CN108155167B - 焊料颗粒 - Google Patents

焊料颗粒 Download PDF

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Publication number
CN108155167B
CN108155167B CN201710456270.7A CN201710456270A CN108155167B CN 108155167 B CN108155167 B CN 108155167B CN 201710456270 A CN201710456270 A CN 201710456270A CN 108155167 B CN108155167 B CN 108155167B
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China
Prior art keywords
copper
solder
layer
free metal
metal layer
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CN201710456270.7A
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CN108155167A (zh
Inventor
安祐营
朴成岏
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Tetos Co Ltd
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Tetos 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
    • H—ELECTRICITY
    • 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
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3485—Applying solder paste, slurry or powder
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
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    • 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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Abstract

公开了一种焊料颗粒，所述焊料颗粒包括：塑料芯；形成在所述塑料芯的外表面上的无铜金属层；以及形成在所述无铜金属层上且含有不少于85重量％的锡的焊料层。因此，可以提供一种具有无铜金属层的焊料颗粒，所述焊料颗粒的强度和导电性优异，并且在回流过程等期间防止或最小化空隙的产生。

Description

焊料颗粒
技术领域
本发明涉及一种焊料颗粒及其制造方法。
背景技术
已经在将半导体芯片、电阻器芯片等小型电子部件安装在印刷线路板(PCB)上时使用焊料颗粒作为接合材料。随着集成电路近来的小型化，焊盘的尺寸或焊盘之间的间隔减小并且焊盘的数量增加，从而由于不必要的电接触而在元件中产生缺陷。
发明内容
因此，本发明旨在解决上述问题，并且本发明的一个目的是提供一种焊料颗粒，所述焊料颗粒可以防止在安装电子部件时由于减小的焊盘尺寸或焊盘之间窄的间隔而引起的接触不良，并且防止在回流过程等期间形成空隙。本发明的该目的仅为了举例说明的目的而给出，并不限制本发明的范围。
根据本发明的一个实施方案，提供了一种焊料颗粒，所述焊料颗粒包括：塑料芯；形成在所述塑料芯的外表面上的无铜金属层；以及形成在所述无铜金属层上且含有不少于85重量％的锡的焊料层。
无铜金属层和焊料层可以通过溅射工艺在一个室中依次形成。
无铜金属层可以包含镍和铬的合金，其中镍含量高于铬含量。
无铜金属层的厚度可以等于或小于焊料层的厚度的百分之一。
焊料颗粒还可以包括在焊料层的外表面上的保护层。
附图说明
根据以下结合附图对示例性实施方案的描述，本发明的上述和/或其他方面将变得明显并且更易于理解，其中：
图1是示意性地示出了根据本发明的一个实施方案的焊料颗粒的主视图；图2是图1所示的焊料颗粒的截面图；图3是根据本发明的另一个实施方案的焊料颗粒的截面图；
图4是根据比较例的焊料颗粒的截面图；
图5是示意性地示出了使用焊料颗粒的封装状态的截面图；图6是对图4的VI部分获取的截面图像；
图7是示意性地示出了制造根据本发明的一个实施方案的焊料颗粒的方法的流程图；图8是在该制造方法中使用的溅射装置的示意图；以及
图9是示意性地示出了制造根据本发明的另一个实施方案的焊料颗粒的方法的流程图。
具体实施方式
下面，将参照附图详细地描述本发明的实施方案，其中相同的附图标记指代相同的元件，并且根据需要避免重复性描述。
在以下实施方案中，术语“第一”、“第二”等用于区分元件而没有任何限制性目的，并且除非上下文另有明确指出，否则以单数使用的词包括复数。
参照图1至图3，焊料颗粒10包括：塑料芯11，在塑料芯11上的无铜金属层13，以及在无铜金属层13上的焊料层15。
塑料芯11是具有平滑的外表面的球形芯，并且包含电绝缘材料。塑料芯11是填充有电绝缘材料的实心球，与中空体的壳型芯不同。电绝缘材料可以包括绝缘树脂。绝缘树脂可以包括以下的至少一种：聚甲基丙烯酸甲酯(PMMA)、聚丙烯酸甲酯等丙烯酸类树脂；聚硅氧烷等硅树脂；聚乙烯、聚丙烯和聚苯乙烯等聚烯烃树脂。或者，绝缘树脂可以包含以下的至少一种：聚碳酸酯、聚砜、聚丁烯、聚酯、聚氨酯、苯乙烯丁二烯、聚醚砜、聚乙烯醇缩丁醛、聚乙烯醇缩甲醛、聚乙酸乙烯酯、苯乙烯二乙烯基苯、环氧类和酚类。根据一些可选实施方案，塑料芯11可以包含在耐热性和冲击强度方面优异的聚甲基丙烯酸甲酯(PMMA)。根据另一个可选实施方案，塑料芯11可以包含在热稳定性和高强度方面优异的硅。
无铜金属层13可以包含导电材料如金属材料，并且通过溅射工艺形成。金属材料可以包含以下之一：镍(Ni)和铬(Cr)的合金、钛(Ti)、钼(Mo)、不锈钢(SUS)、及其合金，并且可以形成为单层或多层。根据一个可选实施方案，无铜金属层13可以包含镍和铬的合金。在包含镍和铬的合金的无铜金属层13中，镍与铬的重量比可以在8:2至9.5:0.5的范围内选择。铬改善塑料芯11与焊料层15之间的粘附力。包含镍和铬的合金的无铜金属层13中的塑料芯11与焊料层15之间的粘附力比仅包含镍的无铜金属层中的塑料芯11与焊料层15之间的粘附力高约1.5倍或更多倍。如果铬的重量比例在上述范围内选择，则无铜金属层13完全覆盖塑料芯11的外表面而不会被剥离，并且改善塑料芯11与焊料层15之间的粘附力。如果铬的重量比例在上述范围之外选择，则无铜金属层13可能被剥离。换言之，无铜金属层13可能与塑料芯11部分分离。
此外，与仅包含镍的无铜金属层相比，包含镍和铬的合金的无铜金属层13在溅射过程期间形成为薄膜的效率更加改善。如果仅用磁性镍进行溅射过程，则无铜金属层13的薄膜的品质如厚度均匀性等可能劣化。在另一方面，如果用铬，即用镍和铬的合金进行溅射过程，则不仅可以改善通过溅射过程形成的薄膜的品质，而且可以如上所述改善塑料芯11与焊料层15之间的粘附力。
参照图4，根据比较例的焊料颗粒S包括在塑料芯1与焊料层5之间铜(Cu)层3。如果如图5所示将这种焊料颗粒S置于布线基底SUB与元件BCP(例如，球栅阵列(BGA)的半导体芯片封装)之间，然后进行回流，则布线基底和元件被连接。元件BCP可以包括基底BCP-S，安装在基底BCP-S上的半导体芯片BCP-C，以及设置在半导体芯片BCP-C上的成型树脂BCP-M。焊料颗粒S被置于基底BCP-S的端子T2与布线基底SUB的端子T1之间。
通过回流过程等，在焊料颗粒S的铜层3与焊料层5之间产生金属间化合物(Cu6Sn5)，从而在焊料颗粒S的界面上，即在铜层3与焊料层5之间的界面上产生柯肯达尔空隙(kirkendall void)Vd，如图6所示。
然而，根据本发明的上述实施方案，在塑料芯11与焊料层15之间形成无铜金属层13，因此未形成铜和锡的金属间化合物(Cu6Sn5)，从而不会在封装过程中产生空隙。此外，如上所述，无铜金属层13包含上述材料以改善塑料芯11与焊料层15之间的粘附力。
再参照图1至图3，焊料层15是基于锡(Sn)的无铅焊接材料，其含有不少于约85重量％的锡(Sn)。根据一些可选实施方案，焊料层15可以含有不少于约90重量％，例如约95重量％的锡(Sn)。
除锡(Sn)之外，焊料层15还可以含有银(Ag)、铜(Cu)、铋(Bi)、锌(Zn)和铟(In)的至少一种。如果焊料层15包含银(Ag)和铜(Cu)，则其可以含有比铜(Cu)更多的银(Ag)以降低熔点。例如，除锡(Sn)之外，焊料层15还可以含有约3.5重量％的银(Ag)和约0.5重量％的铜(Cu)，但这并不解释为限制本发明。
焊料层15通过溅射工艺形成。具体地，根据本发明的无铜金属层13和焊料层15通过溅射工艺在一个室中依次形成。这将在后面描述。
由于焊料层15通过溅射工艺形成在无铜金属层13的表面上，因此焊料层15可以具有基本平滑的外表面和均匀的厚度，以便不仅与无铜金属层13的表面紧密接触，而且基本上从由靶射出的材料(例如，焊接材料)中排除杂质(例如，有机材料)。例如，根据本发明的该实施方案的焊料层15明显不同于i)由于外表面上的多个导电颗粒(或突起物)而具有高表面粗糙度(即，不平坦的外表面)的“焊料层”，以及ii)通过如下电镀工艺而形成的“焊料层”，所述电镀工艺必然涉及来源于不可避免地包含在电镀组合物中的分散剂、酸度控制剂等的有机材料。
根据本发明的实施方案的具有塑料芯11的焊料颗粒10与由焊接材料制成的没有塑料芯的焊料颗粒不同。在没有塑料芯且含有不少于约85重量％的锡(Sn)的焊料颗粒的特定情况下，由于锡(Sn)具有高延展性，焊料颗粒容易变形。如果置于布线基底与元件(例如，BGA的半导体芯片封装)之间的焊料颗粒变形(例如，变形成椭圆形状)，则相邻的焊料颗粒可能彼此接触并因此电连接，从而导致接触不良。
然而，在根据本发明的一个实施方案的具有塑料芯11的焊料颗粒10中，塑料芯11防止或减小变形，并且分散和/或吸收由元件(例如，BGA的半导体芯片封装)的重量而产生的应力。
塑料芯11的直径R与焊料层15的厚度d3之比可以在0.5:1至5.2:1的范围内选择。塑料芯11的直径R可以在20μm至180μm的范围内选择。焊料层15的厚度d3可以在30μm至60μm的范围内选择。如果塑料芯11的直径R和焊料层15的厚度d3在上述范围内，则不仅可以执行焊料颗粒10用于电连接的基本功能，而且可以防止在具有细间距(例如，400μm)的电极的封装中由于焊料颗粒10变形而在相邻焊料颗粒10之间引起不必要的电接触。
无铜金属层13的厚度d1可以等于或小于焊料层15的厚度d3的百分之一。例如，无铜金属层13的厚度d1可以在0.1μm至0.5μm的范围内选择。根据一些可选实施方案，无铜金属层13的厚度d1可以在0.2μm至0.4μm的范围内选择。如果无铜金属层13的厚度d1在上述范围之外选择，则塑料芯11与焊料层15之间的粘附力可能劣化，并且限制减小焊料颗粒10的尺寸。
如图2和图3所示，焊料颗粒10包括直接接触并覆盖塑料芯11的外表面的无铜金属层13，以及直接接触并覆盖无铜金属层13的整个外表面的焊料层15。此外，焊料颗粒10还可以包括在焊料层15的外表面上的保护层17，如图3所示。
保护层17可以包含金属材料。例如，保护层17由无铜金属构成，其中金属材料可以包含以下之一：镍(Ni)和铬(Cr)的合金、钛(Ti)、钼(Mo)、不锈钢(SUS)、及其合金。根据一些可选实施方案，保护层17可以包含与无铜金属层13相同的材料。
保护层17防止焊料层15在制造和分配过程期间被污染。在封装过程期间，保护层17在其被置于布线基底与元件(例如，BGA的半导体芯片封装)之间时，被预定压力破坏。因此，焊料层15可以参与封装过程。为此，保护层17的厚度可以为0.3μm或更小。
图7是示意性地示出了制造根据本发明的一个实施方案的焊料颗粒的方法的流程图，并且图8是在该制造方法中使用的的溅射装置的示意图。
参照图1至图3以及图7和图8，准备塑料芯11(S10)。塑料芯11是指直径在约20μm至180μm的范围内选择的实心球形颗粒。将塑料芯11容纳在溅射装置的容器200中。由于以粉末形式提供多个塑料芯11，因此可以在溅射过程期间通过分离器(未示出)在容器200中将其混合。
可以对塑料芯11进行预处理，以便改善在下一过程中与无铜金属层13的粘附力，和/或以便从塑料芯11的表面除去各种污染物、水、静电等。关于塑料芯11的表面，这样的预处理过程可以包括例如等离子体处理和超声处理的至少一种。
在等离子体处理中，塑料芯11的表面在包含氩气、氧气和氮气中的至少一种的气氛下经受等离子体处理。在超声处理中，超声振动引起塑料芯11之间摩擦，从而从塑料芯11的表面除去多种污染物等。
然后，在一个室100中通过溅射过程依次形成无铜金属层13和焊料层15。此外，在同一室100中还通过溅射过程接着形成保护层17。
具体地，通过排气口105使室100处于真空，即具有内部真空状态。例如，室100的内部的真空度为约0.1毫托至10毫托，但这并不解释为限制本发明。然后，通过溅射过程(S20)在塑料芯11的外表面上形成无铜金属层13。
通过引入口106使室100充满氩气等惰性气体，并对第一靶310的阴极电极施加电力，由此产生等离子体。根据一个实施方案，可以以10sccm至500sccm的流速供应惰性气体，但这并不解释为限制本发明。供应到阴极电极的电力可以包括射频(RF)电力或直流(DC)电力。等离子体离子或中性粒子碰撞第一靶310的表面，因此从第一靶310分离的原子形成为层，即在塑料芯11的外表面上的无铜金属层13。无铜金属层13被形成为完全覆盖塑料芯11的外表面。此外，将阻隔屏400置于第一靶310与第二靶320之间以使得可以防止第二靶320在通过第一靶310形成无铜金属层13时被污染。
置于室100中的第一靶310包含无铜金属材料。无铜金属材料可以包含例如镍和铬的合金、钛、以及不锈钢(SUS)的至少一种。
根据一些可选实施方案，第一靶310可以包含镍和铬的合金，因此使用第一靶310形成的无铜金属层13也可以包含镍和铬的合金，其中镍含量可以高于铬含量。例如，在包含镍和铬的合金的无铜金属层13中，镍和铬的重量比可以在8:2至9.5:0.5的范围内选择。
如果仅用磁性镍进行溅射过程，则溅射过程的效率降低，并且因此无铜金属层13的薄膜的品质如厚度均匀性等劣化。在另一方面，根据本发明的一个实施方案，如果第一靶310包含铬，即由镍和铬的合金构成，则可以改善通过溅射过程形成的薄膜的品质，即改善无铜金属层13的品质。此外，如上所述，还可以改善塑料芯11与焊料层15之间的粘附力。
接下来，断开连接到第一靶310的阴极电极，然后向第二靶320的阴极电极供应电力，从而在无铜金属层13的外表面上溅射焊料层15(S30)。用于形成焊料层15的室100可以具有与用于形成无铜金属层13的室100相同的真空度。与上述过程类似，可以以10sccm至500sccm的流速供应惰性气体，但这并不解释为限制本发明。由于将阻隔屏400置于第二靶320与第一靶310之间，因此可以防止第一靶310在通过第二靶320形成焊料层15时被污染。
当接通第二靶320的阴极电极时，等离子体离子或中性粒子碰撞第二靶320的表面，并且从第二靶320分离的原子形成为层，即在无铜金属层13的外表面上的焊料层15。使用第一靶310的无铜金属层13的溅射过程和使用第二靶320的焊料层15的溅射过程在同一室100中依次进行。因此，防止在无铜金属层13与焊料层15之间形成除无铜金属层13和焊料层15的材料层之外的另一层(例如，氧化物层)。
第二靶320包含基于锡(Sn)的无铅焊接材料。例如，第二靶320含有不少于约85重量％的锡(Sn)。根据一些可选实施方案，第二靶320可以含有不少于约90重量％，例如约95重量％的锡(Sn)。
除锡(Sn)之外，第二靶320还可以含有银(Ag)、铜(Cu)、铋(Bi)、锌(Zn)和铟(In)的至少一种。如果第二靶320包含银(Ag)和铜(Cu)，则其可以含有比铜(Cu)更多的银(Ag)以降低熔点。例如，除锡(Sn)之外，第二靶320还可以含有约3.5重量％的银(Ag)和约0.5重量％的铜(Cu)，但这并不解释为限制本发明。
第二靶320的材料通过等离子体离子或中性粒子从第二靶320分离，并沉积在无铜金属层13的外表面上，从而形成焊料层15。如关于图1至图3所述的，焊料层15的厚度比无铜金属层13的厚度大100倍或更多倍。
如上所述，通过溅射工艺形成的焊料层15不一定包含来源于不可避免地包含在用于电镀工艺的电镀组合物中的各种分散剂、酸度控制剂等的有机材料。通过溅射法形成的焊料层15具有比通过电镀工艺形成的焊料层更致密的膜结构，从而减少或防止在封装过程期间由于元件的重量等产生的裂纹。
图9是示意性地示出了制造根据本发明的另一个实施方案的焊料颗粒的方法的流程图。参照图9，通过前述步骤S10至S30在塑料芯11上依次形成无铜金属层13和焊料层15，然后在焊料层15的外表面上溅射保护层17(S40)。
保护层17可以包含与无铜金属层13相同的材料。例如，在断开连接到第二靶320的阴极电极时，接通连接到第一靶310的阴极电极以产生等离子体，从而在焊料层15的外表面上形成保护层17。
当在封装过程期间将焊料颗粒10布置在布线基底与元件(例如，BGA的半导体芯片封装)之间时，保护层17保护焊料层15，并且由于元件的重量等而开裂，使得焊料层15可以在回流过程期间参与连接布线基底和元件。为此，保护层17的厚度可以小于焊料层15的厚度的百分之一。具体地，保护层17的厚度例如可以等于或小于0.4μm，或者例如可以等于或小于0.3μm。
尽管在图7和图9中未示出，但是可以在形成焊料层15或保护层17之后进行干燥焊料颗粒10的过程。在干燥过程中，可以在相对湿度为25％或更低(例如，相对湿度为5％至25％)和温度为50℃至80℃的条件下将焊料颗粒10干燥1小时至2小时。这样的干燥温度可以通过将温度从室温逐渐升高到特定温度来控制。
根据本发明的实施方案，提供了一种具有无铜金属层的焊料颗粒，所述焊料颗粒的强度和导电性优异，并且在回流过程等期间防止或最小化空隙的产生。当然，本发明的范围不限于这些效果。
虽然已经示出并描述了本发明的几个示例性实施方案，但是这些示例性实施方案仅用于举例说明的目的，并且本领域技术人员应理解，在不脱离本发明的原理和精神的情况下，可以对这些实施方案做出改变，本发明范围在所附权利要求及其等同物中限定。

Claims (4)

1.一种焊料颗粒，包括：
塑料芯；
无铜金属层，所述无铜金属层形成在所述塑料芯的外表面上；和
焊料层，所述焊料层形成在所述无铜金属层上并且含有不少于85重量％的锡；
其中所述无铜金属层包含镍和铬的合金，镍与铬的重量比在8:2至9.5:0.5的范围内。
2.根据权利要求1所述的焊料颗粒，其中所述无铜金属层和所述焊料层通过溅射工艺在一个室中依次形成。
3.根据权利要求1所述的焊料颗粒，其中所述无铜金属层的厚度等于或小于所述焊料层的厚度的百分之一。
4.根据权利要求1所述的焊料颗粒，还包括在所述焊料层的外表面上的保护层。
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