物理化学学报 >> 2011, Vol. 27 >> Issue (01): 143-148.doi: 10.3866/PKU.WHXB20110118

电化学和新能源 上一篇    下一篇

亚甲基二膦酸为配位体的无氰碱性镀铜

郑精武, 陆国英, 乔梁, 姜力强, 蒋梅燕   

  1. 浙江工业大学化学工程与材料学院, 杭州 310032
  • 收稿日期:2010-07-20 修回日期:2010-11-02 发布日期:2010-12-31
  • 通讯作者: 姜力强 E-mail:jiliqi@zjut.edu.cn
  • 基金资助:

    浙江省自然科学基金(Y406406)资助项目

Copper Electrodeposition from Non-Cyanide Alkaline Baths Containing Methylene Diphosphonic Acid as a Complexing Agent

ZHENG Jing-Wu, LU Guo-Ying, QIAO Liang, JIANG Li-Qiang, JIANG Mei-Yan   

  1. College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, P. R. China
  • Received:2010-07-20 Revised:2010-11-02 Published:2010-12-31
  • Contact: JIANG Li-Qiang E-mail:jiliqi@zjut.edu.cn
  • Supported by:

    The project was supported by the Natural Science Foundation of Zhejiang Province, China (Y406406).

摘要:

提出一种以亚甲基二膦酸(MDPA, H4L)为主配位剂的无氰镀铜体系. 采用pH 电位滴定法分别测定MDPA的四级解离常数和MDPA-Cu(II)的稳定常数, 并比较MDPA-Cu(II)和羟基乙叉二膦酸(HEDPA)-Cu(II)的循环伏安曲线和阴极极化曲线. 结果表明: MDPA各级解离常数为, pK1=1.86, pK2=2.65, pK3=6.81, pK4=9.04;MDPA与Cu2+形成分级配合物的稳定常数为, pKML=10.65, pKML2 = 5.59, pKML3 = 2.50; 随着pH升高, 形成的配合物依次为, Cu(H3L)2、[Cu(H3L)(H2L)]-和[Cu(H2L)2]2-; 当pH在7-10 时, MDPA较HEDPA更易与Cu2+配位. 当pH=9 时, MDPA碱性镀铜体系阴极主要发生的是[Cu(H3L)(H2L)]-和[Cu(H2L)2]2-还原生成铜的过程; 在10 °C,MDPA体系的铜配位化合物还原生成铜的电位比HEDPA体系负移, 扩散速度更快.

关键词: 无氰镀液, 亚甲基二膦酸, 铜电沉积, pH电位滴定, 羟基乙叉二膦酸

Abstract:

A cyanide-free alkaline copper deposition bath was developed using methylene diphosphonic acid (MDPA, H4L) as a complexing agent for Cu2+. The plating bath was investigated using potentiometric titrations, voltammetric curves, and polarization curves. The potentiometric titration gave dissociation constants for MDPA of: pK1=1.86, pK2=2.65, pK3=6.81, pK4=9.04, and the stability constants were: pKML= 10.65, pKML2 = 5.59, pKML3 = 2.50. Three different complex species were present in the bath as the pH increases: Cu(H3L)2, [Cu(H3L)(H2L)]-, and [Cu(H2L)2]2-. MDPA was found to be more likely to form complex species with Cu2+ than 1-hydroxyethylene-1,1-diphosphonic acid (HEDPA) from pH 7 to pH 10. At pH 9, [Cu(H3L)(H2L)]- and [Cu(H2L)2]2- were reduced to Cu at the cathode. Compared with the HEDPA system at 10 °C the peak potential shifted to more negative values and the rate of diffusion was faster.

Key words: Non-cyanide bath, Methylene diphosphonic acid, Copper electrodeposition, pH potentiometric titration, 1-Hydroxyethylene-1,1-diphosphonic acid

MSC2000: 

  • O646