CN100359994C - 膜上芯片用铜箔 - Google Patents

膜上芯片用铜箔 Download PDF

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CN100359994C
CN100359994C CNB2004100055458A CN200410005545A CN100359994C CN 100359994 C CN100359994 C CN 100359994C CN B2004100055458 A CNB2004100055458 A CN B2004100055458A CN 200410005545 A CN200410005545 A CN 200410005545A CN 100359994 C CN100359994 C CN 100359994C
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copper
alloy
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nickel
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CN1523951A (zh
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吉原康久
君岛久夫
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Furukawa Electric Co Ltd
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Abstract

为提供一种具有高蚀刻率、电路图形底线的直线性优异且在树脂中不残留形成电路图形的铜箔的铜粒子而制成微图形、焊接球的形成不引起铜箔和树脂基板粘着力降低的、目视性好的在微图形上搭载IC方便的铜箔，本发明的膜上芯片用铜箔具有在和树脂基板粘附的铜箔的粘附面上设置由钴含量、镍含量分别等于或多于铜含量的铜-钴-镍合金构成的合金微细粗化粒子层的特征。具体地说，在和树脂基板粘附的铜箔的粘附面上可设置5～12mg/dm2的铜、6～13mg/dm2的钴、5～12mg/dm2的镍构成的合金微细粗化粒子层，较好对上述合金微细粗化粒子层上进行防锈处理。另外，对上述的合金微细粗化粒子层上最好进行硅烷偶合剂的处理。

Description

膜上芯片用铜箔
技术领域
本发明涉及最适合用于微图形印刷线路板的膜上芯片(chip-on-film)(COF)的铜箔。
背景技术
随着电子设备的小型化、轻量化，近年来的各种电子部件高度集成化。与此相应的是，对印刷线路板的电路图形也要求其高密度化以形成由微细线幅和极小配线间距构成的电路图形。特别高密度化进程中的是驱动个人电脑、移动电话、PDA显示部件的液晶显示器的IC装配基板，因IC被直接搭载在基板膜上，所以被称为膜上芯片(COF)。
在COF装配中，利用透过铜箔所形成的配线图形的膜的光来检出IC的位置，但是，以往的印刷线路板用电解铜箔的目视性(利用光检出IC位置的能力)非常差。其原因是铜箔表面粗糙度粗糙的缘故。这是因为，透光的膜的部分是铜电路部分以外的不需要的铜箔部分被蚀刻除去的部分，将铜箔粘附在膜上时，铜箔表面的凹凸会复制在膜表面上而遗留下来，光透过膜时，膜表面的凹凸会使可直接进入的光量减少，目视性变差的缘故。
以往的印刷线路板用电解铜箔，因其目视性差，所以使用溅射法(薄膜形成的方法)将铜箔形成在聚酰亚胺膜上，并在其上镀铜的双层材料。
但是，该溅射铜层和膜的附着力弱，在电路制成加工时，蚀刻液或电镀液会侵蚀铜箔和膜之间的部分，即引起所谓的侧壁腐蚀(under cut)现象，另外，因该粘着力弱，作为产品，潜伏着使用中发生铜箔剥落事故的危险性。
另一方面，作为线路板用铜箔的处理方法，提出了在铜箔表面上电镀在铜中添加少量的钴和镍的铜-钴-镍合金的粗化处理方法(例如参考日本特许公开公报平2-292894号)。但是，经过这样粗化处理的铜箔虽然其蚀刻性、耐碱腐蚀性及耐盐酸性良好，但存在有在用丙烯酸类粘合剂时，耐热剥离强度会降低，耐氧化性也不充分，色彩也不会变到黑色而为茶色-深茶色的缺点(例如参考日本公开公报平9-87889号)，不能实现实用化。
为此，对这样的铜箔进行改良研究，公开了如下的方法：对铜箔表面进行电镀铜-铜量的1/10左右的钴-铜量的1/40左右的镍的合金后，再在其上形成钴-镍合金电镀层，再形成镀锌层(例如参考日本特许公开公报平9-87888号)，或者形成锌-镍电镀层(例如，参考日本特许公开公报平9-87889号)的3层结构的处理方法；或者，利用电镀铜-铜量的1/10左右的钴-铜量的1/40左右的镍的合金对铜箔表面进行粗化处理后，形成镀钴层，再形成镀锌层(例如参考日本特许公开公报平8-335775号)，或者形成镀锌-镍层(例如参考日本公开公报平8-335776号)的3层结构的处理方法。这些方法特别对改善伴随着半导体设备的小型化、高集成化的线路板制造工序中所进行的一段和达到高温的处理温度及设备使用中的发热所产生的铜箔和树脂基材间的粘着力下降，进一步改善耐热剥离性而提出的。
但是，采用上述3层构造的改良铜箔作为COF的话，存在下面的缺点：采用上述铜箔制造满足微图形化要求的线路板，虽可在该线路板上搭载IC，但为了在线路板上搭载IC，必须在线路板上的铜箔电路中载有焊接球。由于铜箔上载有该焊接球，而为了提高和焊料的粘附性，所以在铜箔上镀锡。该镀锡工序中的镀锡液会溶解设置在铜箔表面上的上述粒子，出现显著损害铜箔和线路板的剥离强度的现象。
发明内容
为了解决上述以往技术中的问题点，本发明以提供一种高蚀刻率、电路图形底线的直线性优异并且在树脂中不残留形成电路图形的铜箔的铜粒子而制成微图形，载有焊接球处理时不引起铜箔和树脂基板粘着力降低、目视性好的、在微图形上搭载IC的性能优异的铜箔来作为目的。
本发明的膜上芯片用铜箔具有铜箔的至少一面上设置有由钴含量、镍含量分别等于或多于铜含量的铜-钴-镍合金构成的合金微细粗化粒子层的特征。
上述合金微细粗化粒子层上最好进行防锈处理。
上述合金微细粗化粒子层上最好进行硅烷偶合剂处理。
这样通过对设置在铜箔表面上的合金微细粗化粒子的表面进行防锈处理或/及偶合剂处理可防止铜箔的氧化和变色。
具体实施方式
以下，对本发明的膜上芯片(COF)用铜箔(以下仍称为COF箔)的实施方式进行说明。
本实施方式的COF箔为：铜箔的至少一面上设置有由钴含量、镍含量分别等于或多于铜含量的合金组成为铜-钴-镍合金构成的合金微细粗化粒子层。
对上述本实施方式中的合金微细粗化粒子层的电镀合金组成，相对以往电镀合金组成，即同时减少添加到铜1中的钴、镍的量，不一定能满足作为COF箔的情况，改变方案，着眼于不同时限制钴、镍添加到铜的量并进行了各种试验，其结果是，通过同时增加钴、镍对铜的添加量并比以往所考虑的添加量多而得到能满足作为COF用箔的铜箔。而且重复试验研究并根据上述结果研究的，在铜箔至少和树脂基板粘接的面上设置由钴含量、镍含量分别等于或多于铜含量的铜-钴-镍合金构成的合金微细粗化粒子层时，即更具体地说，每1dm2铜箔上所粘接的合金微细粗化粒子层的各组成为5～12mg/dm2铜-6～13mg/dm2钴-5～12mg/dm2镍时，即可成功得到带有高蚀刻率、电路图形底线的直线性优异并且在树脂中不残留形成电路图形的铜箔的铜粒子而制成微图形，成功地得到目视性好的COF用铜箔。
将铜箔表面所粘附的微细粗化粒子的铜箔和聚酰亚胺树脂基板粘合，将一边目视IC，一边将经蚀刻形成电路的COF(基板)搭载在IC上，在将铜箔电路和IC的连接工序中，在铜箔上镀锡。在该镀锡工序中，镀锡液的温度有时非常高，电镀液会浸蚀铜箔和树脂基板之间的部分，引起所谓的侧壁腐蚀(under cut)现象，为实现上述用途，必须使上述微细粗化粒子合金组成不出现侧壁腐蚀。
本发明者针对此点进行了探讨，对不引起侧壁腐蚀现象的微细粗化粒子中的合金组成进行了探讨，其结果发现：使每Cu的存在量1mg/dm2，Co为1.2～2.2mg/dm2和Ni为1.0～2.0mg/dm2的箔的组成，就可抑制侧壁腐蚀现象，较为理想，更好是：使每Cu的存在量1mg/dm2，Co为1.5～1.9mg/dm2和Ni为1.3～1.7mg/dm2的箔的组成，可更切实防止侧壁腐蚀现象的发生，而不引起因设置焊接球处理所产生的铜箔和树脂基板的粘合力的下降。
更具体地说，如上述那样，将合金微细粗化粒子层向铜箔表面上附着量较好控制在5～12mg/dm2铜-6～13mg/dm2钴-5～12mg/dm2镍的范围内。设定在上述范围内的原因主要是根据下面的试验结果：
1.铜的附着量
在5mg/dm2以下的话，对于蚀刻液的溶解性变差，蚀刻残渣残留下来。
若在12mg/dm2以上的话，耐热性变差。
2.钴的附着量
在6mg/dm2以下的话，对于蚀刻液的溶解性变差，蚀刻残渣残留下来。
若在13mg/dm2以上的话，不能切实防止侧壁腐蚀现象。
3.镍的附着量
在5mg/dm2以下的话，不能切实防止侧壁腐蚀现象。
若在12mg/dm2以上的话，对于蚀刻液的溶解性变差，蚀刻残渣残留下来。
实施例1-3
在作为铜箔的电解铜箔(B-WS箔，由古河サ一キツトフオイル公司制造)的表面上经铜·钴·镍合金电镀形成合金微细粗化粒子层。
电镀液组成及电镀条件：
Cu：  2g/L
Co：  8g/L
Ni：  8g/L
硫酸铵：40g/L
硼酸：20g/L
pH：3.5
温度：40℃
电流密度：15A/dm2
利用上述条件、变化电镀时间所制得的COF用铜箔的表面的合金组成如表1所示。在表1中，用mg/dm2单位来表示铜、钴及镍的含量，对于铜1的比率表示在括号内。
表    1
    实施例     铜的含量     钴的含量     镍的含量
    1     7.8(1)     12.95(1.66)     11.35(1.45)
    2     6.6(1)     11.02(1.67)     9.44(1.43)
    3     6.6(1)     10.95(1.66)     9.69(1.47)
实施例4
在作为铜箔的压延铜箔(日本制箔公司制造)的表面上经铜·钴·镍合金电镀形成合金微细粗化粒子层。
电镀液组成及电镀条件：
Cu：2g/L
Co：8g/L
Ni：8g/L
硫酸铵：40g/L
硼酸：20g/L
pH：3.5
温度：40℃
电流密度：15A/dm2
利用上述条件所制得的COF用铜箔的表面的合金组成如表2所示，制得具有Rz：0.50、Ra：0.06的平滑表面的铜箔。在表2中，用mg/dm2单位来表示铜、钴及镍的含量，对于铜1的比率表示在括号内。
表    2
    实施例     铜的含量     钴的含量     镍的含量
    4     6.5  (1)     9.5(1.16)     7.5(1.15)
在实施例1-4的表面处理过的粘附有合金微细粗化粒子的铜箔的表面上，经高温高压将A生产厂家制造的聚酰亚胺薄膜粘附后发现粘附性良好。然后，将干膜防蚀层粘贴在铜箔表面上进行蚀刻而制得COF用树脂基板。在制造该COF用树脂基板时，电路没形成波形形状，所以电路的直线性较好，完成了微图形性优异的COF用树脂基板。能够一边目视IC，一边将该COF对合位置在排列着IC的基板上，从膜上能容易确认IC的位置，可正确地将IC和树脂基板电路连接。
然后，以高温高压将B生产厂家制造的聚酰亚胺薄膜粘附在实施例1-4的表面处理过的附着有微细粗化粒子的铜箔表面上后发现粘附性良好，然后，将干膜防蚀层粘贴在铜箔表面上进行蚀刻而制得COF用树脂基板。在制造该COF用树脂基板时，电路没形成波形形状，所以电路的直线性较好，完成了微图形性优异的COF用树脂基板。能够在排列着IC的基板上一边目视IC，一边对该树脂基板调整位置，从膜上能容易确认IC的位置，可正确地将IC和树脂基板电路连接。
粘结铜箔的聚酰亚胺树脂虽会随提供该树脂的厂家的不同，其色彩或与铜箔的粘着力等性能会有一些不同，但实施例1-4的铜箔无论和哪一家的厂家的聚酰亚胺薄膜进行粘合的话，蚀刻而制得电路后，测定了确认IC位置的目视性及两者的粘结力等的结果是：它是满足了如上所述的特性的铜箔。
另外，对实施例1、2所得的铜箔的合金微细粗化粒子层表面上再进行铬防锈处理和硅烷偶合剂处理，测定了其目视性和粘着力等后发现：它具有满足的特性。
如上所述，本发明具有如下优异的效果：具有高蚀刻率、电路图形底线的直线性优异并且在树脂中不残留形成电路图形的铜箔的铜粒子而制成微图形、焊接球的形成不引起铜箔和树脂基板粘着力降低的、目视性好的、在微图形上搭载IC方便。

Claims (3)

1.膜上芯片用铜箔，其特征在于，铜箔的至少一面上设置由铜-钴-镍合金构成的合金微细粗化粒子层，钴的含量、镍的含量分别等于或多于铜的含量。
2.根据权利要求1所述的膜上芯片用铜箔，其特征在于，在上述铜箔表面所设置的上述合金微细粗化粒子层上进行防锈处理。
3.根据权利要求1所述的膜上芯片用铜箔，其特征在于，在上述铜箔表面所设置的上述合金微细粗化粒子层上进行硅烷偶合剂处理。
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