CN102977809A - 电路部件连接用粘接剂以及半导体装置 - Google Patents
电路部件连接用粘接剂以及半导体装置 Download PDFInfo
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- CN102977809A CN102977809A CN2012104557246A CN201210455724A CN102977809A CN 102977809 A CN102977809 A CN 102977809A CN 2012104557246 A CN2012104557246 A CN 2012104557246A CN 201210455724 A CN201210455724 A CN 201210455724A CN 102977809 A CN102977809 A CN 102977809A
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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Abstract
本发明涉及电路部件连接用粘接剂以及半导体装置。本发明提供一种用于连接相对向的电路基板的电路部件连接用粘接剂,所述电路部件连接用粘接剂包含:含有热塑性树脂、热固性树脂和固化剂的树脂组合物;以及分散于该组合物中的金属氢氧化物粒子。本发明的电路部件连接用粘接剂可实现半导体芯片与基板之间的优良的连接可靠性,同时可将用于对准半导体芯片和基板的位置的对准标记的识别性提高至充分实用水平。
Description
本发明是申请号为2008801131597(国际申请号为PCT/JP2008/071727)、申请日为2008年11月28日、发明名称为“电路部件连接用粘接剂以及半导体装置”的发明申请的分案申请。
技术领域
本发明涉及电路部件连接用粘接剂以及使用了所述电路部件连接用粘接剂的半导体装置。
背景技术
作为通过面朝下接合(face down bonding)方式直接将半导体芯片安装于电路基板的方式,已知有:在半导体芯片的电极部分上形成焊接凸点并且焊接到电路基板上的方式,以及将导电性粘接剂涂布在设置于半导体芯片上的突起电极上并且与电路基板电极电连接的方法。然而在这些方式中,在暴露于各种环境下的情况下,由于相连接的芯片和基板的热膨胀系数差从而在连接界面上产生应力,因此会存在连接可靠性降低的问题。
因此,为了缓和连接界面上的应力,有人正在研究:使用环氧树脂等底部填料(under filler)填充芯片与基板之间的间隙的方式。底部填料的填充方式有:在连接芯片和基板之后注入低粘度的液状树脂的方式,以及在基板上设置底部填料之后搭载芯片的方式。作为在预先将底部填料设置于基板之后搭载芯片的方法,有涂布液状树脂的方法和贴附膜状树脂的方法。
然而,在液状树脂涂布中,难以通过分布器控制精确的涂布量,在近年来的芯片薄型化过程中,如果涂布量过多,那么接合(bonding)时溢出的树脂就会流至芯片的侧面,而污染接合工具,因此需要对工具进行洗涤,这便导致量产时的工序变得繁杂。
另一方面,在薄膜状树脂的情况下,容易通过控制薄膜的厚度来实现树脂量的最佳化,但是,将薄膜贴附于基板时,需要称为暂时压合工序的薄膜贴附工序。在此情况下,为了修正安装时的芯片与基板的错位,一般需要使贴附于基板的薄膜的尺寸比芯片的尺寸大,从而妨碍了高密度化安装,这便成为了课题。为了解决此课题,作为供给尺寸与芯片尺寸相同的粘接剂的方法,已提出了如下方法:在单片化成芯片之前的晶片状态下供给粘结剂后,通过切割等而同时进行芯片加工和粘接剂加工,从而获得附有粘接剂的芯片。(参考专利文献1、2)。
专利文献1:日本特许第2833111号公报
专利文献2:日本特开2006-49482号公报
发明内容
发明要解决的技术问题
然而,以往提出的晶片前置型的底部填充(underfill)方法(即:在单片化成芯片之前向晶片供给底部填充剂的加工方法)具有下述那样的问题,因此未在市场上普及。
专利文献1的方法如下:将薄膜状粘接剂贴附于晶片之后,通过切割进行单片化从而获得附有粘接薄膜的芯片。在本发明中,制作晶片/粘接剂/隔膜这样的叠层体,将其切断后,剥离隔膜,从而获得附有粘接剂的芯片,但是在切断叠层体时有时会剥离粘接剂和隔膜,因此存在着单片化的半导体芯片飞散、流出的风险。
专利文献2涉及具有粘着材料层和粘接剂层的晶片加工用带的方法,公开了如下的方法:在将晶片贴附于晶片加工用带之后,进行切割、拾取(pick up),以倒装芯片(flip chip)方式将单片化的芯片连接于基板。一般在倒装芯片方式安装中,为了将芯片电路面的称为凸点(bump)的端子与相对向的基板侧的端子连接,需要通过倒装芯片接合机(bonder)使芯片侧的对准标记(对准位置标记)与基板侧的对准标记对准位置,并贴附。然而,在将粘接剂贴附于芯片的电路面的情况下,由于粘接剂覆盖了电路面的对准标记,因此需要透过粘接剂来识别对准标记。对此,专利文献2中没有提供针对该问题的解决方案。
本发明的目的在于提供一种电路部件连接用粘接剂,其可实现半导体芯片与基板之间的优良的连接可靠性,同时可将用于对准半导体芯片和基板的位置的对准标记的识别性提高至充分实用水平。本发明的目的还在于提供:使用了此电路部件连接用粘接剂的半导体装置。
解决问题的技术方案
本发明提供一种电路部件连接用粘接剂,其用于连接相对向的电路基板,所述电路部件连接用粘接剂包含:含有热塑性树脂、热固性树脂和固化剂的树脂组合物,以及分散于该组合物中的金属氢氧化物粒子。需要说明的是,“相对向的电路基板的连接”包含电连接和/或电路基板的固定。
本发明的电路部件连接用粘接剂可实现半导体芯片与基板之间的优良的连接可靠性、以及使对准标记的识别成为可能的高透光性这样的以往不可能兼备的特性。
连接可靠性要求着:对应于基于芯片与基板的热膨胀系数差而产生的压力的高粘接化,对应于回流温度的高耐热性,对应于高温环境化的低热膨胀性,对应于高温高湿环境下的低吸湿性等。为了提高这些特性,可想到向可实现高耐热性和高粘接性的环氧树脂中添加线膨胀系数小的二氧化硅填料,但是就这样的体系而言,由于在二氧化硅填料和环氧树脂的界面处存在散射等的原因,无法获得透明性。
另一方面,可想到通过添加透明玻璃粒子来确保透明性(例如,日本特许第3408301号公报),但是即使在玻璃粒子为透明的情况下,有时也会由于其与分散玻璃粒子的树脂之间的折射率差以及界面的密合性不良等的原因而损失透明性,由于玻璃粒子的脆弱性和热膨胀系数差的原因,常常无法获得连接可靠性。
针对这样的状况,就本发明的电路部件连接用粘接剂而言,通过用热塑性树脂、热固性树脂和固化剂来构成基材,并且在该基材中添加金属氢氧化物粒子并分散,从而可兼备优良的连接可靠性和高的透光性。
本发明的电路部件连接用粘接剂在未固化时的可见光平行透射率优选为15~100%。通过使可见光平行透射率处于该范围内,可使采用倒装芯片接合机时的对准标记的识别变得更容易。
金属氢氧化物粒子的折射率优选为1.5~1.7,原因在于:可降低与树脂的折射率差,并可将未固化状态时的电路部件连接用粘接剂的光散射控制为最小限度。
关于金属氢氧化物粒子的粒径,优选使平均粒径处于0.1μm~10μm的范围内。通过使金属氢氧化物粒子的平均粒径处于该范围,可提高其分散性和树脂的流动性,还可期待树脂的增强效果。
本发明的电路部件连接用粘接剂在180℃加热20秒后通过差示扫描量热测定测得的反应率优选为75%以上。通过使由差示扫描量热测定而得到的反应率为上述值,可获得稳定的低连接电阻,成为优良的热压合树脂。
本发明的电路部件连接用粘接剂在40℃~100℃的线膨胀系数优选为70×10-6/℃以下。如果使用具有这样特性的电路部件连接用粘接剂来连接半导体芯片和电路基板,连接后的温度变化及加热吸湿所引起的膨胀等就能够得到抑制,可获得高的连接可靠性。
另外,本发明提供一种半导体装置,其具有:用上述电路部件连接用粘接剂接合了的电路基板。
发明效果
本发明提供一种电路部件连接用粘接剂,其可实现优良的半导体芯片与基板之间的连接可靠性,同时可将用于对准半导体芯片和基板的位置的对准标记的识别性提高至充分实用水平。另提供:使用了此电路部件连接用粘接剂的半导体装置。
通过使用本发明的电路部件连接用粘接剂,作为可应对狭间距化以及狭间隙(gap)化的晶片前置型的底部填充技术,在切割时不发生污染,进一步在切割后可简便地获得附有粘接剂的半导体芯片,进一步可通过对晶片的高密合化来抑制切割时的剥离,通过薄膜的高弹性化来抑制切割后的须、毛边、裂缝,在芯片安装时可在低温下且短时间内固化。另外,根据使用了本发明的电路部件连接用粘接剂的晶片前置型底部填充方法,通过将对晶片的密合性以及对切割带的密合性进行最佳化,能够同时实现切割时的剥离抑制、以及切割后的剥离简便,抑制须、毛边、裂缝等的产生,实现用于切割的未固化时的薄膜的高弹性化,在芯片安装时可在低温下且短时间内固化。
具体实施方式
就本发明中的电路部件连接用粘接剂进行说明。
本发明的电路部件连接用粘接剂为:用于将相对向的电路基板进行连接的电路部件连接用粘接剂。作为相对向的电路基板,并没有特别限定的组合,但是可列举出:例如,(I)具有突出的连接端子的半导体芯片和(II)形成有线路图的电路基板。
(I)具有突出的连接端子的半导体芯片中,半导体芯片的突出的连接端子可为:使用金线而形成的金销子(stud)凸点、通过热压合或超声波并用热压合机将金属球固定于半导体芯片的电极而成的端子、以及通过电镀或蒸镀而形成的端子。突出的连接端子并不要求由单一金属来构成,也可包含金、银、铜、镍、铟、钯、锡、铋等多种金属成分,也可为这些的金属层叠层的形态。另外,具有突出的连接端子的半导体芯片也可为:具有突出的连接端子的半导体晶片的状态。为了将半导体芯片的突出的连接端子和形成有线路图的基板以相对向的状态进行配置,通常在半导体芯片的与突出的连接端子相同的面上具有对准标记。在此情况下,优选为在半导体芯片的具有突出的连接端子的面上贴附有电路部件连接用粘接剂的状态下,倒装芯片接合机可透过电路部件连接用粘接剂来识别形成于芯片电路面上的对准标记。
(II)形成有线路图的电路基板可为通常的电路基板,另外也可为半导体芯片。在为电路基板的情况下,线路图可通过将形成于如下基板表面的铜等金属层的不需要部分进行蚀刻去除而形成,所述基板包括:通过将环氧树脂或具有苯并三嗪骨架的树脂浸渍于玻璃布或无纺布而形成的基板,具有增强(buildup)层的基板,或聚酰亚胺、玻璃、陶瓷等的绝缘基板。此外,线路图也可通过在绝缘基板表面上通过电镀来形成,或者还可通过蒸镀等来形成。另外,线路图不必由单一的金属来形成,也可包含金、银、铜、镍、铟、钯、锡、铋等多种金属成分,也可为这些的金属层叠层的形态。另外,基板为半导体芯片的情况下,线路图通常由铝构成,但是其表面也可形成金、银、铜、镍、铟、钯、锡、铋等的金属层。
例如,附有电路部件连接用粘接剂的半导体芯片可通过如下操作来获得:(1)通过层压(laminate)等将面积与半导体晶片同等的电路部件连接用粘接剂贴附于芯片化之前的具有突出的连接端子的半导体晶片的突出的连接端子面上,(2)通过将切割带叠层于前述半导体晶片的背面或前述电路部件连接用粘接剂上的工序而得到叠层体,并通过切割将所述叠层体切断成单片,(3)将单片化的附有电路部件连接用粘接剂的半导体芯片从切割带上剥离。此处使用的切割带可适用:将粘着材涂布于基材带上而成的市售的切割带。切割带可大致分为压敏型和放射线反应型,但是更优选为放射线反应型的切割带,该放射线反应型的切割带可通过UV照射而固化从而减小粘着力,从而使叠层于粘着面的被粘接体容易剥离。
本发明的电路部件连接用粘接剂优选为,在贴附于半导体芯片的具有突出的连接端子的表面上的状态下,可透过电路部件连接用粘接剂来识别形成于芯片电路面上的对准标记。对准标记可以用通常的倒装芯片接合机所搭载的芯片识别用装置来识别。此识别装置通常包含:具有卤素灯的卤素光源、光导(lightguide)、照射装置以及CCD照相机。通过图像处理装置判断由CCD照相机获取的图像与预先录入的对准位置用图像图案之间的一致性,从而进行对准位置作业。本发明所述的可识别对准标记是指:使用倒装芯片接合机的芯片识别用装置获取的对准标记的图像与已录入的对准标记的图像之间的一致性良好,可顺利进行对准位置作业。例如,在使用Athlete FA公司制倒装芯片接合机CB-1050的情况下,在电路部件连接用粘接剂贴附于具有突出连接端子的面而成的叠层体的、与连接端子表面相反的面,将叠层体吸引于倒装芯片接合机的吸附喷嘴。其后,用装置内的芯片识别用装置透过粘接剂层来拍摄半导体芯片表面上所形成的对准标记,当与预先输入到图像处理装置中的半导体芯片的对准标记之间具有一致性而可进行对准位置作业时,将粘接剂辨别为可识别的电路部件连接用粘接剂,当无法对准位置时,辨别为无法识别的电路部件连接用粘接剂。
本发明的电路部件连接用粘接剂在未固化时的可见光平行透射率优选为15~100%,可见光平行透射率更优选为18~100%,可见光平行透射率进一步优选为25~100%。可见光平行透射率小于15%的情况下,有时会无法通过倒装芯片接合机来识别对准标记,从而难以进行对准位置作业。
可见光平行透射率可使用日本电色株式会社制浊度计NDH2000并利用积分球式光电光度法来测定。例如,以膜厚50μm的帝人杜邦制PET薄膜(PUREX,全光线透射率90.45,雾度4.47)作为基准物质进行校正后,以25μm厚度将电路连接用粘接剂涂布于PET基材,对其进行测定。可从测定结果求出浊度、全光线透射率、扩散透射率以及平行透射率。
进一步,可见光平行透射率或可见光透射率可通过日立制U-3310型分光光度计来测定。例如,可以以膜厚50μm的帝人杜邦制PET薄膜(PUREX,555nm透射率86.03%)作为基准物质来进行基线修正测定后,以25μm厚度将电路部件连接用粘接剂涂布于PET基材,测定400nm~800nm的可见光区域的透射率。由于在倒装芯片接合机所使用的卤素光源和光导的波长相对强度中550nm~600nm的强度最强,因此,在本发明中可以555nm的透射率来进行透射率的比较。
将本发明的电路部件连接用粘接剂与切割带进行组合的情况下,电路部件连接用粘接剂对于UV照射后的切割带的粘接力优选为10N/m以下,且对半导体晶片的粘接力优选为70N/m以上。对UV照射后的切割带的粘接力为10N/m以上的情况下,在将切割后的单片化的附有电路部件连接用粘接剂的半导体芯片从切割带剥离的作业中,有时会发生芯片破裂或者粘接剂层变形。另一方面,对半导体晶片的粘接力为70N/m以下的情况下,由于切割时的刀片的旋转切削所产生的冲击和水压的影响,在芯片与粘接剂的界面存在发生剥离的倾向。
电路部件连接用粘接剂与UV照射后的切割带的粘接力可如下进行测定。即,使用将加热温度设定为80℃的层压机,将电路部件连接用粘接剂层压于晶片上,然后将切割带的粘着面朝向电路部件连接用粘接剂以40℃进行层压,然后对切割带侧进行15mW、300mJ左右的UV照射。在UV照射后的切割带上割开10mm宽的切口,制备拉伸测定用的短条。将晶片按压在载物台上,并将短条状的切割带的一端固定于拉伸测定机的拉伸夹具上,进行90°剥除(peel)试验,使电路部件连接用粘接剂和UV照射后的切割带剥离。通过此测定,可测定出电路部件连接用粘接剂与UV照射后的切割带之间的粘接力。
电路部件连接用粘接剂与半导体晶片的粘接力如下测定。通过使用加热温度设定为80℃的层压机,将电路部件连接用粘接剂层压于晶片后,以粘着面朝向电路部件连接用粘接剂的方式将Kapton带(日东电工制,10mm宽,25μm厚)贴附而充分密合,然后,在Kapton带外形的电路部件连接用粘接剂上割开10mm宽的切口。将所制得的电路部件连接用粘接剂和Kapton带的叠层体的一端从晶片上剥离并固定于拉伸测定机的拉伸夹具。将晶片按压在载物台上,通过提拉短条来进行90°剥除试验,将电路部件连接用粘接剂从晶片上剥离。通过此测定,可测定出电路部件连接用粘接剂与半导体晶片的粘接力。
为了抑制半导体芯片和电路基板连接之后的由温度变化和加热吸湿所引起的膨胀等从而实现高连接可靠性,电路部件连接用粘接剂在固化后的40℃~100℃的线膨胀系数优选为70×10-6/℃以下,更优选为60×10-6/℃以下,进一步优选为50×10-6/℃以下。固化后的线膨胀系数大于70×10-6/℃的情况下,由于安装后的由温度变化和加热吸湿引起的膨胀,因此有时就会变得不能保持半导体芯片的连接端子与电路基板的线路之间的电连接。
本发明的电路部件连接用粘接剂包含:含有热塑性树脂、热固性树脂和固化剂的树脂组合物(以下有时会简单地称为“树脂组合物”。),以及金属氢氧化物粒子;树脂组合物的可见光平行透射率优选为15%以上,更优选为50%以上,进一步优选为80%以上。可见光平行透射率为80%以上的情况下,即使金属氢氧化物粒子的填充量高时,也可满足规定的透射率,因而优选。树脂组合物的平行透射率低于15%的情况下,即使在不添加金属氢氧化物粒子的状态下,也难以通过倒装芯片接合机来识别对准标记,有时会妨碍对准位置作业。
如下所详述,树脂组合物中所含的热固性树脂,常采用用作耐热性树脂的环氧树脂,在该情况下,固化催化剂优选采用咪唑化合物或胺系固化剂。已知这样的固化剂为分子内含有氮原子的化合物,并且为高折射率化,因此,电路部件连接用粘接剂在未固化状态下的折射率一般为1.5以上。
另外,在本发明中树脂组合物中含有热塑性树脂,通过含有热塑性树脂,可达到容易将电路部件连接用粘接剂形成为薄膜状的效果。在此情况下,优选采用高分子量的热塑性树脂,这样的高分子量的热塑性树脂优选使用苯氧树脂和丙烯酸树脂(丙烯酸共聚物等)等。采用这样的热塑性树脂的情况下,电路部件连接用粘接剂在未固化状态下的折射率一般为1.7以下。因此,电路部件连接用粘接剂在未固化状态下的折射率优选为1.5~1.7,在此情况下,1.6为中心值。
使用于本发明的金属氢氧化物粒子的折射率可优选为1.5~1.7。折射率低于1.5的情况下,由于与树脂的折射率差变大,粒子分散后的未固化状态的薄膜中会发生光散射,无法获得充分的透过性。另一方面,折射率大于1.7的情况下,同样地由于出现与树脂组合物的折射率差,也难以获得充分的透过性。需要说明的是,树脂的折射率可通过使用阿贝(Abbe)折射仪并以钠D线(589nm)作为光源来进行测定。另外,填料的折射率可通过贝克(Becke)法在显微镜下进行测定。
使用于本发明的金属氢氧化物粒子的平均粒径优选为0.1μm~10μm。平均粒径低于0.1μm的情况下,由于粒子的比表面积大,表面能量也变大,因此粒子彼此之间的相互作用变大,有时会产生凝集体、损害分散性。即使凝集体的分散良好,由于比表面积大,因此分散于树脂时的增粘行为变大,会损害成型性。另一方面,平均粒径大于10μm的情况下,与粒径小的情况相反,由于比表面积变小,因此树脂的流动性变大,在成型时容易产生空泡(void)。另外,关于作为粒子分散的目的之一的树脂的增强效果,由于粒径变大,因此即使以同一添加量将粒子分散,粒子自身的数量也变少,增强效果也降低。因而,分散性良好并可期待增强效果的粒子的平均粒径优选为0.1~10μm。另外,作为粒径大情况下的不良现象,由于进入芯片的凸点与电路基板的电极之间的金属氢氧化物粒子所引发的电气特性的阻害,也成为不优选混入大粒径粒子的理由。特别是在低压下安装的情况下以及在凸点的材质为镍等硬质材质的情况下,金属氢氧化物粒子不会被埋入端子中,这便妨碍了直接接触中的凸点与基板电极的接触,并且也妨碍了在添加了导电粒子的体系中的导电粒子扁平化,有时会阻害电连接。另外,最大粒径为40μm以上的情况下,可能会比芯片与基板的间隙还要大,这便成为在安装时的加压下损伤芯片电路或基板电路的原因。
另外,本发明中使用的金属氢氧化物粒子的比重优选为5以下,比重更优选为2~5,比重进一步优选为2~3.2。在比重大于5的情况下,在添加于粘接树脂组合物的清漆中时,由于比重差大,会在清漆中发生沉降,有时会难以获得均匀分散有金属氢氧化物粒子的电路部件连接用粘接剂。
另外,优选本发明中使用的金属氢氧化物粒子的折射率为1.5~1.7的同时,其与树脂组合物(粘接树脂组合物)之间的折射率差为±0.1以内,折射率差更优选为±0.05以内。折射率差超过±0.1时,可通过添加于树脂组合物(粘接树脂组合物)中来减小透射率,特别是在厚膜的情况下,有时会难以在贴附于半导体芯片的具有突出的连接端子的面上的状态下,透过电路部件连接用粘接剂来识别形成在芯片电路面上的对准标记。
作为这样的金属氢氧化物,只要折射率为1.5~1.7并且平均粒径为0.1μm~10μm,就没有特别限制,可使用公知的金属氢氧化物,但是从稳定性和容易获得的角度考虑,更优选为氢氧化镁、氢氧化钙、氢氧化钡、氢氧化铝。关于金属氢氧化物粒子的线膨胀系数,在0℃至700℃以下的温度范围,优选为7×10-6/℃以下,更优选3×10-6/℃以下。在热膨胀系数大的情况下,为了降低电路部件连接用粘接剂的热膨胀系数,就会需要添加大量的金属氢氧化物粒子。
在电路部件连接用粘接剂中,相对于树脂组合物100重量份,金属氢氧化物粒子优选为20~150重量份,更优选为25重量份~100重量份,进一步优选为50~100重量份。金属氢氧化物粒子少于20重量份的情况下,会导致电路部件连接用粘接剂的线膨胀系数增大和弹性模量降低,因此压合后的半导体芯片与基板的连接可靠性有时会降低。另一方面,配合量多于150重量份的情况下,由于电路部件连接用粘接剂的熔融粘度增加,因此有时不能使半导体的突出电极与基板的电路充分相接。
本发明的电路部件连接用粘接剂的树脂组合物(粘接树脂组合物)是将(a)热塑性树脂、(b)热固性树脂以及(c)固化剂作为成分。
(a)热塑性树脂可列举出:聚酯、聚氨酯、聚乙烯醇缩丁醛、聚芳酯(polyarylate)、聚甲基丙烯酸甲酯、丙烯酸橡胶、聚苯乙烯、苯氧树脂、NBR、SBR、聚酰亚胺或有机硅改性树脂(丙烯酸有机硅、环氧有机硅、聚酰亚胺有机硅)等。另外,(b)热固性树脂有:环氧树脂、双马来酰亚胺树脂、三嗪树脂、聚酰亚胺树脂、聚酰胺树脂、氰基丙烯酸酯树脂、酚树脂、不饱和聚酯树脂、三聚氰胺树脂、尿素树脂、聚氨酯树脂、聚异氰酸酯树脂、呋喃树脂、间苯二酚树脂、二甲苯树脂、苯并胍胺树脂、苯二甲酸二烯丙酯树脂、有机硅树脂、聚乙烯醇缩丁醛树脂、硅氧烷改性环氧树脂、硅氧烷改性聚酰胺酰亚胺树脂、丙烯酸酯树脂,这些可单独使用或以2种以上的混合物来使用。
从耐热性、粘接性的观点考虑,前述热固性树脂中优选为环氧树脂,特别地,从可期待透过性提高和高Tg化(Tg:玻璃化温度)、低线膨胀系数化的角度考虑,优选为:萘酚酚醛清漆型固态环氧树脂,含有芴骨架的液状环氧树脂,或固态环氧树脂。另外,关于本发明中的(c)固化剂(称为热固性树脂的固化剂),作为可与前述热固性树脂反应的成分,可列举出:酚系、咪唑系、酰肼系、硫醇系、苯并噁嗪、三氟化硼-胺配位化合物、锍盐、胺基酰亚胺(アミンイミド)、聚胺的盐、双氰胺、有机过氧化物系的固化剂。另外,为了延长这些的固化剂的可使用时间,也可通过用聚氨酯系、聚酯系的高分子物质等来被覆从而微胶囊化。
另外,为了提高粘接强度,也可含有偶联剂,为了辅助薄膜形成性,也可含有:聚酯、聚氨酯、聚乙烯醇缩丁醛、聚芳酯、聚甲基丙烯酸甲酯、丙烯酸橡胶、聚苯乙烯、苯氧树脂、NBR、SBR、聚酰亚胺或有机硅改性树脂(丙烯酸有机硅、环氧有机硅、聚酰亚胺有机硅)等热塑性树脂,另外,出于金属氢氧化物粒子的表面改性的目的,也可含有:硅油、聚硅氧烷、有机硅低聚物、偶联剂。
本发明的电路部件连接用粘接剂也可通过添加用有机高分子化合物被覆的、粒径为3~5μm的导电粒子和/或金属的导电粒子来作为各向异性导电粘接剂。用有机高分子化合物被覆之前的导电粒子为Au、Ag、Ni、Cu、焊锡等的金属粒子或碳等,为了得到充分的适用期,表层的过渡金属中,相比于Ni、Cu等而言优选为Au、Ag或铂族的贵金属类,更优选为Au。另外,也可用Au等贵金属类被覆Ni、Cu等金属的表面。另外,当作为导电粒子,使用通过被覆等手段在非导电性的玻璃、陶瓷、塑料等上形成前述传导层(由传导材料形成的层)而使最外层为贵金属类的物质的情况下,或者使用热熔融金属粒子的情况下,由于导电粒子具有由加热加压引起的变形性,因此可吸收电极的高低不均匀性,增加连接时的与电极的接触面积,由此提高连接可靠性,因而优选。为了得到良好的连接电阻,贵金属类的被覆层的厚度优选为100埃以上。但是,由于被覆时所产生的贵金属类层的缺损或导电粒子在混合分散时所产生的贵金属类层的缺损等原因,会引起氧化还原作用,当在所述氧化还原作用的作用下产生游离自由基时,会引起保存性降低,因此,在Ni、Cu等金属上设置贵金属类层的情况下,被覆层的厚度优选为300埃以上。但过厚时这些效果就会饱和,因此优选最大为1μm,但这并不限制被覆层的厚度。
通常,用有机高分子化合物被覆这些导电粒子的表面。有机高分子化合物为水溶性时,由于被覆作业性良好,因而优选。水溶性高分子可列举出:海藻酸(alginic acid)、果胶酸(pectic acid)、羧甲基纤维素、琼脂、热凝胶多糖(curdlan)以及普鲁兰多糖(pullulan)等多糖类;聚天冬氨酸、聚谷氨酸、聚赖氨酸、聚苹果酸、聚甲基丙烯酸、聚甲基丙烯酸铵盐、聚甲基丙烯酸钠盐、聚酰胺酸、聚马来酸、聚衣康酸、聚富马酸、聚(对苯乙烯羧酸)、聚丙烯酸、聚丙烯酰胺、聚丙烯酸甲酯、聚丙烯酸乙酯、聚丙烯酸铵盐、聚丙烯酸钠盐、聚酰胺酸、聚酰胺酸铵盐、聚酰胺酸钠盐以及聚乙醛酸等聚羧酸、聚羧酸酯及其盐,聚乙烯醇、聚乙烯吡咯烷酮以及聚丙烯醛等乙烯基系单体等。这些可以使用单一的化合物,也可以并用2种以上的化合物。被覆层的厚度优选为1μm以下,由于导电粒子是排除此被覆层后使连接端子与连接端子电连接,因此在加热、加压时,需要将与连接端子接触的部分的被覆层进行排除。通常,相比于树脂组合物(粘接剂树脂)成分100体积份而言,导电性粒子可在0.1~30体积份的范围根据用途来具体使用。为了防止由过剩的导电性粒子引起的邻接电路的短路等,更优选为0.1~10体积份。
本发明提供一种半导体装置,所述半导体装置具有:用以上说明的电路部件连接用粘接剂接合了的电路基板。这里,电路基板优选通过电路部件连接用粘接剂的固化来接合。具有用本发明的电路部件连接用粘接剂接合了的电路基板的半导体装置的实例,可列举出:半导体存储器、半导体存储器用的密封树脂封装、逻辑控制器用的密封树脂封装等。
实施例
以下,基于实施例和比较例进一步具体地说明本发明,但是本发明不受以下的实施例的限定。
实施例1
将作为三维交联性树脂的20重量份环氧树脂EP-1032-H60(Japan EpoxyResins株式会社制,制品名)、15重量份环氧树脂YL980(Japan Epoxy Resins株式会社制,制品名)、25重量份苯氧树脂YP50S(东都化成株式会社,制品名)、作为微胶囊型固化剂的40重量份HX-3941HP(旭化成株式会社制,制品名)、以及1重量份硅烷偶联剂SH6040(东丽道康宁有机硅株式会社制,制品名)溶解于甲苯和乙酸乙酯的混合溶剂中,获得粘接树脂组合物(树脂组合物)的清漆。使用辊涂机将该清漆的一部分涂布于隔膜(PET薄膜)上后,通过在70℃的烘箱中进行10分钟干燥,在隔膜上获得厚度为25μm的粘接剂树脂组合物的膜。
将此膜设置于阿贝折射仪(钠D线)的样品台,剥离隔膜,向其中滴下1滴匹配油,并装上折射率为1.74的测试片,测定折射率。其结果,粘接剂树脂组合物的折射率为1.60(25℃)。另一方面,称量清漆后,向其中加入59重量份的平均粒径为0.49μm的氢氧化镁MH-30(岩谷化学工业株式会社制,制品名),搅拌而分散于清漆中。使用辊涂机将该清漆涂布于隔膜(PET薄膜)上后,在70℃的烘箱中干燥10分钟,从而在隔膜上获得厚度为25μm的透过性确认用薄膜。采用UV-VIS分光光度计测定所获得的透过性确认用薄膜在555nm下的透射率为65%。接着,另行称量初始的清漆之后,向其中加入59重量份的平均粒径为0.49μm的氢氧化镁,搅拌而分散于清漆中。使用辊涂机将此清漆涂布于隔膜(PET薄膜)上后,在70℃的烘箱干燥10分钟,从而在隔膜上获得厚度为50μm的电路部件连接用粘接剂。
实施例2
除了加入60.5重量份的平均粒径为1.3μm的氢氧化铝BF013(日本轻金属株式会社制,制品名)来代替实施例1的氢氧化镁粒子以外,与实施例1同样地操作而获得电路部件连接用粘接剂。
比较例1
除了加入55.25重量份的平均粒径为0.5μm的二氧化硅粒子SE2050(Admatechs公司制,制品名)来代替实施例1的氢氧化镁粒子以外,与实施例1同样地操作而获得电路连接用粘接剂。
比较例2
除了加入55.25重量份的平均粒径为0.3μm的二氧化硅粒子F-21(株式会社龙森制,制品名)来代替实施例1的氢氧化镁粒子以外,与实施例1同样地操作而获得电路连接用粘接剂。
[表1]
材料名 | 实施例1 | 实施例2 |
EP1032H60 | 20 | 20 |
YL980 | 15 | 15 |
YP50S | 25 | 25 |
HX-3941HP | 40 | 40 |
SH6040 | 1 | 1 |
氢氧化镁(平均粒径0.49μm) | 59 | - |
氢氧化铝(平均粒径1.3μm) | - | 60.5 |
表中的配合单位为重量份
[表2]
材料名 | 比较例1 | 比较例2 |
EP1032H60 | 20 | 20 |
YL980 | 15 | 15 |
YP50S | 25 | 25 |
HX-3941HP | 40 | 40 |
SH6040 | 1 | 1 |
二氧化硅SE2050(平均粒径0.5μm) | 55.25 | - |
二氧化硅F-21(平均粒径0.3μm) | - | 55.25 |
表中的配合单位为重量份
(半导体装置的制作,特性确认)
分别制作出用实施例1~2以及比较例1~2中获得的电路连接用粘接剂来连接的半导体装置,实施了特性确认。
(半导体晶片/电路部件连接用粘接剂/切割带叠层体)
将日本JCM公司制的芯片贴膜安装器(die attach film mounter)的吸附台加热至80℃后,在吸附台上搭载形成有镀金凸点并且厚度为150μm、直径为6英寸的半导体晶片,使凸点侧朝上。将实施例1~2以及比较例1~2记载的电路部件连接用粘接剂连带隔膜切断为200mm×200mm,并使绝缘性粘接剂层侧朝向半导体晶片的凸点侧,从半导体晶片的端部开始,用芯片贴附安装器的贴附辊子推压而层压,以避免卷入空气。层压后,沿着晶片的外形将粘接剂的露出部分切断。切断后,剥离隔膜。接着,将剥离隔膜后的晶片和电路部件连接用粘接剂的叠层体搭载于将载物台温度设定为25℃的芯片贴膜安装器的吸附台,并使粘接剂的贴附面朝下,进一步将12英寸晶片用的切割框设置于晶片外周。将UV固化型切割带UC-334EP-110(古川电工制,制品名)的粘着面朝向半导体晶片侧,从切割框的端部开始,用芯片贴附安装器的贴附辊子推压而层压,以避免卷入空气。层压后,在切割框的外周与内周的中间附近将切割带切断,从而获得固定于切割框的电路部件连接用粘接剂/半导体晶片/切割带叠层体。
切割
将固定于切割框的电路部件连接用粘接剂/半导体晶片/切割带叠层体搭载于株式会社DISCO制全自动切割锯DFD6361上。透过粘接剂对准划线(scribeline)的位置。通过单切(single cut)以10mm×10mm的间隔切断至切割带内。切断后,洗涤,通过吹送空气将水分吹掉后,从切割带侧进行UV照射。此后,从切割带侧向半导体晶片侧往上推,获得电路部件连接用粘接剂形成于凸点侧的10mm×10mm的半导体芯片。
压合
以粘接剂面朝向芯片盘底面的状态,将附有电路部件连接用粘接剂的半导体芯片收纳于芯片盘,将其设置于松下公司制倒装芯片接合机FCB3的芯片盘收纳位置。接着,将镀Au/Ni的Cu电路印刷基板设置于基板搭载台。从电路部件连接用粘接剂侧识别形成于半导体芯片电路面的铝制的对准标记而进行与基板对准位置后,在200℃、10秒、1.86MPa的条件下进行加热加压,从而获得半导体装置。所获得的半导体装置的176个凸点连接菊花链的连接电阻为8.6Ω,确认为连接状态良好。进一步,将半导体装置放置于30℃、相对湿度60%的槽内达192小时后,进行IR回流处理(265℃最大)3次,结果没有发生芯片的剥离以及传导不良。进一步,将IR回流后的半导体装置放置于高温高湿试验机(85℃/85%RH)达200h,确认出:放置后的连接电阻没有发生传导不良。另外,将IR回流后的半导体装置放置于温度循环试验机(-55℃30分钟,室温5分钟,125℃30分钟)内,在槽内进行连接电阻测定,确认出:经过200循环后没有发生传导不良。
关于由实施例1~2以及比较例1~2所获得的电路部件连接用粘接剂,通过下述测定而进行了特性确认。
线膨胀系数测定
将由实施例以及比较例所获得的电路部件连接用粘接剂连带隔膜放置于设定为180℃的烘箱中达3小时,进行加热固化处理。将加热固化后的薄膜从隔膜剥离,切断成30mm×2mm的大小。使用精工株式会社(Seiko Instruments Inc)制TMA/SS6100(制品名),将卡盘间距设定为20mm后,在测定温度范围为20℃~300℃、升温速度为5℃/min、相对于截面积的压力为0.5MPa的荷重条件下,通过拉伸试验模式,进行热机械分析,求出线膨胀系数。
反应率测定
在铝制测定容器中称量2~10mg的实施例以及比较例中获得的电路部件连接用粘接剂后,采用珀金埃尔默(PerkinElmer)公司制的差示扫描量热测定装置DSC(Differential Scaning Calorimeter)Pylis1(制品名)以20℃/min的升温速度从30℃到300℃进行放热量测定,并将其作为初期放热量。接着,通过热压合装置中的加热头被夹在隔膜中的热电偶进行温度确认,设定为在20秒钟后达到180℃的温度。通过此加热头设定,将夹在隔膜中的电路部件连接用粘接剂加热20秒,从而获得被实施与热压合时等同的加热处理的状态的膜。称量2~10mg的加热处理后的薄膜,放入铝制测定容器,采用DSC以20℃/min的升温速度从30℃到300℃进行放热量测定,将其作为加热后放热量。根据下式,由所得的放热量算出反应率(%)。
(初期放热量-加热后放热量)/(初期放热量)×100
对于每个实施例和比较例,将平行透射率、固化后的线膨胀系数、能否用倒装芯片接合机识别对准标记、反应率、进而压合后的连接电阻值以及可靠性试验后的连接电阻值,作为电路部件连接用粘接剂的特性示于表3。
[表3]
项目 | 实施例1 | 实施例2 | 比较例1 | 比较例2 |
平行透射率(%) | 63 | 64 | 2 | 2 |
线膨胀系数(40-100℃)(×10-6/℃) | 43 | 46 | 50 | 48 |
芯片对准标记的识别 | 能 | 能 | 不能 | 不能 |
反应率(%) | 78 | 78 | 75 | 76 |
压合后的连接电阻(Ω) | 8.3 | 8.3 | 传导不良 | 传导不良 |
高温高湿试验200h后的连接电阻(Ω) | 8.5 | 8.6 | - | - |
温度循环试验200循环后的连接电阻(Ω) | 8.5 | 8.5 | - | - |
如实施例中所示,可确认添加了折射率为1.57~1.60的金属氢氧化物粒子的电路部件连接用粘接剂为,1)由于平行透射率为30%以上,因此能够使用倒装芯片接合机的识别系统,透过粘接剂来识别芯片电路面的对准标记,2)固化后的线膨胀系数降低至70×10-6/℃以下,在连接可靠性试验中没有发生传导不良,3)由于在热压合时的加热条件下达到了75%以上的反应率,因此显示了稳定的低连接电阻,即使作为以玻璃基板为对象的各向异性导电性粘接剂、或者以环氧玻璃(glass-epoxy)基板为对象的接触型的热压合树脂,也是优良的。另一方面,比较例1、2中,通过添加折射率为1.46的二氧化硅,与树脂组合物的折射率差变大,产生光散射,平行透射率小。在此情况下,不能通过倒装芯片接合机来识别对准标记,不能对准位置,因此不能确保半导体装置的初期传导。
产业上的利用可能性
本发明的电路部件连接用粘接剂可用作:可应对狭间距化以及狭间隙化的前置的底部薄膜技术。附有粘接剂的半导体芯片,没有切割时的污染,切割后简便地从切割带剥离就可以获得。进一步,本发明的电路部件连接用粘接剂可用作快速固化性的晶片贴附用粘接剂,所述粘接剂能够兼备可实现附有粘接剂的芯片与电路基板之间的高精度对准位置的透明性、以及基于低热膨胀系数化的高连接可靠性。
Claims (7)
1.用于连接相对向的电路基板的电路部件连接用粘接剂,所述电路部件连接用粘接剂包含:含有热塑性树脂、热固性树脂和固化剂的树脂组合物;以及分散于该组合物中的金属氢氧化物粒子。
2.根据权利要求1所述的电路部件连接用粘接剂,其中,未固化时的可见光平行透射率为15~100%。
3.根据权利要求1或2所述的电路部件连接用粘接剂,其中,所述金属氢氧化物粒子的折射率为1.5~1.7。
4.根据权利要求1~3中的任一项所述的电路部件连接用粘接剂,其中,所述金属氢氧化物粒子的平均粒径为0.1μm~10μm。
5.根据权利要求1~4中的任一项所述的电路部件连接用粘接剂,其中,在180℃加热20秒后通过差示扫描量热测定测得的所述电路部件连接用粘接剂的反应率为75%以上。
6.根据权利要求1~5中的任一项所述的电路部件连接用粘接剂,其中,在40℃~100℃的线膨胀系数为70×10-6/℃以下。
7.半导体装置,具有由权利要求1~6中的任一项所述的电路部件连接用粘接剂接合的电路基板。
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CN104312471A (zh) * | 2014-11-10 | 2015-01-28 | 深圳市飞世尔实业有限公司 | 一种含苯并恶嗪的异方性导电膜及其制备方法 |
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JP5372665B2 (ja) * | 2009-08-31 | 2013-12-18 | 株式会社日立メディアエレクトロニクス | 光硬化型接着剤、光ピックアップ装置及びその製造方法 |
JP5445187B2 (ja) * | 2010-02-05 | 2014-03-19 | 日立化成株式会社 | 回路部材接続用接着剤及びこれを用いた半導体装置 |
JP5415334B2 (ja) * | 2010-03-26 | 2014-02-12 | ナミックス株式会社 | 先供給型液状半導体封止樹脂組成物 |
JP6043939B2 (ja) * | 2012-08-24 | 2016-12-14 | ボンドテック株式会社 | 基板上への対象物の位置決め方法及び装置 |
JP6157890B2 (ja) * | 2013-03-26 | 2017-07-05 | 日東電工株式会社 | アンダーフィル材、封止シート及び半導体装置の製造方法 |
JP2014203971A (ja) * | 2013-04-04 | 2014-10-27 | 日東電工株式会社 | アンダーフィルフィルム、封止シート、半導体装置の製造方法及び半導体装置 |
JP2014074181A (ja) * | 2013-12-25 | 2014-04-24 | Hitachi Chemical Co Ltd | 半導体装置の製造方法及びこれを用いて製造されてなる半導体装置 |
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TWI419954B (zh) | 2013-12-21 |
JPWO2009069783A1 (ja) | 2011-04-21 |
KR20100074312A (ko) | 2010-07-01 |
CN101835866B (zh) | 2013-01-02 |
KR101302933B1 (ko) | 2013-09-06 |
JP5088376B2 (ja) | 2012-12-05 |
TW200934851A (en) | 2009-08-16 |
WO2009069783A1 (ja) | 2009-06-04 |
CN101835866A (zh) | 2010-09-15 |
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