低温低应力化学镀铜溶液稳定性的研究

发布时间：2018-04-30 13:41

本文选题：化学镀铜 + 沉积速率　；参考：《陕西师范大学》2015年硕士论文

【摘要】：由于印制电路板(PCB)具有轻量化、微型化、易于标准化等优点,几乎是所有电子设备的核心部件。化学镀铜工艺是印制电路金属化的关键技术。目前,化学镀铜的工厂、车间几乎遍布世界各地,而计算机行业和航空工业的高速发展,对电子组件屏蔽信号干扰的功能提出了更高要求,进而也对化学镀铜提出了新的要求：(1)发展新的添加剂,降低成本,提高沉铜速率,提高经济效益。(2)延长化学镀铜液的寿命。化学镀铜液处于热力学不稳定状态,因此,提高其稳定性,延长使用寿命,对提高镀铜层质量、降低原材料消耗,减少环境污染。其中化学镀铜液的稳定性是决定该化学镀铜液能否应用于实际生产的关键问题,在化学镀溶液中添加各种添加剂是提高镀液稳定性的重要手段之一本文主要致力于研究化学镀铜溶液的寿命问题,为了提高镀液的稳定性,需向镀液中添加合适的稳定剂,而稳定剂的加入会导致沉积速率下降太快。因此本论文首先研究了化学镀铜溶液的加速剂,在添加加速剂的基础上,选择合适的稳定剂,通过沉积速率的测量和SEM图像的观察发现：L-苹果酸、2,6-二氨基吡啶、腺嘌呤和鸟嘌呤有比较好的加速作用；亚硫酸钠、硅酸钠、聚乙烯吡咯烷酮、FC-80、8-羟基-7-碘-5-喹啉磺酸、六氟硅酸钠、FC-134都不同程度的降低了化学镀铜的沉积速率,可作为该体系的稳定剂；并且腺嘌呤与亚硫酸钠、鸟嘌呤与高铁试剂、L-苹果酸与硅酸钠、L-苹果酸与六氟硅酸钠达成了协同作用。在本实验室已得到的低温化学镀铜体系中,分别加入适量六氟硅酸钠、FC-80、FC-134后,化学镀铜膜表面形貌得到优良的改善。然后用X-射线衍射法测定分析了铜膜的表面应力,同样在已得到的体系中,分别加入适量的上述稳定剂,研究发现只有六氟硅酸钠、FC-80、FC-134三种稳定剂能降低铜膜表面的应力,其中FC-134在降低应力方面能到到更好的效果。最后通过氧化还原滴定法和酸碱滴定法对镀液中各成分的损耗进行分析,确定各成分的最佳补充量。在负载为40.0cm2/L的情况下,通过空气搅拌,不断补给,连续施镀,测定镀液的周期。在已得到的低温化学镀铜体系中,再分别加入稳定剂亚硫酸钠、硅酸钠、聚乙烯吡咯烷酮、六氟硅酸钠、全氟FC-80、FC-134、高铁试剂时,化学镀铜溶液的周期个数分别延长到4.68、4.91、5.72、5.61、5.79、6.03、4.41。其中FC-134的稳定性最好,周期最大值为6.03,即化学镀铜溶液能够连续使用54个小时,大大降低了化学镀铜工业的成本,减少了环境污染,对我国印制电路板产业的飞速发展起到了促进作用。本文最终获得了低温低应力的稳定性良好、能够连续使用的化学镀铜溶液,其组成为：五水硫酸铜10g·L-1,酒石酸钾钠28.25g-L-1,甲醛(37%)5mL·L-1,L-苹果酸2.0mg·L-1,2,2'-联吡啶2.0mg·L-1,十二烷基苯磺酸钠(SDBS)5.0mg·L-1, FC-80或FC-134 3.0mg·L-1。在该体系中沉积速率高,铜膜外观较好,应力低,使用周期长。当加入3.0mg·L-1FC-80时,最小应力可达到为-5.80MPa,周期为5.79；当用等量的FC-134替换时,最小应力可达到为4.42MPa,周期为6.03。
[Abstract]:As the printed circuit board (PCB) has the advantages of lightweight, miniaturization, and easy to standardize, it is almost the core component of all electronic devices. Electroless copper plating is the key technology for the metallization of printed circuits. At present, the factory of electroless copper plating is almost all over the world, and the rapid development of the computer industry and the aviation industry, to the electronic group The function of shielding signal interference puts forward higher requirements, and then puts forward new requirements for electroless copper plating: (1) developing new additives, reducing cost, improving copper deposition rate and improving economic efficiency. (2) prolonging the life of electroless copper plating solution. The electroless copper plating solution is in a thermodynamic unstable state, thus improving its stability and prolonging the use of life. In order to improve the quality of copper plating, reduce the consumption of raw materials and reduce the environmental pollution, the stability of the electroless copper plating solution is the key problem to determine whether the electroless copper plating solution can be applied to the actual production, and the addition of various additives in the electroless plating solution is one of the important means to improve the stability of the plating bath. In order to improve the stability of the solution, in order to improve the stability of the bath, it is necessary to add a suitable stabilizer to the bath, and the addition of stabilizers will lead to the deposition rate falling too quickly. The observation of the image shows that L- malic acid, 2,6- two amino pyridine, adenine and guanine have a better acceleration effect. Sodium sulfite, sodium silicate, polyvinylpyrrolidone, FC-80,8- hydroxyl -7- iodide -5- quinoline sulfonic acid, six sodium fluorosilicate, FC-134 can reduce the deposition rate of chemical copper plating in varying degrees, and can be used as stabilizers for this system. And adenine and sodium sulfite, guanine and ferric reagent, L- malic acid and sodium silicate, L- malic acid and six sodium fluorosilicate have reached synergistic effect. In the low temperature electroless copper plating system which has been obtained in this laboratory, the surface morphology of the copper plating film is improved by adding appropriate amount of six sodium fluorosilicate, FC-80, and FC-134. Then it is shot with X-. The surface stress of the copper film is measured and analyzed by line diffraction. The same stabilizer is added to the obtained system. It is found that only six sodium fluosilicate, FC-80, FC-134 can reduce the stress on the surface of the copper film, and FC-134 can achieve better effect in reducing the stress. Finally, the redox titration can be achieved by oxidation reduction titration. The loss of all components in the bath was analyzed by method and acid base titration, and the best supplement of each component was determined. Under the condition of the load of 40.0cm2/L, it was stirred by air, continuously recharged, continuous plating, and determination of the period of the plating bath. The stabilizer sodium sulfite, sodium silicate and polyethylene were added to the obtained low temperature chemical copper plating system. When pyrrolidone, six sodium fluosilicate, perfluoro FC-80, FC-134, and ferric reagent, the periodic number of the electroless copper plating solution is extended to 4.68,4.91,5.72,5.61,5.79,6.03,4.41., respectively, of which the stability of the FC-134 is best, the maximum of the cycle is 6.03, that is, the electroless copper plating solution can be used for 54 hours, greatly reducing the cost of the electroless copper plating industry. Less environmental pollution has played a role in promoting the rapid development of printed circuit board industry in China. This paper has finally obtained a good stability of low temperature and low stress and can be used continuously in electroless copper plating solution, which consists of five water copper sulfate 10g L-1, potassium tartrate sodium 28.25g-L-1, formaldehyde (37%) 5mL. L-1, L- malic acid 2.0mg. L-1,2,2'- couplet. 2.0mg. L-1, twelve alkyl benzene sulfonate (SDBS) 5.0mg. L-1, FC-80 or FC-134 3.0mg. L-1. have high deposition rate in this system. The appearance of the copper film is better, the stress is low and the use period is long. When 3.0mg L-1FC-80 is added, the minimum stress can be reached as -5.80MPa, the period is 5.79. The cycle is 6.03.

【学位授予单位】：陕西师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB306

【参考文献】