CN1936095A - 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
CN1936095A
CN1936095A CNA2006101291921A CN200610129192A CN1936095A CN 1936095 A CN1936095 A CN 1936095A CN A2006101291921 A CNA2006101291921 A CN A2006101291921A CN 200610129192 A CN200610129192 A CN 200610129192A CN 1936095 A CN1936095 A CN 1936095A
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China
Prior art keywords
nickel
gold
layer
phosphorus
acid
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CNA2006101291921A
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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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Publication of CN1936095A publication Critical patent/CN1936095A/zh
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    • 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
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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腐蚀和提高基材的可焊性。所述基材具有金或金合金保护层。

Description

金属二相体及其制备方法
技术领域
本发明涉及具有金或金合金层的低含磷量金属二相体(metal duplex)以及制备该具有金或金合金层的低含磷量金属二相体的方法。更具体来说，本发明涉及具有金或金合金层的低含磷量金属二相体，以及制备所述具有金或金合金层的低含磷量金属二相体，以抑制腐蚀并提高可焊性的方法。
背景技术
在许多工业领域中，防止金和金合金的腐蚀是一个挑战性的问题。在电子材料工业中，金和金合金的腐蚀是一个特别大的问题，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，金和金合金涂层被用于电子学和其他应用中。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。但是金保护层并非总是能防止腐蚀。
具有IC单元、引线框和无源部件(例如电容器和晶体管)的IC器件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单元与外界电路电互连的装置。引线框由铜或铜合金之类的导电性材料形成，或者是通过将金属坯件冲压或蚀刻成大量引线限定出用来安装IC单元的中心区域而形成的。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性质。通常这意味着该表面不会被腐蚀，而且容易与金导线或铝导线、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。焊接通常是包括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腐蚀的程度，共沉积的碳量以及金属间化合物形成的程度。腐蚀是热力学有利的过程，因此是自然发生的。腐蚀的速率取决于温度和时间。温度越高、暴露时间越长，腐蚀越厚。
共沉淀的碳由所选用的镀敷化学方式所决定。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，因此其腐蚀程度通常比光亮的保护层的腐蚀程度更严重。
金属间化合物的形成是金属涂层与下面的金属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。
在将金沉积在基材上的时候，金的某些物理性质，例如其相对多孔性就带来了问题。例如，金的多孔性会在镀敷的表面上产生空隙。这些小的间隔能够促进腐蚀，或者实际上通过金层与下面的基底金属层的电耦合而加快腐蚀。人们认为这是由于基底金属基材和任意附带的下部金属层可能会通过金外表面中的孔暴露于腐蚀性元素而造成的。
另外，许多应用包括使涂敷的引线框暴露于加热情况。在热老化条件下，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导致降低表面性质。
人们已经尝试了至少三种不同的方法来克服腐蚀的问题：1)减少涂层的孔隙，2)抑制由于不同金属的电势差引起的电流效应，以及3)将电镀层中的孔密封起来。减少孔隙这一方法已经被广泛地研究。脉冲镀金和在金镀浴中使用各种润湿剂/晶粒细化剂会影响金的结构，这是两个可以减少金的孔隙的因素。通常在一系列电镀浴或容器中，将进行有规律的碳浴处理和良好的过滤与预防性维护程序相结合，有助于保持金的金属沉积程度，相应地减少表面孔隙。但是其中仍然具有一定的孔隙度。
已经尝试了孔封闭、密封和其他抑制腐蚀的方法，但是所取得的成果很有限。使用具有抑制腐蚀效果的有机沉淀物的潜在的机理是本领域已知的。许多这样的化合物通常可溶于有机溶剂，因此认为它们无法提供长期防腐保护。密封孔或封闭孔的其他方法是基于在孔内形成不溶性化合物。本领域技术人员显而易见的这些不溶性配合物和沉积物也是用来封闭孔的潜在的候选对象。
除了形成孔的问题以外，例如在热老化过程中使金暴露于高温，也会提高金的接触电阻，这是人们所不希望出现的。这种接触电阻的增大会降低金作为电流导体的性能。从理论上来说，工人们认为该问题是由与金一起共沉淀在接触面上的有机材料的扩散造成的。迄今为止已经尝试了各种技术以消除这一问题，这些技术通常包括电解抛光。但是这些技术均无法完全令人满意地达到这一目的，研究仍在继续进行。
Yeh等人在U.S.6,287,896中揭示了在铜或铜合金基板上施加镍-钴合金厚涂层。该专利称，该镍-钴厚层对于减少孔隙的影响和防止铜从基板扩散到用于焊接的表面是很重要的。在该镍-钴厚层上涂敷了镍或镍合金以防其产生裂纹(这是镍-钴层的一个固有问题)。在镍或镍合金层上涂敷了金或金合金层。据称该金或金合金层提高了可焊性。
尽管已经有一些方法尝试解决金属沉积物上的腐蚀和可焊性问题，但是人们仍需要改进的方法来抑制腐蚀和提高可焊性。
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金或金合金层，所述镍磷层包含0.1-10重量％的磷。镍和镍磷层的组合可以抑制或阻止热老化的影响，从而减少了金或金合金层中的孔的形成。金或合金层中的孔的减少可以减少或防止下面的基材的腐蚀，从而提高了该金或金合金保护层的可焊性。
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金或金合金层，所述镍磷层包含0.1-10重量％的磷。
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金或金合金层，所述镍磷层包含0.1-10重量％的磷。
附图摘要
图1是在镍下层上的具有孔的金层的50倍放大的照片；
图2是在镍磷下层上的具有孔的金层的50倍放大的照片。
具体实施方式
在此实施方式中，除非上下文明确地有其他说明，否则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。所有的数值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值范围被限定为总和应为100％。
本发明的方法包括在基材上沉积镍层，在镍层上沉积镍磷层，并在镍磷层上沉积金或金合金，磷镍层包含0.1至10重量％的磷。镍和镍磷层的组合可以减少热老化的影响，从而减少金和金合金层中的孔的形成。通过减少孔的形成，可以减少或消除下面的金属基材的腐蚀，还可提高金或金合金层的可焊性。另外，镍和镍磷层可减少或抑制镍向金或金合金层的迁移。
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。通常在洗涤液中对基材进行超声清洁。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、生物杀伤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酰亚胺钠、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克/升至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，活性硫化合物和染料。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，二磺化的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，磺化的1-(β-羟基乙氧基)-2-丙炔，酚藏红花和品红。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。这些合适的表面活性剂包括但不限于阳离子型和阴离子型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，例如氟化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、多羧酸和多膦酸。这些螯合剂可以以常规的量使用，例如0.01摩尔/升至3摩尔/升，或例如0.1摩尔/升至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，直至在基材上形成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和混合物。镀浴中亚磷酸和磷酸及其盐的含量为5-100毫克/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的相同的温度下，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至20ASD，或例如5ASD至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，将金或金合金表面保护层沉积在镍磷层上。
通过上述方法形成的制品包括镀敷有镍层和位于镍层上的镍磷层、形成二相体的基材。镍磷层的磷含量可为0.1-10重量％，或例如0.5-10重量％，或例如1-9重量％，或例如2-8重量％，或例如3-7重量％。在镍磷层上沉积金或金合金层以形成制品。由镍和镍磷层形成的二相层抑制了金或金合金层中的孔的形成，还抑制了镍向金或金合金层中的迁移。与不包括所述二相层的涂敷了金或金合金的制品相比，焊接在本发明的涂敷了金或金合金的制品上的连接器更为牢固，更加不易分离。
可以使用任何合适的金离子源和合金金属离子源将金或金合金沉积在镍磷层上。金离子源包括但不限于二氰金(I)酸钠、二氰金(I)酸铵和其他二氰金(I)酸盐；四氰金(III)酸钾，四氰金(III)酸钠，四氰金(III)酸铵和其他四氰金(III)酸盐；氰化金(I)，氰化金(III)；二氯金(I)酸盐；四氯金(III)酸，四氯金(III)酸钠和其他四氯金(III)酸化合物；亚硫酸金铵，亚硫酸金钾，亚硫酸金钠和其他亚硫酸金盐；氧化金，氢氧化金及其其它的碱金属盐；以及硝基亚硫酸基金配合物。金源的含量通常为常规用量，例如0.1毫克/升至10克/升或例如1-5毫克/升。
合金金属包括但不限于铜、镍、锌、钴、银、铂族金属、镉、铅、汞、砷、锡、硒、碲、锰、镁、铟、锑、铁、铋和铊。通常所述合金金属是钴。这些合金金属源是本领域众所周知的。镀浴中的合金金属源为常规含量，可根据所用合金金属的种类在很大的范围内变化。
除了金源和合金金属源以外，所述金和金合金浴还可包含一种或多种添加剂。这些添加剂包括但不限于表面活性剂、增白剂、匀平剂、配合剂、螯合剂、缓冲剂和生物杀伤剂。这些添加剂用量为常规量，是本领域技术人员众所周知的。
可通过任何本领域已知的任何合适方法将金或金合金沉积在镍磷层上。这些方法包括但不限于电解沉积和浸没沉积，通常金或金合金是电解沉积的。用来电解沉积金和金合金的电流密度为1-30ASD，或例如5-20ASD。
金或金合金在被沉积到镍磷层上之后，其通常会发生热老化。热老化可通过本领域已知的任何合适的方法进行。目前没有标准的热老化要求，采用各种方法进行热老化。这些方法包括但不限于蒸汽老化和干烘焙。所述镍和镍磷二相体抑制了镍表面扩散进入金表面保护层中，从而提高了可焊性。
除了防止非贵金属扩散进入金和金合金中之外，该二相体还可减少或抑制金和金合金层的孔隙，从而减少渗入金属层中的氧气。金和金合金的孔隙的减少可以减少或防止不希望出现的下层金属的氧化。这又可以提高金和金合金表面保护层的可焊性，并减小接触电阻。
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、铁和它们的合金、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气器件的组件，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℃下，在包含100克/升的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)洗涤液中对三(3)个铜-锡合金引线框进行30秒的超声清洁。
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电镀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
    磺化的萘化合物     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50℃。然后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。在沉积过程中用桨叶搅拌镍浴。将设备与常规的整流器相连。电流密度为10ASD。镍沉积在90秒内完成。
然后在两(2)个镀镍的引线框上镀敷1微米厚的镍磷层。用来镀敷这两个引线框的镍磷浴具有下表2所示的组成。
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毫克/升
    烷基硫酸氢盐     1克/升
    水     余量
所述镍磷浴的pH值为1，在镍磷沉积过程中的温度为60℃。镍磷沉积在薄膜电池中进行，沉积时使用桨叶进行搅拌，镀敷第一引线框的电流密度为10ASD，镀敷第二引线框的电流密度为5ASD。第一引线框的电镀在60秒(10ASD)内完成，第二引线框的电镀在30秒(5ASD)内完成。在10ASD的电流密度下镀敷的镍磷层的磷含量为6重量％，在5ASD的电流密度下镀敷的镍磷层的磷含量为9重量％。磷含量是通常常规的能量分散X射线谱测定的。测量1×1毫米的区域。
然后在这三个引线框上各镀敷0.2-0.5微米厚的金层。金电解质包括12克/升的源自亚硫酸金钠的金离子和常规的金电解质添加剂。镀金在35℃、电流密度3ASD的条件下进行4秒。
然后在235℃下在各个引线框上焊接共熔锡/铅焊料。然后根据军用规范883C，方法2003对焊接后的引线框进行蒸汽老化，该方法包括在95℃、相对湿度95％的条件下蒸汽老化8小时。这模拟了至少6个月的储存期。
在蒸汽老化之后，测定各个引线框的零交叉时间，以测定其可焊性能。使用Menisco ST-50可焊性测试仪测定零交叉时间。不包括镍磷层的引线框的零交叉时间为3-2秒，磷含量为6重量％的引线框的零交叉时间为1.8秒，磷含量为9重量％的引线框的零交叉时间为0.9秒。因此，镍和镍磷层的可焊性能优于不包括镍和镍磷层的引线框。
实施例2(比较例)
在60℃下，在RONACLEANTM CP-100洗涤液中对两(2)个黄铜引线框进行30秒的超声波清洁。然后在室温下将引线框浸没在100毫升/升的工业级硫酸溶液中处理10秒钟。然后使用具有下表3所示组成的镍浴在各个引线框上电镀2微米厚的镍层。
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     5克/升
    醛     0.5克/升
    水     余量
该镍浴的pH值为3，镀浴温度为50℃。将各个引线框置于包含所述电解镍浴的薄膜电池中。在10ASD的电流密度下将镍沉积在引线框上。镍沉积在80秒内完成。在电镀过程中用桨叶搅拌该镀浴。
使用具有下表4所示组成的镀浴在其中一个引线框上镀敷1微米的镍磷层。
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
    磺化的萘化合物     0.5克/升
    二甘油基醚     35毫克/升
    水     余量
所述镍磷层的磷含量为9重量％。所述镀浴的pH值为1，电镀在60℃下完成。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。电镀时，电流密度保持在5ASD，在20秒内完成。
然后在各个引线框上镀敷0.2-0.5微米厚的金层。所述金浴包含12克/升的源自亚硫酸金钠的金离子，以及常规的金电解质添加剂。镀金在30℃、电流密度3ASD的条件下在4秒内完成。
然后将各个引线框置于干燥器中的塑料支架上。然后在室温下向该干燥器中加入浓度大于65％的发烟硝酸蒸汽，处理1小时。然后使用去离子水淋洗除去硝酸。然后将各个引线框的金表面置于50倍放大的Nomarski显微镜下，检查金层是否形成孔。图1显示了没有镀敷镍磷层的引线框的金表面。在金层中形成了大量的孔。相反的，图2显示了包括镍磷层的引线框上的金层。形成的孔很稀疏。因此，金层下的镍和镍磷层能够减少金中的孔的形成。
实施例3(比较例)
在65℃，使用100克/升的ROANACLEANTM CP-100洗涤液中对三(3)个黄铜引线框进行30秒的超声清洁。清洁之后，在室温下将各个引线框浸入100毫升/升的工业级硫酸溶液中处理10秒。然后使用上表1所示的镍电解质在各个引线框上电镀2微米厚的镍层。镍沉积在薄膜电池中进行，其pH值为4，温度为50℃。电流密度为10ASD，沉积在80秒内完成。
然后在两个(2)引线框上镀敷1微米厚的镍磷层。所用的镍磷电解质与上表2所述相同。电解质的pH值为2，镍磷沉积在50℃的温度下进行。其中一个镀浴的电流密度为10ASD，另一个为5ASD。每份镀浴的镍磷沉积都在20秒内完成。
然后在薄膜电池中，在电流密度3ASD的条件下用金对全部三个引线框电镀4秒钟。该金电解质包含12克/升的源自亚硫酸金的金离子以及常规的金电解质添加剂。镀浴的温度为30℃。
然后根据军用规范883C，方法2003对镀金后的各引线框进行蒸汽老化，该方法包括在95℃、相对湿度95％的条件下蒸汽老化8小时。然后对引线框测试渗入镍层中的氧气，以及镍向金层的迁移。
下表4揭示了测试结果。不同溅射深度下的各种元素的原子％是使用常规的X-射线光电子分光仪在超高真空室内测定的。
表4
            Ni/Au          Ni/Ni-P/Au(7重量％P)      Ni/Ni-P/Au(10重量％P)
  深度()     Au     Ni     O     Au     Ni     O     P     Au  Ni     O     P
  0     8.9     32.3     58.8     23.2     19.9     56.9     -     8.1  36.3     55.6     -
  100     15.1     50.6     34.3     97.8     5.4     0.4     -     77.1  17.7     5.2     -
  200     14.1     44.4     41.5     89.6     2.2     -     -     88.7  7.3     2.7     1.3
  300     6.2     54.1     39.7     89.6     9.3     -     1.1     91.9  7.1     1.0     -
  330     5.4     54.4     40.42     58.1     37.5     -     4.4     85.0  13.1     -     1.9
  360     4.9     55.4     39.7     27.6     66.0     -     6.4     63.4  29.4     2.1     5.1
  390     4.5     56.1     39.4     13.2     82.2     -     4.6     42.6  48.0     1.0     8.4
  420     4.5     56.2     39.3     7.4     88.1     -     4.5     26.5  63.4     1.9     8.2
  450     4.2     56.7     39.1     5.2     91.1     -     3.7     16.5  75.6     2.4     5.5
  480     4.3     56.3     39.4     4.3     91.7     -     4.0     11.0  82.4     1.9     4.7
  510     4.2     56.9     38.9     3.7     92.8     -     3.5     7.5  88.5     1.8     2.2
  540     4.0     56.7     39.3     3.5     92.5     0.7     3.3     5.6  91.6     1.8     1.0
  570     4.0     56.9     39.1     3.3     92.0     0.6     4.1     4.3  93.6     1.8     0.3
  600     3.9     57.1     39.0     3.1     92.5     0.4     4.0     3.4  94.9     1.7     -
  630     3.9     57.1     39.0     2.9     92.7     0.7     3.7     2.6  95.6     1.8     -
  660     3.9     57.5     38.6     2.9     92.7     0.4     4.0     2.3  96.0     1.7     -
  690     3.9     57.4     38.7     2.8     93.3     0.4     3.5     2.1  96.2     1.7     -
  720     3.9     57.4     38.7     2.8     93.5     0.3     3.4     2.1  96.2     1.7     -
  750     3.8     57.8     38.4     2.7     93.0     0.7     3.6     1.6  96.8     1.6     -
  780     3.9     57.4     38.7     2.6     93.1     0.4     3.9     1.5  96.7     1.8     -
  810     3.8     58.0     38.2     2.5     93.5     0.4     3.6     1.4  96.7     1.9     -
  840     3.7     58.0     38.3     2.6     93.3     0.4     3.7     1.3  97.0     1.7     -
  870     3.8     58.7     37.5     2.4     93.5     0.5     3.6     1.2  97.2     1.6     -
  900     3.6     58.1     38.3     2.5     93.0     0.3     4.2     1.2  96.9     1.9     -
上表中的结果说明，镀敷了镍磷层的引线框的金属层中的氧含量远低于仅有镍层的引线框的氧含量。具有磷含量为10重量％的镍磷层的引线框的金属层中的氧的原子百分数为：在100的深度处具有5.2原子％的高氧含量，在330具有0原子％的低氧含量。全部深度的平均氧原子％为4.1。磷含量为7重量％的引线框在540具有0.7原子％的高氧含量，在200-510具有0原子％的低氧含量。全部深度的平均氧含量为2.6原子％。相反的，没有镍磷层的引线框在200具有41.5原子％的高氧含量，在100具有34.3原子％的低氧含量。全部深度的平均氧含量为36原子％。因此，镍磷层减少了氧的渗透。
实施例4
重复实施例2，只是使用水性金-钴合金电镀浴在镍或镍磷层上镀敷金-钴层。金-钴合金浴包含4克/升氰化金钾、1克/升的硫酸钴(0.25克/升的钴离子)和150克/升的亚甲膦酸。该水性金-钴镀浴的pH值为4。使用氢氧化钾保持该镀浴的pH值。镀浴保持在40℃，电流密度为1ASD。持续进行电镀直至各引线框的镍磷层上形成0.2-0.5微米的金-钴层为止。
然后如实施例2所述，将各个引线框置于干燥器中的塑料支架上，使其暴露于发烟硝酸。预期具有二相体的引线框上的金-钴层中的孔的数量比只有镍层的引线框上的金-钴层中的孔的数量要少。
实施例5
重复实施例4，只是水性金-钴合金电镀浴包含4克/升的氰化金钾，1克/升的亚甲膦酸钴的四钾盐形式的钴，124克/升的柠檬酸三钾、29克/升的柠檬酸和45克/升的磷酸二氢钾。将镀浴的pH值保持在5，镀浴的温度保持在35℃。电流密度为1ASD，通过镀敷在各个引线框上形成0.2-0.5微米的金-钴层。
使用发烟硝酸处理各个引线框之后，预期具有二相层的引线框上的金-钴层中的孔的数量少于不包括二相层的引线框上的金-钴层中的孔的数量。

Claims (8)

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和在所述镍磷上沉积金或金合金层，所述镍磷层包含0.1-10重量％的磷。
2.如权利要求1所述的方法，其特征在于，所述镍磷层包含1-9重量％的磷。
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金或金合金层，所述镍磷层包含1-10重量％的磷。
4.如权利要求3所述的方法，该方法还包括对所述金或金合金层进行热老化的步骤。
5.一种制品，该制品包括位于基材上的镍层和位于所述镍层上的镍磷层，以及位于所述镍磷层上的金或金合金层，所述镍磷层包含0.1-10重量％的磷。
6.如权利要求5所述的制品，其特征在于，所述镍磷层包含1-9重量％的磷。
7.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。
8.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、连接器、晶片凸块或无源部件。
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