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CN101400831B - 聚酰亚胺基底和用其制备印刷布线板的方法 - Google Patents

聚酰亚胺基底和用其制备印刷布线板的方法 Download PDF

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CN101400831B
CN101400831B CN2006800538982A CN200680053898A CN101400831B CN 101400831 B CN101400831 B CN 101400831B CN 2006800538982 A CN2006800538982 A CN 2006800538982A CN 200680053898 A CN200680053898 A CN 200680053898A CN 101400831 B CN101400831 B CN 101400831B
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马克·沃伊塔谢克
詹姆斯·沃特考斯基
加里·B·拉尔森
彼得·库坎斯基斯
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Abstract

本发明涉及一种聚酰亚胺基底和用其制备印刷布线板的方法。用金属镀敷聚合物基底例如聚酰亚胺的改进方法包括步骤：用等离子体流或电晕放电表面处理对聚合物基底进行表面处理，用包含氢氧化物和离子型钯的蚀刻液调整和蚀刻该聚合物基底，用离子型钯活化该聚合物基底，还原该聚合物基底上的钯，在制备的聚合物基底上镀覆化学镀镍层，并且在整个化学镀镍层上镀覆化学镀铜层。本发明的方法提供了制备用于随后电镀的聚合物基底的改进方法。

Description

聚酰亚胺基底和用其制备印刷布线板的方法
技术领域
本发明涉及金属镀敷聚合物基底，特别是芳族聚合物基底(例如聚酰亚胺)的改进的方法。
背景技术
由芳族聚合物制造的或者是包含芳族聚合物的基底经常应用于某些电子装配的结构中，例如微电子封装。已经发现大量的聚合物可令人满意地用作该基底。发现聚酰亚胺在这一点上特别适合，部分是因为它们优异的热稳定性和耐溶剂性。一种广泛使用且市售的购自Dupont，Wilmington，Delaware的聚酰亚胺的商品名是其它聚酰亚胺的销售商品名是购自Kaneka High-TechMaterials的
Figure G2006800538982D00012
以及购自Uniglobe Kisco，Inc.的
Figure G2006800538982D00013
和
Figure G2006800538982D00014
并且同样被广泛使用。
聚酰亚胺广泛应用于微电子封装应用中，例如柔性电路，刚性-柔性电路，印刷电路板(PCB)，和多层柔性电路，以及硅晶片上的钝化层。但是芳族聚合物，例如聚酰亚胺，本身有可能与随后镀敷的金属(例如铜，镍和金)的粘合力变差，另外，当将化学沉积后的金属用作金属辅助沉积(例如通过电解沉积)的导电层时，聚合物(聚酰亚胺)基底、化学沉积金属和电解沉积金属之间的粘合力必须足够的强。因此有必要开发出某种技术用于提高该金属和这些基底之间的粘合力，为了克服粘合力差的问题已经采用了几种方法。
例如，可以使用粘合剂将金属层粘结到聚酰亚胺膜上，从而制造覆金属聚合物膜。然后用平版印刷法使金属层形成图案。但是，使用这些覆金属膜难以形成细线电路，因为金属层的蚀刻在电路线路中可能会产生侧蚀(undercut)(由于掩模下的蚀刻)，并且需要金属层较厚(至少15微米)，以使其具有足够的机械强度用于分离处理。而且所用的粘合剂可能会导致微导通孔的激光穿孔困难。
用于改进层之间的粘合力的另一方法是在粗化的金属箔(例如铜箔)上涂覆液体聚酰亚胺(或其前体聚酰胺酸)，然后固化。但是，由于金属箔的厚度，细线电路也难以形成。
用于改进粘合力的又一方法是在聚酰亚胺表面上溅射镍和铬的薄层，然后在铬层上溅射铜薄层，使用电镀对其进行增厚。虽然该方法能够制备细线电路(通过在电镀步骤前使用光致抗蚀剂)，但是溅射步骤昂贵且耗费时间。与其它常用方法相比，溅射法的问题还在于设备的尺寸大，成本高，以及生产率低。
因此，需要另外的努力来提供一种制备克服了现有技术缺陷的用于随后镀敷的非导电性基底的改进方法。
发明内容
本发明的一个目的是提供一种制备用于随后镀敷的非导电性基底的改进方法。
本发明的另一目的是提供一种有效利用以及在非导电性基底上制备牢固且粘附的导电层的方法。
本发明的又一目的是提供一种制备印刷电路和耐用且廉价的平板柔性电路系统的方法。
本发明的再一目的是提供一种用于非导电性基底的改进的调节和蚀刻浴组合物。
本发明的又一目的是提供一种用于镀覆非导电性基底的改进的化学镀镍浴。
本发明的这些和其它目的都在本发明的方法中得以实现，其中制备了用于随后电镀的聚合物基底，该方法包括如下步骤：
a)用等离子体流或电晕放电表面处理对聚合物基底的至少一个表面进行处理；
b)用含有碱金属氢氧化物和离子型钯的蚀刻液调节和蚀刻该聚合物基底；
c)用离子型钯活化该聚合物基底；
d)还原该聚合物基底上的钯；
e)在制备的聚合物基底上镀覆化学镀镍层；和
f)在整个化学镀镍层上镀覆化学镀铜层。
具体实施方式
具体地，本发明涉及一种制备聚合物基底的方法，该聚合物基底用于进行随后的电镀，包括步骤：
a)用等离子体流或电晕放电表面处理对聚合物基底的至少一个表面进行处理；
b)用含有碱金属氢氧化物和离子型钯的蚀刻液调节和蚀刻该聚合物基底；
c)用离子型钯活化该聚合物基底；
d)还原该聚合物基底上面的钯；
e)在制备的聚合物基底上面镀覆化学镀镍层；和
f)在整个化学镀镍层上镀覆化学镀铜层。
在优选实施方式中，聚合物基底是聚酰亚胺膜。
化学镀铜层一旦被镀覆在制备的聚合物基底上，那么制备的聚合物基底就可能用电解铜层涂布。
以上的步骤和流程优选在每个步骤之后伴随一个或多个洗涤步骤(即清洗)而进行，优选用去离子水，最好是从基底表面除去在之前步骤中进入与基底表面接触的任何污染物或者是任何材料或组合物。该清洗步骤确保了没有材料或组合物对后面步骤的流程或制品干扰。
上述方法特别适用于将导电金属层化学镀覆到非导电聚合物基底的表面上，例如印刷电路板，特别是包含多个待镀覆的通孔的双面或多层板。
一般的加工流程如下：
(1)表面处理
首先将聚酰亚胺表面进行等离子体或电晕放电表面处理，以在聚酰亚胺表面上引入离子交换基团，它还用于提高聚酰亚胺膜的表面张力。等离子体流或电晕放电表面处理的应用使聚酰亚胺膜的表面张力从约50～52达因/厘米的范围提高到约72达因/厘米。
术语“电晕”指的是基本上在大气压下发生的放电，区别于真空状态下发生的放电，其特征在于阳极和阴极之间的空间强烈的扩散辉光，有时称作“辉光”放电。如果使用电晕放电，聚酰亚胺膜的至少一个表面暴露于优选含氮的大气中进行电晕放电。
还可以利用等离子体处理来处理聚酰亚胺膜的表面。等离子体处理没有特别限定，只要它能够在聚酰亚胺膜表面上引入合适的离子交换基团，它可以是在真空容器中减压下进行的减压等离子体处理，或者是在大气压或约为大气压下进行的常压等离子体处理。如果进行常压等离子体处理，使用的气体没有特别限定，但其例子包括本领域常用的空气、氩气和氮气。等离子体处理在聚酰亚胺树脂膜表面上产生亲水性官能团，例如羟基、羧基和羰基。
在本发明的一个优选实施方式中，利用等离子体处理来处理聚酰亚胺膜的表面。但是任一种方法对于改性或底涂聚酰亚胺表面以提高表面的粘合力和湿润性都是有效的。
优选在表面处理之后的24小时内加工所述膜，以得到最大粘合力。
一旦进行了表面处理，那么优选将处理过的聚酰亚胺表面进行水洗以湿润表面。水洗通常在室温下进行约30至约60秒钟。
(2)调整/蚀刻
聚酰亚胺膜的调整和/或蚀刻通常在145～165℉的温度下进行。
调整/蚀刻组合物是含水溶液，通常包含浓度为约190～385g/l的碱金属氢氧化物。调整/蚀刻组合物还可以包含其它组分例如表面活性剂和有机溶剂。
氢氧化钠或氢氧化钾适度地蚀刻/软化聚酰亚胺表面，便于钯粘结到表面上。本发明实现了双重方案(two-fold scenario)，其中聚酰亚胺膜的表面被蚀刻，并且钯也被施覆到表面上。
因此蚀刻和/或调整液还包含离子型钯约0.1～10.0ppm。
通过将聚酰亚胺膜浸入溶液浴中可以施覆调整/蚀刻液。或者，可以通过在聚酰亚胺膜的至少一个表面上喷射一层溶液而施覆调整/蚀刻液。随后待活化的表面应该与溶液接触合适的一段时间，通常是约1～6分钟的时间。从该步骤沉积在聚酰亚胺膜上的钯的水平显示在约0.2～0.7ug/cm2的范围内。
虽然所需的粘合力水平可以根据聚酰亚胺膜的最终用途而变化，但是通常板与膜的粘合力优选为约0.7kgf/cm。
此后，将调整过并蚀刻过的聚酰亚胺表面在室温下进行水洗约3～5分钟，以从聚酰亚胺膜的表面上洗去调整/蚀刻组合物。
(3)离子型钯活化
接下来，使用含有如下成分的组合物将聚酰亚胺膜进行离子型钯活化：
a)硫酸钯
b)优选的碱性缓冲液，例如硼酸盐，
c)螯合剂，例如氨基吡啶或等同物，
d)碱金属氢氧化物。
组合物中钯的浓度在工作浴中可以从约20至约100ppm变化。在室温至约140℉的温度下将聚酰亚胺膜浸入离子型钯浴中约1～6分钟。钯活化浴的pH必须为碱性以获得最佳的结果，通常在约9.5至约12.0的范围内，优选为约11.2。
在离子型钯活化处理时，聚酰亚胺膜的颜色从柔和的半透明淡黄色变化到浅棕色。发现沉积物中钯的水平在0.6～6.2ug/cm2的范围内。
为了获得最佳结果，溶液移动是必要的。
钯活化之后，聚酰亚胺表面再次进行水洗。在室温下进行水洗约1分钟，并且温和清洗以从聚酰亚胺膜表面清理任何碎屑。
(4)催化(acceleration)或还原
接着在聚酰亚胺膜的活化表面上进行催化或还原步骤。该催化或还原浴组合物一般包含：
a)还原剂，例如次磷酸钠。
通常浴组合物的pH为约5.0～5.5，在温度约100～110℉下施覆约1～5分钟。还原步骤利于膜表面上的钯发生还原。
为了从还原液中除去颗粒，需要进行过滤。虽然其它溶液过滤装置对于本领域技术人员而言是已知的，但是如果使用的话，该步骤通常通过罐型单元进行再循环而完成。
一旦实施了催化或者还原步骤，再次进行水洗。通常在室温下水洗约1分钟，温和清洗以从聚酰亚胺膜的表面清理任何可能的碎屑。
(5)化学镀镍
接着用化学镀镍溶液镀覆制备的聚酰亚胺膜。一种适合的化学镀镍溶液购自MacDermid，Inc.，商品名Macuplex
Figure G2006800538982D0007181803QIETU
J64。但是大多数市售化学镀镍溶液都能使用。
化学镀镍溶液一般包含：
a)镍盐
b)氨水或碱金属氢氧化物
c)次磷酸盐还原剂
d)螯合剂，例如柠檬酸。
优选的化学镀镍溶液包含约6.0至约12.0g/l的氯化铵，更优选约12g/l的氯化铵，这有助于化学镀镍与聚酰亚胺膜的粘合力。化学镀镍一般在温度约85～90℉下进行施覆，本发明的发明人发现较低的温度也有助于化学镀镍与聚酰亚胺膜的粘结。
如果化学镀镍与聚酰亚胺膜的粘合力好的话，就会观察到深灰色的无光色彩。当观察到发亮表面时，粘合力可能受到损害。
化学镀镍优选具有低亚磷型化学物质，沉积物中一般包含约3～5％的磷。沉积层的厚度一般约为5～10微英寸。
如果已经施覆了化学镀镍层的话，室温下温和水洗约1分钟。
(6)化学镀铜
如果已经在制备的聚酰亚胺基底上镀覆了化学镀镍的话，在整个化学镀镍的顶部上镀覆化学镀铜。
化学镀铜溶液一般含有：
a)铜盐
b)碱金属氢氧化物
c)甲醛
d)螯合剂
一种合适的化学镀铜溶液购自MacDermid，Inc.，商品名M-15。然而，大多数市售的化学镀铜溶液都能使用。
如果化学镀铜已镀覆到镍镀聚酰亚胺膜上的话，那么就能看到黯淡的铜的外观。如果观察到明亮的铜的外观，那么与基底的粘合力可能会降低。
尽管化学镀铜溶液的温度不是决定性的，但优选在约85至约115℉的范围内。铜沉积物的厚度不是决定性的，根据消费者的特定需要而定，但通常铜沉积物的厚度小于约5微英寸。化学镀覆铜之后，室温下用温水清洗表面约1分钟。
一旦化学镀铜已被镀覆到聚酰亚胺膜上时，该聚酰亚胺膜遂即准备用于电镀铜。电解铜镀覆浴组合物是本领域已知的，且在本发明的实践中是有用的。
本发明的发明人观察到无等离子体处理的调整步骤达到了所需的粘合力，而无调整步骤的单独等离子体处理步骤不能够达到所需的粘合力。但当等离子体处理和调整步骤都使用时，获得最佳的粘合力。
本发明的调整和蚀刻液中钯活化剂的使用以及在化学镀镍浴中包括氯化铵能够提高聚酰亚胺基底与随后镀覆的金属层间的粘合力。

Claims (10)

1.一种用金属镀敷聚合物基底的方法，所述聚合物基底为聚酰亚胺膜，该方法包括步骤：
a)用等离子体或电晕放电表面处理对该聚合物基底进行表面处理；
b)用调整和蚀刻组合物调整和蚀刻该聚合物基底，以使处理后的该聚合物膜上的钯的水平为0.2～0.7ug/cm2，其中所述组合物为含水溶液，并包含：
i)190～385g/l的碱金属氢氧化物，
ii)0.1～10.0ppm的离子型钯，
iii)钯增溶化合物；和
iv)非强制性选择的表面活性剂；
c)用离子型钯活化该聚合物基底；
d)还原该聚合物基底上的钯；
e)在制备的聚合物基底上镀覆化学镀镍层；和
f)在整个化学镀镍层上镀覆化学镀铜层。
2.根据权利要求1的方法，其中用等离子体处理该表面。
3.根据权利要求1的方法，其中调整和蚀刻步骤在145～165°F的温度下进行。
4.根据权利要求1的方法，其中该蚀刻液中的碱金属氢氧化物选自以下物质构成的组：氢氧化钠、氢氧化钾和氢氧化锂。
5.根据权利要求1的方法，其中该活化溶液包含钯。
6.根据权利要求5的方法，其中钯在该活化溶液中的浓度为20～100ppm。
7.根据权利要求1的方法，其中该活化溶液的pH在9.5～12.0之间。
8.根据权利要求1的方法，其中该化学镀镍溶液包含6.0至12.0g/l的氯化铵。
9.根据权利要求8的方法，其中该化学镀镍溶液包含6g/l的氯化铵。
10.用于处理聚合物基底的蚀刻和调整浴组合物，其中所述组合物为含水溶液，并包含：
a)190～385g/l的碱金属氢氧化物；
b)0.1～10.0ppm的离子型钯；
c)钯增溶化合物；和
d)非强制性选择的表面活性剂。
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