CN102965646A - 化学镀的稳定催化剂 - Google Patents

化学镀的稳定催化剂 Download PDF

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CN102965646A
CN102965646A CN2012103952144A CN201210395214A CN102965646A CN 102965646 A CN102965646 A CN 102965646A CN 2012103952144 A CN2012103952144 A CN 2012103952144A CN 201210395214 A CN201210395214 A CN 201210395214A CN 102965646 A CN102965646 A CN 102965646A
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K·M·米鲁姆
D·E·克莱利
M·A·热兹尼克
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Abstract

催化剂包括催化剂金属纳米微粒和镓酸或镓酸衍生物或其盐。该催化剂用于化学镀。该催化剂不含锡。

Description

化学镀的稳定催化剂
技术领域
本发明涉及用于化学镀的稳定的催化剂水溶液。进一步地，本发明涉及用于化学镀的不含锡、并且由镓酸、镓酸衍生物及其盐进行稳定的稳定催化剂溶液。
背景技术
化学镀金属沉积法是用于基底表面沉积金属层的众所周知的方法。绝缘体表面的化学镀需要预先使用催化剂。最常用的催化或激活绝缘体的方法，如用于生产印刷电路板的薄板基底的非导电部分，是用酸性氯化物介质中的锡/钯胶体水溶液来处理基底。胶体的结构已被广泛研究过。通常来说，胶体包括被锡离子(II)的稳定层包围的钯金属核，所述锡离子实质上是作为避免悬浮液中胶体聚结的表面稳定基团的SnCl3 -配合物壳层。
在活化方法中，锡/钯胶体催化剂吸附到绝缘体基底上，如含有环氧或聚胺的基底，以活化化学金属沉积。理论上，催化剂用作电子转移路径载体，将电子在化学镀槽中从还原剂转移到金属离子上。尽管化学镀的性能受诸多因素影响，如镀层溶液的添加组分，活化步骤是控制化学镀的速率和机理的关键。
近年来，随着电子装置尺寸的减小以及对性能需求的增加，在电子电路组装行业中对无缺陷电子线路的需求在逐渐增加。尽管几十年来在商业上已将锡/钯胶体用作化学镀的催化剂，并提供了可接受的服务，但随着对电子设备质量要求的进一步提高，该类催化剂的诸多弊端也逐渐凸现出来。锡/钯胶体的稳定性是主要的考虑因素。如上所述的锡/钯胶体用一层锡离子(II)进行稳定，其反阴离子能够阻止钯的聚结。催化剂对空气敏感、容易氧化成锡(IV)，这样胶体不能保持其胶体结构。化学镀过程中温度的升高和搅拌会进一步促进这种氧化。如果锡(II)的浓度降至危险水平，如接近于零，钯金属微粒尺寸会变大、产生聚结和沉积，从而失去催化活性。由此便增加了对更稳定的催化剂的需求。另外，钯的高成本和价格波动也促使行业上寻求更廉价的金属。
已付出相当多的努力寻找新型的改进催化剂。因为钯的成本高，很多努力致力于发展不含钯的催化剂，比如胶体银催化剂。另外一个研究方向则是开发不含锡的钯催化剂，这是因为氯化锡成本高以及氧化的锡需要单独的加速步骤。另外，在整个化学镀方法中增加了额外的步骤，在加速步骤中使用的材料经常会剥落被镀基底上的催化剂，从而在镀层中留下不希望的空区。这在通常用于印刷电路板生产的玻璃纤维基底上经常发生。然而，这种不含锡的催化剂用于印刷电路板生产中的通孔的镀时则表现为活性和可靠性不足。并且，通常地这种催化剂在储存中活性会逐渐降低，从而导致该催化剂不稳定、不适于商业应用。
已研究用于锡复合物的另一稳定部分，如聚乙烯基吡咯烷酮(PVP)和树状聚合物。多个研究团体在文献中已公开了由稳定且均一的PVP保护的纳米微粒。文献中已报道了其它的金属胶体，如部分钯被非贵金属取代的银/钯和铜/钯；然而，至今为止还没有商业上可接受的可替代的锡/钯胶体催化剂。因此，对稳定、可靠的化学镀催化剂仍有需求。
发明内容
方法包括：a)提供基底；b)将催化剂水溶液施加到基底上，催化剂水溶液包括一种或多种金属的纳米微粒，金属选自银，金，铂，钯，铱，铜，铝，钴，镍和铁，以及一种或多种选自镓酸，镓酸衍生物及其盐的化合物，催化剂不含锡；以及c)使用化学镀槽将金属化学沉积到基底上。
该催化剂可用于将金属化学镀到包括绝缘材料在内的基底上并且，其在储存和化学镀过程中均能保持稳定；原因在于，与常规的锡/钯催化剂相比，该催化剂不易氧化。该催化剂是可生物降解的，这样就不会产生环境危害。镓酸，镓酸衍生物及其盐如氯化锡在常规锡/钯催化剂中一样，具有稳定剂的功能，但镓酸，镓酸衍生物及其盐不会产生像处理氯化锡时的环境危害。镓酸，镓酸衍生物及其盐以纳米颗粒形态存在时还具有还原剂的功能，其还可作为抗氧化剂以延长催化剂寿命。用镓酸，镓酸衍生物及其盐稳定的金属催化剂无需加速步骤即可进行化学镀和对基底，甚至是印刷电路板的通孔壁进行金属镀。
附图说明
附图1是300ppm Ag/150ppm镓酸稳定的催化剂与常规锡/钯催化剂的背光分级对比图；以及
附图2是400ppm Ag/200ppm镓酸稳定的催化剂与常规锡/钯催化剂的背光分级对比图。
具体实施方式
除了文中明确表明，下述在说明书全文所用的简称具有如下含义：g＝克；mg＝毫克；ml＝毫升；L＝升；cm＝厘米；m＝米；mm＝毫米；μm＝微米；nm＝纳米；ppm＝百万分含量；℃＝摄氏度；g/L＝克每升；DI＝去离子化；wt％＝重量百分含量；以及Tg＝玻璃化转变温度。
本发明全文所用的术语“印刷电路板”和“印刷线路板”可互换使用。本说明书全文的术语“镀”和“沉积”可互换使用。除非特别指明，所有的用量是重量百分含量。所有的数值范围均包含在内并可以任何方式结合，只要逻辑上这些数值范围总量为100％。
催化剂水溶液包括金属的纳米微粒，金属选自银，金，铂，钯，铱，铜，铝，钴，镍和铁，以及一种或多种选自镓酸，镓酸衍生物及其盐的稳定化合物。优选地，金属选自银，钯和金，更优选地金属选自银和钯，最优选金属选自银。优选地，稳定化合物具有通式：
其中R为-H或-(CH2)X-CH3，x为选自2-4的整数，以及R1，R2，R3，R4和R5为-H或-OH，其可相同或不同，条件是至少一个或R1，R2，R3，R4和R5为-OH，优选R为-H，更优选，R是-H且R2，R3和R4为-OH。举例的化合物包括镓酸，二羟基苯甲酸，羟基苯甲酸，2，4，6-三羟基苯甲酸和镓酸酯，如镓酸丙酯。通常地，盐是钠盐或钾盐。优选的化合物是镓酸。
催化剂水溶液中包含足够量的稳定组分以提供所需的稳定性和金属镀。进行少量的试验就能获取获得用以稳定催化剂和金属镀的特定具体稳定剂或稳定剂复合物的使用量。通常，催化剂水溶液中的一种或多种稳定化合物的量为50ppm至1000ppm，优选100ppm至500ppm。
任选的，除了镓酸或镓酸衍生物之外还可含有一种或多种还原剂以将金属离子还原成金属。可使用已知的可将金属离子还原成金属的常规还原剂。所述还原剂包括但不限于二甲基胺硼烷，硼氢化钠，抗坏血酸，异-抗坏血酸，次磷酸钠，水合肼，甲酸和甲醛。所含还原剂的量基本上可将所有的金属离子还原成金属。所述用量通常是常规用量、是所属领域技术人员所熟知的。
金属源包括本领域和文献中已知的常规金属盐水溶液，其可提供具有催化活性的金属。可使用两种或多种催化金属的混合物。包括能提供100ppm至2000ppm、优选300ppm至1500ppm的量的所述金属的盐。银盐包括但不限于硝酸银，醋酸银，三氟醋酸银，甲苯磺酸银，三氟甲磺酸银，氟化银，氧化银，硫代硫酸钠银，***银。钯盐包括但不限于氯化钯，醋酸钯，氯化钾钯，氯化钠钯和硝酸钯。金盐包括但不限于氰化金，三氯化金，三溴化金，氯化金钾，氰化金钾，氯化金钠和氰化金钠。铂盐包括但不限于氯化铂和硫化铂。铱盐包括但不限于三溴化铱，氯化钾铱。铜盐包括但不限于硫酸铜和氯化铜。镍盐包括但不限于氯化镍和硫酸镍。钴盐包括但不限于醋酸钻，氯化钴，溴化钴和硫酸氨钻。铝盐包括但不限于硫酸铝和硫酸钠铝。铁盐包括但不限于柠檬酸亚铁铵，草酸亚铁铵和硫酸亚铁铵。通常地，金属盐是银，钯和金。优选地金属盐是银和钯。更优选金属盐是银。
组成催化剂水溶液的各组分可以任何顺序组合。可使用本领域和文献中已知的任何合适的方法制备催化剂水溶液。组分的具体参数和用量可在不同的方法中作出改变，一般来说，首先将一种或多种稳定化合物溶解在足量水中。将一种或多种金属源的水溶液通过剧烈搅拌与稳定剂溶液混合得到均匀混合物。任选的，再将含一种或多种还原剂的水溶液在剧烈搅拌下与稳定剂和金属盐的混合物相混合。通常方法步骤和溶液在室温下进行；然而，可调整温度以助于溶解反应组分和促进金属离子的还原。不局限于理论，稳定剂可涂覆或包围金属的部分或大部分以稳定催化剂溶液。金属和稳定剂的粒径尺寸范围至少为1nm，一般是1nm至1000nm，或者2nm至500nm。优选地粒径尺寸范围为2nm至300nm，更优选2nm至100nm以及尤其优选2nm至10nm。
所述合成的催化剂的可在酸性至弱碱性的范围内，在将催化剂用于化学镀之前，将pH降至7以下。可将一种或多种酸或其盐加入催化剂中以得到小于7的pH，优选1-6.5，更优选2-6。可使用足够量的无机酸或有机酸或其盐以得到所需范围的pH。也可使用无机和有机酸和其盐的混合物。无机酸的实施例包括盐酸，硫酸和硝酸。有机酸包括单或多羧酸，如二羧酸。有机酸的具体实施例可以是苯甲酸，抗坏血酸，异-抗坏血酸，苹果酸，马来酸，草酸，醋酸，柠檬酸和酒石酸。
催化剂可用于化学镀多种基底。这样的基底包括但不限于包括如玻璃、陶瓷、瓷、树脂，纸，布及其混合物的无机和有机基底材料。金属包层和无金属包层材料可是使用催化剂镀金属的基底。
基底也包括印刷电路板。所述印刷电路板包括金属包层和无金属包层，其使用了热固性树脂，热塑性树脂及其混合物，包括纤维，如玻璃纤维和前述的浸渍的具体实施方式。
热塑性树脂包括但不限于缩醛树脂，丙烯酸酯，如丙烯酸甲酯，纤维素树脂，如乙酸乙酯，丙酸纤维素，纤维素醋酸丁酸盐(cellulose acetate butyreate)和硝酸纤维素，聚醚，尼龙，聚乙烯，聚苯乙烯，苯乙烯混合物，例如丙烯腈苯乙烯和共聚物和丙烯腈-丁二烯苯乙烯共聚物，聚碳酸酯，聚氯三氟乙烯，和乙烯基聚合物和共聚物，例如乙酸乙烯酯，乙烯醇，乙烯基丁缩醛，氯乙烯，氯乙烯-醋酸酯共聚物，偏二氯乙烯和乙烯基甲醛(formal)。
热固性树脂包括但不限于邻苯二甲酸丙烯基酯，呋喃，三聚氰胺-甲醛，苯酚-甲醛和苯酚-糠醛共聚物，其单独使用或与下述树脂混合：丁二烯丙烯腈共聚物或丙烯腈-丁二烯-苯乙烯共聚物，聚丙烯酸酯，有机硅氧聚合物，尿素甲醛，环氧树脂，烯丙基树脂，邻苯二甲酸甘油酯以及聚酯。
多孔材料包括但不限于纸，木材，布和纤维，例如天然和合成纤维，如棉纤维和聚酯纤维。
催化剂可用于镀低和高Tg的树脂。低Tg树脂具有低于160℃的Tg，高Tg树脂具有160℃及以上的Tg的树脂。通常高Tg树脂具有160℃至280℃的Tg，或者为170℃至240℃。高Tg聚合物树脂包括但不限于聚四氟乙烯(PTFE)和聚四氟乙烯混合物。所述混合物包括，例如含聚苯醚的PTFE和氰酸酯。其他类包含具有高Tg树脂的聚合物树脂，包括但不限于环氧树脂，如双功能或多功能环氧树脂，双马来酰亚胺/三嗪和环氧树脂(BT环氧)，环氧/聚苯醚树脂，丙烯腈丁二烯苯乙烯，聚碳酸酯(PC)，聚苯醚(PPO)，聚苯醚(PPE)，聚苯硫醚(PPS)，聚硫砜(PS)，聚酰胺，聚酯如聚对苯二酸乙二酯(PET)和聚对苯二酸丁二酯(PBT)，聚醚酮(PEEK)，液晶聚合物，聚氨酯，聚醚酰亚胺，环氧化物以及它们的复合物。
催化剂可用于在印刷电路板的通孔或通孔的壁上沉积金属。催化剂可用于生产印刷电路板的水平或垂直加工。
催化剂水溶液可用于常规化学镀槽。可以预期，该将催化剂用于化学沉积任何可化学镀的金属，通常地，所述金属选自铜，铜合金，镍或镍合金。更通常地，金属选自铜和铜合金，最通常地使用铜。商业可用的化学铜镀槽是CIRCUPOSITTM880化学铜镀槽(可由美国马萨诸塞州莫尔伯勒市的罗门哈斯电子材料有限公司(Rohm and Haas Electronic Material)获得)。
通常地，铜离子源包括但不限于铜的可溶性卤化物，硝酸盐，醋酸盐，硫酸盐和铜的其它有机或无机酸盐的水溶液。可使用一种或多种所述铜盐的混合物以得到铜离子。实施例包括硫酸铜，如五水硫酸铜，氯化铜，硝酸铜，氢氧化铜和氨基磺酸铜。可在组合物中使用常规量的铜盐。通常组合物中的铜离子浓度范围是0.5g/L至30g/L。
在化学镀组合物中也可以包括一种或多种合金金属。所述合金金属包括但不限于镍和锡。铜合金的例子包括铜/镍和铜/锡。通常地，铜合金是铜/镍。
镍和镍合金化学镀槽的镍离子源可包括一种或多种常规镍盐水溶液。镍离子源包括但不限于硫酸镍和卤化镍。化学镀合金组合物中也可包括常规量的镍离子源。通常地镍离子的量为0.5g/L至10g/L。
用于基底金属化的方法步骤可依赖于被沉积表面是金属或是绝缘体而改变。具体的步骤和步骤顺序可在不同的方法中改变。利用了催化剂的方法中可采用化学镀基底的常规步骤；但是，镓酸和镓酸稳定的金属催化剂水溶液则不同于许多传统化学镀方法，不需要加速步骤。相应地，优选在使用催化剂时不用加速步骤。通常地，将催化剂施加到化学镀金属的基底表面后使用金属镀槽。化学镀参数如温度和时间是常规的。可使用常规的基底制备方法，如基底表面的清洁或去油污，表面的粗糙化或微-粗糙化，表面的蚀刻或微-蚀刻，溶胀应用，通孔去污和多种漂洗和防锈处理。所述方法和配制都是本领域已知和文件中公开的。
通常地，当金属镀的基底是绝缘材料如印刷电路板的表面或者通孔的壁，所述板用水清洗、以及漂洗和防锈后，对通孔壁进行去污处理。通常地，最初用溶胀来预备或软化绝缘表面或通孔去污。
可使用任何传统的溶胀。具体的类型可根据绝缘材料的类型而改变。绝缘体的例子如上所述。可进行小型实验以确定溶胀适用于特殊的绝缘材料。通常绝缘材料的Tg决定了所用溶胀的类型。溶胀包括但不限于乙二醇醚和与其结合的醋酸醚。可使用常规量的乙二醇醚和与其结合的醋酸醚。常规可用的溶胀例子是CIRCUPOSITTM调节剂3302，CIRCUPOSITTM Hole Prep3303和CIRCUPOSITTM Hole Prep4120(可由罗门哈斯电子材料有限公司获得)。
任选的，基底和通孔用水进行清洗。然后使用助剂。可使用常规的助剂。所述助剂包括硫酸，铬酸，碱性高锰酸盐或等离子蚀刻。通常地使用碱性高锰酸钾作为助剂。商业可用的助剂的例子是CIRCUPOSITTM助剂4130和CIRCUPOSITTM MLB助剂3308(可由罗门哈斯电子材料有限公司获得)。
任选的，再用水清洗基底和通孔。然后使用中和剂中和助剂的残渣。可使用常规的中和剂。通常地，中和剂是含有一种或多种胺或3wt％过氧化物和3wt％硫酸溶液的碱性水溶液。商业可用的中和剂的例子是CIRCUPOSITTM MLB中和剂216-5。任选的，基底和通孔用水清洗后干燥。
溶胀和去污后，使用酸性或碱性进行调节。可用常规调节剂。所述调节剂包括一种或多种阳离子表面活性剂、非离子表面活性剂、络合剂和pH调节剂或缓冲剂。商业可用的酸调节剂的例子是CIRCUPOSITTM调节剂3320和CIRCUPOSITTM调节剂3327(可由罗门哈斯电子材料有限公司获得)。合适的碱调节剂包括但不限于含有一个或多个季胺和聚胺的碱性表面活性剂水溶液。商业可用的碱性表面活性剂的例子是CIRCUPOSITTM助剂调节剂231，3325，813和860。任选的，用水清洗基底和通孔。
调节之后进行微-蚀刻。可使用常规的微-蚀刻组分。设计微-蚀刻以在暴露金属(例如，内层和表面蚀刻)的金属表面提供微-粗糙化以促进随后化学沉积的吸附和之后的化学镀。微-蚀刻包括但不限于60g/L至120g/L的过硫酸钠或氧化单过硫酸氧化钠或钾和硫酸(2％)的混合物，或者是一般的硫酸/过氧化氢。商业可用的微-蚀刻组分的例子是CIRCUPOSITTMMicroetch3330和PREPOSITTM748。任选的，用水清洗基底。
然后对微-蚀刻基底和通孔进行预浸。预浸的例子包括2％至5％的盐酸溶液或25g/L至75g/L氯化钠的酸性溶液。商业可用的预浸是CATAPREPTM404(可由罗门哈斯电子材料有限公司获得)。
然后将用镓酸或镓酸衍生物或其盐稳定的催化剂用于基底和通孔。用催化剂灌注处理1-10分钟，通常为2-8分钟。温度范围是室温至80℃，或例如30℃-60℃。任选的，使用催化剂后再用水清洗基底和孔洞。
然后用化学镀槽将金属如铜，铜合金，镍或镍合金镀基底和通孔壁。通常地，铜镀在通孔壁上。镀的时间和温度是常规的。通常地，金属沉积在20℃-80℃，优选在30℃-60℃下进行。可将基底浸渍在化学镀槽中或将镀液喷射到基底上。通常地，沉积可进行5秒至30分钟；然而，可根据基底上金属的厚度调整镀的时间。
任选的，对金属进行防变色处理。可使用常规的防变色组分。防变色的例子是ANTI TARNISHTM7130(可由罗门哈斯电子材料有限公司获得)。任选的，清洗基底然后干燥电路板。
进一步的加工可包括常规的感光成像处理以及进一步地将金属沉积在基底上如铜，铜合金，锡和锡合金的化学金属沉积。
可使用催化剂在基底上进行化学镀金属，该基底包括绝缘体材料的基底、并且该催化剂在储存和化学镀过程中均能保持稳定，相比于常规的锡/钯催化剂，上述催化剂不易氧化。所述催化剂是可生物降解的，因此其不会带来环境危害。如氯化锡在常规锡/钯催化剂一样，镓酸，镓酸衍生物及其盐具有稳定剂的功能，但镓酸，镓酸衍生物及其盐不会产生像处理氯化锡时的环境危害。镓酸，镓酸衍生物及其盐以纳米颗粒形态存在时具有还原剂的功能、其还可作为抗氧化剂以延长催化剂寿命。用镓酸，镓酸衍生物及其盐稳定的金属催化剂无需加速步骤即可进行化学镀和对基底，以及印刷电路板的通孔壁进行金属镀。
下述实施例仅意在解释本发明、不对本发明的范围构成限制。
实施例1
两组且每组具有多个通孔的六个不同的薄板是：NP-175，370HR，TUC-752，SY-1141，SY-1000-2，以及FR-408。NP-175得自Nanya。370HR和FR4-408得自Isola。TUC-752得自台湾联合技术公司(Taiwan Union Technology)，以及SY-1141，SY-1000-2得自盛意(Shengyi)。薄板的Tg值的范围为140℃至180℃。每个薄板为5cm×12cm。每个薄板的通孔用下述方法进行处理：
1.每个薄板的通孔用CIRCUPOSITTM MLB调节剂211在78℃下进行7分钟去污处理；
2.然后用流动水清洗每个薄板的通孔4分钟；
3.用CIRCUPOSITTMMLB助剂213高锰酸钾水溶液在pH为13、78℃下处理通孔10分钟；
4.然后用流动水清洗通孔4分钟；
5.用CIRCUPOSITTMMLB中和剂216-5溶液在46℃下处理通孔5分钟；
6.然后用流动水清洗每个薄板的通孔4分钟；
7.然后在含有3％CIRCUPOSITTM调节剂231的碱性调节剂的水槽中40℃下处理通孔5分钟；
8.然后用流动水处理每个薄板通孔4分钟；
9.然后用PREPOSTTM748在室温下处理通孔2分钟；
10.然后用流动水处理每个薄板的通孔4分钟；
11.然后用300ppm的银催化剂在40℃下灌注六个薄板的通孔5分钟，其中银催化剂来自由150ppm的镓酸在pH2.9下稳定的硝酸银，催化剂颗粒尺寸范围是7-10nm，其它六个薄板的通孔用CATAPREPTM404孔制备剂在室温下处理1分钟，然后用含有100ppm钯及过量氯化锡的常规钯/锡催化剂胶体在40℃下处理5分钟；
12.然后用流动水清洗通孔4分钟；
13.然后将薄板浸渍在38℃、pH为13的CIRCUPOSITTM880化学铜镀槽中，铜在通孔壁上沉积15分钟；
14.然后将铜镀薄板浸入冷水4分钟；
15.用压缩气干燥每个铜镀薄板；以及
16.使用下述背光源方法检测薄板的通孔壁的铜镀覆盖率。
每块板被切成片以暴露出通孔的铜镀壁。从每个板的切片通孔壁取出1mm厚的10个侧面切片以确定通孔壁的覆盖率。使用欧洲背光分级量表。取自每块板的1mm切片放在常规可选的50X倍放大率的显微镜下。铜沉积量是由显微镜下观测到的光的量来确定。如果观测不到光，切片完全是黑的，背光分级是5级，其表示通孔壁的完全的铜覆盖率。如光通过全部切片不存在黑暗区，则表示很少甚至于没有铜沉积在壁上，切片是O级。如果切片有一些黑暗区，还有光区，其级别在0和5之间。
附图1是背光分级分配图，其表示具有六种类型镀板中每一个的两种催化剂的背光性能。图中的钻石型图表示每块板的10个通孔切片的95％置信区间。通过每个钻石中部的水平线表示所测量的十个通孔切片的每部分的平均背光值。除了用银/镓酸催化剂处理的NP-175板之外，银/镓酸催化剂与事实上与常规钯/锡胶体催化剂一样具有4.5或更高的背光值。通常地，4.5或更高的背光值表示其是镀工业中商业上可接受的催化剂。
实施例2
除了含400ppm的来自硝酸银的银、200ppm的镓酸和草酸作为pH调节剂的银/镓酸催化剂之外，重复实施例1的制备方法。所述pH为2.7，银/镓酸纳米微粒尺寸范围是7-10nm。此外，薄板在催化剂中45℃下处理7分钟以及在40℃下镀20分钟。在进行催化剂步骤之前和之后，用去离子水代替流动水用于清洗薄板。背光结果示于附图2中。
事实上所有银/镓酸催化剂的背光结果在都4.5以上，除了NP-175薄板具有与实施例1相同的值。相反，常规钯/锡胶体催化剂的背光值大部分在4.5附近，FR-408薄板在4.3附近，这低于可接受的范围。总体来说，银/镓酸催化剂比常规催化剂具有更好的镀结果。

Claims (6)

1.方法包括：
a)提供基底；
b)把催化剂水溶液施加到基底上，该催化剂水溶液含有一种或多种选自银，金，铂，钯，铱，铜，铝，钴，镍和铁的金属纳米微粒，以及一种或多种选自镓酸，镓酸衍生物及其盐的稳定化合物，所述催化剂水溶液不含锡；以及；
c)用化学镀槽将金属化学沉积到基底上。
2.根据权利要求1的方法，其中金属选自银和钯。
3.根据权利要求1的方法，其中稳定化合物选自镓酸，二羟基苯甲酸，羟基苯甲酸，2，4，6-三羟基苯甲酸和镓酸酯。
4.根据权利要求1的方法，其中化学沉积金属是铜，铜合金，镍或镍合金。
5.根据权利要求1的方法，其中纳米微粒的直径至少为1nm。
6.根据权利要求1的方法，其中一种或多种稳定化合物的用量是50ppm至1000ppm。
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