Wu Bo, Tan Baizhao, Tan Guizhen, Zeng Ming, Luo Jinyi, Hu Guanghui, Luo Jiye, Hao Zhifeng, Lai Shaomei, Liu Binyun
Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, School of Chemical Engineering and Light Industry, Guangdong University of Technology Guangzhou 510006 China
Guangdong Toneset Science & Technology Co., Ltd Guangzhou 511400 China
RSC Adv. 2021 Dec 8;11(62):39153-39168. doi: 10.1039/d1ra07952b. eCollection 2021 Dec 6.
The green cyanide-free gold deposition is an important development direction in electroless gold plating. However, the commonly Au(i) based cyanide-free gold plating bath always suffers from severe corrosion to the Ni-P layer and unsatisfactory service life of the bath. In this work, a green and environmentally friendly cyanide-free gold plating bath was developed with hypophosphite added as a reducing agent into the Au(iii)-DMH (5,5-dimethylhydantoin) based plating bath to retard the corrosion of the Ni-P layer. SEM micrographs combined with XRD and XPS analysis indicated that the electroless deposited gold was pure and compact. And XRD also revealed that the oriented deposition of gold was growing preferentially on Au (111). Corrosion tests, including salt spray tests, potentiodynamic polarization tests, and electrochemical impedance spectroscopy tests, indicated that the obtained Cu/Ni-P/Au coatings had significantly improved corrosion resistance performance with the loading of hypophosphite as the reducing agent. The baths remained transparent and no turbidity or precipitates were detected for 210 days, reflecting good stability. The detection for the Ni concentration in the bath showed that adding hypophosphite could retard the replacement reaction between Au and the Ni-P layer in part and this is important for decreasing the severe corrosion of the Ni-P layer. Moreover, Au was inactive for catalyzing the oxidation of hypophosphite during the deposition process which was confirmed furthermore quantum chemical calculations. Therefore, our developed green cyanide-free electroless gold deposition process can beneficially provide research value and application prospects in microelectronic industry.
绿色无氰金沉积是化学镀金的一个重要发展方向。然而,常见的基于Au(i)的无氰镀液总是对Ni-P层有严重腐蚀,且镀液使用寿命不理想。在本工作中,通过在基于Au(iii)-DMH(5,5-二甲基乙内酰脲)的镀液中添加次磷酸钠作为还原剂,开发了一种绿色环保的无氰镀液,以减缓Ni-P层的腐蚀。扫描电子显微镜(SEM)照片结合X射线衍射(XRD)和X射线光电子能谱(XPS)分析表明,化学沉积的金纯净且致密。XRD还表明,金的择优取向沉积优先在Au(111)上生长。包括盐雾试验、动电位极化试验和电化学阻抗谱试验在内的腐蚀试验表明,随着次磷酸钠作为还原剂加入,所获得的Cu/Ni-P/Au涂层的耐腐蚀性能有显著提高。镀液在210天内保持透明,未检测到浑浊或沉淀,表明稳定性良好。镀液中Ni浓度的检测表明,添加次磷酸钠可以部分减缓Au与Ni-P层之间的置换反应,这对于减少Ni-P层的严重腐蚀很重要。此外,量子化学计算进一步证实,在沉积过程中Au对次磷酸钠的氧化无催化活性。因此,我们开发的绿色无氰化学镀金工艺在微电子工业中具有有益的研究价值和应用前景。