CN103642441A - 粘接剂组合物、半导体装置的制造方法以及半导体装置 - Google Patents
粘接剂组合物、半导体装置的制造方法以及半导体装置 Download PDFInfo
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- CN103642441A CN103642441A CN201310636698.1A CN201310636698A CN103642441A CN 103642441 A CN103642441 A CN 103642441A CN 201310636698 A CN201310636698 A CN 201310636698A CN 103642441 A CN103642441 A CN 103642441A
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Abstract
本发明涉及粘接剂组合物、半导体装置的制造方法以及半导体装置。所述粘接剂组合物为在半导体芯片以及配线电路基板的各自的连接部相互地电连接的半导体装置、或多个半导体芯片的各自的连接部相互地电连接的半导体装置中将所述连接部密封的粘接剂组合物,其含有环氧树脂、固化剂、由具有下述通式(1)所示的基团的化合物进行了表面处理的丙烯酸系表面处理填料以及重均分子量为10000以上的高分子成分,式(1)中,R1表示氢原子或碳原子数1或2的烷基,R2表示碳原子数1~30的亚烷基。
Description
本申请是申请日为2011年9月29日,申请号为201180047053.3,发明名称为《粘接剂组合物、半导体装置的制造方法以及半导体装置》的中国专利申请的分案申请。
技术领域
本发明涉及粘接剂组合物、半导体装置的制造方法以及半导体装置。
背景技术
近年,为了将半导体芯片安装并连接于基板,广泛使用了使用金丝(goldwire)等金属细线的引线接合方式。另一方面,为了应对对于半导体装置的小型化、薄型化、高功能、高集成化、高速化等要求,在半导体芯片与基板之间形成称作凸块的导电性突起而将半导体芯片与基板连接的倒装芯片连接方式(FC连接方式)在持续扩展。
例如,关于半导体芯片与基板之间的连接,活跃应用于BGA(Ball GridArray)、CSP(Chip Size Package)等中的COB(Chip On Board)型的连接方式也相当于FC连接方式。另外,FC连接方式也广泛应用于在半导体芯片上形成连接部(凸块、配线)而将半导体芯片之间连接的COC(Chip On Chip)型的连接方式中(例如参照专利文献1)。
但是,为了应对更进一步的小型化、薄型化、高功能化要求,将上述的连接方式进行层叠、多段化的芯片堆叠型封装体(chip stack type package)、POP(Package On Package)、TSV(Through-Silicon Via)等也开始广泛普及。这样的层叠·多段化技术中由于将半导体芯片等三维地配置,因而与二维地配置的方法相比较而言可减小封装体。特别是,TSV技术对于半导体的性能提高、噪音减低、安装面积削减、省电力化也有效,作为新一代的半导体配线技术受到了关注。
然而,作为用于上述连接部(凸块、配线)的主要金属,有焊锡、锡、金、银、铜、镍等,也使用包含它们中的多种的导电材料。关于用于连接部的金属,由于表面发生氧化而生成氧化膜、在表面附着氧化物等杂质,存在有在连接部的连接面生成杂质的情况。残存这样的杂质时,则存在有如下可能:使半导体芯片与基板之间、2个半导体芯片之间的连接性、绝缘可靠性降低、使采用上述的连接方式的优点受损。
作为抑制这些杂质的产生并且提高连接性的方法,可列举出在连接之前对基板、半导体芯片的表面实施前处理的方法,可列举出施加用于OSP(OrganicSolderbility Preservatives)处理的预焊剂、防锈处理剂的方法。然而,也存在由于在前处理之后预焊剂、防锈处理剂残存并劣化因而导致连接性降低的情况。
另一方面,根据用半导体密封材料(半导体密封用粘接剂)将半导体芯片与基板之间等的连接部密封的方法,可在半导体芯片与基板、半导体芯片彼此的连接的同时将连接部密封。因此,可抑制用于连接部的金属的氧化、杂质对连接部的附着,并且保护连接部不受外部环境的侵害。因此,可有效提高连接性、绝缘可靠性、作业性、生产率。
另外,在由倒装芯片连接方式制造的半导体装置中,为了不使源自半导体芯片与基板的热膨胀系数差、半导体芯片彼此的热膨胀系数差的热应力集中于连接部而引起连接不良,因而需要用半导体密封材料将半导体芯片与基板之间等的空隙密封。特别是,在半导体芯片与基板中经常使用热膨胀系数不同的成分,要求通过半导体密封材料进行密封而提高耐热冲击性。
在采用上述半导体密封材料的密封方式中,进行较大的区分而可列举出毛细管流动方式(Capillary-Flow)和预供给方式(Pre-applied)(例如参照专利文献2~6)。毛细管流动方式是指,在半导体芯片与基板的连接之后通过毛细管现象将液状的半导体密封材料注入于半导体芯片与基板之间的空隙中的方式。预供给方式是指,在半导体芯片与基板的连接之前,向半导体芯片或基板供给糊状、膜状的半导体密封材料,然后将半导体芯片与基板连接的方式。关于这些密封方式,伴随着近年的半导体装置的小型化的进展,半导体芯片与基板之间等的空隙变窄了,因而在毛细管流动方式中存在有:注入需要长时间并且生产率降低的情况、无法注入的情况,另外,即使可注入也存在未填充部分而成为气孔的原因的情况。因此,从作业性、生产率、可靠性的观点考虑,预供给方式作为可实现高功能、高集成、高速化的封装体的制作方法而成为主流。
现有技术文献
专利文献
专利文献1:日本特开2008-294382号公报
专利文献2:日本特开2001-223227号公报
专利文献3:日本特开2002-283098号公报
专利文献4:日本特开2005-272547号公报
专利文献5:日本特开2006-169407号公报
专利文献6:日本特开2006-188573号公报
发明内容
发明要解决的问题
在上述的预供给方式中,由于在通过加热加压而进行连接的同时,通过半导体密封材料将半导体芯片与基板之间的空隙密封,因而需要考虑连接条件而选择半导体密封材料的含有成分。一般而言在连接部彼此的连接中,从充分确保连接性、绝缘可靠性的观点考虑使用了金属接合。由于金属接合是使用了高温(例如200℃以上)的连接方式,因此存在有如下情况:起因于半导体密封材料中残存的挥发成分、因半导体密封材料的含有成分的分解而新生成的挥发成分,半导体密封材料产生发泡。由此,产生被称作气孔的气泡,半导体密封材料从半导体芯片、基板剥离。另外,当在加热加压时、压力释放时,产生上述气孔、半导体芯片等的回弹(spring back)时,产生由将连接部彼此连接的连接凸块的撕裂而导致的连接部的破坏等连接不良。由于这些原因,因而在以往的半导体密封材料中存在有连接性、绝缘可靠性降低的可能。
另外,在半导体密封材料没有充分的焊剂活性(金属表面的氧化膜、杂质的去除效果)的情况下,存在有无法去除金属表面的氧化膜、杂质,不能形成良好的金属-金属接合,无法确保导通的情况。进一步,半导体密封材料的绝缘可靠性低时,则难以应对连接部的狭间距化,发生绝缘不良。也由于这些原因,在以往的半导体密封材料中存在有连接性、绝缘可靠性降低的可能。
关于使用半导体密封材料制造的半导体装置,要求在可靠性、更具体而言耐热性、耐湿性以及耐回流焊性(耐リフロー性)方面实现充分的水平。为了确保耐回流焊性,因而要求在260℃前后的回流焊温度下,维持可抑制贴片层(ダイボンド層)(粘接剂层)的剥离或破坏那样的高的粘接强度。
本发明鉴于上述情形而开发,其目的在于提供可制作耐回流焊性以及连接可靠性以及绝缘可靠性优异的半导体装置的粘接剂组合物、使用了该粘接剂组合物的半导体装置的制造方法以及半导体装置。
用于解决问题的方案
本发明提供一种粘接剂组合物,其为在半导体芯片以及配线电路基板的各自的连接部相互地电连接的半导体装置、或多个半导体芯片的各自的连接部相互地电连接的半导体装置中将连接部密封的粘接剂组合物,其含有环氧树脂、固化剂以及由具有下述通式(1)所示的基团的化合物进行了表面处理的丙烯酸系表面处理填料。
[化学式1]
式(1)中,R1表示氢原子或碳原子数1或2的烷基,R2表示碳原子数1~30的亚烷基。
本发明另外提供一种粘接剂组合物,其为在半导体芯片以及配线电路基板的各自的连接部相互地电连接的半导体装置、或多个半导体芯片的各自的连接部相互地电连接的半导体装置中将连接部密封的粘接剂组合物,其含有环氧树脂、固化剂以及具有下述通式(1)所示的基团的填料。
[化学式2]
式(1)中,R1表示氢原子或碳原子数1或2的烷基,R2表示碳原子数1~30的亚烷基。
上述本发明的粘接剂组合物通过在含有环氧树脂以及固化剂的基础上,进一步含有丙烯酸系表面处理填料或具有由上述通式(1)表示的基团的填料,从而即便在高温(例如200℃以上)进行金属接合的倒装芯片连接方式中适用作半导体密封用粘接剂的情况下,也可实现高的耐回流焊性、连接可靠性以及绝缘可靠性。
为了提高粘接剂组合物的耐回流焊性,需要提高高温下的吸湿后的粘接力。但是,历来使用的填料可减小吸湿率以及热膨胀系数,为了提高连接性、绝缘可靠性是有效的,但是填料自身的粘接性通常缺乏。
此处已知,使硅烷偶联剂与没有进行表面处理的填料一同含有于树脂中时,则可使填料的表面进行硅烷偶联处理,通过硅烷偶联剂的取代基而合成各种各样的表面状态的填料。然而,硅烷偶联剂的挥发性高,在具有需要高温连接的金属接合等高温下的工艺的半导体装置的制造工序中成为产生气孔的原因。同样地,对历来使用的填料进行表面处理的情况下,存在有产生甲醇等挥发性高的有机物的情况,成为气孔产生的原因。
一般而言,在半导体基板上形成有被称作阻焊层的绝缘膜,阻焊层大多包含有丙烯酸系材料。因此,本发明人等发现了,通过含有上述丙烯酸系表面处理填料或具有由上述通式(1)表示的基团的填料,从而提高粘接剂组合物在高温下的弹性模量和吸湿后的粘接力,可实现耐回流焊性。本发明人等推测,在本发明的粘接剂组合物中,使用预先进行了表面处理的丙烯酸系表面处理填料或具有由上述通式(1)表示的基团的填料,从而可抑制挥发性高的物质的产生,并且由于丙烯酸系化合物与阻焊层的粘接性优异因而可提高与基板的连接性。另外本发明人等推测,丙烯酸系表面处理填料或具有由上述通式(1)表示的基团的填料不易降低连接部的绝缘可靠性,不易降低粘接剂组合物的固化物的热膨胀系数以及弹性模量,因此可提高连接可靠性。
丙烯酸系表面处理填料或具有由上述通式(1)表示的基团的填料向树脂成分中的分散性优异,并且可提高使用本发明的粘接剂组合物而制作的半导体装置中的封装体(基板-芯片、芯片-芯片等)末端部的强度。
上述的粘接力提高不受限于阻焊层上,也显现在半导体芯片之间(SiO、SiN等)。
具有由上述通式(1)表示的基团的化合物优选为由下述通式(2)表示的化合物。
[化学式3]
式(2)中,R1表示氢原子或碳原子数1或2的烷基,R2表示碳原子数1~30的亚烷基,R3表示碳原子数1~30的烷基。
本发明的粘接剂组合物通过含有由上述通式(2)所示的化合物进行了表面处理的填料,从而可进一步提高耐回流焊性、连接可靠性以及绝缘可靠性。
在本发明的粘接剂组合物中,从提高粘接剂组合物的耐热性以及成膜性的观点考虑,可进一步含有重均分子量为10000以上的高分子成分。
从进一步提高粘接剂组合物的贴附性、成膜性的观点考虑,上述高分子成分的重均分子量优选为30000以上,玻璃化温度优选为100℃以下。
本发明的粘接剂组合物通过进一步含有焊剂活性剂,可提高焊剂活性,去除连接部的金属表面的氧化膜、杂质,可形成良好的金属-金属接合。
由于可提高通过预供给方式将半导体芯片与配线电路基板的空隙或多个半导体芯片之间的空隙密封的情况下的作业性,因此本发明的粘接剂组合物的形状优选为膜状。
本发明另外提供一种半导体装置的制造方法,其为半导体芯片以及配线电路基板的各自的连接部相互地电连接的半导体装置、或多个半导体芯片的各自的连接部相互地电连接的半导体装置的制造方法,所述方法具备使用上述的粘接剂组合物将连接部密封的工序。
根据本发明的半导体装置的制造方法,通过使用上述粘接剂组合物,从而可提高半导体装置的耐回流焊性、连接可靠性以及绝缘可靠性。
上述连接部含有选自金、银、铜、镍、锡以及铅中的至少一种金属作为主要成分时,则可进一步提高连接部的电传导性、导热性、连接可靠性。
本发明另外提供通过上述半导体装置的制造方法获得的半导体装置。
本发明的半导体装置由于使用上述半导体装置的制造方法而制作,因而成为耐回流焊性、连接可靠性以及绝缘可靠性充分优异的半导体装置。
发明的效果
根据本发明可提供:耐回流焊性、连接可靠性以及绝缘可靠性优异的粘接剂组合物、使用了该粘接剂组合物的半导体装置的制造方法以及半导体装置。附图说明
图1为表示本发明的半导体装置的一个实施方式的模式剖视图。
图2为表示本发明的半导体装置的另一个实施方式的模式剖视图。
图3为表示本发明的半导体装置的另一个实施方式的模式剖视图。
图4是模式地表示本发明的半导体装置的制造方法的一个实施方式的工序剖视图。
图5为表示绝缘可靠性试验用的样品的外观的模式图。
具体实施方式
以下,视情况一边参照附图一边对本发明的优选实施方式进行详细说明。予以说明,在附图中,相同或相当部分付与相同符号并且省略重复的说明。另外,上下左右等位置关系只要没有特别地预先说明,就设为基于附图所示的位置关系的位置关系。进一步,附图的尺寸比率不限于图示的比率。
<粘接剂组合物>
本实施方式的粘接剂组合物(半导体密封用粘接剂)是在半导体芯片以及配线电路基板(以下,视情况而简称为“基板”)的各自的连接部相互地电连接的半导体装置、或多个半导体芯片的各自的连接部相互地电连接的半导体装置中将连接部密封的粘接剂组合物,其含有环氧树脂(以下,视情况而称为“(a)成分”)、固化剂(以下,视情况而称为“(b)成分”)、以及丙烯酸系表面处理填料或具有由上述通式(1)表示的基团的填料(以下,视情况而称为“(c)成分”)。另外,粘接剂组合物根据需要含有重均分子量10000以上的高分子成分(以下,视情况而称为“(d)成分”)或焊剂活性剂(以下,视情况而称为“(e)成分”。)。以下对构成本实施方式的粘接剂组合物的各成分进行说明。
(a)成分:环氧树脂
作为环氧树脂,如果是在分子内具有2个以上的环氧基的环氧树脂则可不受特别限制地使用。作为(A)成分,具体可使用双酚A型、双酚F型、萘型、苯酚酚醛清漆型、甲酚酚醛清漆型、苯酚芳烷基型、联苯型、三苯基甲烷型、双环戊二烯型以及各种多官能环氧树脂。它们可单独使用或以2种以上的混合物的方式使用。
关于(a)成分,从抑制在高温下的连接时分解而产生挥发成分这一情况的观点考虑,在连接时的温度为250℃的情况下,优选使用250℃下的热重损失量率(熱重量減少量率)为5%以下的环氧树脂,在300℃的情况下,优选使用300℃下的热重损失量率为5%以下的环氧树脂。
(b)成分:固化剂
作为(b)成分,例如可列举出酚醛树脂系固化剂、酸酐系固化剂、胺系固化剂、咪唑系固化剂以及膦系固化剂。如果(b)成分包含酚性羟基、酸酐、胺类或咪唑类,那么可显现抑制在连接部产生氧化膜这一情况的焊剂活性,可提高连接可靠性、绝缘可靠性。以下对各固化剂进行说明。
(i)酚醛树脂系固化剂
作为酚醛树脂系固化剂,如果是在分子内具有2个以上的酚性羟基的酚醛树脂系固化剂则没有特别限制,例如可使用苯酚酚醛清漆、甲酚酚醛清漆、苯酚芳烷基树脂、甲酚萘酚甲醛缩聚物、三苯基甲烷型多官能酚醛以及各种多官能酚醛树脂。它们可单独使用或以2种以上的混合物的方式使用。
酚醛树脂系固化剂相对于上述(a)成分的当量比(酚性羟基/环氧基、摩尔比)从良好的固化性、粘接性以及保存稳定性的观点考虑优选为0.3~1.5,更优选为0.4~1.0,进一步优选为0.5~1.0。当量比为0.3以上时,则存在固化性提高并且粘接力提高的倾向,为1.5以下时,则存在未反应的酚性羟基不会过量地残存,将吸水率抑制为低,绝缘可靠性提高的倾向。
(ii)酸酐系固化剂
作为酸酐系固化剂,例如可使用甲基环己烷四羧酸二酐、偏苯三酸酐、均苯四酸二酐、二苯甲酮四羧酸二酐以及乙二醇双脱水偏苯三酸酯。它们可单独使用或以2种以上的混合物的方式使用。
酸酐系固化剂相对于上述(a)成分的当量比(酸酐基/环氧基、摩尔比)从良好的固化性、粘接性以及保存稳定性的观点考虑优选为0.3~1.5,更优选为0.4~1.0,进一步优选为0.5~1.0。当量比为0.3以上时,则存在固化性提高并且粘接力提高的倾向,为1.5以下时,则存在未反应的酸酐不会过量地残存,将吸水率抑制为低,绝缘可靠性提高的倾向。
(iii)胺系固化剂
作为胺系固化剂,可使用例如双氰胺。
胺系固化剂相对于上述(a)成分的当量比(胺/环氧基、摩尔比)从良好的固化性、粘接性以及保存稳定性的观点考虑优选为0.3~1.5,更优选为0.4~1.0,进一步优选为0.5~1.0。当量比为0.3以上时,则存在固化性提高并且粘接力提高的倾向,为1.5以下时则存在未反应的胺不会过量地残存,绝缘可靠性提高的倾向。
(iv)咪唑系固化剂
作为咪唑系固化剂,例如可列举出2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰乙基-2-十一烷基咪唑、1-氰基-2-苯基咪唑、1-氰乙基-2-十一烷基咪唑偏苯三酸酯(トリメリテイト)、1-氰乙基-2-苯基咪唑鎓偏苯三酸酯、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪、2,4-二氨基-6-[2’-十一烷基咪唑基-(1’)]-乙基-均三嗪、2,4-二氨基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-均三嗪、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪异氰尿酸加成物、2-苯基咪唑异氰尿酸加成物、2-苯基-4,5-二羟基甲基咪唑、2-苯基-4-甲基-5-羟基甲基咪唑、以及环氧树脂与咪唑类的加成物。它们之中,从优异的固化性、保存稳定性以及连接可靠性的观点考虑,优选1-氰乙基-2-十一烷基咪唑、1-氰基-2-苯基咪唑、1-氰乙基-2-十一烷基咪唑偏苯三酸酯、1-氰乙基-2-苯基咪唑鎓偏苯三酸酯、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪、2,4-二氨基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-均三嗪、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪异氰尿酸加成物、2-苯基咪唑异氰尿酸加成物、2-苯基-4,5-二羟基甲基咪唑以及2-苯基-4-甲基-5-羟基甲基咪唑。它们可单独使用或并用2种以上来使用。另外,也可制成对它们进行微囊化而得到的潜伏性固化剂。
咪唑系固化剂的含量相对于(a)成分100质量份优选为0.1~20质量份,更优选为0.1~10质量份。咪唑系固化剂的含量为0.1质量份以上时,则存在固化性提高的倾向,为20质量份以下时则存在有在形成金属接合之前粘接剂组合物不会固化,不易发生连接不良的倾向。
(v)膦系固化剂
作为膦系固化剂,例如可列举出三苯基膦、四苯基鏻四苯基硼酸酯、四苯基鏻四(4-甲基苯基)硼酸酯以及四苯基鏻(4-氟苯基)硼酸酯。
膦系固化剂的含量相对于(a)成分100质量份优选为0.1~10质量份,更优选为0.1~5质量份。膦系固化剂的含量为0.1质量份以上时,则存在固化性提高的倾向,为10质量份以下时则存在有在形成金属接合之前粘接剂组合物不会固化,不易发生连接不良的倾向。
酚醛树脂系固化剂、酸酐系固化剂以及胺系固化剂,可分别单独地使用1种或以2种以上的混合物的方式使用。咪唑系固化剂以及膦系固化剂也可分别单独使用,但是也可与酚醛树脂系固化剂、酸酐系固化剂或胺系固化剂一起使用。
粘接剂组合物包含酚醛树脂系固化剂、酸酐系固化剂或胺系固化剂作为(b)成分的情况下,可显现去除氧化膜的焊剂活性,可更为提高连接可靠性。
(c)成分:丙烯酸系表面处理填料或具有由上述通式(1)表示的基团的填料
作为(c)成分,如果是由具有上述通式(1)所示的基团的化合物进行了表面处理的填料则没有特别限制,例如可使用对绝缘性无机填料、晶须(ウィスカー)以及树脂填料进行表面处理而得到的填料。即,作为(C)成分,可使用具有由上述通式(1)表示的基团的填料。
此处,式(1)中,R1表示氢原子或碳原子数1或2的烷基,优选为氢原子、甲基或乙基。存在有如下倾向:R1的碳原子数越增加则体积越变高,碳原子数超过2时则反应性降低。R2表示碳原子数1~30的亚烷基,优选为碳原子数1~15的亚烷基。R2的碳原子数超过30时,则存在有不易对填料进行表面处理的倾向。
(c)成分是否在填料表面具有由上述通式(1)表示的基团,例如可通过以下那样的方法来确认。
将本实施方式的粘接剂组合物加热,使用气相色谱法(例如,SHIMADZU制,制品名“GC-17A”)测定所产生的甲醇。根据该甲醇的量可确认:具有存在于填料表面的由上述通式(1)表示的基团这一情况。在此情况下,同样地测定不包含(C)成分的粘接剂组合物的甲醇量而作为参照。
作为绝缘性无机填料,例如可列举出玻璃、二氧化硅、氧化铝、氧化钛、炭黑、云母、以及氮化硼,优选为二氧化硅、氧化铝、氧化钛以及氮化硼,更优选为二氧化硅、氧化铝以及氮化硼。作为晶须,例如可列举出硼酸铝、钛酸铝、氧化锌、硅酸钙、硫酸镁、以及氮化硼。作为树脂填料,可列举出聚氨酯、聚酰亚胺。这些填料以及晶须可单独使用或以2种以上的混合物的方式使用。填料的形状、粒径以及配合量没有特别限制。也可使用微细的纳米二氧化硅。这些填料之中,由于表面处理的简易度、与树脂成分的相容性比较良好,因此优选二氧化硅填料。
作为(c)成分,可使用由上述通式(2)所示的化合物进行了表面处理的填料。具体可使用:由式(2)中R1为氢原子的丙烯酸系化合物进行了表面处理的二氧化硅填料、由式(2)中R1为甲基的甲基丙烯酸系化合物进行了表面处理的二氧化硅填料、以及由式(2)中R1为乙基的乙基丙烯酸系化合物进行了表面处理的二氧化硅填料。从半导体粘接剂中所含的树脂成分、与半导体基板表面的反应性、键形成的观点考虑,优选上述式(2)中,R1为体积不大的基团,R1为氢原子或碳原子数1或2的烷基、氢原子、甲基或乙基。存在有如下倾向:R1的碳原子数越增加则体积越变高,碳原子数超过2时则反应性降低。即,作为(C)成分,可使用由丙烯酸系化合物、甲基丙烯酸系化合物或乙基丙烯酸系化合物进行了表面处理的二氧化硅填料。
在上述通式(1)或(2)中,R2表示碳原子数1~30的亚烷基,由于挥发成分少因而优选为碳原子数1~15的亚烷基。式(2)中,R3表示碳原子数1~30的烷基,可根据表面处理的容易程度而适当选定。R3的碳原子数为30以下时,则存在有容易对填料进行表面处理的倾向。
(c)成分的形状、粒径根据粘接剂组合物的用途来适当设定即可,没有特别限制。
关于(c)成分的平均粒径,在填料形状为球状的情况下,平均粒径优选为2μm以下,在狭间距化、狭间隙化进展的封装体中,为了避免由捕获(トラッピング)导致的可靠性降低,更优选为1.5μm以下,特别优选为1.0μm以下。另外,从处理性的观点考虑,其下限更优选为0.005μm以上,特别优选为0.01μm以下。
关于(c)成分的配合量,以粘接剂组合物的固体成分全体为基准,优选为5~80质量%,更优选为10~70质量%。当为5质量%以上时,则存在有容易较强地发挥粘接力的提高的倾向,为80质量%以下时,则存在容易调整粘度,不易发生粘接剂组合物的流动性的降低、填料向连接部的咬合(捕获),连接可靠性提高的倾向。
另外,对于硅烷偶联剂,不预先与填料进行表面处理,作为粘接剂组合物的构成成分而添加,在体系中进行表面处理时,则产生甲醇等,导致在高温工艺时发泡。
通过提高粘接剂组合物在260℃附近的吸湿后的粘接力、以及提高在260℃附近的弹性模量,从而可提高耐回流焊性,可防止回流焊后的剥离、连接不良。
(d)成分:重均分子量10000以上的高分子成分
作为(d)成分,例如可列举出苯氧树脂、聚酰亚胺树脂、聚酰胺树脂、聚碳二亚胺树脂、氰酸酯树脂、丙烯酸类树脂、聚酯树脂、聚乙烯树脂、聚醚砜树脂、聚醚酰亚胺树脂、聚乙烯醇缩乙醛树脂、氨基甲酸酯树脂以及丙烯酸类橡胶。它们之中从耐热性以及成膜性优异的观点考虑,优选为苯氧树脂、聚酰亚胺树脂、丙烯酸类橡胶、氰酸酯树脂以及聚碳二亚胺树脂,更优选为苯氧树脂、聚酰亚胺树脂以及丙烯酸类橡胶。这些(d)成分可单独使用或以2种以上的混合物、共聚物的方式使用。但是,在(d)成分中不包含作为(A)成分的环氧树脂。
上述的苯氧树脂、聚酰亚胺树脂等高分子成分可使用市售品,也可使用合成品。
聚酰亚胺树脂例如可通过公知方法使四羧酸二酐与二胺进行缩合反应而获得。更具体而言,在有机溶剂中,使四羧酸二酐与二胺进行等摩尔或大致等摩尔混合(各成分的添加顺序为任意),将反应温度设定为80℃以下、优选设定为0~60℃而进行加成反应即可。予以说明,为了抑制粘接剂组合物的诸特性的降低,优选上述的四羧酸二酐由乙酸酐进行再结晶精制处理。
随着上述加成反应的进行,反应液的粘度缓慢地升高,生成作为聚酰亚胺的前体的聚酰胺酸。聚酰亚胺树脂可对上述聚酰胺酸进行脱水闭环而获得。脱水闭环可通过进行加热处理的热闭环法、使用脱水剂的化学闭环法而进行。上述聚酰胺酸通过在50~80℃加热而解聚,从而可调整其分子量。
作为用作聚酰亚胺树脂的原料的四羧酸二酐,没有特别限制,例如可列举出:均苯四酸二酐、3,3’,4,4’-联苯四羧酸二酐、2,2’,3,3’-联苯四羧酸二酐、2,2-双(3,4-二羧基苯基)丙烷二酐、2,2-双(2,3-二羧基苯基)丙烷二酐、1,1-双(2,3-二羧基苯基)乙烷二酐、1,1-双(3,4-二羧基苯基)乙烷二酐、双(2,3-二羧基苯基)甲烷二酐、双(3,4-二羧基苯基)甲烷二酐、双(3,4-二羧基苯基)砜二酐、3,4,9,10-苝四羧酸二酐、双(3,4-二羧基苯基)醚二酐、苯-1,2,3,4-四羧酸二酐、3,4,3’,4’-二苯甲酮四羧酸二酐、2,3,2’,3’-二苯甲酮四羧酸二酐、3,3,3’,4’-二苯甲酮四羧酸二酐、1,2,5,6-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、1,2,4,5-萘四羧酸二酐、2,6-二氯萘-1,4,5,8-四羧酸二酐、2,7-二氯萘-1,4,5,8-四羧酸二酐、2,3,6,7-四氯萘-1,4,5,8-四羧酸二酐、菲-1,8,9,10-四羧酸二酐、吡嗪-2,3,5,6-四羧酸二酐、噻吩-2,3,5,6-四羧酸二酐、2,3,3’,4’-联苯四羧酸二酐、3,4,3’,4’-联苯四羧酸二酐、2,3,2’,3’-联苯四羧酸二酐、双(3,4-二羧基苯基)二甲基硅烷二酐、双(3,4-二羧基苯基)甲基苯基硅烷二酐、双(3,4-二羧基苯基)二苯基硅烷二酐、1,4-双(3,4-二羧基苯基二甲基甲硅烷基)苯二酐、1,3-双(3,4-二羧基苯基)-1,1,3,3-四甲基双环己烷二酐、对亚苯基双(偏苯三酸酯酐)、乙烯四羧酸二酐、1,2,3,4-丁烷四羧酸二酐、十氢萘-1,4,5,8-四羧酸二酐、4,8-二甲基-1,2,3,5,6,7-六氢萘-1,2,5,6-四羧酸二酐、环戊烷-1,2,3,4-四羧酸二酐、吡咯烷-2,3,4,5-四羧酸二酐、1,2,3,4-环丁烷四羧酸二酐、双(外-双环[2,2,1]庚烷-2,3-二羧酸二酐、双环-[2,2,2]-辛-7-烯-2,3,5,6-四羧酸二酐、2,2-双(3,4-二羧基苯基)丙烷二酐、2,2-双[4-(3,4-二羧基苯基)苯基]丙烷二酐、2,2-双(3,4-二羧基苯基)六氟丙烷二酐、2,2-双[4-(3,4-二羧基苯基)苯基]六氟丙烷二酐、4,4’-双(3,4-二羧基苯氧基)二苯硫醚二酐、1,4-双(2-羟基六氟异丙基)苯双(偏苯三酸酐)、1,3-双(2-羟基六氟异丙基)苯双(偏苯三酸酐)、5-(2,5-二氧代四氢呋喃基)-3-甲基-3-环己烯-1,2-二羧酸二酐、四氢呋喃-2,3,4,5-四羧酸二酐、由下述通式(I)表示的四羧酸二酐以及由下述式(II)表示的四羧酸二酐。
[化学式4]
式(I)中,a表示2~20的整数。
[化学式5]
由上述通式(I)表示的四羧酸二酐可以由偏苯三酸酐单酰氯以及对应的二醇合成,具体可列举出:1,2-(亚乙基)双(偏苯三酸酯酐)、1,3-(三亚甲基)双(偏苯三酸酯酐)、1,4-(四亚甲基)双(偏苯三酸酯酐)、1,5-(五亚甲基)双(偏苯三酸酯酐)、1,6-(六亚甲基)双(偏苯三酸酯酐)、1,7-(七亚甲基)双(偏苯三酸酯酐)、1,8-(八亚甲基)双(偏苯三酸酯酐)、1,9-(九亚甲基)双(偏苯三酸酯酐)、1,10-(十亚甲基)双(偏苯三酸酯酐)、1,12-(十二亚甲基)双(偏苯三酸酯酐)、1,16-(十六亚甲基)双(偏苯三酸酯酐)以及1,18-(十八亚甲基)双(偏苯三酸酯酐)。
作为四羧酸二酐,从可赋予优异的耐湿可靠性的观点考虑,优选由上述式(II)表示的四羧酸二酐。上述四羧酸二酐可单独使用或组合2种以上来使用。
由上述式(II)表示的四羧酸二酐的含量相对于全部四羧酸二酐优选为40摩尔%以上,更优选为50摩尔%以上,进一步优选为70摩尔%以上。含量为40摩尔%以上时,则存在有如下倾向:容易充分地确保基于使用了由上述式(II)表示的四羧酸二酐而得到的耐湿可靠性的效果。
作为用作上述聚酰亚胺树脂的原料的二胺,没有特别限制,例如可列举出:邻苯二胺、间苯二胺、对苯二胺、3,3’-二氨基二苯基醚、3,4’-二氨基二苯基醚、4,4’-二氨基二苯基醚、3,3’-二氨基二苯基甲烷、3,4’-二氨基二苯基甲烷、4,4’-二氨基二苯基醚甲烷、双(4-氨基-3,5-二甲基苯基)甲烷、双(4-氨基-3,5-二异丙苯基)甲烷、3,3’-二氨基二苯基二氟甲烷、3,4’-二氨基二苯基二氟甲烷、4,4’-二氨基二苯基二氟甲烷、3,3’-二氨基二苯基砜、3,4’-二氨基二苯基砜、4,4’-二氨基二苯基砜、3,3’-二氨基二苯硫醚、3,4’-二氨基二苯硫醚、4,4’-二氨基二苯硫醚、3,3’-二氨基二苯基酮、3,4’-二氨基二苯基酮、4,4’-二氨基二苯基酮、2,2-双(3-氨基苯基)丙烷、2,2’-(3,4’-二氨基二苯基)丙烷、2,2-双(4-氨基苯基)丙烷、2,2-双(3-氨基苯基)六氟丙烷、2,2-(3,4’-二氨基二苯基)六氟丙烷、2,2-双(4-氨基苯基)六氟丙烷、1,3-双(3-氨基苯氧基)苯、1,4-双(3-氨基苯氧基)苯、1,4-双(4-氨基苯氧基)苯、3,3’-(1,4-亚苯基双(1-甲基乙叉))双苯胺、3,4’-(1,4-亚苯基双(1-甲基乙叉))双苯胺、4,4’-(1,4-亚苯基双(1-甲基乙叉))双苯胺、2,2-双(4-(3-氨基苯氧基)苯基)丙烷、2,2-双(4-(3-氨基苯氧基)苯基)六氟丙烷、2,2-双(4-(4-氨基苯氧基)苯基)六氟丙烷、双(4-(3-氨基苯氧基)苯基)硫醚、双(4-(4-氨基苯氧基)苯基)硫醚、双(4-(3-氨基苯氧基)苯基)砜、双(4-(4-氨基苯氧基)苯基)砜、3,5-二氨基苯甲酸等芳香族二胺,1,3-双(氨基甲基)环己烷,2,2-双(4-氨基苯氧基苯基)丙烷,由下述通式(III)或(IV)表示的脂肪族醚二胺,由下述通式(V)表示的脂肪族二胺以及由下述通式(VI)表示的硅氧烷二胺。
[化学式6]
式(III)中,Q1、Q2以及Q3分别独立地表示碳原子数1~10的亚烷基,b表示1~80的整数。
[化学式7]
式(IV)中,Q4、Q5、Q6以及Q7分别独立地表示碳原子数1~10的亚烷基,c、d以及e分别独立地表示1~50的整数。
[化学式8]
式(V)中,f表示5~20的整数。
[化学式9]
式(VI)中,Q8以及Q13分别独立地表示碳原子数1~5的亚烷基或可具有或不具有取代基的亚苯基,Q9、Q10、Q11以及Q12分别独立地表示碳原子数1~5的烷基、苯基或苯氧基,g表示1~5的整数。
它们之中,从可赋予低应力性、低温层压性以及低温粘接性的观点考虑,优选为由上述通式(III)、(IV)或(V)表示的二胺,从可赋予低吸水性以及低吸湿性的观点考虑,优选由上述通式(VI)表示的二胺。这些二胺可单独使用或组合2种以上来使用。
由上述通式(III)或(IV)表示的脂肪族醚二胺的含量优选为全部二胺的1~50摩尔%,由上述通式(V)表示的脂肪族二胺的含量优选为全部二胺的20~80摩尔%,由上述通式(VI)表示的硅氧烷二胺的含量优选为全部二胺的20~80摩尔%。为上述含量的范围内时,则存在有赋予低温层压性以及低吸水性的效果变大的倾向。
另外,作为由上述通式(III)表示的脂肪族醚二胺,具体可列举出下述式(III-1)~(III-5)的脂肪族醚二胺。予以说明,在通式(III-4)和(III-5)中,n表示1以上的整数。
[化学式10]
由上述通式(III-4)表示的脂肪族醚二胺的重均分子量例如优选为350、750、1100或2100。另外,由上述通式(III-5)表示的脂肪族醚二胺的重均分子量例如优选为230、400或2000。
上述脂肪族醚二胺之中,从可确保低温层压性和对带有有机抗蚀剂的基板的良好的粘接性的观点考虑,更优选为分别由上述通式(IV)、下述通式(VII)、(VIII)或(IX)表示的脂肪族醚二胺。
[化学式11]
式(VII)中,h表示2~80的整数,更优选为2~70。
[化学式12]
式(VIII)中,c、d以及e表示1~50的整数,更优选为2~40。
[化学式13]
式(IX)中,j以及k分别独立地表示1~70的整数。
作为由上述通式(VII)表示的脂肪族醚二胺,具体可列举出SUN TECHNOCHEMICAL(サンテクノケミカル)(株)制的JEFFAMINE D-230、D-400、D-2000以及D-4000,BASF制的聚醚胺D-230、D-400以及D-2000,作为由上述通式(VIII)表示的脂肪族醚二胺,具体可列举出SUN TECHNOCHEMICAL(株)制的JEFFAMINE ED-600、ED-900、ED-2001,作为由上述式(IX)表示的脂肪族醚二胺,可列举出SUN TECHNO CHEMICAL(株)制的JEFFAMINE EDR-148。
作为由上述通式(V)表示的脂肪族二胺,例如可列举出1,2-二氨基乙烷、1,3-二氨基丙烷、1,4-二氨基丁烷、1,5-二氨基戊烷、1,6-二氨基己烷、1,7-二氨基庚烷、1,8-二氨基辛烷、1,9-二氨基壬烷、1,10-二氨基癸烷、1,11-二氨基十一烷、1,12-二氨基十二烷以及1,2-二氨基环己烷。它们之中,优选1,9-二氨基壬烷、1,10-二氨基癸烷、1,11-二氨基十一烷以及1,12-二氨基十二烷。
作为由上述通式(VI)表示的硅氧烷二胺,在通式(VI)中的g为1的情况下,可列举出:1,1,3,3-四甲基-1,3-双(4-氨基苯基)二硅氧烷、1,1,3,3-四苯氧基-1,3-双(4-氨基乙基)二硅氧烷、1,1,3,3-四苯基-1,3-双(2-氨基乙基)二硅氧烷、1,1,3,3-四苯基-1,3-双(3-氨基丙基)二硅氧烷、1,1,3,3-四甲基-1,3-双(2-氨基乙基)二硅氧烷、1,1,3,3-四甲基-1,3-双(3-氨基丙基)二硅氧烷、1,1,3,3-四甲基-1,3-双(3-氨基丁基)二硅氧烷以及1,3-二甲基-1,3-二甲氧基-1,3-双(4-氨基丁基)二硅氧烷。在g为2的情况下,可列举出:1,1,3,3,5,5-六甲基-1,5-双(4-氨基苯基)三硅氧烷、1,1,5,5-四苯基-3,3-二甲基-1,5-双(3-氨基丙基)三硅氧烷、1,1,5,5-四苯基-3,3-二甲氧基-1,5-双(4-氨基丁基)三硅氧烷、1,1,5,5-四苯基-3,3-二甲氧基-1,5-双(5-氨基戊基)三硅氧烷、1,1,5,5-四甲基-3,3-二甲氧基-1,5-双(2-氨基乙基)三硅氧烷、1,1,5,5-四甲基-3,3-二甲氧基-1,5-双(4-氨基丁基)三硅氧烷、1,1,5,5-四甲基-3,3-二甲氧基-1,5-双(5-氨基戊基)三硅氧烷、1,1,3,3,5,5-六甲基-1,5-双(3-氨基丙基)三硅氧烷、1,1,3,3,5,5-六乙基-1,5-双(3-氨基丙基)三硅氧烷以及1,1,3,3,5,5-六丙基-1,5-双(3-氨基丙基)三硅氧烷。
上述聚酰亚胺树脂可单独使用或以2种以上的混合物的方式使用。
关于(d)成分的玻璃化温度(Tg),从粘接剂组合物对基板、芯片的贴附性优异的观点考虑,优选为100℃以下,更优选为85℃以下。在Tg为100℃以下的情况下,存在有容易通过粘接剂组合物将形成于半导体芯片的凸块、形成于基板的电极、配线图案等凹凸埋入,不会残存气泡,不易产生气孔的倾向。予以说明,上述Tg是指,使用DSC(Perkin-Elmer公司制DSC-7型),在样品量10mg、升温速度10℃/分钟、测定气氛为空气的条件下测定时的Tg。
(d)成分的重均分子量以聚苯乙烯换算计为10000以上,但是为了单独地显示良好的成膜性,优选为30000以上,更优选为40000以上,进一步优选为50000以上。重均分子量为10000以上时,则存在成膜性以及耐热性提高的倾向。予以说明,在本说明书中,重均分子量是指,使用高效液相色谱法(例如,岛津制作所制,制品名“C-R4A”),按照聚苯乙烯换算而测定时的重均分子量。
(d)成分的含量没有特别限制,但是为了良好地保持膜状,相对于(a)成分100质量份,优选为1~500质量份,更优选为5~300质量份,进一步优选为10~200质量份。(d)成分的含量为1质量份以上时,存在有容易获得成膜性的提高效果的倾向,为500质量份以下时,则存在粘接剂组合物的固化性提高、粘接力提高的倾向。
(e)成分:焊剂活性剂
在本发明的粘接剂组合物中可含有(e)成分,即,作为显示焊剂活性(去除氧化物、杂质的活性)的化合物的焊剂活性剂。作为焊剂活性剂,列举出如咪唑类、胺类那样具有非共享电子对的含氮化合物、羧酸类、酚类以及醇类。
它们之中,羧酸类的焊剂活性强、与作为(a)成分的环氧树脂反应、在粘接剂组合物的固化物中不以游离出的状态存在,因此可防止绝缘可靠性的降低。
作为羧酸类,例如可列举出:乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十二烷酸、十四烷酸、十六烷酸、十七烷酸、十八烷酸等脂式饱和羧酸;油酸、亚油酸、亚麻酸、花生油烯酸、二十二碳六烯酸、二十碳五烯酸等脂式不饱和羧酸;马来酸、富马酸、乙二酸、丙二酸、琥珀酸、戊二酸、己二酸等脂式二羧酸;苯甲酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、偏苯三酸、均苯三甲酸、1,2,3-苯三甲酸、均苯四酸、戊烷羧酸、苯六酸(melliticacid)等芳香族羧酸。另外,作为具有羟基的羧酸,例如可列举出乳酸、苹果酸、柠檬酸以及水杨酸。
进一步,也可使用在上述芳香族羧酸中具有吸电子性或供电子性的取代基,根据取代基而使芳香族上的羧酸的酸度发生变化的芳香族系羧酸。存在有羧酸的酸度越高则焊剂活性越提高的倾向,但是酸度过高时则存在有绝缘可靠性降低的情况。作为提高羧酸的酸度的吸电子性取代基,可列举出硝基、氰基、三氟甲基、卤素基团以及苯基。作为减弱羧酸的酸度的供电子性的取代基,可列举出甲基、乙基、异丙基、叔丁基、二甲基氨基以及三甲基氨基。予以说明,关于上述取代基的数目、位置,如果不降低焊剂活性、绝缘可靠性则不受特别限制。
(其它的成分)
在本实施方式的粘接剂组合物中,为了控制粘度、固化物的物性,以及为了抑制连接了半导体芯片以及基板时的气孔的产生、吸湿率的升高,除了(c)成分之外还可进一步配合填料。
作为填料,可使用绝缘性无机填料、晶须或树脂填料。作为绝缘性无机填料、晶须或树脂填料,可使用与上述(c)成分同样的物质。这些填料、晶须以及树脂填料可单独地使用1种或以2种以上的混合物的方式使用。填料的形状、平均粒径以及含量不受特别限制。
进一步,在本实施方式的粘接剂组合物中,也可配合抗氧化剂、硅烷偶联剂、钛偶联剂、流平剂、离子捕获剂等添加剂。它们可单独使用1种或者也可组合使用2种以上。关于它们的配合量,按照显现各添加剂的效果的方式而适当调整即可。
本实施方式的粘接剂组合物可形成为膜状。在下面给出使用了本实施方式的粘接剂组合物的膜状粘接剂的制作方法。首先,将(a)成分、(b)成分以及(c)成分、以及根据需要添加的(d)成分或(e)成分等加入有机溶剂中,通过搅拌混合、混炼等而溶解或分散,从而制备树脂清漆。其后,在实施了脱模处理的基材膜上,使用刮刀涂布机、辊涂机、涂布器涂布树脂清漆,然后通过加热去除有机溶剂,从而可在基材膜上获得膜状粘接剂。
作为用于制备树脂清漆的有机溶剂,优选为具有可将各成分均匀溶解或分散的特性的有机溶剂,例如可列举出二甲基甲酰胺、二甲基乙酰胺、N-甲基-2-吡咯烷酮、二甲基亚砜、二乙二醇二甲基醚、甲苯、苯、二甲苯、甲乙酮、四氢呋喃、乙基溶纤剂、乙基溶纤剂乙酸酯、丁基溶纤剂、二噁烷、环己酮、以及乙酸乙酯。这些有机溶剂可单独使用或组合2种以上来使用。制备树脂清漆时的搅拌混合、混炼例如可使用搅拌机、擂溃机、三辊研磨机、球磨机、珠磨机以及均质分散机(ホモディスパー)而进行。
作为基材膜,如果是具有可耐受挥发有机溶剂时的加热条件的耐热性的基材膜则没有特别限制,可例示出:聚丙烯膜、聚甲基戊烯膜等聚烯烃膜,聚对苯二甲酸乙二醇酯膜、聚萘二甲酸乙二醇酯膜等聚酯膜,聚酰亚胺膜以及聚醚酰亚胺膜。基材膜不受限于由这些膜形成的单层的基材膜,也可以为由2种以上的材料形成的多层膜。
从涂布于基材膜的树脂清漆挥发有机溶剂时的干燥条件优选为充分地挥发有机溶剂的条件,具体优选进行50~200℃、0.1~90分钟的加热。
另外,关于本实施方式的粘接剂组合物,从提高作业性的观点考虑,也可通过直接旋涂于晶片上,根据需要进行干燥,然后将晶片进行单片化而使用。
<半导体装置>
以下使用图1和2对本实施方式的半导体装置进行说明。图1为表示本发明的半导体装置的一个实施方式的模式剖视图。如图1(a)所示,半导体装置100具有:相互对向的半导体芯片10以及基板(电路配线基板)20,分别配置于半导体芯片10以及基板20的相互对向的面的配线15,将半导体芯片10以及基板20的配线15相互连接的连接凸块30,没有间隙地填充于半导体芯片10以及基板20间的空隙的粘接剂组合物40。半导体芯片10以及基板20通过配线15以及连接凸块30而进行倒装芯片连接。配线15以及连接凸块30通过粘接剂组合物40而密封并且从外部环境阻断。
如图1(b)所示,半导体装置200具有:相互对向的半导体芯片10以及基板20,分别配置于半导体芯片10以及基板20的相互对向的面的凸块32,没有间隙地填充半导体芯片10以及基板20间的空隙的粘接剂组合物40。半导体芯片10以及基板20通过对向的凸块32相互连接而进行倒装芯片连接。凸块32通过粘接剂组合物40而密封并且从外部环境阻断。
图2为表示本发明的半导体装置的另一个实施方式的模式剖视图。如图2(a)所示,关于半导体装置300,除了2个半导体芯片10通过配线15以及连接凸块30而进行倒装芯片连接这一点以外,与半导体装置100同样。如图2(b)所示,关于半导体装置400,除了2个半导体芯片10通过凸块32而进行倒装芯片连接这一点以外,与半导体装置200同样。
作为半导体芯片10没有特别限定,可使用由硅、锗等相同种类的元素构成的元素半导体、砷化镓、磷化铟等化合物半导体。
作为基板20,如果是电路基板则没有特别限制,可使用:在以玻璃环氧树脂(glass-epoxy)、聚酰亚胺、聚酯、陶瓷、环氧树脂、双马来酰亚胺三嗪等为主要的成分的绝缘基板的表面上具有通过对不需要金属膜的部位进行蚀刻去除而形成的配线(配线图案)15的电路基板,在上述绝缘基板的表面通过金属镀敷等而形成了配线15的电路基板,在上述绝缘基板的表面印刷导电性物质而形成了配线15的电路基板。
对于配线15、凸块32等连接部,作为主要成分,含有金、银、铜、焊锡(主要成分例如为锡-银、锡-铅、锡-铋、锡-铜、锡-银-铜)、镍、锡、铅等,也可含有多种金属。
上述金属之中,从制成连接部的电传导性、导热性优异的封装体的观点考虑,优选为金、银以及铜,更优选为银以及铜。从制成使成本减低了的封装体的观点考虑,基于廉价而优选为银、铜以及焊锡,更优选铜以及焊锡,进一步优选焊锡。在室温在金属的表面形成氧化膜时则存在有生产率降低的情况、成本增加的情况,因此从抑制氧化膜的形成的观点考虑,优选为金、银、铜以及焊锡,更优选金、银、焊锡,进一步优选金、银。
在上述配线15以及凸块32的表面上,也可通过例如镀敷而形成有以金、银、铜、焊锡(主要成分例如为锡-银、锡-铅、锡-铋、锡-铜)、锡、镍等为主要的成分的金属层。该金属层也可仅由单一的成分来构成,也可由多种成分构成。另外,上述金属层也可制成单层或层叠多种金属层而得到的结构。
另外,本实施方式的半导体装置中也可层叠多个半导体装置100~400所示那样的结构(封装体)。在此情况下,半导体装置100~400也可由包含金、银、铜、焊锡(主要成分为例如锡-银、锡-铅、锡-铋、锡-铜、锡-银-铜)、锡、镍等的凸块、配线相互地电连接。
作为将多个半导体装置层叠的技术,如图3所示,例如可列举出TSV(Through-Silicon Via)技术。图3为表示本发明的半导体装置的另一个实施方式的模式剖视图,并且是使用了TSV技术的半导体装置。在图3所示的半导体装置500中,通过使形成于中介层(interposer)50上的配线15与半导体芯片10的配线15通过连接凸块30而连接,从而半导体芯片10与中介层50进行倒装芯片连接。在半导体芯片10与中介层50之间的空隙中没有间隙地填充着粘接剂组合物40。在上述半导体芯片10中的与中介层50侧为相反侧的表面上,通过配线15、连接凸块30以及粘接剂组合物40而反复重叠着半导体芯片10。半导体芯片10的表面和背面处的图案面的配线15通过填充于贯通半导体芯片10的内部的孔内的贯通电极34而相互连接。予以说明,作为贯通电极34的材质,可使用铜、铝等。
通过这样的TSV技术,也可从通常不使用的半导体芯片的背面取得信号。进一步,由于使贯通电极34垂直地通过半导体芯片10内,因此缩短对向的半导体芯片10之间、半导体芯片10与中介层50之间的距离,可实现柔软的连接。本实施方式的粘接剂组合物,在这样的TSV技术中,可适用作对向的半导体芯片10之间、半导体芯片10与中介层50之间的半导体密封用粘接剂。
另外,在面凸块芯片技术(エリャバンプチップ技術)等自由度高的凸块形成方法中,可不通过中介层而原样地将半导体芯片直接安装于母板(マザーボード)。本实施方式的粘接剂组合物也可适用于这样的将半导体芯片直接安装于母板的情况。予以说明,在将2个配线电路基板层叠的情况下,在将基板间的空隙密封时也可适用本实施方式的粘接剂组合物。
<半导体装置的制造方法>
以下使用图4对本实施方式的半导体装置的制造方法进行说明。图4是模式地表示本发明的半导体装置的制造方法的一个实施方式的工序剖视图。
首先,如图4(a)所示,在具有配线15的基板20上,形成在形成连接凸块30的位置具有开口的阻焊层60。该阻焊层60未必需要设置。但是,通过在基板20上设置阻焊层,可抑制配线15间的电桥(ブリッジ)的产生,可提高连接可靠性、绝缘可靠性。阻焊层60例如可使用市售的封装体用阻焊层用油墨而形成。作为市售的封装体用阻焊层用油墨,具体可列举出SR系列(日立化成工业株式会社制,商品名)以及PSR4000-AUS系列(太阳油墨制造(株)制,商品名)。
接着,如图4(a)所示,在阻焊层60的开口处形成连接凸块30。然后如图4(b)所示,在形成有连接凸块30以及阻焊层60的基板20上贴附膜状的粘接剂组合物(以下,视情况而称为“膜状粘接剂”)40。膜状粘接剂40的贴附可通过热压、辊层压、真空层压等而进行。膜状粘接剂40的供给面积、厚度可根据半导体芯片10以及基板20的尺寸、连接凸块30的高度而适当设定。
如上述那样将膜状粘接剂40贴附于基板20后,使用倒装芯片接合机等连接装置将半导体芯片10的配线15与连接凸块30进行位置对齐。接着,一边对半导体芯片10与基板20在连接凸块30的熔点以上的温度加热一边压接,如图4(c)所示,将半导体芯片10与基板20连接,并且通过膜状粘接剂40将半导体芯片10以及基板20间的空隙进行密封填充。通过以上,可获得半导体装置600。
在本实施方式的半导体装置的制造方法中,也可在进行了位置对齐之后进行临时固定(介由半导体粘接剂的状态),在回流焊炉中进行加热处理,从而将连接凸块30熔融而将半导体芯片10与基板20连接。在临时固定的阶段中并非必需形成金属接合,因而相比较于上述的一边加热一边压接的方法而言,基于低载荷、短时间、低温度的压接即可,可提高生产率,并且可抑制连接部的劣化。
另外,也可将半导体芯片10与基板20连接,然后通过烘箱等进行加热处理,进一步提高连接可靠性、绝缘可靠性。加热温度优选为进行膜状粘接剂的固化的温度,更优选为完全地固化的温度。可适当设定加热温度、加热时间。
在本实施方式的半导体装置的制造方法中,也可在将膜状粘接剂40贴附于半导体芯片10之后将基板20连接。另外,也可在通过配线15以及连接凸块30将半导体芯片10以及基板20连接后,向半导体芯片10以及基板20间的空隙中填充糊状的粘接剂组合物。
从生产率提高的观点考虑,也可将粘接剂组合物供给于多个半导体芯片10连接而成的半导体晶片,然后切割而进行单片化,从而获得在半导体芯片10上供给有粘接剂组合物的结构体。另外,在粘接剂组合物为糊状的情况下,没有特别限制,但是通过旋涂等涂布方法,将半导体芯片10上的配线、凸块埋入,将厚度进行均匀化即可。在该情况下,由于树脂的供给量成为一定,因而可使生产率提高,并且可抑制由埋入不足导致的气孔的产生以及切割性的降低。另一方面,在粘接剂组合物为膜状的情况下,没有特别限制,但通过热压、辊层压以及真空层压等贴附方式按照埋入半导体芯片10上的配线、凸块的方式供给膜状的树脂组合物即可。在该情况下,树脂的供给量成为一定,因而可使生产率提高,可抑制由埋入不足导致的气孔的产生以及切割性的降低。
连接载荷考虑连接凸块30的数量、高度的偏差、基于加压的连接凸块30或接受连接部的凸块的配线的变形量而设定。关于连接温度,优选连接部的温度为连接凸块30的熔点以上,只要是可形成各个连接部(凸块、配线)的金属接合的温度即可。连接凸块30为焊锡凸块的情况下,优选为约240℃以上。
连接时的连接时间因连接部的构成金属而不同,但是从生产率提高的观点考虑越为短时间则越优选。连接凸块30为焊锡凸块的情况下,连接时间优选为20秒以下,更优选为10秒以下,进一步优选为5秒以下。铜-铜或铜-金的金属连接的情况下,连接时间优选为60秒以下。
即使在上述的各种各样的封装体结构的倒装芯片连接部,本发明的粘接剂组合物也显现出优异的耐回流焊性、连接可靠性以及绝缘可靠性。
实施例
以下使用实施例、比较例而说明本发明,但本发明不受限于以下的实施例。
(聚酰亚胺合成)
向具备有温度计、搅拌机以及氯化钙管的300mL烧瓶中,加入1,12-二氨基十二烷2.10g(0.035摩尔)、聚醚二胺(BASF制,商品名“ED2000”、分子量:1923)17.31g(0.03摩尔)、1,3-双(3-氨基丙基)四甲基二硅氧烷(信越化学制,商品名“LP-7100”)2.61g(0.035摩尔)以及N-甲基-2-吡咯烷酮(关东化学制,以下称为“NMP”)150g并且进行了搅拌。将上述二胺溶解后,一边将烧瓶在冰浴中冷却,一边每次少量地添加了由乙酸酐进行再结晶精制而得到的4,4’-(4,4’-异丙叉二苯氧基)双(邻苯二甲酸二酐)(ALDRICH制,商品名“BPADA”)15.62g(0.10摩尔)。在室温下反应8小时后,加入二甲苯100g,一边吹入氮气一边在180℃加热,与水一同将二甲苯共沸去除,获得了聚酰亚胺树脂。从所获得的聚酰亚胺树脂去除溶剂(NMP),将按照成为固体成分50质量%的方式溶解于甲乙酮(MEK)而得到的物质设为“聚酰亚胺A”。聚酰亚胺A的Tg为30℃,重均分子量为50000,SP值(溶解度参数)为10.2。
各实施例和各比较例中使用的化合物如下所述。
(a)环氧树脂
含有三酚基甲烷骨架的多官能固态环氧树脂(日本环氧树脂株式会社制,商品名“EP1032H60”,以下称为“EP1032”。)
双酚F型液状环氧树脂(日本环氧树脂株式会社制,商品名“YL983U”,以下称为“YL983”。)
柔软性环氧树脂(日本环氧树脂株式会社制,商品名“YL7175”,以下称为“YL7175”。)
(b)固化剂
2-苯基-4,5-二羟基甲基咪唑(四国化成株式会社制,商品名“2PHZ-PW”,以下称为“2PHZ”。)
2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪异氰尿酸加成物(四国化成株式会社制,商品名“2MAOK-PW”,以下称为“2MAOK”。)
(c)丙烯酸系表面处理填料或具有由上述通式(1)表示的基团的填料
甲基丙烯酸表面处理二氧化硅填料(株式会社Admatechs制,商品名“SE2050-SMJ”,平均粒径0.5μm,以下称为“SM二氧化硅”。)
甲基丙烯酸表面处理纳米二氧化硅填料(株式会社Admatechs制,商品名“YA050C-SM”,以下称为“SM纳米二氧化硅”。)
(c’)其它的填料
未处理的二氧化硅填料(株式会社Admatechs制,商品名“SE2050”,平均粒径0.5μm,以下,称为“未处理二氧化硅”。)
氨基硅烷处理二氧化硅填料(株式会社Admatechs制,商品名“SE2050-SXJ”,平均粒径0.5μm,以下称为“SX二氧化硅”。)
环氧硅烷处理二氧化硅填料(株式会社Admatechs制,商品名“SE2050-SEJ”,平均粒径0.5μm,以下称为“SE二氧化硅”。)
苯基硅烷处理二氧化硅填料(株式会社Admatechs制,商品名“SE2050-SPJ”,平均粒径0.5μm,以下称为“SP二氧化硅”。)
苯基表面处理纳米二氧化硅填料(株式会社Admatechs制,商品名“YA050C-SP”,平均粒径50nm,以下称为“SP纳米二氧化硅”。)
有机填料(1)(三菱丽阳制,商品名“W5500”,以下称为“W5500”。)
有机填料(2)(Rohm and Haas日本(株)公司制,商品名“EXL-2655”,核壳型有机微粒,以下称为“EXL2655”。)
(d)分子量10000以上的高分子成分
苯氧树脂(东都化成株式会社制,商品名“ZX1356”,Tg:约71℃,Mw:约63000,以下称为“ZX1356”。)
如上述那样合成出的聚酰亚胺A
(e)焊剂活性剂(焊剂,フラックス剤)
二酚酸(东京化成株式会社制)
己二酸(和光纯药工业株式会社制)
<半导体密封用膜状粘接剂的制作>
(实施例1)
将环氧树脂(EP1032)100质量份、固化剂(2PHZ)7.5质量份、填料(SM二氧化硅)175质量份、焊剂活性剂(二酚酸)25质量份以及MEK溶剂按照固体成分为60质量%的方式加料,将直径0.8mm的微珠以及直径2.0mm的微珠与固体成分同量地加入,利用珠磨机(Fritsch Japan株式会社,行星型微粉碎机“P-7”)搅拌30分钟。接着,加入聚酰亚胺A100质量份(按固体成分换算),再次利用珠磨机而搅拌30分钟后,通过过滤而去除用于搅拌的微珠,获得了树脂清漆。
利用小型精密涂布装置(廉井精机制)将所获得的树脂清漆涂布于基材膜(帝人杜邦膜株式会社制,商品名“PUREX A53”),在洁净烘箱(ESPEC株式会社制)中,在70℃干燥10分钟,从而制作出膜状粘接剂。
(实施例2~3以及比较例1~6)
如下述的表1那样变更了所使用的原材料的组成,除此以外,与实施例1同样地制作出实施例2~3以及比较例1~6的膜状粘接剂。
以下,给出由实施例和比较例获得的膜状粘接剂的评价方法。
<260℃下的弹性模量的测定>
将膜状粘接剂切取规定的尺寸(长度37mm×宽度4mm×厚度0.13mm),在洁净烘箱(ESPEC株式会社制)中,在180℃保持3小时而进行了固化。固化后,使用粘弹性测定装置(Rheometrics制,商品名“RASII”),测定出作为耐回流焊性评价时的回流焊炉的到达温度的260℃下的弹性模量。测定以温度范围-30~270℃、升温速度5℃/分钟、测定波长10Hz进行。
<吸湿后的260℃下的粘接力的测定>
将膜状粘接剂切取规定的尺寸(长度5mm×宽度5mm×厚度0.025mm),在60℃贴附于硅芯片(长度5mm×宽度5mm×厚度0.725mm、氧化膜涂布),使用热压接试验机(日立化成Techno-Plant株式会社制),压接于涂布有阻焊层(太阳油墨制,商品名“AUS308”)的玻璃环氧树脂基板(厚度0.02mm)(压接条件:膜状粘接剂的到达温度180℃/10秒/0.5MPa。接着,膜状粘接剂的到达温度245℃/10秒/0.5MPa)。接着,在洁净烘箱(ESPEC株式会社制)中进行了后固化(aftercure)(180℃/3小时)。其后,在85℃、相对湿度60%的恒温恒湿器(ESPEC株式会社制,商品名“PR-2KP”)中放置48小时,取出后,在260℃的热板上使用粘接力测定装置(DAGE公司制,万能型粘合检测仪DAGE4000型),在自基板的工具(tool)高度0.05mm、工具速度0.05mm/秒的条件下进行了测定。
<初始连接性的评价>
将所制作的膜状粘接剂切取规定的尺寸(长度8mm×宽度8mm×厚度0.025mm),贴附于玻璃环氧树脂基板(玻璃环氧树脂基材:420μm厚,铜配线:9μm厚、80μm间距)上,用倒装芯片安装装置“FCB3”(松下公司制,商品名)将带有焊锡凸块的半导体芯片(芯片尺寸:长度7mm×宽度7mm×高度0.15mm,凸块:铜柱以及焊锡、80μm间距)安装(安装条件:膜状粘接剂的到达温度180℃、10秒、0.5MPa。接着,膜状粘接剂的到达温度245℃、10秒、0.5MPa)。由此,获得了与图4同样地使上述玻璃环氧树脂基板与带有焊锡凸块的半导体芯片进行菊花链(ディジーチェーン)连接而得到的半导体装置。
使用万用表(ADVANTEST制,商品名“R6871E”)测定所获得的半导体装置的连接电阻值,从而对安装后可否进行初始导通进行了评价。将连接电阻值为11~14Ω的情况评价为连接性良好“A”,将除此以外的连接电阻值的情况或发生连接不良(Open)而没有显示电阻值的情况评价为“B”。
<耐回流焊性的评价>
使用密封材料(日立化成工业株式会社制,商品名“CEL9700HF10K”),在180℃、6.75MPa、90秒的条件下,将上述的半导体装置塑模为规定的形状,在洁净烘箱(ESPEC株式会社制)中,在175℃固化5小时而获得了封装体。接着,在JEDEC level2条件下将该封装体进行高温吸湿后,使封装体通过于IR回流焊炉(FURUKAWA ELECTRIC制,商品名“SALAMANDER”)。通过与后述的初始连接性的评价同样的方法评价回流焊后的封装体的连接性,作为耐回流焊性的评价。将没有剥离、连接良好的情况设为“A”,将发生剥离、连接不良而没有显示电阻值的情况设为“B”。
<连接可靠性的评价(耐TCT评价)>
使用密封材料(日立化成工业株式会社制,商品名“CEL9700HF10K”),在180℃、6.75MPa、90秒的条件下将上述的半导体装置塑模为规定的形状,在洁净烘箱(ESPEC株式会社制)中,在175℃固化5小时而获得了封装体。接着,将该封装体放置于冷热循环试验机(ETAC制,THERMAL SHOCK CHAMBERNT1200)内,流过1mA的电流,将25℃2分钟/-55℃15分钟/25℃2分钟/125℃15分钟/25℃2分钟设为1个循环而测定连接电阻,对反复进行1000循环后的连接电阻的变化进行了评价。与初始的电阻值波形相比,将在1000循环之后也没有大的变化的情况设为“A”,将产生了1Ω以上的差的情况设为“B”。
<绝缘可靠性的评价(耐HAST评价)>
将所制作的膜状粘接剂切取规定的尺寸(长度10mm×宽度5mm×厚度25μm),贴附于在聚酰亚胺基板上形成有配线铜配线的梳型电极基板(配线间距:0.05mm),如图5所示,制作出在形成有梳型电极90的基板20上层叠膜状粘接剂40而得到的样品。予以说明,在图5中,为了方便而省略了膜状粘接剂的图示。接着,将样品在洁净烘箱(ESPEC株式会社制)中在185℃保持3小时而进行了固化。固化后,取出各样品,设置于加速寿命试验装置(HIRAYAMA公司制,商品名“PL-422R8”,条件:130℃/相对湿度85%/200小时/5V施加),测定了绝缘电阻。经过200小时,将绝缘电阻为108Ω以上的情况设评价为“A”,将不足108Ω的情况评价为“B”。
将各实施例和各比较例的粘接剂组合物的原材料的组成(单位:质量份)示于表1中,将各试验的结果示于表2。
表1
表2
确认了:在使用了丙烯酸系表面处理填料的实施例1~3中,吸湿后的260℃下的粘接力高,耐回流焊性、耐TCT性以及耐HAST性中的任一个特性都优异。
符号说明
10半导体芯片、15配线(连接部)、20基板(配线电路基板)、30连接凸块、32凸块(连接部)、34贯通电极、40粘接剂组合物(膜状粘接剂)、50中介层、60阻焊层、90梳型电极、100、200、300、400、500、600半导体装置。
Claims (7)
1.一种粘接剂组合物,其为在半导体芯片以及配线电路基板的各自的连接部相互地电连接的半导体装置、或多个半导体芯片的各自的连接部相互地电连接的半导体装置中将所述连接部密封的粘接剂组合物,
其含有环氧树脂、固化剂、由具有下述通式(1)所示的基团的化合物进行了表面处理的丙烯酸系表面处理填料以及重均分子量为10000以上的高分子成分,
式(1)中,R1表示氢原子或碳原子数1或2的烷基,R2表示碳原子数1~30的亚烷基。
3.一种粘接剂组合物,其为在半导体芯片以及配线电路基板的各自的连接部相互地电连接的半导体装置、或多个半导体芯片的各自的连接部相互地电连接的半导体装置中将所述连接部密封的粘接剂组合物,
其含有环氧树脂、固化剂、具有下述通式(1)所示的基团的填料以及重均分子量为10000以上的高分子成分,
式(1)中,R1表示氢原子或碳原子数1或2的烷基,R2表示碳原子数1~30的亚烷基。
4.根据权利要求1~3中任一项所述的粘接剂组合物,其中,所述高分子成分的重均分子量为30000以上,玻璃化温度为100℃以下。
5.根据权利要求1~4中任一项所述的粘接剂组合物,其形状为膜状。
6.一种半导体装置的制造方法,其为半导体芯片以及配线电路基板的各自的连接部相互地电连接的半导体装置、或多个半导体芯片的各自的连接部相互地电连接的半导体装置的制造方法,
其具备使用权利要求1~5中任一项所述的粘接剂组合物将所述连接部密封的工序。
7.根据权利要求6所述的制造方法,其中,所述连接部含有选自金、银、铜、镍、锡以及铅中的至少一种金属作为主要成分。
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CN105081614A (zh) * | 2015-09-07 | 2015-11-25 | 东莞市富默克化工有限公司 | 一种osp预浸剂 |
CN109075088A (zh) * | 2016-05-09 | 2018-12-21 | 日立化成株式会社 | 半导体装置的制造方法 |
CN109075088B (zh) * | 2016-05-09 | 2022-01-07 | 昭和电工材料株式会社 | 半导体装置的制造方法 |
CN109716566A (zh) * | 2017-03-31 | 2019-05-03 | 株式会社Lg化学 | 二次电池用粘合剂组合物以及包含其的二次电池用电极和锂二次电池 |
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TW201414795A (zh) | 2014-04-16 |
JPWO2012043764A1 (ja) | 2014-02-24 |
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TW201229176A (en) | 2012-07-16 |
CN103222040A (zh) | 2013-07-24 |
CN103222040B (zh) | 2015-12-02 |
JP5373192B2 (ja) | 2013-12-18 |
CN103642441B (zh) | 2015-05-13 |
WO2012043764A1 (ja) | 2012-04-05 |
KR101728203B1 (ko) | 2017-04-18 |
JP2012149266A (ja) | 2012-08-09 |
TWI424038B (zh) | 2014-01-21 |
KR101455951B1 (ko) | 2014-10-28 |
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