CN102892549B - 混合合金焊料膏 - Google Patents
混合合金焊料膏 Download PDFInfo
- Publication number
- CN102892549B CN102892549B CN201180022297.6A CN201180022297A CN102892549B CN 102892549 B CN102892549 B CN 102892549B CN 201180022297 A CN201180022297 A CN 201180022297A CN 102892549 B CN102892549 B CN 102892549B
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- alloy
- solder
- remaining
- powder
- cream
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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
- B23K35/025—Pastes, creams, slurries
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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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- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
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- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
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- 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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Abstract
焊料膏包括约60wt%至约92wt%之间的量的第一焊料合金粉末;大于0wt%并且小于约12wt%的量的第二焊料合金粉末;和助焊剂;其中第一焊料合金粉末包括第一焊料合金,其固相线温度高于约260℃;和其中第二焊料合金粉末包括第二焊料合金,其固相线温度低于约250℃。
Description
技术领域
本发明一般涉及焊料组合物,并且更具体而言,一些实施方式涉及高温焊接应用的焊料组合物。
相关技术描述
由电子组件的处理产生的铅被认为对环境和人类健康有害。规章逐渐禁止在电子互连和电子封装工业中使用含Pb焊料。已经广泛地研究替换传统低共熔Pb-Sn的无Pb焊料。SnAg、SnCu、SnAgCu和SnZn焊料正在变成用于半导体互连和电子工业中的主流焊料。但是,开发高温无Pb焊料代替常规高铅焊料即Pb-5Sn&Pb-5Sn-2.5Ag仍处在其初期。当组件被焊接在印刷电路板(PWB)上时,高温焊料用于保持组件中元件内的内部连接。
高温焊料的通常用途是用于芯片附着(die-attach)。在示例性方法中,通过使用高温焊料将硅芯片焊接在引线框架上形成组件。接着,被封装或未封装的硅芯片/引线框架组件通过焊接或机械固定附着至PWB。板可暴露于再多几次的回流工艺用于在板上表面安装其他电子器件。在进一步的焊接过程中,应当良好地保持硅芯片和引线框架之间的内部连接。这需要高温焊料经得起多重回流而没有任何功能故障。所以,为了与在工业中使用的焊料回流方案(profile)相容,高温焊料的主要要求包括(i)熔化温度约260℃和更高(根据典型的焊料回流方案),(ii)好的抗热疲劳性,(iii)高的热导率/电导率,和(iv)低成本。
目前,工业中没有可用的滴入式(drop-in)无铅替代物。但是,最近已经提议一些无铅焊料候选物用于高温芯片附着应用,比如(1)Sn-Sb,(2)Zn基合金,(3)Au-Sn/Si/Ge和(4)Bi-Ag。
Sb小于10wt%的Sn-Sb合金保持良好的机械性能而不形成大量的金属间化合物。但是它们的固相线温度不高于250℃,这不能满足260℃的抗回流要求。
包括低共熔的Zn-Al、Zn-Al-Mg和Zn-Al-Cu的Zn基合金的熔化温度高于330℃。但是,Zn、Al和Mg对氧的高亲和力造成在各种金属化表面饰面上的极差的湿润。提议为高温无铅替代焊料之一的Zn-(20-40wt%)Sn焊料合金的液相线温度高于300℃,但是固相线温度仅为约200℃。Zn-Sn焊料在约260℃时的半固体状态被认为在随后的回流期间在元件之间保持良好的互连。但是,当半固体焊料被挤压在封装的包装内并迫使半固体焊料流出时出现问题。这产生预料不到的功能故障的风险。Zn基焊料合金也将在金属化表面和焊料之间形成大量的IMC层。在随后的回流和操作期间,IMC层的存在及其剧烈生长也造成可靠性问题。
由两个金属间化合物组成的低共熔Au-Sn已经被实验显示为可靠的高温焊料,这是因为其熔化温度为280℃、良好的机械性能、高的电导率&热导率、和卓越的抗腐蚀性。但是,极高的成本限制了其在成本超过可靠性考虑因素的领域中的应用。
固相线温度为262℃的Bi-Ag合金满足高温芯片附着焊料的熔化温度要求。但是,存在几个主要问题:(1)在各种表面饰面上差的湿润性和(2)相关的源于差的湿润性的弱结合界面。
难熔的无铅焊料的熔化温度要求使得Sn-Sb和Zn-Sn焊料不合适。富Au焊料的极高成本限制其被行业认可。Zn-Al和Bi-Ag符合熔化温度要求和合理的低成本。但是,由于对氧的高亲和力(在Zn-Al焊料系统中)或由于焊料和基底金属化之间差的反应化学(在Bi-Ag焊料系统中或甚至一些含铅焊料比如Pb-Cu和Pb-Ag系统中),它们差的湿润性使得这些难熔的焊料难以在工业中使用,因为差的湿润性导致的弱结合强度。但是,BiAg和ZnAl的期望的高熔化温度仍使得它们适合作为高温无铅焊料的候选物。
如上所述,焊料差的湿润性源于(1)差的反应化学或(2)焊料的氧化。弱结合通常与差的湿润性相关。例如,Bi基焊料在不同金属化表面上的差的湿润性主要由于Bi和基底材料(即Cu)之间差的反应化学或Bi在回流期间的氧化。已经开发了Ge掺杂的BiAg,目标在于在熔化期间防止合金表面上形成过多的浮渣。但是,该掺杂将不改变Bi和基底金属化表面饰面之间的反应化学。Bi和Cu将不在Bi/Cu界面形成IMC,其是差的湿润性和弱结合界面的主要原因。Bi和Ni将在Bi/Ni界面形成IMC层,但是脆性的IMC(Bi3Ni或BiNi)削弱接缝强度,因为裂缝总是沿着Bi3Ni和焊料基体之间的界面或BiNi和Ni基底之间的界面生长。因此,Bi和基底材料之间的反应化学导致差的湿润性和弱结合强度。
已经做出努力以通过将额外的元素在焊料中合金化改性焊料合金和金属化表面饰面之间的反应化学。但是,合金化通常与一些预料不到的性能损失有关。例如,与Bi相比,Sn具有与基底更好的反应化学。但是,直接将Sn合金化进入BiAg(其中Ag目的在于增加热导率/电导率)可引起(1)熔化温度的显著降低或(2)合金中Ag3Sn IMC的形成。如果在回流期间它们没有足够的时间溶解在熔化的焊料中,这将不改善Sn与基底金属之间的反应化学。因此,直接将元素合金化进入焊料,比如Sn直接进入Bi-Ag合金显示最小的改进。
发明实施方式简述
本发明要求保护设计和制备混合合金焊料膏的新技术,其提供来自组成的合金粉末的结合优势。在一些实施方式中,混合合金焊料膏适合高温焊料应用,比如芯片附着,因为组分提供期望的优势,包括改善的反应化学、良好控制的IMC层厚度、和因此来自第二合金的增强的可靠性和来自第一合金的高熔化温度和良好的热导率/电导率。本发明也提供制备混合合金焊料膏的方法和用该混合合金焊料膏连接电子元件或机械部件的方法。
该发明的技术提供设计混合合金粉末膏的方法,其中添加剂粉末存在于膏中以在相对较低的温度下或与第一合金焊料粉末的熔化一起改善反应化学。在一些实施方式中,混合合金粉末膏包括两种或多种合金粉末和助焊剂。膏中的合金粉末由作为多数的一种焊料合金粉末和作为少数的添加剂合金粉末组成。添加剂提供卓越的化学以在基底的各种金属化表面饰面即通常使用的Cu和Ni表面饰面等上湿润。
在一些实施方式中,添加剂将在多数焊料熔化之前或与多数焊料的熔化一起熔化。熔化的添加剂将在部分或完全熔化的第一合金之前或与其一起在基底上湿润并粘附至基底。添加剂被设计以支配IMC沿着基底金属化表面饰面的形成并在回流过程期间完全被转化成IMC。IMC层的厚度将因此被膏中的添加剂的量良好地控制,因为在IMC形成中添加剂起支配作用。在一些实施方式中,第一合金焊料将对在添加剂和基底之间形成的IMC层具有强的亲和力。该强的亲和力将增强焊料体和IMC之间的结合强度。因此,期望的反应化学和良好控制的IMC层厚度不仅改善湿润性能也增强与湿润性能相关的结合强度。
结合附图,由下列详细说明,本发明的其他特征和方面将变得显而易见,所述附图通过举例的方式图解说明根据本发明实施方式的特征。该简述不意在限制本发明的范围,该范围仅由所附的权利要求限定。
附图简述
参考下列附图详细描述根据一个或多个各种实施方式的本发明。仅仅为了图解的目的提供附图并且仅仅描述本发明典型的或示例性的实施方式。提供这些附图以有助于读者理解本发明并且不应认为限制本发明的宽度、范围或应用。应当注意,为了清楚和容易图解,这些附图没有必要按照比例绘制。
图1图解根据本发明的实施方式实施的回流焊方法。
图2显示在Cu试样和合金42试样上由90wt%Bi10.02Ag3.74Sn+10wt%助焊剂组成的实例焊料膏的湿润性能。
图3显示在Cu试样和合金42试样上由84wt%Bi11Ag+6wt%Bi42Sn+10wt%助焊剂组成的混合合金粉末焊料膏的实例的湿润性能。
图4显示在Cu试样和合金42试样上由84wt%Bi 11Ag+6wt%52In48Sn+10wt%助焊剂组成的混合合金粉末焊料膏的实例的湿润性能。
图5是由84wt%Bi 11Ag+6wt%Sn 15Sb+10wt%助焊剂组成的混合合金粉末焊料膏的DSC图。
图6是由84wt%Bi 11Ag+6wt%Sn3.5Ag+10wt%助焊剂组成的混合合金粉末焊料膏的DSC图。
图7是由84wt%Bi 11Ag+6wt%Bi42Sn+10wt%助焊剂组成的混合合金粉末焊料膏的DSC图。
图8A和B是在Cu和Ni试样上混合合金粉末焊料膏制成的接缝的横截面图像。混合合金粉末膏由84wt%Bi 11Ag+6wt%Sn3.5Ag+10wt%助焊剂组成。
附图不打算是穷尽性的或将本发明限制在所公开的准确形式。应当理解,本发明可通过修改和改变实施,并且本发明仅被权利要求及其等价物限制。
发明实施方式详述
本发明涉及包括不同焊料合金在助焊剂中的混合物的焊料膏。两种或多种焊料合金或金属被并入助焊剂材料。第一焊料合金或金属(“第一合金”)将在回流期间形成焊接缝的主体。根据与金属基底的反应化学或对第一合金的亲和力选择剩余的第二焊料合金或金属或进一步的额外焊料合金或金属(“第二合金”)。第二合金的熔化温度Tm(B)低于第一合金的熔化温度Tm(A)。在回流期间,第二合金首先熔化,并蔓延至基底上。当第一合金熔化时,第二合金的存在有助于将熔化的第一合金置于基底上。第二合金设计用于完全转化成IMC,在最终的接缝中产生最少的低熔点相或不存在低熔点相。
膏中的添加剂改进回流期间的反应化学、改善湿润性、控制IMC的厚度和因此增强结合强度。除了用于高温无铅焊接的具有期望的湿润性和可靠性的焊料外,该设计方法还可扩大到其中使用差湿润性焊料的许多其他焊接应用。例如,Pb-Cu合金具有高熔化温度但在各种金属基底上具有差的湿润性。因此,它们难以在焊接中使用。利用本发明,少的添加剂,比如Sn或含Sn合金,将帮助Pb-Cu湿润各种金属表面。但是,如果Sn在Pb-Cu中仅仅是合金化,Cu6Sn5IMC形成将降低来自Sn的反应化学。在焊料中合金化更大量的Sn将显著降低Pb-Cu的熔化温度,这是不期望的。
图1图解使用根据本发明实施方式的混合焊料膏的回流方法。混合焊料膏包括悬浮在助焊剂中的第一合金焊料颗粒118和第二合金焊料颗粒115。在一些实施方式中,根据其对基底或对许多常用基底的卓越反应化学选择第二合金。混合焊料膏施加至基底124。(为了方便说明,从图中省略了助焊剂。)
在回流期间,组件的温度升高超过第二合金的熔化温度Tm(B)。第二合金熔化并且在基底124上并围绕仍为固体的第一合金颗粒118蔓延112。第二合金的卓越表面反应化学将有助于熔化的焊料合金112在基底124上的湿润。这导致在熔化的第二合金112和基底124之间形成IMC层109。因此,IMC层主要由初始膏中第二合金115的量控制。
另外,设计第二合金以对第一合金具有良好的亲和力。该亲和力可由下列确定(1)第一合金和第二合金之间负的混合焓或(2)由来自第一和第二合金的组成元素组成的低共熔相的形成。在一些实施方式中,该亲和力导致一些第一合金118溶解在熔化的第二合金112中,形成第一和第二合金的混合物106。
随着温度升高超过第一合金的熔化温度Tm(A),第一合金完成熔化,形成第一和第二合金的溶液103,其湿润IMC层109。随着组件保持在Tm(A)之上,第二合金从溶液103中去除,增加IMC层109,并留下熔化的第一合金100。在一些实施方式中,除了形成IMC层109,来自第二合金的过量组分还可与来自第一合金的组分一起并入IMC。第一合金和第二合金之间的亲和力有助于改善第一合金100至IMC层109上的湿润性,从而增强结合强度。
随着组件冷却,焊料凸块131或接缝由结合至IMC 109的基底124组成,所述IMC109结合至凝固的第一合金。凝固之后,获得具有改善的结合界面的均质焊接缝。
即使当单一焊料合金由第一和第二焊料合金的元素组成时,由使用混合焊料膏产生的焊接缝显示使用包含单一焊料合金的焊料膏的大的改善。图2图解使用由90wt%Bi10.02Ag3.74Sn+10wt%助焊剂组成的焊料膏分别在Cu基底200和合金42基底205上形成的焊料凸块201和207。如这些结果显示的,使用单一焊料合金发生显著的反润湿202和206。相比之下,图3图解使用混合焊料膏分别在Cu基底210和合金42基底215上形成的焊料凸块211和216,所述混合焊料膏由84wt%Bi11Ag+6wt%Bi42Sn+10wt%助焊剂组成。如这些结果显示的,混合焊料膏的使用显示一点反润湿至没有可见的反润湿。
在一种实施方式中,混合焊料膏包括BiAg作为第一合金和SnSb作为第二合金。在第二合金中,由于Sn相对于Bi与各种基底更卓越的反应化学而选择Sn。SnSb比BiAg具有更低的熔化温度。根据二元相图,Sn和Bi显示负的混合焓并在宽的组成范围内形成低共熔相。Sb和Bi也显示负的混合焓以及对彼此的无限溶解性。在回流期间,SnSb首先熔化并在基底表面上形成含Sn的IMC层。当温度达到超过BiAg的熔化温度时,膏中的所有合金粉末熔化。Bi和Sn/Sb之间的良好亲和力确保熔化的Bi在含Sn的IMC层上的良好粘附。另外,第一合金中Ag的存在可将任何多余的Sn转化成存在于焊料体中的Ag3Sn IMC。因此,因为通过形成(1)焊料和金属基底之间的IMC层和(2)BiAg焊料凸块内部的Ag3Sn,Sn被完全消耗,留下最少量的低熔点BiSn相或没有留下低熔点BiSn相。
图5图解了由使用84wt%Bi 11Ag+6wt%Sn15Sb+10wt%助焊剂产生的焊接缝的DSC曲线。顶部曲线图解了在陶瓷试样上回流之后的热流曲线。在约138℃的尖峰说明第二合金的存在。底部曲线图解在Cu试样上回流之后的膏的热流曲线。底部曲线中该尖峰的缺少证实BiAg+SnSb系统中低熔点相的消失。图6图解在BiAg+SnAg系统中低熔点相的消失。图6的实验在陶瓷和Cu试样上使用84wt%Bi11Ag+6wt%Sn3.5Ag+10wt%助焊剂,如在图5中。图7图解在BiAg+BiSn系统中的消失。图7的实验在陶瓷和Cu试样上使用84wt%Bi11Ag+6wt%Bi42Sn+10wt%助焊剂,如在图5和6中。在图7中,图解陶瓷上的焊料回流之后热流曲线的顶部曲线显示没有低熔点相。这可能是由于混合焊料膏中少量的反应试剂Sn和Sn与Ag之间的高亲和力,导致第二合金的Sn与第一合金的一些Ag一起并入最终焊料凸块的IMC中。
图8是使用由84wt%Bi 11Ag+6wt%Sn3.5Ag+10wt%助焊剂组成的混合焊料膏产生的焊接缝的显微图。在该实例中,混合焊料膏被施加至Cu试样300。在Cu 300和第二合金之间形成IMC 301。该IMC 301的大小主要取决于膏中第二合金的量。在图解的实例中,6wt%的第二合金Sn3.5Ag产生仅仅几微米厚的IMC。焊接缝的大部分由富含Bi的相302中的Ag 303组成。在150℃下老化2周不明显增加IMC厚度。相比之下,Bi和Cu不形成金属间化合物,所以Bi11Ag单独形成弱的结合,因为在焊料和基底之间不存在IMC层。
在本发明的一个实施方式中,设计混合焊料膏的方法包括根据最终焊接缝的期望特性选择第一合金,并且然后根据可用的基底和与所选择的第一合金的亲和力选择第二合金。第一合金、第二合金和助焊剂的相对量可根据多种因素确定,比如期望的IMC层厚度、需要的施加条件和回流方法。IMC层厚度与焊料膏中第二合金的量、回流曲线和施加之后的老化条件相关。可接受的IMC层厚度可随着不同的应用条件和不同的IMC组成变化。例如,对于Cu6Sn IMC层,10微米可以是大约可接受的厚度。
随着膏中第二合金的量增加,在最终的接缝中可具有低熔点相剩余。如果焊料膏中第二合金的量降低,可能难以实现期望的湿润性能。随着第二合金的量降低,良好的湿润需要使用更大总量的膏印刷在或分散在基底上。但是,增加膏的总量可能干扰焊接包装的几何约束。
对于高温焊料应用,第一合金必须选自各种高熔点焊料合金。在一些实施方式中,使用固相线温度为约258℃和更高的富含Bi的合金,即Bi-Ag、Bi-Cu和Bi-Ag-Cu。第二合金(或添加剂)选自这样的合金,其已经显示卓越的化学以在各种金属化表面饰面上湿润并粘附至各种金属化表面饰面以及对熔化的Bi良好的亲和力。
在这些实施方式中,第二合金将在富含Bi的合金熔化之前或与富含Bi的合金一起熔化并且然后容易地在基底上湿润并粘附至基底。同时,Bi和第二合金之间的良好的亲和力将提供良好的湿润。所以,Sn、Sn合金、In和In合金被选择作为第二合金。基于所选择的第二合金的熔化温度,已经分成3组。组A包括固相线温度在约230℃和250℃之间的添加剂合金,即Sn、Sn-Sb、Sn-Sb-X (X=Ag、Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt和Zn)合金等。组B包含固相线温度在约200℃和230℃之间的焊料合金,包括Sn-Ag、Sn-Cu、Sn-Ag-X (X=A1、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt、Sb和Zn)和Sn-Zn合金等。组C具有固相线温度低于200℃的焊料合金,即Sn-Bi、Sn-In、Bi-In、In-Cu、In-Ag和In-Ag-X(X=A1,Au、Bi、Co、Cu、Ga、Ge、Mn、Ni、P、Pd、Pt、Sb、Sn和Zn)合金等。在这些合金中,Sn是该系统中的反应剂。
在本发明的一个实施方式中,第一合金是来自Bi-Ag系统的合金并且固相线温度为约260℃和更高。在具体的实施方式中,第一合金包括从0至20wt%的Ag,剩余的为Bi。在进一步的实施方式中,第一合金包括从2.6wt%至15wt%的Ag,剩余的为Bi。
在本发明的第二实施方式中,第一合金选自Bi-Cu系统并且固相线温度为约270℃和更高。在具体的实施方式中,第一合金包括从0至5wt%的Cu,剩余的为Bi。在进一步的实施方式中,第一合金包括从0.2wt%至1.5wt%的Cu,剩余的为Bi。
在本发明的第三实施方式中,第一合金选自Bi-Ag-Cu系统并且固相线温度为约258℃和更高。在具体的实施方式中,第一合金包括从0至20wt%的Ag和从0至5wt%的Cu,剩余的为Bi。在进一步的实施方式中,第一合金包括从2.6wt%至15wt%的Ag,和从0.2wt%至1.5wt%的Cu,剩余的为Bi。
在本发明的第四实施方式,第二合金来自Sn-Sb系统并且固相线温度在约231℃和约250℃之间。在具体的实施方式中,第二合金包括从0至20wt%的Sb,剩余的为Sn。在进一步的实施方式中,第二合金包括从0至15wt%的Sb,剩余的为Sn。
在本发明的第五实施方式中,第二合金包括Sn-Sb-X (其中X=Ag、Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt和Zn)并且固相线温度在约230℃和约250℃之间。在具体的实施方式中,第二合金包括从0至20wt%的Sb和从0至20wt%的X,剩余的为Sn。在进一步的实施方式中,第二合金包括从0至10wt%的Sb和从0至5wt%的X,剩余的为Sn。
在本发明的第六实施方式中,第二合金包括Sn-Ag并且固相线温度为约221℃和更高。在具体的实施方式中,第二合金包括从0至10wt%的Ag,剩余的为Sn。在进一步的实施方式中,第二合金包括从0至5wt%的Ag,剩余的为Sn。
在本发明的第七实施方式在,第二合金包括Sn-Cu并且固相线温度为约227℃和更高。在具体的实施方式中,第二合金包括从0至5wt%的Cu,剩余的为Sn。在进一步的实施方式中,第二合金包括从0至2wt%的Cu,剩余的为Sn。
在本发明的第八实施方式,第二合金包括Sn-Ag-X (其中X=Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt、Sb和Zn)并且固相线温度为约216℃和更高。在具体的实施方式中,第二合金包括从0至10wt%的Ag和从0至20wt%的X,剩余的为Sn。在进一步的实施方式中,第二合金包括从0至5wt%的Ag和从0至5wt%的X,剩余的为Sn。
在本发明的第九实施方式中,第二合金包括Sn-Zn并且固相线温度为约200℃和更高。在具体的实施方式中,第二合金包括从0至20wt%的Zn,剩余的为Sn。在进一步的实施方式中,第二合金包括从0至9wt%的Zn,剩余的为Sn。
在本发明的第十实施方式中,第二合金包括Bi-Sn合金,固相线温度为约139℃和更高。在具体的实施方式中,第二合金包括从8wt%至80wt%的Sn,剩余的为Bi。在进一步的实施方式中,第二合金包括从30wt%至60wt%的Sn,剩余的为Bi。
在本发明的第十一实施方式中,第二合金包括Sn-In合金,固相线温度为约120℃和更高。在具体的实施方式中,第二合金包括从0至80wt%In,剩余的为Sn。在进一步的实施方式中,第二合金包括从30wt%至50wt%的In,剩余的为Sn。
在本发明的第十二实施方式中,第二合金包括Bi-In合金,固相线温度在约100和约200℃之间。在具体的实施方式中,第二合金包括从0至50wt%的In,剩余的为Bi。在具体的实施方式中,第二合金包括从20wt%至40wt%的In,剩余的为Bi。
在本发明的第十三实施方式中,第二合金包括In-Cu合金,固相线温度在约100和约200℃之间。在具体的实施方式中,第二合金包括从0至10wt%的Cu,剩余的为In。在具体的实施方式中,第二合金包括从0至5wt%的Cu,剩余的为In。
在本发明的第十四实施方式中,第二合金包括In-Ag合金,固相线温度在约100和约200℃之间。在具体的实施方式中,第二合金包括从0至30wt%的Ag,剩余的为In。在进一步的实施方式中,第二合金包括从0至10wt%的Ag,剩余的为In。
在第十五实施方式中,第二合金是In-Ag-X(X=Al、Au、Ri、Co、Cu、Ga、Ge、Mn、Ni、P、Pd、Pt、Sb、Sn和Zn)合金,固相线温度在约100和约200℃之间。在进一步的实施方式中,第二合金包括从0至20wt%的Ag,0至20wt%的X,剩余的为In。在具体的实施方式中,第二合金包括从0至10wt%的Ag,0至5wt%的X,剩余的为In。
本发明的进一步实施方式提供制造混合焊料膏的方法。在一些实施方式中,形成第一合金的颗粒并且形成第二合金的颗粒。第一和第二合金的颗粒然后与助焊剂混合以形成焊料膏。最终的膏包括第一合金粉末、第二合金粉末,以及余量的助焊剂。在一些实施方式中,第一合金颗粒是固相线温度为至少约260℃的合金。在进一步的实施方式中,第二合金包括固相线温度在约230℃和约250℃之间的合金、固相线温度在约200℃和约230℃之间的合金或固相线温度低于约200℃的合金。在一些实施方式中,膏由约60wt%和约92wt%之间的第一合金粉末、大于0%但小于或等于约12wt%的量的第二合金粉末以及余量的助焊剂组成。在进一步实施方式中,第二合金粉末在混合焊料膏的2wt%和10wt%之间。
在具体的实施方式中,第一合金包括Bi-Ag合金、Bi-Cu合金或Bi-Ag-Cu合金。在进一步的实施方式中,固相线温度在约230℃和约250℃之间的合金包括Sn合金、Sn-Sb合金或Sn-Sb-X(其中X=Ag、Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt和Zn)合金。在另一实施方式中,固相线温度在约200℃和约230℃之间的合金包括Sn-Ag合金、Sn-Cu合金、Sn-Ag-X (其中X=Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt、Sb和Zn)合金或Sn-Zn合金。在仍进一步的实施方式中,固相线温度低于约200℃的合金包括Sn-Bi合金、Sn-In合金或Bi-In合金。
在进一步的实施方式中,第二合金粉末包括由多个合金粉末组成的粉末。例如,第二合金粉末可包括选自本文所述合金的不同合金的混合物。
在一些实施方式中,根据焊料应用确定混合焊料膏中第一和第二合金的相对量。在一些情况下,当膏中第二焊料合金的量增加超过某一阈值时,可能增加在最终焊接缝中保留一些低熔点相的可能性。在一些情况下,当膏中第二焊料合金的量小于某一阈值时,可减少对基底的湿润。在一个实施方式中,确定膏中第二焊料合金的量,以便低熔点相可在回流之后完全转化成高熔点IMC。在进一步的实施方式中,膏中第二合金在大于0wt%但小于约12wt%的量之间变化。在具体的实施方式中,膏中第二合金大于约2wt%但小于约10wt%。
除了各种正常的杂质或少量的不同元素外,其他元素也可添加或并入这些合金中,只要保持Sn的反应性质。
在一些实施方式中,以混合焊料膏用于焊接的回流曲线被设计以迅速加热至第一合金的熔化温度之上。在这些情况下,在低温下更短的浸湿时间可使得反应剂比如Sn迅速流向基底并与为完全熔化池液而不是半固体熔化池液的基底反应。第一和第二合金二者的熔化将有助于来自熔化的焊料的第二合金元素向基底和部件扩散并且“沉”在表面上以形成IMC层。
实施例
测试包括本文所述范围的各种混合合金粉末焊料膏的焊料性能。
表1描述使用包括Bi 11Ag或Bi2.6Ag的第一合金、包括Sn10Ag25Sb或Sn10Ag10Sb的第二合金和助焊剂制造的实施例混合焊料膏的配方。
表1使用组A第二合金的混合焊料合金的重量百分数
表2描述使用包括Bi 11Ag的第一合金、包括Sn3.8Ag0.7Cu、Sn3.5Ag、Sn0.7Cu或Sn9Zn的第二合金和助焊剂制造的实施例混合焊料膏的配方。
表2使用组B第二合金的混合焊料合金的重量百分数
表3描述使用包括Bi11Ag的第一合金、包括Bi42Sn、Bi33In或In48Sn的第二合金和助焊剂制造的实施例混合焊料膏的配方。
表3使用组C第二合金的混合焊料合金的重量百分数
制备表1、2和3所述的每个膏并使用3孔不锈钢丝网印刷至试样上。使用Cu、Ni、合金42和氧化铝试样。每个膏印刷在每个试样上。孔的直径为1/4英寸。用为混合合金粉末焊料膏设计的方案,通过回流炉将印刷的试样回流。在3区域回流炉中,在380℃、400℃和420℃以每分钟13"的带速度在N2气氛下进行回流。
视觉观察Cu和Ni试样上的湿润性能。当与单一BiAg焊料膏比较时所有的混合焊料合金显示改善的湿润。图3和4是代表典型结果的图。图3显示由84wt%Bi11Ag+6wt%Bi42Sn+10wt%助焊剂组成的混合合金粉末焊料膏的实施例的湿润性能。左图显示在Cu试样上回流的膏;右图显示在合金42试样上回流的膏。图4显示由84vvt%Bi11Ag+6wt%52In48Sn+10wt%助焊剂组成的混合合金粉末焊料膏的实施例的湿润性能。左图显示在Cu试样上回流的膏;右图显示在合金42试样上回流的膏。
回流的焊料球从氧化铝试样剥离用于DSC测试。在Cu试样和Ni试样上形成的焊料凸块也被冲压用于DSC测试。使用差示扫描量热仪以10℃/min的加热速度进行DSC测量。代表性DSC曲线显示在图5-7中。图5图解由使用84wt%Bi 11Ag+6wt%Sn15Sb+10wt%助焊剂产生的接缝的DSC曲线。顶部曲线图解在陶瓷试样上回流之后的热流曲线。在约138℃的尖峰说明存在第二合金。底部曲线图解在Cu试样上回流之后膏的热流曲线。底部图曲线中该尖峰的缺少证实BiAg+SnSb系统中低熔点相的消失。图6图解BiAg+SnAg系统中低熔点相的消失。图6的实验在陶瓷和Cu试样上使用84wt%Bi11Ag+6wt%Sn3.5Ag+10wt%助焊剂,如在图5中。图7图解BiAg+BiSn系统中的消失。图7的实验在陶瓷和Cu试样上使用84wt%Bi11Ag+6wt%Bi42Sn+10wt%助焊剂,如图5和6中。在图7中,图解陶瓷上焊料回流之后的热流曲线的顶部曲线显示没有低熔点相。这可能是由于Sn和Ag之间的高亲和力,导致第二合金中的Sn被并入最终焊料凸块中的IMC。
对样品的横截面成像以确定在焊料凸块和Cu或Ni试样之间的界面处的IMC厚度。代表性图像显示在图8中。图8a是在Cu试样上使用84wt%Bi 11Ag+6wt%Sn3.5Ag+10wt%助焊剂的焊料凸块的横截面。图8b是在Ni试样上使用相同焊料膏的焊料凸块的横截面。如这些结果显示,IMC层厚度在两个试样上限制为数μm。
尽管上面已经描述了本发明的各种实施方式,但是应当理解它们仅仅以举例的方式呈现,并不是限制性的。同样地,各图可描绘示例性结构或本发明的其他构造,其帮助理解可包括在本发明中的特征和功能。本发明不限于图解的示例性结构或构造,而是期望的特征可使用各种可选的结构和构造实施。的确,对本领域技术人员而言,可选的功能、逻辑或物理分区和构造可如何实施以执行本发明期望的特征是显而易见的。同样地,除了本文描绘的那些,许多不同的组成模块名称可应用至各个分区。另外,就流程图而言,操作说明和方法权利要求,在本文呈现步骤的顺序不应要求以相同的顺序实施各实施方式以执行所述的功能,除非上下文另外指出。
尽管就各种示例性实施方式和执行方式描述了本发明,但应当理解在一个或多个单独实施方式中描述的各种特征、方面和功能不限于它们适用于描述它们的具体实施方式,而是可单独或以各种组合应用于本发明的一个或多个其他实施方式,无论这类实施方式是否被描述并且无论这类特征是否作为所描述实施方式的一部分呈现。因此,本发明的宽度和范围不应被任何上述示例性实施方式所限制。
在该文中使用的术语和短语及其变型,除非另外明确说明,应当解释为开放式,而非限制性的。作为前述的例子:术语“包括”应当解读为含义“包括,但不限于”或类似含义;术语“实例”用于提供所讨论项目的示例性例子,不是穷尽的或其限制性列举;术语“一个”应当解读为含义“至少一个”、“一个或多个”或类似含义;和形容词比如“常规的”、“传统的”、“通常的”、“标准的”、“已知的”和类似含义意思不应当解释为将所描述的项目限于给定的时间段或限于在给定时间可获得的项目,而是应当解读为包括现在或在将来的任何时间可获得的常规的、传统的、通常的或标准的技术。类似地,当该文提到对于本领域普通技术人员显而易见或熟知的技术时,这类技术包括现在或在将来的任何时间对本领域技术人员显而易见或熟知的那些技术。
范围加宽的词语和短语比如“一个或多个”、“至少”、“但不限于”或其他类似短语在一些情况下出现不应解读为意思是在缺少该范围加宽短语的情况下意指或要求较窄情况。术语“模块”的使用不意味着描述或声称为模块的部分的组件或功能都配置在共同的包装中。实际上,模块的任何或所有的各个组件,无论是控制逻辑或其他组件,可组合在单个包装中或分开保持,并且进一步可分布在多个分组或包装中或在多个位置。另外,本文阐释的各种实施方式以示例性方块图、流程图和其他图解方式描述。如在阅读本文之后本领域技术人员显而易见的,图解的实施方式和它们的各种可选形式可被实施而不限于图解的实例。例如,方块图和它们附随的描述不应解释为针对具体的体系或构造。
Claims (32)
1.焊料膏,其由下列组成:
60wt%至92wt%之间的量的第一焊料合金粉末;
大于0wt%并且小于12wt%的量的第二焊料合金粉末;和
助焊剂;
其中所述第一焊料合金粉末包括第一焊料合金,其固相线温度高于260℃,其中所述第一焊料合金是Bi-Ag合金、Bi-Cu合金或Bi-Ag-Cu合金;和
其中所述第二焊料合金粉末包括第二焊料合金,其固相线温度低于250℃。
2.权利要求1所述的焊料膏,其中所述第二焊料合金的固相线温度在230℃和250℃之间。
3.权利要求2所述的焊料膏,其中所述第二焊料合金包括Sn合金。
4.权利要求3所述的焊料膏,其中所述Sn合金包括Sn-Sb合金、或Sn-Sb-X合金,其中X=Ag、Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt或Zn。
5.权利要求1所述的焊料膏,其中所述第二焊料合金的固相线温度在200℃和230℃之间。
6.权利要求1所述的焊料膏,其中所述第二焊料合金包括Sn-Ag合金、Sn-Cu合金、Sn-Ag-X合金或Sn-Zn合金,其中X=Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt、Sb或Zn。
7.权利要求1所述的焊料膏,其中所述第二焊料合金的固相线温度低于200℃。
8.权利要求7所述的焊料膏,其中所述第二焊料合金包括Sn-Bi合金、Sn-In合金或Bi-In合金。
9.权利要求1所述的焊料膏,其中所述第二焊料合金粉末的量在2wt%和10wt%之间。
10.权利要求1所述的焊料膏,其中所述第一焊料合金包括从0至20wt%的Ag及剩余的为Bi,从0至5wt%的Cu及剩余的为Bi,或从0至20wt%的Ag和从0至5wt%的Cu及剩余的为Bi。
11.权利要求1所述的焊料膏,其中所述第一焊料合金包括从2.6wt%至15wt%的Ag及剩余的为Bi,从0.2wt%至1.5wt%的Cu及剩余的为Bi,或从2.6wt%至15wt%的Ag和从0.2wt%至1.5wt%的Cu及剩余的为Bi。
12.制造焊料膏的方法,其由将下述进行混合组成:
60wt%至92wt%之间的量的第一焊料合金粉末;和
大于0wt%并且小于12wt%的量的第二焊料合金粉末;与
助焊剂;
其中所述第一焊料合金粉末包括第一焊料合金,其固相线温度高于260℃,其中所述第一焊料合金是Bi-Ag合金、Bi-Cu合金或Bi-Ag-Cu合金;和
其中所述第二焊料合金粉末包括第二焊料合金,其固相线温度低于250℃。
13.权利要求12所述的方法,其中所述第二焊料合金包括Sn合金或Bi-In合金。
14.权利要求13所述的方法,其中所述Sn合金包括Sn-Sb合金、Sn-Ag合金、Sn-Cu合金、Sn-Zn合金、Sn-Bi合金或Sn-In合金。
15.权利要求14所述的方法,其中所述Sn合金还包括Sn-Sb-X合金,其中X=Ag、Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt或Zn;或Sn-Ag-X合金,其中X=Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt、Sb或Zn。
16.权利要求12所述的方法,其中所述第二焊料合金粉末的量在2wt%和10wt%之间。
17.权利要求12所述的方法,其中所述第一焊料合金包括从0至20wt%的Ag及剩余的为Bi,从0至5wt%的Cu及剩余的为Bi,或从0至20wt%的Ag和从0至5wt%的Cu及剩余的为Bi。
18.权利要求12所述的方法,其中所述第一焊料合金包括从2.6wt%至15wt%的Ag及剩余的为Bi,从0.2wt%至1.5wt%的Cu及剩余的为Bi,或从2.6wt%至15wt%的Ag和从0.2wt%至1.5wt%的Cu及剩余的为Bi。
19.焊接方法,其包括:
将焊料膏施加在基底和器件之间以形成组件;
使用回流曲线回流焊接所述组件以形成焊接缝;其中所述焊料膏由下列组成:
60wt%至92wt%之间的量的第一焊料合金粉末;
大于0wt%并且小于12wt%的量的第二焊料合金粉末;和
助焊剂;
其中所述第一焊料合金粉末包括第一焊料合金,其固相线温度高于260℃,其中所述第一焊料合金是Bi-Ag合金、Bi-Cu合金或Bi-Ag-Cu合金;和
其中所述第二焊料合金粉末包括第二焊料合金,其固相线温度低于250℃。
20.权利要求19所述的方法,其中所述第二焊料合金包括Sn合金或Bi-In合金。
21.权利要求20所述的方法,其中所述Sn合金包括Sn-Sb合金、Sn-Ag合金、Sn-Cu合金、Sn-Zn合金、Sn-Bi合金或Sn-In合金。
22.权利要求21所述的方法,其中所述Sn合金还包括Sn-Sb-X合金,其中X=Ag、Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt或Zn;或Sn-Ag-X合金,其中X=Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt、Sb或Zn。
23.权利要求19所述的方法,其中所述第二焊料合金粉末的量在2wt%和10wt%之间。
24.权利要求19所述的方法,其中所述第一焊料合金包括从0至20wt%的Ag及剩余的为Bi,从0至5wt%的Cu及剩余的为Bi,或从0至20wt%的Ag和从0至5wt%的Cu及剩余的为Bi。
25.权利要求19所述的方法,其中所述第一焊料合金包括从2.6wt%至15wt%的Ag及剩余的为Bi,从0.2wt%至1.5wt%的Cu及剩余的为Bi,或从2.6wt%至15wt%的Ag和从0.2wt%至1.5wt%的Cu及剩余的为Bi。
26.一种焊接缝,所述焊接缝由下述方法形成:
将焊料膏施加在基底和器件之间以形成组件;
使用回流曲线回流焊接所述组件以形成所述焊接缝;
其中所述焊料膏由下列组成:
60wt%至92wt%之间的量的第一焊料合金粉末;
大于0wt%并且小于12wt%的量的第二焊料合金粉末;和
助焊剂;
其中所述第一焊料合金粉末包括第一焊料合金,其固相线温度高于260℃,其中所述第一焊料合金是Bi-Ag合金、Bi-Cu合金或Bi-Ag-Cu合金;和
其中所述第二焊料合金粉末包括第二焊料合金,其固相线温度低于250℃。
27.权利要求26所述的焊接缝,其中所述第二焊料合金包括Sn合金或Bi-In合金。
28.权利要求27所述的方法,其中所述Sn合金包括Sn-Sb合金、Sn-Ag合金、Sn-Cu合金、Sn-Zn合金、Sn-Bi合金或Sn-In合金。
29.权利要求28所述的方法,其中所述Sn合金还包括Sn-Sb-X合金,其中X=Ag、Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt或Zn;或Sn-Ag-X合金,其中X=Al、Au、Co、Cu、Ga、Ge、In、Mn、Ni、P、Pd、Pt、Sb或Zn。
30.权利要求26所述的焊接缝,其中所述第二焊料合金粉末的量在2wt%和10wt%之间。
31.权利要求26所述的焊接缝,其中所述第一焊料合金包括从0至20wt%的Ag及剩余的为Bi,从0至5wt%的Cu及剩余的为Bi,或从0至20wt%的Ag和从0至5wt%的Cu及剩余的为Bi。
32.权利要求26所述的焊接缝,其中所述第一焊料合金包括从2.6wt%至15wt%的Ag及剩余的为Bi,从0.2wt%至1.5wt%的Cu及剩余的为Bi,或从2.6wt%至15wt%的Ag和从0.2wt%至1.5wt%的Cu及剩余的为Bi。
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2011
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- 2011-04-04 CN CN201180022297.6A patent/CN102892549B/zh active Active
- 2011-04-04 DE DE112011101556.9T patent/DE112011101556B4/de active Active
- 2011-04-04 KR KR1020127028941A patent/KR101820986B1/ko active IP Right Grant
- 2011-04-04 MY MYPI2012004531A patent/MY158123A/en unknown
- 2011-04-04 JP JP2013509074A patent/JP5938032B2/ja active Active
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Also Published As
Publication number | Publication date |
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KR101820986B1 (ko) | 2018-01-22 |
JP2013525121A (ja) | 2013-06-20 |
KR20130056235A (ko) | 2013-05-29 |
US10118260B2 (en) | 2018-11-06 |
JP5938032B2 (ja) | 2016-06-22 |
DE112011101556B4 (de) | 2023-11-09 |
DE112011101556T5 (de) | 2013-02-14 |
US9017446B2 (en) | 2015-04-28 |
US20150224602A1 (en) | 2015-08-13 |
WO2011139454A1 (en) | 2011-11-10 |
MY158123A (en) | 2016-08-30 |
CN102892549A (zh) | 2013-01-23 |
US20110268985A1 (en) | 2011-11-03 |
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