CN105121677A - 无铅软钎料合金 - Google Patents

无铅软钎料合金 Download PDF

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Publication number
CN105121677A
CN105121677A CN201380075708.7A CN201380075708A CN105121677A CN 105121677 A CN105121677 A CN 105121677A CN 201380075708 A CN201380075708 A CN 201380075708A CN 105121677 A CN105121677 A CN 105121677A
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CN
China
Prior art keywords
solder alloy
electrode
layer
lead
plating
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
CN201380075708.7A
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English (en)
Inventor
立花贤
野村光
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.)
Senju Metal Industry Co Ltd
Original Assignee
Senju Metal Industry 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 Senju Metal Industry Co Ltd filed Critical Senju Metal Industry Co Ltd
Priority to CN201910435147.6A priority Critical patent/CN110153588A/zh
Publication of CN105121677A publication Critical patent/CN105121677A/zh
Pending legal-status Critical Current

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Classifications

    • 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
    • B23K35/26—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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
    • 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
    • B23K35/264—Bi as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C12/00—Alloys based on antimony or bismuth
    • 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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Abstract

提供低熔点且延性优异、拉伸强度高、抑制接合界面的P富集层的生成、具有高剪切强度从而抑制基板的应变、具有优异的连接可靠性的Sn-Bi-Cu-Ni系无铅软钎料合金。为了抑制电极的Cu、Ni的扩散且确保软钎料合金的伸长率、润湿性，具有以质量％计包含Bi：31～59％、Cu：0.3～1.0％、Ni：0.01～0.06％、余量Sn的合金组成。

Description

无铅软钎料合金
技术领域
本发明涉及无铅软钎料合金。特别是涉及连接可靠性优异的Sn-Bi-Cu-Ni系无铅软钎料合金。
背景技术
近年来，移动电话等电子设备具有小型化、薄型化的倾向。这种电子设备所使用的半导体装置等电子部件中，已经开始使用使厚度薄至几mm左右～1mm以下的基板。
另一方面，一直以来，作为无铅软钎料广泛使用Sn-Ag-Cu软钎料合金。Sn-Ag-Cu软钎料合金的熔点比较高，即使是属于共晶组成的Sn-3Ag-0.5Cu软钎料合金也表现出220℃左右。因此，利用Sn-Ag-Cu软钎料合金对前述那样的薄基板的电极进行软钎焊时，由于接合时的热而使基板发生应变，有时产生接合不良。
针对这种连接不良，进行如下方法：通过在低温下进行软钎焊，从而抑制薄基板的应变，提高连接可靠性。作为能应对该方法的低熔点软钎料合金，已知有Sn-Bi软钎料合金。该软钎料合金当中，Sn-58Bi软钎料合金的熔点相当低，为140℃左右，能够抑制基板的应变。
但是，Bi原本是较脆的元素，Sn-Bi软钎料合金也脆。即使减少Sn-Bi软钎料合金的Bi的含量，也会由于Bi在Sn中偏析而发生脆化。使用Sn-Bi软钎料合金进行软钎焊而得到的钎焊接头在施加较大应力时担心因其脆性而产生龟裂，机械强度劣化。
另外，为了应对电子部件的小型化，必须缩小其使用的基板的面积，必须实现电极的小型化、电极间的低间距化。进而，用于进行软钎焊的软钎料合金的用量减少，因此钎焊接头的机械强度降低。
于是，专利文献1中，公开了为了能够进行具有高接合强度的软钎料接合而在Sn-Bi软钎料合金中添加Cu和Ni而得到的Sn-Bi-Cu-Ni无铅软钎料合金。根据该文献，使用该软钎料合金的接合部由于在软钎料接合部中和/或软钎料接合界面形成具有六方最密堆积结构的金属间化合物，因此接合强度提高。
现有技术文献
专利文献
专利文献1：日本特开2013-00744号公报
发明内容
发明要解决的问题
电子部件的电极通常为Cu，对于该Cu电极，通常覆盖有无电极镀Ni层、化学镀Ni/Au层、化学镀Ni/Pd/Au层。如此，Cu电极利用Au、Au与Pd的组合那样的贵金属进行了化学镀处理。镀Au层抑制基底的镀Ni层的氧化，改善与熔融软钎料的润湿性。关于化学镀Ni层，形成含有源自化学镀中使用的还原剂(例如，次磷酸钠)的相当大量的P的镀Ni层。这种镀Ni层至少含有几质量百分数的P、例如2～15质量％。
但是，专利文献1中记载了为了在软钎料合金与自电极引出的Cu布线部的接合界面形成六方最密堆积结构的金属间化合物，而在Sn-Bi软钎料合金中添加Cu、Ni，但没有公开具体的合金组成，也没有记载用于证明接合强度提高的效果的结果。该文献中记载了在Sn为57atm％、Bi为43atm％的组成中添加的Cu、Ni的含量的范围，但不清楚是否在该范围内接合强度都会提高。
另外，该文献中记载了作为软钎料合金的接合对象，有印刷基板的Cu布线部、不含Cu的布线部，但除了布线部为Cu之外，不清楚接合对象为怎样的构成。如前所述，该文献中没有公开软钎料合金的具体的合金组成，因此，除了在电极与软钎料合金的接合界面形成金属化合物之外，关于接合界面的状态没有任何公开或启示。因此，很难认为满足该文献中公开的Bi、Cu和Ni的含量的所有软钎料合金在用于例如进行了化学镀Ni处理的Cu电极的软钎焊时能够解决以下那样的问题。
对进行了化学镀Ni处理的电极进行软钎焊时，软钎料合金中的Ni的扩散系数大于P的扩散系数，因此Ni优先地在软钎料合金中扩散，在软钎料合金与电极的接合界面产生P的浓度较高的部分，形成所谓P富集层。该P富集层硬脆，因此使钎焊接头的剪切强度劣化。具有这种P富集层的钎焊接头因剪切而断裂时，发生镀Ni层露出的现象。该断裂不是钎焊接头自身的断裂，而是由电极上形成的P富集层的剥离而引起的。因此，P富集层的形成会对钎焊接头的连接可靠性造成不利的影响。
同样地，对未进行镀覆处理的Cu电极进行软钎焊时，也不清楚满足该文献中公开的各元素的含量范围的所有软钎料合金是否都表现出高接合强度。
此处，本发明的课题在于提供如下的Sn-Bi-Cu-Ni系无铅软钎料合金，即所述无铅软钎料合金为低熔点且延性优异，拉伸强度高，此外，对进行了化学镀Ni处理的Cu电极进行软钎焊时，由该软钎焊形成的钎焊接头表现出高剪切强度，从而抑制软钎料接合时的基板的热应变，具有优异的连接可靠性。另外，本发明的课题在于提供对于未进行镀覆处理的Cu电极，由软钎焊形成的钎焊接头也表现出高剪切强度，从而具有优异的连接可靠性的Sn-Bi-Cu-Ni系无铅软钎料合金。
用于解决问题的方案
本发明人等着眼于，对具有由化学镀Ni处理形成的含P镀Ni层的电极进行软钎焊时，为了提高剪切强度，软钎料合金中的Ni的扩散系数大于P的扩散系数。此外，本发明人等想到通过在软钎焊时抑制Ni向软钎料合金中的扩散，从而能够抑制P富集层的生长，为了提高剪切强度而进行了深入研究。
首先，本发明人等在Sn-Bi软钎料合金中仅添加0.5质量％左右的Cu，对具有化学镀Ni层的Cu电极进行了软钎焊，结果发现由软钎焊形成的钎焊接头的剪切强度差。因此，在该Sn-Bi-Cu软钎料合金中，将Cu的含量增加至1.1质量％，发现剪切强度也没有改善，进而熔点高且延性大幅劣化。换言之，本发明人等发现，仅在Sn-Bi软钎料合金中添加Cu，也无法提高所形成的钎焊接头的剪切强度，根据Cu的含量而产生高熔点、低延性等问题。
因此，本发明人等在通过仅添加Cu而得到的前述见解的基础上，着眼于在Sn-Bi软钎料合金中添加的Cu的含量和与Cu无限固溶的Ni，精密地调查Ni的含量。其结果，本发明人等发现，Cu为0.3～1.0质量％、Ni为0.01～0.06质量％时，为低熔点，延性优异且拉伸强度高，抑制P富集层的生长，具有化学镀Ni层的Cu电极上形成的钎焊接头的剪切强度显著改善。本发明人等发现，由此会减少因基板的薄型化而产生的软钎焊时的基板的应变，表现出优异的连接可靠性。进而，本发明人等为了确认通用性，对不具有化学镀Ni层的Cu电极进行了软钎焊，结果发现，该Cu电极上形成的钎焊接头也与具有化学镀Ni层的Cu电极上形成的钎焊接头同样地表现出高剪切强度，从而完成了本发明。
此处，本发明如下所述。
(1)一种无铅软钎料合金，其具有以质量％计包含Bi：31～59％、Cu：0.3～1.0％、Ni：0.01～0.06％、余量Sn的合金组成。
(2)根据(1)所述的无铅软钎料合金，其还含有以质量％计总计0.003～0.05％的选自由P和Ge组成的组中的1种以上。
(3)一种钎焊接头，其是在具有镀Ni层的Cu电极上使用上述(1)或上述(2)所述的无铅软钎料合金而形成的。
(4)根据上述(3)所述的钎焊接头，其中，前述镀Ni层为含有P的化学镀层。
(5)一种基板，其板厚为5mm以下，具备具有镀Ni层的多个Cu电极，前述Cu电极分别具有使用上述(1)或上述(2)所述的无铅软钎料合金而形成的钎焊接头。
(6)根据上述(5)所述的基板，其中，前述镀Ni层含有P。
本发明的无铅软钎料合金适合于进行过化学镀Ni处理且板厚为5mm以下的薄基板上形成的Cu电极的软钎焊的使用，通过用于具有化学镀Ni层的电极的软钎焊而最能发挥本发明的效果。因此，由于本发明的软钎料合金的低熔点而将软钎焊时的薄基板的翘曲抑制在最小限度。如此，由于抑制作为钎焊接头的剪切强度劣化的原因的接合界面的P富集层的生长、以及软钎料合金的良好的延性(伸长率)和高拉伸强度，因此钎焊接头的连接可靠性得到改善。进而，本发明的软钎料合金也适用于未进行化学镀Ni处理的Cu电极的软钎焊。
附图说明
图1为对经化学镀Ni/Au处理的Cu电极使用Sn-58Bi软钎料合金进行软钎焊并剪切去除软钎料接合部后的、倍率300倍的电极的表面照片。
图2：图2的(a)和图2的(b)为进行了化学镀Ni/Au处理的Cu电极通过软钎焊形成了钎焊接头时的、软钎料接合部与电极的界面附近的倍率800倍的截面照片，图2的(c)和图2的(d)为进行了化学镀Ni/Pd/Au处理的Cu电极通过软钎焊形成了钎焊接头时的、软钎料接合部与电极的界面附近的倍率800倍的截面照片。
图3为示出Sn-40Bi-(0～1.1)Cu-0.03Ni软钎料合金的、Cu含量与剪切强度(Cu电极)的关系的图。
图4为示出Sn-40Bi-(0～1.1)Cu-0.03Ni软钎料合金的、Cu的含量与剪切强度(化学镀Ni/Au电极)的关系的图。
图5为示出Sn-40Bi-(0～1.1)Cu-0.03Ni软钎料合金的、Cu的含量与合金的伸长率的关系的图。
图6为示出Sn-40Bi-0.5Cu-(0～0.07)Ni软钎料合金的、Cu的含量与剪切强度(Cu电极)的关系的图。
图7为示出Sn-40Bi-0.5Cu-(0～0.07)Ni软钎料合金的、Cu的含量与剪切强度(化学镀Ni/Au电极)的关系的图。
图8为示出Sn-40Bi-0.5Cu-(0～0.07)Ni软钎料合金的、Cu的含量与合金的伸长率的关系的图。
具体实施方式
以下进一步详细说明本发明。以下的说明中，关于软钎料合金组成的“％”只要没有特别指定就是“质量％”。
本发明的无铅软钎料合金为含有Cu和Ni的Sn-Bi-Cu-Ni软钎料合金。Cu与Ni无限固溶，因此预先含有Cu和Ni的本发明的无铅软钎料合金中，Cu和Ni的溶解度变低，能够抑制Cu、Ni自电极向软钎料合金的扩散。通过抑制Ni的扩散，从而能够抑制化学镀Ni层上形成的P富集层的生长。此处，也有人认为通过在Sn-Bi软钎料合金中仅添加Cu，增加Cu的含量，能够抑制Cu和Ni的扩散。
但是，即使单纯地在Sn-Bi-Cu软钎料合金中增加Cu的含量，在与电极的接合界面和软钎料合金内CuSn化合物也会增加，因此剪切强度劣化，软钎料合金自体的熔点也升高，延性也劣化。因此，Sn-Bi-Cu软钎料合金无法用于具有化学镀Ni层的Cu电极的软钎焊。
此处，作为降低Ni的溶解度而不会增加Cu的含量的元素，可列举出Ni。此外，通过软钎料合金含有微量的Ni，从而软钎料合金表现出低熔点和高延性，对电极进行了像化学镀Ni/Au或化学镀Ni/Pd/Au那样的化学镀Ni处理时，抑制Ni向软钎料合金的扩散，从而抑制较脆的P富集层的生长，大幅改善钎焊接头的剪切强度。
进而，本发明的无铅软钎料合金由于含有规定量的Cu和Ni，因此Cu的溶解度低。对于不具有化学镀Ni层的Cu电极，也抑制Cu向软钎料合金的扩散，从而抑制接合界面和软钎料合金中生成的较脆的SnCu化合物的过度形成，钎焊接头的剪切强度升高。其结果，本发明中，无论是否对Cu电极进行了镀覆处理，都能够抑制软钎焊时的薄基板的应变，确保优异的连接可靠性。
如前所述，对于化学镀Ni层，通常形成镀Au层、或Pd/Au那样的贵金属或它们的合金的镀层。镀Au层形成在镀Ni层上。但是，镀Au层为0.05μm左右的非常薄的膜厚，通过向软钎料合金中扩散而在软钎焊时消失。因此，本发明中，评价各种特性时，不必特别考虑镀Au层、其它贵金属镀层。
本发明中，限定软钎料合金的合金组成的理由如下所述。
Bi的含量为31～59％。Bi降低软钎料合金的熔点。Bi的含量少于31％时，熔点高，在软钎焊时基板发生应变。Bi的含量多于59％时，由于Bi的析出而使拉伸强度和延性劣化。Bi的含量优选为32～58％、更优选为35～58％。
Cu的含量为0.3～1.0％。Cu抑制化学镀Ni层中的Ni向软钎料合金中的扩散，抑制在镀Ni层与软钎料接合部的界面生成的P富集层的生长。另外，还抑制Cu的扩散，因此抑制在未进行化学镀Ni处理的Cu电极与软钎料接合部的接合界面和软钎料合金中生成的较脆的SnCu化合物的过度形成，钎焊接头的剪切强度升高。Cu的含量少于0.3％时，无法抑制P富集层、SnCu化合物的过度形成，剪切强度降低。Cu的含量多于1.0％时，在软钎料合金中过度形成与Sn的金属间化合物，软钎料合金的延性降低。另外，软钎料合金的熔点明显上升，软钎料合金的润湿性降低。进而，由于发生基板的应变而操作性恶化。Cu的含量优选为0.3～0.8％、更优选为0.3～0.7％。
Ni的含量为0.01～0.06％。通过添加Ni，有助于Cu所具有的抑制Ni扩散的效果，抑制P富集层的生长，进而表现出剪切强度提高的效果。Ni的含量少于0.01％时，无法发挥剪切强度提高的效果。Ni的含量多于0.06％时，软钎料合金中过度形成Sn与Ni的化合物，因此延性降低。Ni的含量优选为0.02～0.05％。
本发明的无铅软钎料合金含有总计0.003～0.05％的选自由P和Ge组成的组中的1种以上作为可选元素。通过添加这些元素，与不添加的情况同样地抑制P富集层的生长，提高钎焊接头的剪切强度，并且，发挥防止软钎料合金因氧化而变色为黄色等(以下适宜地称为“黄变”)的效果。本发明的无铅软钎料合金也可以以焊料球的形态使用。焊料球载置在模块基板上并通过回流焊而搭载于电极。然后，通过图像识别进行是否进行了软钎焊的判定。假如通过回流焊时的加热使焊料球因混入回流焊气氛中的不可避免的氧气而黄变时，黄变后的焊料球在图像识别中无法识别焊料球，判断为不良情况。因此，焊料球在回流焊时不黄变是较好的。本发明的无铅软钎料合金含有选自由P和Ge组成的组中的1种以上，防止由氧气等导致的变色，从而避免凸块质检中的故障。
从这种观点出发，优选含有P，进一步优选含有P和Ge。P的含量优选为0.001～0.03％、更优选为0.01～0.07％。Ge的含量优选为0.001～0.03％、更优选为0.01～0.03％。
关于包含这种合金组成的本发明的无铅软钎料合金，在剪切去除了钎焊接头的软钎料接合部时，电极的化学镀Ni层不会露出。这是因为，如前所述，本发明的无铅软钎料能够抑制化学镀Ni层中的Ni的扩散，抑制在镀层的表面形成的P富集层的生长。其结果，本发明的无铅软钎料合金中，接合部界面的机械特性、特别是剪切强度明显提高。
另外，本发明的无铅软钎料合金可以以预成型体、线、焊膏、焊料球等的形态使用。本发明的无铅软钎料合金具有高拉伸强度和延性，并且具有高剪切强度。因此，以焊料球的形态使用时，能够使其比现有的焊料球小，能够充分应对电子部件等中使用的基板的薄型化、电极的小型化。
本发明的无铅软钎料合金可以接合IC芯片等的PKG(封装体；Package)的电极与PCB(印刷电路板；printedcircuitboard)等基板的电极，形成钎焊接头。此处，本发明的无铅软钎料合金如前所述维持高延性和拉伸强度，并且在用于钎焊接头时具有优异的剪切强度。因此，即使在回流焊时基板产生稍许应变，电极与软钎料接合部也不会断裂，即使使用比以往薄的基板，也能够确保优异的连接可靠性。本发明的钎焊接头由电极和软钎料接合部构成。软钎料接合部表示主要由软钎料合金形成的部分。
本发明的基板的板厚为5mm以下，具备具有镀Ni层的多个Cu电极，Cu电极分别具有使用本发明的无铅软钎料合金而形成的钎焊接头。本发明的基板由于使用熔点低且表现出优异延性的本发明的无铅软钎料合金而形成接头，因此即使板厚为5mm以下，也抑制翘曲的产生，具有优异的连接可靠性。基板的板厚优选为3mm以下、更优选为2mm以下。作为基板的材质，可列举出Si、玻璃环氧、纸酚醛、电木等。作为基板所具有的电极，可列举出未进行镀覆处理的Cu电极、实施了Ni等的镀覆处理的Cu电极、Ni电极等。
本发明的无铅软钎料合金通过使用高纯度材材料或低α射线材料，可以制造低α射线的无铅软钎料合金。通过将该软钎料合金用于存储器周边等，能够防止软错误。
实施例
制作表1中示出的软钎料合金。使用该软钎料合金，求出软钎料合金的熔点、拉伸强度、伸长率(延性)，使用利用该软钎料合金形成的钎焊接头，如以下所示那样求出P富集层的膜厚测定、剪切强度和板露出率。将结果示于表1。
(软钎料合金的熔点)
关于熔点，使用DSC(差示扫描量热计；Differentialscanningcalorimetry)(SeikoInstrumentsInc制造：DSC6200)，在升温速度5℃/min的条件下测定熔点(℃)。
(拉伸强度、伸长率(延性))
使用拉伸强度试验机(株式会社岛津制作所制造、AUTOGRAPHAG-20kN)，将行程速度设为6.0mm/min，将应变速度设为0.33％/sec，将表1中示出的软钎料合金形成为规定的形状，测定拉伸强度(MPa)和伸长率(％)。拉伸强度为70MPa以上、伸长率为65％以上时，可以实用上没有问题地使用。
(P富集层的膜厚)
将表1中示出的软钎料合金与基板的厚度为1.2mm且电极的尺寸为直径0.24mm的PCB的进行了化学镀Ni/Au处理的Cu电极(以下简称为“化学镀Ni/Au电极”)接合，进行软钎焊。关于软钎焊，对于由各软钎料合金制作的直径0.3mm的焊料球、使用水溶性助焊剂(千住金属株式会社制造：WF-6400)在基板上涂布水溶性助焊剂后搭载球，以将峰值温度设为210℃的回流焊曲线通过回流焊法进行软钎焊，得到形成有钎焊接头的试样。
各试样的P富集层的膜厚根据SEM照片通过软钎料接合部与镀Ni层的接合界面附近的截面观察而确定。具体而言，根据使用电子显微镜(日本电子株式会社制造：JSM-7000F)得到的照片进行分析，对P富集层和非P富集层的层标记不同颜色来进行区分，测定P富集层的膜厚(μm)。针对在相同条件下制作的5个样品，同样地测定P富集层的膜厚，将其平均值设为P富集层的膜厚。
(剪切强度)
关于前述PCB的电极，使用未进行镀覆处理的Cu电极(以下简称为“Cu电极”)和化学镀Ni/Au电极这2种，与表1中示出的各软钎料合金接合，进行软钎焊。对于该样品，通过剪切强度测定装置(Dage公司制造：SERIES4000HS)在1000mm/sec的条件下测定剪切强度(N)。剪切强度在Cu电极的情况下为3.00N以上，并且在化学镀Ni/Au电极的情况下为2.60N以上时，可以实用上没有问题地使用。
(板露出率)
关于剪切强度试验后的样品，拍摄剪切去除软钎料接合部后的化学镀Ni/Au电极的表面SEM照片。然后，通过实施EDS分析，从而确定Ni露出的区域，利用西华产业株式会社制造的图像分析软件(Scandium)求出该区域的面积。最后，将镀Ni层露出的区域的面积除以电极整体的面积，算出板露出率(％)。
[表1]
如表1所示，实施例1～33中，熔点均为185度以下，拉伸强度均为70MPa以上，伸长率均为65％以上，P富集层的膜厚均为0.014μm以下，使用Cu电极形成的钎焊接头的剪切强度均为3.00N以上，使用化学镀Ni/Au电极形成的钎焊接头的剪切强度均为2.60N以上，板露出率均为0％。
另一方面，不含Cu和Ni的Sn-58Bi软钎料合金的比较例1中，P富集层的膜厚较厚，Cu电极和化学镀Ni/Au电极的情况下的剪切强度明显较差，板露出率也表现出较高的值。
不含Ni的比较例2和不含Cu的比较例3中，P富集层的膜厚均较厚，Cu电极和化学镀Ni/Au电极的情况下的剪切强度均明显较差。特别是不含Cu的比较例3中板露出率表现出较高的值。
Bi少的比较例4中，合金的熔点高，伸长率也差，因此确认到基板的应变。Bi多的比较例5中，合金的拉伸强度、伸长率差。另外，化学镀Ni/Au电极的情况下的剪切强度差，软钎料合金的伸长率也差。
Cu少的比较例6中，化学镀Ni/Au电极的情况下的剪切强度差，P富集层的膜厚较厚，板露出率表现出较高的值。不含Ni且Cu多的比较例7和Cu多的比较例8中，熔点高，伸长率差，化学镀Ni/Au电极的情况下的剪切强度也差。
Ni的含量少的比较例9中，Cu电极的情况下的剪切强度差。Ni的含量多的比较例10中，合金的伸长率明显较差。
图1为对化学镀Ni/Au电极使用Sn-58Bi软钎料合金进行软钎焊并剪切去除软钎料接合部后的、电极剪切面的SEM照片。比较例1、3、5和6中，均如图1所示，镀Ni层露出。认为这是因为，P富集层生长，在P富集层与化学镀Ni/Au层的界面发生剥脱。
图2的(a)和图2的(b)为对化学镀Ni/Au电极进行软钎焊而得到的钎焊接头的、软钎料连接部与电极的界面附近的截面SEM照片，图2的(c)和图2的(d)为对进行了化学镀Ni/Pd/Au处理的Cu电极进行软钎焊而得到的钎焊接头的、软钎料连接部与电极的界面附近的截面SEM照片。根据图2的(a)和图2的(c)明显可知，Sn-58Bi(比较例1：化学镀Ni/Au电极的情况下的剪切强度为2.01N。)中，通过不含Cu，从而P富集层生长。另一方面，根据图2的(b)和图2的(d)，本发明的Sn-40Bi-0.5Cu-0.03Ni(实施例7：化学镀Ni/Au电极的情况下的剪切强度为2.85N。)中，通过含有规定量的Cu和Ni，从而抑制了P富集层的生长，由这些照片无法确认到P富集层。如此，根据图2可知，通过抑制P富集层的生长，剪切强度明显提高。
根据表1的结果，将示出软钎料合金的Cu和Ni的含量与Cu电极、化学镀Ni/Au电极和伸长率的关系的图示于图3～8。图3～5中，使用了Bi的含量为40％且Ni的含量为0.03％的实施例6～9以及比较例3、6和7的结果。图6～8中，使用了Bi的含量为40％且Cu的含量为0.5％的实施例7、10和11、以及比较例2、8和9的结果。图3为示出Sn-40Bi-(0～1.1)Cu-0.03Ni软钎料合金的Cu含量与剪切强度(Cu电极)的关系的图。图4为示出Sn-40Bi-(0～1.1)Cu-0.03Ni软钎料合金的Cu的含量与剪切强度(化学镀Ni/Au电极)的关系的图。图5为示出Sn-40Bi-(0～1.1)Cu-0.03Ni软钎料合金的Cu的含量与合金的伸长率的关系的图。根据图3～图5明显可知，Cu电极的剪切强度表现出3.0N以上、Ni电极的剪切强度表现出2.6N以上、伸长率表现出65％以上的Cu的范围为0.3～1.0％。
图6为示出Sn-40Bi-0.5Cu-(0～0.07)Ni软钎料合金的Cu的含量与剪切强度(Cu电极)的关系的图。图7为示出Sn-40Bi-0.5Cu-(0～0.07)Ni软钎料合金的Cu的含量与剪切强度(化学镀Ni/Au电极)的关系的图。图8为示出Sn-40Bi-0.5Cu-(0～0.07)Ni软钎料合金的Cu的含量与合金的伸长率的关系的图。根据图6～8明显可知，Cu电极的剪切强度表现出3.0N以上、Ni电极的剪切强度表现出2.6N以上、伸长率表现出65％以上的Ni的范围为0.01～0.06％。

Claims (6)

1.一种无铅软钎料合金，其具有以质量％计包含Bi：31～59％、Cu：0.3～1.0％、Ni：0.01～0.06％、余量Sn的合金组成。
2.根据权利要求1所述的无铅软钎料合金，其还含有以质量％计总计0.003～0.05％的选自由P和Ge组成的组中的1种以上。
3.一种钎焊接头，其是在具有镀Ni层的Cu电极上使用权利要求1或2所述的无铅软钎料合金而形成的。
4.根据权利要求3所述的钎焊接头，其中，所述镀Ni层为含有P的化学镀层。
5.一种基板，其板厚为5mm以下，具备具有镀Ni层的多个Cu电极，所述Cu电极分别具有使用权利要求1或2所述的无铅软钎料合金而形成的钎焊接头。
6.根据权利要求5所述的基板，其中，所述镀Ni层含有P。
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