CN101302615B - 焊接点的表面处理方法 - Google Patents

焊接点的表面处理方法 Download PDF

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CN101302615B
CN101302615B CN2007101049710A CN200710104971A CN101302615B CN 101302615 B CN101302615 B CN 101302615B CN 2007101049710 A CN2007101049710 A CN 2007101049710A CN 200710104971 A CN200710104971 A CN 200710104971A CN 101302615 B CN101302615 B CN 101302615B
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八木伊知郎
鲁德凤
杨小岗
何德裕
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SAE Technologies Development Dongguan Co Ltd
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    • C—CHEMISTRY; METALLURGY
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    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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    • 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
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    • 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
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    • 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
    • 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
    • B23K35/02—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
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    • H01—ELECTRIC ELEMENTS
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    • H01L2224/118—Post-treatment of the bump connector
    • H01L2224/1182—Applying permanent coating, e.g. in-situ coating
    • H01L2224/11822—Applying permanent coating, e.g. in-situ coating by dipping, e.g. in a solder bath
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    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001—Core members of the bump connector
    • H01L2224/13099—Material
    • H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/13101—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of less than 400°C
    • H01L2224/13111—Tin [Sn] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/1354—Coating
    • H01L2224/13599—Material
    • H01L2224/136—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/13601—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of less than 400°C
    • H01L2224/13611—Tin [Sn] as principal constituent
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • H05K2203/0793—Aqueous alkaline solution, e.g. for cleaning or etching

Abstract

本发明公开了一种焊接点的表面处理方法，该方法使用pH值在9.5到11.5的范围内的碱性缓冲溶液，并使以锡或锡合金为材料的焊接点浸入到所述碱性缓冲溶液中。所述碱性缓冲溶液与所述焊接点反应而在焊接点表面形成钝化膜。由于所述钝化膜形成于所述焊接点的表面，因此能阻止焊接点在后续水溶液清洗或水浸渍过程中腐蚀和溶解。另外，所述钝化膜确保了所述焊接点具有良好的外观，同时提供了具有所述焊接点的电子成品好的可靠性以及高的可测试性。

Description

焊接点的表面处理方法 
技术领域
本发明涉及一种具有焊接点的电子装置的处理方法，特别涉及一种焊接点的表面处理方法以阻止焊接点在水溶液清洗或水浸渍过程中腐蚀和溶解。 
背景技术
锡和锡合金是最常见的焊料，用于在众多不同电子装置，如芯片、晶体振荡器，引线架，印制电路板，磁头折片组合(HGA，head gimbal assembly)等中提供焊接连接。除了提供电性连接，所述焊接连接还在电子装置之间提供重要的机械连接。例如，在所述磁头折片组合中，锡球被用来把磁头滑块电性地以及机械地连接到所述磁头折片组合的悬臂件上。 
大量的焊接结构已被提出以用于实现电子部件之间的连接，并且很多连接技术，例如表面安装技术(SMT，surface mount technology)，球阵列封装(BGA，ball grid array)技术，锡球焊接(SBB，solder ball bonding)或者金球焊接(GBB，gold ball bonding)技术等，已为大众悉知，以用于形成所述焊接连接结构。不论采用何种焊接连接结构或形成焊接连接的方法，都会存在三个典型的阶段需要对焊接点表面进行清洗。首先，在进行连接之前的焊料部署中，焊料的处理可能会留下不良的渣滓，所述渣滓将影响焊接触点的良性焊料浸湿，因此需要被除去。第二，为了焊料在焊接触点上可以良好地浸湿，经常使用助焊剂。所述助焊剂需要被除去以避免在所述电子装置上留下腐蚀性的污染物。最后，零件产品装置的重做需要特殊处理，所述处理会要求一个清洗步骤以确保所述组合件的可靠性。 
然而不幸的是，由于清洗过程本身会对所述焊接点和/或电子装置造成腐 蚀，所述助焊剂和所述助焊剂产物的清除以及焊接点的清洗是一个艰巨的任务。另外，焊料还会发生溶解，从而导致形成焊接点的焊料减少，还带来处理问题，因为所述焊料通常是铅/锡合金，所述溶解的合金若直接随清洗的溶液排出会引起环境污染。 
下面详细阐明在清洗过程中焊接点发生的腐蚀和溶解。其中焊料以锡合金为例，清洗剂以水基溶液为例。如图1所示，所述锡(Sn)正在发生电化学腐蚀。所述锡腐蚀过程包括两个联合反应。一个反应是水中的锡溶解，为氧化反应。在这个反应中，锡(Sn)作为阳极，释放电子从而形成锡离子(Sn2+)，该反应由如下的方程式(4)表达。同时，另一个反应，即还原反应，也进行着。在这个反应中，溶解在水溶液中的氧气(O2)作为阴极，通过中和所述电子而还原成氢氧根(OH-)，该反应由如下的方程式(40)表达。由上述两个反应生成的所述锡离子(Sn2+)与所述氢氧根(OH-)相互作用，从而产生氢氧化锡(Sn(OH)2)，该反应由如下的方程式(41)表达。在后面的干燥过程中，如图2a-2d所示，氢氧化锡结晶从而在焊接点表面上形成晶体或者在焊接点表面形成孔洞(见方程式(42))。当所述焊接点冷却时，所述晶体或孔洞会使所述焊接点变得更稀疏，结果轻微的移动会沿着晶体产生裂痕并形成高电阻接头。而且，焊接点的这种结构会影响所述电子成品的可靠性和可测试性。另外，焊接点在水清洗或水浸渍过程中的溶解和形成的结晶使得所述电子成品外观品质变差。 
Figure S071A4971020070605D000021
(4) 
(40) 
Figure S071A4971020070605D000023
(41) 
Figure S071A4971020070605D000024
(42) 
因此，有必要提供一种改进的处理焊接点表面的方法来克服上述缺陷。 
发明内容
本发明的目的是提供一种焊接点表面处理方法，所述方法能阻止后续水溶液清洗或水浸渍过程中焊接点的腐蚀和溶解。 
为了实现上述目的，本发明提供了一种焊接点表面处理方法。所述方法包括如下步骤：(1)配制pH值在9.5到11.5的范围内的碱性缓冲溶液；(2)把具有以锡或锡合金为材料的焊接点的产品浸入到所述碱性缓冲溶液中一段时间；(3)漂洗所述产品以去除残留在所述产品上的碱。经过本发明的方法处理后，所述焊接点的表面上形成一层钝化膜以阻止后续水溶液清洗过程中焊接点腐蚀和溶解。 
在本发明中，所述碱性缓冲溶液包括选自于碳酸盐、氢氧化物、氨、胺以及其混合物的化学物质。 
较佳地，所述步骤(2)中的一段时间为至少5分钟。 
作为本发明的一个实施例，所述碱性缓冲溶液为NaHCO3和Na2CO3的混合溶液。可选地，所述碱性缓冲溶液的pH值保持在10.5。 
作为本发明的另外一个实施例，所述步骤(3)是通过把所述具有焊接点的产品浸入到水中另外一段时间实现的。较佳地，所述步骤(3)中的一段时间为至少2分钟。 
与现有技术相比，本方法使用了pH值在9.5到11.5的范围内的碱性缓冲溶液，并使以锡或锡合金为材料的焊接点浸入到所述碱性缓冲溶液中。所述碱性缓冲溶液与所述焊接点反应而形成钝化膜。由于所述钝化膜形成于所述焊接点的表面，因此能阻止焊接点在后续水溶液清洗或水浸渍过程中腐蚀和溶解。另外，所述钝化膜确保了所述焊接点具有良好的外观，同时提供了具有所述焊接点的电子成品好的可靠性以及高的可测试性。 
为详细说明本发明的技术内容、构造特征、所达目的及效果，以下结合实施例并配合附图详细予以说明。 
附图说明
下面结合附图对本发明作进一步的详细说明。 
图1展示了现有技术中水清洗或水浸渍过程中发生的锡电化学腐蚀的基本原理。 
图2a-2d展示了水清洗或水浸渍后形成有晶体的焊接点表面的例子。 
图3是锡的甫尔拜电位-pH图(Pourbaix potential-pH diagram)。 
图4为一个示例流程图，阐释了本发明焊接点的表面处理方法。 
图5示意性地描述了磁头折片组合的锡球焊接接点的碱性缓冲溶液化学处理过程。 
具体实施方式
现在参考附图描述本发明的实施例，附图中类似的元件标号代表类似的元件。如上所述，本发明提供了一种焊接点表面处理方法。所述方法使用了碱性缓冲溶液，并使焊接点浸入到所述碱性缓冲溶液中。当所述焊接点浸入到所述碱性缓冲溶液中时，所述焊接点与所述碱性缓冲溶液反应并在所述焊接点表面形成一层钝化膜。由于所述钝化膜的存在，本发明成功地阻止焊接点在后续水溶液清洗或水浸渍过程中的腐蚀和溶解。另外，所述钝化膜确保了所述焊接点具有良好的外观，同时提供了具有所述焊接点的电子成品好的可靠性以及高的可测试性。 
本发明的原理是建立在甫尔拜电位-pH图的分析基础之上。详细地，所述甫尔拜电位-pH图是一张划分了独立区域的图。所述独立区域指定了金属在水溶液中的反应产物。另外，所述甫尔拜电位-pH图也描述了发生以下情况的条件：1)金属处于稳定状态，不腐蚀；2)生成可溶解的反应产物，腐蚀发生；3)生成不能溶解的反应产物，钝化发生。因此，所述甫尔拜电位-pH图有助于确定在给定溶液环境中可能发生何种腐蚀反应。一般地，所述甫尔拜电位-pH图是一个金属电位与溶液pH值关系的示意图。 
图3展示了水溶液环境中锡的甫尔拜电位-pH图。所述图展示了物质的稳定的区域。所述物质包括锡(Sn)，锡离子(Sn2+)，氧化锡(SnO2)，锡酸根(SnO2-)以 及氢化锡(SnH4)。所述区域包括锡将会腐蚀的两个区域7和8，钝化膜将会产生的两个区域5和6，以及一个区域4。所述区域4是一个免疫区，其中锡稳定在0氧化状态。 
线10表示氢离子(H+)生成氢气(H2)的氧化还原反应(见方程式(10))。处于线10以下任何电位，所述水中的氢离子(H+)将会与电子反应生成氢气(H2)。 
Figure S071A4971020070605D000051
(10) 
线20表示氧气(O2)与氢离子(H+)结合成水(H2O)的氧化还原反应(见方程式(20))。处于线20以上的任何电位，所述水(H2O)被电离生成氧气(O2)和氢离子(H+)(见方程式(20)的逆向)。 
Figure S071A4971020070605D000052
(20) 
因此，在线10和线20之间的区域，水处于热力学稳定状态，无气体产生。 
从上面的分析以及附图的描述中可知，锡在碱性缓冲溶液中钝化成氧化锡，因此由所述氧化锡构成的钝化膜能够形成在所述锡的表面。详细地，一旦浸入到所述碱性缓冲溶液中，所述锡焊接点不电离而是趋向变成氧化物。也就是说，所述焊接点与所述碱性缓冲溶液反应并因此产生氧化锡。随着反应的进行，所述氧化锡不断增加并逐渐积累，从而在所述焊接点的表面形成一层钝化膜。最后，所述焊接点的整个表面可被所述氧化锡完全覆盖。经过碱性缓冲溶液处理后，所述焊接点表面的钝化膜能够阻止焊接点在后续水溶液清洗或水浸渍过程中腐蚀和溶解，从而确保了所述焊接点具有良好的外观，并因此提供具有所述焊接点的电子成品好的可靠性以及高的可测试性。 
如图4所示，基于上述原理，本发明的焊接点的表面处理方法包括如下步骤：(1)配制碱性缓冲溶液(步骤S1)；(2)把具有焊接点的产品浸入到所述碱性缓冲溶液中一段时间(步骤S2)；(3)通过把所述具有焊接点的产品浸入到水中另外一段时间来漂洗所述产品以去除残留在所述产品上的碱(步骤S3)。经过本发明的方法处理后，所述焊接点的表面上形成一层钝化膜以阻止后续水溶液清洗过程中焊接点腐蚀和溶解。
本发明所使用的碱性缓冲溶液可有一些较佳的替代物。所述替代物可取得更好的有益效果并因此能优化表面处理的品质。详细地，本发明的碱性缓冲溶液的pH值控制在9.5到11.5的范围内。另外，本发明的碱性缓冲溶液可包括选自于无机物或者有机物的化学物质，例如碳酸盐、氢氧化物、氨、胺以及其混合物。较佳地，用于表面处理的所述碱性缓冲溶液为NaHCO3和Na2CO3的混合溶液。所述NaHCO3和Na2CO3的混合溶液的pH值最好控制在10.5。在本发明中，所述步骤(2)中的一段时间为至少5分钟，所述步骤(3)中的一段时间为至少2分钟。 
图5示意性地描述了磁头折片组合111的锡球焊接接点的碱性缓冲溶液化学处理过程。下面将详细说明所述碱性缓冲溶液化学处理方法。 
首先配制具有10.5的恒定pH值、由NaHCO3和Na2CO3组成的碱性缓冲溶液。 
第二个步骤为提供一个用于盛装所述碱性缓冲溶液的碱性缓冲溶液自循环水箱10。详细地，一个用于探测和监视所述碱性缓冲溶液的pH值的常规pH计112、一个水泵113以及一个过滤器114被装配在所述水箱10上。在水泵压力下，所述碱性缓冲溶液被回流到所述碱性缓冲溶液自循环水箱10中。然后，把所述具有锡球焊接接点的磁头折片组合111浸入到所述碱性缓冲溶液中一段预定时间。可理解地，所述时间应很充分，以有效地处理所述磁头折片组合111的表面。在本实施例中，所述要求的时间最好是至少5分钟。在所述时间内，所述磁头折片组合111保持浸入在所述碱性缓冲溶液中，同时所述碱性缓冲溶液的pH值恒定为10.5。所述碱性缓冲溶液在所述过滤器114过滤后被循环使用。 
第三个步骤为提供能够漂洗所述磁头折片组合111的水并且把所述具有锡球焊接接点的磁头折片组合111浸入到所述水中另一段时间以除去残留的碱。在本实施例中，所述水优选为去离子(DI，deionized)水，这是因为所述去离子水再次污染所述磁头折片组合111表面的可能性较小。所述去离子水盛装在一个去离子水漂洗水箱20中。可理解地，所述磁头折片组合111与所述去离子水的接触允许持续一段足够的时间以有效地除去所述碱。在本实施例中，所述 要求的时间最好为至少2分钟。漂洗后，所述磁头折片组合111进行常规清洗作业。由上所述，形成于所述锡球焊接接点上的钝化膜将会阻止清洗过程中的锡球焊接接点腐蚀和钝化。 
以上结合最佳实施例对本发明进行了描述，但本发明并不局限于以上揭示的实施例，而应当涵盖各种根据本发明的本质进行的修改、等效组合。

Claims (7)

1.一种焊接点表面处理方法，包括如下步骤：
(1)配制pH值在9.5到11.5的范围内的碱性缓冲溶液；
(2)把具有以锡或锡合金为材料的焊接点的产品浸入到所述碱性缓冲溶液中一段时间；以及
(3)漂洗所述产品以去除残留在所述产品上的碱，
由此所述焊接点的表面上形成一层钝化膜以阻止后续水溶液清洗过程中焊接点腐蚀和溶解。
2.如权利要求1所述的方法，其特征在于：所述碱性缓冲溶液包括选自于碳酸盐、氢氧化物、氨、胺以及其混合物的化学物质。
3.如权利要求1所述的方法，其特征在于：所述步骤(2)中的一段时间为至少5分钟。
4.如权利要求1所述的方法，其特征在于：所述碱性缓冲溶液为NaHCO3和Na2CO3的混合溶液。
5.如权利要求4所述的方法，其特征在于：所述碱性缓冲溶液的pH值保持在10.5。
6.如权利要求1所述的方法，其特征在于：所述步骤(3)是通过把所述具有以锡或锡合金为材料的焊接点的产品浸入到水中另外一段时间实现的。
7.如权利要求6所述的方法，其特征在于：所述步骤(3)中的一段时间为至少2分钟。
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CN1060923A (zh) * 1990-10-21 1992-05-06 张金祥 整流二极管的制造方法

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Publication number Priority date Publication date Assignee Title
US2544139A (en) * 1947-07-01 1951-03-06 Du Pont Process for enameling aluminumrich alloys
CN1060923A (zh) * 1990-10-21 1992-05-06 张金祥 整流二极管的制造方法

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