CN104553133A - 接合部和电配线 - Google Patents

接合部和电配线 Download PDF

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Publication number
CN104553133A
CN104553133A CN201410528116.2A CN201410528116A CN104553133A CN 104553133 A CN104553133 A CN 104553133A CN 201410528116 A CN201410528116 A CN 201410528116A CN 104553133 A CN104553133 A CN 104553133A
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metal ingredient
metal
conductor
group
junction surface
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CN201410528116.2A
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CN104553133B (zh
Inventor
关根重信
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NAPULA CORP
Napra Co Ltd
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NAPULA CORP
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B23K35/025—Pastes, creams, slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302—Cu as the principal constituent
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    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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Abstract

本发明提供一种不会产生空隙、裂纹等的高品质、高可靠度的电极接合部和电配线。将2个导体接合的接合部含有选自Si、B、Ti、Al、Ag、Bi、In、Sb、Ga的组中的至少一种、Cu和Sn，在其与导体之间形成有纳米复合结构的金属扩散区域。

Description

接合部和电配线
技术领域
本发明涉及接合部和电配线。
背景技术
在各种规模的集成电路、各种半导体元件或者其芯片等电子器件中，作为实现三维电路配置的方法，提出TSV(Through-Silicon-Via，硅穿孔)技术，其是在电路基板上预先设置多个贯通导体、将该电路基板进行层叠而接合的技术。如果在三维电路配置中使用TSV技术，可以将大量功能装入较小的占有面积之中。此外，元件彼此的重要的电配线可以急剧地变短，因此可实现处理的高速化。在日本专利第3869859号公报中公开有TSV技术不可缺少的通孔结构体。
在日本专利第3869859号公报中公开的通孔结构体在含有高熔点金属、低熔点金属或金属合金、以及交联剂的同时必须含有粘合剂和/或反应性单体或聚合物。在通孔内的固化状态下，与合金化金属网一起同时存在由导电性粘接剂的有机成分的交联而生成的聚合物网。
对于在日本专利第3869859号公报中记载的通孔结构体，根据其说明书的记载，在通孔内的固化状态下，与合金化金属网一起同时存在聚合物网，因此电方面的导电性也相应变差。
进而，作为在金属扩散接合中所固有的问题，存在发生由柯肯德尔(Kirkendall)空隙引起的空洞、裂纹等问题。柯肯德尔空隙是由于因相互扩散的不均衡发生的原子空穴(晶格)没有消失而是发生了集聚而产生的。例如，在Sn/Cu的界面的情况下，相对于Cu的扩散，Sn的扩散少，因此空穴集聚在金属间化合物和Cu界面，从而形成柯肯德尔空隙。该柯肯德尔空隙也有时发展成更大的空洞或裂纹，从而使导体的可靠性、品质降低，进而产生断线等。在日本专利第3869859号公报中并未公开其对策方法。
接着，日本特开2002-261105号公报公开有如下技术：利用含有Cu6Sn5的CuSn化合物和具有Cu球的连接部将半导体装置的电极和安装基板的电极连接起来，Cu球彼此也用CuSn化合物连结。但是，由于电极间和Cu球彼此用CuSn化合物连接，因此有在Sn/Cu的界面产生柯肯德尔空隙的可能性。
在晶片的面上取由贯通导体形成的电配线、由平面状导体图案形成的电配线、还有三维系统封装(3D-SiP)等形态的电子器件中，在形成将半导体芯片间连接起来的接合部的情况下也产生同样的问题。
发明内容
本发明要解决的课题
本发明的课题在于提供一种不会产生空洞、裂纹等的接合部和电配线。
本发明的另一课题在于提供一种熔融温度低、凝固后具有高熔点的接合部和电配线。
用于解决课题的方法
为了解决上述课题中的至少一个，本发明是将至少2个导体接合的接合部，其具有含有选自Si、B、Ti、Al、Ag、Bi、In、Sb、Ga、Zn的组中的至少一种、Cu和Sn的化合物区域。上述化合物区域在其与上述导体之间形成纳米复合结构的金属扩散区域。
如上所述，在本发明的接合部中，含有选自Si、B、Ti、Al、Ag、Bi、In、Sb、Ga、Zn的组中的至少一种、Cu和Sn的化合物区域在其与导体间之间形成纳米复合结构的金属扩散区域，因此根据化合物区域所应该含有的金属成分的选择，如果有需要则多级控制熔融温度，可以缓和在上述化合物与导体之间观察到的相互扩散的不均衡。其结果是，可形成避免原子空穴(晶格)的集聚、抑制柯肯德尔空隙的产生、没有柯肯德尔空隙等的接合部。
而且，上述组成的化合物区域可以通过其金属成分的选择和组合而形成熔融温度低、凝固后具有高熔点的接合部。因而，可以利用由高熔点的化合物的连结产生的弹性的内聚力来确保高温强度，在温度循环时可以用柔软的金属成分、例如Sn的柔软性来确保寿命。
本发明也适用于由基板支撑的电配线。该电配线含有选自Si、B、Ti、Al、Ag、Bi、In、Sb、Ga、Zn的组中的至少一种、Cu和Sn，在配线内部含有纳米复合结构的金属扩散区域。
本发明的电配线也发挥在接合部中所述的作用效果。此外，在电配线中包含由贯通导体形成的电配线和由平面状导体图案形成的电配线。
具体而言，本发明的接合部和电配线可以含有第1金属成分、第2金属成分和第3金属成分中的至少两种。在该情况下，既可以含有第1金属成分、第2金属成分和第3金属成分这3种，也可以仅含有其中两种。例如，既可以是含有第1金属成分和第2金属成分的类型，也可以是含有第1金属成分和第3金属成分的类型，还可以是含有第2金属成分和第3金属成分的类型。它们的组合可通过观察第1金属成分、第2金属成分和第3金属成分中的组成成分的种类、组成成分的相对量等来选择。
作为合乎上述目的的具体的第1金属成分，可以列举出含有Cu、和选自Si、B、Ti、Al、Ag、Zn的组中的至少一种的成分。
接着，作为第2金属成分的具体例，可以列举出含有Sn、Cu、和选自Si、B、Ti、Al、Ag、Zn的组中的至少一种的成分。
并且，具体而言，第3金属成分可以含有Sn、Bi、Ga、和选自上述Si、B、Ti、Al、Ag、Zn的组中的至少一种。
作为另一选择项，第3金属成分也可以含有Sn、Bi、In、Sb、和选自Ga、Si、B、Ti、Al、Ag、Zn的组中的至少一种。
发明效果
如上所述，根据本发明，可以获得如下效果。
(a)可以提供一种抑制了柯肯德尔空隙的产生的接合部和电配线。
(b)可以提供一种熔融温度低、凝固后具有高熔点的接合部和电配线。
本发明的其他目的、构成和优点参照附图更详细地进行说明。但是，附图仅是例示。
附图说明
图1是表示使用了本发明的接合部的电子器件的一个例子的图。
图2表示使用以往的Sn-Cu系导电糊剂形成的配线的SEM图像。
图3表示使用本发明的功能性材料形成的金属化层的SEM图像。
图4是表示本发明的电子器件的另一例子的图。
图5是表示本发明的电子器件的又一例子的图。
图6是表示300℃下的高温剪切强度试验结果的图。
符号说明
1 接合部
3、5 电子器件
31、51 基板
321、521 扩散区域
71 基板
72 电配线
73 绝缘层
91 基板
92 电配线
具体实施方式
参照图1，接合部1介于在电子器件3的基板31上设置的导体32和在电子器件5的基板51上设置的导体52之间，将两导体32-52接合。导体32、52也包括被赋予电极、凸块、端子电极等名称的导体。导体32、52的组成、结构等适宜地是公知的组成、结构。例如形成为由Cu、Al、Ni、Sn、Ag、Au、Pt、Pd等构成的单层膜或层叠膜。
接合部1含有化合物区域，该化合物区域含有选自Si、B、Ti、Al、Ag、Bi、In、Sb、Ga、Zn的组中的至少一种、Cu和Sn。化合物区域在其与导体32、52之间具有纳米复合结构的金属扩散区域321、521。纳米复合结构是指金属/合金的结晶、非结晶或它们的化合物以nm尺寸被一体化并复合化而成的结构。与现有技术(日本特开2002-261105号公报等)的对比中，其特征在于，化合物区域除了含有Cu和Sn之外还含有选自Si、B、Ti、Al、Ag、Bi、In、Sb、Ga、Zn的组中的至少一种。
接合部1也可以在其内部具有纳米复合结构的金属扩散区域。
根据上述接合部，在化合物区域和导体32、52之间的金属扩散区域321、521中、相互扩散的不均衡被缓和的结果是，可形成可以避免原子空穴(晶格)的集聚、抑制柯肯德尔空隙的产生、没有柯肯德尔空隙等的导体间接合部。
而且，上述组成的化合物区域可以通过其金属成分的选择和组合而形成熔融温度低、凝固后具有高熔点的接合部。例如，如果设想为通常的Cu导体，则化合物区域与该Cu导体反应而形成纳米复合结构的金属间化合物。该金属间化合物的熔点高，在250℃的软钎焊温度下可以确保充分的强度。因而，两次回流焊时的电子器件的接合部成为分担下述功能的复合材料，可以充分用于高温的温度分级连接用，所述功能为利用由高熔点的化合物的连结产生的弹性的内聚力来确保高温强度、在温度循环时以柔软的金属成分的柔软度来确保寿命的功能。
另外，本发明的接合部也可以在其内部具有纳米复合结构的金属扩散区域。在该情况下，也根据化合物区域所含有的金属成分的选择，如果有需要则多级控制熔融温度，可以缓和相互扩散的不均衡。其结果是，可形成可以避免原子空穴(晶格)的集聚、抑制柯肯德尔空隙的发生、没有柯肯德尔空隙等的接合部。
参照图2和图3所示的SEM(Scanning Electron Microscope，扫描型电子显微镜)图像对以上的内容进行说明。图2表示使用以往的Sn-Cu系导电糊剂形成的配线的SEM图像，图3表示本发明的组成的接合部的SEM图像。
首先，当参照表示使用以往的Sn-Cu系导电糊剂形成的配线的SEM图像的图2时，在Cu结晶与Sn结晶之间的界面存在Cu3Sn的扩散层，沿着Cu3Sn层与Cu结晶的界面的大致整体产生了空隙。
与此相对，当参照图3时，本发明的接合部的在Cu结晶与化合物区域之间的界面产生的扩散层具有与Cu结晶和化合物区域中的任一个的形状相效仿的形状，在没有产生空隙的情况下连续。扩散区域构成层厚为700nm以下的纳米复合结构。
在图3中，Cu结晶区域中的图像颜色的差异呈现出晶体取向的差异。另外，图3表示接合部内的结构，在接合部1与导体32-52之间产生的扩散接合321、521中也可获得如图3所示那样的扩散接合结构。
参照图1～图3来说明的接合部可以含有第1金属成分、第2金属成分和第3金属成分中的至少2种。在该情况下，既可以含有第1金属成分、第2金属成分和第3金属成分这3种，也可以仅含有其中的两种。例如，既可以是含有第1金属成分和第2金属成分的类型，也可以是含有第1金属成分和第3金属成分的类型，还可以是含有第2金属成分和第3金属成分的类型。它们的组合可通过观察第1金属成分、第2金属成分和第3金属成分中的组成成分的种类、组成成分的相对量等来选择。
作为合乎上述目的的具体的第1金属成分，可以列举出含有Cu、和选自Si、B、Ti、Al、Ag、Zn的组中的至少一种的成分。
接着，作为第2金属成分的具体例，可以列举出含有Sn、Cu、和选自Si、B、Ti、Al、Ag、Zn的组中的至少一种的成分。
并且，具体而言，第3金属成分可以含有Sn、Bi、Ga、和选自上述Si、B、Ti、Al、Ag、Zn的组中的至少一种。
作为另一选择项，第3金属成分也可以含有Sn、Bi、In、Sb、和选自Ga、Si、B、Ti、Al、Ag、Zn的组中的至少一种。
第1金属成分、第2金属成分和第3金属成分分别含有多种金属成分。优选第1金属成分～第3金属成分的各自的熔点T1(℃)、T2(℃)、T3(℃)满足T1＞T2＞T3的关系。由此，进一步促进相互扩散的不均衡缓和。其具体例如下所述。
1.第1金属成分
作为第1金属成分的具体例，可以列举出含有Cu、和选自Si、B、Ti、Al、Ag、Zn的组中的至少一种的成分。各组成成分的组成比可以设定为如下的范围。
Cu：99.9wt％以下
Sn：50wt％以下
Si、B、Ti、Al、Ag或Zn：0.01wt％以下
优选Cu或其合金粒子的表面被氧化抑制膜覆盖。作为氧化抑制膜，在Cu或其合金粒子的表面上镀覆的Ag或Sn的镀覆膜是适合的。此外，也可以是在150℃以上升华的树脂的覆膜。
2.第2金属成分
作为第2金属成分的具体例，可以列举出含有作为主成分的Sn、Cu、和选自Si、B、Ti、Al、Ag、Zn的组中的至少一种的成分。各组成成分的组成比可以设定为如下的范围。
Sn：98wt％以下
Cu：30wt％以下
Si、B、Ti、Al、Ag或Zn：0.01wt％以下
3.第3金属成分
(1)作为一个选择项，第3金属成分可以含有Sn、Bi、Ga、和选自Si、B、Ti、Al、Ag、Zn的组中的至少一种。该情况的各组成成分的组成比可以设定为如下的范围。
Sn：40～80wt％
Bi：15～60wt％
Ga：0.1wt％以下
Al：1wt％以下
Si、B、Ti、Ag或Zn：0.01wt％以下
(2)作为另一个选择项，第3金属成分也可以含有Sn、Bi、In、Sb、和选自Ga、Si、B、Ti、Al、Ag、Zn的组中的至少一种。该情况的各组成成分的组成比可以设定为如下的范围。
In：相对于Sn为20wt％以下
Bi：相对于Sn为20wt％以下
Sb：相对于Sn为20wt％以下
Ga、Si、B、Ti、Al、Ag或Zn：1wt％以下
根据上述具体例，熔点T1、T2、T3为如下所示。
T1＝1100℃～500℃
T2＝400℃～250℃
T3＝250℃以下
接合部只要含有上述第1金属成分～第3金属成分中的、第1金属成分、第2金属成分和第3金属成分中的至少两种即可，也可以不含有3种。例如，既可以是以Cu为主成分的第1金属成分和以Sn为主成分的第2金属成分的组合，也可以是第1金属成分和以Sn为主成分的第3金属成分的组合。
也可以是使第1金属成分、第2金属成分和第3金属成分分散于流动性分散介质中而成的材料。作为流动性分散介质，可以使用各种有机粘合剂、水性分散介质或挥发性有机分散介质等。作为该分散介质，已知有各种分散介质，因此选择使用它们即可。具体而言，可以例示出配线用导电糊剂、填充用糊剂、导体用糊剂、密封用糊剂、或接合糊剂等流动性功能性材料。
本发明也可应用于由基板支撑的电配线。关于这点，参照图4和图5进行说明。首先，示出图4所示的电配线在沿着基板71的厚度方向设置的孔或槽内设有贯通导体72的例子。
基板71可以由Si基板、SiC基板或SOI基板等半导体基板构成。也可以是无机或有机的绝缘基板、电介质基板、磁性基板或将它们复合而成的复合基板。
基板71在朝向其厚度方向的纵孔的内部嵌入有贯通导体72。对贯通导体72并无限定，例如直径为60μm以下，也有时包含被进一步小径化而成的10μm以下的贯通导体72。
在基板71为以Si基板等为代表的半导体基板的情况下，利用有机或无机的绝缘层73覆盖贯通导体72的外周。在贯通导体72的两端分别设有端子导体74、75。并且，在基板71的厚度方向的两面分别设有绝缘层76、77。绝缘层76、77既可以是SiO2或SiN的单层，也可以是在SiO2层上层叠SiN而成的层。这些绝缘层76、77除了原来的作为电绝缘层的作用之外，还具有作为基板翘曲抑制层的作用。
成为电配线的贯通导体72和端子导体74、75含有选自Si、B、Ti、Al、Ag、Bi、In、Sb、Ga、Zn的组中的至少一种、Cu和Sn，在导体内部含有如图3所示那样的纳米复合结构的金属扩散区域。
绝缘层73既可以是对纵孔的内壁面进行改性而成的氧化膜或氮化膜，也可以是由填充到纵孔的内部的无机材料或有机材料或者它们的功能性材料形成的绝缘层。作为由无机绝缘层形成的绝缘层73，具体而言，可以将含有绝缘性微粒、Si微粒和有机Si化合物的绝缘性糊剂填充到纵孔的内部并使其固化而形成。在形成绝缘层73时，在纵孔的内部使有机Si化合物和Si微粒相互反应，形成填埋在绝缘性微粒的周围的Si-O键的网络。有机Si化合物和Si微粒的反应可以优选为通过在真空气氛中、例如130℃～150℃的温度范围内进行加热来进行。
接着，如图5所图示的电子器件在基板91的一个面上形成有布图而成的平面状的电配线92。电配线92是含有选自Si、B、Ti、Al、Ag、Bi、In、Sb、Ga、Zn的组中的至少一种、Cu和Sn、在配线内部具有纳米复合结构的金属扩散区域(参照图3)的金属化配线。电配线92如果有需要则由合成树脂膜形成的保护膜93来覆盖。保护膜93既可以是绝缘膜，也可以是绝缘性低的膜。
图4和图5所示的电配线具有与参照图1～图3进行了说明的接合部同样的构成，除了发挥同样的作用效果之外，在高温剪切强度试验中具有高的高温保持可靠性。关于这点，参照图6进行说明。图6是示出300℃下的高温剪切强度试验结果的图，横轴为时间(小时)，纵轴为剪切强度(MPa)。曲线A表示本发明的电配线(图5)的剪切强度特性，曲线B表示使用了日本专利第3869859号公报所记载的导电糊剂的配线的剪切强度特性，曲线C表示使用了Au-12Ge系导电糊剂的以往的配线的剪切强度特性。
首先，使用了日本专利第3869859号公报所记载的导电糊剂形成的配线如曲线B所示那样，剪切强度的初始值低为30(MPa)，在经过了400小时之后降低到10(MPa)。
另外，使用了Au-12Ge系导电糊剂的以往的配线如曲线C所示那样，剪切强度特性虽然初始值示出为80(MPa)的高值，但随着时间的推移，急剧地降低，在经过了500小时之后降低到约20(MPa)。
与此相对，本发明的电配线如曲线A所示那样，剪切强度特性示出初始值为57(MPa)的高值，之后，即使经过了500小时也保持基本不变的剪切强度特性。
这表示本发明的电配线成为基本没有空隙、裂纹、断线的连续的层，成为填充度、致密性提高、导电性变高、机械强度和物理强度高的电配线。图6的实验数据对于使用了相同材料的图1的接合部和图4的电配线也是妥当的。
对于应用本发明的电子器件，作为代表性的是互连导电物(interposer)。此外，既可以是系统LSI、存储器LSI、图像传感器或MEMS等，也可以是含有模拟或数字的电路、CPU这样的逻辑电路等的电子器件，还可以是利用不同的工艺制作模拟高频电路、低频且低耗电的电路这样的不同种类的电路并将它们层叠而成的电子器件。进而，可以含有传感器组件、光电组件、单极晶体管、MOS FET、CMOS FET、存储器单元、或它们的集成电路部件(IC)、或者各种规模的LSI等一般以电子电路为功能要件的几乎所有电子器件。
以上，参照优选的实施例对本发明详细地进行了说明，但本发明并不限定于这些实施例，如果是本领域技术人员，基于该基本的技术构思和教示而想到各种变形例是显而易见的。

Claims (3)

1.一种接合部，其为将至少2个导体接合的结合部，
其具有含有选自Si、B、Ti、Al、Ag、Bi、In、Sb、Ga、Zn的组中的至少一种、Cu和Sn的化合物区域，所述化合物区域在其与所述导体之间形成纳米复合结构的金属扩散区域。
2.根据权利要求1所述的接合部，其中，
所述化合物区域含有第1金属成分、第2金属成分和第3金属成分中的至少两种，
所述第1金属成分含有Cu、和选自Si、B、Ti、Al、Ag、Zn的组中的至少一种，
所述第2金属成分含有Sn、Cu、和选自Si、B、Ti、Al、Ag、Zn的组中的至少一种，
所述第3金属成分
(a)含有Sn、Bi、Ga、和选自Si、B、Ti、Al、Ag、Zn的组中的至少一种，或者
(b)含有Sn、Bi、In、Sb、和选自Ga、Si、B、Ti、Al、Ag、Zn的组中的至少一种。
3.一种电配线，其为由基板支撑的电配线，其含有：
Cu或Cu合金区域；和
化合物区域，该化合物区域含有选自Si、B、Ti、Al、Ag、Bi、In、Sb、Ga、Zn的组中的至少一种、Cu和Sn，在其与所述Cu或Cu合金区域之间形成纳米复合结构的金属扩散区域。
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