CN101445709B - 半导体组装芯片粘接用粘合剂组合物及由其制备的粘合膜 - Google Patents

半导体组装芯片粘接用粘合剂组合物及由其制备的粘合膜 Download PDF

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CN101445709B
CN101445709B CN2008101789194A CN200810178919A CN101445709B CN 101445709 B CN101445709 B CN 101445709B CN 2008101789194 A CN2008101789194 A CN 2008101789194A CN 200810178919 A CN200810178919 A CN 200810178919A CN 101445709 B CN101445709 B CN 101445709B
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solvent
bonding film
film
boiling point
epoxy
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CN101445709A (zh
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崔韩任
宋基态
黄治皙
金惠敬
丁畅范
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Cheil Industries Inc
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Cheil Industries Inc
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    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract

本发明提供一种半导体组装芯片粘接用粘合剂组合物，以及采用该组合物制得的粘合膜，所述组合物包括一种双组分溶剂，其包括沸点为0～100℃的低沸点溶剂和另一种沸点为140～200℃的高沸点溶剂。本发明的溶剂残留量小于2％的粘合膜可在提高固化组分含量时同时满足膜的延展性结构和增强的抗张强度，从而在防止膜被切割的同时提高了硬度。由于产生间隙的挥发性组分具有高沸点，则半导体组装中由溶剂挥发而产生的间隙可得到显著降低。其结果是所述粘合膜显示出在粘合膜表面产生的间隙或空隙的体积膨胀降低，从而保证极好的膜可靠性。

Description

半导体组装芯片粘接用粘合剂组合物及由其制备的粘合膜
对相关申请的交叉引用
本申请要求2007年11月28日向韩国知识产权局提出的专利申请2007-122101的权益，其全部内容通过引用而合并于此。
技术领域
本发明涉及一种在半导体组装中用于芯片粘接(die bonding)的包含高沸点溶剂和低沸点溶剂的粘合剂组合物，以及用该组合物制得的粘合膜。更具体涉及一种半导体组装中芯片粘接用粘合剂组合物，其包括基于双组分的溶剂组合，其中包括沸点为0～100℃的低沸点溶剂和另一种沸点为140～200℃的高沸点溶剂，以及采用该组合物制得的粘合膜。
背景技术
在用于半导体组装中具有可靠性高的粘合膜的常规粘合剂组合物中，主要采用Ag浆来将至少两个半导体器件和/或将一个半导体器件与支撑元件相粘合。然而，当前趋势是在提高半导体容量的同时降低其尺寸，这就要求用于半导体的支撑元件具有减小的尺寸和/或使其最小化。
近年来通常使用的Ag浆具有诸如由于半导体器件的突出或倾斜而导致在引线粘接(wire bonding)中出现异常、起泡、厚度调整困难等一些缺陷。因此，已广泛采用粘合膜来取代银浆。
用于半导体组装中的粘合膜通常与切割膜(dicing film)结合使用。所述切割膜是指在用于制造半导体芯片的系列工艺中的切割工艺中用于固定半导体晶圆的薄膜。切割工艺后通常还有些后续工艺，例如扩展、取晶(或剥离)和/或贴晶。所述切割膜通常是由以下方法形成：将紫外光固化或其他方式固化的粘合剂涂覆在具有聚氯乙烯或聚烯烃结构的基材上，再在该涂覆的薄膜上层压PET类覆膜。已知的用于半导体组装的粘合膜的常规用法是：将粘合膜粘贴到半导体晶圆上，具有上述结构的切割膜与另一片已去除覆膜的切割膜交叠放到上述晶圆层压片上，然后将层压片进行切割用于雕刻。
目前，越来越趋向于将没有PET覆膜的切割膜与粘合膜结合后，半导体晶圆被放置并固定在该结合膜上并随后通过切割工艺雕刻。然而，与常规的切割膜仅用于切割相比，此过程需要解决的难题是在剥离过程中要同时去除芯片和芯片粘合膜，并且在将芯片粘合膜与半导体晶圆背面贴合过程中可产生由不平整表面导致的许多间隙或空隙。如果半导体组装后这些空隙留在芯片和晶圆间的界面，并暴露于高温条件下，这些间隙或空隙会体积膨胀，由此产生裂纹，最终导致半导体器件的可靠性下降和失效。因此，一定要使半导体组装的全部工艺中在芯片和晶圆界面处出现的空隙最少。
作为解决上述问题的典型方法，可能的建议是提高切割膜中可固化部分的含量。但是，这种方案将会降低切割膜的抗张强度，从而导致切割膜在半导体组装过程中在预切期间被切割和/或在切割中产生毛边或发生破裂。此外，由于具有固有的低弹性模量的切割膜对粘合膜有高粘附性，因此粘合膜容易变形，这就可能使得剥离的成功率降低。
对于包括至少两个具有相同尺寸的半导体芯片的半导体衬底来说，具有粘合膜的半导体芯片通常层压在下层芯片上，该下层芯片因带有引线而不平整。在这点上，要求粘合膜既能保障粘合膜和上层半导体芯片间的绝缘，又能填平引线所引起的不平整区域，以使间隙或空隙的产生最小化。
同时，韩国未决公开专利申请10-2001-0019339提供了一种将半导体芯片粘附到衬底上的方法，及一种通过结构改变来阻止粘附过程中间隙和空隙产生的方法。此外，还有韩国未决公开专利申请10-2001-0067985公开了一种改进的采用弹性体组合物的包装，该弹性体组合物含有氢化丁腈橡胶(HNBR)，从而在提高包装的耐湿耐氧化性能的同时减小弹性模量。然而，这些常规的方法都需要采用额外的工序或其他粘合剂或添加剂，并由此产生其他问题。
发明内容
因此，为解决上述常规技术存在的问题，本发明公开了一种用作粘合膜的组合物，以避免粘合过程中在半导体晶圆与芯片粘合膜间界面上的间隙和/或空隙的产生。
本发明公开一种用于制作用于半导体组装的粘合膜的组合物，其特征是该粘合膜在具有增加的可固化组分含量的情况下具有延展性结构，和改进的抗张强度，从而赋予膜更好的硬度，不被切割。
本发明还涉及用上述添加高沸点溶剂的组合物制得的粘合膜。
为实现上述目的，本发明一方面是提供一种用于在半导体组装中制造粘合膜的组合物，包括粘结剂组分、可固化组分和溶剂，其中所述溶剂是双组分溶剂的组合，其中包括沸点为40～100℃的低沸点溶剂，及另一种沸点为140～200℃的高沸点溶剂。
为实现上述目的，本发明另一方面是提供一种采用上述组合物制得的粘合膜，其溶剂残留量小于2％。
具体实施方式
本发明所提供的用于半导体的粘合剂组合物可包括用于制造用在半导体组装中的粘合膜的组合物，其特征是所述组合物包括含有低沸点和高沸点的双组分溶剂组合。
以下对该发明的优选实施方案进行详细说明。
根据本发明的示例性实施方式的组合物，是一种在半导体组装中使用的用于制造粘合膜(常称为“粘合剂组合物”)的粘合剂组合物，其包括粘结剂组分、可固化组分和溶剂，其中所述溶剂是双组分溶剂(常称为“二元溶剂”)，其中包括沸点为40～100℃的低沸点溶剂和另一种沸点为140～200℃的高沸点溶剂。
粘结剂部分可包括从丙烯酸聚合物、含NCO的聚合物和/或含环氧的聚合物中选择的至少一种聚合物。
可固化组分可包括从环氧树脂、聚氨酯树脂、硅树脂、聚酯树脂、酚型固化树脂、胺类固化树脂、三聚氰胺固化树脂、脲固化树脂、酸酐类固化树脂等中选择的至少一种树脂。
该组合物还进一步包括固化催化剂，硅烷偶联剂和/或填料。
优选地，该组合物包括丙烯酸树脂、环氧树脂、酚型固化树脂、固化催化剂、硅烷偶联剂和填料，及上述二元溶剂组合。
该组合物可包括以重量计2～50％(“wt％”)的丙烯酸聚合物，4～50wt％的环氧树脂，3～50wt％的酚型固化树脂，0.01～10wt％的固化催化剂，0.01～10wt％的硅烷偶联剂和0.1～50wt％的填料，以及40～60wt％的二元溶剂。
以下详细说明组合物的各组成成分。
有机溶剂
根据本发明优选实施方案的用于半导体组装的粘合剂组合物包括至少一种有机溶剂。该有机溶剂能充分有效地降低组合物粘度以利于形成粘合膜。由于有机溶剂影响由该组合物所制得的粘合膜的物理性能，这种影响取决于膜的厚度，因此粘合膜中的溶剂残留量小于2％。
此处所用有机溶剂主要是包括低沸点溶剂和高沸点溶剂的二元溶剂。低沸点溶剂是指具有0～100℃，优选40～100℃的低沸点的有机溶剂。另一方面，高沸点溶剂是指具有130～300℃，优选140～200℃的高沸点的有机溶剂。
由于制备粘合膜后高沸点溶剂的少量残留保留在膜中，因此含有高沸点溶剂的二元溶剂增强了粘合膜的延展性结构，由此减少了膜的切割。溶剂组合还能减小由取决于加工温度的挥发产生的空隙(“挥发性空隙”)，从而改进层压空隙问题。
低沸点溶剂可以是从由苯、丙酮、丁酮、四氢呋喃、二甲基甲酰胺和环己烷所构成的组中选择的至少一种溶剂，但本发明不限于此。
同时，高沸点溶剂可以是从丙二醇单甲醚醋酸酯和环己酮中选择的至少一种。
使用两种或更多种低沸点溶剂时，溶剂残留的量优选由干燥温度来控制。这样的低沸点溶剂可包括，例如苯、丁酮和环己烷。
相对于100重量份的低沸点溶剂，二元溶剂包括70～400重量份(“wt份”)，优选100～230重量份的高沸点溶剂。当高沸点溶剂含量低于70重量份，所述膜表面可能有在膜表面产生气泡的问题。当该含量高于400重量份时，则很难将膜中的溶剂残留量调整到低于2％，从而可能导致膜的稳定性问题。
组合物中二元溶剂含量为组合物总重量的40～60wt％。若超过60wt％，组合物的粘度太低，膜难以具有均匀厚度，并且组合物的流痕可留在膜的表面。另一方面，当二元溶剂含量低于40wt％时，组合物可能遇到溶解性问题，难以得到组成比例均一的组合物，并难以制成粘合膜。
含有高沸点溶剂的二元溶剂用于减少制备粘合膜过程中空隙的产生。二元溶剂沸腾后会产生气泡，如果气泡周围的液体被低挥发性成分和/或高沸点溶剂包围，则为热传递而使气泡增大的驱动力被减小，结果降低了半导体晶圆和粘合膜间的界面温差，从而减少气泡的产生并减少该界面上的间隙。如果用本发明组合物制备的粘合膜被固化，该膜的挥发性空隙小于5％。
丙烯酸聚合物
本发明中优选实施方案中所用丙烯酸聚合物树脂是制备薄膜所需的橡胶组分，可包含羟基、羧基或环氧基，更优选是含有环氧基团的粘合剂聚合物树脂。
丙烯酸聚合物树脂具有易于通过聚合反应单体的选择来控制的玻璃化转变温度或分子量，尤其是具有在侧链上容易引入官能团的优点。用于共聚反应的单体可包括诸如丙烯腈、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸2-乙基己基酯、丙烯酸、(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸甲酯、苯乙烯单体、(甲基)丙烯酸缩水甘油酯、丙烯酸异辛酯、甲基丙烯酸十八烷基酯，等等。
丙烯酸聚合物树脂可按环氧当量、玻璃化转变温度和/或分子量来分类。例如市售的环氧当量大于10,000的产品有SG-80H，而SG-P3系列、SG-800H系列产品的环氧当量小于10,000，它们都是Nagase ChemteX公司的产品。
丙烯酸聚合物树脂优选具有玻璃化转变温度Tg在0～30℃的范围内，以防止在室温下膜变脆，和/或防止半导体制造过程中在切割过程中产生毛边或发生破裂。
在此所用丙烯酸聚合物树脂可含有至少一种可交联的具有1,000～10,000环氧当量的官能团。优选，所述环氧当量的范围为2,000～3,000。若所述环氧当量小于1,000，则难以成膜。另一方面，如果超过10,000，所述官能团可能会出现与环氧或酚的部分的相容性问题，从而导致膜的可靠性降低。
丙烯酸聚合物树脂的分子量在100,000～700,000的范围内。
用于半导体组装的粘合剂组合物中，丙烯酸聚合物树脂含量可为所述组合物总重量的2～50wt％，更优选为2～25wt％。若低于2wt％，就难以成膜。相反，若高于50wt％，膜的可靠性则会变差。
环氧树脂
本发明优选实施方案采用环氧树脂可包含具有高交联密度的环氧树脂，以获得强的固化能力与粘附效果。然而，由于具有高交联密度的单一可固化环氧体系可导致脆性膜，所述环氧树脂包括液状的环氧树脂或具有最小化交联密度的单-和/或双-官能环氧树脂的组合。
由上述发明可知，环氧树脂的当量为100～1,500g/当量，进一步优选为150～800g/当量，更优选为150～400g/当量。当环氧当量小于100g/当量时，固化物显示降低的粘附性。另一方面，当环氧当量大于1500g/当量时，则会出现环氧树脂的玻璃化转变温度降低和/或耐热性变差。此处所用环氧树脂可以包括但不特别限制为，包括具有至少一种官能团的环氧树脂，根据膜的形态其可以是固态或固状的。
环氧树脂的优选实施例可包括双酚型环氧树脂、邻甲酚酚醛清漆型环氧树脂(ortho-cresol novolac type epoxy)、多官能环氧树脂、胺型环氧树脂、杂环环氧树脂、取代环氧树脂和/或萘酚型环氧树脂，等等。市售双酚型环氧树脂的具体例子可包括：大日本油墨化学工业株式会社的Epiclon 830-S、EpiclonEXA-830CRP、Epiclon EXA 850-S、Epiclon EXA-835LV等；Yuka Shell EpoxyCo.，Ltd.的Epicoat 807、Epicoat 815、Epicoat 825、Epicoat 827、Epicoat 828、Epicoat 834、Epicoat 1001、Epicoat 1004、Epicoat 1007、Epicoat 1009等；陶氏化学公司的DER-330、DER-301、DER-361等；国都化学有限公司的YD-128或YDF-179。邻甲酚酚醛清漆型环氧树脂可包括例如：国都化学有限公司的YDCN-500-1P、YDCN-500-4P、YDCN-500-5P、YDCN-500-7P、YDCN-500-80P、YDCN-500-90P等；日本化药株式会社的EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1025、EOCN-1027等。多官能团环氧树脂可包括，例如：Yuka Shell Epoxy Co.，Ltd.的Epon 1031S；汽巴精化有限公司提供的Ara|dite 0163；NAGA Celsius Temperature Co.，Ltd.的DetacholEX-611、Detachol EX-614、Detachol EX-614B、Detachol EX-622、DetacholEX-512、Detachol Ex-521、Detachol Ex-421、Detachol EX-411、DetacholEX-321等。胺型环氧树脂可包括，例如：Yuka Shell Epoxy Co.，Ltd.的Epicoat604；国都化学有限公司的YH-434；三菱瓦斯化学株式会社的TETRAD-X或TETRAD-C；住友化学株式会社的ELM-120。杂环环氧树脂可包括，例如：为：汽巴精化有限公司的PT-810。取代型环氧树脂可包括，例如：联合碳化物公司的ERL-4234、ERL-4299、ERL-4221、ERL-4206等。萘酚型环氧树脂可包括，例如：大日本油墨化学工业株式会社的Epiclon HP-4032、EpiclonHP-4032D、Epiclon HP-4700、Epiclon HP-4701等。这些环氧树脂每个可单独使用，或两种或两种以上组合使用。
所述环氧树脂中可含有至少50wt％的多官能环氧树脂。若多官能环氧树脂的含量少于50wt％，则所述环氧树脂具有低交联密度，从而降低结构内部的键合强度，并导致稳定性问题。
本发明示例性实施方式中环氧树脂的含量可为用于半导体组装的粘合剂组合物总重量的4～50wt％，优选为4～35wt％。当所述含量小于4wt％时，粘合膜缺乏可固化组分，导致可靠性下降。相反地，如果所述含量超过50wt％，粘合膜显示相容性下降。环氧树脂的含量进一步优选为小于35wt％，以减少室温下粘合膜的表面粘性，由此可降低剥离时膜与粘合剂之间的粘附力，从而改进剥离效果。
酚型固化树脂
本发明优选实施方式中所用的酚型固化树脂可包括通常所知的树脂，优选包括双酚A、F和/或S型酚类固化树脂，它们是在单个分子中含有至少两个酚羟基，并具有优异的耐吸潮引起的电解腐蚀性的化合物；或者其他酚型树脂，例如苯酚酚醛清漆树脂(phenol novolac)、双酚A型酚醛树脂或甲酚酚醛树脂、聚酚醚型(xylok type)树脂、联苯型树脂等。
酚型固化树脂的优选实例可包括：作为简单酚型固化树脂的Meiwa KaseiCo.，Ltd.的H-1、H-4、HF-1M、HF-3M、HF-4M、HF-45等；作为对二甲苯型树脂的Meiwa Kasei Co.，Ltd.的MEH-78004S、MEF-7800SS、MEH-7800S、MEH-7800M、MEH-7800H、MEH-7800HH、MEH-78003H等；作为联苯型树脂的KOLON Chemical Co.，Ltd.的KPH-F3065，Meiwa Kasei Co.，Ltd.的MEH-7851SS、MEH-7851S、MEH-7851M、MEH-7851H、MEH-78513H、MEH-78514H等；作为三苯甲基型树脂的KOLON Chemical Co.，Ltd.的KPH-F4500，Meiwa Kasei Co.，Ltd.的MEH-7500、MEH-75003S、MEH-7500SS、MEH-7500H等。这些树脂每个可单独使用，或其中两种或更多种组合使用。
酚型固化树脂优选为由通式1表示：
通式1
Figure G2008101789194D00091
其中，R1和R2的每一个独立地为碳原子数为1到4的烷基或氢原子；a和b每一个独立地为0到4的整数；n为0到7的整数。
通式1所示的酚型固化树脂可以是在单个分子内含有至少两个羟基的化合物，并具有优异的耐吸潮电腐蚀性、极好的耐热性，以及低吸湿性，从而显示优异的耐回流性(reflow resistance)。
通式1所示的酚型固化树脂优选具有100～600g/当量，更优选为170～300g/当量的羟基当量。当羟基当量小于100g/当量时，树脂的吸湿性增加，从而使耐回流性变差。另一方面，如果羟基当量大于600g/当量，树脂的玻璃化转变温度降低，耐热性倾向于变差。
酚型固化树脂优选含有至少50wt％的苯酚酚醛清漆树脂，这样固化后固化树脂具有增加的交联密度以增加分子间的凝聚力，因而增强内部结合强度，从而提高组合物的粘附性。此外，含有至少50wt％苯酚酚醛清漆树脂的固化树脂显示出由于外部应力引起的最小限度的形变，因此具有保持膜厚恒定的优点。
根据本发明的示例性实施方式，在此所用的酚型固化树脂可以以用于半导体组装的粘合剂组合物总重量的3～50wt％，优选3～30wt％的量添加。
固化催化剂
本发明优选实施方案中所用固化催化剂是控制固化速率的添加剂，可包括膦类或硼类固化催化剂和咪唑类催化剂。
在此所用膦类催化剂可包括，例如：三苯基膦、三-邻-甲苯基膦、三-间-甲苯基膦、三-对-甲苯基膦、三-2，4-二甲苯基膦、三-2，5-二甲苯基膦、三-3，5-二甲苯基膦、三苯基膦、三(对-甲氧基苯基)膦、三(对-叔丁氧基苯基)膦、二苯基环己基膦、三环己基膦、三环丙基膦、三丁基膦、三-叔丁基膦、三正辛基膦、二苯基对苯乙烯基膦(diphenylphosphinostyrene)、二苯基氯化膦、三正辛基氧化膦、二苯基氢醌氧化膦(diphenylphosphinyl hydroquinone)、四丁基氢氧化膦、四丁基膦醋酸盐、苄基三苯基膦六氟锑酸盐、四苯基膦四苯基硼酸盐、四苯基膦四对甲苯基硼酸盐、苄基三苯基膦四苯基硼酸盐、四苯基膦四氟硼酸盐、对甲苯基三苯基膦四对甲苯基硼酸盐、三苯膦三苯基硼烷、1，2-双(二苯基膦基)乙烷、1，3-双(二苯基膦基)丙烷、1，4-双(二苯基膦基)丁烷、1，5-双(二苯基膦基)戊烷等。在此所用的硼类固化催化剂可包括，例如：苯硼酸、4-甲基苯硼酸、4-甲氧基苯硼酸、4-三氟代甲氧基苯硼酸、4-叔丁氧基苯硼酸、3-氟4-甲氧基苯硼酸、吡啶三苯基硼、四苯硼化(2-乙基-4-甲基)咪唑、1，8-二氮杂二环[5.4.0]十一碳烯-7-四苯基硼酸盐、1，5-二氮杂二环[4.3.0]壬烯-5-四苯基硼酸盐、三苯基正丁基硼酸锂等。在此所用的咪唑类固化催化剂可包括，例如：2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-苯基咪唑、1，2-二甲基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-十一烷基咪唑、1-氰乙基-2-苯基咪唑、1-氰乙基-2-十一烷基咪唑基-偏苯三酸酯、1-氰乙基-2-苯基咪唑-偏苯三酸酯、2，4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪、2，4-二氨基-6-[2’-十一烷基咪唑基--(1’)]-乙基-s-三嗪、2，4-二氨基-6-[2’-甲基咪唑--(1’)]-乙基-s-三嗪异氰尿酸加成物脱水物(adduct dehydrate)、2-苯基咪唑异氰尿酸加成物、2-甲基咪唑异氰尿酸加成物脱水物、2-苯基-4，5-二羟甲基咪唑、2-苯基-4-甲基-5-羟甲基咪唑、2，3-二氢-1H-吡咯并[1，2-a]苯并咪唑、4，4’-亚甲基双(2-乙基-5-甲基咪唑)、2-甲基咪唑啉、2-苯基咪唑啉、2，4-二氨基-6-乙烯基-1，3，5-三嗪、2，4-二氨基-6-乙烯基-1，3，5-三嗪三异氰尿酸加成物、2，4-二氨基-6-甲基丙烯酰氧乙基-1，3，5-三嗪三异氰尿酸加成物、1-(2-氰基乙基)-2-乙基-4-甲基咪唑、1-氰基乙基-2-甲基咪唑、1-(2-氰基乙基)-2-苯基-4，5-二-(氰基乙氧基甲基)咪唑、1-乙酰-2-苯肼、2-乙基-4-甲基咪唑啉、2-苄基-4-甲基二咪唑啉、2-乙基咪唑啉、2-苯基咪唑、2-苯基-4，5-二羟甲基咪唑、三聚氰胺、二聚氨基氰等。这些催化剂每个可单独使用，或其两种或更多种组合使用。
示例性实施方式中所用固化催化剂可为至少一种选自通式2和3所表示化合物。
通式2
Figure G2008101789194D00111
其中，R1到R8的每一个独立地为氢原子、卤素原子或烷基。
通式3
Figure G2008101789194D00112
与胺类固化剂或咪唑固化催化剂相比，由通式2或3表示的固化催化剂引发固化反应的温度更高，这有利于得到一致的固化速率，并且在室温下反应性较低，由此顺利地保证良好的储存效果。使用胺类固化剂和/或咪唑类固化催化剂，由通式1表示的酚型树脂若在室温下长期储存后会部分固化，从而可能具有不规律的固化性能。结果在半导体组装期间可能容易出现空隙和/或粘结强度降低。
然而，将通式2或3表示的固化催化剂加入通式1表示的酚型树脂中，可防止室温下固化反应的发生，从而可减少因不规律的固化性能而导致半导体组装失败。
此外，与含有胺类固化剂或咪唑类固化催化剂相比，含有上述固化催化剂的半导体组装用粘合剂组合物具有相对较低的电导率，从而在加压蒸煮测试(Pressure Cooker Test，PCT)中具有优异的可靠性。
固化催化剂的添加量为半导体组装用粘合剂组合物总重量的0.01～10wt％。固化催化剂的添加量进一步优选为半导体组装用粘合剂组合物总重量的0.01～2wt％。如果固化剂催化剂含量超过10wt％，组合物的储存稳定性可能会降低。
硅烷偶联剂
在本发明优选实施方案中，组合物中所添加的硅烷偶联剂是一种粘附力增强剂，用于提高诸如硅等无机材料表面与粘合膜中树脂间的粘附力，可以是相关技术领域常用的任意硅烷偶联剂，但不限于此。在此所用的硅烷偶联剂可包括含硅烷的环氧基团，或含硅烷的巯基。含硅烷的环氧基团优选实例为2-(3，4-环氧环己基)乙基三甲氧基硅烷、3-缩水甘油醚氧三甲氧基硅烷和/或3-缩水甘油醚氧丙基三乙氧基硅烷。含硅烷的氨基优选实例为N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷、N-(2-氨基乙基)-3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-三乙氧基硅烷基-(1，3-二甲基亚丁基)丙胺和N-苯基-3-氨基丙基三甲氧基硅烷。含硅烷的巯基优选实例为3-巯基丙基甲基二甲氧基硅烷和3-巯基丙基三乙氧基硅烷。含有硅烷的异氰酸酯优选实例为3-异氰酸酯丙基三乙氧基硅烷。这些硅烷偶联剂的每一个可单独使用，或其两种或更多种组合使用。
硅烷偶联剂的添加量为半导体组装用粘合剂组合物总重量的0.01～10wt％。
填料
根据本发明优选实施方案的组合物可进一步包括任意所需的填料，以使该组合物具有触变性，从而具有可控的熔融粘度。该填料可任选地包括无机或有机填料。无机填料可包括金属组分如粉末状的金、银、铜和/或镍，以及无机组分如矾土、氢氧化铝、氢氧化镁、碳酸钙、碳酸镁、硅酸钙、硅酸镁、氧化钙、氧化镁、氧化铝、氮化铝、二氧化硅、氮化硼、二氧化钛、玻璃、铁酸盐、陶瓷等。有机填料可包括碳、橡胶填料、聚合物类填料等。填料的形状或尺寸没有特别限制，必要时可具有疏水性的球状表面。
在此作为填料的球状二氧化硅颗粒优选粒径为500nm～10μm。粒径大于10μm的无机填料可能与半导体电路不相容，从而导致电路的损坏。
本发明优选实施方案中加入用于半导体组装的粘合剂组合物中的填料量可以为组合物总重量的0.1～50wt％。本发明中用于半导体组装的粘合膜主要用作芯片粘合膜，此时填料的含量优选为10～40wt％。若超过50wt％，则难以形成粘合膜，从而导致膜的抗张强度的降低。
本发明的另一方面是提供了一种用上述组合物制得的用于半导体组装的粘合膜，其中所含溶剂残留量小于2％。
该粘合膜可在80～120℃干燥10～60分钟，但本发明对此没有特别限制。
优选调节干燥温度或时间以使得组合物中残余的低沸点溶剂得以去除，同时高沸点溶剂含量可控制在低于2％。
该粘合膜在120～150℃固化1～10小时。
更具体的是该固化可采用组合工艺，包括在120～130℃使粘合膜进行第一固化1～3小时，然后在130～150℃使第一固化的粘合膜进行第二固化10～60分钟。该组合工艺可重复1次到约8次。根据该组合固化工艺，由溶剂残留引起的挥发性的发泡程度可被限制。
考虑到组合物中残留溶剂的种类和含量及组合物的其他物理性能，可通过该组合固化工艺来控制残留溶剂挥发的可能性。
若使粘合膜内残留溶剂中仅有的高沸点溶剂组分含量最小化，可显著降低可能出现在芯片粘贴(die-attaching)工艺中由挥发性组分引起的空隙，也可减小该工艺中所产生气泡的体积膨胀。
更具体地，如果只使用沸点低于固化温度125℃的溶剂，则会在固化过程中出现由溶剂残留引起的挥发性空隙。若采用沸点至少为200℃的溶剂，膜内溶剂残留为2％或更高，这可能导致在EMC封胶(molding)或膜层可靠性评估时的体积膨胀，从而使膜的可靠性降低。
组合物中低沸点溶剂和高沸点溶剂优选的构成比例和/或含量已在以上公开的实施方式中给出。具有理想含量的高沸点溶剂可抑制半导体晶圆与粘合膜界面上产生的间隙和/或空隙的体积膨胀，由此可使空隙最小化，并同时可抑制在引线填充期间引起的间隙和/或空隙的体积膨胀，从而制成具有高可靠性的用于半导体组装的粘合膜。此外，该组合物可有效降低固化前粘合膜的脆性，从而可防止切割或贴晶时膜碎片引起的污染，并具有使膜易于处理的优点。
粘合膜中溶剂残留量大于0wt％且小于约2wt％。因而粘合膜可含有固体膜部分含量至少为98％。如果固体膜部分含量低于98％，则粘合膜的可靠性会因残留溶剂的发泡或吸潮性能而降低。
该粘合膜可具有伸长率为150～400％。
该粘合膜25℃时的储能模量为0.1～10MPa，80℃时为0.01～0.10MPa，25℃时的熔融粘度在1,000,000～5,000,000P范围内，并具有小于0.1gf的表面粘着值(surface tacking value)。由于粘合膜内的残留溶剂不影响组合物的粘度或表面粘着性能，因此对半导体组装所要求的粘合膜的物理性能影响很小。也就是说，固化前粘合剂的储能弹性模量、流动性和/或表面粘着性能将保持恒定，不会因高沸点溶剂的存在而发生变化。因此，高沸点溶剂不会影响粘合膜的室温储存性。
由于与使用低沸点溶剂形成的粘合膜相比，本发明优选实施方案中的粘合膜在125～175℃具有较小的挥发速度和挥发量，因此该粘合膜具有柔性结构以防止膜的脆性，并具有防止产生空隙的效果，从而使得半导体组装中所产生的层压空隙最小化到小于5％。因而，根据本发明优选实施方案的粘合膜抑制粘合膜可靠性的下降。
在本发明再一方面中，提供一种包含根据本发明优选实施方案的用于半导体组装的粘合膜的切割芯片粘接膜(dicing die-bongding)。切割芯片粘接膜包括基膜、和依次层压到基膜上粘合层和粘贴膜层(attachment film layer)。在此粘贴膜层主要由根据本发明优选实施方案制得的粘合膜形成。
切割芯片粘接膜中的粘合层可用任何常规的粘合剂组合物形成，优选包括100重量份(wt份)的聚合物粘结剂，相对于所述聚合物粘结剂重量20～150重量份的紫外固化丙烯酸酯，相对于所述紫外固化丙烯酸酯重量0.1～5重量份的光引发剂。
切割芯片粘接膜的基膜具有透射性(或射线可透性)，若使用基于紫外照射反应的辐射固化型粘结剂，可用至少一种选自具有有利的透光性的聚合材料来制备。这样的聚合材料可包括，例如：聚烯烃均聚物或共聚物，如聚乙烯、聚丙烯、丙烯乙烯共聚物、乙烯与丙烯酸乙酯的共聚物、乙烯与丙烯酸甲酯的共聚物、乙烯与乙酸乙烯酯的共聚物等；聚碳酸酯；聚甲基丙烯酸甲酯；聚氯乙烯；聚氨酯共聚物，等等。考虑到抗张强度、延展性、射线可透性等性质，基膜的厚度优选为50～200μm。
通过以下具体实施例对所公开的实施方式进行更详细的说明。但这些实施例仅用于说明的目的，而不解释为对本发明范围的限制。
实施例1和2，对比例1～5
将下述组分加入到装有高速搅拌器的1L的圆柱形瓶子中，然后将混合物先在3000rpm下低速搅拌20分钟，再在4000rpm下高速搅拌5分钟以制备组合物。然后用孔径50μm的过滤膜将组合物过滤，通过涂覆器将组合法涂布到基膜上以制成厚度为60μm的粘合膜。所制备的膜在80℃干燥20分钟、再在90℃干燥20分钟后，制备完成的膜在室温下储存一天。
实施例1
a)高沸点溶剂：丙二醇单甲醚醋酸酯(PGMEA)，b.p.145℃，Sam Chun PureCo.，Ltd.生产，252g；低沸点溶剂：环己酮，b.p.80℃，Sam Chun Pure Co.，Ltd.生产，108g；
b)含环氧的丙烯酸聚合物树脂：KLS-104a(EEW＝2,000～3,000)，FujikuraKasei Co.，Ltd.生产，220g；
c)多官能环氧树脂：EP-5100R，国都化学有限公司生产，80g；
d)苯酚酚醛清漆固化树脂：DL-92，Meiwa Plastic Industries，Ltd.生产，60g；
e)膦类固化催化剂：TPP-K，TPP或TPP-MK，Meiwa Plastic Industries，Ltd.生产，3.8g；
f)环氧硅烷偶联剂：KBM-303，Shin-Etsu Chemical Co.，Ltd.生产，2.2g；和
g)球状二氧化硅：SC-4500SQ，SC-2500SQ，Admatechs Co.，Ltd.生产，70g。
实施例2
a)高沸点溶剂：丙二醇单甲醚醋酸酯(PGMEA)，Sam Chun Pure Co.，Ltd.生产，252g；低沸点溶剂：环己酮，Sam Chun Pure Co.，Ltd.生产，108g；
b)含环氧的丙烯酸聚合物树脂：KLS-104a，Fujikura Kasei Co.，Ltd.生产，220g；
c)多官能环氧树脂：EP-5100R，国都化学有限公司生产，60g；双酚F型环氧树脂：YDF 2001，国都化学有限公司生产，20g；
d)苯酚酚醛清漆固化树脂：DL-92，Meiwa Plastic Industries，Ltd.，60g；
e)膦类固化催化剂：TPP-K，TPP或TPP-MK，Meiwa Plastic Industries，Ltd.生产，3.8g；
f)环氧硅烷偶联剂：KBM-303，Shin-Etsu Chemical Co.，Ltd.生产，2.2g；和
g)球状二氧化硅：SC-4500SQ，SC-2500SQ，Admatechs Co.，Ltd.生产，70g。
对比例1对由含有60％二元溶剂的组合物所制成的粘合膜进行了研究。对比例2和3研究了二元溶剂构成比例对粘合膜耐久性的影响和残留溶剂对粘合膜性能的影响。尤其是在只采用高沸点溶剂的对比例2中测定了固体部分和空隙条件，并关于粘合膜的可靠性和稳定性与实施例1和2的那些测定结果相比较。对比例3只采用了低沸点溶剂，未使用高沸点溶剂。对比例3中，测定了最小的挥发残留，并对使用低沸点溶剂组合体系的粘合膜的表面状况进行了观察。对比例4采用了包括沸点为40～100℃的低沸点溶剂和沸点为120～140℃的中沸点溶剂的二元溶剂，未使用高沸点溶剂。将对比例4测定的挥发性间隙或空隙和/或空隙膨胀与实施例1和2进行比较。最后，对比例5采用了三组分溶剂体系(即三元溶剂)，其中包括三种不同沸点范围的三种溶剂。在对比例5中，对膜的表面状况和空隙变化量进行了观察。
对比例1
a)高沸点溶剂：丙二醇单甲基醚醋酸酯(PGMEA)，Sam Chun Pure Co.，Ltd.生产，504g；低沸点溶剂：环己酮，Sam Chun Pure Co.，Ltd.生产，216g；
b)含环氧的丙烯酸聚合物树脂：KLS-104a，Fujikura Kasei Co.，Ltd.生产，220g；
c)多官能环氧树脂：EP-5100R，国都化学有限公司生产，60g；双酚F型环氧树脂：YDF-2001，国都化学有限公司生产，20g；
d)苯酚酚醛清漆固化树脂：DL-92，Meiwa Plastic Industries，Ltd.生产，60g；
e)膦类固化催化剂：TPP-K，TPP或TPP-MK，Meiwa Plastic Industries，Ltd.生产，3.8g；
f)环氧硅烷偶联剂：KBM-303，Shin-Etsu Chemical Co.，Ltd.生产，2.2g；和
g)球状二氧化硅：SC-4500SQ，SC-2500SQ，Admatechs Co.，Ltd.生产，70g。
对比例2
a)高沸点溶剂：丙二醇单甲基醚醋酸酯(PGMEA)，Sam Chun Pure Co.，Ltd.生产，360g；
b)含环氧的丙烯酸聚合物树脂：KLS-104a(EEW＝2,000～3,000)，FujikuraKasei Co.，Ltd.生产，220g；
c)多官能环氧树脂：EP-5100R，国都化学有限公司生产，60g；双酚F型环氧树脂：YDF 2001，国都化学有限公司生产，20g；
d)苯酚酚醛清漆固化树脂：DL-92，Meiwa Plastic Industries，Ltd.生产，60g；
e)膦类固化催化剂：TPP-K，TPP或TPP-MK，Meiwa Plastic Industries，Ltd.生产，3.8g；
f)环氧硅烷偶联剂：KBM-303，Shin-Etsu Chemical Co.，Ltd.生产，2.2g；和
g)球状二氧化硅：SC-4500SQ，SC-2500SQ，Admatechs Co.，Ltd.生产，70g。
对比例3
a)低沸点溶剂：丁酮(MEK)，Sam Chun Pure Co.，Ltd.生产，252g；低沸点溶剂：环己酮，Sam Chun Pure Co.，Ltd.生产，108g；
b)含环氧的丙烯酸聚合物树脂：KLS-104a(EEW＝2,000～3,000)，FujikuraKasei Co.，Ltd.生产，220g；
c)多官能环氧树脂：EP-5100R，国都化学有限公司生产，60g；双酚F型环氧树脂：YDF-2001，国都化学有限公司生产，20g；
d)苯酚酚醛清漆固化树脂：DL-92，Meiwa Plastic Industries，Ltd.生产，60g；
e)膦类固化催化剂：TPP-K，TPP或TPP-MK，Meiwa Plastic Industries，Ltd.生产，3.8g；
f)环氧硅烷偶联剂：KBM-303，Shin-Etsu Chemical Co.，Ltd.生产，2.2g；和
g)球状二氧化硅：SC-4500SQ，SC-2500SQ，Admatechs Co.，Ltd.生产，70g。
对比例4
a)中沸点溶剂：甲基异丁基酮(MIBK)，Sam Chun Pure Co.，Ltd.生产，252g；低沸点溶剂：环己酮，Sam Chun Pure Co.，Ltd.生产，108g；
b)含环氧的丙烯酸聚合物树脂：KLS-104a(EEW＝2,000～3,000)，FujikuraKasei Co.，Ltd.生产，220g；
c)多官能环氧树脂：EP-5100R，国都化学有限公司生产，60g；双酚F型环氧树脂：YDF-2001，国都化学有限公司生产，20g；
d)苯酚酚醛清漆固化树脂：DL-92，Meiwa Plastic Industries，Ltd.生产，60g；
e)膦类固化催化剂：TPP-K，TPP或TPP-MK，Meiwa Plastic Industries，Ltd.生产，3.8g；
f)环氧硅烷偶联剂：KBM-303，Shin-Etsu Chemical Co.，Ltd.生产，2.2g；和
g)球状二氧化硅：SC-4500SQ，SC-2500SQ，Admatechs Co.，Ltd.生产，70g。
对比例5
a)高沸点溶剂：丙二醇单甲基醚醋酸酯(PGMEA)，Sam Chun Pure Co.，Ltd.生产，30g；中沸点溶剂：甲基异丁基酮(MIBK)，Sam Chun Pure Co.，Ltd.生产，222g；低沸点溶剂：环己酮，Sam Chun Pure Co.，Ltd.生产，108g；
b)含环氧的丙烯酸聚合物树脂：KLS-104a(EEW＝2,000～3,000)，FujikuraKasei Co.，Ltd.生产，220g；
c)多官能环氧树脂：EP-5100R，国都化学有限公司生产，60g；双酚F型环氧树脂：YDF-2001，国都化学有限公司生产，20g；
d)苯酚酚醛清漆固化树脂：DL-92，Meiwa Plastic Industries，Ltd.生产，60g；
e)膦类固化催化剂：TPP-K，TPP或TPP-MK，Meiwa Plastic Industries，Ltd.生产，3.8g；
f)环氧硅烷偶联剂：KBM-303，Shin-Etsu Chemical Co.，Ltd.生产，2.2g；和
g)球状二氧化硅：SC-4500SQ，SC-2500SQ，Admatechs Co.，Ltd.生产，70g。
(1)粘合膜的膜加工性能和表面状况
为测定所述膜的膜加工性能(即膜形成)和表面形态，将组合物在烘箱中于100℃干燥30分钟。观察组合物是否成膜和是否有气泡产生的结果示于表1。
(2)挥发性起泡的测定
为测定125～150℃的挥发性起泡，在60℃下在玻璃板上层压尺寸为18mm×18mm的粘合膜，然后在粘合剂区域外切下层压物。将具有沟槽和图案的尺寸为30mm×30mm的PCB衬底置于100℃的热板上，再将所制备具有粘合剂部分的晶圆片以1.0kgf的力压到基板上保持1.0秒。用显微镜观察粘贴到基板上的层压物的外观。然后以上过程于125℃保持1小时和150℃保持10分钟分别重复三次。用显微镜观察压层物外观是否有挥发性起泡产生的空间。表2用百分比示出了挥发性起泡比例。膜的表面状况也示于表2中。
(3)间隙和空隙的体积膨胀
为测定间隙和/或空隙在125～175℃的体积膨胀，在60℃下在玻璃板上层压尺寸为18mm×18mm的粘合膜，然后在粘合剂区域外切下层压物。将具有沟槽和图案的尺寸为30mm×30mm的PCB衬底置于100℃的热板上，再将所制备的具有粘合剂部分的晶圆片以1.0kgf的力压到衬底上保持1.0秒(这样间隙和/或空隙的一部分形成在圆片的中部)。用显微镜观察具有间隙和/空隙的衬底上层压物的外观。然后以上过程于125℃保持1小时和于150℃保持10分钟分别重复三次。在将晶片置于175℃两小时后，用显微镜观察空隙和/或空隙的体积膨胀，计算体积膨胀百分比。结果示于表2。
(4)固体部分测定
为测定膜内的溶剂残留量，通过层压制备具有2g重量的每个膜。将膜的重量校正为零，在将膜置于170℃十分钟后，测定膜重量的变化量。测定结果示于表2。
(5)溶剂残留的鉴定
为测定膜内的溶剂残留，0.5g的样品于200℃预处理30分钟。通过GC/MS分析所产生的挥发气体成分来检测溶剂残留成分。所检测出的溶剂残留成分属于低沸点溶剂的记为“低”，中沸点溶剂记为“中”，高沸点溶剂记为“高”。测试结果示于表2。
(6)伸长率：
为测定粘合膜的伸长率，将各膜取样处理成5mm×20mm大小，足以用夹具将两侧夹紧。伸长率通过装有100N负载传感器的UTM仪器来测定，测试结果示于表2。
(7)熔融粘度的测试
为测定各膜的粘度，通过在60℃将四个粘合层一起层压形成粘合膜，并切成直径为25mm、厚度为400～440μm的圆片。在将温度以5℃/min的升温速度从30℃升到130℃期间，测定膜熔融粘度。表3列出了不同温度时的Eta值，尤其包括：固化前的25℃；作为芯片贴装温度的100℃，在该温度下测定流动性；130℃，在该温度下填充引线的不平整部分被测定。
(8)固化前后弹性模量的测定
为测定各膜的弹性模量，通过在60℃将四个粘合层一起层压形成粘合膜，并切成直径为25mm、固化前厚度为400～440μm、固化后为200～300μm的大小。固化完成后，在将温度以4℃/min的升温速度从30℃升到260℃期间，测定弹性模量。测试使用DMA，TA Instruments，型号Q800。
(9)粘附能力的测定
将涂有二氧化物膜的厚度为725μm的晶圆切成5mm×5mm大小。将所得晶圆片在60℃与粘合膜层压，然后切割层压物得到覆有粘合剂的晶圆片。将另一片涂有感光性聚酰亚胺、厚度为725μm、10mm×10mm大小的晶圆置于100℃的热板上，再将第一片晶圆片以1.0kgf的力压到第二片晶圆片上，保持1.0秒。重复这样的压制在125℃保持1小时，再于175℃保持3小时。然后将所处理的晶圆片于85℃、湿度为85％RH下吸潮48小时后，于270℃测定其断裂强度。
(10)储存稳定性测试
将各膜在室温下储存30天后，测试膜层100℃时的熔融粘度及其粘附能力。测试结果示于表3，表中结果是相对初始测量值的变化值。
表1
实施例1和2     对比例1 对比例2 对比例3 对比例4和5    
膜加工性能 ○ × ○ ○ ○
膜表面状况 好 图案沾污 表面粘着 大量气泡 好
表2
实施例1 实施例2 对比例2 对比例3 对比例4 对比例5
挥发性起泡(％)       <5 <5 <5 <5 <15 <10
间隙和/或空隙体积膨胀  1 1 1 1 10 5
固体部分(％)     99.2 99.1 97 99.9 99.4 99.3
残留成分 高 高 高 低 中，高 中，高
伸长率(％) 200 250 500 50 75 100
表3
Figure G2008101789194D00221
表2可清楚说明，采用了高沸点溶剂的实施例1和2产生的发泡间隙(由挥发性物质引起的)小于5％。发泡间隙即使在经过125到175℃的工艺温度变化之后，也未发现有明显的体积膨胀。与实施例1和2相似，只采用低沸点溶剂的对比例3也产生了气泡间隙，且几乎未观察到有体积膨胀。然而，对于只含低沸点溶剂的组合物，在粘合膜表面观察到有大量气泡，从而导致如表面不平整等问题。另一方面，对于对比例4和5，采用的组合物含中沸点和低沸点溶剂而不含高沸点溶剂，或含小于10％的高沸点溶剂，在工艺温度下可观察到挥发性起泡及间隙或间距的较大体积膨胀。可以预见，在EMC封胶中或高温高湿条件下这些结果可能引起由于间隙导致的膜可靠性问题。
对于“无粘附空隙型”且完全填平引线的粘合膜，则其主要特征是确保在半导体组装中有出色的可靠性，尤其是在如实施例1和2所述的芯片-芯片层压结构制造中，对这种粘合膜的要求，重点要注意的是采用高沸点溶剂可降低挥发性空隙的产生并控制空隙和/或间隙的体积膨胀。这与对比例3中所观察到的结果有明显区别，对比例3中有10～15％或更多由于粘合膜的硬表面而产生的间隙，并且其中的粘合膜不是“无粘附空隙型”膜，因此不能用于半导体组装中的引线填充。在主要特征为“无粘附空隙型”膜且完全填平引线的粘合膜中，对比例4和5中的粘合膜因芯片粘贴后中沸点溶剂残留而使得空隙体积膨胀增加了5到10％。体积膨胀的增加可能引起层压间隙，增加高温时的体积膨胀，从而导致粘合膜的可靠性失效。
对比例2说明了由高沸点溶剂引起的挥发性空隙及空隙的体积膨胀，其结果与实施例1和2中的结果相似。但由于粘合膜中溶剂残留量至少为2％，从而具有过高的延展性使得膜的伸长率是实施例1和2的2到3倍，此外，增加的表面粘着性能导致芯片粘贴期间粘合膜与另一个粘贴膜分离中出现问题。
由实施例1和2及对比例2到5得到的粘合膜的物理性能比较示于表3。实施例1和2中的粘合膜具有增强的延展性结构以防止膜被切割，并在改进硬度的同时也有很好的伸长率。这些结果可在表2所示的测定的伸长率中得到验证。“无粘附空隙型”粘合膜通常含有更高含量的可固化组分，及相对大量的填料粒子，从而导致膜的高脆性。然而，本实施例中制备的粘合膜采用高沸点溶剂可消除这样的问题。
如上所述，根据本发明优选实施例的组合物有利于制造高沸点溶剂残留量小于2％的粘合膜，并且所制造的粘合膜可同时满足柔性结构和甚至在提高固化部分含量时也具有增强的抗张强度，从而在不被切割的同时显示改善的硬度。此外，由于可产生间隙的挥发性组分具有高沸点，则半导体组装中由溶剂挥发而产生的间隙可得到显著降低。其结果是在粘合膜表面产生的间隙或空隙的体积膨胀也被降低，从而确保半导体组装的高可靠性。
因此，由实施例1和2得到的具有良好的高温流动性的各粘合膜都是“无粘附空隙型”膜并可完全填平引线，从而可降低在半导体组装中，尤其是在制造芯片-芯片层压结构时由于引线的不平整部分而引起的空隙或间隙，从而确保半导体组装的优异可靠性。
虽然已示出并说明了本发明的若干优选实施方式，但本领域技术人员应理解的是，可以在这些实施方式上进行改变但不背离本发明的原则和精神，本发明的范围由权利要求及其等同物来限定。

Claims (16)

1.一种用于在半导体组装中用的粘合膜的组合物，包括粘结剂组分、可固化组分和溶剂，其中所述溶剂是二元溶剂，包括沸点在40～100℃范围内的低沸点溶剂和另一种沸点在140～200℃范围内的高沸点溶剂；
所述粘结剂组分包括从丙烯酸聚合物、含NCO聚合物和/或含环氧基团的聚合物中选择的至少一种；可固化组分包括从环氧树脂、酚型固化树脂、聚氨酯树脂、硅树脂、聚酯树脂、胺类固化树脂、三聚氰胺固化树脂、脲固化树脂和酸酐类固化树脂中选择的至少一种；
所述低沸点溶剂与所述高沸点溶剂的重量比为：所述高沸点溶剂的含量相对于100重量份所述低沸点溶剂为70～400重量份。
2.根据权利要求1所述的组合物，其中所述组合物包括丙烯酸聚合物、环氧树脂、酚型固化树脂、固化催化剂、硅烷偶联剂、填料和二元溶剂。
3.根据权利要求1所述的组合物，其中所述低沸点溶剂是从由丙酮、丁酮、四氢呋喃、二甲基甲酰胺和环己烷所构成的组中选择的至少一种溶剂。
4.根据权利要求1所述的组合物，其中所述高沸点溶剂是从丙二醇单甲醚醋酸酯和环己酮中选择的至少一种溶剂。
5.根据权利要求2所述的组合物，其中所述组合物包括：2～50wt％的丙烯酸聚合物；4～50wt％的环氧树脂；3～50wt％的酚型固化树脂；0.01～10wt％的固化催化剂；0.01～10wt％的硅烷偶联剂；0.1～50wt％的填料；40～60wt％的二元溶剂。
6.根据权利要求2所述的组合物，其中所述丙烯酸聚合物含有至少一种环氧当量在1,000～10,000范围内的可交联的环氧基团。
7.根据权利要求2所述的组合物，其中所述丙烯酸聚合物的重均分子量在100,000～700,000的范围内。
8.根据权利要求2所述的组合物，其中所述环氧树脂含有至少50wt％的多官能团环氧基团。
9.根据权利要求2所述的组合物，其中所述酚型固化树脂含有至少50wt％的苯酚酚醛清漆树脂。
10.一种由权利要求1～9任一项所述的组合物制造的半导体组装用粘合膜，其中含有含量小于2wt％的溶剂残留。
11.根据权利要求10所述的粘合膜，其中所述粘合膜在120～150℃固化1～10小时。
12.根据权利要求10所述的粘合膜，其中所述粘合膜具有在150～400％范围内的伸长率。
13.根据权利要求10所述的粘合膜，其中所述粘合膜在25℃时具有0.1～10MPa的储能弹性模量，及在80℃时具有0.01～0.10MPa的另一个储能弹性模量。
14.根据权利要求10所述的粘合膜，其中所述粘合膜在25℃时具有在1,000,000～5,000,000P范围内的熔融粘度，且具有小于0.1gf的表面粘着值。
15.根据权利要求10所述的粘合膜，其中所述粘合膜含有小于5％的挥发性空隙。
16.一种切割芯片粘接膜，包括顺序层压在基膜上的粘合层和根据权利要求10所述粘合膜。
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TW200932858A (en) 2009-08-01

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