CN103029369A - 耐高温的银涂层基体 - Google Patents

耐高温的银涂层基体 Download PDF

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CN103029369A
CN103029369A CN2012105172471A CN201210517247A CN103029369A CN 103029369 A CN103029369 A CN 103029369A CN 2012105172471 A CN2012105172471 A CN 2012105172471A CN 201210517247 A CN201210517247 A CN 201210517247A CN 103029369 A CN103029369 A CN 103029369A
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silver
nickel
tin
layer
copper
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CN103029369B (zh
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W·张-伯格林格
M·克劳斯
M·P·托本
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Rohm and Haas Electronic Materials LLC
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Abstract

本发明涉及耐高温的银涂层基体。将锡薄膜直接镀于具有镍涂层的金属基体上，然后直接在锡薄膜上镀银。所述银即使在高温下也与基体具有良好的附着性。

Description

耐高温的银涂层基体
技术领域
本发明涉及一种耐高温的银涂层含铜基体。更确切地，本发明涉及一种耐高温的银涂层含铜基体，且改善了该银涂层对于含铜基体的附着性。
背景技术
电镀和化学镀银已被广泛应用，例如制造电接插件、印刷电路板、发光二极管，以及利用银出色的沉积性能在塑料或装饰性制件上镀银。当把银镀在铜或铜合金的基体上时，通常会在镀银之前先将一个镍底层镀于铜或铜合金上。镍在此的作用是作为屏障阻止铜扩散到银中，同时也可以提供更好的表面形态。为了在镍层上附着银层，一个薄的银冲击镀层通常会先于最终的较厚的银层施加在镍层上。如果正确进行镀膜工艺，镀膜后或使用期间的短时间内，镍和银之间不会出现附着失败。
目前不同企业都持续关注银涂层的高温应用，通常高于150℃。在这样高的温度下，由于铜的快速扩散，镍阻挡层是必须的。而且在如此高的温度条件下，在银下层的镍会发生快速氧化而导致镍和银之间的附着失败。这种高温下银下层的镍加速氧化的现象至今尚未被完全了解。一般来说，用于增强银与镍附着性的常规方法，如银冲击镀层和镍表面催化并不能克服在高温应用时的氧化和附着问题。
三菱材料集团(Mitsubishi Materials Corp.)的日本专利申请JP2003-293170，披露了一种高温电导体，例如一种燃料电池的电流提取终端，可以在高温环境下使用。所述导体的基底可以为铁、镍或钴合金。在导体基底上镀一个镍层，然后再在镍上镀银。该专利申请披露了该导体在500-960℃的高温环境下并不会氧化，同时还可保持电的连续性。虽然有制件其为铁、镍或钴合金基底具有银和镍层的，镍在高温环境下不会氧化，但是仍然需要能够承受高温具有铜或铜合金基底上的制件，基底具有其上有银层的镍层。
发明内容
一种制件包括含有铜或铜合金的基体，一相邻附于基体的铜或铜合金的含镍层，一相邻于含镍层上的含锡层，以及一相邻于含锡层的银层，所述银层具有至少两倍于所述含锡层的厚度。
一种方法包括提供一种含有铜或铜合金的基体；在相邻于含有铜或铜合金的基体处沉积镍层；在相邻于所述含镍层处沉积含锡层；和在相邻于所述含锡层处沉积银层，所述银层具有至少两倍于所述含锡层的厚度。
在沉积银之前施加相邻于镍或镍合金的锡或锡合金薄膜抑制了含镍层的氧化，因此抑制了银和含铜或铜合金基体之间在高温应用中的附着失败。相应的，所述制件可以用于高温环境，且对银层附着失败的忧虑最少。
附图说明
图1为在铜基体上叠镍阻挡层、再叠锡预镀层(tin strike layer)、再叠银层的制件的横截面示意图。
图2为在200℃下存储1000小时后，显示在银和镍的界面处的间隙的镍上叠银层10000倍SEM剖面照片。
图3为温度200℃下存储1000小时后，在镍和银层之间具有金冲击镀层，在金冲击镀层和镍界面间出现裂隙的10000倍SEM横截面照片。
图4为温度200℃下存储1000小时后，在镍与沉积其上的银层之间具有钯/镍合金冲击镀层的，在钯/镍合金冲击镀层和镍层的界面间出现裂隙的10000倍SEM剖面照片。
图5为温度200℃下存储1000小时后，在镍与沉积其上的银层之间具有Sn/Ag和Sn/Ni金属间化合物的，在各层界面间未观察到任何裂隙的10000倍SEM剖面照片。
具体实施方式
在本说明书中，术语“沉积”和“镀膜”可互换使用。术语“组成物”和“镀液”可互换使用。术语“附着”的意思是相邻或紧靠同时结合。不明确的词语“一”或“一个”可表示单数或复数。以下缩写具有以下含义，除非本文明确指出其它含义：℃＝摄氏度；g＝克；ml＝毫升；L＝升；ASD＝A/dm2＝安培/平方分米；PVD＝物理气相沉积；CVD＝化学气相沉积；PCB＝印刷电路板或印刷线路板；SEM＝扫描电子显微镜；EDX＝EDS＝能谱仪；cm＝厘米；μm＝微米；nm＝纳米。
所有百分比和比率都表示质量百分比除非特别指出。所有范围都包括所有，同时可以任何顺序进行组合除非经逻辑推理得出这些数字的范围相加高于100％。
图1示出的制件为含铜的基体1，具有与铜基基体相邻的含镍的阻挡层2。一含锡冲击镀层3与含镍阻挡层相邻，以及一具有至少两倍于含锡预镀层厚度的银层4与含锡预镀层相邻。任选的，表层的银层可以具有一防锈层(未示出)。本制件可作为元件广泛用于电子设备，如可能会暴露于150℃以及更高温度如200℃至600℃的温度下的设备，其在金属层间可以保持良好的附着性。
将一层或多层镍或镍合金沉积到含铜的基体上。镍的功能是作为阻止铜向银表层扩散的阻挡层。所述基体基本上可以为所有的铜或包括一种或多种铜合金，例如但不局限于锡/铜、银/同、金/铜、铜/铋、铜/锌、铜/镍、锡/银/铜和锡/铜/铋合金。所述基体可以为具有铜或铜合金层的PCB或介电材料，例如塑料或树脂材料。沉积所述镍或镍层使其与基体的铜或铜合金层的表面相接并与基体表面的铜或铜层形成界面。一般，所述镍或镍合金层至少为0.5μm厚。优选地，所述镍或镍合金层为0.5μm至10μm厚，更优地，1μm至5μm厚。可以用现有技术中的常规方法沉积所述一层或多层镍或镍合金层，从而将镍或镍合金沉积到基体上。这些方法包括但不局限于PVD、CVD、电解镀和化学镀。这些方法在现有技术和文献中是已知的。优选地，使用电解镀将镍或镍合金沉积到含铜的基体上。
一般而言，镍或镍合金的电镀要在至少0.01ASD的电流密度下才能进行。常规的电流密度为从0.1ASD到5ASD，更常规的是从0.5ASD到2ASD。有少数实验曾对特定基体所需电流密度进行过测试。本文所述电镀过程为常规过程。
使用适当的溶液可溶性镍化合物、通常是水溶性镍盐提供镀膜组合物中的镍离子。所述镍化合物包括但不局限于，硫酸镍、氯化镍、氨基磺酸镍和磷酸镍。可将镍化合物的混合物用于镀膜组合物。所述混合物可以为具有相同金属离子但不同化合物组成的金属化合物，例如硫酸镍和氯化镍的混合物。所述镍的化合物加入镀膜组合物中的量为使提供的镍离子在镀膜组合物中的浓度达到0.1g/L至150g/L，优选为0.5g/L至100g/L，更优选为1g/L至70g/L。
包括酸和碱的大量不同种类的电解质可以用于镀镍组合物。所述电解质包括但不局限于烷基磺酸如甲磺酸、乙磺酸和丙磺酸；脂肪醇磺酸；芳基磺酸如甲苯磺酸、苯磺酸和酚磺酸；含氨基的磺酸如酰胺磺酸；氨基磺酸；无机酸；羧酸如蚁酸和卤代乙酸；氢卤酸；和焦磷酸。酸和碱的盐也可以用作电解质。更进一步，所述电解质可以包含酸的混合物、碱的混合物或者一种或多种酸或碱的混合物。所述电解质通常可以从多种渠道以商业形式得到，例如威斯康辛州密尔沃基的Aldrich化学公司。
任选的，多种表面活性剂可以用于所述镀镍组合物。任何的阴离子、阳离子、两性和非离子表面活性剂在不影响镀镍效能的情况下均可使用。所述表面活性剂可根据常规用量使用，这在现有技术中已有公开。
任选的，所述镀镍组合物可以包括一种或多种添加剂成分。所述添加剂包括但不局限于光亮剂、晶粒细化剂和延性增强剂。所述添加剂在现有技术中已公知，用量也是常规用量。
所述镀镍组合物还任选的包括缓冲剂。典型的缓冲剂包括但不局限于硼酸盐缓冲剂(如硼砂)、磷酸盐缓冲剂、柠檬酸盐缓冲剂、碳酸盐缓冲剂和氢氧化物缓冲剂。所述缓冲剂的使用量为能使镀液成分的pH值保持到所需水平，所述用量在本领域现有技术中已经公知。
一种或多种合金化金属可以包含在镀镍组合物中。所述合金化金属包括但不局限于锡、铜和铋。镍磷合金是优选的合金。所述金属以其可溶性盐的形式提供，这也是现有技术中公知的。镀镍组合物中包含所述金属的常规用量以提供镍合金的沉积。
合适的镀镍电镀槽可以由商业途径获得，同时也以被文献披露。可由商业途径获得的电镀镍槽的例子可以为NICKEL GLEAMTM电镀镍产品和NIKALTMSC电镀镍产品，上述产品可同时由美国马萨诸塞州马尔堡的罗姆和哈斯电子材料有限责任公司获得。其它适合的电镀镍槽的例子为在US3041255中披露的瓦特型电镀槽。
化学镀镍组合物可以包括或不包括还原剂。通常，化学镀组合物会包括还原剂成分。所述还原剂包括但不局限于次磷酸钠、次磷酸钾、硫脲和硫脲衍生物、乙内酰脲和乙内酰脲衍生物、对苯二酚和对苯二酚衍生物、间苯二酚、蚁醛和蚁醛衍生物、DEA(二乙基胺硼烷)、氢硼化钠和联氨。所述还原剂可以使用常规用量，例如从0.1g/L至40g/L。可从商业渠道获得的化学镀镍组合物包括DURAPOSITTM SMT 88化学镀镍和NIPOSITTM PM 980和PM 988化学镀镍。上述产品都可从罗姆和哈斯电子材料有限责任公司获得。
镀镍组合物的pH的范围从1至14，优选从1至12，更优选为1-8。镀膜过程中镀镍组合物的工作温度为从10℃至100℃，或者例如从20℃至50℃。
镍或镍合金沉积后，将一层或多层锡或锡合金冲击镀层沉积在一个或多个镍或镍合金层上。锡或锡合金层可以用现有技术中的常规方法进行沉积，例如电镀、化学镀或浸镀锡或锡合金层。优选地，锡或锡合金层是电镀或化学镀到镍或镍合金层上的。更优选地，锡或锡合金是电镀到镍或镍合金层上的。所述锡或锡合金层具有至少0.01μm的厚度，优选地为0.01μm至2μm，更优选地为从0.1μm至1μm。
合适的锡或锡合金的镀液可以为酸式或碱式。一个酸式镀锡液的实例包含一种或多种可溶性锡化合物、一种或多种酸性电解质，以及任选的一种或多种添加剂。适合的锡化合物包括但不局限于盐，如卤化锡，硫酸锡，烷基磺酸锡如甲磺酸锡、芳基磺酸锡如苯磺酸锡、苯酚磺酸锡和甲苯磺酸锡以及烷醇基磺酸锡。优选的锡化合物为硫酸锡、氯化锡、烷基磺酸锡或芳基磺酸锡，更优选的锡化合物为硫酸锡或甲基磺酸锡。锡化合物在上述组合物中的含量通常为能够提供锡离子含量达到5g/L至150g/L的量，或更优选的30g/L至80g/L。也可以使用锡化合物的混合物。
任何酸性可溶性电解质，只要不会对电解液组分产生不利影响，都适用于提供稳定的锡电解质。合适的酸性电解质包括但不局限于烷基磺酸，例如甲磺酸、乙磺酸和丙磺酸；芳基磺酸，例如苯磺酸、苯酚磺酸和甲苯磺酸；硫酸；氨基磺酸；盐酸；氢溴酸；氟硼酸和以上物质的混合物。优选的，酸性电解质的含量范围为10g/L至400g/L，更优选为50g/L至400g/L。
在锡合金镀液中，除锡外还将使用一种或多种合金化金属化合物。适当的合金化金属化合物包括但不局限于铅、镍、铜、铋、锌、银、锑和铟。可用的合金化金属化合物为任何可溶形式的为电解质组分提供金属的化合物。因此，所述合金化金属化合物包括但不局限于，盐例如金属卤化物、金属硫酸盐，金属烷基磺酸盐例如金属甲磺酸盐，金属芳基磺酸盐例如金属苯磺酸盐和金属甲苯磺酸盐以及金属烷醇基磺酸盐。合金化金属化合物种类的选择和其在电解质组分中的含量取决于，例如锡合金的沉积，同时这些技术在现有技术中可以得到。优选的，锡合金为锡/同、锡/铋、锡/银、锡/锌、锡/银/铜和锡/银/铋合金。
一种或多种添加剂可用于所述锡或锡合金电镀液，例如还原剂，晶粒细化剂如羟基芳族化合物，以及其他润湿剂、光亮剂和抗氧化剂。也可使用所述添加剂的混合物。
还原剂可以加入所述锡或锡合金电解液组合物中以协助保持锡处于可溶的二价态。合适的还原剂包括但不局限于，对苯二酚，和羟化芳香族化合物例如间苯二酚和邻苯二酚。合适的还原剂已在例如美国专利4871429中得到披露。优选所述还原剂的含量为0.1g/L至5g/L。
通过添加光亮剂到锡或锡合金电解液组合物中可以得到光亮的沉积膜。所述光亮剂在现有技术中已公知。适当的光亮剂包括但不局限于，芳醛类如萘甲醛、苯甲醛、烯丙基苯甲醛、甲氧苯甲醛和氯苯甲醛，芳醛衍生物如苄基丙酮和苯亚甲基丙酮，脂族醛如乙醛或戊二醛，以及酸如丙烯酸、甲基丙烯酸和甲基吡啶酸。优选的，光亮剂的用量为0.1g/L至3g/L。
适合的非离子表面活性剂或润湿剂包括但不局限于，具有低相对分子量的具有一个或多个最多7个碳原子的烷基的脂肪醇环氧乙烷(EO)衍生物，或具有最多两个芳环的芳香醇环氧乙烷衍生物，所述芳环能合并以及可以被具有最多6个碳原子的烷基取代。所述脂肪醇可以为饱和或不饱和的。所述芳香醇通常在与环氧乙醇发生衍生作用前具有最高20个碳原子。所述脂肪醇和芳香醇可以进一步被取代，例如被硫酸盐或磺酸盐取代。优选的，所述非离子表面活性剂或润湿剂的添加量为0.1g/L至50g/L。
羟基芳族化合物或其他润湿剂可以加入所述电解液组合物中提供进一步的晶粒细化。所述晶粒细化剂加入后可进一步提高沉积物表面形态同时对电流密度范围起作用。适合的其他润湿剂包括但不局限于，烷氧基化物例如聚乙氧基胺JEFFAMINETM T-403或TRITONTM RW，硫酸烷基乙氧基化物例如TRITONTMQS-15，和明胶或明胶衍生物。所述晶粒细化剂起效的含量在现有技术中已公知，优选为0.01ml/L至20ml/L。
任选地，在电解液组分中使用抗氧化化合物来减小或阻止二价锡氧化的发生，例如从二价态转化为四价态。适合的抗氧化剂包括，例如二羟基苯和元素周期表中的IVB、VB和VIB族元素的多价化合物，例如钒、铌、钽、钛、锆和钨。优选的，所述抗氧化剂在电解液组成中的含量为0至2g/L。
锡或锡合金的沉积温度为20℃至60℃，优选为35℃至45℃。当电镀锡或锡合金时，电流密度优选为0.5ASD至10ASD。
随后一个或多个银层沉积附着到锡或锡合金层上。所述银层的厚度与所述锡或锡合金层的厚度的比为至少2∶1，优选地为2∶1至30∶1，更优选地为5∶1至25∶1。通常，银层具有至少0.02μm的厚度，优选地从0.02μm至60μm，更优选地从0.5μm至25μm。可以用常规方法将银沉积在锡或锡合金上。通常使用电镀、化学镀或浸镀沉积银。优选地用电镀法镀银。
可以使用常规的电镀银组合物。所述银组合物可以为含氰化物的银组合物或无氰银组合物。优选地，镀银浴为含氰化物的浴。银离子的来源可以包括但不局限于：氰化银钾、硝酸银、硫代硫酸钠银、葡萄糖酸银；银-氨基酸复合物例如银-半胱氨酸复合物；烷基磺酸银例如甲磺酸银。也可以使用银化合物的混合物。镀液中银离子的浓度通常为2g/L至40g/L。所述银化合物一般可以通过各种渠道以商业手段获得，例如威斯康辛州密尔沃基的Aldrich化学公司。可用的镀银化合物商业产品的例子为从罗姆和哈斯电子材料有限公司获得的SILVER GLOTM 3K银电镀液，SILVERJETTM 300银电镀液，SILVER GLEAMTM360银电镀液，ENLIGHTTM镀银液600和620。
许多常规表面活性剂都可以用于镀银组合物，例如阴离子、阳离子、两性和非离子表面活性剂。表面活性剂可以用常规用量。所述镀银组合物可以包含一种或多种常规添加剂。所述添加剂包括但不局限于电解质、缓冲剂、光亮剂、晶粒细化剂、螯合剂、络合剂、还原剂、流平剂和延性增强剂。所述添加剂在现有技术中已公知，使用时用常规用量。
镀银组合物的pH值范围为1至14，优选为1至12，更优选的为1-8。镀银时镀银组合物的工作温度为10至100℃，或例如从20至60℃。优选电流密度为0.1ASD至50ASD，更优选的为1ASD至20ASD。
任选的，一防锈层可以沉积在银层上。可以使用常规防锈组合物。所述防锈材料的商业产品的例子为NOTARNTMPM3防锈制剂，PORE BLOCKER 100防锈制剂和PORE BLOCKERTM 200防锈制剂(可从罗姆和哈斯电子材料有限公司获得)。
厚度至少两倍于与镍或镍合金相邻的锡或锡合金层，并与该锡或锡合金层相邻的银层会阻止镍层的氧化，因此可以防止在高温使用时银和基体之间发生附着失败。镍/锡的金属间化合物在锡层和镍层的界面处形成，而锡/银的金属间化合物在锡层和银层的界面处形成。而不受限于理论，锡/银金属间化合物的形成可能会改变银层的微结构并阻止氧气到达镍或镍合金层的表面，而镍/锡金属间化合物的形成可能会增加镍或镍合金层的抗氧化性。镍或镍合金层的氧化可以用现有技术中的标准EDS或EDX分析法测量。本发明的制件可以用于高温环境同时对银层附着失败的影响最小化。一般而言，所述制件可以用于PCB组件、电连接器、发光二极管(LED)、电动车和其他会使银层暴露于150℃或更高温度的应用中。
以下实施例用以说明本发明但不将本发明局限于以下范围。
实施例1(对比例)
三个清洗后的2cm×5cm的铜基试样(铜或铜/锌)置于具有表1所述配方的镍电镀液中。
表1
组分 含量
提供镍离子的六水合硫酸镍 60g/L
提供镍离子的六水合氯化镍 10g/L
硼酸 45g/L
糖精钠盐 0.5g/L
乙氧基硫酸脂肪醇 2ml/L
所述试样与一整流器相连，反电极是镀铂的钛电极。在镀镍过程中保持镍镀液的温度为30摄氏度。电流密度为1ASD。当每个铜试样表面沉积了厚度为2μm的镍层时停止电镀。将试样从镀液中取出并在室温下用去离子水冲洗。
然后将所述试样置于银冲击镀液中，所述银冲击镀液含有2g/L提供银离子的氰化银和100g/L的氰化钾。所述镀镍的铜试样与一整流器相连。反电极为镀铂的钛电极。电镀银在60℃下进行，使用的电流密度为0.1ASD，当镍表面沉积了0.1μm厚的银冲击镀层时停止镀银。
随后将试样置于含有表2所述配方的银电镀液中。
表2
组分 含量
提供银离子的氰化银 35g/L
氰化钾 90g/L
碳酸钾 15g/L
氰化硒 0.5ppm
所述试样与一整流器相连，反电极为镀铂的钛电极。镀银液保持在60℃。电流密度为2ASD。当沉积到银冲击镀层的银层厚度达到5μm厚时停止镀银。
镀银后的试样从银电镀液中取出后在室温下用去离子水冲洗并空气干燥。然后使用标准正交和胶带测试来检测各试样上银层的附着性。所有试样都表现出优秀的附着性。从镀银的试样上撕下的胶带上未观察到银。
随后将试样在常规的对流式烤箱中保持200℃存放1000小时。每隔200小时测量一次试样上银层的附着性，是通过将试样冷却到室温用正交胶带测试法测量的。400小时后，所有的试样都表现出较差的银附着性的迹象。1000小时后将试样从烤箱中取出并冷却到室温。
每个试样的横截面都是用装配了蔡司EDX能谱仪的SIGMA SEM扫描电子显微镜进行观察。所有SEM照片都显示出镍和银层的界面处有裂隙。图2即为其中一个所测试铜试样的横截面。SEM照片的上半部分是用于固定试样进行横截面分析的包埋树脂。电镀银层在包埋树脂之下，在高温存储中形成的裂隙可以在银层和直接在银层之下的镍层之间的界面处看到。铜基底直接在镍层之下。
实施例2(对比例)
准备如实施例1所述的三个铜基试样，不同之处仅在于在镍层上镀有金冲击镀层而不是银冲击镀层。金冲击镀液的成分在表3中示出。
表3
组分 含量
提供金离子的氰化金钾 2g/L
提供钴离子的碳酸钴 0.5g/L
柠檬酸三钾 50g/L
金冲击镀液保持在40℃，使用的电流密度为0.2ASD。当沉积在镍层上的金层达到0.1μm时停止镀金。
每个试样随后使用表2所述的氰化银镀液电镀上5μm厚的银层。镀银使用的参数与实施例1中相同。
镀银后的试样从镀银液中取出在室温下用去离子水冲洗后空气干燥。随后用正交胶带测试对每个试样的银层的附着性进行检测。所有试样都表现出优秀的附着性。从镀银的试样上撕下的胶带上未观察到银。
随后将试样在常规的对流式烤箱中保持200℃存放1000小时。每隔200小时测量一次试样上银层的附着性，是通述将试样冷却到室温用正交胶带测试法测量的。400小时后，所有的试样都表现出较差的银附着性的迹象。1000小时后将试样从烤箱中取出并冷却到室温。
每个试样的横截面都用扫描电子显微镜进行观察。所有SEM照片都显示出镍和金冲击镀层的界面处有裂隙。图3即为其中一个所测试铜试样的横截面。SEM示出在高温存储过程中银层和镍层之间出现剥离。
实施例3(对比例)
准备如实施例1所述的三个铜基试样，不同之处仅在于在镍层上镀有钯镍合金的冲击镀层，而不是银冲击镀层。钯镍合金冲击镀液的配方见表4。
表4
组分 含量
提供钯的硫酸四胺钯 20g/L
提供镍的硫酸镍 8g/L
氢氧化铵 50g/L
所述钯镍合金镀液保持在60℃，电流密度为0.2ASD。当钯镍合金厚度达到0.1μm时停止电镀。
每个试样随后使用表2所述的氰化银镀液电镀上5μm厚的银层。镀银使用的参数与实施例1中相同。
镀银后的试样从镀银浴中取出在室温下用去离子水冲洗后空气干燥。随后用正交胶带测试对每个试样的银层的附着性进行检测。所有试样都表现出优秀的附着性。从镀银的试样上撕下的胶带上未观察到银。
随后将试样在常规的对流式烤箱中保持200℃存放1000小时。每200小时测量一次试样上银层的附着性，是通过将试样冷却到室温用正交胶带测试法测量的。400小时后，所有的试样都表现出较差的银附着性的迹象。1000小时候将试样从烤箱中取出并冷却到室温。
每个试样的横截面都用扫描电子显微镜进行观察。所有SEM照片都显示出镍和钯镍冲击镀层的界面处有间隙。图4即为其中一个所测试铜试样的横截面(铜基底在该图中未示出)。SEM示出在高温存储过程中银层和镍层之间出现剥离。
实施例4
准备如实施例1所述的三个铜基试样，不同之处仅在于在镍层上镀有锡冲击镀层，而不是银冲击镀层。镀锡的镀液的配方见表5。
表5
组分 含量
提供锡离子的甲磺酸锡 60g/L
甲磺酸 150ml/L
EO/PO共聚物1 2ml/L
对苯二酚 1g/L
1TERGITOLTM L162非离子表面活性剂(可从陶氏化学公司获得)
锡冲击镀液的温度保持在60℃，电流密度为0.1ASD。当沉积到镍层上的锡层厚度达到0.2μm时停止镀锡。
每个试样随后使用表2所述的氰化银镀液电镀上5μm厚的银层。镀银使用的参数与实施例1中相同。
镀银后的试样从镀银浴中取出在室温下用去离子水冲洗后空气干燥。随后用正交胶带测试对每个试样的银层的附着性进行检测。所有试样都表现出优秀的附着性。从镀银的试样上撕下的胶带上未观察到银。
所述试样随后在200℃下存储在常规的对流式烤箱中持续1000小时。每200小时测试一次银的附着性。而任何每200小时都未观测到银层和试样之间出现附着失败。1000小时后将试样从烤箱中移出并使其在室温下冷却。随后使用标准正交胶带测试对每个试样的银层的附着性进行检测。在银和镍层之间没有出现附着失败的迹象。所有试样均具有优秀的附着性。
每个试样的横截面都在扫描电子显微镜下进行观测。在所有SEM照片上的金属层的界面处都未观测到可视的裂隙。图5即为其中一个所测试铜试样的横截面。从SEM上未观测到银和镍之间具有剥离现象。镍和锡以及锡和银的金属间化合物在银和镍层之间的界面处形成。

Claims (7)

1.一种制件包括含有铜或铜合金的基体，一相邻于所述基体的铜或铜合金的镍层，一相邻于所述镍层的锡层和一相邻于所述锡层的银层，所述银层具有至少两倍于所述锡层的厚度。
2.根据权利要求1所述的制件，其中所述锡层具有至少0.01μm的厚度。
3.根据权利要求1所述的制件，其中所述银层具有至少0.02μm的厚度。
4.根据权利要求1所述的制件，其中所述制件包括镍和锡，以及锡和银的金属间化合物的一种或多种。
5.根据权利要求1所述的制件，其中所述制件是电接插件、印刷电路板、发光二极管或电动车的组件。
6.一种方法，包括
a)提供含有铜或铜合金的基体；
b)在所述铜或铜合金基体上沉积与其相邻的镍层；
c)在与所述镍层上沉积与其相邻的锡层；和
d)在所述锡层上沉积与其相邻的银层，所述银层具有至少两倍于所述锡层的厚度。
7.根据权利要求6所述的方法，其中所述银是从含氰化物的镀液沉积的。
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