CN104690440A - 无铅焊料、焊料膏和半导体器件 - Google Patents

无铅焊料、焊料膏和半导体器件 Download PDF

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CN104690440A
CN104690440A CN201410725376.9A CN201410725376A CN104690440A CN 104690440 A CN104690440 A CN 104690440A CN 201410725376 A CN201410725376 A CN 201410725376A CN 104690440 A CN104690440 A CN 104690440A
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China
Prior art keywords
weight
lead
solder
scope
free solder
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Inventor
洪性在
金槿铢
李昌祐
方政丸
高溶浩
李爀模
张宰源
具滋显
文晶琸
李荣佑
洪湲植
金辉中
李在洪
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Korea Advanced Institute of Science and Technology KAIST
MK Electron Co Ltd
Korea Electronics Technology Institute
Academic Cooperation Foundation of Hoseo University
Korea Institute of Industrial Technology KITECH
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Korea Advanced Institute of Science and Technology KAIST
MK Electron Co Ltd
Korea Electronics Technology Institute
Academic Cooperation Foundation of Hoseo University
Korea Institute of Industrial Technology KITECH
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Publication of CN104690440A publication Critical patent/CN104690440A/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
    • 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
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B23K35/025—Pastes, creams, slurries
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    • 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
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/362—Selection of compositions of fluxes
    • 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
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    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/36—Electric or electronic devices
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Abstract

所提供的是无铅焊料、焊料膏和半导体器件，并且更具体地，一种无铅焊料，所述无铅焊料包含在约0.1重量％至约0.8重量％的范围内的Cu，在约0.001重量％至约0.1重量％的范围内的Pd，在约0.001重量％至约0.1重量％的范围内的Al，在约0.001重量％至约0.1重量％的范围内的Si，以及Sn和不可避免的杂质作为余量，焊料膏和半导体器件包括所述无铅焊料。所述的无铅焊料和所述焊料膏是环境友好的并且具有高的高温稳定性和高可靠性。

Description

无铅焊料、焊料膏和半导体器件
相关申请
本申请要求2013年12月4日在韩国专利局提交的韩国专利申请号10-2013-0149999的权益，其公开通过引用以其全部内容结合在此。
技术领域
一个或多个示例实施方案涉及无铅焊料、焊料膏和半导体器件。
背景技术
印刷电路板(PCB)已经在家用电器中广泛使用，如电视机、移动电话或计算机。最近，大量PCB在汽车中使用。对于在家用电器中使用的焊料，已经使用了大量Sn-Pb合金族产品。特别是，铅(Pb)充当决定Sn-Pb合金的可润湿性、强度和机械性质的成分。同样，因为在Sn-Pb合金中包含铅，焊料的熔点可以降低至183℃，并且因此，可以防止电子部件与半导体器件之间的焊接过程中出现的热损坏。
归因于与Pb相关的严格的环境规章，提出了无铅焊料合金，换言之，Sn-Ag-Cu的三元体系。然而，因为该三元体系对于氧化是弱的，并且具有低覆盖性和低可润湿性，所以可加工性差并且耐冲击性低。同样，该三元体系不适合于如在汽车的发动机室中的超过130℃的高温气氛，并且因为包含Ag而是昂贵的。
发明内容
一个或多个示例实施方案包括一种无铅焊料，所述无铅焊料是环境友好的，具有出色的高温稳定性，并且具有高可靠性。
一个或多个示例实施方案包括焊料膏，所述焊料膏是环境友好的，具有高的高温稳定性，并且具有高可靠性。
一个或多个示例实施方案包括半导体器件，所述半导体器件是环境友好的，具有高的高温稳定性，并且具有高可靠性。
另外的方面部分将在后面的说明书中地给出，并且部分将从说明书是显见的，或者可以通过本发明的实施方案的实施而学得。
根据一个或多个示例实施方案，无铅焊料包括：在约0.1重量％至约0.8重量％的范围内的Cu；在约0.001重量％至约0.1重量％的范围内的Pd；在约0.001重量％至约0.1重量％的范围内的Al；在约0.001重量％至约0.1重量％的范围内的Si；以及Sn和不可避免的杂质，所述Sn和不可避免的杂质为余量。
无铅焊料还可以包含选自由以下各项组成的组的至少一种元素：在约0.001重量％至约0.05重量％的范围内的Ge，在约0.001重量％至约0.05重量％的范围内的Bi，在约0.001重量％至约0.05重量％的范围内的P，和在约0.001重量％至约0.05重量％的范围内的In。
无铅焊料可以具有在约45％至约65％的范围内的伸长率。
根据一个或多个示例实施方案，焊料膏包含在5至25重量份/100重量份的无铅焊料的范围内的焊剂，其中所述100重量份的无铅焊料具有上述组成。
根据一个或多个示例实施方案，半导体器件包括：基板，在所述基板中形成有多个第一端子；半导体芯片，所述半导体芯片安装在基板上并且包括多个分别对应于第一端子的第二端子；和多个焊料凸块(solder bump)，所述焊料凸块分别连接相应的第一和第二端子，其中所述焊料凸块包含：在约0.1重量％至约0.8重量％的范围内的Cu，在约0.001重量％至约0.1重量％的范围内的Pd，在约0.001重量％至约0.1重量％的范围内的Al，在约0.001重量％至约0.1重量％的范围内的Si，以及Sn和不可避免的杂质，所述Sn和不可避免的杂质为余量。
附图说明
从实施方案的以下叙述，结合附图，这些和/或其他方面将变得显见并且更容易地理解，其中：
图1是根据本发明原理的实施方案的半导体部件的截面图；
图2A至2D是显示根据本发明原理分别根据比较例和实施例1至3制造的无铅焊料的可润湿性的测试结果的照片。
具体实施方式
现在将详细参考实施方案，其实例在附图中示出。在这方面，本发明的实施方案可以具有不同的形式并且不应当解释为限定于本文给出的说明。提供这些实施方案以使得本公开将是彻底和完整的，并且将本发明的范围完整地传递给本领域技术人员。相同的附图标记贯穿全文是指相同的元件。在附图中，示意性地画出多个元件和区域。因此，根据本发明原理的实施方案不限于附图中描绘的相对尺寸和空隙。
将明白的是，虽然术语‘第一’、‘第二’等在本文可以用于描述多种元素，这些元素不应当受这些术语限制。这些术语仅用于使用将一种元素与另一种区分。例如，可以将第一元素称为第二元素，并且，类似地，可以将第二元素称为第一元素，而不脱离示例实施方案的范围。
本文使用的术语仅用于描述实施方案的目的，并且不意图是示例实施方案的限定。除非上下文明确地另外指出，单数形式包括复数形式。还应当明白的是，当在本文使用时，术语″包含″和/或″包括″是指所述特征、整数、步骤、操作、元素和/或组分的存在，但是不排除一个或多个其他特征、整数、步骤、操作、元素、组分和/或它们的组的存在或加入。
除非另外定义，本文使用的所有术语包括技术和科学术语具有与本发明所属领域技术人员通常理解的相同的含义。还应当明白的是术语，如字典中通常使用的那些定义，应当解释为具有与它们在相关领域的内容中的含义一致的含义，并且除非在本文明确定义，将不以理想化的或过度正式的含义解释。
在根据本发明原理的实施方案中，重量通过合金的总重量中相应的组分的重量百分比重量％指明。
根据本发明原理的实施方案的无铅焊料可以包括Cu、Pd、Al和Si，使用Sn作为主要组分。更具体地，根据本发明原理的实施方案的无铅焊料可以包含在约0.1重量％至约0.8重量％的范围内的Cu，在约0.001重量％至约0.1重量％的范围内的Pd，在约0.001重量％至约0.1重量％的范围内的Al，在约0.001重量％至约0.1重量％的范围内的Si，以及Sn和不可避免的杂质，所述Sn和不可避免的杂质为余量。
这里，′主要组分′是指重量超过合金的总重量的50％的组分。同样，在根据本发明原理的实施方案的无铅焊料中，可以包含不可避免的杂质元素。
铜可以影响无铅焊料的抗拉强度。如果Cu含量过小，无铅焊料的抗拉强度可能不像想要的那样增加。如果Cu含量过大，无铅焊料可能硬化，并且因此，可能容易出现织构损坏。
同样，Cu可以影响无铅焊料的高温稳定性。如果Cu含量过小，无铅焊料可能是热学上弱的，并且因此，在高温损坏。如果Cu含量过大，可能产生Cu浮渣，并且因此，焊接可能是困难的。
根据本发明原理的实施方案的无铅焊料可以包含在约0.1重量％至约0.8重量％的范围内的Cu。根据本发明原理的实施方案的无铅焊料可以包含大约0.5重量％的Cu。
根据本发明原理的实施方案的无铅焊料可以包含在约0.001重量％至约0.1重量％的范围内的Pd。根据本发明原理的实施方案的无铅焊料可以包含在约0.005重量％至约0.05重量％的范围内的Pd。根据本发明原理的实施方案的无铅焊料可以包含大约0.01重量％的Pd。
Pd可以影响无铅焊料的抗拉强度。如果Pd含量过小，无铅焊料的抗拉强度可能不像想要的那样增加。同样，可能难以减少电极被无铅焊料的溶解。如果Pd含量过大，无铅焊料可能硬化，并且因此，可能容易出现织构损坏。而且，如果Pd含量过大，可能是不经济的。
根据本发明原理的实施方案的无铅焊料可以基本上不包含Ag。这里，″无铅焊料可以基本上不包含Ag″是指可以包含小量的Ag作为不可避免的杂质。
因为根据本发明原理的实施方案的无铅焊料基本上不包含Ag，根据本发明原理的实施方案的无铅焊料比现有技术的Sn-Ag-Cu无铅焊料更便宜。
根据本发明原理的实施方案的无铅焊料可以包含在约0.001重量％至约0.1重量％的范围内的Al。该无铅焊料可以包含在约0.01重量％至约0.05重量％的范围内的Al。该无铅焊料可以包含大约0.03重量％的Al。
Al可以影响无铅焊料的伸长率。如果Al含量过小，可能获得不了作为本发明原理的益处的伸长率上的增加。如果Al含量过大，同当Al含量过小的时候一样，可能减少伸长率。
根据本发明原理的实施方案的无铅焊料可以包含在约0.001重量％至约0.1重量％的范围内的Si。无铅焊料可以包含在约0.001重量％至约0.02重量％的范围内的Si。无铅焊料可以包含大约0.01重量％的Si。
如果Si含量过小，可能实现不了发明原理的益处，即可润湿性和伸长率上的增加。如果Si含量过大，晶粒由于析出而粗化，且降低机械特征。
无铅焊料可以具有在约45％至约65％的范围内的伸长率。如果无铅焊料的伸长率过低，脆性明显地增加，并且因此，可能对外部冲击是弱的，并且可靠性降低。如果无铅焊料的伸长率过高，抗拉强度可能不足。
根据本发明原理的实施方案的无铅焊料还可以包含选自由以下各项组成的组的至少一种元素：Ge、Bi、P和In。以上元素可以帮助无铅焊料的可润湿性上的增加。
Ge的含量可以在约0.001重量％至约0.05重量％的范围内。Bi的含量可以在约0.001重量％至约0.05重量％的范围内。P的含量可以在约0.001重量％至约0.05重量％的范围内。In的含量可以在约0.001重量％至约0.05重量％的范围内。
无铅焊料是环境友好的并且归因于其高熔点具有出色的高温稳定性，并且归因于高可润湿性和伸长率具有高可靠性。同样，因为无铅焊料不包含Ag，无铅焊料可以以低成本制造。
根据本发明原理的一个方面，提供一种焊料膏。焊料膏可以包含5至25重量份/100重量份的无铅焊料之间的焊剂。
焊剂可以是，例如，中等活性松香(RMA)型，并且可以在室温处于液体状态。不过，根据本发明原理的焊剂不限于此。
无铅焊料可以是上述无铅焊料。因此，将不重复关于无铅焊料的叙述。
无铅焊料和焊剂的混合物可以在室温形成膏状相。
除了以上之外，无铅焊料可以以焊料条状态或焊料球状态提供。
根据本发明原理的一个方面，提供一种半导体器件100。图1显示根据本发明原理的实施方案的半导体器件100。
参考图1，提供基板110，其中在其中形成多个第一端子112。基板110可以是例如印刷电路板(PCB)或柔性印刷电路板(FPCB)。
第一端子112可以是凸块可以结合至其上的凸块焊点，并且可以包括单个金属层或具有其中层叠多个金属的结构。同样，第一端子112可以由Cu、Al、Ni或这些金属中的两种以上的合金形成，但是不限定于此。
半导体芯片120可以安装在基板110上，其中半导体芯片120具有分别对应于第一端子112的多个第二端子122。第二端子122可以是，例如，闪存、相变化RAM(PRAM)、阻变RAM(RRAM)、铁电RAM(FeRAM)或磁RAM(MRAM)，但是不限定于其中。闪存可以是NAND闪存。半导体芯片120可以形成为单个半导体芯片或多个半导体芯片的层叠体。同样，半导体器件120自身可以是单个半导体芯片或者可以是半导体封装，其中半导体芯片安装在封装基板上，并且半导体芯片通过包封部件密封。
第一端子112和第二端子122可以通过焊料凸块130连接。在这点上，焊料凸块130可以具有上述组成。
当基板110和半导体器件120通过使用焊料凸块130连接时，因为不包含铅，半导体器件120是环境友好的，并且归因于其高温稳定性和高可润湿性，半导体器件120可以用于汽车半导体。
根据本发明原理的方面，提供一种无铅焊料和焊料膏，并且无铅焊料是环境友好的，具有出色的高温稳定性，和高可靠性。
这里，发明原理的构造和益处将参考实际实施方案和比较例详细描述。然而，应明白的是，下面描述的实施方案仅使得本领域技术人员能够清楚地理解本发明原理并且不限制本发明原理的范围。
<差示扫描量热法(DSC)分析>
在制备具有如表1中所示的组成的5mg的样品之后，在氮氛下进行DSC分析。以5℃/分钟的速率升高温度。
[表1]
组合物(重量％) 起始温度(℃) 起始温度(℃) 过冷(℃)
Sn Cu Pd Al Si (加热，T1) (冷却，T2) (ΔT＝T1-T2)
实施例1 余量 0.5 0.01 0.01 0.001 229.9 227 2.9
实施例2 余量 0.5 0.01 0.03 0.004 231 227 4
实施例3 余量 0.5 0.01 0.05 0.007 232.2 227 5.2
实施例4 余量 0.5 0.01 0.08 0.015 233.7 226.8 6.9
比较例1 余量 0.5 - - - 229.5 227.9 1.6
作为结果，如表1中所示，起始温度(onset temperature)在加热过程中在约230℃至约234℃的范围内，并且在冷却过程中为大约227℃。换言之，根据实施方案1在4的无铅焊料具有与根据现有技术的Sn-Cu系焊料相似的熔点。同样，其熔点比具有Sn/3％-Ag/0.5％-Cu的组成的传统无铅焊料的熔点(217℃)高得多，并且因此，提高了出色的高温稳定性。
<可润湿性分析>
在将具有500μm的直径的焊料球在250℃回流90秒之后，通过测量在铜基板上的接触角评价可润湿性。使用RMA型焊剂，并且结果总结在表2中。同样，比较例1和实施例1至3的结果分别在图2A至2D中示出。换言之，图2A显示比较例1的结果，图2B显示实施方案1的结果，图2C显示实施方案2的结果，并且图2D显示实施方案3的结果。
[表2]
如表2中所示，在实施例1至3的情况下，接触角以及，因此，可润湿性与比较例1的那些相似。同样，所看出的是可润湿性通过Ge、Bi、P和In的加入提高。
<焊料膏的制造>
在通过使用真空气体雾化器制造各自具有如实施例1至12和比较例1至5中所示的组成的粉末之后，通过使用筛获得具有在约20μm至约38μm的范围内的直径的4型粉末(powders of type-4)。在这一点，熔融温度为550℃并且使用氩气。
之后，在加入12重量份/100重量份粉末的用于膏的RMA型焊剂之后，通过将粉末以1,000rpm的速度通过使用膏混合器混合3分钟30秒制造焊料膏。
<焊料条和焊料球的制造>
具有如实施例1至12和比较例1至5中所示的组成的合金焊料条通过使用真空脱气合金器件制造。在这一点，处理温度为500℃。同样，在进行鼓泡过程和真空脱气过程以制造合金焊料条之后，轻敲(tap)所得到的产品。
同样，使用所制造的合金焊料条制造具有0.3mm的直径的焊料球。
<伸长率的测量>
如表3中所示，对于所制造的焊料球测量焊料球的伸长率。焊料球的伸长率基于ASTM E8通过使用Instron Corp.的产品Universal TestingMachine 3300测量。
[表3]
如表3中所示，当Al含量超过0.1重量％时(比较例2)，伸长率可能达不到40％。同样，当Al含量低于0.001重量％时(比较例3)，伸长率与其中不包含Al的比较例1的水平相似。
可以看出，当Si含量超过0.1重量％时(比较例4)，伸长率可能达不到40％。当Si含量低于0.001重量％时(比较例5)，伸长率与其中不包含Si的比较例1的伸长率相似。
虽然参考附图描述了一个或多个示例实施方案，本领域技术人员将明白的是其中可以在形式和细节上进行多种改变而不脱离由以下权利要求定义的本发明原理的精神和范围。

Claims (7)

1.一种无铅焊料，所述无铅焊料包含：
在约0.1重量％至约0.8重量％的范围内的Cu；
在约0.001重量％至约0.1重量％的范围内的Pd；
在约0.001重量％至约0.1重量％的范围内的Al；
在约0.001重量％至约0.1重量％的范围内的Si；以及
Sn和不可避免的杂质，所述Sn和不可避免的杂质为余量。
2.权利要求1所述的无铅焊料，其中所述无铅焊料是非Ag系焊料。
3.权利要求1所述的无铅焊料，所述无铅焊料还包含选自由以下各项组成的组的至少一种元素：在约0.001重量％至约0.05重量％的范围内的Ge，在约0.001重量％至约0.05重量％的范围内的Bi，在约0.001重量％至约0.05重量％的范围内的P，和在约0.001重量％至约0.05重量％的范围内的In。
4.权利要求1所述的无铅焊料，其中所述无铅焊料具有在约45％至约65％的范围内的伸长率。
5.权利要求1所述的无铅焊料，其中所述Al含量在约0.01重量％至约0.05重量％的范围内，并且所述Si含量在约0.001重量％至约0.02重量％的范围内。
6.一种焊料膏，所述焊料膏包含在5至25重量份/100重量份的无铅焊料的范围内的焊剂，其中所述100重量份的无铅焊料具有权利要求1至5中的任一项所述的组成。
7.一种半导体器件，所述半导体器件包括：
基板，在所述基板中形成有多个第一端子；
半导体芯片，所述半导体芯片安装在所述基板上并且包含多个分别对应于所述第一端子的第二端子；和
多个焊料凸块，所述焊料凸块分别连接相应的第一和第二端子，其中所述焊料凸块包含：在约0.1重量％至约0.8重量％的范围内的Cu，在约0.001重量％至约0.1重量％的范围内的Pd，在约0.001重量％至约0.1重量％的范围内的Al，在约0.001重量％至约0.1重量％的范围内的Si，以及Sn和不可避免的杂质，所述Sn和不可避免的杂质为余量。
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