CN101848974A - 具有优异的毛刺性能和可靠性的切割模片粘合膜以及应用该粘合膜的半导体器件 - Google Patents

具有优异的毛刺性能和可靠性的切割模片粘合膜以及应用该粘合膜的半导体器件 Download PDF

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CN101848974A
CN101848974A CN200880114602A CN200880114602A CN101848974A CN 101848974 A CN101848974 A CN 101848974A CN 200880114602 A CN200880114602 A CN 200880114602A CN 200880114602 A CN200880114602 A CN 200880114602A CN 101848974 A CN101848974 A CN 101848974A
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die bonding
dicing die
bonding film
film according
methyl
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CN101848974B (zh
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柳贤智
金章淳
洪宗完
朴孝淳
高东汉
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LG Corp
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LG Chemical Co Ltd
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Abstract

本发明涉及一种用于半导体封装工艺的切割模片粘合膜和应用该切割模片粘合膜的半导体器件。设置该切割模片粘合膜，从而使晶片和模片粘合部分的粘合层之间的粘合力X与模片粘合部分和切割部分的粘性层之间的粘性力Y的比值X/Y为0.15-1，并且模片粘合部分的粘合层在常温下的储能模量为100-1000MPa。根据本发明的切割模片粘合膜在切割工艺中能减少毛刺的产生，由此制备的半导体器件具有优异的可靠性并且没有由于覆盖结合区的毛刺而因差的连接可靠性所导致的劣化。

Description

具有优异的毛刺性能和可靠性的切割模片粘合膜以及应用该粘合膜的半导体器件
技术领域
本发明涉及一种切割模片粘合膜和一种半导体器件，更具体而言，本发明涉及一种切割模片粘合膜和应用该粘合膜的半导体器件，该粘合膜在模片粘合膜的粘附力与切割膜的粘性力之间具有可控的比值，以减少在半导体封装过程的切割工序中毛刺的产生。
背景技术
随着半导体芯片的最小化和高度集成，一种更先进的封装技术称为多芯片封装(MCP)。MCP是一种在一个芯片上安装额外的芯片的技术，因此与现有技术相比，MCP使得在一个同样大小的封装里安装更多的元件成为可能。
在MCP方法中，使用膜状粘合剂而不是使用现有的液体环氧树脂粘贴使半导体芯片和半导体基板的粘合(日本未审查专利公开H3-192178和H4-234472)。应用膜状粘合剂的方法包括膜元件粘合方法和晶片背面粘合方法。在膜元件粘合方法中，膜状粘合剂被切成或冲压成适合芯片的片并粘合到半导体的基板上。此后，从晶片上拾取芯片，在其上进行模片粘合，然后通过后处理步骤(如导线焊接和成型)而制得半导体器件。
另一方面，在晶片背面粘合方法中，将膜状粘合剂的一侧粘附到晶片的背面上，并且将具有粘性层的切割胶带另外粘附到膜状粘合剂的另一侧而不是粘附到晶片的背面，从而使晶片被切割成单个的芯片。拾取分开的芯片并以模片形式将其粘合到半导体基板上，然后通过导线焊接和成型加工成半导体器件。但晶片背面粘合方法在薄晶片的运送、增加工序数目、对各种厚度和大小的芯片的适应性、膜的薄度以及高功能半导体器件的可靠性方面存在困难。
为了解决上述问题，有人提出的方法是将在一层上同时具有粘合剂和粘性剂的膜粘合到晶片的背面上(日本未审查专利公开H2-32181、H8-53655和H10-8001)。这种方法不需要两个层压过程而只需要一个层压过程，同时还提供支持晶片的晶片环，使得在运送晶片时不存在问题。根据上述文献，切割模片粘合集成膜由基板和粘性/粘合剂组成，其中粘性/粘合剂是由包含辐射固化粘性剂和热固性粘合剂的混合物的特定组合物组成的。该粘合剂在切割工序中起到了粘性剂的作用，然后通过辐射固化过程失去其粘性力以便于从晶片上拾取芯片。并且，与在模片粘合工序中的粘合剂一样，该粘合剂也是热固性的，这使得芯片被牢固地粘合到半导体基板上。然而，切割模片粘合集成膜的粘性力在辐射固化后没有被充分地降低，以致于在切割后的半导体芯片拾取工序中，不能很容易地从基板上分离芯片，这会导致缺陷。
为了解决集成膜的问题，有人提出了切割模片粘合分离膜，其由两层粘性层和粘合层组成，使其既可以在切割工序中用作为切割胶带，又可以在模片粘合工序中用作粘合剂。因为在切割工序以后，通过加热或辐射固化可以很容易地分离粘性层和粘合层，所以切割模片粘合分离膜在半导体芯片拾取工序中不会产生任何问题，同时在模片粘合过程中也可以很方便地容许膜的厚度更薄。与现有的液体环氧树脂粘贴相比，虽然膜状粘合剂在粘合到半导体基板上时存在填充方面的问题，但由于上述优点，膜状粘合剂更频繁地被应用到实际的封装过程中。
然而，这种切割模片粘合分离膜具有多层结构，由于不同层之间性能的差异，以至于在切割工序中出现严重的外部条件时便会产生毛刺。因此，为了将切割模片粘合分离膜应用到半导体芯片上，以满足更小和更薄的设计和较高的可靠性，除了切割模片粘合膜的基本性能以外，急需要发展出一种方法来保证各层之间的平衡性能并因此使毛刺最小化。
发明内容
技术问题
为了解决上述现有技术中的问题而提出了本发明。本发明的目的是通过保证具有多层结构的切割模片粘合膜的各层之间的平衡性能而提供一种具有提高的封装工序可靠性的切割模片粘合膜，并因此在切割工序中使毛刺的产生最小化，以及应用该切割模片粘合膜的半导体晶片和半导体器件。
技术方案
为了实现上述目的，本发明的一个方面提供了一种切割模片粘合膜，其包括：具有粘合到晶片上的粘合层的模片粘合部分；和具有粘性层的切割部分，其中，晶片和模片粘合部分的粘合层之间的粘合力X与模片粘合部分和切割部分的粘性层之间的粘性力Y的比值X/Y为0.15-1，并且模片粘合部分的粘合层在常温下的储能模量为100-1000Mpa。
为了实现上述目的，本发明的另一个方面提供了一种半导体晶片，其中，将根据本发明的切割模片粘合膜的粘合层粘附到晶片的一侧，并且将该切割模片粘合膜的粘性层固定到晶片环的框架上。
为了实现上述目的，本发明的再一个方面提供了一种半导体器件，其包括：布线基板；根据本发明的切割模片粘合膜的粘合层，其粘附在该布线基板的芯片安装面上；和半导体芯片，其安装在该粘合层上。
有益效果
本发明的切割模片粘合膜在被粘附到晶片的背面并被切割成单个芯片的工序中能使在粘合层中毛刺的产生最小化到小于2％，在粘附连接的可靠性方面没有任何缺陷，因为毛刺覆盖了结合区，因此可制备具有优异可靠性的半导体器件。
附图说明
图1是根据本发明实施方式的模片粘合膜的剖视图。
图2是根据本发明实施方式的切割模片粘合膜的剖视图。
图3是根据本发明实施方式的半导体器件的剖视图。
[附图中所示主要部件的附图标记的说明]
1：半导体芯片               30：切割部分的粘性层
10：模片粘合部分的保护膜    40：切割部分的基板膜
20：模片粘合部分的粘合层    50：布线基板
具体实施方式
本发明涉及一种切割模片粘合膜，其包括：具有粘合到晶片上的粘合层的模片粘合部分；和具有粘性层的切割部分，其中，晶片和模片粘合部分的粘合层之间的粘合力X与模片粘合部分和切割部分的粘性层之间的粘性力Y的比值X/Y为0.15-1，并且模片粘合部分的粘合层在常温下的储能模量为100-1000Mpa。
通常，半导体晶片在切割工序中所形成的模式是被切割成单个的元件，由于晶片和旋转刀片之间夹有金钢石砂粒而产生摩擦而使温度升高。这种热量会使粘附到晶片背面的切割模片粘合膜产生流动，这会引起聚合物在切割线上的聚集，并且由于在横切工序中旋转刀片在模片的边缘产生毛刺。
如果晶片和模片粘合部分的粘合层之间的粘合力X与模片粘合部分和切割部分的粘性层之间的粘性力Y的比值X/Y为0.15-1，减少由上述因素导致的毛刺的产生就成为可能。优选地，晶片和模片粘合部分的粘合层之间的粘合力X与模片粘合部分和切割部分的粘性层之间的粘性力Y的比值X/Y为0.2-0.8，更优选为0.25-0.5。如果该比值小于0.15，毛刺产生的几率就会增加。而且，如果芯片被单一切割成小尺寸，在芯片和模片粘合部分的粘合层之间的界面上会发生分离，从而会造成芯片散射。而且，如果该比值超过1，晶片从切割胶带上的拾取性能会变差。
另外，用于本发明的切割模片粘合膜中的模片粘合部分的粘合层在常温下的储能模量为100-1000Mpa，优选为100-500Mpa，更优选为100-300Mpa。如果模片粘合部分的粘合层在常温下的储能模量小于100Mpa，虽然粘合层对晶片的紧密粘合力提高了，但膜自身的耐热性退化了，这会对高温可靠性产生不良影响。如果在常温下的储能模量超过1000Mpa，对晶片的紧密粘合力会下降，这会引起毛刺的产生或芯片的散射。
而且，在切割模片粘合膜中，晶片和模片粘合部分的粘合层之间的粘合力X为20gf或更高。优选地，粘合力X为25-100gf，更优选为30-75gf。如果粘合力X小于20gf，模片粘合部分的粘合层对晶片背面的粘合力劣化，因此在切割工序中会造成芯片的散射。
下面，将详细描述根据本发明切割模片粘合膜的各部分。
具有粘合层的模片粘合部分
在本发明中，模片粘合部分的粘合层应该满足在一个封装中的芯片和基板之间降低弯曲和释放应力这两个特征。所述芯片的热膨胀系数(CTE)为4ppm/℃，基板的CTE为10-15ppm/℃，而CTE的差异在高温下会引起弯曲和撕裂。
因此，为了实现上述性能，本发明的粘合层使用a)热固性多官能团环氧树脂，以降低CTE，从而使弯曲最小化并提高如粘合力和耐热性等性能；和b)低弹性高分子树脂，在高温和低温条件下以释放应力。即通过应用聚合物合金技术使两种相互之间具有不同弹性的树脂混合并使用，软链段和硬链段相互共存，因此能满足两个特征。
a)热固性多官能团环氧树脂
用于本发明的a)热固性多官能团环氧树脂可包含任何树脂而没有限制，只要其在主链上包含至少有两个环氧基并且玻璃化转变温度为50℃或以上，例如，可以使用在主链上具有作为环氧基骨架的芳香结构的重复单元的环氧树脂。如果该玻璃化转变温度低于50℃，粘合层的粘性会增加，这会使对粘合层的处理变得困难，而且其与切割胶带的剥离性能也会变差。
这种环氧树脂经过固化过程形成交联结构，因此其发生硬化并具有优异的粘合力，耐热性和机械强度。
优选地，热固性多官能团环氧树脂的平均环氧当量为180-1000。如果该环氧当量低于180，交联密度如此地高，从而使所有的粘合膜都会显示出刚性特征。如果该环氧当量超过1000，玻璃化转变温度会降低，这与本发明所要求的高的耐热性的特征正好相反。例如，所述环氧树脂可为甲酚线形酚醛环氧树脂、双酚A型线形酚醛环氧树脂、苯酚线形酚醛环氧树脂、4官能团环氧树脂、联苯型环氧树脂、三苯酚甲烷型环氧树脂、烷基改性的三苯酚甲烷型环氧树脂、萘型环氧树脂、二环戊二烯型环氧树脂或二环戊二烯改性的苯酚型环氧树脂，其可以单独使用或以至少两种的混合物的形式使用。
热固性多官能团环氧树脂的软化点优选为50-100℃。如果该软化点低于50℃，粘合膜的模量在A阶段状态发生劣化，而且粘性增加使其加工性能变差。如果软化点高于100℃，对晶片的粘合性能变差，这会导致在切割过程中芯片的散射。
基于100重量份的b)低弹性高分子树脂，热固性多官能团环氧树脂的含量优选为10-200重量份，更优选为20-100重量份。如果该含量低于10重量份，耐热性和加工性能会变差。如果该含量超过200重量份，膜的刚性会增加，其易加工性和可靠性变差。
b)低弹性高分子树脂
用于本发明的b)低弹性高分子树脂的玻璃化转变温度为50℃或更低，在其固化之前保持具有高分子量的膜状并且不发生断裂，与a)热固性多官能团环氧树脂或c)固化剂(将在后面描述)形成交联结构，并在形成交联材料以后仍然具有粘弹性。所有具有上述特征的树脂都可用而没有限制。而且，在形成膜状前的清漆状态下，其与a)热固性多官能团环氧树脂或c)固化剂应是相容的，并具有储存稳定性，例如，不会经历相分离。
在固化前，低弹性高分子树脂的玻璃化转变温度优选为-30-50℃，更优选为-20-40℃，最优选为0-30℃。如果该玻璃化转变温度低于-30℃，在膜形成过程中的流动性会增加，从而使加工性能变差。如果该玻璃化转变温度超过50℃，对晶片的粘合性能会变差，从而在切割工序中引起芯片的散射或使冲洗水渗透到粘合剂和芯片之间的间隙中。
低弹性高分子树脂的平均分子量优选为100,000-2,500,000，更优选为100,000-800,000。如果该平均分子量低于100,000，膜的强度会劣化，因此降低了加工性能和耐热性，并且会使在半导体基板的电路灌注期间难于控制流动性。如果该平均分子量超过2,500,000，弹性模量会增加，而且在模片粘合工序中流动性被严重地压制，因此降低了粘合膜的可靠性和电路灌注。
玻璃化转变温度为-30-50℃、平均分子量为100,000-2,500,000的低弹性高分子树脂优选具有优异的自身弹性(self elasticity)的结构，例如，其可为包含羧基的丁腈橡胶(NBR)；具有高分子量的脂族环氧树脂；橡胶改性的环氧树脂；包含缩水甘油基、羧基、羟基或胺基的丙烯酸共聚物；马来酸改性的苯乙烯乙烯丁二烯苯乙烯共聚物(SEBS)等等，其可以单独使用或以至少两种的混合物的形式使用。
c)固化剂
模片粘合部分的粘合层可进一步包含固化剂。用于本发明的c)固化剂可以包括任何树脂而没有限制，只要其可与a)热固性多官能团环氧树脂和/或b)低弹性高分子树脂反应形成交联结构。然而，由于固化剂能分别与b)低弹性高分子树脂形成软链段和a)热固性多官能团环氧树脂形成硬链段而形成交联结构以提高粘合剂固化材料的耐热性，同时又在两个树脂a)热固性多官能团环氧树脂和b)低弹性高分子树脂之间的界面处产生连结的作用以极大地提高半导体封装的可靠性，固化剂优选包括既能与a)热固性多官能团环氧树脂又能与b)低弹性高分子树脂反应形成交联结构的树脂。
对于这种树脂，在耐热性上，多官能团酚树脂是优选的，酚树脂的羟基当量优选为100-1000。如果该羟基当量小于100，虽然会随着树脂种类的不同会有差异，但与环氧树脂反应的固化材料通常会硬化，因此会降低粘合膜在半导体封装过程中的剥离效果。如果该羟基当量超过1000，与环氧树脂反应的固化材料的交联密度会下降，这会降低耐热性。
多官能团酚树脂可包括：双酚A树脂、线型酚醛树脂、甲酚线型酚醛树脂、双酚A线型酚醛树脂、苯酚芳烷基树脂、多官能团线型酚醛清漆树脂、二环戊二烯线型酚醛树脂、氨基三嗪线型酚醛树脂、聚丁二烯线型酚醛树脂、联苯型树脂或其他类型的多官能团树脂，其可以单独使用或以至少两种的混合物的形式使用。
而且，固化剂的软化点优选为50-150℃。如果该软化点低于50℃，粘性性能会增加，从而使加工性能变差，并导致差的耐热性。如果该软化点高于150℃，粘合膜的硬度会增加，从而使粘合膜和晶片之间的粘合力降低，这会导致在切割工序中的缺陷，如芯片散射。
固化剂的当量优选为a)热固性多官能团环氧树脂的环氧当量的0.4-2倍，更优选为0.8-1.2倍。如果固化剂的当量小于a)热固性多官能团环氧树脂的环氧当量的0.4倍，大量未反应的环氧会留在其中，从而降低了玻璃化转变温度并使耐热性变差，而且需要在高温时提供热量或需要长时间来使未反应的环氧基反应。如果固化剂的当量大于a)热固性多官能团环氧树脂的环氧当量的2倍，虽然交联密度增加了，但未反应的羟基会降低储存稳定性并增加吸湿率和介电特性。
d)固化促进剂
模片粘合部分的粘合层可进一步包含固化促进剂，用于本发明的固化促进剂在种类上没有特别的限制，可以包括咪唑、三苯基膦(TPP)、叔胺等等。咪唑固化促进剂可为2-甲基咪唑(2MZ)、2-乙基-4-甲基咪唑(2E4MZ)，2-苯基咪唑(2PZ)、1-氰乙基-2-苯基咪唑(2PZ-CN)、2-十一烷基咪唑(C11Z)、2-十七烷基咪唑(C17Z)或1-氰乙基-2-苯基咪唑(1-cyanoethyl-2-phenylimidazoletrimethalate)(2PZ-CNS)，其可以单独使用或以至少两种的混合物的形式使用。
基于100重量份的a)热固性多官能团环氧树脂和b)低弹性高分子树脂的总量，固化促进剂的含量优选为0.1-10重量份，更优选为0.5-3重量份。如果固化促进剂的含量小于0.1重量份，反应速率会下降，这导致环氧树脂的交联不充分，因此使耐热性变差。如果该含量超过10重量份，固化反应突然地发生，从而使储存稳定性变差。
e)无机填料
模片粘合部分的粘合层可进一步包含无机填料，无机填料的加入可以提高加工性能、耐热性和对熔体粘度的控制。填料可包括有机填料和无机填料，就性能而言优选无机填料。对无机填料没有特别的限制，但优选为硅石、氢氧化铝、碳酸钙、氢氧化镁、氧化铝、滑石、氮化铝等等。
对填料的含量没有特别的限制，基于100重量份的不包含填料的树脂，该含量优选为0.5-100重量份，更优选为5-50重量份。如果该含量小于0.5重量份，所加入的填料不能在耐热性和加工性能方面提供充分的改进。如果该含量超过100重量份，易加工性和基板粘合性能会劣化。
填料的平均直径优选为0.001-10μm，更优选为0.005-1μm。如果该平均直径小于0.001μm，填料会很容易地在粘合层上凝聚而导致差的外观。但如果该平均直径超过10μm，填料会很容易地从粘合层的表面上露出，在与晶片的热压时会损坏芯片，而且降低粘合效果。
保护膜
根据本发明的切割模片粘合膜的模片粘合部分优选在粘合层的一侧包括保护膜。并且，优选该保护膜经过处理容易剥离。
用于本发明的保护膜可包括：塑料膜，如聚对苯二甲酸乙二醇酯膜、聚四氟乙烯膜、聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、氯乙烯共聚物膜、聚酰亚胺膜等等。
在保护膜的表面上用于剥离处理的剥离剂可为基于醇酸、基于硅、基于氟、基于不饱和酯、基于聚烯烃或基于石蜡的树脂，其中，由于其耐热性，基于醇酸、基于硅、基于氟的树脂是优选的。
保护膜的厚度通常为10-500μm，优选为20-200μm。如果该厚度低于10μm，在干燥过程中膜会容易地变形，从而导致粘合层不规则的外观。如果该厚度超过500μm会不经济。
模片粘合部分的制备方法
根据本发明的切割模片粘合膜的模片粘合部分可通过以下步骤制备：将上述粘合层组合物溶解或分散在溶剂中以制备树脂清漆；将树脂清漆涂布到经过剥离处理的保护膜上；和加热该保护膜以除去溶剂。
粘合层组合物已在上面描述过，制备粘合层组合物所使用的制备清漆的溶剂一般为甲基乙基酮(MEK)、丙酮、甲苯、二甲基甲酰胺(DMF)、甲基溶纤剂(MCS)、四氢呋喃(THF)或N-甲基吡咯烷酮(NMP)。因为保护膜的耐热性差，所以优选使用低沸点的溶剂。然而，也可用高沸点的溶剂来提高膜的均匀性，或者也可使用至少两种所述溶剂的混合物。
可以用常规的方法将树脂清漆涂布在保护膜上。例如，可以使用刮涂法、辊涂法、喷涂法、凹板涂布法、帘式涂布法、点涂法或叶涂法。
在粘合层组合物中包含填料的情况下，为了提高填料在粘合层中的分散性，可以单独或联合使用球磨机、珠磨机、三辊研磨机或粉碎机。球或珠可由玻璃、铝土或锆制成，在颗粒的分散性上，优选由锆制成的球或珠。
在本发明中，先将溶剂和填料在球磨机或珠磨机中混合一定的时间，然后将a)热固性多官能团环氧树脂和c)固化剂加入其中并混合，最后将b)低弹性高分子树脂和添加剂(若需要)加入进行混合，通过上述操作易于缩短混合时间并提高分散度。
此外，在加热保护膜除去溶剂时，加热条件优选在70-250℃温度下进行1-10分钟。
具有粘性层的切割部分
本发明的切割部分的粘性层可包含任何粘性剂而没有限制，只要其能在切割过程中固定晶片环和晶片以阻止在单一元件化工序中芯片的散射以及通过加热和/或辐射失去粘性力以保证良好的拾取工序。总的来说，基于丙烯酰基的共聚物优选用作粘性剂。
用于本发明的热固性粘性剂的基于丙烯酰基的共聚物没有特别的限制，但优选包括现有技术中的所有粘性剂。例如，基于丙烯酰基的共聚物优选是通过共聚合含有C1-C12烷基的基于(甲基)丙烯酸酯的单体和含有交联官能团的单体来获得的。
含有C1-C12烷基的基于(甲基)丙烯酸酯的单体可包括：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正十四烷酯等等，其可以单独使用或以至少两种的混合物的形式使用。
此外，含有交联官能团的单体可包括：例如，包含羟基的单体，如(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、(甲基)丙烯酸-4-羟丁酯、(甲基)丙烯酸-6-羟己酯、(甲基)丙烯酸-2-羟基乙二醇酯或(甲基)丙烯酸-2-羟基丙二醇酯；包含羧基的单体，如(甲基)丙烯酸、马来酸或富马酸；包含氮的单体，如丙烯酰胺、N-乙烯基吡咯烷酮或N-乙烯基己内酰胺等等，其可以单独使用或以至少两种的混合物的形式使用。
对基于(甲基)丙烯酸烷基酯的单体和含有交联官能团的单体的重量比没有限制，但是基于100重量份的(甲基)丙烯酸酯的单体，含有交联官能团的单体优选为1-20重量份。
为了赋予基于丙烯酰基的共聚物粘性力和凝聚力，基于(甲基)丙烯酸烷基酯的单体可与具有高玻璃化转变温度的共聚单体共聚合。可共聚合的共聚单体可包括：丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、乙酸乙烯酯、苯乙烯、丙烯腈等等，其可以单独使用或以至少两种的混合物的形式使用。包含可聚合的乙烯基的任何单体都是优选的。
在本发明中，对基于丙烯酰基的共聚物的聚合没有特别的限制，可通过各种聚合方法完成，所述聚合方法例如溶液聚合法、光聚合法、本体聚合法、悬浮聚合法和乳液聚合法，其中优选溶液聚合法。
此外，粘性层可进一步包括多功能交联剂，从而控制粘性剂的粘性。多功能交联剂通过与羧基和羟基反应而起到提高粘性剂的凝聚力和控制粘性力的作用。基于100重量份的基于丙烯酰基的共聚物，多功能交联剂的含量优选为0.01-10重量份。
多功能交联剂可包括：基于异氰酸酯、基于环氧、基于氮丙啶、基于金属螯合物的交联剂等，其中基于异氰酸酯的交联剂是优选的。基于异氰酸酯的交联剂可包括：甲苯二异氰酸酯、二甲苯二异氰酸酯、二苯甲烷二异氰酸酯、1，6-己二异氰酸酯、异构重整二异氰酸酯(isoform diisocyanate)、四甲代苯二甲撑二异氰酸酯、萘二异氰酸酯，或上述化合物与如三羟甲基丙烷的多元醇的反应物。
此外，基于环氧的交联剂可为乙二醇二缩水甘油醚、三缩水甘油醚、三羟甲基丙烷三缩水甘油醚、N，N，N，N’-四缩水甘油乙二胺或甘油二缩水甘油醚等。基于氮丙啶的交联剂可为N，N’-甲苯-2，4-双(1-氮丙啶羰基化物)、N，N’-二苯基甲烷-4，4’-双(1-氮丙啶羰基化物)、三亚乙基三聚氰胺、二间苯二酰-1-(2-甲基氮丙啶)(bisisoprotaloly-1-(2-methylaziridine))和三-1-氮丙啶氧化膦等。
基于金属螯合物的交联剂可包括这样的化合物，在该化合物中的多价金属如铝、铁、锡、锌、钛、锑、镁和钒与乙酰丙酮或乙酰乙酸乙酯配合。
本发明的粘性层不需要用特别限定的方法来制备，而是通过普通的方法将基于丙烯酰基的共聚物和多功能交联剂混合来制备的。其中，在形成粘性层的混合过程中，只有当多功能交联剂的官能团的交联反应没有充分地发生时，多功能交联剂才能进行均匀的涂布过程。在涂布过程完成后，然后再进行干燥和老化过程，交联结构就形成了，从而制得具有弹性和强凝聚力的粘性层。此时，粘性剂的强粘性力提高了粘性性能和切削性能，如粘性产品的持久的可靠性。
在本发明中，为了特殊的目的，可以额外地混合基于丙烯酰基的低分子材料、提供粘性的树脂、环氧树脂、固化剂等，而且基于一般的目的还可以适当地加入UV稳定剂、抗氧剂、着色剂、增强剂、填充剂、消泡剂、表面活性剂、增塑剂、发泡剂等。
辐射固化粘性剂可为橡胶-减压粘性剂、基于丙烯酰基的粘性剂等。辐射固化粘性剂可通过向热固性粘性剂中加入辐射固化组合物来制备。该组合物可为具有至少两个不饱和键的加成聚合化合物、光聚合化合物或光聚合引发剂。
具有至少两个不饱和键的加成聚合化合物可为基于多价醇的丙烯酸酯或甲基丙烯酸酯、酯类低聚物、基于环氧的化合物、基于聚氨酯的化合物等。
将具有环氧基的光聚合化合物，如烷氧基硅烷，加入到热固性粘性组合物中，然后混合，涂布和热固化。此后，其在非固化状态下使用。基于100重量份的热固性粘性树脂，光聚合化合物的含量优选为3-500重量份。
用于固化光聚合化合物的光聚合引发剂，作为具体的例子，可为羰基化合物、有机硫化合物、过氧化物、胺或基于鎓盐的化合物。基于100重量份的光聚合化合物，光聚合引发剂的含量优选为0.1-20重量份。
此外，辐射固化粘性剂可包含含有能发生自由基反应的不饱和基团或在分子侧链上含有环氧基的基于丙烯酰基的聚合物，或者可进一步加入在其分子内具有一个以上环氧基的环氧基多功能交联剂(如乙二醇二缩水甘油醚)，以提高交联效率。
根据本发明的切割模片粘合膜的切割部分进一步包括在粘性层上的基板膜。
用于本发明的基板膜，例如，可为由聚丙烯、聚乙烯、聚酯、聚碳酸酯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯共聚物、乙烯-丙烯酸乙酯共聚物、聚氯乙烯或两种以上的混合物所制成的膜，而且包括其他聚合物膜、金属箔等。基板膜合适的厚度为10-200μm，优选为50-180μm，更优选为80-150μm。如果基板膜的厚度小于10μm，不能稳定控制切割工序中的切割深度。如果该厚度超过200μm，由于基板膜太厚会在切割工序中增大毛刺产生的可能性，并且具有低的伸展度，这使得精确地进行拉伸过程变得困难了。
在本发明中，对通过在基板膜上形成粘性层来制备切割胶带的方法没有特别的限制，但可包括：用棒涂器将粘性剂直接涂布在基板膜的表面上然后干燥的方法，和将粘性剂涂布在可剥离的基板表面上、干燥、然后将形成于可剥离的基板表面上的粘性层转移至基板膜的表面上再老化的方法。粘性层的厚度优选为1-100μm，更优选为5-30μm。如果粘性层的厚度小于上述厚度范围，获得均匀的粘性层就会变得困难，结果获得的是性能不均匀的粘性膜。
制备根据本发明的切割模片粘合膜的方法可包括使用加热辊和压力机将切割胶带和模片粘合部分层压的方法，其中，在连续加工的可能性和效率上，加热辊层压方法是优选的。加热辊层压方法优选在10-100℃下压力为0.1-10kgf/cm2下完成。
本发明还涉及一种半导体晶片，其中，将根据本发明的切割模片粘合膜的粘合层粘附在晶片的一侧，并且将该切割模片粘合膜的粘性层固定到晶片环的框架上。
上述半导体晶片可通过将切割模片粘合膜的粘合层在0-180℃下粘附到晶片的背面并且将切割模片粘合膜的粘性层固定到晶片环的框架上而制得。
此外，本发明还涉及一种半导体器件，其包括：布线基板；根据本发明的切割模片粘合膜的粘合层，其粘附到该布线基板的芯片安装面上；和半导体芯片，其安装在该粘合层上。
下面将描述半导体器件的制备工艺
粘附有上述切割模片粘合膜的半导体晶片通过切割装置被完全地切割并被分割成单个的芯片。
然后，如果切割胶带为辐射固化粘性剂，从基板的一侧照射该粘性层而使其固化。但是，如果切割胶带为热固性粘性剂，加热该粘性剂而使其固化。通过辐射或加热固化的粘性层显示出对粘合层降低的粘合力，因此在后续工序中可以更容易地拾取芯片。其中，如果需要，切割模片粘合膜还可以拉伸。如果进行这种拉伸过程，芯片之间会出现间隙，因此可以更容易拾取芯片。另外，粘合层和粘性层相互交叉，因此拾取过程变得更加有效。
拾取过程是连续的。其中，半导体晶片和切割模片粘合膜的粘合层从切割模片粘合膜的粘性层上分开，因此获得只与粘合层粘附的芯片。将具有与其粘附的粘合层的芯片粘附到半导体基板上。芯片通常在100-180℃下压力为0.5-2kgf/cm2下进行粘附0.5-3秒。
上述工序完成后，通过导线焊接和成型工序来制备半导体器件。
半导体器件的制备方法并不局限于上述方法，但可包括任何可供选择的工艺或根据变化的工艺顺序来进行。例如，可按下列顺序进行所述方法：粘性层固化、切割和拉伸步骤；或者按照切割、拉伸和粘性层固化的顺序进行。在芯片粘附过程完成以后，可进一步包括加热或冷却步骤。
实施例
为了具体地描述本发明，将基于实施例对本发明进行更详细的说明。然而，本发明的实施例可以以各种不同的方式进行改变，而且本发明的范围也不局限于下述实施例。
实施例1
将包含以下组分的组合物在甲基乙基酮中搅拌并进行混合而制得清漆：20重量份的芳族环氧树脂(软化点为80℃的线型酚醛清漆型环氧树脂)、10重量份的作为环氧树脂的固化剂的苯酚树脂(软化点为90℃的苯酚线型酚醛树脂)、70重量份的包含环氧基的丙烯酰基共聚物(SA-55，LG Chem.制造，Tg＝5℃，平均分子量为500,000)、0.3重量份的固化促进剂(2-苯基-4-甲基咪唑(2P4MZ))和10重量份的作为填料的硅石(平均直径为75nm的熔化硅石)。
将粘合剂树脂组合物涂布到厚度为38μm的剥离膜(SKC，RS-21G)上，然后干燥，而制得膜厚度为20μm的粘合膜，该膜被广泛地用在封装领域。在180℃下用层压机(Fujisok公司)将该粘合膜和粘性力为160gf/inch的切割胶带一起层压到SUS304上，而得到用于半导体的切割模片粘合膜。
实施例2
除了使用70重量份的包含环氧基的丙烯酰基共聚物(SA-05，LG Chem.制造，Tg＝0℃，平均分子量为500,000)和20重量份的作为填料的硅石(平均直径为75nm的熔化硅石)以外，按照与实施例1相同的方法制备树脂，然后制得粘合膜。
实施例3
除了使用70重量份的包含环氧基的丙烯酰基共聚物(SA-34，LG Chem.制造，Tg＝20℃，平均分子量为300,000)和5重量份的作为填料的硅石(平均直径为75nm的熔化硅石)以外，按照与实施例1相同的方法制备树脂，然后制得粘合膜。
实施例4
除了使用33重量份的芳族环氧树脂(软化点为80℃的线型酚醛清漆型环氧树脂)、17重量份的作为环氧树脂的固化剂的苯酚树脂(软化点为90℃的苯酚线型酚醛树脂)、50重量份的包含环氧基的丙烯酰基共聚物(SA-55，LGChem.制造，Tg＝5℃，平均分子量为500,000)和5重量份的作为填料的硅石(平均直径为75nm的熔化硅石)以外，按照与实施例1相同的方法制备树脂，然后制得粘合膜。
对比实施例1
将包含以下组分的组合物在甲基乙基酮中搅拌并进行混合而制得清漆：20重量份的芳族环氧树脂(软化点为80℃的线型酚醛清漆型环氧树脂)，10重量份的作为环氧树脂的固化剂的苯酚树脂(软化点为90℃的苯酚线型酚醛树脂)、70重量份的包含环氧基的丙烯酰基共聚物(SA-34，LG Chem.制造，Tg＝20℃，平均分子量为300,000)、0.3重量份的固化促进剂(2-苯基-4-甲基咪唑(2P4MZ))和20重量份的作为填料的硅石(平均直径为75nm的熔化硅石)。按照与实施例1相同的方法使用该清漆制备切割模片粘合膜。
对比实施例2
除了未添加填料以外，按照与实施例1相同的方法制备切割模片粘合膜。
对比实施例3
在180℃下用层压机(Fujisok公司)将实施例1中制备的粘合膜和粘性力为400gf/inch的切割胶带一起层压到SUS304上，从而得到用于半导体的切割模片粘合膜。
对比实施例4
在180℃下用层压机(Fujisok公司)将实施例1中制备的粘合膜和粘性力为50gf/inch的切割胶带一起层压到SUS304上，从而得到用于半导体的切割模片粘合膜。
<性能评价>
测定了实施例1-4和对比实施例1-4的切割模片粘合膜的下述性能，并将其评价结果示于表1中。
1.晶片背面粘合性能评价
维持50℃条件下用胶带贴片机(DS Precision Ind.)将制备的A阶段状态的粘合膜层压到8英寸硅晶片上10秒钟。根据层压后有没有空隙来评价背面粘合性能。
2.常温下的储能弹性(storage elasticity)
将粘合膜按一定方向切成宽15mm×长45mm的大小备用。用夹具将样品的两端固定，用TA(纹理分析)方法对样品长度为25mm的测量部分进行测量，在12.8mm/min条件下对样品进行拉伸，测定储能弹性。
3.晶片和模片粘合部分的粘合层之间的界面粘合力
将切割模片粘合膜切成宽25mm×长150mm的大小备用。用50℃的热辊层压机将制备的膜层压而使粘合膜和晶片接触。在300mm/min条件下用TA(纹理分析)方法测定180℃的剥离力。
4.模片粘合部分的粘合层和切割胶带的粘性层之间的界面粘性力
将切割模片粘合膜切成宽25mm×长150mm的大小备用。将制备的膜的模片粘合部分的粘合层固定到玻璃板上，并在300mm/min条件下拉动切割膜用TA(纹理分析)方法测定180℃的剥离力。
5.观测芯片散射和毛刺产生
在50℃下用帖片机将切割模片粘合膜层压到100μm的晶片和晶片环上。在4000rpm和进料速度20mm/sec条件下，使用Neon Tech Co.生产的切割设备将晶片切割成2mm×2mm大小的芯片，然后检测有没有发生芯片散射和具有毛刺的被切割成单个芯片的数量％。
6.拾取成功率
在切割过程后，将粘附有粘合层的被切割成单个的芯片从切割胶带上拾取，然后如果没有拾取缺陷被评价为好，如果发生拾取的缺陷就被评价为差。
7.封装可靠性
通过粘合膜将芯片粘附到PCB基板上，然后进行5次耐高温周期实验(其中一个周期定义为芯片被单独在-55℃下保持15分钟，然后在125℃下保持15分钟的过程)。然后，将芯片在85℃/85％的恒温恒湿的室中保持72小时，然后，将样品通过其温度已经设定的IR回流，使样品表面的最高温度在260℃温度下保持20秒。然后使样品在室温下独自冷却。该过程进行3次，用超声波显微镜观察样品中的裂纹，如果没有如分裂或裂纹这样的断裂就评价为好，如果在一个或多个部分出现断裂就评价为差。
表1
Figure GPA00001127719000161
如表1所示，可以看出与对比实施例1-4的切割模片粘合膜相比，根据本发明制备的实施例1-4的切割模片粘合膜在背面粘合性能、芯片散射、毛刺产生、拾取和封装可靠性等所有方面都表现优异。也就是说，毛刺的产生在将芯片单一元件化过程中被最小化到2％或更低，因此，在晶片和模片粘合部分的粘合层之间的粘合力X与模片粘合部分和切割部分的粘性层之间的粘性力Y的比值X/Y为0.25-1，以及模片粘合部分的粘合层在常温下的储能弹性为100-1000Mpa情况下，提高了半导体封装的连接可靠性和使由毛刺产生的缺陷率最小化。
另外，在比值X/Y较低而常温下的储能弹性较高的情况下，如对比实施例1，尤其当X较低时，在将芯片切割为非常小的尺寸的工序中，在芯片和模片粘合部分的界面处会发生芯片散射，而且毛刺的产生超过标准水平。而且，在常温储能弹性较低和没有使用无机填料的情况下，如对比实施例2，在粘接工序中，并没有发现能覆盖布线的伸长毛刺的产生，但产生了拾取缺陷。高温时如沿边缘拉起芯片时，观察到了封装可靠性的劣化。在虽然X较大，但因Y也较大，所以比值X/Y较低的情况下，如对比实施例3，观察到毛刺的产生超过标准水平，以及产生了拾取缺陷。在比值X/Y较高的情况下，如对比实施例4，在晶片单一元件化过程中，在粘合层和切割胶带的界面处发生芯片散射，而且毛刺的产生超过标准水平。

Claims (29)

1.一种切割模片粘合膜，其包括：
具有粘合到晶片上的粘合层的模片粘合部分；和
具有粘性层的切割部分，
其中，所述晶片和模片粘合部分的粘合层之间的粘合力X与模片粘合部分和切割部分的粘性层之间的粘性力Y的比值X/Y为0.15-1，并且该模片粘合部分的粘合层在常温下的储能模量为100-1000Mpa。
2.根据权利要求1所述的切割模片粘合膜，其中，所述晶片和模片粘合部分的粘合层之间的粘合力X为20gf或更高。
3.根据权利要求1所述的切割模片粘合膜，其中，所述模片粘合部分的粘合层包含：a)热固性多官能团环氧树脂；和b)低弹性高分子树脂。
4.根据权利要求3所述的切割模片粘合膜，其中，所述a)热固性多官能团环氧树脂在主链上包含至少两个环氧基，并且其玻璃化转变温度为50℃或更高。
5.根据权利要求3所述的切割模片粘合膜，其中，所述a)热固性多官能团环氧树脂的平均环氧当量为180-1000。
6.根据权利要求3所述的切割模片粘合膜，其中，所述a)热固性多官能团环氧树脂为选自甲酚线型酚醛环氧树脂、双酚A型线型酚醛环氧树脂、苯酚线型酚醛环氧树脂、4官能团环氧树脂、联苯型环氧树脂、三苯酚甲烷型环氧树脂、烷基改性的三苯酚甲烷环氧树脂、萘型环氧树脂、二环戊二烯型环氧树脂和二环戊二烯改性的苯酚型环氧树脂中的至少一种。
7.根据权利要求3所述的切割模片粘合膜，其中，所述a)热固性多官能团环氧树脂的软化点为50-100℃。
8.根据权利要求3所述的切割模片粘合膜，其中，所述b)低弹性高分子树脂的玻璃化转变温度为50℃或更低。
9.根据权利要求3所述的切割模片粘合膜，其中，所述b)低弹性高分子树脂的平均分子量为100,000-2,500,000。
10.根据权利要求3所述的切割模片粘合膜，其中，所述b)低弹性高分子树脂为选自包含羧基的丁腈橡胶；具有高分子量的脂族环氧树脂；橡胶改性的环氧树脂；包含缩水甘油基、羧基、羟基或胺基的丙烯酸共聚物；和马来酸改性的苯乙烯乙烯丁二烯苯乙烯共聚物中的至少一种。
11.根据权利要求3所述的切割模片粘合膜，其中，所述模片粘合部分的粘合层进一步包含固化剂。
12.根据权利要求11所述的切割模片粘合膜，其中，所述固化剂为多官能团酚树脂。
13.根据权利要求12所述的切割模片粘合膜，其中，所述多官能团酚树脂的羟基当量为100-1000。
14.根据权利要求12所述的切割模片粘合膜，其中，所述多官能团酚树脂为选自双酚A树脂、线型酚醛树脂、甲酚线型酚醛树脂、双酚A线型酚醛树脂、苯酚芳烷基树脂、多官能团线型酚醛清漆树脂、二环戊二烯线型酚醛树脂、氨基三嗪线型酚醛树脂、聚丁二烯线型酚醛树脂和联苯型树脂中的至少一种。
15.根据权利要求11所述的切割模片粘合膜，其中，所述固化剂的软化点为50-100℃。
16.根据权利要求11所述的切割模片粘合膜，其中，所述固化剂的当量为所述a)热固性多官能团环氧树脂的当量的0.4-2倍。
17.根据权利要求3所述的切割模片粘合膜，其中，所述模片粘合部分的粘合层进一步包含固化促进剂。
18.根据权利要求17所述的切割模片粘合膜，其中，所述固化促进剂为选自2-甲基咪唑(2MZ)、2-乙基-4-甲基咪唑(2E4MZ)、2-苯基咪唑(2PZ)、1-氰乙基-2-苯基咪唑(2PZ-CN)、2-十一烷基咪唑(C11Z)、2-十七烷基咪唑(C17Z)和1-氰乙基-2-苯基咪唑(2PZ-CNS)中的至少一种。
19.根据权利要求17所述的切割模片粘合膜，其中，基于100重量份的a)热固性多官能团环氧树脂和b)低弹性高分子树脂的总量，所述固化促进剂的含量为0.1-10重量份。
20.根据权利要求3所述的切割模片粘合膜，其中，所述模片粘合部分的粘合层进一步包含无机填料。
21.根据权利要求1所述的切割模片粘合膜，其中，所述模片粘合部分进一步包括保护膜。
22.根据权利要求1所述的切割模片粘合膜，其中，所述切割部分的粘性层包含基于丙烯酰基的共聚物。
23.根据权利要求22所述的切割模片粘合膜，其中，所述基于丙烯酰基的共聚物是通过共聚合含有C1-C12烷基的基于(甲基)丙烯酸酯的单体和含有交联官能团的单体来获得的。
24.根据权利要求23所述的切割模片粘合膜，其中，所述含有C1-C12烷基的基于(甲基)丙烯酸酯的单体为选自(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸正辛酯和(甲基)丙烯酸正十四烷酯中的至少一种。
25.根据权利要求23所述的切割模片粘合膜，其中，所述含有交联官能团的单体为选自(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、(甲基)丙烯酸-4-羟丁酯、(甲基)丙烯酸-6-羟己酯、(甲基)丙烯酸-2-羟基乙二醇酯、(甲基)丙烯酸-2-羟基丙二醇酯、(甲基)丙烯酸、马来酸、富马酸、丙烯酰胺、N-乙烯基吡咯烷酮和N-乙烯基己内酰胺中的至少一种。
26.根据权利要求22所述的切割模片粘合膜，其中，所述切割部分的粘性层包含多功能交联剂。
27.根据权利要求1所述的切割模片粘合膜，其中，所述切割部分包含基板膜。
28.一种半导体晶片，其中，将根据权利要求1-27中任一项所述的切割模片粘合膜的粘合层粘附在晶片的一侧，并且将该切割模片粘合膜的粘性层固定在晶片环的框架上。
29.一种半导体器件，其包括：
布线基板；
根据权利要求1-27中任一项所述的切割模片粘合膜的粘合层，其粘附在该布线基板的芯片安装面上；和
半导体芯片，其安装在该粘合层上。
CN2008801146022A 2007-12-27 2008-10-28 具有优异的毛刺性能和可靠性的切割模片粘合膜以及应用该粘合膜的半导体器件 Active CN101848974B (zh)

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