CN1315591A - 用于印刷电路板的镀铬铜的成形方法 - Google Patents
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Abstract
本发明涉及一种把金属涂覆到铜层上的方法,包括以下步骤:通过把一稳定层涂覆到其表面上把铜层的表面稳定化,该稳定层由氧化锌,氧化铬,镍,氧化镍或它们的组合物构成,其厚度约在5A-70A之间;以及将从铝,镍,铬,铜,铁,铟,锌,钽,锡,钒,钨,锆,钼以及它们的合金中选出的一种金属气相沉积到铜层的稳定化表面上。本发明还涉及一种由此形成的板材。
Description
本发明涉及处理铜的工艺,更具体地说,涉及向铜箔的至少一侧涂覆金属的工艺。
铜箔用于印刷电路板的生产中。在生产印刷电路板时,通常需要把铜箔粘合在一个绝缘基板上,以便保持铜箔的尺寸和结构稳定性。尽管铜箔是一种极好的导电体,但在使用铜箔时有其固有的问题。例如,铜箔容易被氧化和被腐蚀,而铜本身,不管是电镀的还是轧制的,都不能很好地粘合在这类基板上。同时,众所周知,铜会加速或催化绝缘基板的分解。由于这些原因,通常在铜箔的表面上涂覆一个或多个保护层后再出售。
众所周知,沉积到铜箔上的薄铬层在印刷电路板中有许多用途。有两种方法将薄的铬层沉积到铜的表面上。一种方法是利用电沉积工艺,另一种方法是采用真空沉积工艺。
电沉积工艺具有几个缺点。首先,这种工艺利用对环境有害的材料,这种材料很难进行处理和清除掉,而且处理费用昂贵。进而,这种工艺是不精确的和低效率的。
对于真空沉积工艺,为了确保在被涂覆的铬和铜之间具有令人满意的附着力,需要对铜进行大量的和严格的预处理,以便在真空沉积铬之前从其表面上清除铜的氧化物。
本发明为了克服这些和其它问题,提供一种利用真空沉积工艺形成具有金属涂层的铜的方法,这种沉积工艺不需要长时间的严格的预处理工艺。
根据本发明的一个优选实施例,提供了一种将金属涂覆到铜层上的方法,该方法包括以下步骤,即:通过涂覆一个稳定层将铜层的表面稳定化,所述稳定层由氧化锌,氧化铬,氧化镍或者它们的组合物构成,其厚度在约5-70之间;以及将一种金属真空沉积到铜层的已被稳定化的表面上,所述金属选自铝,镍,铬,铜,铁,铟,锌,钽,锡,钒,钨,锆,钼以及它们的合金。这里,一种特别值得考虑的合金是镍-铬合金。
根据本发明的另一方面,提供一种由铜层和铜表面上的稳定层构成的板材。该稳定层由氧化锌,氧化铬,氧化镍或它们的组合物构成,其厚度在约5-70之间。在该稳定层上设有气相沉积金属。
本发明的目的是提供一种用于制造印刷电路板的镀铬铜层。
本发明的另一个目的是提供一种利用真空沉积工艺形成如上所述的镀铬铜层的方法,所述真空沉积工艺不需要在沉积铬之前对铜表面进行长时间的严格预处理。
本发明的另一个目的是提供一种把金属真空沉积到铜表面上的方法。
本发明的又一个目的是提供一种如上所述的通常为连续的工艺。
本发明的这些和其它目的将从下面参照附图对优选实施例进行的描述中变得更加清楚。
本发明在某些部分及其配置方面可能采取一些具体的形式,其中的一个实施例将在下面参照附图进行详细描述,所述附图也构成本说明书的一部分,其中,
图1是表示根据本发明的将金属涂覆到铜箔表面上的工艺过程的示意图;
图2是沿图1所示的铜箔片的2-2线截取的剖视图;
图3是沿图1的3-3线截取的放大剖视图,示出了其上带有稳定层的图2所示的铜箔片;
图4是沿图1的4-4线截取的剖视图,表示在其无光泽的侧面上具有气相沉积金属的铜箔片。
本发明涉及向铜的表面上涂覆金属的工艺。这里所用的“金属”一词指的是可利用这里所公开的方法进行真空沉积的金属和合金。本发明特别适合于将铬涂覆在铜箔上并特别对此加以描述,但应当理解,所公开的工艺也可用于将诸如铝,镍,铜,铁,铟,锌,钽,锡,钒,钨,锆,钼及它们的合金涂覆在铜箔上。
本发明所用的铜箔可用两种技术之一制造。锻造或轧制的铜箔是通过诸如轧制工艺机械地缩小铜或铁合金带或坯料的厚度制造而成的。电沉积铜箔是通过在一个旋转的阴极鼓上沉积铜离子然后从阴极上剥离沉积的铜箔制造而成的。在本发明中,电沉积铜箔具有非常有利的应用。
铜箔通常具有从约0.0002英寸到约0.02英寸的标称厚度。铜箔的厚度有时也用重量表示,本发明的铜箔典型地具有从约1/8到约14盎司/每平方英寸(oz/ft2)的重量或厚度。特别有用的铜箔是具有1/3,1/2,1或2盎司/每平方英寸(oz/ft2)的重量的铜箔。
电沉积铜箔具有一个光滑的或有光泽的(鼓)侧面,和一个粗糙或无光泽的(铜沉积生长前沿)侧面。在本发明的工艺中,所涂覆的稳定层可被涂覆在箔的任何一侧,有时也可涂覆在两侧。在一个实施例中,由本发明的工艺所涂覆的层施加在箔的有光泽的一侧上。
利用本发明的工艺施加涂层的箔的一侧或两侧可以是一“标准光洁度表面”,“高光洁度表面“或“极高光洁度表面”。有利的实施例包括使用具有高光洁度表面和极高光洁度表面的铜箔。这里所用的“标准光洁度表面”一词指的是具有Rtm(IPC-MF-105F)大于10.2微米的箔表面。“高光洁度表面”一词指的是具有Rtm(IPC-MF-105F)小于10.2微米的箔表面。“极高光洁度表面”一词指的是具有Rtm(IPC-MF-105F)小于5.1微米的箔表面。Rtm(IPC-MF-105F)是每五个连续取样测量中最高点一最低点垂直测量最大值的平均值,每次测量可采用由英国Rank Taylor Hobson Ltd.,出售的SURTRONIC3表面光洁度仪进行。
熟悉本领域的人员将会理解,本发明不仅适用于其表面具有稳定层的铜箔,同时也适用于已沉积或粘结到其它基板上的铜层,以及在沉积到其它基板上之后或粘结到其它基板上之前或之后其表面上涂覆有稳定层的铜层,这种基板包括但不限于聚酰亚胺(参见美国专利Nos.5,685,970和5,681,443,该专利在这里特别引用为参考文献),其它聚合物基板,有机基板,铝(参见美国专利No.5,153,050,该专利在这里特别引用为参考文献),金属基板(参见美国专利No.5,674,596,该专利在这里特别引用为参考文献),或者铜和INVAR合金(因瓦合金)叠层基板。
现在参照附图,其中,图中所示仅仅是为了说明本发明的优选实施例的目的,而不是对其加以限制。图1是一个用于说明本发明的优选实施例的连续制造工艺10的示意图,所示工艺用于将金属涂覆到铜表面上。在图中所示的实施例中,一滚筒11提供一个通常为连续的由铜箔12构成的带。图2是铜箔12的放大剖面图。铜箔12具有一个有光泽的侧面14和一个无光泽的侧面16(在图中,为了进行说明起见,以夸大的方式表示出铜箔12的无光泽侧面16)。
铜箔12优选地经受一个在图中用标号20表示的第一清洗工艺,以便除去其表面上的氧化膜。在图中所示的实施例中,铜箔12借助导辊26围绕一个导辊24被输送到一个槽22中。槽22中装有清洗溶液,用于从铜箔12的表面上清除氧化膜。优选地,采用酸溶液,以便从铜箔12上除去氧化层。用于清洗铜箔12的典型的酸溶液可包括10-80g/l的H2SO4。在一个实施例中,采用50g/l的H2SO4,以便从铜箔12上除去铜氧化层。
在清洗工艺20之后,铜箔12经受一个用标号30表示的漂洗工艺,其中,在铜箔12的上方和下方布置喷射部件32,用水喷射铜箔12的表面。在喷射部件32的下方布置一个槽34,用于收集从其中喷射出来的水。
在清洗工艺20和漂洗工艺30之后,铜箔12经受一个用标号40表示的稳定化处理工艺。铜箔12被导向一个槽42,并围绕在一个导辊44上。铜箔12借助导辊46相对于导辊44定位。槽42中装有电解液。根据本发明的一个实施例,电解液包括锌离子和铬离子。电解液中的锌离子源可以是锌盐,例如包括ZnSO4,ZnCO3,ZnCrO4等。电解液中的铬离子源可以是任何六价的铬盐或者化合物,例如ZnCrO4,CrO3等。
电解液中锌离子的浓度通常在约0.1-2g/l的范围内,优选地为约0.3-0.6g/l,更优选地为约0.4-0.5g/l。电解液中的铬离子的浓度通常在约0.3-5g/l的范围内,优选地为约0.5-3g/l。更优选地为约1.0g/l。
在另一个实施例中,镍的氧化物或镍金属被单独沉积或者和锌氧化物或者铬氧化物共同沉积或者和它们一起形成稳定层。用于电解液的镍离子源可以是下述材料之一或者它们的组合:如Ni2SO4,NiCO3等。
电解液中镍离子的浓度通常在约0.2g/l到约1.2g/l的范围内。
在另一个实施例中,其它的稳定层例如含磷的稳定层公开在美国专利No.5,908,544中,该专利在这里特别被引用为参考文献。
在电解液中,可包含其它的传统添加剂,例如Na2SO4,其浓度范围为约1-50g/l,优选地为约10-20g/l,更优选地为约12-18g/l。电解液的pH值通常在约3-6的范围内,优选地约4-5,更优选地为约4.8-5。
电解液的温度通常在约20℃到100℃的范围内,优选地约从25℃到45℃,更优选地为从约26℃到44℃。
如从图1中可以看出的,阳极48被设置于靠近铜箔12的每个侧面处,以便向铜箔12施加一个电流密度。导辊46是阴极辊,其中,当由一个电源(未示出)向阳极48供能时,由氧化锌和氧化铬构成的稳定层49被沉积到铜箔12的光泽侧面14和无光泽侧面16上。图3是一个剖视图,示出了在有光泽侧面14和无光泽侧面16上具有稳定层的铜箔12。
电流密度通常为约1-100安培/ft2,优选地为约25-50安培/ft2,更优选地为30安培/ft2。在采用多阳极的情况下,阳极之间的电流密度可以变化。
所用电镀时间通常在约1-30秒的范围内,优选地为约5-20秒,更优选地为约15秒。在一个实施例中,在有光泽或平滑侧面上的总处理时间为约3-10秒,在无光泽侧面上的总处理时间为约1-5秒。
在一个实施例中,在电解液中,铬离子对锌离子的摩尔比通常在0.2到10左右的范围内,优选地约为1到5,更优选地为1.4左右。
根据本发明,涂覆在铜箔12上的稳定层49的厚度为约5到70之间,优选地约为50。
在前面所示的实施例中,稳定层49包括氧化铬和氧化锌。根据本发明的另一个方面,稳定层49只由氧化铬构成。涂覆氧化铬稳定层的镀液的化学和工艺条件如下:
1-10g/l的CrO3溶液
优选为5g/l的CrO3溶液
pH-2
镀液温度:25℃
10-30安培/ft2,5-10秒
或者浸渍处理:10秒钟。
在稳定化工艺40之后,其上带有稳定层49的铜箔12经受一个在图中以标号50示出的漂洗工艺。设置在铜箔12上部和下部的喷射部件52向铜箔12(带有稳定层49)的表面上喷射水,用于漂洗和清洗所示铜箔12,以便除去残留于其上的电解液。一个设置在喷嘴52下方的槽54收集漂洗液。
其上带有稳定层49的铜箔12经受一个在图1中以标号60示出的干燥工艺。在图示的实施例中,在铜箔12的上方和下方设置一强制空气干燥器62,以将空气导向铜箔12,并干燥其表面。
根据本发明,在涂覆稳定层49之后,将一种金属真空沉积到铜箔12的一个或两个稳定化表面上。在图1所示的实施例中,金属被涂覆在铜箔12的无光泽侧面16上。所述金属可以是任何可进行真空沉积的金属,包括从铝,镍,铬,铜,铁,铟,锌,钽,锡,钒,钨,锆,钼及它们的合金中选择出来的任何一种。根据本发明,所述金属可利用真空沉积技术直接涂覆到稳定层49上,所述真空沉积技术包括诸如溅射、化学气相沉积、电子束沉积、热蒸发、离子镀(经过基底)或者这些工艺的组合。在图示的实施例中,示意性地表示出了一个溅射工艺70。如从图1可以看出的,其上带有稳定层49的铜箔12被传递到一个用标号72表示的沉积室内。一个电子束枪74将电子束射向一个由金属制成的靶76,轰击金属物质使之游离并沉积到铜箔12的表面上。在图中所示的实施例中,沉积工艺将一种金属涂覆到铜箔12的无光泽侧面上。被涂覆的金属优选地具有约为50-5,000的厚度。在图示的实施例中,表示出一个单靶76。但可以理解,如果需要的话,也可使用多靶,以把金属涂覆在箔12的无光泽侧面16和有光泽侧面14两个侧面上。
在本发明的一个优选实施例中,铬被溅射沉积到作为一粘合层的铜箔12的无光泽侧面16上,以提高铜箔向基板的粘合力。已经发现,上述工艺提供了一种具有良好粘合特性的镀铬铜箔。
为了对本发明进行说明,提供了如下几个例子。除非特别声明,在下述的各实施例以及在整个说明书和权利要求书中,所有的比例和百分比都是以重量计,所有的温度都是摄氏度,所有的压力都是大气压。
例1
原始电沉积铜箔(1/3oz/ft2)的两个侧面用如下的稳定层进行预处理:
稳定化处理:
0.53g/l的ZnSO4形式的锌,0.6g/l的CrO3形式的铬,11g/l的Na2SO4
镀液pH:5.0
镀液温度:42℃
电流密度:8-15安培/ft2(无光泽侧面)
2-2.5安培/ft2(有光泽侧面)
电镀时间:有光泽侧面:6-8秒
无光泽侧面:3-4秒
然后以如下方式向稳定化层上涂覆铬:
铬溅射:
14”溅射机
功率:5-8千瓦
线速度:1.4至2.2ft/min.
铬厚度:1,200,对于无光泽侧面
1,300,对于有光泽侧面
例2
聚酰亚胺膜的两个侧面均镀铜(18微米铜/50微米聚酰亚胺/5微米铜);该产品是由Gould Electonics Inc.制造的Gould产品系列之一,并作如下处理:
稳定化处理:
0.53g/l的ZnSO4形式的锌,0.6g/l的CrO3形式的铬,11g/l的Na2SO4
镀液pH:5.0
镀液温度:42℃
电流密度:25安培/ft2,对于两个侧面
电镀时间:对任一侧或两侧:3-8秒
然后以如下方式向稳定化层上涂覆铬:
铬溅射:
14”溅射机
功率:5-8千瓦
线速度:1.8至2.8ft/min.
铬厚度:1,000,对于18微米的铜一侧
对于5微米的铜一侧不涂覆铬
例3
聚酰亚胺膜的两个侧面均镀铜(18微米铜/50微米聚酰亚胺/5微米铜);该产品是由Gould Electonics Inc.制造的Gould产品系列之一,并作如下处理:
稳定化处理:
5g/l的CrO3形式的Cr
镀液pH:2.0
镀液温度:25℃
浸渍处理
然后以如下方式在稳定化层上涂覆铬:
铬溅射:
14”溅射机
功率:5-8千瓦
线速度:1.8至2.8ft/min.
铬厚度:1,000,对于18微米铜的一侧
例4
在INVAR合金(因瓦合金)的8微米电沉积铜(8微米Cu/1.5milINVAR/8微米Cu)的两个侧面以如下方式进行稳定化层的预处理:
稳定化处理:
0.53g/l的ZnSO4形式的锌,0.6g/l的CrO3形式的铬,
11g/lNa2SO4
镀液pH:5.0
镀液温度:42℃
电流密度:25安培/ft2
电镀时间:3-4秒
然后以如下方式在稳定化层上涂覆铬:
铬溅射:
14”溅射机
功率:5-8千瓦
线速度:1.8-2.8ft/min.
铬厚度:1,000,对于8微米厚的铜一侧
上面所述为本发明的特定实施例。应当理解,该实施例仅仅是为了说明的目的进行描述的,对于熟悉本领域的人员可进行各种改变和并型而不超出本发明的主旨和范围。例如,如果工艺10是一个原始铜的电沉积工艺的延续并将原始铜直接导入工艺流程,则可以不需要清洗工艺20。进而,尽管上述工艺流程是相对于铜箔描述的,但该工艺也可用于将一种金属(例如铬)涂覆到作为一个涂覆有铜的聚合物的一部分的铜上。所有这些改变或变型都应包括在本发明的范围内。
Claims (21)
1、一种将金属涂覆到铜层上的方法,包括以下步骤:
通过向其上涂覆一个稳定层将铜层的表面稳定化,所述稳定层包括氧化锌,氧化铬,镍,氧化镍或者它们的组合物,其厚度在5-70之间;以及
把从铝,镍,铬,铜,铁,铟,锌,钽,锡,钒,钨,锆,钼及它们的合金中选择出的一种金属气相沉积到所述铜层的稳定化表面上。
2、如权利要求1所述的方法,其特征在于,所述铜层可从铜箔,聚酰亚胺上的铜或INVAR合金上的铜中选择。
3、如权利要求2所述的方法,其特征在于,所述金属是铬。
4、如权利要求3所述的方法,其特征在于,所述稳定层由氧化锌和氧化铬构成。
5、如权利要求4所述的方法,其特征在于,所述铜箔具有一个有光泽侧面和一个无光泽侧面,所述铬被涂覆在所述无光泽侧面或所述有光泽侧面上。
6、如权利要求3所述的方法,其特征在于,所述稳定层由氧化铬构成。
7、如权利要求6所述的方法,其特征在于,所述铜箔具有一个有光泽侧面和一个无光泽侧面,所述铬被涂覆在所述无光泽侧面或所述有光泽侧面上。
8、如权利要求1所述的方法,其特征在于,所述铜层是一个连续的带材,所述稳定层和气相沉积金属在一个连续的工艺过程中被涂覆。
9、一种板材,包括:
一个铜层,
一个位于所述铜层表面上的稳定层,所述稳定层由氧化锌,氧化铬或它们的组合物构成,其厚度在5-70之间;以及
一种气相沉积到所述稳定层上的金属。
10、如权利要求9所述的板材,其特征在于,所述金属选自铝,镍,铬,铜,铁,铟,锌,钽,锡,钒,钨,锆,铝及它们的合金。
11、如权利要求10所述的板材,其特征在于,所述金属为铬。
12、如权利要求11所述的板材,其特征在于,所述稳定层由氧化锌,氧化铬构成。
13、如权利要求11所述的板材,其特征在于,所述稳定层由氧化铬构成。
14、如权利要求10所述的板材,其特征在于,所述铬具有约50-5,000的厚度。
15、如权利要求10所述的板材,其特征在于,所述气相沉积金属是溅射到所述稳定层上的。
16、如权利要求15所述的板材,其特征在于,所述稳定层是用电沉积工艺涂覆的。
17、如权利要求15所述的板材,其特征在于,所述稳定层是用机械浸渍工艺涂覆的。
18、如权利要求15所述的板材,其特征在于,所述铜箔是通过电沉积制成的。
19、一种板材,包括:
一个铜层,
一个在所述铜层表面上的稳定层,所述稳定层具有约5-70的厚度,以及
一个位于所述稳定层上的气相沉积金属。
20、如权利要求19所述的板材,其特征在于,所述稳定层选自镍,氧化镍及它们的组合物。
21、如权利要求19所述的板材,其特征在于,所述稳定层含有磷。
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- 2000-02-08 US US09/500,192 patent/US6489034B1/en not_active Expired - Lifetime
- 2000-10-05 CA CA002322363A patent/CA2322363C/en not_active Expired - Fee Related
- 2000-10-05 TW TW089120719A patent/TW593756B/zh not_active IP Right Cessation
- 2000-10-20 KR KR1020000061861A patent/KR100352280B1/ko active IP Right Grant
- 2000-10-24 JP JP2000323398A patent/JP3311338B2/ja not_active Expired - Lifetime
- 2000-12-07 EP EP00204364A patent/EP1123988B1/en not_active Expired - Lifetime
- 2000-12-07 DE DE60039407T patent/DE60039407D1/de not_active Expired - Lifetime
-
2001
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100396817C (zh) * | 2001-10-30 | 2008-06-25 | 日矿金属株式会社 | 表面处理铜箔 |
CN101209605B (zh) * | 2006-12-26 | 2013-10-23 | 古河电气工业株式会社 | 表面处理铜箔 |
TWI745566B (zh) * | 2017-03-29 | 2021-11-11 | 美商康寧公司 | 基板塗覆設備和方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1123988B1 (en) | 2008-07-09 |
DE60039407D1 (de) | 2008-08-21 |
CA2322363A1 (en) | 2001-08-08 |
JP3311338B2 (ja) | 2002-08-05 |
CA2322363C (en) | 2004-09-14 |
KR100352280B1 (ko) | 2002-09-12 |
TW593756B (en) | 2004-06-21 |
CN1280448C (zh) | 2006-10-18 |
EP1123988A1 (en) | 2001-08-16 |
US6489034B1 (en) | 2002-12-03 |
JP2001220689A (ja) | 2001-08-14 |
KR20010077901A (ko) | 2001-08-20 |
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