CN101523587B - 晶片接合用树脂浆料、半导体装置的制造方法及半导体装置 - Google Patents

晶片接合用树脂浆料、半导体装置的制造方法及半导体装置 Download PDF

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CN101523587B
CN101523587B CN2007800367502A CN200780036750A CN101523587B CN 101523587 B CN101523587 B CN 101523587B CN 2007800367502 A CN2007800367502 A CN 2007800367502A CN 200780036750 A CN200780036750 A CN 200780036750A CN 101523587 B CN101523587 B CN 101523587B
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resin
semiconductor device
die bonding
semiconductor
chip
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CN101523587A (zh
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森修一
长谷川雄二
杉浦实
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Resonac Corp
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Hitachi Chemical Co Ltd
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Abstract

本发明涉及一种晶片接合用树脂浆料，其含有由下述通式(I)表示的聚氨酯酰亚胺树脂、热固性树脂、填料和印刷用溶剂。通式(I)中，R1表示包含芳香环或脂肪环的2价有机基团，R2表示分子量100～10,000的2价有机基团，R3表示包含4个以上碳原子的4价有机基团，n和m各自独立地表示1～100的整数。
Figure D2007800367502A00011

Description

晶片接合用树脂浆料、半导体装置的制造方法及半导体装置
技术领域
本发明涉及晶片接合用树脂浆料、半导体装置的制造方法及半导体装置，更具体地涉及用作IC、LSI等半导体元件与引线框或绝缘性支持基板等支持部件的接合材料(晶片接合材料)的晶片接合用树脂浆料、以及使用该浆料的半导体装置的制造方法及半导体装置。
背景技术
作为IC、LSI与引线框的接合材料迄今已知有Au-Si共晶合金、焊料或银浆料等。另外，早先还提出了使用特定的聚酰亚胺树脂的粘接膜、向特定的聚酰亚胺树脂加入导电性填料或无机填料的晶片接合用粘接膜(参照专利文献1～3)。
专利文献1：日本特开平07-228697号公报
专利文献2：日本特开平06-145639号公报
专利文献3：日本特开平06-264035号公报
发明内容
上述Au-Si共晶合金的耐热性和耐湿性高，但是由于弹性模量大，因此，在适用于大型芯片时存在容易发生裂纹的问题。并且，Au-Si共晶合金还存在价格昂贵的问题。另一方面，焊料虽然价格便宜，但是耐热性较差，其弹性模量与Au-Si共晶合金同样高，难以适用于大型芯片。
相反，银浆料的价格便宜，耐湿性高，弹性模量也比Au-Si共晶合金和焊料低，还具有350℃的可适用于热压合型晶片接合程度的耐热性。因此，现在银浆料成为晶片接合材料的主流。但是，随着IC、LSI的高集成化发展，芯片逐渐变得大型化，当用银浆料将IC、LSI与引线框接合时，扩展至芯片整个面涂布银浆料存在困难。
另外，近年来伴随着封装的小型化和轻量化，绝缘性支持基板的使用变得广泛，并且，为了降低制造成本，以量产性高的印刷法供给晶片接合材料的方法备受关注。在这种情况下，如果要有效地将像上述专利文献1～3中记载的粘接膜供给并粘贴于绝缘性支持基板，需要事先切成(或者冲裁)芯片尺寸而粘贴粘接膜。
对于将粘接膜切成芯片尺寸而粘贴于基板的方法，需要用于提高生产效率的粘贴装置。并且，对于冲裁粘接膜而一起粘贴多个芯片部分的方法，容易产生粘接膜的浪费。进而，绝缘性支持基板的大部分由于在基板内部形成有内层配线，从而在粘贴粘接膜的表面凹凸较多，粘贴粘接膜时会产生空隙，可靠性容易降低。
另外，就事先在基板上形成晶片接合材料、再向其粘贴半导体芯片的方法而言，在粘贴半导体芯片前，对涂布到基板的晶片接合材料进行干燥半固化(B阶段化)，再向其压粘半导体芯片，作为后固化例如在180℃的烘箱中对晶片接合材料固化1小时。但是，最近正在寻求即使从缩短工艺管理和组装时间的角度考虑省略了后固化工序，也可以进行后面的组装工序即引线接合和密封的晶片接合材料。通常引线接合的作业温度为120～150℃，密封的作业温度为170～190℃，随后作为密封材料的固化工序例如在180℃加热2～5小时。省略后固化工序的情况下，芯片压粘后的晶片接合材料在引线接合和密封工序后、密封材料的固化工序中同时进行后固化。从而，在省略后固化工序的组装工序中，B阶段状态的晶片接合材料需要具有在180℃左右的耐热性和芯片粘接性。
本发明是鉴于这样的情况而完成的，其目的在于提供一种晶片接合用树脂浆料，该浆料即使省略粘贴半导体芯片后的树脂浆料的固化工序也可以进行后面的工序，即在B阶段状态可以具有充分的耐热性和芯片粘接性。另外，本发明的目的在于提供使用了上述晶片接合用树脂浆料的半导体装置的制造方法以及半导体装置。
为了实现上述目的，本发明提供了一种晶片接合用树脂浆料，其含有由下述通式(I)表示的聚氨酯酰亚胺树脂、热固性树脂、填料和印刷用溶剂。
[化1]
Figure G2007800367502D00031
式中，R1表示包含芳香环或脂肪环的2价有机基团，R2表示分子量为100～10,000的2价有机基团，R3表示包含4个以上碳原子的4价有机基团，n和m各自独立地表示1～100的整数。
采用这样的晶片接合用树脂浆料，通过同时含有由上述通式(I)表示的聚氨酯酰亚胺树脂、热固性树脂、填料和印刷用溶剂，可以在B阶段状态得到充分的耐热性和芯片粘接性，可以具有即使省略粘贴半导体芯片后的后固化工序也能够进行后面的组装工序这样的效果。另外，根据具有上述构成的晶片接合用树脂浆料，可以通过印刷法容易地向需要在比较低的温度粘贴半导体芯片的基板进行供给和涂布。
另外，本发明还提供一种半导体装置的制造方法，包括：在基板上涂布上述本发明的晶片接合用树脂浆料而形成涂膜的涂布工序，以及在上述涂膜上搭载半导体芯片的半导体芯片搭载工序。
根据这样的半导体装置的制造方法，由于使用了上述本发明的晶片接合用树脂浆料，可以在比较低的温度将半导体芯片粘贴在基板上，可以得到具有优异的耐热性和芯片粘接性的半导体装置。
另外，本发明的半导体装置的制造方法，优选在上述涂布工序后，进一步包括干燥上述涂膜而进行B阶段化的干燥工序，并在上述半导体芯片搭载工序中在已B阶段化的上述涂膜上搭载半导体芯片。
本发明的晶片接合用树脂浆料可以在B阶段状态得到充分的耐热性和晶片粘接性，因此通过包括上述干燥工序，可以得到可靠性更优异的半导体装置。
进而，本发明提供一种通过上述本发明的半导体装置的制造方法得到的半导体装置。这样的半导体装置由于使用了上述本发明的晶片接合用树脂浆料而在基板上粘贴半导体芯片，从而可以得到优异的耐热性和芯片粘接性。
根据本发明，可以提供能够通过印刷法容易地对需要在比较低的温度粘贴半导体芯片的基板进行供给和涂布的晶片接合用树脂浆料。并且，本发明的晶片接合用树脂浆料具有耐热性，容易操作，低应力性和低温粘接性优异。进而，由于在B阶段状态的耐热性优异，因此，可以省略半导体芯片压粘后的后固化工序，有助于半导体装置组装时的工艺管理和组装时间的缩短。本发明的晶片接合用树脂浆料作为晶片接合用途，可以适宜地用于有机基板等绝缘性支持基板和铜引线框，还可以用于42合金引线框。进而，根据本发明，可以提供使用了上述本发明的晶片接合用树脂浆料的半导体装置的制造方法以及通过该制造方法制造的半导体装置。
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截面示意图。
符号说明
2...半导体芯片、4...粘接剂、6...基板、8...焊球(焊锡球)、10...导线、12...密封树脂、100...半导体装置
具体实施方式
下面针对本发明的优选实施方式详细地进行说明。
本发明涉及的晶片接合用树脂浆料(下面有时简称为“树脂浆料”)含有(A)由下述通式(I)表示的聚氨酯酰亚胺树脂(下面有时称为“(A)成分”)。
[化2]
Figure G2007800367502D00041
式中，R1表示包含芳香环或脂肪环的2价有机基团，R2表示分子量100～10,000的2价有机基团，R3表示包含4个以上碳原子的4价有机基团，n和m各自独立地表示1～100的整数。
另外，本发明的树脂浆料优选在含有上述(A)成分的同时还含有(B)具有羧酸末端基的丁二烯聚合物(均聚物或共聚物)(下面有时称为“(B)成分”)。
另外，本发明的树脂浆料在含有上述(A)成分的同时还含有(C)热固性树脂(下面有时称为“(C)成分”)、(D)填料(下面有时称为“(D)成分”)以及(E)印刷用溶剂(下面有时称为“(E)成分”)。下面针对各成分详细地进行说明。
(A)聚氨酯酰亚胺树脂由上述通式(I)表示。在此，上述通式(I)中R1表示的包含芳香环或脂肪环的2价有机基团优选为二异氰酸酯残基，更优选包含10～100mol％由下述通式(II)表示的结构。
[化3]
Figure G2007800367502D00051
另外，作为其余的二异氰酸酯残基可举出下述各式等，这些残基可以使用1种或组合2种以上而使用。
[化4]
Figure G2007800367502D00052
上述通式(I)中由R2表示的分子量100～10,000的2价有机基团优选为二醇残基，更优选包含10～100mol％由下述通式(III)表示的重复单元构成的结构。
[化5]
-(CH2-CH2-CH2-CH2-O)-    (III)
另外，作为其余的二醇残基可举出具有下述各式等重复单元的残基，这些残基可以使用1种或组合2种以上而使用。它们的重均分子量优选为100～10,000，更优选为500～5,000，
[化6]
-(CH2-CH(CH3)-O)-、
-(CH2-CH2-O)-、
-(CH2-CH2-CH2-CH2-O)-、
-(CH2-CH(CH3)-O)a-(CH2-CH2-O)b-(a/b＝9～1/1～9mol％的共聚物)、
-[CO-(CH2)4-CO-O-(CH2)2-O]-、
-[CO-(CH2)4-CO-O-(CH2)2-O-(CH2)2-O]-、
-[CO-(CH2)4-CO-O-CH2-CH(CH3)-O]-、
-[CO-(CH2)4-CO-O-(CH2)4-O]-、
-[CO-(CH2)4-CO-O-(CH2)6-O]-、
-[CO-(CH2)4-CO-O-CH2-C(CH3)2-CH2-O]-、
-[CO-(CH2)8-CO-O-(CH2)6-O]-、
-[CO-(CH2)5-O]-、
-[CO-O-(CH2)6-O]-、
-R4-(Si(CH3)2-O)-R4-(R4是碳数为1～10的有机基团)。
上述通式(I)中由R3表示的包含4个以上碳原子的4价有机基团优选为四羧酸酐残基，可举出下述各式表示的残基等。这些残基可以使用1种或组合2种以上而使用。
[化7]
Figure G2007800367502D00071
另外，需要上述通式(I)中n和m各自独立地为1～100的整数，更优选为1～50的整数。
(A)聚氨酯酰亚胺树脂可以由溶液聚合法等通常的方法来合成。例如在溶液聚合法的情况下，将二异氰酸酯和二醇溶解在可溶解生成的聚氨酯酰亚胺树脂的溶剂例如N-甲基-2-吡咯烷酮(NMP)等中，在70～180℃反应1～5小时，合成氨酯低聚物。接着，添加四羧酸二酐，在70～180℃反应1～10小时，从而可以得到聚氨酯酰亚胺树脂的NMP溶液。随后，根据情况也可以进一步添加1价的醇、肟、胺、异氰酸酯、酸酐等继续反应，修饰聚氨酯酰亚胺树脂的末端。并且，在合成时也可以使用水、醇、叔胺等作为催化剂。
得到的聚氨酯酰亚胺树脂溶液也可以根据目的通过利用水的再沉淀法等分离聚氨酯酰亚胺树脂。构成氨酯低聚物的二异氰酸酯和二醇的组成比优选，相对于二异氰酸酯1.0mol，二醇成分为0.1～1.0mol。构成聚氨酯酰亚胺树脂的聚氨酯低聚物和四羧酸二酐的组成比优选，四羧酸二酐相对于聚氨酯低聚物1.0mol为0.1～2.0mol。
本发明中(A)聚氨酯酰亚胺树脂利用以四氢呋喃为溶剂的凝胶渗透色谱法测定的聚苯乙烯换算的重均分子量优选为5,000～500,000，更优选为10,000～100,000。重均分子量小于5,000时，树脂的强度往往会降低；超过500,000时，树脂的溶解性往往会变差。
树脂浆料中(A)成分的配合量以树脂浆料中的固体成分总量为基准优选为20～60质量％。该配合量大于60质量％时，固化性往往会降低；小于20质量％时，在B阶段状态的芯片粘接性往往会降低。
对于作为(B)成分的具有羧酸末端基的丁二烯的均聚物或共聚物来说，例如可以适宜使用的物质可举出：作为向主链导入丙烯腈的低分子量液态聚丁二烯且在末端具有羧酸的“Hycer CTB-2009×162”、“CTBN-1300×31”、“CTBN-1300×8”、“CTBN-1300×13”、“CTBNX-1300×9”(均为宇部兴产株式会社制造)，或者作为具有羧酸基的低分子量液态聚丁二烯的“NISSO-PB-C-2000”(日本曹达株式会社制造)等。这些物质可以单独使用1种或组合2种以上而使用。
树脂浆料中(B)成分的配合量相对上述(A)成分100质量份优选为200质量份以下，更优选为100质量份以下。该配合量大于200质量份时，在B阶段状态的芯片粘接性往往会降低。
作为(C)成分的热固性树脂，优选的树脂可举出例如环氧树脂。并且，作为(C)成分还可以使用包括环氧树脂、酚树脂或者在分子中具有酚性羟基的化合物以及固化促进剂的树脂混合物。通过含有(C)热固性树脂，树脂浆料在与密封材料同时固化后可以得到高的可靠性。
环氧树脂为在分子内包含至少二个环氧基的树脂，从固化性和固化物特性的角度考虑，优选酚的缩水甘油醚型的环氧树脂。作为这样的树脂可举出双酚A、双酚AD、双酚S、双酚F或者卤化双酚A与表氯醇的缩合物、苯酚酚醛清漆树脂的缩水甘油醚、甲酚酚醛清漆树脂的缩水甘油醚、双酚A酚醛清漆树脂的缩水甘油醚等。这些树脂可以单独使用1种或组合2种以上而使用。
(C)成分使用环氧树脂的情况，其配合量优选相对上述(A)成分100质量份为300质量份以下，更优选为200质量份以下，特别优选为5～100质量份。该配合量大于300质量份时，树脂浆料的保存稳定性往往容易降低。
酚树脂为在分子中具有至少二个酚性羟基的树脂，可举出例如苯酚酚醛清漆树脂、甲酚酚醛清漆树脂、双酚A酚醛清漆树脂、聚对乙烯基苯酚、苯酚芳烷基树脂等。这些树脂可以单独使用1种或组合2种以上而使用。
(C)成分中酚树脂或者在分子中具有酚性羟基的化合物的配合量，优选相对上述环氧树脂100质量份为150质量份以下，更优选为120质量份以下，特别优选为10～120质量份。该配合量大于150质量份时，固化性可能会不充分。另一方面，该配合量小于10质量份时，固化性也可能会不充分。
固化促进剂只要是可用于使环氧树脂固化的物质就没有特别限制。作为这样的固化促进剂可举出例如咪唑类、双氰胺衍生物、二羧酸二酰肼、三苯基膦、四苯基鏻四苯基硼酸酯、2-乙基-4-甲基咪唑-四苯基硼酸酯、1，8-二氮杂双环(5，4，0)十一碳烯-7-四苯基硼酸酯等。这些物质可以单独使用1种或组合2种以上而使用。
(C)成分中固化促进剂的配合量优选相对上述环氧树脂100质量份为50质量份以下，更优选为20质量份以下，特别优选为0.1～20质量份。该配合量大于50质量份时，树脂浆料的保存稳定性可能会降低。另一方面，该配合量小于0.1质量份时，得不到充分的固化促进作用，固化性可能会不充分。
另外，作为(C)热固性树脂也可以使用在1个分子中具有至少二个热固性酰亚胺基的酰亚胺化合物。作为这样的化合物的例子，可举出邻二马来酰亚胺苯、间二马来酰亚胺苯、对二马来酰亚胺苯、1，4-二(对马来酰亚胺枯基)苯、1，4-二(间马来酰亚胺枯基)苯等。这些化合物可以单独使用1种或组合2种以上而使用。进而，作为酰亚胺化合物也优选使用由下述通式(IV)～(VI)表示的酰亚胺化合物等。
[化8]
Figure G2007800367502D00091
[化9]
[化10]
Figure G2007800367502D00102
上述式(IV)～(VI)中，X和Y各自独立地表示-O-、-CH2-、-CF2-、-SO2-、-S-、-CO-、-C(CH3)2-或-C(CF3)2-，R11、R12、R13、R14、R15、R16、R17和R18各自独立地表示氢原子、低级烷基、低级烷氧基、氟原子、氯原子或溴原子，D表示具有烯类不饱和双键的二羧酸残基，p表示0～4的整数。
作为(D)成分的填料，可举出例如银粉、金粉、铜粉等导电性(金属)填料，二氧化硅、氧化铝、氧化钛、玻璃、氧化铁、陶瓷等无机物质填料等。通过含有(D)成分，在印刷时可以对树脂浆料赋予必要的触变性。
填料中银粉、金粉、铜粉等导电性(金属)填料为了赋予粘接剂以导电性、传热性或触变性而添加到粘接剂中。另外，二氧化硅、氧化铝、氧化钛、玻璃、氧化铁、陶瓷等无机物质填料为了赋予低热膨胀性、低吸湿率、触变性而添加到粘接剂中。这些填料可以单独使用1种或组合2种以上而使用。
另外，还可以添加无机离子交换体作为提高半导体装置的电可靠性的填料。关于无机离子交换体，当在热水中萃取浆料固化物时可有效确认到在水溶液中萃取的离子例如Na+、K+、Cl-、F-、RCOO-、Br-等的离子捕捉作用。作为这样的离子交换体的例子可举出天然产出的沸石、沸石类、酸性白土、白云石、水滑石类等天然矿物，人工合成的合成沸石等。
这些导电性填料或无机物质填料可以分别单独使用1种或者混合2种以上而使用。并且，在不损害物性的范围，也可以混合使用1种以上导电性填料和1种以上无机物质填料。
(D)填料的配合量通常相对(B)成分100质量份优选为1～100质量份，更优选为2～50质量份。从对树脂浆料赋予充分的触变性(例如触变指数：1.5以上)的角度考虑，该填料的配合量优选为1质量份以上。进而，从粘接性的角度考虑，该填料的配合量优选为100质量份以下；配合量大于100质量份时，固化物的弹性模量会增加，其结果是，可能会发生晶片接合材料的应力缓和能力降低，半导体装置的安装可靠性降低。
(D)填料的混合、混炼适宜地组合常用的搅拌机、混砂机、三辊研磨机、球磨机等分散机来进行。
作为(E)成分的印刷用溶剂优选从能够均匀地混炼或分散(D)填料的溶剂中进行选择。并且，考虑到印刷时防止溶剂挥发，优选选择沸点100℃以上的溶剂。通过(E)印刷用溶剂可以调节树脂浆料的粘度。
作为上述印刷用溶剂可举出例如N-甲基-2-吡咯烷酮、二甘醇二甲醚(也称为“双(2-甲氧基乙基)醚”)、三甘醇二甲醚(也称为“二缩三乙二醇二甲醚”)、二甘醇二乙醚、2-(2-甲氧基乙氧基)乙醇、γ-丁内酯、异佛尔酮、卡必醇、醋酸卡必醇酯、1，3-二甲基-2-咪唑烷酮、醋酸-2-(2-丁氧基乙氧基)乙酯、乙基溶纤剂、乙基溶纤剂醋酸酯、丁基溶纤剂、二噁烷、环己酮、苯甲醚，除此以外，还可举出用作印刷用油墨的溶剂的以石油蒸馏物为主体的溶剂等。这些溶剂可以单独使用1种或混合2种以上而使用。
上述(E)印刷用溶剂的配合量优选按使树脂浆料的固体成分为40～90质量％来配合。上述固体成分为40质量％以上时，从抑制浆料干燥后基于体积减少引起的形状变化的角度考虑是优选的；为90质量％以下时，从提高浆料的流动性和印刷作业性的角度考虑是优选的。
树脂浆料的印刷中气泡、孔隙的产生明显时，向上述(E)印刷用溶剂中添加脱泡剂、破泡剂、抑泡剂等添加剂是有效的。从发挥抑泡效果的角度考虑，以(E)印刷用溶剂和添加剂的总量为基准，添加量优选为0.01质量％以上；从粘接性和浆料的粘度稳定性的角度考虑，优选为10质量％以下。
另外，为了提高粘接力，可以适宜地向树脂浆料中添加硅烷偶联剂、钛系偶联剂、非离子系表面活性剂、氟系表面活性剂、硅酮系添加剂等。
树脂浆料的触变指数优选为1.0～8.0。树脂浆料的触变指数为1.0以上时，往往可以抑制由印刷法供给、涂布的浆料中的塌陷(ダレ)等的发生，良好地保持印刷形状。进而，该触变指数为8.0以下时，往往可以抑制由印刷法供给、涂布的浆料的缺口或不足(カスレ)等的发生。
树脂浆料的粘度(25℃)优选为5～1000Pa·s。树脂浆料的粘度为5～1000Pa·s时，从印刷作业性的角度考虑是优选的。另外，树脂浆料的粘度优选根据印刷法的种类适宜地进行调整，例如像丝网版等那样网孔等在掩模开口部伸展的情况下，考虑网孔部的透过性优选调整至5～100Pa·s范围；在模版等的情况下，优选调整至20～500Pa·s范围。另外，干燥后的浆料中残存的孔隙较多的情况下，调整至150Pa·s以下的粘度是有效的。
上述粘度为，使用E型旋转粘度计在25℃、转速0.5rpm的条件下测定时的值。触变指数定义为，使用E型旋转粘度计在25℃、转速1rpm的条件下测定时的值与在25℃、转速10rpm的条件下测定时的值之比(触变指数＝(1rpm下的粘度)/(10rpm下的粘度))。
得到的晶片接合用树脂浆料可以通过印刷法供给、涂布到下述物品上，进行B阶段化：42合金引线框或铜引线框等引线框，或者聚酰亚胺树脂、环氧树脂、聚酰亚胺系树脂等塑料薄膜，或者对玻璃无纺布等基材浸渍、固化聚酰亚胺树脂、环氧树脂、聚酰亚胺系树脂等塑料后的基材，或者氧化铝等陶瓷制的支持部件。由此，得到带B阶段粘接剂的支持基板。在该带B阶段粘接剂的支持基板上粘贴IC、LSI等半导体元件(芯片)，通过加热将芯片接合于支持基板上。随后，通过使树脂浆料后固化的工序将芯片搭载在支持基板上。在安装组装工序中没有问题的情况下，该树脂浆料的后固化可以在密封材料的后固化工序时一起进行。
本发明的半导体装置的制造方法至少包括在基板上涂布树脂浆料而形成涂膜的涂布工序，以及在该涂膜上搭载半导体芯片的半导体芯片搭载工序，优选是在涂布工序后进一步包括干燥涂膜而进行B阶段化的干燥工序的方法。更具体而言，本发明的半导体装置的制造方法包括上述的各工序。另外，本发明的半导体装置通过包括以上各工序的制造方法来制造。
上述晶片接合用树脂浆料虽然含有溶剂，但在用于半导体装置的制造方法时，通过在干燥工序中进行B阶段化，大部分溶剂挥发，因此可以组装在晶片接合层孔隙少、具有良好的安装可靠性的半导体装置。
另一方面，通过印刷法供给、涂布树脂浆料后，如果对封装可靠性没有影响，也可以不进行干燥半固化而粘贴半导体元件，随后通过加热将芯片接合于支持基板。
从而，本发明的其他半导体装置的制造方法包括在基板上涂布规定量的上述晶片接合用树脂浆料，在树脂浆料上搭载半导体芯片的各工序。另外，本发明的其他半导体装置通过包括以上各工序的制造方法来制造。
在此，图1为表示本发明的半导体装置(存储器用BOC结构的基板)的一个实施方式的截面示意图。在图1所示的半导体装置100中，IC芯片等半导体芯片2通过本发明的晶片接合用树脂浆料所构成的粘接剂4粘接到具有焊球8的基板6上。在此，焊球8形成在电路层14上，该电路层14形成在基板6的表面。并且，在电路层14上形成有抗蚀剂层16。进而，半导体装置100具有如下结构：半导体芯片2的连接端子通过金导线等导线10与基板6进行电连接，并且通过密封树脂12进行密封。
实施例
下面基于实施例和比较例更具体地说明本发明。
(实施例1～5和比较例1～4)
在1-甲基-2-吡咯烷酮(以下称为“NMP”)中氮气氛围下、在100℃使二苯基甲烷-4，4’-二异氰酸酯(1.0mol)、二苯基甲烷-2，4’-二异氰酸酯(1.0mol)及重均分子量1,000的聚四亚甲基二醇(0.8mol)反应1小时，随后向其中添加4，4’-氧双邻苯二甲酸酐(1.0mol)、NMP(60.0mol)，进而在100℃搅拌3小时。接着，进一步添加苄醇(0.49mol)并在100℃搅拌1小时，结束反应。将得到的溶液加入剧烈搅拌过的水中，过滤分离生成的沉淀物，将其在真空中、80℃干燥8小时，得到聚氨酯酰亚胺树脂。使用GPC测定得到的聚氨酯酰亚胺树脂的结果是，以聚苯乙烯换算Mw＝93,700、Mn＝38,800。另外，将得到的聚氨酯酰亚胺树脂以固体成分浓度40质量％溶解到醋酸卡必醇酯(CA)中，得到聚氨酯酰亚胺树脂溶液。
另外，按照以下顺序制作聚酰亚胺树脂1。首先，向具有温度计、搅拌机和硅胶管的500ml四口烧瓶中，加入4，9-二氧杂癸烷-1，12-二胺10.9g(0.05mol)、2，2-二(4-氨基苯氧基苯基)丙烷20.5g(0.05mol)及NMP150g，并进行搅拌。随后，在冰浴中冷却烧瓶的同时一点点地添加1，10-(十亚甲基)二(偏苯三酸二酐)52.0g(0.1mol)。添加结束后，在冰浴中反应3小时，进一步在室温反应4小时后，加入二甲苯100g，边吹入氮气边在180℃加热3小时，与水一起共沸除去二甲苯。随后，进一步添加NMP，得到固体成分浓度40质量％的聚酰亚胺树脂1的NMP溶液。
另外，按照以下顺序制作聚酰亚胺树脂2。首先，向具有温度计、搅拌机和硅胶管的500ml四口烧瓶中，加入聚氧丙烯二胺(商品名：D2000、BASF社制造)60.0g(0.03mol)、1，12-二-氨基十二烷14.0g(0.07mol)和NMP150g，并进行搅拌。随后，在冰浴中冷却烧瓶的同时一点点地添加2，2-二[4-(3，4-二羧基苯氧基)苯基]丙烷二酐49.4g(0.1mol)。添加结束后，在冰浴中反应3小时，进一步在室温反应4小时后，加入二甲苯100g，边吹入氮气边在180℃加热3小时，与水一起共沸除去二甲苯。随后，进一步添加NMP，得到固体成分浓度40质量％的聚酰亚胺树脂2的NMP溶液。
另外，准备甲酚酚醛清漆型环氧树脂(商品名：YDCN-702S、东都化成(株)制造、环氧当量200)14.1质量份、双酚A酚醛清漆树脂(商品名：VH-4170、大日本油墨化学工业(株)制造、OH当量118)9.9质量份的醋酸卡必醇酯(36质量份)溶液。进而，分别准备羧酸末端液态聚丁二烯(商品名：CTBNX-1300×9、宇部兴产(株)制造、官能团数2.3/mol)、四苯基鏻四苯基硼酸酯(商品名：TPPK、东京化成工业(株)制造)及阿艾劳即路(アエロジル)(商品名：AEROSIL 50、商品名：AEROSIL 380、日本アエロジル(株)制造、二氧化硅的微粉末)。
将这些材料按照下述表1所示比例的固体质量比加入混砂机中，混炼后，在5Torr以下进行1小时脱泡混炼，得到实施例1～5和比较例1～4的晶片接合用树脂浆料。另外，表1中的醋酸卡必醇酯(CA)的配合量表示聚氨酯酰亚胺树脂溶液中，以及，环氧树脂和酚树脂的醋酸卡必醇酯溶液中作为溶剂包含的醋酸卡必醇酯的量。
另外，关于该树脂浆料的特性，对半导体芯片压粘后在180℃的受热晶片接合剪切强度(die shear)进行了测定。受热晶片接合剪切强度的测定方法如下所述。即，将实施例1～5和比较例2～4的树脂浆料印刷在42合金引线框上，在150℃的烘箱中干燥70分钟，形成B阶段状态的涂膜(晶片接合层)。比较例1的树脂浆料印刷在42合金引线框上后，在140℃的烘箱中干燥90分钟，形成B阶段状态的涂膜(晶片接合层)。随后，在180℃的热盘上利用1.5kg的载荷在晶片接合层上压粘5×5mm的硅芯片(厚度0.5mm)1秒钟。使用自动粘接力试验机(商品名：serie-4000、デイジ社制造)对其测定180℃的剪切强度(kgf/芯片)。其结果表示在表1中。
表1
Figure G2007800367502D00151
表1中，对于比较例3，树脂间不能相溶，不能够浆料化，从而不能测定受热晶片接合剪切强度。另外，对于比较例4，在测定受热晶片接合剪切强度时，树脂浆料因受热熔融，测定值小于0.1kgf/芯片。
如表1所述，本发明的树脂浆料(实施例1～5)经过印刷、B阶段化及芯片压粘后，不进行后固化而具有高的耐热性，与以往的树脂浆料(比较例1～4)相比，在180℃的受热晶片接合剪切强度显示出良好的结果。
产业上利用的可能性
如上所述，利用本发明，可以提供通过印刷法能够容易地对需要在比较低的温度粘贴半导体芯片的基板进行供给和涂布的晶片接合用树脂浆料。并且，本发明的晶片接合用树脂浆料具有耐热性，容易操作，低应力性和低温粘接性优异。进而，由于在B阶段状态的耐热性优异，因此，可以省略半导体芯片压粘后的后固化工序，有助于半导体装置组装时的工艺管理和组装时间的缩短。本发明的晶片接合用树脂浆料，作为晶片接合用途，可以适宜地用于有机基板等绝缘性支持基板和铜引线框，还可以用于42合金引线框。进而，根据本发明，可以提供使用了上述本发明的晶片接合用树脂浆料的半导体装置的制造方法以及通过该制造方法制造的半导体装置。

Claims (4)

1.一种晶片接合用树脂浆料，其是用于通过印刷法在基板上进行供给和涂布的印刷用晶片接合用树脂浆料，
含有由下述通式(I)表示的聚氨酯酰亚胺树脂、热固性树脂、填料和印刷用溶剂，
Figure FSB00000767344900011
式中，R1表示包含芳香环或脂肪环的2价有机基团，R2表示分子量为100～10,000的2价有机基团，R3表示包含4个以上碳原子的4价有机基团，n和m各自独立地表示1～100的整数；
所述印刷用溶剂的配合量，按使树脂浆料的固体成分为40～90质量％来配合；
所述热固性树脂是包括环氧树脂、酚树脂或者在分子中具有酚性羟基的化合物以及固化促进剂的树脂混合物；
所述酚树脂或者在分子中具有酚性羟基的化合物的配合量，相对所述环氧树脂100质量份为10～120质量份。
2.一种半导体装置的制造方法，包括：在基板上涂布权利要求1所述的晶片接合用树脂浆料而形成涂膜的涂布工序，以及在所述涂膜上搭载半导体芯片的半导体芯片搭载工序。
3.根据权利要求2所述的半导体装置的制造方法，其中，在所述涂布工序后，进一步包括干燥所述涂膜而进行B阶段化的干燥工序，并且，在所述半导体芯片搭载工序中在已B阶段化的所述涂膜上搭载半导体芯片。
4.一种半导体装置，由权利要求2或3所述的半导体装置的制造方法得到。
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