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CN110167695A - 无加压接合用铜糊料、接合体及半导体装置 - Google Patents

无加压接合用铜糊料、接合体及半导体装置 Download PDF

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Publication number
CN110167695A
CN110167695A CN201780082937.XA CN201780082937A CN110167695A CN 110167695 A CN110167695 A CN 110167695A CN 201780082937 A CN201780082937 A CN 201780082937A CN 110167695 A CN110167695 A CN 110167695A
Authority
CN
China
Prior art keywords
copper
pressurization
engagement
component
thickener
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
CN201780082937.XA
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English (en)
Inventor
中子伟夫
蔵渕和彦
江尻芳则
石川大
须镰千绘
川名祐贵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of CN110167695A publication Critical patent/CN110167695A/zh
Pending legal-status Critical Current

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    • 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
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
    • B22F7/064—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts using an intermediate powder layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
    • C—CHEMISTRY; METALLURGY
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • H01B1/20—Conductive material dispersed in non-conductive organic material
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Abstract

本发明涉及一种无加压接合用铜糊料，其是包含金属粒子和分散介质的无加压接合用铜糊料，其中，金属粒子包含体积平均粒径为0.01μm以上且0.8μm以下的亚微米铜粒子和体积平均粒径为2.0μm以上且50μm以下的微米铜粒子，分散介质包含具有300℃以上的沸点的溶剂，且具有300℃以上的沸点的溶剂的含量以无加压接合用铜糊料的总质量为基准，为2质量％以上。

Description

无加压接合用铜糊料、接合体及半导体装置
技术领域
本发明涉及无加压接合用铜糊料及使用了该铜糊料的接合体、以及半导体装置。
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(支撑部件)接合，使用了各种各样的接合材料。在半导体装置中，在150℃以上的高温下工作的功率半导体、LSI等的接合也一直使用高熔点铅焊料作为接合材料。近年来，由于半导体元件的高容量化以及省空间化，工作温度上升到高熔点铅焊料的熔点附近，变得难以确保连接可靠性。另一方面，随着RoHS管制强化，要求使用不含铅的接合材料。
迄今为止，正在研究使用了除铅焊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中提出了使银纳米粒子烧结而形成烧结银层的技术。已知这样的烧结银对于功率循环的连接可靠性高(非专利文献1)。
另外，作为其他的材料，还提出了使铜粒子烧结而形成烧结铜层的技术。例如，在下述专利文献2中公开了包含铜纳米粒子、铜微米粒子或铜亚微米粒子、或者这两者的接合材料，也记载了该接合材料能够无加压地将部件接合。
现有技术文献
专利文献
专利文献1：日本专利第4247800号
专利文献2：日本特开2014-167145号公报
非专利文献
非专利文献1：R.Khazaka,L.Mendizabal,D.Henry:J.ElecTron.Mater,43(7),2014,2459-2466
发明内容
发明所要解决的课题
上述专利文献1中记载的方法为了得到高连接可靠性，必须使烧结银层致密化，因此需要伴随加压的热压接工艺。在进行伴随加压的热压接工艺的情况下，存在生产效率降低、成品率降低等课题。此外，在使用银纳米粒子的情况下，由银带来的材料成本的显著增加等成为问题。
上述专利文献2中记载的方法在无加压下进行烧结，但由于以下原因供于实用尚不充分。即，铜纳米粒子为了抑制氧化和提高分散性而需要用保护剂对表面进行修饰，但由于铜纳米粒子的比表面积大，因此存在在以铜纳米粒子为主成分的接合材料中表面保护剂的配合量增加的倾向。另外，为了确保分散性，存在分散介质的配合量增加的倾向。因此，上述专利文献2中记载的接合材料为了保管或涂布等的供给稳定性而增加表面保护剂或分散介质的比例，烧结时的体积收缩容易变大，另外烧结后的致密度有容易降低的倾向，难以确保烧结体强度。
另外，使用了接合材料的无加压下的接合在所接合的部件彼此的材质相同或接近的情况下良好地进行，但在所接合的部件彼此的材质不同的情况下接合力容易大幅降低。通过本发明者们的研究，表明例如在将被粘接面具有铜的铜板与被粘接面具有镍的铜块接合的情况下、和将被粘接面具有铜的铜板、和被粘接面具有镍的硅芯片接合的情况下，存在在无加压的烧结条件下由于接合用铜糊料的组成而后者的接合强度大幅降低的情况。即，在将如铜块和硅芯片那样、热膨胀率不同的部件彼此在无加压下接合的情况下，有时会发生接合不良。
本发明的目的在于提供一种即使在将热膨胀率不同的部件彼此在无加压下接合的情况下也能够得到充分的接合强度的无加压接合用铜糊料。本发明的目的还在于提供使用无加压接合用铜糊料的接合体和半导体装置、以及它们的制造方法。
用于解决课题的手段
为了解决上述课题，本发明者们进行了以下的研究。首先，就利用接合用铜糊料进行的接合而言，在接合时的干燥工序或烧结工序中的升温时，分散介质挥发后，残留有干燥后的铜系粒子的堆积物。干燥后的铜系粒子的堆积物在粒子间没有分散介质的凝聚力等结合力，处于非常脆弱的状态。认为此时，在所接合的部件彼此的材质不同的情况下，由于室温与干燥工序温度的温度差、或者室温与烧结工序温度的温度差，在所接合的部件间由热膨胀率差产生的剪切力发挥作用，铜系粒子的堆积物层变得容易剥离。当在烧结工序中对部件积极地进行加压，则剥离消除而铜系粒子的堆积物的烧结物与部件接合，但在无加压的情况下有可能保持剥离状态。从抑制这样的剥离的观点出发，对控制升温时堆积物的状态进行研究的结果发现，通过以特定的比例使用特定的溶剂作为分散介质，即使在将热膨胀率不同的部件彼此在无加压下接合的情况下，也能够得到充分的接合强度，从而完成了本发明。
本发明涉及一种无加压接合用铜糊料，其是包含金属粒子和分散介质的无加压接合用铜糊料，其中，金属粒子包含体积平均粒径为0.01μm以上且0.8μm以下的亚微米铜粒子和体积平均粒径为2.0μm以上且50μm以下的微米铜粒子，分散介质包含具有300℃以上的沸点的溶剂，且具有300℃以上的沸点的溶剂的含量以无加压接合用铜糊料的总质量为基准，为2质量％以上。
本说明书中，“无加压”是指受到所接合的部件的自重或在其自重之外受到0.01MPa以下的压力的状态。
本发明还涉及一种无加压接合用铜糊料，其是包含金属粒子和分散介质的无加压接合用铜糊料，其中，金属粒子包含体积平均粒径为0.01μm以上且0.8μm以下的亚微米铜粒子和体积平均粒径为2.0μm以上且50μm以下的微米铜粒子，分散介质包含具有300℃以上的沸点的溶剂，且具有300℃以上的沸点的溶剂的含量以无加压接合用铜糊料的总容量为基准，为8体积％以上。
根据本发明的无加压接合用铜糊料，即使在将热膨胀率不同的部件彼此在无压力下接合的情况下，也能够得到充分的接合强度。关于可得到这样的效果的理由，本发明者们推测如下。即，认为通过使分散介质含有特定量的具有300℃以上的沸点的溶剂，在接合时的升温过程中具有规定量的300℃以上的沸点的溶剂能够残留在位于部件之间的铜糊料中。认为通过该残留溶剂对铜糊料赋予挠性和附着性，即使在热膨胀率差产生的剪切力作用的情况下，也能够使位于部件之间的铜糊料变形、追随，能够无剥离地接合于各个部件。
本发明中，上述具有300℃以上的沸点的溶剂可以具有选自由羟基、醚基及酯基组成的组中的至少一种基团。在无加压接合用铜糊料含有这样的溶剂的情况下，可以使用有机酸、有机胺、含羟基的聚合物、聚乙烯吡咯烷酮等的汉森溶解度参数(Hansen solubilityparameter)相近的表面处理剂。
本发明的无加压接合用铜糊料也可以在将存在于2个部件之间的无加压接合用铜糊料在250℃以上且低于350℃的温度下加热时，将微米铜粒子和亚微米铜粒子烧结而形成金属键，2个部件之间以芯片抗切强度(die shear strength)为10MPa以上、热导率为100W/(m·K)以上接合。如果是这样的无加压接合用铜糊料，则在热膨胀率不同的部件彼此接合时，容易得到充分的接合强度。
本发明的无加压接合用铜糊料从25℃升温至300℃时残留的具有300℃以上的沸点的溶剂的含量以升温至300℃时的无加压接合用铜糊料的质量为基准，可以为1质量％以上。此时存在下述倾向：容易维持无加压接合用铜糊料组合物的挠性，在将热膨胀率不同的部件彼此接合的情况下，无加压接合用铜糊料容易针对部件进行变形、追随，因此容易提高接合强度的。
本发明还提供一种接合体，其具备第一部件、具有与第一部件不同的热膨胀率的第二部件、以及将第一部件和第二部件接合的上述无加压接合用铜糊料的烧结体。
根据本发明的接合体，通过利用上述无加压接合用铜糊料的烧结体进行接合，即使是具有不同热膨胀率的部件彼此，也能够成为部件彼此以充分的接合强度接合的接合体。
本发明还涉及一种接合体的制造方法，其具备下述工序：准备层叠有第一部件、在该第一部件的自重作用的方向一侧依次为上述无加压接合用铜糊料及具有与第一部件不同的热膨胀率的第二部件的层叠体，在受到第一部件的自重、或所述第一部件的自重及0.01MPa以下的压力的状态下对无加压接合用铜糊料进行烧结。
根据本发明的接合体的制造方法，通过使用上述本发明的无加压接合用铜糊料，即使是具有不同热膨胀率的部件彼此，也能够制造部件彼此以充分的接合力接合、连接可靠性优异的接合体。
本发明还提供一种半导体装置，其具备第一部件、具有与第一部件不同的热膨胀率的第二部件、以及将第一部件和第二部件接合的上述无加压接合用铜糊料的烧结体，其中，第一部件及第二部件中的至少一个是半导体元件。
根据本发明的半导体装置的制造方法，通过使用上述本发明的无加压接合用铜糊料，即使在构成半导体装置的部件具有不同的热膨胀率的情况下，也能够制造部件彼此以充分的接合力接合、连接可靠性优异的半导体装置。
发明效果
本发明能够提供一种即使在将热膨胀率不同的部件彼此在无加压下接合的情况下，也能够得到充分的接合强度的无加压接合用铜糊料。本发明还能够提供使用无加压接合用铜糊料的接合体和半导体装置、以及它们的制造方法。
附图说明
图1是表示使用本实施方式的无加压接合用铜糊料制造的接合体的一个例子的示意截面图。
图2是表示使用本实施方式的无加压接合用铜糊料制造的半导体装置的一个例子的示意截面图。
图3是表示实施例1的接合样品的截面的SEM图像的图。
图4是表示比较例1的接合样品的截面的SEM图像的图。
图5是表示具有300℃以上的沸点的溶剂在无加压接合用铜糊料中所占的比例与芯片抗切强度的关系的图。
图6是表示分散介质的沸点与芯片抗切强度的关系的图。
具体实施方式
以下，对用于实施本发明的方式(以下称为“本实施方式”)进行详细说明。本发明并不限于以下的实施方式。
<无加压接合用铜糊料>
本实施方式的无加压接合用铜糊料是包含金属粒子和分散介质的无加压接合用铜糊料，其中，金属粒子包含亚微米铜粒子和微米铜粒子。
(金属粒子)
作为本实施方式的金属粒子，可列举出亚微米铜粒子、微米铜粒子、除这些铜粒子以外的其他金属粒子等。
(亚微米铜粒子)
作为亚微米铜粒子，只要是在250℃以上且350℃以下的温度范围内具有烧结性的铜粒子即可。作为亚微米铜粒子，可列举出包含粒径为0.01μm以上且0.8μm以下的铜粒子的粒子，例如可以使用体积平均粒径为0.01μm以上且0.8μm以下的铜粒子的铜粒子。若亚微米铜粒子的体积平均粒径为0.01μm以上，则容易得到抑制亚微米铜粒子的合成成本、良好的分散性、抑制表面处理剂的用量等的效果。当亚微米铜粒子的体积平均粒径为0.8μm以下时，容易得到亚微米铜粒子的烧结性优异的效果。从进一步发挥上述效果的观点出发，亚微米铜粒子的体积平均粒径的上限可以为0.6μm以下，可以为0.5μm以下，也可以为0.4μm以下。另外，亚微米铜粒子的体积平均粒径的下限可以为0.02μm以上，可以为0.05μm以上，也可以为0.1μm以上。作为亚微米铜粒子的体积平均粒径，例如可以为0.01μm以上且0.5μm以下，可以为0.12μm以上且0.8μm以下，可以为0.15μm以上且0.8μm以下，可以为0.15μm以上且0.6μm以下，可以为0.2μm以上且0.5μm以下，也可以为0.3μm以上且0.45μm以下。
另外，本申请说明书中，体积平均粒径是指50％体积平均粒径。在求算铜粒子的体积平均粒径的情况下，可以通过下述方法等求算：通过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，株式会社岛津制作所制))对使用分散剂将作为原料的铜粒子、或从无加压接合用铜糊料中除去了挥发成分的干燥铜粒子分散到分散介质中而成者进行测定。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，可以使用己烷、甲苯、α-松油醇、4-甲基-1,3-二氧杂戊环-2-酮等。
亚微米铜粒子的含量以金属粒子的总质量为基准，可以为20质量％以上且90质量％以下，可以为30质量％以上且90质量％以下，可以为35质量％以上且85质量％以下，也可以为40质量％以上且80质量％以下。若亚微米铜粒子的含量在上述范围内，则容易确保使无加压接合用铜糊料烧结而制造的接合体的接合强度，在将无加压接合用铜糊料用于半导体元件的接合的情况下，存在半导体装置显示出良好的芯片抗切强度及连接可靠性的倾向。
亚微米铜粒子的含量以亚微米铜粒子的质量和微米铜粒子的质量的总和为基准，优选为20质量％以上且90质量％以下。若亚微米铜粒子的上述含量为20质量％以上，则能够充分地填充微米铜粒子之间，容易确保使无加压接合用铜糊料烧结而制造的接合体的接合强度，在将无加压接合用铜糊料用于半导体元件的接合的情况下，存在半导体装置显示出良好的芯片抗切强度和连接可靠性的倾向。若亚微米铜粒子的含量为90质量％以下，则能够充分抑制烧结无加压接合用铜糊料时的体积收缩，因此容易确保使无加压接合用铜糊料烧结而制造的接合体的接合强度，在将无加压接合用铜糊料用于半导体元件的接合的情况下，存在半导体装置显示出良好的芯片抗切强度及连接可靠性的倾向。从进一步发挥上述效果的观点出发，亚微米铜粒子的含量以亚微米铜粒子的质量和微米铜粒子的质量的合计为基准，可以为30质量％以上且85质量％以下，可以为35质量％以上且85质量％以下，也可以为40质量％以上且80质量％以下。
亚微米铜粒子的形状没有特别限定。作为亚微米铜粒子的形状，可列举出例如球状、块状、针状、薄片状、大致球状及它们的凝聚体。从分散性及填充性的观点出发，亚微米铜粒子的形状可以为球状、大致球状、薄片状，从燃烧性、分散性、与薄片状微米粒子的混合性等观点出发，可以为球状或大致球状。本说明书中，“薄片状”包括板状、鳞片状等平板状的形状。
从分散性、填充性和与薄片状微米粒子的混合性的观点出发，亚微米铜粒子的长宽比可以为5以下，也可以为3以下。本说明书中，“长宽比”表示粒子的长边/厚度。粒子的长边及厚度的测定例如可以由粒子的SEM图像求出。
亚微米铜粒子可以用特定的表面处理剂处理。作为特定的表面处理剂，可列举出例如碳原子数为2～18的有机酸。作为碳原子数为2～18的有机酸，可列举出例如乙酸、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、肉豆蔻酸、十五碳烯酸、十六碳烯酸、棕榈烯酸、Sapienic acid、油酸、异油酸、亚油酸、亚麻油酸(linolein acid)、亚麻酸(linoleic 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，也可以组合使用2种以上。通过将这样的有机酸与上述亚微米铜粒子组合，存在能够兼顾亚微米铜粒子的分散性与烧结时的有机酸的脱离性的倾向。
表面处理剂的处理量可以是在亚微米铜粒子的表面附着单分子层～三分子层的量。该量可以由附着于亚微米铜粒子表面的分子层数(n)、亚微米铜粒子的比表面积(Ap)(单位为m2/g)、表面处理剂的分子量(Ms)(单位为g/mol)、表面处理剂的最小覆盖面积(SS)(单位为m2/个)和阿伏伽德罗数(NA)(6.02×1023个)算出。具体而言，表面处理剂的处理量根据表面处理剂的处理量(质量％)＝{(n·Ap·Ms)/(SS·NA+n·Ap·Ms)}×100％的式子算出。
亚微米铜粒子的比表面积可以通过用BET比表面积测定法测定干燥后的亚微米铜粒子来计算。在表面处理剂为直链饱和脂肪酸的情况下，表面处理剂的最小覆盖面积为2.05×10-19m2/1分子。在除此以外的表面处理剂的情况下，例如可以通过根据分子模型的计算、或《化学と教育》(上江田捷博、稲福純夫、森巌、40(2)，1992，p114－117)中记载的方法来测定。示出了表面处理剂的定量方法的一个例子。表面处理剂可以通过从无加压接合用铜糊料除去分散介质后的干燥粉的热脱离气/气相色谱质谱仪进行鉴定，由此可以确定表面处理剂的碳原子数和分子量。表面处理剂的碳含量比例可以通过碳含量分析来分析。作为碳含量分析法，可列举出例如高频感应加热炉燃烧/红外线吸收法。由鉴定出的表面处理剂的碳原子数、分子量和碳含量比例通过上述式可以算出表面处理剂量。
表面处理剂的上述处理量可以为0.07质量％以上且2.1质量％以下，可以为0.10质量％以上且1.6质量％以下，也可以为0.2质量％以上且1.1质量％以下。
由于上述亚微米铜粒子具有良好的烧结性，因此能够降低主要使用铜纳米粒子的接合材料所导致的高昂的合成成本、不良好的分散性、烧结后的体积收缩的降低等课题。
作为本实施方式的亚微米铜粒子，可以使用市售的粒子。作为市售的亚微米铜粒子，可列举出例如CH-0200(三井金属矿业株式会社制，体积平均粒径为0.36μm)、HT-14(三井金属矿业株式会社制，体积平均粒径为0.41μm)、CT-500(三井金属矿业株式会社制，体积平均粒径为0.72μm)、Tn-Cu100(太阳日产公司制，体积平均粒径为0.12μm)。
(微米铜粒子)
作为微米铜粒子，可以使用粒径为2.0μm以上且50μm以下的铜粒子，例如可以使用体积平均粒径为2.0μm以上且50μm以下的铜粒子。若微米铜粒子的体积平均粒径在上述范围内，则能够充分降低烧结无加压接合用铜糊料时的体积收缩、空隙的产生等，容易确保使无加压接合用铜糊料烧结而制造的结合体的接合强度，在将无加压接合用铜糊料用于半导体元件的接合的情况下，存在半导体装置显示出良好的芯片抗切强度及连接可靠性的倾向。从进一步发挥上述效果的观点出发，微米铜粒子的体积平均粒径可以为2μm以上且20μm以下，可以为2μm以上且10μm以下，可以为3μm以上且20μm以下，也可以为3μm以上且10μm以下。
微米铜粒子的含量以金属粒子的总质量为基准，可以为10质量％以上且90质量％以下，可以为15质量％以上且65质量％以下，也可以为20质量％以上且60质量％以下。若微米铜粒子的含量在上述范围内，则容易确保使无加压接合用铜糊料烧结而制造的接合体的接合强度，在将无加压接合用铜糊料用于半导体元件的接合的情况下，存在半导体装置显示出良好的芯片抗切强度及连接可靠性的倾向。
亚微米铜粒子的含量和微米铜粒子的含量的合计可以以金属粒子的总质量为基准，可以为80质量％以上。若亚微米铜粒子的含量和微米铜粒子的含量的合计在上述范围内，则能够充分降低烧结无加压接合用铜糊料时的体积收缩，容易确保使无加压接合用铜糊料烧结而制造的接合体的接合强度。在将无加压接合用铜糊料用于半导体元件的接合的情况下，存在半导体装置显示出良好的芯片抗切强度及连接可靠性的倾向。从进一步发挥上述效果的观点出发，亚微米铜粒子的含量和微米铜粒子的含量的合计以金属粒子的总质量为基准，可以为90质量％以上，可以为95质量％以上，也可以为100质量％。
微米铜粒子的形状没有特别限定。作为微米铜粒子的形状，可列举出例如球状、块状、针状、薄片状、大致球状、及它们的凝聚体。其中，微米铜粒子的形状中优选薄片状。通过使用薄片状的微米铜粒子，无加压接合用铜糊料内的微米铜粒子相对于接合面大致平行地取向，由此能够抑制使无加压接合用铜糊料烧结时的体积收缩，容易确保使无加压接合用铜糊料烧结而制造的接合体的接合强度。在将无加压接合用铜糊料用于半导体元件的接合的情况下，存在半导体装置显示出良好的芯片抗切强度及连接可靠性的倾向。从进一步发挥上述效果的观点出发，作为薄片状的微米铜粒子，其中，长宽比可以为4以上，也可以为6以上。
微米铜粒子中，有无表面处理剂的处理没有特别限定。从分散稳定性和耐氧化性的观点出发，微米铜粒子可以用表面处理剂进行处理。表面处理剂可以在接合时被除去。作为这样的表面处理剂，可列举出例如十二烷酸、棕榈酸、十七烷酸、硬脂酸、花生酸、亚油酸、亚麻油酸、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剂等。表面处理剂可以单独使用1种，也可以组合使用2种以上。
表面处理剂的处理量可以在粒子表面为一分子层以上的量。这样的表面处理剂的处理量根据微米铜粒子的比表面积、表面处理剂的分子量、以及表面处理剂的最小覆盖面积的变化而变化。表面处理剂的处理量通常为0.001质量％以上。关于微米铜粒子的比表面积、表面处理剂的分子量和表面处理剂的最小覆盖面积，可以通过上述方法算出。
在仅由上述亚微米铜粒子制备无加压接合用铜糊料的情况下，由于伴随分散介质干燥的体积收缩和烧结收缩大，因此在接合用铜糊料烧结时更容易从被粘接面剥离，在半导体元件等的接合中难以得到充分的芯片抗切强度和连接可靠性。在仅由上述微米铜粒子制备无加压接合用铜糊料的情况下，存在烧结温度高温化、需要400℃以上的烧结工序的倾向。通过并用亚微米铜粒子和微米铜粒子，能够抑制使无加压接合用铜糊料烧结时的体积收缩，接合体能够具有充分的接合强度。在将无加压接合用铜糊料用于半导体元件的接合的情况下，可得到半导体装置显示出良好的芯片抗切强度及连接可靠性的效果。
作为本实施方式的微米铜粒子，可以使用市售的物质。作为市售的微米铜粒子，可列举出例如MA-C025KFD(三井金属矿业株式会社制，体积平均粒径为7.5μm)、3L3(福田金属箔粉工业株式会社制，体积平均粒径为8.0μm)、1110F(三井金属矿业株式会社制，体积平均粒径为3.8μm)HWQ3.0μm(福田金属箔粉工业株式会社制，体积平均粒径为3.0μm)。
(除上述铜粒子以外的其它金属粒子)
作为金属粒子，可以含有除亚微米铜粒子和微米铜粒子以外的其它金属粒子，例如可以含有铜纳米粒子、镍、银、金、钯、铂等粒子。除铜粒子以外的其它金属粒子的体积平均粒径可以为0.01μm以上且10μm以下，可以为0.01μm以上且5μm以下，也可以为0.05μm以上且3μm以下。在含有其他金属粒子的情况下，从得到充分的接合性的观点出发，其含量以金属粒子的总质量为基准，可以低于20质量％，也可以为10质量％以下。也可以不含有其他金属粒子。其他金属粒子的形状没有特别限定。
在含有除铜粒子以外的金属粒子的情况下，能够得到多种金属固溶或分散而成的烧结体，因此烧结体的屈服应力、疲劳强度等机械特性得到改善，连接可靠性容易提高。另外，通过添加多种金属粒子，无加压接合用铜糊料的烧结体能够对特定的被粘接物具有充分的接合强度。在将无加压接合用铜糊料用于半导体元件的接合的情况下，半导体装置的芯片抗切强度及连接可靠性容易提高。
(分散介质)
分散介质包含具有300℃以上的沸点的溶剂。在无加压接合用铜糊料烧结时，从不妨碍烧结和致密化且在达到接合温度时迅速蒸发、除去的观点出发，作为具有300℃以上的沸点的溶剂的沸点，可以为300℃以上且450℃以下，可以为305℃以上且400℃以下，也可以为310℃以上且380℃以下。
关于具有300℃以上的沸点的溶剂，为了提高所含有的金属粒子的分散性，优选选择与金属粒子表面的亲和性高的结构。在金属粒子用含有烷基的表面处理剂进行表面处理的情况下，优选选择具有烷基的溶剂。作为这样的具有300℃以上的沸点的溶剂，可列举出异冰片基环己醇(MTPH，日本Terpene公司制)、硬脂酸丁酯、EXCEPARL BS(花王公司制)、硬脂酸硬脂酯，EXCEPARL SS(花王公司制)、硬脂酸2-乙基己酯、EXCEPARL EH-S(花王公司制)、硬脂酸异十三烷基酯、EXCEPARL TD-S(花王公司制)、异十八烷醇、FINE OXOCOL 180(日产化学公司制)、FINE OXOCOL 180T(日产化学公司制)、2-己基癸醇、FINE OXOCOL 1600(日产化学公司制)、三丁酸甘油酯、四乙二醇、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、十六腈、十七腈、苯甲酸苄酯、环庚草醚(cinmethylin)等。
作为具有300℃以上的沸点的溶剂，从提高分散性的观点出发，优选选择与表面处理剂的汉森溶解度参数相近的溶剂。作为表面处理剂，从有机酸、有机胺、含羟基的聚合物、聚乙烯基吡咯烷酮等容易处理的方面考虑，具有300℃以上的沸点的溶剂优选具有选自由羟基、醚基及酯基组成的组中的至少1种基团。汉森溶解度参数例如可以从下述公开文献的卷末数据库中检索，或者通过数据库和模拟合并软件HSPiP进行检索/计算。
公开文献：《HANSEN SOLUBILITY PARAMETERS：A USER’S HANDBOOK》(CRC Press，1999)
具有300℃以上的沸点的溶剂的含量以无加压接合用铜糊料的总质量为基准，可以为2质量％以上。具有300℃以上的沸点的溶剂的含量以无加压接合用铜糊料的总质量为基准，可以为2.2质量％以上，也可以为2.4质量％以上。若具有300℃以上的沸点的溶剂的含量为上述范围，则在烧结本实施方式的无加压接合用铜糊料时，存在一定量的溶剂能够残留在无加压接合用铜糊料中，容易维持部件间的铜糊料的挠性和附着性，即使在用于接合的部件彼此具有不同的热膨胀率的情况下，也能够无剥离地接合的倾向。具有300℃以上的沸点的溶剂的含量的上限没有特别限定。从能够抑制烧结温度下直至分散介质被除去为止的时间、缩短烧结时间的观点出发，以无加压接合用铜糊料的总质量为基准，可以为9质量％以下。
另外，本实施方式的无加压接合用铜糊料中，具有300℃以上的沸点的溶剂的含量以无加压接合用铜糊料的总容量为基准，可以为8体积％以上，可以为17体积％以上，也可以为23体积％以上。若具有300℃以上的沸点的溶剂的含量为上述范围，则在烧结本实施方式的无加压接合用铜糊料时，存在一定量的溶剂能够残留在无加压接合用铜糊料中，容易维持部件间的铜糊料的挠性和附着性，即使在用于接合的部件彼此具有不同的热膨胀率的情况下，也能够无剥离地接合的倾向。具有300℃以上的沸点的溶剂的含量的上限没有特别限定。从能够抑制烧结温度下直至分散介质被除去为止的时间、缩短烧结时间的观点出发，以无加压接合用铜糊料的总容量为基准，可以为60体积％以下。
分散介质可以含有具有低于300℃的沸点的溶剂。作为具有低于300℃的沸点的溶剂，可列举出α-松油醇、二乙二醇单丁醚、二乙二醇单丁醚乙酸酯、4-甲基-1,3-二氧杂戊环-2-酮、二乙二醇单丁醚等。具有低于300℃的沸点的溶剂在烧结工序之前的干燥工序或升温过程中能够容易地除去。分散介质可以从具有300℃以上的沸点的溶剂和具有低于300℃的沸点的溶剂中单独使用1种，也可以组合使用2种以上。
分散介质的含量以金属粒子的总质量为100质量份，可以为5～50质量份。若分散介质的含量在上述范围内，则能够将无加压接合用铜糊料调整为更适当的粘度，另外也不易阻碍铜粒子的烧结。
分散介质中的具有300℃以上的沸点的溶剂的含量以分散介质的总质量为基准，为20质量％以上且100质量％以下即可。若分散介质中的具有300℃以上的沸点的溶剂的含量在上述范围内，则容易确保相对于无加压接合用铜糊料的总质量的具有300℃以上的沸点的溶剂的含量。
无加压接合用铜糊料组合物中所含的分散介质的种类例如可以通过高温脱离气体的气相色谱-质谱分析法、以及TOF-SIMS进行分析。作为其他分析方法，也可以通过通常的有机分析、例如FT-IR、NMR、液相色谱以及它们的组合来鉴定通过离心分离将粒子成分分离而得到的上清液。分散介质的种类的比率可以通过液相色谱、NMR等进行定量。
(添加剂)
无加压接合用铜糊料中根据需要可以适当添加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等。
对于本实施方式的无加压接合用铜糊料，使糊剂从25℃升温至300℃时残留的具有300℃以上的沸点的溶剂的含量以升温至300℃时的无加压接合用铜糊料的质量为基准，优选为1质量％以上。升温速度可以为9.2(℃/分钟)。在该情况下，容易维持部件间的铜糊料的挠性，即使在将热膨胀率不同的部件彼此接合时由热膨胀率差产生的剪切力发挥作用的情况下，铜糊料也能够针对部件进行变形、追随，因此存在能够牢固地接合的倾向。将糊剂从25℃升温至300℃时残留的具有300℃以上的沸点的溶剂的含量的上限没有特别限定，从能够抑制烧结温度下直至分散介质被除去为止的时间、缩短烧结时间的观点出发，可以为9质量％以下。
本实施方式的无加压接合用铜糊料在接合时能够具有充分的挠性，因此在将存在于2个部件之间的无加压接合用铜糊料在250℃以上且低于350℃的温度下加热时，微米铜粒子和亚微米铜粒子烧结、形成金属键，能够以芯片抗切强度为10MPa以上、热导率为100W/(m·K)以上将2个部件间接合。
作为本实施方式的无加压接合用铜糊料的一个方式，可列举出下述无加压接合用铜糊料，其中，上述金属粒子包含体积平均粒径为0.01μm以上且0.8μm以下的亚微米铜粒子和体积平均粒径为2.0μm以上且50μm以下的微米铜粒子，分散介质包含具有300℃以上的沸点的溶剂，且具有300℃以上的沸点的溶剂的含量以无加压接合用铜糊料的总质量为基准，为2质量％以上。
作为上述无加压接合用铜糊料，可列举出下述无加压接合用铜糊料，其由体积平均粒径为0.01μm以上且0.8μm以下的亚微米铜粒子、体积平均粒径为2.0μm以上且50μm以下的微米铜粒子、包含具有300℃以上的沸点的溶剂的分散介质、和根据需要的其它上述成分配合而成，且具有300℃以上的沸点的溶剂的配合量以无加压接合用铜糊料的总质量为基准，为2质量％以上。
即使是将具有烧结性的亚微米铜粒子和具有补强效果的微米铜粒子与通常的沸点低于300℃的分散介质混合而得到的糊状组合物，若所接合的部件彼此没有显著的热膨胀率的差，则能够高强度地接合(例如参照表1中的对比较例1的Ni镀Cu板的芯片抗切强度)。然而，在将这样的糊状组合物用于热膨胀率不同的部件彼此的接合的情况下，接合力容易大幅降低(例如参照表1中的对比较例1的Ni镀Si芯片的芯片抗切强度)。作为接合力降低的主要原因，认为如果分散介质的沸点低于接合温度，则在升温过程中分散介质蒸发，在达到接合温度之前糊状组合物成为干固的脆的组合物。在该状态下，当热应力作用于热膨胀率不同的各个部件时，干固的脆的组合物无法追随部件而发生剥离或龟裂，因此作为结果，接合力降低。
接合温度下，通过包含分散介质能够残留的具有300℃以上的沸点的溶剂，能够在升温过程中优选1质量％以上的具有300℃以上的沸点的溶剂残留于无加压接合用铜糊料中，因此能够对无加压接合用铜糊料赋予挠性及附着性。因此，即使在接合时热应力作用于热膨胀率不同的各个部件的情况下，无加压接合用铜糊料也能够变形、追随而将部件无剥离地接合。
(无加压接合用铜糊料的制备)
无加压接合用铜糊料可以通过将上述的亚微米铜粒子、微米铜粒子、其它金属粒子和任意的添加剂混合到作为分散介质的具有300℃以上的沸点的溶剂中来制备。也可以在各成分的混合后进行搅拌处理。无加压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，分散液的最大粒径可以为20μm以下，也可以为10μm以下。
无加压接合用铜糊料可以通过预先将亚微米铜粒子、表面处理剂、作为分散介质的具有300℃以上的沸点的溶剂混合、进行分散处理来制备亚微米铜粒子的分散液，进而将微米铜粒子、其它金属粒子和任意的添加剂混合来制备。通过为这样的步骤，亚微米铜粒子的分散性提高，与微米铜粒子的混合性变得良好，能够进一步提高无加压接合用铜糊料的性能。也可以通过分级操作从亚微米铜粒子的分散液中除去凝聚物。
搅拌处理可以使用搅拌机进行。作为搅拌机，可列举出例如石川式搅拌机、Silverson搅拌器、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、超高压式分散机、薄层剪切分散机。
分级操作例如可以使用过滤、自然沉降、离心分离来进行。作为过滤用的过滤器，可列举出例如水梳子、金属网、金属过滤器、尼龙网。
作为分散处理，可列举出例如薄层剪切分散机、珠磨机、超声波均质器、高速混合机、窄间隙三辊研磨机、湿式超微粒化装置、超音速式气流粉碎机、超高压均质器。
无加压接合用铜糊料在成型的情况下可以调整为适于各种印刷、涂布方法的粘度。作为无加压接合用铜糊料的粘度，例如可以为25℃下的Casson粘度为0.05Pa·s以上且2.0Pa·s以下，也可以为0.06Pa·s以上且1.0Pa·s以下。
＜接合体及半导体装置＞
以下，参照附图对优选的实施方式进行详细说明。需要说明的是，附图中对相同或者相当的部分标注相同的附图标记，并省略重复的说明。另外，附图的尺寸比率并不限于图示的比率。
图1是表示使用本实施方式的无加压接合用铜糊料制造的接合体的一个例子的示意截面图。本实施方式的接合体100具备第一部件2、具有与第一部件不同的热膨胀率的第二部件3、以及将第一部件2与第二部件3接合的上述无加压接合用铜糊料的烧结体1。
作为第一部件2以及第二部件3，可列举出例如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、铜带、金属块、端子等供电用部件、散热板、水冷板等。
第一部件2及第二部件3可以在无加压接合用铜糊料的与烧结体1接触的面4a及4b中含有金属。作为金属，可列举出例如铜、镍、银、金、钯、铂、铅、锡、钴等。金属可以单独使用1种，也可以组合使用2种以上。另外，与烧结体接触的面也可以是含有上述金属的合金。作为用于合金的金属，除了上述金属以外，还可列举出锌、锰、铝、铍、钛、铬、铁、钼等。作为在与烧结体接触的面中包含金属的部件，可列举出例如具有各种金属镀层的部件、导线、具有金属镀层的芯片、散热片、贴付有金属板的的陶瓷基板、具有各种金属镀层的引线框或由各种金属构成的引线框、铜板、铜箔。
从充分接合第一部件和第二部件的观点出发，接合体的芯片抗切强度可以为10MPa以上，可以为15MPa以上，可以为20MPa以上，也可以为30MPa以上。芯片抗切强度可以使用万能型Bond Tester(4000系列、DAGE公司制)等进行测定。
从散热性和高温化下的连接可靠性的观点出发，无加压接合用铜糊料的烧结体的热导率可以为100W/(m·K)以上，可以为120W/(m·K)以上，也可以为150W/(m·K)以上。热导率可以根据无加压接合用铜糊料的烧结体的热扩散率、比热容量及密度算出。
第一部件与第二部件的热膨胀率之差可以为2ppm～30ppm，可以为3ppm～23ppm，也可以为5ppm～15ppm。
接着，对使用了本实施方式的无加压接合用铜糊料的接合体的制造方法进行说明。
使用了本实施方式的无加压接合用铜糊料的接合体的制造方法具备下述工序：准备层叠有第一部件、在该第一部件的自重作用的方向一侧依次为上述无加压接合用铜糊料及具有与第一部件不同的热膨胀率的第二部件的层叠体，在受到第一部件的自重、或第一部件的自重及0.01MPa以下的压力的状态下对无加压接合用铜糊料进行烧结。第一部件的自重作用的方向也可以称为重力作用的方向。
上述层叠体例如可以通过在第二部件的需要部分上设置本实施方式的无加压接合用铜糊料，接着在无加压接合用铜糊料上配置第一部件来准备。
作为将本实施方式的无加压接合用铜糊料设置于第二部件的需要部分上的方法，只要是使无加压接合用铜糊料堆积的方法即可。作为这样的方法，可列举出例如丝网印刷、转印印刷、胶版印刷、喷射印刷法、分配器、喷射分配器、针分配器、逗点涂布机、狭缝涂布机、模涂机、凹版涂布机、狭缝涂布、凸版印刷、凹版印刷、gravure印刷、型板印刷、软刻、棒涂、涂胶机、粒子堆积法、喷涂机、旋涂机、浸涂机、电沉积涂装等。无加压接合用铜糊料的厚度可以为1μm以上且1000μm以下，可以为10μm以上且500μm以下，可以为50μm以上且200μm以下，可以为10μm以上且3000μm以下，可以为15μm以上且500μm以下，可以为20μm以上且300μm以下，可以为5μm以上且500μm以下，可以为10μm以上且250μm以下，也可以为15μm以上且150μm以下。
从抑制烧结时的流动及空隙的产生的观点出发，设置于第二部件上的无加压接合用铜糊料可以适当干燥。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、甲酸等还原气氛中。干燥方法可以是通过常温放置的干燥，也可以是加热干燥，还可以是减压干燥。在加热干燥或减压干燥中，例如可以使用加热板、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。干燥的温度和时间可以根据所使用的分散介质的种类和量进行适当调整。作为干燥的温度和时间，例如可以在50℃以上且180℃以下干燥1分钟以上且120分钟以下。
作为在无加压接合用铜糊料上配置第一部件的方法，可列举出例如芯片安装机、倒装片接合机、碳制或陶瓷制的定位夹具。
通过对层叠体进行加热处理，进行无加压接合用铜糊料的烧结。加热处理可以使用例如加热板、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。
从烧结体、第一部件及第二部件的氧化抑制的观点出发，烧结时的气体气氛可以为无氧气氛。从除去无加压接合用铜糊料的铜粒子的表面氧化物的观点出发，烧结时的气体气氛可以为还原气氛。作为无氧气氛，可列举出例如氮气、稀有气体等无氧气体的导入、或真空下。作为还原气氛，可列举出例如在纯氢气中、在以成型气体为代表的氢和氮的混合气体中、在含有甲酸气体的氮中、在氢和稀有气体的混合气体中、在含有甲酸气体的稀有气体等。
从降低对第一部件和第二部件的热损伤及提高成品率的观点出发，加热处理时的到达最高温度可以为250℃以上且450℃以下，可以为250℃以上且400℃以下，也可以为250℃以上且350℃以下。如果到达最高温度为200℃以上，则存在到达最高温度保持时间为60分钟以下时烧结充分进行的倾向。
从使分散介质充分挥发、且提高成品率的观点出发，到达最高温度保持时间可以为1分钟以上且60分钟以下，也可以为1分钟以上且小于40分钟，也可以为1分钟以上且小于30分钟。
通过使用本实施方式的无加压接合用铜糊料，在对层叠体进行烧结时，即使在进行无加压下的接合的情况下，接合体也能够具有充分的接合强度。即，在仅由层叠于无加压接合用铜糊料的第一部件产生的自重、或在第一部件的自重之外还受到0.01MPa以下、优选为0.005MPa以下的压力的状态下，能够得到充分的接合强度。若烧结时受到的压力在上述范围内，则不需要特别的加压装置，因此不会损害成品率，能够进一步提高空隙的减少、芯片抗切强度及连接可靠性。作为无加压接合用铜糊料受到0.01MPa以下的压力的方法，例如可列举在第一部件上载置重物的方法等。
在上述接合体中，第一部件以及第二部件中的至少一个可以是半导体元件。作为半导体元件，可列举出例如二极管、整流器、晶闸管、MOS栅极驱动器、功率开关、功率MOSFET、IGBT、肖特基二极管、快速放电二极管等构成的功率模块、发送机、放大器、LED模块等。在这样的情况下，上述接合体成为半导体装置。所得到的半导体装置能够具有充分的芯片抗切强度及连接可靠性。
在半导体装置中，第一部件与第二部件的热膨胀率之差第一部件与第二部件的热膨胀率之差可以为2ppm～30ppm，可以为3ppm～23ppm，也可以为5ppm～15ppm。
图2是表示使用本实施方式的无加压接合用铜糊料制造的半导体装置的一个例子的示意截面图。图2所示的半导体装置110由在引线框5a上经由本实施方式的无加压接合用铜糊料的烧结体1连接的半导体元件8、以及对它们进行铸模的铸模树脂7构成。半导体元件8经由导线6与引线框5b连接。
作为使用本实施方式的无加压接合用铜糊料制造的半导体装置，可列举出例如二极管、整流器、晶闸管、MOS栅极驱动器、功率开关、功率MOSFET、IGBT、肖特基二极管、快速放电二极管等构成的功率模块、发送机、放大器、高亮度LED模块、半导体激光模块、逻辑块、传感器等。
上述半导体装置可以与上述接合体的制造方法同样地制造。即，半导体装置的制造方法具备下述工序：第一部件及第二部件中的至少一个使用半导体元件，准备层叠有第一部件、在该第一部件的自重作用的方向一侧依次为上述无加压接合用铜糊料及第二部件的层叠体，在受到第一部件的自重、或者第一部件的自重以及0.01MPa以下的压力的状态下对无加压接合用铜糊料进行烧结。可列举出例如在引线框5a上设置无加压接合用铜糊料，配置半导体元件8进行加热的工序。得到的半导体装置即使在进行了无加压下的接合的情况下，也能够具有充分的芯片抗切强度及连接可靠性。本实施方式的半导体装置通过具备具有充分的接合力且热传导率和熔点高的铜的烧结体，从而具有充分的芯片抗切强度、连接可靠性优异，并且功率循环耐性也优异。
实施例
[实施例1]
(无加压接合用铜糊料的制备)
称量作为亚微米铜粒子的CH-0200(50％体积平均粒径为0.36μm，三井金属公司制)15.84g(52.8质量％)、作为具有300℃以上的沸点的溶剂的异冰片基环己醇(沸点为308℃，以下简写为MTPH)3.6g(12质量％)，用自动研钵混合5分钟。进而将该混合物利用超声波均质器(US-600，日本精机制公司制)以19.6kHz、600W进行10分钟分散处理。
将分散处理后的混合物移至塑料瓶后，称量并加入作为微米铜粒子的MA-C025KFD(50％体积平均粒径为5μm，三井金属公司制)10.56g(35.2质量％)，以2000rpm、2分钟、减压的条件加入到Thinky公司制搅拌机(Thinkymixer ARE-310)中，得到无加压接合用铜糊料。
(固体成分测定)
取无加压接合用铜糊料加入到磁性坩埚中，由磁性坩埚的皮重和放入无加压接合用铜糊料后的磁性坩埚的重量之差得到无加压接合用铜糊料的重量。在加热至600℃的马弗炉中设置放入无加压接合用铜糊料后的磁性坩埚，处理1小时。由处理后的坩埚重量与磁性坩埚的皮重之差，得到无加压接合用铜糊料的不挥发成分的重量。无加压接合用铜糊料的固体成分(质量％)由下式算出。
无加压接合用铜糊料的固体成分(质量％)＝{(无加压接合用铜糊料的不挥发成分的重量)/(加热前的无加压接合用铜糊料的重量)}×100
(残留溶剂比例的测定)
测量从室温(25℃)升温至300℃时的残留于无加压接合用铜糊料中的分散介质的比例(残留溶剂比例)。测量铜板及芯片的质量后，在铜板上印刷无加压接合用铜糊料，在其上搭载芯片，得到层叠体。在该阶段测量层叠体的质量。将层叠体在氮下的烘箱中用30分钟从25℃升温至300℃后，取出层叠体，在黄铜块上急速冷却。测定冷却后的层叠体的质量，作为达到300℃时的质量。由下式算出达到300℃时的残留溶剂比例。
[数学式1]
(芯片抗切强度试验用接合样品的制作)
(使用了Si芯片的接合样品)
使用具有3×3mm2的正方形开口的厚度为75μm的不锈钢掩模和刮板(squeegee)，将无加压接合用铜糊料型板印刷到尺寸25×20×厚3mm的铜板上。在无加压接合用铜糊料的印刷物上，以镍面与无加压接合用铜糊料组合物接触的方式放置在厚度为400μm、尺寸为3×3mm的接合面整面上依次溅射有钛/镍的Si芯片(被粘接面为镍)，用镊子轻轻按压芯片，使镍面与无加压接合用铜糊料密合。将其设置于管状炉，对内部进行氩气置换，然后导入氢，以升温30分钟、300℃、10分钟的条件进行烧结。然后，停止氢气，在氩气气流下冷却至50℃以下，在空气中取出接合样品。
(使用了Cu板的接合样品)
除了使用在厚度为250μm、尺寸为2×2mm的整面上镀有镍的Cu板(被粘接面为镍)以外，与上述同样地制作接合样品。
(芯片抗切强度试验)
芯片抗切强度样品的接合强度通过芯片抗切强度进行评价。将接合样品使用安装有DS-100测力传感器的万能型Bond Tester(4000系列，DAGE Japan株式会社制)，以5mm/分钟的测定速度、50μm的测定高度在水平方向按压Si芯片或Cu板，测定芯片抗切强度。将抗切强度为20MPa以上记为接合良好。
[比较例1]
除了不使用异冰片基环己醇而使用α-松油醇(沸点为220℃)9.0质量份以外，与实施例1同样地得到无加压接合用铜糊料。除了使用该无加压接合用铜糊料以外，与实施例1同样地测定芯片抗切强度。将结果示于表1。
表1
使分散介质的一部分为沸点为308℃的MTPH的实施例1的样品对Si芯片显示出31MPa的良好的芯片抗切强度。而使用了不包含具有300℃以上的沸点的溶剂的无加压接合用铜糊料的比较例1的样品对Si芯片的芯片抗切强度为9MPa，接合不良。
测定残留溶剂比例时，实施例1中达到300℃时也残留有1.2质量％的溶剂。其以体积计为10体积％，考虑该残留溶剂将能够充分吸收由于铜板与Si芯片的热膨胀率差而施加于无加压接合用铜糊料的移位的挠性和密合性赋予给无加压接合用铜糊料。另一方面，比较例1中达到300℃时残留的溶剂为0.3质量％，另外以体积计为3体积％。因此，对于比较例1的无加压接合用铜糊料，认为在粒子间不存在充分的溶剂，由于热膨胀率差所引起的移位，无加压接合用铜糊料与芯片剥离、芯片抗切强度降低。
观察了将铜基板与Si芯片接合后的芯片接合部的Si芯片/芯片接合层界面的截面SEM图像。SEM图像的观察中使用的试验样品使用在(芯片抗切强度试验用接合样品的制作)中制作的样品。将实施例1的截面SEM图像示于图3，将比较例1的截面SEM图像示于图4。实施例1的样品中，具有Ti/Ni镀层10的硅芯片9与无加压接合用铜糊料的烧结体11良好地接合。另一方面，比较例1的样品中，由于在具有Ti/Ni镀层10的硅芯片9与无加压接合用铜糊料的烧结体11之间产生了剥离部(裂纹)12，因此接合不良。认为这是由于铜基板与Si芯片的热膨胀率之差所引起的移位，接合前在Si芯片/芯片接合层界面处发生剥离。
[实施例2～5、比较例2]
(铜糊料组合物的制备)
将作为具有300℃以上的沸点的溶剂的异冰片基环己醇(沸点为308℃，以下简称为MTPH)、作为其他溶剂的α-松油醇(沸点为220℃)按照表2的比例进行混合。向其中称量作为微米铜离子的MA-C025KFD(50％体积平均粒径为5μm，三井金属公司制)10.56g(35.2质量％)、作为亚微米铜离子的CH-0200(50％体积平均粒径为0.36μm，三井金属公司制)15.84g(52.8质量％)，用自动研钵混合5分钟。将混合物转移到塑料瓶后，以2000rpm、2分钟、减压的条件加入到Thinky公司制搅拌器(Thinkymixer ARE-310)中，得到无加压接合用铜糊料组合物。
(芯片抗切试验样品制作)
与实施例1同样地制作使用了在尺寸为3×3mm的接合面整面依次溅射有钛/镍的Si芯片的接合样品(Si)。进而使用在尺寸为2×2mm的整面上镀有镍的铜板，与实施例1同样地制作接合后的接合样品(铜板)。对于各个接合样品，与实施例1同样地测定芯片抗切强度。将结果示于表2和图5中。
[实施例6]
除了使用三丁酸甘油酯(沸点为310℃)作为具有300℃以上的沸点的溶剂以外，与实施例1同样地制备无加压接合用铜糊料。除了使用该无加压接合用铜糊料以外，与实施例1同样地制作使用了在尺寸为3×3mm的接合面整面依次溅射有钛/镍的Si芯片的接合样品(Si)，测定芯片抗切强度。其结果，芯片抗切强度显示出20MPa的良好的值。
[实施例7]
除了使用FINE OXOCOL 180(异十八烷醇、沸点为302℃、日产化学工业公司制)作为具有300℃以上的沸点的溶剂以外，与实施例1同样地制备无加压接合用铜糊料。除了使用该无加压接合用铜糊料以外，与实施例1同样地制作使用了在尺寸为3×3mm的接合面整面依次溅射有钛/镍的Si芯片的接合样品(Si)，测定芯片抗切强度。其结果，芯片抗切强度显示出23MPa的良好的值。
[实施例8]
除了使用硬脂酸丁酯(沸点为343℃)作为具有300℃以上的沸点的溶剂以外，与实施例1同样地制备无加压接合用铜糊料。除了使用该无加压接合用铜糊料以外，与实施例1同样地制作使用了在尺寸为3×3mm的接合面整面依次溅射有钛/镍的Si芯片的接合样品(Si)，测定芯片抗切强度。其结果，芯片抗切强度显示出25MPa的良好的值。
[实施例9]
除了使用辛酸辛酯(沸点为311℃)作为具有300℃以上的沸点的溶剂组合物以外，与实施例1同样地制备无加压接合用铜糊料。除了使用该无加压接合用铜糊料以外，与实施例1同样地制作使用了在尺寸为3×3mm的接合面整面依次溅射有钛/镍的Si芯片的接合样品(Si)，测定芯片抗切强度。其结果，芯片抗切强度显示出26MPa的良好的值。
[比较例3]
除了使用二乙二醇单丁醚(沸点为230℃、以下简称为DEGBE)作为分散介质以外，与实施例1同样地制备无加压接合用铜糊料。除了使用该无加压接合用铜糊料以外，与实施例1同样地制作使用了在尺寸为3×3mm的接合面整面依次溅射有钛/镍的Si芯片的接合样品(Si)，测定芯片抗切强度。其结果，芯片抗切强度为6MPa，判断为连接不良。
[比较例4]
除了使用二乙二醇单丁醚乙酸酯(沸点为247℃、以下简称为BDGAC)作为分散介质以外，与实施例1同样地制备无加压接合用铜糊料。除了使用该无加压接合用铜糊料以外，与实施例1同样地制作使用了在尺寸为3×3mm的接合面整面依次溅射有钛/镍的Si芯片的接合样品(Si)，测定芯片抗切强度。其结果，芯片抗切强度为5MPa，判断为连接不良。
表3示出了实施例6～9和比较例3、4的结果。图6中绘制了相对于溶剂的沸点的使用了实施例1、6、7、8、9和比较例1、3、4的无加压接合用铜糊料的接合样品(Si)的芯片抗切强度。在使用了具有300℃以上的沸点的溶剂的实施例中，均得到了20MPa以上的良好的芯片抗切强度。另一方面，在使用了具有低于300℃的沸点的溶剂的比较例中，均为9MPa以下的低的芯片抗切强度，接合不良。
符号说明
1 无加压接合用铜糊料的烧结体
2 第一部件
3 第二部件
5a、5b 引线框
6 导线
7 铸模树脂
8 半导体元件
9 硅芯片
10 Ti/Ni镀层
11 无加压接合用铜糊料的烧结体
12 剥离部

Claims (8)

1.一种无加压接合用铜糊料，其是包含金属粒子和分散介质的无加压接合用铜糊料，其中，
所述金属粒子包含体积平均粒径为0.01μm以上且0.8μm以下的亚微米铜粒子和体积平均粒径为2.0μm以上且50μm以下的微米铜粒子，
所述分散介质包含具有300℃以上的沸点的溶剂，且所述具有300℃以上的沸点的溶剂的含量以所述无加压接合用铜糊料的总质量为基准，为2质量％以上。
2.一种无加压接合用铜糊料，其是包含金属粒子和分散介质的无加压接合用铜糊料，其中，
所述金属粒子包含体积平均粒径为0.01μm以上且0.8μm以下的亚微米铜粒子和体积平均粒径为2.0μm以上且50μm以下的微米铜粒子，
所述分散介质包含具有300℃以上的沸点的溶剂，且所述具有300℃以上的沸点的溶剂的含量以所述无加压接合用铜糊料的总容量为基准，为8体积％以上。
3.根据权利要求1或2所述的无加压接合用铜糊料，其中，
所述具有300℃以上的沸点的溶剂具有选自由羟基、醚基及酯基组成的组中的至少一种基团。
4.根据权利要求1～3中任一项所述的无加压接合用铜糊料，其中，将存在于2个部件之间的无加压接合用铜糊料在250℃以上且低于350℃的温度下加热时，所述微米铜粒子及所述亚微米铜粒子烧结而形成金属键，所述2个部件之间以芯片抗切强度为10MPa以上、热导率为100W/(m·K)以上接合。
5.根据权利要求1～4中任一项所述的无加压接合用铜糊料，其中，
从25℃升温至300℃时残留的所述具有300℃以上的沸点的溶剂的含量以升温至300℃时的无加压接合用铜糊料的质量为基准，为1质量％以上。
6.一种接合体，其具备第一部件、具有与所述第一部件不同的热膨胀率的第二部件、以及将所述第一部件和所述第二部件接合的权利要求1～5中任一项所述的无加压接合用铜糊料的烧结体。
7.一种接合体的制造方法，其具备下述工序：
准备层叠有第一部件、在该第一部件的自重作用的方向一侧依次为权利要求1～5中任一项所述的无加压接合用铜糊料及具有与所述第一部件不同的热膨胀率的第二部件的层叠体，在受到所述第一部件的自重、或所述第一部件的自重及0.01MPa以下的压力的状态下对所述无加压接合用铜糊料进行烧结。
8.一种半导体装置，其具备第一部件、具有与所述第一部件不同的热膨胀率的第二部件、以及将所述第一部件和所述第二部件接合的权利要求1～5中任一项所述的无加压接合用铜糊料的烧结体，其中，
所述第一部件及所述第二部件中的至少一个是半导体元件。
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114450103A (zh) * 2019-09-25 2022-05-06 昭和电工材料株式会社 烧结铜柱形成用铜膏及接合体的制造方法
CN114502301A (zh) * 2019-09-30 2022-05-13 昭和电工材料株式会社 接合用铜糊料、接合体的制造方法及接合体
CN114521271A (zh) * 2019-09-27 2022-05-20 材料概念有限公司 氧化铜糊剂及电子部件的制造方法
CN115023305A (zh) * 2020-01-28 2022-09-06 三菱综合材料株式会社 接合用片
CN115223964A (zh) * 2021-04-19 2022-10-21 三菱电机株式会社 半导体装置及半导体装置的制造方法
CN115397584A (zh) * 2020-04-07 2022-11-25 昭和电工材料株式会社 铜膏、毛细结构的形成方法及热管
CN116325096A (zh) * 2020-09-30 2023-06-23 同和电子科技有限公司 接合用金属糊剂和接合方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110431657A (zh) * 2017-03-24 2019-11-08 三菱电机株式会社 半导体装置及其制造方法
KR20190096731A (ko) * 2018-02-09 2019-08-20 현대자동차주식회사 반도체 장치용 소결 접합 방법
TWI835866B (zh) 2018-09-28 2024-03-21 日商納美仕有限公司 導電性膏
US11890681B2 (en) 2018-11-29 2024-02-06 Resonac Corporation Method for producing bonded object and semiconductor device and copper bonding paste
JP7150144B2 (ja) * 2019-03-29 2022-10-07 三井金属鉱業株式会社 加圧接合用組成物、並びに導電体の接合構造及びその製造方法
CN111933603A (zh) * 2020-06-28 2020-11-13 深圳第三代半导体研究院 一种半导体芯片封装结构及其制备方法
FR3113774B1 (fr) 2020-09-03 2023-04-21 Commissariat Energie Atomique Procédé d’interconnexion de composants d’un système électronique par frittage
FR3113773B1 (fr) 2020-09-03 2023-04-21 Commissariat Energie Atomique Procédé d’interconnexion de composants d’un système électronique par frittage
JP2022149606A (ja) * 2021-03-25 2022-10-07 富士電機株式会社 半導体素子接合部及び半導体装置
CN114054746B (zh) * 2021-10-14 2022-08-16 华南理工大学 粒径呈纳米至微米三峰分布铜粉末及其一次性合成方法与应用

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007294633A (ja) * 2006-04-25 2007-11-08 Kyocera Chemical Corp セラミック電子部品用導電性ペーストおよびセラミック電子部品
CN101875158A (zh) * 2009-04-28 2010-11-03 日立化成工业株式会社 导电性接合材料、采用它的接合方法、以及由其接合的半导体装置
CN102632651A (zh) * 2011-02-10 2012-08-15 三菱综合材料株式会社 焊料接合用层压体及接合体
CN102812520A (zh) * 2010-03-18 2012-12-05 古河电气工业株式会社 导电性糊料和由该糊料得到的导电连接部件
CN102958631A (zh) * 2010-06-11 2013-03-06 同和电子科技有限公司 低温烧结性接合材料及使用该接合材料的接合方法
JP2013247060A (ja) * 2012-05-29 2013-12-09 Harima Chemicals Group Inc 導電性金属厚膜形成用材料および導電性金属厚膜の形成方法
EP2799164A1 (de) * 2013-05-03 2014-11-05 Heraeus Materials Technology GmbH & Co. KG Verbesserte Sinterpaste mit teilweise oxidierten Metallpartikeln
CN104246910A (zh) * 2012-10-30 2014-12-24 化研科技株式会社 导电性糊料和芯片焊接方法
JP2016160456A (ja) * 2015-02-27 2016-09-05 日立化成株式会社 銅含有粒子、導体形成組成物、導体の製造方法、導体及び装置

Family Cites Families (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1229095B1 (en) * 1999-08-25 2006-10-18 Hitachi Chemical Company, Ltd. Adhesive agent, method for connecting wiring terminals and wiring structure
TWI230104B (en) * 2000-06-12 2005-04-01 Hitachi Ltd Electronic device
US7790063B2 (en) * 2003-09-26 2010-09-07 Hitachi Chemical Company, Ltd. Mixed conductive power and use thereof
JP4247800B2 (ja) 2006-11-29 2009-04-02 ニホンハンダ株式会社 可塑性を有する焼結性金属粒子組成物、その製造方法、接合剤および接合方法
JP4914705B2 (ja) 2006-12-08 2012-04-11 ハリマ化成株式会社 微細な銅系配線パターンの形成方法
JP4872663B2 (ja) * 2006-12-28 2012-02-08 株式会社日立製作所 接合用材料及び接合方法
JP4897778B2 (ja) * 2008-11-20 2012-03-14 ソニーケミカル＆インフォメーションデバイス株式会社 接続フィルム、並びに、接合体及びその製造方法
WO2011007402A1 (ja) * 2009-07-14 2011-01-20 Ｄｏｗａエレクトロニクス株式会社 金属ナノ粒子を用いた接合材および接合方法
JP5395641B2 (ja) 2009-11-30 2014-01-22 シャープ株式会社 通信システム及び移動局装置及び基地局装置及び処理方法
PT2567257T (pt) * 2010-05-06 2021-07-20 Immunolight Llc Composição de ligação adesiva e método de utilização
JP5506042B2 (ja) * 2010-07-27 2014-05-28 ハリマ化成株式会社 導電性銅ペースト
EP2431438B1 (en) * 2010-09-20 2012-11-28 Henkel AG & Co. KGaA Electrically conductive adhesives
JP5830302B2 (ja) 2011-08-11 2015-12-09 古河電気工業株式会社 加熱接合用材料、加熱接合用シート体、及び加熱接合用成形体
JP2013151591A (ja) * 2012-01-24 2013-08-08 Taiyo Holdings Co Ltd 無機粒子含有ペーストおよび無機回路
JP2013153051A (ja) 2012-01-25 2013-08-08 Tokuyama Corp メタライズドセラミックスビア基板及びその製造方法
JP6179520B2 (ja) 2012-09-05 2017-08-16 日立化成株式会社 銀ペースト組成物及びそれを用いた半導体装置
JP5972844B2 (ja) * 2012-09-18 2016-08-17 デクセリアルズ株式会社 異方性導電フィルム、異方性導電フィルムの製造方法、接続体の製造方法、及び接続方法
JP2014077101A (ja) * 2012-10-12 2014-05-01 Hitachi Chemical Co Ltd リン含有銅合金粒子を用いた接着剤組成物及びそれを用いた半導体装置
US11440142B2 (en) * 2012-11-16 2022-09-13 Ormet Circuits, Inc. Alternative compositions for high temperature soldering applications
JP6199048B2 (ja) 2013-02-28 2017-09-20 国立大学法人大阪大学 接合材
JP6032110B2 (ja) 2013-04-17 2016-11-24 株式会社豊田中央研究所 金属ナノ粒子材料、それを含有する接合材料、およびそれを用いた半導体装置
JP6154194B2 (ja) * 2013-05-17 2017-06-28 トヨタ自動車株式会社 接合用金属ペースト
JP6372978B2 (ja) 2013-06-28 2018-08-15 古河電気工業株式会社 導電性ペースト
JP6132716B2 (ja) * 2013-09-10 2017-05-24 株式会社東芝 金属粒子ペースト、これを用いた硬化物、および半導体装置
JP6303392B2 (ja) * 2013-10-22 2018-04-04 日立化成株式会社 銀ペースト及びそれを用いた半導体装置、並びに銀ペーストの製造方法
JP2015133317A (ja) 2013-12-10 2015-07-23 Ｄｏｗａエレクトロニクス株式会社 導電性ペーストおよびそれを用いた導電膜の製造方法
JP6293524B2 (ja) * 2014-03-11 2018-03-14 デクセリアルズ株式会社 異方性導電フィルム及びその製造方法、並びに、接続方法及び接合体
BR112016029118A2 (pt) * 2014-06-12 2017-08-22 Alpha Metals materiais de sinterização e métodos de fixação usando os mesmos
JP5908571B1 (ja) * 2014-12-16 2016-04-26 ニホンハンダ株式会社 ペースト状金属粒子組成物、接合方法および電子装置
WO2016174584A1 (en) * 2015-04-28 2016-11-03 Ormet Circuits, Inc. Sintering pastes with high metal loading for semiconductor die attach applications
US10685943B2 (en) * 2015-05-14 2020-06-16 Mediatek Inc. Semiconductor chip package with resilient conductive paste post and fabrication method thereof
JP7005121B2 (ja) * 2015-12-04 2022-01-21 昭和電工マテリアルズ株式会社 無加圧接合用銅ペースト、接合体、及び半導体装置
MY194769A (en) * 2016-04-28 2022-12-15 Hitachi Chemical Co Ltd Copper paste for joining, method for manufacturing joined body, and method for manufacturing semiconductor device
SG11201906718UA (en) * 2017-03-15 2019-10-30 Hitachi Chemical Co Ltd Metal paste for joints, assembly, production method for assembly, semiconductor device, and production method for semiconductor device

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007294633A (ja) * 2006-04-25 2007-11-08 Kyocera Chemical Corp セラミック電子部品用導電性ペーストおよびセラミック電子部品
CN101875158A (zh) * 2009-04-28 2010-11-03 日立化成工业株式会社 导电性接合材料、采用它的接合方法、以及由其接合的半导体装置
CN102812520A (zh) * 2010-03-18 2012-12-05 古河电气工业株式会社 导电性糊料和由该糊料得到的导电连接部件
CN102958631A (zh) * 2010-06-11 2013-03-06 同和电子科技有限公司 低温烧结性接合材料及使用该接合材料的接合方法
CN102632651A (zh) * 2011-02-10 2012-08-15 三菱综合材料株式会社 焊料接合用层压体及接合体
JP2013247060A (ja) * 2012-05-29 2013-12-09 Harima Chemicals Group Inc 導電性金属厚膜形成用材料および導電性金属厚膜の形成方法
CN104246910A (zh) * 2012-10-30 2014-12-24 化研科技株式会社 导电性糊料和芯片焊接方法
EP2799164A1 (de) * 2013-05-03 2014-11-05 Heraeus Materials Technology GmbH & Co. KG Verbesserte Sinterpaste mit teilweise oxidierten Metallpartikeln
JP2016160456A (ja) * 2015-02-27 2016-09-05 日立化成株式会社 銅含有粒子、導体形成組成物、導体の製造方法、導体及び装置

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114450103A (zh) * 2019-09-25 2022-05-06 昭和电工材料株式会社 烧结铜柱形成用铜膏及接合体的制造方法
CN114521271A (zh) * 2019-09-27 2022-05-20 材料概念有限公司 氧化铜糊剂及电子部件的制造方法
CN114521271B (zh) * 2019-09-27 2023-12-26 材料概念有限公司 氧化铜糊剂及电子部件的制造方法
CN114502301A (zh) * 2019-09-30 2022-05-13 昭和电工材料株式会社 接合用铜糊料、接合体的制造方法及接合体
CN115023305A (zh) * 2020-01-28 2022-09-06 三菱综合材料株式会社 接合用片
CN115397584A (zh) * 2020-04-07 2022-11-25 昭和电工材料株式会社 铜膏、毛细结构的形成方法及热管
CN116325096A (zh) * 2020-09-30 2023-06-23 同和电子科技有限公司 接合用金属糊剂和接合方法
CN115223964A (zh) * 2021-04-19 2022-10-21 三菱电机株式会社 半导体装置及半导体装置的制造方法
US12080692B2 (en) 2021-04-19 2024-09-03 Mitsubishi Electric Corporation Semiconductor device and method for manufacturing semiconductor device

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