CN101479839A - 电子元件、使用该电子元件的电子元件装置及其制造方法 - Google Patents

电子元件、使用该电子元件的电子元件装置及其制造方法 Download PDF

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Publication number
CN101479839A
CN101479839A CNA2007800237000A CN200780023700A CN101479839A CN 101479839 A CN101479839 A CN 101479839A CN A2007800237000 A CNA2007800237000 A CN A2007800237000A CN 200780023700 A CN200780023700 A CN 200780023700A CN 101479839 A CN101479839 A CN 101479839A
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electrode
mentioned
electronic component
metal nanoparticle
bonding
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舟木达弥
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Abstract

本发明提供一种具有连接至少表面由Al或Al合金形成的电极和金属纳米粒子的烧结体的连接部的电子元件、使用该电子元件的电子元件装置及其制造方法，该电子元件具有：电子元件本体以及电极，该电极包含至少表面由Al或Al合金形成的第1电极、和在上述第1电极上键合的由金属纳米粒子的烧结体形成的第2电极；其特征在于，上述第1电极和第2电极的键合界面具有从上述第1电极侧向上述第2电极侧，以(a)主成分为Al的第1层，(b)主成分为Al氧化物的第2层，(c)主成分为Al和金属纳米粒子的构成元素的合金的第3层，(d)主成分为金属纳米粒子的构成元素的第4层的顺序排列的多层结构。

Description

电子元件、使用该电子元件的电子元件装置及其制造方法
技术领域
本发明涉及一种具有至少表面由Al或Al合金形成的电极的电子元件，使用该电子元件的电子元件装置以及其制造方法。
背景技术
近年来，随着电子设备的小型化，对半导体封装高度集成化的要求越来越强烈。即使在基板上安装和固定半导体封装，获得电导通这样的安装技术中也进一步要求高集成度、高密度。
为此，在半导体封装的整个背面以格子状排列作为电极的焊料球这样的所谓BGA(球栅阵列，Ball Grid Array)的键合方式受到关注，被应用于实践中。如上所述，由于此BGA方式的半导体封装，在整个背面上配置电极，所以能够提高半导体封装的每单位面积的电极数，进而能对高密度安装和缩小安装面积发挥很大的作用。
但是，使用BGA方式的情形，随着焊料球的间隔的狭小化，回流时产生所谓焊料桥接，电极之间容易发生短路。这在通过加热一度熔化、液状化焊料合金后，进行冷却、凝固，经过这样的过程进行键合的微焊技术中可以说是不可避免的现象。
此外，多数键合所需的电子元件制造1个电子元件装置时，虽然每重复进行电子元件的键合时，依次使用熔点低的焊接材料，进行所谓分步焊接，但进行此分步焊接的情况下，在第1步的焊料键合中必须使用高温焊料。作为这样的高温焊接的实用材料，可列举Pb-5Sn类，但随着近来的环境保护的要求对使用Pb的规定越来越严格，强烈希望开发替代材料。
为了解决以上这样的课题，提案有作为具有多个电极的基体，利用以通过用有机物结合、覆盖平均粒径约100nm以下的金属核的周围所生成的复合型金属纳米粒子为主材的键合材料，将基体的电极键合在设置在另一基体上的电极上的这样的电极配设基体以及此电极键合方法(参照专利文献1及专利文献2)。
在图12中示出了示意性地表示作为上述这样的键合材料使用的金属纳米粒子膏的结构。金属纳米粒子膏300，是用可与金属微粒子中所包含的金属元素配位的分散剂302(氨络物类、醇类、硫醇类等)覆盖平均粒径1～100nm的Au、Ag、Cu等的金属纳米粒子301的表面，使其在分散剂即有机溶剂303(甲苯、二甲苯、萜品醇、矿油精、癸醇、十四烷等)中稳定地分散的物质。再有，除这些以外也可以有粘合剂成分、还原剂等添加物(参照专利文献3)。
如果使用上述这样的非Pb材料的金属纳米粒子膏的话，则由于不是像现有的焊接材料那样使其熔化后、通过凝固来键合，而是低温烧结金属微粒子才能形成键合部，因此能够减少环境负荷，还能够得到键合可靠性高的电子元件装置。
作为专利文献1及2所公开的电极配设基体及其电极键合方法的一例，在图13中示出使用专利文献3所公开的金属纳米粒子膏通过倒装芯片连接得到的电子元件装置的一例的剖面图，在图14中示出了其制造工序的一例。
使用图14说明制造工序，首先如图14(a)所示，制备在上表面上形成有用于获得与电子元件205电导通的基板电极202、抗蚀剂膜203及堤墙部203的基板201后，在此基板电极202上涂敷金属纳米粒子膏204。
接着，如图14(b)所示，制备在上表面上形成有用于获得与基板201电导通的电子元件电极206、钝化膜207及堤墙部207′的电子元件205后，使电子元件205上下反转，使基板201和电子元件205位置对准以使基板电极202及电子元件电极206相面对。
接着，如图14(c)所示，重叠基板201和电子元件205后进行加热，烧结金属纳米粒子膏204，形成金属纳米粒子烧结体208，由此将两者键合，得到图13所示的电子元件装置200。
此外，还提出有在为了使与金属粒子的键合性良好对配设在基板上的电极的表面进行电镀后，通过金属微粒子的烧结形成微细图形连接用的多孔质金属凸起(参照专利文献4)。
专利文献1：JP特开平9-326416号公报
专利文献2：JP特开2004-128357号公报
专利文献3：JP特开2002-299833号公报
专利文献4：JP特开2003-174055号公报
发明内容
但是，作为在表示专利文献1及2所公开的电极配设基体以及其电极键合方法的一例的图13及图14中所示出的电子元件205的电子元件电极206，虽然基于导电性及加工性(尺寸精度、加工速度等)观点，通常多使用Al或Al合金，但如图16(b)所示，Al电极的表面通常为被Al氧化物膜209覆盖的状态。
因此，仍旧进行上述这样的键合时，则实际中如图14(c)及将其放大表示的图15所示，在基板电极202和电子元件电极206之间插入了Al氧化物膜209。此种情况下，金属纳米粒子烧结体208和Al氧化物膜209之间键合不充分，存在所谓键合可靠性及导电性恶化的问题。
此外，即使在专利文献4中所公开的方法中，作为配设在基板上的电极的材料使用Al的情况下，如上所述，由于通常为Al电极的表面被Al氧化物膜覆盖的状态，所以首先需要另外去除Al氧化膜的工序，此后必须进行电镀。因此，工序变复杂，进而可出现所谓电子元件装置的制造成本变高的问题。
因此，本发明的目的在于，提供一种虽然制造工序简单、制造成本低但键合可靠性及导电性高且具有连接至少表面由Al或Al合金形成的电极和金属纳米粒子的烧结体的连接部的电子元件、使用此电子元件的电子元件装置以及其制造方法。
为了解决上述的技术课题，权利要求1的电子元件，具有：电子元件本体以及电极，该电极含至少表面由Al或Al合金形成的第1电极和在上述第1电极上键合的由金属纳米粒子的烧结体形成的第2电极；其特征在于，上述第1电极和第2电极的键合界面具有从上述第1电极侧向上述第2电极侧，按以下顺序排列的多层结构：
(a)主成分为Al的第1层，
(b)主成分为Al氧化物的第2层，
(c)主成分为Al和金属纳米粒子的构成元素的合金的第3层，
(d)主成分为金属纳米粒子的构成元素的第4层。
此外，权利要求2的电子元件，为权利要求1所述的电子元件，其特征在于，上述金属纳米粒子由Ag或Ag合金形成。
此外，权利要求3的电子元件装置，通过键合部电连接第1电子元件的电极和第2电子元件的电极，其特征在于，其中，上述第1电子元件和上述第2电子元件的至少一个是权利要求1或2所述的电子元件，并且，该电子元件的通过上述键合部电连接的电极包含上述第1电极和上述第2电极，上述第1电极和上述第2电极的键合界面具有上述多层结构。
此外，权利要求4的电子元件装置，为权利要求3所述的电子元件装置，其特征在于，以相面对的状态连接上述第1电子元件的电极和上述第2电子元件的电极。
此外，权利要求5的电子元件的制造方法，该电子元件具有电子元件本体以及电极，该电极含至少表面由Al或Al合金形成的第1电极和在上述第1电极上键合的由金属纳米粒子的烧结体形成的第2电极；该制造方法的特征在于，包括：第1工序，在上述电子元件本体上形成上述第1电极；第2工序，在上述第1电极上涂敷含平均粒径1～100nm的金属纳米粒子、分散剂、有机溶剂的金属纳米粒子膏；第3工序，在涂敷在上述第1电极上的上述金属纳米粒子膏的周围保持规定的空间的状态下，通过以可去除上述金属纳米粒子膏中所含的分散剂和有机溶剂的温度以上，且低于上述金属纳米粒子的熔点的温度进行加热，烧结上述金属纳米粒子，来使上述第2电极键合在上述第1电极上，形成上述电极。
此外，权利要求6的电子元件的制造方法，为权利要求5所述的电子元件的制造方法，其特征在于，在上述第2工序中，涂敷在上述第1电极上的上述金属纳米粒子膏的涂敷厚度为0.1～20μm。
此外，权利要求7的电子元件的制造方法，为权利要求5所述的电子元件的制造方法，其特征在于，在上述第2工序中，涂敷在上述第1电极上的上述金属纳米粒子膏的涂敷厚度为0.1～15μm。
此外，权利要求8的电子元件的制造方法，为权利要求5～7所述的电子元件的制造方法，其特征在于，在上述第3工序中，在含有大气中所含的量以上的氧的环境中进行加热。
此外，权利要求9的电子元件装置的制造方法，在第1电子元件的电极和第2电子元件的电极之间涂敷膏状的键合材料后，通过硬化上述膏状的键合材料来形成上述第1电子元件的电极和上述第2电子元件的电极的键合部，其特征在于，上述第1电子元件和上述第2电子元件的至少一个的制造方法是权利要求5～8所述的电子元件的制造方法，并且通过上述第1～第3工序来形成该电子元件的由上述键合部键合的电极。
此外，权利要求10的电子元件装置的制造方法，为权利要求9所述的电子元件装置的制造方法，其特征在于，在使上述第1电子元件的电极和上述第2电子元件的电极相面对的状态下，形成上述第1电子元件的电极和上述第2电子元件的电极的键合部。
发明效果
由于本发明(权利要求1)相关的电子元件，具有：电子元件本体以及电极，该电极含至少表面由Al或Al合金形成的第1电极和在上述第1电极上键合的由金属纳米粒子的烧结体形成的第2电极；其中，在上述第1电极和第2电极的键合界面具有从上述第1电极侧向上述第2电极侧，按以下顺序排列的多层结构：
(a)主成分为Al的第1层，
(b)主成分为Al氧化物的第2层，
(c)主成分为Al和金属纳米粒子的构成元素的合金的第3层，
(d)主成分为金属纳米粒子的构成元素的第4层，
所以与基板电极键合时，能够得到高的键合可靠性及导电性。
即，由于在键合性容易产生问题，在主成分为Al氧化物的层和由金属纳米粒子烧结体构成的层之间插入了对于以Al和金属纳米粒子的构成元素的合金为主成分的、Al氧化物及金属纳米粒子烧结体双方都表现出良好的键合性的合金层，所以能够牢固地使二者键合。
再有，如权利要求2所述，在权利要求1所述的电子元件中，由于在上述金属纳米粒子由Ag或Ag合金形成的情况下，能够在大气中进行形成金属纳米粒子烧结体的过程，并且能够提高导电性，所以优选。
此外，由于本发明(权利要求3)相关的电子元件装置，通过键合部电连接第1电子元件的电极和第2电子元件的电极；其中，上述第1电子元件和上述第2电子元件的至少一个是权利要求1或2所述的电子元件，并且，该电子元件的通过上述键合部电连接的电极包含上述第1电极和上述第2电极，上述第1电极和上述第2电极的键合界面具有上述多层结构，所以能够在上述第1电子元件和上述第2电子元件之间得到高的导电性。
此外，如权利要求4，在权利要求3所述的电子元件装置中，由于在以相面对的状态连接上述第1电子元件的电极和上述第2电子元件的电极的情况下，上述第1电子元件或上述第2电子元件的至少一个是上述权利要求1或2所述的电子元件，所以即使在当提高电子元件的每单位面积的电极数实现高密度安装、安置面积缩小时，必须形成微细的连接部的情况下，也能确保充分的键合可靠性。
此外，由于本发明(权利要求5)相关的电子元件的制造方法，该电子元件具有电子元件本体，以及电极，含至少表面由Al或Al合金形成的第1电极、和在上述第1电极上键合的由金属纳米粒子的烧结体形成的第2电极；其中该制造方法具有：第1工序，在上述电子元件本体上形成上述第1电极；第2工序，在上述第1电极上涂敷含平均粒径1～100nm的金属纳米粒子、分散剂、有机溶剂的金属纳米粒子膏；第3工序，在涂敷在上述第1电极上的上述金属纳米粒子膏的周围保持规定的空间的状态下，通过以可去除上述金属纳米粒子膏中所含的分散剂和有机溶剂的温度以上，且低于上述金属纳米粒子的熔点的温度进行加热，烧结上述金属纳米粒子，来使上述第2电极键合在上述第1电极上，形成上述电极，所以即使因氧化膜的插入键合性容易产生问题，具有至少表面由Al或Al合金形成的电极，也能够在与基板电极键合时得到键合可靠性及导电性高的电子元件。
即，由于在键合性容易产生问题，在主成分为Al氧化物的层和由金属纳米粒子烧结体构成的层之间插入了以Al和金属纳米粒子的构成元素的合金为主成分的、对于Al氧化物及金属纳米粒子烧结体双方都表现出良好的键合性的合金层，所以能够牢固地使两二者键合。
现有的键合方法中，如图14(c)所示，在重叠基板和芯片部件后加热，可以说是以在基板电极上的金属纳米粒子膏上覆盖电子元件形成盖的状态进行烧结。此情况下，容易残留金属纳米粒子膏中所含的分散剂、有机溶剂等有机成分，残留的有机成分起使金属纳米粒子膏凝聚的作用，会引起所谓因此作用而产生的凝聚体首先会被烧结的现象。因此，纳米级别中活性度高的金属微粒子会变大到微米级别，由此活性度下降，作为电子元件电极使用Al或Al合金的情况下，由于与电子元件电极上的Al的氧化物膜的反应性下降了，所以无法得到充分的键合性。
另一方面，在本发明相关的电子元件的制造方法中，以在涂敷在至少表面由Al或Al合金形成的第1电极上的金属纳米粒子膏的周围保持规定的空间的状态，通过以可去除金属纳米粒子膏中所含的分散剂和有机溶剂的温度以上、低于上述金属纳米粒子的熔点的温度进行加热，烧结上述金属纳米粒子，来使上述第2电极键合在第1电极上。
在此，在金属纳米粒子膏的周围保持规定的空间的状态是指第1电极以外或配设用于不使涂敷的金属纳米粒子膏扩宽浸润的堤墙部的时候，金属纳米粒子膏不粘合第1电极和堤墙部以外的任何一个，上述以外的金属纳米粒子膏的周围成为开放状态的状态。
通过以在此状态下能够去除金属纳米粒子膏中所含的分散剂和有机溶剂的温度以上、低于金属纳米粒子的熔点的温度进行加热，就能够充分分解去除金属纳米粒子膏中所含的分散剂、有机溶剂等有机成分，膏中的金属纳米粒子能够维持最初的大小。即使在金属纳米粒子活性度极其高、使用Al或Al合金作为电子元件电极的情况下，也与电子元件电极上的Al氧化物膜反应，容易形成金属纳米粒子的构成元素和Al的合金层。在此合金层中，为了具有相反倾向的浓度梯度而使Al和金属纳米粒子的构成元素相互扩散，由于表现出对Al氧化物及金属纳米粒子烧结体双方都良好的键合性，所以能够牢固地使二者键合。
因此，不预先去除至少表面由Al或Al合金形成的电子元件电极上的Al氧化物膜也能够具有足够的键合强度键合金属纳米粒子烧结体，即使在与基板电极的键合时也能够得到键合可靠性及导电性高的电子元件。
此外，虽然根据上述制造方法能够使用金属纳米粒子膏作为有用的键合材料，但另一方面金属纳米粒子膏也可用作基板电极/布线的形成材料。由此，作为供应金属膏的装置，就能够共用电极/布线形成工序中使用的设备。由于这样的设备共用，在简化工序、抑制设备开发费的同时，还能够解决所谓基板制造工序中的电极间隔设计规则和安装工序中的电极间隔设计规则乖离的问题。
此外，如权利要求6，在权利要求5所述的电子元件的制造方法的第2工序中，通过使涂敷在上述第1电极上的上述金属纳米粒子膏的涂敷厚度为0.1μm以上，就能够充分地确保成为键合部的金属纳米粒子膏烧结体的厚度，此外，通过使涂敷厚度为20μm以上，即使改变金属纳米粒子膏的分散剂成分也能够充分地分解去除分散剂和有机溶剂，能够确保稳定、键合可靠性，所以进行优选。
此外，如权利要求7，在权利要求5所述的电子元件的制造方法的第2工序中，通过使涂敷在上述第1电极上的上述金属纳米粒子膏的涂敷厚度为15μm以下，即使改变金属纳米粒子膏的分散剂成分也能够进一步确实地分解去除分散剂和有机溶剂，能够进一步提高键合可靠性，因此优选。
此外，如权利要求8，在权利要求5～7所述的电子元件的制造方法的第3工序中，由于通过在含有大气中所含有的量以上的氧的环境中进行加热，能够充分分解去除金属纳米粒子膏中所含的分散剂、有机溶剂等有机成分，所以进行优选。
此外，如权利要求9，在向第1电子元件的电极和第2电子元件的电极之间提供膏状的键合材料后，通过硬化上述膏状的键合材料来形成上述第1电子元件的电极和上述第2电子元件的电极的键合部的电子元件装置的制造方法中，在上述第1电子元件和上述第2电子元件的至少一个的制造方法是权利要求5～8所述的电子元件的制造方法，并且通过上述第1～第3工序来形成该电子元件的由上述键合部键合的电极的情况下，即使第1电子元件的电极和第2电子元件的至少一个因氧化膜的插入而键合性容易产生问题，具有至少表面由Al或Al合金形成的电极，也能够得到第1电子元件的电极和第2电子元件的电极之间的可靠性及导电性高的电子元件装置。
此外，如权利要求10，在权利要求9所述的电子元件装置的制造方法中，在使上述第1电子元件的电极和上述第2电子元件的电极相面对的状态下，形成上述第1电子元件的电极和上述第2电子元件的电极的键合部的情况下，由于通过上述权利要求5～8所述的电子元件的制造方法来制造上述第1电子元件或上述第2电子元件的至少一个，所以即使在当提高电子元件的每单位面积的电极数实现高密度安装、安置面积缩小时，必须形成微细的连接部的情况下，也能确保充分的键合可靠性。
附图说明
图1是表示本发明相关的电子元件装置的一例的剖面图。
图2是表示本发明相关的电子元件装置的制造工序的一例的示意图。
图3是表示图2(b)的阶段中的电子元件电极和金属纳米粒子烧结体的键合部的详细的区域结构的剖面图。
图4是表示图2(e)的阶段中的电子元件电极和基板电极之间的详细的区域结构的剖面图。
图5是表示电子元件电极和金属纳米粒子烧结体的键合界面的TEM观察结果的照片。
图6是表示通过EDX对图5的键合界面附近进行组成分析的结果的曲线图。
图7是表示电子元件电极和金属纳米粒子烧结体的键合界面的SIM观察结果的照片。
图8是表示涉及欧姆连接率的金属纳米粒子膏的涂敷厚度的影响的曲线图。
图9是表示本发明相关的电子元件装置的另一个例子的剖面图。
图10是表示本发明相关的电子元件装置的另一个例子的剖面图。
图11是表示本发明相关的电子元件装置的另一个例子的剖面图。
图12是表示金属纳米粒子膏的结构的示意图。
图13是表示现有的电子元件装置的一例的剖面图。
图14是表示现有的电子元件装置的制造工序的一例的示意图。
图15是表示图14(c)阶段中的电子元件电极和基板电极之间的详细区域结构的剖面图。
符号说明
1  电子元件装置(倒装芯片安装结构)
2、14、20、205  电子元件
3、15、21、206  电子元件电极(Al或Al合金)
4、16、207  钝化膜
4′、16′、207′  堤墙部
5、10、204  涂敷后的金属纳米粒子膏
6、11、17、22、30、208  金属纳米粒子烧结体
7、18、23、201  基板
8、19、202  基板电极
9、203  抗蚀剂膜
9′、203′  堤墙部
12、209  Al氧化物膜
13  Al和金属纳米粒子的构成元素的合金层
24  基板电极(Al或Al合金)
25  第1层基板
26  第2层基板
27  第3层基板
28、29  内部电极(Al或Al合金)
31、32  电子元件
33  连接部
100  电子元件装置(面向上的裸芯片安装结构)
110  电子元件装置(芯片元件安装结构)
120  电子元件装置(多层基板结构)
300  金属纳米粒子膏
301  金属纳米粒子
302  分散剂
303  分散溶剂(有机溶剂)
具体实施方式
以下根据图1～图6，详细地说明本发明相关的电子元件、电子元件装置的实施方式以及其制造方法。
作为本发明相关的电子元件及电子元件装置的示意图，在图1中示出其剖面图。
此电子元件装置1是在基板7上所谓倒装芯片安装了电子元件2的装置。说明电子元件装置1的结构，在电子元件2上配设由Al或Al合金形成的电子元件电极3、钝化膜4、在将钝化膜4的一部分搭在电子元件电极3上形成的堤墙部4′。另一方面，在基板7上配设用于获得与电子元件2电导通的基板电极8、抗蚀剂膜9、将抗蚀剂膜9的一部分搭在基板电极8上形成的堤墙部9′。堤墙部4′及9′是为了在后述的电子元件的制造工序时不使金属纳米粒子膏浸润扩宽而设置的，并不是不可缺少的。此外，在此实施方式中，虽然是将钝化膜4及抗蚀剂膜9的一部分分别搭在电子元件电极3及基板电极8上形成堤墙部，但也可通过不同的构成部件另外形成堤墙部。
利用平均粒径1～100nm的金属纳米粒子烧结体11键合上述电子元件电极3和基板电极8。图4中示出了电子元件电极3和金属纳米粒子烧结体11的键合界面的详细区域结构。即，上述键合界面具有从电子元件电极3侧向金属纳米粒子烧结体11侧，以(a)主成分为Al的第1层3→(b)主成分为Al氧化物膜的第2层→12(c)主成分为Al和金属纳米粒子的构成元素的合金的第3层13→(d)主成分为金属纳米粒子的构成元素的第4层11的顺序排列的多层结构。
图5及图6中示出了通过组成分析明确上述多层结构的结果的一例。图5是TEM(透过型电子显微镜)观察电子元件电极3和金属纳米粒子烧结体11的键合界面的结果，图6是沿图5的A-A线上通过EDX(能量分散型X线微量分析仪)进行组成分析的结果。再有，此例中，作为电子元件电极3的材质使用Al，作为金属纳米粒子使用Ag纳米粒子。
参照图5，作为电子元件电极虽然可识别出由Al形成的第1层、由Al氧化物膜12形成的第2层、由Ag纳米粒子烧结体形成的第4层，但不能识别由Al和Ag的合金形成的第3层。另一方面，在图6的组成分析中，能够在由Al氧化物膜形成的第2层和由Ag纳米粒子烧结体形成的第4层之间明了地识别出由Al和Ag的合金形成的第3层。
在此，由Al和Ag的合金形成的第3层，具有从Al氧化物膜侧向Ag纳米粒子烧结体侧Al浓度降低、与此相应Ag浓度增加这样的浓度梯度。即，由于由Al和Ag的合金形成的第3层，对于由Al氧化物层形成的第2层及由Ag纳米粒子烧结体形成的第4层双方都表现出良好的键合性，所以能够牢固地使两二者键合。
接着，作为本发明相关的电子元件及电子元件装置的制造方法的一例，在图2中示出了示意性地表示图1所示的通过倒装芯片安装的电子元件装置的制造工序。
首先，如图2(a)所示，使用分配器等在电子元件2的由Al或Al合金形成的电子元件电极3上涂敷金属纳米粒子膏5。此时，也可以在电子元件2上设置钝化膜4、堤墙部4′。如上所述，由于用Al氧化膜12覆盖电子元件电极3的表面，所以实际中，隔着Al氧化膜12就在电子元件电极3上涂敷金属纳米粒子膏5。
接着，在图2(a)中，以在金属纳米粒子膏的周围保持规定的空间的状态，即以在电子元件电极3和堤墙部4′以外的任何之处都不接触金属纳米粒子膏5、上述以外的金属纳米粒子膏的周围成为开放状态的状态，通过以能够去除金属纳米粒子膏5中所含的分散剂和有机溶剂的温度以上、低于金属纳米粒子的熔点的温度进行加热，就如图2(b)所示，将金属纳米粒子烧结体6键合在电子元件电极3上。
由于通过以在金属纳米粒子膏5的周围保持规定的空间的状态下进行加热，可充分分解去除金属纳米粒子膏5中的有机成分，能够维持金属纳米粒子最初的大小，所以活性度极高的金属纳米粒子与电子元件电极3上的Al氧化物膜12反应，能够容易地形成金属纳米粒子的构成元素和Al的合金层13。
即，此阶段中，如图3所示，虽然电子元件电极3和金属纳米粒子烧结体6夹持Al氧化物膜12，但通过金属纳米粒子的构成元素和Al的合金层13也会牢固地键合，即使在以后与基板电极键合时，也能够得到键合可靠性及导电性高的电子元件。
接着，如图2(c)所示，使用分配器在基板7的基板电极8上涂敷金属纳米粒子膏10。此时，也可以在基板7上设置抗蚀剂膜9、堤墙9′。再有，在此实施方式中，虽然在基板电极8侧也涂敷金属纳米粒子膏10作为键合材料，但在不使用Al或Al合金作为基板电极8的材质的情况下，由于在表面上未形成氧化膜，或键合材料不必为高活性度，所以通常也可以使用例如焊料膏、导电性粘合剂等，金属纳米粒子膏以外的键合材料。
接着，如图2(d)所示，使在图2(b)工序中制备的电子元件2上下反转，相对于在图2(c)工序中制备的基板7进行位置对准。
接着，如图2(e)所示，使位置对准了的电子元件2和基板7重叠以使得电子元件电极3和基板电极8相面对，在此状态下进行加热，烧结金属纳米粒子膏10，形成键合电子元件电极3和基板电极8的键合部(金属纳米粒子烧结体11)。
即在此阶段中，如图4所示，虽然电子元件电极3和基板电极8夹持Al氧化物膜12但通过金属纳米粒子的构成元素和Al的合金层13也会牢固地键合，能够得到键合可靠性及导电性高的电子元件装置。
以下说明本发明中的进一步的具体实施例。
实施例1
此实施例是基于上述图1所示的倒装芯片安装的电子元件装置，作为在电子元件装置1中使用的电子元件2，使用Si类的小型半导体元件。在其下面配设的电子元件电极3由Al形成，电极厚度被形成为约0.5～2.0μm。此外，在电子元件电极3的表面自然地存在约5～10nm厚的Al氧化膜12。在电子元件2上配设由SiN形成的钝化膜4。对与钝化膜4的电子元件电极3对应的部位进行开口，通过将钝化膜4的一部分搭在电子元件电极3上而在此开口部的周围形成用于防止后述的金属纳米粒子膏的扩宽的堤墙部4′。
作为基板7，使用采用可低温焙烧的氧化铝类材料的陶瓷基板。在基板7的上面，在搭载电子元件2的位置配设多个基板电极8，在基板7的上面的几乎一整面地配设由聚酰亚胺类树脂形成的抗蚀剂膜9。对与抗蚀剂膜9的基板电极8对应的部位进行开口，通过将抗蚀剂膜9的一部分搭在基板电极8上而在开口部的周围形成用于防止后述的金属纳米粒子膏的扩宽的堤墙部9′。
基板电极8为Cu/Ni/Au的多层结构。形成基板电极8的布线宽度为约10～150μm，布线厚度为约5～50μm。再有，虽然未图示，但在基板上设置用于搭载另一表面安装元件等的不同的基板电极。
作为金属纳米粒子膏，使用含约75重量％的平均粒径5nm左右的Ag的Harima(ハリマ)化成株式会社制的Ag纳米粒子膏。使用分配器在电子元件电极3上涂敷涂敷厚度约15μm左右的此Ag纳米粒子膏。
如此这样，在加热温度100～300℃、加热时间1～60min、加热环境为大气中这样的条件下使用热风循环型干燥箱加热涂敷了Ag纳米粒子膏的电子元件2，烧结Ag纳米粒子膏。
在图7中示出了在此阶段中的电子元件电极3和Ag纳米粒子烧结体6的键合界面的SIM(扫描型离子显微镜)的观察结果。如图7所表明的，电子元件电极3和Ag纳米粒子烧结体6牢固地键合。
此外，还基于电导通的观点评价键合性。图8示出了向电子元件电极3上涂敷的金属纳米粒子膏5的厚度对欧姆连接率的影响。进行此评价时，使用分散剂的不同的2种Ag纳米粒子膏。在此，欧姆连接率是在电子元件电极3和基板电极8之间测量电流-电压特性时，得到欧姆连接(欧姆定律成立)的概率，如果欧姆连接率高的话，则表示电子元件电极3和金属纳米粒子烧结体6牢固地键合。
参照图8时可知，即使使用任意的Ag纳米粒子膏，通过使涂敷厚度为20μm以下，欧姆连接率也为实用上无问题的级别即80％以上，通过使涂敷厚度为15μm以下，为表现出极其良好的键合性的100％。基于此情况，为了即使使用各种金属纳米粒子膏也能得到稳定的键合可靠性，优选金属纳米粒子膏的涂敷厚度为20μm以下，进一步优选为15μm以下。
在此，金属纳米粒子膏的涂敷厚度变薄时容易得到牢固的键合是因为当涂敷厚度变薄时，有每单位时间/单位体积的分散剂的燃烧气体排气和向键合界面附近供给氧的量增加的倾向。
当燃烧气体排气和向键合界面附近提供的氧的量增加时，则每单位时间的分散剂的分解/去除率上升，金属纳米粒子就会与仍旧维持活性表面(金属纳米粒子的表面原来是极其活性的、不能利用分散剂进行活性化)的Al氧化膜12的表面接触。其结果，金属纳米粒子的构成元素和存在于电子元件电极3的表面上的Al氧化膜中的Al进行反应，形成金属纳米粒子的构成元素和Al的合金层13。
接着，在基板7的基板电极8上通过倒装芯片安装键合电子元件2和基板7，却以足够的量以上涂敷不足连接相邻的各个电极的量的Ag纳米粒子膏10。
接着，使在由Al形成的电极3上键合了Ag纳米粒子烧结体6的电子元件2上下反转，相对于在基板电极8上涂敷了规定量的Ag纳米粒子膏10的基板7进行位置对准。
接着，使电子元件电极3和基板电极8相对地位置对准了的电子元件2和基板7重叠，在此状态下按加热温度100～300℃、加热时间1～60min、加热环境为大气中这样的条件，使用回流炉进行加热，烧结Ag纳米粒子膏10，形成键合电子元件电极3和基板电极8的键合部(Ag纳米粒子烧结体11)。
再有，此实施例所示的电子元件、电子元件装置的实施方式以及其制造方法是一个例子，在此之外，如果是本发明的内容的范围内，则可以进行各种的变形。
例如，作为电子元件2使用Si类以外的GaAs类半导体、表面弹性波元件等也能构成电子元件装置1。
此外，配设在电子元件2上的钝化膜4及配设在基板7上的抗蚀剂膜9，是按照要求设置的，不是不可缺少的。同样地，在金属纳米粒子膏难以浸润扩宽的电子元件及基板材质的情况下，也可以不形成堤墙部4′及9′。
此外，电子元件电极3可使用含90重量％以上的Al这样的Al-1Cu、Al-1Si、Al-Si-0.5Cu等。此外，即使在电子元件电极3的至少表面是Al或Al合金的情况下，即在形成Au、Cu的凸起后，通过溅射或蒸发等方法形成膜状Al或上述这样的Al合金的情况下，由于在其表面上存在Al氧化膜，所以也能有效地应用本发明。基板电极8既可以使用Au、Ag、Cu等作为单层结构，也可以形成为通路结构。
此外，作为金属纳米粒子，除Ag纳米粒子以外可以使用Ag-Pd合金等Ag纳米粒子、Au纳米粒子或Cu纳米粒子等。例如，在Ag中使用添加了15重量％左右的Pd的Ag-Pd合金纳米粒子的情况下，能够根据电子元件装置的使用环境有效地抑制有可能产生的Ag迁移。
此外，金属纳米粒子膏的涂敷能够使用喷墨装置、丝网印刷或转印等适合电极面积的方法来进行。特别地，在进行微量的金属纳米粒子膏的涂敷时，优选使用可高精度地控制吐出量的微量分析仪、喷墨装置。
此外，在烧结金属纳米粒子膏时，优选在充分分解去除金属纳米粒子膏中所含的分散剂、有机溶剂等有机成分却有足够的氧被提供的状态下，即在含有大气中所含的量以上的氧的环境中进行加热。作为加热装置，运用红外线加热炉、热板、或回流焊炉等进行，能够使用适应电子元件的形态、处理数量的装置。
此外，在此实施例中，虽然在基板7的基板电极8侧通过倒装芯片安装键合电子元件2和基板7，却以足够的量以上、涂敷不足连接相邻的各个电极的量的Ag纳米粒子膏10，但也可以涂敷在电子元件电极3侧、或基板电极8侧和电子元件电极3侧双方。
此外，电子元件2及基板7不是以各自单片的状态键合，而以分割前的晶片状态及集合基板状态键合，此后进行分割成为电子元件装置1也是可以的。通过这样能够提高生产性。
此外，也可以追加在制造出的电子元件装置1的电子元件2和基板7之间填充底层填料树脂，进行硬化的工序。通过追加此工序，本发明的电子元件装置1能够降低实际使用时在连接部产生的变形(电子元件2和基板7的线膨胀系数差引起的变形)，能够进一步提高耐环境性能。作为电子元件2，在使用集合基板作为分割前的基板7的情况下，也可以设置键合、填充树脂后，将电子元件装置1分离为单片的工序。
实施例2
图9中示出了本发明的另一实施例。此实施例是面向上基板安装裸芯片的结构的电子元件装置，作为在电子元件装置100中使用的电子元件14，使用Si半导体元件。在电子元件14的上面配设电子元件15和钝化膜16，以将钝化膜16的一部分搭在电子元件电极15上的形式形成堤墙部16′。
此外，基板18可使用采用可低温焙烧的陶瓷类材料的陶瓷基板。在基板18的上面配设成为Cu/Ni/Au的多层结构的基板电极19，通过Ag纳米粒子烧结体17与电子元件电极15电导通。
在此，电子元件电极15由Al形成，其表面被Al氧化膜12覆盖，在与Ag纳米粒子烧结体17的键合界面形成Ag和Al的合金层13，从电子元件电极15侧向Ag纳米粒子烧结体17侧具有图6所示的多层结构。
替代实施例1中的倒装芯片，将面向上预先键合Ag纳米粒子烧结体的电子元件14装载在基板18上后，以与实施例1相同的加热条件等就制造此电子元件装置100。
实施例3
图10中示出了本发明的另一实施例。此实施例是基板安装无源元件的结构的电子元件装置，作为在电子元件装置110中使用的电子元件20，使用采用BaTiO3类介质材料的叠层陶瓷电容器。在电子元件20的两端部配设在由Cu烧结体形成的基底电极之上实施Ni/Sn电镀的电极21。
此外，基板23使用采用玻璃环氧的复合材料基板。在基板23的上面配设成为Al的单层结构的基板电极24，通过Ag纳米粒子烧结体22与电子元件电极21电导通。
此实施例的情况下，由于基板电极24的表面被Al氧化膜12覆盖，所以在基板电极24上涂敷Ag纳米粒子膏，在基板电极24侧形成Ag和Al的合金层13和Ag纳米粒子烧结体。因此，从基板电极24侧向Ag纳米粒子烧结体22侧具有图6所示的多层结构。
通过芯片安装等向预先键合Ag纳米粒子烧结体的基板23上装载电子元件20后，以与实施例1相同的加热条件等就能制造此电子元件装置110。
实施例4
图11中示出了本发明的再另一实施例。此实施例是多层基板结构的电子元件装置，在电子元件装置120中含有第1层基板25、第2层基板26及第3层基板27。在第1层基板25中内包有由Al形成的内部电极28和叠层陶瓷电容器等电子元件31，此外，在第3层基板27中内包有与第1层相同的由Al形成的内部电极29和叠层陶瓷电容器等电子元件31。通过硬化了形成在第2层中的通孔中的导电膏的连接部连接内部电极28和29。作为多层基板的材料，可使用在环氧树脂中混合了二氧化铝等无机物质的填充料的复合材料。
此实施例中，由于内部电极28和29的表面被Al氧化膜12覆盖，所以在内部电极28、29上涂敷Ag纳米粒子膏，形成Ag和Al的合金层13和Ag纳米粒子烧结体30。因此，从内部电极28、29侧向Ag纳米粒子烧结体30侧具有图6所示的多层结构。
作为多层基板的制造方法，首先，预先布图形成内部电极28和29，在其上分别安装电子元件31和32后，按压预浸料状的多层基板材料，使内部电极28、29及电子元件31、32内包在预浸料中。
接着，在规定的条件下硬化预浸料后，在内部电极的露出面侧涂敷Ag纳米粒子膏，以与实施例1相同的加热条件进行烧结，由此制作键合了Ag纳米粒子烧结体的第1层基板25和第3层基板27。
接着，在第2层预浸料中开设出通孔，填充热硬化性导电膏后，在第1层基板25和第3层基板27之间插入成为第2层基板26的预浸料，进行位置对准并重叠后加以加热键合。

Claims (10)

1、一种电子元件，具有：电子元件本体以及电极，该电极包含至少表面由Al或Al合金形成的第1电极、和在上述第1电极上键合的由金属纳米粒子的烧结体形成的第2电极；其特征在于，
上述第1电极和第2电极的键合界面具有从上述第1电极侧向上述第2电极侧，按以下顺序排列的多层结构：
(a)主成分为Al的第1层，
(b)主成分为Al氧化物的第2层，
(c)主成分为Al和金属纳米粒子的构成元素的合金的第3层，
(d)主成分为金属纳米粒子的构成元素的第4层。
2、根据权利要求1所述的电子元件，其特征在于，上述金属纳米粒子由Ag或Ag合金形成。
3、一种电子元件装置，通过键合部电连接第1电子元件的电极和第2电子元件的电极，其特征在于，
上述第1电子元件和上述第2电子元件的至少一个是权利要求1或2所述的电子元件，并且，该电子元件的通过上述键合部电连接的电极包含上述第1电极和上述第2电极，上述第1电极和上述第2电极的键合界面具有上述多层结构。
4、根据权利要求3所述的电子元件装置，其特征在于，以相面对的状态连接上述第1电子元件的电极和上述第2电子元件的电极。
5、一种电子元件的制造方法，该电子元件具有电子元件本体以及电极，该电极包含至少表面由Al或Al合金形成的第1电极、和在上述第1电极上键合的由金属纳米粒子的烧结体形成的第2电极；
该制造方法的特征在于，包括：
第1工序，在上述电子元件本体上形成上述第1电极，
第2工序，在上述第1电极上涂敷含平均粒径1～100nm的金属纳米粒子、分散剂、有机溶剂的金属纳米粒子膏，
第3工序，在涂敷在上述第1电极上的上述金属纳米粒子膏的周围保持规定空间的状态下，通过以可去除上述金属纳米粒子膏中所含的分散剂和有机溶剂的温度以上，且低于上述金属纳米粒子的熔点的温度进行加热，烧结上述金属纳米粒子，来使上述第2电极键合在上述第1电极上，形成上述电极。
6、根据权利要求5所述的电子元件的制造方法，其特征在于，
在上述第2工序中，涂敷在上述第1电极上的上述金属纳米粒子膏的涂敷厚度为0.1～20μm。
7、根据权利要求5所述的电子元件的制造方法，其特征在于，
在上述第2工序中，涂敷在上述第1电极上的上述金属纳米粒子膏的涂敷厚度为0.1～15μm。
8、根据权利要求5～7所述的电子元件的制造方法，其特征在于，
在上述第3工序中，在含有大气中所含的量以上的氧气的环境中进行加热。
9、一种电子元件装置的制造方法，在第1电子元件的电极和第2电子元件的电极之间涂敷膏状的键合材料后，通过硬化上述膏状的键合材料来形成上述第1电子元件的电极和上述第2电子元件的电极的键合部，其特征在于，
上述第1电子元件和上述第2电子元件的至少一个的制造方法是权利要求5～8所述的电子元件的制造方法，并且通过上述第1～第3工序来形成该电子元件的由上述键合部键合的电极。
10、根据权利要求9所述的电子元件装置的制造方法，其特征在于，
在使上述第1电子元件的电极和上述第2电子元件的电极相面对的状态下，形成上述第1电子元件的电极和上述第2电子元件的电极的键合部。
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