CN102482780A - 沉积适用于将电线粘结在印刷电路板导体上的钯层的方法及所述方法中使用的钯浴 - Google Patents

沉积适用于将电线粘结在印刷电路板导体上的钯层的方法及所述方法中使用的钯浴 Download PDF

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CN102482780A
CN102482780A CN2010800275555A CN201080027555A CN102482780A CN 102482780 A CN102482780 A CN 102482780A CN 2010800275555 A CN2010800275555 A CN 2010800275555A CN 201080027555 A CN201080027555 A CN 201080027555A CN 102482780 A CN102482780 A CN 102482780A
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J·艾伯
E·马卡
W·马舒特
S·奥尔舒兰格
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Doduco Contacts and Refining GmbH
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Abstract

本发明公开了一种用于生成可与金导线粘接的表面的方法。所述表面通过以下步骤获得：首先在印刷电路板的导体（尤其是由铜或导电糊制成的导体上）沉积由本发明的电解质制成的交换钯层。然后，所述交换钯层用由化学钯电解质沉积的钯层加强。为了保护钯，接着涂覆交换金层。根据本发明，所使用的交换钯浴中包含有机光亮剂。

Description

沉积适用于将电线粘结在印刷电路板导体上的钯层的方法及所述方法中使用的钯浴
技术领域
 本发明涉及一种具有权利要求1前序所述特征的方法。该种方法可从WO 2006/074902 A2获知。
背景技术
根据已知的方法，首先，镍通过化学还原从化学镀镍浴中沉积（即不施加外部电流）在由铜制成的导体上，该导体位于有机或陶瓷印刷电路板上。不施加外部电流从相应的镍合金浴沉积镍合金而不是镍也是可行的。然后10 nm-40 nm厚的薄钯层通过来自钯交换浴的电荷交换沉积在镍层或镍合金层上。钯交换浴通常由无机或有机酸与所述酸的钯盐以及至少一种元素的无机化合物构成，所述元素为铜、铊、硒和碲，优选硫酸铜。钯交换浴的pH值小于1，即该浴为强酸。钯交换浴也称为钯浸渍浴或者钯活化浴，来自该浴的沉积物被称为浸镀或者活化沉积物。
最后，厚度小于0.1 μm的由金制成的覆层沉积在钯层上。优选从金交换浴中沉积出上述金。该金层可从化学金浴中通过自身催化沉积即通过还原沉积增加到较大厚度。
首先，钯是作为后续通过粘接附着的由金或铝制成的金属丝的基础。此外，所述钯层用于防止镍扩散到金表面，以保持其粘接能力。使用金层的目的是为了保护钯表面免受由于其高催化活性而受到的化学变化，该化学变化可导致，例如，所谓的“褐色粉末”（brown powder）效应。
WO 2006/074902 A2中的公开内容指出，仅当除钯盐以外至少一种元素（铜、铊，硒和碲）的无机化合物，特别是硫酸铜，添加到钯浴中时，才能满足与多种焊接和粘接能力有关的现有要求。不将至少一种所述元素的无机化合物添加到钯交换浴中时，钯层不能获得足够的粘附和屏蔽效果。
已知市面上有多种用于将铜导线涂覆到印刷电路板上的方法，根据这些方法，钯首先从常用的钯交换浴沉积到铜上。然后更多的钯从化学（还原）钯浴沉积到第一层上，最后沉积金层作为覆层。根据制造商的意见，已知的方法会导致多层的建立，多层适用于焊接，但不适用于由金和铝制成的电线的粘接。
市面上还已知一种方法，其可以在印刷电路板的铜导体上形成可粘合的表面。该方法是先从常用的钯活化浴中将钯沉积到铜导体上。然后从化学（还原）镍浴在其上沉积一镍层。另一钯层从常用的钯活化浴沉积到镍层上，并且所述钯层的厚度通过钯从化学（活化）钯浴沉积出来而增加。最后，通过浸渍涂覆来制备金层以保护钯表面。该已知的方法包含了非凡的努力。
发明内容
本发明的目的是提供一种替代的方法，根据该方法，可通过较少的努力把能够粘接的钯层可沉积在印刷电路板的导体上，特别是沉积在铜制成的导体上。
所述目的通过具有权利要求1所述特征的方法实现。权利要求10的主题是特别适合于进行所述方法的钯浴。本发明有利的改进是从属权利要求的主题。
根据本发明，钯层通过电荷交换从包含有机光亮剂的钯交换浴中沉积在印刷电路板的导体上，特别是沉积在铜制成的导体上。
除了由WO 2006/074902 A2获知的方法，这为本领域技术人员提供了另一种方法，用于使能够粘接的钯层沉积在印刷电路板的导体上。该方法具有下面的附加优点：
· 钯层不仅可以沉积在预先用镍涂覆的导体上，而且可以直接沉积在由铜制成的导体上。
· 现有技术中已知的中间镍层因此可有可无。
· 由于由镍制成的中间层可有可无，所述钯涂层还适用于高频应用，而镍由于其磁学性质不太适合于高频应用。
· 从包含有机光亮剂的钯交换浴中沉积出来的钯层经证实非常密集、颗粒细小并且均匀。因此与常规钯活化浴相比，使用来自还原钯浴的钯，可形成合适的基础以进一步增加钯层的厚度。优选从化学钯浴还原沉积该种类型的钯，以产生0.05 mm-0.5 mm的厚度，特别是0.1 mm-0.3 mm的厚度。这比下层钯层的厚度大，根据本发明所述下层钯层从钯交换浴沉积，并且其特别适合于由金或铝通过粘接进行的连接，同时作为本发明的改进是很有利的。
·  本发明的浴的合适pH值维持在小于4。特别优选在pH值为2下实施本发明的浴。
· 本发明的钯交换浴足够稳定。
优选地，合适的有机光亮剂包括来自权利要求2所述的化合物构成的组的化合物。特别优选3-(1-吡啶)-1-丙烷磺酸作为光亮剂，并且得到下述物质，其中通式中的残基R1-R5为氢，残基R6为-CH2-CH2-CH2-，并且其中X为SO2。在缺乏该种化合物时，从交换浴沉积的钯看上去暗到发黑，尤其是在印刷电路板的孔内和孔处，这样得到的沉积物是多孔的，类似海绵。但是，在所述有机化合物的存在下，在钯交换浴中形成明显更好、更明亮、更均匀并且光学上美观的钯层。
适宜地，该浴包含浓度为0.01-50 g/l，优选1-10 g/l的有机光亮剂。当钯交换浴中3-(1-吡啶)-1-丙烷磺酸的浓度为3-6 g/l时，可获得特别好的结果。在低浓度下，光亮剂在钯交换浴中的效果降低。随着光亮剂浓度的增加，沉积速率降低，这表示有机光亮剂的浓度不应超过50 g/l。
适宜地，本发明的钯交换浴中存在的钯的含量为150 mg/l至250 mg/l，优选的以氯化钯溶液的形式存在。较低的浓度会导致在获得所需层厚度的浴中的停留时间增加或不适当地延长。因此，钯浓度不应低于150 mg/l。随着钯浓度的增加，得到的沉积速率增加并且可获得超过50 nm厚的层。但是，多孔性的钯层在这种情况下也增加，并且钯层的均匀性和同质性降低，同时钯层下面的导体有可能被强烈地腐蚀，构成导体的次贵金属被贵金属钯取代。因此，优选地限制交换浴中钯的浓度至250 mg/l。
另一合适的光亮剂包括苯甲醛类，特别是苯甲醛-2-磺酸，其浓度为0.1-50 g/l，优选地约为1 g/l。
钯优选地以氯化钯并且溶于盐酸的形式存在于钯交换浴中。但是，用其它盐形成钯交换浴也是可行的，例如，溶于硫酸中的硫酸钯，或溶于磷酸中的磷酸钯，或溶于醋酸中的醋酸钯。但是，优选使用溶于盐酸中的氯化钯，因为所述浴经证实特别稳定。
为了稳定，本发明的钯交换浴优选地还包含含量高达150 g/l，优选30-80 g/l的无机络合剂。虽然沉积速率随络合剂浓度的增加而降低，但是该浴对无机络合剂浓度的变化并不十分敏感，因此其浓度不应超过150 g/l，优选80 g/l，。
铵盐特别适合作为无机络合剂，其阴离子应优选地与钯盐的阴离子相同。因此，如果钯交换浴中使用氯化钯（如优选的那样），无机络合剂应同样为氯化物，特别是氯化铵。如果使用硫酸钯作为钯盐，推荐同样使用硫酸盐作为无机络合剂，特别是硫酸铵。如果使用醋酸钯作为钯盐，那么无机络合剂应同样为醋酸盐，特别是醋酸铵，等。但是，在无机络合剂中使用与铵不同的阳离子也是可行的，例如钠或钾，但是铵盐使获得的浴具有稍微较好的稳定性。
已发现，有机络合剂的添加甚至可以进一步改善钯从钯交换浴的沉积。特别是，可减少所述钯浴在次贵金属基质大量连续表面上形成斑点或较黑的沉积物斑点的倾向。有机络合剂的该有益效果有助于本发明使用的有机光亮剂的有益效果，以获得均匀明亮、密集和颗粒细小的钯沉积。此外，已发现有机络合剂显著改进该浴的稳定性，尤其是当印刷电路板通过浴的流量较大时。
非常适合作为有机络合剂的是碳酸、胺、EDTA和EDTA衍生物。已证实二乙烯三胺特别合适，特别是浓度为0.01 ml/l至5 ml/l之间。沉积速率随钯交换浴中有机络合剂浓度的增加而降低。
在沉积过程期间钯交换浴的温度适宜维持在室温至60℃之间，优选在35℃-50℃的温度范围内。已证实该范围特别合适。使用所述的温度和优选组成的浴，所需厚度的层可在5分钟内沉积，所述层厚度优选25 nm-35 nm，并且不应超过50 nm。优选地，沉积过程限制为2-3分钟。
如上所述，本发明的钯交换浴应优选调节pH值为2。在以氯化钯和氯化铵形式存在作为无机络合剂的包含钯的盐酸浴中，pH值可通过添加盐酸或氨来调节。在高于pH=2的pH值下，钯的络合更彻底，即较少的自由钯可用于沉积。因此，沉积速率随pH值增加而降低。在高于4的pH下，不再有任何显著的沉积。
从钯交换浴沉积的钯层厚度可由更多的钯通过还原剂从化学钯浴中沉积出来而增加。根据本发明，从钯交换浴沉积的钯层特别适合用作增加所述钯层厚度的基质，由于使用了有机光亮剂，其特别地密集、颗粒细小并且均匀。特别是，无需使用镍层作为扩散阻挡层来防止铜扩散进入通过钯的还原沉积形成的钯层下面的钯层中。如果通过从还原钯浴沉积更多的钯时，所述层的厚度不再增加，那么推荐在从钯交换浴沉积的钯层下面设置镍层。增加厚度可以形成具有几个mm厚的钯层。但是，对于粘接过程，几个mm厚的钯层是不经济的。用于粘接的钯层厚度的优选范围为50 nm-500 nm。
具体实施方式
已经知道用于沉积钯的合适化学（还原）浴。非常合适的浴具有下面的组成：
0.5-3 g/l的钯，其存在形式为溶解的氯化物、硫酸盐、醋酸盐、磷酸盐或类似的盐的形式，或结合了钯的络合物，例如氯络合物、氨基络合物、亚硝酸盐络合物或类似的络合物。
还原剂，5-50 g/l的次磷酸钠或1-50 g/l的甲酸钠或1-50 g/l的甲酸。
无机络合剂，例如柠檬酸钠、丙二酸盐、丁二酸盐、磷酸钾、磷酸二氢钾、硫酸铵。
有机络合剂，例如EDTA、EDTA衍生物、胺，例如三乙醇胺、三-（2-氨乙基）-胺、二乙撑三胺、三乙撑四胺、1,3-二氨基丙烷，其中的每个可以单独使用或结合使用。
此外，化学钯浴可包含其它的成分，主要是本领域技术人员从EP 0698 130 B1知道的稳定剂和促进剂。
所述类型的化学钯浴在40℃-90℃，特别是在约70℃温度下操作。根据所需的层厚度，涂覆时间可从30分钟至60分钟。已知的化学钯浴通常在弱酸至弱碱范围内操作。在上述类型的化学钯浴中，在pH值为8下操作是可行的。
下面描述钯沉积的示范性方法中最重要的步骤，其中可使用上述化学钯浴并使用包含150-250 mg钯（以氯化钯形式）每升、50g氯化铵每升、3g 3-（1-吡啶）-1-丙烷磺酸每升以及1-5 ml二乙烯三胺每升的化学钯浴，其可在35℃-50℃以及pH=2下操作。
使用所述浴处理具有铜制导体的印刷电路板包括以下步骤：
1.在弱酸性去油脂浴中除油；
2.用水冲洗；
3.浸入蚀刻液中活化铜表面；
4.冲洗；
5.在本发明的钯交换浴中涂覆钯；
6.浸入稀盐酸溶液中以除去钯表面的外来物质（foreign seeds）；
7.用水冲洗；
8.在化学（还原）钯浴中沉积钯；
9.静态漂洗浸泡以收集附着到印刷电路板上的残余钯浴材料，并防止残留物浸入随后的浴；
10.用水冲洗；
11.沉积镀金；
12.静态漂洗浸泡；
13.用水冲洗；
14.干燥。
镀金的厚度可为例如20 nm-30 nm，通常用其来保护钯表面并为本领域技术人员所知。金优选由交换浴沉积。

Claims (20)

1.一种用于沉积钯层的方法，通过从钯交换浴中沉积出钯，该钯层适用于粘接在印刷电路板的导体尤其是由铜制成的导体上，其特征在于：使用包含有机光亮剂的钯交换浴。
2.根据权利要求1所述的方法，其特征在于：所述有机光亮剂选自下述化合物组成的组：
（a）
Figure DEST_PATH_IMAGE002A
其中
R1-R5每个为氢原子或卤原子或甲酰基、氨基甲酰基、C1-4烷基、氨基、苯基或苄基，其中烷基、苯基和苄基部分可以选择性地由一个或多个羟基或氨基或由卤原子取代，
R6是由饱和或不饱和脂肪烃获得的具有1-6个C原子的基团，其中该基团能够被取代，以及
X为SO2基团或CO基团，
（b）苯甲醛。
3.根据权利要求2所述的方法，其特征在于：使用3-（1-吡啶）-1-丙烷磺酸或苯甲醛-2-磺酸作为光亮剂。
4.根据前述权利要求中任一项所述的方法，其特征在于：钯交换浴中有机光亮剂的浓度调节并维持在0.01 g/l至50 g/l之间的值，优选1 g/l至10 g/l之间的值。
5.根据权利要求4的方法，其特征在于：使用3-（1-吡啶）-1-丙烷磺酸的浓度为3 g/l至6 g/l或使用苯甲醛-2-磺酸的浓度为1 g/l。
6.根据前述权利要求中任一项所述的方法，其特征在于：沉积过程中钯交换浴维持在室温至60℃之间的温度，优选35℃-50℃之间的温度。
7.根据前述权利要求中任一项所述的方法，其特征在于：钯交换浴在pH值小于4下操作，优选在pH值为2下操作。
8.根据前述权利要求中任一项所述的方法，其特征在于：印刷电路板在钯交换浴中的停留时间不超过5分钟，优选为2-3分钟。
9.根据前述权利要求中任一项所述的方法，其特征在于：从钯交换浴中沉积钯后，从化学（还原）钯浴中沉积钯。
10.   用在根据前述权利要求中任一项所述的方法中的钯交换浴，包含溶于酸性水溶液中的钯盐形式的钯，其特征在于：其包含来自下述化合物的组的光亮剂：
（a）
Figure DEST_PATH_IMAGE004A
其中
R1-R5每个为氢原子或卤原子或甲酰基、氨基甲酰基、C1-4烷基、氨基、苯基或苄基，其中烷基、苯基和苄基部分可以选择性地由一个或多个羟基或氨基或由卤原子取代，
R6是由饱和或不饱和脂肪烃获得的具有1-6个C原子的基团，其中基团能够被取代，以及
X为SO2基团或CO基团，
（b）苯甲醛。
11.   根据权利要求10所述的浴，其特征在于：所述光亮剂为3-（1-吡啶）-1-丙烷磺酸或苯甲醛-2-磺酸。
12.   根据权利要求10或11所述的浴，其特征在于：其包含的钯的含量为150 mg/l至250 mg/l。
13.   根据权利要求10、11或12所述的浴，其特征在于：其包含氯化钯形式的钯。
14.   根据权利要求10-13任一项所述的浴，其特征在于：其包含的有机光亮剂的浓度为0.01-50 g/l，优选为1-10 g/l。
15.   根据权利要求10-13任一项所述的浴，其特征在于：其包含浓度为3 g/l至6 g/l的3-（1-吡啶）-1-丙烷磺酸或浓度为1 g/l的苯甲醛-2-磺酸。
16.   根据权利要求10-15任一项所述的浴，其特征在于：其还包含含量高达150 g/l的无机络合剂。
17.   根据权利要求16所述的浴，其特征在于：其包含30-80 g/l的无机络合剂。
18.   根据权利要求16或17所述的浴，其特征在于：无机络合剂为铵盐。
19.   根据权利要求13和18所述的浴，其特征在于：铵盐为氯化铵。
20.根据权利要求10-19任一项所述的浴，其特征在于：其包含二乙烯三胺作为无机络合剂，优选浓度在0.01 ml/l至5 ml/l之间。
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