CN1922340A - 在铝上电镀的方法 - Google Patents

在铝上电镀的方法 Download PDF

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CN1922340A
CN1922340A CNA2005800051765A CN200580005176A CN1922340A CN 1922340 A CN1922340 A CN 1922340A CN A2005800051765 A CNA2005800051765 A CN A2005800051765A CN 200580005176 A CN200580005176 A CN 200580005176A CN 1922340 A CN1922340 A CN 1922340A
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J·L·斯特鲁贝
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Abstract

本发明是用于后续电镀的铝表面的浸锌方法，在该方法中所述铝表面被清洁，与包含过氧化合物的酸性蚀刻溶液接触，该酸性蚀刻溶液基本上不含腐蚀性硝酸盐化合物，并用含有6～60g/l锌和100～500g/l氢氧离子的浸锌溶液接触该铝表面。为了简化废物处理，该酸性蚀刻溶液基本上不含有毒的无机氟化物化合物。参照图2特别是步骤6可以理解本发明。

Description

在铝上电镀的方法
技术领域
本发明所处领域是在铝上电镀。更具体地说，本发明涉及浸锌(zincating)方法，尤其涉及在具有铝芯内接地层(ground plane)的多层印刷线路板中形成电镀通孔的方法。
背景技术
用于铝的电镀方法需要时间长、成本高的预处理过程，以准备用于电镀的铝。实施电镀的最流行的方法是将锌的浸渍涂层施加到清洁的铝表面上的浸锌(zincate)法。在典型的在铝上镀覆金属的方法中，首先清洁铝基体以除去灰尘、脂、油，然后蚀刻以提供适合于浸锌涂层粘附的基底。然后用硝酸对蚀刻的基底进行除垢以除去表面氧化铝，然后对铝基底进行浸锌，接着进行电镀。该浸锌层是临时涂层，其在随后的电镀操作中消失。通常使用二次浸锌法，其中用硝酸剥除第一浸锌层，然后将第二浸锌层施加到铝基底上。二次浸锌工艺施加第一锌涂层，接着在50％硝酸中浸渍以剥除该锌层。然后施加比第一锌涂层均匀得多的第二锌涂层。用于对铝进行除垢和用于二次浸锌工艺的硝酸会强烈地蚀刻铜，因此常规的浸锌工艺不能用于制造印刷线路板。
标准浸锌工艺从铝表面的两步碱蚀刻开始，即在77℃(170)在缓冲的碱性清洁溶液中1～3分钟，然后于55℃(130)在氢氧化钠蚀刻溶液中0.50～1分钟。碱蚀刻在铝上留下污垢，其可以通过强酸，例如50％硝酸溶液，或25％热硫酸继之以50％硝酸溶液，或者3份硝酸和1份氢氟酸的溶液除去。在除垢之后，通过在浸锌溶液(zincatesolution)中浸渍用锌涂覆铝表面。浸锌溶液通常含有120～500g/l氢氧化钠、20～100g/l氧化锌、10～60g/l罗谢尔盐(酒石酸钾钠)或其它络合有机酸盐，如葡糖酸盐和水杨酸盐，以及添加剂如硝酸钠，铜、铁或镍盐。
每单位面积具有高元件密度的印刷线路板需要散热装置。随着半导体工业将愈来愈多的电子处理和功能放到愈来愈小的封装中，问题的复杂性增加。最重要的问题之一是将热从元件和印刷线路板中移出，并维持元件与印刷线路板之间可靠的连接。两种最常用的途径是外部无源散热器(heatsink)和内部有源散热器。
外部无源散热器是连结在印刷线路板的外层上的金属板。该金属板或是铝，或是铜。热散选取决于散热器材料、材料的厚度和散热器与印刷线路板之间的连结材料的散热性能。外部无源散热器层(heatsink plane)要求具有低密度电镀通孔的设计，这是主要的缺点。
内部有源散热器层既可作为接地层又可作为散热器。在印刷线路板内用作内接地层和散热器的铜板可被容易地层压、钻孔和电镀，为电和热的需要提供双重支撑。然而，充分的热散逸所需要的厚铜板是重的，在重量敏感的应用中的使用是有限的。
美国专利No.4,601,916(Arachtingi)描述了铝芯印刷线路板。铝芯在两面都层压以覆铜的半固化片(pregreg)。孔钻穿过铜覆层和铝芯。孔壁上暴露的铝表面用环氧树脂电泳涂覆，并通过常规技术形成印刷线路图案和电镀通孔。铝芯是无源支撑，因为在Arachtingi方法中无法制造与铝芯具有电连接的电镀通孔。
美国专利No.5,538,616(Arai)涉及制造印刷线路板的方法，如具有内部铝导体的多层印刷线路板，铝导体通过电镀通孔连接。在Arai方法中，用钯/锡催化剂处理设置有通孔的多层层压板。然后层压板经历碱性清洁溶液和酸性清洁溶液以蚀刻暴露的铝表面。在酸性清洁溶液之后用含有硝酸镍和硝酸钠的热的酸性溶液处理层压板。Arai指出，这种热的酸性硝酸镍处理导致铝的表面被纯镍以亚微米间隙取代。此镍是通过无电镀镍进一步生长的基础。在无电镀镍之后，通过常规的铜电镀来电镀通孔。
Arai的酸性清洁溶液是20％硝酸和50g/l二氟化铵。镍取代处理也是酸性硝酸处理。硝酸溶液强烈地腐蚀铜表面，如覆铜的层压板，蚀刻、点蚀铜表面，并产生有害的氮氧化物的烟雾。Arai未说明在无电镀镍之前掩蔽铜表面。除非在无电镍沉积之前掩蔽这些表面，否则外铜表面就会被无电镍镀覆。掩蔽和随后剥除掩模会给该工艺增加额外的步骤。如果不掩蔽外铜表面，表面导体图案就必须蚀刻穿过无电镍层。以精细的图案蚀刻穿过无电镍，如在多层印刷线路板中所要求的那样，是极其困难的，因为需要强蚀刻剂蚀腐蚀镍层并在镍和铜层之间形成腐蚀电池。酸性氟化物溶液例如二氟化铵是剧毒的，在它们的应用中和在处理含有它们的废溶液过程中必须采取特殊的预防措施。由于这些原因，Arai的方法尚未在印刷线路工业中获得认同。
发明内容
本发明的目的是提供一种对铝基底进行浸锌的方法；该方法避免了使用环境不友好并可能难以废物处理的硝酸和酸性氟化物。
本发明是用于后续电镀的铝表面的浸锌方法，在该方法中铝表面被清洁，与包含过氧化合物的酸性蚀刻溶液接触，该酸性蚀刻溶液基本上不含腐蚀性硝酸盐化合物，并用含有6～60g/l锌和100～500g/l氢氧离子的浸锌溶液接触铝表面。为了简化废物处理，酸性蚀刻溶液基本上不含有毒的无机氟化物化合物。
一方面，本发明是一种在有机层压板上制造印刷线路板的方法，该印刷线路板具有铝导体层和镀铜的通孔。该方法包括提供具有至少一个铝导体和与该铝导体接触的孔；清洁孔的壁和暴露的铝导体；用酸性蚀刻溶液接触孔的壁和暴露的铝导体，该酸性蚀刻溶液基本上不含腐蚀性硝酸盐；用浸锌溶液接触暴露的铝导体，该浸锌溶液含有6～60g/l锌和100～500g/l氢氧离子；用碱性电镀溶液中的铜电镀暴露的铝导体；使孔的壁金属化；电镀孔壁形成镀铜通孔，和处理具有镀铜通孔的层压板以形成成品印刷线路板。
附图说明
本发明通过附图来说明，其中图1是根据本发明制造多层印刷线路板的总的工艺流程图。
图2是显示在铝基底上浸锌和镀铜的工艺流程的图。
图3是具有铝接地层的多层印刷电路板中的电镀通孔的示意性横截面。
具体实施方式
本发明的浸锌方法从在碱性清洁溶液中蚀刻铝表面开始，接着在氢氧化钠蚀刻溶液或酸性清洁溶液中进行短暂蚀刻。这些处理在铝表面上留下污垢，其在无硝酸剥离剂溶液中剥除。无硝酸剥离剂是过氧化合物如过二硫酸盐或过硫酸盐的水溶液。一种这样的剥离剂是25g/的过一硫酸钾。过一硫酸钾可从DuPont以OxoneTM、从DegussaCorp.，Parsippany，NJ以CaratTM得到。剥离剂或蚀刻溶液后面是漂洗。
过一硫酸钾剥离剂通常含有10～100g/l的过一硫酸钾；优选的浓度是20～30g/l。在除垢之后，通过在浸锌溶液中浸渍用锌涂覆铝表面。浸锌溶液典型地含有120～500g/l氢氧化钠、20～100g/l氧化锌、10～60g/1罗谢尔盐(酒石酸钾钠)或其他络合有机酸盐如葡糖酸盐和水杨酸盐以及添加剂如硝酸钠，铜、铁或镍盐。
本发明的产品和制造该产品的方法可应用于简单的双面印刷线路板和具有至少一个铝导体层或具有铝芯的印刷线路板。然而本发明特别适用于具有多个信号层和一个或多个铝散热器和/或接地层的高密度多层线路板。
在具有铝接地层的多层板的制造中，以常规的方式通过在覆铜的基底上蚀刻希望的图案来制备内信号层。以与层压到铜接地层上时使用的相同的方式将信号层和外覆铜层层压到铝接地层上。在层压之后，穿过外覆铜层、信号层和铝接地层钻出所需要的通孔。也可以钻出任何需要的盲孔。
为了在铝散热器/接地层内形成电镀通孔，必须在铝及铜导体上和导体层之间的绝缘介质上电镀。
制备铝芯多层的方法概述于图1中。一套蚀刻的内导体层、半固体片、铝层和外覆铜层被组配并层压在一起。多层层压板被钻以通孔。
在钻孔之后准备通孔用于电镀，如图2中所示。在第一步中将多层板装到电镀架中。步骤2是在碱性清洁溶液中浸渍。可以通过循环泵搅拌碱性清洁剂溶液。合适的碱性清洁溶液是公知和广泛可得的；一种这样的溶液在55℃(130)含有35～45g/l浓度的AtotechBasiclean LpTM。AtotechTM产品可以从Atotech USA Inc.，1750Overview Drive，Rock Hill，South Carolina得到。在漂洗即步骤3之后，将多层板浸在酸性清洁剂溶液中，即图2，步骤4。一种适合的酸性清洁剂是Atotech Acid Cleaner AFTM，浓度为145～225g/l、温度为43℃(110)。步骤5是漂洗；漂洗可以是空气搅拌。步骤6是无硝酸剥离剂溶液。无硝酸剥离剂可以在室温操作并可通过循环泵搅拌。无硝酸剥离剂是过氧化合物如过二硫酸盐或过一硫酸盐的水溶液。一种这样的剥离剂是25g/l的过一硫酸钾。过一硫酸钾可从DuPont以OxoneTM、从Degussa Corp.，Parsippany，NJ以CaratTM得到。剥离剂或蚀刻溶液后是漂洗，漂洗可以是空气搅拌，即图2，步骤7。
过一硫酸钾剥离剂典型地含有10～100g/l的过一硫酸钾；优选的浓度是20～30g/l。剥离剂中的铜浓度将随时间增加。当铜浓度大于4g/l时，剥离剂的效力就较低了，优选将铜浓度控制在3g/l以下。
图2，步骤8是浸锌溶液。实施本发明的技术人员会选择适合在已用基本上不含硝酸和/或氢氟酸的除垢溶液处理的铝表面上使用的浸锌溶液。技术人员也会选择不使用使用硝酸剥离剂的“二次浸锌”工艺就可施加足够锌涂层的浸锌溶液。虽然可以使用具有无硝酸剥离剂的“二次浸锌”工艺，但是优选一次浸锌工艺。浸锌溶液可以从可从金属精加工工业供应商得到的那些中选择。优选的浸锌溶液含5～50g/l氧化锌、50～125g/l氢氧离子。更优选的浸锌溶液含6～15g/l氧化锌、55-80g/l氢氧离子。适合的、商业上可以得到的浸锌溶液是来自Taskem，Inc.，4639Van Epps Rd，Brooklyn Heights，OH的OptibondTM A&B。Optibond溶液可以在32～38℃(90～100)使用，氧化锌和氢氧化钠的浓度分别为6～12g/l和110～160g/l，并可以通过循环泵混合。
如图2中所示，步骤8即浸锌步骤后面是漂洗(步骤9)，然后在步骤10中在碱性镀铜浴中电镀浸锌的铝。优选的碱性镀铜浴是氰化铜浴。氰化铜电镀浴含30～75g/l氰化铜、50～100g/l氰化钠(或60～120g/l氰化钾)、30～60g/l碳酸钠(碳酸钾)和30～100g/l罗谢尔盐。好的碱性铜触击镀(strike)配方是40g/l氰化铜、90g/l氰化钠、25g/l碳酸钠和80g/l罗谢尔盐。可以在60℃(140)的温度和3A/dm2(12A/英尺2)的电流密度下使用这种铜触击镀浴。来自触击电镀浴的铜沉积应为2～5μm(0.1～0.2密耳)厚。如图2中所示，在碱性铜触击镀之后是漂洗、干燥和卸载(unracking)，即步骤11、12、13和14。步骤11通常是拖动(dragout)或非循环漂洗。步骤12应是在室温操作的流动漂洗。任选地，在步骤12之后，可以如图1所示的那样通过酸性铜触击镀加强碱性铜触击镀。在印刷线路板工业中通常使用光亮酸性镀铜溶液。一种这样的光亮酸性镀铜浴是来自Atotech USA Inc.，1750Overview Drive，Rock Hill，SC的Atotech BLCT。来自光亮酸性铜浴的触击镀沉积也可以是2～5μm(0.1～0.2密耳)厚。
如图1中所示，多层印刷线路板现在经历常规的多层印刷线路处理。按照美国专利No.4,683,036(Morrissey等人)，可以通过石墨处理、催化和化学镀铜、或在钯处理的表面上直接电镀实现用于通孔导电性的通孔的电介质层的金属化。在将通孔金属化之后，用干膜抗蚀剂在外铜层上形成电路图案。用光亮酸性铜电解镀覆通孔和外电路图案，并继之以电解焊锡镀覆。然后将选择性抗蚀剂施加到外电路图案上，留下暴露的接触区。从接触区剥离锡/铅板。在除去锡/铅板之后，将接触区镀以镍和金。铝基底的暴露区域和边缘也可任选镀以镍或者镍和金。剥除抗蚀剂并蚀刻外铜层以形成表面导体。优选的蚀刻剂是印刷线路板工业中通常使用的含氨铜蚀刻剂。融化焊锡镀覆的表面，使锡/铅板回流形成平滑、光亮的镀面。将多层板切割到应有的尺寸；通过Chemcoat或刷镀金保护暴露的铝，并予以最终检查。
图3示出了多层印刷线路板中的铝芯电镀通孔的横截面，通孔铜镀层坚实地连结在铝层上。在图3中，多层层压板的环氧树脂介质表示为1；通孔为2。3表示铝层，4为在内层上的铜导体。在外层上蚀刻的铜导电图案标为5，而从碱性铜触击电镀浴沉积的铜表示为6。铜通孔镀层标为7，焊锡镀层表示为8。
也可以用无电镍触击镀代替碱性铜镀来制造具有内铝导体层的多层印刷线路板(图2，步骤10)。清洁通孔的壁，暴露的铝用不含硝酸的剥离剂溶液处理(图2，步骤6)；漂洗；铝用浸锌溶液处理(图2，步骤8)；漂洗，然后用无电镍镀覆。由于铜金属不是无电镀镍的催化剂，所以内铜层不被镍镀覆。如果必要的话，为了确保内铜层不意外活化，所述层可以覆以掩模或给以正电偏压以防止镍沉积。在无电镍触击镀之后，接着进行常规处理，以制造成品多层印刷线路板。
也可以通过本方法的适当改进来制造具有盲孔、仅具有铜表面或具有其它金属表面的多层印刷线路板。这些改进对于本领域的技术人员是公知的。

Claims (12)

1.一种使铝表面浸锌以进行随后的电镀的方法，其包括：
清洁所述铝表面；
用包含过氧化合物的酸性蚀刻溶液接触所述铝表面，所述酸性蚀刻溶液基本上不含腐蚀性硝酸盐化合物；和
用浸锌溶液接触所述铝表面，所述浸锌溶液含6～60g/l锌和100～500g/l氢氧离子。
2.权利要求1的方法，其中所述酸性蚀刻溶液基本上不含无机氟化物化合物。
3.权利要求1的方法，其中所述过氧化合物选自过二硫酸、过硫酸、过二硫酸盐和过硫酸盐。
4.权利要求3的方法，其中所述过氧化合物是过二硫酸钠或过一硫酸钾。
5.权利要求1的方法，其中所述浸锌溶液含5～50g/l氧化锌和50～125g/l氢氧离子，优选其中所述浸锌溶液含6～15g/l氧化锌和55～80g/l氢氧离子。
6.权利要求1的方法，其中所述铝表面是具有至少一个铝导体层的有机层压印刷线路板上的多层印刷线路板的一部分。
7.根据权利要求6制造具有铝导体层的印刷线路板的方法，其包括：
提供具有至少一个铝导体和与该铝导体接触的孔的层压板；
清洁所述孔的壁和暴露的铝导体；
用酸性蚀刻溶液接触所述孔的壁和所述暴露的铝导体，所述酸性蚀刻溶液基本上不含腐蚀性硝酸盐；
用浸锌溶液接触所述暴露的铝导体，所述浸锌溶液含6～60g/l锌和100～500g/l氢氧离子；
用碱性电镀溶液中的铜电镀所述铝；
金属化所述孔的壁；
电镀所述孔壁以形成镀铜的通孔；和
处理具有镀铜通孔的层压板以形成成品印刷线路板。
8.权利要求7的方法，其中清洁所述孔壁和所述暴露的铝导体包括与碱性清洁溶液接触。
9.权利要求8的方法，其中清洁所述孔壁和所述暴露的铝导体还包括与酸性清洁溶液接触。
10.权利要求7的方法，其中所述碱性电镀溶液包括氰化铜电镀浴。
11.权利要求7的方法，其中用来自酸性硫酸铜电镀浴的一层铜电镀所述孔壁以形成镀铜通孔。
12.根据权利要求7制造具有铝导体层的印刷线路板的方法，其包括：
提供具有至少一个铝导体和与该铝导体接触的孔的层压板；
清洁所述孔的壁和所述暴露的铝导体；
用酸性蚀刻溶液接触所述孔的壁和所述暴露的铝导体，所述酸性蚀刻溶液基本上不含腐蚀性硝酸盐；
用浸锌溶液接触所述暴露的铝导体，所述浸锌溶液含6～60g/l锌和100～500g/l氢氧离子；
用无电镀镍溶液中的镍镀覆所述暴露的铝导体；
金属化所述孔的壁；
电镀所述孔壁以形成镀铜的通孔；和
处理具有镀铜通孔的层压板以形成成品印刷线路板。
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CN105103663A (zh) * 2012-12-07 2015-11-25 安普泰科电子韩国有限公司 印刷电路板及其制造方法
CN104105334A (zh) * 2013-04-12 2014-10-15 安普泰科电子韩国有限公司 印刷电路板及其制造方法
CN104105334B (zh) * 2013-04-12 2018-12-14 安普泰科电子韩国有限公司 印刷电路板及其制造方法
CN103225091A (zh) * 2013-05-22 2013-07-31 南通鑫平制衣有限公司 一种铝材镀铜液
CN109326530A (zh) * 2017-07-31 2019-02-12 英飞凌科技股份有限公司 将导体焊接到铝金属化物
CN109326530B (zh) * 2017-07-31 2023-06-06 英飞凌科技股份有限公司 将导体焊接到铝金属化物
TWI649612B (zh) * 2018-01-11 2019-02-01 美商微相科技股份有限公司 Mask surface treatment method for photomask
CN108336473A (zh) * 2018-02-06 2018-07-27 北京宏诚创新科技有限公司 铜-铝纳米接面常温制程方法

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US20050178669A1 (en) 2005-08-18

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