PCB上镀锡工艺研究及其电化学过程探讨
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摘要
本文通过大量实验研究了甲基磺酸型电镀锡和化学镀锡工艺配方,分析了镀液组成和工艺条件对镀层及镀液性能的影响,得到了一种新的镀锡体系,满足PCB中不同工序的要求,并对甲基磺酸镀锡中添加剂的作用机理进行了探讨。
确定了一种甲基磺酸型电镀工艺配方,其组成和工艺条件为：甲基磺酸亚锡8.0ml/L～10.0ml/L、甲基磺酸96m1/L～112m1/L、hg11添加剂0.16g/L～0.24g/L、酚酞0.8ml/L-1.2ml/L、稳定剂0.8g/L-1.5g/L、分散剂1.0ml/L-1.4ml/L、温度为15℃～30℃、电流密度1.0A/dm2～3.0A/dm2、机械搅拌。采用SEM、AFM、金相显微镜、电化学工作站和其他检测方法,结果表明：该镀液分散能力和覆盖能力好,镀层厚度能达到3μm以上；形成了晶粒细致、平滑致密的镀层,与基体的结合强度高,能满足PCB上图形电镀的基本要求。并探讨了镀液中甲基磺酸、hgl1、酚酞和分散剂对锡沉积的作用机理。
确定了一种甲基磺酸型化学镀工艺配方。首先通过单因素实验,研究了各因素对镀锡层厚度及微观形貌的影响,阐述了各组成的作用,之后通过正交试验得到了一个最优工艺配方。该镀锡液性能稳定,镀层银白细致,结合能力强,厚度能达到0.8μm以上,适合PCB板材焊锡的需要。AFM和SEM结果说明：随着温度和时间的增加,镀锡层的厚度逐渐增加,但是表面晶粒度越来越大,造成粗糙度随之增大；另外镀液中的PH值(甲基磺酸含量)也对镀层厚度和表观质量有影响。
通过极化曲线与SEM相结合的方式研究了镀液中添加剂的作用机理。hg22能够在抑制亚锡离子在凸点的还原,减小基体附近的金属离子匮乏区的厚度,提高了镀液的分散能力和镀层表面质量,从而得到光亮镀层。XRD分析结果说明温度和时间对镀锡层的择优取向没有影响,晶面结构都是以Sn(220)和Sn(211)生长占优势,而次亚磷酸钠有利于晶面Sn(101)的形成。
In this research, by large number of experiments, the process formula of electroplating and electroless plating tin in methane sulfonic acid bath was studied, the effect of bath composition and process conditions on coating and plating solution was analysed. And then, got a new tin-plating technology can reach the different requirement of PCB. meanwhile, function and electrodeposition mechanism of addtives was disscussed.
A new process of electroplating tin in methane sulfonic acid bath was established, which process contained that:Stannous methanesulfonate 8.0ml/L～10.0ml/L、methanesulfonate 96ml/L-112ml/L、hgll 0.16g/L-0.24g/L、phenolphthalein 0.8ml/L～1.2ml/L、stablizing agent 0.8g/L-1.5g/L、dispersing agent 1.0ml/L～1.4ml/L、temperature 15℃-30℃、current density 1.0A/dm2～3.0A/dm2、mechanical agitation. Tested by SEM、AFM、Metalloscope、electrochemical measurement and other methods, the results showed the dispersion ability and coverage ability of the bath were well, the thickness of coating can reach 3μm, fine grained and smooth & compact electrodeposits were obtained, with high binding power, and the process met to the requirements of Pattern Plating. Then, electrodepositon mechanism of methanesulfonate、hg11、phenolphthalein and dispersing agent were discussed also.
A new process of electroless plating tin in methane sulfonic acid bath was established. Firstly, by single factor experiment, the effect of every factor on coating thickness and surface microstructure were disscussed, and the the role of the various components was described, afterwards, through analyzing orthogonal test result, make sure the complete composition of plating bath. The properties of bath was stable and the coating was a silvery-white & smooth deposits, with high binding power, the thickness of coating can reach 0.8μm, it could reach the requirement of solderability coating. The results showed that the coating thickness will become increase with increase of time and temperature by AFM&SEM, but the grain sizes and surface roughness of the deposits increase also; in addition, the PH of bath(methanesulfonate content) could influence the thickness and surface quality of the deposits too.
Then, studied the functon of additives by Polarization curves and SEM. The reduction of stannous ions at the pointed sites (protrusions) of the substrate. was suppressed by hg22, at the same time, the thickness of the MIDL(metal-ion denuted layer) above the substrate surface was decreased, and improved the dispersion ability and the surface quality, accordingly,obtained deposits with brightness surfaces. What is more, XRD analysis indicated that time and temperature had nothing influence on the crystal texture of tin deposits that exhibited growth orientation of crystal face (220) and (211), while the sodium hypophosphite was conducive to form crystal faces of Sn (101).
确定了一种甲基磺酸型电镀工艺配方,其组成和工艺条件为：甲基磺酸亚锡8.0ml/L～10.0ml/L、甲基磺酸96m1/L～112m1/L、hg11添加剂0.16g/L～0.24g/L、酚酞0.8ml/L-1.2ml/L、稳定剂0.8g/L-1.5g/L、分散剂1.0ml/L-1.4ml/L、温度为15℃～30℃、电流密度1.0A/dm2～3.0A/dm2、机械搅拌。采用SEM、AFM、金相显微镜、电化学工作站和其他检测方法,结果表明：该镀液分散能力和覆盖能力好,镀层厚度能达到3μm以上；形成了晶粒细致、平滑致密的镀层,与基体的结合强度高,能满足PCB上图形电镀的基本要求。并探讨了镀液中甲基磺酸、hgl1、酚酞和分散剂对锡沉积的作用机理。
确定了一种甲基磺酸型化学镀工艺配方。首先通过单因素实验,研究了各因素对镀锡层厚度及微观形貌的影响,阐述了各组成的作用,之后通过正交试验得到了一个最优工艺配方。该镀锡液性能稳定,镀层银白细致,结合能力强,厚度能达到0.8μm以上,适合PCB板材焊锡的需要。AFM和SEM结果说明：随着温度和时间的增加,镀锡层的厚度逐渐增加,但是表面晶粒度越来越大,造成粗糙度随之增大；另外镀液中的PH值(甲基磺酸含量)也对镀层厚度和表观质量有影响。
通过极化曲线与SEM相结合的方式研究了镀液中添加剂的作用机理。hg22能够在抑制亚锡离子在凸点的还原,减小基体附近的金属离子匮乏区的厚度,提高了镀液的分散能力和镀层表面质量,从而得到光亮镀层。XRD分析结果说明温度和时间对镀锡层的择优取向没有影响,晶面结构都是以Sn(220)和Sn(211)生长占优势,而次亚磷酸钠有利于晶面Sn(101)的形成。
In this research, by large number of experiments, the process formula of electroplating and electroless plating tin in methane sulfonic acid bath was studied, the effect of bath composition and process conditions on coating and plating solution was analysed. And then, got a new tin-plating technology can reach the different requirement of PCB. meanwhile, function and electrodeposition mechanism of addtives was disscussed.
A new process of electroplating tin in methane sulfonic acid bath was established, which process contained that:Stannous methanesulfonate 8.0ml/L～10.0ml/L、methanesulfonate 96ml/L-112ml/L、hgll 0.16g/L-0.24g/L、phenolphthalein 0.8ml/L～1.2ml/L、stablizing agent 0.8g/L-1.5g/L、dispersing agent 1.0ml/L～1.4ml/L、temperature 15℃-30℃、current density 1.0A/dm2～3.0A/dm2、mechanical agitation. Tested by SEM、AFM、Metalloscope、electrochemical measurement and other methods, the results showed the dispersion ability and coverage ability of the bath were well, the thickness of coating can reach 3μm, fine grained and smooth & compact electrodeposits were obtained, with high binding power, and the process met to the requirements of Pattern Plating. Then, electrodepositon mechanism of methanesulfonate、hg11、phenolphthalein and dispersing agent were discussed also.
A new process of electroless plating tin in methane sulfonic acid bath was established. Firstly, by single factor experiment, the effect of every factor on coating thickness and surface microstructure were disscussed, and the the role of the various components was described, afterwards, through analyzing orthogonal test result, make sure the complete composition of plating bath. The properties of bath was stable and the coating was a silvery-white & smooth deposits, with high binding power, the thickness of coating can reach 0.8μm, it could reach the requirement of solderability coating. The results showed that the coating thickness will become increase with increase of time and temperature by AFM&SEM, but the grain sizes and surface roughness of the deposits increase also; in addition, the PH of bath(methanesulfonate content) could influence the thickness and surface quality of the deposits too.
Then, studied the functon of additives by Polarization curves and SEM. The reduction of stannous ions at the pointed sites (protrusions) of the substrate. was suppressed by hg22, at the same time, the thickness of the MIDL(metal-ion denuted layer) above the substrate surface was decreased, and improved the dispersion ability and the surface quality, accordingly,obtained deposits with brightness surfaces. What is more, XRD analysis indicated that time and temperature had nothing influence on the crystal texture of tin deposits that exhibited growth orientation of crystal face (220) and (211), while the sodium hypophosphite was conducive to form crystal faces of Sn (101).
引文
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