CN103276375A - 镀敷催化剂及方法 - Google Patents

镀敷催化剂及方法 Download PDF

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CN103276375A
CN103276375A CN2012105992841A CN201210599284A CN103276375A CN 103276375 A CN103276375 A CN 103276375A CN 2012105992841 A CN2012105992841 A CN 2012105992841A CN 201210599284 A CN201210599284 A CN 201210599284A CN 103276375 A CN103276375 A CN 103276375A
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周文佳
邝淑箔
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

本发明涉及一种镀敷催化剂及方法。具体来说，本发明提供了一种含有贵金属纳米颗粒和由具有两个或更多个羧基或羧酸盐基团的至少一种单体聚合而成的聚合物的溶液。所述溶液在非导电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，本发明涉及一种含贵金属纳米颗粒的催化剂溶液，其纳米颗粒是利用特定化合物稳定化的，所述催化剂溶液可以应用于电子起见制造和装饰性涂层的对非导电性基材的无电金属镀敷。
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，包括装饰性镀敷和电子器件制造。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。目前已开发出若干种催化基材的方法。
U.S.3，011，920披露了一种催化基材的方法，该方法将基材浸入由钯离子和亚锡离子形成的钯一锡胶体制备的胶态催化剂中。这种方法在对基材表面进行催化后还需要一个促进步骤，从而暴露了催化剂核。U.S.3，904，792披露了一种改进了的胶态钯-锡催化剂，在一种酸性较小的环境下提供催化剂。在此盐酸被该酸的可溶性盐部分取代。这种钯-锡催化系统仍存在一些局限。催化剂胶体SnCl4 2-的外层很容易被氧化，因此催化剂颗粒尺寸变大，极大地降低了其催化表面积。
U.S.4，725，314披露了一种用于在水性溶液制备催化吸附物的方法，该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。
由于钯的成本很高，人们付出了大量的努力发展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中的应用，随后减少基材上的水合氧化物涂层为接下来的无电镀敷获得至少一定程度的活化。U.S.6，645，557披露了一种形成导电金属层的方法，其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表面，然后用敏化表面接触一种pH值在约5到约10之间的含银盐的水溶液以形成催化的表面。JP10229280A披露了一种由硝酸银或硫酸铜组成的催化剂溶液，该溶液同时还含有阴离子表面活性剂，如聚氧乙烯月桂醚硫酸钠和还原剂，如硼氢化钠。JP11241170A披露了一种无钯催化剂，其含有铁、镍、钴和银盐中的至少一种，结合阴离子表面活性剂和还原剂。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披露了一种基于银胶体的预处理溶液，其含有三种组分：(i)银胶体颗粒；(ii)一种或多种选白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；和(iii)一种或多种离子，其选自羟基羧酸根离子、羧磷酸盐离子和氨基羧酸根离子。
通常，胶体银纳米颗粒的水溶液是不含锡的催化剂。其较之会在空气搅拌下就能轻易氧化为锡(IV)的含亚锡离子的体系稳定得多。这种胶体银催化剂体系可以降低成本而且相对钯体系而言更不易受不稳定的贵金属干扰。这种胶体银催化剂体系还在无电镀敷工艺中表现出前景广阔的催化性能而无需牺牲互连的可靠性。
因此，人们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，所述聚合物是由单体聚合得到的，所述单体包括至少一种具有两个或更更多个羧基或羧酸盐基的单体。
一种在非导电表面进行无电镀敷金属的方法，所述方法包括将待镀敷的基材浸入溶液的步骤，该溶液含贵金属纳米颗粒和聚合物，所述聚合物是由单体聚合得到的，所述单体包括至少一种含两个或更更多个羧基或羧酸盐基的单体；以及在不进行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，其所含的贵金属纳米颗粒被特定种类的聚合物稳定化，所述聚合物由单体聚合得到，所述单体包括至少一种具有两个或更多个羧基或羧酸盐基的单体，同时该催化剂体系不含锡，该体系表现出在优异的稳定性和对于无电镀敷良好的催化活性之间的平衡。而且，这种胶体催化剂体系具有很大的操作区间，即在较宽的pH值范围内的有效性，因此在工业应用中非常有用。
发明的详细说明
除明确给出解释的外，本说明书中所用缩写具有如下含义：g＝克；mg＝毫克；ml＝毫升；L＝升；m＝米；min.＝分钟；s＝秒；h＝小时；ppm＝百万分之一；M＝摩尔；g/L＝克每升；cm＝厘米；mmol＝毫摩尔；rpm＝转每分钟；Ag＝银；Cu＝铜；PAA＝聚丙烯酸；以及PESA＝聚环氧琥珀酸。
在本说明书中使用的“沉积’’和“电镀”可互换。本说明书中的“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敷的溶液，其包含贵金属纳米颗粒和聚合物，所述聚合物由单体聚合得到，所述单体包括至少一种具有两个或更多个羧基或羧酸盐基团的单体。用于本发明的聚合物是由单体聚合得到的，所述单体包括至少一种具有两个或更多个羧基或羧酸盐基团的单体。换言之，所述聚合物是至少由不饱和聚羧酸或其盐聚合而成的，同时所述聚合物在重复单元上具有至少两个羧基或羧酸盐基团。所述聚合物可以为不饱和聚羧酸或其盐与另一聚合单体的共聚物。聚羧酸或其盐的例子包括马来酸、富马酸、衣康酸及它们的盐。优选使用马来酸。下面将会提到，相对于含由具有一个羧基的单体聚合而成的聚合物如聚丙烯酸的溶液，本发明中使用的聚合物能在较大范围pH值的溶液中获得稳定催化剂溶液的良好结果。本发明中使用的聚合物与由具有一个羧基的单体聚合而成的聚合物的区别在于含有这些聚合物的溶液的pKa。与含有聚丙烯酸的具有一个pKa值(pKa＝～4.58)的溶液相比，含有用于本发明的聚合物的溶液具有至少两个pKa值。
虽不希望受限于理论，但可以相信本发明中的聚合物既作为缓冲剂又作为贵金属纳米颗粒的稳定剂，因此本发明的含有聚合物的溶液具有反应性和在较大pH值范围内的胶体催化剂稳定性之间更好的平衡，同时在所述聚合物中的独特的含氧骨架也在较大的pH值范围内贡献了纳米颗粒吸附性。
优选地，用于本发明的聚合物在其主链或聚合物骨架中具有一个氧原子作为醚键。含有这种聚合物的溶液在宽pH范围内具有特别高的催化活性同时还保持其稳定性。
所述聚合物的分子量(Mw)为400到100000，更优选的为800到10000。Mw值越高，胶体的稳定性越好，但会直接牺牲催化活性，即导致较差的催化活性。
由包括至少一种含有两个或更多个羧基或羧酸基团的单体的单体聚合而成的聚合物的例子包括聚马来酸、丙烯酸和马来酸的共聚物、甲基丙烯酸和马来酸的共聚物、膦酸和马来酸的共聚物、丙烯酸和柠康酸的共聚物、膦酸和柠康酸的共聚物，以及磺酸和马来酸的共聚物。
由包括至少一种含有两个或更多个羧基或羧酸盐基团的单体的单体聚合而成，同时还进一步包括在主链上作为醚键的氧原子的聚合物的例子包括，聚环氧琥珀酸、聚[氧[1-羧基-1-(羧甲基)-1，2-乙烷二基]]、膦酸和环氧琥珀酸的共聚物。
所述聚合物占催化剂溶液总量的优选含量为0.05-20g/L，更优选地为1.0-4.0g/L。
本发明所述溶液的贵金属纳米颗粒可由任何可以用于催化剂的贵金属提供。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质量的量为10-20000ppm，优选100-10000ppm，最优选200-5000ppm。
任选的，本发明还包含一种或多种常用于无电镀敷催化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，以及简单酸，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。其他溶剂还有例如醇或可用于本发明的、任何可以溶于水的溶剂的混合物。
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阶段中使用的还原剂。优选地，本发明溶液通常具有大于5的pH值，更优选地，pH值为6-9，以及进一步优选地，pH为碱性，即具有大于7至9的pH值。
本发明的溶液为纳米颗粒的稳定溶液，用于在待镀敷的非导电性表面进行无电镀敷的催化剂。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。加速老化试验是将溶液置于40℃浴中并空气鼓泡一个月，加速贮藏寿命测试是在-20℃和60℃进行48小时。
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聚合物的溶液，所述溶液由单体聚合得到，所述单体包括至少一种具有两个或更多个羧基或羧酸盐基团的单体，以及(b)边搅拌边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。有机或无机酸可以用于贵金属源，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己提及，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、氯化钯(II)、氯化铂(IV)、氯化金和氯化钌。
贵金属离子的含量取决于金属盐的溶解性以及本发明所述溶液中所需的贵金属纳米颗粒的含量。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贵金属还原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与贵金属的比例决定，例如为贵金属离子的摩尔含量的0.5-2倍。通常，用量为0.01-10g/L，更优选为0.05-5g/L，取决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聚合物的溶液，所述聚合物由单体聚合得到，所述单体包括至少一种具有两个或更多个羧基或羧酸盐基团的单体；和(b)边搅拌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聚合物的溶液，所述聚合物由单体聚合得到，所述单体包括至少一种具有两个或更多个羧基或羧酸盐基团的单体。所述溶液包括贵金属离子，所述聚合物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溶剂，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溶剂中。
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。
还原剂边搅拌边加入上述溶液。在强力搅拌条件下，金属离子被还原为金属的同时迅速形成很多纳米晶体，作为下一步颗粒生长的晶种。如果搅拌不充分，颗粒尺寸就会不均匀，一些颗粒会长得很大而很容易沉淀。从某种意义上来说，强力搅拌能够让较小的纳米颗粒分布在较窄的颗粒尺寸范围内形成。通常的混合速率可以为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℃。
虽不希望受限于理论，发明人相信在存在本发明所述聚合物的条件下形成稳定的贵金属纳米颗粒的机理如下：一般而言，由于布朗运动、对流运动、重力和其他因素的作用，纳米颗粒倾向于互相碰撞，这样就可能导致胶体的团聚和不稳定。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，聚合物分子在颗粒之间产生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聚环氧琥珀酸的溶液，然后在20-40℃和200-1000rpm的强力搅拌下加入10-80mmol/L的二甲基氨基硼烷。
所述含有贵金属纳米颗粒和聚合物的溶液，本发明的胶体催化剂，可用于制造印刷电路板的无电镀工艺，所述溶液中的聚合物由单体聚合得到，所述单体包括至少一种具有两个或更多个羧基或羧酸盐基团的单体。在印刷电路板上用钻、冲或其他任何现有技术形成通孔。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沾污物去除。通常，对通孔的表面沾污物去除是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表面沾污物去除。溶剂溶胀包括但不局限于乙二醇醚类及其的相关醚的醋酸酯。可使用乙二醇醚类及其的相关醚乙酸酯的常规用量。这种溶剂溶胀试剂在现有技术中己公知。市售的溶剂溶胀试剂包括，但不局限于，CIRCUPOSIT CONDITIONERTM3302，CIRCUPOSITHOLE 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。这种促进剂包括硫酸、铬酸、碱性高锰酸盐或等离子刻蚀。通常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，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。通常中和剂是碱性水性溶液，含有一种或多种有机胺，或含有3wt％双氧水和3wt％硫酸的溶液。任选的，用水冲洗通孔然后对印刷电路板进行干燥。
去除表面沾污物步骤后，将一种酸或碱的调节剂施加到通孔。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、3325，813和860溶液，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。微蚀刻用来在裸露的铜上形成微观粗糙化的铜表面，例如内层和表层蚀刻，从而增强其后无电镀敷或电镀的镀层附着性。微蚀刻包括但不局限于60g/L-120g/L的过硫酸钠，或一氧单过硫酸钾或一氧单过硫酸钠和2％的硫酸的混合物，或者一般的硫酸/双氧水。可从商业获得的微蚀刻组合物的例子包括可从所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、硼酸和它们的盐。任选的，用冷水冲洗通孔。
一种催化剂，即前述过的含有贵金属纳米颗粒的溶液随后被用于通孔。通孔的壁随后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(Rohm and HaasElectronic Materials)获得的CIRCUPOSITTM880无电镀铜浴。
通孔的壁上沉积铜后，可任选地用水冲洗通孔。任选的，将防锈组合物用于通孔壁所沉积的金属上。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。然后干燥电路板。
以下实施例旨在进一步阐述本发明，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观察使用以下方法无电镀铜的样品进行评价的。使用来自shengyi的常规FR-4层压板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。使用具有铜中间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)将测试样品浸渍在不同pH值(2.9到10.9，如各个实施例所示)下，在40℃的催化剂溶液中10分钟。用去离子水清洗测试样品。
(4)在35℃或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 BSA00000863207700091
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标准进行评估的。
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。
从每块板上取下的1mm厚的剖面被置于常规光学显微镜的透射模式下以50倍放大倍数进行观察。沉积的铜的质量是由在显微镜下观察到的亮度与欧洲背光分级量表(0-5)对比得到的。如果未观察到光，该剖面完全呈黑色则是背光量级的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，该部分为0级。如果同时有黑暗区域和有光透过的区域，则根据与标样比较从0至5分级。
3.ICD测试
镀膜的可靠性是由以下ICD测试(互连缺陷测试)进行评判的。
将钻了至少30个具有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。该处理从清除表面污物步骤至PTH(在孔中镀敷)步骤最后到电镀铜步骤都要进行。任何在样品边缘的Cu都被磨掉。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。所述步骤重复6次。
样品的微剖面在蚀刻前进行ICD处理和检测。记录缺陷和互连区域的数目并计算级别。
样品被氨水溶液(20ml氨水，20ml水和10滴双氧水)蚀刻。重新确认ICD。
4.加速老化测试(AAT)
加速老化测试以如下步骤进行：
制备50ml定容的浓催化剂加工浴，然后以10ml/min的空气鼓泡率在40℃的浴温下加速老化测试7天或几周。然后再使用这些加速老化催化剂加工浴进行覆盖测试和背光测试来验证催化活性是否丧失。同时，还进行其他相应测试，如UV光谱吸收测试。
催化剂制备实施例1：Ag-PESA催化剂体系
步骤1：称量3.3g聚环氧琥珀酸(Mw＝400-1500)的钠盐，然后将其与3000ml去离子水在5升的烧杯中搅拌混合。将5g硝酸银边搅拌边加入上述溶液。
步骤2：将15ml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的转速下进行强力搅拌。搅拌持续2h结束。
实施例1-4：4Ag-PESA催化剂体系
使用如催化剂制备实施例1中的方法制备Ag-PESA催化剂溶液，区别在于将硝酸银替换为以下表2中所示的不同银盐。
对实施例1-4的催化剂溶液进行性能测试。各使用200ppm的每种催化剂溶液(Ag-PESA体系)。背光测试的结果在表2中示出。
表2背光测试结果
Figure BSA00000863207700111
这些催化剂在pH＝4到pH＝7的范围内表现出了很高的背光测试结果，因此具有很宽的操作区间。
对实施例1的催化剂的加速老化测试(AAT)之前和之后都进行了覆盖测试和背光测试。使用了200ppm的催化剂溶液(Ag-PESA体系)。结果如表3和表4所示。
表3
Figure BSA00000863207700112
“Init.时间”是指启动时间。该时间是指所需能够在裸露的层压板上得到可观察到的无电镀敷沉积的铜所需的时间。这是根据层压板的颜色从黄变暗来判断的。
表4
Figure BSA00000863207700113
“缺陷类型”表示的是无电镀铜的沉积缺陷。沉积状态由以下级别分类表示：
TAG：在玻璃周围的薄镀层
STAG：在玻璃周围的略薄镀层
TOG：在玻璃上的薄铜镀层
STOG：在玻璃上的略薄铜镀层
TGV：横贯玻璃的缺陷
GTV：玻璃尖端缺陷
ROP：珠状环形缺陷
SROP：珠状小环形缺陷
“形态”表示的是在玻璃纤维上无电镀沉积铜的形态，这是由光学显微镜在面光模式下进行检测的。以下示出分级。
VR-gl：在玻璃纤维上非常粗糙
R-gl：在玻璃纤维上粗糙
sR-gl：在玻璃纤维上轻微粗糙
实施例5-12Ag-CP5催化体系
使用如催化剂制备实施例1中的方法制备Ag-CP5催化剂溶液，区别在于将PESA替换为丙烯酸和马来酸的共聚物，钠盐(Mw＝70000，Sokalan CP5，BSAF化学公司)和每种成分的浓度的变化如表5所示。
表5
使用实施例10制备的催化剂溶液进行性能测试。使用了270ppm的催化剂溶液(Ag-CP5体系)。结果在表6中示出。
表6
这种催化剂在pH值2.9至5.0之间表现出高的背光测试结果，因此具有很宽的操作区间。
对比实施例1-4Ag-PAA体系
Ag-PAA溶液使用实施例1的方法制备，区别在于将PESA替换为聚丙烯酸(Mw＝100000，35％的水溶液，自埃尔德里奇公司(Aldrich)购得)，每种成分的浓度变化如表7所示。
表7
Figure BSA00000863207700132
对对比实施例1进行性能测试。使用270ppm的催化剂溶液(Ag-PAA体系)。结果在表8中示出。
表8
这种催化剂在pH3.5到pH4.5之间表现出高的背光测试结果，因此与实施例1-4和10相比，其操作区间较窄。
对比实施例5Ag-柠檬酸体系
Ag-柠檬酸溶液使用催化剂制备实施例1的方法制备，区别在于将PESA替换为柠檬酸根。在pH＝3，6，9和12的条件下进行性能测试。只有在pH＝9时才表现出比pH值为4时更好的背光测试结果，因此这种催化剂与实施例1-4和10的结果相比操作空间更窄。
经过实施例和相对的对比实施例的披露，本发明所述的溶液(所述溶液含有贵金属纳米颗粒和由包含具有两个或更多个羧基或羧酸盐基团的至少一种单体的单体聚合而成的聚合物)具有更高的吸附能力和催化活性以及与含其他成分的溶液相比在较大的pH范围内表现出好的浴液稳定性。尤其是，含有Ag纳米颗粒和聚环氧琥珀酸的钠盐的溶液具有更高的吸附性和催化活性，更宽的操作区间(在较宽的pH范围内都有效)以及好的浴液稳定性。而且，含有Ag纳米颗粒和聚环氧琥珀酸的钠盐的溶液不含可能会带来环境问题的氮原子和含磷基团，是一种绿色溶液。

Claims (8)

1.一种含有贵金属纳米颗粒和聚合物的溶液，所述聚合物是由单体聚合而成的，所述单体包括至少一种具有两个或更多个羧基或羧酸盐基团的单体。
2.根据权利要求1所述的溶液，其中所述聚合物在主链上具有作为醚键的氧原子。
3.根据权利要求2所述的溶液，其中所述聚合物是聚环氧琥珀酸或其盐。
4.根据权利要求1所述的溶液，其中所述聚合物是聚马来酸或由马来酸和选自丙烯酸、甲基丙烯酸、膦酸和磺酸的另一种单体聚合而成的聚合物。
5.根据权利要求1所述的溶液，其中所述聚合物包含丙烯酸和柠康酸，或包含膦酸和柠康酸的单体。
6.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。
7.一种制备含有贵金属纳米颗粒和聚合物的溶液的方法，其中所述聚合物是由单体聚合而成的，所述单体包括具有两个或更多个羧基或羧酸盐基团的至少一种单体，所述方法包括：
a)制备含有贵金属离子和由单体聚合而成的聚合物的溶液，所述单体包括至少一种具有两个或更多个羧基或羧酸盐基团的单体；和
b)向所述溶液添加还原剂，并搅拌所述溶液。
8.一种在非导电性表面无电镀金属的方法，所述方法包括以下步骤：
a)将待镀的基材浸入权利要求1所述的溶液中；和
b)在不进行促进步骤的情况下，在基材上进行无电镀敷。
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