CN101641773B - 用于半导体的粘合膜和使用该粘合膜的半导体器件 - Google Patents
用于半导体的粘合膜和使用该粘合膜的半导体器件 Download PDFInfo
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Abstract
本发明提供了用于半导体的粘合膜,其包括热塑性树脂(A)、环氧树脂(B)和固化剂(C),其特征在于,所述用于半导体的粘合膜从室温开始以10℃/分钟的升温速度在50℃~180℃的温度范围内,其最小熔融粘度为0.1Pa·s~500Pa·s,并且挥发性组分的含量为5.0%或更少。通过该粘合膜,半导体元件可以与用于半导体元件安装的支撑部件结合得更加紧密,从而避免产生空隙。由此,可以提供可靠性更高的半导体器件。
Description
技术领域
本发明涉及用于半导体的粘合膜和使用所述粘合膜的半导体器件。
背景技术
在近来的半导体封装件中,已经越来越多地使用有机基板,例如双马来酰亚胺三嗪基板和聚酰亚胺基板,来代替引线框。
上述半导体封装件含有以下组成:半导体元件、用于安装半导体元件的支撑部件和封装材料,并且,已经使用例如聚酰亚胺系列的用于半导体的粘合膜,用于将半导体元件与用于半导体元件的支撑部件相接合。 专利文献1:日本特开1994-264035号公报 专利文献2:日本特开2000-200793号公报 专利文献3:日本特开2003-96426号公报
发明内容
然而,上述专利文献所述的相关技术在以下方面具有可改进的空间。 目前有如下问题:当使用已知的用于半导体的粘合膜来制造具有半导体元件和有机基板相接合的结构的半导体器件时,易于产生裂纹,导致可靠性低。 出于本发明的目的,已经发现上述半导体器件能够通过如下方式变得更为可靠:从室温开始以10℃/分钟的速度升温,在50℃~180℃的温度范围内(包括两个端点值),将其最小熔融粘度控制为0.1Pa·s~500Pa·s(包 括两个端点值),且将其挥发性组分的含量控制为5.0%或更少。
根据本发明,提供一种用于半导体的粘合膜,其包括热塑性树脂(A)、环氧树脂(B)和固化剂(C),其中用于半导体的粘合膜从室温开始以10℃/分钟的速度升温,在50℃~180℃的温度范围内(包括两个端点值),其最小熔融粘度为0.1Pa·s~500Pa·s(包括两个端点值),且其挥发性组分的含量为5.0%或更少。 本发明的用于半导体的粘合膜在特定的温度范围内具有特定范围的最小熔融粘度。温度范围在施用膜时是可以设定的,并且当本发明的用于半导体的粘合膜在产生最小熔融粘度的温度附近施用时,熔融粘度可以足够低以填充到电路基板上的缝隙中,使得粘合剂没有空隙(void)。由于含有较多挥发物的填充材料会引起裂纹,可将挥发物的含量同时控制在5.0%或更少,以防止由于生成气体而形成空隙。
本发明的半导体粘合膜可用于将半导体元件紧密接合到用于安装半导体元件的支撑部件上,特别是有机基板上,而不产生空隙,从而能够提供可靠性高的半导体器件。
附图说明
参考下面描述的合适实施方案以及下面所附的附图,进一步清楚地理解这些和其它目的、特征和优点。
图1示意性地显示本发明的用于半导体的粘合膜的熔融粘度与温度之间的关系。 图2为示意性地显示本发明的半导体器件的一个实例的剖面图。
本发明的最佳实施方式
本发明的用于半导体的粘合膜是如下用于半导体的粘合膜,其包括热 塑性树脂(A)、环氧树脂(B)和固化剂(C),其中用于半导体的粘合膜从室温开始以10℃/分钟的速度升温,在50℃~180℃的温度范围内(包括两个端点值),其最小熔融粘度为0.1Pa·s~500Pa·s(包括两个端点值),并且其挥发性物质的含量为5.0%或更少。
当通过使用常规的用于半导体的粘合膜聚酰亚胺系列半导体粘合膜将半导体元件接合到用于安装半导体元件的支撑部件上来制备半导体器件时,在可靠性方面存在问题,例如在粘合界面产生裂纹。我们已经利用剖面分析和扫描声波层析成象法(SAT)认真研究了常规的半导体器件,发现当使用常规的用于半导体的粘合膜时,在制备半导体器件之后立刻在半导体元件与用于半导体元件的支撑部件之间形成空隙。
当使用在其表面具有金属互连的有机基板作为用于安装半导体元件的支撑部件时,该现象非常显著。可以想到,当金属互连在有机基板上形成时,互连的厚度在基板上引起缝隙,其不能在与半导体元件接合时被粘合膜充分地填充,因而导致空隙,并由此导致可靠性劣化。
假设不平整的部分得不到充分填充可能是由于在粘合时用于半导体的粘合膜的熔融粘度高,我们测量了作为常规的用于半导体的粘合膜的聚酰亚胺半导体粘合膜的熔融粘度,发现熔融粘度在粘合温度大约为4000Pa·s。 我们已经发现在本发明中,半导体器件的可靠性能够通过合理填充上述空隙而改善,通过将用于半导体的粘合膜在粘合时的熔融粘度调节为0.1Pa·s~500Pa·s(包括两个端点值),其充分低于常规的熔融粘度,并且将挥发物的含量控制到5.0%或更少,来合理填充上述空隙。此外,可以通过将产生该熔融粘度的温度调节为50℃~180℃(包括两个端点值),其明显低于常规的粘合温度,从而防止半导体元件的热损伤。
在本发明中,如果以10℃/分钟的速度升温在50℃~180℃的范围内,测定的最小熔融粘度为0.1Pa·s~500Pa·s,可以采用产生该最小熔融粘度 的温度附近的温度作为粘合温度,从而选择合适的粘合温度。
可以通过使用例如作为粘弹性测量工具的流变仪,以10℃/分钟的升温速度,以1Hz的频率向膜样品施加剪应力,在本发明测定熔融粘度。
图1示意性地显示本发明的用于半导体的粘合膜的熔融粘度与温度之间的关系的实例。纵坐标代表熔融粘度(η),横坐标代表温度(t)。本发明的用于半导体的粘合膜具有图1中所示的特征,在将用于半导体的粘合膜以10℃/分钟的升温速度从25℃加热到其熔融温度的过程中,熔融粘度在初始阶段降低(图中箭头A),在某个温度(t1)达到最小熔融粘度(η1),然后升高(图中箭头B)。图2显示具有本发明的用于半导体的粘合膜的半导体器件的一个实例。如图2所示,半导体元件(2)与用于安装半导体元件的支撑部件(3)通过用于半导体的粘合膜(1)接合。
此处,用于半导体的粘合膜被设计为在50℃~180℃的范围内,具有0.1Pa·s~500Pa·s(包括两个端点值)的最小熔融粘度。熔融粘度优选1Pa·s~100Pa·s(包括两个端点值),特别是5Pa·s~50Pa·s(包括两个端点值)。当它为500Pa·s或更低时,热压接合时的可流动性得到改善,使得在有机基板中形成的膜与电路之间的空隙能够被填充。当它为0.1Pa·s或更高时,能够防止用于半导体的粘合膜的过度流动,以降低半导体元件污染的风险,并且能够防止在热固化用于半导体的粘合膜时,由用于半导体的粘合膜夹带来自有机基板的气体而形成的空隙。
可以通过使用热塑性树脂(A)、环氧树脂(B)和固化剂(C)的方法来获得上述最小熔融粘度,其中环氧树脂(B)或固化剂(C)是高流动性的、含有在25℃时为液体的小分子单体。通过与在25℃时为固体的单体组合,最小熔融粘度可以设计为上述范围,同时防止用于半导体的粘合膜的粘性增加,导致可加工性改善。 或者,可以加入例如具有分子内辐射可聚合性的碳-碳双键的单体的组分,其对于热塑性树脂(A)、环氧树脂(B)和固化剂(C)是惰性的,并且在25℃时为液体。特定的例子包括主要由丙烯酸化合物构成的紫外固化树脂;主要由聚氨酯丙烯酸酯低聚物或聚酯聚氨酯丙烯酸酯低聚物构成的紫外固化树脂;和主要由选自环氧树脂和乙烯基酚树脂中的至少一种构成的紫外固化树脂。 此外,最小粘度通过增加环氧树脂(B)和固化剂(C)相对于热塑性树脂(A)的含量而获得。特别地,其能够在0.1≤a/(a+b+c)≤0.5时获得,其中热塑性树脂(A)的含量为“a”重量份;环氧树脂(B)的含量为“b”重量份;而固化剂(C)的含量为“c”重量份。
在本发明的用于半导体的粘合膜中,挥发物的含量为5.0%或更低。挥发物可以包括在将用于半导体的粘合膜热固化时,包含在用于半导体的粘合膜中的未反应的热固性树脂及其分解产物,以及不参与热固反应的材料及其分解产物。特别地,通过使用不含不参与热固反应的材料的膜,挥发物的含量能够为5.0%或更少。挥发物的具体例子包括紫外固化树脂,例如具有(甲基)丙烯酸基团的化合物;和紫外固化引发剂,例如二苯甲酮、苯乙酮、安息香、安息香异丁醚、安息香苯甲酸甲酯、安息香苯甲酸、安息香甲醚、苄基苯基硫醚、联苯酰、联苄和丁二酮。本发明中挥发物的量确定为,例如,将切割为50mm×50mm的正方形的用于半导体的粘合膜在200℃加热2小时后的重量减少量。本发明中挥发物的含量优选5.0%或更少,特别优选3.0%或更少。这样,当在通过加热使膜固化过程中用于半导体的粘合膜的熔融粘度降低时,没有气体组分从膜中产生,使得用于半导体的粘合膜能够固化而不形成空隙,并因此当在将器件安装在基板上的过程中半导体器件被回流焊炉加热至高温时,能够避免由于空隙的热膨胀而形成的裂缝。
在粘合后,本发明的用于半导体的粘合膜优选具有1MPa或更高的芯片剪切强度(die-shear strength),更优选2MPa或更高。这样,当在将器件安装在基板上的过程中,半导体器件被回流焊炉加热至高温时,由粘合力降低引起的脱离能够避免,从而防止由脱离引起的回流裂纹。使用通过将用于半导体的粘合膜夹在尺寸为4×4mm、厚度为550μm的硅片与涂覆有阻焊剂的双马来酰亚胺三嗪基板(TAIYO INK MFG Co.Ltd.:商品名AUS308)之间而制备,并随后在130℃和5N热压1秒而热固化的样品,来测量晶片抗切强度,并且该晶片抗切强度被确定为通过将样品放置在260℃的热板上20秒,然后向样品以0.5mm/分钟的速率从硅片侧施加剪切应力所观察到的剪切强度。
本发明涉及一种用于半导体的粘合膜,其含有热塑性树脂(A)、环氧树脂(B)和固化剂(C)。下面将说明本发明的用于半导体的粘合膜中的每个组分。下述说明仅仅是出于举例说明的目的,不以任何方式限制本发明。
如本文所使用,热塑性树脂(A)是指热塑性聚合物树脂,其一般具有有直链化学结构的主链骨架。具体例子包括聚酰亚胺树脂、例如聚醚酰亚胺树脂的聚酰亚胺型树脂、聚酰胺树脂、例如聚酰胺-酰亚胺树脂的聚酰胺型树脂、和例如丙烯酸酯共聚物的丙烯酸树脂。
上述热塑性树脂中,优选丙烯酸树脂。由于丙烯酸树脂的低玻璃转化温度,其能够改善初始粘合性。此处,术语“初始粘合性”是指在用于半导体的粘合膜中,将半导体元件粘合到支撑部件的初始阶段中的粘合性,即,将用于半导体的粘合膜固化之前的粘合性。
丙烯酸树脂是指基于丙烯酸及其衍生物作为主要起始单体的树脂。具体例子包括丙烯酸、甲基丙烯酸、例如丙烯酸甲酯和丙烯酸乙酯的丙烯酸酯、例如甲基丙烯酸甲酯和甲基丙烯酸乙酯的甲基丙烯酸酯、丙烯腈、丙烯酰胺等的聚合物,以及与其它单体的共聚物。 在本发明中,优选基于如下化合物的丙烯酸树脂(特别地,丙烯酸酯共聚物):具有例如环氧基、羟基、羧基和腈基的化合物。这样,与例如半导体元件的接合材料的粘合性能够得到改善。具有上述官能团的化合物的例子包括具有缩水甘油醚基的甲基丙烯酸缩水甘油酯、具有羟基的羟基甲基丙烯酸酯、具有羧基的羧基甲基丙烯酸酯、和具有氰基的丙烯腈。其 中,特别优选具有腈基的丙烯酸酯共聚物。这样,与接合材料的粘合性能够得到改善。
具有上述官能团的化合物的含量相对于丙烯酸树脂的重量是,但不限于,优选0.5重量%~40重量%(包括两个端点值),特别优选5重量%~30重量%(包括两个端点值)。含量为0.5重量%或以上可导致粘合性的有效改善,而含量为40重量%或以下可导致充分控制的粘合力以改善可加工性。
本发明所使用的热塑性树脂(A)的重均分子量优选为100,000或更大,特别优选150,000~1,000,000。当重均分子量在上述范围内时,可特别改善用于半导体的粘合膜的成膜性。此外,当重均分子量在上述范围内时,即使当热塑性树脂具有热固性官能团时,单独使用该树脂基本不表现出热固化行为。
本发明中使用的热塑性树脂(A)的玻璃转化温度为,但不限于,优选-20℃~60℃(包括两个端点值),特别优选-10℃~50℃(包括两个端点值)。当玻璃转化温度为-20℃或更高时,用于半导体的粘合膜的粘合力可被控制以有效地改善可加工性。当玻璃转化温度为60℃或更低时,可改善低温粘合性。
本发明中使用的热塑性树脂(A)的含量为,但不限于,优选0.1≤a/(a+b+c)≤0.5,更优选0.15≤a/(a+b+c)≤0.4,特别优选0.2≤a/(a+b+c)≤0.3,其中“a”、“b”和“c”分别为热塑性树脂(A)、环氧树脂(B)和固化剂(C)的重量份含量。当其为0.1或更大时,树脂组分的成膜性得到改善,并且用于半导体的粘合膜的韧度得到改善。当其为0.5或更小时,粘合膜可在粘合过程具有改善的可流动性,使得在热压接合过程中,有机基板中的电路间隔(circuit step)可由粘合膜填充。
本发明中使用的环氧树脂(B)是指任何单体、寡聚物和聚合物。实 例包括联苯型环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂、氢化双酚A型环氧树脂、脂肪族型环氧树脂、均二苯代乙烯型环氧树脂、邻甲酚酚醛清漆型环氧树脂、苯酚酚醛清漆型环氧树脂、改性苯酚型环氧树脂、三苯酚甲烷(triphenolmethane)型环氧树脂、烷基改性的三苯酚甲烷型环氧树脂、含三嗪核的环氧树脂、萘型环氧树脂、二环戊二烯型环氧树脂、二环戊二烯改性的苯酚型环氧树脂、缩水甘油胺型环氧树脂、双酚A酚醛清漆型环氧树脂、溴代苯酚酚醛清漆型环氧树脂和萘酚型环氧树脂。
环氧树脂(B)的含量相对于10重量份的热塑性树脂(A)优选为10重量份或更高,特别优选20重量份。这样,粘合过程中的可流动性可得到改善。环氧树脂(B)的含量相对于10重量份的热塑性树脂(A)优选为100重量份或更低,特别优选50重量份或更低。这样,用于半导体的粘合膜的韧度得到改善。
本发明中使用的固化剂(C)可合适地选自用于环氧树脂的固化剂。本发明中使用的固化剂(C)的具体例子包括胺型固化剂,包括例如二乙撑三胺、三乙撑四胺和间苯撑二甲基二胺的脂肪族聚胺,例如二氨基二苯甲烷、间苯撑二胺和二氨基二苯砜的芳香族聚胺,以及例如双氰胺和有机酸二酰肼的聚胺化合物;酸酐型固化剂,包括例如六氢邻苯二甲酸酐和甲基四氢邻苯二甲酸酐的脂肪族酸酐,以及例如偏苯三酸酐和均苯四酸-二苯甲酮四羧酸酐的芳香族酸酐;酚型固化剂(phenol type curing agent),例如苯酚酚醛清漆树脂、甲酚酚醛清漆树脂、苯酚芳烷基(含有亚苯基或亚联苯基骨架)树脂、萘酚芳烷基树脂、三苯酚甲烷树脂、二环戊二烯型苯酚树脂、双(单-或二-t-丁基苯酚)丙烷、亚甲基双(2-丙烯基)苯酚、亚丙基双(2-丙烯基)苯酚、双[(2-丙烯氧基)苯基]甲烷、双[(2-丙烯氧基)苯基]丙烷、4,4’-(1-甲基乙叉)双[2-(2-丙烯基)苯酚]、4,4’-(1-甲基乙叉)双[2-(1-苯基乙基)苯酚]、4,4’-(1-甲基乙叉)双[2-甲基-6-羟基甲基苯酚]、4,4’-(1-甲基乙叉)双[2-甲基-6-(2-丙烯基)苯酚]和4,4’-(1-甲基十四叉)双苯酚。 在本发明中,优选使用在25℃粘度为30Pa·s(30,000cps)或更低的液体固化剂,进一步优选在25℃粘度为10Pa·s(10,000cps)或更低的液 体固化剂。通过将本发明中使用的固化剂在25℃的粘度控制在特定值以下,可改善初始粘合性和可靠性。
本发明中使用的优选的固化剂(C)包括液体酚化合物。液体酚化合物的具体例子包括双(单-或二-t-丁基苯酚)丙烷、亚甲基双(2-丙烯基)苯酚、亚丙基双(2-丙烯基)苯酚、双[(2-丙烯氧基)苯基]甲烷、双[(2-丙烯氧基)苯基]丙烷、4,4’-(1-甲基乙叉)双[2-(1-丙烯基)苯酚]、4,4’-(1-甲基乙叉)双[2-(2-苯基乙基)苯酚]、4,4’-(1-甲基乙叉)双[2-甲基-6-羟基甲基苯酚]、4,4’-(1-甲基乙叉)双[2-甲基-6-(2-丙烯基)苯酚]和4,4’-(1-甲基十四叉)双苯酚。
本发明中使用的固化剂(C)的含量可以通过计算环氧当量与固化剂当量的比例来确定。环氧树脂(B)的环氧当量与固化剂(C)的官能团当量(例如酚树脂(phenol resin)中的羟基当量)的比例优选为0.5或更高,特别是0.7或更高。这样,用于半导体的粘合膜的耐热性可得到改善。比例优选为1.5或更低,特别是1.3或更低。这样,用于半导体的粘合膜的贮存稳定性可得到改善。
本发明中使用的固化剂(C)优选为式(1)代表的化合物。式(1)代表的化合物是烯丙基苯酚与甲醛的缩聚产物,特别是2-(2-丙烯基)苯酚的缩聚产物。
在本发明中,也可能加入固体酚树脂作为固化剂(C)。组合固体酚 树脂将导致用于半导体的粘合膜在室温时的粘性减低,导致改善的可加工性。此外,固体酚树脂是指具有至少两个酚羟基基团的一般单体、寡聚物或聚合物,其能够在与环氧树脂(B)的固化反应之后形成交联结构,并且在25℃和环境压力下为固体;例如,苯酚酚醛清漆树脂、甲酚酚醛清漆树脂、苯酚芳烷基(含有亚苯基或亚联苯基骨架)树脂、萘酚芳烷基树脂、三苯酚甲烷树脂、二环戊二烯型苯酚树脂,其可单独使用或两个或多个组合使用。
如果必要,上述树脂组合物可含有用于加速固化反应的固化促进剂。固化促进剂的具体例子包括胺型催化剂,例如咪唑和1,8-二氮杂双环(5,4,0)十一碳烯;和磷型催化剂,例如三苯膦。
如果必要,本发明粘合膜层可进一步含有偶联剂。其可以提高树脂与接合材料或与树脂的粘合性。
偶联剂可以是硅烷型、钛型或铝型偶联剂,特别优选硅烷型偶联剂。偶联剂的实例包括乙烯基三氯硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷、γ-缩水甘油氧基丙基三甲氧基硅烷、γ-缩水甘油氧基丙基甲基二甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基甲基二乙氧基硅烷、γ-甲基丙烯酰氧基丙基三乙氧基硅烷、N-β(氨乙基)γ-氨丙基甲基二甲氧基硅烷、N-β(氨乙基)γ-氨丙基三甲氧基硅烷、N-β(氨乙基)γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、N-苯基-γ-氨丙基三甲氧基硅烷、γ-氯丙基三甲氧基硅烷、γ-巯基丙基三甲氧基硅烷、3-异氰酸丙基三乙氧基硅烷(3-isocyanatopropyltriethoxysilane)和3-丙烯酰氧基丙基三甲氧基硅烷。
相对于100重量份上述丙烯酸酯共聚物,上述偶联剂的含量为,但不限于,优选0.01重量份或更多,特别优选0.1重量份或更多。这样,粘合性可以进一步有效改善。含量优选10重量份或更少。这样,可防止脱气 或空隙形成。
如果必要,上述树脂组合物可含有含氰酸酯的有机化合物作为附加组分。这样,与接合材料的粘合性以及耐热性可进一步得到改善。 含氰酸酯的有机化合物的实例包括双酚A二氰酸酯、双酚F二氰酸酯、双(4-氰酰苯基)醚、双酚E二氰酸酯和氰酰酚醛清漆树脂。
可以通过例如将上述树脂组合物溶解在诸如甲乙酮、丙酮、甲苯和二甲基甲酰胺的溶剂中以制备清漆,利用逗点式涂布机(comma coater)、铸模涂布机(die coater)、凹板涂布机(gravure coater)或类似物将清漆涂布于离型板(release sheet)上,将其干燥,然后除去离型板,从而获得本发明的用于半导体的粘合膜。 用于半导体的粘合膜的厚度为,但不限于,优选3μm~100μm(包括两个端点值),特别优选5μm~70μm(包括两个端点值)。当厚度在上述范围内时,可以特别精确地控制厚度。
下面将说明用于半导体的粘合膜的实施例和比较例。 (实施例1) (1)用于半导体的粘合膜的清漆的制备 将以下物质溶解在甲乙酮(MEK)中,以制备树脂固体含量为49%的树脂清漆:100重量份的丙烯酸酯共聚物(丙烯酸丁酯-丙烯腈-丙烯酸乙酯-甲基丙烯酸缩水甘油酯共聚物,Nagase Chemtex Corp.,SG-80HDR,Tg:10℃,重均分子量:350,000),其作为热塑性树脂(A);97重量份的环氧树脂(EOCN-1020-80(邻甲酚酚醛清漆型环氧树脂),环氧当量200g/eq,Nippon Kayaku Co.,Ltd.),其作为硬化树脂;146重量份的NC6000(环氧当量200g/eq,Nippon Kayaku Co.,Ltd.);110重量份的液体酚化合物(MEH-8000H,羟基当量141g/OH基团,Meiwa PlasticIndustries,Ltd.);47重量份的固体酚树脂(PR-HF-3,羟基当量104g/OH基团,Sumitomo Bakelite Co.,Ltd.);0.75重量份的咪唑化合物(2P4MHZ-PW,Shikoku Chemicals Corp.),其作为固化促进剂;和1.3 重量份的γ-缩水甘油氧基丙基三甲氧基硅烷(KBM403E,Shin-EtsuChemical Co.,Ltd.),其作为偶联剂。
(2)用于半导体的粘合膜的制备 将上述树脂清漆利用逗点式涂布机施加到作为基材膜(I)的聚对苯二甲酸乙二酯膜(Mitsubishi Polyester Film Corp.,目录号:MRX50,厚度50μm)上,然后在90℃干燥5分钟,以提供厚度为25μm的用于半导体的粘合膜。
(3)基材膜(II)和粘合剂层的制备 利用挤出机使由60重量份HYBRAR(注册商标)和40重量份聚丙烯组成的Cleartech CT-H717(Kuraray Co.,Ltd.)成形为厚度为100μm的膜作为基材膜(∏),然后对其表面进行电晕处理(corona-treated)。然后将通过50重量份丙烯酸-2-乙基己酯、10重量份丙烯酸丁酯、37重量份乙酸乙烯酯和3重量份甲基丙烯酸-2-羟乙酯的共聚而制成的重均分子量为500,000的共聚物涂布在厚度为38μm的剥离处理的聚酯膜上,从而使干燥后的厚度为10μm,并将膜在80℃下干燥5分钟,从而得到粘合剂层。然后将粘合剂层层压在基材膜(∏)的经电晕处理的表面,从而获得具有基材膜(∏)的粘合剂层。
(4)切割芯片贴合膜(dicing die attach film)的制备将保护膜层压在具有基材膜(I)的上述粘合膜层上,并将基材膜(I)和粘合膜层切割成两半,其层压在基材膜(II)上的上述粘合剂层上。将保护膜除去,得到由基材膜(II)、粘合剂层、基材膜(I)和粘合膜层顺序层压的切割芯片贴合膜。
(5)半导体器件的制备将在各个实施例和比较例中制备的切割芯片贴合膜在60℃附于5英寸、200μm晶片的背面,得到具有切割芯片贴合膜的晶片。然后,利用轴频率为30,000rpm、切割速度(dicing rate)为50mm/sec的切割锯,将具有切割芯片贴合膜的晶片切割(切断)成5mm×5mm的方形半导体元件。然后,从切割芯片贴合膜的背面推元件,从而使基材膜(II)与粘合膜层分离。将具有芯片贴合膜的半导体元件与涂布有阻焊剂(Taiyo Ink Mfg.Co.,Ltd.,商品名:AUS308)的双马来酰亚胺-三嗪树脂基板(电路间隔:5-10μm)在130℃、5N下接合1秒,并且通过在120℃加热1小时将半导体粘合膜半固化。随后,元件由树脂密封并在175℃下加热2小时,并且使密封树脂固化以得到半导体器件。制备10个器件。
下面是本发明的用于半导体的粘合膜的详细评估测试。
(最小熔融粘度的测量方法)将数个用于半导体的粘合膜层压为100μm厚以制备样品,随后使用HAAKE Corp.Rheostress RS-150在其上以1Hz频率和10℃/分钟的升温速度施加剪切力(shear force)。
(挥发物的测量方法)使用尺寸为50×50mm、测量重量为M1的用于半导体的粘合膜作为样品,其在热气循环恒温加热炉中于200℃加热2小时,然后称重(M2)。使用如下公式计算挥发物的含量:[(M2-M1)/M1]×100=挥发物含量(%)。
(粘合后芯片剪切强度的测量方法) 将用于半导体的粘合膜插入4×4mm的硅片(厚度:550μm)与涂布有阻焊剂(Taiyo Ink Mfq.Co.,Ltd.,商品名:AUS308)的双马来酰亚胺三嗪基板之间,在130℃和5N下将样品接合1秒,接着在120℃加热1小时,随后在175℃加热2小时。样品在260℃的热板上停留20秒,然后利用推拉力计(push-pull gauge)以0.5mm/min的速度向样品施加剪应力,测定剪切强度即得芯片剪切强度。
(电路填充性能) 通过扫描式声波层析成像仪(SAT)确定在树脂密封前,具有用于半导体的粘合膜的半导体器件中的有机基板上的电路间隔的填充率,评估电路填充性能。符号具有如下含义。 ◎:填充率=100% ○:填充率=80%或更大且小于100% △:填充率=40%或更大且小于80% ×:填充率小于40%
下面是使用本发明的用于半导体的粘合膜制备的半导体器件的详细评估测试。
(湿处理后的粘合性) 对各个实施例和比较例中制备的、树脂密封前的半导体器件,在85℃/85%RH/168小时的条件下进行吸湿处理,评估半导体元件与有机基板之间于260℃的剪切强度。◎:剪切强度=1.0MPa或更大 ○:剪切强度=0.75MPa或更大且小于1.0MPa △:剪切强度=0.5MPa或更大且小于0.75MPa ×:剪切强度小于0.5MPa
(抗裂性(crack resistance)) 将各个实施例和比较例中制备的半导体器件在85℃/85%RH/168小时的条件下进行吸湿处理,进行三次260℃下IR回流,然后通过扫描式声波层析成像仪(SAT)评价其抗裂性。符号具有如下含义。 ◎:裂纹数=0/10 ○:裂纹数=1/10~3/10(包括两个端点值) △:裂纹数=4/10~9/10(包括两个端点值) ×:裂纹数=10/10
表1详细显示实施例和比较例中制备的用于半导体的粘合膜的物理性质和各种评价结果,以及具有用于半导体的粘合膜的半导体器件的评价结果。
(实施例2) 如实施例1所述进行实验,不同的是,使用99重量份的EOCN-1020-80(环氧当量200g/eq,Nippon Kayaku Co.,Ltd.),其作为环氧树脂;148重量份的NC6000(环氧当量200g/eq,Nippon Kayaku Co.,Ltd.);92重量份的MEH-8000H(羟基当量141g/OH基团,Meiwa Plastic Industries,Ltd.),其作为液体酚化合物(C);和62重量份的PR-HF-3(羟基当量104g/OH基团,Sumitomo Bakelite Co.,Ltd.),其作为固体酚树脂。表1示出组成和实验结果。
(实施例3) 如实施例1所述进行实验,不同的是,使用110重量份的MEH-8000-4L(羟基当量141g/OH基团,Meiwa Plastic Industries,Ltd.)作为液体酚化合物(C)。表1示出组成和实验结果。
(实施例4) 如实施例1所述进行实验,不同的是,使用47重量份的PR53647(羟基当量104g/OH基团,Sumitomo Bakelite Co.,Ltd.)作为固体酚树脂。表1示出组成和实验结果。
(实施例5) 如实施例1所述进行实验,不同的是,使用200重量份的EOCN-1020-80(环氧当量200g/eq,Nippon Kayaku Co.,Ltd.),其作为环氧树脂;和141重量份的MEH-8000H(羟基当量141g/OH基团,MeiwaPlastic Industries,Ltd.),其作为液体酚化合物(C)。表1示出组成和实验结果。
(实施例6) 如实施例1所述进行实验,不同的是,使用60重量份的EOCN-1020-80(环氧当量200g/eq,Nippon Kayaku Co.,Ltd.),其作为环氧树脂(B); 和42重量份的MEH-8000H(羟基当量141g/OH基团,Meiwa PlasticIndustries,Ltd.),其作为液体酚化合物(C)。表1示出组成和实验结果。
(实施例7) 如实施例1所述进行实验,不同的是,使用400重量份的EOCN-1020-80(环氧当量200g/eq,Nippon Kayaku Co.,Ltd.),其作为环氧树脂(B);和282重量份的MEH-8000H(羟基当量141g/OH基团,Meiwa Plastic Industries,Ltd.),其作为液体酚化合物(C)。表1示出组成和实验结果。
(实施例8) 在60℃、0.1MPa和50mm/sec的条件下,将各个实施例和比较例中制备的用于半导体的粘合膜的一面层压到5英寸、200μm的半导体晶片的背面,并且将用于半导体的粘合膜的一面固定到切割膜(Sumilite(注册商标)FSL-N4003,Sumitomo Bakelite Co.,Ltd.)上。然后,利用切割锯以30,000rpm的轴频率和50mm/sec的切割速度,将具有用于半导体的粘合膜的半导体晶片切割(切断)成5mm×5mm的方形半导体元件,以获得具有用于半导体的粘合膜的半导体元件。然后,从切割膜中光透明的基材一面利用紫外射线照射元件20秒,达到250mJ/cm2的曝光量,随后从切割膜的背面推元件。接着,将具有用于半导体的粘合膜的半导体元件与涂布有阻焊剂(Taiyo Ink Mfg.Co.,Ltd.,AUS308)的双马来酰亚胺-三嗪基有机基板(表面间隙:5-10μm)在130℃、5N下接合1秒,并且在120℃加热1小时,将半导体粘合膜半固化。元件由树脂密封并在175℃下加热2小时,以固化密封树脂,从而得到半导体器件。图2示意性地示出由此得到的半导体器件。发现该半导体器件在各种评价测试中表现出更高的可靠性。
(比较例1) 如实施例1所述进行实验,不同的是,没加入环氧树脂(B)、液体酚化合物(C)、固体酚树脂或固化促进剂。表1示出组成和实验结果。
(比较例2) 如实施例1所述进行实验,不同的是,环氧树脂(B)是200重量份的EOCN-1020-80(环氧当量200g/eq,Nippon Kayaku Co.,Ltd.);固体酚树脂是104重量份的PR-HF-3(羟基当量104g/OH基团,SumitomoBakelite Co.,Ltd.);并且不加入液体酚化合物(C)。表1示出组成和实验结果。
(比较例3) 如实施例1所述进行实验,不同的是,环氧树脂(B)是200重量份的EOCN-1020-80(环氧当量200g/eq,Nippon Kayaku Co.,Ltd.);固体酚树脂是104重量份的PR-HF-3(羟基当量104g/OH基团,SumitomoBakelite Co.,Ltd.);UV可固化单体是120重量份的1,6-己二醇二甲基丙烯酸酯(1,6-HX,制造商:Kyoeisha Chemical Co.,Ltd.);并且不加入液体酚化合物(C)。表1示出组成和实验结果。
(比较例4) 如实施例1所述进行实验,不同的是,环氧树脂(B)是526重量份的NC6000(环氧当量200g/eq,Nippon Kayaku Co.,Ltd.);液体酚化合物(C)是371重量份的MEH-8000H(羟基当量141g/OH基团,MeiwaPlastic Industries,Ltd.);并且不加入固体酚树脂。表1示出组成和实验结果。
(比较例5) 将以下物质溶解在N-甲基-2-吡咯烷酮(NMP)中,以制备树脂固体含量为43%的树脂清漆:100重量份的聚酰亚胺树脂(使用43.85g(0.15mol)1,3-双(3-氨基苯氧基)苯(Mitsui Chemicals,Inc.,APB)作为二胺组分,125.55g(0.15mol)α,ω-双(3-氨基丙基)聚二甲基硅氧烷(平均分子量:837)(Fuso Chemical Co.,Ltd.,G9),和93.07g(0.30mol)4,4’-氧双邻苯二甲酸酐(Manac Incorporated,ODPA-M)作为酸组分而制备的 聚酰亚胺树脂,Tg:70℃,重均分子量:30,000),其作为热塑性树脂(A);10重量份(EOCN-1020-80(邻甲酚酚醛清漆型环氧树脂),环氧当量200g/eq,Nippon Kayaku Co.,Ltd.),其作为环氧树脂(B);和5重量份的N-苯基-γ-氨基丙基三甲氧基硅烷(KBM573,Shin-Etsu Chemical Co.,Ltd.),其作为偶联剂。将清漆涂覆到保护膜聚对苯二甲酸乙二酯膜(Mitsubishi Polyester Film Corp.,目录号:MRX-50,厚度50μm)上,然后在180℃干燥10分钟,以制备厚度为25μm的用于半导体的粘合膜。该膜用于评估。实验结果如表1所示。
如表1所示,实施例1~7在粘合膜评估和半导体器件评估方面均表现出较好的结果,而比较例1~5中的任何一个均表现出不好的结果。 具体而言,在比较例4中,最小熔融粘度低至0.1Pa·s或更小,使得在半导体芯片层压过程中,粘合膜从接合处流出,导致半导体芯片的不当层压。
Claims (12)
1.用于半导体的粘合膜,其包括热塑性树脂(A)、环氧树脂(B)和固化剂(C),
其中所述用于半导体的粘合膜从室温开始以10℃/分钟的速度升温,在50℃~180℃的温度范围内,其最小熔融粘度为0.1Pa·s~500Pa·s,且其挥发性组分的含量为5.0%或更少。
2.如权利要求1所述的用于半导体的粘合膜,其中粘合后的芯片剪切强度为1MPa或更大。
3.如权利要求1或2所述的用于半导体的粘合膜,其中所述热塑性树脂(A)是丙烯酸树脂。
4.如权利要求1或2所述的用于半导体的粘合膜,其中所述热塑性树脂(A)是具有选自环氧基团、羟基基团、羧基基团和腈基团中的至少一个基团的化合物。
5.如权利要求1或2所述的用于半导体的粘合膜,其中所述热塑性树脂(A)的重均分子量为100,000~1,000,000。
6.如权利要求1或2所述的用于半导体的粘合膜,其中所述热塑性树脂(A)的玻璃转化温度为-20℃~60℃。
7.如权利要求1或2所述的用于半导体的粘合膜,其满足公式0.1≤a/(a+b+c)≤0.5,其中所述热塑性树脂(A)的含量为“a”重量份,所述环氧树脂(B)的含量为“b”重量份,所述固化剂(C)的含量为“c”重量份。
8.如权利要求1或2所述的用于半导体的粘合膜,其中相对于10重量份的所述热塑性树脂(A),所述环氧树脂(B)的含量为10重量份~100重量份。
9.如权利要求1或2所述的用于半导体的粘合膜,其中所述固化剂(C)是酚树脂。
10.如权利要求9所述的用于半导体的粘合膜,其中所述酚树脂在25℃为液体。
11.半导体器件,其具有如下结构:利用如权利要求1~10中任一项所述的用于半导体的粘合膜将半导体元件连接到接合部件上。
12.如权利要求11所述的半导体器件,其中吸湿处理后的剪切强度为1MPa或更大。
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CN101980861B (zh) * | 2008-04-08 | 2014-08-06 | 亚利桑那董事会,代表亚利桑那州立大学行事的亚利桑那州法人团体 | 用于降低半导体加工期间挠性基材的翘曲度和弯曲度的组件和方法 |
JP4939574B2 (ja) * | 2008-08-28 | 2012-05-30 | 日東電工株式会社 | 熱硬化型ダイボンドフィルム |
US8399338B2 (en) * | 2008-11-19 | 2013-03-19 | Denki Kagaku Kogyo Kabushiki Kaisha | Electronic component manufacturing method |
WO2010098324A1 (ja) | 2009-02-27 | 2010-09-02 | ソニーケミカル&インフォメーションデバイス株式会社 | 半導体装置の製造方法 |
JP4816750B2 (ja) * | 2009-03-13 | 2011-11-16 | 住友電気工業株式会社 | プリント配線基板の接続方法 |
KR101359831B1 (ko) * | 2009-05-13 | 2014-02-07 | 히타치가세이가부시끼가이샤 | 접착 시트 |
JP2012049388A (ja) * | 2010-08-27 | 2012-03-08 | Shin Etsu Chem Co Ltd | 半導体ウエハ保護膜形成用シート |
JP5310750B2 (ja) * | 2011-01-19 | 2013-10-09 | デクセリアルズ株式会社 | 異方性導電フィルム |
KR101298368B1 (ko) * | 2011-03-31 | 2013-08-20 | 세키스이가가쿠 고교가부시키가이샤 | 예비 경화물, 조화 예비 경화물 및 적층체 |
JP6193663B2 (ja) * | 2013-07-26 | 2017-09-06 | 日東電工株式会社 | ダイシングテープ付きダイボンドフィルム、及び、半導体装置の製造方法 |
JP6469654B2 (ja) * | 2014-03-31 | 2019-02-13 | 明和化成株式会社 | フェノール樹脂、該フェノール樹脂を含むエポキシ樹脂組成物、該エポキシ樹脂組成物の硬化物、及び該硬化物を有する半導体装置 |
KR101799499B1 (ko) * | 2014-12-24 | 2017-12-20 | 주식회사 엘지화학 | 반도체 접착용 수지 조성물, 접착 필름, 다이싱 다이본딩 필름 및 반도체 장치 |
KR101953774B1 (ko) * | 2015-07-10 | 2019-05-17 | 주식회사 엘지화학 | 반도체 접착용 수지 조성물 및 다이싱 다이본딩 필름 |
KR101770505B1 (ko) * | 2016-03-03 | 2017-08-22 | 주식회사 케이씨씨 | 다이 본딩용 에폭시 수지 조성물 |
KR102012789B1 (ko) | 2016-03-28 | 2019-08-21 | 주식회사 엘지화학 | 반도체 장치 |
WO2019013040A1 (ja) * | 2017-07-10 | 2019-01-17 | Dic株式会社 | 積層体、それを用いたプリント配線板、フレキシブルプリント配線板及び成形品 |
EP3524462A1 (en) * | 2018-02-13 | 2019-08-14 | D. Swarovski KG | Decorative composite body |
TWI695453B (zh) * | 2019-01-04 | 2020-06-01 | 台灣愛司帝科技股份有限公司 | 半導體晶片修補方法以及半導體晶片修補裝置 |
KR20210070639A (ko) | 2019-12-05 | 2021-06-15 | 주식회사 두산 | 반도체 패키지용 언더필 필름 및 이를 이용하는 반도체 패키지의 제조방법 |
WO2021215745A1 (ko) * | 2020-04-24 | 2021-10-28 | 주식회사 엘지화학 | 경화제, 이를 포함하는 반도체 접착용 조성물, 반도체 접착용 필름 및 이를 이용한 반도체 패키지 |
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US20070073008A1 (en) * | 2005-09-28 | 2007-03-29 | Cookson Singapore Pte, Ltd. | Compositions effective to suppress void formation |
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