CN103628051A - 镀敷催化剂及方法 - Google Patents

镀敷催化剂及方法 Download PDF

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CN103628051A
CN103628051A CN201210599285.6A CN201210599285A CN103628051A CN 103628051 A CN103628051 A CN 103628051A CN 201210599285 A CN201210599285 A CN 201210599285A CN 103628051 A CN103628051 A CN 103628051A
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solution
polymkeric substance
acid
metal
carboxyl
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周文佳
邝淑筠
D·C·Y·陈
D·K·W·余
周卫娟
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Rohm and Haas Electronic Materials LLC
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Abstract

本发明涉及镀敷催化剂及方法。具体来说，本发明涉及一种含有贵金属纳米颗粒以及具有羧基和氮原子的聚合物的催化剂溶液。所述催化剂溶液在非导电性表面无电镀金属方法中用作催化剂。

Description

镀敷催化剂及方法
发明领域
本发明涉及一种含有贵金属纳米颗粒的催化剂溶液。更具体的，本发明涉及一种包含贵金属纳米颗粒的催化剂溶液，其纳米颗粒是利用可应用于电子器件制造和装饰涂层的无电金属镀敷非导电性基材中的特定化合物来稳定化的。
背景技术
在没有电源的情况下，无电金属沉积或无电金属镀敷对于在非导电或电介质表面沉积金属或金属混合物是很有用的。在非导电或电介质基材上的镀敷应用广泛，包括装饰性镀层和电子器件制造。主要应用之一为制造印刷电路板。将一种金属无电沉积到基材上通常要求对基材表面进行预处理或敏化处理以使表面在沉积过程中能够得到催化。目前已有若干种催化表面的方法。
U.S.3，011，920披露了一种催化基材的方法，将基材浸入由钯离子和亚锡离子形成的钯-锡胶体制备的胶体催化剂中。这种方法在对基材表面进行催化后还需要一个促进步骤，因而使得催化剂核暴露了。U.S.3，904，792披露了一种改进了的胶体钯-锡催化剂，在酸性较小的环境中提供催化剂。在此盐酸部分被该酸的可溶性盐取代。从而这种钯-锡催化剂体系表现出很多局限。催化剂胶体(SnC14)2-的外层很容易被氧化，同时催化剂颗粒变大因此极大的降低了其催化表面积。
U.S.4，725，314披露了一种在水性溶液中制备催化吸附物的方法，利用有机悬浮剂保护胶体使其最大颗粒尺寸不超过500埃。聚乙烯吡咯烷酮可以作为有机悬浮剂。
由于钯的高成本，人们付出了大量的努力开发非贵金属催化剂体系。U.S.3，993，799披露了非贵金属水合氧化物胶体在处理非导电基材上的应用，随后还原基材上的水合氧化物涂层为接下来的无电镀敷获得一定程度的活化。U.S.6，645，557披露了一种形成导电金属层的方法，该方法通过用一种含亚锡盐的水溶液与非导电表面接触形成敏化了的表面，然后将敏化的表面接触一种pH值在约5到约10之间的含银盐的水溶液以形成催化性表面。
JP10229280A披露了一种催化剂溶液，其由硝酸银或硫酸铜组成，同时还含有一种阴离子表面活性剂，如聚氧乙烯月桂基醚硫酸钠和一种还原剂，如硼氢化钠。JP11241170A披露了一种无钯催化剂，其至少含有铁、镍、钴和银盐的一种，还含有一种阴离子表面活性剂和一种还原剂。
JP2001044242A披露了一种具有高导电性的高分散性胶体金属溶液的制备方法，其含有至少一种氨基和一种羧基。U.S.7，166，152披露了一种银胶体基的预处理溶液，其含有三种组分：(i)银胶体颗粒；(ii)一种或多种选自具有能在溶液中将银离子还原为金属银的电位的金属离子的离子；和(iii)一种或多种离子，其选自羟基羧酸根离子、聚磷酸根离子和氨基羧酸根离子。通常，无锡银胶体水溶液比在空气搅拌下就能轻易氧化为锡(IV)的含二价锡离子体系更加稳定。这种银胶体催化剂体系还在无电镀工艺中表现出前景广阔的催化性能而无需牺牲互连可靠性。因此，期望得到一种同时具有镀液稳定性、吸附能力和催化活性的平衡的胶体催化剂体系。
发明内容
一种含有贵金属纳米颗粒和聚合物的溶液，所述聚合物在聚合物重复单元中有羧基和氮原子。
一种在非导电表面进行无电镀金属的方法，包括将待镀基材浸入溶液的步骤，该溶液含贵金属纳米颗粒和聚合物的溶液，所述聚合物在其重复单元中有羧基和氮原子；在无需促进步骤的情况下在基材上进行无电镀敷。
本发明的发明人已经发现一种贵金属胶体催化剂体系，该体系包含贵金属纳米颗粒，所述纳米颗粒被具有羧基和氮原子的特定聚合物稳定化，同时该体系不含锡，该体系表现出优异的稳定性和对于无电镀敷良好的催化活性。
发明的详细说明
除明确给出解释的外，本说明书中所用的缩写具有如下含义：g＝克；mg＝毫克；ml＝毫升；L＝升；m＝米；cm＝厘米；min.＝分钟；s＝秒；h＝小时；ppm＝百万分之一；M＝摩尔；g/L＝克每升；mmol＝毫摩尔；Mw＝分子质量；rpm＝转每分钟；以及DI＝去离子。
在本说明书中，“沉积”和“镀敷”可互换，“催化”和“活化”可互换使用。本说明书中的“含贵金属纳米颗粒的溶液”和“催化剂溶液”可互换使用。
本发明提供了一种用于无电镀的溶液，其包含贵金属纳米颗粒以及含羧基和氮原子的聚合物。所述用于本发明的聚合物要求同时具有羧基和氮原子。优选地，该聚合物在该聚合物重复单元中同时具有羧基和氮原子。如下所示，同时含有羧基和氮原子的聚合物的溶液与仅有氮原子而无羧基的聚合物如聚丙烯酰胺和聚乙烯基吡咯烷酮相比能获得稳定催化剂溶液的更好结果。然而不希望受限于理论，可以相信羧基对于纳米颗粒的静电稳定性更重要，而氮原子对于纳米颗粒的吸附性有用。
本申请所述聚合物要求一种聚合物。如下所示，本发明的发明人进行了将溶液中的聚合物替换成L-天冬氨酸盐的对比实施例。L-天冬氨酸盐是一种具有羧基和氮原子的低分子量化合物。用L-天冬氨酸盐制备的纳米颗粒与用聚合物制备的纳米颗粒相比较不稳定，且其只能在碱性pH值的介质中稳定化。而且，用含L-天冬氨酸的溶液进行的背光测试与含有具有羧基和氮原子的聚合物的溶液得到的结果相比很差。
组分中使用的聚合物的分子量(Mw)为400-1000000，更优选的为1000-10000。
本发明所述聚合物优选为聚氨基酸和它们的共聚物。聚氨基酸和它们的共聚物的例子包括聚天冬氨酸、聚谷氨酸、聚蓝藻素、L-天冬氨酸和L-丙氨酸的共聚物、L-天冬氨酸和甘氨酸的共聚物、L-谷氨酸和甘氨酸的共聚物、苯丙氨酸和甘氨酸的共聚物。
另外的优选聚合物包括含有酰胺结构的单体和具有羧基的单体的共聚物。具有酰胺结构的单体的例子为丙烯酰胺、甲基丙烯酰胺、乙烯基吡咯烷酮、N-(羟甲基)甲基丙烯酰胺，和2-丙烯酰胺-2-甲基丙烷磺酸。具有羧基的单体的例子为丙烯酸、甲基丙烯酸、马来酸和柠康酸。
所述聚合物占催化剂溶液总量的优选量为0.05-20g/L，更优选的为0.5-5.0g/L。
本发明所述溶液的贵金属纳米颗粒可由任何具有催化活性的贵金属提供。贵金属的例子包括银、金、铂、钯、铑、钌、铱和锇。优选的贵金属为银。
也可使用贵金属的混合物，例如银和钯的混合物。贵金属纳米颗粒占溶液的量(以重量计)为10-20000ppm，优选100-10000ppm，最优选200-5000ppm。
在所述溶液中，金属和含羧基和氮原子的聚合物的比率是由金属和羧基在聚合物中的摩尔数比例决定的，例如从1∶0.1到1∶10，优选从1∶0.5到1∶5。
任选的，本发明还包含一种或多种常用于无电镀敷催化剂配方中的不同种类的添加剂，例如表面活性剂、缓冲剂、络合剂和pH调节剂。pH调节剂可以含有例如但不局限于氢氧化钠和氢氧化钾的碱，以及酸，例如但不局限于硫酸、草酸、醋酸、柠檬酸和其他简单羧酸。pH调节剂的用量选择取决于目标pH值。
本发明中使用的溶剂优选水，例如自来水或去离子水。其他溶剂还有例如酒精或可用于本发明的、任何可以与水混合的溶剂的混合物。
通常，本发明溶液具有3-10的pH值。本发明溶液的优选pH值取决于聚合物的种类和用量以及在纳米颗粒制备步骤中使用的还原剂。优选地，本发明溶液通常具有大于4的pH值，更优选地，pH值为6到9，以及进一步优选地，pH为碱性，即具有大于7到9的pH值。
本发明的溶液为纳米颗粒的稳定溶液，可以作为催化剂用于在待镀材料非导电性的表面进行无电镀敷。优选地，本发明所述溶液不形成可见的沉淀物。更优选地，本发明所述溶液在加速老化测试和加速贮藏寿命测试后不形成可见的沉淀物。极端老化条件例如在40℃温度、空气鼓泡的条件下贮藏，高温或低温贮藏进行测试。
将贵金属离子、聚合物以及还原剂在溶液中混合就可以制得本发明所述溶液。优选地，制备本发明所述溶液的方法为(a)准备含有贵金属离子和含有羧基和氮原子的聚合物的溶液，以及(b)在搅拌的条件下将还原剂加入所述溶液。
用于本发明的贵金属离子可由任何可溶于溶剂的贵金属源提供。可以将有机酸或无机酸与贵金属源一起使用，以帮助贵金属溶解于溶液中。贵金属元素选自前述提及的如银、金、铂、钯、铑、钌、铱和锇。优选贵金属元素前述已提及，为银。
优选的贵金属离子源为贵金属的有机或无机盐。优选的贵金属离子源的例子包括金属的硝酸盐、金属亚硝酸盐、金属卤化物、金属氧化物、金属醋酸盐、金属硫酸盐、金属亚硫酸盐、金属氰化物、金属葡萄糖酸盐、金属氟硼酸盐、金属烷基磺酸盐、金属硫代硫酸盐和金属硫氰酸盐。金属盐的例子包括但不局限于硝酸银、醋酸银、硫酸银、甲磺酸银、对甲苯磺酸银、苯甲酸银、磷酸银、三氟醋酸银、硝酸钯、氯化钯、硫酸钯、醋酸钯、四氯钯酸钠、四氯钯酸铵、二氯二胺化钯和二氯四胺化钯。
贵金属离子的含量取决于金属盐的溶解度以及本发明所述溶液中所需的贵金属纳米颗粒的浓度。例如，使用的银盐的量以金属计占催化剂溶液总量的0.01-100g/L，优选0.1-10g/L，更优选0.1-5.0g/L。
用于还原贵金属离子的还原剂可以为任何能够将溶解的贵金属离子还原为还原的贵金属形式同时不产生任何会影响催化剂溶液催化性能的副产物的还原剂。优选的还原剂为二甲基氨基硼烷、硼氢化钠、联氨、次磷酸钠、水合肼、抗坏血酸、异抗坏血酸、硫酸羟胺、甲酸和甲醛。
还原剂的量为任何足够还原所需贵金属离子的量。优选的还原剂的量可以由其与贵金属的比例决定，例如0.5-2倍于贵金属离子的摩尔含量。通常，用量为0.01-10g/L，更优选为0.01-2g/L，基于催化剂溶液中金属浓度总量以及用于反应的还原剂的选择。
制备本发明所述溶液的方法为(a)制备含有贵金属离子和具有羧基和氮原子的聚合物的溶液；和(b)边搅拌所述溶液边向所述溶液添加还原剂。
所述方法的第一步是制备含有贵金属离子和具有羧基和氮原子的聚合物的溶液。所述包含贵金属离子和聚合物的溶液可以用任意方法制备。例如，将聚合物溶解于一种溶剂，如水，然后把贵金属盐或贵金属盐的水溶液加入该溶液，或者在溶剂中溶解贵金属离子，然后将聚合物或聚合物溶液加入该溶液中。
所述方法的第二步是边搅拌边向所述溶液添加还原剂。用于该步骤的还原剂的量是任何足够形成所需贵金属纳米颗粒的量。
在搅拌的同时将还原剂加入上述溶液。在强力搅拌下，金属离子被还原为金属的同时迅速形成很多纳米晶体，为下一步颗粒生长作为晶种。如果搅拌不充分，颗粒尺寸就会不均匀，一些颗粒会长的较大而很容易沉淀。换而言之，强力搅拌能够让更小的纳米颗粒以较窄的颗粒尺寸分布范围形成。通常的混合速率为200-1000rpm。
在第二个步骤中溶液的温度为10-40℃，通常在室温上下或20℃。
虽不希望被理论所束缚，发明人相信在存在本发明所述聚合物的情况下形成稳定的贵金属纳米颗粒的机理如下：一般而言，在布朗运动、对流运动、重力和其他力的作用下，纳米颗粒倾向于相互碰撞，这样就可能导致胶体的团聚和不稳定化。胶体的静电稳定性和空间稳定性是胶体稳定化的两个基本机制。在存在聚合物的情况下，制备的纳米颗粒可能会被聚合物分子包围，聚合物分子就在颗粒之间制造了补偿范德华吸引力的排斥力。
优选的制备胶体催化剂溶液的方法为，制备含1-5g/L银离子和1-5g/L聚天冬氨酸钠的溶液，然后在20-40℃和200-800rpm的强力搅拌下加入10-80mmol/L的二甲基氨基硼烷。
含有贵金属纳米颗粒和具有羧基和氮原子的聚合物的溶液可以用于印刷电路板的无电镀敷。在印刷电路板中用钻、冲或其他任何现有技术已知的方法形成通孔。形成通孔后，电路板用水和常规有机溶剂进行冲洗，以对电路板清洗和脱脂，然后对通孔壁进行去表面污染物处理。通常，对通孔的去表面污染物处理从应用溶剂溶胀开始。任何常规的溶剂溶胀都可以用于通孔的去表面污染物处理。溶剂溶胀包括但不局限于二醇醚类和它们的相关醚乙酸酯。可使用二醇醚类和他们的相关醚乙酸酯的常规用量。这种溶剂溶胀在现有技术中已公知。市售的溶剂溶胀包括，但不局限于，CIRCUPOSIT CONDITIONERTM3302溶液，CIRCUPOSIT HOLE PREPTM3303和CIRCUPOSIT HOLE PREPTM4120溶液，皆可从美国马萨诸塞州马堡市的罗门哈斯电子材料公司(Rohm and HaasElectronic Materials)获得。
任选的，可用水冲洗通孔。随后将促进剂施于通孔。可以使用常规促进剂。这些促进剂包括硫酸、铬酸、碱性高锰酸盐或等离子体刻蚀。通常将碱性高锰酸盐用做促进剂。市售的促进剂的例子为可从罗门哈斯电子材料公司获得的CIRCUPOSIT PROMOTERTM4130溶液。
任选的，可用水再次冲洗通孔。然后在通孔上使用中和剂以中和任何由促进剂留下的残留物。可以使用常规中和剂。通常中和剂是含有一种或多种胺的碱性水溶液，或含有3wt％双氧水和3wt％硫酸的溶液。任选的，用水冲洗通孔然后干燥印刷电路板。
去表面污染物步骤后，可以将一种酸或碱的调节剂用于通孔。可以使用常规调节剂。这种调节剂可以包括一种或多种的阳离子表面活性剂、非离子表面活性剂、络合剂和pH调节剂或缓冲剂。市售的酸调节剂包括但不局限为CIRCUPOSIT CONDITIONERTM3320和CIRCUPOSIT CONDITIONERTM3327溶液，可从罗门哈斯电子材料公司获得。适合的碱性调节剂包括但不局限于，含有一种或多种季胺和聚胺类的碱性表面活性剂水溶液。市售的碱性表面活性剂包括但不局限于CIRCUPOSIT CONDITIONERTM231、3325和860溶液，均可从罗门哈斯电子材料公司获得。任选的，调节剂处理后用水冲洗通孔。
调节剂处理后对通孔进行微蚀刻处理。可以使用常规的微蚀刻组合物。微蚀刻设计用来在裸露的铜上形成微粗糙化的铜表面，例如内层和表层蚀刻，从而增强其后沉积的无电镀敷或电镀的镀层的附着性。微蚀刻包括但不局限于60g/L-120g/L的过硫酸钠，或氧基一过硫酸钾或钠和2％的硫酸的混合物，或者常规的硫酸/双氧水。市售的微蚀刻组合物的例子包括可从罗门哈斯电子材料公司获得的CIRCUPOSIT MICROETCHTM3330溶液。任选的，用水冲洗通孔。
然后对进行微蚀刻后的通孔进行预浸渍。任何可以去除铜表面上的氧化铜而又不干扰催化剂溶液的酸性溶液都可使用。预浸渍的例子包括草酸、醋酸、抗坏血酸、酚酸、磷酸、硼酸和他们的盐。任选的，用冷水冲洗通孔。
一种催化剂，即前述的含有贵金属纳米颗粒的溶液随后应用于通孔。通孔的壁随后采用碱性无电镀敷组合物镀铜。可以使用任何常规无电镀浴。市售的无电镀铜浴包括但不限于可从罗门哈斯电子材料公司获得的CIRCUPOSITTM880无电镀铜浴。
通孔的内壁上沉积铜后，通孔可任选地用水冲洗。任选的，将防锈组合物施加于通孔壁上沉积的金属上。可以使用常规防锈组合物。防锈组合物的例子包括可从罗门哈斯电子材料公司获得的ANTI TARNISHTM7130和CUPRATECTM3组合物。任选的，用热水在超过30℃的温度下冲洗通孔。然后可干燥电路板。
以下实施例旨在进一步说明本发明，而非限定本发明的范围。
实施例
测试方法
催化剂的性能是通过使用以下方法观察无电镀铜的测试样品进行评价的。使用来自shengyi的常规FR-4层压板和SY-1141(正常Tg)作为测试样品。使用裸露的层压板进行表面覆盖测试。使用具有铜内层的覆铜层压板进行背光测试。
(1)将测试样品切为1×6cm2的片，其边缘用#240SiC颗粒进行喷砂处理，然后在RO(反渗透)水中清洗数次后吹干。
(2)将测试样品用表1中所示的溶胀、氧化、中和、调节和微蚀刻步骤进行处理。
(3)将测试样品浸渍在各实施例中所述的特定pH值下，40℃的催化剂溶液中3-10分钟。用去离子水清洗测试样品。
(4)在40℃下对测试样品进行无电镀铜15分钟。
表1无电Cu沉积测试的工艺流程
Figure BSA00000863205500081
1.镀敷覆盖测试
测试样品的镀敷覆盖测试是使用以下定义的镀敷覆盖分级量表进行评估的。
完全覆盖——测试样品表面超过95％的面积被镀覆。
高度覆盖——测试样品表面大于75％而小于95％的面积被镀覆。
中度覆盖——测试样品表面大于50％而小于75％的面积被镀覆。
低度覆盖——测试样品表面大于5％而小于50％的面积被镀覆。
无覆盖——测试样品表面小于5％的面积被镀覆。
2.背光测试
使用如下步骤进行背光测试。
每块板1mm厚的剖面被置于常规光学显微镜的透射模式下进行50倍放大。沉积的铜的质量是由在显微镜下观察到的量与欧洲背光分级量表(0-5)对比得到的。如果未观察到光，该剖面完全呈黑色，为背光量级的5.0级。这表示铜完全覆盖。如果光完全透过而无任何黑暗区域的话，这表示极少或无铜金属沉积在壁上，该剖面为0级。如果同时有黑暗区域和有光透过的区域，则根据标准从0至5分级。
3.ICD测试
镀敷的可靠性是由以下ICD测试(互连缺陷测试)进行评判的。
对钻了至少30个1mm孔径的孔的MLB(多层板)样品进行切割。样品边缘用240#粒度的SiC纸进行打磨。在RO水中超声清洗数次。该处理从除表面污物清除步骤至PTH(镀敷的通孔)步骤最后到电镀铜步骤都进行。任何在样品边缘的Cu都被打磨掉。样品在125℃烘烤6h。在干燥炉膛中冷却。可作为替换的是对其在288℃浸焊10秒，然后在室温下冷却110秒。所述周期重复6次。
样品的微剖面在蚀刻前进行ICD处理和检测。在互联区域记录缺陷的数目并计算级别。
样品被氨水溶液(20ml氨水，20ml水和10滴双氧水)蚀刻。确认ICD测试中的缺陷数。
实施例1：Ag-PASP催化剂体系
步骤1：将1.0g聚琥珀酰亚胺与200ml去离子水搅拌混合，然后在加热30-90℃的情况下，边搅拌边将10ml/L的1.0mol/L氢氧化钠加入上述混合溶液中。使用GPC方法测得化合物的分子量约为1100。
步骤2：将200ml的上述溶液与800ml去离子水混合，然后边搅拌边向该溶液中加入1.7g的硝酸银。
步骤3：将10ml刚刚配制的2.0mol/L的二甲基氨基硼烷(DMAB)迅速加入上述溶液，同时使用磁力搅拌器在500rpm下进行强力搅拌。搅拌持续2h结束。
加速老化测试是保持40℃浴温度下以10mL/min的鼓泡速率对溶液进行测试。一个月后，催化剂溶液仍然保持良好状态。
还在-20℃和60℃进行了48h的加速贮藏寿命测试，同样无可观测到的沉淀物出现，也未损失催化活性。
实施例2：Ag-PASP催化剂体系
步骤1：将3.2g的40％聚天冬氨酸钠(PASP)溶液(Mw＝3000-5000)与990ml的去离子水在搅拌下混合。边搅拌边向该溶液中加入1.7g的硝酸银。
步骤2：将10ml刚刚配制的2.0mol/L的二甲基氨基硼烷(DMAB)迅速注射入上述溶液，同时使用磁力搅拌器在500rpm下进行强力搅拌。搅拌持续2h结束。得到的溶液pH值为9.0。
进行了如实施例1中的加速老化测试和加速贮藏寿命测试，无可观测到的沉淀或浑浊。
实施例3-13：Ag-PASP催化剂体系
如实施例2中的方法配制Ag-PASP催化剂溶液，区别在于每种成分的浓度和温度如表2中所示的变化。
表2
Figure BSA00000863205500101
对实施例2进行性能测试。覆盖测试、背光测试和ICD测试的结果在表3中示出。使用硫酸或氢氧化钠调节pH值。
表3
Figure BSA00000863205500102
Figure BSA00000863205500111
实施例14-21：Ag-PGA催化剂体系
Ag-聚谷氨酸溶液采用实施例2的方法制备，区别在于将PASP替换为聚谷氨酸(PGA)(Mw＞500000)，同时每种成分的浓度变化在表4中示出。
表4
Figure BSA00000863205500112
对实施例19进行性能测试。覆盖测试和背光测试的结果在表5中示出。
表5
Figure BSA00000863205500113
实施例22-25：Ag-AA和AMPS共聚物催化剂体系
如实施例2中的方法制备Ag-丙烯酸(AA)和2-丙烯酰胺-2甲基丙磺酸(AMPS)共聚物溶液，区别在于将PASP替换为丙烯酸(AA)和2-丙烯酰胺-2甲基丙磺酸(AMPS)共聚物(Mw＝10000)，各成分浓度的变化在表6中示出。
表6
Figure BSA00000863205500114
对实施例24进行性能测试。覆盖测试和背光测试的结果在表7中示出。
表7
Figure BSA00000863205500121
对比实施例1：Ag-ASP催化剂体系
如实施例2中的方法制备Ag-L-天冬氨酸盐溶液，区别在于将PASP替换为L-天冬氨酸(ASP)，将DMAB替换为NaBH4，同时各成分浓度的变化在表8中示出。
表8
Figure BSA00000863205500122
对对比实施例1进行性能测试。覆盖测试和背光测试的结果在表9中示出。
表9
Figure BSA00000863205500123
使用L-天冬氨酸盐得到的纳米颗粒的稳定性比使用聚天冬氨酸盐得到的纳米颗粒差，且其仅能在碱性pH介质中稳定化，而使用聚天冬氨酸盐得到的纳米颗粒在更宽的如4-10的pH值范围内稳定。
对比实施例2-5：Ag-PAM催化剂体系
尝试用实施例2中的方法获得Ag-聚丙烯酰胺(PAM)溶液，区别在于将PASP替换为0.2-2.0g/L的PAM，同时各成分浓度的变化在表10中示出。
表10
Figure BSA00000863205500124
然而，加入0.2或0.4g/L的PAM作为稳定剂，在注入还原剂10到20分钟后出现了棕色沉淀物。当加入1.0g/L的PAM，仍然在1天的老化后在容器底部出现沉淀。当加入2.0g/L的PAM，反应发生的相当缓慢而且导致溶胶立即形成。使用PAM作为稳定剂无法得到稳定的胶体催化剂。
对比实施例6-11：Ag-PVP催化剂体系
如实施例2中的方法制备Ag-聚乙烯基吡咯烷酮(PVP)催化剂体系，区别在于将PASP替换为0.2-9.0g/L的PVP(Fluka K25，Mw＝24000)，同时各成分浓度的变化在表11中示出。
表11
所有溶液均出现浑浊现象。
对对比实施例10进行性能测试。覆盖测试的结果在表12中示出。
表12
如实施例和对比实施例所述，本发明所述溶液(含有贵金属纳米颗粒和具有羧基和氮原子的聚合物的溶液)具有高的吸附能力和催化活性，同时与含其他组成的溶液相比具有很好的浴液稳定性。

Claims (6)

1.一种含有贵金属纳米颗粒和聚合物的溶液，其中所述聚合物在该聚合物的重复单元中含有羧基和氮原子。
2.根据权利要求1所述的溶液，其中所述聚合物是聚氨基酸。
3.根据权利要求1所述的溶液，其中所述聚合物是聚天冬氨酸盐。
4.根据权利要求1所述的溶液，其中所述贵金属是银、金、铂、钯、铑、钌、铱或锇。
5.一种制备含有贵金属纳米颗粒和聚合物的溶液的方法，其中所述聚合物含有羧基和氮原子，所述方法包括：
制备含有贵金属离子和具有羧基和氮原子的聚合物的溶液，
边搅拌边向上述溶液中加入还原剂。
6.一种在非导性电表面无电镀金属的方法，所述方法包括以下步骤：
将待镀基材浸入权利要求1所述的溶液中，
在无需促进步骤的情况下进行基材的无电镀敷。
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