CN102165103A - 增强表面可焊性的方法 - Google Patents

增强表面可焊性的方法 Download PDF

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CN102165103A
CN102165103A CN2009801374199A CN200980137419A CN102165103A CN 102165103 A CN102165103 A CN 102165103A CN 2009801374199 A CN2009801374199 A CN 2009801374199A CN 200980137419 A CN200980137419 A CN 200980137419A CN 102165103 A CN102165103 A CN 102165103A
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silver
plating
metallic surface
sulfydryl
weldability
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CN102165103B (zh
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E·朗
L·M·托斯卡诺
C·麦柯里埃尔
P·罗曼
D·柯洛格
S·A·卡斯塔尔迪
C·P·施泰内克
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    • 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
    • H05K3/22—Secondary treatment of printed circuits
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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
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
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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
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Abstract

本发明公开了一种增强金属表面的可焊性的方法，其中将金属表面在焊接前镀以银镀层，将此浸渍银镀层用一种包含巯基取代或硫取代硅烷化合物的添加剂处理。优选的后处理包含3-巯丙基三甲氧基硅烷和/或3-辛酰基硫-1-丙基三乙氧基硅烷。

Description

增强表面可焊性的方法
技术领域
本发明涉及一种处理表面的方法，该处理能够增强表面可焊性。此方法对于印刷电路板的制造及组装特别有用。
背景技术
焊接通常用于形成对各种物品的机械、电机或电子连接。期望的链接点的功能间的特异性是重要的，因为各个应用对表面制备有着其本身的特定要求。三种焊接应用中，形成电子连接的要求是最为严格的。
在制造使用印刷电路的电子设备时，电子元件对印刷电路的连接是通过将元件的引线焊接到通孔、周围的垫、盘及其它连接点(概括为“连接区域”)而形成的。一般而言，连接是通过各种焊接技术完成的。
为了利于焊接操作，印刷电路制造者需要安排使通孔、垫、盘及其它连接点可接受后续的焊接方法。因此这些表面必须易被焊锡湿润且可与电子元件的引线或表面整体地导电性连接。因为这些需求，印刷电路制造者已设计各种保护及增强表面可焊性的方法。
一种讨论的为表面安排良好的可焊性的手段为对表面提供预涂覆焊锡，其一般通过一种称为热气焊锡调平的方法或经某些形式的镀敷方法实行。然而在印刷电路制造中，此方法有严重的缺点。使用热气焊锡调平由于短路而可能造成无法接受的高缺陷比率，特别是在处理小型电路时。如果使用镀敷，则由于不易对这些区域选择性地提供焊锡，其必须将板的全部导电区域镀焊锡而对后续施敷阻焊剂造成严重的问题。此外，以上方法效率低且相当昂贵。
另一种为这些表面安排良好的可焊性的手段为将其镀以贵金属(如金、钯或铑)的最终表面处理涂层。美国专利第5,235,139号(Bengston等人)，其内容在此并入作为参考，提议一种得到此贵金属最终表面处理涂层的方法。Bengston等人提议对待焊铜区域镀以化学镀镍-硼，然后镀以如金等贵金属涂层。类似方法也可以参见Juskey，Jr.等人的美国专利第4,940,181号，其内容在此并入作为参考，其教导镀以化学镀铜，继而镀以电解铜，继而镍，继而金成为可焊接表面。这些方法表现良好但耗时且昂贵。
现已进行各种尝试以仅对所需区域选择性地涂布焊锡。一种此方法涉及在连接的镀焊锡区域上使用有机抗蚀剂，继而在涂布阻焊剂前从铜残迹中选择性剥去锡-铅。参见Durnwith等人的美国专利第4,978,423号。其它已知的选择性焊接方法还可参见Larson的美国专利第5,160,579号，其内容在此并入作为参考。
直接焊接铜表面为困难及不合理的。这些问题主要由于在全部焊接操作中无法使铜表面保持清洁及无氧化。现已发展各种有机处理以将铜表面维持在易焊接状态。例如参见美国专利第5,173,130号(Kinoshita)，其教导使用特定2-烷基苯并咪唑作为铜的预助焊剂以保护铜表面的可焊性。如Kinoshita教导的处理已证明为成功的，但是仍有提高该方法的可靠性的需求。
在此提出的保护可焊性的方法为对待焊铜表面在焊接前涂以银镀层。然而现已发现在使用以上方法时，银镀层具有腐蚀的趋势，特别是如果暴露于含硫成分的环境。即使是在焊接结束后，此腐蚀仍可在界面处持续，因而减弱焊锡连接。
本发明的一个目的为提议一种保护及增强铜表面的可焊性的方法，其通过将该铜表面镀以浸渍银镀层继而后处理，因而使银镀层较现有技术浸渍银沉积物更具抗腐蚀性且确保坚固、长期的焊锡黏结。
发明内容
本发明提议使用浸渍或化学银涂层作为各种表面(特别是铜表面)的改良的可焊性保护剂。还公开了用于沉积银涂层的优选组合物。所提出的镀银方法产生的银镀层比传统的银沉积物更加抗腐蚀及抗降解。所提出的方法为有效地保护表面(特别是铜表面及印刷电路板上的连接区域)可焊性的多样化、低成本方法。
具体实施方式
本发明涉及一种保护及增强金属表面(特别是铜表面)的可焊性的方法。所提出的方法包括以下步骤：
a)清洁金属表面；
b)非强制选择地蚀刻金属表面；
c)使用浸渍或化学镀银溶液处理金属表面；
d)使用包含巯基硅烷或硫代硅烷化合物的溶液处理镀银表面。
优选的镀银溶液为浸渍或化学镀银溶液。现已发现浸渍银沉积物提供优良的可焊性保护剂，其对于制造印刷电路板特别有用。已意外地发现，在印刷电路应用中用简单浸渍或化学银沉积得到的可焊性超越了用现有技术的镀镍-金法(如美国专利第5,235,139号所述)得到的可焊性，并且意外地超越其它浸渍沉积。如由以下实例可知，本发明的方法产生在不利条件下为高可焊性的表面。在印刷电路应用中，根据本发明制备的表面是可引线接合的。浸渍镀敷为一种由置换反应引起的方法，其中将待镀表面溶于溶液中，同时镀敷金属从镀液中沉积在表面上。浸渍镀敷不需要预先表面活化而引发。待镀金属通常比表面金属贵重。因此浸渍镀敷通常比化学镀敷更易控制及节省成本，化学镀敷可能需要复杂的自动催化镀液及镀敷前的表面活化过程。结果，在本发明的方法中优选浸渍镀银。
镀银液通常包含酸性含水基质中的可溶性银离子源。可溶性银离子源可从各种银化合物衍生而来。本发明人已发现硝酸银最佳。镀液中的银浓度通常可为每升0.1至25克，但是最优选以每升0.5至2克的浓度存在。虽然各种酸均适用于此配方，但本发明人已发现甲磺酸或硝酸最佳。镀液中的酸浓度通常可为每升1至150克，但是优选为每升5至50克。
本发明人已发现，包含下式的咪唑或咪唑衍生物对用于本发明的浸渍镀液(特别是浸渍银镀液)产生的镀层具有显著的正面影响：
Figure BPA00001331796600041
其中R1、R2、R3和R4独立地选自取代或未取代烷基、取代或未取代芳基、卤素、硝基和氢。
包含上述咪唑使镀敷沉积物变亮且提高所得镀敷沉积物的完整性与物理性质。此外，咪唑还能延长浸渍镀液的使用寿命。本发明人已发现，组胺酸为用于这些方法的优选的咪唑。
包含咪唑通常对浸渍镀液提供显著的优点，但是对浸渍镀银特别有用及有利。本发明人已发现，由含咪唑的镀浴生成的浸渍银沉积物与由不具有咪唑的镀浴生成的浸渍银沉积物相比更亮、更光滑并更具粘性。此外，具有咪唑的浸渍镀浴与无咪唑的镀浴相比具有更长的有效寿命。
关于可用于本发明的浸渍银组合物，镀液非强制选择地还有利地含氧化剂。本发明人已发现，关于此点优选为硝基芳族化合物，最佳为二硝基化合物，如3，5-二硝基羟基苯甲酸。溶液中的这种氧化剂的浓度可为每升0.1至25克，但是优选为每升0.5至2克。
浸渍银溶液可在范围为室温至200°F的温度用于本发明的方法，但是优选在80至120°F使用。在镀液中浸渍的时间可为1至30分钟，但是优选为1至5分钟。
本发明的浸渍银溶液因此用于将薄银层镀在待焊表面上。为了使表面可焊性有效地增强和保护，据信所得银涂层应为1至100微英寸厚，优选为10至60微英寸厚。虽然此方法对于焊接许多表面是有效的，但其对焊接铜表面(如印刷电路板上的连接区域)特别有用。
在将连接区域镀银后，其应以一种包含巯基硅烷或硫代硅烷化合物的溶液处理(接触)。本发明的巯基取代或硫取代硅烷优选为以下化学式的多官能巯基取代或硫取代有机硅烷：
Figure BPA00001331796600051
其中R1、R2、R3和R4独立地选自烷氧基(例如甲氧基、乙氧基或类似烷氧基)、烷基、芳基和氢，其中n为1至5的整数，但是优选为2至3的整数。特别优选的巯基取代硅烷为3-巯丙基三甲氧基硅烷：
Figure BPA00001331796600061
本发明人已发现，3-巯丙基三甲氧基硅烷或3-辛酰基硫-1-丙基三乙氧基硅烷为用于本发明的最优选的巯基取代或硫取代硅烷。这些硅烷可以商品名
Figure BPA00001331796600062
A-189硅烷和
Figure BPA00001331796600063
A599从康乃狄克州Wilton的G.E.Silicones获得。其它可用的巯基取代或硫取代硅烷包括可以从瑞士Buchs的Fluka Chemie AG获得的(3-巯丙基)甲基二甲氧基硅烷。本发明人意外地发现，与不具有巯基取代基或硫取代基的其它硅烷相比，这些巯基取代或硫取代硅烷上的巯基提供明显更好的腐蚀保护。因此，本发明人相信，硅烷上的巯基取代或硫取代相对非巯基取代或硫取代硅烷对腐蚀保护与黏附性促进提供了显著及意料之外的增强。
巯基取代或硫取代硅烷优选以合适溶剂溶解到处理溶液中。处理溶液中的巯基取代或硫取代硅烷浓度可为0.5至10重量％，但优选为2至4重量％。巯基取代硅烷(如γ-巯丙基三甲氧基硅烷)可能无法以有效地实施本发明所需的程度溶于水本身。本发明人已发现，将这些巯基取代硅烷有效地溶于水基质中可能需要水与合适溶剂的组合。用于此目的的合适溶剂包括N-甲基-2-吡咯烷酮、丁内酯、二乙二醇丁醚、己二醇、乙二醇单丁醚和醇。巯基取代硅烷的最佳溶解基质为乙二醇单丁醚或二醇单醚，如可从Dow Chemical Company获得的
Figure BPA00001331796600071
DPM，其每种可以和水一同使用或单独作为溶解基质。优选将巯基取代硅烷加入到溶剂(例如乙二醇单丁醚)中，然后如果需要水则将基质加入到水中，搅拌以形成处理溶液。本发明人已发现，乙二醇单丁醚的水溶液优良地溶解巯基取代硅烷并且从处理表面蒸发时留下无斑点表面涂层。此外，还可接受仅将硅烷溶于一种或多种所列有机溶剂中而无水地制备后处理溶液。如果使用水，则必须调整水中的溶剂浓度以将巯基取代硅烷适当地溶解及/或保持在溶液中。本发明人已发现，按体积百分比计为65/35至94/6的水对乙二醇单丁醚的浓度比例适用于体积百分比为5至0.5的巯基取代硅烷浓度。巯基取代硅烷的水溶液将硅烷水解且提高其处理金属表面的效果。处理溶液的pH应小于7，而且优选为约3至5。本发明人已发现，使用以上溶剂与巯基取代硅烷的水溶液，则处理溶液自然地调配成约4的pH。乙酸可用以完成任何所需的pH调整。巯基取代或硫取代硅烷的浓度可为处理溶液的0.5至10体积％，但是优选为2至5体积％。最佳为将巯基取代或硫取代硅烷无水地溶于一种或多种所列有机溶剂，而且在此情形不必考虑pH。
在应用本发明的硅烷后处理后，经处理表面优选用水洗涤，然后在约100℃至150℃干燥1至30分钟，优选在130℃至150℃干燥约10分钟。
虽然此技术可有利地用于几乎任何表面，其对于制造印刷电路板最有用，特别是裸铜覆阻焊膜(SMOBC)板。因此在制造SMOBC板时，在板的表面施加阻焊剂，然后曝光及显影以显现连接区域。然后这些连接区域实际上仅为板上铜的曝光区域，其余实际上被阻焊剂覆盖。在制造循环中稍后将电子元件置于板上时，这些连接区域因此注定为附着点，在大部分的情形下通过焊接附着。因此，这些暴露点(通常为铜)的可焊性必须增强及保护。
因此根据本发明，这些区域优选随后使用酸清洁剂清洁，继而微蚀刻以制备可接受浸渍镀敷用的表面。在该优选的制备后，将板浸于浸渍镀银液，使得得到合适厚度的银沉积物，然后以本发明教导的后处理进行处理。
本发明进一步在以下实施例中仅为了例证目的而叙述，其绝非限制本发明。
实施例I
按以下步骤处理电路板：
a)酸清洁剂，5分钟，120°F
b)用水洗涤
c)用过硫酸钠/硫酸微蚀刻，1分钟，95°F
d)用水洗涤
e)使用以下组合物镀银：
Figure BPA00001331796600081
f)用水洗涤。
实施例II
如实施例1所示处理电路板，不同之处在于在本实施例中在步骤(f)后如下进一步处理电路板：
g)使用含以下成分的水溶液处理：
Figure BPA00001331796600091
h)用水洗涤
i)在140℃烘烤10分钟。
然后测试实施例I及II的电路板在含硫气氛中的可焊性及抗腐蚀性。经实施例II的后处理方法处理的零件显示比实施例I少约80％的腐蚀。相比于实施例I，实施例II的零件还显示出增强的可焊性。

Claims (9)

1.一种改善金属表面可焊性的方法，该方法包括：
a)使金属表面与镀银液接触，从而在金属表面上产生银镀层；然后
b)使用一种包含巯基取代或硫取代硅烷的溶液来处理镀银的金属表面。
2.如权利要求1所述的方法，其中该镀银液包含选自咪唑、苯并咪唑、咪唑衍生物和苯并咪唑衍生物的材料。
3.如权利要求1所述的方法，其中该镀银液还包含氧化剂。
4.如权利要求1所述的方法，其中该金属表面包含铜。
5.如权利要求1所述的方法，其中该添加剂选自3-巯丙基三甲氧基硅烷和3-辛酰基硫-1-丙基三乙氧基硅烷。
6.如权利要求4所述的方法，其中该镀银液包含选自咪唑、苯并咪唑、咪唑衍生物和苯并咪唑衍生物的材料。
7.如权利要求6所述的方法，其中该镀银液还包含氧化剂。
8.如权利要求7所述的方法，其中该添加剂选自3-巯丙基三甲氧基硅烷和3-辛酰基硫-1-丙基三乙氧基硅烷。
9.如权利要求5所述的方法，其中该溶液包含二醇单醚。
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