CN104040025A - 用于在激光直接成型基底上无电铜沉积的水性活化剂溶液和方法 - Google Patents

用于在激光直接成型基底上无电铜沉积的水性活化剂溶液和方法 Download PDF

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CN104040025A
CN104040025A CN201280060646.8A CN201280060646A CN104040025A CN 104040025 A CN104040025 A CN 104040025A CN 201280060646 A CN201280060646 A CN 201280060646A CN 104040025 A CN104040025 A CN 104040025A
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activator solution
substrate
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metal salt
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爱德温·W·巴斯滕贝克
哈拉尔德·奥尔斯切尔
乌利齐·普林茨
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MacDermid Enthone Inc
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Abstract

本发明涉及一种用于在激光直接成型基底表面上无电沉积铜的水性活化剂溶液和方法。通过本发明，提出包含强还原剂的水性活化剂溶液，以增强LDS基底的受辐照的表面区域的催化活性。

Description

用于在激光直接成型基底上无电铜沉积的水性活化剂溶液和方法
技术领域
所公开的发明涉及一种用于在激光直接成型基底表面上无电沉积铜的水性活化剂溶液和方法。
背景技术
激光直接成型(LDS)在制造电气器件和电子器件的领域中是熟知的方法。尤其出于微型化的目的，LDS能够使器件的尺寸减小，而同时使器件配备有更大的功能性，如，更高的电路密度。这种电子器件的示例是注塑成型的电路载体，也称为模塑互连器件(MID)。MID被设计成是三维的(3D-MID)。这种3D-MID的一个目的是将电气功能性和机械功能性结合在单个部件中。这种器件中的电路路径被集成到外壳中，因此取代了常规的电路板。与传统的电子器件相比，这种器件的重量和包装尺寸显著减小，并且其它功能的集成(像例如传感器或天线的集成)被简化。MID技术提供了较大的设计自由度，并且由于缩短的工艺链，提供了显著的合理化潜能。通过MID的激光成型方法，也可以在复杂的三维载体结构上形成高分辨率电路布局，因此将先前作为分开的单元的壳体和电路板集成在一个器件中。
MID技术的主要应用领域是汽车电子设备和无线电通信。然而，MID技术的好处也被利用在计算机技术、家用电器以及医疗设备的领域中。
在制造这种MID的各种技术中，增材激光成型或减材激光成型是公知的。
在US2004/0241422中，公开了一种用于电路路径的激光成型的方法。在该方法中，电路路径结构形成在不导电的载体材料上，其中，这些路径包括金属种子，随后向这些种子实施金属化。金属种子由不导电的金属化合物的建立所产生，该不导电的金属化合物通过电磁辐射以非常精细分开的形式包含在载体材料中。在这情况下，不导电的金属化合物由非常热稳定的无机金属化合物构成，该无机金属化合物在酸性金属化水性浴或碱性金属化水性浴中是不可溶解的且稳定的并且在未受激光辐射的区域中仍是不变的。该工艺基于腐败的热塑性材料，在该热塑性材料上，将被实现为电路路径的轨道通过聚焦激光束而激活。随后，所述激活的轨道在镀浴(例如无电镀铜浴)中被金属化。
如今，可利用已掺杂复合的金属-有机络合物的不同的载体材料，当激光激活时，该金属-有机络合物释放所需的金属种子。这种载体材料的示例是聚碳酸酯、聚碳酸酯丙烯腈丁二烯苯乙烯共混物、聚酰胺、聚氨酯树脂、液晶聚合物、聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯、和这些物质的共聚物。
EP1584708A2公开了一种用于处理通过激光成型的塑料基底或用于在表面上生成适合于随后的金属化的种子结构的方法。在激光成型之后，基底与适合于去除在激光成型期间产生的非故意的沉积物的处理溶液接触。在金属化之前，用润湿剂和支持清洗的组合物的混合物来处理激光成型的基底，导致充分地去除非故意沉积的金属种子，而对计划成型的表面路径没有持久的破坏作用。
US2007/0163887A1公开了一种制造电路载体的方法，且提出了所述方法的使用，所述方法包括：在提供印刷电路板(a)之后，在该电路板的至少一侧上对所述电路板涂覆电介质(b)，利用激光烧蚀，进行成型电介质，以在电介质中形成沟槽和孔(c)。接下来，将底漆层沉积到电介质上，沉积到电介质的整个表面上或仅沉积到所产生的沟槽和孔中(d)。将金属层沉积到底漆层上，沟槽和孔完全填满金属，用于在其中形成导体结构(e)。最后，去除过量的金属和底漆层，直到如果底漆层被沉积到电介质的整个表面上，则电介质外露，导体结构仍未受损伤(f)。
用于LDS的填充催化剂的塑料可利用无电铜镀溶液而在激光激活的区域中铜镀。事实上，与在塑料基底上的钯激活的镀铜相比，在激光结构基底区域上铜生长的引发是缓慢的。对于如ABS(丙烯腈丁二烯苯乙烯)或ABS/PC(聚碳酸酯)共混物的塑料尤其如此，该塑料广泛地用于例如移动电话天线。观测到长的沉积时间和/或激活区域的非充分的覆盖。为了克服这个缺点，在如今的方法中，经常使用两步镀概念。在第一步中，使用高活性、但不稳定的电镀电解溶液，该溶液提供快速的覆盖(闪铜)。随后，使用更加稳定的电解质溶液，该溶液仅在在待被镀的表面上已沉积了铜的时候起作用。这种两步概念是费时且成本高的。
发明内容
因此，本发明的目的是提供改进在激光直接成型器件上铜沉积的工艺的工具，尤其是提供减少对于铜沉积工艺所需的时间的工具。
另一方面，本发明的目的是提供一种用于在激光直接成型基底上无电铜沉积的改进方法。
具体实施方式
关于用于改进铜沉积的工艺的工具，通过本发明，提出了用于激光直接成型基底的水性活化剂溶液，所述溶液包含强还原剂。
惊人地发现，当在无电镀之前，将激光直接成型基底与包含强还原剂的活化剂溶液接触时，实现了显著改善的铜沉积。认为还原剂增强了LDS基底的受辐照表面的催化活性，由于此，反过来改善了无电铜沉积的引发。因此，用于引发和镀敷的时间明显缩短。而且，在热力学和动力学上，可以以较低的能量水平来操作无电铜电解液，通过此，增大了沉积工艺以及所用的电解液的稳定性。与从现有技术已知的无电工艺相比，这使该工艺具有显著的环境和经济效益。
此外，由于改进的沉积，废弃了对用以构建所期望厚度的铜沉积层的第二铜工艺的使用。这使用于镀铜步骤的总工艺时间减少，反过来，这点进一步使本发明具有经济效益。
根据本发明的实施方式，活化剂溶液包含具有E°≤+0.35V的能斯特还原电势的还原剂。
根据下面的公式计算能斯特还原电势：
其中，E为还原电势，E°为标准还原电势，R为通用气体常数，T为以K计的绝对温度，a为相关氧化还原伙伴的化学活性，该化学活性可由该氧化还原伙伴的简单浓度代替，F为法拉第常数，ze为在氧化还原反应中转移的电子的数目。
发现，具有这种还原电势的还原剂能够增强LDS基底的受辐照表面的催化活性。
根据本发明的另一实施方式，包含在活化剂溶液中的还原剂为硼氢化碱金属盐、亚硫酸碱金属盐、连二亚硫酸碱金属盐、硫代硫酸碱金属盐、和锌中的至少一种化合物或其混合物。优选地，包含在活化剂溶液中的还原剂为硼氢化钠、硼氢化锂、二甲基氨基硼烷、亚硫酸钠、亚硫酸锂、连二亚硫酸钠、连二亚硫酸锂、硫代硫酸钠、次磷酸钠、和硫代硫酸锂、甲醛、甲酸铵、乙醛酸、间苯二酚、肼、水合肼中的至少一种化合物或其混合物。
根据本发明的另一实施方式，还原剂可以以在≥0.001mol/l和≤5.0mol/l之间的范围包含在活化剂溶液中。已发现，在大于0.001mol/l的浓度下，实现了LDS基底的受辐照表面的催化活性的显著增强。
在本发明的另一实施方式中，活化剂溶液还包含稳定剂、络合剂和表面活性剂中的至少一种添加剂。这种添加剂的示例为菲咯啉(如1,10-菲咯啉鎓氯化物)、二吡啶、菲(如新亚铜试剂)、喹啉(如苯并喹啉和亚铜试剂(即2,2'-联喹啉))、浴铜灵二磺酸、双硫腙、二苯卡巴腙、二苯卡巴肼、偶氮化合物(如甲基橙)、五元杂环(如吡咯、吡唑、咪唑、1,2,4-三唑、1,2,4-苯并三唑、噻吩和噻唑)、六元杂环(如吡啶和烟酸)、硫脲、尿素、二硫代草酰氨、2-巯基苯并噻唑、乙酰胺、氰化钠、雷氏盐(NH4[Cr(NCS)4(NH3)2]·H2O)、安息香肟(α-安息香肟)、和铜铁试剂(N-亚硝基-N-苯基羟胺的铵盐)。
在本发明的另一优选实施方式中，活化剂的pH值的范围在pH≥0和pH≤14之间。惊奇地发现，取决于所含有的还原剂，本发明的活化剂溶液可在从强酸性至强碱性的整个pH值范围内起作用。
在另一方面，本发明涉及一种用于在激光直接成型基底的表面上无电沉积铜层的方法，该方法包括下列步骤：
-提供激光直接成型基底；
-将所提供的基底与用于激光直接成型基底的水性活化剂溶液接触以获得活化的基底，所述溶液包含强还原剂；和
-将所活化的基底与无电镀铜电解液接触。
优选地，在范围在≥5℃和≤95℃之间的温度下，优选在范围在15℃和40℃之间的温度下，LDS基底与活化剂溶液接触。
进一步优选地，使LDS基底与活化剂溶液接触的时间范围在≥10秒和≤60分钟之间。对于接触，应理解为例如将基底浸在活化剂溶液中、将活化剂溶液喷洒到基底上、或任何其他能够使包含在活化剂溶液中的还原剂与LDS基底的受辐照的表面区域发生化学反应的适宜方法。
惊奇地发现，本发明的方法能够改善在任何常见的LDS基底材料上的无电铜沉积，该LDS基底材料例如为：聚酰胺(PA)；聚氨酯树脂(PU)；丙烯腈丁二烯苯乙烯(ABS)；聚碳酸酯(PC)；聚对苯二甲酸乙二醇酯(PET)；聚对苯二甲酸丁二醇酯(PBT)；液晶聚合物(LCP)；聚邻苯二甲酰胺(PPA)；其共混物、共聚合产物或复合结构。市售的材料的示例为T 4381 LDS、T4381LDS sw23215、B4300GM24LDS(所有购自BASF股份公司)；DP7102LDS、DPT7140LDS(都购自Lanxess)；E840iLDS(购自Ticona GmbH)；RTP 2599X113384A、RTP2599X113384C、RTP 2599X113384D、RTP399X113385B、RTP3499-3X113393A、RTP4099X117359D(所有购自RTP公司)；ForTiiTMNC1107A、ForTiiTMNC 1119D(购自帝斯曼工程塑料公司(DSM Engeneering Plastics B.V.))；LDS3710、RC 3711、LDS 3720、RC 3722、RC3723、LDS3730、RX 3732、RX 3733、lupilon MTB1000R8920F(所有购自三菱工程塑料株式会社(Mitsubishi Engineering-PlasticsCorporation))；X9423、HTplus TGP3586、HTplusTGP 3586(购自赢创工业公司(Evonik Industries))；TPJF231F(购自华宏新技股份有限公司(Wah Hong Industrial Corp.))；NX07354、NX07354P、NX10302、UX08325、NX11302(所有购自沙伯基础创新塑料有限公司(Sabic InnovativePlastics))；和Grilamid1SBVX-50H LDS(购自EMS-Chemie股份公司)。
根据下面的实施例进一步描述本发明。
通过根据下列方法步骤(在步骤之间的冲洗是可选择的且未单独列出)，处理LDS(激光直接成型)基底：
1)根据塑料的稳定性，在从室温到50℃的温度下，将基底在酸性或碱性的清洗液中清洗5分钟到20分钟；
2)在从25℃到90℃的温度下，将所清洗的基底在本发明的包含还原剂的活化剂溶液中浸渍5min到1h；
3)可选择的：在从室温到约50℃的温度下，将所活化的基底在含有金属盐的溶液中浸渍5min到30min；
4)根据待获得的沉积厚度，在从30℃到70℃的温度下，将所预处理的基底在无电镀铜溶液(如LDS Cu400(购自Enthone公司))中浸渍30min到2h。
用在可选择的步骤3)中的含有金属盐的溶液包含0.0001mol/l至0.1mol/l的浓度的金属盐，如CuSO4、PdCl2、或另一种适宜金属的盐。
如果在步骤2)中使用的活化剂溶液为碱性溶液，则建议进行随后的酸洗步骤或酸后浸渍步骤。
下面的表包括根据本发明的活化剂溶液组合物的示例。酸性环境意为pH大约为2或低于2，中性环境意为pH大约为5至8，碱性环境意为pH大约为12或高于12。还原剂在活化剂溶液中的浓度为0.01mol/l。
当引入本发明的元素或本发明的优选实施方式时，冠词“一”、“该”和“所述”意为存在一个或多个元素。术语“包含”、“包括”和“具有”是包含的，意为可以存在除了所列出的元素之外的额外的元素。
由于可在上文中进行各种变化，而不脱离本发明的范围，这意为包含在以上描述中的所有内容应被解读为说明性的，没有限制性的含义。本发明的范围通过所附的权利要求书而限定，且可以对上文的实施方式进行不脱离本发明的范围的修改。

Claims (14)

1.一种用于激光直接成型基底的水性活化剂溶液，所述活化剂溶液包括强还原剂。
2.根据权利要求1所述的活化剂溶液，其中，所述还原剂具有E°≤+0.35V的能斯特还原电势。
3.根据前述权利要求中的任一项所述的活化剂溶液，其中，所述还原剂为硼氢化碱金属盐、亚硫酸碱金属盐、连二亚硫酸碱金属盐、硫代硫酸碱金属盐、和锌中的至少一种化合物或其混合物。
4.根据前述权利要求中的任一项所述的活化剂溶液，其中，所述还原剂为硼氢化钠、硼氢化锂、二甲基氨基硼烷、亚硫酸钠、亚硫酸锂、连二亚硫酸钠、连二亚硫酸锂、硫代硫酸钠、次磷酸钠、和硫代硫酸锂、甲醛、甲酸铵、乙醛酸、间苯二酚、肼、水合肼中的至少一种化合物或其混合物。
5.根据前述权利要求中的任一项所述的活化剂溶液，其中，所述还原剂在所述活化剂溶液中是在≥0.001mol/l和≤5.0mol/l之间的范围内。
6.根据前述权利要求中的任一项所述的活化剂溶液，其中，所述活化剂溶液还包含稳定剂、络合剂和表面活性剂中的至少一种添加剂。
7.根据前述权利要求中的任一项所述的活化剂溶液，其中，所述活化剂溶液的pH值在pH≥0和pH≤14之间的范围内。
8.一种用于在激光直接成型基底的表面上无电沉积铜层的方法，所述方法包括下列步骤：
-将激光直接成型基底与根据权利要求1至7中的任一项所述的活化剂溶液接触，以获得活化的基底；和
-将所述活化的基底与无电镀铜组合物接触。
9.根据权利要求8所述的方法，其中，在≥5℃和≤95℃之间的范围内的温度下，所述基底与所述活化剂溶液接触。
10.根据权利要求8和9中的任一项所述的方法，其中，所述基底与所述活化剂溶液的接触时间在≥10s和≤30min之间的范围内。
11.根据权利要求8至10中的任一项所述的方法，其中，所述基底至少部分地由以下材料制成：聚酰胺(PA)；聚氨酯树脂(PU)；丙烯腈丁二烯苯乙烯(ABS)；聚碳酸酯(PC)；聚对苯二甲酸乙二醇酯(PET)；聚对苯二甲酸丁二醇酯(PBT)；液晶聚合物(LCP)；聚邻苯二甲酰胺(PPA)；其共混物、共聚合产物或复合结构。
12.根据权利要求8至11中的任一项所述的方法，其中，在所述基底与所述活化剂溶液接触之后，将所述基底与金属盐溶液接触。
13.根据权利要求12所述的方法，其中，使所述基底与包含CuSO4和/或PdCl2的金属盐溶液接触。
14.根据权利要求12或13中的一项所述的方法，其中，所述金属盐在所述金属盐溶液中的浓度在≥0.0001mol/l至≤0.1mol/l之间的范围内。
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