CN104540983B - 非氰系电解镀金液 - Google Patents

非氰系电解镀金液 Download PDF

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CN104540983B
CN104540983B CN201380041203.9A CN201380041203A CN104540983B CN 104540983 B CN104540983 B CN 104540983B CN 201380041203 A CN201380041203 A CN 201380041203A CN 104540983 B CN104540983 B CN 104540983B
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gold
plating liquid
gold plating
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cyanogen
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CN104540983A (zh
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露木纯子
伊东正浩
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EEJA Ltd
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Abstract

本发明提供一种非氰(non‑cyanogen)系电解镀金液，其即使在进行热处理时，也可形成可维持高硬度的镀敷覆膜。本发明的非氰系电解镀金液，其含有包含亚硫酸金碱盐或亚硫酸金铵的金源、及包含亚硫酸盐及硫酸盐的导电盐，且当中所含铱、钌、铑的任一种的1种以上的盐的金属浓度为1至3000mg/L。同时，以含结晶调整剂为佳，特别以铊更佳。

Description

非氰系电解镀金液
技术领域
本发明是涉及一种非氰系电解镀金液，特别是涉及适于凸块形成的镀金处理中执行的非氰系电解镀金液及使用此电解镀金液的镀金方法。
背景技术
镀金处理，由于具有优良的电气特性而广泛地利用在电子、电气部件、音响机器部件等工业领域。例如，在半导体的电气组件等电子部件中形成凸块时，为确保电气接合而多利用镀金处理。
在此类镀金处理中所使用的镀金液，已提出有各种氰系及非氰系镀金液。氰系镀金液，是以氰化金盐为金的供给源，由于电镀液的稳定性高、电镀条件控制容易及电镀液本身的成本低等，一直以来常被使用。但近年来，因环境问题的观点，提出有许多非氰系电解镀金液，例如，已知有以亚硫酸金钠等亚硫酸金盐作为金的供给源(参考专利文献1、2)。
然而，近年中，所制造的电气组件的轻薄短小更为显著，使所形成的凸块也变微小，最近也施行数十μm正方的凸块的形成。形成如此微小的凸块时，热处理后的凸块的硬度成为重要的因素。在微小的凸块时，在凸块之间及与配线电路等之间间隙狭窄时，经热处理的凸块硬度小时，不只会因凸块而使电连接的信赖性降低，也有发生短路(short)等不良原因的倾向。
因此，为使热处理后的镀金硬度变高，也提出有在非氰系电解镀金液中添加有机化合物(参考专利文献2)，但也被指出有机化合物会因分解及消耗而无法确保溶液稳定性的问题。
专利文献
[专利文献1]日本专利特开2008-115449号公报
[专利文献2]日本专利特开2008-115450号公报
发明内容
[发明所欲解决的课题]
本发明是鉴于所述问题而成，其目的是提供一种非氰系电解镀金液，是在该非氰系电解镀金液中，即使进行热处理时，也可以具有高电镀硬度进行镀金处理。
[用以解决课题的手段]
本发明人等，对一直以来的非氰系电解镀金液，对各种添加剂进行研究的结果，发现本发明的镀金液。
本发明的非氰系电解镀金液，是含有包含亚硫酸金碱盐或亚硫酸金铵的金源、及包含亚硫酸盐及硫酸盐的导电盐，其中，以金属浓度1至3000mg/L含有铱、钌、铑的任一种的1种以上的盐。如依本发明，在热处理后可形成具有高硬度的镀金覆膜，即使在形成微细的金凸块时，也可有效地防止因接合时的压接力等使凸块形状的变形，例如凸块的破坏等的变形，因而可提高金凸块的信赖性。
本发明中的铱、钌、铑的任1种以上的盐，在金属浓度未达1mg/L时，会有热处理后的硬度减低的倾向，而在超过3000mg/L时，会使铱及钌不易溶解，因此有发生沉淀的倾向。在含该铱、钌的任一种或两种时，优选浓度1mg/L至50mg/L，更优选3mg/L至30mg/L。
本发明的非氰系电解镀金液，优选还含有结晶调整剂。含有结晶调整剂，即具有促进镀金的析出的效果。该结晶调整剂，优选使用铊(thallium)、铋、铅、锑等，特别优选铊。
本发明中，金源的金浓度优选5至20g/L，结晶调整剂优选1至50mg/L，导电盐优选50至300g/L。金浓度未达5g/L时，会有镀敷覆膜的结晶变粗的倾向，而在超过20g/L时在成本方面不佳。结晶调整剂未达1mg/L时，会有使热处理后的硬度变低的倾向，而在超过50mg/L时会有使镀敷覆膜的结晶变粗的倾向。
本发明的非氰系电解镀金液，优选在电流密度0.2至2.0A/dm2、液温40至65℃的条件进行电解镀敷。电流密度未达0.2A/dm2时，会有使结晶变粗的倾向，而在超过2.0A/dm2时会有电镀烧伤(plating burn)的倾向。同时，液温在未达40℃时会有使结晶变为过细的倾向，而在超过65℃时会有使结晶变粗的倾向。实际操作上，特别优选电流密度0.2至1.2A/dm2、液温50至60℃。
本发明的非氰系电解镀金液，在芯片等基板上进行电解镀金处理、构成图样，以形成金凸块及金配线时，极为适宜。以本发明的非氰系电解镀金液所形成的镀金覆膜(15μm)，即使以250℃、2小时进行热处理，也可达到维克氏(Vikers)硬度70Hv以上的硬度。同时，以本发明的非氰系电解镀金液所形成的镀金覆膜(15μm)，即使以300℃、2小时进行高温热处理，仍有达到维克氏硬度70Hv以上的高硬度的情形。
所述本发明的非氰系电解镀金液，也可再适当地添加使溶液的稳定性提高的抗氧化剂、及使析出物的平滑性增加的涂平剂、或是使电镀液的表面张力减低的界面活性剂。
在以本发明的镀金液形成镀金覆膜时，镀金覆膜中也含0.05wt％以下的铱、钌、铑。因此推测在覆膜中所含的铱、钌、铑，在进行热处理时也有维持硬镀金的作用。
发明的效果
因此以本发明的非氰系电解镀金液操作，即使以250℃热处理，也可达成高硬度的镀金覆膜。
具体实施方式
[发明的实施方式]
以下，对本发明的实施方式，再以实施例加以说明。
第一实施方式：第一实施方式中，是对含铱(Ir)的非氰系电解镀金液研究的结果加以说明。首先，于表1表示在开始时研究铱浓度的电解镀金液的各组成。
[表1]
金源：亚硫酸金钠(换算金浓度为15g/L)
Ir：铱化合物六溴铱酸钠
导电盐：亚硫酸钠50g/L
液温：60℃
电流密度：0.8A/dm2
为了比较而评定不含铱时、及超过本发明的Ir含量范围的镀金液(比较例1-1至1-3)。对各镀金液的评定，是进行镀金覆膜的硬度测定、凸块形成后的表面粗糙度及外观的观察。
预先制作如表1所示的各镀金液。将以可形成40μm×60μm大小的角形凸块(高度15μm)的方式图案化的光掩模涂布于Au溅镀芯片基板作为试验样品用基板。然后，在各镀金液，以电流密度0.8A/dm2、液温60℃，进行镀金处理。
然后，在去除光掩模后，再对角柱状的凸块表面的硬度及表面粗糙度进行测定。其结果如表1所示。
而且，硬度测定，是在氮气环境中、以250℃的热处理温度下进行2小时的各热处理，热处理前后并进行镀金的维克氏硬度的测定。维克氏硬度的测定，是使用显微硬度计＜Future-Tech株式会社制造＞，在负载15g、承载时间15秒下，测定5处并以其平均值作为硬度值。同时，表面粗糙度Ra，是以表面粗糙度测定器(Tencor：KLA-Tencor株式会社制造)进行。
由表1的结果可知，如为实施例1-1至5的镀金液时，可使其热处理后的硬度为70Hv以上，因此可维持高硬度。同时，在表面粗糙度Ra方面，也包含在实际使用时凸块的粘着特性所要求的表面粗糙度至的范围中。另一方面，在比较例1-3中，电镀液在制作时会发生沉淀，因此无法进行镀金处理。同时，在溶液组成不含铱的比较例1-1中，热处理后的硬度减低为60.5，而在溶液组成含铱0.5mg/L的比较例1-2中，热处理后的硬度降为65.1的低值。
其次，再对铱与结晶调整剂(铊)的关系研究的结果加以说明。表2表示评定的镀敷液的组成。同时，并对使用各镀金液所形成的镀金覆膜，测定其硬度及粗糙度。试验样品用基板、镀敷、测定条件是与表1所说明相同。也表示其硬度及粗糙度的结果于表2。
[表2]
金源：亚硫酸金钠(换算金浓度为15g/L)
Ir：铱化合物六溴铱酸钠
结晶调整剂：甲酸铊
导电盐：亚硫酸钠50g/L
液温：60℃
电流密度：0.8A/dm2
由表2的结果可知，通过添加作为结晶调整剂的铊，其表面粗糙度、硬度相关的特性，相较于表1所示的未添加铊的镀金液，呈现为同等或稍为更佳的结果。同时，在确认镀敷外观时，相对于未添加铊的表1，镀敷的表面粗糙而呈现具有凹凸的外观，而在添加有铊的表2时，外观为平滑的表面。
第二实施方式：在该第二实施方式中，是对含钌(Ru)的非氰系电解镀金液研究的结果加以说明。首先，表示研究钌浓度的电解镀金液的各组成于表3。
[表3]
金源：亚硫酸金钠(换算金浓度为15g/L)
Ru：氯化钌
导电盐：亚硫酸钠50g/L
液温：55℃
电流密度：0.8A/dm2
为进行比较，在不含钌时、及超过本发明的钌含量的范围的镀金液加以评定。在各镀金液的评定方面，是进行镀金覆膜硬度的测定、凸块形成后的表面粗糙度的测定。各评定方法，与第一实施方式相同，表示其结果于表3。
由表3的结果可知，如为实施例2-1至3的镀金液时，以250℃热处理后的硬度为70Hv以上，因此可维持高硬度。同时，在表面粗糙度Ra方面，也包含在实际使用时凸块的粘着特性所要求的表面粗糙度至的范围中。另一方面，如比较例2-1的情形，在不含钌时，会使热处理后的硬度减低为60Hv。而且，在钌为4000mg/L时，会使镀敷液发生沉淀，因此无法进行镀敷处理。
其次，再对钌与结晶调整剂(铊)的关系研究的结果加以说明。表4表示评定的镀敷液的组成。同时，并对使用各镀金液的镀金覆膜，测定其硬度及粗糙度。试验样品基板、镀敷、测定条件是与第一实施方式中所说明的相同。也表示其硬度及粗糙度的结果于表4。
[表4]
金源：亚硫酸金钠(换算金浓度为15g/L)
Ru：氯化钌
结晶调整剂：甲酸铊
导电盐：亚硫酸钠50g/L
液温：55℃
电流密度：0.8A/dm2
由表4的结果可知，通过添加作为结晶调整剂的铊，表面粗糙度、硬度相关的特性，相较于表3所示的未添加铊的镀金液，为同等或稍为更佳的结果。同时，在镀敷外观的确认上，相较于未添加铊的表3时的镀敷的表面呈粗糙、具有凹凸的外观，而添加有铊的表4，其外观为平滑的表面。
第三实施方式：在该第三实施方式中，是对含铑(Rh)的非氰系电解镀金液研究的结果加以说明。当中在铑方面，也合并对有无结晶调整剂(铊)加以评定。表示研究的电解镀金液的各组成于表5。
[表5]
金源：亚硫酸金钠(换算金浓度为15g/L)
Rh：硫酸铑
结晶调整剂：甲酸铊
导电盐：亚硫酸钠50g/L
液温：60℃
电流密度：0.8A/dm2
各镀金液的评定，是进行镀金覆膜的硬度测定、凸块形成后的表面粗糙度测定。各评定方法，是与第一实施方式相同。表示其结果于表5。
由表5的结果可知，如为单独添加铑、添加铑及铊的镀金液时，可使热处理后的硬度为70Hv以上，因此可维持高的硬度。同时，在表面粗糙度Ra方面，也包含在实际使用时凸块的粘着特性所要求的表面粗糙度至的范围中。另一方面，在不含铑时，会使热处理后的硬度较70Hv为低的值。同时，在镀敷外观的确认上，相较于未添加铊的实施例3-1时的镀敷表面呈粗糙、具有凹凸的外观，而在添加有铊的实施例3-2时，外观为较实施例3-1平滑的表面。
第四实施方式：在第四实施方式中，对以含铱(Ir)的非氰系电解镀金液所形成的金凸块，以300℃的高温进行热处理时加以说明。形成金凸块的电解镀金液是如下述。而且，金凸块的形成、硬度、表面粗糙度的测定，与第一实施方式相同。
金源：亚硫酸金钠(换算金浓度为15g/L)
Ir：铱化合物六溴铱酸钠(铱浓度为10mg/L)
结晶调整剂：甲酸铊(铊浓度为15mg/L)
导电盐：亚硫酸钠50g/L
液温：55℃
电流密度：0.8A/dm2
所形成的金凸块，是测定热处理前及以300℃、2小时的高温热处理后的硬度。热处理前为117.3Hv而热处理后为97.5Hv。
[产业上的可利用性]
本发明中，以非氰系电解镀金液，所形成的镀金覆膜即使进行热处理也可维持高硬度，因此可形成适宜电气组件等的凸块。

Claims (5)

1.一种非氰系电解镀金液，其其特征于含有：
包含亚硫酸金碱盐或亚硫酸金铵且金浓度为5至20g/L的金源及
包含亚硫酸盐及硫酸盐的50至300g/L的导电盐，
还含有10至100mg/L的铱及10至50mg/L的钌的任一种的1种以上的盐。
2.一种非氰系电解镀金液，其特征在于含有：
包含亚硫酸金碱盐或亚硫酸金铵且金浓度为5至20g/L的金源及
包含亚硫酸盐及硫酸盐的50至300g/L的导电盐，
还含有1至100mg/L的铱及1至50mg/L的钌的任一种的1种以上的盐，
又还含有1至50mg/L的结晶调整剂。
3.根据权利要求2所述的非氰系电解镀金液，其特征在于，所述结晶调整剂为铊。
4.一种金凸块或金配线的形成方法，是使用根据权利要求1或2所述的非氰系电解镀金液在图案化的芯片上进行电解镀金。
5.一种电子部件，是使用根据权利要求4所述的金凸块或金配线的形成方法所制造。
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