CN108220930A - 无电镀法 - Google Patents

无电镀法 Download PDF

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CN108220930A
CN108220930A CN201711398750.9A CN201711398750A CN108220930A CN 108220930 A CN108220930 A CN 108220930A CN 201711398750 A CN201711398750 A CN 201711398750A CN 108220930 A CN108220930 A CN 108220930A
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substrate
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electroless plating
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羽切义幸
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Rohm and Haas Electronic Materials LLC
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    • 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
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    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating

Abstract

使用阳离子聚合物等提供一种发泡特性比常规调节剂小但粘附性比常规调节剂高的调节剂，和使用所述调节剂的无电镀法。本发明的进行无电镀的方法包括以下步骤：(a)使衬底与含有由以下通式(1)表示的化合物的组合物接触：H2N‑R1‑NH‑R2‑NH2(1)其中R1和R2各自独立地是具有3到10个碳原子的亚烷基；(b)使衬底与催化剂组合物接触；以及(c)使衬底与无电镀组合物接触。

Description

无电镀法
技术领域
本发明涉及一种在树脂衬底、特别是印刷线路板上进行无电金属镀覆的方法，并且更具体来说，涉及一种用含有特定化合物的预处理溶液在树脂衬底的表面上形成具有高粘附性的金属膜的方法。
背景技术
印刷线路板的各层之间的电连接通常通过被称为通孔的极小的孔进行。关于在印刷线路板的表面上和在这些通孔的内壁表面中形成导电膜的方法，通常使用以下方法：用含有阳离子聚合物和表面活性剂的预处理溶液(也被称作调节剂)处理，施加含有钯等的催化剂，然后通过无电镀法形成金属膜。
为了改善树脂衬底与导电膜之间的粘附性，通常在调节剂处理之前，使用主要含有溶剂的处理溶液进行树脂溶胀工艺，然后使用主要含有高锰酸盐的处理溶液进行粗糙化工艺，然后进行一系列去污/粗糙化工艺，通过中和工艺去除锰。去污/粗糙化工艺使得在树脂表面上形成了细微的不均匀度，从而通过锚定效应改善了树脂衬底与导电膜之间的粘附性。
然而，在主要通过锚定效应提供粘附性的方法的情况下，如果树脂衬底表面的粗糙度减小，那么衬底与金属膜之间的粘附性将降低，并且获得具有高粘附性的镀膜将变得困难。因此，需要一种即使在具有低粗糙度的树脂衬底的表面上仍具有高粘附性的调节剂来代替常规调节剂，并需要一种使用这种调节剂的无电镀法。此外，取决于加入到调节剂中的化合物，可能在液体表面上生成气泡；因此，需要没有这种发泡特性的调节剂。
第2006-77289号日本特许公开专利公布公开了一种用于无电镀的预处理溶液，所述预处理溶液含有在一个分子中具有至少两个氨基的化合物(特别是乙烯胺(共)聚合物或烯丙胺(共)聚合物)。此外，第2010-106337号日本特许公开专利公布公开了通过向含有阳离子聚合物和非离子表面活性剂的调节剂中进一步加入二氟化氢铵来形成具有高粘附性的金属膜的方法。
发明内容
因此，本发明的一个目的是使用阳离子聚合物等提供一种发泡特性比常规调节剂小但粘附性比常规调节剂高的调节剂，和使用所述调节剂的无电镀法。
本发明人进行了大量研究并发现，向调节剂中加入具有特定亚烷基链长的三胺化合物来代替阳离子聚合物能够产生粘附性比阳离子聚合物高但发泡特性比阳离子聚合物小的调节剂。已基于这些发现完成了本发明。
换句话说，本发明涉及一种在衬底上进行无电镀的方法，包含以下步骤：
(a)使衬底与含有由以下通式(1)表示的化合物的组合物接触：
化学式1：
H2N-R1-NH-R2-NH2 (1)
其中R1和R2各自独立地是具有3到10个碳原子的亚烷基；
(b)使衬底与催化剂组合物接触；以及
(c)使衬底与无电镀组合物接触。
附图说明
图1是SEM照片(放大倍数：2000倍)，显示经历了实例1中的镀铜的微导通孔的内壁表面。
图2是SEM照片(放大倍数：2000倍)，显示经历了实例2中的镀铜的微导通孔的内壁表面。
图3是SEM照片(放大倍数：2000倍)，显示经历了比较实例1中的镀铜的微导通孔的内壁表面。
图4是SEM照片(放大倍数：2000倍)，显示经历了比较实例2中的镀铜的微导通孔的内壁表面。
图5是SEM照片(放大倍数：2000倍)，显示经历了比较实例3中的镀铜的微导通孔的内壁表面。
图6是SEM照片(放大倍数：2000倍)，显示经历了比较实例4中的镀铜的微导通孔的内壁表面。
图7是SEM照片(放大倍数：2000倍)，显示经历了比较实例5中的镀铜的微导通孔的内壁表面。
具体实施方式
除非另外指明，否则本说明书通篇中所用的缩写具有以下含义。
g＝克；mg＝毫克；℃＝摄氏度；min＝分钟；m＝米；cm＝厘米；L＝升；mL＝毫升；并且N＝牛顿。所有的值的范围都包括边界值，并且可以任何顺序组合。此外，在本说明书中，除非另外说明，否则百分比(％)意指重量％。
在本发明方法中，使用含有由以下通式(1)表示的化合物的组合物：
H2N-R1-NH-R2-NH2 (1)
组合物还可以称为调节剂。在通式(1)中，R1和R2各自独立地是具有3到10个碳原子的亚烷基。亚烷基可以是直链或支链，但在本发明中直链亚烷基是优选的。亚烷基链优选地具有3到8个碳原子，更优选3到6个碳原子。特定的通式(1)化合物包括二亚丙基三胺、双(亚丁基)三胺、双(亚己基)三胺等。
本发明人已发现，通过使用具有含3到10个碳原子的亚烷基链的三胺化合物，粘附性特征性地改善了。虽然这不受理论限制，但是可以认为，具有含3到10个碳原子的亚烷基链的三胺具有极佳的亲水亲油平衡，容易吸附在树脂衬底上并且同时，容易在后续催化剂施加步骤中与催化剂结合。因此，有可能形成具有高粘附性的金属膜。此外，虽然常用的阳离子聚合物对树脂具有高粘附性，但是因为其分子量大，所以认为它容易吸附过度。因此，在树脂表面与金属膜之间留下相对较大量的阳离子聚合物，从而降低了粘附性。
调节剂中由通式(1)表示的化合物的含量优选是0.1到10g/L，更优选是1到8g/L，并且最优选是2到5g/L。
本发明中所用的调节剂的特征之一是能够形成具有高粘附性的金属膜，即便它不含表面活性剂。含有阳离子聚合物的调节剂通常含有表面活性剂来提高调节剂成分进入通孔和盲孔的渗透性，并赋予玻璃和树脂均一的调节作用。然而，取决于使用条件，含有表面活性剂的调节剂可能在液体表面上产生气泡，从而降低了可加工性。通过使用由通式(1)表示的化合物，本发明的调节剂即使不含表面活性剂，都展现比常规调节剂高的粘附性。
除了由通式(1)表示的化合物之外，本发明中所用的调节剂可含有任何组分。举例来说，其可含有螯合剂作为任选的组分。螯合剂通过在金属离子溶解到调节剂中时与金属离子形成螯合化合物来发挥延长调节剂的使用寿命的作用。优选螯合剂的实例包括乙醇胺、三乙醇胺、乙二胺四乙酸(ethylenediaminetetraacetic acid，EDTA)、乙二胺n，n′二琥珀酸(ethylenediamine n，n′disuccinic acid，EDDS)以及亚氨基二乙酸(iminodiaceticacid，IDA)。相对于调节剂，所加入的螯合剂的量优选是0.1到0.2mol/L。
必要时，本发明中所用的调节剂还可以含有添加剂作为额外任选组分，如pH调节剂等。本发明中所用的调节剂优选含有水作为溶剂。可以使用任何水，如去离子水，自来水等。此外，可以将溶剂与水混合并加以使用，溶剂例如醇。
树脂衬底可以是印刷线路板，并且印刷线路板可具有玻璃布/树脂。树脂衬底可具有被称为通孔的小孔或被称为盲孔的小非通孔。此外，在以高性能半导体封装板为代表的高密度印刷线路板的情况下，使用功能性绝热树脂材料板作为树脂衬底。通过本发明方法，如果衬底中存在孔，如通孔等，那么镀层不仅能够均一地沉积在印刷线路板的表面上，而且能够均一地沉积在孔的内壁表面上。
树脂衬底的实例包括由以下制成的衬底：环氧树脂、氰酸酯树脂、双马来酰亚胺三嗪树脂、聚酰胺、ABS、聚苯醚、聚砜、含氟树脂、聚碳酸酯、聚缩醛、聚苯醚、聚丙烯以及液晶聚合物等。
使用任何能使调节剂与树脂衬底接触的方法。举例来说，可通过以下进行处理：在衬底在必要时经历了所谓的去污或粗糙化工艺之后，将其浸没于调节剂中；或将调节剂喷涂在衬底上。在浸没时，衬底可以是在30到60℃、优选40到50℃的温度下，在调节剂中浸没1到10分钟，优选2到6分钟。
在调节剂与树脂衬底接触之后，进行催化剂施加步骤以使树脂衬底与催化剂组合物接触，从而将催化剂吸附到树脂衬底的表面上。然而，在树脂衬底与催化剂组合物接触之前，还可以任选地进行将树脂衬底浸没在如过硫酸钠、过硫酸铵、硫酸以及过氧化氢混合溶液等水溶液中的步骤(也被称作微蚀刻)和用如硫酸等酸洗涤树脂衬底的表面的步骤。即使在进行这些步骤之后，本发明中所用的调节剂仍能保持在树脂衬底的表面上和孔的内壁表面上，并且在后续催化剂施加步骤中，足够量的催化剂可被吸附在树脂衬底的表面和孔的内壁表面上。微蚀刻步骤通常可以使用水溶液在20到35℃的温度下进行0.5到10分钟，优选1到3分钟，并且酸洗步骤通常可以在20到35℃，优选25到30℃的温度下进行0.5到5分钟，优选1到3分钟。
可使用通常已知的催化剂组合物。催化剂组合物的实例包括钯-锡胶体溶液、含有金属离子的组合物等，金属离子例如钯、铂、银或铜。举例来说，可使用CIRCUPOSITTM ADV8530催化剂和CIRCUPOSITTM6530催化剂(均由罗门哈斯电子材料公司(Rohm and HaasElectronic Materials Co.，Ltd.)制造)。在使用CIRCUPOSITTM ADV 8530催化剂作为催化剂组合物的情况下，举例来说，将树脂衬底在35到60℃，优选40到50℃的温度下在催化剂组合物中浸没1到10分钟，优选3到5分钟，然后可以用CIRCUPOSITTM6540还原剂进行钯离子的扣除处理。
可使用通常已知的无电镀组合物。举例来说，可使用含有金属或其混合物的无电镀组合物，金属例如铜、镍、钴、铁等。在使用印刷线路板作为树脂衬底时，无电镀铜通常是优选的。举例来说，可使用CIRCUPOSITTM 6550无电铜、CIRCUPOSITTM ADV 8550无电铜和CIRCUPOSITTM 328铜混合浓缩物(全由罗门哈斯电子材料公司制造)。
在下文中，将参考实例更详细地描述本发明，但本发明不限于这些实例。
在以下实例和比较实例中，通过SEM观察来评估镀层在通孔内壁表面上的沉积。还根据以下程序评估粘附强度：将经历了无电镀的衬底的表面在室温下用去离子水洗涤3分钟，并加热且干燥(120℃，30分钟)。然后，将待镀覆材料的表面浸没在含有硫酸的酸清洁剂中(液体温度35℃，2分钟)。之后进行酸洗，并用电解镀铜MICRO FILLTMEVF进行电解镀铜处理。所得已镀覆材料的表面在室温下用去离子水洗涤3分钟，然后加热并干燥(180℃，60分钟)。所得镀铜膜的膜厚度是20到25μm，并将此镀膜切成1cm的宽度。使用INSTRONTM5564测试仪，以50毫米/分钟的拉伸速度和90°的角度，根据JIS C5012印刷线路板测试方法测量衬底树脂与镀膜之间的粘附强度(剥离强度)。
实例1到6和比较实例1到5
使用以下树脂衬底1到3作为待处理材料的树脂衬底。
树脂衬底
树脂衬底1：Ra：100(nm)
树脂衬底2：Ra：250(nm)
环氧树脂衬底3：Ra：80(nm)
注意：Ra表示算术平均粗糙度。
将表1或表2中所示的每个化合物按表1或表2中所示的量加入到去离子水中来制备调节剂。使用高锰酸盐，使树脂衬底1到3经历去污/粗糙化工艺，然后在45℃的温度下在调节剂中浸没5分钟。接着使用过硫酸钠进行软蚀刻。在用酸洗涤之后，使用碱性钯催化剂(CIRCUPOSITTMADV 8530催化剂)进行催化剂给予处理并使用CIRCUPOSITTM6540还原剂进行还原处理。然后，通过在32℃的温度下在无电镀铜溶液(CIRCUPOSITTMADV 8550无电铜)中浸没20分钟进行无电镀铜。在每次处理之间，在室温下用去离子水洗涤2分钟。用SEM观察无电镀铜之后微导通孔中的镀层沉积的状态。接着进行电解镀铜处理，然后进行粘附性测试。评估结果也显示在表1或表2中。
在实例1和2中，分别加入二亚丙基三胺和双(亚己基)三胺作为调节剂的化合物(调节剂组分)。在比较实例1和2中，使用二乙烯三胺和单乙醇胺代替实例的化合物，并且在比较实例3中，不加入任何调节组分，仅用去离子水实施试验。在比较实例4和5中，分别使用商业调节剂231和3328(均由罗门哈斯电子材料公司制造，含有阳离子聚合物、螯合剂、非离子表面活性剂和水，pH：约10和1)。表1
表2
表3

Claims (4)

1.一种在衬底上进行无电镀的方法，包含以下步骤：
(a)使所述衬底与含有由以下通式(1)表示的化合物的组合物接触：
H2N-R1-NH-R2-NH2 (1)
其中R1和R2各自独立地是具有3到10个碳原子的亚烷基；
(b)使所述衬底与催化剂组合物接触；以及
(c)使所述衬底与无电镀组合物接触。
2.根据权利要求1所述的方法，其中所述组合物中所述由通式(1)表示的化合物的含量是0.1到10g/L。
3.根据权利要求1或2所述的方法，其中所述无电镀是无电镀铜。
4.一种衬底，其表面的至少一部分上具有通过根据权利要求1所述的方法获得的金属膜。
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