CN104294240A - 用于化学镀金属化的含有亚氨基二乙酸和衍生物的催化剂 - Google Patents
用于化学镀金属化的含有亚氨基二乙酸和衍生物的催化剂 Download PDFInfo
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Abstract
用于化学镀金属化的含有亚氨基二乙酸和衍生物的催化剂。提供了一种方法,所述方法包括:a)提供一种催化剂,所述催化剂包含金属离子和一种或多种具有下式的化合物或其盐的络合物;b)将催化剂施涂至基材上;c)向催化剂施加还原剂;并且d)将基材浸没到金属镀覆液中,从而在基材上进行金属化学镀。
Description
技术领域
本发明涉及用于化学镀金属化的含有亚氨基二乙酸(iminodiaceticacid)及其衍生物的催化剂。更具体的,本发明涉及用于在储存和化学镀金属化过程中能保持稳定的用于化学金属化的含有亚氨基二乙酸和衍生物的催化剂。
发明背景
常规的印刷线路板(PCB)包含层压的非导电性介电基材,其依赖于钻和镀通孔(PTH)在相对两侧和/或线路板的内层之间形成连接。化学镀是用于在表面上制备金属涂层的众所周知的方法。介电表面的化学镀需要先沉积催化剂。在化学镀之前,最常用的催化或活化层压的非导电性介电基材区域的方法是使用酸性氯化物介质中的锡-钯胶体水溶液处理印刷线路板。胶体包含有锡(II)离子的稳定层包围的钯金属核。[SnCl3]-络合物的壳作为表面稳定基团,以避免悬浮液中的胶体团聚。
在活化步骤中,钯基胶体吸附到绝缘基材例如环氧或聚酰亚胺上,从而活化金属化学镀沉积。理论上,对于金属化学镀沉积,催化剂颗粒在从还原剂到镀液中的金属离子之间的电子转移途经中作为载体。尽管化学镀铜的工艺的性能受到多种因素影响,例如沉积溶液的组成和配体的选择,活化步骤是控制速率和化学沉积机理的关键因素。钯/锡胶体在商业上用作金属化学沉积的催化剂已经几十年,并且它的结构已被广泛研究。然而,其对空气的敏感性和高成本给改善和/或替代留下了空间。
尽管胶体钯催化剂具有良好的性能,随着印刷线路板的制造质量提高,其具有越来越明显的诸多缺点。近年来,随着电子设备尺寸的变小和性能的提高,电子线路的封装密度变得越来越高,并且因此需要在化学镀之后没有缺陷。结果是,越来越需要可靠的替代性的催化组合物。胶体钯催化剂的稳定性也是一个关注点。如上所述,钯/锡胶体被锡(II)离子层稳定并且其对离子可以阻止钯团聚。锡(II)离子很容被易氧化为锡(IV),因此,胶体不能维持其胶体结构。通过升高温度和搅拌,可以促进这种氧化。如果使锡(II)浓度降低到接近于0,然后钯颗粒可能尺寸增加、团聚,并且沉淀。
为了寻找新的,更好的催化剂以付出相当的努力,例如因为钯的成本高,很多努力致力于发展不含钯的或双金属的替代催化剂。过去,问题包括以下事实:对于通孔电镀它们不够活化或可靠性不足,而且这些催化剂通常在存放时活性逐渐降低。这种活性降低使该催化剂不可靠并且对于商业应用来说不实用。相应地,仍然需要钯/锡的替代催化剂。
发明内容
方法包括提供一种催化剂,包含金属离子和一种或多种具有下式的化合物或其盐的络合物:
其中,R1,R2和R3可相同或不同并且为氢或具有下式的基团:
其中,Y为氢,羧基,羟基,(C1-C3)烷氧基,取代或未取代的氨基,取代或未取代的芳基,取代或未取代的脂环基,取代或未取代的杂脂环基或取代或未取代的杂芳基,Z为
n为0-15的整数,m为0-5的整数,以及r为0-5的整数,前提是:
R1,R2和R3中的至少两个同时为结构式(II)以及Y为羧基,以及R4,R5,R6,R7,R8,R9和R10可相同或不同并且为氢,羧基,羟基,直链或支化(C1-C5)烷基,直链或支化(C1-C5)羟基烷基,取代或未取代的氨基或磺酸基;
将催化剂施涂至基材上;向催化剂中施加还原剂;并且将基材浸没到金属镀覆液中,在基材上进行金属化学镀。
催化剂基本上由以下物质组成:金属离子和一种或多种具有下式的化合物或其盐:
其中,R1,R2和R3可相同或不同并且为氢或具有下式的基团:
其中,Y为氢,羧基,羟基,(C1-C3)烷氧基,取代或未取代的氨基,取代或未取代的芳基,取代或未取代的脂环基,取代或未取代的杂脂环基或取代或未取代的杂芳基,Z为
n为0-15的整数,m为0-5的整数,以及r为0-5的整数,前提是:
R1,R2和R3中的至少两个同时为结构式(II)以及Y为羧基,以及R4,R5,R6,R7,R8,R9和R10可相同或不同并且为氢,羧基,羟基,直链或支化(C1-C5)烷基,直链或支化(C1-C5)羟基烷基,取代或未取代的氨基或磺酸基。
催化剂可以用于在包括介电材料在内的基材上进行金属化学镀,并且在储存和金属化学镀过程中均能保持稳定;因为与常规的锡/钯催化剂相比,它们不易氧化。它们不需要强酸制备或保持稳定性,因而它们比常规催化剂腐蚀性更低。它们不需要用于稳定的锡化合物并且可以是无卤的,因为卤素可能是腐蚀性的。该催化剂在制造印刷线路板的过孔和通孔填充过程中具有良好的金属覆盖率。
具体实施方式
除非上下文另有明确说明,整个发明中使用的下列缩略词具有下述含义:g=克;mg=毫克;mL=毫升;L=升;cm=厘米;m=米;mm=毫米;μm=微米;ppm=百万分之一份;℃=摄氏度;g/L=克/升;min=分钟;DI=去离子的;Pd=钯;wt%=重量百分比;以及Tg=玻璃化转变温度。
在整个说明书中,术语“印刷电路板”和“印刷线路板”可互换使用。在整个说明书中,术语“镀覆”和“沉积”可互换使用。术语“基团”表示部分分子,分子片段或分子结构片段。除非另有说明,所有含量为重量百分比。所有数值范围均包括端点值并且以任意顺序组合,除非这类数值范围毫无疑义地局限于总和为100%。
水性催化剂溶液包括选自银、金、铂、钯、铜、钴和镍的金属离子,和一种或多种具有下列化学式的化合物或其盐的络合物:
其中,R1,R2和R3可相同或不同并且为氢或具有下式的基团:
其中,Y为氢,羧基,羟基,(C1-C3)烷氧基,取代或未取代的氨基,取代或未取代的芳基,取代或未取代的脂环基,取代或未取代的杂脂环基或取代或未取代的杂芳基,Z为
n为0-15,优选0-5,更优选0-2的整数,m为0-5,优选0-3,更优选0-1的整数,以及r为0-5,优选0-3,更优选0-1的整数,前提是:
R1,R2和R3中的至少两个同时为结构式(II)以及Y为羧基,当变量n,m或r为0时,相邻基团通过共价键连接在一起;以及R4,R5,R6,R7,R8,R9和R10可相同或不同并且为氢,羧基,羟基,直链或支化(C1-C5)烷基,直链或支化(C1-C5)羟基烷基,取代或未取代的氨基或磺酸基。
优选地,R1,R2和R3可相同或不同并且为氢或结构式(II),其中n,m和r为0-5,Y为氢,羧基,羟基,(C1-C3)烷氧基,取代或未取代的(C3-C6)脂环基,取代或未取代的(C5-C6)杂脂环基,取代或未取代的(C5-C6)芳基,或取代或未取代的(C5-C6)杂芳基,或磺酸基,前提是:R1,R2和R3中的至少两个为结构式(II),其中Y优选为羧基;以及R4,R5,R6,R7,R8,R9和R10可相同或不同并且优选为氢,羧基,羟基或磺酸基。更优选地,R1,R2和R3可相同或不同并且为氢或结构式(II),其中,n为0-2的整数,m为0-3的整数以及r为0-1的整数,Y为氢,羧基,羟基,甲氧基或磺酸基,前提是:R1,R2和R3中的至少两个为结构式(II),其中Y更优选为羧基;以及R4,R5,R6,R7,R8,R9和R10可相同或不同并且更优选为氢,羧基,或羟基。最优选地,R1,R2和R3可相同或不同并且为氢或结构式(II),其中,n为0-2的整数,m和r为0,Y为氢,羧基或羟基,前提是:R1,R2和R3中的至少两个为结构式(II),其中Y最优选为羧基;以及R4和R5可相同或不同并且最优选为氢,羧基,或羟基。
杂脂环基和杂芳基的杂原子包括,但不限于氮和氧。杂脂环基和杂芳基的实例为呋喃,吡啶,嘧啶和巴比妥酸。
取代基包括,但不限于:羟基,羧基,取代或未取代的氨基,酰胺基,亚氨基二乙酸,(C1-C3)烷氧基,以及(C1-C5)羟基烷基。
前述化合物的盐通常为碱金属盐。优选盐为前述化合物的钠盐或钾盐。
这类化合物的实例包括亚氨基二乙酸,N-(2-羟乙基)亚氨基二乙酸,甲基亚氨基二乙酸,次氮基三乙酸,N-(2-甲氧基乙基)亚氨基二乙酸,N-(2-羟基-羧乙基)亚氨基二乙酸,N-(2-羧乙基)亚氨基二乙酸,N-(2-羧基-丙磺酰基)亚氨基二乙酸,N-(3-甲氧基丙基)亚氨基二乙酸,N-(2-羟基-丙磺酰基)亚氨基二乙酸,N-(2-羟丙基)亚氨基二乙酸,N-(2-氨乙基)亚氨基二乙酸,N-(2-羧基-羧乙基)亚氨基二乙酸,N-(1-羧基-环戊基)亚氨基二乙酸,N-(二甲基羧甲基)亚氨基二乙酸,N-(3-二甲基氨丙基)亚氨基二乙酸,o-吡啶甲基亚氨基二乙酸,N-(2-甲基呋喃基)亚氨基二乙酸,N-(o-羟基苄基)亚氨基二乙酸,2,6-[双(羧甲基)氨甲基]-4-乙酰氨基酚,5-(N,N-双(羧甲基)氨基)-巴比妥酸,N-(羧甲基)-N-(2-羟基-磺丙基)丙氨酸,羟乙基乙二胺三乙酸,乙二胺-N,N’-二乙酸,三亚乙基四胺-N,N,N’,N”,N”’,N””-六乙酸,1,3-二氨基-2-羟基丙烷-N,N,N’,N”-四乙酸以及二亚乙基三胺五乙酸及其盐。通常盐为碱金属盐。优选盐为钠盐或钾盐。
金属离子源包括任何本领域和文献中已知的常规水溶性金属盐,其可提供具有催化活性的金属。可以使用一类催化金属离子或可以使用两种或更多催化金属的混合物。这类盐可以按提供含量为20ppm至350ppm,优选25ppm至250ppm的金属离子进行加入。银盐包括,但不限于硝酸银,乙酸银,三氟乙酸银,甲苯磺酸银,三氟甲烷磺酸银,氟化银,氧化银,硫代硫酸钠银和氰化钾银。钯盐包括,但不限于氯化钯,乙酸钯,氯化钯钾,四氯钯酸钠,以及硝酸钯。金盐包括,但不限于氰化金,三氯化金,三溴化金,氯化金钾,氰化金钾,氯化金钠和氰化金钠。铂盐包括,但不限于氯化铂和硫酸铂。铜盐包括,但不限于硫酸铜和氯化铜。镍盐包括,但不限于氯化镍和硫酸镍。钴盐包括,但不限于乙酸钴,氯化钴,溴化钴和硫酸钻铵。优选地,金属离子为银,钯和金的离子。更优选地,金属离子为银和钯的离子。最优选地,离子为钯。
组成水性催化剂的各组分可以以任何顺序混合。可使用本领域和文献中已知的任何合适的方法制备该水性催化剂。包含在水性催化剂溶液中的亚氨基二乙酸或其衍生物的络合化合物和一种或多种金属离子的含量如下:络合化合物与金属离子的摩尔比为1∶1-4∶1,优选1∶1-2∶1。一般来说,首先将一种或多种络合化合物溶解在足量水中。将一种或多种金属离子源溶解在最少量的水中,然后在搅拌下与络合化合物溶液混合,得到均匀的水溶液。通常,催化剂溶液在室温下进行制备,但是为了加速溶解一些组分,可能需要某些加热步骤。所制备的催化剂的pH值范围可以从酸性至碱性。通常,pH范围为2-11。通常酸性范围为2-6以及碱性范围为8-11。可使用足量的无机酸或有机酸或其盐以保持pH在期望范围内。也可使用无机酸和有机酸及其盐的混合物。无机酸包括,但不限于盐酸,硫酸,硼酸,磷酸和硝酸。有机酸包括,但不限于一元或多元羧酸,如二羧酸。有机酸的实例为苯甲酸,抗坏血酸,异抗坏血酸,苹果酸,马来酸,草酸,乙酸,柠檬酸和酒石酸。
在将催化剂施涂至基材之后以及金属化之前,将一种或多种还原剂施加到催化基材上,从而将金属离子还原成它们的金属状态。可使用将金属离子还原成金属的已知的常规还原剂。这类还原剂包括,但不限于二甲基胺硼烷,硼氢化钠,抗坏血酸,异抗坏血酸,次磷酸钠,水合肼,甲酸和甲醛。优选地,还原剂选自次磷酸钠。所含还原剂的量基本上可将全部金属离子还原成金属。这类含量是常规用量并且是所属领域技术人员熟知的。可使用过量还原剂,以确保所有金属离子被还原。
催化剂可用于对各种基材进行金属化学镀。这类基材包括,但不限于,包括无机和有机物质如玻璃、陶瓷、半导体、瓷器、树脂、纸、布及其组合的材料。金属包层和无金属包层材料还可是使用催化剂电镀金属的基材。
基材还包括印刷线路板。这类印刷线路板包括具有金属包层和无金属包层的热固性树脂,热塑性树脂及其混合物,包括纤维,如玻璃纤维和前述的浸液实施方式。
热塑性树脂包括,但不限于缩醛树脂,丙烯酸树脂,如丙烯酸甲酯,纤维素树脂,如乙酸乙酯,丙酸纤维素,乙酸丁酸纤维素和硝酸纤维素,聚醚,尼龙,聚乙烯,聚苯乙烯,苯乙烯掺混物,例如丙烯腈苯乙烯和共聚物和丙烯腈-丁二烯苯乙烯共聚物,聚碳酸酯,聚氯三氟乙烯,以及乙烯基聚合物和共聚物,例如乙酸乙烯酯,乙烯醇,乙烯基丁缩醛,氯乙烯,氯乙烯-乙酸酯共聚物,偏二氯乙烯和乙烯基甲醛。
热固性树脂包括,但不限于邻苯二甲酸烯丙基酯,呋喃,三聚氰胺-甲醛,酚-醛和苯酚-糠醛共聚物,单独使用或与下述树脂混合:丁二烯丙烯腈共聚物或丙烯腈-丁二烯-苯乙烯共聚物,聚丙烯酸酯,硅酮,脲醛树脂,环氧树脂,烯丙基树脂,邻苯二甲酸甘油酯以及聚酯。
多孔材料包括,但不限于纸,木材,玻璃纤维,布和纤维,例如天然和合成纤维,如棉纤维和聚酯纤维。
催化剂可用于镀覆低Tg和高Tg的树脂。低Tg树脂具有低于160℃的Tg以及高Tg树脂具有160℃及以上的Tg。通常高Tg树脂的Tg为160℃-280℃,或例如为170℃-240℃。高Tg聚合物树脂包括,但不限于聚四氟乙烯(PTFE)和聚四氟乙烯掺混物。这类掺混物包括,例如具有聚苯醚和氰酸酯的PTFE。其它类型的包含具有高Tg树脂的聚合物树脂,包括但不限于环氧树脂,如双官能团或多官能团环氧树脂,双马来酰亚胺/三嗪和环氧树脂(BT环氧),环氧/聚苯醚树脂,丙烯腈丁二烯苯乙烯,聚碳酸酯(PC),聚苯醚(PPO),聚苯醚(PPE),聚苯硫醚(PPS),聚砜(PS),聚酰胺,聚酯如聚对苯二酸乙二酯(PET)和聚对苯二酸丁二酯(PBT),聚醚醚酮(PEEK),液晶聚合物,聚氨酯,聚醚酰亚胺,环氧树脂以及它们的复合物。
催化剂可用于在印刷线路板的贯通孔或通孔壁上沉积金属。催化剂可用于生产印刷线路板的水平或垂直工艺。
水性催化剂可以与常规的金属化学镀液一起使用。可以预期,该催化剂可用于化学沉积任何可化学镀的金属,通常,金属选自铜,铜合金,镍或镍合金。更通常地,金属选自铜和铜合金,最通常地使用铜。商业途径得到的化学镀铜液的示例为CIRCUPOSITTM 880化学镀铜液(购自美国马萨诸塞州莫尔伯勒市的陶氏先进材料公司(Dow Advanced Materials,Marlborough,MA))。
通常铜离子源包括,但不限于铜的水溶性卤化物,硝酸盐,醋酸盐,硫酸盐和其它有机或无机盐。可使用一种或多种这类铜盐的混合物以得到铜离子。实例包括硫酸铜,如五水硫酸铜,氯化铜,硝酸铜,氢氧化铜和氨基磺酸铜。可在组合物中使用常规量的铜盐。通常,组合物中的铜离子浓度范围为0.5g/L至30g/L。
在化学镀组合物中,还可以包括一种或多种合金金属。这类合金金属包括,但不限于镍和锡。铜合金的实例包括铜/镍和铜/锡。通常地,铜合金为铜/镍。
用于镍和镍合金电镀液的镍离子源可以包括一种或多种常规的水溶性镍盐。镍离子源包括,但不限于,硫酸镍和卤化镍。镍离子源可以以常规的用量包含在合金化学镀组合物中。通常,所包含的镍离子源含量为0.5g/L至10g/L。
用于基材金属化的方法步骤可根据被镀覆表面是金属还是电介质而改变。从一种方法到另一种方法,特定步骤和步骤顺序还可以改变。用于对基材进行金属化学镀的常规步骤可以结合催化剂一起使用;然而,水性催化剂不需要许多传统化学镀工艺中的加速步骤,在该步骤中,锡被剥除,以使钯金属暴露出来。相应地,在使用该催化剂时,不用加速步骤。优选地,将催化剂施涂到待金属化学镀的基材表面,然后将还原剂施加到催化基材表面上并且随后施涂金属镀液。金属化学镀参数,如温度和时间可以是常规的。可使用常规的基材制备方法,如基材表面的清洁或去污,表面的粗糙化或微-粗糙化,表面的蚀刻或微-蚀刻,溶剂溶胀应用,通孔去污以及多种漂洗和防锈处理。这类方法和配方均为本领域已知和文献中公开的。
通常地,当待金属镀的基材是介电材料如在印刷线路板的表面上或贯通孔(through-hole)壁上,这类板用水清洗,以及漂洗和防锈,然后对贯通孔壁进行去污处理。通常地,首先用溶剂溶胀来预处理或软化电介质表面或贯通孔去污。
可使用任何常规的溶剂溶胀。具体的类型可根据介电材料的类型而改变。电介质的实例如上所述。可进行小型实验以确定何种类型的溶剂溶胀适用于特定的电介质材料。电介质材料的Tg经常决定所用溶剂溶胀的类型。溶剂溶胀包括,但不限于二醇醚和相应的醚乙酸酯。可使用常规量的二醇醚和相应的醚乙酸酯。常规可用的溶剂溶胀实例是CIRCUPOSITTMConditioner 3302,CIRCUPOSITTMHole Prep 3303和CIRCUPOSITTMHole Prep 4120(购自陶氏先进材料公司)。
在溶剂溶胀后,可以使用促进剂。可使用常规的促进剂。这类促进剂包括硫酸,铬酸,碱性高锰酸盐或等离子刻蚀。通常地使用碱性高锰酸钾作为促进剂。商业上可获得的促进剂的实例是CIRCUPOSITTMPromoter 4130和CIRCUPOSITTMMLB Promoter 3308(购自陶氏先进材料公司)。任选地,基材和贯通孔用水漂洗。
然后应用中和剂中和促进剂留下的残渣。可使用常规的中和剂。通常地,中和剂是含有一种或多种胺的酸性水溶液或3wt%过氧化氢和3wt%硫酸的溶液。商业上可获得的中和剂是CIRCUPOSITTMMLB Neutralizer 216-5。任选地,基底和贯通孔用水漂洗后干燥。
中和后,可以使用酸性或碱性调节剂。可用常规调节剂。这类调节剂包括一种或多种阳离子表面活性剂,非离子表面活性剂,络合剂和pH调节剂或缓冲剂。商业上可获得的酸调节剂的实例是CIRCUPOSITTMConditioner 3320和3327(购自陶氏先进材料公司)。合适的碱调节剂包括,但不限于含有一个或多个季胺和多胺的碱性表面活性剂水溶液。商业上可获得的碱性表面活性剂的例子是CIRCUPOSITTMConditioner 231,3325,813和860。任选地,基底和贯通孔用水漂洗后干燥。
调节后可以进行微-蚀刻。可使用常规的微-蚀刻组分。设计微-蚀刻以在暴露金属(例如,内层和表面蚀刻)上提供微-粗糙化的金属表面以促进随后化学镀金属的吸附和之后的电镀。微-蚀刻包括,但不限于60g/L-120g/L的过硫酸钠或过氧单硫酸钠或钾和硫酸(2%)的混合物,或者通常为硫酸/过氧化氢。商业上可获得的微-蚀刻组分的实例是CIRCUPOSITTMMicroetch 3330蚀刻溶液和PREPOSITTM748蚀刻溶液,均购自陶氏先进材料公司。任选地,基材用水漂洗。
任选地,然后将预浸施涂至微-蚀刻基材和贯通孔。预浸液的实例包括有机盐如酒石酸钠钾或柠檬酸三钠,0.5%-3%的硫酸或25g/L-75g/L氯化钠的酸性水溶液。
随后,将水性催化剂施涂到基材上。施涂可以使用现有技术中所用的常规方法进行,例如将基材浸没在催化剂溶液中,或者使用常规装置进行喷涂或原子化。催化剂停留时间可以从1分钟到10分钟变化,对于垂直装置通常从2分钟到8分钟以及对于水平装置从25秒到120秒。催化剂可以在从室温到80℃,通常从30℃到60℃的温度下进行施涂。在施涂催化剂之后,任选地,基材和贯通孔可以用水漂洗。
然后,将还原溶液施加在基材上,以便使催化剂的金属离子还原到它们的金属状态。还原溶液可以通过下列手段进行施涂,将基材浸泡在还原溶液中,将还原溶液喷涂到基材上或通过原子化施涂溶液。溶液的温度范围可以从室温到65℃,通常从30℃到55℃。在施涂金属化学镀液之前,还原溶液与催化基材的接触时间可以从30秒到5分钟变化。在施涂还原剂之后,任选地,基材和贯通孔可以用水漂洗。
随后,基材和贯通孔壁使用化学镀液进行金属的化学镀,例如铜,铜合金,镍,或镍合金。通常,铜被镀到贯通孔壁上。镀覆时间和温度可以是常规的。通常,金属沉积在20℃到80℃,更通常从30℃到60℃的温度下进行。基材可以浸泡在化学镀液中或化学镀液可以喷涂到基材上。通常,化学镀可以进行5秒钟到30分钟;然而,镀覆时间可以根据所期望的金属厚度而变化。
任选地,可以将抗变色剂施涂到金属上。可使用常规的抗变色组合物。抗变色剂的实例是ANTI TARNISHTM7130(购自陶氏先进材料公司)。基材可以任选地用水漂洗后干燥线路板。
进一步的处理可以包括通过光成像的常规处理,以及在基材上进一步的金属沉积,例如,电解的金属沉积,例如铜,铜合金,锡,锡合金。
催化剂可以用于在包括介电材料在内的基材上进行金属化学镀,并且在储存和金属化学镀过程中均能保持稳定;因为与常规的锡/钯催化剂相比,它们不易氧化。它们不需要强酸制备或保持稳定性,因而它们比常规催化剂腐蚀性更低。它们不需要用于稳定的锡化合物并且可以是无卤的,因为卤素可能是腐蚀性的。该催化剂在制造印刷线路板的过孔和通孔填充过程中具有良好的金属覆盖率。
下列实施例不是用来限制本发明的范围,而是进一步阐释它,
实施例1
通过将6.2mL份的15g/L的亚氨基二乙酸储备溶液用900mL的DI水稀释,制备在一升水中含有75ppm的钯离子和93ppm的亚氨基二乙酸的催化剂。将208mg的四氯钯酸钠溶解于最小量的DI水中,并且将其加入到亚氨基二乙酸溶液中。随后将混合物稀释到1L,并且在室温下搅拌30分钟。亚氨基二乙酸与钯离子的摩尔比是2∶1。溶液的pH值是3.4。
制备在一升水中含有75ppm的钯离子和135ppm的次氮基三乙酸的第二催化剂。将9mL份的15g/L的次氮基三乙酸储备溶液用900mL的DI水稀释。将188mg的二水硝酸钯溶解于最小量的DI水中,并且将其加入到次氮基三乙酸中。随后将混合物稀释到1L,并且在室温下搅拌30分钟。次氮基三乙酸与钯离子的摩尔比是2∶1。溶液的pH值使用1M的氢氧化钠调解至8.5。
随后使用两种催化剂根据下列方法对NY-1140非包层的层压板(购自Nan Ya)进行化学镀。
1.在50℃下,将每种非包层的层压板浸泡在CIRCUPOSITTMConditioner3325溶液中5分钟,随后用自来水漂洗4分钟。
2.在室温下,将层压板随后浸泡在PREPOSITTM 748蚀刻溶液中1分钟,并且随后用流动的DI水漂洗4分钟;
3.每个层压板在40℃下浸泡在钯离子和亚氨基二乙酸催化剂或钯离子和次氮基三乙酸催化剂的溶液中,随后用流动的DI水漂洗1分钟;
4.随后,在50℃下,将层压板浸泡在0.25M次磷酸钠溶液中1分钟,使钯离子还原成钯金属,随后用流动的DI水漂洗1分钟;
5.在40℃和pH值为13的条件下,将活化的层压板浸泡在CIRCUPOSITTM880化学镀铜液15分钟,在层压板上镀铜。
6.在镀铜之后,层压板用流动的自来水漂洗4分钟。
检查每个层压板的镀铜性,两个层压板看起来具有曲棍球状的均匀的铜沉积。
实施例2
重复实施例1的方法,除了催化剂含有70ppm的来自硝酸银的银离子,和86ppm的亚氨基二乙酸,并且制备70ppm的来自硝酸银的银离子和124ppm的次氮基三乙酸。催化剂通过与实施例1所述的实质上相同的方法制备。络合剂与银离子的摩尔比是1∶1。每种催化剂溶液的pH值是3。制备NY-1140非包层的层压板,用于实施例1所述的铜化学镀。在层压板电镀之后,检查铜沉积的质量。两个层压板具有光滑和曲棍球状的铜沉积。
实施例3
重复实施例1的方法,使用相同类型的层压板,除了催化剂溶液含有75ppm的钯离子和250ppm N-(2-羟乙基)亚氨基二乙酸。将500mg的N-(2-羟乙基)亚氨基二乙酸溶解于1900mL的DI水并且使用1M氢氧化钠将溶液的pH值调节至10.2。将375mg的水合硝酸钯溶解于最小量的DI水中,并且将其加入到含有络合剂的溶液中。随后将溶液稀释到2L,并且在室温下搅拌30分钟。溶液的最终pH值为8.5。络合剂与钯离子的摩尔比是2∶1。在层压板电镀之后,检查铜沉积的质量。层压板期望地具有光滑和曲棍球状的铜沉积。
实施例4
重复实施例1的方法,除了催化剂溶液含有75ppm的钯离子和140ppm N-(2-羧乙基)亚氨基二乙酸。将0.24g的N-(2-羧乙基)亚氨基二乙酸溶解于400mL的DI水。使用1M氢氧化钠将溶液的pH值调节至10.5。将375mg的水合硝酸钯溶解于最小量的DI水中,并且将其加入到N-(2-羧乙基)亚氨基二乙酸溶液中。随后将钯离子和N-(2-羧乙基)亚氨基二乙酸的溶液加入到含有1g酒石酸钠钾和3.8g十水合四硼酸钠的一升溶液中。该溶液在室温下搅拌30分钟。络合剂与钯离子的摩尔比是2∶1并且溶液的pH值为9。在层压板电镀之后,检查铜沉积的质量。层压板期望地具有光滑和曲棍球状的铜沉积。
实施例5
重复实施例1的方法,除了使用银离子和N-(2-羟基-羧乙基)亚氨基二乙酸催化剂活化层压板。在催化剂中包含150ppm来自乙酸银的银和460ppm的N-(2-羟基-羧乙基)亚氨基二乙酸。催化剂通过与实施例1实质上相同的方法制备。络合剂与银离子的摩尔比是1.5∶1。在层压板电镀之后,检查铜沉积的质量。层压板期望地具有光滑和曲棍球状的铜沉积。
实施例6
重复实施例1的方法,除了使用金离子和o-甲基吡啶基亚氨基二乙酸以及铂和o-甲基吡啶基亚氨基二乙酸制备催化剂。金离子由氯金酸钾提供,以及铂离子由四氯铂酸钾提供。催化剂通过与实施例1实质上相同的方法制备。金和络合物催化剂包含160ppm的金离子和182ppm的络合剂。铂和络合剂催化剂包含80ppm的铂离子和92ppm的络合剂。o-甲基吡啶基亚氨基二乙酸与金属离子的摩尔比是1∶1。步骤和参数实质上与上述实施例1相同。层压板期望地具有光滑和曲棍球状的铜沉积。
实施例7
重复实施例1的方法,除了催化剂溶液含有75ppm的钯离子和366ppm 5-(N,N-双(羧甲基)氨基)-巴比妥酸。将0.24g的5-(N,N-双(羧甲基)氨基)-巴比妥酸溶解于400mL的DI水。使用1M氢氧化钠将溶液调解至pH 10.5。将375mg的水合硝酸钯溶解于最小量的DI水中,并且将其加入到5-(N,N-双(羧甲基)氨基)-巴比妥酸溶液中。然后,将钯离子和络合物的溶液加入到含有1g柠檬酸三钠和3.8g十水四硼酸钠的一升溶液中。该溶液在室温下搅拌30分钟。络合剂与钯离子的摩尔比是2∶1并且溶液的pH值是9。在层压板电镀之后,检查铜沉积的质量。层压板期望地具有光滑和曲棍球状的铜沉积。
Claims (10)
1.一种方法,所述方法包括:
a)提供一种催化剂,所述催化剂包含金属离子和一种或多种具有下式的化合物或其盐的络合物:
其中,R1,R2和R3可相同或不同并且为氢或具有下式的基团:
其中,Y为氢,羧基,羟基,(C1-C3)烷氧基,取代或未取代的胺基,取代或未取代的氨基,取代或未取代的芳基,取代或未取代的脂环基,取代或未取代的杂脂环基,取代或未取代的杂芳基或磺酸基,Z为
n为0-15的整数,m为0-5的整数,以及r为0-5的整数,前提是:
R1,R2和R3中的至少两个同时为结构式(II)以及Y为羧基,并且R4,R5,R6,R7,R8,R9和R10可相同或不同并且为氢,羧基,羟基,直链或支化(C1-C5)烷基,直链或支化(C1-C5)羟基烷基,取代或未取代的氨基或磺酸基;
b)将催化剂施涂至基材上;
c)向催化剂施加还原剂;并且
d)将基材浸没到金属镀覆液中,从而在基材上进行金属化学镀。
2.根据权利要求1所述的方法,其中所述一种或多种化合物选自亚氨基二乙酸,N-(2-羟乙基)亚氨基二乙酸,甲基亚氨基二乙酸,次氮基三乙酸,N-(2-甲氧基乙基)亚氨基二乙酸,N-(2-羟基-羧乙基)亚氨基二乙酸,N-(2-羧乙基)亚氨基二乙酸,N-(2-羧基-丙磺酰基)亚氨基二乙酸,N-(3-甲氧基丙基)亚氨基二乙酸,N-(2-羟基-丙磺酰基)亚氨基二乙酸,N-(2-羟丙基)亚氨基二乙酸,N-(2-氨乙基)亚氨基二乙酸,N-(2-羧基-羧乙基)亚氨基二乙酸,N-(1-羧基-环戊基)亚氨基二乙酸,N-(二甲基羧甲基)亚氨基二乙酸,N-(3-二甲基氨丙基)亚氨基二乙酸,o-吡啶甲基亚氨基二乙酸,N-(2-甲基呋喃基)亚氨基二乙酸,N-(o-羟基苄基)亚氨基二乙酸,2,6-[双(羧甲基)氨甲基]-4-乙酰氨基酚,5-(N,N-双(羧甲基)氨基)-巴比妥酸,N-(羧甲基)-N-(2-羟基-磺丙基)丙氨酸,羟乙基乙二胺三乙酸,乙二胺-N,N’-二乙酸,三亚乙基四胺-N,N,N’,N”,N”’,N””-六乙酸,1,3-二氨基-2-羟基丙烷-N,N,N’,N”-四乙酸以及二亚乙基三胺五乙酸及其盐。
3.根据权利要求1所述的方法,其中所述一种或多种化合物或其盐与所述金属离子的摩尔比是1∶1-4∶1。
4.根据权利要求1所述的方法,其中所述金属离子选自钯,银,金,铂,铜,镍和钴。
5.根据权利要求1所述的方法,其中所述金属镀覆液的金属选自铜,铜合金,镍和镍合金。
6.根据权利要求1所述的方法,其中所述一种或多种化合物的含量是25ppm-1000ppm。
7.一种催化剂,所述催化剂基本上由以下物质组成:金属离子和一种或多种具有下式的化合物或其盐的络合物:
其中,R1,R2和R3可相同或不同并且为氢或具有下式的基团:
其中,Y为氢,羧基,羟基,(C1-C3)烷氧基,取代或未取代的氨基,取代或未取代的芳基,取代或未取代的脂环基,取代或未取代的杂脂环基,取代或未取代的杂芳基或磺酸基,Z为
n为0-15的整数,m为0-5的整数,以及r为0-5的整数,前提是:R1,R2和R3中的至少两个同时为结构式(II)以及Y为羧基,以及R4,R5,R6,R7,R8,R9和R10可相同或不同并且为氢,羧基,羟基,直链或支化(C1-C5)烷基,直链或支化(C1-C5)羟基烷基,取代或未取代的氨基或磺酸基。
8.根据权利要求7所述的催化剂,其中所述一种或多种化合物选自亚氨基二乙酸,N-(2-羟乙基)亚氨基二乙酸,甲基亚氨基二乙酸,次氮基三乙酸,N-(2-甲氧基乙基)亚氨基二乙酸,N-(2-羟基-羧乙基)亚氨基二乙酸,N-(2-羧乙基)亚氨基二乙酸,N-(2-羧基-丙磺酰基)亚氨基二乙酸,N-(3-甲氧基丙基)亚氨基二乙酸,N-(2-羟基-丙磺酰基)亚氨基二乙酸,N-(2-羟丙基)亚氨基二乙酸,N-(2-氨乙基)亚氨基二乙酸,N-(2-羧基-羧乙基)亚氨基二乙酸,N-(1-羧基-环戊基)亚氨基二乙酸,N-(二甲基羧甲基)亚氨基二乙酸,N-(3-二甲基氨丙基)亚氨基二乙酸,o-吡啶甲基亚氨基二乙酸,N-(2-甲基呋喃基)亚氨基二乙酸,N-(o-羟基苄基)亚氨基二乙酸,2,6-[双(羧甲基)氨甲基]-4-乙酰氨基酚,5-(N,N-双(羧甲基)氨基)-巴比妥酸,N-(羧甲基)-N-(2-羟基-磺丙基)丙氨酸,羟乙基乙二胺三乙酸,乙二胺-N,N’-二乙酸,三亚乙基四胺-N,N,N’,N”,N”’,N””-六乙酸,1,3-二氨基-2-羟基丙烷-N,N,N’,N”-四乙酸以及二亚乙基三胺五乙酸及其盐。
9.根据权利要求7所述的催化剂,其中所述一种或多种化合物或其盐与所述金属离子的摩尔比是1∶1-4∶1。
10.根据权利要求7所述的催化剂,其中所述一种或多种化合物的含量是25ppm-1000ppm。
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CN112779524A (zh) * | 2019-11-11 | 2021-05-11 | 罗门哈斯电子材料有限责任公司 | 无电镀铜以及抵消钝化 |
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JP2015020167A (ja) | 2015-02-02 |
TWI549752B (zh) | 2016-09-21 |
TW201515703A (zh) | 2015-05-01 |
EP2826562A2 (en) | 2015-01-21 |
US20150024123A1 (en) | 2015-01-22 |
KR20150009483A (ko) | 2015-01-26 |
EP2826562A3 (en) | 2015-02-11 |
JP6562597B2 (ja) | 2019-08-21 |
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