CN100575438C - 薄膜状粘结剂以及使用该粘结剂的半导体封装体 - Google Patents

薄膜状粘结剂以及使用该粘结剂的半导体封装体 Download PDF

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CN100575438C
CN100575438C CN200510115115A CN200510115115A CN100575438C CN 100575438 C CN100575438 C CN 100575438C CN 200510115115 A CN200510115115 A CN 200510115115A CN 200510115115 A CN200510115115 A CN 200510115115A CN 100575438 C CN100575438 C CN 100575438C
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film
binding agent
polyimide
adhesive layer
layer
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CN1789361A (zh
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儿玉洋一
伊丹清次
佐藤邦章
田原修二
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Mitsui Chemicals Inc
Mitsui Chemical Industry Co Ltd
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Abstract

本发明提供低温粘接性和埋入性优异的能够在半导体封装体内适宜地使用的具有芯片键合薄膜功能的薄膜状粘结剂,以及低温粘接性和埋入性优异的同时起到芯片键合薄膜的功能和切割胶带的功能的薄膜状粘结剂。本发明的薄膜状粘结剂,其特征在于,包括含有玻璃转化温度小于等于100℃的热塑性聚酰亚胺为主成分的粘结剂层(C)以及在50℃的储藏剪切弹性模量小于等于1×106Pa的粘着剂层(D)。上述薄膜状粘结剂进一步包括基材(A)和粘着剂层(B)。

Description

薄膜状粘结剂以及使用该粘结剂的半导体封装体
技术领域
本发明涉及薄膜状粘结剂,更详细地涉及能够在半导体封装体内适宜地使用的具有芯片键合薄膜功能的薄膜状粘结剂,同时具有芯片键合薄膜的功能和在该封装体安装工序中作为切割胶带的功能的薄膜状粘结剂。
背景技术
使用薄膜状粘结剂的半导体封装体的制造工序,通常要经过如下工序:①在大口径的晶片背面粘贴薄膜状粘结剂的工序;②在薄膜状粘结剂侧粘贴切割胶带的工序;③切割,将芯片单片化的工序;④将单片化的芯片从切割胶带揭取的工序;⑤通过薄膜状粘结剂芯片键合到被粘接体衬底上的工序;⑥引线键合芯片/衬底间的工序;⑦用密封剂成型的工序。
薄膜状粘结剂起到芯片键合薄膜的功能,在上述①工序中是对晶片进行粘接,而在上述⑤工序中是对衬底进行粘接。如果着眼于对晶片的粘接,近年来晶片的厚度越来越薄,在高温粘接时会发生晶片翘曲的问题,因此对薄膜状粘结剂要求具有更优异的低温粘接性。另一方面,如果着眼于对衬底的粘接,近年来单个封装体内的芯片层积级数在增加,与芯片引线键合时的温度、时间更加高温化、长时间化,因此以往的薄膜状粘结剂就会在引线键合中固化,存在对衬底表面凹凸的埋入不良的问题。从而,为了确保可靠性,对于薄膜状粘结剂要求即使在更苛刻的引线键合条件下,也要具有对衬底表面凹凸的更加优异的埋入性。
进而,近年来,出于简化工序的目的,要求同时具有芯片键合薄膜的功能和切割胶带的功能的切割·芯片键合薄膜(参照特开2004-83602号公报和特开2004-95844号公报)。由此可以同时进行上述制造工序的①和②。
但现状是尚未开发出低温粘接性和埋入性优异的切割·芯片键合薄膜。
发明内容
本发明就是鉴于如上所述状况而进行的,目的在于提供低温粘接性和埋入性优异的能够在半导体封装体内适宜地使用的具有芯片键合薄膜的功能的薄膜状粘结剂,以及同时具有芯片键合薄膜的功能和在该封装体安装工序中作为切割胶带的功能的薄膜状粘结剂。
本发明人等通过刻苦研究,完成了本发明。
即,第一发明是薄膜状粘结剂,其特征在于,包括含有玻璃化转移温度小于等于100℃的热塑性聚酰亚胺为主成分的粘结剂层(C)以及在50℃的储藏剪切弹性模量小于等于1×106Pa的粘着剂层(D)。
所述薄膜状粘结剂进一步包括基材(A)和粘着剂层(B)可以赋予作为切割胶带的功能,从而为优选的方式。从揭取时的膨胀性的角度考虑,优选所述基材(A)是在25℃的拉伸弹性模量小于等于500MPa的薄膜。从揭取性的角度考虑,优选所述粘着剂层(B)与所述粘结剂层(C)的180°剥离强度是0.1~2.5N/25mm。
从耐热性的角度考虑,优选所述粘结剂层(C)由除了聚酰亚胺以外还含有热固性树脂和填料的树脂组合物构成。
从低温粘接性的角度考虑,优选所述聚酰亚胺为使含有在分子内具有链状聚醚的二胺的二胺成分与四羧酸二酐成分反应而得到的聚酰亚胺。
从低温粘接性的角度考虑,优选所述聚酰亚胺为使含有在分子内具有至少一个酚羟基的二胺和在分子内具有链状聚醚的二胺的二胺成分与四羧酸二酐成分反应而得到的、玻璃转化温度为40℃~100℃的聚酰亚胺。
第二发明是薄膜状粘结剂,其特征在于,具有至少一层含有玻璃转化温度小于等于100℃的聚酰亚胺、并且在180℃温度保持1小时时储藏剪切弹性模量在180℃温度下为小于等于5.0×106Pa的粘结剂层(C’)。
从低温粘接性和耐热性的角度考虑,优选所述粘结剂层(C’)由以热塑性聚酰亚胺和热固性树脂为必要成分的树脂组合物构成,所述热塑性聚酰亚胺通过使含有在分子内具有链状聚醚的二胺的二胺成分与四羧酸二酐成分反应而得到。
从低温粘接性和耐热性的角度考虑,优选所述粘结剂层(C’)由以热塑性聚酰亚胺和热固性树脂为必要成分的树脂组合物构成,所述热塑性聚酰亚胺通过使含有在分子内具有至少一个酚羟基的二胺和在分子内具有链状聚醚的二胺的二胺成分与四羧酸二酐成分反应而得到,且玻璃转化温度为40℃~100℃。
第三发明是使用所述薄膜状粘结剂制造的半导体封装体。
本发明的薄膜状粘结剂,具有能够在半导体封装体内适宜地使用的芯片键合薄膜的功能,低温粘接性优异,并且对衬底表面凹凸的埋入性优异。进而,通过同时具有在该封装体安装工序中作为切割胶带的功能,可以使工序简化。
具体实施方式
本发明的薄膜状粘结剂由在半导体封装体内起到芯片键合薄膜功能的粘结剂层(C)和粘着剂层(D)或粘结剂层(C’)构成。优选依次层积起到切割胶带功能的支持基材(A)和粘着剂层(B)、以及在半导体封装体内起到芯片键合薄膜功能的粘结剂层(C’)的构成。更优选依次层积起到切割胶带功能的支持基材(A)和粘着剂层(B)、以及在半导体封装体内起到芯片键合薄膜功能的粘结剂层(C)和粘着剂层(D)的构成。
起到切割胶带功能的支持基材(A)和粘着剂层(B)的材质没有特别限制,只要能够在切割时不发生不良情况且在揭取时能够容易地剥离,可以是UV式、非UV式(压敏式)的任一种。从揭取时的膨胀性的角度考虑,支持基材(A)在25℃的拉伸弹性模量优选小于等于500MPa,更优选小于等于400MPa。
作为支持基材(A),具体地可以列举聚乙烯、聚丙烯等聚烯烃、聚氯乙烯等。
作为粘着剂(B),具体地可以列举聚烯烃系粘着剂、丙烯酸系粘着剂。
作为市售品,UV式可以举出例如电气化学工业株式会社制UHP系列或古河电气工业株式会社制UC系列等。非UV式可以举出例如三井化学株式会社制MPF系列等。
基材(A)和粘着剂层(B)的厚度没有特别限制,但从操作的角度考虑,优选基材(A)为50~150μm左右,粘着剂层(B)为5~20μm左右。
在半导体封装体内起到芯片键合薄膜功能的粘结剂层(C’)、粘结剂层(C)和粘着剂层(D)的材质没有特别限制,只要是半导体封装体制造工序中在250℃或其以上的回流工序中不发生膨胀或剥离等不良情况即可。
粘结剂层(C)和粘结剂层(C’)含有主成分热塑性聚酰亚胺,该聚酰亚胺的玻璃转化温度优选小于等于100℃,从低温粘接性的角度考虑,进一步优选为40℃~80℃。
从耐热性的角度考虑,粘结剂层(C)和粘结剂层(C’)优选进一步含有热固性树脂和填料。
从低温粘接性的角度考虑,热塑性聚酰亚胺优选为使含有在分子内具有链状聚醚的二胺的二胺成分与四羧酸二酐成分反应而得到的聚酰亚胺。
作为在分子内具有链状聚醚的二胺的具体例,可以举出例如聚亚丁基氧-二邻氨基苯甲酸酯、聚亚丁基氧-二间氨基苯甲酸酯、聚亚丁基氧-二对氨基苯甲酸酯、聚亚丙基氧-二邻氨基苯甲酸酯、聚亚丙基氧-二间氨基苯甲酸酯、聚亚丙基氧-二对氨基苯甲酸酯等,但并不限于这些。优选聚亚丁基氧-二对氨基苯甲酸酯。
在分子内具有链状聚醚的二胺在全体二胺成分中所占的量优选为10摩尔%~90摩尔%。如果不足10摩尔%,则玻璃转化温度会增高,从而并非优选;另外如果超过90摩尔%,则玻璃转化温度会过低,从而并非优选。
另外,从粘接性的角度考虑,优选二胺成分中进一步含有在分子内具有至少一个酚羟基的二胺。
具有酚羟基的二胺没有特别限制,但优选用通式(1)~(3)表示的二胺。
Figure C20051011511500071
Figure C20051011511500081
(Z各自独立地表示直接连接或者二价有机基团。)
Z的二价有机基团可以举出碳原子数2~27的脂肪族基团、脂环族基团、单环式芳香族基团、缩合多环式芳香族基团、还有芳香族基团直接或者由交联员相互连接而形成的非缩合环式芳香族基团等。
作为用通式(1)~(3)表示的二胺的具体例,例如可以举出2,3-二氨基苯酚、2,4-二氨基苯酚、2,5-二氨基苯酚、2,6-二氨基苯酚、3,4-二氨基苯酚、3,5-二氨基苯酚、3,6-二氨基苯酚、4,5-二氨基苯酚、4,6-二氨基苯酚、3,3’-二氨基-4,4’-二羟基联苯、4,4’-二氨基-3,3’-二羟基联苯、4,4’-二氨基-2,2’-二羟基联苯、4,4’-二氨基-2,2’,5,5’-四羟基联苯、3,3’-二氨基-4,4’-二羟基二苯基甲烷、4,4’-二氨基-3,3’-二羟基二苯基甲烷、4,4’-二氨基-2,2’-二羟基二苯基甲烷、4,4’-二氨基-2,2’,5,5’-四羟基二苯基甲烷、2,2-双[3-氨基-4-羟基苯基]丙烷、2,2-双[4-氨基-3-羟基苯基]丙烷等。
具有酚羟基的二胺优选在全体二胺成分中为0.1~10摩尔%,进一步优选为1~5摩尔%。如果不足0.1摩尔%,则无法得到充分的耐热性;如果超过10摩尔%,则存在低温粘接性会下降的倾向。
能够在本发明中使用的在分子内具有链状聚醚的二胺和在分子内具有至少一个酚羟基的二胺以外的其他二胺,只要是制成聚酰亚胺时玻璃转化温度小于等于100℃,就可以没有特别限制地使用。例如可以举出间苯二胺、邻苯二胺、对苯二胺、双(3-氨基苯基)硫化物、双(4-氨基苯基)硫化物、双(3-氨基苯基)亚砜、双(4-氨基苯基)亚砜、双(3-氨基苯基)砜、双(4-氨基苯基)砜、2,2-双[4-(3-氨基苯氧基)苯基]丁烷、1,1,3,3-四甲基-1,3-双(3-氨基丙基)二硅氧烷、1,1,3,3-四苯基-1,3-双(3-氨基丙基)二硅氧烷、1,3-双(3-氨基苯氧基)苯、聚亚丁基氧-二邻氨基苯甲酸酯、聚亚丁基氧-二间氨基苯甲酸酯、聚亚丁基氧-二对氨基苯甲酸酯、聚亚丙基氧-二邻氨基苯甲酸酯、聚亚丙基氧-二间氨基苯甲酸酯、聚亚丙基氧二对氨基苯甲酸酯等。
另外,同样地,对于能够在本发明中使用的四羧酸二酐成分,只要是制成聚酰亚胺时玻璃转化温度小于等于100℃,就可以没有特别限制地使用。例如可以举出均苯四甲酸二酐、3,3’,4,4’-苯甲酮四羧酸二酐、3,3’,4,4’-联苯四羧酸二酐、氧代-4,4’-二邻苯二甲酸二酐、乙二醇双偏苯三酸二酐、2,2-双(4-(3,4-二羧基苯氧基)苯基)丙烷二酐、α,ω-聚二甲基硅氧烷四羧酸二酐、α,ω-双(3,4-二羧基苯基)聚二甲基硅氧烷二酐等。
聚酰亚胺的制造方法包括公知方法,可以使用能够制造聚酰亚胺的所有方法。其中,优选在有机溶剂中进行反应。作为在该反应中使用的溶剂,例如可以举出N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、甲苯、二甲苯、均三甲苯、苯酚、甲酚等。
另外,在该反应中的反应原料在溶剂中的浓度通常为2~50重量%,优选为5~40重量%,四羧酸二酐成分与二胺成分的反应摩尔比以四羧酸成分/二胺成分计优选为0.8~1.2的范围。如果在该范围,耐热性就不会下降,因此是优选的。
作为聚酰亚胺前驱体的聚酰胺酸合成中的反应温度,通常小于等于60℃,优选为10℃~50℃。反应压力没有特别限制,在常压就可以充分地实施。另外,反应时间因反应原料的种类、溶剂的种类以及反应温度而异,但通常0.5~24小时就足够。对于本发明涉及的聚酰亚胺,通过把这样得到的聚酰胺酸加热至100~400℃进行酰亚胺化,或者使用醋酸酐等酰亚胺化剂进行化学酰亚胺化,来得到具有与聚酰胺酸对应的重复单元结构的聚酰亚胺。
另外,通过在130℃~250℃进行反应,同时进行聚酰胺酸的生成与热酰亚胺化反应,可以得到本发明涉及的聚酰亚胺。即,通过把二胺成分和四羧酸二酐在有机溶剂中悬浮或者溶解,在130~250℃的加热条件下进行反应,同时进行聚酰胺酸的生成与脱水酰亚胺化,可以得到本发明涉及的聚酰亚胺。
本发明的聚酰亚胺的分子量没有特别限制,可以根据用途和加工方法设定为任意分子量。对于本发明的聚酰亚胺,通过调节所使用二胺成分、四羧酸二酐的用量比,例如把聚酰亚胺以0.5g/dl的浓度溶解到N-甲基-2-吡咯烷酮中后,能够使在35℃测定的对数粘度值为0.1~3.0dl/g的任意值。
本发明中,所谓聚酰亚胺除了100%酰亚胺化而形成的聚酰亚胺以外,还包括共存有一部分作为其前驱体的聚酰胺酸的树脂。
另外,在上述反应中得到的聚酰亚胺溶液可以直接使用,但也可以把该聚酰亚胺溶液投入到贫溶剂中将聚酰亚胺再沉淀析出。
热固性树脂和填料的材质没有特别限制,但从对衬底表面凹凸的埋入性的角度考虑,优先选择把粘结剂层(C)或粘结剂层(C’)在180℃温度保持1小时时储藏剪切弹性模量小于等于5.0×106Pa的材料,更优先选择小于等于3.0×106Pa的材料。如果超过5.0×106Pa,则埋入性会恶化,存在耐热性恶化的倾向。
作为热固性树脂的具体例,例如可以举出双酚A、双酚S、双酚F的缩水甘油醚、苯酚酚醛清漆型环氧树脂、联苯型环氧化合物等。
相对于100重量份热塑性聚酰亚胺,热固性树脂的混合量为1~200重量份,优选为1~100重量份。如果在该范围,就可以维持耐热性,薄膜形成性优异。
另外,也可以根据需要混合固化剂。固化剂可以举出例如咪唑系固化剂、苯酚系固化剂、胺系固化剂、酸酐系固化剂等。从树脂组合物的保存稳定性的角度考虑,优选具有热潜在性和长的可使用时间的固化剂。
相对于100重量份热固性树脂,固化剂的混合量优选在0~20重量份的范围内。如果在该范围内,则不容易在树脂溶液状态下生成凝胶,树脂溶液的保存稳定性优异。
另外,也可以根据需要混合填料。填料可以举出例如环氧树脂、三聚氰胺树脂、脲树脂、酚醛树脂等有机填料;氧化铝、氮化铝、硅石等无机填料。
相对于100重量份热塑性聚酰亚胺,填料的混合量为0~5000重量份,优选在0~3000重量份的范围内。如果在该范围,则树脂溶液状态下填料不容易沉降,树脂溶液的保存稳定性优异。另一方面,如果填料过多,则粘接性就会下降。
另外,也可以根据需要添加偶联剂。只要是不损害本发明目的,对于偶联剂没有特别限制,但优选在树脂溶液溶剂中的溶解性良好的偶联剂。可以举出例如硅烷系偶联剂、钛系偶联剂等。
相对于100重量份聚酰亚胺,偶联剂的混合量为0~50重量份,优选在0~30重量份的范围内。如果在该范围内,则耐热性就不会下降。
从对衬底表面凹凸的埋入性的角度考虑,粘结剂层(C)和粘结剂层(C’)的厚度优选为5~100μm。如果不足5μm,则不能充分埋入,但即使超过100μm,埋入也得不到提高。
优选粘着剂层(B)与粘结剂层(C)或粘结剂层(C’)相接,其间的180°剥离强度优选为0.1~2.5N/25mm。如果不足0.1N/25mm,则在切割时容易产生芯片飞出的问题;如果超过2.5N/25mm,则在揭取时有时无法揭取,或者芯片会出现裂缝。
粘着剂层(D)优选在50℃的储藏剪切弹性模量小于等于1.0×106Pa,更优选小于等于105Pa。如果超过1.0×106Pa,则存在低温粘接困难的倾向。
通过粘着剂层(D)把薄膜状粘结剂粘贴到硅晶片上,能够以更低的温度进行粘贴,粘贴到小于等于100μm的薄晶片上时,可以减少晶片翘曲。
粘着剂层(D)的具体例可以举出有机硅系粘着剂、丙烯酸系粘着剂等。
从对硅晶片的密合性和耐热性的角度考虑,粘着剂层(D)的厚度优选为1~10μm。如果不足1μm,则无法获得粘附力;如果超过10μm,则存在耐热性恶化的倾向。
制造本发明涉及的薄膜状粘结剂的方法没有特别限制,例如可以举出如下方法:把所含主成分为聚酰亚胺树脂的溶液涂布到PET等支持薄膜上,并干燥,形成粘结剂层(C),然后在其上进一步涂布粘着剂溶液,并干燥,形成粘着剂层(D),将其与事先用挤出成型法等制备的由基材(A)和粘着剂层(B)构成的胶带层压,使粘着剂层(B)和粘结剂层(C)相接。
芯片键合薄膜部分(粘结剂层C+粘着剂层D或粘结剂层C’)或切割胶带部分(基材A+粘着剂层B)可以根据需要事先进行圆周切割。
制造本发明涉及的半导体封装体的方法没有特别限制,通常可以按照如下方法制造:①在大口径的晶片背面通过粘着剂层(D)粘贴薄膜状粘结剂;②切割,将芯片单片化;③在粘着剂层(B)和粘结剂层(C)之间揭取单片化的芯片;④通过粘结剂层(C)芯片键合到被粘接体衬底上;⑤引线键合芯片/衬底间;⑥用密封剂成型。
实施例
下面,根据实施例进一步详细说明本发明,但本发明并不限于这些实施例。这里,实施例中的各物性值用以下方法测定。
(储藏剪切弹性模量的测定方法)
测定装置:レオメトリツクス社制,ARES
测定模式:温度分散(控制变形),扭曲模式
测定温度范围:30~200℃(5℃/分钟),氮气氛围下
频率:1Hz
(储藏剪切弹性模量时间分解的测定方法)
测定装置:レオメトリツクス社制,ARES
测定模式:时间分散(控制变形),扭曲模式
测定温度范围:180℃,5小时,氮气氛围下
频率:1Hz
(拉伸弹性模量的测定方法)
测定装置:东洋精机社制,ストログラフM-1
测定模式:拉伸模式
(剥离强度的测定方法)
测定装置:东洋精机社制,ストログラフM-1
测定模式:180°剥离
合成例1
在备有搅拌机、氮气导入管、温度计、盛有均三甲苯的迪安-斯达克(Dean-Stark)管的300ml可分离五口烧瓶中,称取聚亚丁基氧-二对氨基苯甲酸酯(イハラケミカル工业株式会社制,商品名:エラスマ一1000,平均分子量1268)18.75g、氧代-4,4’-二邻苯二甲酸二酐45.87g、N-甲基-2-吡咯烷酮100g、均三甲苯45g,在氮气氛围下溶解,向其中一点一点地添加二氨基丙基四甲基二硅氧烷(信越化学工业株式会社制,商品名:PAM-E)32.00g。然后,把氮气导入管插入溶液内(成冒泡状态),将体系内温度加热至170℃~180℃,在共沸去除水的条件下保持12小时。冷却后,加入均三甲苯145g稀释,再添加4,4’-二氨基-3,3’-二羟基联苯(和歌山精化工业株式会社制,商品名:HAB)0.93g,得到热塑性聚酰亚胺的溶液。得到的聚酰亚胺的玻璃转化温度为56℃(拉伸弹性模量测定中的Tanδ的峰值温度)。
对得到的聚酰亚胺固体组分100重量份混合环氧化合物(三井化学株式会社制,VG3101)20重量份、硅石系填料(株式会社龙森制,1-FX)40重量份,用搅拌机充分地混合,得到树脂组合物1。
合成例2
在备有搅拌机、氮气导入管、温度计、盛有均三甲苯的迪安-斯达克管的300ml可分离五口烧瓶中,称取1,3-双(3-(3-氨基苯氧基)苯氧基)苯15.00g、硅酮二胺(α,ω-双(3-氨基丙基)聚二甲基硅氧烷(东丽道康宁有机硅株式会社制,BY16-853U,平均分子量920)43.44g、N-甲基-2-吡咯烷酮110.61g、均三甲苯47.40g,在氮气氛围下加热至50℃将其溶解,向其中一点一点地添加氧代-4,4’-二邻苯二甲酸二酐18.49g、乙二醇双偏苯三酸二酐8.15g。然后,把氮气导入管插入溶液内(成冒泡状态),将体系内温度加热至170℃~180℃,在注意到暴沸的情况下保持30分钟,共沸去除水,从而得到热塑性聚酰亚胺溶液。得到的聚酰亚胺的玻璃转化温度为67℃(拉伸弹性模量测定中的Tanδ的峰值温度)。
对得到的聚酰亚胺固体组分100重量份混合环氧化合物(三井化学株式会社制,VG3101L)20重量份、咪唑系固化剂(四国化成工业株式会社,2MAOK-PW)1重量份、硅石系填料(株式会社龙森制,1-FX)39重量份,用搅拌机充分地混合,得到树脂组合物2。
合成例3
在备有搅拌机、氮气导入管、温度计、盛有均三甲苯的迪安-斯达克管的300ml可分离五口烧瓶中,称取聚亚丁基氧-二对氨基苯甲酸酯(イハラケミカル工业株式会社制,商品名:エラスマ一1000,平均分子量1268)13.95g、1,3-双(3-氨基苯氧基)苯28.00g、氧代-4,4’-二邻苯二甲酸二酐34.12g、N-甲基-2-吡咯烷酮100g、均三甲苯40g,在氮气氛围下溶解,把氮气导入管插入溶液内(成冒泡状态),把体系内温度加热至170℃~180℃,在共沸去除水的条件下保持12小时。冷却后,加入N-甲基-2-吡咯烷酮290g进行稀释,再添加4,4’-二氨基-3,3’-二羟基联苯(和歌山精化工业株式会社制,商品名:HAB)0.7g,得到热塑性聚酰亚胺的溶液。得到的聚酰亚胺的玻璃转化温度为157℃(拉伸弹性模量测定中的Tanδ的峰值温度)。
对得到的聚酰亚胺固体组分100重量份混合环氧化合物(三井化学株式会社制,VG3101)5重量份,用搅拌机充分地混合,得到树脂组合物3。
实施例1
把树脂组合物1涂布到表面处理PET薄膜(帝人杜邦薄膜株式会社制,A54,厚度50μm)上,在100℃加热30分钟,得到厚度20μm的粘结剂层(C)。另外,在180℃温度保持1小时时储藏剪切弹性模量为0.96×106Pa。
在该粘结剂层(C)的上面,进一步涂布在100重量份硅酮树脂(东丽道康宁株式会社制,SD4560)中添加0.9重量份铂催化剂溶液(东丽道康宁株式会社制,NC-25)而形成的溶液,在100℃加热5分钟,形成厚度5μm的粘着剂层(D)。这里,粘着剂层(D)在50℃的储藏剪切弹性模量为5.7×104Pa。
以相当于8英寸晶片的大小对得到的由粘结剂层(C)和粘着剂层(D)构成的芯片键合薄膜部分进行冲孔,在粘结剂层(C)侧通过粘着剂层(B)在60℃层压由支持基材(A)和粘着剂层(B)构成的切割胶带(三井化学株式会社制,非UV式,商品名MPF,厚度100μm,支持基材(A)的拉伸弹性模量400MPa),得到本发明的薄膜状粘结剂。这里,粘着剂层(B)和粘结剂层(C)的180°剥离强度为1N/25mm。
通过得到的薄膜状粘结剂的粘着剂层(D),在室温与玻璃晶片粘贴到环形架上,以5mm正方形大小进行切割,但没有发生浸水、芯片飞出、毛边等问题。并且,随后进行揭取(在粘着剂层(B)和粘结剂层(C)之间剥离),但没有发生揭取失败等问题。
通过得到的5mm正方形玻璃芯片上的粘结剂层(C),在20mm正方形的硅上进行100℃、10MPa、10秒钟的假想芯片固定的加热压接后,在180℃无负载的条件下加热固化3小时。把该试验片在260℃的烘箱中放置30分钟,但没有发现膨胀和剥离等问题,可以知道耐热性(埋入性)优异。
实施例2
除了使用丙烯酸树脂(三井杜邦ポリケミカル制,ベ一マツク)100重量份、环氧化合物(三井化学株式会社制,VG3101)20重量份、固化催化剂(四国化成制,2maok-PW)1重量份构成的混合物来代替实施例1中的粘着剂层(D)的硅酮树脂/铂催化剂溶液以外,采用与实施例1同样的方法制作试验片,进行评价。
将评价结果示于表1。
实施例3
除了用树脂组合物2代替实施例1中的树脂组合物1以外,采用与实施例1同样的方法制作试验片,并进行评价。
将评价结果示于表1。
实施例4
除了用树脂组合物1代替实施例1中的粘着剂层(D)的硅酮树脂/铂催化剂溶液以外,采用与实施例1同样的方法制作试验片,并进行评价。将评价结果示于表1。
比较例1
除了用树脂组合物3代替实施例1中的树脂组合物1以外,采用与实施例1同样的方法制作试验片,并进行评价。
将评价结果示于表1。
表1
  实施例1   实施例2   实施例3   实施例4   比较例1
基材(A)   聚烯烃系(85μm)
粘着剂层(B)   聚烯烃系(15μm)
粘结剂层(C)   树脂组合物1(20μm)   树脂组合物2(20μm)   树脂组合物1(20μm)   树脂组合物3(20μm)
粘着剂层(D)   硅酮系(5μm)   丙烯酸系(5μm)   硅酮系(5μm)   树脂组合物1(5μm)   硅酮系(5μm)
  基材(A)的拉伸弹性模量 400MPa
  粘着剂层(B)与粘结剂层(C)的180°剥离强度 1N/25mm
  热塑性聚酰亚胺的玻璃转化温度 56℃ 67℃ 56℃ 157℃
  粘结剂层(C)在180℃温度保持1小时时储藏剪切弹性模量 0.96×10<sup>6</sup>Pa 5.3×10<sup>6</sup>Pa 0.96×10<sup>6</sup>Pa 2.0×10<sup>6</sup>Pa
  粘着剂层(D)在50℃的储藏剪切弹性模量 5.7×10<sup>4</sup>Pa 1.3×10<sup>5</sup>Pa 5.7×10<sup>4</sup>Pa 1.6×10<sup>6</sup>Pa 5.7×10<sup>4</sup>Pa
  粘着剂层(D)的晶片层压性 可室温层压 可室温层压 可室温层压   室温层压稍微困难 可室温层压
  粘结剂层(C)的芯片键合性 良好 良好 良好 良好   100℃键合困难
  切割性   良好   良好   良好   良好   良好
  揭开性   良好   良好   良好   良好   良好
  耐热性   良好   良好   稍微不良   良好   良好
产业上的利用可能性
本发明的薄膜状粘结剂,可以作为能够在半导体封装体内适宜地使用的芯片键合薄膜以及芯片键合薄膜和该封装体安装工序中的切割胶带,低温粘接性、对衬底凹凸的埋入性优异,因此产业上的利用价值高。

Claims (11)

1.薄膜状粘结剂,其特征在于,包括含有玻璃转化温度小于等于100℃的热塑性聚酰亚胺为主成分的粘结剂层C以及在50℃的储藏剪切弹性模量小于等于1×106Pa的用于粘贴到硅晶片上的粘着剂层D。
2.根据权利要求1所述的薄膜状粘结剂,其特征在于,进一步在所述粘结剂层C侧,经由粘着剂层B层积有起到切割胶带功能的支持基材A和所述粘着剂层B。
3.根据权利要求2所述的薄膜状粘结剂,其特征在于,所述支持基材A为在25℃的拉伸弹性模量小于等于500MPa的薄膜。
4.根据权利要求2所述的薄膜状粘结剂,其特征在于,所述粘着剂层B和所述粘结剂层C的180°剥离强度为0.1~2.5N/25mm。
5.根据权利要求3所述的薄膜状粘结剂,其特征在于,所述粘着剂层B和所述粘结剂层C的180°剥离强度为0.1~2.5N/25mm。
6.根据权利要求1~5的任意一项所述的薄膜状粘结剂,其特征在于,所述粘结剂层C由除了热塑性聚酰亚胺以外还含有热固性树脂和填料作为必要成分的树脂组合物而构成。
7.根据权利要求6所述的薄膜状粘结剂,其特征在于,所述聚酰亚胺为使含有在分子内具有链状聚醚的二胺的二胺成分与四羧酸二酐成分反应而得到的聚酰亚胺。
8.根据权利要求6所述的薄膜状粘结剂,其特征在于,所述聚酰亚胺为使含有在分子内具有至少一个酚羟基的二胺和在分子内具有链状聚醚的二胺的二胺成分与四羧酸二酐成分反应而得到的、玻璃转化温度为40℃~100℃的聚酰亚胺。
9.根据权利要求1所述的薄膜状粘结剂,其特征在于,将所述粘结剂层C在180℃温度保持1小时时储藏剪切弹性模量在180℃温度下为小于等于5.0×106Pa。
10.根据权利要求9所述的薄膜状粘结剂,其特征在于,所述粘结剂层C由除了聚酰亚胺以外还含有热固性树脂和填料的树脂组合物构成,所述聚酰亚胺为使含有在分子内具有至少一个酚羟基的二胺和在分子内具有链状聚醚的二胺的二胺成分与四羧酸二酐成分反应而得到的、玻璃转化温度为40℃~100℃的聚酰亚胺。
11.使用权利要求1~10的任意一项所述的薄膜状粘结剂制造的半导体封装体。
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