CN111168274B - 焊料球、钎焊接头和接合方法 - Google Patents

焊料球、钎焊接头和接合方法 Download PDF

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CN111168274B
CN111168274B CN201911087156.7A CN201911087156A CN111168274B CN 111168274 B CN111168274 B CN 111168274B CN 201911087156 A CN201911087156 A CN 201911087156A CN 111168274 B CN111168274 B CN 111168274B
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solder ball
mass
solder
ball
comparative example
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CN111168274A (zh
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川崎浩由
中村优里
宗形修
鹤田加一
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Senju Metal Industry Co Ltd
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Senju Metal Industry Co Ltd
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    • 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
    • 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
    • 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
    • B23K3/00—Tools, devices, or special appurtenances for soldering, e.g. brazing, or unsoldering, not specially adapted for particular methods
    • B23K3/06—Solder feeding devices; Solder melting pans
    • B23K3/0607—Solder feeding devices
    • B23K3/0623—Solder feeding devices for shaped solder piece feeding, e.g. preforms, bumps, balls, pellets, droplets
    • 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
    • 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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    • H01L23/49816—Spherical bumps on the substrate for external connection, e.g. ball grid arrays [BGA]
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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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process
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Abstract

本发明涉及焊料球、钎焊接头和接合方法。[课题]焊料球如下：In为0.1质量％以上且10质量％以下、且余量为Sn，所述焊料球的L*a*b*色度体系中的黄色度(b*)为2.8以上且15.0以下，所述焊料球的L*a*b*色度体系中的亮度(L*)为60以上且100以下。

Description

焊料球、钎焊接头和接合方法
技术领域
本发明涉及焊料球、钎焊接头和接合方法。
背景技术
随着最近的电子部件的小型化、高密度安装化，在印刷电路基板等上安装电子部件时，使用有BGA(球栅阵列封装)、CSP(芯片尺寸封装)技术。作为电子部件的软钎焊中使用的软钎料合金的组成，可以举出Sn-In系的无铅软钎料。Sn-In系的无铅软钎料中，已知通过在Sn中添加规定量的In，从而发挥各种效果。
例如，对依次实施了Ni、Au的处理的Cu电极的表面进行软钎焊的情况下，Au向Sn中的扩散速度极快，由于Au向Sn中的扩散而Au镀层从电极上消失，从而存在Au的基底层的Ni、Cu与无铅软钎料的Sn的IMC的生长容易推进的问题。另外，还存在无铅软钎料的湿润性会降低的问题。因此，例如，非专利文献1中公开了如下技术：通过使用增加了In的含量的Sn-In系的无铅软钎料，从而减慢In向Sn中的扩散速度。
现有技术文献
非专利文献
非专利文献1：宗司郁夫著“Au与In-Sn系软钎料的界面中的金属间化合物生长过程”电子安装学会期刊、1999年、p.121-126
发明内容
发明要解决的问题
然而，Sn-In系的无铅软钎料中，增加In的添加量时，存在如下问题：作为稀有金属的In量的增加所导致的成本上升，且作为低温软钎料的Sn-In的软钎料中软钎料熔点急剧降低。因此，期望通过添加恒定量的In而能进一步发挥In的添加所产生的效果的Sn-In系的无铅软钎料材料。
因此，本发明是鉴于上述课题而作出的，其目的在于，提供：Sn-In系软钎料中，在不增加In的添加量的情况下能确保钎焊接合时的软钎料的湿润性的焊料球、钎焊接头和接合方法。
用于解决问题的方案
为了解决上述课题，本发明人等改良了现有的Sn-In系的无铅软钎料合金，发现：对于将Sn-In系的无铅软钎料合金加工成球状的焊料球，在将焊料球接合前的阶段，对焊料球本身实施加热等熟化处理，在焊料球表面形成In富集了的氧化膜，从而可以抑制钎焊接合时的Au向软钎料中的扩散。
本发明如下所述。
(1)一种焊料球，其In为0.1质量％以上且10质量％以下、且余量为Sn，所述焊料球的L*a*b*色度体系中的黄色度(b*)为2.8以上且15.0以下，所述焊料球的L*a*b*色度体系中的亮度(L*)为60以上且100以下。
(2)根据上述(1)所述的焊料球，其中，In为0.1质量％以上且7质量％以下。
(3)根据上述(1)或(2)所述的焊料球，其中，球径为0.1μm以上且120μm以下。
(4)根据上述(1)～(3)中任一项所述的焊料球，其中，添加有：Ag：0以上且4质量％以下、Cu：0以上且1.0质量％以下、来自Bi、Sb的组的总计为0～3质量％、来自Ni、Co、Fe、Ge、P的组的总计为0～0.1质量％中的至少1种以上的元素(其中，除Ag：3质量％、Cu：0.5质量％、In：0.2质量％、余量为Sn的焊料球之外)。
(5)一种钎焊接头，其使用上述(1)～(4)中任一项所述的焊料球。
(6)一种接合方法，其具备如下工序：将上述(1)～(4)中任一项所述的多个焊料球配置于电极上的工序；和，用有机酸气体，使配置于前述电极上的前述多个焊料球熔融的工序。
发明的效果
根据本发明，针对使用Sn-In系的无铅软钎料时产生的问题，也可以防止In的添加量增加，且抑制钎焊接合时的Au向软钎料中的扩散，从而可以在不有损软钎料的湿润性的情况下抑制IMC的生长。
具体实施方式
本实施方式的焊料球以Sn为主成分，且包含超过0质量％且10质量％以下的In，所述焊料球的L*a*b*色度体系中的黄色度(b*)为2.8以上且15.0以下。焊料球的L*a*b*色度体系中的亮度(L*)为60以上且100以下，焊料球的球径为0.1μm以上且120μm以下。另外，本实施方式的焊料球在其表面具有由规定的厚度形成的氧化膜。氧化膜通过实施熟化处理而形成。作为熟化处理，例如可以举出大气暴露(放置)、加热处理。
(1)In：超过0质量％且10.0质量％以下
焊料球中的In的含量为超过0质量％且10.0质量％以下。通过使In的含量超过0质量％，从而可以确保恒定量的In，因此，可以防止Au向软钎料中的扩散。另外，通过使In的含量为10.0质量％以下，从而可以将氧化膜的生长抑制为恒定的范围，因此，可以在不使软钎料的湿润性降低的情况下，防止Au向软钎料中的扩散。进而，通过使In的含量为上述范围，从而可以减少In的含量，因此，可以实现低成本化。另外，作为In的含量的优选范围，为超过0.1质量％且7.0质量％以下，作为更优选的范围，为3.0质量％以上且7.0质量％以下。需要说明的是，In的上述含量通过基于熟化处理的In的富集而实现。
(2)焊料球的球径：0.1μm以上且120μm以下
焊料球的球径为0.1μm以上且120μm以下。这是由于，焊料球的球径超过120μm的情况下，变得难以进行细间距下的软钎焊，无法应对基板的微小化、电子部件的电极的窄间距化的要求。对于下限值，作为技术上能用于焊料凸块形成用的球径的限度，设为0.1μm以上。如此，通过使焊料球的球径为0.1μm以上且120μm以下的范围，从而能应对电子部件的小型化、高集成化。进而，焊料球的粒径越缩小，上述Au向软钎料中的扩散防止效果越得到发挥。因此，焊料球的球径优选120μm以下、更优选80μm以下、进一步优选50μm以下、最优选30μm以下。
(3)L*a*b*色度体系中的黄色度(b*)：2.8以上且15.0以下
焊料球的L*a*b*色度体系中的黄色度(b*)为2.8以上且15.0以下。黄色度(b*)如果为2.8以上且15.0以下的范围，则可以有效地抑制钎焊接合时Au向软钎料中的扩散。如果对焊料球在规定温度下进行规定时间的熟化处理，则在焊料球的表面形成含有大量氧化In(InO)的氧化膜，引起焊料球的表面的In的浓度变高的富集现象。如本实施方式那样，使In的含量为超过0质量％且10.0质量％以下的低浓度的情况下，有意地使焊料球表面氧化，从而可以使焊料球表面的In高浓度化，因此，可以得到抑制Au向软钎料中的扩散的效果。此处认为，使焊料球过度氧化而提高焊料球表面的In的浓度的情况下，可以进一步提高Au向软钎料中的扩散抑制效果。然而，球径为120μm以下的焊料球中，氧化膜的影响变得特别大，因此，存在会使钎焊接合时的可靠性降低的问题。因此，需要管理满足考虑了软钎焊性的氧化膜厚、与考虑了基于In富集的Au向软钎料中的扩散抑制效果的氧化膜厚这两者条件的氧化膜厚。因此，本实施方式中，为了简易且迅速地管理形成于焊料球的表面的氧化膜厚，采用L*a*b*色度体系中的黄色度(b*)，且通过制作L*a*b*色度体系中的黄色度(b*)成为2.8以上且15.0以下的焊料球，从而实现规定的氧化膜厚的焊料球。这是由于，黄色度(b*)低于2.8的情况下，In未被富集，焊料凸块形成时有时无法有效地抑制Au向软钎料中的扩散。与此相对，黄色度(b*)超过15.0的情况下，焊料球接合时的软钎料的湿润性可能受损，且软钎料材的成本上升。需要说明的是，黄色度(b*)更优选7以下。
(4)L*a*b*色度体系中的亮度(L*)：60以上且100以下
焊料球存在如下相关性：通过熟化处理而氧化膜变厚时，L*a*b*色度体系中的黄色度(b*)上升，而L*a*b*色度体系中的亮度(L*)下降。因此，作为焊料球的基于熟化处理的氧化膜厚的管理方法，在上述L*a*b*色度体系中的黄色度(b*)的基础上，L*a*b*色度体系中的亮度(L*)也可以作为管理氧化膜的指标之一使用。焊料球的L*a*b*色度体系中的亮度(L*)为60以上且100以下。亮度(L*)低于60的情况下，In未被富集，焊料凸块形成时有时无法有效地抑制Au向软钎料中的扩散。与此相对，亮度(L*)超过100的情况下，焊料球接合时的软钎料的湿润性有时可能受损。需要说明的是，亮度(L*)的上限值更优选80以下。
(5)添加有：Ag：0以上且4质量％以下、Cu：0以上且1.0质量％以下、来自Bi、Sb的组的总计为0以上且3质量％以下、来自Ni、Co、Fe、Ge、P的组的总计为0以上且0.1质量％以下中的至少1种以上的元素
构成本发明的焊料球以上述范围含有Ag、Cu、Bi、In、Sb、Ni、Co、Fe、Ge、P。由此，可以实现接合可靠性的改善。Ag、Cu、Bi、In、Ni、Sb、Co、Fe、Ge、P的含量不妨碍In与接合构件的反应，因此，优选Ag：0质量％以上且4质量％以下、Cu：0质量％以上且1.0质量％以下、来自Bi、In、Sb的组的总计为0质量％以上且3质量％以下、来自Ni、Co、Fe、Ge、P的组的总计为0质量％以上且0.1质量％以下。
(6)余量：Sn
本发明的焊料球的余量为Sn。即，焊料球的主成分为Sn，焊料球中的金属元素中，经常含量变得最多。除前述元素之外，还可以含有不可避免的杂质。含有不可避免的杂质的情况下，也不对前述效果造成影响。另外，本发明中不含有的元素以不可避免的杂质含有也不对前述效果造成影响。
(7)α射线剂量：0.0200cph/cm2以下
从抑制软错误的观点出发，本发明的焊料球的α射线剂量为0.0200cph/cm2以下。其为电子部件的高密度安装中软错误不成为问题的程度的α射线剂量。从抑制进一步的高密度安装中的软错误的观点出发，α射线剂量更优选0.0010cph/cm2以下。
(8)焊料球的制造方法
首先，制作球径为0.1μm以上且120μm以下、且含有超过0质量％且10.0质量％以下的In的焊料球。作为焊料球的制作方法，可以采用：滴加熔融了的软钎料并加工成球状的滴加法；气体雾化法等公知的方法。在焊料球中可以添加由Ag、Cu、Bi、Ni、Sb、Co、Fe、Ge、P的组构成的1种或2种以上的元素。
接着，对制作好的焊料球进行熟化处理，在焊料球表面形成氧化膜，从而进行控制使得提高焊料球的表面的In的浓度。熟化处理中，设定为形成焊料球的黄色度(b*)成为2.8以上且15.0以下的氧化膜厚那样的加热温度和加热时间。另外，作为进行控制使得提高In的浓度的其他方法，有如下方法：在室温下在大气暴露下进行长时间保管、利用造球时的氧浓度增大的熟化、造球时或造球后的至少任一者实施氧等离子体照射等。如此，可以制造在表面形成有由恒定的厚度形成的氧化膜的焊料球。
根据本实施方式的焊料球，例如在包含Au的电极上使用焊料球的情况下，在不增加In的添加量的情况下，也可以通过形成于焊料球表面的氧化膜来抑制Au向软钎料中的扩散，可以防止钎焊接合时的软钎料的湿润性的降低。另外，可以抑制Sn中的In的添加量，因此，可以防止软钎料熔点急剧降低。
需要说明的是，本发明的焊料球也可以用于形成接合电极间的钎焊接头。本发明中，例如，将焊料凸块安装于印刷基板的电极上的结构称为钎焊接头。焊料凸块例如是指，在半导体芯片的电极上安装有焊料球的结构。
另外，本发明的焊料球也可以用于在不使用助焊剂的情况下进行接合的接合方法。例如，将进行了熟化处理的多个焊料球载置(配置)于基板的电极上后，用有机酸气体，使载置后的多个焊料球熔融，从而形成焊料凸块。需要说明的是，焊料球使用的是，50个焊料球的直径的测定值的算术平均成为120μm的焊料球。上述情况下，可以有效地抑制Au向软钎料中的扩散。
实施例
首先，制成球径为120μm、各实施例所示的合金组成的Sn-In的焊料球。接着，对制成的各焊料球分别在不同的条件下预先实施熟化处理，特意使焊料球的表面氧化，提高其表面的In的浓度，从而制成形成有含有高浓度的氧化In、例如In2O3等的氧化膜的焊料球。接着，分别测定各焊料球中的、黄色度(b*)、亮度(L*)和焊料球表面的In的浓度。
(1)焊料球的黄色度(b*)和亮度(L*)的测定
焊料球的黄色度(b*)和亮度(L*)使用Konica Minolta制CM-2600d型分光测色计而测定。
(2)焊料球表面的In的浓度的测定
焊料球的表面的In的浓度用场发射电子探针显微分析仪(Field EmissionElectron Probe MicroAnalyser：FE-EPMA)进行定性分析，引用半定量分析值。需要说明的是，焊料球表面的In的浓度中，为了比较浓度变化，算出半定量分析值。
(3)焊料球表面的In的浓度的评价
准备未进行熟化处理的Sn-In的焊料球，将该焊料球的半定量分析值作为基准，进行熟化处理，比较得到的各焊料球中的In的半定量分析值，从而进行In的富集的评价。
(a)实施例或比较例的焊料球的半定量分析值超过基准的焊料球的半定量分析值的情况：〇(富集大)
(b)实施例或比较例的焊料球的半定量分析值为基准的焊料球的半定量分析值以下的情况：×(富集不充分)
(4)软钎料的湿润性的评价
使用依次实施了镀Ni和镀Au处理的Cu板，在其Cu板上印刷助焊剂WF-6400(千住金属工业株式会社制)，在其上安装各焊料球。以升温速度5℃/sec、在N2气氛下将安装有焊料球的电极焊盘(電極パッド)从25℃升温至250℃，之后进行1分钟回流焊。在100个焊料球中实施这样的处理。
(a)100个焊料球全部在电极焊盘整体中浸润铺开的情况：〇(良好)
(b)1个以上焊料球在电极焊盘整体中未浸润铺开的情况：×(不可)
表1中示出合金组成为Sn-7质量％In-3质量％Ag-0.5质量％Cu的各测定结果和评价结果。需要说明的是，表1中的In的富集的评价以未实施熟化处理的焊料球的浓度为基准。另外，表1中，In的单位为质量％。
[表1]
Figure BDA0002265767360000081
实施例1中，对于Sn-7质量％In-3质量％Ag-0.5质量％Cu的焊料球，进行了在20℃～30℃的常温下持续暴露于大气中90天的熟化处理。根据实施例1，选定黄色度(b*)为2.83、亮度(L*)为67.04的焊料球的情况下，焊料球的表面的In的半定量分析值成为7.9质量％，确认了与未实施熟化处理的比较例1的焊料球相比In的富集得到促进。另外确认了，焊料球表面处的In的富集(氧化膜厚)如果为恒定范围内，则可以良好地维持软钎料的湿润性，且也可以抑制IMC的生长。
实施例2中，对于Sn-7质量％In-3质量％Ag-0.5质量％Cu的焊料球，进行在200℃下持续暴露于大气中60分钟的熟化处理。根据实施例2，选定黄色度(b*)为8.33、亮度(L*)为63.08的焊料球的情况下，焊料球的表面的In的半定量分析值成为10.8质量％，确认了与未实施熟化处理的比较例1的焊料球相比In的富集得到促进。另外确认了，焊料球表面处的In的富集(氧化膜厚)如果为恒定范围内，则可以良好地维持软钎料的湿润性，且也可以抑制IMC的生长。
比较例1中，使用未进行熟化处理的状态的Sn-7质量％In-3质量％Ag-0.5质量％Cu的焊料球。比较例1中，选定黄色度(b*)为2.75、亮度(L*)为69.11的焊料球的情况下，焊料球的表面的In的半定量分析值成为7.2质量％。需要说明的是，表1中，对于比较例1的接合时的In是否富集的评价，未实施熟化处理的比较例1成为基准，因此，用“-”表示而不是用“×”表示。焊料球的湿润性的评价成为“〇”。
比较例2中，对于Sn-7质量％In-3质量％Ag-0.5质量％Cu的焊料球，进行了在200℃下持续暴露于大气中120分钟的熟化处理。根据比较例2，选定黄色度(b*)为15.59、亮度(L*)为48.00的焊料球的情况下，焊料球的表面的In的半定量分析值成为13.1质量％，确认了与未实施熟化处理的比较例1的焊料球相比In的富集得到促进。然而，随着熟化处理的In的富集而氧化In变厚，因此，确认了软钎料的湿润性降低。
比较例3中，对于Sn-7质量％In-3质量％Ag-0.5质量％Cu的焊料球，进行了在200℃下持续暴露于大气中180分钟的熟化处理。根据比较例3，选定黄色度(b*)为24.40、亮度(L*)为32.19的焊料球的情况下，焊料球的表面的In的半定量分析值成为14.9质量％，确认了与未实施熟化处理的比较例1的焊料球相比In的富集得到促进。然而，随着熟化处理的In的富集而氧化In变厚，因此，确认了软钎料的湿润性降低。
比较例4中，对于Sn-7质量％In-3质量％Ag-0.5质量％Cu的焊料球，进行了在200℃下持续暴露于大气中240分钟的熟化处理。根据比较例4，选定黄色度(b*)为24.45、亮度(L*)为33.45的焊料球的情况下，焊料球的表面的In的半定量分析值成为15.4质量％，确认了与未实施熟化处理的比较例1的焊料球相比In的富集得到促进。然而，随着熟化处理的In的富集而氧化In变厚，因此，确认了软钎料的湿润性降低。
比较例5中，对于Sn-7质量％In-3质量％Ag-0.5质量％Cu的焊料球，进行了在200℃下持续暴露于大气中300分钟的熟化处理。根据比较例5，选定黄色度(b*)为22.77、亮度(L*)为36.90的焊料球的情况下，焊料球的表面的In的半定量分析值成为18.3质量％，确认了与未实施熟化处理的比较例1的焊料球相比In的富集得到促进。然而，随着熟化处理的In的富集而氧化In变厚，因此，确认了软钎料的湿润性降低。
表2中示出合金组成为Sn-1质量％In-0.7质量％Cu的各测定结果和评价结果。需要说明的是，表2中的In的富集的评价以未实施熟化处理的焊料球的浓度为基准。另外，表2中，In的单位为质量％。
[表2]
Figure BDA0002265767360000101
实施例3中，对于Sn-1质量％In-0.7质量％Cu的焊料球，进行了在20℃～30℃的常温下持续暴露于大气中90天的熟化处理。根据实施例3，选定黄色度(b*)为3.01、亮度(L*)为67.37的焊料球的情况下，焊料球的表面的In的半定量分析值成为2.1质量％，确认了与未实施熟化处理的比较例6的焊料球相比In的富集得到促进。另外确认了，焊料球表面处的In的富集(氧化膜厚)如果为恒定范围内，则可以良好地维持软钎料的湿润性，且也可以抑制IMC的生长。
实施例4中，对于Sn-1质量％In-0.7质量％Cu的焊料球，进行在200℃下持续暴露于大气中60分钟的熟化处理。根据实施例4，选定黄色度(b*)为4.47、亮度(L*)为67.33的焊料球的情况下，焊料球的表面的In的半定量分析值成为2.2质量％，确认了与未实施熟化处理的比较例6的焊料球相比In的富集得到促进。另外确认了，焊料球表面处的In的富集(氧化膜厚)如果为恒定范围内，则可以良好地维持软钎料的湿润性，且也可以抑制IMC的生长。
实施例5中，对于Sn-1质量％In-0.7质量％Cu的焊料球，进行了在200℃下持续暴露于大气中120分钟的熟化处理。根据实施例5，选定黄色度(b*)为6.20、亮度(L*)为67.16的焊料球的情况下，焊料球的表面的In的半定量分析值成为2.5质量％，确认了与未实施熟化处理的比较例6的焊料球相比In的富集得到促进。另外确认了，焊料球表面处的In的富集(氧化膜厚)如果为恒定范围内，则可以良好地维持软钎料的湿润性，且也可以抑制IMC的生长。
实施例6中，对于Sn-1质量％In-0.7质量％Cu的焊料球，进行了在200℃下持续暴露于大气中180分钟的熟化处理。根据实施例6，选定黄色度(b*)为10.23、亮度(L*)为65.34的焊料球的情况下，焊料球的表面的In的半定量分析值成为2.7质量％，确认了与未实施熟化处理的比较例6的焊料球相比In的富集得到促进。另外确认了，焊料球表面处的In的富集(氧化膜厚)如果为恒定范围内，则可以良好地维持软钎料的湿润性，且也可以抑制IMC的生长。
实施例7中，对于Sn-1质量％In-0.7质量％Cu的焊料球，进行了在200℃下持续暴露于大气中240分钟的熟化处理。根据实施例7，选定黄色度(b*)为12.66、亮度(L*)为62.15的焊料球的情况下，焊料球的表面的In的半定量分析值成为2.8质量％，确认了与未实施熟化处理的比较例6的焊料球相比In的富集得到促进。另外确认了，焊料球表面处的In的富集(氧化膜厚)如果为恒定范围内，则可以良好地维持软钎料的湿润性，且也可以抑制IMC的生长。
比较例6中，使用未进行熟化处理的状态的Sn-1质量％In-0.7质量％Cu的焊料球。比较例6中，选定黄色度(b*)为2.79、亮度(L*)为69.30的焊料球的情况下，焊料球的表面的In的半定量分析值成为1.2质量％。需要说明的是，表2中，对于比较例6的接合时的In是否富集的评价，未实施熟化处理的比较例6成为基准，因此，用“-”表示而不是用“×”表示。焊料球的湿润性的评价成为“〇”。
比较例7中，对于Sn-1质量％In-0.7质量％Cu的焊料球，进行了在200℃下持续暴露于大气中300分钟的熟化处理。根据比较例7，选定黄色度(b*)为15.30、亮度(L*)为59.89的焊料球的情况下，焊料球的表面的In的半定量分析值成为3.0质量％，确认了与未实施熟化处理的比较例6的焊料球相比In的富集得到促进。然而，随着熟化处理的In的富集而氧化In变厚，因此，确认了软钎料的湿润性降低。
表3中示出合金组成为Sn-1质量％In-0.1质量％Bi-0.001质量％Ni-0.7质量％Cu的各测定结果和评价结果。需要说明的是，表3中的In的富集的评价以未实施熟化处理的焊料球的浓度为基准。另外，表3中In的单位为质量％。
[表3]
Figure BDA0002265767360000121
实施例8中，对于Sn-1质量％In-0.1质量％Bi-0.001质量％Ni-0.7质量％Cu的焊料球，进行在200℃下持续暴露于大气中60分钟的熟化处理。根据实施例8，选定黄色度(b*)为4.61、亮度(L*)为64.22的焊料球的情况下，焊料球的表面的In的半定量分析值成为2.0质量％，确认了与未实施熟化处理的比较例1的焊料球相比In的富集得到促进。另外确认了，焊料球表面处的In的富集(氧化膜厚)如果为恒定范围内，则可以良好地维持软钎料的湿润性，且也可以抑制IMC的生长。
比较例8中，使用未进行熟化处理的状态的Sn-1质量％In-0.1质量％Bi-0.001质量％Ni-0.7质量％Cu的焊料球。比较例8中，选定黄色度(b*)为2.79、亮度(L*)为68.76的焊料球的情况下，焊料球的表面的In的半定量分析值成为0.9质量％。需要说明的是，表3中，对于比较例1的接合时的In是否富集的评价，未实施熟化处理的比较例1成为基准，因此，用“-”表示而不是用“×”表示。焊料球的湿润性的评价成为“〇”。
表4中示出合金组成为Sn-1质量％In-0.1质量％Sb-0.001质量％Co-0.7质量％Cu的各测定结果和评价结果。需要说明的是，表4中的In的富集的评价以未实施熟化处理的焊料球的浓度为基准。另外，表4中In的单位为质量％。
[表4]
Figure BDA0002265767360000122
实施例9中，对于Sn-1质量％In-0.1质量％Sb-0.001质量％Co-0.7质量％Cu的焊料球，进行在200℃下持续暴露于大气中60分钟的熟化处理。根据实施例9，选定黄色度(b*)为4.55、亮度(L*)为63.81的焊料球的情况下，焊料球的表面的In的半定量分析值成为2.5质量％，确认了与未实施熟化处理的比较例9的焊料球相比In的富集得到促进。另外确认了，焊料球表面处的In的富集(氧化膜厚)如果为恒定范围内，则可以良好地维持软钎料的湿润性，且也可以抑制IMC的生长。
比较例9中，使用未进行熟化处理的状态的Sn-1质量％In-0.1质量％Sb-0.001质量％Co-0.7质量％Cu的焊料球。比较例9中，选定黄色度(b*)为2.76、亮度(L*)为67.21的焊料球的情况下，焊料球的表面的In的半定量分析值成为1.5质量％。需要说明的是，表4中，对于比较例9的接合时的In是否富集的评价，未实施熟化处理的比较例9成为基准，因此，用“-”表示而不是用“×”表示。焊料球的湿润性的评价成为“〇”。
表5中示出合金组成为Sn-0.1质量％In-0.7质量％Cu的各测定结果和评价结果。需要说明的是，表5中的In的富集的评价以未实施熟化处理的焊料球的浓度为基准。另外，表5中In的单位为质量％。
[表5]
Figure BDA0002265767360000131
实施例10中，对于Sn-0.1质量％In-0.7质量％Cu的焊料球，进行在200℃下持续暴露于大气中60分钟的熟化处理。根据实施例10，选定黄色度(b*)为4.08、亮度(L*)为67.35的焊料球的情况下，焊料球的表面的In的半定量分析值成为0.3质量％，确认了与未实施熟化处理的比较例10的焊料球相比In的浓度增大。另外确认了，焊料球表面处的In的富集(氧化膜厚)如果为恒定范围内，则可以良好地维持软钎料的湿润性，且也可以抑制IMC的生长。
比较例10中，使用未进行熟化处理的状态的Sn-0.1质量％In-0.7质量％Cu的焊料球。比较例10中，选定黄色度(b*)为2.65、亮度(L*)为70.11的焊料球的情况下，焊料球的表面的In的半定量分析值成为0.1质量％。需要说明的是，表5中，对于比较例10的接合时的In是否富集的评价，未实施熟化处理的比较例10成为基准，因此，用“-”表示而不是用“×”表示。焊料球的湿润性的评价成为“〇”。
由以上的结果，确认了In含量超过0质量％且10质量％以下、球径为120μm以下的焊料球的情况下，通过熟化处理制作黄色度(b*)为2.8以上且15.0以下的焊料球，从而In在焊料球的表面明显富集。由此，形成于焊料球的表面的含有氧化In(InO)的氧化膜作为保护膜发挥功能，从而还确认了与未进行熟化处理的一般的焊料球、熟化处理超过恒定条件的焊料球相比，可以确保钎焊接合时的软钎料的湿润性。
需要说明的是，本发明的保护范围不限定于上述实施方式，在不脱离本发明的主旨的范围内，包含对上述实施方式加以各种变更的方案。

Claims (5)

1.一种焊料球，其In为0.1质量％以上且10质量％以下、且余量为Sn，
所述焊料球的L*a*b*色度体系中的黄色度b*为2.8以上且15.0以下，
所述焊料球的L*a*b*色度体系中的亮度L*为60以上且100以下，
其中，添加有：
Ag：0以上且4质量％以下、
Cu：0以上且1.0质量％以下、
来自Bi、Sb的组的总计为0～3质量％、
来自Ni、Co、Fe、Ge、P的组的总计为0～0.1质量％中的至少1种以上的元素，
其中，除Ag：3质量％、Cu：0.5质量％、In：0.2质量％、余量为Sn的焊料球之外。
2.根据权利要求1所述的焊料球，其中，
所述In为0.1质量％以上且7质量％以下。
3.根据权利要求1或2所述的焊料球，其中，
球径为0.1μm以上且120μm以下。
4.一种钎焊接头，其使用权利要求1～3中任一项所述的焊料球。
5.一种接合方法，其具备如下工序：
将权利要求1～3中任一项所述的多个焊料球配置于电极上的工序；和，
用有机酸气体，使配置于所述电极上的所述多个焊料球熔融的工序。
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