CN106170851A - 电子元器件模块、以及电子元器件模块的制造方法 - Google Patents

电子元器件模块、以及电子元器件模块的制造方法 Download PDF

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Publication number
CN106170851A
CN106170851A CN201580007207.4A CN201580007207A CN106170851A CN 106170851 A CN106170851 A CN 106170851A CN 201580007207 A CN201580007207 A CN 201580007207A CN 106170851 A CN106170851 A CN 106170851A
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Prior art keywords
copper
particle
copper particle
electronic component
component module
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CN201580007207.4A
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CN106170851B (zh
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清野绅弥
林俊孝
藤田颂
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
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    • H05K1/181—Printed circuits structurally associated with non-printed electric components associated with surface mounted components
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    • 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
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    • 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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Abstract

本发明提供一种电子元器件模块及其制造方法，具备使用到接合材料的内部为止都能切实烧结的铜粒子糊料形成的、铜粒子的耐氧化性优异且接合可靠性高的接合部。使用铜粒子糊料将外部端子与连接对象接合，铜粒子糊料包括：粒度分布的粒径峰值在0.1～5.0μm范围内且烧结前的平均微晶粒径在30～100nm范围内且粒子表面不具有抑制凝集的分散剂的铜粒子、及在铜粒子烧结时的煅烧温度下起到还原作用的有机化合物。在电子元器件(31)具备的外部端子(33)经由接合材料(34)与连接对象(36)电连接以机械连接的电子元器件模块(30)中，上述接合材料为通过上述铜粒子糊料烧结形成的平均微晶粒径在60～150nm范围内的烧结体。

Description

电子元器件模块、以及电子元器件模块的制造方法
技术领域
本发明涉及使用铜粒子糊料制造的电子元器件模块、以及电子元器件模块的制造方法。
背景技术
随着近些年的电子技术的发展，例如将表面安装型的电子元器件安装在电路基板上来构成的电子元件模块被广泛使用。
而且，在将表面安装型的电子元器件(以下，仅称为电子元器件)安装在电路基板上时，使用导电性的接合材料将电子元器件的外部端子与配置在电路基板上的安装用电极(连接对象)进行机械连接、电连接。
作为上述的接合材料，在专利文献1中，提出了一种烧结性接合材料，该材料是包含粒径1000nm以下的铜纳米粒子的液体或者糊料，其中，铜纳米粒子的个数基准的粒径分布的粒径峰值在粒径为1～35nm的区间、以及粒径比35nm大且1000nm以下的区间中分别有一个以上，铜纳米粒子包含一次粒子和作为一次粒子的融合物的二次粒子。
并且，在专利文献1中，公开了在上述的烧结性接合材料中包含分散剂(分散稳定剂)，此外，公开了氢、甲酸或者乙醇的气氛作为煅烧工序的还原气氛。
专利文献1除此以外，还公开了在使用上述烧结性结合材料对电子元器件进行接合的情况下，在接合电子元器件的方向上加压并且实施烧结热处理。
现有技术文献
专利文献
专利文献1：日本专利特开2013－91835号公报
发明内容
发明所要解决的技术问题
然而，在粒径为1～35nm的区间中存在粒径峰值的情况下，存在以下问题：具有上述的粒径的粒子即尺寸较小的粒子容易凝集，此外比表面积较大，容易氧化，因此材料的稳定性较差。
此外，在包含分散剂的情况下，在煅烧时容易引起体积收缩，形成空隙，因此存在接合强度降低的问题。
并且，在将氢、甲酸或者乙醇的气氛作为煅烧气氛的情况下，例如，存在以下问题：在电子元器件和连接对象的接合区域较大的情况下，还原气氛气体不能提供至接合部的内部区域，难以在期望的还原性气氛下对内部区域进行煅烧。即存在以下问题：在与还原性气氛接触的接合部的外周附近容易进行煅烧，在内部区域难以进行煅烧，因此在内部区域形成未烧结区域，从而降低接合强度。
本发明是为了解决上述技术问题，其目的是提供一种电子元器件模块、以及电子元器件模块的制造方法，该电子元器件模块使用如下的铜粒子糊料来制造：作为导电成分的铜粒子的稳定性(耐氧化性)优异，并且难以形成空隙，能形成接合可靠性较高的接合部，并且不仅构成接合部的接合材料的表面附近能可靠地烧结，接合材料的内部都能可靠地烧结。
解决技术问题的技术方案
为了解决上述技术问题，本发明的电子元器件模块具有如下结构：
电子元器件具备的外部端子经由接合材料与连接对象电连接以及机械连接，其特征在于，
所述接合材料通过使铜粒子糊料烧结来形成，该铜粒子糊料包括：
铜粒子，该铜粒子的粒径分布的粒径峰值在0.1～5.0μm范围内，并且烧结前的平均微晶粒径在30～100nm范围内，并且在粒子表面不具有抑制凝集的分散剂；以及
有机化合物，该有机化合物在使所述铜粒子烧结时的煅烧温度下起到还原作用。
此外，所述接合材料优选为烧结后的铜粒子的平均微晶粒径在60～150nm范围内的铜烧结体。
通过使烧结后的平均微晶粒径在60～150nm，从而形成稳定的铜烧结体。
此外，在上述的铜粒子糊料中，所述有机化合物优选为具有羟基的有机化合物。
通过使用具有羟基的有机化合物作为在用于烧结铜粒子的煅烧温度下起到还原作用的有机化合物，从而能在煅烧工序中去除形成在铜粒子的表面的氧化物膜，在煅烧工序中铜不被氧化而切实地烧结，从而能使本发明更具实效性。
此外，所述有机化合物优选为包含选自由三乙醇胺、甘油、乙二醇、三甘醇、二乙二醇、二丙二醇构成的群的至少一种。
通过使用选自上述群的至少一种，从而能使本发明更具实效性。
此外，所述连接对象优选为配置在电路基板上的安装用电极。
通过以本发明的方法将电子元器件的外部端子连接至电路基板上的安装用电极，从而能切实地制造可靠性较高的电子元器件模块，其具有如下结构：例如在电路基板上搭载IC芯片和层叠陶瓷电容器等的表面安装型的电子元器件。
此外，所述连接对象优选为安装在所述外部端子的金属端子。
通过以本发明的方法将电子元器件的外部端子安装到金属端子上，从而能切实地制造可靠性较高的带有端子的电子元器件模块。
此外，本发明的电子元器件模块的制造方法中，
该电子元器件模块具有如下结构：电子元器件具备的外部端子经由接合材料与连接对象电连接以及机械连接，其特征在于，包括如下工序：
对所述电子元器件和所述接合对象进行定位，使得所述电子元器件的所述外部端子经由铜粒子糊料与所述连接对象相对的工序，该铜粒子糊料包括：铜粒子，该铜粒子的粒径分布的粒径峰值在0.1～5.0μm范围内，并且烧结前的平均微晶粒径在30～100nm范围内，并且在粒子表面不具有抑制凝集的分散剂；以及有机化合物，该有机化合物在使所述铜粒子烧结时的煅烧温度下起到还原作用；以及
通过进行热处理使包含在所述铜粒子糊料中的所述铜粒子烧结，从而形成铜粒子的平均微晶粒径在60～150nm内的铜烧结体，并且将所述电子元器件的所述外部端子和所述连接对象经由所述铜烧结体接合的工序。
在本发明的电子元器件模块的制造方法中，优选为将所述电子元器件放置在所述接合对象上，以使所述电子元器件的所述外部端子经由所述铜粒子糊料与所述连接对象相对，在该状态下，进行所述热处理而无需从外部施加力。
通过使用上述那样的铜粒子糊料，从而能进行热处理而无需从外部施加力，由于没有加压，能减少对电子元器件的损坏，并且能形成微小的接合部。
此外，优选为在惰性气氛中实施所述热处理。
通过在惰性气氛中进行热处理，从而能进一步切实地使构成铜粒子糊料的铜粒子烧结，从而能使本发明更具实效性。
发明效果
用作为构成上述铜粒子糊料的铜粒子的粒度分布的粒径峰值在0.1～5.0μm范围内的铜粒子不会过于微细，因此难以氧化且稳定性优异，另一方面是在烧结性方面，平均微晶粒径为30～100nm的低值，能在300℃以下的低温进行烧结，在烧结后成为平均微晶粒径60～150nm左右的铜烧结体，是会成为稳定的接合材料的铜粒子。
此外，铜粒子由于在其表面不具有抑制凝集的分散剂，因此由烧结获得的铜烧结体的密度较高，能获得空隙所占比例较小的烧结体。
即，铜粒子的粒径为100nm以下的所谓纳米粒子若不存在分散剂就会凝集，但是在上述的铜粒子糊料中，铜粒子的粒度分布的粒径峰值在0.1～5.0μm的范围内，因此即使不使用分散剂也能抑制凝集。
此外，在平均微晶粒径为100nm以下的纳米粒子的情况下，利用其效果(纳米尺寸效果)能在低温下烧结，但是在本发明中通过将铜粒子的平均微晶粒径设为30～100nm的范围内，从而能在300℃以下进行低温烧结。
即，通过将铜粒子的粒度分布的粒径峰值设为0.1～5.0μm的高值，并且将微晶粒径设为30～100nm的低值，从而可以即使不掺合分散剂也不会凝集，并且能在300℃以下进行低温烧结。
此外，上述的铜粒子糊料由于包含有在用于烧结铜粒子的煅烧温度下起还原作用的有机化合物(例如溶剂)，因此通过该有机化合物的还原作用，成为阻碍烧结的主要因素的铜粒子表面的铜氧化物被还原，因此不需要特别在还原性气氛中进行煅烧，能在惰性气氛下进行烧结。此外，若在使用还原气体的还原气氛下进行煅烧，则在将上述的铜粒子糊料作为接合材料使用的情况下，存在以下问题：在接合部的表面和周边部进行烧结，而在接合部的内部烧结容易不充分地进行，但是如上所述，通过含有起到还原作用的有机化合物(例如溶剂)，从而不需要在还原气氛下进行煅烧，能解决上述问题。
此外，在上述的铜粒子糊料中，铜粒子在低温下烧结可以认为是根据如下说明的机理。
图1A～图1D是示意性地示出铜粒子的烧结过程的图。
如图1A所示，用于上述的铜粒子糊料的铜粒子10中，微晶11的平均尺寸(平均微晶粒径)为30～100nm的低值，具有较大的晶界能量。此外，铜粒子10在常温下，其表面被氧化膜(铜氧化膜)12覆盖。
该铜粒子糊料(铜粒子)1若加热至回流温度(例如230℃)，则如图1B所示在铜粒子10的周围存在的在用于使铜粒子烧结的煅烧温度下起到还原作用的有机化合物(例如溶剂)13起到还原剂的作用，铜粒子10的表面的氧化物(铜氧化物)12被还原。
由此，若铜粒子10的表面的氧化膜(铜氧化膜)12被还原，则平均微晶粒径较小且具有较大的晶界能量的铜粒子10即使在回流温度左右的较低温度下也会生长晶颈，如图1C所示合二为一，从而微晶粒径变大。其结果，如图1D所示，铜粒子10自身变大，并且平均微晶粒径也成为60～150nm的高值，形成稳定的铜烧结体。
构成上述的铜粒子糊料的铜粒子根据上述的机理，在低温下也能高效地烧结。
此外，本发明的电子元器件模块具有以下的结构：电子元器件具备的外部端子经由通过对上述的铜粒子糊料进行烧结而形成的接合材料，与连接对象电连接以及机械连接，电子元器件的外部端子和连接对象经由密度较高、空隙所占的比例较低的铜烧结体构成的接合部可靠地接合，因此能切实地提供具备高可靠性的电子元器件模块。
此外，在本发明的电子元器件模块的制造方法中，在对电子元器件与接合对象进行定位以使电子元器件的外部端子经由上述的铜粒子糊料与连接对象相对的状态下进行热处理，对包含在铜粒子糊料中的铜粒子进行烧结，并且将电子元器件的外部端子和连接对象利用平均微晶粒径为60～150nm的铜烧结体进行接合，因此电子元器件的外部端子和连接对象经由密度较高、空隙所占比例较低的铜烧结体构成的接合部能可靠地接合，从而能高效地制造可靠性较高的电子元器件模块。
附图说明
图1A是示意性地示出在铜粒子糊料中使用的铜粒子的烧结过程的一个工序的图。
图1B是示意性地示出在上述的铜粒子糊料中使用的铜粒子的烧结过程的另一个工序的图。
图1C是示意性地示出在上述的铜粒子糊料中使用的铜粒子的烧结过程的又一个工序的图。
图1D是示意性地示出在上述的铜粒子糊料中使用的铜粒子的烧结过程的又一个工序的图。
图2是示出使用上述的铜粒子糊料来接合的接合部的图。
图3是说明使用上述的铜粒子糊料来接合的接合部的接合强度的测定方法的图。
图4A是示出使用平均微晶粒径为56.7nm的铜粒子的铜粒子糊料在煅烧前的铜粒子的状态的显微镜照片(SEM图像)。
图4B是示出使用平均微晶粒径为56.7nm的铜粒子的铜粒子糊料在煅烧后的铜粒子的状态的显微镜照片(SEM图像)。
图5A是示出使用平均微晶粒径为107.2nm的铜粒子的铜粒子糊料在煅烧前的铜粒子的状态的显微镜照片(SEM图像)。
图5B是示出使用平均微晶粒径为107.2nm的铜粒子的铜粒子糊料在煅烧后的铜粒子的状态的显微镜照片(SEM图像)。
图6A是用于确认三乙醇胺的作为还原剂的作用的图，将涂布三乙醇胺后的氧化亚铜粉在230℃下加热10min时的XRD图表。
图6B是用于确认三乙醇胺的作为还原剂的作用的图，将涂布三乙醇胺后的氧化亚铜粉在200℃下加热10min时的XRD图表。
图7是示出本发明的实施方式1所涉及的电子元器件模块的结构的图。
图8是示出本发明的实施方式2所涉及的电子元器件模块的结构的图。
图9是示出本发明的实施方式2所涉及的电子元器件模块中的电子元器件和电路基板的接合部附近的显微镜照片(SEM图像)。
图10是示出本发明的实施方式3所涉及的电子元器件模块的结构的图。
具体实施方式
以下示出本发明的实施方式，对于本发明的特征部分进一步详细地说明。
[实施方式1]
本发明的实施方式1所涉及的电子元器件模块是具有如下结构的电子元器件模块：电子元器件具备的外部端子经由通过烧结铜粒子糊料来形成的接合材料，与连接对象电连接以及机械连接。
在制作构成接合材料的铜粒子糊料时，首先，作为铜粒子，准备粒度分布的粒径峰值在0.1～5.0μm范围内，并且烧结前的平均微晶粒径在30～100nm范围内的铜粒子。
此外，准备在常温下为液体的三乙醇胺作为在烧结铜粒子时的煅烧温度下起到还原作用的有机化合物。
接着，通过将铜粒子和三乙醇胺以重量比为87：13的比例进行掺和并混炼，从而制作铜粒子糊料。
此外，铜粒子的粒度分布的粒径峰值用下述的方法求出。首先，使用扫描型电子显微镜观察铜粒子，对于视野中的200个粒子，测定水平方向弗里特直径。然后，将获得的测定值换算为球体，计算出体积平均粒径，根据其结果求出粒径峰值。
此外，烧结前的平均微晶粒径用下述的方法求出。首先，对铜粒子进行X射线衍射测定，获得峰<111>、<200>、<311>这3个峰值。然后，使用获得的3个峰值，根据里德伯尔德法算出微晶粒径，将其平均值作为平均微晶粒径。
<铜粒子糊料的评价>
(1)接合强度
使用如上所述制作的铜粒子糊料，用以下说明的方法，将无氧铜试料片与无氧铜试料片彼此接合，测定接合强度。
此处，如图2所示，将平面尺寸为纵横5mm、且厚度为1mm的第1无氧铜试料片21、和平面尺寸为纵横3mm、且厚度为1mm的第2无氧铜试料片22，经由将如上所述制作的铜粒子糊料烧结形成的铜烧结体23接合。
在使用铜粒子糊料将第1无氧铜试料片21和第2无氧铜试料片22接合时，使用具备使铜粒子糊料通过的贯通孔(此处，直径为2000μm的平面形状为圆形的贯通孔)的金属掩模，在第1无氧铜试料片21上印刷铜粒子糊料，使其涂布厚度为40μm。
然后，在第1无氧铜试料片21上印刷的铜粒子糊料上，放置第2无氧铜试料片22，不特别施加应力，在锻烧温度：230℃、煅烧时间：60min、煅烧气氛：氮气的条件下煅烧，如图2所示，将第1无氧铜试料片21和第2无氧铜试料片22经由接合材料(使铜粒子糊料烧结的铜烧结体)23接合。
然后，对于第1无氧铜试料片21和第2无氧铜试料片22的接合强度进行测定。接合强度的测定通过使用Dage公司产的通用型粘合力试验机Dage4000测定剪切强度来进行。
此外，在测定时，如图3所示，将下侧的第1无氧铜试料片21利用固定夹具固定，使用刀具宽度4mm的剪切刀具24，将剪切速度设为50μm/s，将从无氧铜试料片21的表面到刀具前端的距离设为50μm进行剪切。然后，拍摄断裂面，利用图像处理测定接合面积。
接着，将上述剪切强度值除以接合面积，求出单位面积的剪切强度(MPa)。
其结果，确认获得剪切强度为36Mpa的高强度。
(2)关于煅烧前以及煅烧后的平均微晶粒径
煅烧前的微晶粒径是将铜粒子糊料以油墨的方式涂布在玻璃板上，以上述的方法，即根据进行X射线衍射测定获得的峰<111>、<200>、<311>的3个峰值，利用里德伯尔德法算出微晶粒径，并求出其平均值的方法来测定。煅烧后的微晶粒径是将剪切后的烧结体用镊子抽出载置在玻璃板上，以上述的方法，即根据进行X射线衍射测定获得的峰<111>、<200>、<311>的3个峰值，利用里德伯尔德法算出微晶粒径，并求出其平均值的方法来测定。
即，使用具备直径为2000μm(2mm)的平面形状为圆形的贯通孔的金属掩模，在第1无氧铜试料片21上印刷铜粒子糊料，使其涂布厚度为40μm，在温度：230℃、煅烧时间：60min、煅烧气氛：氮气的条件下进行煅烧，并测定煅烧前后的微晶粒径。
其结果，确认到在煅烧前的阶段，平均微晶粒径为62nm，但是在煅烧后变大至102μm。
由此，在将煅烧前的阶段的平均微晶粒径减小至满足本发明的条件中规定的范围的情况下，不使用分散剂也能防止铜粒子的凝集，并且根据参照图1A～图1D说明的机理在低温下能进行烧结。其结果，不需要在高温下进行煅烧，也能形成由密度较高、空隙所占的比例较低的铜烧结体形成的接合材料。
在图4A、图4B以及图5A、图5B中，示出使用在本发明的条件中规定的范围内的铜粒子以及在范围以外的铜粒子的铜粒子糊料进行煅烧前后的铜粒子的显微镜照片(SEM图像)。
此外，图4A示出使用在本发明的条件中规定的范围内的平均微晶粒径为56.7nm的铜粒子的铜粒子糊料在煅烧前的铜粒子状态的显微镜照片(SEM图像)，图4B是示出煅烧后的铜粒子状态的显微镜照片(SEM图像)。
此外，图5A示出使用在本发明的条件中规定的范围以外的平均微晶粒径为107.2nm的铜粒子的铜粒子糊料在煅烧前的铜粒子状态的显微镜照片(SEM图像)，图5B是示出煅烧后的铜粒子状态的显微镜照片(SEM图像)。
根据图5A、图5B可知，在使用平均微晶粒径为107.2nm的铜粒子10的在本发明的条件中规定的范围以外的铜粒子糊料的情况下，基本没有确认到铜粒子10有晶颈生长。
对此，根据图4A、图4B可知，在使用平均微晶粒径为56.7nm的铜粒子10的在本发明的条件中规定的范围内的铜粒子糊料的情况下，确认到铜粒子10有晶颈生长、即充分地进行煅烧。
(3)三乙醇胺的还原性评价
在上述的铜粒子糊料中，作为在烧结铜粒子时的煅烧温度下起到还原作用的有机化合物(溶剂)使用的三乙醇胺的还原性用以下方法测定。
在确认三乙醇胺的还原性时，使用市售的氧化亚铜(Cu2O)粉，进行以下说明的试验。首先，将氧化亚铜粉放置在玻璃基板上，在常温下涂布液体的三乙醇胺，利用加热板，在规定的温度下进行10min加热后，利用XRD进行组分分析。
此处，对于在200℃下加热10min的情况、在作为电极材料一般使用的Sn的熔点附近的温度条件即230℃下加热10min的情况的结果，参照图6A、图6B进行说明。
此外，图6A是表示将涂布了三乙醇胺的氧化亚铜粉在作为电极材料一般使用的Sn的熔点附近的温度条件即230℃下加热10min时的XRD图表的图，图6B是示出在将涂布了三乙醇胺的氧化亚铜粉在200℃下加热10min时的XRD图表的图。
其结果，如图6B所示，在加热温度为200℃时，并没有Cu的峰，而氧化亚铜(Cu2O)的峰仍然较大，从而可以确认没有起到还原作用。
另一方面，在加热温度为作为电极材料一般使用的Sn的熔点附近的温度条件即230℃时，如图6A所示，可清晰地看到Cu的峰，而氧化亚铜(Cu2O)的峰变小，即可以确认到起到还原作用。
此外，在该实施方式中，虽然使用三乙醇胺作为具有还原性的有机化合物，但是在三乙醇胺以外，甘油、乙二醇、三甘醇、二乙二醇、二丙二醇等具有羟基的有机化合物也确认具有还原性，这些物质也可以作为具有还原性的有机化合物使用。
此外，作为起到还原作用的有机化合物，还能使用其他的有机化合物。在本发明中，作为起到上述的还原作用的有机化合物，优选为使用在常温下为液体的有机化合物，根据不同的情况，也可以使用在常温下为固体的物质，此时，根据需要可以在其他溶剂中使其溶解来使用。
图7是示出本发明的实施方式(实施方式1)所涉及的电子元器件模块的图，该电子元器件模块是具有如下结构：经由通过对如上所述制作的铜粒子糊料进行烧结来形成的接合材料，与连接对象电连接以及机械连接。。
该电子元器件模块30如图7所示，具有如下的结构：在IC芯片(本发明的电子元器件)31的表面电极32上形成的金凸点(外部端子)33经由铜烧结体(接合材料)34与形成在电路基板35上的例如由铜构成的安装用电极(连接对象)36进行电连接以及机械连接，并且IC芯片(电子元器件)31利用密封树脂37密封。
此外，在图7中，虽然示出在电路基板35上搭载IC芯片31的结构，但是也可以搭载例如芯片电容器和芯片电阻等的其他电子元器件。
上述的接合材料即铜烧结体34是通过将上述的铜粒子糊料烧结来形成的，是烧结后的平均微晶粒径在60～150nm的范围内的铜烧结体。
接着，对于电子元器件模块30的的制造方法进行说明。在制造该电子元器件模块时，首先准备在表面具备安装用电极(连接盘电极)36的电路基板35。
此外，准备在表面电极32上形成有金凸点(外部端子)33的IC芯片(本发明的电子元器件)31。
然后，在电路基板35的安装用电极36上提供上述的铜粒子糊料，以IC芯片(电子元器件)31的金凸点(外部端子)33位于电路基板35的安装用电极36上所提供的铜粒子糊料上的方式，将IC芯片(电子元器件)31搭载在电路基板35的安装用电极36上。接着，无需特意将IC芯片(电子元器件)31向电路基板35按压，在氮气气氛(惰性气氛)中且230℃下对IC芯片(电子元器件)31进行煅烧，从而使包含在铜粒子糊料中的铜粒子烧结，经由铜烧结体(接合材料)34，将金凸点(外部端子)33与安装用电极(连接对象)36连接。
然后，将搭载在电路基板35上的IC芯片(电子元器件)31利用密封树脂37密封。由此，获得具有图7所示的结构的电子元器件模块30。
该电子元器件模块30具有如下结构：IC芯片(电子元器件)31的金凸点(外部端子33)经由通过对上述的铜粒子糊料烧结来形成且烧结后的平均微晶粒径在60～150nm的范围内的铜烧结体(接合材料)34，与作为连接对象的电路基板35的安装用电极(连接对象)36进行电连接以及机械连接。
因而，能提供一种高可靠性的电子元器件模块，其IC芯片(电子元器件)31的金凸点(外部端子)33和安装用电极(连接对象)36经由由密度较高、并且空隙所占的比例较低的铜烧结体形成的接合材料34切实地接合。
此外，根据上述的电子元器件模块的制造方法，对IC芯片(电子元器件)31和安装用电极(连接对象)36进行定位，使得IC芯片(电子元器件)31的金凸点(外部端子)33经由在煅烧后成为铜烧结体34的铜粒子糊料与连接对象36相对，并在此状态下进行热处理，因此IC芯片(电子元器件)31的金凸点(外部端子)33和连接对象36能利用由密度较高、并且空隙所占的比例较低的铜烧结体形成的接合材料(铜烧结体)34切实地接合。
因而，能高效地制造高可靠性的电子元器件模块，其IC芯片(电子元器件)31的金凸点(外部端子)33和连接对象36切实地接合。
此外，由于进行热处理时无需从外部施加力，因此可以减少对IC芯片(电子元器件)31的损伤，并且能形成微小的接合部。
此外，在实施方式1中，对于IC芯片(电子元器件)的凸点由金构成且安装用电极(连接盘电极)由铜构成的情况举例进行了说明，但是作为凸点的构成材料，可以使用Ag、Cu、Ni、Ag－Pd等，此外，作为安装用电极(连接盘电极)的构成材料，可以使用Au、Ag、Ni、Ag－Pd等。
[实施方式2]
图8是示出本发明的实施方式(实施方式2)所涉及的电子元器件模块的图。
该电子元器件模块40如图8所示，是具有如下结构的电子元器件模块：层叠陶瓷电容器41具备的由铜构成的外部端子42经由铜烧结体(接合材料)44，与形成在电路基板(氧化铝基板)45的由铜构成的安装用电极(本发明的连接对象)46电连接以及机械连接。
在该电子元器件模块40中，可确认安装用电极(连接盘电极)46和外部端子42的接合强度为45Mpa。
该电子元器件模块40通过以下方式来形成：在形成在电路基板45的表面的安装用电极(连接盘电极)46上提供煅烧后成为铜烧结体44的铜粒子糊料，将两端形成有外部端子42的层叠陶瓷电容器41配置成安装用电极(连接盘电极)46和上述外部端子42经由铜粒子糊料相对，并且不用特别从外部施加应力，通过在氮气气氛(惰性气氛)中且在230℃下进行煅烧，使包含在铜粒子糊料中的铜粒子烧结。
图9是层叠陶瓷电容器41和电路基板45的接合部附近的显微镜照片(SEM图像)。
由图9可知，层叠陶瓷电容器41的由铜构成的外部端子42与电路基板45上的由铜构成的安装用电极46经由由铜烧结体44构成的接合材料进行接合。
根据该实施方式2，可知在层叠陶瓷电容器41的外部端子42不用形成Sn镀层或焊接镀层等，通过使用上述的铜粒子糊料，层叠陶瓷电容器41的由铜构成的外部端子42和电路基板45上的由铜构成的安装用电极46直接接合，从而能实现较高可靠性的接合而不会形成金属间化合物。
此外，层叠陶瓷电容器的外部端子的构成材料不限于铜，也可以由金、银、银－钯、镍等形成。此外，也可以在铜中含有玻璃。
[实施方式3]
图10是示出本发明的另一个实施方式(实施方式3)所涉及的带有金属端子的电子元器件(广义的电子元器件模块)的图。
图10所示的电子元器件(例如层叠陶瓷电容器)50是如下的带有金属端子的电子元器件50，利用通过将上述的铜粒子糊料烧结形成的铜烧结体(接合材料)54，将金属端子(本示例中，L字形的金属端子)53与形成在电子元器件元件51的表面的外部电极52接合来构成。
该实施方式3的带有金属端子的电子元器件50是例如在形成在电子元器件元件51的表面的外部电极52或者金属端子53中的至少一个涂布上述的铜粒子糊料，在使两者接合的状态下，在规定的条件下实施热处理，通过使铜粒子糊料中的铜粒子烧结，从而能方便并且切实地制作。
此外，该带有金属端子的电子元器件50中，电子元器件元件51的外部电极52和作为连接对象的金属端子53利用密度较高、并且空隙所占的比例较低的铜烧结体构成的接合材料(铜烧结体)54切实地接合，具备较高的可靠性。
此外，金属端子不限于上述那样的结构，也可以是构成其他的电子元器件的一部分的金属端子。这种情况下也能获得相同的效果。金属端子53的构成材料没有特别的限制，可以使用金、银、同、银－钯、镍等构成。
此外，上述的铜粒子糊料不限于在实施方式1、2中说明的电子元器件模块和实施方式3中说明的带有金属端子的电子元器件(广义的电子元器件模块)等用途，也可以适用于如下等用途：
(a)配置在多层陶瓷基板的内部的内置元器件的连接材料
(b)用于层间连接的过孔导体形成用材料
(c)用于形成布线和电极的电极形成用材料
(d)导电性密封材料
(e)芯片焊接用的连接材料
本发明还在其他方面也不限定于上述实施方式，在发明的范围内可以进行增加各种应用、变形。
标号说明
10 铜粒子
11 微晶
12 氧化膜(铜氧化物)
13 起到还原作用的有机化合物(溶剂)
21 第1无氧铜试料片
22 第2无氧铜试料片
23 煅烧铜粒子糊料来构成的铜烧结体
24 剪切刀具
30 电子元器件模块
31 IC芯片(电子元器件)
32 表面电极
33 金凸点(外部端子)
34 铜烧结体(接合材料)
35 电路基板
36 安装用电极(连接对象)
37 密封树脂
40 电子元器件模块
41 层叠陶瓷电容器
42 外部端子
44 铜烧结体(接合材料)
45 电路基板(氧化铝基板)
46 安装用电极(连接对象)
50 电子元器件
51 电子元器件元件
52 外部电极
53 金属端子
54 铜烧结体(接合材料)

Claims (9)

1.一种电子元器件模块，其具有如下结构：电子元器件具备的外部端子经由接合材料与连接对象电连接以及机械连接，其特征在于，
所述接合材料通过使铜粒子糊料烧结来形成，该铜粒子糊料包括：
铜粒子，该铜粒子的粒径分布的粒径峰值在0.1～5.0μm范围内，并且烧结前的平均微晶粒径在30～100nm范围内，并且在粒子表面不具有抑制凝集的分散剂；以及
有机化合物，该有机化合物在使所述铜粒子烧结时的煅烧温度下起到还原作用。
2.如权利要求1所述的电子元器件模块，其特征在于，
所述接合材料是烧结后的铜粒子的平均微晶粒径在60～150nm范围内的铜烧结体。
3.如权利要求1或2所述的电子元器件模块，其特征在于，
所述有机化合物是具有羟基的有机化合物。
4.如权利要求1至3中任意一项所述的电子元器件模块，其特征在于，
所述有机化合物包含选自由三乙醇胺、甘油、乙二醇、三甘醇、二乙二醇、二丙二醇构成的群中的至少一种。
5.如权利要求1至4中任意一项所述的电子元器件模块，其特征在于，
所述连接对象是配置在电路基板上的安装用电极。
6.如权利要求1至4中任意一项所述的电子元器件模块，其特征在于，
所述连接对象是安装在所述外部端子上的金属端子。
7.一种电子元器件模块的制造方法，该电子元器件模块具有如下结构：电子元器件具备的外部端子经由接合材料与连接对象电连接以及机械连接，其特征在于，包括如下工序：
对所述电子元器件和所述接合对象进行定位，使得所述电子元器件的所述外部端子经由铜粒子糊料与所述连接对象相对的工序，该铜粒子糊料包括：铜粒子，该铜粒子的粒径分布的粒径峰值在0.1～5.0μm范围内，并且烧结前的平均微晶粒径在30～100nm范围内，并且在粒子表面不具有抑制凝集的分散剂；以及有机化合物，该有机化合物在使所述铜粒子烧结时的煅烧温度下起到还原作用；以及
通过进行热处理使包含在所述铜粒子糊料中的所述铜粒子烧结，从而形成铜粒子的平均微晶粒径为60～150nm的铜烧结体，并且将所述电子元器件的所述外部端子和所述连接对象经由所述铜烧结体接合的工序。
8.如权利要求7所述的电子元器件模块的制造方法，其特征在于，
将所述电子元器件放置在所述接合对象上，以使所述电子元器件的所述外部端子经由所述铜粒子糊料与所述连接对象相对，在该状态下，进行所述热处理而不从外部施加力。
9.如权利要求7或8所述的电子元器件模块的制造方法，其特征在于，
在惰性气氛中实施所述热处理。
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