CN1936094A - 金属二相体及其制备方法 - Google Patents

金属二相体及其制备方法 Download PDF

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Publication number
CN1936094A
CN1936094A CNA2006101291917A CN200610129191A CN1936094A CN 1936094 A CN1936094 A CN 1936094A CN A2006101291917 A CNA2006101291917 A CN A2006101291917A CN 200610129191 A CN200610129191 A CN 200610129191A CN 1936094 A CN1936094 A CN 1936094A
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China
Prior art keywords
tin
nickel
layer
phosphorus
acid
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CNA2006101291917A
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CN1936094B (zh
Inventor
刘异军
郭伟民
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Rohm and Haas Electronic Materials LLC
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Rohm and Haas Electronic Materials LLC
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
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    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
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    • C25D5/623—Porosity of the layers
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Abstract

揭示了方法和制品。所述方法涉及在基材上沉积镍二相层，以抑制锡和锡合金的表面氧化，以及改进基材的可焊性。

Description

金属二相体及其制备方法
技术领域
本发明涉及具有锡或锡合金层的金属二相体(metal duplex)以及制备该具有锡或锡合金层的金属二相体的方法。更具体来说，本发明涉及具有锡或锡合金层的金属二相体，以及制备所述具有锡或锡合金层的金属二相体，以抑制锡和锡合金的腐蚀，并提高锡和锡合金的可焊性的方法。
背景技术
在许多工业领域中，防止锡和锡合金的腐蚀是一个具有挑战性的问题。在电子材料工业中，锡和锡合金的腐蚀是一个特别严重的问题，在此工业中，腐蚀会使电子器件中的部件之间形成电接触故障。例如，多年来，电镀的锡和锡合金涂层被用于电子学和其他应用中，例如用作导线和刚带。在电子学中，它们被作为用于触点和连接器的可焊且耐腐蚀的表面。它们还在集成电路(IC)制造中用于引线保护层。
具有IC单元、引线框和无源部件的IC器件，例如电容器和晶体管在包括消费电子产品、家用电器、电子计算机、汽车、远程通信产品、机器人和军用设备之类的产品中具有广泛应用。IC单元包括IC芯片和包括位于塑料或陶瓷基座上的一种或多种IC芯片和其他电子元件的混合电路小结。
引线框或连接器是用来将IC单元与外部电路进行电互连的装置。引线框由铜或铜合金之类的电导材料形成，或者是通过将金属坯件冲压或蚀刻出大量引线限定出用来安装IC部件的中心区域而形成的。
引线框通常具有锡或锡合金的表面保护层。可通过各种连接技术将引线框与组件中的IC单元相连。这些技术包括导线接合、焊接、管芯连接和封装。通常采用焊接将IC结合在组件中。在一切情况下，连接都需要引线框表面具有特别的质量。这通常意味着该表面不含氧化物，而且已经准备好与金导线或铝导线、银填充的环氧树脂或焊料之类的其他部件发生相互作用。
一个问题是长期可焊性，长期可焊性定义为表面保护层熔融并形成与其他部件的良好焊点(所述焊点不含会削弱电连接或机械连接的缺陷)的能力。焊接通常是涉及三种材料的连接方法：(1)基材，(2)需要连接在基材上的部件或其他器件，以及(3)焊接材料本身。
有许多因素决定着良好的可焊性，其中三个最重要的因素是形成表面氧化物(腐蚀)的程度、共沉积的碳的量以及形成金属间化合物的程度。表面氧化物的形成是热力学有利的过程，因此是自然发生的。表面氧化物的形成速率取决于温度和时间。温度越高、暴露时间越长，形成的表面氧化物越厚。在电镀的锡或锡合金的涂层或沉积物中，表面氧化物的形成还取决于所述涂层或沉积物的表面形态。例如，纯锡与锡合金涂层相比，如果其他条件都相同的话，锡合金通常形成较少或较薄的表面氧化物。
共沉淀的碳由所选用的镀敷化学物质所决定。光亮的保护层的碳含量高于无光泽的保护层。无光泽的保护层通常比光亮的保护层更粗糙，其表面积更大，因此形成的表面氧化物通常比光亮的保护层上的表面氧化物更多。
金属间化合物的形成缘于锡或锡合金涂层与基材之间的化学反应。其形成速率也取决于温度和时间。较高的温度和较长的时间会形成较厚的金属间化合物层。
为确保可焊性，很重要的是1)沉积足够的锡或锡合金层，使得表面氧化物或金属间化合物的形成不会消耗掉整个层，以及2)防止镀锡表面长期暴露于高温，或使得这种暴露最小化。
1)很容易做到，但是2)难以做到。镀敷了锡或锡合金沉积物之后的后处理的温度和时间，通常是由组装规范以及现有的制造工艺和具体实施过程来决定的。例如，在“双调(two tone)”引线框技术中，在镀敷了锡或锡合金之后，整个IC单元要经历许多处理步骤(即进行长时间的这些处理)，这些处理需要在高达175℃的温度下进行多次热偏移。这样会不可避免地形成更多和更厚的表面氧化物，这又会减低所述锡或锡合金沉积物的可焊性。在目前的工艺中，这些额外的步骤无法省去，否则最终部件和组件将会无法完成。因此，需要找到一种方法来防止在这些部件上形成表面氧化物，或者使其最小化。
一种解决表面氧化物问题的方法是在锡或锡合金沉积物的表面上提供保形涂层。该技术可概括为两个大类：一类是施涂贵金属涂层，另一类是施涂有机涂层。第一大类要采用昂贵的额外步骤，因此不是所希望的保护锡或锡合金沉积物的方法。第二类会由于沉积的有机涂层的非选择性特性在引线框或电子部件的关键区域引入杂质，因此也是人们所不希望的。这些杂质对随后的引线框和IC组件的处理是有害的。
从导线连接和可焊性的方面来看，存在于引线表面的氧化镍之类的镍产品也是有重要意义的。氧化镍会影响导线连接和焊接，而且很难通过常规的酸洗技术除去。
另外，许多应用包括使涂敷的引线框受热。在热陈化条件下，如果下面的金属扩散入贵金属表面层，例如镍扩散入金，金属在层之间的扩散可能会降低表面质量。
Zhang等人的U.S.2004/0099340(WO 2004/050959)尝试通过在金属和金属合金的沉积物中结合痕量的磷来解决金属和金属合金沉积物上的表面氧化物问题。例如，在镍沉积物中，磷的含量约等于或小于200ppm，对于锡和锡合金，磷含量约等于或小于50ppm。Zhang等人称在沉积物中结合痕量的磷可减少表面氧化物在沉积物上的形成。所述磷化合物包含在金属和金属合金的电镀浴中，与所述金属或金属合金共沉淀。
尽管已经有一些方法尝试解决金属沉积物上的表面氧化物问题，但是人们仍需要改进的方法来抑制在金属保护层上形成表面氧化物和改进可焊性。
发明内容
本发明涉及方法，所述方法包括在基材上沉积镍层，在镍层上沉积镍磷(nickel phosphorous)层，并在所述镍磷层上沉积锡或锡合金。镍和镍磷层的组合可以抑制或阻止在表面保护层以及下面的金属层上形成氧化物，从而提高可焊性。氧化物的形成会使电子器件中的金属部件出现电学故障，从而降低器件的性能，因此是不希望出现的。
在另一方面，本发明涉及方法，该方法包括在基材上沉积1-10微米的镍层，在镍层上沉积0.1-5微米的镍磷层，然后在镍磷层上沉积锡或锡合金层。
在另一方面，本发明涉及制品，所述制品包括位于基材上的镍层，位于镍层上的镍磷层，以及位于所述镍磷层上的锡或锡合金层。
具体实施方式
在此实施方式中，除非上下文明确地另外说明，以下缩写的含义如下：℃＝摄氏度；g＝克；mg＝毫克；L＝升；ml＝毫升；＝埃＝1×10-4微米；ASD＝安培/分米2；重量％＝重量百分数。在此说明书中，术语“沉积”和“镀敷”可以互换地使用。所有的数据范围均包括端值且可以以任意顺序互相组合，除非从逻辑上说这些数据范围之和应为100％。
本发明的方法包括在基材上沉积镍，在镍上沉积镍磷层，并在镍磷层上沉积锡或锡合金。镍和镍磷层的组合可以抑制或防止在锡和锡合金表面层和下面的金属层上形成氧化物，从而提高可焊性。由于氧化物的形成会造成电器件中金属部件的电学故障，降低器件的性能，因此是不希望出现的。另外，镍和镍磷层的组合可减少或抑制镍向更多贵金属的迁移。
可任选地在金属化之前清洁基材。可采用金属化领域中可接受的任何合适的清洁法。通常在洗涤液中超声清洁基材。这些洗涤液可包含硅酸盐化合物、碱金属碳酸盐和其他化合物，例如碱金属氢氧化物、乙二醇醚和一种或多种螯合剂。清洁可以在30-80℃的温度下进行。
可任选地在清洁步骤之后用无机酸之类的合适的酸活化基材。使用稀的无机酸。这种酸的一个例子是硫酸。然而，也可使用其它的无机酸，例如盐酸和硝酸。使用这些酸时的浓度是本领域中众所周知的常规浓度。活化通常在室温至30℃的温度下进行。
然后通过沉积镍金属来镀敷基材。浴温为30-70℃，例如40-60℃。
可以使用任何合适的镍镀浴在基材上沉积镍层。这些镍镀浴包含一种或多种镍离子源。镍离子源包括，但不限于氯化镍之类的卤化镍、硫酸镍和氨基磺酸镍。这些镍离子源在镍浴中的含量为50毫克/升至500毫克/升，或例如100毫克/升至250毫克/升。
除了一种或多种镍离子源以外，镍镀浴还可包含一种或多种添加剂。这些添加剂包括但不限于增白剂、晶粒细化剂、匀平剂、表面活性剂、防针孔剂、螯合剂、缓冲剂、生物杀灭剂和本领域技术人员已知的其他添加剂，从而调节镀浴以获得所需的光亮保护层或无光泽的保护层和深镀能力。
增白剂包括但不限于芳族磺酸盐、磺酰胺、磺酰亚胺、脂族和芳族-脂族烯类或炔类的不饱和磺酸盐、磺酰胺和磺酰亚胺。这些增白剂的例子为邻磺基苯甲亚胺钠、1，5-萘二磺酸二钠、1，3，6-萘三磺酸三钠、苯单磺酸钠、二苯磺酰胺、烯丙基磺酸钠、3-氯-2-丁烯-1-磺酸钠、β-苯乙烯磺酸钠、炔丙磺酸钠、单烯丙基硫酰胺、二烯丙基硫酰胺和烯丙基磺酰胺。这些增白剂可以常规用量使用，例如0.5-10克/升，或例如2-6克/升。
其他增白剂包括但不限于环氧化物与α-羟基炔类醇的反应产物，例如二乙氧基化的2-丁炔-1，4-二醇或二丙氧基化的2-丁炔-1，4-二醇，N-杂环族化合物，其他炔类化合物，活性硫化物和染料。这些增白剂的例子是1，4-二-(β-羟基乙氧基)-2-丁炔，1，4-二-(β-羟基-γ-氯代丙氧基)-2-丁炔，1，4-二-(β-，γ-环氧丙氧基)-2-丁炔，1，4-二-(β-羟基-γ-丁烯氧基)-2-丁炔，1，4-二-(2’-羟基-4’-氧杂-6’-庚烯氧基)-2-丁炔，氯化N-(2，3-二氯-2-丙烯基)-吡啶，溴化2，4，6-三甲基-N-炔丙基吡啶，溴化N-烯丙基喹哪啶鎓、2-丁炔-1，4-二醇，炔丙醇，2-甲基-3-丁炔-2-醇，喹哪啶基-N-丙磺酸甜菜碱，二甲基硫酸喹哪啶，溴化N-烯丙基吡啶，异喹哪啶基-N-丙磺酸甜菜碱，二甲基硫酸异喹哪啶，溴化N-烯丙基异喹哪啶，二磺化1，4-二-(β-羟基乙氧基)-2-丁炔，1-(β-羟基乙氧基)-2-丙炔，1-(β-羟基丙氧基)-2-丙炔，磺化1-(β-羟基乙氧基)-2-丙炔，酚藏花红和品红。这些增白剂的用量为常规的用量，例如5-1000毫克/升，或例如20-500毫克/升。
可使用任何合适的表面活性剂。合适的表面活性剂包括但不限于阳离子和阴离子表面活性剂之类的离子型表面活性剂，非离子型表面活性剂和两性表面活性剂。表面活性剂可以常规的量使用，例如0.05-30毫克/升，或例如1-20毫克/升，或例如5-10毫克/升。
合适的表面活性剂的一个例子是用1-8个磺酸基(-SO3H)磺化的萘。这些表面活性剂的例子是萘-1，3，6-三磺酸和萘-1，3，7-三磺酸。也可使用钠盐和钾盐之类的碱金属盐。
其他合适的表面活性剂的例子为烷基硫酸氢盐，例如月桂基硫酸钠，月桂基醚硫酸钠和二烷基磺基琥珀酸钠。其他可用的表面活性剂的例子为包括全氟化季胺的季铵盐，例如全氟十二烷基三甲基铵。
合适的螯合剂包括但不限于氨基羧酸、多元羧酸和多膦酸。这些螯合剂可以以常规的量使用，例如0.01-3摩尔/升，或例如0.1-0.5摩尔/升。
镍浴的pH值可为1-10，或例如3-8。可通过各种方法保持镍浴的pH值。可使用任何所需的酸或碱，可使用任何无机酸、有机酸、无机碱或有机碱。除了硫酸、盐酸或氨基磺酸之类的酸以外，还可使用乙酸、氨基乙酸或抗坏血酸之类的用作螯合剂的酸。除了氢氧化钠或氢氧化钾之类的无机碱和各种胺之类的有机碱以外，还可使用碳酸镍之类的碱。另外，如果pH值会由于操作条件而波动，可使用硼酸之类的pH值缓冲组分。可根据需要的量加入缓冲剂以保持所需的pH值。
也可在镍金属镀浴中加入本领域技术人员众所周知的其他常规添加剂。它们可以常规用量使用，将镍层调节为所需的无光泽、半光亮或光亮的保护层。
将镍沉积在基材上，直至形成1-10微米，或例如2-5微米厚的镍层。然后使用镍磷浴在镍层上镀敷镍磷层。
镍磷浴包含一种或多种上述镍离子源，可包含一种或多种上述添加剂。另外，镍磷浴包含一种或多种磷源。可使用任何合适的亚磷酸或磷酸或其盐盐和混合物。镀浴中亚磷酸和磷酸及其盐的含量为5-100毫克/毫升，或例如10-80毫克/升，或例如20-50毫克/升。亚磷酸的通式为H3PO3，也被称为原亚磷酸。磷酸包括但不限于例如磷酸(H3PO4)(也称为原磷酸)之类的无机磷酸。也可使用多磷酸。无机磷酸可表示为：Hn+2PnO3n+1，式中n是等于或大于1的整数。当n是等于或大于2的整数时，该式表示多磷酸。当无机磷酸是多磷酸时，n通常是一定的整数，使得多磷酸的平均分子量为110-1,500原子量单位。通常使用亚磷酸。
可使用磷酸盐，例如碱金属磷酸盐和磷酸铵。碱金属磷酸盐包括磷酸氢二钠、磷酸三钠、磷酸氢二钾和磷酸三钾。也可使用多磷酸盐。也可使用无机磷酸及其盐的混合物。这些酸可以在市场上购得，或者可根据文献的描述制备。
在与将镍层沉积在基材上相同的温度下，在镍层上沉积镍磷层。持续进行沉积，直至在镍层上沉积了0.1-5微米、或例如0.2-1微米的镍磷层，以形成二相体。
通常二相体中镍与镍磷的重量比为2∶1至8∶1。可采用本领域已知的任何合适的电解沉积法沉积镍层和镍磷层。可使用常规的镀敷设备来沉积镍和镍磷层。电流密度可为1ASD-20ASD，或例如5ASD-15ASD。
通常镍和镍磷二相层的厚度为2-3微米。在将镍和镍磷层沉积在基材上之后，将锡或锡合金表面保护层沉积在镍磷层上。可使用任何合适的锡或锡合金浴。用于镀浴的锡离子源包括但不限于硫酸锡、烷基磺酸锡(例如磺酸锡、链烷醇磺酸锡)和氯化锡之类的卤化锡。锡浴也可包含硫酸、烷基磺酸盐、链烷醇磺酸盐和卤代盐之类的电解质，以提供导电基质。也可包含表面活性剂和其他常规添加剂以提供所需的锡层。这些组分的用量为常规用量，是本领域众所周知的，可以由文献中获得。U.S.5,174,887和U.S.5,871,631揭示了合适的电镀浴。U.S.4,880,507和U.S.4,994,155揭示了合适的锡-铅镀浴。除了锡-铅以外，还可使用其它的锡合金，这些合金包括但不限于锡-铜，锡-铜-银和锡-银，锡-铋，锡-镍，锡-锑，锡-铟和锡-锌。用来沉积这些锡合金的镀浴的配方是本领域众所周知的，可以由文献获得。
可以通过任何本领域已知的合适方法沉积锡和锡合金。通常通过电解法将锡和锡合金沉积在镍磷层上。通常持续进行锡或锡合金沉积，直至镀敷在镍磷层上的锡或锡合金层厚度达到10-50微米。
通常锡和锡合金浴温为15-40℃，或例如25-30℃。电流密度通常为1-35ASD，或例如5-30ASD，或例如10-20ASD。但是也可使用任何用来电镀锡和锡合金的常规电流密度。在文献中揭示了许多这样的镀敷条件。
在将锡或锡合金层沉积在镍磷层上之后，对锡或锡合金层进行重熔处理。重熔可以通过以下加热、气相重熔、激光重熔、等离子、加热炉熔融和使电流通过锡或锡合金来进行，或者能够将锡或锡合金加热至高于其液相线温度的其他方法进行。这些重熔处理是本领域众所周知的。
通常在传导/对流加热炉内进行重熔。重熔温度可为100-350℃。锡或锡合金可以在该范围内的温度区间中保持特定的时间，然后加热至更高的温度区间。通常锡或锡合金在一定温度区间内保持20-50秒。在重熔循环结束时，将锡或锡合金冷却至室温。
通过上述方法形成的制品包括镀敷有镍层和镍层上的镍磷层、形成二相体的基材。镍磷层的磷含量可为0.1-15重量％，或例如1-10重量％，或例如3-8重量％。可以在镍磷层上沉积锡或锡合金层以形成制品。由镍和镍磷层形成的二相层抑制了镀敷在其上的锡和锡合金的氧化。另外，对在锡或锡合金层上形成氧化物的抑制提高了制品的可焊性。相对于发生表面氧化的锡或锡合金涂敷的制品，锡或锡合金涂敷的制品上焊接的连接器更加牢固，更不易分离。
重熔之后，锡和锡合金会形成氧化锡(SnO和SnO2)。这可以通过重熔之后，沉积的锡的表面发生变色而表现出来。重熔的锡暴露的时间越久，温度越高，变色越明显。通常观察到的是锡表面由白变黄。在更剧烈的氧化的情况下，在重熔之后，锡可能呈棕色甚至紫色。锡的氧化可能会导致镀锡的电子器件(例如印刷电路板和引线框)中发生导电性变差或短路现象。另外，锡或锡合金表面的氧化会降低随后的任何焊接过程的性能。焊接不良会在电子器件制造中导致焊接的部件分离。所述二相体减少或抑制了不希望存在的氧化，从而提供了优于具有氧化的锡或锡合金的制品的焊接连接。
这些方法可用来在任何合适的基材上沉积镍和镍磷的二相体。通常这些基材是金属或金属合金。合适的金属包括但不限于铜、铁、它们的合金、不锈钢和贵金属，例如金、铂、钯、银和它们的合金。通常基材是铜、铜合金、铁和铁合金。合适的铜合金包括但不限于铜-锡、铜-银、铜-金、铜-银-锡、铜-磷-金、铜-锌、铜-银-镁、铜-铁-锌、铜-锡-镍-硅、铜-锆、铜-铁-磷-锌和铜-镍-硅-镁。合适的铁合金包括但不限于铁-铜和铁-镍。这些基材包括但不限于电器件的部件，例如印刷电路板、连接器、晶片凸块、引线框以及无源部件，例如用于IC单元的电阻和电容器。
通过以下本发明实施例进一步说明本发明，但是这些实施例并不会对其范围构成限制。
实施例
实施例1(比较例)
在65℃、包含100克/升RONACLEANTM CP-100(该试剂是购自美国宾夕法尼亚州，费城，罗门哈斯公司的包含硅酸盐的清洁组合物)的洗涤液中对九(9)个铜-锡合金引线框进行超声清洁30秒。
清洁之后，在室温下将各个引线框浸入100毫升/升的工业级硫酸中处理10秒。然后在各个引线框上镀敷1-2微米厚的镍层。用来对各个引线框进行镀敷的镍浴具有下表1所示的组成。
表1
    组分     浓度
    氨基磺酸镍     125克/升
    氯化镍     8克/升
    硼酸     35克/升
    磺化萘化合物     0.5克/升
    苯并硫酰亚胺化合物     5克/升
    醛     0.5克/升
    水     余量
镍浴的pH值为4，镀浴温度为55℃。将各个引线框置于包含电解镍浴的薄膜电池(Hull cell)内。引线框作为阴极，阳极是硫/镍电极。在镍沉积过程中用桨叶搅拌镍浴。将镀敷设备与常规的整流器相连。电流密度为5-10ASD。镍沉积在4-90秒内完成，在引线框上提供镍层。
然后使用具有下表2所示的组成的镀浴在八(8)个具有镍层的引线框上镀敷镍磷层。
表2
    组分     浓度
    氨基磺酸镍     125克/升
    亚磷酸     50克/升
    硼酸     35克/升
    二甘油基醚     30豪克/升
    烷基硫酸氢盐     1毫克/升
    水     余量
所述镍磷浴的pH值为1.5，在镀敷过程中的温度为55℃。镍磷沉积在薄膜电池中进行，沉积时使用桨叶进行搅拌，电流密度为5-10ASD。在16-94秒内对八(8)个镀镍的引线框进行电镀，以提供具有各种厚度的镍磷层。镍磷层的厚度为0.1-1微米。
然后在包含锡电镀浴的薄膜电池中对全部九(9)个引线框进行电镀，在各个引线框上形成光亮的锡层。所述锡浴包含60克/升来自甲磺酸锡的锡离子，以及250毫升/升的70％甲磺酸作为基质。镀锡在室温、电流密度为10ASD的条件下进行30秒。
将全部九个镀锡引线框置于Sikama FalconTM 8500传导/对流加热炉内，使它们的锡层重熔。温度曲线为125℃-180℃-240℃-260℃-240℃，然后冷却至室温。每个引线框在各温度区间保持30秒。
重熔之后，检查引线框暴露于空气24小时之后锡层表面发生氧化的情况。采用目视检查标准0-5。如果未观察到氧化，引线框评为0级；如果发生严重变色，引线框评为5级。镀敷了镍层且未镀敷镍磷层的引线框很明显地发生了变色，因此评为了5级。引线框表面上具有紫色的污点。剩下八个镀敷有位于镍层之上的镍磷层二相体的引线框被评为1级。它们发生一定的变白，但是并未发生不含二相层的引线框那样严重的变色。
结果表明，相对于不包括二相层的引线框，在镍层上添加镍磷层可以减少对锡层的表面氧化。
实施例2(比较例)
在65℃下，在包含100克/升RONACLEANTM CP-100(一种包含硅酸盐的组合物)的洗涤液中对九(9)个铜-锡合金引线框进行超声波清洁。
清洁之后。在室温下将各个引线框浸没在100毫升/升的工业级硫酸中处理10秒钟。然后在各个引线框上镀敷1-2微米厚的镍层。用来镀敷各个引线框的镍浴的组分如下表3所示。
表3
    组分     浓度
    氨基磺酸镍     125克/升
    氯化镍     8克/升
    氨基乙酸     30克/升
    磺化的萘化合物     1克/升
    苯并硫酰亚胺化合物     5克/升
    醛     0.5克/升
    水     余量
该镍浴的pH值为3，镀浴温度为55℃。将各个引线框置于包含所述电解镍浴的薄膜电池中。引线框作为阴极，阳极是硫/镍电极。在镍沉积过程中，用桨叶搅拌镍浴。将镀敷设备与常规的整流器相连。电流密度为5-10ASD。镍沉积在4-90秒内完成。
使用具有下表4所示组成的镀浴在具有镍层的八个(8)引线框上镀敷镍磷层。
表4
    组分     浓度
    氨基磺酸镍     125克/升
    亚磷酸     50克/升
    硼酸     30克/升
    氨基乙酸     25克/升
    磺化萘化合物     0.5克/升
    二甘油基醚     35豪克/升
    水     余量
所述镍磷浴的pH值为1，在电镀过程中的温度为55℃。在薄膜电池中进行镍磷沉积，在沉积过程中用桨叶进行搅拌，电流密度为5-10ASD。在16-94秒内，在八个镀锡的引线框上进行镀敷。镍磷的厚度为0.1-1微米。
然后在包含锡镀浴的薄膜电池内对全部九个引线框进行电镀，在每个引线框上形成明亮的锡层。所述锡镀浴包含60克/升来自甲磺酸盐的锡离子和250毫升/升作为基质的70％甲磺酸。镀锡在室温、电流密度10ASD的条件下进行30秒。
将全部九个镀锡的引线框置于Sikama FalconTM8500传导/对流加热炉内，使它们的锡层重熔。温度曲线为125℃-180℃-240℃-260℃-240℃，然后冷却至室温。各引线框在每个温度区间保持30秒。
重熔之后，检查引线框暴露于空气24小时之后锡层发生表面氧化的情况。采用目视检查标准0-5。如果未观察到氧化，引线框评为0级；如果发生严重变色，引线框评为5级。镀敷了镍层且未镀敷镍磷层的引线框很明显地发生了变色，因此评为了5级。引线框表面上具有紫色的污点。剩下八个镀敷有位于镍层之上的镍磷层二相体的引线框被评为1级。它们发生一定的变白，但是并未发生不含二相层的引线框那样严重的变色。结果表明，相对于不包括二相层的引线框，在镍层上添加镍磷层可以减少对锡层的表面氧化。
实施例3
重复以上实施例1中所述的过程，其不同之处仅在于，各引线框在锡-铜合金电镀浴中、电流密度10ASD的条件下进行电镀，在镍磷层上形成锡-铜合金层。所述锡-铜合金镀浴包含50克/升的甲磺酸锡(II)形式的锡；1克/升的甲磺酸铜(II)形式的铜；160克/升的游离甲磺酸，27克/升的乙氧基化的β-萘酚；7克/升的乙氧基化的双酚A，1克/升的增亮剂；3克/升的甲基丙烯酸；0.8克/升的晶粒细化剂和5克/升的羧甲基化的聚乙烯亚胺(分子量为50,000道尔顿，羧基化程度为80％，商品名为TRILON ES9300)。
重熔和暴露于空气24小时之后，在包括镍和镍磷二相体的引线框的锡-铜表面上未观察到氧化。相反，仅有镍层的引线框上的锡-铜层发生了氧化。
实施例4
重复实施例2所述的过程，其不同之处在于，在引线框上镀敷了锡-银合金层而非锡层。在50ASD的电流密度下对各个引线框镀敷了锡-银层。锡-银合金镀浴包含50克/升甲磺酸锡形式的锡；1.5克/升的甲磺酸银形式的银；6克/升的硫脲；200毫升/升的甲磺酸；2克/升的聚烷氧基化物；0.25克/升的乙基麦芽醇和0.25克/升的3-甲基-1，2-环戊酮。
在进行了重熔并且暴露于空气24小时之后，在具有镍和镍磷二相体的引线框的锡-银表面上未观察到氧化。相反，仅含镍层的引线框上的锡-银层发生了氧化。
实施例5
重复实施例2的过程，其不同之处在于，用锡-铅合金代替锡来镀敷引线框。在5ASD的电流下，对每个引线框镀敷锡-铅层。锡铅合金浴包含40克/升来自甲磺酸锡的锡；26克/升来自甲磺酸铅的铅和200毫升/升的甲磺酸。
在进行了重熔并且暴露于空气24小时之后，在具有镍和镍磷二相体的引线框的锡-铅表面上未观察到氧化。相反，仅含镍层的引线框上的锡-铅层发生了氧化。

Claims (10)

1.一种方法，该方法包括在基材上沉积镍层，在所述镍层上沉积镍磷层，以及在所述镍磷层上沉积锡或锡合金层。
2.如权利要求1所述的方法，该方法还包括对所述锡或锡合金层重熔的步骤。
3.一种方法，该方法包括在基材上沉积1-10微米的镍层，在所述镍层上沉积0.1-5微米的镍磷层，以及在所述镍磷层上沉积锡或锡合金层。
4.如权利要求3所述的方法，其特征在于，所述镍磷层中的磷含量为0.1-15重量％。
5.一种制品，该制品包括位于基材上的镍层，位于所述镍层上的镍磷层和位于所述镍磷层上的锡或锡合金层。
6.如权利要求5所述的制品，其特征在于，所述镍磷层包含0.1-15重量％的磷。
7.如权利要求6所述的制品，其特征在于，所述镍磷层包含1-10重量％的磷。
8.如权利要求5所述的制品，其特征在于，所述镍层的厚度为1-10微米，所述镍磷层的厚度为0.1-5微米。
9.如权利要求5所述的制品，其特征在于，所述镍层和镍磷层的厚度为2-3微米。
10.如权利要求5所述的制品，其特征在于，所述制品是印刷电路板、引线框、电连接器、晶片凸块或无源部件。
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CN101784165A (zh) * 2010-03-19 2010-07-21 中兴通讯股份有限公司 一种印制电路板耐腐蚀可焊涂层处理方法
CN101784165B (zh) * 2010-03-19 2014-11-05 中兴通讯股份有限公司 一种印制电路板耐腐蚀可焊涂层处理方法
CN103687983A (zh) * 2011-05-19 2014-03-26 安科有限两合公司 用于电解应用的润湿剂及其应用

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SG131043A1 (en) 2007-04-26
KR20070028266A (ko) 2007-03-12
JP2007070730A (ja) 2007-03-22
US7615255B2 (en) 2009-11-10
US20070052105A1 (en) 2007-03-08
HK1101603A1 (en) 2007-10-18
SG131046A1 (en) 2007-04-26
EP1762641A3 (en) 2008-05-07
EP1762640A3 (en) 2008-05-21
EP1762640A2 (en) 2007-03-14
TWI371797B (en) 2012-09-01
CN1936094B (zh) 2011-06-22
TW200714732A (en) 2007-04-16
US20070054138A1 (en) 2007-03-08
EP1762641A2 (en) 2007-03-14
KR20070028265A (ko) 2007-03-12
TWI326717B (en) 2010-07-01
JP2007070731A (ja) 2007-03-22
CN1936095A (zh) 2007-03-28
JP5026031B2 (ja) 2012-09-12

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