CN111344813B - 烧结接合用组合物、烧结接合用片、及带烧结接合用片的切割带 - Google Patents

烧结接合用组合物、烧结接合用片、及带烧结接合用片的切割带 Download PDF

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CN111344813B
CN111344813B CN201880073022.7A CN201880073022A CN111344813B CN 111344813 B CN111344813 B CN 111344813B CN 201880073022 A CN201880073022 A CN 201880073022A CN 111344813 B CN111344813 B CN 111344813B
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bonding
sintering
sintered
sheet
composition
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CN111344813A (zh
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市川智昭
菅生悠树
下田麻由
三田亮太
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Nitto Denko Corp
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Nitto Denko Corp
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Abstract

本发明的烧结接合用组合物含有含导电性金属的烧结性颗粒。该烧结性颗粒的平均粒径为2μm以下，并且该烧结性颗粒中的粒径100nm以下的颗粒的比例为40质量％以上且不足80质量％。本发明的烧结接合用片(10)具备由这样的烧结接合用组合物形成的粘合层。本发明的带烧结接合用片的切割带(X)具备这样的烧结接合用片(10)及切割带(20)。切割带(20)具有包含基材(21)和粘合剂层(22)的层叠结构，烧结接合用片(10)位于切割带(20)的粘合剂层(22)上。本发明的烧结接合用组合物、烧结接合用片、及带烧结接合用片的切割带适于实现基于高密度的烧结层的烧结接合。

Description

烧结接合用组合物、烧结接合用片、及带烧结接合用片的切 割带
技术领域
本发明涉及可以用于半导体装置的制造等的烧结接合用组合物、烧结接合用片、及带烧结接合用片的切割带。
背景技术
半导体装置的制造中，对于引线框、绝缘电路基板等支撑基板，作为用于将半导体芯片与支撑基板侧电连接的同时进行芯片接合的方法，已知：在支撑基板与芯片之间形成Au-Si共晶合金层来实现接合状态的方法；利用焊料、含有导电性颗粒的树脂作为接合材料的方法。
另一方面，承担电力的供给控制的功率半导体装置的普及近年来变得显著，但功率半导体装置常常由于工作时的通电量大而发热量大。因此，功率半导体装置的制造中，关于将半导体芯片与支撑基板侧电连接的同时与支撑基板进行芯片接合的方法，要求在高温工作时也能够实现可靠性高的接合状态。采用SiC、GaN作为半导体材料从而实现了高温工作化的功率半导体装置中，这种要求特别强烈。而且，为了响应这样的要求，作为伴有电连接的芯片接合方法，提出了使用含有烧结性颗粒和溶剂等的烧结接合用的组合物的技术。
使用含烧结性颗粒的烧结接合用组合物进行的芯片接合中，首先，半导体芯片借助烧结接合用组合物在规定的温度·载荷条件下载置于支撑基板的芯片接合预定部位。之后，以在支撑基板与其上的半导体芯片之间产生烧结接合用组合物中的溶剂的挥发等且烧结性颗粒间发生烧结的方式，进行规定的温度·加压条件下的加热工序。由此，在支撑基板与半导体芯片之间形成烧结层，半导体芯片与支撑基板进行电连接的同时进行机械接合。这种技术例如记载于下述专利文献1、2。
现有技术文献
专利文献
专利文献1：国际公开第2008/065728号
专利文献2：日本特开2013-039580号公报
发明内容
发明要解决的问题
对于使用含烧结性颗粒的烧结接合用组合物进行的芯片接合，以往，对于在支撑基板与半导体芯片之间形成的烧结层，由于其孔隙率大而有时无法确保充分的接合可靠性。
本发明是基于如上所述的实际情况而想到的，其目的在于，提供适于实现基于高密度的烧结层的烧结接合的烧结接合用组合物、烧结接合用片、及带烧结接合用片的切割带。
用于解决问题的方案
根据本发明的第1方面，提供烧结接合用组合物。该烧结接合用组合物含有含导电性金属的烧结性颗粒。本组合物中的烧结性颗粒的平均粒径为2μm以下。与其同时，该烧结性颗粒中的粒径100nm以下的颗粒的比例为40质量％以上且不足80质量％。即，该烧结性颗粒中粒径超过100nm的颗粒所占的比例超过20质量％并且为60质量％以下。这样的构成的本组合物可以用于将接合对象物间烧结接合。例如，本组合物在半导体装置的制造中可以用于对支撑基板将半导体芯片与支撑基板侧电连接的同时进行烧结接合。
使用烧结接合用组合物实现烧结接合的过程中，例如，在该组合物夹在接合对象物间的状态下将接合对象物彼此在规定条件下压接而临时固定，然后进行规定的温度·加压条件下的高温加热工序，将接合对象物间接合的烧结层由该组合物形成。本发明人等得到了如下见解：关于这样的烧结接合工艺中使用的烧结接合用组合物中配混的含导电性金属的烧结性颗粒的上述粒度分布构成、即平均粒径为2μm以下、粒径100nm以下的颗粒的比例为40质量％以上且不足80质量％这样的构成，适于使该组合物经过烧结接合工艺而形成的烧结层实现高密度化。例如，如后述的实施例及比较例所示。认为根据平均粒径2μm以下的烧结性颗粒的上述粒度分布构成，本烧结接合用组合物中的烧结性颗粒的含有比例例如大为85质量％以上的情况下，粒径100nm以下的颗粒群及粒径超过100nm的颗粒群在组合物中容易成为通过烧结而容易形成高密度烧结层的填充(packing)状态。
另外，本发明人等还得到了如下见解：有由含有含导电性金属的烧结性颗粒的组合物形成的烧结层的密度越高，该烧结层可得到越高的接合可靠性的倾向。例如，如后述的实施例及比较例所示。在用于对支撑基板将半导体芯片与支撑基板侧电连接的同时进行机械接合的烧结接合中，特别是对基于烧结层的接合对象物间的接合，要求能够确保高度的可靠性。适于实现基于高密度的烧结层的烧结接合的本组合物适于使该烧结层实现高的接合可靠性。
如上所述，本发明的第1方面的烧结接合用组合物适于实现基于高密度的烧结层的烧结接合，因此，适于使该烧结层实现高的接合可靠性。
本烧结接合用组合物中的烧结性颗粒的含有比例优选为90～98质量％、更优选为92～98质量％、更优选为94～98质量％。这样的构成在实现形成的烧结层的高密度化的方面是适合的。
本烧结接合用组合物经过了300℃、40MPa、及2.5分钟的条件下的烧结后的孔隙率(即，通过该烧结由本组合物形成的烧结层的孔隙率)优选为10％以下，更优选为8％以下，更优选为6％以下，更优选为4％以下。这样的构成在实现形成的烧结层的高密度化的方面是适合的。
本烧结接合用组合物经过了300℃、40MPa、及2.5分钟的条件下的烧结后的通过纳米压痕法测定的25℃下的弹性模量(即，对通过该烧结由本组合物形成的烧结层通过纳米压痕法测定的25℃下的弹性模量)优选为60GPa以上、更优选为65GPa以上、更优选为70GPa以上、更优选为75GPa以上。具有这样的硬度的烧结层在实现高接合可靠性的方面是适合的。
本烧结接合用组合物优选在含有含导电性金属的上述烧结性颗粒的同时包含热分解性高分子粘结剂。本发明中，热分解性高分子粘结剂是指，能够在烧结接合用的高温加热过程中被热分解的粘结剂成分。根据这样的构成，在上述临时固定下的温度、例如70℃及其附近的温度范围内容易利用热分解性高分子粘结剂的粘弹性从而确保本烧结接合用组合物的内聚力，因此容易确保该组合物的粘接力。因此，本构成在抑制以本烧结接合用组合物夹在接合对象物间的状态压接接合对象物彼此时、压接后这些接合对象物产生位置偏移的方面是适合的。
本烧结接合用组合物中的热分解性高分子粘结剂的重均分子量优选为10000以上。这样的构成在利用热分解性高分子粘结剂的粘弹性从而确保本烧结接合用组合物的内聚力、粘接力的方面是适合的。
本烧结接合用组合物中的热分解性高分子粘结剂优选为聚碳酸酯树脂和/或丙烯酸类树脂。如上所述，使用烧结接合用组合物实现烧结接合的过程中，在接合对象物间被该组合物临时固定的基础上，进行烧结接合用的高温加热。烧结接合用的高温加热例如在300℃及包含其附近温度的温度范围进行时，聚碳酸酯树脂及丙烯酸类树脂作为在300℃左右的温度下分解/挥发的高分子粘结剂容易准备。因此，本构成对于使在要利用本烧结接合用组合物进行烧结接合的接合对象物间形成的烧结层中减少有机残渣的方面是适合的。有烧结层中的有机残渣越少、该烧结层越坚固的倾向，因此，该烧结层容易获得高的接合可靠性。
本烧结接合用组合物中的烧结性颗粒优选包含选自由银、铜、银氧化物、及铜氧化物组成的组中的至少一种。这样的构成在要使用本烧结接合用组合物进行烧结接合的接合对象物间形成坚固的烧结层的方面是适合的。
根据本发明的第2方面，提供烧结接合用片。该烧结接合用片具有由本发明的第1方面的上述烧结接合用组合物形成的粘合层。这样的构成适于对接合对象物间以均匀的厚度供给烧结接合用组合物从而由均匀的厚度的烧结层将接合对象物间烧结接合。基于均匀的厚度的烧结层的烧结接合例如在实现半导体芯片对支撑基板的高的接合可靠性的方面是适合的。而且，本烧结接合用片适于在抑制烧结金属自接合对象物间的溢出、烧结金属在接合对象物侧面的向上蔓延的同时将接合对象物间烧结接合。本烧结接合用片由于以不易流动化的片的形态供给烧结接合用材料，因此适于抑制这样的溢出、向上蔓延。这样的溢出、向上蔓延的抑制在提高伴随烧结接合的半导体装置等制造目标物的成品率的方面是适合的。
根据本发明的第3方面，提供带烧结接合用片的切割带。该带烧结接合用片的切割带具备切割带和本发明的第2方面的上述烧结接合用片。切割带具有包含基材和粘合剂层的层叠结构，烧结接合用片配置于切割带的粘合剂层上。这样的构成的切割带在半导体装置的制造过程中可以用于得到带有芯片尺寸的烧结接合用片的半导体芯片。而且，根据本切割带，在半导体装置制造过程中的烧结接合中，可得到与上面关于本发明的第1方面的烧结接合用组合物叙述的同样的效果，并且可得到与上面关于本发明的第2方面的烧结接合用片叙述的同样的效果。
附图说明
图1为本发明的一个实施方式的烧结接合用片的部分截面示意图。
图2表示使用图1所示的烧结接合用片进行的半导体装置制造方法中的一部分工序。
图3表示使用图1所示的烧结接合用片进行的半导体装置制造方法中的一部分工序。
图4表示使用图1所示的烧结接合用片进行的半导体装置制造方法中的一部分工序。
图5为本发明的一个实施方式的带烧结接合用片的切割带的部分截面示意图。
图6表示使用图5所示的带烧结接合用片的切割带进行的半导体装置制造方法中的一部分工序。
具体实施方式
图1为本发明的一个实施方式的烧结接合用片10的部分截面示意图。烧结接合用片10用于将接合对象物间烧结接合，具备由本发明的烧结接合用组合物形成的粘合层11。粘合层11和/或形成其的烧结接合用组合物在本实施方式中至少包含：含导电性金属的烧结性颗粒、热分解性高分子粘结剂、和低沸点粘结剂。这样的烧结接合用片10例如在半导体装置的制造过程中可以用于对支撑基板将半导体芯片与支撑基板侧电连接的同时进行烧结接合。
烧结接合用片10和/或其粘合层11中包含的烧结性颗粒为含有导电性金属元素而能烧结的颗粒。作为导电性金属元素，例如可列举出金、银、铜、钯、锡及镍。作为这种烧结性颗粒的构成材料，例如可列举出金、银、铜、钯、锡、镍及选自它们的组中的两种以上金属的合金。作为烧结性颗粒的构成材料，也可列举出银氧化物、铜氧化物、钯氧化物、锡氧化物等金属氧化物。另外，烧结性颗粒可以为具有核壳结构的颗粒。例如，烧结性颗粒可以为具有如下的核和壳的核壳结构的颗粒：以铜为主成分的核；和以金、银等为主成分且覆盖核的壳。本实施方式中，烧结性颗粒优选包含选自由银颗粒、铜颗粒、银氧化物颗粒、及铜氧化物颗粒组成的组中的至少一种。从使形成的烧结层实现高导电性及高导热性的观点出发，优选银颗粒及铜颗粒作为烧结性颗粒。此外，从耐氧化性的观点出发，银颗粒容易处理，故优选。例如，半导体芯片向带有银镀层的铜基板的烧结接合中，使用含有铜颗粒作为烧结性颗粒的烧结材料时，需要在氮气气氛下等非活性环境下进行烧结工艺，但是使用银颗粒构成烧结性颗粒的烧结材料时，即使在空气气氛下，也能适当地实施烧结工艺。
烧结接合用片10和/或其粘合层11中包含的烧结性颗粒的平均粒径为2μm以下。对于烧结性颗粒，从实现低的烧结温度等从而确保良好的烧结性的观点出发，该烧结性颗粒的平均粒径优选为1.5μm以下，更优选为1.2μm以下，更优选为1μm以下，更优选为700nm以下，更优选为500nm以下。对于粘合层11和/或用于形成其的组合物中的烧结性颗粒，从确保良好的分散性的观点出发，该烧结性颗粒的平均粒径优选为70nm以上、更优选为100nm以上、更优选为200nm以上。
烧结性颗粒的平均粒径可以基于使用扫描型电子显微镜(SEM)进行的观察来求出。对于粘合层含有烧结性颗粒的情况下的该烧结性颗粒的平均粒径，具体可以通过如下的方法来求出。首先，对包含烧结性颗粒的粘合层在冷却环境下实施离子抛光而使粘合层的截面露出。接着，使用场发射型扫描电子显微镜SU8020(Hitachi High-TechnologiesCorporation制)对该露出截面进行拍摄，得到背散射电子图像作为图像数据。对于拍摄条件，将加速电压设为5kV、将倍率设为50000倍。接着，对得到的图像数据使用图像解析软件Image J实施自动2值化处理后，根据该图像数据算出颗粒的平均粒径。
粘合层11中的烧结性颗粒的含有比例例如为85质量％以上、优选为90～98质量％、更优选为92～98质量％、更优选为94～98质量％。
粘合层11中的烧结性颗粒中的粒径100nm以下的颗粒的比例为40质量％以上且不足80质量％。该比例优选为45质量％以上、更优选为48质量％以上，并且优选为70质量％以下，更优选为65质量％以下。即，粘合层11中的烧结性颗粒中的粒径超过100nm的颗粒的比例超过20质量％，优选为30质量％以上、更优选为35质量％以上，并且为60质量％以下，优选为55质量％以下、更优选为52质量％以下。
烧结接合用片10和/或其粘合层11中包含的热分解性高分子粘结剂为在烧结接合用的高温加热过程中能够被热分解的粘结剂成分，在直至该加热过程前，为有助于保持烧结接合用片10和/或其粘合层11的片形状的要素。本实施方式中，从担保片形状保持功能的观点出发，热分解性高分子粘结剂在常温(23℃)下为固体的材料。作为这种热分解性高分子粘结剂，例如可列举出聚碳酸酯树脂及丙烯酸类树脂。
对于作为热分解性高分子粘结剂的聚碳酸酯树脂，例如可列举出在主链的碳酸酯基(-O-CO-O-)间不含苯环等芳香族化合物而由脂肪族链形成的脂肪族聚碳酸酯、及在主链的碳酸酯基(-O-CO-O-)间包含芳香族化合物的芳香族聚碳酸酯。作为脂肪族聚碳酸酯，例如可列举出聚碳酸亚乙酯及聚碳酸亚丙酯。作为芳香族聚碳酸酯，可列举出主链包含双酚A结构的聚碳酸酯。
对于作为热分解性高分子粘结剂的丙烯酸类树脂，例如可列举出具有碳数4～18的直链状或支链状的烷基的丙烯酸酯和/或甲基丙烯酸酯的聚合物。以下，以“(甲基)丙烯酸”表示“丙烯酸”和/或“甲基丙烯酸”。对于用于形成作为热分解性高分子粘结剂的丙烯酸类树脂的(甲基)丙烯酸酯的烷基，例如可列举出甲基、乙基、丙基、异丙基、正丁基、叔丁基、异丁基、戊基、异戊基、己基、庚基、环己基、2-乙基己基、辛基、异辛基、壬基、异壬基、癸基、异癸基、十一烷基、十二烷基、十三烷基、十四烷基、硬脂基、及十八烷基。
作为热分解性高分子粘结剂的丙烯酸类树脂可以为包含源自上述(甲基)丙烯酸酯以外的其他单体的单体单元的聚合物。作为这种其他单体，例如可列举出含羧基单体、酸酐单体、含羟基单体、含磺酸基单体、及含磷酸基单体。具体而言，作为含羧基单体，例如可列举出丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、衣康酸、马来酸、富马酸及巴豆酸。作为酸酐单体，例如可列举出马来酸酐、衣康酸酐。作为含羟基单体，例如可列举出(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸4-羟基丁酯、(甲基)丙烯酸6-羟基己酯、(甲基)丙烯酸8-羟基辛酯、(甲基)丙烯酸10-羟基癸酯、(甲基)丙烯酸12-羟基月桂酯、及(甲基)丙烯酸4-(羟基甲基)环己基甲酯。作为含磺酸基单体，例如可列举出苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺丙酯、及(甲基)丙烯酰氧基萘磺酸。作为含磷酸基单体，例如可列举出2-羟基乙基丙烯酰基磷酸酯。
热分解性高分子粘结剂的重均分子量优选为10000以上。热分解性高分子粘结剂的重均分子量采用通过凝胶渗透色谱法(GPC)测定并通过聚苯乙烯换算算出的值。
对于粘合层11中的热分解性高分子粘结剂的含有比例，从适当地发挥上述片形状保持功能的观点出发，优选为0.5～10质量％、更优选为0.8～8质量％、更优选为1～6质量％。
烧结接合用片10和/或其粘合层11中包含的低沸点粘结剂设为：使用动态粘弹性测定装置(商品名“HAAKE MARS III”，Thermo Fisher Scientfic公司制)测定的23℃下的粘度显示1×105Pa·s以下的液态或半液态的粘结剂。本粘度测定中，使用
Figure BDA0002486486460000091
的平行板作为夹具，将板间间隙设为100μm，将旋转剪切中的剪切速度设为1s-1。
作为粘合层11中包含的低沸点粘结剂，例如可列举出萜烯醇类、除了萜烯醇类之外的醇类、亚烷基二醇烷基醚类、及除了亚烷基二醇烷基醚类之外的醚类。作为萜烯醇类，例如可列举出异冰片基环己醇、香茅醇、香叶醇、橙花醇、香苇醇、及α-松油醇。作为除了萜烯醇类之外的醇类，例如可列举出戊醇、己醇、庚醇、辛醇、1-癸醇、乙二醇、二乙二醇、丙二醇、丁二醇及2,4-二乙基-1,5-戊二醇。作为亚烷基二醇烷基醚类，例如可列举出乙二醇丁基醚、二乙二醇甲基醚、二乙二醇乙基醚、二乙二醇丁基醚、二乙二醇异丁基醚、二乙二醇己基醚、三乙二醇甲基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丁基醚、二乙二醇丁基甲基醚、二乙二醇异丙基甲基醚、三乙二醇二甲基醚、三乙二醇丁基甲基醚、丙二醇丙基醚、二丙二醇甲基醚、二丙二醇乙基醚、二丙二醇丙基醚、二丙二醇丁基醚、二丙二醇二甲基醚、三丙二醇甲基醚、及三丙二醇二甲基醚。作为除了亚烷基二醇烷基醚类之外的醚类，例如可列举出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、及乙二醇苯基醚。作为粘合层11中包含的低沸点粘结剂，可以使用一种低沸点粘结剂、也可以使用两种以上的低沸点粘结剂。作为粘合层11中包含的低沸点粘结剂，从常温下的稳定性的观点出发，优选萜烯醇类、更优选异冰片基环己醇。
烧结接合用片10和/或其粘合层11在以上的成分的基础上还可以含有例如增塑剂等。
粘合层11的23℃下的厚度优选为5μm以上、更优选为10μm以上，并且优选为100μm以下，更优选为80μm以下。另外，粘合层11和/或形成其的烧结接合用组合物的70℃下的粘度例如为5×103～1×107Pa·s、优选为1×104～1×106Pa·s。
粘合层11和/或形成其的烧结接合用组合物经过包括40MPa的加压下的300℃下的2.5分钟的加热工序的烧结后的孔隙率(即，通过该烧结由粘合层11形成的烧结层的孔隙率)优选为10％以下，更优选为8％以下，更优选为6％以下，更优选为4％以下。
粘合层11和/或形成其的烧结接合用组合物经过包括40MPa的加压下的300℃下的2.5分钟的加热工序的烧结后的通过纳米压痕法测定的25℃下的弹性模量(即，对通过该烧结由粘合层11形成的烧结层通过纳米压痕法测定的25℃下的弹性模量)优选为60GPa以上、更优选为65GPa以上、更优选为70GPa以上、更优选为75GPa以上。
基于纳米压痕法的弹性模量的测定例如可以使用纳米压痕仪(商品名“Triboindenter”，Hysitron公司制)来进行。本测定中，测定模式设为单一压入测定，测定温度设为25℃，使用压头采用Berkovich(三角锥)型的金刚石压头，压头相对于测定对象物的压入深度设为2μm，该压头的压入速度设为200nm/秒，压头自测定对象物的拔出速度设为200nm/秒。基于纳米压痕法的弹性模量的导出通过使用装置来进行。对于具体的导出方法，例如，如Handbook of Micro/nano Tribology(Second Edition)Edited by BharatBhushan,CRC Press(ISBN 0-8493-8402-8)中所说明那样。
烧结接合用片10例如可以如下制作：将上述各成分在溶剂中混合，制备清漆，在作为基材的隔离体上涂布该清漆而形成涂膜，使该涂膜干燥，由此制作。作为清漆制备用的溶剂，可以使用有机溶剂、醇溶剂。作为有机溶剂，例如可列举出二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、丙酮、甲乙酮、环己酮、甲苯、及二甲苯。作为醇溶剂，例如可列举出乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2-丁烯-1,4-二醇、1,2,6-己三醇、甘油、辛二醇、2-甲基-2,4-戊二醇、及松油醇。作为基材和/或隔离体，可以使用聚对苯二甲酸乙二醇酯(PET)薄膜、聚乙烯薄膜、聚丙烯薄膜、以及用剥离剂(例如，氟系剥离剂、丙烯酸长链烷基酯系剥离剂)进行了表面涂布的各种塑料薄膜、纸等。清漆向基材上的涂布可以使用例如模涂机、凹版涂布机、辊涂机、逆转涂布机、逗点涂布机、或管刮刀涂布机(Pipe doctor coater)。另外，涂膜的干燥温度例如为70～160℃、涂膜的干燥时间例如为1～5分钟。
图2到图4表示使用烧结接合用片10进行的半导体装置制造方法的一部分工序。
本方法中，首先，如图2的(a)所示，准备烧结接合用片10及多个半导体芯片C。烧结接合用片10具有由本发明的烧结接合用组合物形成的上述构成的粘合层11，在其单面带有剥离衬垫L。多个半导体芯片C分别已经安装有规定的半导体元件，并固定于芯片固定用带T1的粘合面T1a上。各半导体芯片C中，贴合烧结接合用片10侧的表面(图2中为上表面)已经形成有平面电极作为外部电极(省略图示)。平面电极的厚度例如为10～1000nm。该平面电极例如由银形成。另外，平面电极可以在形成于半导体芯片表面的钛薄膜上层叠形成。钛薄膜的厚度例如为10～1000nm。这些平面电极及钛薄膜例如可以通过蒸镀法来形成。另外，在各半导体芯片C的另一面(图2中为下表面)根据需要形成有其他电极焊盘(pad)等(省略图示)。
接着，如图2的(b)所示，对多个半导体芯片C贴合烧结接合用片10。具体而言，将烧结接合用片10从其剥离衬垫L侧向半导体芯片C侧按压、并且对多个半导体芯片C贴合烧结接合用片10和/或粘合层11。作为按压手段，例如可列举出压接辊。贴合温度例如为50～90℃，贴合用的载荷例如为0.01～5MPa。
接着，如图2的(c)所示，进行剥离衬垫L的剥离。由此，烧结接合用片10和/或其粘合层11的各处被转印至各半导体芯片C的表面，得到带有芯片尺寸的烧结接合用片10的半导体芯片C。
接着，如图3的(a)所示，进行半导体芯片C向支撑基板S的临时固定(临时固定工序)。具体而言，例如使用芯片安装机，将带烧结接合用片的半导体芯片C借助其烧结接合用片10按压于支撑基板S而进行临时固定。作为支撑基板S，例如，可列举出表面带有铜布线等布线的绝缘电路基板、及引线框。支撑基板S中的芯片搭载部位可以为铜布线、引线框等的基础表面，也可以为在基础表面上形成的镀膜的表面。作为该镀膜，例如可列举出镀金膜、镀银膜、镀镍膜、镀钯膜、及镀铂膜。本工序中，临时固定用的温度条件例如为70℃及为包含其附近温度的温度范围的50～90℃，按压的载荷条件例如为0.01～5MPa，接合时间例如为0.01～5秒钟。
接着，如图3的(b)所示，经过高温加热过程从而将半导体芯片C接合于支撑基板S(烧结接合工序)。具体而言，通过经过规定的高温加热过程，在支撑基板S与半导体芯片C之间使粘合层11中的低沸点粘结剂挥发，使热分解性高分子粘结剂热分解而挥散，然后使烧结性颗粒的导电性金属烧结。由此，在支撑基板S与各半导体芯片C之间形成烧结层12，对支撑基板S进行半导体芯片C与支撑基板S侧的电连接并接合。本工序中，烧结接合的温度条件例如为300℃及包含其附近温度的200～400℃，优选为330～350℃。烧结接合的压力条件例如为0.05～40MPa，优选为0.1～20MPa。另外，烧结接合的接合时间例如为0.3～300分钟，优选为0.5～240分钟。例如，在所述条件的范围内，适宜设定用于实施烧结接合工序的温度曲线、压力曲线。以上那样的烧结接合工序可以使用能够同时进行加热和加压的装置来进行。作为这样的装置，例如可列举出倒装芯片接合机及平行平板加压机。另外，从参与烧结接合的金属的抗氧化的观点出发，本工序优选在氮气气氛下、减压下、或还原气体气氛下中的任意气氛下进行。
半导体装置的制造中，接着，如图4的(a)所示，根据需要借助接合引线W将半导体芯片C的上述电极焊盘(省略图示)与支撑基板S具有的端子部(省略图示)电连接(引线接合工序)。半导体芯片C的电极焊盘、支撑基板S的端子部与接合引线W的连接例如通过伴随加热的超声波焊接而实现。作为接合引线W，例如可以使用金线、铝线、或铜线。引线接合中的引线加热温度例如为80～250℃，优选为80～220℃。另外，其加热时间为几秒～几分钟。
接着，如图4的(b)所示，形成用于保护支撑基板S上的半导体芯片C、接合引线W的密封树脂R(密封工序)。本工序中，例如通过使用模具进行的传递成型技术形成密封树脂R。作为密封树脂R的构成材料，例如可以使用环氧系树脂。本工序中，用于形成密封树脂R的加热温度例如为165～185℃，加热时间例如为60秒～几分钟。本密封工序中，密封树脂R的固化未充分进行的情况下，在本工序之后进行用于使密封树脂R完全固化的后固化工序。
如上进行，可以经过使用了烧结接合用片10的过程来制造半导体装置。
图5为本发明的一个实施方式的带烧结接合用片的切割带X的截面示意图。带烧结接合用片的切割带X具有包含本发明的一个实施方式的上述烧结接合用片10和切割带20的层叠结构，在半导体装置的制造中可以用于得到带有芯片尺寸的烧结接合用片的半导体芯片。另外，带烧结接合用片的切割带X具有与半导体装置的制造过程中的加工对象的半导体晶圆相对应的尺寸的例如圆盘形状。
切割带20具有包含基材21和粘合剂层22的层叠结构。
切割带20的基材21为作为切割带20和/或带烧结接合用片的切割带X中的支撑体而发挥功能的要素。作为基材21，例如可以使用塑料薄膜等塑料基材。作为该塑料基材的构成材料，例如可列举出聚氯乙烯、聚偏氯乙烯、聚烯烃、聚酯、聚氨酯、聚碳酸酯、聚醚醚酮、聚酰亚胺、聚醚酰亚胺、聚酰胺、全芳香族聚酰胺、聚苯硫醚、芳纶、氟树脂、纤维素系树脂、及有机硅树脂。作为聚烯烃，例如可列举出低密度聚乙烯、直链状聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、无规共聚聚丙烯、嵌段共聚聚丙烯、均聚丙烯、聚丁烯、聚甲基戊烯、乙烯-乙酸乙烯酯共聚物、离子键树脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-丁烯共聚物、及乙烯-己烯共聚物。作为聚酯，例如可列举出聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯、及聚聚对苯二甲酸丁二醇酯(PBT)。基材21可以由一种材料形成，也可以由两种以上的材料形成。基材21可以具有单层结构、也可以具有多层结构。基材21上的粘合剂层22为紫外线固化型的情况下，基材21优选具有紫外线透过性。另外，基材21为塑料薄膜的情况下，可以为未拉伸薄膜、可以为单轴拉伸薄膜、也可以为二轴拉伸薄膜。
基材21中的粘合剂层22侧的表面可以实施用于提高与粘合剂层22的密合性的处理。作为这样的处理，例如可列举出电晕放电处理、等离子体处理、喷砂消光加工处理、臭氧暴露处理、火焰暴露处理、高压电击暴露处理、及离子化辐射线处理等物理处理、铬酸处理等化学处理、以及底涂处理。
对于基材21的厚度，从确保基材21作为切割带20和/或带烧结接合用片的切割带X中的支撑体而发挥功能的强度的观点出发，优选为40μm以上、更优选为50μm以上、更优选为55μm以上、更优选为60μm以上。另外，从切割带20和/或带烧结接合用片的切割带X实现适度的挠性的观点出发，基材21的厚度优选为200μm以下，更优选为180μm以下，更优选为150μm以下。
切割带20的粘合剂层22含有粘合剂。作为粘合剂，例如，可以使用以丙烯酸系聚合物为基础聚合物的丙烯酸系粘合剂、橡胶系粘合剂。另外，该粘合剂可以是能够通过加热、辐射线照射等来自外部的作用有意地降低粘合力的粘合剂(粘合力降低型粘合剂)，也可以是粘合力几乎或完全不因来自外部的作用而降低的粘合剂(粘合力非降低型粘合剂)。作为粘合力降低型粘合剂，例如，可列举出辐射线固化型粘合剂(具有辐射线固化性的粘合剂)、加热发泡型粘合剂。作为粘合力非降低型粘合剂，例如可列举出压敏型粘合剂。
粘合剂层22含有丙烯酸系粘合剂的情况下，作为该丙烯酸系粘合剂的基础聚合物的丙烯酸系聚合物优选包含源自丙烯酸烷基酯和/或甲基丙烯酸烷基酯的单体单元作为质量比例最多的单体单元。
作为用于形成丙烯酸系聚合物的单体单元的(甲基)丙烯酸烷基酯，例如，可列举出具有直链状或支链状的烷基的(甲基)丙烯酸烷基酯、及(甲基)丙烯酸环烷基酯。作为(甲基)丙烯酸烷基酯，例如可列举出(甲基)丙烯酸的甲基酯、乙基酯、丙基酯、异丙基酯、丁基酯、异丁基酯、仲丁基酯、叔丁基酯、戊基酯、异戊基酯、己基酯、庚基酯、辛基酯、2-乙基己基酯、异辛基酯、壬基酯、癸基酯、异癸基酯、十一烷基酯、十二烷基酯、十三烷基酯、十四烷基酯、十六烷基酯、十八烷基酯、或二十烷基酯。作为(甲基)丙烯酸环烷基酯，例如，可列举出(甲基)丙烯酸的环戊基酯或环己基酯。作为丙烯酸系聚合物用的(甲基)丙烯酸烷基酯，可以使用一种(甲基)丙烯酸烷基酯、也可以使用两种以上的(甲基)丙烯酸烷基酯。对于用于形成丙烯酸系聚合物的全部单体成分中的(甲基)丙烯酸烷基酯的比例，从粘合剂层22中适当地表现出基于(甲基)丙烯酸烷基酯的粘合性等基本特性的方面考虑，例如为50质量％以上。
对于丙烯酸系聚合物，出于其内聚力、耐热性等的改性的目的，可以包含源自能与(甲基)丙烯酸烷基酯共聚的其他单体的单体单元。作为这样的单体，例如，可列举出含羧基单体、酸酐单体、含羟基单体、含磺酸基单体、含磷酸基单体、丙烯酰胺、及丙烯腈。作为含羧基单体，例如，可列举出丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、衣康酸、马来酸、富马酸、及巴豆酸。作为酸酐单体，例如，可列举出马来酸酐及衣康酸酐。作为含羟基单体，例如，可列举出(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸4-羟基丁酯、(甲基)丙烯酸6-羟基己酯、(甲基)丙烯酸8-羟基辛酯、(甲基)丙烯酸10-羟基癸酯、(甲基)丙烯酸12-羟基月桂基酯、及(甲基)丙烯酸4-(羟基甲基)环己基甲酯。作为含磺酸基单体，例如，可列举出苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺丙酯、及(甲基)丙烯酰氧基萘磺酸。作为含磷酸基单体，例如，可列举出2-羟基乙基丙烯酰基磷酸酯。作为丙烯酸系聚合物用的该其他单体，可以使用一种单体、也可以使用两种以上的单体。对于用于形成丙烯酸系聚合物的全部单体成分中的(甲基)丙烯酸烷基酯以外的单体的比例，从粘合剂层22适当地表现出基于(甲基)丙烯酸烷基酯的粘合性等基本特性的方面考虑，例如为50质量％以下。
对于丙烯酸系聚合物，为了在该聚合物骨架中形成交联结构，可以包含源自能与(甲基)丙烯酸烷基酯共聚的多官能性单体的单体单元。作为这样的多官能性单体，例如，可列举出己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯、(甲基)丙烯酸缩水甘油酯、聚酯(甲基)丙烯酸酯、及氨基甲酸酯(甲基)丙烯酸酯。作为丙烯酸系聚合物用的多官能性单体，可以使用一种多官能性单体、也可以使用两种以上的多官能性单体。对于用于形成丙烯酸系聚合物的全部单体成分中的多官能性单体的比例，从粘合剂层22适当地表现出基于(甲基)丙烯酸烷基酯的粘合性等基本特性的方面考虑，例如为40质量％以下。
丙烯酸系聚合物可以将用于形成其的原料单体聚合而得到。作为聚合方法，例如，可列举出溶液聚合、乳液聚合、本体聚合、及悬浮聚合。从使用切割带20和/或带烧结接合用片的切割带X的半导体装置制造方法中的高度的洁净性的观点出发，优选切割带20和/或带烧结接合用片的切割带X中的粘合剂层22中的低分子量成分少，丙烯酸系聚合物的数均分子量例如为10万以上。
对于粘合剂层22和/或用于形成其的粘合剂，为了提高丙烯酸系聚合物等基础聚合物的数均分子量，例如可以含有外部交联剂。作为用于与丙烯酸系聚合物等基础聚合物反应而形成交联结构的外部交联剂，可列举出多异氰酸酯化合物、环氧化合物、氮丙啶化合物、及三聚氰胺系交联剂。粘合剂层22和/或用于形成其的粘合剂中的外部交联剂的含量相对于基础聚合物100质量份例如为5质量份以下。
粘合剂层22可以为因受到紫外线等辐射线的照射而照射部位的交联度增高从而粘合力降低的辐射线固化型粘合剂层。作为用于形成这样的粘合剂层的辐射线固化型粘合剂，例如可列举出添加型的辐射线固化型粘合剂，其含有：上述丙烯酸系聚合物等基础聚合物、和具有辐射线聚合性的碳-碳双键等官能团的辐射线聚合性的单体成分、低聚物成分。
作为辐射线聚合性的单体成分，例如可列举出氨基甲酸酯(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇单羟基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、及1,4-丁二醇二(甲基)丙烯酸酯。作为辐射线聚合性的低聚物成分，例如，可列举出氨基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各种低聚物，分子量100～30000左右者是适当的。对于粘合剂层22和/或用于形成其的辐射线固化型粘合剂中的辐射线聚合性的单体成分、低聚物成分的含量，在可使形成的粘合剂层22的粘合力适当地降低的范围内来决定，相对于丙烯酸系聚合物等基础聚合物100质量份，例如为40～150质量份。另外，作为添加型的辐射线固化型粘合剂，例如也可以使用日本特开昭60-196956号公报中公开的辐射线固化型粘合剂。
作为用于形成粘合剂层22的辐射线固化型粘合剂，例如也可列举出内在型的辐射线固化型粘合剂，其含有在聚合物侧链、聚合物主链中、聚合物主链末端具有辐射线聚合性的碳-碳双键等官能团的基础聚合物。这样的内在型的辐射线固化型粘合剂在抑制形成的粘合剂层22内的低分子量成分的移动所引起的粘合特性的不期望的经时变化的方面是适合的。
作为内在型的辐射线固化型粘合剂中含有的基础聚合物，优选以丙烯酸系聚合物为基本骨架。作为形成这样的基本骨架的丙烯酸系聚合物，可以采用上述丙烯酸系聚合物。作为辐射线聚合性的碳-碳双键向丙烯酸系聚合物中的导入方法，例如可列举出如下方法：使包含具有规定官能团(第1官能团)的单体的原料单体共聚而得到丙烯酸系聚合物后，使具有能与第1官能团之间发生反应而键合的规定的官能团(第2官能团)和辐射线聚合性碳-碳双键的化合物在维持碳-碳双键的辐射线聚合性的情况下与丙烯酸系聚合物进行缩合反应或加成反应。
作为第1官能团和第2官能团的组合，例如可列举出羧基和环氧基、环氧基和羧基、羧基和氮丙啶基、氮丙啶基和羧基、羟基和异氰酸酯基、异氰酸酯基和羟基。这些组合之中，从反应追踪的容易性的观点出发，羟基和异氰酸酯基的组合、及异氰酸酯基和羟基的组合是适当的。另外，制作具有反应性高的异氰酸酯基的聚合物的技术难度高时，从丙烯酸系聚合物的制作或获得的容易性的观点出发，丙烯酸系聚合物侧的上述第1官能团为羟基并且上述第2官能团为异氰酸酯基是更适当的。该情况下，作为兼具辐射线聚合性碳-碳双键和作为第2官能团的异氰酸酯基的异氰酸酯化合物，例如，可列举出甲基丙烯酰基异氰酸酯、2-甲基丙烯酰氧基乙基异氰酸酯、及间异丙烯基-α,α-二甲基苄基异氰酸酯。另外，作为带有第1官能团的丙烯酸系聚合物，包含源自上述含羟基单体的单体单元者是适当的，包含源自2-羟基乙基乙烯基醚、4-羟基丁基乙烯基醚、二乙二醇单乙烯基醚等醚系化合物的单体单元者也是适当的。
用于形成粘合剂层22的辐射线固化型粘合剂优选含有光聚合引发剂。作为光聚合引发剂，例如，可列举出α-酮醇系化合物、苯乙酮系化合物、苯偶姻醚系化合物、缩酮系化合物、芳香族磺酰氯系化合物、光活性肟系化合物、二苯甲酮系化合物、噻吨酮系化合物、樟脑醌、卤素化酮、酰基氧化膦、及酰基膦酸酯。作为α-酮醇系化合物，例如，可列举出4-(2-羟基乙氧基)苯基(2-羟基-2-丙基)酮、α-羟基-α,α’-二甲基苯乙酮、2-甲基-2-羟基苯丙酮、及1-羟基环己基苯基酮。作为苯乙酮系化合物，例如，可列举出甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、及2-甲基-1-[4-(甲硫基)-苯基]-2-吗啉基丙烷-1-酮。作为苯偶姻醚系化合物，例如，可列举出苯偶姻乙基醚、苯偶姻异丙基醚、及茴香偶姻甲基醚。作为缩酮系化合物，例如可列举出苯偶酰二甲基缩酮。作为芳香族磺酰氯系化合物，例如可列举出2-萘磺酰氯。作为光活性肟系化合物，例如，可列举出1-苯酮-1,2-丙烷二酮-2-(O-乙氧基羰基)肟。作为二苯甲酮系化合物，例如，可列举出二苯甲酮、苯甲酰基苯甲酸、及3,3’-二甲基-4-甲氧基二苯甲酮。作为噻吨酮系化合物，例如，可列举出噻吨酮、2-氯噻吨酮、2-甲基噻吨酮、2,4-二甲基噻吨酮、异丙基噻吨酮、2,4-二氯噻吨酮、2,4-二乙基噻吨酮、及2,4-二异丙基噻吨酮。用于形成粘合剂层22的辐射线固化型粘合剂中的光聚合引发剂的含量相对于丙烯酸系聚合物等基础聚合物100质量份例如为0.05～20质量份。
粘合剂层22和/或用于形成其的粘合剂中除了以上的成分以外，还可以含有交联促进剂、增粘剂、防老剂、着色剂等添加剂。着色剂可以为受到辐射线照射而进行着色的化合物。作为这样的化合物，例如可列举出隐色染料。
对于粘合剂层22的厚度，例如，从粘合剂层22在辐射线固化前后对烧结接合用片10的粘接力的平衡的观点出发为1～50μm。
具有以上那样的构成的带烧结接合用片的切割带X例如可以如下来制作。
对于带烧结接合用片的切割带X的切割带20，可以通过在准备的基材21上设置粘合剂层22来制作。例如树脂制的基材21可以通过压延制膜法、有机溶剂中的浇铸法、密闭体系中的吹塑挤出法、T模挤出法、共挤出法、干层压法等制膜方法来制作。粘合剂层22可以如下来形成：制备粘合剂层22形成用的粘合剂组合物后，在基材21上或规定的隔离体(即剥离衬垫)上涂布该粘合剂组合物而形成粘合剂组合物层，根据需要使该粘合剂组合物层干燥(此时，根据需要进行加热交联)，由此形成。作为粘合剂组合物的涂布方法，例如可列举出辊涂覆、丝网涂覆、及凹版涂覆。粘合剂组合物层的干燥用的温度例如为80～150℃，时间例如为0.5～5分钟。粘合剂层22形成于隔离体上的情况下，将带有该隔离体的粘合剂层22贴合于基材21。如上进行，可以制作切割带20。
对于带烧结接合用片的切割带X的烧结接合用片10，如上所述，例如可以通过制备烧结接合用片10形成用的清漆、在作为基材的隔离体上涂布该清漆而形成涂膜、使该涂膜干燥来制作。
带烧结接合用片的切割带X的制作中，接着，将烧结接合用片10例如压接并贴合于切割带20的粘合剂层22侧。贴合温度例如为30～50℃。贴合压力(线压)例如为0.1～20kgf/cm。粘合剂层22为如上所述的辐射线固化型粘合剂层的情况下，接着例如可以从基材21侧对粘合剂层22照射紫外线等辐射线。照射量例如为50～500mJ/cm2，优选为100～300mJ/cm2。带烧结接合用片的切割带X中，进行作为粘合剂层22的粘合力降低措施的照射的区域(照射区域D)例如为粘合剂层22中的烧结接合用片贴合区域内的除其边缘部以外的区域。
如上进行，可以制作例如图5所示的带烧结接合用片的切割带X。可以在带烧结接合用片的切割带X上以覆盖带有烧结接合用片10的粘合剂层22的方式设置有隔离体(省略图示)。该隔离体是用于保护使得粘合剂层22及烧结接合用片10不露出的要素，在带烧结接合用片的切割带X的使用前从该薄膜被剥离。作为隔离体，可以使用聚对苯二甲酸乙二醇酯(PET)薄膜、聚乙烯薄膜、聚丙烯薄膜、以及以剥离剂(例如，氟系剥离剂、丙烯酸长链烷基酯系剥离剂)进行了表面涂布的各种塑料薄膜、纸等。
图6表示使用带烧结接合用片的切割带X进行的半导体装置制造方法的一部分工序。
本方法中，首先，如图6的(a)所示，将半导体晶圆30贴合于带烧结接合用片的切割带X的烧结接合用片10上。具体而言，半导体晶圆30被压接辊等按压于带烧结接合用片的切割带X的烧结接合用片10侧，从而贴附于带烧结接合用片的切割带X和/或烧结接合用片10。半导体晶圆30已经安装有多个半导体元件，贴附于烧结接合用片10侧的表面(图6中为下表面)已经形成有平面电极(省略图示)作为外部电极。平面电极的厚度例如为10～1000nm。该平面电极例如由银形成。另外，平面电极可以在形成于半导体晶圆表面的钛薄膜上层叠形成。钛薄膜的厚度例如为10～1000nm。这些平面电极及钛薄膜例如可以通过蒸镀法来形成。另外，在半导体晶圆30的另一面(图6中为上表面)在每个半导体元件根据需要形成有其他电极焊盘等(省略图示)。本工序中，贴附温度例如为50～90℃，贴附用的载荷例如为0.01～10MPa。带烧结接合用片的切割带X中的粘合剂层22为辐射线固化型粘合剂层的情况下，可以代替带烧结接合用片的切割带X的制造过程中的上述辐射线照射，在半导体晶圆30向带烧结接合用片的切割带X的贴合后从基材21侧对粘合剂层22照射紫外线等辐射线。照射量例如为50～500mJ/cm2，优选为100～300mJ/cm2。带烧结接合用片的切割带X中进行作为粘合剂层22的粘合力降低措施的辐射线照射的区域(图5中表示为照射区域D)例如为粘合剂层22中的烧结接合用片贴合区域内的除其边缘部以外的区域。
接着，如图6的(b)所示，对半导体晶圆30进行切割。具体而言，在半导体晶圆30被保持于带烧结接合用片的切割带X的状态下，使用切割装置等旋转刀片将半导体晶圆30切割而单片化为半导体芯片单元(图中示意性地用粗线表示切断部位)。由此，形成带有芯片尺寸的烧结接合用片10的半导体芯片C。
然后，根据需要经过对带有带烧结接合用片的半导体芯片C的切割带20中的半导体芯片C侧用水等清洗液进行清洗的清洁工序后，从切割带20拾取带烧结接合用片的半导体芯片C(拾取工序)。例如，对于拾取对象的带烧结接合用片的半导体芯片C，在切割带20的图中下侧使拾取机构的销构件(省略图示)上升并隔着切割带20顶起后，用吸附夹具(省略图示)进行吸附保持。
接着，如图3的(a)所示，进行半导体芯片C向支撑基板S的临时固定(临时固定工序)，如图3的(b)所示，通过经过用于烧结接合的高温加热过程将半导体芯片C接合于支撑基板S(烧结接合工序)。对于这些工序的具体实施方式及具体的条件，与参照图3的(a)及图3的(b)的关于使用烧结接合用片10进行的半导体装置制造方法中的临时固定工序及烧结接合工序在上面叙述的内容同样。
接着，如图4的(a)所示，根据需要借助接合引线W将半导体芯片C的上述电极焊盘(省略图示)和支撑基板S具有的端子部(省略图示)电连接(引线接合工序)。接着，如图4的(b)所示，形成用于保护支撑基板S上的半导体芯片C、接合引线W的密封树脂R(密封工序)。对于这些工序的具体实施方式及具体的条件，与参照图4的(a)及图4的(b)对使用烧结接合用片10进行的半导体装置制造方法中的引线接合工序及密封工序在上面叙述的内容同样。
如上进行，可以经过使用了带烧结接合用片的切割带X的过程来制造半导体装置。
对于烧结接合用片10的粘合层11和/或形成其的烧结接合用组合物，关于其中所含的含导电性金属的烧结性颗粒，如上所述，具有平均粒径为2μm以下、且粒径100nm以下的颗粒的比例为40质量％以上且不足80质量％这样的粒度分布构成。该比例如上所述优选为45质量％以上、更优选为48质量％以上，并且优选为70质量％以下，更优选为65质量％以下。烧结性颗粒的这样的粒度分布构成适于使形成粘合层11的烧结接合用组合物经过烧结接合工艺而形成的烧结层实现高密度化。可以认为根据平均粒径为2μm以下的烧结性颗粒的上述粒度分布构成，形成粘合层11的烧结接合用组合物中的烧结性颗粒的含有比例例如较大而为85质量％以上的情况下，粒径100nm以下的颗粒群及粒径超过100nm的颗粒群在组合物中容易成为通过烧结而容易形成高密度的烧结层12的填充状态。
另外，有由含有含导电性金属的烧结性颗粒的组合物形成的烧结层12的密度越高，烧结层12可得到越高的接合可靠性的倾向。适于实现基于高密度的烧结层12的烧结接合的粘合层11和/或形成其的烧结接合用组合物适于使烧结层12实现高的接合可靠性。
如上所述，上述烧结接合用片10的粘合层11和/或形成其的烧结接合用组合物适于实现基于高密度的烧结层12的烧结接合，因此，适于使烧结层12实现高的接合可靠性。
烧结接合用片10的粘合层11和/或形成其的烧结接合用组合物中的烧结性颗粒的含有比例如上所述，优选为90～98质量％、更优选为92～98质量％、更优选为94～98质量％。这样的构成在实现形成的烧结层12的高密度化的方面是适合的。
烧结接合用片10的粘合层11和/或形成其的烧结接合用组合物如上所述，经过了300℃、40MPa、及2.5分钟的条件下的烧结后的孔隙率优选为10％以下，更优选为8％以下，更优选为6％以下，更优选为4％以下。这样的构成在实现形成的烧结层12的高密度化的方面是适合的。
烧结接合用片10的粘合层11和/或形成其的烧结接合用组合物如上所述，经过了300℃、40MPa、及2.5分钟的条件下的烧结后的通过纳米压痕法测定的25℃下的弹性模量优选为60GPa以上、更优选为65GPa以上、更优选为70GPa以上、更优选为75GPa以上。具有这样的硬度的烧结层12在实现高的接合可靠性的方面是适合的。
烧结接合用片10的粘合层11和/或形成其的烧结接合用组合物如上所述，在含有含导电性金属的上述烧结性颗粒的同时优选还含有热分解性高分子粘结剂，该热分解性高分子粘结剂的重均分子量优选为10000以上。根据所述构成，在上述临时固定工序中的临时固定温度、即70℃及为包含其附近温度的温度范围的50～90℃下例如容易利用热分解性高分子粘结剂的粘弹性从而确保粘合层11的内聚力，因此容易确保粘合层11的粘接力。
烧结接合用片10的粘合层11和/或形成其的烧结接合用组合物中包含的热分解性高分子粘结剂如上所述优选为聚碳酸酯树脂和/或丙烯酸类树脂。聚碳酸酯树脂及丙烯酸类树脂作为在300℃左右的温度下进行分解/挥散的高分子粘结剂而容易准备，因此该构成对于使在要利用烧结接合用片10进行烧结接合的支撑基板S与半导体芯片C之间形成的烧结层12中减少有机残渣的方面是适合的。有烧结层12中的有机残渣越少，该烧结层12越坚固的倾向，因此，该烧结层12容易得到优异的接合可靠性。
烧结接合用片10由于以容易以均匀的厚度制作的片的形态供给烧结接合用材料，因此利用烧结接合用片10，能将支撑基板S和半导体芯片C用均匀的厚度的烧结层12接合。基于均匀的厚度的烧结层12的烧结接合在实现半导体芯片C对支撑基板S的高的接合可靠性的方面是适合的。
另外，烧结接合用片10由于以不易流动化的片的形态供给烧结接合用材料，因此适于在抑制烧结金属自作为接合对象物的支撑基板S与半导体芯片C间的溢出、抑制烧结金属向半导体芯片C侧面的向上蔓延的同时对支撑基板S烧结接合半导体芯片C。这样的溢出、向上蔓延的抑制在提高伴随烧结接合的半导体装置中的成品率的方面是适合的。
实施例
〔实施例1〕
使用混合搅拌机(商品名“HM-500”，KEYENCE CORPORATION制)在其搅拌模式下将作为烧结性颗粒的第1银颗粒(平均粒径60nm，粒径分布5～100nm，DOWA ElectronicsMaterials Co.,Ltd.制)35.86质量份、作为烧结性颗粒的第2银颗粒(平均粒径1100nm，粒径分布400～5000nm，三井金属矿业株式会社制)23.90质量份、作为热分解性高分子粘结剂的聚碳酸酯树脂(商品名“QPAC40”，重均分子量为150000，常温下为固体，EmpowerMaterials公司制)0.87质量份、作为低沸点粘结剂的异冰片基环己醇(商品名“TerusolveMTPH”，常温下为液体，Nippon Terpene Chemicals,Inc.制)3.47质量份、和作为溶剂的甲乙酮35.91质量份混合，制备清漆。搅拌时间设为3分钟。然后，将得到的清漆涂布于脱模处理薄膜(商品名“MRA50”，三菱树脂株式会社制)后使其干燥，形成烧结接合用的厚度40μm的粘合层、即烧结接合用组合物的厚度40μm的片体。干燥温度设为110℃、干燥时间设为3分钟。如上进行，制作具有包含烧结性颗粒、热分解性高分子粘结剂和低沸点粘结剂的粘合层的实施例1的烧结接合用片。实施例1的烧结接合用片(烧结接合用组合物)中的烧结性颗粒的含有比例为93.2质量％、该烧结性颗粒中的粒径100nm以下的颗粒的比例为60质量％。将关于这样的实施例1的烧结接合用片的组成记载于表1(关于后述的实施例及比较例也同样。另外，表1中，表示组成的各数值的单位是相对的“质量份”)。
〔实施例2〕
使用混合搅拌机(商品名“HM-500”，KEYENCE CORPORATION制)在其搅拌模式下将作为烧结性颗粒的第1银颗粒(平均粒径60nm，粒径分布5～100nm，DOWA ElectronicsMaterials Co.,Ltd.制)40.86质量份、作为烧结性颗粒的第3银颗粒(平均粒径800nm，粒径分布300～3500nm，三井金属矿业株式会社制)27.24质量份、作为热分解性高分子粘结剂的聚碳酸酯树脂(商品名“QPAC40”，重均分子量为150000，常温下为固体，Empower Materials公司制)0.75质量份、作为低沸点粘结剂的异冰片基环己醇(商品名“Terusolve MTPH”，常温下为液体，Nippon Terpene Chemicals,Inc.制)3.02质量份、和作为溶剂的甲乙酮28.13质量份混合，制备清漆。搅拌时间设为3分钟。然后，将得到的清漆涂布于脱模处理薄膜(商品名“MRA50”，三菱树脂株式会社制)后使其干燥，形成烧结接合用的厚度40μm的粘合层、即烧结接合用组合物的厚度40μm的片体。干燥温度设为110℃、干燥时间设为3分钟。如上进行，制作具有包含烧结性颗粒、热分解性高分子粘结剂和低沸点粘结剂的粘合层的实施例2的烧结接合用片。实施例2的烧结接合用片(烧结接合用组合物)中的烧结性颗粒的含有比例为95质量％、该烧结性颗粒中的粒径100nm以下的颗粒的比例为60质量％。
〔实施例3〕
代替第3银颗粒(平均粒径800nm，三井金属矿业株式会社制)27.24质量份，使用第4银颗粒(平均粒径300nm，粒径分布145～1700nm，DOWA Electronics Materials Co.,Ltd.制)27.24质量份，除此以外，与实施例2的烧结接合用片同样地操作，制作实施例3的烧结接合用片。实施例3的烧结接合用片(烧结接合用组合物)中的烧结性颗粒的含有比例为95质量％、该烧结性颗粒中的粒径100nm以下的颗粒的比例为60质量％。
〔实施例4〕
代替第3银颗粒(平均粒径800nm，三井金属矿业株式会社制)27.24质量份，使用第2银颗粒(平均粒径1100nm，粒径分布400～5000nm，三井金属矿业株式会社制)27.24质量份，除此以外，与实施例2的烧结接合用片同样地操作，制作实施例4的烧结接合用片。实施例4的烧结接合用片(烧结接合用组合物)中的烧结性颗粒的含有比例为95质量％、该烧结性颗粒中的粒径100nm以下的颗粒的比例为60质量％。
〔实施例5〕
将第1银颗粒(平均粒径60nm，粒径分布5～100nm，DOWA Electronics MaterialsCo.,Ltd.制)的配混量设为34.05质量份来代替40.86质量份、及使用第4银颗粒(平均粒径300nm，粒径分布145～1700nm，DOWA Electronics Materials Co.,Ltd.制)34.05质量份来代替第3银颗粒(平均粒径800nm，三井金属矿业株式会社制)27.24质量份，除此以外，与实施例2的烧结接合用片同样地操作，制作实施例5的烧结接合用片。实施例5的烧结接合用片(烧结接合用组合物)中的烧结性颗粒的含有比例为95质量％、该烧结性颗粒中的粒径100nm以下的颗粒的比例为50质量％。
〔实施例6〕
代替第1银颗粒35.86质量份及第2银颗粒23.90质量份，使用第5银颗粒(平均粒径20nm，粒径分布1～50nm，DOWA Electronics Materials Co.,Ltd.制)41.83质量份及第6银颗粒(平均粒径500nm，粒径分布80～3000nm，三井金属矿业株式会社制)17.93质量份，除此以外，与实施例1的烧结接合用片同样地操作，制作实施例6的烧结接合用片。实施例6的烧结接合用片(烧结接合用组合物)中的烧结性颗粒的含有比例为93.2质量％、该烧结性颗粒中的粒径100nm以下的颗粒的比例为70质量％。
〔比较例1〕
代替第1银颗粒40.86质量份及第3银颗粒27.24质量份，使用第4银颗粒(平均粒径300nm，粒径分布145～1700nm，DOWA Electronics Materials Co.,Ltd.制)68.10质量份，除此以外，与实施例2的烧结接合用片同样地操作，制作比较例1的烧结接合用片。比较例1的烧结接合用片(烧结接合用组合物)中的烧结性颗粒的含有比例为95质量％、该烧结性颗粒中的粒径100nm以下的颗粒的比例为0质量％。
〔比较例2〕
代替第1银颗粒40.86质量份及第3银颗粒27.24质量份，使用第2银颗粒(平均粒径1100nm，粒径分布400～5000nm，三井金属矿业株式会社制)68.10质量份，除此以外，与实施例2的烧结接合用片同样地操作，制作比较例2的烧结接合用片。比较例2的烧结接合用片(烧结接合用组合物)中的烧结性颗粒的含有比例为95质量％、该烧结性颗粒中的粒径100nm以下的颗粒的比例为0质量％。
〈烧结接合样品的制作〉
使用实施例1～6及比较例1、2的各烧结接合用片进行烧结接合，对于每个实施例1～6及比较例1、2的烧结接合用片，制作后述的各评价中使用的所需数量的样品。
在样品的制作中，首先，准备一个面具有平面电极(5mm见方)的硅芯片(5mm见方，厚度350μm)。平面电极具有硅芯片表面上的Ti层(厚度50nm)与其上的Au层(厚度100nm)的层叠结构。接着，对硅芯片的平面电极使用具备压接辊的层压机贴合烧结接合用片。贴合温度为70℃，贴合用的载荷(基于压接辊的压力)为0.3MPa，压接辊的速度为10mm/秒。如此操作，得到在单面具有5mm见方的烧结接合用片和/或粘合层的硅芯片。
接着，将得到的带烧结接合用片的硅芯片对整体被Ag膜(厚度5μm)覆盖的铜板(厚度3mm)进行烧结接合。具体而言，在烧结接合用片夹在该铜板与硅芯片之间的层叠状态下使用烧结装置(商品名“HTM-3000”，伯东株式会社制)进行烧结工序。本工序中，对烧结接合对象物沿其厚度方向负载的加压力为40MPa(实施例1～5和比较例1、2的烧结接合用片)或10MPa(实施例6的烧结接合用片)，烧结用的加热温度为300℃，加热时间为2.5分钟。
如上进行，对于每个实施例1～6及比较例1、2的烧结接合用片，制作所需数量的烧结接合样品。
〈烧结后的孔隙率〉
对实施例1～6及比较例1、2的每个烧结接合用片如下地操作来研究烧结接合样品中的烧结层的孔隙率。具体而言，首先，通过机械研磨使烧结接合样品中沿硅芯片对角线的截面露出。接着，对该露出截面使用离子抛光装置(商品名“Cross section polisher SM-09010”，日本电子株式会社制)进行离子抛光。接着，使用场发射型扫描电子显微镜SU8020(Hitachi High-Technologies Corporation制)对该露出截面中的烧结层区域内的SEM图像(通过扫描型电子显微镜得到的图像)进行拍摄，得到背散射电子图像作为图像数据。对于拍摄条件，将加速电压设为5kV、将倍率设为2000倍。接着，对得到的图像数据使用图像解析软件Image J进行2值化为金属部分及孔隙部分和/或气孔部分的自动2值化处理。然后，根据该2值化后的图像求出孔隙部分的合计面积和整体(金属部分+孔隙部分)的面积，用孔隙部分的合计面积除以整体面积来算出孔隙率(％)。将其结果记载于表1。
〈基于纳米压痕法的弹性模量〉
对实施例1～6及比较例1、2的每个烧结接合用片如下地通过纳米压痕法来研究烧结接合样品中的烧结层的弹性模量。具体而言，首先，通过机械研磨使烧结接合样品中沿硅芯片对角线的截面露出。接着，对该露出截面使用离子抛光装置(商品名“Cross sectionpolisher SM-09010”，日本电子株式会社制)进行离子抛光。接着，在该露出截面中的烧结层区域内的合计3点，使用纳米压痕仪(商品名“Triboindenter”，Hysitron公司制)进行纳米压痕试验，测定弹性模量。测定点是在样品露出截面的烧结层区域中沿烧结层面内方向以20μm间隔隔开的3点，其正中的测定点位于烧结层区域的中央。本测定中，测定模式设为单一压入测定，测定温度设为25℃，使用压头采用Berkovich(三角锥)型的金刚石压头，压头相对于测定对象物的压入深度设为2μm，该压头的压入速度设为200nm/秒，压头自测定对象物的拔出速度设为200nm/秒。将在这样的纳米压痕试验后在使用装置中导出的上述3点处的弹性模量(GPa)的平均值记载于表1。
〈接合可靠性〉
对实施例1～6及比较例1、2的每个烧结接合用片如下地操作来研究烧结接合样品中的烧结层的接合可靠性。具体而言，首先，使用冷热冲击试验机(商品名“TSE-103ES”，ESPEC Corp.制)，对样品施加500个循环的-40℃～200℃的温度范围内的冷热冲击。1个循环的温度曲线中包括-40℃下的15分钟的保持期间及200℃下的15分钟的保持期间。接着，使用超声波断层扫描摄影装置(Scanning Acoustic Tomograph)(商品名“FineSAT II”，Hitachi Construction Machinery Fine Tech Co.,Ltd.制)，进行用于确认烧结接合样品的铜板与硅芯片间的基于烧结层的接合状态的拍摄。该拍摄中，对于作为传感器(Transducer)的探针，使用PQ-50-13：WD[频率50MHz]。得到的图像中，将维持了接合状态的区域用灰色表示，并且将发生了剥离的区域用白色表示，算出接合区域总面积相对于整体面积的比例作为接合率(％)。将其结果示于表1。
[评价]
利用实施例1～6的烧结接合用片(烧结接合用组合物)时，与利用比较例1、2的烧结接合用片相比，在接合对象物间能够形成高密度且高弹性模量的烧结层，能够实现接合可靠性高的烧结接合。关于烧结性颗粒的含有比例，实施例1、6的烧结接合用片与比较例1、2的烧结接合用片为相同程度，实施例2～5的烧结接合用片与比较例1、2的烧结接合用片相同。另外，实施例1～5的烧结接合用片的烧结接合样品的烧结层、及比较例1、2的烧结接合用片的烧结接合样品的烧结层是经过相同的烧结条件(300℃，40MPa，2.5分钟)而形成的，实施例6的烧结接合用片的烧结接合样品的烧结层与比较例1、2的烧结接合用片的烧结接合样品的烧结层相比，是经过显著低的加压力条件(如上所述为10MPa)而形成的。尽管这样，利用实施例1～6的烧结接合用片时，与利用比较例1、2的烧结接合用片的情况相比，能够形成孔隙率显著低、为密度高、并且弹性模量显著高的烧结层，能够实现上述冷热冲击试验后的接合率显著高的烧结接合。
[表1]
Figure BDA0002486486460000321
作为以上的总结，以下以附记的形式将本发明的构成及其变形列出来。
〔附记1〕
一种烧结接合用组合物，其包含：平均粒径为2μm以下、并且粒径100nm以下的颗粒的比例为40质量％以上且不足80质量％的含导电性金属的烧结性颗粒。
〔附记2〕
根据附记1所述的烧结接合用组合物，其中，前述烧结性颗粒的前述平均粒径为1.5μm以下、1.2μm以下、1μm以下、700nm以下、或500nm以下。
〔附记3〕
根据附记1或2所述的烧结接合用组合物，其中，前述烧结性颗粒的前述平均粒径为70nm以上、100nm以上、或200nm以上。
〔附记4〕
根据附记1～3中任一项所述的烧结接合用组合物，其中，前述烧结性颗粒中的粒径100nm以下的颗粒的比例为45质量％以上或48质量％以上。
〔附记5〕
根据附记1～4中任一项所述的烧结接合用组合物，其中，前述烧结性颗粒中的粒径100nm以下的颗粒的比例为70质量％以下或65质量％以下。
〔附记6〕
根据附记1～5中任一项所述的烧结接合用组合物，其中，前述烧结性颗粒的含有比例为90～98质量％、92～98质量％、或94～98质量％。
〔附记7〕
根据附记1～6中任一项所述的烧结接合用组合物，其经过了300℃、40MPa、及2.5分钟的条件下的烧结后的孔隙率为10％以下、8％以下、6％以下、或4％以下。
〔附记8〕
根据附记1～7中任一项所述的烧结接合用组合物，其经过了300℃、40MPa、及2.5分钟的条件下的烧结后的通过纳米压痕法测定的25℃下的弹性模量为60GPa以上、65GPa以上、70GPa以上、或75GPa以上。
〔附记9〕
根据附记1～8中任一项所述的烧结接合用组合物，其中，还包含热分解性高分子粘结剂。
〔附记10〕
根据附记9所述的烧结接合用组合物，其中，前述热分解性高分子粘结剂的重均分子量为10000以上。
〔附记11〕
根据附记9或10所述的烧结接合用组合物，其中，前述热分解性高分子粘结剂为聚碳酸酯树脂和/或丙烯酸类树脂。
〔附记12〕
根据附记1～11中任一项所述的烧结接合用组合物，其中，前述烧结性颗粒包含选自由银、铜、氧化银、及氧化铜组成的组中的至少一种。
〔附记13〕
根据附记1～12中任一项所述的烧结接合用组合物，其70℃下的粘度为5×103～1×107Pa·s或1×104～1×106Pa·s。
〔附记14〕
一种烧结接合用片，其具备由附记1～13中任一项所述的烧结接合用组合物形成的粘合层。
〔附记15〕
根据附记14所述的烧结接合用片，其中，前述粘合层的23℃下的厚度为5μm以上或10μm以上。
〔附记16〕
根据附记14或15所述的烧结接合用片，其中，前述粘合层的23℃下的厚度为100μm以下或80μm以下。
〔附记17〕
一种带烧结接合用片的切割带，其具备：
切割带，所述切割带具有包含基材和粘合剂层的层叠结构；及
前述切割带中的前述粘合剂层上的附记14～16中任一项所述的烧结接合用片。
附图标记说明
10 烧结接合用片
11 粘合层
12 烧结层
C 半导体芯片
X 带烧结接合用片的切割带
20 切割带
21 基材
22 粘合剂层
30 半导体晶圆

Claims (10)

1.一种烧结接合用组合物，其中，烧结性颗粒的含有比例为85质量%以上，
该烧结性颗粒中的粒径100nm以下的颗粒的比例为40质量%以上且70质量%以下，
所述组合物包含平均粒径为70nm以上且1μm以下的含导电性金属的烧结性颗粒。
2.根据权利要求1所述的烧结接合用组合物，其中，所述烧结性颗粒的含有比例为90~98质量%。
3.根据权利要求1或2所述的烧结接合用组合物，其经过了300℃、40MPa、及2.5分钟的条件下的烧结后的孔隙率为10%以下。
4.根据权利要求1或2所述的烧结接合用组合物，其经过了300℃、40MPa、及2.5分钟的条件下的烧结后的通过纳米压痕法测定的25℃下的弹性模量为60GPa以上。
5.根据权利要求1或2所述的烧结接合用组合物，其中，还包含热分解性高分子粘结剂。
6.根据权利要求5所述的烧结接合用组合物，其中，所述热分解性高分子粘结剂的重均分子量为10000以上。
7.根据权利要求5所述的烧结接合用组合物，其中，所述热分解性高分子粘结剂为聚碳酸酯树脂和/或丙烯酸类树脂。
8.根据权利要求1或2所述的烧结接合用组合物，其中，所述烧结性颗粒包含选自由银、铜、银氧化物、及铜氧化物组成的组中的至少一种。
9.一种烧结接合用片，其具备由权利要求1~8中任一项所述的烧结接合用组合物形成的粘合层。
10.一种带烧结接合用片的切割带，其具备：
切割带，所述切割带具有包含基材和粘合剂层的层叠结构；及
所述切割带中的所述粘合剂层上的、权利要求9所述的烧结接合用片。
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