CN105637031A - 环氧树脂组合物、半导体密封剂和半导体装置 - Google Patents

环氧树脂组合物、半导体密封剂和半导体装置 Download PDF

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CN105637031A
CN105637031A CN201480056670.3A CN201480056670A CN105637031A CN 105637031 A CN105637031 A CN 105637031A CN 201480056670 A CN201480056670 A CN 201480056670A CN 105637031 A CN105637031 A CN 105637031A
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epoxy resin
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CN105637031B (zh
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小原和之
山泽朋也
小越弘大
阿部信幸
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Abstract

一种环氧树脂组合物,其包含(A)环氧树脂、(B)固化剂、(C)0.1~10质量%的平均粒径为10nm以上100nm以下的二氧化硅填料以及(D)40~75质量%的平均粒径为0.3μm以上5μm以下的二氧化硅填料,所述(C)成分和所述(D)成分的总计为40.1~77质量%。

Description

环氧树脂组合物、半导体密封剂和半导体装置
技术领域
<交叉引用>
本发明主张基于2013年11月29日申请的日本专利申请“特願2013-247267”的优先权,通过参照引入该日本申请的内容。
本发明涉及环氧树脂组合物、半导体密封剂和半导体装置。
背景技术
倒装芯片安装法是将半导体元件(半导体芯片)安装于基板(或封装体)的方法之一。倒装芯片安装是使用凸点(焊料球)将半导体元件和基板电连接的技术。为了加强凸点的周围,在半导体元件和基板之间填充树脂组合物(所谓的底部填充剂)。
在半导体元件的安装中,为了改善基板表面与密封剂之间的润湿性,在涂布密封剂之前,对基板进行等离子体处理。然而,如果在经等离子体处理过的基板上涂布密封剂,则存在下述情况:产生来源于密封剂的液状成分在半导体元件的周围渗出(溢出(ブリード))这样的现象。溢出不仅会引起外观不良,而且有时会引起电极的导电性不良。
为了解决所述的问题,开发了各种树脂组合物。专利文献1公开了包含具有羧基或氨基的液状有机硅化合物的液状密封树脂组合物。专利文献2公开了包含硅橡胶微粉末的绝缘性糊剂。
专利文献3和专利文献4公开了含有用甲基丙烯酸烷基酯共聚物、非反应性有机硅化合物进行了表面处理的无机填充剂、以及改性有机硅树脂的侧填充材料。
现有技术文献
专利文献
专利文献1:日本专利公开公报特开2006-219575号
专利文献2:日本专利公开公报特开平05-174629号
专利文献3:日本专利公开公报特开2005-36069号
专利文献4:日本专利公开公报特开2005-105243号
发明内容
本发明要解决的技术问题
对此,本发明提供一种具有更简单的组成,并且能出色地抑制溢出的环氧树脂组合物。
解决技术问题的技术方案
本发明提供一种环氧树脂组合物,其包含(A)环氧树脂、(B)固化剂、(C)0.1~10质量%的平均粒径为10nm以上100nm以下的二氧化硅填料以及(D)40~75质量%的平均粒径为0.3μm以上5μm以下的二氧化硅填料,所述(C)成分和所述(D)成分的总计为40.1~77质量%。
优选的是,所述(C)成分和所述(D)成分中的至少一方用硅烷偶联剂进行了表面处理。
优选的是,所述(D)成分通过用式(1)表示的氨基硅烷进行了表面处理。
[化1]
优选的是,所述(A)成分与所述(B)成分的当量比为0.5~1.8。
优选的是,所述(B)成分为胺固化剂。
优选的是,所述(A)成分包含双酚F型环氧树脂、双酚A型环氧树脂、萘型环氧树脂和氨基酚型环氧树脂中的至少一种。
优选的是,在所述环氧树脂组合物的固化物的溢出试验中产生的溢出物为300μm以上且小于1900μm。
优选的是,通过将所述(C)成分与所述(A)成分的至少一部分混合而生成母料,将其它成分与所述母料混合,由此制备所述环氧树脂组合物。
此外,本发明还提供一种半导体密封剂,其使用了所述的环氧树脂组合物。
此外,本发明还提供一种半导体装置,其使用了所述的半导体密封剂。
发明效果
按照本发明,使用具有更简单的组成的环氧树脂组合物,就能够抑制溢出。
附图说明
图1A是说明溢出的图。
图1B是说明溢出的图。
具体实施方式
1关于溢出
图1A和图1B是说明在半导体元件的安装中产生的溢出的图。在此,表示了通过底部填充剂将半导体元件2接合在基板1之上的例子。图1A表示从芯片上方看到的图。图1B表示图1A的A-A截面。在半导体元件2的周围,存在底部填充剂UF(密封剂)堆起的部分(下面称为“填充剂圆角(フィレット)”)。在其外侧产生的为溢出物。溢出不仅在外观上因变色而能看到,而且有时会影响装置的特性和可靠性。
为了研究溢出的产生原因,本发明的发明人用SEM(扫描电子显微镜)观察通过在基板上安装半导体元件而制备的试样上的溢出部和非溢出部。在该试样的制备中,作为密封剂,使用了包含环氧树脂、固化剂、二氧化硅填料和其它添加物的组合物。结果发现了,在溢出部不存在二氧化硅填料。此外,本发明人通过XPS(X射线光电子能谱)对溢出部和非溢出部进行了分析。其结果,在溢出部和非溢出部中,除了二氧化硅填料以外,没有特别发现成分的不同。
根据所述的结果,认为溢出是由于密封剂中的二氧化硅填料以外的成分(例如环氧树脂和固化剂)渗出到填充剂圆角外而形成的。此外,对在密封剂涂布前进行了等离子体处理的试样和没有进行等离子体处理的试样进行了比较。其结果,在进行了等离子体处理的试样中产生了溢出,但是,在没有进行等离子体处理的试样中没有产生溢出。
根据以上的内容,本发明的发明人认为,填料以外的液状树脂成分由于毛细管现象渗出到等通过离子体处理形成的基板表面的微细凹凸,由此产生了溢出。因此,为了抑制液状树脂成分由于毛细管现象而产生的渗出,想到了使用微小直径的填料,来防止液状树脂成分的渗出。
2.树脂组合物
本发明的环氧树脂组合物包含(A)环氧树脂、(B)固化剂、(C)小直径的二氧化硅填料以及(D)大直径的二氧化硅填料。
作为(A)成分的例子,可以列举双酚A型环氧树脂、双酚F型环氧树脂、萘型环氧树脂、氨基酚型环氧树脂、酚醛型环氧树脂、脂环族环氧树脂、硅氧烷型环氧树脂、联苯型环氧树脂、缩水甘油酯型环氧树脂、缩水甘油胺型环氧树脂以及乙内酰脲型环氧树脂。其中,优选的是双酚F型环氧树脂、双酚A型环氧树脂、萘型环氧树脂以及氨基酚型环氧树脂。在环氧树脂组合物中,可以单独使用在此例示的化合物,也可以将2种以上在此例示的化合物混合使用。
作为(B)成分的例子,可以列举胺系固化剂、酸酐系固化剂和酚系固化剂。从密封用液状树脂组合物的耐回流性和耐湿性的观点出发,优选使用胺系固化剂。(A)成分与(B)成分的当量比优选为0.5~1.8。
作为(C)成分和(D)成分的例子,可以列举无定形二氧化硅、结晶二氧化硅、熔融二氧化硅、粉碎二氧化硅和纳米二氧化硅。从固化后的树脂组合物的热膨胀系数的观点出发,优选使用无定形二氧化硅。作为(C)成分和(D)成分的形状的例子,可以列举球状、鳞片状、和无定形。(C)成分和(D)成分的平均粒径例如可以通过动态光散射式Nanotrac粒度分析仪进行测定。另外,在此所述的平均粒径是D50(中值粒径)。
(C)成分和(D)成分中的至少一方可以用硅烷偶联剂进行表面处理。作为用于表面处理的硅烷偶联剂,可以列举环氧系、甲基丙烯酸系、胺系、乙烯基系、缩水甘油醚氧基系、和巯基系等各种硅烷偶联剂。其中,在(D)成分的表面处理中优选使用下面的式(1)的氨基硅烷。
[化2]
除了(A)成分、(B)成分、(C)成分和(D)成分以外,环氧树脂组合物还可以包含离子捕集剂、颜料、染料、消泡剂、应力缓和剂、pH调节剂、促进剂、表面活性剂、和偶联剂等添加剂。
例如可以通过将(A)成分~(D)成分和其它的添加剂等同时或分别边根据需要进行加热处理边进行搅拌、熔融、混合或分散,由此制备环氧树脂组合物。所述的混合、搅拌和分散等方法没有特别的限定,可以使用具有搅拌和加热装置的擂溃机、三辊磨机、球磨机、行星式搅拌机或者珠磨机等。此外,也可以将这些装置组合使用。在此,可以将(A)成分和(C)成分混合,制备出母料。通过将得到的母料与其它成分混合,可以制备出环氧树脂组合物。
此外,优选的是,环氧树脂组合物在后述的溢出试验中产生的溢出物显示出300以上且小于1900的值。
环氧树脂组合物可以用作半导体元件等电子元件进行倒装芯片安装或BGA(球栅阵列封装)/CSP(芯片尺寸封装)安装时的密封剂(底部填充剂)。该环氧树脂组合物可以用作将电子元件与基板或封装体粘合时的粘合剂。
在倒装芯片安装或BGA/CSP安装时,首先将半导体元件与基板(或封装体)接合。接着,在半导体元件和基板之间注入密封剂。具体地说,沿着半导体元件的外周涂布密封剂。密封剂通过毛细管现象扩散到间隙内。因此,优选的是,密封剂在进行该过程的温度下为液状。注入的密封剂通过加热(例如80~165℃)而热固化。
实施例
3.实施例
3-1.环氧树脂组合物的制备
表1~4表示在实施例1~25和比较例1~6中用作密封剂的环氧树脂组合物的组成。此外,这些表也表示后述的、作为密封剂的环氧树脂组合物的评价结果。在表1~4中,除了当量比以外,环氧树脂组合物的组成用质量%表示。
作为表中的(A)成分,使用环氧树脂a1~a5中的任意一种。作为环氧树脂a1,使用新日铁住金化学株式会社制的YDF8170。作为环氧树脂a2,使用DIC株式会社制的850CRP。作为环氧树脂a3,使用DIC株式会社制的HP-4032D。作为环氧树脂a4,使用三菱化学株式会社制的jer630。作为环氧树脂a5,使用东都化成株式会社制的ZX1658GS。
作为表中的(B)成分,使用固化剂b1~b5中的任意一种。固化剂b1~b3是胺系固化剂。固化剂b4是酸酐系固化剂。固化剂b5是酚系固化剂。作为固化剂b1,使用日本化药株式会社制的カヤハードAA。作为固化剂b2,使用株式会社ADEKA制的EH105L。作为固化剂b3,使用Albermarle公司制的ETHACURE100。作为固化剂b4,使用三菱化学株式会社制的YH307。作为固化剂b5,使用明和化成株式会社制的MEH-8005。
作为表中的(C)成分,使用AdmatechsCompanyLimited制的YA010C(平均粒径:10nm)、YA050C(平均粒径:50nm)和YC100C(平均粒径:100nm)中的任意一种。所述平均粒径为中值粒径(D50)。此外,该平均粒径是通过电场放射型扫描电子显微镜(FE-SEM)测定得到的值。
作为表中的(D)成分,可以使用UBEEXSYMOCO.,LTD制的ハイプレシカ0.2μm(平均粒径:0.2μm)、AdmatechsCompanyLimited制的SE-1050(平均粒径:0.3μm)、SE-2300(平均粒径:0.6μm)、SE-4050(平均粒径:1μm)、和电气化学工业株式会社制的FB-5D(平均粒径:5μm)。所述平均粒径为中值粒径(D50)。此外,该平均粒径是通过激光衍射散射式粒度分布仪测定得到的值。
作为所述(D)成分的表面处理剂,使用了表面处理剂e1~e3中的任意一种。作为表面处理剂e1,使用了信越化学工业株式会社制的KBM403(3-缩水甘油醚氧基丙基三甲氧基硅烷)。作为表面处理剂e2,使用了信越化学工业株式会社制的KBM503(3-甲基丙烯酰氧基丙基三甲氧基硅烷)。作为表面处理剂e3,使用了信越化学工业株式会社制的KBE9103(3-三乙氧基硅烷基-N-(1,3-二甲基丁烯基)丙胺)。
除了所述(A)成分~(D)成分以外,作为固化促进剂,使用了四国化成株式会社制的2P4MZ。
3-2.评价方法
对在实施例1~25和比较例1~6中使用的环氧树脂组合物进行了以下的评价。
3-2-1.溢出试验
作为试样,使用了具有阻焊剂(PSR4000AUS703)的有机基板(FR-4基板)。首先,将试样在150℃下干燥了1小时。然后对该试样进行了等离子体处理。等离子体处理的条件如下所述。
离子种类:Ar
气体流量:21sccm
供给功率:400W
处理时间:300sec
向该试样滴下(涂布)了0.5mg的所述作为密封剂的环氧树脂组合物(评价用试样)。在滴下后,在150℃、2小时的条件下使密封剂热固化了。在固化后,测量了产生的溢出物的长度。
3-2-2.粘度
使用BROOKFIELD旋转粘度计,以50rpm测定了25℃下的所述环氧树脂组合物的粘度。
3-2-3.TI(触变指数)值
以5rpm和50rpm测定了所述环氧树脂组合物的粘度。将用测定得到的5rpm下的粘度值除以50rpm下的粘度值得到的值作为TI值。
3-2-4.注入性
在110℃下,将所述环氧树脂组合物注入了20μm的缝隙(间隙)。测量了注入的环氧树脂组合物到达距入口20mm位置处的时间。到达的时间越短,注入性就越好。另外,在“注入性”这栏中的“×”的记载的意思是指环氧树脂不能到达20mm的位置(即不良)。
3-2-5.粘合性
在FR-4上灌封了约0.5mg的所述作为密封剂的环氧树脂组合物(评价用试样)。在该密封剂上放置了2mm见方的硅芯片。在该状态下,将硅芯片在室温下放置了5分钟。然后,使用送风干燥机,在150℃、120分钟的条件下,使密封剂固化了。针对由此得到的试验片,使用桌上型强度测定机(AIKOHENGINEERING株式会社制的1605HTP)测定了粘合强度。另外,将通过测定10次得到的测定值的平均值作为检查值。
3-3.评价结果
比较例1表示使用了没有添加(C)成分的环氧树脂组合物的例子。在没有添加(C)成分的情况下,试样溢出物的长度为2000μm。以下,以此为基准,在溢出实验中,将显示出1900μm以上的溢出物长度的试样判定为不良。实施例1~4和比较例1~3表示了(C)成分的含量变化的例子。(C)成分相对于树脂组合物总量的含量越多,则溢出物长度越短。如果(C)成分的含量成为0.1质量%以上,则溢出物长度小于1900μm。即,(C)成分的含量如果成为0.1质量%以上,则能够抑制溢出。然而,如果(C)成分的含量成为11质量%,则粘度成为121Pa·s。因此,从作为密封剂的适当的粘度的观点出发,(C)成分的含量优选为10质量%以下。因此,(C)成分相对于树脂组合物总量的含量优选为0.1~10质量%。
实施例2、5、6以及比较例4表示了(C)成分的平均粒径改变的例子。另外,在比较例4中,使用平均粒径0.2μm(即200nm)的(D)成分代替了(C)成分。(C)成分的平均粒径越小,则溢出物长度越短。如果(C)成分的平均粒径成为200nm以上,则在溢出实验中会产生不良。另一方面,在平均粒径处于10~100nm的范围时,能够抑制溢出。另外,实施例2在以下会反复提及,因此为了便于说明,在表1~4中反复记载了实施例2。
比较例5以及实施例2、7、8示出了(D)成分的平均粒径改变的例子。(D)成分的平均粒径越大,则粘度越能得到改善。如果(D)成分的平均粒径成为0.2μm以下,则粘度成为179Pa·s。从作为密封剂的适当的粘度的观点出发,(D)成分的平均粒径优选为0.3μm以上。
实施例2和实施例9~12以及比较例6示出了(D)成分的含量改变的例子。(D)成分的含量越少,则注入性越提高。在(D)成分的含量处于40~75质量%的范围时,显示出良好的注入性,并且也能够抑制溢出。然而,如果(D)成分的含量成为76质量%以上,则在注入性实验中产生不良。因此,从作为密封剂的适当的注入性的观点出发,(D)成分的含量优选为75质量%以下。此外,(C)成分和(D)成分相对于树脂组合物的总量,优选合计含有40.1~77质量%。
实施例2和实施例13~15示出了(D)成分的表面处理剂改变的例子。通过进行表面处理,能够进一步抑制溢出。此外,通过使用表面处理剂e1,能够改善粘度和注入性。
实施例2、16、17示出了改变环氧树脂((A)成分)与固化剂((B)成分)的当量比的例子。在当量比处于0.5~1.8的范围时,能够抑制溢出。
实施例2和实施例18~21示出了(A)成分改变的例子。使用环氧树脂a1~a5中的任意一种,都能够抑制溢出。
实施例2和实施例22~25示出了(B)成分改变的例子。使用固化剂b1~b5中的任意一种,都能够抑制溢出。
此外,本发明的环氧树脂组合物可以是以下的第一环氧树脂组合物~第八环氧树脂组合物。
所述第一环氧树脂组合物,其包含(A)环氧树脂、(B)固化剂、(C)0.1~10质量%的平均粒径为10~100nm的二氧化硅填料以及(D)40~75质量%的平均粒径为0.3μm~5μm的二氧化硅填料,所述(C)成分和所述(D)成分的总计为40.1~77质量%。
所述第二环氧树脂组合物,其是所述的第一环氧树脂组合物,其中,所述(C)成分和所述(D)成分中的至少一方用硅烷偶联剂进行了表面处理。
所述第三环氧树脂组合物,其是所述的第一环氧树脂组合物或第二环氧树脂组合物,其中,所述(D)成分用式(1)结构的氨基硅烷进行了表面处理。
[化3]
所述第四环氧树脂组合物,其是所述的第一环氧树脂组合物~第三环氧树脂组合物中的任一种环氧树脂组合物,其中,所述(A)成分与所述(B)成分的当量比为0.5~1.8。
所述第五环氧树脂组合物,其是所述的第一环氧树脂组合物~第四环氧树脂组合物中的任一种环氧树脂组合物,其中,所述(B)成分为胺固化剂。
所述第六环氧树脂组合物,其是所述的第一环氧树脂组合物~第五环氧树脂组合物中的任一种环氧树脂组合物,其中,所述(A)成分包含双酚F型环氧树脂、双酚A型环氧树脂、萘型环氧树脂和氨基酚型环氧树脂中的至少一种。
所述第七环氧树脂组合物,其是所述的第一环氧树脂组合物~第六环氧树脂组合物中的任一种环氧树脂组合物,其中,在固化物的溢出试验中产生的溢出物为300μm以上且小于1900μm。
所述第八环氧树脂组合物,其是所述的第一环氧树脂组合物~第七环氧树脂组合物中的任一种环氧树脂组合物,其中,将所述(C)成分与所述(A)成分的至少一部分混合而生成母料,将其它成分与所述母料混合,由此制备所述环氧树脂组合物。
此外,本发明的半导体密封剂使用了所述的第一环氧树脂组合物~第八环氧树脂组合物中的任一种环氧树脂组合物。
此外,本发明的半导体装置使用了所述的第九的半导体密封剂。

Claims (10)

1.一种环氧树脂组合物,其特征在于,所述环氧树脂组合物包含(A)环氧树脂、(B)固化剂、(C)0.1~10质量%的平均粒径为10nm以上100nm以下的二氧化硅填料以及(D)40~75质量%的平均粒径为0.3μm以上5μm以下的二氧化硅填料,所述(C)成分和所述(D)成分的总计为40.1~77质量%。
2.根据权利要求1所述的环氧树脂组合物,其特征在于,所述(C)成分和所述(D)成分中的至少一方用硅烷偶联剂进行了表面处理。
3.根据权利要求1或2所述的环氧树脂组合物,其特征在于,所述(D)成分通过用式(1)的结构式表示的氨基硅烷进行了表面处理,
4.根据权利要求1或2所述的环氧树脂组合物,其特征在于,所述(A)成分与所述(B)成分的当量比为0.5~1.8。
5.根据权利要求1或2所述的环氧树脂组合物,其特征在于,所述(B)成分为胺固化剂。
6.根据权利要求1或2所述的环氧树脂组合物,其特征在于,所述(A)成分包含双酚F型环氧树脂、双酚A型环氧树脂、萘型环氧树脂和氨基酚型环氧树脂中的至少一种。
7.根据权利要求1或2所述的环氧树脂组合物,其特征在于,在所述环氧树脂组合物的固化物的溢出试验中产生的溢出物为300μm以上且小于1900μm。
8.根据权利要求1或2所述的环氧树脂组合物,其特征在于,通过将所述(C)成分与所述(A)成分的至少一部分混合而生成母料,将其它成分与所述母料混合,由此制备所述环氧树脂组合物。
9.一种半导体密封剂,其特征在于,所述半导体密封剂使用了权利要求1~8中任一项所述的环氧树脂组合物。
10.一种半导体装置,其特征在于,所述半导体装置使用了权利要求9所述的半导体密封剂。
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