CN103328686A - 采用等离子体聚合预处理对物件的金属涂覆 - Google Patents

采用等离子体聚合预处理对物件的金属涂覆 Download PDF

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CN103328686A
CN103328686A CN2011800541100A CN201180054110A CN103328686A CN 103328686 A CN103328686 A CN 103328686A CN 2011800541100 A CN2011800541100 A CN 2011800541100A CN 201180054110 A CN201180054110 A CN 201180054110A CN 103328686 A CN103328686 A CN 103328686A
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metal
plasma
substrate
carboxyl
monomer
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思文·歌德
比约恩·阿特霍夫
卡尔-贡纳·拉尔森
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CUPTRONIC Tech Ltd
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Abstract

一种在基底上施加金属的方法，包含：a)在等离子体中处理以涂覆涂层，所述等离子体包含选自于不饱和单体和多达10个碳原子的烷烃类中的化合物，和b1)在所述基底的表面上生成聚合物，所述聚合物包含羧基和吸附的第二金属的离子，还原所述离子为第二金属，或替代地b2)在表面上生成聚合物，将所述基底的表面与至少一种第二金属的胶态金属颗粒的分散体接触，和c)在所述第二金属上沉积所述第一金属。优势包括可以涂覆对例如低pH或溶剂敏感的材料。包含玻璃、几乎不含有不可提取的氢原子的SiO2以及含有卤素原子的聚合材料的基底具有良好的涂覆附着力。

Description

采用等离子体聚合预处理对物件的金属涂覆
技术领域
本发明一般地涉及一种将金属施加到基底上的方法以及使用该方法涂覆的物件。 
背景技术
WO98/34446公开了一种以独特的图案将导电材料施加到有机基底上的方法，根据所述不同的模式对表面层进行化学改性以获得的不同粘结区域，此后将导电材料施加到这些区域上。 
WO2007/116056公开了一种将金属施加到基底上的方法，包含：a)在基底的表面上生成聚合物，其中所述聚合物包含羧基和至少一种其它金属的吸附离子，b)将所述离子还原为第二金属和c)将第一金属沉积在还原的离子上。提及的等离子体处理作为初始步骤以提高施加至所述表面的随后溶液的湿润性，以及作为清洗步骤。 
WO2007/116057公开了应用于纸张的上述方法。 
WO00/20656公开了一种将金属施加到固体聚合物基底上的方法，包含：a)使基底表面接触气体等离子体以在其上产生自由基，b)使用等离子体增强的聚合方法在所述表面上形成层，c)使用PVD或CVD方法沉积金属原子以提供短暂表面沉积，和d)任选地使用常规无电镀浴提供表面金属化。 
对于使用CVD和/或PVD的方法，如何提高金属层的附着力是一个问题。 
US6,383,575公开了一种在固体基底上生产金属膜的方法，其包括使用金属前体涂覆基底表面并通过非平衡等离子体处理还原所述金属前体，所述等离子体处理有效地将金属前体还原为相应的金属。还公开了一种实施方式，其中基底对金属前体溶液是不可湿的(例如PTFE基底)，然后可以首先沉积等离子体聚合物耦合层(例如马来酸酐、烯丙胺、丙烯酸等)以提高金属前体与基底的附着力。然后可以将金属前体沉积到该等离子体聚合物层上并随后还原。金属前体的例子为有机金属化合物、金属有机化合物和合适的金属的盐。 
尽管公布文本WO2007/116056和WO2007/116057中公开的包括生成 具有羧基和吸附离子的聚合物的方法能够以优异的附着力在大多数基底上施加金属层，但发现对于一些基底还有改进的空间。如果基底材料中具有可以被提取的氢原子，上述公布中描述的技术表现优异。对于上述方法中使用的溶液敏感的基底可能难以用金属涂覆。一个例子是聚碳酸酯/丙烯腈-丁二烯-苯乙烯(PC/ABS)塑料，其对低pH和高pH的溶液敏感。另外，卤素聚合物以及不含有或几乎不含有可提取氢原子的聚合物可能不太适合根据此技术状况进行涂覆。另外，玻璃和陶瓷材料可能难以涂覆。 
发明内容
本发明的目的是减少至少一些现有技术的不足并提供一种改良的方法，其提高附着力并能够以良好的附着力涂覆更广泛的基底。 
在第一方面，提供了一种至少部分地将第一金属施加到基底的表面上的方法，包含步骤： 
a)在等离子体中处理所述基底以涂覆涂层，所述等离子体包含选自于不饱和单体和多达10个碳原子的烷烃类中的至少一种化合物， 
实施步骤b1和b2之一， 
b1)在所述基底的表面上生成聚合物，所述聚合物包含羧基和至少一种第二金属的吸附离子，还原所述离子为第二金属， 
b2)在所述基底的表面上生成聚合物，所述聚合物包含羧基，将所述基底的表面与至少一种第二金属的胶体金属粒子的至少一种分散体接触，其中所述颗粒具有5-500nm范围的直径， 
c)在所述第二金属上沉积所述第一金属。 
在第二方面，提供了一种由所述方法制造的物件。 
进一步的具体实施方式在说明书和所附权利要求中详细描述。 
本发明的优势包括对所使用的溶液的比如低pH/高pH或其它性质敏感的基底如PC/ABS能够涂以金属，因为所涂覆的等离子体聚合材料的薄涂层充当为保护屏障。进一步的优势为能够涂覆几乎不含有(环氧树脂)不可提取的氢原子的基底，因为所涂覆的等离子体聚合材料的薄涂层具有可提取的氢原子。此外，含有部分去活化接枝过程的卤素原子（如溴）的聚合物材料也可以使用。进一步的优势在于无机材料包括但不限于玻璃、SiO2可以用作基底并成功地被涂覆。 
具体实施方式
在详细公开和描述本发明之前，应当理解本发明并不局限于本文所公 开的特定化合物、组合、方法步骤、基底和材料，因为这些化合物、组合、方法步骤、基底和材料可能会有所改变。还应理解的是本文所用的术语只是为了描述特定的具体实施方式并不意味着限制，因为本发明的范围只受所附的权利要求书及其等同物限制。 
必须注意的是，除非上下文另有明确规定，本说明书和所附权利要求书中使用的单数形式“一个”、“一个”和“这个”包括复数形式。 
如无其他定义，本文使用任何术语和科学用语的目的是使本领域技术人员通俗地理解本发明所涉及的内容。 
整个说明书和权利要求书中使用的术语“约”与数值相关，表示精确的区间并为本领域技术人员熟知且接受。所述区间为±10%。 
整个说明书和权利要求书中使用的术语等离子体表示物质取得气体状云或离子束形式的特殊态，一种对电磁场做出强烈且共同响应的带电粒子的集合。由于等离子体中的颗粒带电(通常被夺去电子)，其经常被描述为“离子化气体”。 
在第一方面，提供一种至少部分地将第一金属施加到基底的表面上的方法，包含步骤： 
a)在等离子体中处理所述基底以涂覆涂层，所述等离子体包含选自于不饱和单体和多达10个碳原子的烷烃类中的至少一种化合物， 
实施步骤b1和b2之一， 
b1)在所述基底的表面上生成聚合物，所述聚合物包含羧基和至少一种第二金属的吸附离子，还原所述离子为第二金属， 
b2)在所述基底的表面上生成聚合物，所述聚合物包含羧基，将所述基底的表面与至少一种第二金属的胶体金属粒子的至少一种分散体接触，其中所述颗粒具有5-500nm范围的直径， 
c)在所述第二金属上沉积所述第一金属。 
等离子体创造一薄涂层(等离子体聚合物)。在本发明中，利用等离子体以涂覆涂层。在等离子体中，发生提供包含聚合物的聚合涂层的聚合反应，该聚合物是由存在于等离子体气体中的单体形成的。等离子体聚合层的厚度可以变化。在一个具体实施方式中，一个等离子体聚合层的厚度为2nm至50nm。气体中的单体可以是一类提供均质聚合物的单体。或者，气体中具有提供异质聚合物的单体混合物。 
在一个具体实施方式中，通过在所述基底的表面上生成聚合物以将第二金属施加到所述表面上，所述聚合物包含羧基和至少一种第二金属的吸附离子，并且此后还原所述离子为第二金属。这称为步骤b1。 
或者，通过在所述基底的表面上生成聚合物并且随后将所述基底的表面与至少一种第二金属的胶体金属粒子的至少一种分散体接触以将第二金属施加到所述表面上，所述聚合物包含羧基，其中所述颗粒具有5-500nm范围的直径。本具体实施方式中的第二金属是从第二金属小颗粒的胶体分散体中沉积的。这称为步骤b2。 
或者实施步骤b1、或者实施步骤b2。使用步骤b1的方法和使用步骤b2的方法两者也都包含作为单独的方法。 
可以以多种方式制得等离子体聚合涂层。 
等离子体聚合涂层的例子包括但不局限于： 
1层由一种化合物组成的等离子体聚合涂层 
1屋由两种或多种化合物组成的等离子体聚合涂层 
2层或多层等离子体聚合涂层，其中各层由一种化合物组成 
2层或多层等离子聚合涂层，其中各层由两种或多种化合物组成 
2层或多层等离子体聚合涂层，其中各层由一种化合物组成或由两种/多种化合物组成。 
在一个具体实施方式中，等离子体包含选自于烯烃类、炔烃类、丙烯酸类、甲基丙烯酸类、氨、胺类(包括伯胺、仲胺和叔胺)、异氰酸酯类、降冰片烯、烯丙醚类和乙烯醚类中的至少一种化合物。 
在一个具体实施方式中，等离子体包含选自于烯烃类、丙烯酸类、烯丙醚类、乙烯醚类和降冰片烯中的至少一种化合物。 
在一个具体实施方式中，等离子体包含丙烷。 
在一个具体实施方式中，等离子体进一步包含选自于氧、氮或氩中的至少一种化合物。 
在一个具体实施方式中，通过将所述表面与a)至少一类单体(其中的至少一种包含羧基)、b)选自于由钌、铑、钯、锇、铱、铂和铜组成的组中的至少一种第二金属的离子或具有5-500nm范围直径的胶态金属颗粒的分散体、和c)至少一种引发剂接触以在所述表面上生成聚合物。 
在一个替代的具体实施方式中，通过将所述表面与a)至少一类单体(其中的至少一种包含羧基)、和b)至少一种引发剂接触，然后将所述表面与包含选自于由钌、铑、钯、锇、铱、铂和铜组成的组中的至少一种第二金属的离子或具有5-500nm范围直径的胶态金属颗粒的分散体的溶液接触，以在所述表面上生成聚合物。 
在一个具体实施方式中，所述至少一类单体选自于由丙烯酸和甲基丙烯酸组成的组。 
在又一个替代的具体实施方式中，通过将所述表面与a)至少一类单体(其中的至少一种包含隐蔽的羧基)、和b)至少一种引发剂接触，此后将所述表面处于适合于将所述隐蔽的羧基转化为羧基的条件，此后将所述表面与包含选自于由钌、铑、钯、锇、铱、铂和铜组成的组中的至少一种第二金属的离子或具有5-500nm范围直径的胶态金属颗粒的分散体的溶液接触，以在所述表面上生成聚合物。在一个具体实施方式中，包含隐蔽的羧基的单体是选自于由丙烯酸叔丁酯、马来酸酐、甲基丙烯酸酐和丙烯酸酐组成的组中的至少一种物质。在一个具体实施方式中，适合于将隐蔽的羧基转化为羧基的条件是通过将表面与光致布朗斯台德
Figure BDA00003165971400051
酸接触来实现的。在一个具体实施方式中，布朗斯台德酸选自于由锍盐和碘鎓盐组成的组。 
隐蔽的羧基是指能够发生化学反应以生成羧基的化学基团。 
在一个具体实施方式中，引发剂选自于由噻吨酮、噻吨酮衍生物、樟脑醌、二苯甲酮、4-氯二苯甲酮、4,4'-二氯二苯甲酮、4-苄基二苯甲酮、苄基萘、氧杂蒽酮、蒽醌、9-芴酮、苯乙酮、苯甲酰基二甲基缩酮、羟基-环己基苯乙酮、双乙酰、3,4-己烷二酮、2,3-戊烷二酮、1-苯基-1,2-丙烷二酮、苯、苯甲酰甲酸、甲醛、乙醛、丙酮、2-戊酮、3-戊酮、环己酮、二苯甲酮的甲醇磺酸酯及其混合物组成的组。 
在一个具体实施方式中，第二金属是钯。 
在一个具体实施方式中，所述方法进一步包含使用铵离子。在一个具体实施方式中，铵离子和钯离子在同一溶液中。本领域技术人员明白在包含离子的溶液中存在适合的反离子。 
在一个具体实施方式中，在pH大于7时离子被吸附。在一个替代的具体实施方式中，在pH大于10时离子被吸附。 
在一个具体实施方式中，第一金属选自于由铜、银、金、镍、钛和铬组成的组。 
在一个具体实施方式中，表面进一步的进行以下步骤：e)选择性地以不同的模式向所述表面沉积第三金属，和f)从所述的没有被第三金属覆盖部分的所述表面上去除所述第一和第二金属。在一个具体实施方式中，在所述基底上以不同的模式施加金属。在一个具体实施方式中，将金属施加到整个基底上。在一个具体实施方式中，第三金属是铜。 
在第二方面，提供一种包含如上所述制备的基底的物件。涉及施加金属的方法的所有具体实施方式和特征也都适用于包含基底的物件。 
在一个具体实施方式中，所述第一金属层的厚度为约0.2μm至约30 μm。在一个替代的具体实施方式中，所述第一金属层的厚度为约0.2μm至约10μm。 
在许多不同领域中，金属涂覆的物件的应用是众多的。此处给出了一些应用的非限制性实例。在一个具体实施方式中，物件包含电路。在一个具体实施方式中，物件为印刷线路板。在一个具体实施方式中，物件是用于射频电磁波的天线。在一个具体实施方式中，物件是电信用天线。在一个具体实施方式中，物件是燃料电池。在一个具体实施方式中，物件是太阳能电池。在一个具体实施方式中，物件是反光镜。在一个具体实施方式中，物件是汽车反光镜。 
在一个具体实施方式中，物件包含多于一层的导体，所述导体间彼此电绝缘。通过在层间具有绝缘材料的多层中施加多层导电性金属，为在多层中形成电路提供了可能。 
实施例
实施例1
等离子体-涂覆了尺寸为8x8cm的五种不同的聚合物基底：1) 
Figure BDA00003165971400061
基于环氧树脂的材料；2)Panasonic无卤玻璃环氧多层材料层压体R-1
Figure BDA00003165971400062
其包含环氧基体；3)PC/ABS(聚碳酸酯/丙烯腈-丁二烯-苯乙烯)；和4)GX13，Ajinomoto组合膜ABF-
Figure BDA00003165971400063
在环氧基体中包含颗粒；5)PA6(聚酰胺6)。 
在等离子体聚合涂层试验之前，在异丙醇(PA)中超声清洗基底15分钟，然后用乙醇漂洗。然后在选定的基底上，使基底进行丙烯的等离子体聚合。在减压下将丙烯气体导入到等离子腔中。然后在外部施加的电磁场的作用下，将丙烯气体激发为等离子体，碎片化并沉积在样品基底上作为超薄等离子体-聚合的丙烯(PPP)涂层。在小型等离子体反应器中进行等离子体聚合试验。 
等离子体条件：在三个不同的等离子体条件下制备PPP涂层，并且每种类型的涂层沉积在四种不同的基底上。在每个等离子体条件下涂覆每种基底的三个样品。使用了以下等离子体条件： 
等离子体-1(中等强度)
前体：丙烯
等离子体频率：13.56MHz
等离子体功率：150W
丙烯流量：45-55sccm
[0065] 
底压力：3-6mtorr
压力w.丙烯：80mtorr
等离子体期间的压力：81-82mtorr
等离子体-2(低强度)
前体：丙烯
等离子体频率：13.56MHz
等离子体功率：50W
丙烯流量：45-55sccm
底压力：3-6mtorr
压力w.丙烯：80mtorr
等离子体期间的压力：80-81mtorr
等离子体-3(高强度)
前体：丙烯
等离子体频率：13.56MHz
等离子体功率：250W
丙烯流量：15-20sccm
底压力：3-6mtorr
压力w.丙烯：40mtorr
等离子体期间的压力：41-42mtorr
将等离子体聚合的样品与丙烯酸/乙烯基单体混合物接枝，此后暴露于碱性氯化钯溶液中，所述氯化钯在还原介质中被还原为钯金属。然后将样品暴露在化学铜中。20分钟后，样品上覆盖了铜膜层。 
评价了总共36个等离子体涂覆的样品的附着力。使用胶带法(剩余沉积层的百分比(%))测试已经沉积于等离子体膜上的化学铜膜的附着力。 
Figure BDA00003165971400082
实施例2
使用两种不同的处理时间，通过后氧等离子体处理提高了GX13基底上PPP涂层的表面能。每个条件(无后处理、1秒O2等离子体和5秒O2等离子体)制备了三个复制品以用于接枝测试，且每个条件制备了一个样品以用于湿润性测试。 
使用了以下丙烯等离子体参数： 
等离子体频率：13.56MHz
等离子体功率：150W
丙烯流量：45-55sccm
底压力：3-6mtorr
压力w.丙烯：80mtorr
等离子体期间的压力：81-82mtorr
沉积时间：2min
后O2等离子体处理之前和之后，PPP涂层的表面能，表示为达因数(Dyne Number)。 
样品达因数(mN/m) 
PPP涂层，无后O2等离子体 34-36
PPP涂层，1秒后O2等离子体 60-62
PPP涂层，5秒后O2等离子体 60-62
如表中所示，即使非常短(约1秒)的O2等离子体处理，对PPP涂层的表面能也具有巨大的影响。 
附着力测试 
材料 胶带附着力测试
GX 13 0%
PPP涂层，无后O2等离子体 100%
PPP涂层，1秒后O2等离子体 100%
PPP涂层，5秒后O2等离子体 100%
使用胶带测试的所有等离子体处理的GX 13板的附着力都由0%附着力提高到100%附着力。 
实施例3
在一个小型等离子体反应器中使用标准等离子体条件在GX 13基底上沉积等离子体聚合的丙烯酸层(PPA)。使用了以下等离子体参数： 
等离子体频率：163kHz
等离子体功率：10W
丙烯酸流量：1.6-2.0sccm
底压力：5-8mtorr
压力w.丙烯酸：25mtorr
等离子体期间的压力：33mtorr
沉积时间：2min
将等离子体聚合的样品与丙烯酸/乙烯基单体混合物接枝，此后将暴露于碱性氯化钯溶液中，所述氯化钯在还原介质中被还原为钯金属。然后将样品暴露于化学铜中。20分钟后，该样品上覆盖了铜膜层。 
材料 胶带附着力测试 十字划割附着力测试
GX 13 0% 0%
PPP涂层，无后O2等离子体 100% 90%
PPP涂层，1秒后O2等离子体 100% 100%
PPA涂层 100% 100%
实施例4
在24升等离子体反应器Nano(来自Diener Electronic,Gmbh,Germany)中使用标准等离子体条件在PC/ABS基底上沉积等离子体聚合的氨层(PPNH3)。使用了以下的等离子体参数： 
等离子体频率：40kHz
等离子体功率：150W(最大值的50%)
氨流量：3.0-4.0sccm
底压力：0,2mbar
[0092] 
压力w.氨：0.3mbar
等离子体期间的压力：0.3mbar
沉积时间：1.5min
将等离子体聚合的样品与丙烯酸/乙烯基单体混合物接枝，此后将其暴露于碱性氯化钯溶液中，所述氯化钯在还原介质中被还原为钯金属。然后将样品暴露于化学铜中。20分钟后，样品上覆盖了铜膜层。 
材料 胶带附着力测试 十字划割附着力测试
PC/ABS N/A N/A
PPNH3涂层 100% 100%
结论：PC/ABS对接枝过程化学品的敏感性被其上的PPNH3层所避免。在等离子处理后，其还显示出优异的附着力结果。 
实施例5
在24升等离子体反应器Nano(来自Diener Electronic,Gmbh,Germany)中使用标准等离子体条件在GX-13基底上沉积等离子体聚合的氨层(PPNH3)。使用了以下的等离子体参数： 
等离子体频率：40kHz
等离子体功率：150W(最大值的50%)
氨流量：3.0-4.0sccm
底压力：0.2mbar
压力w.氨：0.3mbar
等离子体期间的压力：0.3mbar
沉积时间：1.5min
将等离子体聚合的样品与丙烯酸/乙烯基单体混合物接枝，此后将其暴露于碱性氯化钯溶液中，所述氯化钯在还原介质中被还原为钯金属。然后将样品暴露于化学铜中。20分钟后，样品上覆盖了铜膜层。 
材料 胶带附着力测试 十字划割附着力测试
GX-13 0% 0%
GX-13上的PPNH3涂层 100% 100%
结论：在等离子体处理后，具有10nm PPNH3层的GX-13显示出优异的附着力结果。 
实施例6
在24升等离子体反应器Nano(来自Diener Electronic,Gmbh,Germany)中，使用标准等离子体条件在Polyclad基底上沉积由丙烷和氨的等离子体聚合的混合物形成的层(PPPN)。使用了以下等离子体参数： 
等离子体频率：40kHz
等离子体功率：225W
氨流量：3.0-4.0sccm
丙烷流量：5.0sccm
底压力：0.2mbar
压力w.气体混合物：0.3mbar
等离子体期间的压力：0.3mbar
沉积时间：2.0min
将等离子体聚合的样品与丙烯酸/乙烯基单体混合物接枝，此后将其暴露于碱性氯化钯溶液中，所述氯化钯在还原介质中被还原为钯金属。然后将样品暴露于化学铜中。20分钟后，样品上覆盖了铜膜层。 
材料 胶带附着力测试 十字划割附着力测试
Polyclad 15% 20%
PPPN涂层 100% 95%
结论：在等离子体处理后，顶部具有PPPN层的Polyclad显示出优异的附着力结果。 
实施例7
在24升等离子体反应器Nano(来自Diener Electronic,Gmbh,Germany)中，使用标准等离子体条件在PC/ABS基底上沉积等离子体聚合的2层材料(PP2)，其由第一层(PPP=等离子体聚合物丙烷)和在第一层上的第二层(PPNH3=等离子体聚合的氨)组成。使用了以下等离子体参数： 
Figure BDA00003165971400111
将等离子体聚合的样品与丙烯酸/乙烯基单体混合物接枝，此后将其暴露于碱性氯化钯溶液中，所述氯化钯在还原介质中被还原为钯金属。然后将样品暴露于化学铜中。20分钟后，样品上覆盖了铜膜层。 
材料 十字划割附着力测试
PC/ABS N/A
PP2涂层 100%
结论：PC/ABS对接枝过程化学品的敏感性被其上的PP2层所避免。在等离子体处理后，其还显示出优良的十字划割附着力结果。 
实施例8
在24升等离子体反应器Nano(来自Diener Electronic,Gmbh,Germany)中，使用标准等离子体条件在GX-13基底上沉积等离子体聚合的氨层(PPNH3)。使用了以下等离子体参数： 
等离子体频率：40kHz
等离子体功率：150W(最大值的50%)
氨流量：3.0-4.0sccm
底压力：0.2mbar
压力w.氨：0.3mbar
等离子体期间的压力：0.3mbar
沉积时间：1.5min
材料 胶带附着力测试 十字划割附着力测试
GX-13 0% 0%
GX-13上的PPNH3涂层 100% 100%
将等离子体聚合的样品与丙烯酸/乙烯基单体混合物接枝，此后将其暴露于胶体钯溶液中。胶体溶液、调节剂和预浸来自Rohm&Haas。来自Rohm&Haas的化学品为Circuposit Conditioner 3320 Mild酸性调节剂、Circuposit Predip 3340/4400盐预浸(用于保护催化剂以防有害物带入)和CIRCUPOSITTM催化剂3344/4444(其为胶体钯-锡催化剂，其确保无电镀铜的可靠、最佳覆盖和附着力)。 
将样品暴露在化学铜浴中。20分钟后，样品上覆盖了铜膜层。 
结论：在等离子处理后，具有10nm PPNH3层、接枝层、胶体金属和铜沉积的GX-13显示出优异的附着力结果。 

Claims (36)

1.一种至少部分地在基底的表面上施加第一金属的方法，包含步骤：
a)在等离子体中处理所述基底以涂覆涂层，所述等离子体包含选自于不饱和单体和多达10个碳原子的烷烃类中的至少一种化合物，
实施步骤b1和b2之一，
b1)在所述基底的表面上生成聚合物，所述聚合物包含羧基和至少一种第二金属的吸附离子，还原所述离子为第二金属，
b2)在所述基底的表面上生成聚合物，所述聚合物包含羧基，将所述基底的表面与至少一种第二金属的胶态金属颗粒的至少一种分散体接触，其中所述颗粒具有5-500nm范围的直径，
c)在所述第二金属上沉积所述第一金属。
2.根据权利要求1所述的方法，其中所述等离子体包含选自于烯烃类、炔烃类、丙烯酸类、甲基丙烯酸类、氨、胺类、异氰酸酯类、降冰片烯、烯丙醚类和乙烯醚类中的至少一种化合物。
3.根据权利要求1所述的方法，其中所述等离子体包含选自于烯烃类、丙烯酸类、烯丙醚类、乙烯醚类和降冰片烯中的至少一种化合物。
4.根据权利要求1所述的方法，其中所述等离子体包含丙烷。
5.根据权利要求1-4任一项所述的方法，其中所述等离子体进一步包含选自于氧、氮或氩中的至少一种化合物。
6.根据权利要求1-5任一项所述的方法，其中所述涂层至少包含一层。
7.根据权利要求1-6任一项所述的方法，其中所述涂层至少包含两层。
8.根据权利要求6或7任一项所述的方法，其中每一层包含一种化合物。
9.根据权利要求6或7任一项所述的方法，其中每一层至少包含两种化合物。
10.根据权利要求7所述的方法，其中每一层至少包含一种化合物，并且其中所述至少一种化合物不同于不同层的化合物。
11.根据权利要求1-10任一项所述的方法，其中通过将所述表面与
a)至少一种类型的单体，该单体中的至少一种包含羧基，
b)选自于由钌、铑、钯、锇、铱、铂和铜组成的组中的至少一种第二金属的离子或具有5-500nm范围的直径的胶态金属颗粒的分散体，和
c)至少一种引发剂接触以在所述表面上生成聚合物。
12.根据权利要求1-11任一项所述的方法，其中通过将所述表面与
a)至少一种类型的单体，该单体中的至少一种包含羧基，和
b)至少一种引发剂接触，并且
此后将所述表面与包含选自于由钌、铑、钯、锇、铱、铂和铜组成的组中的至少一种第二金属的离子或具有5-500nm范围的直径的胶态金属颗粒的分散体的溶液接触，以在所述表面上生成聚合物。
13.根据权利要求11或12任一项所述的方法，其中所述至少一种类型的单体选自于由丙烯酸和甲基丙烯酸组成的组。
14.根据权利要求1-10任一项所述的方法，其中通过将所述表面与
a)至少一种类型的单体，该单体中的至少一种包含隐蔽的羧基，和
b)至少一种引发剂接触，并且
此后将所述表面处于适合于将所述隐蔽的羧基转化为羧基的条件，此后将所述表面与包含选自于由钌、铑、钯、锇、铱、铂和铜组成的组中的至少一种第二金属的离子或具有5-500nm范围直径的胶态金属颗粒的分散体的溶液接触，以在所述表面上生成聚合物。
15.根据权利要求14所述的方法，其中所述包含隐蔽的羧基的单体是选自于由丙烯酸叔丁酯、马来酸酐、甲基丙烯酸酐和丙烯酸酐组成的组中的至少一种物质。
16.根据权利要求14或15所述的方法，其中所述适合于将隐蔽的羧基转化为羧基的条件是通过将表面与光致布朗斯台德酸接触来实现的。
17.根据权利要求16所述的方法，其中所述布朗斯台德酸选自于由锍盐和碘鎓盐组成的组。
18.根据权利要求11-17任一项所述的方法，其中所述引发剂选自于由噻吨酮、噻吨酮衍生物、樟脑醌、二苯甲酮、4-氯二苯甲酮、4,4'-二氯二苯甲酮、4-苄基二苯甲酮、苄基萘、氧杂蒽酮、蒽醌、9-芴酮、苯乙酮、苯甲酰基二甲基缩酮、羟基-环己基苯乙酮、双乙酰、3,4-己烷二酮、2,3-戊烷二酮、1-苯基-1,2-丙烷二酮、苯、苯甲酰甲酸、甲醛、乙醛、丙酮、2-戊酮、3-戊酮、环己酮、二苯甲酮的甲醇磺酸酯及其混合物组成的组。
19.根据要求1-18任一项所述的方法，其中所述第二金属是钯。
20.根据权利要求19所述的方法，其中所述方法进一步包含使用铵离子。
21.根据权利要求1-20任一项所述的方法，其中所述第一金属选自于由铜、银、金、镍、钛和铬组成的组。
22.根据权利要求1-21任一项所述的方法，其中所述表面进一步进行以下步骤：d)以不同的模式选择性地将第三金属沉积至所述表面上，和e)从所述的没有被第三金属覆盖部分的所述表面上去除所述第一和第二金属。
23.根据权利要求22所述的方法，其中所述金属以不同的模式施加在所述基底上。
24.根据权利要求22所述的方法，其中所述金属施加在整个基底上。
25.根据权利要求22-24任一项所述的方法，其中所述第三金属是铜。
26.一种包含根据权利要求1-25任一项制备的基底的物件。
27.根据权利要求26的物件，其中所述第一金属层的厚度为约0.2μm至约30μm。
28.根据权利要求26-27任一项所述的物件，其中所述物件包含电路。
29.根据权利要求26-28任一项所述的物件，其中所述物件是印刷线路板。
30.根据权利要求26-29任一项所述的物件，包含多于一层的导体，该导体彼此间电绝缘。
31.根据权利要求26所述的物件，其中所述物件是用于射频电磁波的天线。
32.根据权利要求26所述的物件，其中所述物件是电信用天线。
33.根据权利要求26所述的物件，其中所述物件是燃料电池。
34.根据权利要求26所述的物件，其中所述物件是太阳能电池。
35.根据权利要求26所述的物件，其中所述物件是反光镜。
36.根据权利要求26所述的物件，其中所述物件是汽车反光镜。
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Application publication date: 20130925