CN115404469A - 化学镀Co-W镀膜和化学镀Co-W镀液 - Google Patents
化学镀Co-W镀膜和化学镀Co-W镀液 Download PDFInfo
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- CN115404469A CN115404469A CN202210555723.2A CN202210555723A CN115404469A CN 115404469 A CN115404469 A CN 115404469A CN 202210555723 A CN202210555723 A CN 202210555723A CN 115404469 A CN115404469 A CN 115404469A
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- electroless
- plating
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- film
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- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 2
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
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- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
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- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种新的化学镀镀膜以及适合该化学镀镀膜的化学镀镀液。本发明提供的化学镀Co‑W镀膜中的W含量为35~58质量%,且所述化学镀Co‑W镀膜的膜厚为0.05μm以上。本发明的化学镀镀膜能够防止熔融焊料扩散到构成导体的金属材料中。
Description
技术领域
本发明涉及化学镀Co-W镀膜和化学镀Co-W镀液。
背景技术
在半导体的制备工序中,为了防止熔融焊料扩散到构成形成于基板上的配线焊盘等的导体的金属材料中,在焊料处理前在导体上进行例如化学镀Ni镀覆处理。然而,由于焊料处理温度随着焊料材料的无铅化而高温化,因此熔融焊料扩散到金属材料中,配线焊盘的导电性显著降低等,焊料接合部的连接可靠性恶化。
作为上述问题的对策,例如使用高磷型的Ni-P镀液在基板的金属材料上形成厚10μm左右的化学镀Ni-P镀膜。
另外,作为改善化学镀Ni-P镀膜和焊料的润湿性的技术,例如广泛使用在基板的金属材料上层叠化学镀Ni-P镀膜和膜厚0.05μm左右的化学镀Au镀膜的技术(Ni/Au镀膜)。
但是,如果使用无铅焊料,则由于回流的反复而Ni镀膜消失,或粘附性降低而接合部的连接可靠性降低,作为其对策,例如在专利文献1中公开了控制Ni/Au镀膜的镀金层的厚度。另外,专利文献2中公开了除去Ni/Au镀膜的Ni镀膜表面的Ni从而形成富P表层的技术。
现有技术文件
专利文献
专利文献1:日本发明专利公开公报特开2002-327279号
专利文献2:日本发明专利公开公报特开2010-147245号
发明内容
近年来,由于对半导体基板的高密度安装的要求,导体的窄间距化、微配线化不断发展,焊料接合部也要求薄膜化。然而,在将化学镀Ni-P镀膜进行薄膜化时,由于受热过程,熔融焊料扩散到构成导体的金属材料中,因此难以使化学镀Ni-P镀膜薄膜化。
本发明是针对上述情况而提出的,本发明的目的在于提供一种新的化学镀镀膜以及适合该化学镀镀膜的化学镀镀液,该化学镀镀膜能够防止熔融焊料扩散到构成导体的金属材料中。
能够解决上述课题的本发明的化学镀Co-W镀膜具有以下的构成。
[1]一种化学镀Co-W镀膜,其中,所述化学镀Co-W镀膜中的W含量为35~58质量%,且所述化学镀Co-W镀膜的膜厚为0.05μm以上。
[2]根据[1]所述的化学镀Co-W镀膜,其中,所述化学镀Co-W镀膜为非晶质。
[3]根据[1]或[2]所述的化学镀Co-W镀膜,其中,所述化学镀Co-W镀膜还含有B。
[4]一种层叠镀膜,其为包含[1]~[3]中任意一项所述的化学镀Co-W镀膜的层叠镀膜,
且包含Ni电镀膜或化学镀Ni-P镀膜。
[5]根据[4]所述的层叠镀膜,其中,所述化学镀Ni-P镀膜中的P含量为10~13质量%。
[6]根据[4]或[5]所述的层叠镀膜,其中,所述Ni电镀膜或所述化学镀Ni-P镀膜的膜厚为0.5~5μm。
[7]一种镀覆基材,其与被镀覆物表面接触而形成有[1]~[3]中任意一项所述的化学镀Co-W镀膜。
[8]一种镀覆基材,其为在被镀覆物上形成有[4]~[6]中任意一项所述的层叠镀膜的镀覆基材,其中,
所述化学镀Co-W镀膜与所述被镀覆物表面接触而形成,
所述Ni电镀膜或化学镀Ni-P镀膜与所述化学镀Co-W镀膜表面接触而形成。
[9]一种化学镀Co-W镀液,其为用于形成[1]~[3]中任意一项所述的化学镀Co-W镀膜的镀液,所述化学镀Co-W镀液含有:
水溶性钴盐和水溶性钨盐;以及
二烷基胺硼烷。
[10]根据[9]所述的化学镀Co-W镀液,其中,所述化学镀Co-W镀液中的所述水溶性钴盐的浓度(以Co换算)为0.2g/L以上且5g/L以下;
所述化学镀Co-W镀液中的所述水溶性钨盐的浓度(以W换算)为1g/L以上且23g/L以下。
[11]根据[9]或[10]所述的化学镀Co-W镀液,其中,所述化学镀Co-W镀液中的所述二烷基胺硼烷的浓度为1.7~8.4g/L。
如果使用本发明的化学镀Co-W镀膜,则能够防止熔融焊料扩散到构成导体的金属材料(以下,称为导体)中。另外,根据本发明,可以提供适于该化学镀Co-W镀膜的化学镀Co-W镀液。
附图说明
图1是本发明的镀覆基材的概略截面图。
图2是本发明的镀覆基材的概略截面图。
图3是实施例1的试样截面的图面代用照片。
符号的说明
1 基板
2 导体
3 化学镀Co-W镀膜
4 Ni镀膜
5 焊料
具体实施方式
本发明人对发挥能够防止熔融焊料扩散到导体中的阻挡作用的化学镀膜进行了深入研究。其结果发现,满足下述条件的化学镀Co-W镀膜发挥对熔融焊料的阻挡效果。另外,本发明人等研究的结果发现,在化学镀Co-B镀膜等、化学镀Co-W镀膜以外的化学镀镀膜中不能得到阻挡效果。虽然化学镀Co-W以外的化学镀镀膜中不能得到阻挡效果的原因可以考虑为各种原因,但例如,在化学镀镀膜形成过程中产生的氢气等导致在化学镀膜中产生缺陷等,熔融焊料从该缺陷侵入。
发挥优异的阻挡效果的本发明的化学镀Co-W镀膜,
化学镀Co-W镀膜中的W含量为35~58质量%,化学镀Co-W镀膜的膜厚为0.05μm以上。
以下,对本发明的化学镀Co-W镀膜进行说明。
化学镀Co-W镀膜的组成:W含量为35~58质量%
本发明的化学镀Co-W镀膜中的W(钨)含量为35~58质量%。使W含量为上述范围时,除了阻挡效果以外,还可得到提高与被镀覆物的粘附性的效果。W含量超过35~58质量%时,不能得到阻挡效果,另外也不能得到粘附性提高效果。特别是W含量过少时,即使是致密且均匀的化学镀Co-W镀膜,也得不到阻挡效果。
化学镀Co-W镀膜中的W含量优选为55质量%以下,更优选为53质量%以下,进一步优选为50质量%以下,优选为40质量%以上,更优选为45质量%以上。
本发明的化学镀Co-W镀膜中的Co含量没有特别限定,Co含量可以是除了上述W含量以外的余量、或者除了上述W含量和第三成分以外的余量,优选为37质量%以上,更优选为42质量%以上,进一步优选为45质量%以上,更进一步优选为50质量%以上,优选为65质量%以下,更优选为60质量%以下,进一步优选为55质量%以下。含有第三成分的情况下,优选从这些数值中除去下述第三成分含量后的值。
在本发明的化学镀Co-W镀膜中,在不阻碍阻挡效果的范围内,可以含有Co(钴)、W(钨)以外的合金成分(第三成分)。作为第三成分,例如可以举出B(硼)等。
本发明中,即使在不积极地添加第三成分的情况下,有时也会来自于镀液等而含在镀膜中。例如,B有时来自在形成化学镀Co-W镀膜时使用的化学镀Co-W镀液中的还原剂而含有。
第三成分含量过多时,镀膜的性质会变化而无法获得阻挡效果,因此第三成分含量优选为0.7质量%以下,更优选为0.3质量%以下,进一步优选为0质量%(不含第三成分)。
化学镀Co-W镀膜的膜厚:0.05μm以上
为了发挥阻挡效果,需要在被镀覆物上以规定的膜厚均匀地形成致密的化学镀Co-W镀膜。当膜厚小于0.05μm时,不能得到防扩散效果。膜厚过薄时,例如无法均匀地形成致密的化学镀Co-W镀膜,在被镀覆物的一部分产生未被化学镀Co-W镀膜覆盖的空隙(空白),熔融焊料扩散到导体。另外,膜厚过薄时,在导体等被镀覆物的表面存在瑕疵或凹部等缺陷的情况下,该缺陷部分未被覆盖,熔融焊料扩散。另外,例如膜厚过薄时,也得不到粘附性提高效果。
化学镀Co-W镀膜的膜厚需要为0.05μm以上,优选为0.1μm以上,更优选为0.15μm以上,进一步优选为0.2μm以上。从阻挡效果的观点出发,化学镀Co-W镀膜的上限没有限定,但考虑到焊料接合部的薄膜化,优选为0.6μm以下,更优选为0.3μm以下,进一步优选为0.25μm以下。
化学镀Co-W镀膜的膜质
本发明的化学镀Co-W镀膜的膜质可以是结晶质、非晶质中的任一种,优选为非晶质。非晶质膜由于没有来自晶界的熔融焊料的浸入,因此发挥比结晶质的化学镀Co-W镀膜更优异的阻挡效果。
Ni电镀膜或化学镀Ni-P镀膜
本发明也可以是包含上述化学镀Co-W镀膜、以及Ni电镀膜或化学镀Ni-P镀膜的层叠镀膜。形成Ni电镀膜或化学镀Ni-P镀膜(以下有时将两者统称为Ni镀膜)时,能够提高焊料润湿性。镀膜的形成顺序是从基板侧依次为化学镀Co-W镀膜、Ni镀膜。Ni镀膜形成在与焊料接触的最表面,由此层叠镀膜发挥优异的镀覆润湿性。
化学镀Ni-P镀膜中的P含量,只要适当调整以得到所希望的效果即可,可以是低磷型(P含量:8质量%以下)、中磷型(P含量:超过8质量%且小于10质量%)、高磷型(P含量:10~13质量%)中的任一种。在本发明中,优选结晶结构为无定形的高磷型的化学镀Ni-P镀膜。化学镀Ni-P镀膜具有无定形结构时,可以得到良好的耐腐蚀性和耐酸性。中磷型的化学镀Ni-P镀膜由于具有微晶结构和无定形结构,因此耐腐蚀性差。另外,低磷型化学镀Ni-P镀膜为微晶结构,耐腐蚀性差。另外,在本发明中,从提高化学镀Ni-P镀膜的耐腐蚀性的观点出发,优选不含硫。
Ni镀膜的膜厚没有限定,但膜厚变厚时,Ni镀膜的上述效果提高。另一方面,即使Ni镀膜的膜厚过厚,所得到的效果也饱和。本发明中,由于在被镀覆物侧形成具有阻挡效果的化学镀Co-W镀膜,因此即使Ni镀膜的膜厚比以往薄,熔融焊料也不会扩散到导体上。
Ni镀膜的膜厚优选为0.5μm以上,更优选为0.7μm以上,进一步优选为1.0μm以上,更进一步优选为2.0μm以上,优选为5μm以下,更优选为3μm以下。
镀覆基材
本发明还包括与被镀覆物表面接触而形成有化学镀Co-W镀膜的镀覆基材。本发明的化学镀Co-W镀膜通过阻挡效果能够防止熔融焊料透过化学镀Co-W镀膜。如图1所示那样,化学镀Co-W镀膜3可以与在基片1上形成的导体2的表面接触而形成,虽然未图示但根据需要在导体表面形成任意的镀膜的情况下,化学镀Co-W镀膜3也可以与该任意的镀膜表面接触而形成。
在导体表面形成本发明的化学镀Co-W镀膜时,除了阻挡效果以外,还可以得到化学镀Co-W镀膜相对于导体的高粘附性,因此优选。满足上述规定的要件的本发明的化学镀Co-W镀膜具有与构成导体的金属材料、特别是Al、Al基合金、Cu、Cu基合金的粘附性优异的效果。
作为本发明的优选结构,还包括形成有上述Ni镀膜的镀覆基材。在形成层叠镀膜的情况下,优选从基板侧依次为上述化学镀Co-W镀膜和与该化学镀Co-W镀膜表面接触而形成的Ni镀膜的2层结构,本发明中,根据需要可以为包含任意的镀膜的3层以上。在为双层结构的情况下,如图2所示那样,优选的结构是,与在基板1上形成的导体2的表面接触而形成化学镀Co-W镀膜3,与该化学镀Co-W镀膜3的表面接触而形成Ni镀膜4。
任意的镀膜可以在化学镀Co-W镀膜的下层(导体侧)、化学镀Co-W镀膜与Ni镀膜之间、Ni镀膜的上层(与导体相对的一侧)等任意的位置设置1层以上。
作为任意的镀膜,例如可以举出化学镀Au镀膜和/或化学镀Pd镀膜等。化学镀Au镀膜设置在与焊料接触的最表层时,能够提高焊料润湿性。另外,化学镀Pd镀膜设置于化学镀Au镀膜的下层时,即使在化学镀Pd镀膜的下层侧产生熔融金属,也能够防止该熔融金属向上层侧的镀膜例如化学镀Au镀膜扩散。
本发明的镀覆基材,由于镀膜整体的膜厚比以往薄,因此有助于例如印刷基板、半导体芯片等各种电子部件的薄膜化。
以下,对本发明的化学镀Co-W镀膜的形成方法进行说明。
在本发明中,优选根据需要对被镀覆物进行脱脂或活化等前处理后,形成化学镀Co-W镀膜。
作为被镀覆物,可以举出:例如在基板的表面形成的例如构成电极、配线等的导体的金属材料;在导体上形成的任意的镀膜。
在导体上形成的任意的镀膜,例如可以举出:Al、Al基合金等的Al镀膜,Cu、Cu基合金等的Cu镀膜,Ni、Ni基合金等的Ni镀膜。
作为构成导体的金属材料,只要是能够形成化学镀Co-W镀膜的材料即可,例如可以举出Al、Al基合金、Cu、Cu基合金等各种公知的金属材料,优选为Cu或Cu基合金。作为合金成分,例如可以例示:Zn、Sn、Al、Cu、Be、Fe、Mn等各种公知的合金成分。合金成分可以使用1种,也可以并用2种以上。
作为基板,例如可以举出:树脂基板、陶瓷基板、玻璃基板、晶片基板等各种公知的绝缘基板。
作为前处理,可以采用与被镀覆物的材质相应的公知的前处理。作为前处理,例如可以例示脱脂处理、软蚀刻处理、酸洗处理、预浸处理等,可以根据需要适当选择。另外,在上述处理后,也可以根据需要进行水洗处理。各前处理可以采用各种公知的处理方法、处理条件。
化学镀Co-W处理
化学镀Co-W镀覆处理是将被镀覆物浸渍在化学镀Co-W镀液中而形成化学镀Co-W镀膜。被镀覆物的浸渍时间没有特别限定,只要能够形成上述规定膜厚的化学镀Co-W镀膜即可。在化学镀Co-W镀覆处理中,根据需要也可以进行镀液的搅拌或被镀覆物的摇动。
化学镀Co-W镀液
本发明的化学镀Co-W镀液含有水溶性钴盐和水溶性钨盐作为必要成分。使用本发明的化学镀Co-W镀液对被镀覆物实施化学镀Co-W镀覆处理时,能够在被镀覆物表面形成上述化学镀Co-W镀膜。在本发明中,为了得到由化学镀Co-W镀膜产生的阻挡效果,需要适当地控制处理时的化学镀Co-W镀液的组成、温度、pH、处理时间等,形成满足上述各要件的化学镀Co-W镀膜。
水溶性钴盐
水溶性钴盐为钴离子供给源。钴离子是与钨离子一起起到阻挡层的功能的镀膜成分。
钴离子的供给源只要是释放钴离子的水溶性钴化合物即可,优选为水溶性钴盐。
作为水溶性钴盐,例如可以例示:硫酸钴、氯化钴等无机的水溶性钴盐;碳酸钴、乙酸钴等有机的水溶性钴盐。优选的钴化合物为无机水溶性钴盐,更优选为硫酸钴。它们可以使用1种,或者并用2种以上。
关于化学镀Co-W镀液中的水溶性钴盐的浓度(以Co换算),通过提高水溶性钴盐的浓度,能够提高的镀覆速度,并且得到的化学镀Co-W镀膜发挥更加优异的阻挡效果。水溶性钴盐的浓度过高时,会成为化学镀Co-W镀液的稳定性降低的原因。
化学镀Co-W镀液中的水溶性钴盐的浓度(单独含有时为单独的浓度,并用2种以上时为合计浓度:以Co换算)优选为0.2g/L以上,更优选为1.0g/L以上,进一步优选为1.5g/L以上,优选为5g/L以下,更优选为3g/L以下,进一步优选为2.5g/L以下。
另外,本发明的镀液的组成分析使用ICP发光分光分析装置进行。
水溶性钨盐
水溶性钨盐为钨离子供给源。钨离子是与钴离子一起起到阻挡层的功能的镀膜成分。
钨离子的供给源只要是释放钨离子的钨化合物即可,优选为水溶性钨盐。
作为水溶性钨酸盐,例如可以例示:氯化钨、钨酸和钨酸盐,作为钨酸盐,可以例示:钨酸钠、钨酸钾和钨酸铵。它们可以单独使用,或者并用2种以上。
关于化学镀Co-W镀液中的钨盐的浓度(以W换算),提高钨盐的浓度时,能够提高镀覆析出速度,并且得到的化学镀Co-W镀膜发挥更加优异的阻挡功能。钨盐的浓度过高时,会成为化学镀Co-W镀液的稳定性降低的原因。
化学镀Co-W镀液中的水溶性钨盐的浓度(单独含有时为单独的浓度,并用2种以上时为合计浓度:以W换算)优选为1g/L以上,更优选为3.5g/L以上,进一步优选为5.0g/L以上,更进一步优选为7.0g/L以上,优选为23g/L以下,更优选为20g/L以下,进一步优选为15g/L以下,更进一步优选为9g/L以下。另外,如果水溶性钨盐的浓度为9g/L以下,则能够得到非晶质的化学镀Co-W镀膜,因此特别优选。
还原剂
本发明中使用的还原剂只要具有钴离子和钨离子的还原析出作用即可。作为还原剂,例如可以举出:次磷酸;次磷酸钠、次磷酸钾、次磷酸铵等的次磷酸盐;如碳酸肼、硫酸肼、中性硫酸肼、盐酸肼等的肼盐、肼等的肼类;二烷基胺硼烷等。它们中优选能够形成非晶质的化学镀Co-W镀膜的二烷基胺硼烷。
另外,使用了化学镀Co-W镀液的化学镀镀膜中,含有来自二烷基胺硼烷的B。
作为二烷基胺硼烷,可以例示:二甲基胺硼烷、二乙基胺硼烷、三甲基胺硼烷等,优选为二甲基胺硼烷。二烷基胺硼烷可以使用一种或2种以上。
化学镀Co-W镀液中的还原剂的浓度,根据还原剂的种类而不同,但优选调整为能够得到充分的还原作用的浓度。考虑到镀覆析出速度,优选提高还原剂浓度,但还原剂的浓度过高时,镀液的稳定性会降低。特别是二烷基胺硼烷,优选提高二甲基胺硼烷的浓度,由此能够进一步抑制跳镀现象等的镀膜不良,能够在被镀覆物上形成致密即没有未析出部分地形成化学镀Co-W镀膜,而且能够形成没有毛边(かじり)等外观不均的均匀的化学镀Co-W镀膜。二烷基胺硼烷的浓度过高时,浴稳定性会降低。
镀液中的二烷基胺硼烷的浓度(单独含有时为单独的浓度,并用2种以上时为合计浓度),优选地,二甲基胺硼烷的浓度优选为1.7g/L以上,更优选为3.0g/L以上,进一步优选为4.0g/L以上,优选为8.4g/L以下,更优选为8g/L以下。
络合剂
本发明的化学镀Co-W镀液优选含有络合剂。络合剂对于防止钴和钨的沉淀以及控制钴和钨的析出反应是有效的。
本发明中,只要是达到上述效果的络合剂,就没有特别限定。作为络合剂,例如可以举出:柠檬酸、苹果酸、琥珀酸、乙酸、丙二酸、酒石酸、乳酸、草酸等的有机酸;甘氨酸、丙氨酸、天冬氨酸、谷氨酸等的氨基酸类;乙二胺、三乙醇胺、EDTA等的胺类。络合剂可以使用1种或2种以上。
化学镀Co-W镀液中的络合剂的浓度过低时,会发生Co或W的沉淀和镀液的分解。络合剂的浓度过高时,会产生未形成化学镀Co-W镀膜的部分。
络合剂的浓度只要以能够得到期望的效果的方式适当调整即可,优选为0.001mol/L以上,更优选为0.005mol/L以上,进一步优选为0.01mol/L以上,优选为1mol/L以下,更优选为0.5mol/L以下,进一步优选为0.1mol/L以下。
另外,作为镀液调制用的原料,可以获得的水溶性钴盐溶液或水溶性钨盐溶液中,有时预先含有络合剂。如果化学镀Co-W镀液中含有足够的来自原料的络合剂,则不需要添加,但也可以根据需要在制备后的化学镀Co-W镀液中添加络合剂。
本发明的化学镀Co-W镀液是将上述成分溶解于溶剂、优选水中而调制的。本发明的化学镀Co-W镀液中可以根据需要含有各种公知的添加剂。例如可以举出:稳定剂、pH调节剂、表面活性剂等。另外,这些添加剂有时也来自原料而含于化学镀Co-W镀液中。
添加剂等的任意成分的含量没有特别限定,优选在不阻碍本发明的化学镀Co-W镀液的浴稳定性、所形成的化学镀Co-W镀膜的阻挡性和粘附性等的范围内。
稳定剂
作为稳定剂,可以使用对镀液的稳定性具有效果的各种公知的稳定剂。
作为稳定剂,例如可以举出:硝酸铅、乙酸铅等的铅化合物;硝酸镉、乙酸镉等的镉化合物;硝酸铊、硝酸铊等的铊化合物;氯化锑、酒石酸锑钾等的锑化合物;氧化铬、硫酸铬等的铬化合物等。
稳定剂可以单独使用,或者并用2种以上。
对化学镀Co-W镀液中的稳定剂的浓度没有特别限定,只要是能够得到稳定性提高效果的程度即可。稳定剂的浓度(单独含有时为单独的浓度,并用2种以上时为合计浓度)优选为0.01mg/L以上,更优选为0.1mg/L以上,优选为100mg/L以下,更优选为10mg/L以下。
pH调节剂
作为pH调节剂,可以使用具有将镀液的pH调节为规定的值的效果的各种公知的pH调节剂。
作为pH调节剂,例如可以使用:盐酸、硫酸、磷酸等的酸;氢氧化钠、氢氧化钾、氨水等的碱。
化学镀Co-W镀液的pH过低时,钴、钨的析出速度降低,化学镀Co-W镀膜的成膜性降低,并且会在膜表面产生孔等的缺陷。另一方面,pH过高时,钴、钨的析出速度变得过快,会难以控制膜厚。
化学镀Co-W镀液的pH优选为7以上,更优选为8以上,进一步优选为9以上,优选为12以下,更优选为11以下,进一步优选为10以下。
表面活性剂
作为表面活性剂,例如可以单独使用或者并用2种以上的非离子性、阴离子性、阳离子性、两性等各种公知的表面活性剂。
对化学镀Co-W镀液中的表面活性剂的浓度没有特别限定,只要是能够得到添加效果的程度即可。表面活性剂的浓度(单独含有时为单独的浓度,并用2种以上时为合计浓度)优选为0.01mg/L以上,更优选为0.1mg/L以上,优选为100mg/L以下,更优选为10mg/L以下。
温度
化学镀Co-W镀液的处理时的液温,考虑处理时间而适当设定,以能够形成所希望的膜厚即可。液温过低时,析出速度会变慢。另一方面,液温过高时,析出速度过剩,或者来自镀液的水分蒸发量变多,液体组成会变动。
化学镀Co-W镀液的液温优选为20℃以上,更优选为25℃以上,进一步优选为50℃以上,更进一步优选为60℃以上,优选为90℃以下,更优选为80℃以下,进一步优选为75℃以下。
通过上述化学镀Co-W镀覆处理,能够在被镀覆物表面形成本发明的化学镀Co-W镀膜。
后处理
根据需要,可以对化学镀Co-W镀覆处理后的被镀覆物实施各种公知的后处理。
例如,根据需要实施酸洗处理、水洗处理,除去残留在化学镀Co-W镀膜上的不需要的镀膜成分等。酸洗处理可以采用各种公知的酸洗方法、酸洗条件。
在形成了Co-W镀膜的被镀覆物上,可以进一步形成化学镀Ni-P镀膜或Ni电镀膜。形成化学镀Ni-P镀膜或Ni电镀膜时,能够提高焊料润湿性。
化学镀Ni-P镀覆处理
在进行化学镀Ni-P镀覆处理时,在化学镀Ni-W镀膜表面析出镍,并且磷被共析,形成化学镀Ni-P镀膜。化学镀Ni-P镀覆处理条件可以采用各种公知的化学镀Ni-P镀液、镀覆处理条件。
化学镀Ni-P镀液
化学镀Ni-P镀液的组成,可以使用与用途相应的组成,没有特别限定。化学镀Ni-P镀液例如优选为含有水溶性镍盐和还原剂的镀液。
水溶性镍盐为镍离子供给源,可以使用释放镍离子的各种公知的水溶性镍盐。水溶性镍盐例如可以举出:硫酸镍、氯化镍、次磷酸镍等的无机的水溶性镍盐,以及乙酸镍、苹果酸镍等的有机的水溶性镍盐等。它们可以使用1种,或者并用2种以上。
化学镀Ni-P镀液中的水溶性镍盐的浓度,可以根据用途适当选择。通过提高水溶性镍盐的浓度,能够提高化学镀Ni-P镀膜的析出速度。水溶性镍盐的浓度过高时,镀液的稳定性降低,或者在形成的膜上产生凹坑。
关于化学镀Ni-P镀液中的水溶性镍盐的浓度(以Ni换算)的下限,浓度按0.5g/L以上、1g/L以上、2g/L以上、3g/L以上的顺序越高越优选。另外,水溶性镍盐的浓度的上限,浓度按20g/L以下、15g/L以下、10g/L以下的顺序越低越优选。
还原剂
还原剂可以使用公知的化学镀镍镀液用的含磷还原剂。还原剂例如可以举出次磷酸钠、次磷酸钠等的次磷酸盐。
适当地调整还原剂的浓度时,镀液中的镍离子的还原变慢,能够更有效地防止成膜花费时间和镀液的分解等。
例如次磷酸盐的浓度优选为10g/L以上,优选为40g/L以下,更优选为35g/L以下。
化学镀Ni-P镀液中的磷浓度可以使用低磷型(P含量:1~4质量%)、中磷型(超过4质量%且小于10质量%)、高磷型(10质量%~13质量%)中的任一种,根据用途适当选择即可。
络合剂
络合剂是用于防止镍化合物的沉淀并且使镍的析出反应为适度的速度的有效成分,可以使用公知的化学镀镍镀液中使用的各种公知的络合剂。作为络合剂,例如可以举出:甘氨酸、丙氨酸、精氨酸、天冬氨酸、谷氨酸等的氨基酸;乳酸、丙酸、乙醇酸、葡萄糖酸等的单羧酸;酒石酸、草酸、琥珀酸、苹果酸等的二羧酸;柠檬酸等的三羧酸等,还包括这些例示的盐。另外,作为盐,例如可以举出:钠、钾等的碱金属盐;钙等的碱土金属盐;铵盐。另外,它们可以使用1种,或者并用2种以上。
适当地调整络合剂的浓度时,能够防止氢氧化镍的沉淀、因氧化还原反应过快而导致的镀液的分解等。另外,能够防止镀镍膜的析出速度变慢、镀液的粘度变高导致的均匀析出性的降低等。
络合剂的浓度优选为0.001mol/L以上,更优选为0.002mol/L以上,优选为2mol/L以下,更优选为1mol/L以下。
另外,在作为镀液调制用的原料可以获得的水溶性镍盐溶液中,有时预先含有络合剂。如果化学镀Ni-P镀液中含有足够的来自原料的络合剂,则不需要添加,但也可以根据需要在调制后的化学镀Ni-P镀液中添加络合剂。
添加剂
在本发明的化学镀Ni-P镀液中,根据需要,也可以添加在化学镀Ni-P镀液中配合的公知的各种添加剂。作为添加剂,例如可以举出:反应促进剂、光泽剂、表面活性剂、功能赋予剂、pH调节剂、稳定剂、表面活性剂等。
另外,在本发明中,优选在化学镀Ni-P镀液中作为添加剂不含有硫系的添加剂。
pH
化学镀Ni-P镀液的pH过低时,镍的析出速度降低,成膜性降低,并且在被膜表面产生孔等的缺陷。另一方面,pH过高时,镍的析出速度变得过快,会难以控制膜厚。pH可以使用各种公知的pH调节剂来调节。
化学镀Ni-P镀液的pH优选为3以上,更优选为4以上,进一步优选为4.5以上,优选为8以下,更优选为7以下,进一步优选为6以下。
温度
化学镀Ni-P镀液的处理时的液温,考虑处理时间而适当设定,以能够形成所希望的膜厚即可。液温过低时,析出速度会变慢。另一方面,液温过高时,析出速度过剩,或者来自镀液的水分蒸发量变多,液体组成会变动。
化学镀Ni-P镀液的液温优选为20℃以上,更优选为25℃以上,进一步优选为50℃以上,优选为95℃以下,更优选为93℃以下,进一步优选为90℃以下。
Ni电镀处理
为了提高焊料润湿性,也可以在化学镀Co-W镀膜表面形成Ni电镀膜。在进行Ni电镀处理时,在化学镀Co-W镀膜表面上析出镍,形成Ni电镀膜。Ni电镀处理条件可以采用各种公知的Ni电镀液、电镀处理条件。
Ni电镀液
Ni电镀液的组成可以使用与用途相应的组成,没有特别限定。作为Ni电镀液,可以使用例如含有水溶性镍盐和缓冲剂的Ni电镀液,可以使用例如以硫酸镍为主要成分的瓦特浴和以氨基磺酸镍为主要成分的氨基磺酸浴等的各种公知的Ni电镀液。
水溶性镍盐,例如可以例示:硫酸镍、氯化镍、溴化镍、氨基磺酸镍、甲磺酸镍等。它们可以使用1种,或者并用2种以上。
水溶性镍盐的浓度越高,越能够提高电流密度,因此优选,但过高时,会导致镀覆不良。
Ni电镀液中的水溶性镍盐的浓度(以Ni换算)优选为5g/L以上,更优选为7g/L以上,优选为100g/L以下,更优选为50g/L以下。
缓冲剂
缓冲剂可以使用Ni电镀液中所使用的各种公知的缓冲剂。缓冲剂可以使用例如硼酸、柠檬酸、酒石酸、琥珀酸、醋酸等的水溶性有机羧酸或其盐。作为盐,可以例示:铵盐、镁盐、铝盐、钙盐、钡盐等。它们可以使用1种,或者并用2种以上。
Ni电镀液中的缓冲剂的浓度只要适当调整即可,例如优选为20g/L以上,更优选为40g/L以上,优选为100g/L以下,更优选为80g/L以下。
另外,在作为电镀液调制用的原料可以获得的水溶性镍盐溶液中,有时预先含有络合剂。如果Ni电镀液中含有足够的来自原料的络合剂,则无需添加,但也可以根据需要在调制后的Ni电镀液中添加络合剂。
添加剂
Ni电镀液中可以含有光泽剂、平滑剂、辅助电解质剂、凹坑防止剂等的各种公知的添加剂。
pH
Ni电镀液的pH以得到适当的电流效率的方式适当调整即可,例如优选在pH3~6之间控制。
温度
Ni电镀液的处理时的液温,考虑处理时间而适当设定,以能够形成所期望的膜厚即可。液温过低时,析出速度变慢。另一方面,液温过高时,析出速度过剩,会成为镀覆不良的原因。
Ni电镀液的液温优选为20℃以上,更优选为25℃以上,进一步优选为50℃以上,优选为90℃以下,更优选为80℃以下,进一步优选为75℃以下。
电流密度
从提高析出速度的同时形成均匀的镀膜的观点出发,阴极电流密度可以适当控制,优选为0.01A/dm2以上,更优选为0.1A/dm2以上,优选为100A/dm2以下,更优选为50A/dm2以下。
阳极
作为阳极,可以使用作为Ni电镀的阳极使用的各种公知的镍板。
实施例
以下,列举实施例对本发明进行更具体的说明,但本发明当然不受下述实施例限制,当然也可以在能够符合前、后述的主旨的范围内适当地加以变更而实施,它们均包含在本发明的技术范围内。
被镀覆物
作为被镀覆物使用霍尔槽铜板(B-60-P05,山本镀金试验器公司制备),对该铜板进行下述前处理后,进行化学镀Co-W镀覆处理。
前处理
首先,用清洁剂(ACL-007,上村工业公司制备)对上述被镀覆物进行脱脂处理(50℃,5分钟)。接着,用100g/L的过硫酸钠溶液(SPS)和10g/L的硫酸(H2SO4)溶液进行软蚀刻处理(25℃,1分钟)。接着,进行用10%硫酸(H2SO4)溶液除去蚀刻残渣的酸洗处理(25℃,1分钟)、用3%硫酸(H2SO4)溶液进行预浸处理(25℃,1分钟)。
化学镀Co-W处理
前处理后,将被镀覆物浸渍于表1所示的化学镀Co-W镀液(EPITHAS HWB-31,上村工业公司制备)中,进行化学镀Co-W镀覆处理。
实施例1、4、5、6的化学镀Co-W处理液是在容器中依次添加500mL含有硫酸钴的液体(EPITHAS HWB-31-M,上村工业公司制备)、200mL离子交换水、40mL含有水溶性钨盐的液体(EPITHAS HWB-31-W,上村工业公司制备)、80mL含有二甲基胺硼烷的液体(EPITHAS HWB-31-R,上村工业公司制备)并搅拌。添加20%氢氧化钠溶液或10%硫酸溶液进行调节,使其成为表中所示的pH。然后,一边搅拌一边加热至表1所示的浴温。
另外,对于其他实施例、比较例,也调整各液中的浓度或添加量以成为表中的浓度,制作了镀液。
化学镀Co-W镀覆处理后,使用原子吸光光度计(偏振塞曼原子吸收分光光度计ZA3300,日立高新技术科学公司制备)测定得到的化学镀Co-W镀膜的析出量。
化学镀Co-W镀膜的膜厚通过将试样沿膜厚方向通过CP加工(离子铣削加工)切断,并使用场致发射型扫描电子显微镜(FE-SEM:JSM-7800F,日本电子公司制备)测定该镀膜截面。
FE-SEM的观察条件如下。
·测定倍率:1000~50000倍
·加速电压:10kv
·照射电流编号:8
·检测器:BED-C
化学镀Co-W镀膜的膜质使用X射线衍射装置(RING-2500V,Rigaku公司制备),利用薄膜法进行X射线衍射光谱测定。测定任意3处,将3处全部为非晶质的情况记为“非晶质”,晶质只要有1处,就记为“晶质”。
X射线衍射条件如下所述。
·X射线
X射线源:CuKα射线
X射线输出电压:50kV
X射线输出电流:150mA
扫描范围:20~120°
扫描步幅:0.02°
扫描速度:3°/min
化学镀Co-W镀膜的组成
对于化学镀Co-W镀膜的组成,基于X射线光电子能谱分析法(XPS:X-rayphotoelectron spectroscopy),使用X射线光电子能谱分析装置(PHI Quantera II,ULVAC-PHI公司制备)沿膜厚方向(Depth方向)进行膜组成分析。
测定条件如下。
测定区域:直径100μm
蚀刻速率:0.8nm/min
解析速率:每3nm
另外,在使用场致发射型扫描电子显微镜(FE-SEM)对上述化学镀Co-W镀膜的膜厚进行截面观察时,使用能量分散型X射线分光器(EDS,日本电子公司制备的JED-2300F)从截面进行组成分析。另外,组成是基于XPS来判断,EDS是用于确认的参考值。
测定条件如下。
模式:定性分析
点分析:Co、W
加速电压:10kV
照射电流编号:10~12号
另外,化学镀Co-W镀膜以外的镀膜也同样地进行测定。
化学镀Ni-P镀覆处理
除了实施例6以外,将形成有上述化学镀Co-W镀膜的被镀覆物在表1所示的条件下浸渍在高磷型的化学镀Ni-P镀液(NIMUDEN DX,上村工业公司制备)中,制作在化学镀Co-W镀膜表面形成厚度1μm的化学镀Ni-P镀膜的试样。
得到的化学镀Ni-P镀膜的析出量和膜厚使用与化学镀Co-W镀膜同样的装置进行测定。
比较例3
除了使用表1的化学镀Co镀液代替化学镀Co-W镀液进行化学镀Co镀覆处理以外,与上述实施例相同地制作依次形成有化学镀Co镀膜、化学镀Ni-P镀膜的试样。化学镀Co镀液使用上村工业公司制备的EPITHAS HWB-31-M和EPITHAS HWB-31-R,与上述化学镀Co-W镀液同样地调制。
比较例4
不形成化学镀Co-W镀膜,而是在被镀覆物表面直接形成上述化学镀Ni-P镀膜,从而制成试样。
对各试样评价以下特性。
(1)化学镀Co-W镀膜的析出性
关于化学镀Co-W镀膜的析出性,通过上述FE-SEM观察将试样切断而露出的化学镀Co-W镀膜的截面,并按照以下基准进行评价。另外,测定倍率为10,000~30,000倍。
致密:基材被化学镀Co-W镀膜覆盖,未镀覆率为0%。
粗:在基材上至少存在部分未被化学镀Co-W镀膜覆盖的部位(未镀覆率超过0%)。
(2)化学镀Ni-P镀覆析出性
对于化学镀Ni-P镀膜的析出性,使用上述FE-SEM以测定倍率10,000~30,000倍观察将试样切断而露出的化学镀Ni-P镀膜的截面,按照以下基准进行评价。
致密:化学镀Co-W镀膜被化学镀Ni-P镀膜覆盖,未镀覆率为0%。
粗:在化学镀Co-W镀膜上至少存在部分未被化学镀Ni-P镀膜覆盖的部位(未镀覆率超过0%)。
(3)化学镀Co-W镀膜外观性
化学镀Co-W镀膜的外观性是使用金属显微镜(BX51M,奥林巴斯公司制备)和上述FE-SEM以测定倍率1,000~30,000倍观察化学镀Co-W镀膜截面(任意3处),并按照以下基准进行评价。
均匀:镀膜的膜厚均匀。
不均匀:有化学镀Co-W镀膜的膜厚不均匀的部位。
(4)化学镀Ni-P镀膜外观性
化学镀Ni-P镀膜的外观性是用金属显微镜和上述FE-SEM以测定倍率1,000~30,000倍观察化学镀Ni-P镀膜截面,按以下标准进行评价。
均匀:化学镀Ni-P镀膜的膜厚均匀。
不均匀:有化学镀Ni-P镀膜的膜厚不均匀的部位。
(5)阻挡性能
·阻挡层评价
使用回流设备(RSS-450-210,UniTemp公司制备)在表1所示的回流温度(TOP温度)下对各试样进行焊接处理(通过合成气体(H23%)的还原回流)。焊料材料使用千住金属公司制备的M725:Sn-Cu-Ni焊料。在焊接后,通过CP加工(离子铣削加工)切断试料,使用上述FE-SEM以测定倍率1,000~30,000观察切断面,评价了焊料材料向阻挡层和Cu基材的扩散状态。
(阻挡效果)有:在焊接处理后的Cu基材上没有熔融焊料的扩散,确认到阻挡效果。
(阻挡效果)无:在焊接处理后的Cu基材的至少一部分确认到熔融焊料的扩散,没有确认到阻挡效果。
·扩散状态评价
除了阻挡层评价以外,还评价了扩散状态。扩散状态的评价是在使用上述FE-SEM对上述切断面进行截面观察时,使用上述EDS从截面进行组成分析,再次确认有无焊料材料向Cu基材的扩散。另外,测定倍率为1,000~30,000倍。
扩散状态按以下基准进行评价。
◎:在Cu基材中未确认到焊料材料的扩散。
×:在Cu基材中确认到焊接材料的扩散。
(6)粘附性
在试样的化学镀Ni-P镀膜表面通过大气回流焊接M5螺母后,以表1所记载的强度(N)通过拉伸强度试验机(1311VC,AIKOH ENGINEERING CO.,LTD.制备)测定粘附强度。
◎:断裂部位为焊料-焊料间。
△:断裂部位为焊料-焊料间,但一部分在焊料(镀覆)-基材间断裂,可见基材。
×:断裂部位为焊料(镀覆)-基材间,可见基材。
[表1]
从以上的结果可以考察以下的内容。
实施例1~10是形成满足本发明要件的化学镀Co-W镀膜的例子。这些均显示出优异的阻挡性能。另外,还得到了粘附性提高的效果,在基材和化学镀Co-W镀膜间没有剥离。图3表示阻挡性能评价时的实施例1的评价照片。
另外,使化学镀Ni-P镀膜层叠的实施例1~5、7~10的焊料润湿性提高,在粘附性评价中,在化学镀Ni-P镀膜与焊料之间没有剥离。
没有形成化学镀Ni-P镀膜的实施例6,焊料润湿性差,不能评价粘附性。
另外,实施例1~5、8、9(300℃)与实施例7、10(280℃)相比,即使在更严格的回流温度下也显示出优异的阻挡性能。
比较例1是化学镀Co-W镀膜的膜厚薄的例子。在比较例1中,由于膜厚过薄,因此不能得到阻挡效果,确认到熔融焊料在基材中扩散。另外,得不到充分的粘附性,一部分化学镀Co-W镀膜剥离。另外,比较例1在回流温度280℃下阻挡性也同样差。
比较例2是Co-W镀膜中的W含量少的例子。在比较例2中,由于W含量少,因此确认到熔融焊料扩散到基材中。另外,与比较例1同样,不能得到充分的粘附性。另外,比较例2在回流温度280℃下阻挡性也同样差。
比较例3是形成化学镀Co-B镀膜代替化学镀Co-W镀膜的例子。在比较例3中,不能得到阻挡效果。另外,比较例3由于焊料润湿性显著差,因此无法进行粘附性试验所需的M5螺母的焊接。
比较例4是仅形成了化学镀Ni-P镀膜的例子。在比较例4中,不能得到阻挡效果。另外,由于粘附性低,因此在焊料基材间断裂。
Claims (11)
1.一种化学镀Co-W镀膜,其中,所述化学镀Co-W镀膜中的W含量为35~58质量%,且所述化学镀Co-W镀膜的膜厚为0.05μm以上。
2.根据权利要求1所述的化学镀Co-W镀膜,其中,所述化学镀Co-W镀膜为非晶质。
3.根据权利要求1或2所述的化学镀Co-W镀膜,其中,所述化学镀Co-W镀膜还含有B。
4.一种层叠镀膜,其为包含权利要求1~3中任意一项所述的化学镀Co-W镀膜的层叠镀膜,其中,该层叠镀膜包含Ni电镀膜或化学镀Ni-P镀膜。
5.根据权利要求4所述的层叠镀膜,其中,所述化学镀Ni-P镀膜中的P含量为10~13质量%。
6.根据权利要求4或5所述的层叠镀膜,其中,所述Ni电镀膜或所述化学镀Ni-P镀膜的膜厚为0.5-5μm。
7.一种镀覆基材,其与被镀覆物表面接触而形成有权利要求1~3中任意一项所述的化学镀Co-W镀膜。
8.一种镀覆基材,其为在被镀覆物上形成有权利要求4~6中任意一项所述的层叠镀膜的镀覆基材,
其中,所述化学镀Co-W镀膜与所述被镀覆物表面接触而形成,所述Ni电镀膜或化学镀Ni-P镀膜与所述化学镀Co-W镀膜表面接触而形成。
9.一种化学镀Co-W镀液,其为用于形成权利要求1~3中任意一项所述的化学镀Co-W镀膜的镀液,
其中,所述化学镀Co-W镀液含有:水溶性钴盐和水溶性钨盐;以及二烷基胺硼烷。
10.根据权利要求9所述的化学镀Co-W镀液,其中,所述化学镀Co-W镀液中的所述水溶性钴盐的浓度以Co换算为0.2g/L以上且5g/L以下;
所述化学镀Co-W镀液中的所述水溶性钨盐的浓度以W换算为1g/L以上且23g/L以下。
11.根据权利要求9或10所述的化学镀Co-W镀液,其中,所述化学镀Co-W镀液中的所述二烷基胺硼烷的浓度为1.7~8.4g/L。
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