电颗粒与绝缘颗粒的体积比可在1.5:1至1:3.5的范围内。
导电粘合剂层可具有导电颗粒直径的50%至150%的厚度。
导电颗粒与绝缘颗粒的直径比可在1.5:1至1:1.5的范围内。
本发明的再一个实施方式涉及制造各向异性导电膜的方法，各向异性导电膜包括含有导电颗粒和绝缘颗粒的导电粘合剂层以及不含导电颗粒的绝缘粘合剂层。该方法包括：
i）形成含有导电颗粒和绝缘颗粒的导电粘合剂层，其中，导电粘合剂层的导电颗粒和绝缘颗粒具有7.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2）的总颗粒密度（其中，d是以μm表示的导电颗粒直径），或者导电粘合剂层的导电颗粒和绝缘颗粒以各向异性导电膜的总面积的80%或更大的总颗粒面积比存在；和
ii）在导电粘合剂层上形成不含导电颗粒的绝缘粘合剂层，或者形成单独的绝缘粘合剂层，然后将导电粘合剂层与单独的绝缘粘合剂层结合，以形成包括导电粘合剂层和绝缘粘合剂层的各向异性导电膜。
根据本发明的方法可进一步包括在操作i）中均匀地混合导电颗粒与绝缘颗粒。
根据本发明的方法可进一步包括在操作i）中确定导电颗粒和绝缘颗粒的总颗粒密度。此外，根据本发明的方法可进一步包括在操作i）中确定导电颗粒与绝缘颗粒的总颗粒面积比。颗粒密度可在调节光学显微镜的放大率的同时由光学显微镜通过观察导电粘合剂层而确定。这里，观察到约180μm×130μm（23,400μm2）的区域。计算该区域中导电颗粒和绝缘颗粒的总数并除以测量的面积以计算每μm2的颗粒密度。最终，由上述结果获得每平方毫米（mm2）的总颗粒密度（颗粒）。导电颗粒与绝缘颗粒的总颗粒面积比可在调节光学显微镜的放大率的同时由光学显微镜通过观察各向异性导电膜而测量。这里，观察到约180μm×130μm（23,400μm2）的面积。然后，使用图像分析程序（Image Analyzer,IMT i-Solution,产品名:i-Solution）计算导电颗粒和绝缘颗粒相对于总面积所占的面积，以获得导电颗粒和绝缘颗粒相对于总面积的颗粒面积比（百分比%）。
在操作i）的导电粘合剂膜中，导电颗粒与绝缘颗粒的体积比可在1.5:1至1:3.5的范围内，优选1.2:1至1:3.2，更优选1:1至1:3。当该体积比在1.5:1至1:3.5的范围内时，能够在绝缘性能和连接性能方面都得到改善。
导电粘合剂层可具有导电颗粒直径的50%至150%的厚度。在这个范围内，可抑制经热压缩的导电颗粒的移动，从而改善绝缘性能和连接性能。
导电颗粒与绝缘颗粒的直径比可在1.5:1至1:1.5的范围内。优选地，导电颗粒和绝缘颗粒具有基本相同的直径。
根据本发明的方法可进一步包括操作ii）之后在导电粘合剂层的其它表面上形成第二绝缘粘合剂层。
各向异性导电膜的导电粘合剂层和绝缘粘合剂层的每个可进一步包含选自由溶剂、阻聚剂、抗氧化剂、热稳定剂和固化促进剂组成的组中的至少一种添加剂。添加剂在每个粘合剂层中的含量可为1wt%至5wt%。
对于溶剂，可使用任何溶剂，例如甲苯或甲乙酮。阻聚剂可为选自由对苯二酚、对苯二酚单甲醚、对苯醌、吩噻嗪和它们的混合物组成的组中的至少一种，但不限于此。抗氧化剂用于防止组合物因热引起的氧化或者提供热稳定性，并且可选自支链的酚或羟基肉桂酸酯材料，但不限于此。固化促进剂可包括选自固体咪唑固化促进剂以及固体和液体胺固化促进剂中的至少一种，但不限于此。
不需要特定的仪器和设备形成根据本发明的各向异性导电膜。例如，可通过在溶剂中搅拌和混合导电颗粒和绝缘颗粒以制备均匀的分散体，然后向混合物中加入粘结剂树脂和固化剂，或者通过在不引起导电颗粒或绝缘颗粒粉碎的速度下搅拌导电颗粒、绝缘颗粒、粘结剂树脂和固化剂某段时间，将混合物涂布到离型膜上达到0.5μm至15μm的厚度，然后以充足的时间干燥混合物以蒸发溶剂，而制备各向异性导电膜。
或者，可通过以预定的一段时间搅拌粘结剂树脂、固化剂和溶剂，将混合物涂布到离型膜上达到0.5μm至80μm的厚度，然后以充足的时间干燥混合物以蒸发溶剂，而形成绝缘粘合剂膜。然后，将导电粘合剂膜与绝缘粘合剂膜结合，以形成具有双层或更多层结构的各向异性导电膜。
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。
将省略对本领域技术人员来说明显的细节说明。
实施例
1.实施例1至6的各向异性导电膜的制备
实施例1
就固含量而言，使用35wt%的苯氧树脂（Kukdo Chemical Co.,Ltd.）、20wt%的环氧树脂EP-630（JER Co.,Ltd.）和45wt%的潜伏性固化剂HP3941HP（Asahi Kasei,K.K.）制备绝缘粘合剂层，并且就固含量而言，使用20wt%的苯氧树脂、4wt%的环氧树脂EP-630、23wt%的潜伏性固化剂HP3841HP、38wt%的具有3μm颗粒直径的镀镍导电颗粒和15wt%的由丙烯酰类共聚物树脂形成的并具有3μm颗粒直径的绝缘颗粒制备导电粘合剂层。这里，通过在溶剂中溶解和分散上述组分而制备各组合物，并将该组合物涂布到PET离型膜上，然后蒸发溶剂，从而制备12μm厚的绝缘粘合剂层或1.5μm厚的导电粘合剂层。然后，将绝缘粘合剂层与导电粘合剂层结合以形成实施例1的各向异性导电膜。
实施例2
除了导电粘合剂层具有4.5μm的厚度以外，以与实施例1相同的方式制备实施例2的各向异性导电膜。
实施例3
除了就固含量而言，使用26wt%的苯氧树脂、4wt%的环氧树脂EP-630、29wt%的潜伏性固化剂HP3841HP、19wt%的具有3μm颗粒直径的镀镍导电颗粒和22wt%的由丙烯酰类共聚物树脂形成的并具有3μm颗粒直径的绝缘颗粒制备导电粘合剂层以外，以与实施例1相同的方式制备实施例3的各向异性导电膜。这里，通过在溶剂中溶解和分散上述组分而制备组合物，并将该组合物涂布到PET离型膜上，然后蒸发溶剂，从而制备3μm的导电粘合剂层，导电粘合剂层与绝缘粘合剂层结合以形成各向异性导电膜。
实施例4
除了就固含量而言，使用32wt%的苯氧树脂、4wt%的环氧树脂EP-630、36wt%的潜伏性固化剂HP3841HP、13wt%的具有3μm颗粒直径的镀镍导电颗粒和15wt%的由丙烯酰类共聚物树脂形成的并具有3μm颗粒直径的绝缘颗粒制备导电粘合剂层以外，以与实施例1相同的方式制备实施例4的各向异性导电膜。这里，通过在溶剂中溶解和分散上述组分而制备组合物，并将组合物涂布到PET离型膜上，然后蒸发溶剂，从而制备3μm的导电粘合剂层，导电粘合剂层与绝缘粘合剂层结合以形成各向异性导电膜。
实施例5
除了就固含量而言，使用23wt%的苯氧树脂、3wt%的环氧树脂EP-630、25wt%的潜伏性固化剂HP3841HP、34wt%的具有4μm颗粒直径的镀镍导电颗粒和15wt%的由丙烯酰类共聚物树脂形成的并具有4μm颗粒直径的绝缘颗粒制备导电粘合剂层以外，以与实施例1相同的方式制备实施例5的各向异性导电膜。这里，通过在溶剂中溶解和分散上述组分而制备组合物，并将组合物涂布到PET离型膜上，然后蒸发溶剂，从而制备4μm的导电粘合剂层，导电粘合剂层与绝缘粘合剂层结合以形成各向异性导电膜。
实施例6
除了就固含量而言，使用21wt%的苯氧树脂、2wt%的环氧树脂EP-630、23wt%的潜伏性固化剂HP3841HP、39wt%的具有3μm颗粒直径的镀镍导电颗粒和15wt%的由丙烯酰类共聚物树脂形成的并具有2.5μm颗粒直径的绝缘颗粒制备导电粘合剂层以外，以与实施例1相同的方式制备实施例6的各向异性导电膜。这里，通过在溶剂中溶解和分散上述组分而制备组合物，并将组合物涂布到PET离型膜上，然后蒸发溶剂，从而制备3μm的导电粘合剂层，导电粘合剂层与绝缘粘合剂层结合以形成各向异性导电膜。
2.对比例1和2的各向异性导电膜的制备
对比例1
除了就固含量而言，使用17wt%的苯氧树脂、3wt%的环氧树脂EP-630、14wt%的潜伏性固化剂HP3841HP、51wt%的具有3μm颗粒直径的镀镍导电颗粒和15wt%的由丙烯酰类共聚物树脂形成的并具有3μm颗粒直径的绝缘颗粒制备导电粘合剂层以外，以与实施例1相同的方式制备对比例1的各向异性导电膜。这里，通过在溶剂中溶解和分散上述组分而制备组合物，并将组合物涂布到PET离型膜上，然后蒸发溶剂，从而制备3μm的导电粘合剂层，导电粘合剂层与绝缘粘合剂层结合以形成各向异性导电膜。
对比例2
除了就固含量而言，使用35wt%的苯氧树脂、5wt%的环氧树脂EP-630、39wt%的潜伏性固化剂HP3841HP、10wt%的具有3μm颗粒直径的镀镍导电颗粒和11wt%的由丙烯酰类共聚物树脂形成的并具有3μm颗粒直径的绝缘颗粒制备导电粘合剂层以外，以与实施例1相同的方式制备对比例2的各向异性导电膜。这里，通过在溶剂中溶解和分散上述组分而制备组合物，并将组合物涂布到PET离型膜上，然后蒸发溶剂，从而制备3μm的导电粘合剂层，导电粘合剂层与绝缘粘合剂层结合以形成各向异性导电膜。
3.各向异性导电膜的性能评价
通过下述方法对于导电颗粒与绝缘颗粒的体积比、导电颗粒和绝缘颗粒的总颗粒密度、连接电阻和绝缘电阻评价实施例1至6以及对比例1和2中制备的各向异性导电膜。表1和2中显示了结果。
1）导电颗粒与绝缘颗粒的体积比
通过光学显微镜BX51（OLYMPUS）观察实施例1至6以及对比例1和2中制备的每个各向异性导电膜。在调节显微镜的放大率的同时观察到导电膜约180μm×130μm（23,400μm2）的区域。计算导电颗粒和绝缘颗粒的总数，以计算体积比。
2）导电颗粒与绝缘颗粒的总颗粒密度
通过光学显微镜BX51（OLYMPUS）观察实施例1至6以及对比例1和2中制备的每个各向异性导电膜。在调节显微镜的放大率的同时观察到导电膜约180μm×130μm（23,400μm2）的区域。计算这个区域中的导电颗粒和绝缘颗粒的总数，并除以测量的面积以计算每μm2的颗粒密度。最终，由该结果获得每平方毫米（mm2）的总颗粒密度（颗粒）。
3）导电颗粒与绝缘颗粒的总颗粒面积比
通过光学显微镜BX51（OLYMPUS）观察实施例1至6以及对比例1和2中制备的每个各向异性导电膜。在调节显微镜的放大率的同时观察到导电膜约180μm×130μm（23,400μm2）的区域。然后，使用图像分析程序（Image Analyzer,IMT i-Solution,产品名:i-Solution）计算导电颗粒和绝缘颗粒相对于总面积所占的面积，以获得导电颗粒和绝缘颗粒相对于总面积的颗粒面积比（百分比%）。
4）连接电阻
将每个各向异性导电膜切成2mm×25mm的尺寸，并粘结到基板，用于评价连接电阻。这里，通过在60℃和1MPa的条件下预压缩1秒钟将各向异性导电膜放置在0.5mm厚的玻璃基板上，然后从各向异性导电膜去除PET膜。然后，在膜上排列芯片（芯片长度：19.5mm，芯片宽度：1.5mm，隆起长度：100μm，隆起宽度：12μm），然后在200℃和90MPa的条件下主压缩1秒钟。通过4探针法使用电阻测试仪测量各向异性导电膜的连接电阻，4探针法为使用连接到电阻测试仪的4个探针测量4个针之间的电阻。基于在施加到电阻测试仪1mA时测量的电压计算连接电阻。
5）绝缘电阻
将每个各向异性导电膜切成2mm×25mm的尺寸，并粘结到基板，用于评价绝缘电阻。这里，通过在60℃和1MPa的条件下预压缩1秒钟将各向异性导电膜放置在0.5mm厚的玻璃基板上，然后从各向异性导电膜去除PET膜。然后，在膜上排列芯片（芯片长度：19.5mm，芯片宽度：1.5mm,隆起间距：8μm），然后在200℃和90MPa的条件下主压缩1秒钟。通过向其施加50V的电压用2探针法检测在总的38个点发生的短路。
表1
表2
对比例1 对比例2
导电颗粒和绝缘颗粒的含量 66% 21%
颗粒比（体积比） 2:1 1:3
导电粘合剂层的厚度（μm） 3 3
导电颗粒的颗粒直径（μm） 3 3
绝缘颗粒的颗粒直径（μm） 3 3
颗粒密度（每mm2） 120,000个颗粒 55,000个颗粒
面积比（%） 95 58
连接电阻（Ω） 1.25 0.50
绝缘电阻（Ω） 短路 1.0×109
如表1和表2显示，当导电颗粒和绝缘颗粒在导电粘合剂层中的总颗粒密度在7.0×105/d2至10.0×105/d2（颗粒）每平方毫米（mm2）的范围内时，各向异性导电膜在连接电阻和绝缘电阻方面具有良好的性能。另一方面，在对比例1的各向异性粘合剂膜中，其中膜的总颗粒密度超过10.0×105/d2（颗粒）每平方毫米（mm2），颗粒未在单层中排列，而使颗粒移动，引起连接电阻的增加，并且在对比例2中，其中膜的总颗粒密度小于7.0×105/d2（颗粒）每平方毫米（mm2），各向异性粘合剂膜具有大的颗粒移动空间，引起连接电阻的增加。
此外，在实施例1至6中，其中导电粘合剂层中导电颗粒与绝缘颗粒的体积比在1:1至1:3的范围内，各向异性粘合剂膜在连接电阻和绝缘电阻方面都具有良好的性能，而在对比例1中，其中体积比为2:1，由于过量导电颗粒造成不充分的绝缘而发生短路。
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、变化和等同的实施方式。本发明的范围应仅由所附权利要求书限定。

Claims (18)

1.一种各向异性导电膜，包括含有导电颗粒和绝缘颗粒的导电粘合剂层以及不含导电颗粒的绝缘粘合剂层，
其中，所述导电粘合剂层的所述导电颗粒和所述绝缘颗粒具有7.0×105/d2至10.0×105/d2每平方毫米的总颗粒密度，其中，d是以μm表示的所述导电颗粒直径。
2.如权利要求1所述的各向异性导电膜，其中，就固含量而言，基于所述导电粘合剂层的总重量，所述导电颗粒和所述绝缘颗粒的含量为25wt%至60wt%。
3.如权利要求1所述的各向异性导电膜，其中，所述导电颗粒与所述绝缘颗粒的体积比在1.5:1至1:3.5的范围内。
4.如权利要求1至3的任一项所述的各向异性导电膜，其中，所述导电颗粒具有1μm至10μm的颗粒直径d。
5.如权利要求1至3的任一项所述的各向异性导电膜，其中，所述导电粘合剂层具有为所述导电颗粒直径的50%至150%的厚度。
6.如权利要求1至3的任一项所述的各向异性导电膜，其中，所述导电颗粒与所述绝缘颗粒的直径比在1.5:1至1:1.5的范围内。
7.如权利要求1至3的任一项所述的各向异性导电膜，其中，所述绝缘粘合剂层在所述导电粘合剂层的一个表面或两个表面上形成。
8.如权利要求7所述的各向异性导电膜，其中，所述绝缘粘合剂层与所述导电粘合剂层的厚度比大于1/5且小于10。
9.一种各向异性导电膜，包括含有导电颗粒和绝缘颗粒的导电粘合剂层以及不含导电颗粒的绝缘粘合剂层，
其中，所述导电粘合剂层的所述导电颗粒和所述绝缘颗粒以所述各向异性导电膜的总面积的80%或更大的总颗粒面积比存在。
10.如权利要求9所述的各向异性导电膜，其中，就固含量而言，基于所述导电粘合剂层的总重量，所述导电颗粒和所述绝缘颗粒的含量为25wt%至60wt%。
11.如权利要求9所述的各向异性导电膜，其中，所述导电颗粒与所述绝缘颗粒的体积比在1.5:1至1:3.5的范围内。
12.如权利要求9至11的任一项所述的各向异性导电膜，其中，所述导电粘合剂层具有为所述导电颗粒直径的50%至150%的厚度。
13.如权利要求1至3和权利要求9至11的任一项所述的各向异性导电膜，其中，所述导电粘合剂层或所述绝缘粘合剂层包含粘结剂树脂和固化剂。
14.如权利要求13所述的各向异性导电膜，其中，就固含量而言，基于所述导电粘合剂层的总重量，所述粘结剂树脂的含量为10wt%至60wt%，并且所述固化剂的含量为10wt%至40wt%。
15.如权利要求13所述的各向异性导电膜，其中，就固含量而言，基于所述绝缘粘合剂层的总重量，所述粘结剂树脂的含量为30wt%至80wt%，并且所述固化剂的含量为20wt%至70wt%。
16.如权利要求1至3和权利要求9至11的任一项所述的各向异性导电膜，其中，所述绝缘粘合剂层与所述导电粘合剂层的厚度比大于1/5且小于10。
17.一种各向异性导电膜，包括含有导电颗粒和绝缘颗粒的导电粘合剂层以及不含导电颗粒的绝缘粘合剂层，
其中，所述导电粘合剂层的所述导电颗粒和所述绝缘颗粒具有7.0×105/d2至10.0×105/d2每平方毫米的总颗粒密度，其中，d是以μm表示的所述导电颗粒直径，所述导电粘合剂层具有为所述导电颗粒直径的50%至150%的厚度，并且所述导电颗粒和所述绝缘颗粒的中心位于相同的平面上。
18.一种半导体装置，包括：
a）布线基板；
b）如权利要求1至17的任一项所述的各向异性导电膜的所述导电粘合剂层和所述绝缘粘合剂层，所述各向异性导电膜粘附于所述布线基板；和
c）安装在所述导电粘合剂层或所述绝缘粘合剂层上的半导体芯片。
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