CN106061669A - 无铅钎焊合金、钎焊材料及接合结构体 - Google Patents

无铅钎焊合金、钎焊材料及接合结构体 Download PDF

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CN106061669A
CN106061669A CN201580009860.4A CN201580009860A CN106061669A CN 106061669 A CN106061669 A CN 106061669A CN 201580009860 A CN201580009860 A CN 201580009860A CN 106061669 A CN106061669 A CN 106061669A
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mass
present
lead
lead solders
brazing alloy
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入泽淳
和田理枝
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Koki Co Ltd
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Koki Co Ltd
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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
    • B23K35/22—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
    • B23K35/02—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
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    • 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
    • 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
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Abstract

本发明为含有超过3.0质量％且10质量％以下的Sb、作为剩余部分含有Sn的无铅钎焊合金等。

Description

无铅钎焊合金、钎焊材料及接合结构体
关联申请的相互参照
本申请主张日本国专利申请2014－33234号的优先权，并通过引用纳入本申请说明书的记载中。
技术领域
本发明涉及用于电子零件的钎焊的无铅钎焊合金、包含该无铅钎焊合金的钎焊材料及包含所述无铅钎焊合金的接合结构体。
背景技术
近年，基于环境问题的观点，几乎不含铅的无铅钎焊料被用于将电子零件装配在印制电路板等电路衬底上。
另一方面，随着装配衬底及配线的微细化，零件也逐渐微小化，其结果就是，钎焊接合部也在逐渐微小化。
伴随该钎焊接合部的微小化，会导致因发生电迁移(electromigration)而使钎焊接合部出现空隙、进而断线的问题。因此，研究了各种无铅钎焊中用于抑制电迁移的技术。
例如，专利文献1中记载了一种在连接端子表面设置由Ag－Sn金属构成的保护层的技术。但是，当这样在连接端子表面设置保护层的情况下，需要对连接结构本身进行变更，因此，需要重新大幅度地调整制造工序。另外，由于需要设置保护层的工序，因此制造工序变得繁琐。因此，研究通过对钎焊合金的组成进行调整，来抑制电迁移。例如，专利文献2中记载了一种无铅钎焊合金，其含有特定含量的Cu及In，剩余部分为Sn。另外，专利文献3中记载了一种无铅钎焊合金，其含有Pd、Mn、Zn、Al、Sb、In等金属。
但是，在专利文献2及3记载的钎焊合金中，抑制电迁移的效果不充分。
现有技术文献
专利文献
专利文献1：日本国特开2013－135014号
专利文献2：日本国特开2013－252548号
专利文献3：日本国特开2014－27122号
发明内容
发明要解决的问题
本发明是鉴于所述那样现有技术中的问题点而作出的发明，其课题在于提供能够充分抑制钎焊接合部中发生电迁移的无铅钎焊合金、钎焊材料及接合结构体。
用于解决问题的方案
本发明的无铅钎焊合金含有超过3.0质量％且10质量％以下的Sb，作为剩余部分含有Sn。
本发明的无铅钎焊合金作为剩余部分还可以含有从由Ag、Cu、Ni、Co及Ge构成的组中选择的至少一种金属。
本发明的无铅钎焊合金还可以含有4.0质量％以下的所述Ag。
本发明的无铅钎焊合金还可以含有1.0质量％以下的所述Cu。
本发明的无铅钎焊合金还可以合计含有0.1质量％以下的所述Ni、Co及Ge。
本发明的钎焊材料含有所述无铅钎焊合金、和助焊剂。
本发明的接合结构体是具有电极的衬底和半导体元件介由钎焊接合部被接合的接合结构体，所述钎焊接合部含有所述无铅钎焊合金。
附图说明
图1是表示试片的概要的SEM照片。
图2是表示电迁移试验所使用的装置的概要的概要图。
具体实施方式
以下，对本发明的无铅钎焊合金、钎焊材料及接合结构体进行说明。
首先，本实施方式的无铅钎焊合金是含有超过3.0质量％且10质量％以下的Sb(锑)、且剩余部分为Sn(锡)的无铅钎焊合金。
此外，本实施方式中，剩余部分是指Sb以外的成分。
本实施方式的无铅钎焊合金是指JIS Z 3282中规定的用于无铅钎焊的钎焊合金。
本实施方式的无铅钎焊合金(以下，也仅称作“钎焊合金”)含有超过3.0质量％且10质量％以下的Sb，优选含有3.3质量％以上且5质量％以下的Sb。
本实施方式的钎焊合金是以Sn为主要成分的无铅钎焊合金。
在该以Sn为主要成分的钎焊合金中，由于含有所述范围内的Sb，因此，在将钎焊合金用于钎焊接合的情况下，能够充分抑制电迁移。
此外，本实施方式中，超过3.0质量％是指，比3.0质量％大的质量％。以下，“超过”的含义相同。
电迁移是指，在金属中流通高密度电流时，金属电子发生移动的现象，因该金属电子的移动，会导致金属部分产生缺损部分(空隙)。尤其，若因装配零件的微细化以致钎焊接合部也变得微小，则虽然电流小但电流密度增高，因此，容易发生电迁移。例如，如电连接半导体元件和中介层衬底的内部凸起那样的钎焊接合部等，在与以往的印制衬底的零件装配中的钎焊接合部相比极微小的钎焊接合部中，在钎焊接合部流通高密度电流从而导致发生电迁移，并有可能产生空隙或断线等。该电迁移通常容易发生在10kA/cm2以上的高密度电流下，但在钎焊接合部为球状的凸起的情况下，在为直径80μm的凸起的情况下，即使为31.4mA左右的电流也可能在电流集中部中流通10kA/cm2以上的高密度电流。因此，钎焊接合部越小，即使更小的电流也容易发生电迁移。
本实施方式的钎焊合金，由于难以发生电迁移，因此，尤其优选适用于电连接半导体元件和中介层衬底的内部凸起那样的微小的钎焊接合部。
本实施方式的钎焊合金，例如，熔融开始温度即固相线温度为220℃～240℃，优选为230℃～236℃，凝固开始温度即液相线温度为221℃～250℃，优选为230℃～245℃的范围。
固相线温度及液相线温度成为所述范围，由此，能够抑制电迁移，同时能够将钎焊合金的流动性维持在适当的范围，且能够抑制钎焊接合后的熔融。
已知：通常以Sn为主要成分的无铅钎焊合金，由于不含有熔融温度比Sn低的铅，因此熔融温度高。因此，通过使其成为含有熔融温度比Sn低的金属的合金而能够对钎焊合金的熔融温度进行调整。另一方面，若熔融温度过低，则例如在用于前述那样的内部凸起的情况下，在将零件装配于作为母板的衬底上时，会引起内部凸起熔融的问题。因此，用于内部凸起的钎焊合金，其液相线温度优选为例如泛用无铅钎焊(Sn3Ag0.5Cu)的液相线温度即220℃以上。
本实施方式的钎焊合金的熔融温度在所述范围内，由此，能够抑制电迁移，同时能够将钎焊合金的流动性维持在适当的范围内，且能够抑制钎焊接合后的熔融。
本实施方式的钎焊合金作为剩余部分，除Sn以外，还可以包含从Ag(银)、Cu(铜)、Ni(镍)、Co(钴)及Ge(锗)构成的组中选择的至少一种金属。
由于还含有这些金属，因此，能够进一步抑制电迁移。
剩余部分中各金属的优选含量没有特别限定，例如，Sn为94.9质量％以上且100质量％以下，优选为96质量％以上且100质量％以下。
另外，Ag、Cu、Ni、Co及Ge的总量为剩余部分中的0.001质量％以上且5.1质量％以下，优选为0.5质量％以上且4.0质量％以下。
各成分的更具体的含量例如如下所述。
本实施方式的钎焊合金还可以含有84.4质量％以上且97.0质量％以下的Sn。
本实施方式的钎焊合金可以含有0.1质量％以上且4.5质量％以下的Ag，优选含有1.0质量％以上且3.5质量％以下的Ag。
通过含有所述范围的Ag，能够进一步抑制电迁移。
本实施方式的钎焊合金在含有Cu的情况下，可以含有0.1质量％以上且1.2质量％以下的Cu，优选含有0.5质量％以上且0.7质量％以下的Cu。
本实施方式的钎焊合金在含有Ni的情况下，可以含有0.01质量％以上且0.1质量％以下的Ni，优选含有0.03质量％以上且0.07质量％以下的Ni。
本实施方式的钎焊合金在含有Co的情况下，可以含有0.01质量％以上且0.1质量％以下的Co，优选含有0.03质量％以上且0.07质量％以下的Co。
本实施方式的钎焊合金在含有Ge的情况下，可以含有0.001质量％以上且0.1质量％以下的Ge，优选含有0.005质量％以上且0.01质量％以下的Ge。
此外，作为Ni、Co、Ge的合计含量，可以为超过0质量％且0.1质量％以下。
该情况下，Ni、Co、Ge的合计含量是指，从由Ni、Co及Ge组成的组中选择的至少一种金属的合计量，且在仅含有一种的情况下，其含义是指该金属的含量。
通过使Cu、Ni、Co、Ge的含量为所述范围，能够进一步抑制电迁移。
即，作为本实施方式的钎焊合金的一例，能够列举一种无铅钎焊合金，该无铅钎焊合金由超过3.0质量％且10质量％以下的Sb、和作为剩余部分的Sn构成。
该情况下，剩余部分为100质量％的Sn。
另外，作为本实施方式的钎焊合金的其他的一例，能够列举一种无铅钎焊合金，该无铅钎焊合金含有超过3.0质量％且10质量％以下的Sb，且剩余部分由Sn、和从由Ag、Cu、Ni、Co及Ge组成的组中选择的至少一种金属构成。
该情况下，剩余部分中，Sn为84.69质量％以上且96.999质量％以下，由从Ag、Cu、Ni、Co及Ge组成的组中选择的至少一种金属的合计量为3.001质量％以上且15.31质量％以下。
此外，本实施方式的钎焊合金作为剩余部分还可以含有不可避免的杂质。
该情况下，作为本实施方式的钎焊合金的一例的无铅钎焊合金，由超过3.0质量％且10质量％以下的Sb、和作为剩余部分的Sn及不可避免的杂质构成。
另外，作为本实施方式的钎焊合金的其他的一例，为无铅钎焊合金，其含有超过3.0质量％且10质量％以下的Sb，且剩余部分由Sn、和从由Ag、Cu、Ni、Co及Ge组成的组中选择的至少一种金属和不可避免的杂质构成。
此外，在本实施方式中，所述各金属的含量是利用电火花放电发光分光分析并通过JIS Z 3910记载的方法测定的值。
接下来，对利用前述那样的本实施方式的钎焊合金的钎焊材料进行说明。
本实施方式的钎焊材料是含有所述无铅钎焊合金和助焊剂的钎焊材料。
助焊剂没有特别限定，能够使用公知的助焊剂，能够列举例如松香系、合成树脂系等公知的用于钎焊材料的助焊剂。
本实施方式的钎焊材料中的钎焊合金及助焊剂的含量没有特别限定，但例如，钎焊合金为85质量％以上且95质量％以下，优选为88质量％以上且90质量％以下；助焊剂为5质量％以上且15质量％以下，优选为10质量％以上且12质量％以下。
用于本实施方式的钎焊材料的钎焊合金优选为粉末状。在为粉末状的钎焊合金的情况下，通过与所述助焊剂混合，能够容易地得到糊状的钎焊材料(焊料糊)。
此外，本实施方式的钎焊合金如前所述形成为粉末状并与助焊剂混合后作为焊料糊等使用，除此以外，还可以成形为棒状、带状或球状等各种形状进行使用。
接下来，对使用前述那样的本实施方式的钎焊合金及钎焊材料的接合结构体进行说明。
本实施方式的钎焊接合体是具有电极的衬底和半导体元件介由钎焊接合部被接合的接合结构体，所述钎焊接合部含有前述的本实施方式的无铅钎焊合金。
本实施方式的接合结构体是具有电极的衬底和半导体元件介由钎焊接合部被接合的接合结构体，所述钎焊接合部含有前述的无铅钎焊合金。
作为具有电极的衬底和半导体元件介由钎焊接合部被接合的接合结构体，能够列举例如通过倒装而形成的半导体封装件。
通过倒装形成的半导体封装件，在半导体元件的下表面形成钎焊凸起，并通过钎焊接合与衬底上的电极连接，因此无需将引线向半导体元件的旁边引出，能够得到与半导体元件的尺寸接近的微小的半导体封装件。
另一方面，该接合结构体中的钎焊接合部由于形成为极微小的尺寸，因此，容易流通高密度电流，且容易发生电迁移。
而且，该接合结构体的钎焊接合部，由于在将接合结构体进一步装配于成为母板的衬底上时也会被曝露在热环境下，因此，要求在一旦装配完半导体元件后不容易熔融。
在本实施方式的接合结构体中，在使用前述那样的本实施方式的钎焊材料的情况下，能够充分抑制电迁移，同时，在接合半导体元件时使其在适当的温度下熔融，并在将接合结构体装配在衬底上时使其不发生熔融。
此外，本实施方式的钎焊合金被用于具有电极的衬底和半导体元件介由钎焊接合部被接合的接合结构体的钎焊接合部，除此以外，本实施方式的钎焊合金还可以用于通常的电子零件和印制衬底的电极的接合部。
本实施方式的钎焊合金、钎焊材料及接合结构体如上所述，但这里公开的实施方式的全部内容仅为例示，不应被认为是用于进行限制的内容。本发明的范围并非由所述说明表示而是通过权利要求书的范围表示，其意图包含与权利要求书的范围等同的含义及范围内的全部变更。
本发明的无铅钎焊合金含有超过3.0质量％且10质量％以下的Sb，作为剩余部分含有Sn，因此，在用作接合部的钎焊材料的情况下，也能够充分抑制电迁移。
因此，根据本发明，能够提供一种能充分抑制钎焊接合部中发生电迁移的无铅钎焊合金、钎焊材料及接合结构体。
实施例
下面，就本发明的实施例与比较例一起进行说明。此外，本发明不被下述实施例限定并解释。
(钎焊合金)
准备表1记载的组成的各钎焊合金。
[表1]
(电迁移耐性试验)
图1中示出了用于测定电迁移耐性的试片的概要。
试片(试验片)是使用烙铁尖200μm的焊烙铁(UNIX－JBC，JAPANUNIX公司制)在铜电极之间对各钎焊合金进行钎焊来制作的。钎焊接合部的厚度被调整为9μm。
另外，铜电极表面利用#2000的耐水研磨纸进行研磨，之后用#4000的耐水研磨纸进行精研磨。
使用各试片，在图2所示的装置中测定电迁移。测定方法为，使探针与铜电极接触，以平均电流密度50kA/cm2进行通电并测定电压值。试片被载置于陶瓷加热器上，以60℃边进行加热边通电。
将无法测定电压值的时间作为破裂时间表示在表1中。
另外，以同样的测定方法，对实施例1、4及比较例1以平均电流密度100kA/cm2、200kA/cm2进行通电并测定电压值，将无法测定电压值的时间作为破裂时间表示在表2中。
而且，关于实施例4及比较例1，以平均电流密度10kA/cm2进行通电并测定电压值，将无法测定电压值的时间作为破裂时间表示在表2中。
[表2]
(熔融性能试验)
对各钎焊合金的熔融性能进行测定。
通过差示扫描量热测定法(Differential scanning calorimetry；DSC法)以10K/min的升温速度对各钎焊合金的固相线温度及液相线温度进行测定。
将结果表示在表1中。
如表1所示，实施例的破裂时间都为150小时以上，明显能够抑制电迁移的发生。
另外，实施例中，固相线温度为230℃以上、且液相线温度为240℃。即，在实施例中，熔融性能能够被调整到合适的范围。
而且，如表2所示，比较例1中，即使平均电流密度为10kA/cm2，破裂时间也很短，即，会发生电迁移。另一方面，在实施例1及4中，即使平均电流密度为10kA/cm2、及为更高的平均电流密度即50kA/cm2、100kA/cm2、200kA/cm2，与比较例1相比，破裂时间也长，即，能够进一步抑制电迁移的发生。
通过以上，在各实施例中，在较宽的电流密度的范围内明显能够可靠地抑制电迁移的发生。

Claims (7)

1.一种无铅钎焊合金，含有超过3.0质量％且10质量％以下的Sb，作为剩余部分含有Sn。
2.根据权利要求1所述的无铅钎焊合金，作为剩余部分还含有从由Ag、Cu、Ni、Co及Ge构成的组中选择的至少一种金属。
3.根据权利要求2所述的无铅钎焊合金，含有4.0质量％以下的所述Ag。
4.根据权利要求2或3所述的无铅钎焊合金，含有1.0质量％以下的所述Cu。
5.根据权利要求2至4的任一项所述的无铅钎焊合金，合计含有0.1质量％以下的所述Ni、Co及Ge。
6.一种钎焊材料，含有权利要求1至5的任一项所述的无铅钎焊合金、和助焊剂。
7.一种接合结构体，是具有电极的衬底和半导体元件介由钎焊接合部被接合的接合结构体，所述钎焊接合部含有权利要求1至5的任一项所述的无铅钎焊合金。
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