CN100546018C - 防止环氧树脂渗出的试剂和方法、布线基板及半导体封装体 - Google Patents

防止环氧树脂渗出的试剂和方法、布线基板及半导体封装体 Download PDF

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CN100546018C
CN100546018C CNB2007800000508A CN200780000050A CN100546018C CN 100546018 C CN100546018 C CN 100546018C CN B2007800000508 A CNB2007800000508 A CN B2007800000508A CN 200780000050 A CN200780000050 A CN 200780000050A CN 100546018 C CN100546018 C CN 100546018C
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相场玲宏
中村久
三村智晴
土田克之
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Nippon Mining and Metals Co Ltd
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Abstract

本发明提供一种防止环氧树脂渗出的试剂，其即使在使用低应力型的芯片接合树脂的情况下，对芯片接合强度、组装特性也没有坏影响，且不损害防变色处理、封孔处理效果。本发明的在芯片接合工艺中防止环氧树脂渗出的试剂，其特征在于，含有含氟有机化合物，该含氟有机化合物含有碳原子数为3～24个的氟烃基CxHyFz-和极性基R-，其中x＝3～24、y＝0～48、z＝1～49、y+z≤2x+1。

Description

防止环氧树脂渗出的试剂和方法、布线基板及半导体封装体
技术领域
本发明涉及一种在用环氧树脂将引线框、印刷布线板等的半导体布线基板与IC芯片粘合固定的芯片接合(die bonding)工艺中，防止环氧树脂渗出的试剂和防止环氧树脂渗出的方法。
背景技术
在用环氧树脂将引线框、印刷布线板等的半导体布线基板与IC芯片粘合固定的芯片接合工艺中，如果粘合面(通常实施了金、银、铜、钯等的镀覆)的表面粗糙度过大、或表面被防变色剂、封孔处理剂等的有机物污染，则在涂布环氧树脂时，树脂或添加剂会渗出(环氧树脂渗出)。该环氧树脂的渗出会降低芯片接合强度，成为其后的引线接合(wirebonding)工艺不良的原因。目前，为了防止这样的环氧树脂渗出，要减小粘合面的表面粗糙度以抑制毛细管现象，或洗涤表面以除去污染物。但是由于粘合面的表面粗糙度影响芯片接合强度、组装设备的图像识别能力，因此不能一概降低表面粗糙度。另外，表面洗涤由于损害防变色处理、封孔处理效果，因此也存在问题。
为了解决上述问题，如专利文献1所述那样，通过将基板浸渍到以羧酸、硫醇等为主要成分的溶液中，使其吸附厚度为1到几个分子左右的有机被膜，从而不会改变基板面的表面粗糙度、或洗涤剥离防变色被膜、封孔处理被膜，另外由于吸附的有机被膜非常薄，所以对引线接合性能、模塑性能等的组装特性(assembly characteristics)没有不利影响，可以防止环氧树脂渗出。
但是，随着最近的半导体芯片的大型化、半导体封装体的薄型化，为了改善翘曲的问题等，低应力、低弹性、低粘度的芯片接合树脂(以下称为低应力型的芯片接合树脂)的使用越来越多，由于这些树脂含有易渗出的成分的情况较多，其结果导致容易发生环氧树脂渗出。上述专利文献1的技术不能应对使用低应力型的芯片接合树脂的情况，会发生环氧树脂的渗出。因此希望开发一种也应对低应力型的芯片接合树脂的防止环氧树脂渗出的试剂。
专利文献1：特开平11-195662号公报
发明内容
本发明的目的在于提供一种防止环氧树脂渗出的试剂，其在用环氧树脂将引线框、印刷布线板等的半导体布线基板与IC芯片粘合固定的芯片接合工艺中，即使在使用上述的低应力型的芯片接合树脂的情况下，对芯片接合强度、组装特性也没有不利影响，且不损害防变色处理、封孔处理效果，可以防止环氧树脂渗出的发生。
本发明者们进行了深入研究，结果发现一组有机化合物，其在通过将基板浸渍到含有防止环氧树脂渗出的试剂的溶液中，使有机被膜吸附在镀层面的表面上来防止环氧树脂渗出的过程中，与现有产品比较，即使对低应力型的芯片接合树脂，也具有更好的防渗出效果。即，发现了比上述文献所述的羧酸、硫醇化合物等的防止环氧树脂渗出效果更高的化合物，从而完成了本发明。
本发明如下所述。
(1)一种在芯片接合工艺中防止环氧树脂渗出的试剂，其特征在于，含有含氟有机化合物，该含氟有机化合物具有碳原子数为3个～24个的氟烃基CxHyFz-(x＝3～24、y＝0～48、z＝1～49、y+z≤2x+1)和极性基R-。
(2)如上述(1)所述的防止环氧树脂渗出的试剂，其特征在于，极性基R-是含有硫(S)、氮(N)、磷(P)、氧(O)中的任一种的极性基。
(3)如上述(2)所述的防止环氧树脂渗出的试剂，其特征在于，极性基R-是巯基、氨基、含氮杂环基、磷酸酯基、羧基中的任一种。
(4)如上述(3)所述的防止环氧树脂渗出的试剂，其特征在于，含氮杂环基是咪唑基、三唑基、四唑基、及它们的衍生物中的任一种。
(5)如上述(1)～(4)的任一项所述的防止环氧树脂渗出的试剂，其特征在于，含有防变色剂或封孔处理剂。
(6)如上述(5)所述的防止环氧树脂渗出的试剂，其特征在于，防变色剂含有含氮杂环化合物。
(7)如上述(6)所述的防止环氧树脂渗出的试剂，其特征在于，含氮杂环化合物是咪唑衍生物、三唑衍生物、四唑衍生物、噻唑衍生物中的任一种。
(8)一种防止环氧树脂渗出的方法，其特征在于，将布线基板浸渍到含有上述(1)～(7)的任一项所述的防止环氧树脂渗出的试剂的溶液中，或者将含有该防止环氧树脂渗出的试剂的溶液散布或涂布到布线基板上。
(9)一种布线基板，其特征在于，通过将布线基板浸渍到含有上述(1)～(7)的任一项所述的防止环氧树脂渗出的试剂的溶液中，或者将含有该防止环氧树脂渗出的试剂的溶液散布或涂布到布线基板上，而实施了防止环氧树脂渗出的处理。
(10)一种布线基板，其特征在于，在表面吸附有上述(1)～(7)的任一项所述的防止环氧树脂渗出的试剂。
(11)一种半导体封装体，其特征在于，使用了上述(9)或(10)所述的布线基板。
发明效果
通过使用本发明的防止环氧树脂渗出的试剂，进行使具有防止环氧树脂渗出功能的有机化合物吸附在引线框、印刷布线板等的半导体布线基板表面上的、防止环氧树脂渗出的处理，使得即使对低应力型的芯片接合树脂，也可以不损害防变色效果、封孔处理效果，可以防止芯片接合工艺中的环氧树脂的渗出。另外，对引线接合特性、模塑特性等的组装特性也没有不利影响。
附图说明
图1是表示在实施例的耐环氧树脂渗出性能评价时的环氧树脂渗出量的测定方法的图。
具体实施方式
本发明的防止环氧树脂渗出的试剂，含有含氟有机化合物，该含氟有机化合物具有碳原子数为3个～24个的氟烃基CxHyFz-(x＝3～24、y＝0～48、z＝1～49、y+z≤2x+1)和极性基R-。
作为上述氟烃基，可以列举出氟烷基、含有双键的氟链烯基、含有三键的氟链炔基等，优选为氟烷基。另外，这些氟烃基如果氟烃基整体的碳原子数为3个～24个，则可以是直链状的，也可以带有侧链。氟烃基的碳原子数x为3～24，特别优选为5～12。如果碳原子数过少，则防止环氧树脂渗出的效果差，如果过多，则使模塑性能(模塑树脂的粘合性)降低。另外，氟原子数z越多，防止环氧树脂渗出的效果越高，但在碳原子数多从而分子链长的情况下，如果氟原子数过多，则有时也会导致模塑性能的降低，因而氟原子数z优选为11～25。
作为上述氟烃基，可以优选使用F(CF2)6-、F(CF2)8-、F(CF2)10-、F(CF2)6(CH2)2-、F(CF2)8(CH2)2-、F(CF2)10(CH2)2-等。
另外，作为上述极性基R-，可以优选使用含有硫(S)、氮(N)、磷(P)、氧(O)中的任一种的极性基，例如巯基、氨基、含氮杂环基、磷酸酯基、羧基中的任一种，作为含氮杂环基，可以优选使用例如咪唑基、三唑基、四唑基、及它们的衍生物。
在上述极性基为磷酸酯基时，可以使用单酯(-OP(O)(OH)2)、二酯((-O)2P(O)(OH))、三酯((-O)3P(O))。
关于作为含氮杂环基的咪唑基、三唑基、四唑基，存在异构体，但在本发明中可以使用任一种异构体，另外也可以使用其混合物。在合成的方便性上，含氮环状化合物的氮直接与氟烃基结合的化合物容易获得，可以优选使用。另外，作为咪唑基、三唑基、四唑基的衍生物，可以列举出作为取代基具有烷基、苯基等的衍生物。
因此，作为本发明的防止环氧树脂渗出的试剂中优选的含氟有机化合物，如果用A-表示上述氟烃基CxHyFz-，则可以列举出例如A-SH、A-NH2、A-OP(O)(OH)2、(A-O)2 P(O)(OH)、(A-O)3 P(O)、A-COOH、A-N2C3H3(1-咪唑基)、A-N3C2H2(1，2，3-三唑-1-基)、A-N4CH(1-四唑基)等。
本发明的防止环氧树脂渗出的试剂是，将其溶解于水、有机溶剂等的溶剂中，以防止环氧树脂渗出的试剂的溶液的形式来使用的。上述防止环氧树脂渗出的试剂的溶液中的上述有机化合物的浓度为0.1mg/L～100g/L，优选为10mg/L～10g/L。
如果上述有机化合物的浓度过低，则无防止环氧树脂渗出的效果，另外，如果浓度过高，则由于效果饱和，不能得到更好的效果，因而不优选。
当用水作为溶剂时，在上述有机化合物难溶于水的情况下，根据需要，添加醇、酮等有机溶剂。添加量可以是使上述有机化合物溶于水所必要的浓度，但通常为0.1g/L～200g/L，优选为1g/L～50g/L。如果添加量过少，则溶解性低，另外，如果过多，则不但不能改变上述有机化合物的溶解效果，而且上述有机化合物的浓度过稀，因而也不优选。
进而，当上述有机化合物难以溶解于水时，根据需要添加1μg/L～10g/L，优选为10μg/L～1g/L的阴离子系、阳离子系、非离子系的表面活性剂的任一种或它们的混合物。
另外，在防止环氧树脂渗出试剂的溶液中，根据需要添加0.1g/L～200g/L，优选为1～50g/L的磷酸系、硼酸系、有机酸系的pH缓冲剂。如果添加量过低，则pH缓冲效果低，如果过多，则由于效果饱和，因此多添加是无益的。
另外，在防止环氧树脂渗出试剂的溶液中有金属溶出的情况下，根据需要，作为金属掩蔽剂添加0.1g/L～200g/L，优选为1g/L～50g/L的胺系、氨基羧酸系、羧酸系的络合剂。如果添加量过低，则将金属络合、进行掩蔽的效果小，如果过多，则由于效果饱和，因此多添加是无益的。
对防止环氧树脂渗出试剂的溶液的pH没有必要进行特别限定，但通常为pH1～14之间，优选在pH2～12之间进行处理。如果偏离该范围，则对材料的损害大，防止环氧树脂渗出的效果差。
另外，防止环氧树脂渗出试剂的溶液的温度，可以在能够以水溶液进行的温度范围内，通常为5～90℃，优选为10～60℃。如果温度过低，则防止环氧树脂渗出的效果差，如果过高，则效果饱和，且不利于操作，提高温度没有益处。
当用有机溶剂作为溶剂时，作为有机溶剂，可以列举出甲醇、乙醇、异丙醇等的醇、丙酮、甲乙酮等的酮。使用有机溶剂时的防止环氧树脂渗出试剂的溶液的温度优选为室温。
进而，用防止环氧树脂渗出试剂的溶液进行处理的时间为0.1秒以上300秒以下，可以根据效果，适当调整，考虑到操作的重现性和效率，优选为1秒以上120秒以下。如果过短，则防止环氧树脂渗出的效果差，且操作的重现性低，如果过长，则效果饱和，且操作效率降低。
另外，防止环氧树脂渗出的方法，可以是将布线基板浸渍到防止环氧树脂渗出试剂的溶液中，或者将防止环氧树脂渗出试剂的溶液通过喷淋、喷雾等散布到基板上、或通过旋涂机等涂布到基板上等等而进行接触后，水洗、干燥。
另外，通过使防止环氧树脂渗出的试剂中含有作为主要成分的上述含氟有机化合物的同时还含有镀覆皮膜、金属材料等的金属表面的防变色剂、封孔处理剂，可以同时赋予防变色效果、封孔处理效果和防渗出效果。
作为这种防变色剂或封孔处理剂，可以分别使用公知的试剂。例如，作为防变色剂，优选使用咪唑衍生物、三唑衍生物、四唑衍生物、噻唑衍生物等的含氮杂环化合物。
通过进行上述那样的防止环氧树脂渗出的处理，上述含氟有机化合物吸附在布线基板表面的镀层面上，形成厚度为1到几个分子左右的含有含氟有机化合物的被膜。因此，可增大镀层面与环氧树脂的接触角，抑制环氧树脂的渗出。另外，由于吸附的含氟有机化合物的被膜非常薄，因此对于引线接合性能、模塑性能等组装性能没有不利影响。另外也不损害防变色效果、封孔处理效果。采用上述方法实施了防止环氧树脂渗出的处理的布线基板、和使用了该布线基板的半导体封装体也包括在本发明中。
实施例
下面基于实施例来说明本发明，但本发明并不限定于这些实施例。
实施例1～10
在铜合金(Cu：97.7％-Sn：2.0％-Ni：0.2％-P：0.03％)制的引线框基板上，进行铜触击镀覆作为基底，以提高粘合性，然后在引线框的整个面上进行镀金、镀银、镀铜中的任一种。然后，通过浸渍来进行如表1所述的防止环氧树脂渗出的处理。
另外，实施例8、9、10中使用的防止环氧树脂渗出的试剂的极性基-N2C3H3、-N3C2H2、-N4CH分别是1-咪唑基、1，2，3-三唑-1-基、1-四唑基。
对这些基板进行芯片接合，评价耐环氧树脂渗出性(耐EBO性)、引线接合性能(W/B性)、模塑性能和耐变色性。结果如表1所示。表1中，浴组成中的[-]表示未添加，评价中的[-]表示不是评价对象。
按照下面的方法进行耐环氧树脂渗出性的评价。
将市售的用于低应力芯片接合的环氧树脂(エイブルボンド 8340、エイブルステイツク社制)，用注射器涂布到经防止环氧树脂渗出的试剂处理了的镀层面上，然后在大气中采用电热板在175℃下加热30分钟以固化，然后，用金属显微镜(100倍)观察环氧树脂涂布部。测定如图1所示的芯片接合用环氧树脂的周围可见环氧树脂渗出(图1中，将芯片接合用环氧树脂用黑圆表示，该黑圆周围颜色稍淡的宽度窄的部分表示环氧树脂渗出部)区域中，环氧树脂渗出最严重的部分的渗出量(EBO量)，如以下那样进行评价。
○：不到10μm
△：10μm以上、小于100μm
×：100μm以上
按照下面的方法进行引线接合性能的评价。
采用25μm的金丝，通过并用超声波的热压接方式(温度：200℃，载荷：50g，时间：10毫秒)进行引线接合，用拉力试验机测定扯拉强度，如以下那样进行评价。
○：10gf以上
×：小于10gf
按照以下方法进行模塑性能的评价。
将市售的用于模塑的环氧树脂(住友ベ一クライト制EME-6300)涂布到经防止环氧树脂渗出的试剂处理了的镀面上后，在175℃下加热5小时以固化，然后测定剪切强度，如以下那样进行评价。
○：10kgf/cm2以上
×：小于10kgf/cm2
按照下面方法进行防变色效果的评价。
在40℃、湿度90％下加湿96小时后，观察外观，如以下那样进行评价。
○：无变色
×：有变色
比较例1
使用羧酸作为主成分，实施如表1所述的防止环氧树脂渗出的试剂处理，除此之外，与实施例1同样地进行防止环氧树脂渗出的试剂处理，与实施例1同样进行评价。结果如表1所示。
比较例2
使用表1所述的基板，不进行防止环氧树脂渗出的试剂处理，除此之外，与实施例1同样进行操作，与实施例1同样进行评价。结果如表1所示。
另外，本发明中表示数值范围的“以上”、“以下”均包括本数。
Figure C20078000005000111
Figure C20078000005000121
Figure C20078000005000131

Claims (11)

1、一种在芯片接合工艺中防止环氧树脂渗出的试剂，其特征在于，含有含氟有机化合物，该含氟有机化合物具有碳原子数为3～24个的氟烃基CxHyFz-和极性基R-，其中x＝3～24、y＝0～48、z＝1～49、y+z≤2x+1。
2、如权利要求1所述的防止环氧树脂渗出的试剂，其特征在于，所述极性基R-是含有硫、氮、磷、氧之中的任一种的极性基。
3、如权利要求2所述的防止环氧树脂渗出的试剂，其特征在于，所述极性基R-是巯基、氨基、含氮杂环基、磷酸酯基、羧基中的任一种。
4、如权利要求3所述的防止环氧树脂渗出的试剂，其特征在于，所述含氮杂环基是咪唑基、三唑基、四唑基、及它们的衍生物之中的任一种。
5、如权利要求1～4的任一项所述的防止环氧树脂渗出的试剂，其特征在于，含有防变色剂或封孔处理剂。
6、如权利要求5所述的防止环氧树脂渗出的试剂，其特征在于，防变色剂含有含氮杂环化合物。
7、如权利要求6所述的防止环氧树脂渗出的试剂，其特征在于，含氮杂环化合物是咪唑衍生物、三唑衍生物、四唑衍生物、噻唑衍生物中的任一种。
8、一种防止环氧树脂渗出的方法，其特征在于，将布线基板浸渍到含有权利要求1～7的任一项所述的防止环氧树脂渗出的试剂的溶液中，或者将含有该防止环氧树脂渗出的试剂的溶液散布或涂布到布线基板上。
9、一种布线基板，其特征在于，通过将布线基板浸渍到含有权利要求1～7的任一项所述的防止环氧树脂渗出的试剂的溶液中，或者将含有该防止环氧树脂渗出的试剂的溶液散布或涂布到布线基板上，而实施了防止环氧树脂渗出的处理。
10、一种布线基板，其特征在于，在表面上吸附有权利要求1～7的任一项所述的防止环氧树脂渗出的试剂。
11、一种半导体封装体，其特征在于，使用了权利要求9或10所述的布线基板。
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JP4082625B2 (ja) 2008-04-30
WO2007083538A1 (ja) 2007-07-26
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