CN103534384B - 用于无电镀的方法 - Google Patents
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- CN103534384B CN103534384B CN201280023397.5A CN201280023397A CN103534384B CN 103534384 B CN103534384 B CN 103534384B CN 201280023397 A CN201280023397 A CN 201280023397A CN 103534384 B CN103534384 B CN 103534384B
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1889—Multistep pretreatment with use of metal first
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/40—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal all coatings being metal coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
- C03C17/10—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the liquid phase
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12597—Noncrystalline silica or noncrystalline plural-oxide component [e.g., glass, etc.]
Landscapes
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
本发明公开了一种用于在包含金属(例如钼或钛)和含有所述金属的合金的金属或金属合金结构上无电镀金属或金属合金的方法。所述方法包括以下步骤：活化，在包含至少一种含氮化合物或羟基羧酸的水溶液中处理，以及无电镀金属或金属合金。
Description
发明领域
本发明涉及一种在制造平板显示器和相关装置中无电沉积金属和金属合金的方法。
发明背景
通过气相沉积方法，通过沉积金属(例如铝、钼、铬和钛)，实现用于基于薄膜晶体管(TFT)的平板显示器的不同特征(例如门结构和电路)的金属化。提高板尺寸需要TFT线路较高的导电性，以保持非常短的像素响应时间和避免快速移动图像序列中的运动模糊效应。
由于其低比电阻，铜为代替其它金属（像以前称为TFT线路材料的那些）的合适候选。溅射铜为常规的方法。然而，当所需的膜厚度超过1μm时，溅射铜就变得愈发更有问题。溅射的铜膜通常呈现显著量的内部应力，其最终可引起下层玻璃基材弯曲或甚至开裂。由于相当低的溅射产率，溅射厚的铜层也遭受显著的材料损失。最后，清洁溅射室的增加的维修工作可导致延长的闲置时间并限制总体过程生产率。
将铜无电沉积到用于平板显示器应用的基材上的方法公开于S.Fang等人的“HighlyAdhesiveCopperWiringforFPDusingInkjetPrintedCatalystandNeutralElectrolessDeposition(使用喷墨印刷催化剂和中性无电沉积的用于FPD的高粘性铜线)”(IDW'07-Proceedingsofthe14thInternationalDisplayWorkshops(2007)，第2卷，第713-714页)。此处，在无电金属沉积之前使用通过喷墨印刷沉积的催化油墨将基材活化。
通过在钼层上无电镀来沉积铜的另一种方法公开于H.Ning等人的“TheFeasibilityofCuPlatingTechnologyinLCD(在LCD中Cu镀覆技术的可行性)”(ProceedingsofASIADisplay2007AD'07上海，2007年3月12-16日)。所述方法利用带图案的光阻来选择性沉积铜。
发明目的
因此，本发明的第一个目的是提供具有高导电性的表面层。
本发明的第二个目的是提供具有光滑表面的金属和金属合金层。
本发明的第三个目的是提供良好粘合在下层金属或金属合金层上的表面层。
本发明的第四个目的是提供具有低内部应力的金属和金属合金层。
发明概述
通过本发明的总体过程序列来解决这些目的，所述总体过程序列按照该顺序包括以下步骤：
(i)提供非传导性基材，其在至少一侧上具有由选自钼、钛、锆、铝、铬、钨、铌、钽和它们的合金的金属或金属合金结构组成的表面，
(ii)使所述基材与包含贵金属的活化剂接触，
(iii)使所述基材与含有至少一种含氮物质和羟基羧酸的水溶液接触，和
(iv)通过无电镀在所述活化的表面上沉积金属或金属合金。
在步骤(iv)中沉积的金属或金属合金对基材表面的下层金属或金属合金结构具有高粘度。此外，在步骤(iv)中沉积的所述金属或金属合金层具有光滑的表面、低内部应力和足够的导电性。
发明详述
用于平板显示器和相关装置的基材由玻璃或聚合物箔(例如PET箔)制成。这样的非传导性基材在至少一侧上包含通常通过化学或物理气相沉积而沉积的金属或金属合金结构。所述金属或金属合金结构由以下的一个或多个组成：钼、钛、锆、铝、铬、钨、铌、钽和它们的合金。
术语“金属或金属合金结构”此处应该是指
a)在非传导性基材的一侧或两侧上的整个表面被薄的金属或金属合金层覆盖(较不优选)，或
b)“金属或金属合金结构”在非传导性基材的一侧或两侧上包含金属图案(优选)。
基材通过本领域已知的方法清洁。包含湿润剂的水性组合物可用于该目的。
任选，在基材顶部的金属或金属合金结构随后在包含过氧化物和酸的水性组合物中微蚀刻。
不活化所述金属或金属合金结构(根据总体过程序列的步骤(ii))，则通过无电镀在所述金属或金属合金结构上沉积金属或金属合金不可行。
金属或金属合金结构首先使用选自银、金、钌、铑、钯、锇、铱和铂的贵金属活化。用于活化金属或金属合金结构的最优选金属为钯。
贵金属可按离子形式或作为胶体提供。
通过溶解部分的下层次贵金属或金属合金结构，与基材表面上的下层次贵金属或金属合金结构进行浸没型反应，以离子形式提供的贵金属以金属态沉积。在将金属或金属合金结构活化用于使用贵金属离子无电镀的情况下，贵金属以金属态沉积。
当使用离子形式的贵金属时，基材表面仅活化用于在由金属或金属合金结构组成的基材表面的那些区域上相继无电镀。因此，在根据总体过程序列的步骤(iv)中，不需要掩膜(例如带图案的光阻)用于选择性无电沉积。
以胶体形式提供的贵金属通过吸附在整个基材表面上沉积，即，在金属或金属合金结构和下层非传导性基材两者上。在金属或金属合金在根据总体过程序列的步骤(iv)中要通过无电镀沉积的情况下，在贵金属以胶体形式沉积之前，需要通过掩膜(例如带图案的光阻)覆盖在步骤(iv)中不应沉积金属或金属合金的基材表面的那些部分。如果基材的这些部分不被覆盖，则金属或金属合金将在步骤(iv)中沉积到整个基材表面上。在这样的情况下，在无电镀之后，需要应用蚀刻过程，以得到具有高导电性的带图案的金属或金属合金层。
优选，贵金属活化剂包含钯离子。在这种情况下，无需蚀刻过程，并且基材的透明度比胶态贵金属(钯)活化剂高。
提供离子或胶态形式的贵金属的适用的活化剂组合物例如公开于ASMHandbook，第5卷，SurfaceEngineering，1194，第317-318页。
接着，包含贵金属的基材表面在根据总体过程序列的步骤(iii)中与包含至少一种含氮物质和羟基羧酸的水性组合物接触。
优选，在步骤(iii)中使用包含至少一种含氮物质的水性组合物。
含氮物质优选选自季铵聚合物、聚酰氨基胺、具有带有2-6个碳原子的烷基的四铵羟基化合物、烷醇胺、氨基羧酸、基于脂肪胺的季铵盐和季铵化的脂族胺乙氧基化物。
更优选，含氮物质选自季铵聚合物和聚酰氨基胺。
合适的季铵聚合物包括交联的季铵聚合物和非交联的季铵聚合物。
合适的交联季铵聚合物包括由以下形成的共聚物：大量的单烯属不饱和单体或单体的混合物，和少量的多烯属不饱和单体或用于使聚合物交联的单体的混合物。单烯属不饱和单体的实例包括多环芳族化合物，例如苯乙烯、取代的苯乙烯，包括乙基乙烯基苯、乙烯基甲苯和乙烯基氯化苄；和芳基单体，例如甲基丙烯酸和丙烯酸的酯，包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯。优选丙烯酸的低级脂族酯。合适的多不饱和交联单体包括二乙烯基苯、二乙烯基吡啶、二乙烯基甲苯、二甲基丙烯酸乙二醇酯等。上述乳液共聚物可通过本领域已知的方法转化为带正电荷的离子交换树脂。例如，可在路易斯酸(例如氯化铝)存在下用氯甲基甲基醚将交联的苯乙烯乳液聚合物氯甲基化，并且所得到的中间乳液共聚物可随后用叔胺(例如三甲基胺)处理，以形成氯化季胺官能团。或者，强碱性季胺树脂可如下制备：用含有叔胺基团和伯胺或仲胺基团两者的二胺(例如二甲基氨基丙基胺或二(3-二甲基氨基丙基)胺)处理交联的丙烯酸酯乳液共聚物，和使用烷基卤化物(例如甲基氯阴离子)季铵化所得到的弱碱性树脂。
合适的非交联的季铵聚合物包括用表氯醇或氧化乙烯季铵化的二甲基氨基乙基甲基丙烯酸酯聚合物、聚-N,N-二甲基-3,5-亚甲基哌啶鎓盐、聚亚乙基胺、二甲基二烯丙基铵盐的聚合物，其中盐的反离子可为任何水溶性离子，例如氯离子；二甲基胺或单乙基胺和表氯醇的共聚物，和上述共聚物的季铵化形式，和改性天然有机聚电解质，例如经二乙基氨基乙基氯化物盐酸盐处理的瓜耳胶。
其它合适的阳离子聚合物包括基于脂肪胺的阳离子季铵盐和基于脂肪胺的两性季铵盐。
基于脂肪胺的阳离子季铵盐包含1-丙铵-N-(2-羟基乙基)-N,N-二甲基-3-[(1-氧十八烷基)-氨基]盐、1-丙铵-N,N,N-三甲基-3-[(1-氧十二烷基)-氨基]烷基酯盐、1-丙铵-(3-十二烷氧基)-2-羟基-N,N-双(2-羟基乙基)-N-甲基烷基酯盐。合适的阴离子例如为磷酸根、硝酸根、硫酸根和甲基硫酸根。
其它合适的阳离子季铵盐为季铵化的脂族胺乙氧基化物，其中氮原子被季铵化。此外，可采用烷基苄基二甲基氯化铵，其中烷基衍生自脂肪酸。
合适的烷醇胺化合物为低级烷醇胺化合物，例如二乙醇胺、三乙醇胺、单异丙醇胺、二异丙醇胺、三异丙醇胺、单仲丁醇胺、二仲丁醇胺、2-氨基-2-甲基-1-丙二醇、2-氨基-2-乙基-1,3-丙二醇、2-二甲基氨基-2-甲基-1-丙醇、三(羟基甲基)氨基乙烷和前述烷醇胺化合物的混合物。
合适的氨基羧酸包括乙二胺四乙酸、羟基乙二胺四乙酸、次氮基三乙酸、羟基乙二胺三乙酸、N-二羟基乙基甘氨酸、亚乙基双(羟基苯基甘氨酸)、赖氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、脯氨酸、苯基丙氨酸、色氨酸、蛋氨酸、甘氨酸、丝氨酸、苏氨酸、半胱氨酸、酪氨酸、天冬酰胺、谷氨酰胺、天冬氨酸、谷氨酸、精氨酸、组氨酸和它们的混合物。
合适的羟基羧酸包括酒石酸、柠檬酸、葡糖酸、5-磺基水杨酸和它们的混合物。
至少一种含氮化合物或羟基羧酸的浓度通常为0.1-30g/L，更优选1-10g/L，最优选2-5g/L。
任选用于步骤(iii)的水溶液包含湿润剂和/或抗絮凝剂。
任选，基材表面随后用水漂洗。
接着，通过无电镀，至少一层金属或金属合金在步骤(iv)中在活化的基材表面上沉积。
可在本发明的方法中通过无电镀过程沉积的金属和金属合金的实例为铜、镍、金、钯、钌、锡、银和它们的合金。
优选，铜、铜合金、镍和镍合金在步骤(iv)中沉积。
最优选，铜或铜合金在步骤(iv)中沉积。
铜无电镀电解质通常包含铜离子源、pH调节剂、络合剂例如EDTA、烷醇胺或酒石酸盐、加速剂、稳定剂添加剂和还原剂。在大多数情况下，甲醛用作还原剂，其它常见的还原剂为次磷酸盐、二甲基胺硼烷和硼氢化物。用于无电铜镀覆电解质的典型稳定剂添加剂为以下化合物：例如巯基苯并噻唑、硫脲、各种其它硫化合物、氰化物和/或铁氰化物和/或钴氰化物的盐、聚乙二醇衍生物、杂环氮化合物、甲基丁醇和丙腈。此外，通过使稳定的空气流通过铜电解质，分子氧通常用作稳定剂添加剂(ASMHandbook，第5卷5:SurfaceEngineering，第311-312页)。
无电金属和金属合金镀覆电解质的另一个重要实例为用于沉积镍和其合金的组合物。这样的电解质通常基于次磷酸盐化合物作为还原剂，并且还含有选自以下的稳定剂添加剂的混合物：第VI族元素(S、Se、Te)化合物、含氧阴离子(AsO2 -、IO3 -、MoO4 2-)化合物、重金属阳离子(Sn2+、Pb2+、Hg+、Sb3+)化合物和不饱和有机酸(马来酸、衣康酸)化合物(ElectrolessPlating:FundamentalsandApplications(无电镀：原理和应用)，编辑：G.O.Mallory，J.B.Hajdu，AmericanElectroplatersandSurfaceFinishersSociety，ReprintEdition，第34-36页)。
本发明的一个优选的过程序列按照该顺序包括以下步骤：
(i)提供非传导性基材，其在至少一侧上具有由选自钼、钛、锆、铝、铬、钨、铌、钽和它们的合金的金属或金属合金结构组成的表面，
(ii)使所述基材与包含贵金属（为贵金属离子）的活化剂接触，从而仅金属或金属合金结构被活化，
(iii)使所述基材与含有至少一种含氮物质和羟基羧酸的水溶液接触，和
(iv)通过无电镀，在所述活化的金属或金属合金结构上沉积金属或金属合金。
通过本发明的方法在由金属(例如钼、钛、锆、铝、铬、钨、铌、钽)及其合金组成的金属或金属合金结构上沉积的金属或金属合金层具有高粘度、足够的导电性、均匀的厚度分布和光滑的表面。
实施例
现在参考以下非限制性实施例来说明本发明。
实施例1(对比)
将一侧附着有钼层的玻璃基材用包含季铵聚合物的调节剂活化，随后通过浸没型镀覆钯。接着，由包含铜离子、甲醛、EDTA和稳定剂的电镀浴沉积铜层。因此，没有应用根据总体过程序列的步骤(iii)。
不含步骤(iii)，沉积的铜层呈现坍塌的泡的典型结构，说明在钼层上的低粘度。
实施例2
通过浸没型镀覆钯使一侧附着有钼层的玻璃基材活化。随后将活化的基材浸泡在pH值为12-12.5并且包含3.1g/L的聚酰氨基胺的水溶液中20秒。接着，由包含铜离子、甲醛、EDTA和稳定剂的电镀浴沉积铜层。因此，这次应用了根据总体过程序列的步骤(iii)。
含有步骤(iii)，沉积的铜层显示在钼层上足够的粘度。
Claims (6)
1.一种用于无电镀的方法，所述方法按照该顺序包括以下步骤：
(i)提供非传导性基材，在与之相连的至少一侧上具有选自钼、钛、锆、铝、铬、钨、铌、钽和它们的合金的金属或金属合金结构，
(ii)使所述基材与包含钯离子的活化剂接触，
(iii)使所述基材与含有至少一种含氮物质和羟基羧酸的水溶液接触，和
(iv)通过无电镀在活化的表面上沉积金属或金属合金。
2.权利要求1的方法，其中在步骤(i)中所述金属或金属合金结构选自钼、钛和它们的合金。
3.前述权利要求中任一项的方法，其中在步骤(iii)中所述至少一种含氮物质选自季铵聚合物、聚酰氨基胺、具有带有2-6个碳原子的烷基的四铵羟基化合物、烷醇胺、氨基羧酸、基于脂肪胺的季铵盐和季铵化的脂族胺乙氧基化物，以及它们的混合物。
4.权利要求1的方法，其中在步骤(iii)中所述羟基羧酸选自酒石酸、柠檬酸、葡糖酸、5-磺基水杨酸和它们的混合物。
5.权利要求1的方法，其中在步骤(iv)中沉积的所述金属或金属合金选自铜、铜合金、镍和镍合金。
6.一种玻璃基材，在其至少一侧上具有选自钼、钛、锆、铝、铬、钨、铌、钽和它们的合金的金属或金属合金结构，并且在所述金属或金属合金结构上，附着有铜或铜合金层，其中所述铜或铜合金通过权利要求1-5中任一项的方法沉积。
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| EP2524976B1 (en) | 2016-06-29 |
| TWI580816B (zh) | 2017-05-01 |
| EP2524976A1 (en) | 2012-11-21 |
| KR20140023368A (ko) | 2014-02-26 |
| KR101945555B1 (ko) | 2019-02-07 |
| US20140113158A1 (en) | 2014-04-24 |
| JP6005144B2 (ja) | 2016-10-12 |
| JP2014513755A (ja) | 2014-06-05 |
| WO2012156162A2 (en) | 2012-11-22 |
| WO2012156162A3 (en) | 2013-08-15 |
| CN103534384A (zh) | 2014-01-22 |
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