CN104602862B - 无铅焊料球 - Google Patents

无铅焊料球 Download PDF

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Publication number
CN104602862B
CN104602862B CN201280075513.8A CN201280075513A CN104602862B CN 104602862 B CN104602862 B CN 104602862B CN 201280075513 A CN201280075513 A CN 201280075513A CN 104602862 B CN104602862 B CN 104602862B
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China
Prior art keywords
solder ball
solder
mass
lead
electrode
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CN201280075513.8A
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CN104602862A (zh
Inventor
山中芳恵
立花贤
吉川俊策
野村光
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Senju Metal Industry Co Ltd
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Senju Metal Industry Co Ltd
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Priority to CN201610934617.XA priority Critical patent/CN106964917B/zh
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L24/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • 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
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B23K35/0261—Rods, electrodes, wires
    • 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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    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • 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
    • 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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    • 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
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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Abstract

本发明提供一种焊料球，其为抑制焊料球接合界面的界面剥离、并且抑制焊料球与焊膏之间产生的未熔合的焊料球，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。本发明是一种无铅焊料球，其为Ag1.6～2.9质量％、Cu0.7～0.8质量％、Ni0.05～0.08质量％、余量为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，耐热疲劳性和耐落下冲击性这二者均优异。进而，也可以在该组成中以总计0.003～0.1质量％添加1种以上选自Fe、Co、Pt的元素，或者以总计0.003～0.1质量％添加1种以上选自Bi、In、Sb、P、Ge的元素。

Description

无铅焊料球
技术领域
本发明涉及半导体等电子部件的电极所使用的无铅焊料球。
尤其涉及由未熔合造成的不良情况少的无铅焊料球。
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 GridArray)、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基板的背面作为电极设置于基板网眼状位置。
为了将BGA安装于印刷电路板，用焊料将BGA的电极与印刷电路板的焊盘接合，但是对每个电极逐个供给焊料进行焊接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，使用预先在BGA的电极上堆放焊料的方法。将其称为焊料凸块的形成。
在BGA的焊料凸块形成中使用焊料球、焊膏等。用焊料球形成焊料凸块时，在BGA的电极上涂布粘合性的助焊剂，在涂布有助焊剂的电极上载置焊料球。然后，将该BGA基板用回流焊炉等加热装置进行加热，使焊料球熔融，从而在电极上形成焊料凸块。需要说明的是，将BGA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、印刷电路板等不造成热影响的熔点。而且，其具有柔软的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，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耐热疲劳性优异，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，因此耐落下冲击性差。为了改善此耐落下冲击性，开发了添加有Ni的Sn-Ag-Cu-Ni系的焊料合金。
但是，这些焊料球所使用的Sn-Ag-Cu系、Sn-Ag-Cu-Ni系的焊料组成由于与现有的Sn-Pb系焊料相比润湿性差，因此使用焊膏将BGA搭载到印刷电路板上时，会发生熔融的焊料球的焊料成分与焊膏的焊料成分未完全地混合、在焊料球与焊膏之间出现Sn的氧化皮膜的层的“未熔合”这样的现象，这会成为问题。作为未熔合现象的一个例子，将BGA与印刷电路板的接合例示于图1。将BGA部件1与安装基板2接合的焊料凸块3虽然发生了熔合，但是焊料凸块4发生未熔合。图2是包含发生了安装加热后的未熔合现象的焊料球5和焊膏6的焊料凸块。将图2放大而成的图3中能够确认发生了未熔合的接合部7仅为单纯地接触，因此施加外部冲击时接合部会被轻易地破坏。此外，发生未熔合时，对搭载有BGA的电子设备施加落下等外部冲击时变得容易发生故障。
为了防止由未熔合造成的不良情况，电子设备的制造商通过利用测定电子设备的电阻值等方法对发生了未熔合的接合进行事前检查，从而将发生了未熔合的印刷电路板改正或替换，防止故障于未然。
作为BGA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，申请人已公开了在BGA等模块的电极部涂布助焊剂的方法(WO2006-134891A公报，专利文献1)。
作为BGA等用的Sn-Ag-Cu-Ni系的焊料球的组成，公开了：一种无铅焊料合金，其包含(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(WO2006/129713A公报，专利文献2)；一种无铅焊料合金，其特征在于，其包含Ag：1.0～2.0质量％、Cu：0.3～1.5质量％，且包含余量Sn和不可避免的杂质；以及一种无铅焊料合金，其还包含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％的一种或两种以上，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3)；一种无铅焊料合金，其以质量％计包含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Sn和不可避免的杂质(WO2007/081006A公报，专利文献4)；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Sn和不可避免的杂质(WO2007/102588A公报，专利文献5)。
现有技术文献
专利文献
专利文献1：WO2006/134891A公报
专利文献2：WO2006/129713A公报
专利文献3：日本特开2002-239780号公报
专利文献4：WO2007/081006A公报
专利文献5：WO2007/102588A公报
发明内容
发明要解决的问题
在使用BGA等的安装中，一般通过如下方式进行焊接的工序：将包含焊料合金粉末例如Sn-Ag-Cu合金粉末和助焊剂的焊膏印刷在安装基板上，在BGA等上搭载形成有Sn-Ag-Cu系的焊料合金凸块的电子部件，并加热熔解。最近，在该工序中，即使在充分地超过焊料合金的熔点的温度下进行安装时，BGA等模块基板的焊料凸块与焊膏、或者引线部件与焊膏不熔合，引起通导不良这样的“未熔合”的现象成为问题。毋庸讳言，未熔合会引起通导不良，导致不满足作为电子设备产品的功能，根据情况的不同，有可能会发展到顾客抱怨的地步。模块与印刷电路板的焊接跟印刷电路板与翘曲小的芯片部件的焊接不同，其特征在于，模块和印刷电路板均会由于回流焊的加热而发生大的翘曲。该现象在部件电极的无铅化以前也被确认到，但是多被确认发生在部件电极的无铅化的情况下，因此今后成为主流的无铅焊料电极中的对策变为当务之急。
对于BGA等模块的焊料凸块表面的腐蚀的影响、基板和/或部件的翘曲作为未熔合现象的主要原因而起作用。尤其是，对于焊料凸块表面而言，在凸块形成时使用的助焊剂的清洗不良、部件被暴露在高温高湿下的情况下等，会在凸块表面生成坚固的氧化皮膜。原本，承担将该表面氧化皮膜洁净化的功能的成分是在表面安装工艺中被印刷于印刷电路板的焊膏中的助焊剂。但是，在如前述这样表面氧化皮膜坚固、表面为难以还原的状态、进而加热安装时发生基板、部件的翘曲的情况下，有时所印刷的焊膏与部件的焊料凸块分离，发生未熔合的可能性变高。其发生率在市场报告中报道为ppm级，而在实验性地暴露在使焊球表面腐蚀的高温高湿的情况下，确认其上升至50～70％的水平。
本次，本发明人等发现，作为未熔合的原因，除了前述的原因以外，由于焊料球的组成而在焊料内部形成的化合物即Cu6Sn5或(Cu、Ni)6Sn5也有影响。将接合有焊料球的部件搭载在安装基板上时，对印刷涂布有焊膏的安装基板，使BGA等模块的接合了焊料球的电极侧朝下地进行搭载。之后进行加热，在焊膏熔融的同时焊料球也熔融至熔合。但是，在焊料球球内部形成的化合物Cu6Sn5或(Cu、Ni)6Sn5较多地生成的情况下，会发生在焊料球熔融时化合物在球内部沉降而在凸块最表面附近析出的现象。发现该现象是导致阻碍与焊膏的熔合、引起未熔合的原因。(图3)
作为未熔合的对策，可以考虑彻底消除在部件、安装基板产生的翘曲的对策，提高焊膏的活性的对策等。但是，依靠现有的技术消除，基板的翘曲在现实中是不可能的，焊膏中助焊剂的活性化由于促进与焊料粉末的反应，因此从经时变化的方面出发，有损害焊膏可靠性之虞，因此是困难的，尚没有有效的熔合不良的对策。因此，虽然会增加工序并导致成本上升，但是通过专利文献1这样的方法来消除未熔合的做法是通常的。
本发明要解决的问题是找到能够不采取专利文献1这样的增加工序的方法而仅利用焊料球的组成来消除未熔合的方法。
用于解决问题的方案
本发明人等发现，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和Cu形成金属间化合物，并在焊料球表面析出，从而妨碍了焊料球的焊料成分与焊膏的焊料成分混合。另外，焊料球的润湿性也会造成与焊膏的未熔合现象，伴随着Ag量降低的润湿性降低也承担着发生未熔合现象的部分责任。
因此发现，通过在Sn-Ag-Cu中包含Ni的四元合金中将Sn和Cu和Ni的量设定为某一范围，能够抑制Sn和Cu和Ni的金属间化合物的生成量，并且减少在焊料球表面析出的化合物，发挥对于与焊膏的熔合而言充分的润湿性，由此急剧减少未熔合，从而完成本发明。
本发明为一种无铅焊料球，其为在BGA、CSP用的模块基板的背面作为电极用途而设置的焊料球，其焊料组成包含Ag1.6～2.9质量％、Cu0.7～0.8质量％、Ni0.05～0.08质量％、余量Sn。
为了提高焊料球的热疲劳特性，向焊料中添加Ag、Cu、Ni而形成Sn与Ag、Sn和Cu和Ni等的金属间化合物，该金属间化合物以网眼状形成网络结构，从而形成坚固的焊料合金。另外，为了提高耐落下冲击性，采取了添加Ni的方法来代替如专利文献4那样降低坚硬的Ag的含量。但是，为了提高强度而添加的Ni易于与Cu形成金属间化合物，因此容易成为化合物，在焊料球表面上析出，使焊料球的润湿性变差。在该焊料球表面上产生的润湿性差的部分即使搭载于印刷电路板上与焊膏一起加热，也不会在回流焊的加热时间内与焊膏熔合，以显现轮廓线的状态凝固。其为未熔合。
本申请人关注了以下方面：为了在Sn-Ag-Cu-Ni组成的焊料合金中减少在焊料球表面析出的Ni化合物的量而减少与Ni反应的Cu的量时，Sn和Cu和Ni的金属间化合物不会在焊料球表面上析出。但是，减少Cu量时，与Cu电极的焊接中耐落下冲击性降低。因此申请人发现，通过将向焊料合金中添加的Cu的量设定为低共熔点附近即0.75质量％附近，由网络结构形成造成的Cu的消耗和由形成Cu与Ni的化合物造成的Cu的消耗竞合，Cu与Ni的化合物不会在焊料球表面上较多地析出，不会发生未熔合。
即，通过设为焊料球组成中1.6～2.9质量％的Ag和0.7～0.8质量％的Cu和0.05～0.08质量％的Ni的四元合金组成，从而存在Sn-Ag-Cu的金属间化合物的网络结构、以及为此消耗而减少了的Cu与Ni反应而成的Cu-Ni的金属间化合物，因此Cu不与Ni优先进行反应，在焊料球表面上Cu与Ni的金属间化合物也不会在焊料球表面上析出。因此，印刷电路板与焊膏即使进行焊接也显示出良好的润湿性，不会发生未熔合。
发明的效果
本发明的焊料球由于在焊料球表面不析出润湿性差的Sn和Cu和Ni的金属间化合物，因此能够良好地焊接，即使使用印刷电路板和焊膏进行焊接，也能够进行不引起未熔合的良好的焊接。
另外，本发明的焊料球能够在Cu电极与Ni电极两者的焊接中进行耐热疲劳性和耐落下冲击性两者均优异的BGA等的电极与印刷电路板的焊料接合。
附图说明
图1为BGA与印刷电路板的接合例。
图2为图1的4的放大图。
图3为示出图2的焊料球与焊膏接合界面的未熔合发生的图。
图4为示出表1的实施例2的BGA侧电极的图。
图5为示出表1的比较例6的BGA侧电极的图。
具体实施方式
本发明的不发生未熔合、耐热疲劳性和耐落下冲击性两者均优异的焊料球优选用于向具有下表面电极的BGA等封装部件上形成凸块。
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1.6质量％时，由于焊料球的润湿性降低，对焊膏的润湿也差，熔合性变差，未熔合变得易于发生。另外，Ag的含量不足1.6质量％时，焊料的强度降低，耐热疲劳性变差。Ag的含量超过2.9质量％时，焊料球变硬、耐落下冲击性变差。因此，本发明的焊料球用的合金的Ag的含量为1.6～2.9质量％是较好的。更优选为1.9～2.3质量％。
本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金在Cu的含量不足0.7质量％时，由于自Sn-Ag-Cu的低共熔点(eutectic point)偏离，因此用于Cu电极时Cu自Cu电极向焊料中扩散，从而在Cu电极界面Cu6Sn5的金属间化合物层变厚，耐落下冲击性变差。
接着，Sn-Ag-Cu-Ni系焊料合金的Cu的含量超过0.8质量％时，焊料球中的Cu与Ni的金属间化合物量增加，在焊料球表面上Cu与Ni的金属间化合物析出，因此未熔合变多。另外，Cu的含量超过0.8质量％时，自Sn-Ag-Cu的低共熔点偏离，因此变得容易在焊料合金与Cu电极的反应层中生成Cu6Sn5的金属间化合物，作为其结果，在Cu电极与焊料接合部界面形成的Cu6Sn5的金属间化合物变厚。
因此，本发明的不发生未熔合、耐落下冲击性优异的焊料球的Sn-Ag-Cu-Ni系焊料合金中含有的Cu的含量必须为0.7～0.8质量％。
本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金在Ni的含量不足0.05质量％时，耐落下冲击性变差。进而，Ni的含量不足0.05质量％时，不显现添加Ni的效果，Ni变得易于自Ni电极扩散，变得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含量必须为0.05质量％以上。
同样地，Ni含量超过0.08质量％时，焊料球中的Sn和Cu和Ni的金属间化合物量增加，因此在焊料球表面上Sn和Cu和Ni的金属间化合物量析出，因此未熔合发生率变高。进而，Ni含量超过0.08质量％时，在接合界面形成的金属间化合物中的Ni浓度上升而接合强度降低，并且因伴有焊料硬度的上升，因此在施加了冲击的情况下，变得容易发生界面剥离。
因此，本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金中的Ni的含量必需为0.05～0.08质量％。
本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金中也可以进一步以总计0.003～0.1质量％添加1种以上选自Fe、Co、Pt的元素。向焊料球用的合金中的添加Fe、Co、Pt元素由于会使在接合界面形成的金属间化合物层微细化、抑制其厚度，因此具有落下改善的效果。选自Fe、Co、Pt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，显现出在冲击下发生界面剥离的弊端。
本发明的焊料球的Sn-Ag-Cu-Ni系焊料合金中也可以进一步以总计0.003～0.1质量％添加1种以上选自Bi、In、Sb、P、Ge的元素。焊料球被搭载于模块基板后，利用图像识别进行是否焊接了的判定。若焊料球存在黄色等变色，则在图像识别中判定为不良情况。因此，焊料球在回流焊中未变色是较好的。由Bi、In、Sb、P、Ge添加取得的效果可以通过防止由热等造成的变色而规避在凸块品质检查中的错误。选自Bi、In、Sb、P、Ge的元素不足0.003质量％时，极难得到上述效果，超过0.1质量％添加时，焊料凸块的硬度增加，有损害落下改善效果之虞。
本发明的焊料球用作电极用途。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持续进行微细化。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将内置倒装芯片的BGA、CSP作为对象的电极用焊料球以0.1mm以上为主流。
实施例
制作表1的组成的焊料合金，以气中造球法制作直径0.3mm的焊料球。使用该焊料球，评价未熔合、以及热疲劳试验和落下冲击试验。
[表1]
1.未熔合的发生数量的评价按照以下的步骤进行。将制作的各组成的焊料球在温度110℃、湿度85％下实施24小时的时效处理。对于尺寸36×50mm、厚度1.2mm玻璃环氧基板(FR-4)，用焊膏按照电极图案进行印刷，搭载实施了时效处理的焊料球，在220℃以上40秒、峰值温度245℃的条件下进行回流焊。使用实体显微镜，计测焊料球与焊膏的未熔合数量。
2.接着，热疲劳试验和落下冲击试验按照以下的步骤来实施。使用千住金属工业株式会社制造的Reflux WF-6400、将所制作的各组成的焊料球回流焊接到尺寸12×12mm的CSP用的模块基板上，制作将各组成的焊料用作电极用的CSP。
3.在尺寸30×120mm、厚度0.8mm的玻璃环氧基板(FR-4)上用焊膏按照电极图案进行印刷，搭载2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，制作评价基板。
4.热疲劳试验在以下条件下实施。使用3中制作的评价基板，利用串联电路随时测定电阻。使用ESPEC Corp.制造的冷热冲击装置TSA101LA在-40℃、+125℃的环境下分别反复使其负荷10分钟，将电阻值超过15Ω的时刻视为断裂，记录热疲劳循环次数。
5.落下冲击中也使用与热疲劳试验同样的评价基板，在下述条件下实施落下冲击试验。试验方法是对于评价基板使用专用夹具将基板两端固定于自基座起提高10mm的位置上。按照JEDEC标准，反复施加加速度1500G的冲击，将自初始电阻值上升至1.5倍的时刻视为断裂，记录落下次数。
表1的实施例2由于Ag、Cu、Ni的含量为最佳值的范围内，因此未熔合、耐热疲劳性、耐落下冲击性均得出优异的结果。图4为实施例2的接合界面化合物层，可知在BGA电极9和焊料球5的接合部形成了薄的Cu6Sn5的金属间化合物层。
比较例1、4、11中的Ag含量超过2.9质量％地含有的焊料球合金组成虽然对热疲劳、未熔合发挥了改善效果，但是对于落下冲击而言Ag含量没有取得最佳，因此未得到耐性，落下次数低于20次，作为改善是不充分的。
另外，关于比较例2、3、9、12、14，Ag含量低于1.6质量％，因此失去对热疲劳的耐性，循环次数未到达1500次。进而由于Ag含量不足造成的润湿性降低，未熔合的发生数量超过10，得到了丧失抑制效果的结果。
进而，比较例5、6、7、8虽然选择了最佳的Ag含量，但是未实现Cu和Ni含量的最优化，因此结果没有兼备对未熔合、落下冲击的改善效果。图5为比较例6的接合界面化合物层，已知形成了较厚的Cu6Sn5的金属间化合物层。
作为结论，对于包含1.6～2.9质量％Ag、0.7～0.8质量％Cu、0.05～0.08质量％Ni、余量Sn的焊料组成，可得到抑制未熔合、且兼具对热疲劳和落下冲击这两者的改善效果的焊料合金。
产业上的可利用性
根据本发明，提供具有抑制未熔合的效果，并且无论对于Cu电极(Cu-OSP电极、在Cu上涂布有水溶性助焊剂)而言、还是对于Ni电极(电解Ni/Au电极、无电解Ni/Pd/Au电极)而言耐热疲劳性和耐落下冲击性两者均优异的电极用焊料球。抑制未熔合可实现制造上的初始不良的减少。另外，一直以来需要根据产品的要求特性来选择焊料组成，但是通过具有落下冲击和热疲劳这两特性的耐性，还能够拓展至向自便携设备至电脑设备、车载之类的广泛领域、以及当今取得急速发展的移动PC之类的新兴领域。
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 未熔合处
8 妨碍熔合的化合物
9 BGA侧电极
10 Cu6Sn5的金属间化合物层

Claims (11)

1.一种无铅焊料球，其为在具有选自电解Ni/Au电极、无电解Ni/Pd/Au电极、Cu-OSP电极中的电极的BGA、CSP用的模块基板的背面作为电极用途而设置的焊料球，其用于形成焊接到设有焊膏的安装基板上的焊料凸块，所述无铅焊料球的焊料组成包含Ag1.6～2.9质量％、Cu0.7～0.8质量％、Ni0.05～0.08质量％、余量Sn。
2.根据权利要求1所述的无铅焊料球，其中，所述焊料组成为包含Ag1.9～2.3质量％、Cu0.7～0.8质量％、Ni0.05～0.08质量％、余量Sn的焊料组成。
3.根据权利要求1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％添加有1种以上选自Fe、Co、Pt的元素。
4.根据权利要求2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％添加有1种以上选自Fe、Co、Pt的元素。
5.根据权利要求1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％添加有1种以上选自Bi、In、Sb、P、Ge的元素。
6.根据权利要求2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％添加有1种以上选自Bi、In、Sb、P、Ge的元素。
7.根据权利要求1～6中的任一项所述的无铅焊料球，其中，所述焊料球具有直径为0.1mm以上的直径。
8.根据权利要求1～6中的任一项所述的无铅焊料球，其中，所述焊料球具有直径为0.3mm以上的直径。
9.根据权利要求1～6中的任一项所述的无铅焊料球，其中，所述焊料球具有直径为0.5mm以上的直径。
10.根据权利要求1所述的无铅焊料球，其中，在所述无铅焊料球中，未熔合试验中的未熔合的发生数量为0。
11.一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，所述焊料凸块是朝下地焊接到设有焊膏的安装基板上的焊料凸块，所述方法使用权利要求1～10中的任一项所述的焊料球进行焊接。
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US20180005970A1 (en) 2018-01-04
US20150221606A1 (en) 2015-08-06
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US20190088611A1 (en) 2019-03-21
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KR20140015242A (ko) 2014-02-06
PH12014502831B1 (en) 2015-02-02
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