CN115103730A - 接合用片及接合结构 - Google Patents

接合用片及接合结构 Download PDF

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Publication number
CN115103730A
CN115103730A CN202180014769.7A CN202180014769A CN115103730A CN 115103730 A CN115103730 A CN 115103730A CN 202180014769 A CN202180014769 A CN 202180014769A CN 115103730 A CN115103730 A CN 115103730A
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China
Prior art keywords
bonding
bonded
copper
film
copper foil
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CN202180014769.7A
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CN115103730B (zh
Inventor
穴井圭
赵亭来
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Mitsui Mining and Smelting Co Ltd
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Mitsui Mining and Smelting Co Ltd
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    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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    • C—CHEMISTRY; METALLURGY
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Abstract

本发明的接合用片(1)具有铜箔(2)和在铜箔(2)的两面形成的可烧结的接合用膜(3)。接合用膜(3)包含铜颗粒和固体还原剂。接合用片(1)用于与接合对象物(5)接合，所述接合对象物(5)在表面具有金、银、铜和镍中的至少一种金属。另外，本发明还提供接合对象物(5)与铜箔(2)借助接合层(30)电连接而成的接合结构(10)，所述接合对象物(5)在表面具有金、银、铜和镍中的至少一种金属，所述接合层(30)由铜颗粒彼此的烧结结构形成。

Description

接合用片及接合结构
技术领域
本发明涉及接合用片及接合结构。
背景技术
随着近年来世界性的节能化潮流，作为变换器等电力转换/控制装置，被称作功率器件的半导体装置开始被广泛使用。为了实现半导体元件的高效率化及省空间化，使用在金属陶瓷基板上配置多个半导体元件、并在该半导体元件的上表面配置有金属层和金属线的被称作功率模块的电子部件。
以提高功率模块的导电可靠性为目的，专利文献1公开了一种半导体装置，其具备：第1导体板、在第1导体板上配置的多个半导体元件、以及与第1导体板连接的第1外部连接端子。该文献还公开了该半导体装置分别焊接有多个半导体元件。
现有技术文献
专利文献
专利文献1：US2019/244888A1
发明内容
然而，专利文献1记载的半导体装置使用导热性低的焊料作为接合用材料，因此功率模块驱动时的热无法充分地散热，有引起该模块的故障的担忧。在此基础上，还有驱动时的热导致焊料熔融，从而损害导电可靠性的担忧。
因此，本发明提供导热性和导电可靠性优异的接合用片及接合结构。
本发明提供一种接合用片，其具有铜箔和在该铜箔的两面形成的可烧结的接合用膜，
前述各接合用膜包含铜颗粒和固体还原剂，
前述接合用膜中的至少一者用于与接合对象物接合，所述接合对象物在表面具有金、银、铜和镍中的至少一种金属。
进而，本发明还提供一种接合结构，其为第1接合对象物与第2接合对象物借助接合层电连接的接合结构，所述第1接合对象物在表面具有金、银、铜和镍中的至少一种金属，所述第2接合对象物在表面具有金、银、铜和镍中的至少一种金属，所述接合层由铜颗粒的烧结结构形成，
前述接合层中形成有以下的结构(3)。
Figure BDA0003798442040000021
(式(3)中，R3～R5分别独立地表示氢原子、羟基、碳原子数1以上且10以下的烃基、或具有羟基的碳原子数1以上且10以下的烃基，*表示与铜的键合部位。)
附图说明
图1为示意性地示出接合用片的一个实施方式的侧视图。
图2的(a)为示意性地示出接合结构的一个实施方式的侧视图，图2的(b)为示意性地示出接合结构的另一实施方式的侧视图。
图3为示意性地示出接合结构的另一实施方式的侧视图。
具体实施方式
以下，基于优选的实施方式对本发明的接合用片及接合结构进行说明。如图1所示，接合用片1具有铜箔2以及在其两面形成的接合用膜3、3。各接合用膜3均包含铜颗粒和固体还原剂。
接合用片1适宜地用于与在表面具有金、银、铜和镍中的至少一种金属的接合对象物5(以下也将其简称为“接合对象物”)接合。另外，本发明的接合用片的接合用膜3形成在铜箔2的两面，因此也可以在2个接合对象物5、5之间配置接合用片1，以接合用膜3的两面与接合对象物5接合的方式使用。作为接合对象物5的表面存在的金属的形态，可列举出例如在接合对象物5的表面形成为层状的金属层。
接合用片1所配置的各接合用膜3、3均为可烧结的结构。“可烧结”是指铜颗粒彼此以未熔接的状态存在于接合用膜3中，通过使接合用膜3中的铜颗粒烧结，能够形成由铜颗粒彼此熔接而成的铜颗粒的烧结结构形成的烧结体。接合用片1中的接合用膜3和接合对象物5优选在加压下进行焙烧，由此可以使接合用片1中的铜箔2与接合对象物5接合。
如图2的(a)和(b)所示，焙烧后的接合用膜3成为由铜颗粒的烧结结构形成的导电性的接合层30。接合层30使铜箔2与两个接合对象物5、5接合并导通。接合用片1例如可以通过后述的制造方法得到。
构成接合用片1的铜箔2为由铜和余量的不可避免的杂质形成的铜箔，或者为由包含铜和铜以外的金属的铜合金形成的铜箔。
从兼顾铜箔自身的强度和接合结构的导电性的观点来看，铜箔2中优选包含97质量％以上的铜，更优选包含99质量％以上，进一步优选由铜及余量的不可避免的杂质形成。
从同样的观点来看，铜箔的厚度优选为0.5μm以上且1000μm以下，进一步优选为1μm以上且500μm以下。铜箔的厚度例如可以通过使用扫描电子显微镜观察接合用片的厚度方向的截面来测定。
如图1所示，接合用片1中的接合用膜3可以在铜箔2的两面的全部区域形成，也可以在铜箔2的一个面不连续地形成且在铜箔2的另一面的全部区域形成，还可以在铜箔2的两面不连续地形成。接合用膜3在铜箔2的面上不连续地形成时，未形成接合用膜3的部位成为铜箔2露出的部位。
如图1所示，接合用片1中，优选在铜箔2与接合用膜3之间不插入任何固体层。
另外，如同图所示，接合用片1中，在接合用片1的第1面1A和第2面1B中，优选也不存在以追加的铜箔、追加的接合用膜为代表的其他固体层。
需要说明的是，只要能发挥本发明的效果，在接合用片1的表面的至少一侧存在其他固体层也无妨。
接合用膜3中包含的铜颗粒例如可以采用以下任意的形态：(i)仅由铜和余量的不可避免的杂质形成的铜颗粒、(ii)由包含铜和铜以外的其他金属的铜合金形成的铜颗粒、(iii)前述(i)和(ii)的混合物。本发明中，也将这些形态简单地总称为“铜颗粒”。另外，根据上下文，“铜颗粒”指铜颗粒本身，或者指作为铜颗粒的集合体的铜粉。
从兼顾导热性的提高和导电性的提高的观点来看，铜颗粒优选包含50质量％以上的铜，更优选包含70质量％以上，进一步优选包含90％质量以上的铜且余量由不可避免的杂质形成。另外，从同样的观点来看，作为铜颗粒的含有方式，进一步优选为(i)仅由铜及余量的不可避免的杂质形成的铜颗粒的集合体。铜颗粒的集合体中包含多种颗粒时，以全部铜颗粒为基准计算铜的含量。
接合用膜3中包含的固体还原剂在1个大气压、室温(25℃)下为固体，可以用于促进接合用膜3的焙烧所带来的铜颗粒的烧结。为了该目的，固体还原剂为具有至少1个氨基及多个羟基的化学结构的物质是有利的。通过使用具有这样的结构的还原剂，与具有多个羟基且不包含氨基的还原剂相比，可以抑制烧结时的铜颗粒的氧化，因此可以得到铜颗粒之间的烧结促进所带来的致密的烧结结构。其结果，可以得到导热性及导电可靠性高的接合结构。“室温(25℃)下为固体”是指固体还原剂的熔点大于25℃。
固体还原剂的熔点优选为300℃以下。另外，固体还原剂的沸点优选比后述的液体介质的沸点高。通过使用具有这样的物性的固体还原剂，在对接合用膜3进行焙烧时，还原剂会熔融而在接合用膜3中均匀地扩散，由此铜颗粒的烧结被均匀地促进，具有更致密的烧结结构。其结果，可以兼顾并提高导热性及导电可靠性，且得到耐热性高的接合结构。
在此基础上，由于固体还原剂在焙烧前于接合用膜3中以固体的形式残留，因此可以提高接合用膜3的形状保持性。其结果，在焙烧接合用膜3时，即使在接合用膜3被加压的情况下，接合用膜3也难以从接合对象物5与铜箔2之间渗出，厚度的控制变得更容易，因此可以得到接合强度高的接合结构。
具有上述构成的接合用片1通过在接合用膜3中包含固体还原剂，在与接合对象物5烧结时，铜颗粒彼此充分地烧结，形成致密的烧结结构。其结果，可以在铜箔2与接合对象物5之间得到兼顾并提高导热性和导电可靠性的烧结结构。在此基础上，可以得到在铜箔2与接合对象物5之间表现出高接合强度的烧结结构。
另外，由于铜箔2和接合用膜3均包含铜，因此在制造功率模块的过程中使用接合用片1时，能够不另行进行用于提高接合强度的金属喷镀等表面处理工序地使其接合，因此可以得到高水平地表现出导热性和导电可靠性、并且接合强度高的功率模块。
从兼顾烧结结构中的高导热性和高导电可靠性的观点来看，接合用膜3优选包含氨基醇化合物作为固体还原剂，进一步优选包含以下化学式(1)或(2)所示的氨基醇化合物。“氨基醇化合物”是指在一个化学结构中具有伯胺～叔胺中的至少一种胺、和伯醇～叔醇中的至少一种醇的有机化合物。
Figure BDA0003798442040000051
化学式(1)或(2)中，R1～R6分别独立地表示氢原子、羟基、碳原子数1以上且10以下的烃基、或具有羟基的碳原子数1以上且10以下的烃基。作为烃基，可列举出饱和或不饱和的脂肪族基团。该脂肪族基团可以为直链状，或者也可以为支链状。作为R1～R6中的烃基的例子，可列举出甲基、乙基、丙基等。
式(2)中，R7表示碳原子数1以上且10以下的烃基、或具有羟基的碳原子数1以上且10以下的烃基。作为烃基，可列举出饱和或不饱和的脂肪族基团。该脂肪族基团可以为直链状，或者也可以为支链状。作为R7中的烃基的例子，可列举出亚甲基、亚乙基、亚丙基、亚丁基等。
化学式(1)中，从提高铜颗粒的烧结性的观点来看，R1～R5中的至少2个包含羟基。即，R1～R5中的至少2个为羟基、或具有羟基的碳原子数1以上且10以下的烃基。另外，式(2)中，R1～R6中至少2个包含羟基。即，R1～R6中的至少2个为羟基、或具有羟基的碳原子数1以上且10以下的烃基。特别是在化学式(1)中，优选R1～R5中的至少2个为具有羟基的碳数1以上且4以下的烃基。另外，化学式(2)中，优选R1～R6中的至少2个为具有羟基的碳数1以上且4以下的烃基。此时，羟基烷基中的羟基优选与烷基的末端键合。
从提高铜颗粒的烧结性的观点来看，化学式(1)所示的还原剂优选R1～R5之中的3个以上包含羟基，更优选4个以上包含羟基，进一步优选R1～R5全部包含羟基。从同样的观点来看，化学式(2)所示的还原剂优选R1～R6之中的3个以上包含羟基，更优选4个以上包含羟基。
作为化学式(1)或(2)所示的氨基醇化合物的具体例，可列举出双(2-羟乙基)亚氨基三(羟甲基)甲烷(BIS-TRIS、熔点：104℃、沸点：大于300℃、对应化学式(1))、2-氨基-2-(羟甲基)-1,3-丙烷二醇(TRIS、熔点：169～173℃、沸点：大于300℃、对应化学式(1))、1,3-双(三(羟甲基)甲基氨基)丙烷(BIS-TRIS propane、熔点：164～165℃、沸点：大于300℃、对应化学式(2))等。这些之中，从提高铜颗粒彼此的烧结性从而得到具有致密的接合层的接合结构的观点来看，优选使用双(2-羟乙基)亚氨基三(羟甲基)甲烷(BIS-TRIS)作为固体还原剂。
上述的固体还原剂可以单独使用一种，或者可以组合使用两种以上。任意情况下，从提高铜颗粒的烧结性的观点来看，接合用膜中的固体还原剂的比例优选相对于铜颗粒100质量份为0.1质量份以上，进一步优选为1质量份以上。另外，从维持接合用组合物中铜颗粒所占的比例，并发挥对铜箔的适宜的涂布性能的观点来看，设为10质量份以下是现实的，优选设为8质量份以下，进一步优选设为5质量份以下。
接合用膜3还可以包含1个大气压下的沸点小于300℃的液体介质。在形成接合用膜时，液体介质用于使接合用膜3的成形性良好。从这样的观点来看，上述的液体介质优选在1个大气压、室温(25℃)下为液体。
接合用膜中含有液体介质时，从抑制铜颗粒的氧化的观点来看，液体介质优选为非水介质。
从兼具接合用膜的成形性和液体介质的适度的挥发性的观点来看，液体介质优选为一元醇或多元醇，进一步优选为多元醇。作为多元醇，可列举出例如丙二醇(沸点：188℃)、乙二醇(沸点：197℃)、己二醇(沸点：197℃)、二乙二醇(沸点：245℃)、1,3-丁二醇(沸点：207℃)、1,4-丁二醇(沸点：228℃)、二丙二醇(沸点：231℃)、三丙二醇(沸点：273℃)、甘油(沸点：290℃)、聚乙二醇200(沸点：250℃)、聚乙二醇300(沸点：250℃)等。液体介质可以单独使用一种或组合使用两种以上。这些之中，从提高接合用膜3的形状保持性，并且提高接合用膜3中的成分的分散性，从而制成均匀且致密的烧结结构的观点来看，液体介质优选包含己二醇、以及聚乙二醇200和聚乙二醇300等聚乙二醇中的一种以上。
接合用膜包含液体介质时，从提高接合用膜的形状保持性的观点来看，接合用膜中的液体介质的含量优选相对于铜颗粒100质量份为9质量份以下，进一步优选为7质量份以下。关于接合用膜中的液体介质的含有比例，例如在按照后述的制造方法进行制造时，由于涂膜与作为使该涂膜干燥而成的干燥涂膜的接合用膜3的、除液体介质以外的各构成材料的含量实质上相同，因此例如可以测定干燥前后的涂膜的质量变化来计算。
接合用膜3中包含的铜颗粒的形状例如为球状、扁平状(片状)、枝晶状(树枝状)、棒状等，这些可以单独或组合多种使用。铜颗粒的形状取决于其制造方法。例如，作为铜颗粒的制造方法，使用湿式还原法、雾化法时，容易得到球状的颗粒。使用电解还原法时，容易得到枝晶状、棒状的颗粒。扁平状的颗粒例如可以通过对球状的颗粒施加机械外力使其塑性变形而得到。
铜颗粒优选其形状为球状。此时，球状的铜颗粒的粒径可以利用扫描电子显微镜像的图像分析测定。具体而言，使用Mountech co.,ltd.制Mac-View，读取利用扫描电子显微镜获得的铜颗粒的图像数据后，将图像数据上的铜颗粒随机选择50个以上，分别测定该颗粒的粒径(Heywood径)、该颗粒的二维投影图像的面积S、以及该颗粒的二维投影图像的周长L。然后，根据得到的Heywood径，计算假设颗粒为正球时的体积，作为该体积的累积体积50容量％下的体积累积粒径DSEM50。
另外，关于铜颗粒是否为球形，根据通过上述方法随机选择的各颗粒的面积S和周长L计算圆形度系数4πS/L2，进而计算其算术平均值。圆形度系数的算术平均值为0.85以上、特别是为0.90以上时，将铜颗粒定义为球状。
球状的铜颗粒的粒径用上述的累积体积50容量％下的体积累积粒径DSEM50表示，优选为30nm以上且200nm以下，进一步优选为40nm以上且180nm以下。通过成为这样的结构，在铜箔与接合对象物的接合时可以形成致密的烧结结构，其结果，使用接合用片的接合结构兼具并表现高导热性、耐热性及高接合强度。除此以外，即使为温度较低的烧结条件，也可以形成致密的烧结结构，因此可以抑制制造时对接合对象物的过度的热负荷，可以得到能够表现期望的性能的接合结构。
铜颗粒优选包含形状为扁平状的铜颗粒。此时，扁平状的铜颗粒的基于激光衍射散射式粒度分布测定法的累积体积50容量％下的体积累积粒径D50优选为0.3μm以上且100μm以下，更优选为0.5μm以上且70μm以下，进一步优选为0.7μm以上且50μm以下。通过包含这样的粒径的颗粒，使用接合用片的接合结构兼顾并表现高导热性和导电可靠性，并且兼具并表现耐热性及高接合强度。除此以外，即使为温度较低的烧结条件，也可以形成致密的烧结结构。扁平状是指具有形成颗粒的主面的一对板状面、和与这些板状面交叉的侧面的形状，板状面及侧面可以分别独立地为平面、曲面或凹凸面。
D50的测定中，例如将0.1g测定试样和纯水50mL混合，用超声波均化器(株式会社日本精机制作所制、US-300T)使其分散1分钟。之后，作为激光衍射散射式粒度分布测定装置，使用例如Microtrac·BEL株式会社制MT3300EXII，测定粒度分布。
包含扁平状的铜颗粒时，扁平状铜颗粒的板状面的长轴的长度相对于短轴的长度的比(以下也将其称作“长径比”。)优选为2以上且80以下，优选为5以上且40以下。通过进一步包含这样形状的颗粒，可以形成致密地烧结而成的接合层，从而实现导热性的提高、和导电可靠性的提高。
扁平状铜颗粒的长轴及短轴的长度如下求出。即，利用扫描电子显微镜观察测定对象的颗粒，在与该颗粒的板状面水平的方向上，使其旋转360度，对于各二维投影图像中的假想的外接长方形进行考察时，对于其中外接长方形的一边最大者，以其长边为长轴，以其短边为短轴。同样地，随机选择50个以上该颗粒，分别测定长轴及短轴，根据它们的算术平均值求出。
接着，对上述的接合用片1的制造方法进行说明。接合用片1的制造方法例如具备：在铜箔2的表面涂布接合用组合物从而形成涂膜的涂布工序；及、使该涂膜干燥，形成作为干燥涂膜的接合用膜3的干燥涂膜形成工序。
作为接合用片1的制造方法，例如可以(a)作为第1涂布工序，在铜箔2的一面涂布接合用组合物形成涂膜后，进行第1干燥涂膜形成工序；然后，作为第2涂布工序，可以在铜箔2的另一面涂布接合用组合物形成涂膜后，进行第2干燥涂膜形成工序。或者，也可以(b)在铜箔2的两面涂布接合用组合物形成涂膜后，进行干燥涂膜形成工序。以下的说明适用于前述(a)及(b)两种方案。
首先，将包含铜颗粒和固体还原剂的接合用组合物涂布于铜箔2的表面，形成涂膜。接合用组合物的涂布的手段没有特别限制，可以使用公知的涂布手段。可以使用例如丝网印刷、点胶印刷、凹版印刷、胶版印刷等。从高效地进行接合用组合物的涂布工序的观点来看，接合用组合物优选为包含液体介质的糊剂状或墨状的接合用组合物。接合用组合物可以通过将上述的铜颗粒和固体还原剂、以及根据需要的上述的液体介质混合而得到。
从得到具有高形状保持性的接合用膜的观点、以及形成稳定地表现导热性及导电可靠性的接合结构的观点来看，形成的涂膜的厚度在刚涂布后优选设定为1μm以上且1000μm以下，进一步优选设定为5μm以上且700μm以下。
在接合用组合物包含液体介质的情况下，从对接合用组合物赋予适度的粘性，从而提高将该接合用组合物涂布在铜箔上时的涂膜的形状保持性的观点来看，接合用组合物中的液体介质的含量优选相对于铜颗粒100质量份为40质量份以下，进一步优选为35质量份以下。另外，接合用组合物中的液体介质的含量优选为10质量份以下。
从提高涂膜对铜箔的涂布性和形状保持性的观点来看，未加热时，接合用组合物在剪切速度10s-1及25℃下的粘度优选为20Pa·s以上且200Pa·s以下，进一步优选为25Pa·s以上且180Pa·s以下。对于接合用组合物的粘度，可以将传感器设为平行板型，使用流变仪(粘弹性测定装置)测定。
只要能够发挥本发明的效果，接合用组合物也可以包含其他成分。作为其他成分，可列举出例如粘结剂成分、表面张力调节剂、消泡剂、粘度调节剂等。关于其他成分的比例，其总量优选相对于铜颗粒100质量份为0.1质量份以上且10质量份以下。
接着，使铜箔表面形成的涂膜干燥，得到具有接合用膜3和铜箔2的接合用片1。本工序中，通过进行涂膜的干燥，将液体介质中的至少一部分从该涂膜中去除，从而在铜箔2的表面形成涂膜中的液体介质的量减少的接合用膜3。通过将液体介质从涂膜中去除，可以进一步提高接合用膜3的形状保持性。进而，在通过焙烧使具有铜箔2和接合用膜3的接合用片1与接合对象物5接合时，可以提高接合层30的密合性，兼顾并提高导热性及导电可靠性。接合用膜3如上所述，液体介质的比例优选相对于铜颗粒100质量份为9质量份以下。本工序中，对于涂膜与作为使该涂膜干燥而成的干燥涂膜的接合用膜3而言，除液体介质以外的各构成材料的含量实质上相同。另外，对于本工序中形成的接合用膜而言，接合用膜中的铜颗粒彼此并未熔接，是可烧结的。
为了将液体介质干燥去除，可以使用利用该液体介质的挥发性的自然干燥、热风干燥、红外线的照射、热板干燥等干燥方法来使液体介质挥发。本工序可以根据所要使用的接合用组合物的组成进行适当变更，但优选在小于铜颗粒的熔点下进行，例如可以在大气气氛下，以60℃以上且150℃以下、大气压、1分钟以上且30分钟以下进行。
从提高与接合对象物5的密合性，得到具有优异的导热性及导电可靠性的接合结构10的观点来看，接合用膜3的厚度优选为0.5μm以上，进一步优选为3μm以上。另外，从实现电子部件的省空间化的观点来看，接合用膜3的厚度优选为980μm以下，进一步优选为600μm以下。接合用膜3的厚度例如可以通过适当调整上述工序中形成的涂膜的厚度来调节。接合用膜3的厚度例如可以通过使用扫描电子显微镜观察接合用片1的厚度方向截面来测定。
接着，对接合结构10的制造方法进行说明。作为一个实施方式，可以将经上述的工序而得到的接合用片1与接合对象物5接合，从而得到具有图2的(a)和(b)所示出的结构的接合结构10。本实施方式中的接合结构10的第1接合对象物51与第2接合对象物52借助接合层30电连接，所述第1接合对象物51在表面具有金、银、铜和镍中的至少一种金属，所述第2接合对象物52在表面具有金、银、铜和镍中的至少一种金属，所述接合层30由铜颗粒彼此的烧结结构形成。
作为接合结构10中的接合对象物5，可列举出例如由金、银、或铜等金属形成的间隔物、散热板、半导体元件、以及在表面具有金、银、铜和镍中的至少一种金属的基板等。作为基板，可以使用例如DBC(Direct Bonded Copper，直接敷铜)基板等在陶瓷或氮化铝的板的表面具有铜的绝缘基板等。
在接合结构10的制造工序中，首先，经上述的工序得到接合用片1后，如图2的(a)和(b)所示，使接合用片1中的接合用膜3与接合对象物5相对，得到在接合对象物5与该接合用片1中的铜箔2之间配置有接合用膜3的层叠体10A。
在图2的(a)示出的实施方式中，层叠体10A以接合用片1中作为接合用膜3的存在面的第1面1A与第1接合对象物51彼此面接触的状态配置。在此基础上，层叠体10A以接合用片1中作为接合用膜3的存在面的第2面1B与第2接合对象物52彼此面接触的状态配置。
即，图2的(a)示出的层叠体10A在第1接合对象物51与第2接合对象物52之间配置有接合用片1。在形成层叠体10A的状态下，接合用膜3均未被烧结。
在图2的(b)示出的实施方式中，层叠体10A以第1接合用片1S中作为接合用膜3的存在面的第1面1A与第1接合对象物51彼此面接触的状态配置。在此基础上，层叠体10A以第1接合用片1S中作为接合用膜3的存在面的第2面1B与第3接合对象物53彼此面接触的状态配置。
进而，层叠体10A以第2接合用片1T中作为接合用膜3的存在面的第1面1C与第3接合对象物53彼此面接触的状态配置。在此基础上，层叠体10A以第2接合用片1T中作为接合用膜3的存在面的第2面1D与第2接合对象物52彼此面接触的状态配置。
即，图2的(b)示出的层叠体10A在第1接合对象物51与第2接合对象物52之间配置有第3接合对象物53，在第1接合对象物51与第3接合对象物53之间、以及第2接合对象物52与第3接合对象物53之间分别配置有接合用片1S、1T。本实施方式中，在形成层叠体10A的状态下，接合用膜3也均未被烧结。
作为层叠体10A中的接合对象物5，可以使用与接合结构10中的接合对象物5同样的接合对象物。在图2的(b)示出的实施方式中，第3接合对象物53优选为半导体元件、或者为在表面具有金、银、铜和镍中的至少一种金属的基板。
然后，加热该层叠体10A，使接合用膜3中包含的铜颗粒烧结，形成接合对象物5与铜箔2接合的接合层30。
烧结时的气氛优选氮等非活性气体气氛。
烧结温度优选小于300℃，更优选为150℃以上且小于300℃，进一步优选为200℃以上且小于300℃，更进一步优选为230℃以上且小于300℃。
关于烧结时间，以烧结温度为前述范围为条件而优选为30分钟以下，更优选为0.5分钟以上且25分钟以下，进一步优选为1分钟以上且20分钟以下。
烧结优选在加压下进行，此时对接合用膜施加的压力优选为0.001MPa以上，更优选为0.001MPa以上且20MPa以下，进一步优选为0.01MPa以上且15MPa以下。
经以上的工序而形成的接合层30为接合用膜3中包含的铜颗粒的烧结结构。即，接合层30由接合用膜3中包含的铜颗粒的烧结体形成，是接合用膜3被烧结形成的。
在将图2的(a)示出的实施方式的层叠体10A烧结的情况下，各接合用膜3中包含的铜颗粒烧结，配置有接合用片1的部位成为具有铜箔2和在铜箔2的两面形成的接合层30的复合接合层1L。因此，对图2的(a)示出的实施方式的层叠体10A进行烧结而得到的接合结构10的第1接合对象物51与第2接合对象物52借助具有铜箔2和在铜箔2的两面形成的接合层30,30的复合接合层1L电连接。
另外，在将图2的(b)示出的实施方式的层叠体10A烧结的情况下，各接合用膜3中包含的铜颗粒烧结，各接合用片1S、1T分别成为具有铜箔2和在铜箔2的两面形成的接合层30的复合接合层1L。因此，对图2的(b)示出的实施方式的层叠体10A进行烧结而得到的接合结构10在第1接合对象物51与第3接合对象物53之间、以及第2接合对象物52与第3接合对象物53之间分别借助复合接合层1L电连接。
对图2的(a)和(b)示出的实施方式的层叠体10A进行烧结时，在接合用膜3包含上述化学式(1)或(2)所示的固体还原剂的情况下，在接合层30中会形成源自铜颗粒中的铜和固体还原剂的以下的结构(3)。
Figure BDA0003798442040000131
式(3)中，R3～R5分别独立地表示氢原子、羟基、碳原子数1以上且10以下的烃基、或具有羟基的碳原子数1以上且10以下的烃基。R3～R5的详细内容可以适当适用上述化学式(1)和(2)的说明。另外，*表示与铜的键合部位。
关于接合层30中是否形成有前述结构(3)，可以通过以接合层的截面为对象进行基于TOF-SIMS的质谱分析等来确认。例如使用BIS-TRIS作为固体还原剂时，TOF-SIMS中的正极侧的质谱中会观察到源自C-N(Cu)2的分子量152的碎片。
对于接合层30而言，其厚度优选以将铜箔与接合对象物确实地结合、且成为充分高的导电性和导热性的方式调节。具体而言，优选将接合层30的厚度设为0.1μm以上且950μm以下，进一步优选设为1μm以上且500μm以下。接合层30在其制造过程中成为接合用膜3中的液体介质不存在的状态，因此接合层30的厚度与接合用膜3的厚度相同、或者变得比接合用膜3的厚度薄。
接合层30的厚度例如可以通过对使用上述的接合用组合物形成的膜的厚度、接合用膜3的厚度、或焙烧时的加压条件进行调整来适当控制。另外，接合层30的厚度可以通过将该接合层树脂包埋后进行研磨、并利用电子显微镜观察其研磨面来测定。
关于具有上述的接合用片1和上述的接合层30的接合结构10，通过活用其高导热性及导电可靠性的特性，可以适宜地用于会安装在暴露于高温的环境的例如车载用电子电路、功率器件的电子电路中。
接合结构10可适宜地用作功率模块结构体。作为功率模块结构体，可列举出例如多个接合结构10与引线框等电极分别借助由金、铜等金属形成的金属线电连接的方式。金属线例如在半导体元件、表面具有铜等金属的基板等接合对象物5上单独配置或配置多个，分别与接合结构10和电极电连接。
若参照图2的(b)对功率模块结构的一例进行说明，则使用半导体元件作为第1接合对象物51，使用由铜等金属形成的散热板作为第2接合对象物52，使用DBC基板作为第3接合对象物53。于是，能够制成在两接合对象物51、52之间以及两接合对象物52、53之间中的至少一处形成有属于接合用片1的烧结体的复合接合层1L的接合结构10。
以上，基于优选实施方式对本发明进行了说明，但本发明并不限定于前述实施方式。例如，将图2的(b)示出的实施方式的层叠体10A烧结而得到的接合结构10呈各接合对象物51、52、53之间分别配置有复合接合层1L的形态，但并不限定于该方式。详细而言，可以在各接合对象物51、53之间配置有复合接合层1L，且在各接合对象物52、53之间仅配置有接合层30；也可以在各接合对象物51、53之间仅配置有接合层30，且在各接合对象物52、53之间配置有复合接合层1L。
另外，如图3所示，也可采用在2个接合对象物5、5之间仅配置有接合层30的接合结构10。作为该接合结构10的制造方法，例如可以在第1接合对象物51上涂布接合用组合物而形成涂膜，并使该涂膜干燥而得到接合用膜3。之后，可以在接合用膜3上配置第2接合对象物52，使接合用膜3与各接合对象物51、52一同烧结并接合，由此形成。本实施方式中，各接合对象物51、52仅借助接合层30电连接。与使用接合用片1的设计相比，该实施方式以成为所需最低限度的尺寸的方式仅形成会成为接合层30的接合用膜3即可，因此有在制造过程中无需将多余形成的接合层30(或接合用膜3)去除等后加工的优点。涉及接合用组合物、接合用膜3、各接合对象物5以及接合层30的说明适宜地使用上述的各实施方式的相关说明。
另外，在不损害本发明的效果的范围内，以防腐等为目的，铜箔2的至少一面也可用苯并三唑等有机化合物进行表面处理。
产业上的可利用性
根据本发明，提供导热性和导电可靠性优异的接合用片及接合结构。

Claims (6)

1.一种接合用片，其具有铜箔和在该铜箔的两面形成的可烧结的接合用膜，
所述各接合用膜包含铜颗粒和固体还原剂，
所述接合用膜中的至少一者用于与接合对象物接合，所述接合对象物在表面具有金、银、铜和镍中的至少一种金属。
2.根据权利要求1所述的接合用片，其中，所述接合用膜的两面用于与所述接合对象物接合。
3.根据权利要求1或2所述的接合用片，其中，所述固体还原剂为氨基醇化合物。
4.一种接合结构，其为第1接合对象物与第2接合对象物借助接合层电连接的接合结构，所述第1接合对象物在表面具有金、银、铜和镍中的至少一种金属，所述第2接合对象物在表面具有金、银、铜和镍中的至少一种金属，所述接合层由铜颗粒的烧结结构形成，
所述接合层中形成有以下的结构(3)，
Figure FDA0003798442030000011
式(3)中，R3～R5分别独立地表示氢原子、羟基、碳原子数1以上且10以下的烃基、或具有羟基的碳原子数1以上且10以下的烃基，*表示与铜的键合部位。
5.根据权利要求4所述的接合结构，其中，第1接合对象物与第2接合对象物借助复合接合层电连接，所述复合接合层具有铜箔和在该铜箔的两面形成的所述接合层。
6.根据权利要求4或5所述的接合结构，其中，
第1接合对象物与第2接合对象物之间还配置有第3接合对象物，
第1接合对象物与第3接合对象物之间、以及第2接合对象物与第3接合对象物之间分别借助所述接合层电连接或借助复合接合层电连接，所述复合接合层具有铜箔和在该铜箔的两面形成的该接合层，
第3接合对象物为半导体元件，或者为在表面具有金、银、铜和镍中的至少一种金属的基板。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2876606A1 (fr) * 2004-10-19 2006-04-21 Corus Aluminium Walzprod Gmbh Procede de production d'une feuille de brasage en alliage d'aluminium et d'ensembles legers et brases pour echangeur de chaleur.
US20130068373A1 (en) * 2011-09-20 2013-03-21 Heraeus Materials Technology Gmbh & Co. Kg Paste and method for connecting electronic component to substrate
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