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CN103282454A - 粘接剂组合物及使用其的半导体装置 - Google Patents

粘接剂组合物及使用其的半导体装置 Download PDF

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Publication number
CN103282454A
CN103282454A CN2012800045355A CN201280004535A CN103282454A CN 103282454 A CN103282454 A CN 103282454A CN 2012800045355 A CN2012800045355 A CN 2012800045355A CN 201280004535 A CN201280004535 A CN 201280004535A CN 103282454 A CN103282454 A CN 103282454A
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CN
China
Prior art keywords
silver particles
adhesive composite
silver
boiling point
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2012800045355A
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English (en)
Inventor
今野馨
林宏树
名取美智子
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Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
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Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of CN103282454A publication Critical patent/CN103282454A/zh
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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Abstract

本发明的粘接剂组合物包含：通过X射线光电子分光法测定的源自银氧化物的氧的状态比率小于15%的片状银粒子（A）、和具有300℃以上的沸点的醇或羧酸（B）。

Description

粘接剂组合物及使用其的半导体装置
技术领域
本发明涉及粘接剂组合物及使用其的半导体装置。进一步详细而言，涉及适于将功率IC、LSI、发光二极管（LED）等半导体元件粘接于引线框、陶瓷配线板、玻璃环氧配线板、聚酰亚胺配线板等基板上的粘接剂组合物及使用其的半导体装置。
背景技术
制造半导体装置时，作为将半导体元件与引线框（支撑构件）粘接的方法，有在环氧系树脂、聚酰亚胺系树脂等树脂中分散银粉等填充剂并制成糊状（例如，银糊），将其用作粘接剂的方法。该方法中，使用分配器、印刷机、压印机等，将糊状粘接剂涂布于引线框的芯片焊垫（die pad）上。然后，对半导体元件进行芯片接合，通过加热固化而进行粘接，制成半导体装置。
近年，随着半导体元件的高速化、高集成化进展，为了确保半导体装置的工作稳定性而要求高散热特性。另外，为了降低半导体部件的成本，不采用高价的贵金属镀敷（Au或Ag等）而多数采用表面为贱金属（Ni镀敷或Cu等）的引线框。即，为了满足上述要求，需要兼具高导热性和对贱金属表面的高粘接性的粘接剂组合物。
作为实现比以往的利用金属粒子彼此接触的导电性粘接剂更高的散热性的手段，提出了如下组合物：高填充热导率高的银粒子的组合物（专利文献1～3）；包含低熔点焊锡的组合物（专利文献4）；使用烧结性优异的平均粒径0．1μm以下的金属纳米粒子的组合物（专利文献5）；通过使用实施了特殊的表面处理的微小尺寸的银粒子，从而利用100℃以上400℃以下的加热将银粒子彼此烧结那样的粘接剂组合物（专利文献6）。
现有技术文献
专利文献
专利文献1：日本特开2006－73811号公报
专利文献2：日本特开2006－302834号公报
专利文献3：日本特开平11－66953号公报
专利文献4：日本特开2005－93996号公报
专利文献5：日本特开2006－83377号公报
专利文献6：日本专利第4353380号公报
发明内容
发明要解决的问题
然而，以往的高填充热导率高的银粒子的方法中，为了确保近年的功率IC、LED所要求的20W／m·K以上的热导率，需要银粒子填充量为95质量％以上这样非常大量的银粒子。
银粒子填充量增多时，粘度上升，从而导致分配时发生拉丝等、无法确保操作性成为问题。如果为了确保操作性而大量添加溶剂，则空隙发生或残存溶剂引起的粘接强度降低成为问题。
另外，使用包含低熔点焊锡的组合物，通过金属结合形成热传导路径和与被粘接体进行金属化的方法中，将功率IC或LED等封装体（PKG）安装于基板上的情况下，在回流焊炉内被暴露于260℃中。由于该热历程，存在接合部再熔融而得不到连接可靠性这样的问题。
进一步，在使用金属纳米粒子的方法中，虽然能够避免接合部再熔融的问题，但存在为了制作纳米尺寸的金属粒子而花费巨大成本的担忧。另外，粘接剂组合物中的纳米粒子的含量少时，存在高导热性的表现变难的问题。
进而另外，在对银粒子实施特定的表面处理的方法中，虽然可促进烧结，得到导电性和导热性优异的固体状银，但存在如下问题：对半导体安装部件中多数采用的贱金属表面（Ni、Cu等）的粘接强度弱。
因此，本发明的目的在于提供一种粘接剂组合物及使用其的半导体装置，该粘接剂组合物即使在不施加载荷而于300℃以下的固化温度接合的情况下也具有高导电性和热导率，并且即使在大气氛围下接合的情况下也具有对贱金属表面充分的粘接强度。
解决问题的方法
鉴于上述情况，本发明的粘接剂组合物包含通过X射线光电子分光法测定的源自银氧化物的氧的状态比率小于15%的片状银粒子（A）、和具有300℃以上的沸点的醇或羧酸（B）。予以说明的是，本发明中的沸点是指1个大气压下的沸点。
上述粘接剂组合物优选还包含沸点为100℃以上且小于300℃的挥发性成分（C）。
上述银粒子优选为实施了除去其氧化膜的处理和利用表面保护材料的表面处理的银粒子。
银粒子优选包含平均粒径为0.1μm以上50μm以下的银粒子。
将本发明的粘接剂组合物热固化而形成的固化物的体积电阻率和热导率分别优选为1×10-4Ω·cm以下、30W／m·K以上。
优选上述粘接剂组合物在100～300℃、5秒～10小时的条件下固化，更优选在150～300℃、30分～5小时的条件下固化，进一步优选在200～300℃、1～2小时的条件下固化，特别优选在250℃、1小时的条件下固化。
进一步，本发明提供一种半导体装置，其具有通过上述本发明的粘接剂组合物将半导体元件与半导体元件搭载用支撑构件粘接的结构。
发明效果
根据本发明，能够提供一种粘接剂组合物及使用其的半导体装置，该粘接剂组合物即使在不施加载荷而于300℃以下的固化温度接合的情况下也具有高导电性和热导率，并且即使在大气氛围下接合的情况下也具有对贱金属表面充分的粘接强度。这样的粘接剂组合物适合用作导电性连接材料、导电性粘接剂或芯片接合材料。
附图说明
图1是对表面的氧化膜少的银粒子实施了利用表面保护材料的表面处理的银粒子的示意图。
图2是表示图1所示的银粒子的表面保护材料脱离，银粒子彼此烧结的状态的示意图。
图3是对表面的氧化膜多的银粒子实施了利用表面保护材料的表面处理的银粒子的示意图。
图4是表示虽然图3所示的银粒子的表面保护材料脱离，但银粒子彼此无法烧结的状态的示意图。
图5是对氧化膜多的银粒子实施了除去表面氧化膜的处理和利用表面保护材料的表面处理的银粒子的示意图。
图6是表示图5所示的银粒子的表面保护材料脱离，银粒子彼此烧结的状态的示意图。
图7是表示本实施方式的半导体装置的一例的示意剖面图。
图8是表示本实施方式的半导体装置的其他例的示意剖面图。
具体实施方式
以下，一边参照附图一边对本发明的优选实施方式进行详细说明。
本实施方式的粘接剂组合物将通过X射线光电子分光法测定的源自银氧化物的氧的状态比率小于15%的片状银粒子（A）（以下，也称为“（A）成分”。）、和具有300℃以上的沸点的醇或羧酸（B）（以下，也称为“（B）成分”。）作为必须成分。以下对各成分进行详细描述。
（（A）成分）
本实施方式的粘接剂组合物所使用的银粒子中，源自银氧化物的氧的状态比率小于15%。源自银氧化物的氧的状态比率为15％以上时，在300℃以下的温度或没有促进氧化膜除去的还原剂的环境下，氧化膜广泛覆盖银粒子的表面而阻碍银粒子彼此的烧结，银粒子彼此的金属结合的路径未充分形成，因此使用该银粒子的粘接剂组合物的热导率降低。另外，源自银氧化物的氧的状态比率优选小于10％，为了实现高粘接力，为了进一步紧密地形成银粒子彼此或与被粘接体的金属结合的路径，更优选小于5％。
银粒子表面上的氧化膜的量以由通过X射线光电子分光法测定的数据算出的状态比率为基准。X射线光电子分光法的分析装置使用Surface ScienceInstrument公司的S－Probe ESCA Model 2803，照射X射线时使用Al Kα射线。源自银氧化膜的氧是在531±1eV处具有峰的成分，与源自表面保护剂等其他成分的氧有区别。“状态比率”是指测定样品中特定元素的浓度，通过由元素的强度使用装置附属的相对灵敏度系数而算出的值表示。
另外，本实施方式的粘接剂组合物中使用的银粒子包含形状为片状的粒子。银粒子的形状为根据扫描型电子显微镜(Scannig Electron Microscope;SEM)观察进行解析时的形状，作为SEM的观察装置，可以使用philipsXL30。本实施方式中，将根据SEM观察的结果进行解析，平均厚度t为0.1μm～15μm、纵横比（平均粒径a／平均厚度t）为2～1000的范围设为片状。这里所说的平均粒径a定义为，对任意选择的5个银粒子求俯视片状银粒子时的面积S的平方根而得到的平均值。
作为片状粒子的一例，包含板状、盘状、鳞片状、被称为薄片状的形状的粒子。使片状的银粒子彼此接触的情况下，与使粒状的银粒子彼此接触的情况相比接触面积增加。因此可认为，使包含片状银粒子的粘接剂组合物热固化时，银粒子彼此的烧结的致密性增加，结果除了粘接剂组合物的固化物的热导率和导电率提高以外，对贱金属表面的粘接强度也提高。
另外，球状银粒子的平均粒径设为，通过激光衍射散射式粒度分布测定法而得到的粒度分布中的累计值（体积）50％时的粒径。球状银粒子的平均粒径优选为0.1μm以上50μm以下。考虑粒子的制造成本时，优选0.1μm以上，为了提高热导率而考虑提高粒子的填充率时，优选50μm以下。
为了提高热导率，上述银粒子在粘接剂组合物中的比例在粘接剂组合物100质量份中，优选80质量份以上，为了实现与高温焊锡同等以上的热导率，更优选87质量份以上。另外，为了将粘接剂组合物制成糊状，银粒子的比例优选99质量份以下，为了提高分配器、印刷机的操作性，更优选为95质量份以下。
通过使用这样的银粒子可获得上述效果的理由不一定清楚，基于图1和图2的示意图来说明本发明人等的考察。
首先，在对表面的氧化膜少的片状银粒子实施了利用表面保护材料的表面处理的情况下，认为形成了图1所示那样的状态。即认为，形成了如下的状态（3’）：在片状银粒子3上，存在少量残留的氧化膜2，同时为了遮挡氧化膜2，表面保护材料1覆盖银粒子3。
该情况下，通过在300℃以下进行加热，如图2所示表面保护材料1脱离，银粒子3的活性表面露出。该活性表面与其他的银粒子的活性表面接触从而促进烧结，形成银粒子彼此的金属结合的路径。进一步，由于各银粒子3形成了片状，因此银粒子彼此接触时的接触面积大。本发明人等推测：由于以上的事项，含有银粒子的粘接剂组合物即使在300℃以下加热而固化的情况下，也具有高热导率和导电率，并且对贱金属表面的粘接强度提高。
银粒子优选为实施了除去其氧化膜的处理和利用表面保护材料的表面处理的银粒子。由此，能够防止再氧化、银粒子的凝聚。关于除去氧化膜的处理、和利用表面保护材料的表面处理，例如可以通过以下所示的方法来进行。
首先，在溶解、分散有表面保护材料的酸性溶液中添加银粒子，一边搅拌一边除去氧化膜，并进行表面保护。此时，银粒子相对于酸性溶液100质量份的添加量优选1～50质量份。
接着，过滤溶液而取出银粒子后，用溶剂洗涤物理吸附于银粒子表面的表面保护材料、酸成分。然后，通过减压干燥银粒子而除去剩余的溶剂，得到干燥状态的进行了表面处理的银粒子。
另外，在氧化膜除去的工艺中在不含表面保护材料的酸性溶液中进行氧化膜处理的情况下，银粒子彼此凝聚，有可能得不到具有与氧化膜处理前的粒子同等平均粒径的粉体状的银粒子。为了防止银粒子的凝聚，优选在酸性溶液中添加表面保护材料，同时进行氧化膜除去和表面处理。
对酸性溶液没有限制，作为酸，可以使用硫酸、硝酸、盐酸、醋酸、磷酸等。酸的稀释溶剂也没有限制，但优选与酸的相溶性良好并且表面保护材料的溶解性、分散性优异的溶剂。
关于酸性溶液的酸浓度，为了除去氧化膜，将酸性溶液整体设为100质量份时，优选1质量份以上，包含氧化膜厚的银粒子的情况下，更优选5质量份以上。
另外，酸的浓度过浓时，金属会大量溶解于溶液中，因此优选50质量份以下，为了防止粒子彼此凝聚，更优选40质量份以下。
表面保护材料优选具有对银粒子表面的吸附良好的末端官能团的化合物。作为其具体例，可列举具有羟基、羧基、氨基、硫醇基、二硫醚基的化合物。另外为了进一步高度防止银粒子的再氧化、剩余的有机物的吸附污染，优选化合物的主骨架具有可紧密填充表面保护材料那样的直链烷烃骨架的化合物。
直链烷烃骨架更优选为碳原子数4个以上。具有这样的直链烷烃骨架的表面保护剂通过碳链彼此的分子间力而被更加紧密地填充。
另外，直链烷烃骨架更优选为碳原子数18个以上。具有这样的直链烷烃骨架的表面保护剂由于表面保护材料从金属表面的脱离温度低于300℃，因此能够在300℃以下的低温度下将银粒子烧结。
关于酸性溶液中表面保护材料的浓度，将酸性溶液整体设为100质量份时，为了防止银粒子彼此的凝聚，优选0.0001质量份以上，为了防止表面保护材料对银粒子的过剩物理吸附，优选0.1质量份以下。
这里，关于即使在使用氧化膜多的银粒子的情况下也可获得本实施方式的效果的理由，基于图3～6的示意图来说明本发明人等的考察。
图3所示那样的氧化膜5多的银粒子6的情况下，认为在300℃以下加热时，如图4所示虽然表面保护材料4脱离，但银粒子6的表面被氧化膜5广泛覆盖，因此银粒子6彼此的烧结难以发生。
与此相对，即使在使用氧化膜多的银粒子的情况下，在实施了除去表面的氧化膜5的处理和利用表面保护材料的表面处理的情况下，如图5所示，也可得到不存在氧化膜5、表面整体被表面保护材料7覆盖的状态的银粒子8’。
该情况下，与图1所示的银粒子3同样地，通过在300℃以下进行加热，表面保护材料7脱离，银粒子8的活性表面露出。该活性表面与其他的银粒子的活性表面接触从而促进烧结，形成银粒子彼此的金属结合的路径。此时，由于与图1的银粒子相比银粒子8的活性表面露出的面积更大，因此认为可更加促进烧结，进一步认为可得到高热导率。
（（B）成分）
作为具有300℃以上的沸点的醇或羧酸，只要不妨碍银粒子的烧结就没有特别限制。
作为（B）成分的一例，可列举棕榈酸、硬脂酸、花生酸、对苯二酸、油酸等脂肪族羧酸，均苯四酸、邻苯氧基苯甲酸等芳香族羧酸，鲸蜡醇、异龙脑基环己醇（isobornyl cyclohexanol）、四乙二醇等脂肪族醇，对苯基苯酚等芳香族醇。其中，这些醇或羧酸的熔点优选低于施加热历程时的温度。这是因为，加热时，与固体相比，液体与被粘接体和银粒子的润湿性提高，反应性提高，因此能够提高对被粘接体的粘接强度。其中特别地，更优选碳原子数为6～20的脂肪族的醇或羧酸。这是因为，包含这些羧酸或醇的粘接剂组合物不仅银粒子的烧结性良好，而且由于银粒子的分散性提高和沉降防止，使得粘接剂组合物使用分配器、印刷机的涂布操作性优异。
（B）成分可以使用1种或根据需要将2种以上的化合物混合使用。将粘接剂组合物总量设为100质量份时，（B）成分优选为0.1质量份～20质量份。（B）成分多于20质量份时，施加规定的热历程时残存的（B）成分会阻碍银粒子的凝聚或烧结，损害各银粒子间的烧结的致密性，从而有可能损害导电性、导热性或对贱金属表面的粘接强度，小于0.1质量份时，有可能无法充分获得银粒子的烧结促进效果，粘接强度降低。
（（C）成分）
本实施方式的粘接剂组合物也可以进一步包含挥发性成分（C）（以下，视情况也称为“（C）成分”）。作为挥发性成分，只要是沸点为100℃以上且小于300℃、对与银粒子的混合物施加规定的热历程时银粒子烧结的物质就没有特别限制。
作为这样的挥发性成分，可列举戊醇、己醇、庚醇、辛醇、癸醇、乙二醇、二乙二醇、丙二醇、丁二醇、α-萜品醇等一元和多元醇类，乙二醇丁醚、乙二醇苯醚、二乙二醇甲醚、二乙二醇乙醚、二乙二醇丁醚、二乙二醇异丁醚、二乙二醇己醚、三乙二醇甲醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丁醚、二乙二醇丁基甲醚、二乙二醇异丙基甲醚、三乙二醇二甲醚、三乙二醇丁基甲醚、丙二醇丙醚、二丙二醇甲醚、二丙二醇乙醚、二丙二醇丙醚、二丙二醇丁醚、二丙二醇二甲醚、三丙二醇甲醚、三丙二醇二甲醚等醚类，乙二醇乙醚乙酸酯、乙二醇丁醚乙酸酯、二乙二醇乙醚乙酸酯、二乙二醇丁醚乙酸酯、二丙二醇甲醚乙酸酯、乳酸乙酯、乳酸丁酯、γ-丁内酯等酯类，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，环己酮、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，适当的硫醇包含1至18碳原子的例如乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、戊基、己基和十二烷基硫醇那样的硫醇，或者环己基硫醇包含5至7碳原子的环戊基、环己基或环庚基硫醇那样的硫醇类。其中，优选沸点为150℃以上的挥发性成分。这是因为，包含沸点为150℃以上的挥发性成分的粘接剂组合物在安装操作中的粘度上升极少，分配等半导体装置制作时的涂布操作稳定性优异。其中特别地，更优选碳原子数为4～12的醇、酯、醚类。这是因为，这些挥发性成分对实施了氧化膜除去和表面处理的银粒子的分散性优异，银粒子的沉降等所引起的分配堵塞等担忧少。
挥发性成分可以使用1种或根据需要将2种以上的成分混合使用，为了提高导热性，在粘接性组合物100质量份中优选为20质量份以下。
本实施方式的粘接剂组合物中，也可以包含用于提高操作性的稀释剂、润湿性提高剂和消泡剂的一种以上。另外，本实施方式的粘接剂组合物也可以包含这里所列举以外的成分。
本实施方式的粘接剂组合物中，根据需要进一步可以适当添加氧化钙、氧化镁等吸湿剂、硅烷偶联剂、钛酸酯偶联剂、铝偶联剂、铝锆偶联剂等粘接力提高剂、非离子系表面活性剂、氟系表面活性剂等润湿提高剂、硅油等消泡剂、无机离子交换体等离子捕获剂、阻聚剂等。
这里，作为硅烷偶联剂，例如，可列举乙烯基三（β－甲氧基乙氧基）硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、γ－甲基丙烯酰氧基丙基三甲氧基硅烷、β－（3,4－环氧环己基）乙基三甲氧基硅烷、γ－环氧丙氧基丙基三甲氧基硅烷、γ－环氧丙氧基丙基甲基二乙氧基硅烷、N－苯基－γ－氨基丙基三甲氧基硅烷、γ－巯基丙基三甲氧基硅烷、六甲基二硅氮烷、N,O－（二三甲基甲硅烷基）乙酰胺、N－甲基－3－氨基丙基三甲氧基硅烷、4,5－二氢咪唑丙基三乙氧基硅烷、γ－巯基丙基三乙氧基硅烷、γ－巯基丙基甲基二甲氧基硅烷、3－氰基丙基三甲氧基硅烷、甲基三（甲基丙烯酰氧基乙氧基）硅烷、甲基三（缩水甘油氧基）硅烷、2－乙基己基－2－乙基己基膦酸酯、γ－环氧丙氧基丙基甲基二甲氧基硅烷、乙烯基三乙酰氧基硅烷、γ－苯胺基丙基三甲氧基硅烷、γ－巯基丙基甲基二甲氧基硅烷、γ－甲基丙烯酰氧基丙基甲基二甲氧基硅烷、N－三甲基甲硅烷基乙酰胺、二甲基三甲基甲硅烷基胺、二乙基三甲基甲硅烷基胺、三甲基甲硅烷基咪唑、三甲基甲硅烷基异氰酸酯、二甲基甲硅烷基二异氰酸酯、甲基甲硅烷基三异氰酸酯、乙烯基甲硅烷基三异氰酸酯、苯基甲硅烷基三异氰酸酯、四异氰酸酯硅烷、乙氧基硅烷三异氰酸酯。
作为上述钛酸酯偶联剂，例如，可列举异丙基三异硬脂酰基钛酸酯、异丙基三辛酰基钛酸酯、异丙基二甲基丙烯酰基异硬脂酰基钛酸酯、异丙基三（十二烷基）苯磺酰基钛酸酯、异丙基异硬脂酰基二丙烯酰基钛酸酯、异丙基三（二辛基磷酸酯）钛酸酯、异丙基三枯基苯基钛酸酯、异丙基三（二辛基焦磷酸酯）钛酸酯、四异丙基双（二辛基亚磷酸酯）钛酸酯、四辛基双（二－十三烷基亚磷酸酯）钛酸酯、四（2,2－二烯丙氧基甲基－1－丁基）双（二－十三烷基）亚磷酸酯钛酸酯、二枯基苯基氧基乙酸酯钛酸酯、双（二辛基焦磷酸酯）氧基乙酸酯钛酸酯、二异硬脂酰基亚乙基钛酸酯、双（二辛基焦磷酸酯）亚乙基钛酸酯、二异丙氧基双（2,4－戊二酮基）钛（IV）、二异丙基双三乙醇氨基钛酸酯、钛乳酸酯、乙酰乙酸乙酯钛酸酯、二－异丙氧基双（乙酰丙酮基）钛、二－正丁氧基双（三乙醇胺根合）钛、二羟基双（乳酸根合）钛、钛－异丙氧基亚辛基乙醇酸酯、钛硬脂酸酯、三－正丁氧基钛单硬脂酸酯、钛乳酸乙酯、氨化三乙醇钛。
本实施方式的粘接剂组合物中，根据需要进一步可以添加渗漏抑制剂。作为渗漏抑制剂，例如，有全氟辛酸、辛酸酰胺、油酸等脂肪酸，全氟辛基乙基丙烯酸酯、有机硅。
制造上述粘接剂组合物时，将（A）成分和（B）成分与根据需要添加的（C）成分等一次性或分开地，适当组合搅拌器、混砂机、三辊研磨机、行星式混合器等分散·溶解装置，并根据需要加热，进行混合、溶解、解粒混炼或分散，形成均匀的糊状即可。
图7是表示使用本实施方式的粘接剂组合物而制造的半导体装置的一例的示意剖面图。图7所示的半导体装置包括：3个引线框（散热体）12a、12b、12c；在引线框12a上通过本实施方式的粘接剂组合物13而连接的芯片（发热体）11；和将它们铸型的铸型树脂15。芯片11通过2根导线14分别连接在引线框12b、12c上。
图8是表示使用本实施方式的粘接剂组合物而制造的半导体装置的其他例的示意剖面图。图8所示的半导体装置包括：基板16；以包围基板16的方式形成的2个引线框17；在引线框17上通过本实施方式的粘接剂组合物13而连接的LED芯片18；和将它们密封的透光性树脂19。LED芯片18通过导线14连接在引线框17上。
本实施方式的半导体装置可通过使用本实施方式的粘接剂组合物将半导体元件粘接在支撑构件上而得到。将半导体元件粘接在支撑构件上后，根据需要进行引线接合工序、密封工序。
作为支撑构件，例如，可列举42合金引线框、铜引线框、钯PPF引线框等引线框，玻璃环氧基板（由玻璃纤维增强环氧树脂形成的基板）、BT基板（由氰酸酯单体及其低聚物与双马来酰亚胺形成的BT树脂使用基板）等有机基板。
使用本实施方式的粘接剂组合物将半导体元件粘接于引线框等支撑构件上时，可以通过首先将粘接剂组合物通过分配法、丝网印刷法、压印法等涂布在支撑构件上后，搭载半导体元件，然后使用烘箱或加热块等加热装置进行加热固化来进行。加热固化通常通过在100～300℃加热5秒～10小时来进行。进一步，经过引线接合工序之后，通过通常的方法进行密封，从而能够形成完成的半导体装置。
实施例
以下，通过实施例详细说明本发明，但本发明并不受其限制。实施例和参考例中使用的材料是如下制作的材料或者获得的材料。
（1）具有300℃以上的沸点的醇或羧酸：硬脂酸（沸点；376℃、和光纯药工业（株））、棕榈酸（沸点；390℃、和光纯药工业（株））、异龙脑基环己醇（沸点；308℃、以下，简称MTPH）
（2）挥发性成分：二丙二醇二甲醚（沸点；175℃、以下，简称DMM、大赛璐化学（株））、γ－丁内酯（沸点；204℃、以下，简称GBL、三协化学（株））、三乙二醇丁基甲醚（沸点；261℃、以下，简称BTM、东邦化学工业（株））、二乙二醇单丁醚（沸点；231℃、以下，简称BDG、大赛璐化学（株））
（3）银粒子：AgF10S（德力化学研究所（株）、商品名、银粉、平均粒径10μm、球状、氧状态比率15％）、AgC－212D（福田金属箔粉（株）、商品名、银粉、平均粒径3.1μm、片状、氧状态比率5％）
（4）表面处理银粒子：
（i）表面处理球状银粉
用乙醇（关东化学（株））稀释盐酸（关东化学（株））28质量份，调制80质量份的酸性溶液。在该酸性溶液中添加作为表面保护材料的十八硫醇（东京化成工业（株））0.29质量份，调制表面处理液。在该表面处理液中添加20质量份上述的AgF10S，在保持为40℃的状态下搅拌1小时，从而进行氧化膜除去和表面处理。然后，通过过滤除去表面处理液，添加40℃的乙醇来洗涤表面处理银粉。进一步通过过滤除去乙醇的洗涤液，将该洗涤、过滤的工序重复10次左右，从而除去物理吸附在表面处理银粉表面上的十八硫醇和盐酸。最后通过减压干燥洗涤后的表面处理银粉而除去乙醇，得到干燥状态的表面处理银粉。确认到所得的表面处理银粉的氧的状态比率为0％，除去了氧化膜。
（ii）表面处理片状银粉
用乙醇（关东化学（株））稀释盐酸（关东化学(株)）4质量份，调制80质量份的酸性溶液。在该酸性溶液中添加作为表面保护材料的硬脂酸（和光纯药工业(株)）0.28质量份，调制表面处理液。在该表面处理液中添加20质量份上述的AgC－212D，在保持为40℃的状态下搅拌1小时，从而进行氧化膜除去和表面处理。然后，通过过滤除去表面处理液，添加40℃的乙醇来洗涤表面处理银粉。进一步通过过滤除去乙醇的洗涤液，将该洗涤、过滤的工序重复10次左右，从而除去物理吸附在表面处理银粉表面上的硬脂酸和盐酸。最后通过减压干燥洗涤后的表面处理银粉而除去乙醇，得到干燥状态的表面处理银粉。确认到所得的表面处理银粉的氧的状态比率为1％，除去了氧化膜。
（实施例1～7和参考例1～6）
按照表1或2所示的配合比例，通过混砂机将材料（1）和（2）混炼10分钟，得到液状成分。进一步，添加表面处理或未处理的银粒子（3）或（4），通过混砂机混炼15分钟，得到粘接剂组合物。
通过下述所示方法来研究粘接剂组合物的特性，将测定结果示于表1和表2。
芯片剪切强度：将约0.2mg粘接剂组合物涂布在镀Ag的Cu引线框（连接盘（land）部：10×5mm）上，在其上粘接2mm×2mm的镀Ni的Cu芯片（Ni镀层厚：1μm、芯片厚：150μm），将其在洁净烘箱（TABAI ESPEC CORP．制、PVHC－210）中于250℃热处理1小时。对其使用万能型推拉力试验机（DAGE公司制、4000系列），在测定速度500μm／s、测定高度100μm的条件下测定剪切强度（MPa）。
粘接剂组合物固化物的热导率：将上述粘接剂组合物在洁净烘箱（TABAIESPEC CORP．制、PVHC－210）中于250℃加热处理1小时，得到10×10×1mm的试验片。通过激光闪解法（NETZSCH公司制、LFA 447、25℃）测定该试验片的热扩散率，进一步根据该热扩散率、通过差示扫描量热测定装置（Perkinelmer公司制Pyris1）得到的比热容量与通过阿基米德法得到的比重的积，算出25℃时的粘接剂组合物的固化物热导率（W／m·K）。
体积电阻率：将上述粘接剂组合物在洁净烘箱（TABAI ESPECCORP．制、PVHC－210）中于250℃加热处理1小时，在玻璃板上得到1×50×0.03mm的试验片。对该试验片在25℃下通过4端子法(Advantest(株)制、R687E DIGITAL MULTIMETER)测定体积电阻率的值。
表1
Figure BDA00003449672500131
表2
Figure BDA00003449672500141
*由于银粒子未烧结，因此无法制作体积电阻率和热导率测定用的试验片。
如表1和表2所示，根据实施例1～4，通过将包含氧的状态比率小于15％的片状银粉（表面处理片状银粉）、挥发性成分、和具有300℃以上沸点的醇或羧酸的组合物在250℃热处理1小时，从而实现了5.2×10-6Ω·cm以下的体积电阻率、167W／m·K以上的高热导率和26MPa以上的高剪切强度。
由实施例5可知，通过将包含氧的状态比率小于15％的片状银粉（表面处理片状银粉）和氧的状态比率小于15％的球状银粉（表面处理球状银粉）、挥发性成分、和具有300℃以上的沸点的醇或羧酸的组合物在250℃热处理1小时，从而实现了4.2×10-6Ω·cm的体积电阻率、179W／m·K的高热导率和25MPa的高剪切强度。
根据实施例6、7，通过将包含氧的状态比率小于15％的片状银粉（表面处理片状银粉）、挥发性成分、和具有300℃以上的沸点的醇或羧酸的组合物在250℃热处理1小时，从而实现了4.8×10-6Ω·cm以下的体积电阻率、166W／m·K以上的高热导率和23MPa以上的高剪切强度。
由上述结果可知，实施例中记载的粘接剂组合物具有Sn95Pb焊锡以上的高导电性、高导热性（30W／m·K）和高粘接强度。
根据参考例1～3，包含氧的状态比率为15％的银粉（AgF10S）、挥发性成分和具有300℃以上沸点的醇或羧酸的组合物在250℃下未发生银粒子彼此的烧结，因此无法制作体积电阻率和热导率测定用的试验片，与被粘接体也未连接。
由参考例4可知，包含氧的状态比率小于15％的片状银粉（表面处理片状银粉）和挥发性成分的组合物通过在250℃热处理1小时，表现出5.2×10-6Ω·cm的体积电阻率、182W／m·K的高热导率，但与被粘接体的镀Ni部分的粘接强度非常弱，剪切强度为2.5MPa，与Sn95Pb焊锡相比粘接强度差。
由参考例5可知，包含氧的状态比率小于15％的片状银粉（表面处理片状银粉）、挥发性成分和具有小于300℃的沸点的醇（BDG）的组合物通过在250℃热处理1小时，表现出4.9×10-6Ω·cm的体积电阻率、174W／m·K的高热导率，但与被粘接体的镀Ni部分的粘接强度非常弱，剪切强度为3.3MPa，粘接强度与Sn95Pb焊锡相比差。可推定这是因为，施加规定的热历程时BDG的挥发时机早，因此Ni表面的氧化膜或有机被膜被除去，在银粒子与Ni表面之间未能形成牢固的粘接相，因此剪切强度降低。
由参考例6可知，包含氧的状态比率小于15％的球状银粉（表面处理球状银粉）、挥发性成分和具有300℃以上的沸点的醇或羧酸（硬脂酸）的组合物通过在250℃热处理1小时，表现出4.2×10-6Ω·cm的体积电阻率、183W／m·K的高热导率，但与被粘接体的镀Ni部分的粘接强度弱，剪切强度为12MPa，粘接强度与实施例1～7中记载的粘接剂组合物相比差。可推定这是因为，银粒子的形状为球状，与片状的银粒子相比银粒子彼此或与Ni表面的接触面积变小，因此剪切强度降低。
符号说明
1，4，7：表面保护材料、2，5：氧化膜、3，6，8：银粒子、3’，8’：被表面保护材料覆盖的银粒子、11：芯片、12a，12b，12c：引线框、13：粘接剂组合物、14：导线、15：铸型树脂、16：基板、17：引线框、18：芯片、19：透光性树脂。

Claims (6)

1.一种粘接剂组合物，其包含：通过X射线光电子分光法测定的源自银氧化物的氧的状态比率小于15%的片状银粒子（A）、和具有300℃以上的沸点的醇或羧酸（B）。
2.根据权利要求1所述的粘接剂组合物，还包含沸点为100℃以上且小于300℃的挥发性成分（C）。
3.根据权利要求1或2所述的粘接剂组合物，所述银粒子是实施了除去其氧化膜的处理和利用表面保护材料的表面处理的银粒子。
4.根据权利要求1～3中任一项所述的粘接剂组合物，所述银粒子包含平均粒径为0.1μm以上50μm以下的银粒子。
5.根据权利要求1～4中任一项所述的粘接剂组合物，将所述粘接剂组合物热固化而形成的固化物的体积电阻率和热导率分别为1×10-4Ω·cm以下、30W／m·K以上。
6.一种半导体装置，其具有通过权利要求1～5中任一项所述的粘接剂组合物将半导体元件与半导体元件搭载用支撑构件粘接而成的结构。
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CN110036450A (zh) * 2016-12-02 2019-07-19 田中贵金属工业株式会社 导电性接合材料及半导体装置的制造方法
CN110036450B (zh) * 2016-12-02 2020-12-01 田中贵金属工业株式会社 导电性接合材料及半导体装置的制造方法

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