CN111876760A - 一种印刷电路板用化学镀银液及电路板的制备方法 - Google Patents

一种印刷电路板用化学镀银液及电路板的制备方法 Download PDF

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CN111876760A
CN111876760A CN202010679124.2A CN202010679124A CN111876760A CN 111876760 A CN111876760 A CN 111876760A CN 202010679124 A CN202010679124 A CN 202010679124A CN 111876760 A CN111876760 A CN 111876760A
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宋会毫
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Guangzhou Haoyue New Energy Equipment Co ltd
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Abstract

本发明公开一种用于印刷电路板用化学镀银液，包括以下组分：水溶性银离子15～30g/L、铜离子络合剂20～50 g/L、水性离子液体缓蚀剂3.5～5g/L、稳定剂0.5～1.5 g/L、晶粒控制剂0.1～0.5g/L、迁移抑制剂1～5g/L、pH调节剂1～20g/L、pH值为5.5～6.5。通过上述化学镀银液能够有效降低后续印刷电路板制备过程中咬蚀铜线的倾向，并获得镀层致密、晶粒尺寸均匀，导电性能以及耐腐蚀性好的电路板，能够有效降低生产成本，可广泛用于印刷电路行业的生产。

Description

一种印刷电路板用化学镀银液及电路板的制备方法
技术领域
本发明涉及印制电路板制备领域，更具体涉及一种用于印刷电路板用化学镀银液及电路板的制备方法。
背景技术
在使用印刷电路的电子设备的制造中，通过将部件的引线焊接到通孔，周围的焊盘，焊盘和其他连接点(统称为“连接区域”)。为了促进这种焊接操作，要求印刷电路制造商布置通孔，焊盘，连接盘和其他连接点可以接受后续的焊接工艺。因此，这些表面必须易于被焊料润湿，并允许与电子部件的引线或表面进行整体导电连接。由于这些需求，印刷电路制设计出各种方法来增强表面的可焊性。其中镀银层有着良好的可焊、耐候和导电性能被广泛用于电路板中。
中国专利CN109423635A公开了一种印制线路板表面处理用化学镀银溶液，其特征在于：1L该化学镀银溶液由下述质量配比的原料组成：络合剂10～100克，Cu2+0.1～3.0克，表面活性剂0.5～15克，铜防氧化剂0.1～5.0克，银离子0.4～1.0克，足量硝酸将溶液酸度调整至0.08～0.3，蒸馏水加至1升。能有效保障线路板后续装配元器件的可焊性；能经得住5次回流焊而不变色；能保障对铜线的咬蚀不超铜厚的10％；能保障经24小时中性盐雾而无锈蚀或变色。然而该化学镀银溶液pH为0.08～0.3，具有很强的腐蚀性，容易对铜层过腐蚀影响电路板性能。
中国专利CN109338343A公开了一种化学镀银液，其特征在于，所述化学镀银液包括以下浓度的原料：银离子1.0～2.0g/L、铜离子络合剂5～30g/L、双噻唑类化合物0.5～1.8g/L、含氮杂吲哚类化合物0.5～1.5g/L、苯并三氮唑0.05～0.075g/L、甲烷磺酸40～60ml/L、聚苯四甲酰二苯亚胺0.5～1.3g/L。虽然考虑到银电子迁移现象，但是化学镀银液的pH值在0.5～1之间，依然存在对铜层过腐蚀的风险。
如何寻求适合于印刷电路板化学镀银用镀液依然是现有技术研究的重要方向。
发明内容
针对现有技术存在的缺陷，本发明的目的之一在于提供一种印刷电路板用化学镀银液，通过该镀银液制备的印刷电路板具有优异的可焊性、可降低银板电迁移的趋势。本发明的目的之二在于提供一种印刷电路板的制备方法。
为实现上述目的，本发明采用以下技术方案：
一种印刷电路板用化学镀银液，包括以下组分：
Figure BDA0002585213490000021
进一步地，一种印刷电路板用化学镀银液，包括以下组分：
Figure BDA0002585213490000022
进一步地，一种印刷电路板用化学镀银液，包括以下组分：
Figure BDA0002585213490000023
Figure BDA0002585213490000032
进一步地，所述水溶性银离子选自氯化银、氨基磺酸银、乙酸银中的一种或多种。
进一步地，所述铜离子络合剂选自乙酰内脲、5-甲基乙酰内脲、单甲羟基二甲基乙酰内脲中的一种或多种。
进一步地，所述水性离子液体缓蚀剂选自式(Ⅰ)中的一种或多种。
Figure BDA0002585213490000031
式(Ⅰ)；其中R1、R2、R3、R4独立的为C1～C6的烷基。C-选自氯离子或苯磺酸根离子。
进一步地，所述稳定剂2,2'-联吡啶、2-巯基苯并噻唑、硫脲及其衍生物中的一种或多种。
进一步地，所述晶粒控制剂选自聚氧乙烯山梨醇酐单棕榈酸酯、聚氧乙烯(20)山梨醇酐单月桂酸酯中的一种或多种。
进一步地，所述迁移抑制剂选自硬脂肪酸、十六烷酸、油酸中的一种或多种。
进一步地，所述pH调节剂选自氢氧化钠、氢氧化钾、乙酸、稀盐酸中的一种或几种。
一种印刷电路板的制备方法，包括以下步骤：
(1)提供陶瓷基板，清洗、粗化；
(2)磁控溅射沉积金属铜作为种子层，厚度为400～600nm；
(3)将干膜贴在陶瓷基板上，随后在50～60℃下固化5～10min；
(4)曝光、显影获得所需线路图案；
(5)电镀厚铜，厚度为25～40μm；
(6)磁控溅射制备金属镍层，厚度为300～500nm；
(7)将陶瓷基板置于印刷电路板用化学镀银液中，温度为40～60℃、时间为1～10min；
(8)去除多余的干膜；
(9)去除金属铜种子层，清洗并吹干陶瓷基体。
进一步地，步骤(2)中工艺参数：高纯金属铜作为靶材、高纯氩气流量150～300sccm、工作气压为2～5Pa，基板温度为350～450℃，溅射功率为300～400W，靶材与基板间距60～90mm，溅射时间为15～30min。
进一步地，电镀厚铜工艺参数为：硫酸铜：40～60g/L、羟基乙叉二膦酸100～150g/L、碳酸钾40～60g/L、柠檬酸钠10～40g/L、聚乙二醇1～5g/L、pH值9～11、温度30～50℃、电流密度5～10A/dm2、施镀时间15～30min。
进一步地，步骤(6)中工艺参数：高纯金属镍作为靶材、高纯氩气流量200～300sccm、工作气压3～5Pa，基板温度为350～450℃，溅射功率为350～500W，靶材与基板间距60～90mm，溅射时间为10～20min。
为了阻止或降低在印刷电路板应用中银镀层电迁移的趋势，发明人发现有必要通过在化学镀银液中添加电迁移抑制剂。合适的电迁移抑制剂硬脂肪酸、十六烷酸、油酸中的一种或多种，所述电迁移抑制剂在化学镀银液的浓度范围可以为1～5g/L，更优选为2～4g/L。在本发明的方法中使用的浸镀银溶液制备的印刷电路板具有明显的积极效果。
水性离子液体缓蚀剂能够有效形成保护膜，抑制铜层以及镍层在酸性镀液中的腐蚀。
晶粒控制剂能控制银沉积时晶粒过度的增大，可以使镀层更加致密均。电迁移抑制剂能够使金属发生电化学腐蚀时发生的电子迁移得到有效地抑制，进而避免或减弱电化学腐蚀的发生。
本发明与现有技术相比较，其具有以下有益效果：
(1)本发明所述化学镀银液不含HNO3，且pH范围在5.5～6.5内，避免了强酸以及强氧化性环境的影响，可有效降低咬蚀铜线的倾向。
(2)本发明所制备的印刷电路板表面银层致密、晶粒尺寸均匀，具有良好的导电性能(即电导率低)。
(3)显著降低了镀银层的电迁移趋势，同时也提高了银镀层的耐腐蚀性。
(4)本发明的化学镀银液稳定性好，能够有效降低生产成本。
附图说明
图1为实施例1～2制备得到的印刷电路板表面银镀层的SEM图。
图2为实施例1～2制备得到的印刷电路板的Tafel极化曲线图。
具体实施方式
下面结合具体实施例对本发明进一步说明，具体实施例的描述本质上仅仅是范例，而不是对本发明公开的内容及其应用或使用进行限制。
实施例1
一种印刷电路板用化学镀银液，包括以下组分：氯化银20g/L、乙酰内脲30g/L、水性离子液体缓蚀剂4g/L、2,2'-联吡啶1g/L、聚氧乙烯山梨醇酐单棕榈酸酯0.2g/L、十六烷酸2g/L、稀盐酸8.9g/L、去离子水余量、pH值5.9。
所述水性离子液体缓蚀剂选自
Figure BDA0002585213490000051
其中R1、R2、R3、R4均为甲基。C-为氯离子。
一种印刷电路板的制备方法，包括以下步骤：(1)提供陶瓷基板，清洗、粗化；(2)磁控溅射沉积金属铜作为种子层，厚度为466nm；其中工艺参数：高纯金属铜作为靶材、高纯氩气流量160sccm、工作气压为2.3Pa，基板温度为350℃，溅射功率为300W，靶材与基板间距80mm，溅射时间为20min。(3)将干膜贴在陶瓷基板上，随后在50℃下固化5min；(4)曝光、显影获得所需线路图案；(5)电镀厚铜，厚度为32μm；其中电镀厚铜工艺参数为：硫酸铜40g/L、羟基乙叉二膦酸120g/L、碳酸钾45g/L、柠檬酸钠20g/L、聚乙二醇1.5g/L、pH值9.8、温度40℃、电流密度6A/dm2、施镀时间18min。(6)磁控溅射制备金属镍层，厚度为400nm；其中工艺参数：高纯金属镍作为靶材、高纯氩气流量250sccm、工作气压3.6Pa，基板温度为400℃，溅射功率为500W，靶材与基板间距90mm，溅射时间为17min(7)将陶瓷基板置于上述印刷电路板用化学镀银液中，温度为45℃、时间为3min。(8)去除多余的干膜(9)去除金属铜种子层，清洗并吹干陶瓷基体。
实施例2
一种印刷电路板用化学镀银液，包括以下组分：氨基磺酸银25g/L、乙酰内脲40g/L、水性离子液体缓蚀剂4.5g/L、2-巯基苯并噻唑1.2g/L、聚氧乙烯(20)山梨醇酐单月桂酸酯0.4g/L、油酸4g/L、乙酸10.5g/L、去离子水余量、pH值6.1。所述水性离子液体缓蚀剂选自
Figure BDA0002585213490000061
其中R1、R2、R3、R4均为乙基。C-为苯磺酸根离子。
一种印刷电路板的制备方法，包括以下步骤：(1)提供陶瓷基板，清洗、粗化；(2)磁控溅射沉积金属铜作为种子层，厚度为550nm；其中工艺参数：高纯金属铜作为靶材、高纯氩气流量250sccm、工作气压为4.8Pa，基板温度为400℃，溅射功率为400W，靶材与基板间距90mm，溅射时间为25min。(3)将干膜贴在陶瓷基板上，随后在55℃下固化5min；(4)曝光、显影获得所需线路图案；(5)电镀厚铜，厚度为37μm；其中电镀厚铜工艺参数为：硫酸铜60g/L、羟基乙叉二膦酸150g/L、碳酸钾55g/L、柠檬酸钠30g/L、聚乙二醇3g/L、pH值10.2、温度45℃、电流密度8A/dm2、施镀时间25min。(6)磁控溅射制备金属镍层，厚度为500nm；其中工艺参数：高纯金属镍作为靶材、高纯氩气流量300sccm、工作气压4.5Pa，基板温度为450℃，溅射功率为450W，靶材与基板间距60mm，溅射时间为15min(7)将陶瓷基板置于上述印刷电路板用化学镀银液中，温度为50℃、时间为5min。(8)去除多余的干膜(9)去除金属铜种子层，清洗并吹干陶瓷基体。
对实施例1～2制备得到的印刷电路板表面银镀层进行扫描电镜表征。从说明书附图图1观测可知，镀银层表面致密均匀，表面形貌呈连续岛状；根据SEM测量，实施例1中晶粒尺寸分布在0.65～0.70微米、实施例2中晶粒尺寸分布在0.47～0.51微米内。由此可推断本发明化学镀银液可以控制晶粒尺寸范围，从而制备得到晶粒尺寸均匀的银层。
用四探针测量仪测量实施例1～2制备得到的印刷电路板表面银镀层的电阻率，分别为6.74×10-5、8.25×10-5Ω·cm。由此可见，本发明所制备的镀银层具有较低的电阻率，从而也就具有优异的导电性。
将印刷电路板其他部分用环氧树脂封闭留出镀银层，将其作为工作电极、饱和甘汞电极作为辅助电极、铂电极作为参比电极，置于3.5％NaCl溶液中进行Tafel极化曲线测试。表1为Tafel极化曲线拟合得到的电极腐蚀电位(Ecorr)、腐蚀电流密度(Icorr)。从拟合数据可知，腐蚀电流密度低至10～7。由此可见，本发明所制备的银镀层具有良好的耐腐蚀性能。一方面这得益于镀银层的致密结构。
表1
I<sub>corr</sub> A/cm<sup>2</sup> E<sub>corr</sub>/V
实施例1 7.85×10<sup>-7</sup> -0.32
实施例2 1.17×10<sup>-7</sup> -0.27
可焊性测试也表明了可焊性较差等级1，老化后的可焊性等级2，即老化后依然可以达到较好的可焊性。
上面所述的实施例仅仅是对本发明的优选实施方式进行描述，并非对本发明的构思和范围进行限定。在不脱离本发明设计构思的前提下，本领域普通人员对本发明的技术方案做出的各种变型和改进，均应落入到本发明的保护范围，本发明请求保护的技术内容，已经全部记载在权利要求书中。

Claims (10)

1.一种印刷电路板用化学镀银液，其特征在于，包括以下组分：
Figure FDA0002585213480000011
pH值为5.5～6.5。
2.根据权利要求1所述印刷电路板用化学镀银液，其特征在于，包括以下组分：
Figure FDA0002585213480000012
pH值为5.8～6.2。
3.根据权利要求1～2任一项所述印刷电路板用化学镀银液，其特征在于，包括以下组分：
Figure FDA0002585213480000013
pH值为5.8～6.2。
4.根据权利要求1～2任一项所述印刷电路板用化学镀银液，其特征在于，所述水溶性银离子选自氯化银、氨基磺酸银、乙酸银中的一种或多种；所述铜离子络合剂选自乙酰内脲、5-甲基乙酰内脲、单甲羟基二甲基乙酰内脲中的一种或多种。
5.根据权利要求1～2任一项所述印刷电路板用化学镀银液，其特征在于，所述水性离子液体缓蚀剂选自式(Ⅰ)中的一种或多种；
Figure FDA0002585213480000021
式(Ⅰ)；其中R1、R2、R3、R4独立的为C1～C6的烷基；C-选自氯离子或苯磺酸根离子。
6.根据权利要求1～2任一项所述印刷电路板用化学镀银液，其特征在于，所述稳定剂2,2'-联吡啶、2-巯基苯并噻唑、硫脲及其衍生物中的一种或多种；所述晶粒控制剂选自聚氧乙烯山梨醇酐单棕榈酸酯、聚氧乙烯(20)山梨醇酐单月桂酸酯中的一种或多种；所述迁移抑制剂选自硬脂肪酸、十六烷酸、油酸中的一种或多种；所述pH调节剂选自氢氧化钠、氢氧化钾、乙酸、稀盐酸中的一种或几种。
7.一种印刷电路板的制备方法，其特征在于，包括以下步骤：
(1)提供陶瓷基板，清洗、粗化；
(2)磁控溅射沉积金属铜作为种子层，厚度为400～600nm；
(3)将干膜贴在陶瓷基板上，随后在50～60℃下固化5～10min；
(4)曝光、显影获得所需线路图案；
(5)电镀厚铜，厚度为25～40μm；
(6)磁控溅射制备金属镍层，厚度为300～500nm；
(7)将陶瓷基板置于权利要求1～6任一项所述一种印刷电路板用化学镀银液中，温度为40～60℃、时间为1～10min；
(8)去除多余的干膜；
(9)去除金属铜种子层，清洗并吹干陶瓷基体。
8.根据权利要求7所述印刷电路板的制备方法，其特征在于，步骤(2)中工艺参数：高纯金属铜作为靶材、高纯氩气流量150～300sccm、工作气压为2～5Pa，基板温度为350～450℃，溅射功率为300～400W，靶材与基板间距60～90mm，溅射时间为15～30min。
9.根据权利要求7～8任一项所述印刷电路板的制备方法，其特征在于，电镀厚铜工艺参数为：硫酸铜：40～60g/L、羟基乙叉二膦酸100～150g/L、碳酸钾40～60g/L、柠檬酸钠10～40g/L、聚乙二醇1～5g/L、pH值9～11、温度30～50℃、电流密度5～10A/dm2、施镀时间15～30min。
10.根据权利要求7～8任一项所述印刷电路板的制备方法，其特征在于，步骤(6)中工艺参数：高纯金属镍作为靶材、高纯氩气流量200～300sccm、工作气压3～5Pa，基板温度为350～450℃，溅射功率为350～500W，靶材与基板间距60～90mm，溅射时间为10～20min。
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