CN114502301A - 接合用铜糊料、接合体的制造方法及接合体 - Google Patents
接合用铜糊料、接合体的制造方法及接合体 Download PDFInfo
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- CN114502301A CN114502301A CN201980100833.6A CN201980100833A CN114502301A CN 114502301 A CN114502301 A CN 114502301A CN 201980100833 A CN201980100833 A CN 201980100833A CN 114502301 A CN114502301 A CN 114502301A
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- copper
- copper paste
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Abstract
接合用铜糊料含有金属粒子和分散介质,作为金属粒子包含铜粒子,作为分散介质包含二氢松油醇。接合体的制造方法为具备第1构件、第2构件及接合第1构件和第2构件的接合部的接合体的制造方法,具备:第1工序,在第1构件及第2构件中的至少一者的接合面上印刷上述接合用铜糊料,并准备具有依次层叠第1构件、接合用铜糊料、第2构件的层叠结构的层叠体;第2工序,对层叠体的接合用铜糊料进行烧结。
Description
技术领域
本发明涉及一种接合用铜糊料、接合体的制造方法及接合体。
背景技术
在制造半导体装置时,为了使半导体元件与引线框等(支撑构件)接合,使用各种接合材料。在半导体装置中,在150℃以上的高温下工作的功率半导体、LSI等的接合中,作为接合材料使用高熔点铅钎料。近年来,随着半导体元件的高容量化及省空间化,工作温度上升至高熔点铅钎料的熔点附近,变得难以确保连接可靠性。另一方面,随着RoHS管制强化,需要不含铅的接合材料。
在此之前,也研究了使用铅钎料以外的材料的半导体元件的接合。例如,在下述专利文献1中,作为用于接合半导体元件和电极的接合材料,公开了包含平均粒径为1nm~50μm的氧化铜粒子及还原剂的接合材料。并且,在下述专利文献2中,公开了含有铜纳米粒子、铜微米粒子或铜亚微米粒子、或者它们两者的接合材料。
以往技术文献
专利文献
专利文献1:日本专利第5006081号
专利文献2:日本特开2014-167145号公报
发明内容
发明要解决的技术课题
考虑到半导体装置的制造中的批量生产工艺,要求接合材料具有适合于基于丝网印刷机等自动印刷机的印刷工艺的印刷性。通常,将金属粒子分散到分散介质中的糊料通过配合有机溶剂等分散介质而低粘度化,能够提高印刷性。但是,在包含铜粒子的糊料的情况下,若粒子浓度过低,则难以获得足够的接合强度等可能会对接合性产生影响,兼顾在自动印刷中的印刷条件下能够没有模糊或缺陷地进行印刷的印刷性和接合性并不一定容易。
本发明是鉴于上述情况而完成的,其目的在于提供一种能够维持足够的接合性的同时提高印刷性的接合用铜糊料、以及使用该接合用铜糊料接合体的制造方法及接合体。
用于解决技术课题的手段
本发明的一方面涉及一种接合用铜糊料,其含有金属粒子和分散介质,作为金属粒子包含铜粒子,作为分散介质包含二氢松油醇。
上述接合用铜糊料通过具有上述结构,能够维持足够的接合性的同时提高印刷性。根据上述接合用铜糊料,通过使用丝网印刷机等自动印刷机的批量生产工艺能够高效率地制造接合体。
虽然获得这种效果的原因尚不清楚,但可认为,由于二氢松油醇与铜粒子的亲和性优异,因此铜粒子的分散性提高,能够在足够的铜粒子浓度下降低粘度,而能够兼顾印刷性和接合性。并且,本发明人等推测,由于二氢松油醇能够提高糊料的触变性,因此以高水准兼顾印刷时的流动性和印刷后的糊料的形状保持力也是可获得上述效果的主要原因之一。
上述接合用铜糊料中,以接合用铜糊料总量为基准,金属粒子的含量可以是85~98质量%。在这种情况下,容易确保接合强度,并容易应对接合的构件的大小(例如,半导体元件的尺寸)增大的情况。
上述接合用铜糊料作为分散介质能够还包含沸点为300℃以上的化合物。在这种情况下,直到即将开始烧结之前,对接合用铜糊料赋予可塑性和密合性,在无加压下的接合变得容易。
上述接合用铜糊料在25℃下的粘度可以是100~200Pa·s。在这种情况下,对自动印刷机的适合性进一步提高。
以金属粒子的总质量为基准,铜粒子的含量可以是80~100质量%。
上述接合用铜糊料可以是丝网印刷用。
另外,在本说明书中,丝网印刷也称为钢板印刷,是指在具有孔(开口)的版上刮擦糊料的印刷方式。对于刮刀及刮板等并无特别限制,能够适当地应用公知的刮刀及刮板。
接合用铜糊料作为所述铜粒子,包含体积平均粒径为0.12~0.8μm的亚微米铜粒子及最大直径为2~50μm且纵横比为3.0以上的片状微米铜粒子。在这种情况下,适合于在无加压下的接合。
另外,在本说明书中,无加压是指接合用铜糊料只承受接合的构件的重量(即,不承受除构件的重量以外的压力)、或除了其重量以外还承受0.01MPa以下的微压力的状态。
以铜粒子的总质量为基准,接合用铜糊料中的上述亚微米铜离子的含量可以是30~90质量%,以铜粒子的总质量为基准,上述微米铜粒子的含量可以是10~70质量%。
接合用铜糊料可以是无加压接合用。
本发明的另一方面涉及一种接合体的制造方法,所述接合体具备第1构件、第2构件及接合第1构件和第2构件的接合部,所述接合体的制造方法具备:第1工序,在第1构件及第2构件中的至少一者的接合面上印刷上述接合用铜糊料,并准备具有依次层叠有第1构件、接合用铜糊料及第2构件的层叠结构的层叠体;第2工序,对层叠体的接合用铜糊料进行烧结。根据该制造方法,通过使用上述接合用铜糊料,能够兼顾印刷性和接合性,并且能够高效率地制造接合体。
上述印刷可以是丝网印刷。
在上述第2工序中,可以对接合用铜糊料在无加压下进行加热并烧结。在这种情况下,能够通过无加压接合而减少对接合的构件的损坏。
上述第1构件及第2构件中的至少一者可以是半导体元件。在这种情况下,作为接合体能够获得半导体装置。
本发明的另一方面涉及一种接合体,其具备第1构件、第2构件及接合第1构件和第2构件的接合部,接合部由上述接合用铜糊料的烧结体构成。
上述第1构件及第2构件中的至少一者可以是半导体元件。即,接合体可以是半导体装置。
发明效果
根据本发明,能够提供一种能够维持足够的接合性的同时提高印刷性的接合用铜糊料、以及使用该接合用铜糊料接合体的制造方法及接合体。
附图说明
图1是用于说明丝网印刷的示意图。
图2是表示使用本实施方式的接合用铜糊料制造的接合体的一例的示意剖视图。
图3是表示使用本实施方式的接合用铜糊料制造的半导体装置的一例的示意剖视图。
图4是用于说明图2所示的接合体的制造方法的示意剖视图。
图5是用于说明图3所示的半导体装置的制造方法的示意剖视图。
图6是表示使用本实施方式的接合用铜糊料制造的接合体的一例的示意剖视图。
图7是用于说明图6所示的接合体的制造方法的示意剖视图。
图8是表示使用本实施方式的接合用铜糊料制造的接合体的一例的示意剖视图。
图9是用于说明图8所示的接合体的制造方法的示意剖视图。
具体实施方式
首先,对本实施方式的接合用铜糊料的详细情况进行说明。
<接合用铜糊料>
本实施方式的接合用铜糊料含有金属粒子和分散介质,作为金属粒子包含铜粒子,作为分散介质包含二氢松油醇。另外,在本说明书中,为了方便,多个铜粒子的集合也称为“铜粒子”。对于除铜粒子以外的金属粒子也相同。
(铜粒子)
作为铜粒子,可以举出亚微米铜粒子、微米铜粒子及除这些以外的铜粒子。
[亚微米铜粒子]
亚微米铜粒子为具有0.01μm以上且小于1.00μm的粒径的铜粒子。亚微米铜粒子优选在150℃以上且300℃以下的温度范围内具有烧结性。亚微米铜粒子优选包含粒径为0.01~0.80μm的铜粒子。亚微米铜粒子可以包含10质量%以上的粒径为0.01~0.80μm的铜粒子,也可以包含20质量%以上,也可以包含30质量%以上,也可以包含100质量%。铜粒子的粒径例如能够由SEM图像算出。利用刮铲将铜粒子的粉末载置于SEM用碳带上,制作SEM用样品。利用SEM装置以5000倍对该SEM用样品进行观察。利用图像处理软件对外接于该SEM图像的铜粒子的四边形进行作图,将其一边作为该粒子的粒径。
亚微米铜粒子的体积平均粒径优选为0.01~0.80μm。若亚微米铜粒子的体积平均粒径为0.01μm以上,容易获得抑制亚微米铜粒子的合成成本、分散性良好、抑制表面处理剂的使用量等效果。若亚微米铜粒子的体积平均粒径为0.80μm以下,则容易获得亚微米铜粒子的烧结性优异的效果。从更进一步发挥上述效果的观点考虑,亚微米铜粒子的体积平均粒径可以为0.02μm以上、0.05μm以上、0.10μm以上、0.11μm以上、0.12μm以上、0.15μm以上、0.2μm以上或0.3μm以上。并且,从更进一步发挥上述效果的观点考虑,亚微米铜粒子的体积平均粒径可以为0.60μm以下、0.50μm以下、0.45μm以下或0.40μm以下。亚微米铜粒子的体积平均粒径例如可以为0.01~0.60μm、0.01~0.50μm、0.02~0.80μm、0.05~0.80μm、0.10~0.80μm、0.11~0.80μm、0.12~0.80μm、0.15~0.80μm、0.15~0.60μm、0.20~0.50μm、0.30~0.45μm或0.30~0.40μm。
在本说明书中,体积平均粒径是指50%体积平均粒径。金属粒子(例如,铜粒子)的体积平均粒径例如能够通过以下方法来测定。首先,使用分散剂将作为原料的金属粒子或从金属糊料中去除挥发成分而获得的干燥金属粒子分散于分散介质中。接着,用光散射法粒度分布测定装置(例如,岛津纳米粒径分布测定装置(SALD-7500nano、ShimadzuCorporation制))测定所获得的分散体的体积平均粒径。在使用光散射法粒度分布测定装置的情况下,作为分散介质,能够使用己烷、甲苯、α-萜品醇、4-甲基-1,3-二氧戊环-2-酮等。
亚微米铜粒子的形状并无特别限定。作为亚微米铜粒子的形状,例如可以举出球状、块状、针状、柱状、片状、近似球状及它们的凝聚体。从分散性及填充性的观点考虑,亚微米铜粒子的形状可以是球状、近似球状或片状,从燃烧性、分散性、与片状微米粒子(例如,片状微米铜粒子)的混合性等的观点考虑,可以是球状或近似球状。在本说明书中,“片状”包含板状、鳞片状等平板状的形状。
从分散性、填充性及与片状的微米粒子(例如,片状的微米铜粒子)的混合性的观点考虑,亚微米铜粒子的纵横比可以为5.0以下,可以为3.0以下,可以为2.5以下,可以为2.0以下。在本说明书中,“纵横比”是指“粒子的长边/粒子的厚度”。粒子的长边及粒子的厚度例如能够由粒子的SEM图像求出。
从亚微米铜粒子的分散性的观点考虑,亚微米铜粒子可以用表面处理剂处理。表面处理剂例如可以通过氢键等吸附于亚微米铜粒子的表面,也可以与亚微米铜粒子反应而结合于亚微米铜粒子的表面。即,亚微米铜粒子可以具有源自特定的表面处理剂的化合物。表面处理剂包含于接合用铜糊料中所包含的有机化合物。
作为表面处理剂,例如可以举出碳原子数2~18的有机酸。作为碳原子数2~18的有机酸,例如可以举出乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、甲基庚酸、乙基己酸、丙基戊酸、壬酸、甲基辛酸、乙基庚酸、丙基己酸、癸酸、甲基壬酸、乙基辛酸、丙基庚酸、丁基己酸、十一烷酸、甲基癸酸、乙基壬酸、丙基辛酸、丁基庚酸、月桂酸、甲基十一烷酸、乙基癸酸、丙基壬酸、丁基辛酸、戊基庚酸、十三烷酸、甲基十二烷酸、乙基十一烷酸、丙基癸酸、丁基壬酸、戊基辛酸、肉豆蔻酸、甲基十三烷酸、乙基十二烷酸、丙基十一烷酸、丁基癸酸、戊基壬酸、己基辛酸、十五烷酸、甲基十四烷酸、乙基十三烷酸、丙基十二烷酸、丁基十一烷酸、戊基癸酸、己基壬酸、棕榈酸、甲基十五烷酸、乙基十四烷酸、丙基十三烷酸、丁基十二烷酸、戊基十一烷酸、己基癸酸、庚基壬酸、十七烷酸、十八烷酸、甲基环己烷羧酸、乙基环己烷羧酸、丙基环己烷羧酸、丁基环己烷羧酸、戊基环己烷羧酸、己基环己烷羧酸、庚基环己烷羧酸、辛基环己烷羧酸、壬基环己烷羧酸等饱和脂肪酸;辛烯酸、壬烯酸、甲基壬烯酸、癸烯酸、十一碳烯酸、十二碳烯酸、十三碳烯酸、十四碳烯酸、肉豆蔻脑酸、十五碳烯酸、十六碳烯酸、棕榈油酸、十六碳烯酸(sapienic acid)、油酸、异油酸、亚油酸(linolic acid)、亚麻仁油酸(1inoleic acid)、亚麻酸(linolenic acid)等不饱和脂肪酸;对苯二甲酸、均苯四酸、邻苯氧基苯甲酸、甲基苯甲酸、乙基苯甲酸、丙基苯甲酸、丁基苯甲酸、戊基苯甲酸、己基苯甲酸、庚基苯甲酸、辛基苯甲酸、壬基苯甲酸等芳香族羧酸。有机酸可以单独使用1种,也可以将2种以上组合使用。通过将这种有机酸与上述亚微米铜粒子组合,具有能够兼顾亚微米铜粒子的分散性和烧结时的有机酸的消去性的倾向。
从亚微米铜粒子的分散性的观点考虑,以表面处理后的亚微米铜粒子的总质量为基准,表面处理剂的处理量可以为0.07~2.10质量%、0.10~1.60质量%或0.20~1.10质量%。以表面处理后的亚微米铜粒子的总质量为基准,表面处理剂的处理量可以为0.07质量%以上、0.10质量%以上或0.20质量%以上。以表面处理后的亚微米铜粒子的总质量为基准,表面处理剂的处理量可以为2.10质量%以下、1.60质量%以下或1.10质量%以下。
表面处理剂的处理量可以是在亚微米铜粒子的表面上附着一分子层~三分子层的量。该处理量通过以下方法来测定。在大气中以700℃处理2小时的氧化铝制坩埚(例如,AS ONE Corporation制、型号:1-7745-07)中,量取经表面处理的亚微米铜粒子W1(g),在大气中以700℃烧制1小时。然后,在氢气中,在300℃下处理1小时,并测量坩埚内的铜粒子的质量W2(g)。接着,根据下述式,计算表面处理剂的处理量。
表面处理剂的处理量(质量%)=(W1-W2)/W1×100
作为亚微米铜粒子,能够使用市售品。作为包含市售的亚微米铜粒子的材料,例如可以举出CH-0200(MITSUI MINING&SMELTING CO.,LTD.制、体积平均粒径0.36μm)、HT-14(MITSUI MINING&SMELTING CO.,LTD.制、体积平均粒径0.41μm)、CT-500(MITSUI MINING&SMELTING CO.,LTD.制、体积平均粒径0.72μm)、Tn-Cu100(TAIYO NIPPON SANSOCORPORATION制、体积平均粒径0.12μm)及Cu-C-40(Fukuda Metal Foil&Powder Co.,Ltd.制、体积平均粒径0.2μm)。
以接合用铜糊料中所包含的铜粒子的总质量为基准,亚微米铜粒子的含量可以为30质量%以上、35质量%以上、40质量%以上或50质量%以上,也可以为90质量%以下或85质量%以下。并且,以接合用铜糊料中所包含的铜粒子的总质量为基准,亚微米铜粒子的含量可以为30~90质量%、35~90质量%、40~85质量%或50~85质量%。若亚微米铜粒子的含量在上述范围内,则容易确保对接合用铜糊料进行烧结而制造的接合体的接合强度。当将接合用铜糊料用于微型器件的接合时,微型器件倾向于显示出良好的芯片剪切强度及连接可靠性。
[微米铜粒子]
微米铜粒子为具有1μm以上且小于50μm的粒径的铜粒子。微米铜粒子优选包含粒径为2.0~50μm的铜粒子。微米铜粒子可以包含50质量%以上的粒径为2.0~50μm的铜粒子,也可以包含70质量%以上,也可以包含80质量%以上,也可以包含100质量%。
微米铜粒子的体积平均粒径优选为2.0~50μm。若微米铜粒子的体积平均粒径在上述范围内,则能够减少对接合用铜糊料进行烧结时的体积收缩、孔隙的产生等,容易确保对接合用铜糊料进行烧结而制造的接合体的接合强度。当将接合用铜糊料用于微型器件的接合时,微型器件倾向于显示出良好的芯片剪切强度及连接可靠性。从更进一步发挥上述效果的观点考虑,微米铜粒子的体积平均粒径可以为2.0~20μm、2.0~10μm、3.0~20μm或3.0~10μm。微米铜粒子的体积平均粒径可以为2.0μm以上或3.0μm以上。微米铜粒子的体积平均粒径可以为50μm以下、20μm以下或10μm以下。
微米铜粒子的形状并无特别限定。作为微米铜粒子的形状,例如可以举出球状、块状、针状、片状、近似球状及它们的凝聚体。其中,优选的微米铜粒子的形状为片状。微米铜粒子可以包含50质量%以上的片状微米铜粒子,也可以包含70质量%以上,也可以包含80质量%以上,也可以包含100质量%。
通过使用片状微米铜粒子,接合用铜糊料内的微米铜粒子相对于接合面大致平行的取向,能够抑制对接合用铜糊料进行烧结时的接合面方向的体积收缩,容易确保对接合用铜糊料进行烧结而制造的接合体的接合强度。当将接合用铜糊料用于微型器件的接合时,微型器件倾向于显示出良好的芯片剪切强度及连接可靠性。从更进一步发挥上述效果的观点考虑,片状微米铜粒子的纵横比优选为3.0以上,更优选为4.0以上,进一步优选为6.0以上。
片状微米铜粒子的最大直径及平均最大直径可以为2.0~50μm、3.0~50μm或3.0~20μm。片状微米铜粒子的最大直径及平均最大直径例如能够由粒子的SEM图像求出。片状微米铜粒子的最大直径及平均最大直径例如作为片状微米铜粒子的长径X及长径的平均值Xav求出。长径X在片状微米铜粒子的三维形状中是外切于片状微米铜粒子的平行二平面中、以该二平面间的距离达到最大的方式所选择的平行二平面的距离。
在微米铜粒子中,有无表面处理剂的处理并无特别限定。从分散稳定性及抗氧化性的观点考虑,微米铜粒子可以由表面处理剂处理。即,微米铜粒子可以具有源自表面处理剂的化合物。表面处理剂可以通过氢键等吸附于微米铜粒子的表面,也可以与微米铜粒子反应而结合于微米铜粒子的表面。
表面处理剂可以通过接合时的加热而被去除。作为这种表面处理剂,例如可以举出十二烷酸、棕榈酸、十七烷酸、硬脂酸、花生酸、亚油酸(linolic acid)、亚麻仁油酸(linoleic acid)、油酸等脂肪族羧酸;对苯二甲酸、均苯四酸、邻苯氧基苯甲酸等芳香族羧酸;鲸蜡醇、硬脂醇、异冰片基环己醇、四乙二醇等脂肪族醇;对苯基苯酚等芳香族醇;辛胺、十二烷基胺、硬脂胺等烷基胺;硬脂腈、癸腈等脂肪族腈;烷基烷氧基硅烷等硅烷偶联剂;聚乙二醇、聚乙烯醇、聚乙烯基吡咯烷酮、有机硅低聚物等高分子处理材料等。表面处理剂可以单独使用1种,也可以将2种以上组合使用。
作为微米铜粒子,能够使用市售品。作为包含市售的微米铜粒子的材料,例如可以举出1050YF(MITSUI MINING&SMELTING CO.,LTD.制、体积平均粒径1.7μm)、MA-C025KFD(MITSUI MINING&SMELTING CO.,LTD.制、体积平均粒径7.5μm)、3L3(Fukuda Metal Foil&Powder Co.,Ltd.制、体积平均粒径8.0μm)、2L3N(Fukuda Metal Foil&Powder Co.,Ltd.制、体积平均粒径9.9μm)、3L3N(Fukuda Metal Foil&Powder Co.,Ltd.制、体积平均粒径7μm)及1110F(MITSUI MINING&SMELTING CO.,LTD.制、体积平均粒径3.8μm)。
以接合用铜糊料中所包含的铜粒子的总质量为基准,微米铜粒子的含量可以为10质量%以上、15质量%以上或20质量%以上,也可以为70质量%以下、50质量%以下、45质量%以下或40质量%以下。并且,以接合用铜糊料中所包含的铜粒子的总质量为基准,微米铜粒子的含量可以为10~70质量%、10~65质量%、10~50质量%、15~60质量%、15~50质量%或15~45质量%。若微米铜粒子的含量在上述范围内,能够抑制接合部(例如,烧结体)的剥离、孔隙及裂纹的产生而确保接合强度。当将接合用铜糊料用于微型器件的接合时,微型器件倾向于显示出良好的芯片剪切强度及连接可靠性。片状微米铜粒子的含量可以与上述微米铜粒子的含量的范围相同。当片状微米铜粒子的含量在这种范围内时,有更进一步发挥上述效果的倾向。
[其他铜粒子]
作为除亚微米铜粒子及微米铜粒子以外的铜粒子,可以举出铜纳米粒子。铜纳米粒子是指具有小于0.01μm的粒径的铜粒子。铜纳米粒子通常在表面上由羧酸或胺包覆(表面包覆材料)。铜纳米粒子与铜微米粒子相比具有比表面积大、且每单位质量所占的表面包覆材料的比例增加的倾向。因此,烧结时(加热时)脱离的表面包覆材料增多,因此与铜微米粒子相比具有烧结时的体积收缩增大的倾向。从减少体积收缩的观点考虑,以铜粒子的总质量为基准,铜纳米粒子的含量优选为10质量%以下,更优选为5质量%以下,进一步优选不包含。
以接合用铜糊料中所包含的金属粒子的总质量为基准,本实施方式的接合用铜糊料中的铜粒子的含量可以为80~100质量%,也可以为90~100质量%,也可以为95~100质量%。
本实施方式的接合用铜糊料更优选包含亚微米铜粒子及微米铜粒子。当并用亚微米铜粒子和微米铜粒子时,容易抑制干燥引起的体积收缩及烧结收缩,烧结时接合用铜糊料不易从接合面剥离。即,通过并用亚微米铜粒子和微米铜粒子,能够抑制对接合用铜糊料进行烧结时的体积收缩,接合体具有更充分的接合强度。当将并用亚微米铜粒子和微米铜粒子的接合用铜糊料用于微型器件的接合时,微型器件倾向于显示出更好的芯片剪切强度及连接可靠性。
以接合用铜糊料中所包含的金属粒子的总质量为基准,亚微米铜粒子的含量和微米铜粒子的含量的总计可以为80~100质量%。若亚微米铜粒子的含量和微米铜粒子的含量的总计在上述范围内,则能够充分降低对接合用铜糊料进行烧结时的体积收缩,并且容易确保对接合用铜糊料进行烧结而制造的接合体的接合强度。当将接合用铜糊料用于微型器件的接合时,微型器件倾向于显示出良好的芯片剪切强度及连接可靠性。从进一步发挥上述效果的观点考虑,以金属粒子的总质量为基准,亚微米铜粒子的含量和微米铜粒子的含量的总计可以为90质量%以上,也可以为95质量%以上,也可以为100质量%。
本实施方式的接合用铜糊料可以包含体积平均粒径为0.12~0.8μm的亚微米铜粒子及最大直径为2~50μm且纵横比为3.0以上的片状微米铜粒子。在这种情况下,适合于在无加压下的接合。在这种情况下,以铜粒子的总质量为基准,接合用铜糊料中的上述亚微米铜离子的含量可以为30~90质量%,以铜粒子的总质量为基准,上述微米铜粒子的含量可以是10~70质量%。
[其他金属粒子]
本实施方式的接合用铜糊料能够包含除铜粒子以外的金属粒子(也称为“其他金属粒子”。)。
作为其他金属粒子,例如可以举出锌、镍、银、金、钯、铂等粒子。其他金属粒子的体积平均粒径可以为0.01~10μm、0.01~5μm或0.05~3μm。其他金属粒子的形状并无特别限定。从获得充分的接合性的观点考虑,以接合用铜糊料中所包含的金属粒子的总质量为基准,其他金属粒子的含量可以小于20质量%,也可以为10质量%以下,也可以为5质量%以下,也可以为1质量%以下,也可以为0质量%。
以接合用铜糊料总量为基准,本实施方式的接合用铜糊料中的金属粒子的含量可以为85~98质量%,也可以为85~95质量%,也可以为85~90质量%,也可以为87~89质量%。
(分散介质)
分散介质只要具有使金属粒子分散的功能,则并无特别限定,可以是挥发性分散介质。作为挥发性分散介质,例如可以举出一元醇、多元醇等醇类、醚类、酯类、酰胺、脂肪族烃、芳香族烃等。具体而言,可以举出环己醇、乙二醇、二甘醇、丙二醇、丙二醇、α-松油醇(α-萜品醇)、二氢松油醇(二氢萜品醇)等醇类;二甘醇二甲基醚、二甘醇二乙基醚、二甘醇二丁基醚、二甘醇丁基甲基醚、二甘醇异丙基甲基醚、三甘醇二甲基醚、三甘醇丁基甲基醚、丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二丁基醚、丙二醇二丙基醚、三丙二醇二甲基醚等醚类;乙二醇乙基醚乙酸酯、乙二醇丁基醚乙酸酯、二乙二醇乙基醚乙酸酯、二乙二醇丁基醚乙酸酯、二丙二醇甲基醚乙酸酯(DPMA)、乳酸乙酯、乳酸丁酯、γ-丁内酯、碳酸亚丙酯等酯类;N-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺等酰胺;环己烷、辛烷、壬烷、癸烷、十一烷等脂肪族烃;苯、甲苯、二甲苯等芳香族烃。
从兼顾印刷性和接合性的观点考虑,本实施方式的接合用铜糊料作为分散介质包含二氢松油醇。
以接合用铜糊料的总质量为基准,分散介质的含量可以为2质量%以上、5质量%以上或10质量%以上,也可以为50质量%以下、30质量%以下、20质量%以下或15质量%以下。例如,以接合用铜糊料的总质量为基准,分散介质的含量可以为2~50质量%,也可以为5~30质量%,也可以为5~20质量%。并且,将接合用铜糊料中所包含的金属粒子的总质量作为100质量份,分散介质的含量可以为2~50质量份,可以为5~50质量份,可以为2~15质量份,可以为5~15质量份,可以为10~15质量份,可以为11~13质量份。若分散介质的含量在上述范围内,则能够将接合用铜糊料调整为更适当的粘度,并且,不易阻碍铜粒子的烧结。
以分散介质的总质量为基准,本实施方式的接合用铜糊料中的二氢松油醇的含量可以为50~100质量%,也可以为50~90质量%,也可以为60~80质量%,也可以为100质量%。
接合用铜糊料优选包含具有300℃以上的沸点的化合物(以下,有时称为高沸点分散介质)作为分散介质。通过包含高沸点分散介质,直到即将开始烧结之前,对接合用铜糊料赋予可塑性和密合性,在无加压下的接合变得容易。从在接合用铜糊料的烧结时不妨碍烧结及致密化,达到接合温度时迅速蒸发并去除的观点考虑,高沸点分散介质的沸点可以为300~450℃,也可以为305~400℃,也可以为310~380℃。另外,沸点是指大气压下(1气压)下的温度。并且,在本说明书中,有时将具有小于300℃的沸点的分散介质称为低沸点分散介质。
作为高沸点分散介质,可以举出异冰片基环己醇(MTPH、NIPPON TERPENECHEMICALS,INC.制)、硬脂酸丁酯、EXCEPARL BS(Kao Corporation制)、硬脂酸硬脂酯、EXCEPARL SS(Kao Corporation制)、硬脂酸2-乙基己酯、EXCEPARL EH-S(Kao Corporation制)、硬脂酸异十三烷基酯、EXCEPARL TD-S(Kao Corporation制)、十七烷、十八烷、十九烷、二十烷、二十一烷、二十二烷、甲基十七烷、十三烷基环己烷、十四烷基环己烷、十五烷基环己烷、十六烷基环己烷、十一烷基苯、十二烷基苯、十四烷基苯、十三烷基苯、十五烷基苯、十六烷基苯、十七烷基苯、壬基萘、二苯基丙烷、辛酸辛酯、肉豆蔻酸甲酯、肉豆蔻酸乙酯、亚油酸甲酯、硬脂酸甲酯、三乙二醇双(2-乙基己酸)、柠檬酸三丁酯、戊基苯酚、癸二酸二丁酯、油醇、鲸蜡醇、甲氧基苯乙醇、苄基苯酚(C13H12O)、十六腈、十七腈、苯甲酸苄酯、环庚草醚(cinmethylin)等、双(2-乙基己基)己二酸酯等。从无加压下的接合变得更简单的观点考虑,高沸点分散介质优选包含选自由异冰片基环己醇、三丁酸甘油酯、硬脂酸丁酯及辛酸辛酯组成的组中的至少一种。
以接合用铜糊料的总质量为基准,高沸点分散介质的含量可以为2质量%以上、2.2质量%以上或2.4质量%以上,也可以为50质量%以下、45质量%以下、40质量%以下、20质量%以下、10质量%以下或5质量%以下。例如,以接合用铜糊料的总质量为基准,具有300℃以上的沸点的化合物的含量可以为2~50质量%,可以为2~20质量%,可以为2~5质量%。
以分散介质的总质量为基准,高沸点分散介质的含量可以为10~50质量%,也可以为20~40质量%,也可以为25~35质量%。
(其他成分)
接合用铜糊料作为添加剂能够含有非离子系表面活性剂、氟系表面活性剂等润湿提高剂;表面张力调节剂;烷基胺、烷基羧酸等分散剂;硅油等消泡剂;无机离子交换体等离子捕获剂;饱和高级醇等。添加剂的含量能够在不损害本发明的效果的范围内适当地调整。
上述接合用铜糊料的粘度并无特别限定,从丝网印刷等方法、尤其适于自动印刷机的印刷条件的观点考虑,25℃下的粘度可以为100~250Pa·s,可以为100~200Pa·s,可以为100~170Pa·s。
接合用铜糊料的粘度能够根据JIS标准化的焊糊的粘度测定方法(JIS Z3284-1:2014)来测定,上述粘度表示利用粘度计TV-33(Toki Sangyo Co.,Ltd制、产品名称)和作为测定用夹具的SPP转子,在转速2.5rpm、测量时间144秒的条件下测定时的值。
根据本实施方式的接合用铜糊料,能够维持足够的接合性的同时提高印刷性。因此,根据本实施方式的上述接合用铜糊料,通过使用丝网印刷机等自动印刷机的批量生产工艺能够高效率地制造接合体。并且,本实施方式的接合用铜糊料可以是无加压接合用。
<接合用铜糊料的制备>
接合用铜糊料能够通过将上述铜粒子、分散介质、根据情况含有的其他金属粒子及添加剂混合而制备。混合各成分后,可以进行搅拌处理。接合用铜糊料可以通过分级操作来调整分散液的最大粒径。此时,分散液的最大粒径能够设为20μm以下,也能够设为10μm以下。上述亚微米铜粒子等金属粒子可以使用经表面处理剂处理的金属粒子。
当作为铜粒子使用亚微米铜粒子及微米铜粒子时,接合用铜糊料例如可以通过以下方法来制备。首先,在分散介质中根据需要添加分散剂,然后混合亚微米铜粒子,进行分散处理。接着,添加微米铜粒子及根据需要的其他金属粒子,进行分散处理。亚微米铜粒子和微米铜粒子的适于分散的分散方法及分散条件有时不同。通常,亚微米铜粒子比微米铜粒子更难以分散,为了使亚微米铜粒子分散,需要比使微米铜粒子分散时施加的强度更高的强度。另一方面,微米铜粒子不仅容易分散,而且当为了使其分散而施加高强度时可能会发生变形。因此,通过设为如上所述的步骤,能够容易获得良好的分散性,进一步提高接合用铜糊料的性能。
分散处理能够使用分散机或搅拌机进行。作为分散机及搅拌机,例如可以举出石川式搅拌机、Silverson搅拌机、空化搅拌机、自转公转型搅拌装置、超薄膜高速旋转式分散机、超声波分散机、Raikai器、双螺杆混炼机、珠磨机、球磨机、三辊研磨机、均质混合机、行星式混合机、超高压型分散机及薄层剪切分散机。
分级操作例如能够使用过滤、自然沉降及离心分离来进行。作为过滤用过滤器,例如可以举出水梳子、金属网、金属过滤器及尼龙网。
搅拌处理能够使用搅拌机来进行。作为搅拌机,例如可以举出石川式搅拌机、自转公转型搅拌装置、Raikai器、双螺杆混炼机、三辊研磨机及行星式混合机。
<接合体的制造方法>
本实施方式的接合体的制造方法为具备第1构件、第2构件及接合第1构件和第2构件的接合部的接合体的制造方法,所述接合体的制造方法具备:第1工序,在第1构件及第2构件中的至少一者的接合面上印刷本实施方式的接合用铜糊料,并准备具有依次层叠有第1构件、接合用铜糊料及第2构件的层叠结构的层叠体;第2工序,对层叠体的接合用铜糊料进行烧结。
作为第1构件及第2构件,例如可以举出IGBT、二极管、肖特基势垒二极管、MOS-FET、晶闸管、逻辑电路、传感器、模拟集成电路、LED、半导体激光器、发射器等半导体元件;引线框;金属板粘贴陶瓷基板(例如DBC);LED封装等半导体元件搭载用基材;铜及金属框架等金属配线;金属块等块体;端子等供电用构件;散热板;水冷板等。
第1构件及第2构件的接合用铜糊料的与烧结体接触的表面可以包含金属。作为金属,例如可以举出铜、镍、银、金、钯、铂、铅、锡、钴等。金属可以单独使用1种,也可以将2种以上组合使用。并且,与烧结体接触的表面可以是包含上述金属的合金。作为用于合金的金属,除了上述金属以外,还可以举出锌、锰、铝、铍、钛、铬、铁、钼等。作为在与烧结体接触的面包含金属的构件,例如可以举出具有各种金属镀层的构件(具有金属镀层的芯片、具有各种金属镀层的引线框等)、导线、散热片、贴附有金属板的陶瓷基板、由各种金属构成的引线框、铜板、铜箔等。
作为在构件的接合面印刷本实施方式的接合用铜糊料的方法,可以举出丝网印刷(钢板印刷)、转印印刷、胶版印刷、凸版印刷、凹版印刷、照相凹版印刷、钢板印刷、喷射印刷等。并且,也可以使用利用分配器(例如,、喷射式分配器、针形分配器)、逗点涂布机、狭缝涂布机、模涂机、凹版涂布机、狭缝涂布、棒涂机、涂抹器、喷涂机、旋涂机、浸涂机等的方法、基于软光刻的方法、粒子堆积法、基于电沉积涂装的方法等。
接合用铜糊料的厚度可以为1μm以上、5μm以上、10μm以上、15μm以上、20μm以上或50μm以上,也可以为3000μm以下、1000μm以下、500μm以下、300μm以下、250μm以下或150μm以下。例如,接合用铜糊料的厚度也可以为1~1000μm,也可以为10~500μm,也可以为50~200μm,也可以为10~3000μm。也可以为15~500μm,也可以为20~300μm,也可以为5~500μm,也可以为10~250μm,也可以为15~150μm。
在本实施方式中,从批量生产工艺的观点考虑,能够通过丝网印刷来印刷本实施方式的接合用铜糊料,能够应对印刷速度提高、掩模的开口的面积扩大等。掩模的开口面积例如可以为4mm2以上,也可以为9mm2以上,也可以为25mm2以上,也可以为49mm2以上,也可以为100mm2以上。
图1是用于说明丝网印刷的示意图。图1的(a)~(d)示出使用掩模32和具备刮刀36的丝网印刷机,在配置于载物台35上的第1构件30上印刷本实施方式的接合用铜糊料34时的一系列的工艺。在该工艺中,使用2个刮刀进行往复印刷。首先,向掩模32的一端供给糊料34(图1的(a))。接着,一边以规定的印刷压力将一个刮刀36按压到掩模32一边向一个方向移动,在掩模32的开口部印刷(涂布)糊料34(图1的(b))。在此,根据需要可以将糊料供给到涂层终端部。接着,在涂层终端位置一边以规定的印刷压力按压另一个刮刀36一边使其向相反方向移动,从而印刷(print)糊料34(图1的(c))。然后,从掩模32取下第1构件30,完成印刷(图1的(d)。这样,在第1构件30上印刷具有规定形状的接合用铜糊料38。
印刷压力例如能够设为0.01~0.3MPa。印刷速度例如能够在15~300mm/s的范围内调整。
在本实施方式中,也可以代替2个刮刀,安装刮板和刮刀,用刮板将糊料填充到掩模的开口部,用刮刀将填充的糊料转印到构件上而进行印刷。
从抑制烧结时的流动及孔隙的产生的观点考虑,可以适当地干燥印刷在构件上的接合用铜糊料。干燥时的气体气氛可以是在大气中,也可以是在氮气、稀有气体等无氧气氛中,也可以是在氢气、甲酸等还原气氛中。干燥方法可以是通过常温放置(例如,10~30℃)的干燥,也可以是加热干燥,也可以是减压干燥。加热干燥或减压干燥中,例如能够使用加热板、热风干燥机、热风加热炉、氮气干燥机、红外线干燥机、红外线加热炉、远红外线加热炉、微波加热装置、激光加热装置、电磁加热装置、加热器加热装置、蒸汽加热炉、热板加压装置等。干燥的温度及时间可以根据所使用的挥发成分(例如,1元脂肪族醇及溶剂成分)的种类及量来适当地调整。干燥条件(干燥的温度及时间)例如可以是在50~180℃下干燥1~120分钟的条件。
层叠体能够通过将一个构件配置于另一个构件上的方法来获得。作为具体方法(例如,在印刷接合用铜糊料的第2构件上配置第1构件的方法),例如可以举出使用芯片安装机、倒装片接合机、碳制或陶瓷制的定位夹具等的方法。
在第2工序中,通过对层叠体进行加热处理,能够进行接合用铜糊料的烧结。由此可获得成为接合部的烧结体。加热处理中,例如能够使用加热板、热风干燥机、热风加热炉、氮气干燥机、红外线干燥机、红外线加热炉、远红外线加热炉、微波加热装置、激光加热装置、电磁加热装置、加热器加热装置、蒸汽加热炉等。
从抑制烧结体、构件(例如,第1构件及第2构件)的氧化的观点考虑,烧结时的气体气氛可以是无氧气氛。从去除接合用铜糊料中的铜粒子的表面氧化物的观点考虑,烧结时的气体气氛可以为还原气氛。作为无氧气氛,例如可以举出氮气、稀有气体等无氧气体气氛或真空。作为还原气氛,例如可以举出纯氢气气氛、以成型气体为代表的氢和氮的混合气体、含有甲酸气体的氮气气氛、氢和稀有气体的混合气体气氛、含有甲酸气体的稀有气体气氛等。
从能够减少对构件(例如,第1构件及第2构件)的热损坏的观点及提高成品率的观点考虑,加热处理时的温度(例如,达到最高温度)可以为170℃以上、190℃以上或200℃以上,也可以为250℃以下、小于250℃、225℃以下或小于225℃。例如,达到最高温度可以为170~250℃,也可以为170℃以上且小于250℃,也可以为190~225℃,也可以为190℃以上且小于225℃,也可以为200~225℃,也可以为200℃以上且小于225℃。
在第2工序中,可以对接合用铜糊料在无加压下进行加热并烧结。即,能够在只承受基于层叠于接合用铜糊料的构件(例如,第1构件)的重量或除了层叠的构件的重量以外还承受0.01MPa以下、优选为0.005MPa以下的压力的状态下烧结层叠体,即使在这种情况下,也可能够获得充分的接合强度。若烧结时所承受的压力在上述范围内,则不需要特殊的加压装置,因此不损害成品率就能够更进一步减少孔隙、更进一步提高芯片剪切强度及连接可靠性。作为承受接合用铜糊料为0.01MPa以下的压力的方法,例如可以举出在配置于铅垂方向上侧的构件(例如,第1构件)上放置重物的方法等。
此外,参考附图对本实施方式的接合体的制造方法进行说明。
图2是表示使用本实施方式的接合用铜糊料制造的接合体的一例的示意剖视图。
图2所示的接合体100具备第1构件2、第2构件3及接合第1构件2和第2构件3的接合部1,接合部1由上述接合用铜糊料的烧结体构成。
对于第1构件2及第2构件3能够举出上述构件。通过使用本实施方式的接合用铜糊料,根据使用丝网印刷机等自动印刷机的批量生产工艺也能够高效率地制造具有充分的接合强度的接合体。
从使第1构件2和第2构件3充分接合的观点考虑,接合体100的芯片剪切强度可以为15MPa以上,也可以为20MPa以上,也可以为25MPa以上,也可以为30MPa以上。芯片剪切强度能够使用通用粘合测试仪(Royce650,Royce Instruments公司制)或万能型粘合测试仪(4000系列、DAGE公司制)等来测定。
从放热性及高温化的连接可靠性的观点考虑,接合用铜糊料的烧结体1的导热率可以为100W/(m·K)以上,也可以为120W/(m·K)以上,可以为150W/(m·K)以上。导热率能够由接合用铜糊料的烧结体的热扩散率、比热容量及密度算出。
在上述接合体100中,当第1构件2为半导体元件时,上述接合体100成为半导体装置。所获得的半导体装置能够具有充分的芯片剪切强度及连接可靠性。
图3是表示使用本实施方式的接合用铜糊料制造的半导体装置的一例的示意剖视图。图3所示的半导体装置110具备本实施方式所涉及的接合用铜糊料的烧结体11、引线框15a、引线框15b、导线16、经由烧结体11连接于引线框15a上的半导体元件18及将这些进行模制的注塑树脂17。半导体元件18经由导线16而连接于引线框15b。
作为本实施方式所涉及的半导体装置,例如可以举出二极管、整流器、晶闸管、MOS门驱动器、电源开关、功率MOSFET、IGBT、肖特基二极管、快恢复二极管等功率模块;信号发送器;放大器;高亮度LED模块;传感器等。
图4(图4(a)及图4(b))是用于说明接合体100的制造方法的示意剖视图。本实施方式所涉及的接合体100的制造方法具备:第1工序(图4(a)),准备第1构件2、在该第1构件2的重量起作用的方向侧上述接合用铜糊料10、及第1构件3依次层叠的层叠体50;及第2工序,在承受第1构件2的重量的状态、或承受第1构件2的重量及0.01MPa以下的压力的状态下,以规定温度对接合用铜糊料10进行烧结。由此,可获得接合体100(图4(b))。第1构件2的重量起作用的方向也能够称为重力作用的方向。
本实施方式所设计的第1工序及第2工序能够与上述第1工序及第2工序同样地实施。
本实施方式所涉及的半导体装置110能够以与上述接合体100的制造方法相同的方式制造。即,半导体装置的制造方法具备以下工序:第1构件及第2构件中的至少一者使用半导体元件,准备第1构件、在该第1构件的重量作用的方向侧上述接合用铜糊料及第2构件依次层叠的层叠体,在承受第1构件的重量的状态、或承受第1构件的重量及0.01MPa以下的压力的状态下,以规定温度对接合用铜糊料进行烧结。
例如,如图5(图5(a)~图5(c))所示,在引线框15a上印刷接合用铜糊料20,配置半导体元件18而获得层叠体60之后(图5(a)),加热该层叠体60,并烧结接合用铜糊料20,从而获得接合体105(图5(b))。接着,通过导线16连接所获得的接合体105中的引线框15b和半导体元件18,并利用密封树脂将它们进行密封。通过以上工序获得半导体装置110(图5(c))。所获得的半导体装置110即使在无加压下进行接合的情况下,也能够具有充分的芯片剪切强度及连接可靠性。本实施方式的半导体装置具有充分的接合力,并具备包含导热率及熔点高的铜的接合用铜糊料的烧结体,由此具备充分的芯片剪切强度,连接可靠性优异,并且功率循环耐性也优异。并且,通过使用印刷性及接合性优异的本实施方式的接合用铜糊料,能够高效率地制造上述半导体装置。
以上、对使用本实施方式的接合用铜糊料制造的接合体及半导体装置的一例进行了说明,但是使用本实施方式的接合用铜糊料制造的接合体及半导体装置并不限于上述实施方式。使用本实施方式的接合用铜糊料制造的接合体例如可以是图6及图8所示的接合体。
图6所示的接合体120具备第1构件2、第2构件3、第3构件4、第4构件5、接合第1构件2和第2构件3的上述接合用铜糊料的烧结体(接合部)1a、接合第1构件2和第3构件4的上述接合用铜糊料的烧结体(接合部)1b、及接合第3构件4和第4构件5的上述接合用铜糊料的烧结体(接合部)1c。
这种接合体120例如如图7(图7(a)及图7(b))所示,能够通过具备如下工序的方法来获得(图7(b)):准备具有第3构件4、在该第3构件4的重量作用的方向侧第2接合用铜糊料10b、第1构件2、第1接合用铜糊料10a、及第2构件3依次层叠的层叠部分、及第3构件4、在该第3构件4的重量作用的方向侧第3接合用铜糊料10c、及第4构件5依次层叠的层叠部分的层叠体70(图7(a)),以与上述接合体100的制造方法相同的方式,对第1接合用铜糊料10a、第2接合用铜糊料10b及第3接合用铜糊料10c进行烧结。在上述方法中,第1接合用铜糊料10a、第2接合用铜糊料10b及第3接合用铜糊料10c为本实施方式所涉及的接合用铜糊料,通过烧结第1接合用铜糊料10a而获得烧结体1a,通过烧结第2接合用铜糊料10b而获得烧结体1b,通过烧结第3接合用铜糊料10c而获得烧结体1c。
并且,接合体120也能够通过具备如下工序的方法来获得:例如在获得上述接合体100之后,形成第3构件4、在该第3构件4的重量作用的方向侧第2接合用铜糊料10b、及第1构件2依次层叠的层叠部分、及第3构件4、在该第3构件4的重量作用的方向侧第3接合用铜糊料10c、及第4构件5依次层叠的层叠部分,以与上述接合体100的制造方法相同的方式,对第2接合用铜糊料10b及第3接合用铜糊料10c进行烧结。
图8所示的接合体130具备第1构件2、第2构件3、第3构件4、第4构件5、第5构件6、接合第1构件2和第2构件3的上述接合用铜糊料的烧结体(接合部)1a、接合第3构件4和第4构件5的上述接合用铜糊料的烧结体(接合部)1c、接合第1构件2和第5构件6的上述接合用铜糊料的烧结体(接合部)1d、及接合第3构件4和第5构件6的上述接合用铜糊料的烧结体(接合部)1e。
这种接合体130例如如图9(图9(a)及图9(b))所示,能够通过具备如下工序的方法来获得(图9(b)):准备具有第3构件4、在该第3构件4的重量作用的方向侧第5接合用铜糊料10e、第5构件6、第4接合用铜糊料10d、第1构件2、第1接合用铜糊料10a、及第2构件3依次层叠的层叠部分、及第3构件4、在该第3构件4的重量作用的方向侧第3接合用铜糊料10c、及第4构件5依次层叠的层叠部分的层叠体80(图9(a)),以与上述接合体100的制造方法相同的方式,对第1接合用金属糊料10a、第3接合用铜糊料10c、第4接合用铜糊料10d及第5接合用铜糊料10e进行烧结。在上述方法中,第1接合用铜糊料10a、第3接合用铜糊料10c、第4接合用铜糊料10d及第5接合用铜糊料10e为本实施方式所涉及的接合用铜糊料,通过烧结第1接合用铜糊料10a而获得烧结体1a,通过烧结第3接合用铜糊料10c而获得烧结体1c,通过烧结第4接合用铜糊料10d而获得烧结体1d,通过烧结第5接合用铜糊料10e而获得烧结体1e。
并且,接合体130也能够通过具备如下工序的方法来获得:准备第3构件4、在该第3构件4的重量作用的方向侧第5接合用铜糊料10e、第5构件6、第4接合用铜糊料10d、第1构件2、第1接合用铜糊料10a及第2构件3依次层叠的层叠体,以与上述接合体100的制造方法相同的方式,对第1接合用铜糊料10a、第4接合用铜糊料10d及第5接合用铜糊料10e进行烧结后,形成第3构件4、在该第3构件4的重量作用的方向侧第3接合用铜糊料10c及第4构件5依次层叠的层叠部分,以与上述接合体100的制造方法相同的方式,对第3接合用铜糊料10c进行烧结。
并且,接合体130也能够通过具备如下工序的方法来获得:在获得上述接合体100之后,形成第3构件4、在该第3构件4的重量作用的方向侧第5接合用铜糊料10e、第5构件6、第4接合用铜糊料10d及第1构件2依次层叠的层叠部分、及第3构件4、在该第3构件4的重量作用的方向侧第3接合用铜糊料10c、及第4构件5依次层叠的层叠部分,以与上述接合体100的制造方法相同的方式,对第3接合用铜糊料10c、第4接合用铜糊料10d及第5接合用铜糊料10e进行烧结。
在上述变形例中,作为第3构件4、第4构件5及第5构件6的例子,与第2构件3的例子相同。并且,第3构件4、第4构件5及第5构件6的接合用铜糊料的与烧结体接触的面可以包含金属。可以含有的金属的例子与第1构件及第2构件在接合用铜糊料的与烧结体接触的面中可含有的金属的例子相同。并且,在上述变形例中使用的第1接合用铜糊料10a、第2接合用铜糊料10b、第3接合用铜糊料10c、第4接合用铜糊料10d、第5接合用铜糊料10e可以分别相同,也可以不同。
实施例
以下,根据实施例及比较例,进一步具体说明本发明,但是本发明并不限定于以下实施例。
<接合用铜糊料的制备>
(实施例1)
将作为包含亚微米铜粒子的材料的CH-0200(Mitsui Mining&Smelting Co.,Ltd.制、产品名称、50%体积平均粒径:0.3μm)60.7质量份、二氢松油醇(NIPPON TERPENECHEMICALS,INC.制)8.0质量份、三丁酸甘油酯(沸点:305℃、FUJIFILM Wako PureChemical Corporation制)3.6质量份及FINE OXOCOL-180T(FUJIFILM Wako PureChemical Corporation制)0.4质量份,在2000rpm、1分钟的条件下在THINKY CORPORATION制搅拌机(商品名:“Thinkymixer ARE-310”、以下相同。)中进行了混合。然后,用三辊磨机进行10次分散处理,获得了混合物。
将通过分散处理而获得的混合物转移到聚乙烯制容器中后,将作为包含片状微米铜粒子的材料的3L3N(Mitsui Mining&Smelting Co.,Ltd.制、产品名称、50%体积平均粒径:7μm)27.1质量份添加到容器中,在2000rpm、1分钟的条件下在THINKY CORPORATION制搅拌机中进行了混合。然后,用三辊磨机进行5次分散处理,获得了接合用铜糊料。
(实施例2及参考例1)
实施例2中,减少实施例1中的糊料的溶剂量,并将金属粒子浓度调整为89质量%。参考例1中除了将接合用铜糊料的组成变更为表1所示的组成(数值的单位为质量份)以外,以与实施例1相同的方式制备了接合用铜糊料。
<接合用铜糊料的评价>
对于上述获得的接合用铜糊料,根据下述方法进行了粘度、印刷性及接合性的评价。将粘度的结果示于表1。
(粘度)
根据JIS标准化的焊糊的粘度测定方法(JIS Z 3284-1:2014),并利用粘度计TV-33(Toki Sangyo Co.,Ltd制、产品名称)和作为测定用夹具的SPP转子,在转速2.5rpm、测量时间144秒的条件下测定了接合用铜糊料的粘度。
(印刷性)
在下述条件下通过丝网印刷机在铜板上进行印刷,评价了印刷性。另外,开口尺寸设为3mm□、5mm□、7mm□、及10mm□。
在铜板上放置具有各印刷形状(3mm□、5mm□、7mm□、及10mm□)的开口的不锈钢制金属掩模(厚度:200μm),通过具备金属刮刀的钢板印刷,在去程:速度150mm/s、印刷压力0.2MPa、回程:100mm/s、印刷压力0.1MPa的条件下印刷了接合用铜糊料。
在实施例1及2中,能够以所有开口尺寸良好地进行印刷。在参考例1中,在印刷区域中观察到开口边缘部的缺失和印刷面的粗糙。
(接合性)
通过以下述方法制作的接合体的接合面积率(%)评价了接合用铜糊料的接合性。
<接合体的制作>
在铜板上放置具有各印刷形状(3mm□、5mm□、7mm□、及10mm□)的开口的不锈钢制金属掩模(厚度:200μm),通过使用金属刮刀的钢板印刷,在去程:速度150mm/s、印刷压力0.2MPa、回程:100mm/s、印刷压力0.1MPa的条件下印刷了接合用铜糊料。在印刷后的铜糊料放置形成有Ni层的Si芯片,使用热板(AS ONE Corporation制、产品名称“EC-1200N”),在60℃下进行了5分钟或10分钟的干燥。接着,将放置有芯片的样品设置于管式炉(R-DEC Co.,Ltd.制),以3L/min通入氩气5分钟进行了置换。然后,以500mL/min通入氢气,在30分钟内升温至接合温度。升温后,一边通入氢气一边在225℃下保持60分保之后,经15分钟冷却至200℃。最后,一边以0.3L/min通入氩气,一边通过鼓风从管式炉的外侧强制冷却而使样品温度成为60℃以下,然后将样品取出到空气中。
<接合面积率>
对于接合体的样品,使用超声波探伤装置(Insight CO.,LTD.制、Insight-300)进行分析,获得了接合部的超声波探伤图像(SAT像)。将所获得的SAT图像进行二值化处理,计算出对芯片面积的接合面积率(area%)。
在实施例1及2中,所有开口尺寸处接合面积率为99%以上。
表中的各成分的详细情况如下。
(铜粒子)
亚微米铜粒子A:CH-0200(Mitsui Mining&Smelting Co.,Ltd.制、产品名称、50%体积平均粒径:0.3μm)
微米铜粒子A:3L3N(Fukuda Metal Foil&Powder Co.,Ltd.制、产品名称、50%体积平均粒径:7μm)
(其他金属粒子)
锌粒子A:Zinc powder(Alfa Aesar公司制、产品名称、50%体积平均粒径:4μm)
(分散介质)
二氢松油醇:NIPPON TERPENE CHEMICALS,INC.制、产品名称、沸点208℃
松油醇C:NIPPON TERPENE CHEMICALS,INC.制、产品名称、沸点220℃
三丁酸甘油酯:FUJIFILM Wako Pure Chemical Corporation制、产品名称、沸点305℃
(添加剂)
添加剂A:FINE OXOCOL-180T(FUJIFILM Wako Pure Chemical Corporation制、异十八醇)
如表1所示,确认到在假定为自动印刷的印刷条件下,实施例1及2的接合用铜糊料能够以开口尺寸3~10mm□进行良好地印刷,能够实现充分的接合性。二氢松油醇中将松油醇的分子结构中所包含的双键氢化而成为单键,认为其分子结构和特性与松油醇非常相似,却能够大幅降低铜糊料的粘度,获得充分的接合性,可以说这是意想不到的效果。
符号说明
1、1a、1b、1c、1d、1e、11-接合用铜糊料的烧结体(接合部),2-第1构件,3-第2构件,10、10a、10b、10c、10d、10e、20-接合用铜糊料,15a、15b-引线框,16-导线,17-注塑树脂,18-半导体元件,30-第1构件,32-掩模,34、38-接合用铜糊料,35-载物台,36-刮刀,50、60、70、80-层叠体,100、105、120、130-接合体,110-半导体装置。
Claims (15)
1.一种接合用铜糊料,其含有金属粒子和分散介质,
作为所述金属粒子包含铜粒子,
作为所述分散介质包含二氢松油醇。
2.根据权利要求1所述的接合用铜糊料,其中,
以接合用铜糊料总量为基准,所述金属粒子的含量为85~98质量%。
3.根据权利要求1或2所述的接合用铜糊料,其中,
作为所述分散介质,还包含沸点为300℃以上的化合物。
4.根据权利要求1至3中任一项所述的接合用铜糊料,其在25℃下的粘度为100~200Pa·s。
5.根据权利要求1至4中任一项所述的接合用铜糊料,其中,
以所述金属粒子的总质量为基准,所述铜粒子的含量为80~100质量%。
6.根据权利要求1至5中任一项所述的接合用铜糊料,其用于丝网印刷。
7.根据权利要求1至6中任一项所述的接合用铜糊料,其中,
作为所述铜粒子,包含体积平均粒径为0.12~0.8μm的亚微米铜粒子及最大直径为2~50μm且纵横比为3.0以上的片状微米铜粒子。
8.根据权利要求7所述的接合用铜糊料,其中,
以所述铜粒子的总质量为基准,所述亚微米铜粒子的含量为30~90质量%,
以所述铜粒子的总质量为基准,所述微米铜粒子的含量为10~70质量%。
9.根据权利要求1至8中任一项所述的接合用铜糊料,其为无加压接合用。
10.一种接合体的制造方法,其具备第1构件、第2构件及接合所述第1构件和所述第2构件的接合部,所述接合体的制造方法具备:
第1工序,在所述第1构件及所述第2构件中的至少一者的接合面印刷权利要求1至8中任一项所述的接合用铜糊料,并准备具有依次层叠有所述第1构件、所述接合用铜糊料及所述第2构件的层叠结构的层叠体;及
第2工序,对所述层叠体的所述接合用铜糊料进行烧结。
11.根据权利要求10所述的接合体的制造方法,其中,
所述印刷为丝网印刷。
12.根据权利要求10或11所述的接合体的制造方法,其中,
在所述第2工序中,对所述接合用铜糊料在无加压下进行加热并烧结。
13.根据权利要求10至12中任一项所述的接合体的制造方法,其中,
所述第1构件及所述第2构件中的至少一者为半导体元件。
14.一种接合体,其具备第1构件、第2构件及接合第1构件和第2构件的接合部,
所述接合部由权利要求1至8中任一项所述的接合用铜糊料的烧结体构成。
15.根据权利要求14所述的接合体,其中,
所述第1构件及所述第2构件中的至少一者为半导体元件。
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