CN1523074A - 室温可印刷粘合剂 - Google Patents

室温可印刷粘合剂 Download PDF

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CN1523074A
CN1523074A CNA2004100074321A CN200410007432A CN1523074A CN 1523074 A CN1523074 A CN 1523074A CN A2004100074321 A CNA2004100074321 A CN A2004100074321A CN 200410007432 A CN200410007432 A CN 200410007432A CN 1523074 A CN1523074 A CN 1523074A
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何锡平
贫德
D·申菲尔德
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National Starch and Chemical Investment Holding Corp
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Abstract

一种含有液体粘合树脂的粘合剂，其在低于最终固化温度时部分固化成胶粘状态，在高于用于达到胶粘状态的温度时完全固化成固体状态。在其胶粘状态，在室温和低于1千克力的条件下，粘合剂具有足够的强度将硅芯片粘结到衬底上。对于使用更大的力将可能断裂的较薄的管芯而言，这种能力是关键的。

Description

室温可印刷粘合剂
                          发明领域
本发明涉及一种可印刷粘合剂，能够用于粘合薄材料，尤其适用于将薄硅片粘结在衬底上。
                          背景技术
在一个制造半导体封装的方案中，硅片用导电粘合剂粘结到诸如金属引线框架的衬底上，然后进一步通过焊接到引线框架上的焊垫(bond pad)的导线连接到其它电路。在此方案的多数操作中，粘合剂施布到衬底上，然后硅芯片在足够压力下与粘合剂接触，并且有时通过加热使得芯片粘合。在此方案中，粘合剂必须具有粘性和流变能力使其易于施布，并且施布后，当芯片被压入到粘合剂中时能够保持在一个位置。
由于电子器件的发展力图更薄和更小，芯片设计得更薄，衬底和芯片安置更紧密并且芯片边沿和焊垫的设置更近。对于更薄的芯片和更小的空间，当前使用的粘合剂是不适当的，因为受到与粘合剂接触的管芯的压力，它们容易从衬底和薄芯片之间较小的间距中挤出。粘合剂可以沿着较薄的管芯向上流动，流到其表面破坏焊垫和电路。如果粘合剂导电，任何溢出也会损害芯片边缘和焊垫之间的短距离，并且任何散逸的导电颗粒可能导致电路短路。
由于半导体硅芯片设计得更薄产生了其它问题。在操作中薄管芯有更大的变形倾向并且当前的膏状粘合剂不能固定薄管芯平面。管芯变形引起装配问题，例如：破坏从管芯到引线框架的电线连接。并且，在施加在衬底上粘结单硅芯片所需要的压力时，薄管芯更加容易被破坏或折断。
这些新的封装设计产生了对一种粘合剂的需要，在施加使半导体芯片和粘合剂接触的压力时，该粘合剂不容易流动，并且在室温下固定芯片板时，该粘合剂对压力敏感并具有初始粘合性，使硅芯片稳定不会弯曲。
                          发明内容
本发明涉及一种粘合剂，其中含有至少一种液体粘合剂树脂，在低于最终固化温度时，所述树脂部分固化成胶粘状态，在高于用于达到胶粘状态的温度时，所述树脂完全固化成固体状态。在其胶粘状态，在室温和低于1千克力的条件下，粘合剂具有足够的强度将硅芯片粘结到衬底上。对于使用更大的力将可能断裂的较薄的管芯而言，这种能力是关键的。
在装配形成胶粘状态的加热操作阶段称为B-阶段，并且粘合剂称为B-阶段的粘合剂。粘合剂的粘度在10,000cps-800,000cps范围内。
                        具体实施方式
用于制备本发明粘合剂的合适的液态树脂是环脂族化合物环氧化合物、脂肪族环氧化合物、芳香族环氧化合物、双酚A和双酚F的单官能和多官能缩水甘油醚，条件是所述液态树脂在室温或低于室温时固化为胶粘压敏状态和在高于室温时完全固化。这些环氧树脂购自，例如，CIBA、Sumitomo、Dainippon或Resolution Technology、CVC Specialty Chemicals、Resolution PerformanceProducts LLC和National Starch和Chemical Company。
另外合适的树脂是环氧线性酚醛树脂，其通过酚醛树脂和环氧氯丙烷的反应制备。优选的环氧线性酚醛树脂是聚(苯基缩水甘油醚)共甲醛。其它合适的环氧树脂是联苯环氧树脂，通常由联苯树脂和环氧氯丙烷反应制得，二环戊二烯酚醛环氧树脂；萘树脂；环氧官能丁二烯丙烯腈共聚物；环氧官能聚二甲基硅氧烷以及上述它们的混合物。
也可以使用非缩水甘油醚环氧化物。合适的例子包括3，4-环氧环己基甲基-3，4-环氧环己烷羧酸酯，其中含有两个作为环结构组成部分的环氧基和一个酯键；乙烯基环己烯二氧化物，其中含有两个环氧基并且其中一个作为环结构的组成部分；3，4-环氧-6-甲基环己基甲基-3，4-环氧环己烷羧酸酯；和二环戊二烯二氧化物。
更多的合适的环氧树脂的例子包括：
Figure A20041000743200051
和
Figure A20041000743200052
用于环氧树脂的合适的催化剂或固化剂包括咪唑或咪唑-酸酐加合物。单独使用的或用于形成加合物的优选的咪唑包括非N-取代咪唑，例如，2-苯基-4-甲基咪唑、2-苯基咪唑和咪唑。其它可用的咪唑是烷基取代咪唑、N-取代咪唑及其混合物。
用于形成加合物的优选的酸酐是环脂族酸酐，例如，苯均四酸二酐，购自Aldrich的PMDA。其它合适的酸酐包括甲基六氢邻苯二甲酸酐(购自LonzaInc.Intermediates and Actives的MHHPA)、甲基四氢邻苯二甲酸酐、桥亚甲基四氢邻苯二甲酸酐(nadic methyl anhydride)、六氢邻苯二甲酸酐、四氢邻苯二甲酸酐、邻苯二甲酸酐、十二烷基琥珀酸酐、二苯基二酸酐、二苯甲酮四酸二酐及其混合物。
两个优选的加合物是一份1，2，4，5-苯四甲酸酐和四份2-苯基-4-甲基咪唑的络合物和一份1，2，4，5-苯四酸二酐和两份2-苯基-4-甲基咪唑的络合物。加合物是在受热的情况下，将组分溶于合适的溶剂例如丙酮中制备。通过冷却，加合物沉淀析出。这种加合物以任何有效量使用，但以组合物中有机材料的重量计，优选1％-20％。
固化树脂为胶粘状态的通常温度在50℃-200℃的范围内。或者，也可以使用紫外线辐射，波长通常是400-500nm。完全固化温度高于达到胶粘状态的固化温度，通常是在高达200℃的范围。
对于一些配方来说，允许使用一定比例的固体树脂。那样的话，以液体树脂的重量计，这个比例优选50％或更少。优选该固体树脂可溶于液态树脂或溶剂之中，该溶剂能够溶解该固体树脂，并且在B阶段的加热温度下蒸发。
溶解固体树脂的合适溶剂的例子包括1-甲氧基-2-丙醇、丙二醇甲基醚醋酸酯、乙二醇醚、乙二醇醋酸酯或醇类。这些溶剂也可用于改进组合物粘度的目的。
除了上述环氧树脂外，其它合适的树脂包括环脂族环氧化合物，例如CIBACY179；芳香族环氧化合物，例如双酚A二环氧化物，具有苯酚硬化剂和膦基固化剂；丙烯酸化合物，例如，可以购自Sartomer，具有光敏引发剂；环氧化合物，例如，购自National Starch、CIBA、Sumitormo或Dainippon，具有潜在的胺或咪唑固化剂；双马来酰亚胺化合物(电子受体)，例如，购自Ciba SpecialtyChemicals或National Starch and Chemical Company，具有(电子供体)乙烯基醚、乙烯基硅烷、苯乙烯化合物、肉桂基化合物。
电子供体树脂合适的例子包括含有以下结构的化合物：
其中C36表示源于亚油酸和油酸的36个碳的直链或支链烷基；
和
Figure A20041000743200073
其中C36表示源于亚油酸和油酸36个碳的直链或支链烷基。
诸如自由基引发剂、热引发剂和光引发剂的固化剂以有效量存在固化组合物。通常，以组合物中有机物质(也就是说，不包括任何无机填充剂在内)总重计，这些固化剂的量的范围是0.1％-30％，优选1％-20％。实际的固化组成随组分的变化而变化，并且不需要专业人员进行过多的试验就可以确定。
可固化组合物中可以含有绝缘的或电或热传导填充剂。合适的绝缘填充剂是蛭石、云母、硅灰石、碳酸钙、二氧化钛、沙、玻璃、熔凝二氧化硅、煅制二氧化硅、硫酸钡的颗粒，以及卤代乙烯高聚物，比如四氟乙烯、三氟乙烯、1，1-二氟乙烯、氟乙烯、1，1-二氯乙烯和氯乙烯。合适的传导性填充剂是炭黑、石墨、金、银、铜、铂、钯、镍、铝、碳化硅、钻石和氧化铝。如果存在，以配方的重量计，填充剂的量最高达98％。
粘合剂可以通过丝网或模版印刷到选用于半导体的衬底上。所述衬底包括，例如，FR4BT板、柔性聚酰亚胺薄膜、陶瓷。在用于半导体封装操作的衬底上的丝网或模版印刷技术是现有技术中公知的。或者，在晶片被分割成芯片之前，粘合剂可以丝网或模版印刷到半导体晶片的无源面。这种情况下，为了在运输或保存期间起保护作用，一个剥离衬里或反面可以放置在未干的B阶段的粘合剂表面。其它能够使用的保护层是切割带，当晶片被切割成单独的芯片时，切割带将保留在粘合剂的表面。这些操作在现有技术中也是已知的。
在另一个实施方案中，本发明涉及一种集合，其包括用于半导体芯片或管芯的衬底，和如上所述的附着在衬底上的B-阶段的粘合剂，所述粘合剂部分固化至胶粘状态。当组合物固化到胶粘状态时，需要较小的力来粘合半导体管芯。这对于例如3密耳的薄管芯或更薄的管芯而言是非常重要的。
实施例：使用下表所示组分及其百分数制备粘合剂制剂。然后将粘合剂附着到一个80×80的陶瓷管芯上，并固化(B阶段)到胶粘状态。B阶段的条件在表中给出。然后将每个管芯在表中列举的作为附着温度和力下附着于陶瓷衬底上。对管芯的观察显示，在施加压力时没有粘合剂的流动和管芯变形。管芯接触到衬底后，通过加热30分钟温度斜线上升到175℃，并保持175℃在1个小时，使粘合剂固化。管芯的剪切强度在室温和245℃下通过Daye 4000测试仪测量，结果列于表中。所有制剂的触变指数在10.-1.3的范围内，该范围适于商业应用。数据显示，由液态树脂制备的配方D、E和F的粘合剂，能够在室温下施布，并固化到胶粘状态，然后在室温下以小于1千克力的压力用于粘结半导体管芯。最后固化的粘合剂提供了市场上可接受的管芯剪切强度，并且在压力作用下没有流动。
制剂重量百分含量  B阶段条件  附着条件 管芯剪切强度室温(MPa)  管芯剪切强度245℃(MPa)
制剂A固体硅氧烷环氧树脂 48.24固体酚醛树脂       12.72溶剂*             30.19表面活性剂         00.34环氧催化剂         00.43粘合剂促进剂       00.32填充剂             07.76  100℃30分钟  100℃1千克 66.27  7.86
制剂B固体硅氧烷环氧树脂 45.03固体酚醛树脂       11.87溶剂               30.87表面活性剂         00.36环氧催化剂         00.14粘合剂促进剂       00.30填充剂             11.43  110℃30分钟  115℃1千克 59.98  8.56
制剂C固体硅氧烷环氧树脂 47.18固体酚醛树脂       12.43溶剂               34.27表面活性剂         00.38环氧催化剂         00.14粘合剂促进剂       00.32填充剂             05.28  110℃30分钟  115℃1千克 47.86  3.53
制剂D液体双马来酰亚胺  30.43液体环氧树脂      07.61液体丙烯酸        08.10液态橡胶环氧树脂  06.09表面活性剂        00.53咪唑              00.17自由基引发剂      00.60粘合剂促进剂      00.63填充剂            45.84  110℃10分钟 室温700g  31.76  9.01
制剂E液体双马来酰亚胺  33.95液体环氧树脂      08.49液体丙烯酸        09.03液态橡胶环氧树脂  06.79表面活性剂        00.60咪唑              00.18自由基引发剂      00.68粘合剂促进剂      00.70填充剂            39.58  130℃30分钟 室温700g  29.45  7.74
制剂F液体双马来酰亚胺  32.65液体环氧树脂      08.16液体丙烯酸        08.69液态橡胶环氧树脂  06.53表面活性剂        00.58咪唑              00.18自由基引发剂      00.66粘合剂促进剂      00.67填充剂            41.88  130℃20分钟 室温700g  22.87  7.70
*溶剂是二丙二醇甲醚或丙二醇甲醚醋酸酯或其混合物

Claims (3)

1.一种粘合剂，包含选自于环氧树脂、双马来酰亚胺树脂、丙烯酸树脂和其混合物的液体树脂和用于该树脂的固化剂，其中液体树脂在一种温度下能够固化成胶粘状态，并在更高的温度下固化成固体状态。
2.根据权利要求1的粘合剂，进一步包含一种填充剂。
3.根据权利要求1的粘合剂，其被施用于衬底并且固化成胶粘状态。
CNA2004100074321A 2003-02-06 2004-02-06 室温可印刷粘合剂 Pending CN1523074A (zh)

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US10/361,347 US20040158008A1 (en) 2003-02-06 2003-02-06 Room temperature printable adhesive paste
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