CN103547408A - 无铅焊料球 - Google Patents

无铅焊料球 Download PDF

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Publication number
CN103547408A
CN103547408A CN201280024585.XA CN201280024585A CN103547408A CN 103547408 A CN103547408 A CN 103547408A CN 201280024585 A CN201280024585 A CN 201280024585A CN 103547408 A CN103547408 A CN 103547408A
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China
Prior art keywords
solder ball
quality
electrode
solder
scolder
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CN201280024585.XA
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CN103547408B (zh
Inventor
大西司
山中芳惠
立花贤
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Senju Metal Industry Co Ltd
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Senju Metal Industry 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
    • B23K35/02—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
    • 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
    • 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
    • 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
    • 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
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    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract

本发明提供一种焊料球，其为抑制焊料球的接合界面的界面剥离并抑制焊料球与焊膏之间产生的未熔合的、电子部件落下时的故障模式低的焊料球，为镀Au等的Ni电极部与在Cu上涂布有水溶性预焊剂的Cu电极部均可使用的焊料球。本发明为一种无铅焊料球，其为Ag0.5～1.1质量%、Cu0.7～0.8质量%、Ni0.05～0.08质量%、余量Sn的BGA、CSP的电极用无铅焊料球，无论被接合的印刷电路板为Cu电极，还是表面处理使用镀Au、镀Au/Pd的Ni电极，落下冲击性都良好。进而，该组成中还可以以总计0.003～0.1质量%添加一种以上选自Fe、Co、Pt中的元素，或者以总计0.003～0.1质量%添加一种以上选自Bi、In、Sb、P、Ge中的元素。

Description

无铅焊料球
技术领域
本发明涉及在半导体等电子部件的电极中使用的无铅焊料球。尤其涉及镀Au等的Ni电极部和在Cu上涂布有水溶性预焊剂的Cu电极部都可使用的、搭载有电极的电子部件落下时的故障模式低的无铅焊料球。
背景技术
近来，由于电子设备的小型化、电信号的高速化等，电子设备所使用的电子部件也被小型化、多功能化。作为小型化、多功能化的电子部件，有BGA（球栅阵列；Ball Grid Array）、CSP（芯片尺寸封装；Chip Size Package）、MCM（多芯片模块；Multi Chip Module）（以下代表性地称为BGA）。BGA在BGA基板的背面有复数的电极设置于基板网眼状位置。将BGA安装于印刷电路板时，通过将BGA的电极与印刷电路板的焊盘用焊料接合来进行。向印刷电路板安装BGA时，对每个电极逐个供给焊料进行焊接的情况下不仅会耗费很大的劳力，而且无法从外部对位于基板中间的电极供给焊料。因此，为了将BGA安装于印刷电路板，会进行预先在BGA的电极上堆放焊料的方法。将其称为焊料凸块的形成。
于BGA上形成焊料凸块时，使用焊料球、焊膏等。用焊料球形成焊料凸块时，在BGA电极上涂布粘合性的焊剂，在涂布有该焊剂的电极上载置焊料球。然后，将该BGA基板用回流焊炉那样的加热装置进行加热，使焊料球熔融，从而在电极上形成焊料凸块。将BGA基板、CSP基板等半导体基板统称为模块基板。另外，用焊膏在晶圆的焊盘上形成焊料凸块时，会设置在与晶圆的焊盘一致的位置穿设有与焊盘同等水平的孔的金属掩模，用刮板从金属掩模的上方刮扫焊膏，由此在晶圆的焊盘上印刷涂布焊膏。然后，将晶圆用回流焊炉加热，使焊膏熔融，从而形成焊料凸块。
然而，现有的BGA使用Sn-Pb合金的焊料球作为焊料凸块形成用。该Sn-Pb焊料球不仅对BGA的电极的焊接性优异，尤其是Sn-Pb的共晶组成具有在焊接时对BGA元件、基板等不造成热影响的熔点，而且具有柔软的Pb，因此即使所使用的电子部件、电子设备等落下，也可吸收冲击，对电子部件、电子设备等的寿命作出很大贡献。目前，在世界范围内Pb的使用逐渐受到限制，当然现有的焊接中使用的Sn-Pb的共晶组成也开始受到限制。
一直以来，作为BGA用的无铅焊料球的组成，使用Sn-3.0Ag-0.5Cu、Sn-4.0Ag-0.5Cu等Sn-Ag-Cu系的焊料合金。这些无铅焊料合金虽然温度循环特性优异，但使用了这些焊料合金组成的焊料球的移动电子设备在落下时容易发生从焊料球连接界面剥离的界面剥离，因此认为落下冲击性差。
作为防止移动电子设备的落下冲击的无铅焊料球用的焊料合金组成，有：一种无铅焊料合金，其以质量%计由（1）Ag:0.8～2.0%、（2）Cu:0.05～0.3%、以及（3）选自In:0.01%以上且不足0.1%、Ni:0.01～0.04%、Co:0.01～0.05%、和Pt:0.01～0.1%中的一种或两种以上、余量Sn构成（WO2006/129713A公报，专利文献1）；一种无铅焊料合金，其特征在于，包含Ag：1.0～2.0质量%、Cu：0.3～1.5质量%，且包含余量的Sn和不可避免的杂质；以及，一种无铅焊料合金，其包含一种或两种以上Sb：0.005～1.5质量%、Zn：0.05～1.5质量%、Ni：0.05～1.5质量%、Fe：0.005～0.5质量%，且Sb、Zn、Ni、Fe的总含量为1.5质量%以下（日本特开2002-239780号公报，专利文献2）；一种无铅焊料合金，其以质量%计由0.1～1.5%的Ag、0.5～0.75%的Cu、满足12.5≤Cu/Ni≤100的关系的Ni、余量的Sn和不可避免的杂质构成（WO2007/081006A公报，专利文献3）；一种无铅焊料合金，其含有Ag：1.0～2.0质量%、Cu：0.3～1.0质量%、Ni：0.005～0.10质量%，且包含余量的Sn和不可避免的杂质（WO2007/102588A公报，专利文献4）。另外，作为BGA基板那样的模块与印刷电路板的接合时产生的未熔合的解决方法，已公开了在模块基板的电极部涂布焊剂的方法（WO2006-134891A公报，专利文献5）。
现有技术文献
专利文献
专利文献1：WO2006/129713A公报
专利文献2：日本特开2002-239780号公报
专利文献3：WO2007/081006A公报
专利文献4：WO2007/102588A公报
专利文献5：WO2006/134891A公报
发明内容
发明要解决的问题
这些专利文献1～4是为了改善Sn-Ag-Cu系焊料球的耐落下冲击性而降低Ag的含量使焊料的硬度下降来提高冲击吸收量、或者降低Cu的含量使焊盘与焊料的接合面产生的Cu6Sn5等金属间化合物层变薄来防止在接合界面发生剥离的技术方案，通过添加Ni、Fe、Co等铁族元素来改善由降低Ag和Cu的含量而产生的焊料自身的强度。
然而，即使采用如专利文献1～4那样的应对耐落下冲击性的焊料球，依然出现了由电子设备的落下造成的不良情况没有减少的问题。对这一点进行分析时逐渐发现，与现有的Sn-Pb焊料相比增加的电子设备的落下造成的故障并不仅在专利文献1～5那样的焊料球与基板的接合界面产生。这是因为，BGA基板等模块基板与印刷电路板接合时，BGA的电极所使用的焊料球的焊料成分与印刷电路板的焊接所使用的焊膏的焊料成分未混合（图1）的称为“未熔合”的不良情况伴随由现有的Sn-Pb焊料向无铅焊料的过渡而作为新的不良情况产生。
但是，已经发现，未熔合的产生随着由Sn-3.0Ag-0.5Cu组成的焊料球过渡到作为应对耐落下冲击性的对策而开发的Sn-Ag-Cu-Ni组成的焊料球而大量发生。大致可以认为未熔合的原因是：为了改善焊料球的落下冲击而添加的Ni与Sn形成金属间化合物，在焊料球表面析出，从而妨碍焊料球的焊料成分与焊膏的焊料成分混合。
另外，作为未熔合的产生原因，也考虑了以下方面。印刷电路板被加热而大幅翘曲时，焊料球与焊膏脱离。若在焊料球与焊膏脱离的状态下加热，则焊料球会因高温而导致表面氧化。从焊膏渗出的焊剂覆盖焊料球的表面，若该焊剂失去活性能力（active force），则在冷却的过程中翘曲恢复时，即使焊膏与焊料球接触，也无法去除焊料球的表面的氧化膜，因此导致未熔合。作为其对策，专利文献5的方法是有效的。
并且，由实施例判明，未熔合起因于根据焊料球的组成的不同而在焊料球内部形成的化合物、Cu6Sn5或（Cu、Ni）6Sn5。将接合了焊料球的部件搭载到安装基板上时，对印刷涂布有焊膏的安装基板、以焊料球所接合的电极侧朝下的方式进行搭载。然后进行加热，在焊膏熔融的同时焊料球也熔融从而达成熔合。但是，在焊料球内部形成的化合物Cu6Sn5或（Cu、Ni）6Sn5大量生成时，会产生焊料球熔融时化合物在球内部沉淀并在凸块最外层的表面附近析出的现象。确认到该现象会妨碍与焊膏的熔合而成为引起熔合不良的主要原因（图2、图3）。
用于BGA、CSP的焊料球被要求耐落下冲击。对耐落下冲击而言有效的手段之一为界面化合物的改性，如专利文献1～4中公开的那样，Ni的添加为改善的手段。但是，在未熔合的观点上，Ni也是会生成化合物的元素，因此可以添加的量受限。考虑到未熔合而抑制Cu、Ni的添加时，耐落下冲击特性损失，因此对于多用于在BGA、CSP等移动设备上搭载的焊料球是不适合的。
本发明想要解决的问题在于开发即使是耐落下冲击性等焊料强度得到提高的Sn-Ag-Cu-Ni组成的焊料球也不产生未熔合的焊料球用的焊料合金，通过抑制焊料球的接合界面的界面剥离并抑制焊料球与焊膏之间产生的未熔合，得到电子部件落下时的故障模式低、接合的印刷电路板无论在Cu电极、还是在对Ni基底实施过镀Au、镀Au/Pd表面处理的电解Ni/Au电极和无电解Ni/Pd/Au电极上都具有该效果的BGA、CSP用的焊料球。
用于解决问题的方案
本发明人等发现，耐落下冲击性和未熔合产生率都低的焊料球用焊料合金由移动电子设备的落下造成的不良情况少，耐落下冲击性焊料合金中所含的Ni等铁族的金属在焊料球表面析出时，未熔合产生率变高，由移动电子设备的落下造成的不良情况常常发生，通过规定在焊料合金中添加的Ni的量，由未熔合、进而移动电子设备的落下导致的不良情况变少，从而完成了本发明。
在本发明中，将作为基质的Sn-Ag-Cu焊料设为：Ag为0.5～1.1质量%、Cu为0.7～0.8质量%、余量为Sn。作为其理由，本发明的焊料球与通过减少Sn-Ag-Cu三元组成的焊料合金中的Cu的含量来抑制在Cu电极界面形成Cu6Sn5的金属间化合物的专利文献1～4的技术不同，Sn-Ag-Cu三元组成的焊料合金中的Cu的含量在作为共晶点的0.75质量%附近，即便不通过添加Ni来减少焊料中的Cu的含量，也可抑制在Cu电极界面形成Cu6Sn5的金属间化合物。
这是通过将本发明的Sn-Ag-Cu三元组成的焊料合金中的Cu的含量限定于作为共晶点的0.75质量%附近，抑制Cu从Cu电极扩散到Cu为饱和状态的Sn-Ag-Cu三元组成的焊料合金中。
本发明的焊料球的另一个特征在于，通过将Sn-Ag-Cu三元组成的焊料合金中的Cu的含量设为作为共晶点的0.75质量%附近，不仅抑制自Cu电极的Cu扩散，而且对具有与Cu完全固溶的关系的Ni也可得到同样的效果，因此，对于Ni电极也具有抑制Ni扩散的功能。进而，通过在焊料中预先添加Ni，自部件电极和基板电极的Ni和Cu的扩散抑制效果提高，而且通过利用微细的金属间化合物形成接合界面，对于Ni电极，耐落下冲击性也提高。
在本发明的Ag为0.5～1.1质量%、Cu为0.7～0.8质量%、余量为Sn的焊料球用焊料组成中添加的Ni的量为0.05～0.08质量%。在本发明中，通过将在Sn-Ag-Cu的焊料合金中添加的Ni量设为0.05～0.08质量%，能够得到Ni不会在Sn-Ag-Cu焊料球表面集中地析出的、温度循环特性和耐落下冲击性都优异的BGA用电极用的焊料球。
在本发明中，Sn-Ag-Cu三元组成的焊料合金中的Cu的含量在作为共晶点的0.75质量%附近，即便不通过添加Ni来减少焊料中的Cu的含量，也会抑制在Cu电极界面形成Cu6Sn5的金属间化合物。进而，通过在Sn-Ag-Cu三元组成的焊料合金中添加本发明的少量的Ni量，焊料中的SnCu化合物：Cu6Sn5微细化，形成于部件和基板电极界面的金属间化合物的颗粒也变得细小，形成不易发生破坏的接合界面。
Ni添加量不足0.05质量%而过少时，难以得到前述效果，无法实现耐落下冲击性的提高。另外，添加量超过0.08质量%而过量时，接合界面化合物中的Ni的浓度上升，形成脆且容易破坏的接合界面，因此耐落下冲击性减少。另外，过量的Ni添加还无法避免焊料硬度的上升，对于耐落下冲击是不适合的。综上所述，Ni添加量不适当时，存在耐落下冲击性降低的倾向。
发明的效果
通过使用本发明的焊料球，可以使用对于Cu电极和Ni电极两者都具有耐落下冲击性且由于未熔合抑制的效果导致的搭载有电极的电子部件落下时的故障模式低的焊料球，具有能够灵活地应对频繁进行的电极的设计变更的优点。
通过使用本发明的焊料球，对于在Cu焊盘上涂布有水溶性预焊剂（也称为OSP；Organic Solderbility Preservatives；有机可焊性保护剂）的Cu电极、包括将镀Au、镀Pd/Au等的在基底使用Ni的电极的Ni电极，都能得到电子部件落下时的故障模式低的BGA、CSP的电极与印刷电路板的接合。
具体实施方式
本发明的对Cu电极和Ni电极都具有耐落下冲击性的焊料球优选用于对具有下面电极的BGA、CSP等PKG部件的凸块形成。
在本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金中，Ag的含量不足0.5质量%时，焊料的强度降低，存在负荷由落下等带来的冲击应力时容易发生焊料断裂的问题。Ag的含量超过1.1质量%时，焊料的硬度变高，冲击吸收降低，因此会发生在界面的剥离。因此，本发明的焊料球用的合金的Ag的含量必须为0.5～1.1质量%、更优选为0.9～1.1质量%。
另外，本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金的Cu的含量不足0.7质量%时，会偏离Sn-Ag-Cu的共晶点，因此用于Cu电极时Cu从Cu电极扩散到焊料中，因而在Cu电极界面上Cu6Sn5的金属间化合物层变厚，耐落下冲击性变差。Sn-Ag-Cu-Ni系焊料合金的Cu的含量超过0.8质量%时，从Sn-Ag-Cu的共晶点偏离，因此在焊料合金和Cu电极的反应层中容易形成Cu6Sn5的金属间化合物，作为其结果，形成于Cu电极与焊料接合部界面的Cu6Sn5的金属间化合物变厚。因此，本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金所含的Cu的含量必须为0.7～0.8质量%。
进而，本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金的Ni的含量不足0.05质量%时，无法表现出添加Ni的效果，Ni容易从Ni电极扩散，容易在界面形成金属间化合物，因此Sn-Ag-Cu-Ni系焊料合金中的Ni的含量必须为0.05质量%以上。同样地，Ni的含量超过0.08质量%时，形成于接合界面的金属间化合物中的Ni浓度上升而接合强度降低，此外，由于伴随焊料硬度的上升，因此在负荷冲击时，容易产生界面剥离。另外，Ni的含量超过0.08质量%时，未熔合产生率变高。因此，本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金中的Ni的含量需要为0.05～0.08质量%。
在本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金中，还可以进一步以总计0.003～0.1质量%添加一种以上选自Fe、Co、Pt中的元素。Fe、Co、Pt元素在焊料球用的合金中的添加会使形成于接合界面的金属间化合物层微细化，抑制厚度，因此具有改善落下的效果。选自Fe、Co、Pt中的元素不足0.003质量%时，极难得到上述效果，超过0.1质量%地添加时，焊料凸块硬度上升，会出现面对冲击产生界面剥离的弊病。
在本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金中，还可以进一步以总计0.003～0.1质量%添加一种以上选自Bi、In、Sb、P、Ge中的元素。
焊料球被搭载到模块基板上后，通过图像识别进行是否被焊接的判定。如果焊料球中存在黄色等的变色，则在图像识别中判定为不良情况。因此，焊料球不因回流焊而变色是较好的。
由添加Bi、In、Sb、P、Ge得到的效果是能够通过防止由热等造成的变色来避免凸块质量检验中的错误。选自Bi、In、Sb、P、Ge中的元素不足0.003质量%时，极难得到上述效果，超过0.1质量%地添加时，焊料凸块的硬度增加，担心落下改善效果受损。
本发明的焊料球用作电极用。焊料球的直径为0.1mm以上、优选为0.3mm以上、更优选为0.5mm以上。近年来，电子设备的小型化推进，搭载于电子部件的焊料球也不断微细化。在倒装芯片的接合中，广泛使用0.1mm以下的焊料球，本发明焊料球这样的以内置倒装芯片的CSP、BGA为对象的电极用焊料球为0.1mm以上是主流的。
实施例
制作下面的表的组成的焊料合金，通过气中造球法制作直径0.3mm的焊料球。使用该焊料球按照以下的步骤制作CSP基板。
[表1]
Figure BDA0000418660370000091
1.使用千住金属工业株式会社制造的焊剂WF-6400将制作的各组成的焊料球回流焊焊接到具有尺寸12×12mm的电解Ni/Au、电解Ni/Pd/Au、用OSP处理Cu焊盘而得到的电极的CSP用的模块基板上，制作使用各组成的焊料作为电极用的CSP。
2.在尺寸30×120mm、厚度0.8mm的玻璃环氧基板（FR-4）上用焊膏根据电极图案进行印刷，搭载1中制作的CSP，在220℃以上40秒、峰值温度245℃的条件下进行回流焊。
3.在下面的条件下实施落下冲击试验。试验方法为：使用2中制作的搭载有CSP的玻璃环氧基板，使用专用夹具将基板两端固定于距基座浮起10mm的位置。按照JEDEC标准，重复施加加速度1500G的冲击，将从初始阻力值上升了1.5倍时的时间点视为断裂，记录落下次数。
判明使用专利文献2那样的大量含有Ni的Sn-Ag-Cu-Ni系焊料合金的焊料球在与Ni电极焊接时也没有得到耐落下冲击性。
对于未熔合产生率，也使用同样的焊料球，按照以下的步骤制作CSP基板。
1.对制作的各组成的焊料球实施温度110℃、湿度85%、时间24hr的处理。
2.在尺寸36×50mm、厚度1.2mm的玻璃环氧基板（FR-4）上用焊膏根据电极图案进行印刷，搭载1中制作的焊料球，在220℃以上40秒、峰值温度245℃的条件下进行回流焊。
3.使用立体显微镜记录焊料球与焊膏的未熔合数，算出未熔合产生率。
接着使用制作的焊料球按照以下的步骤实施润湿扩展。使用的基板材质使用与研究未熔合产生率的基板同样的材质。
1.使用形成有0.24mm×16mm的狭缝状的电极的厚度1.2mm的玻璃环氧基板（FR-4），印刷0.24mmφ×厚度0.1mm的千住金属工业株式会社制造的焊剂WF-6400，搭载焊料球，在220℃以上40秒、峰值温度245℃的条件下进行回流焊。
2.使用立体显微镜，测定润湿扩展面积。
比较例7、9、10、11、13为Cu含量超过0.8质量%或者Ni含量超过0.07质量%地含有的焊料球合金组成，因此未熔合产生率高于8%。未得到抑制效果。
尤其，比较例13中的专利文献2所记载的焊料组成Sn-1.5Ag0.5Cu-0.5Ni的未熔合产生率显著增加，这是由于焊料中的Ni含量过多，因此生成化合物量变得过多，损害与焊膏的熔合性，作为其结果，使未熔合的产生率增加。
同样地，关于比较例10、11，由于Cu含量过多，因此生成化合物变得过多，导致未熔合产生。
进而，比较例1～2中，由于Ag量少，发现明显的润湿扩展的降低。实际上与实施例1相比，润湿扩展面积约降低了20%以上。润湿扩展不充分时，存在得不到良好的接合而无法充分保持接合强度的可能性。
比较例3～6、8、12、14、15中，尽管未熔合产生率低于5%且确保了充分的润湿扩展，但是，由于Ag、Cu、Ni含量没有被优化，因此得不到落下改善效果。
此处，将Sn1Ag中的Cu含量固定在0.7质量%，着眼于Ni含量。在使Ni含量超过0.08质量%而选择0.1质量%时，未熔合产生率明显增加。反之，在低于0.05质量%而选择0.02质量%时，虽然具有对未熔合的抑制效果，但得不到落下特性的耐性。由此，通过以0.05～0.08质量%选择Ni含量，能够得到兼具未熔合抑制和耐落下改善的焊料合金。
接着，对于将Sn1Ag中的Ni含量固定于0.05质量%时的Cu含量，确认伴有未熔合抑制和耐落下改善的范围。在使Cu含量超过0.8质量%而选择1质量%时，未熔合产生率明显增加。进而，在低于0.7质量%而选择0.5质量%时，未伴有落下改善效果，作为兼具两者的焊料合金，判断Cu含量0.7～0.8质量%最佳。
作为结论，对于由Ag0.5～1.1质量%、Cu0.7～0.8质量%、Ni0.05～0.08质量%、余量Sn构成的焊料组成而言，其在镀Au等的Ni电极部以及在Cu上涂布有水溶性预焊剂的Cu电极部均可使用，由于兼具界面剥离抑制效果和未熔合抑制效果两者，因此可以得到搭载有电极的电子部件落下时的故障模式低的焊料合金。
产业上的可利用性
根据本发明，提供对Cu电极和Ni电极都具有耐落下冲击性的电极用焊料球。Sn-Ag-Cu的三元组成的焊料合金中添加的Ni的量超过0.1质量%而过量时，在焊料球表面容易有含Ni的化合物析出，而且容易发生与安装的焊膏的熔合不良。本发明的焊料球由于将Ni量抑制在0.05～0.08质量%，因此不易出现化合物在焊料球表面上析出的现象，对未熔合现象的抑制也具有效果。
附图说明
图1是未熔合现象的一个例子
图2是由焊料球内部的化合物造成的妨碍与焊膏熔合的例子
图3是由焊料球内部的化合物造成的妨碍与焊膏熔合的例子放大图
图4是实施例2的接合界面化合物层
图5是比较例9的接合界面化合物层
图6是比较例10的接合界面化合物层
图7是界面剥离的示意图
图8是未熔合的示意图
附图标记说明
1    BGA部件
2    安装基板
3    焊料凸块熔合
4    焊料凸块未熔合
5    安装加热后的焊料球
6    安装加热后的焊膏
7    未熔合位置
8    导致妨碍熔合的化合物
9    BGA侧电极
10   具有耐落下特性的接合界面化合物
11   焊料凸块
12   由于Cu含量不足而不具有耐落下特性的接合界面化合物
13   由于Ni含量不足而不具有耐落下特性的接合界面化合物
14   焊盘

Claims (9)

1.一种无铅焊料球，其为安装于BGA、CSP用的模块基板的、用作电极用的焊料球，其焊料组成由Ag0.5～1.1质量%、Cu0.7～0.8质量%、Ni0.05～0.08质量%、余量Sn构成。
2.根据权利要求1所述的无铅焊料球，其中，所述焊料组成为由Ag0.9～1.1质量%、Cu0.7～0.8质量%、Ni0.05～0.08质量%、余量Sn构成的焊料组成。
3.根据权利要求1所述的无铅焊料球，其中，所述焊料组成为由Ag1.0质量%、Cu0.75质量%、Ni0.07质量%、余量Sn构成的焊料组成。
4.根据权利要求1～3中的任一项所述的焊料球，其特征在于，在所述焊料组成中以总计0.003～0.1质量%添加了一种以上选自Fe、Co、Pt中的元素。
5.根据权利要求1～3中的任一项所述的焊料球，其特征在于，在所述焊料组成中以总计0.003～0.1质量%添加了一种以上选自Bi、In、Sb、P、Ge中的元素。
6.根据权利要求1～5中的任一项所述的无铅焊料球，所述焊料球具有直径为0.1mm以上的直径。
7.根据权利要求1～5中的任一项所述的无铅焊料球，所述焊料球具有直径为0.3mm以上的直径。
8.根据权利要求1～5中的任一项所述的无铅焊料球，所述焊料球具有直径为0.5mm以上的直径。
9.一种模块基板的焊料凸块形成方法，其为对具有选自电解Ni/Au电极、无电解Ni/Pd/Au电极、Cu-OSP电极中的电极的模块基板形成焊料凸块的方法，所述方法使用权利要求1～8中的任一项所述的焊料球进行焊接。
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