CN104073789B - 化学镀的方法和用于该方法的溶液 - Google Patents

化学镀的方法和用于该方法的溶液 Download PDF

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CN104073789B
CN104073789B CN201310702945.3A CN201310702945A CN104073789B CN 104073789 B CN104073789 B CN 104073789B CN 201310702945 A CN201310702945 A CN 201310702945A CN 104073789 B CN104073789 B CN 104073789B
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D·K·W·余
M·C·Y·唐
M·W·贝叶斯
叶家明
陈俊文
陈鸿达
李翠翘
廖乐乐
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Abstract

化学镀的方法和用于该方法的溶液。提供了一一种用于选择性金属化的方法，所述方法包括以下步骤：通过化学或物理改性在待镀覆区域之中的表面来制备不导电材料的表面；将不导电材料与包含调节剂和碱性物质的预处理溶液接触；将不导电材料与包含催化金属离子、具有至少一个磺酸根基团的酸和氯离子的催化溶液接触；以及化学镀覆该不导电材料表面上的那些待镀覆的区域。

Description

化学镀的方法和用于该方法的溶液
技术领域
本发明涉及一种用于在不导电材料表面上化学铜镀覆的预处理方法和一种用于该方法的溶液。更特别的，本发明涉及一种用于不导电材料表面进行选择性化学镀的方法，在待镀覆的区域内已经通过化学或物理局部改性。
背景技术
化学镀覆已经在许多应用中被用于各种各样的基板，包括电子器件的制造。这种电子器件的表面通常要求通过金属镀覆形成导线图案。近日，激光直接成型技术(LDS)已经发展并应用于模压塑料材料的选择性镀覆，即所谓的模塑互连设备(MID)。对于LDS，它能够在复杂的3维基板上实现高功能的电路布局。该工艺的基础包括具有无机填料的掺杂添加剂的热塑性材料或热固性材料，其可以借助于激光活化形成电路迹线，随后用化学镀覆金属化。纳入这种塑料的含有金属的添加剂通过激光光束活化，并且活化作为用于在待镀覆塑料表面的处理区域上的化学镀铜的催化剂。除了活化，激光处理可以创建显微粗糙表面，其中在金属化过程中铜牢固锚定该显微粗糙表面。
然而，根据发明人的调查研究，这种基板并不总是容易通过沉积工艺被金属化，在所述沉积工艺中部件在激光处理之后直接被引入到化学镀铜浴中。为确保具有所需铜厚度的沉积形成在激光辐射过的所有区域，高活性化学镀铜浴(所谓打底浴)通常需要形成一个薄且均匀的初始层，然后在另一个更加稳定的化学镀铜浴(完整构建浴)中铜层的厚度增加至所需值。因为打底浴通常在导致浴的成分的更高消耗且温度比正常化学镀铜浴更高的条件下运行，浴的寿命更短，导致频繁需要准备新打底浴的不便。
US4659587中井村等人公开了一种在受到激光束处理的工件表面上选择性化学镀的方法。该专利公开了当激光辐射破坏基板时，在基板上选择性形成镀膜可能受到将其直接浸入到化学镀覆浴中的影响，不需要进行初步的活化处理。
US7060421中Naundorf等人公开了一种在包括尖晶石型金属氧化物的不导电材料上制造导线迹线结构的方法。在该文献中公开的模塑不导电材料通过电磁辐射辐照，如从Nd：YAG激光到击穿，且释放形成镀覆图案的金属核。处理之后，辐照的材料在超声波清洗浴中用水清洗，随后进行铜镀覆。
Schildmann在US7578888中公开了一种用于处理激光结构化塑料表面的方法。该专利公开了在引入化学镀浴前，将激光结构化基板与处理溶液接触，该处理溶液适合于除去无意沉积的金属种子，以便在没有使用激光处理的表面区域中减少寄生镀覆。
然而，当发明人尝试在这些美国专利中公开的方法并在已经激光辐射的表面上用传统化学镀铜浴进行镀覆时，电路迹线区域上的铜沉积并不完整(漏镀)。当发明人在化学镀之前使用传统的胶体催化溶液时，铜并不仅在被激光辐照的区域而且还在没有辐照的区域上沉积，因此选择性镀覆没有实现(过多镀覆)。因此，需要一种能够改善MID-LDS基板的选择性化学镀金属化的方法。
发明内容
本申请的发明人已经研究了很多种作为用于选择性化学镀的预处理溶液原料的化学物质及这些化学物质的组合，并且现在已经发现化学物质的特定组合提供化学镀的良好的选择性，即良好的覆盖，没有漏镀或过多镀覆，并且能为工业生产过程提供可接受的沉积速率。
本发明的一个目的是提供一种在不导电材料的表面上选择性金属化的方法。
本发明的另一个目的是用于该方法的溶液，包括催化金属离子，含有磺酸根基团的酸和氯离子(chloride ion)，溶液中催化金属离子和氯离子的重量比在1至10和1至1000之间。
附图说明
图1是具有良好的沉积铜覆盖的模塑树脂样品的照片。
图2是轻微漏镀的模塑树脂样品的照片。
图3是没有镀覆的模塑树脂样品的照片。
具体实施方式
在整个说明书中所使用的，除非内容清楚地指明否则，下面给出的缩写具有以下含义：g＝克；mg＝毫克；L＝升；m＝米；min＝分钟；s＝秒；h.＝小时；ppm＝百万分之一；g/L＝克每升。
在整个说明书中所使用的，词语“沉积”、“镀覆”和“金属化”可以互换使用。在整个说明书中所使用的，词语“溶液”和“浴”可以互换使用。除非内容清楚的指明否则，溶液和浴中包含水。
本发明的方法涉及不导电材料的表面的选择性金属化。在这个实施方式中，词语“选择性金属化”意思是仅在材料表面的预定镀覆的那些区域金属化(镀覆)，除了预定区域的其他区域中基本上没有沉积。当在预定镀覆的区域中沉积不充分(漏镀)时，不能够得到所需的导电性能。当在不需要镀覆的区域中有大量沉积(过多镀覆)时，电路通路结构的功能被削弱，从而在电子电路中由于短路导致问题。该方法包括四个步骤。
该方法的第一个步骤是通过化学或物理改性待镀的表面区域来制备不导电材料的表面。
不导电材料优选是热固性或热塑性材料。可作为不导电材料的塑料的实例包括聚碳酸酯(PC)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚丙烯酸酯(PA)、液晶聚合物(LCP)、(聚邻苯二酰胺)(PPA)、和丙烯腈-丁二烯-苯乙烯共聚物(ABS)及其混合物。优选塑料是使用上述热塑性材料生产的模制塑料。
不导电材料可选的包含一种或更多种常规使用的无机填料，例如氧化铝、硅酸盐、滑石或其衍生物。
不导电材料任选包含一种或更多种金属或金属化合物。金属化合物包括金属氧化物、金属硅酸盐、金属磷酸盐和金属螯合物。该金属或金属化合物与不导电材料混合，这些化合物的一部分在经过化学或物理改性后形成在材料表面上，并且被活化以在金属沉积中表现为催化剂。金属的实例包括但不限于，贵金属，如钯，过渡金属，如铜、铬、钴、铁、锌及其混合物。US7060421中公开了这样的材料。
该材料在待镀覆的区域中进行化学或物理改性。不导电材料表面的化学改性的实例包括用碱性或酸性溶液蚀刻。物理改性的实例包括用激光处理，例如用Nd：YAG激光。待镀覆区域基于在材料表面上需要形成的导电迹线选择。化学或物理改性创建了显微粗糙表面，有益于沉积金属层的固定。这种材料是市场上可以买到的，如来自德国LPKF激光和AG电子公司。
该方法的第二个步骤是(b)将不导电材料与包含调节剂和碱性物质的预处理溶液相接触。
预处理溶液是一种组合物，该组合物显示出在激光处理过的材料表面上选择性增强催化剂材料吸收的性能。优选的调节剂包括阴离子表面活性剂和有机酸。本发明中阴离子表面活性剂的优选组成包括聚氧乙烯烷基苯酚磷酸酯和聚醚磷酸酯。有机酸的优选组成的实例是烷基磺酸或芳族磺酸，如酚磺酸。调节剂的浓度取决于组合物的种类，但当阴离子表面活性剂被用作调节剂时，优选浓度通常在1至50g/L之间，更优选为2.5至15g/L。当磺酸，例如芳族磺酸被用作调节剂时，优选浓度通常为1至50g/L，更优选为2.5至25g/L。
碱性材料通常用碱金属氢氧化物添加。在预处理溶液中的碱金属氢氧化物的浓度通常为1至200g/L，优选10至90g/L。
预处理溶液可选的包含多羟基化合物。该成分的优选浓度通常为0至100g/L，优选10至50g/L。溶液的pH值通常超过12，优选超过13。
将待镀覆材料与溶液接触的方法可以为任何类型的方法，例如浸渍或喷涂。将材料与预处理溶液接触的条件是例如在40至90℃将材料浸入溶液中1至20分钟。优选的，上述步骤可以在之后用水冲洗。
该方法的第三个步骤是(c)将不导电材料与催化溶液接触，该催化溶液包括催化金属离子、含有至少一个磺酸根基团的酸和氯离子。催化金属离子优选是贵金属离子，例如钯离子。任意种类的钯离子源可以被用于该溶液，只要钯离子源在该溶液中产生钯离子。钯离子源的例子包括氯化钯、硫酸钯、乙酸钯、溴化钯和硝酸钯。
具有至少一个磺酸根基团的酸包括有机酸和无机酸。有机酸的例子包括甲磺酸，无机酸的例子包括硫酸。优选酸为硫酸。
任意种类的氯离子源可以用于该溶液只要该氯离子源在溶液中提供氯离子。氯离子源的例子包括氯化钠、盐酸和氯化钾。优选氯离子源为氯化钠。
溶液之中每种成分的优选含量通常为催化金属离子1至50ppm，硫酸50至150g/L，和0.1至10g/L的氯离子，基于溶液的重量。更优选，溶液之中每种成分的含量为5至25ppm的催化金属离子，75至125g/L的硫酸，和5至5.0g/L的氯离子，基于溶液的重量。
在溶液中优选的催化金属离子和氯离子的比例为1至10和1至1000之间，更优选为1至20和1至500之间，进一步优选在1至50和1至200之间。如果氯离子比例超过1000，可以观察到漏镀。如果氯离子比例低于10，可以观察到过多镀覆。
可选的，本发明的溶液可能包括一种或更多的用于化学镀的预处理溶液的各种添加剂，例如表面活性剂、络合剂、pH值调节剂、缓冲剂、稳定剂、铜离子和促进剂。溶液的pH值通常为0.2至2，优选0.2至1。用于本溶液的优选表面活性剂是阳离子表面活性剂。表面活性剂的量取决于表面活性剂的种类，但通常是基于溶液的重量0.1至10g/L。
接触溶液的方法可以是任意种类的方法，例如浸渍或喷涂。将材料与催化剂溶液接触的条件为例如在20至80℃将材料浸入溶液，优选50至70℃浸入1至20分钟，优选5至20分钟。优选的，上述步骤可以之后用水冲洗。
该方法的第四个步骤是(d)在不导电材料的表面上化学镀待金属化区域。化学镀方法和镀铜组合物是本领域众所周知的。可以使用传统方法和化学镀铜浴。这种铜浴的例子包括1至5g/L的铜离子，10至50g/L的络合剂，0.01至5g/L的表面活性剂，5至10g/L的氢氧化钠和2至5g/L的还原剂。可以使用传统的化学镀铜浴，例如可向陶氏电子材料有限公司购买的CIRCUPOSITTM71HS化学镀铜液，CIRCUPOSITTMLDS91化学镀铜液。
化学镀的条件是例如在20至70℃优选45至65℃将材料浸入化学镀铜浴中，保持足够的时间沉积需要的铜厚度，例如20至300分钟。优选，上述步骤可以在之后进行一次或更多的水冲洗。
本发明的催化溶液用作用于不导电材料的选择性化学镀的预处理溶液。溶液的成分和第三个步骤中描述的溶液相同。溶液之中催化金属离子和氯离子的重量比为1至10和1至1000之间。
本发明的方法能够消除常规方法中使用的化学镀铜打底浴。该方法能够仅在不导电材料的表面上待镀覆的特定区域之中直接金属化。
用本发明的方法获得的材料仅在那些化学或物理改性的区域选择性金属化，即具有良好的覆盖和均匀的厚度，没有过多镀覆和漏镀。此外，沉积速率对工业生产工艺是可接受的。
实施例
实施例1
一个由PC和ABS(PC/ABS)树脂共混物制作的LDS基板样本用激光处理那些待镀覆的区域(LPKF激光和AG电子)。该基板样本在70℃被浸入包含70g/L NaOH和5g/L阴离子表面活性剂(聚酯磷酸酯，由陶氏电子材料提供的TRITONTMQS-44表面活性剂)的预处理溶液中5分钟。溶液的pH值大约为14。用去离子水清洗之后，该基板样本在69℃被浸入包含18.4mg/L硫酸钯(9.5ppm钯离子)、60mL/L98％硫酸和1.7g/L氯化钠的催化剂溶液中10分钟。然后用去离子水清洗该基板样本，并且在56℃化学镀覆120分钟(CIRCUPOSITTM71HS化学镀铜液，陶氏电子材料有限公司)。镀覆完的基板样本用水清洗，然后通过以下所述的标准评级。用X射线荧光(XRF)测定铜层的厚度为9微米，沉积质量的等级为5-5。图1显示了在激光处理过的表面上完整的铜沉积。
等级
铜的沉积用光学显微镜观察并在激光处理过和没处理过的区域均从1至5评测。第一个数字显示了在激光处理区域的性能，而第二个数字显示了非激光处理区域的性能。在激光处理区域，“1”表示没有沉积和“5”表示没有漏镀的完整铜覆盖。评级为“3”表示铜覆盖不完整。其他等级数据表明了这些定义水平之间的行为。在非激光处理区域，“5”表示在那个区域没有沉积(不过多镀覆)和“1”表示观察到大量的超额镀覆(严重过多镀覆)。5-5的等级表示最好的整体性能。
实施例2
重复实施例1的步骤，除了包含70g/L NaOH和5g/L阴离子表面活性剂的预处理溶液被替换为包含39g/L NaOH和17g/L苯酚磺酸的预处理溶液，且预处理溶液的浸渍时间从5分钟被变为10分钟。铜层的厚度为8.4微米且沉积质量的等级为4-5。
实施例3
重复实施例1的步骤，除了包含70g/L NaOH和5g/L阴离子表面活性剂的预处理溶液被替换为包含30g/L NaOH、8.7g/L苯酚磺酸和36.8g/L甘油的预处理溶液，且预处理溶液的浸渍时间从5分钟被变为10分钟。铜层的厚度为8.8微米且沉积质量的等级为4.5-5。图2显示了在激光处理过的平坦表面上完整的铜覆盖，但是在孔区中有轻微的漏镀。
表1
比较例1
重复实施例1的步骤，除了包含70g/L NaOH和5g/L阴离子表面活性剂的预处理溶液被替换为包含5g/L阴离子表面活性剂的预处理溶液。铜层的厚度为8.4微米且沉积质量的等级为3-5。
比较例2
重复实施例1的步骤除了包含18.4mg/L钯硫酸盐、60mL/L98％硫酸和1.7g/L氯化钠的催化溶液被替换为包含18.4mg/L钯硫酸盐和60mL/L98％硫酸的催化溶液。铜层的厚度为3.0微米且沉积质量的等级为1-5。图3显示了在激光处理过的表面没有镀覆。
表2

Claims (5)

1.一种用于选择性金属化的方法，所述方法包括以下步骤：
(a)通过化学或物理改性在待镀覆区域之中的表面以选择性地暴露金属中的一种或多种来制备不导电材料的表面，其中，所述不导电材料包含选自下组的一种或多种金属：混合在所述不导电材料中的钯、铜、铬、钴、铁和锌；
(b)将不导电材料与包含调节剂和碱性物质的预处理溶液接触；
(c)将不导电材料与催化溶液接触，所述催化溶液由以下成分组成：选自贵金属离子的催化金属离子，具有至少一个磺酸根基团的酸和氯离子，一种或多种选自表面活性剂、络合剂、pH值调节剂、缓冲剂、铜离子和促进剂的任选的组分，以及水；以及
(d)化学镀覆该不导电材料表面上的那些待镀覆的区域。
2.权利要求1的方法，其中预处理溶液中的调节剂选自阴离子表面活性剂和有机酸。
3.权利要求1的方法，其中在催化溶液中的催化金属离子和氯离子的重量比为1至10和1至1000之间。
4.权利要求1的方法，其中该催化溶液包括1至50ppm的催化金属离子，基于溶液重量。
5.权利要求1的方法，其中催化溶液包括50至150g/L的硫酸，基于溶液重量。
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