CN103184014A - 用于半导体的粘附组合物、粘附膜和半导体装置 - Google Patents

用于半导体的粘附组合物、粘附膜和半导体装置 Download PDF

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Publication number
CN103184014A
CN103184014A CN2012105813061A CN201210581306A CN103184014A CN 103184014 A CN103184014 A CN 103184014A CN 2012105813061 A CN2012105813061 A CN 2012105813061A CN 201210581306 A CN201210581306 A CN 201210581306A CN 103184014 A CN103184014 A CN 103184014A
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China
Prior art keywords
adhesive film
semi
curing
conductive adhesive
cured resin
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CN2012105813061A
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English (en)
Inventor
魏京台
金相珍
金哲洙
梁承龙
崔裁源
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Cheil Industries Inc
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Cheil Industries Inc
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Publication of CN103184014A publication Critical patent/CN103184014A/zh
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    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • 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

本发明涉及一种用于半导体的粘附组合物、粘附膜和半导体装置。更具体地，本发明涉及一种粘附组合物，所述粘附组合物利用高粘结特性通过固化率的提高可以允许PCB烘烤工艺和PCB等离子体工艺省略，并且为了减少工艺时间在导线粘结过程中通过应用到在线工艺而部分固化，从而使固化工艺（或半固化或B阶段）省略或减少。对于本发明的粘附组合物，将酚醛树脂和胺固化树脂共同用作固化剂以允许固化工艺的省略或减少，并且将咪唑固化剂或微胶囊型潜在固化剂用作固化剂以提高固化率。

Description

用于半导体的粘附组合物、粘附膜和半导体装置
技术领域
本发明涉及一种用于半导体的粘附组合物和包含该组合物的粘附膜。更具体地，本发明涉及一种粘附组合物，所述粘附组合物利用高粘结特性通过固化率的提高可以使PCB烘烤工艺和PCB等离子体工艺省略，并且为了减少工艺时间在导线粘结过程中通过应用到在线工艺而部分固化，从而允许固化工艺（或半固化或B阶段）省略或减少。对于本发明的粘附组合物，将酚醛树脂和胺固化树脂共同用作固化剂以允许固化工艺的省略或减少，并且将咪唑固化剂或微胶囊型潜在固化剂用作固化剂以提高固化率。 
背景技术
半导体装置的高容量在质量方面可以通过电路集成实现，其中每单位面积原电池的数量得到增加，或者在数量方面可以通过封装实现，其中芯片一个堆叠在另一个之上。 
在封装技术中，通常使用多芯片封装（下文中“MCP”），其中多个芯片通过粘合剂一个堆叠在另一个之上并且通过导线粘结彼此电连接。 
为确保芯片粘结工艺中芯片和印刷电路板（PCB）之间足够的粘结力，进行了PCB烘烤和PCB等离子体工艺。此外，芯片在120℃粘结数秒后，必须进行固化工艺（或半固化或B阶段）以确保导线粘结时足够的粘结力。然后，在150℃导线粘结2至20分钟后，产物经EMC（环氧模制固化）模制，然后在175℃模制后固化（PMC）2小时。 
PCB烘烤工艺、PCB等离子体工艺、后固化工艺（或半固化或B阶段工艺）和模制后固化工艺都为单独的工艺，上述工艺使减少时间和工人的数目变难，从而降低了生产率。 
因此，为了在半导体制造中提高生产率，对于在线工艺的需求不断增长，在该工艺中PCB在轨道上转移的同时连续进行芯片粘结和导线粘结。因此，需要开发可以应用于在线工艺的用于半导体的新型粘结膜的。尤其是，在在线工艺中，由于使粘结层 形成充分交联结构的热步骤显著减少，因此需要一种即使在固化工艺（或半固化或B阶段工艺）和/或PMC工艺省略或者固化工艺时间减小的条件下也能允许快速固化的组合物，以便在导线粘结过程中不会发生粘结失败、芯片分离和可靠性劣化。 
韩国专利申请第2010-0075212号和第2010-0067915号公开了粘附组合物，该组合物包括热塑性树脂、环氧树脂、酚醛环氧树脂固化剂、固化促进剂、偶联剂和填料。然而，这些粘附组合物仅使用酚醛固化树脂作为固化剂，且固化过程进展缓慢，因此这些粘附组合物不适于本发明的工艺，本发明中省略了固化工艺（或半固化或B阶段工艺）和/或PMC工艺。 
发明内容
本发明的一个方面为提供一种粘附膜，所述粘附膜仅通过芯片粘结工艺呈现出足够的粘附强度以允许PCB烘烤工艺和PCB等离子体工艺省略。 
本发明的另一个方面为提供一种用于半导体的粘附组合物和包含该组合物的粘附膜，所述组合物即使在芯片粘结后的固化工艺（或半固化或B阶段工艺）省略或减小的情况下仍呈现出足够的粘附强度和弹性以应用于在线工艺。 
本发明的再一个方面为提供一种用于半导体的粘附组合物和包含该组合物的粘附膜，所述组合物允许PMC工艺（在175℃进行2小时）的省略。 
本发明的一个方面提供了一种粘附膜，所述粘附膜在120℃通过芯片粘结5秒具有4kgf/芯片或更高的晶片剪切强度，并在150℃固化20分钟后在150℃具有2×106达因/cm2或更高的储能模量。 
本发明的另一个方面提供了一种粘附膜，所述粘附膜包含热塑性树脂、环氧树脂、酚醛固化树脂、胺固化树脂和固化促进剂，并且在120℃通过芯片粘结5秒具有4kgf/芯片或更高的晶片剪切强度。 
本发明的再一个方面提供了一种粘附组合物，基于100重量份的所述粘附组合物，所述粘附组合物按照固含量包含（a）51至80重量份的热塑性树脂，（b）5至20重量份的环氧树脂，（c）2至10重量份的酚醛固化树脂，（d）2至10重量份的胺固化树脂和（e）0.1至10重量份的固化促进剂。 
根据本发明的用于半导体的粘附组合物仅通过芯片粘结工艺就呈现出足够的粘结力，从而使PCB烘烤工艺和PCB等离子体工艺省略。 
此外，根据本发明的用于半导体的粘附组合物允许芯片粘结后的固化工艺（或半固化或B阶段工艺）和/或PMC工艺的省略或减少，从而提高了制造效率和生产率。 
进一步，即使省略了芯片粘结后的固化工艺和/或PMC工艺，根据本发明的粘附组合物仍然满足粘结相同种类半导体芯片所需的可加工性和可靠性。 
具体实施方式
现将详细说明本发明的实施方式。应该理解提供以下实施方式仅用于说明的目的，并非以任何方式解释为限制本发明的范围。 
在一个方面，本发明涉及一种用于半导体的粘附膜，所述膜在120℃通过芯片粘结5秒具有4kgf/芯片或更高的晶片剪切强度，且在150℃固化20分钟后在150℃具有2×106达因/cm2或更高的储能模量。通常，进行PCB烘烤和PCB等离子体工艺以提供芯片粘结工艺中芯片和PCB之间足够的粘结力。在本发明中，考虑到芯片粘结工艺而确定晶片剪切强度。根据本发明的粘附膜仅通过在120℃芯片粘结5秒就具有4kgf/芯片或更高的晶片剪切强度，优选5kgf/芯片或更高，以便通过芯片粘结可以获得足够的粘结力，从而允许PCB烘烤和PCB等离子体工艺的省略。 
可以通过将具有5mm×5mm尺寸并在60℃层压于粘合剂膜上的芯片放置在具有10mm×10mm尺寸530μm厚的晶片上，然后在10kgf的负荷下于120℃在热板上压制芯片5秒钟而测量晶片剪切强度。 
根据本发明的用于半导体的粘附膜在150℃固化20分钟并在175℃模制120秒后，具有10%或更小的空隙面积比，优选7%或更小，更优选5%或更小。为获得该空隙面积比，将芯片（粘合剂＋芯片）（10mm×10mm）在120℃粘附到预处理的PCB在1kgf的负荷下1秒，并在150℃在热板上固化20分钟，然后在175℃进行EMC模制120秒，所述芯片在其一侧具有根据本发明的用于半导体的粘附膜。然后，暴露模制的样品粘附层，并用显微镜（放大率25×）拍照，以通过图像分析检查孔隙的存在。为计算空隙的数目，使用网格计数法。具体地，将整个面积在纵向分成10格并在横向分成10格，计算包含空隙的格子数目并转换成百分比（%）（空隙面积比）。 
空隙面积比=（空隙面积/总面积）×100% 
根据本发明，用于半导体的粘附膜在150℃固化20分钟后在150℃具有2×106达因/cm2或更高的储能模量。该储能模量根据芯片粘结工艺后的导线粘结工艺确定。通常，固化工艺（或半固化或B阶段工艺）必须在120℃至150℃进行约30分钟至1小时，以通过导线粘结提供足够的粘结力。根据本发明，用于半导体的粘附膜在模拟导线粘结工艺（在150℃固化20分钟）后，具有2×106达因/cm2或更高的高储能模量，优选3×106达因/cm2或更高，更优选4×106达因/cm2或更高，以致即使在固化工艺（或 半固化或B阶段工艺）省略或减少时，空隙或可靠性缺陷也不会出现。 
本发明中，通过在60℃堆叠数层粘附膜，将粘附膜的叠层切成具有400至450μm厚度和8mm直径的圆形样品，于150℃在热板上加热样品20分钟，然后用ARES（Advanced Rheometric Expansion System，先进流变扩展系统）在30℃至200℃的温度范围内以10℃/min温度升高的条件下测量，可以测得样品的储能模量。 
根据本发明，粘附膜在150℃加热20分钟并在250℃经红外线（IR）回流3分钟后表征为6kgf/芯片或更高的晶片剪切强度。该条件通过工艺模拟确定，其中焊球粘附（SBA）在导线粘结后未进行PMC（模制后固化）工艺就立即进行。因此，粘附膜在150℃加热20分钟并在250℃经红外线（IR）回流3分钟后具有6kgf/芯片或更高的晶片剪切强度，优选7kgf/芯片或更高，从而使PMC工艺省略。 
根据本发明，如差示扫描量热仪（DSC）所确定，粘附膜具有20%或更小的固化残余比。即，在150℃的热板上加热20分钟并在250℃的峰值温度经IR回流3分钟后产生的热量为固化前热量的20%或更少。 
基于100重量份的粘附膜，根据本发明的粘附膜按照固含量可以包含（a）51至80重量份的热塑性树脂；（b）5至20重量份的环氧树脂；（c）2至10重量份的酚醛固化树脂；（d）2至10重量份的胺固化树脂；和（e）0.1至10重量份的固化促进剂，其中(a):[(b)+(c)+(d)]的重量比可以为51至80重量份:9至40重量份，环氧树脂（b）、酚醛固化树脂（c）和胺固化树脂（d）作为固化体系存在。 
在另一个方面，本发明涉及一种粘附膜，该粘附膜包含热塑性树脂、环氧树脂、酚醛固化树脂、胺固化树脂和固化促进剂，并在120℃通过芯片粘结5秒具有4kgf/芯片或更高的晶片剪切强度。 
在这方面，粘附膜具有小于130℃的固化起始温度，优选小于120℃。固化起始温度可以定义为当以10℃/min的温度上升速率从0℃至300℃扫描粘附膜时放热峰开始出现的温度。 
在这方面，胺固化树脂优选为芳胺固化树脂，更优选由通式1表示的芳胺固化树脂： 
Figure BDA00002667615100041
其中A为单键或选自由-CH2-、-CH2CH2-、-SO2-、-NHCO-、-C(CH3)2-和-O-组成的组中，且R1至R10各自独立地为氢、C1至C4烷基、C1至C4烷氧基和胺基，附带条件为R1至R10包含至少两个胺基。 
在这方面，酚醛固化树脂可以在主链上包含联苯基，优选由通式6表示的酚醛固化树脂： 
Figure BDA00002667615100051
其中R1和R2各自独立地为C1至C6烷基，且n为2至100。 
在这方面，固化促进剂可以包括咪唑或微胶囊型潜在固化剂，优选微胶囊型潜在固化剂。 
咪唑固化促进剂的实例包括2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苯基-2-甲基咪唑、2-乙基咪唑、2-异丙基咪唑、2-苯基-4-苄基咪唑、2-苯基-4,5-二羟甲基咪唑、2-苯基-4-甲基-5-羟甲基咪唑、2-苯基-4-苄基-5-羟甲基咪唑、-4'-亚甲基双-(2-乙基-5-甲基咪唑)、2-氨乙基-2-甲基咪唑和1-氰乙基-2-苯基-4,5-二(氰乙氧基甲基)咪唑，但不限于此。可商购的咪唑固化促进剂的实例包括2MZ、2E4MZ、C11Z、C17Z、2PZ、2PZ-CN、2P4MZ、1B2MZ、2EZ、2IZ、2P4BZ、2PH2-PW、2P4MHZ、2P4BHZ、2E4MZ-BIS、AMZ和2PHZ-CN（Asahi Kasei公司），但不限于此。具体地，2-苯基-4,5-二羟甲基咪唑或2-苯基-4-甲基咪唑可以优选用作咪唑固化促进剂。 
在本发明中，可以使用本领域中已知的任何微胶囊型潜在固化催化剂而无具体限制。例如，微胶囊型潜在固化剂包括韩国专利公开第10-2010-0072030A号中公开的微胶囊型潜在固化剂，其中胶囊芯包含胺加合物和胶囊包含含有异氰酸酯和活性氢基和/或水的化合物的反应产物；韩国专利公开第2011-0100235号公开的微胶囊固化剂，其中胶囊芯包含咪唑化合物，而胶囊壳包含有机聚合物、无机化合物或两者，胶囊壳覆盖于胶囊芯的表面；和韩国专利公开第2008-0040793号中公开的微胶囊潜在固化剂，但不限于此。优选地，可以使用
Figure BDA00002667615100052
HX-3721、HX-3748、HX-3741、HX-3613、HX-3722、HX-3742、HX-3088、HX-3792、HX-3921HP、HX-4921HP、HX-3922HP和HX-3932HP。特别优选地，可以使用HX-3741、HX-3088和HX-3792。 
在另一个方面，本发明涉及一种粘附组合物，基于100重量份的粘附组合物，该组合物按照固含量包含：（a）51至80重量份的热塑性树脂；（b）5至20重量份的环氧树脂；（c）2至10重量份的酚醛固化树脂；（d）2至10重量份的胺固化树脂；和（e）0.1至10重量份的固化促进剂。在这方面，粘附组合物可以进一步包含硅烷偶联剂和/或填料。基于100重量份的粘附组合物，硅烷偶联剂按照固含量可以按0.01至5重量 份的量存在，且填料可以按5至20重量份的量存在。 
接下来，将详细说明用于半导体的粘附组合物的各个组分，如热塑性树脂、环氧树脂、酚醛固化树脂、胺固化树脂和固化促进剂。 
热塑性树脂
适用于粘附组合物的热塑性树脂的实例可以包括聚酰亚胺树脂、聚苯乙烯树脂、聚乙烯树脂、聚酯树脂、聚酰胺树脂、丁二烯橡胶、丙烯橡胶、(甲基)丙烯酸酯树脂、氨基甲酸乙酯树脂、、聚醚酰亚胺树脂、苯氧树脂、聚碳酸酯树脂、聚苯醚树脂、改性的聚苯醚树脂及其混合物，但不限于此。优选地，热塑性树脂可以包含环氧基。在一些实施方式中，含环氧基的(甲基)丙烯酸共聚物可以用作热塑性树脂。 
热塑性树脂可具有-30至80℃的玻璃化转变温度，优选5至60℃，更优选5至35℃。在热塑性树脂的这一范围内，组合物可以确保高流动性以呈现优异的空隙去除能力，并提供高粘附性和可靠性。 
在一些实施方式中，热塑性树脂可以具有50,000至5,000,000g/mol的重均分子量。 
基于100重量份的组合物，热塑性树脂按照固含量可以按51至80重量份的量存在，优选55至75重量份，更优选60至72重量份。当热塑性树脂的量小于51重量份时，就空隙产生和可靠性而言不理想。 
进一步，热塑性树脂（a）与作为固化体系的环氧树脂（b）、酚醛固化剂（c）和胺固化剂（d）的混合物的重量比，即(a):[(b)+(c)+(d)]的重量比，可以为51至80重量份:9至40重量份，优选55至75重量份:15至30重量份。在组合物的这一范围内，可以有利地抑制气泡产生。 
环氧树脂
环氧树脂可以固化并起到赋予组合物粘附性的作用。环氧树脂可以为液体环氧树脂、固体环氧树脂或其混合物。 
合适的液体环氧树脂的实例包括双酚A类液体环氧树脂、双酚F类液体环氧树脂、三或三以上多官能液体环氧树脂、橡胶改性的液体环氧树脂、氨基甲酸乙酯改性的液体环氧树脂、丙烯酸改性的液体环氧树脂和光敏性液体环氧树脂，这些液体环氧树脂可以单独或作为混合物使用。更优选地，使用双酚A类液体环氧树脂。 
液体环氧树脂可以具有约100至约1500g/eq的环氧当量。液体环氧树脂优选具有约150g/eq至约800g/eq的环氧当量，更优选约150g/eq至约400g/eq。在该范围内，在保持了玻璃化转变温度的同时可以获得具有良好的粘附性和耐热性的固化产品。 
液体环氧树脂可以具有100g/mol至1000g/mol的重均分子量。该范围在高流动性方面具有优势。 
固体环氧树脂可以为室温为固态或准固态且具有一个或多个官能团的一种环氧树脂。固体环氧树脂可以具有30至100℃的软化点（SP）。合适的固体环氧树脂的实例包括双酚环氧树脂、苯酚酚醛环氧树脂、邻甲酚酚醛环氧树脂、多官能环氧树脂、胺环氧树脂、杂环环氧树脂、取代的环氧树脂、萘酚类环氧树脂、联苯类环氧树脂及其衍生物。 
作为可商购的固体环氧树脂，双酚环氧树脂的实例包括YD-017H、YD-020、YD020-L、YD-014、YD-014ER、YD-013K、YD-019K、YD-019、YD-017R、YD-017、YD-012、YD-011H、YD-011S、YD-011、YDF-2004、YDF-2001（Kukdo Chemical有限公司）等。苯酚酚醛环氧树脂的实例包括EPIKOTE152和EPIKOTE154(Yuka ShellEpoxy有限公司）；EPPN-201（Nippon Kayaku有限公司）；DN-483（Dow Chemical公司）；YDPN-641、YDPN-638A80、YDPN-638、YDPN-637、YDPN-644、YDPN-631（Kukdo Chemical有限公司）等。邻甲酚酚醛环氧树脂的实例包括：YDCN-500-1P、YDCN-500-2P、YDCN-500-4P、YDCN-500-5P、YDCN-500-7P、YDCN-500-8P、YDCN-500-10P、YDCN-500-80P、YDCN-500-80PCA60、YDCN-500-80PBC60、YDCN-500-90P、YDCN-500-90PA75（Kukdo Chemical有限公司）；EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1025、EOCN-1027（Nippon Kayaku有限公司）；YDCN-701、YDCN-702、YDCN-703、YDCN-704（Tohto Kagaku有限公司）；Epiclon N-665-EXP（Dainippon Ink and Chemicals公司）等。双酚酚醛环氧树脂的实例包括KBPN-110、KBPN-120、KBPN-115（Kukdo Chemical有限公司）等。多官能环氧树脂的实例包括Epon1031S（Yuka Shell Epoxy有限公司）；Araldite0163(CibaSpecialty Chemicals)；Detachol EX-611、Detachol EX-614、Detachol EX-614B、DetacholEX-622、Detachol EX-512、Detachol EX-521、Detachol EX-421、Detachol EX-411、Detachol EX-321（NAGA Celsius Temperature Kasei有限公司）；EP-5200R、KD-1012、EP-5100R、KD-1011、KDT-4400A70、KDT-4400、YH-434L、YH-434、YH-300（KukdoChemical有限公司）等。胺环氧树脂的实例包括EPIKOTE604（Yuka Shell Epoxy有限公司）等；YH-434（Tohto Kagaku有限公司）等；TETRAD-X和TETRAD-C（MitsubishiGas Chemical Company公司）；ELM-120（Sumitomo Chemical Industry有限公司）等。杂环环氧树脂的实例包括PT-810（Ciba Specialty Chemicals）。取代的环氧树脂的实例包括：ERL-4234、ERL-4299、ERL-4221、ERL-4206（UCC有限公司）等。萘酚环氧树脂的实例包括：Epiclon HP-4032、Epiclon HP-4032D、Epiclon HP-4700和Epiclon HP-4701（Dainippon Ink and Chemicals公司）等。非酚醛环氧树脂的实例包括YX-4000H（Japan Epoxy Resin）、YSLV-120TE、GK-3207(Nippon steel chemical)、NC-3000（NipponKayaku）等。这些环氧树脂可以单独或作为混合物使用。 
基于100重量份的组合物，环氧树脂按照固含量可以按5至20重量份的量存在，优选7至15重量份。在该范围内，可以获得高可靠性和优异的机械性质。 
固化剂
适用于粘附组合物的固化剂可以为具有不同反应温度区的两种固化剂。 
在一些实施方式中，固化剂为酚醛固化剂和胺固化剂。 
尽管可以使用本领域中已知的任何酚醛固化剂而无限制，但是可使用在一个分子中包含两个或多个酚醛羟基并通过水解呈现出优异的抗电解腐蚀性的双酚树脂，如双酚A、双酚F、双酚S等；苯酚酚醛树脂；双酚A酚醛树脂；和酚醛树脂，如二甲苯树脂、甲酚酚醛树脂、联苯树脂等。作为可商购的酚醛固化剂，酚醛固化剂的实例包括H-1、H-4、HF-1M、HF-3M、HF-4M和HF-45（Meiwa Plastic Industries有限公司）；对二甲苯酚醛固化剂的实例包括MEH-78004S、MEH-7800SS、MEH-7800S、MEH-7800M、MEH-7800H、MEH-7800HH和MEH-78003H（Meiwa Plastic Industries有限公司），PH-F3065（Kolong Industries有限公司）；联苯固化剂的实例包括MEH-7851SS、MEH-7851S、MEH-7851M、MEH-7851H、MEH-78513H、MEH-78514H（Meiwa Plastic Industries有限公司）和KPH-F4500（Kolong Industries有限公司）；且三苯甲基固化剂的实例包括MEH-7500、MEH-75003S、MEH-7500SS、MEH-7500S、MEH-7500H（Meiwa Plastic Industries有限公司）等。它们可以单独或作为其混合物使用。 
适用于粘附组合物的酚醛固化剂可以具有由通式6表示的结构： 
Figure BDA00002667615100081
其中R1和R2各自独立地为C1至C6烷基，且n的范围为2至100。 
酚醛固化剂的实例包括，但不限于可以从Meiwa Plastic Industries有限公司商购的MEH-7851SS、MEH-7851S、MEH-7851M、MEH-7851H和MEH-78514H。 
基于100重量份的粘附组合物，酚醛固化剂按照固含量可以按2至10重量份的量存在。 
胺固化剂可以为根据固化率调整的芳胺固化剂。优选地，胺固化树脂为在一个分子中具有两个或多个胺基的芳香化合物，但不限于此，例如，由通式1至至5表示。 
Figure BDA00002667615100091
其中A为单键或选自由-CH2-、-CH2CH2-、-SO2-、-NHCO-、-C(CH3)2-和-O-组成的组中，R1至R10各自独立地为氢、C1至C4烷基、C1至C4烷氧基和胺基，附带条件为R1至R10包括至少两个胺基。 
Figure BDA00002667615100092
其中R11至R18包括至少一个或多个胺基，且为C1至C4烷基、烷氧基、羟基、氰基或卤素。 
Figure BDA00002667615100093
其中Z1为氢、C1至C4烷基、烷氧基或羟基；且R19至R33包括至少一个或多个胺基，且为氢、C1至C4烷基、烷氧基、羟基、氰基或卤素。 
Figure BDA00002667615100094
其中R34至R41包括至少一个或多个胺基，且为氢、C1至C4烷基、烷氧基、羟基、 氰基或卤素。 
Figure BDA00002667615100101
其中X3选自由-CH2-、-NH-、-SO2-、-S-和-O-组成的组中；且R42至R49包括至少一个或多个胺基，且为氢、C1至C4烷基、烷氧基、羟基、氰基或卤素。 
通式1的固化剂的实例可包括3,3'-二氨基联苯胺、4,4'-二氨基二苯甲烷、4,4'-或3,3'-二氨基二苯砜、对苯二胺、间苯二胺、间甲苯二胺、4,4'-二氨基二苯醚、4,4'-或3,3'-二氨基苯甲酮、1,4'-或1,3'-双(4-或3-氨基枯基)苯、1,4'-双(4-或3-氨基苯氧基)苯、2,2'-双[4-(4-或3-氨基苯氧基)苯基]丙烷、双[4-(4-或3-氨基苯氧基)苯基]砜、2,2'-双[4-(4-或3-氨基苯氧基)苯基]六氟代砜、2,2'-双[4-(4-或3-氨基苯氧基)苯基]六氟代丙烷、4,4'-二氨基-3,3',5,5'-四丁基二苯酮、4,4'-二氨基-3,3',5,5'-四乙基二苯酮、4,4'-二氨基-3,3',5,5'-四-正丙烯二苯酮、4,4'-二氨基-3,3',5,5'-四异丙基二苯酮、4,4'-二氨基-3,3',5,5'-四甲基二苯酮、4,4'-二氨基-3,3',5,5'-四-正丙基二苯甲烷、4,4'-二氨基-3,3',5,5'-四甲基二苯甲烷、4,4'-二氨基-3,3',5,5'-四异丙基二苯甲烷、4,4'-二氨基-3,3',5,5'-四乙基二苯甲烷、4,4'-二氨基-3,3'-二甲基-5,5'-二乙基二苯甲烷、4,4'-二氨基-3,3'-二甲基-5,5'-二异丙基二苯甲烷、4,4'-二氨基-3,3'-二乙基-5,5'-二乙基二苯甲烷、4,4'-二氨基-3,5'-二甲基-3',5'-二乙基二苯甲烷、4,4'-二氨基-3,5-二甲基-3',5'-二异丙基二苯甲烷、4,4'-二氨基-3,5-二乙基-3',5'-二丁基二苯甲烷、4,4'-二氨基-3,5-二异丙基-3',5'-二丁基二苯甲烷、4,4'-二氨基-3,3'-二异丙基-5,5'-二丁基二苯甲烷、4,4'-二氨基-3,3'-二甲基-5,5'-二丁基二苯甲烷、4,4'-二氨基-3,3'-二乙基-5,5'-二丁基二苯甲烷、4,4'-二氨基-3,3'-二甲基二苯甲烷、4,4'-二氨基-3,3'-二乙基二苯甲烷、4,4'-二氨基-3,3'-二-正丙基二苯甲烷、4,4'-二氨基-3,3'-二异丙基二苯甲烷、4,4'-二氨基-3,3'-二丁基二苯甲烷、4,4'-二氨基-3,3',5-三甲基二苯甲烷、4,4'-二氨基-3,3',5-三乙基二苯甲烷、4,4'-二氨基-3,3',5-三-正丙基二苯甲烷、4,4'-二氨基-3,3',5-三异丙基二苯甲烷、4,4'-二氨基-3,3',5-三丁基二苯甲烷、4,4'-二氨基-3-甲基-3'-乙基二苯甲烷、4,4'-二氨基-3-甲基-3'-异丙基二苯甲烷、4,4'-二氨基-3-甲基-3'-丁基二苯甲烷、4,4'-二氨基-3-异丙基-3'-丁基二苯甲烷、2,2'-双(4-氨基-3,5-二甲苯基)丙烷、2,2'-双(4-氨基-3,5-二乙苯基)丙烷、2,2'-双(4-氨基-3,5-二-正丙苯基)丙烷、2,2'-双(4-氨基-3,5-二 异丙苯基)丙烷、2,2'-双(4-氨基-3,5-二丁苯基)丙烷、4,4'-二氨基-3,3′,5,5'-四甲基二苯基苯酰替苯胺、4,4'-二氨基-3,3',5,5'-四乙基二苯基苯酰替苯胺、4,4'-二氨基-3,3',5,5'-四-正丙基二苯基苯酰替苯胺、4,4'-二氨基-3,3',5,5'-四异丙基二苯基苯酰替苯胺、4,4'-二氨基-3,3',5,5'-四丁基二苯基苯酰替苯胺、4,4'-二氨基-3,3',5,5'-四甲基二苯砜、4,4'-二氨基-3,3',5,5'-四乙基二苯砜、4,4'-二氨基-3,3',5,5'-四-正丙基二苯砜、4,4'-二氨基-3,3',5,5'-四异丙基二苯砜、4,4'-二氨基-3,3',5,5'-四甲基二苯醚、4,4'-二氨基-3,3',5,5'-四乙基二苯醚、4,4'-二氨基-3,3',5,5'-四-正丙基二苯醚、4,4'-二氨基-3,3′,5,5'-四异丙基二苯醚、4,4'-二氨基-3,3',5,5'-四丁基二苯醚、3,4-二氨基苯甲酮、3,3'-二氨基二苯醚、3,3'-二氨基二苯甲烷、3,4'-二氨基二苯甲烷、2,2'-二氨基-1,2-二苯乙烷或4,4'-二氨基-1,2-二苯乙烷、2,4-二氨基二苯胺、4,4'-二氨基八氟代联苯、邻联茴香胺等。 
通式2的固化剂的实例包括1,5-二氨基萘、1,8-二氨基萘、2,3-二氨基萘等。通式3的固化剂的实例包括副品红（paraosaniline）等。通式4的固化剂的实例包括1,2-二氨基蒽醌、1,4-二氨基蒽醌、1,5-二氨基蒽醌、2,6-二氨基蒽醌、1,4-二氨基-2,3-二氯蒽醌、1,4-二氨基-2,3-二氰基-9,10-蒽醌、1,4-二氨基-4,8-二羟基-9,10-蒽醌等。通式5的固化剂的实例包括3,7-二氨基-2,8-二甲基二苯并噻吩砜、2,7-二氨基芴、3,6-二氨基咔唑等。 
基于100重量份的粘附组合物，胺固化树脂按照固含量可以按2至10重量份的量存在。 
固化促进剂
用于半导体的粘附组合物可以包含固化促进剂。适用于根据本发明的组合物的固化促进剂起到了在半导体工艺中减少环氧树脂固化时间的作用。尽管可以使用本领域已知的任何固化促进剂，但是可以使用三聚氰胺、咪唑或微胶囊型潜在固化催化剂和三苯基膦固化催化剂。优选地，使用咪唑或微胶囊型潜在固化剂，特别优选地，使用微胶囊型潜在固化剂。 
适用于根据本发明的组合物的咪唑固化促进剂的实例包括2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苯基-2-甲基咪唑、2-乙基咪唑、2-异丙基咪唑、2-苯基-4-苄基咪唑、2-苯基-4,5-二羟甲基咪唑、2-苯基-4-甲基-5-羟甲基咪唑、2-苯基-4-苄基-5-羟甲基咪唑、4-4'-亚甲基双-(2-乙基-5-甲基咪唑)、2-氨乙基-2-甲基咪唑、1-氰乙基-2-苯基-4,5-二(氰乙氧基甲基)咪唑等。可商购的咪唑固化促进剂包括2MZ、2E4MZ、C11Z、C17Z、2PZ、2PZ-CN、2P4MZ、1B2MZ、2EZ、2IZ、2P4BZ、2PH2-PW、2P4MHZ、2P4BHZ、2E4MZ-BIS、 AMZ和2PHZ-CN（Asahi Kasei公司），但不限于此。具体地，2-苯基-4,5-二羟甲基咪唑或2-苯基-4-甲基咪唑可以优选地用作咪唑固化促进剂。 
适用于根据本发明的组合物的微胶囊型潜在固化剂的实例包括韩国专利公开第10-2010-0072030A号公开的微胶囊型潜在固化剂，其中胶囊芯包含胺加合物和胶囊包括含有异氰酸酯和活性氢基和/或水的化合物的反应产物；韩国专利公开第2011-0100235号公开的微胶囊型固化剂，其中胶囊芯包含咪唑化合物，且胶囊壳包含有机聚合物、无机化合物或两者并覆盖胶囊芯的表面；和韩国专利公开第2008-0040793号中公开的微胶囊潜在固化剂，但不限于此。（应该理解将这些公开的全部内容并入本文以供参考）。优选地，可以使用
Figure BDA00002667615100121
HX-3721、HX-3748、HX-3741、HX-3613、HX-3722、HX-3742、HX-3088、HX-3792、HX-3921HP、HX-4921HP、HX-3922HP和HX-3932HP。特别优选地，可以使用HX-3741、HX-3088和HX-3792。 
膦类固化催化剂的实例包括可从HOKKO Chemical Industry有限公司商购的TBP、TMTP、TPTP、TPAP、TPPO、DPPE、DPPP和DPPB。 
基于100重量份的粘附组合物，固化促进剂可以按0.1至10重量份的量存在，优选0.3至7重量份。在固化促进剂的这一范围内，可以获得高热阻、高流动性和高连接性能，而不会引起环氧树脂的快速反应。 
硅烷偶联剂
用于半导体的粘附组合物可以进一步包括硅烷偶联剂。硅烷偶联剂在组合物的混合过程中起到了粘附促进剂的作用，以通过无机材料表面和有机材料之间的化学耦合增强诸如填料的无机材料表面，和有机材料之间的粘附。 
本领域已知的任何硅烷偶联剂可以用于本发明的组合物，其实例包括：含环氧基的硅烷偶联剂，如2-(3,4-环氧环己基)-乙基三甲氧基硅烷、3-缩水甘油醚氧基三甲氧基硅烷和3-缩水甘油醚氧基丙基三乙氧基硅烷；含胺基的硅烷偶联剂，如N-2-(氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、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、3-三乙氧基甲硅烷基-N-(1,3-二甲基丁烯基)丙胺和N-苯基-3-氨基丙基三甲氧基硅烷；含巯基的硅烷偶联剂，如3-巯丙基甲基二甲氧基硅烷和3-巯丙基三乙氧基硅烷；以及含异氰酸酯的硅烷偶联剂，如3-异氰酸酯丙基三乙氧基硅烷。这些硅烷偶联剂可以单独或作为其混合物使用。 
基于100重量份的粘附组合物，硅烷偶联剂按照固含量可以按0.01至5重量份的量存在，优选0.1至3重量份，更优选0.5至2重量份。在该范围内，可以获得高粘附 可靠性，并且可以减少气泡的产生。 
填料
本发明的组合物可以进一步包含填料。 
适用于本发明的组合物的填料的实例包括：金属粉，如金、银、铜和镍粉；和非金属，如氧化铝、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、氧化铁和陶瓷。优选使用二氧化硅。 
对于填料的形状和尺寸没有具体限制。球形二氧化硅或无定形二氧化硅通常用作填料。二氧化硅的颗粒尺寸可以为5nm～20μm。 
基于100重量份的粘附组合物，填料按照1～30重量份的量存在，优选5至25重量份。在该范围内，可以获得高流动性、高成模性和高粘附。 
溶剂
粘附组合物可以进一步包含溶剂。溶剂起到了降低粘附组合物粘度的作用，从而促进粘附膜的形成。适用于粘附组合物的溶剂的具体实例包括有机溶剂，如甲苯、二甲苯、丙二醇单甲醚乙酸酯、苯、丙酮、甲乙酮、四氢呋喃、二甲基甲酰胺和环己酮，但不限于此。 
本发明的另一个方面涉及一种包含根据本发明的粘附组合物的用于半导体的粘附膜。不需要特别的仪器和设备利用根据本发明的粘附组合物而形成用于半导体的粘附膜，可以使用本领域通常已知的任何方法制造该粘附膜。例如，将各组分溶于溶剂中，并用珠磨机（beads-mill）充分揉捏，然后将产物沉积在经过离型处理的聚对苯二甲酸乙二醇酯（PET）的膜上，并在烘箱中于100℃干燥10至30分钟以制备具有合适厚度的粘附膜。 
在一个实施方式中，用于半导体的粘附膜可以包括基膜、粘附层、粘结层和保护层，它们按该次序顺序堆叠。 
粘附膜优选具有5至200um的厚度，更优选10至100um。在该范围内，粘附膜在提供经济可行性的同时呈现出足够的粘附性。还更优选地，粘附膜具有15至60um的厚度。 
接下来，参考以下实施例，本发明将变得更加清楚，应该理解以下实施例仅是为 说明的目的提供的，而不会限制本发明的范围，本发明的范围仅由权利要求及其等同方式所限定。 
实施例 
实施例1-2：用于半导体的粘附组合物的制备 
将溶剂（环己酮）加到如表1所列的热塑性树脂、环氧树脂、酚醛固化剂、胺固化树脂、固化促进剂、填料和硅烷偶联剂中，以便溶液中的固含量为20wt％，然后用球磨机充分揉捏，从而制备用于半导体的粘附组合物。 
对比例1至3：用于半导体的粘附组合物的制备 
除了表2中列出的一些组分，用与实施例1和2相同的方式制备用于半导体的粘附组合物。 
用于实施例和对比例的各个化合物的说明如下： 
表1 
  实施例1 实施例2 对比例1 对比例2 对比例3
热塑性树脂(1) 70 70 70 70 50
环氧树脂(2) 8 8 8 8 16
环氧树脂(3) 5 5 5 5 10
酚醛固化树脂(4) 4 4   7 8
胺固化树脂(5) 3 3 7   6
硅烷偶联剂(6) 1 1 1 1 1
固化促进剂(7) 0.5   0.5 0.5 0.5
固化促进剂(8)   0.5      
填料(9) 8.5 8.5 8.5 8.5 8.5
总计（重量份） 100 100 100 100 100
（1）热塑性树脂：SG-P3（Nagase Chemtex有限公司） 
（2）环氧树脂：YDCN-500-90P（Kukdo Chemical有限公司） 
（3）环氧树脂：EPPN-502H（Nippon Kayaku有限公司） 
（4）酚醛固化树脂：HF-1M（Eq.：106，Meiwa Chemicals有限公司） 
（5）胺固化树脂：DDM（Tokyo Chemical Industries有限公司） 
（6）硅烷偶联剂：KBM-403（Shinetsu有限公司） 
（7）固化促进剂：2PZ-CN（HOKKO Chemical Industry有限公司） 
（8）固化促进剂：HXA-3792（Asahi有限公司） 
（9）填料：R-972（Degussa GmbH) 
（10）溶剂：环己酮 
粘合剂膜的制备
将实施例1和2及对比例1、2和3中制备的各个粘附组合物用工具沉积于经过离型处理的PET膜上，然后在烘箱中于100℃干燥10至30分钟，从而提供60um厚的粘附膜。 
实验例：用实施例和对比例的粘附组合物制备的粘附膜的物理性质评估 
用以下方法评估用实施例1和2及对比例1、2和3的粘附组合物制备的各个粘附膜的物理性质，结果示于表2中。 
表2 
（1）芯片剪切强度：将530μm厚的晶片切成具有5mm×5mm尺寸的芯片。在60℃将这些芯片与每个粘附膜层压并切割至仅留下接合的部分。将具有5mm×5mm尺寸的上芯片放置在具有10mm×10mm尺寸的晶片上，然后在热板上于120°C施加5秒钟10kgf的力。然后用DAGE4000测量芯片剪切强度，结果示于表2中。 
（2）固化起始温度：从0℃至300℃扫描直至出现放热峰的同时用DSC以10℃/min的温度上升速率测量为固化制得的粘附组合物所产生的热量。 
（3）储能模量：将数层粘附膜在60℃层压，并切割以制备具有8mm直径的圆形样品。样品具有约400至450um的厚度。然后，样品在热板上于150℃加热20分钟，并用ARES在30℃至200℃的温度范围内测量样品的储能模量。在150℃的储能模量示于表2中。此处，温度上升速率为10℃/min。 
（4）回流后的芯片剪切强度：制备用于测量芯片剪切强度（1）的样品后，样 品在热板上于150℃加热20分钟，并在250℃的峰值温度经IR回流3分钟。然后，用Dage4000在260℃测量芯片剪切强度。 
（5）固化残余比：制得的粘附组合物在热板上于150℃加热20分钟，并在250℃的峰值温度经IR回流3分钟。然后，用DSC测量固化过程中产生的热量，并除以用于固化的初始热量以计算固化残余比。在热板上于150℃加热20分钟前，用DSC测量粘附组合物的初始热量。 
（6）模制后的空隙面积比：与放置在贴膜机的加热板上并用异丙醇（IPA）去除异物的抛光晶片一起，将晶片的镜面放置在粘附膜的粘附表面上。此处，贴膜机的温度设置为60℃，这是常规的表面温度。将晶片-粘附膜组件用锯切成10mm×10mm的芯片尺寸，并在120℃和1kgf/l秒时粘附到在表3的条件下经过预处理的PCB上，从而制备每个都在其一侧具有粘合剂的芯片。 
表3 
PCB：62mm单触发PCB
PCB烘烤：在120℃的烘箱中1小时
烘烤后的等离子体处理
然后，将制得的样品在热板上于150℃经过1次固化循环20分钟，并在表4的条件下进行EMC模制，然后测量空隙的比例。. 
表4 
Figure BDA00002667615100161
然后，为了测量模制后的空隙比力，用分割锯将产物分成单个单元，，接着去除PCB并用研磨机研磨直到使粘附膜的粘附层暴露。此处，为便于观察空隙，研磨产物使得PCB的阻焊层部分地保持为半透明的点。 
研磨后，用显微镜（放大率：25×）拍摄暴露的粘附层，并通过图像分析检查空隙的存在。为计算空隙的数目，使用网格计数法。计算孔隙的数目，使用网格计数法。具体地，将样品的整个区域分成10格的行和10格的列，并且计算含孔隙的格子数并转换成%（空隙面积比）。 
空隙面积比=（空隙面积/总面积）×100% 
（7）熔融粘度：将数层粘附膜在60℃层压，并切割以制备具有8mm直径的圆形样品。样品具有约400至450μm的厚度。然后，将样品在热板上于150℃加热20分钟， 用ARES在30至200℃的温度范围内测量熔融粘度。 
如表2所示，可见实施例1和2的粘附组合物仅通过在120℃芯片粘结5秒就具有4kgf/芯片或更高的晶片剪切强度，并且在模拟导线粘结（在150℃固化20分钟）后具有2×106达因/cm2或更高的储能模量，从而仅通过芯片粘结提供了足够的粘附或者使得PCB烘烤和PCB等离子体工艺能够省略。此外，即使在省略或减少固化工艺（或半固化或B阶段工艺）的情况下，也没有空隙的生成和可靠性的劣化。进一步，由于实施例1和2的粘附组合物在150℃加热20分钟并在250℃经IR回流3分钟后，具有6kgf/芯片或更高的晶片剪切强度，因此能够省略PMC工艺。 
相反，对于使用胺固化剂单一固化体系的对比例1的粘附组合物和使用酚醛固化剂单一固化体系的对比例2的粘附组合物来说，通过在150℃不充分加热20分钟，未形成充分的交联结构，并且储能模量低，因而在耐回流性测试中引起破裂。进一步，使用51wt%或更少的热塑性树脂的对比例3的粘附组合物在空隙产生和可靠性方面受到损害。 
尽管已经提供了一些实施方式，但是本领域的技术人员应清楚这些实施方式仅是以说明的方式给出的，并且可以进行各种修改、变更、替换和等效实施方式而不背离本发明的精神和范围。本发明的范围应该仅由所附权利要求及其等效形式所限定。 

Claims (14)

1.一种用于半导体的粘附膜，所述粘附膜在120℃通过芯片粘结5秒具有4kgf/芯片或更高的晶片剪切强度，并在150℃固化20分钟后在150℃具有2×106达因/cm2或更高的储能模量。
2.如权利要求1所述的用于半导体的粘附膜，其中所述粘附膜在150℃加热20分钟并在250℃经红外线回流3分钟后具有6kgf/芯片或更高的晶片剪切强度。
3.如权利要求1所述的用于半导体的粘附膜，其中所述粘附膜在150℃固化20分钟并在175℃模制120秒后具有10%或更小的空隙面积比。
4.如权利要求1所述的用于半导体的粘附膜，其中，基于100重量份的所述粘附膜，按照固含量，所述粘附膜包含：
（a）51至80重量份的热塑性树脂；
（b）5至20重量份的环氧树脂；
（c）2至10重量份的酚醛固化树脂；
（d）2至10重量份的胺固化树脂；和
（e）0.1至10重量份的固化促进剂。
5.如权利要求4所述的用于半导体的粘附膜，其中(a)与(b)+(c)+(d)的重量比为51至80重量份:9至40重量份，所述环氧树脂（b）、所述酚醛固化树脂（c）和所述胺固化树脂（d）作为固化体系存在。
6.一种用于半导体的粘附膜，所述粘附膜包含热塑性树脂、环氧树脂、酚醛固化树脂、胺固化树脂和固化促进剂，其中所述粘附膜在120℃通过芯片粘结5秒具有4kgf/芯片或更高的晶片剪切强度。
7.如权利要求6所述的用于半导体的粘附膜，其中所述粘附膜具有小于130℃的固化起始温度。
8.如权利要求6所述的用于半导体的粘附膜，其中所述胺固化树脂包括芳胺固化树脂。
9.如权利要求8所述的用于半导体的粘附膜，其中所述芳胺固化树脂由通式1表示：
Figure FDA00002667615000011
其中A为单键或选自由-CH2-、-CH2CH2-、-SO2-、-NHCO-、-C(CH3)2-和-O-组成的组中，且R1至R10各自独立地为氢、C1至C4烷基、C1至C4烷氧基和胺基，附带条件为R1至R10包含至少两个胺基。
10.如权利要求6至9的任一项所述的用于半导体的粘附膜，其中所述酚醛固化树脂由通式6表示：
Figure FDA00002667615000021
其中R1和R2各自独立地为C1至C6烷基且n在2至100的范围内。
11.如权利要求6至9的任一项所述的用于半导体的粘附膜，其中所述固化促进剂包括选自咪唑固化促进剂和微胶囊型潜在固化剂中的至少一种或多种。
12.一种用于半导体的粘附组合物，其中，基于100重量份的所述粘附组合物，按照固含量，所述粘附组合物包含：
（a）51至80重量份的热塑性树脂；
（b）5至20重量份的环氧树脂；
（c）2至10重量份的酚醛固化树脂；
（d）2至10重量份的胺固化树脂；和
（e）0.1至10重量份的固化促进剂。
13.如权利要求12所述的用于半导体的粘附组合物，其中所述固化促进剂包括选自咪唑固化促进剂和微胶囊型潜在固化剂中的一种或多种。
14.一种半导体装置，所述半导体装置利用根据权利要求1至11任一所述的用于半导体的粘附膜或根据权利要求12或13任一所述的用于半导体的粘附组合物连接。
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