化学学报 ›› 2008, Vol. 66 ›› Issue (21): 2434-2438. 上一篇    下一篇

研究论文

N’,N’-二乙基硫脲添加剂对铜微沉积工艺电化学行为的影响

张 涛*,a 吴一辉b 杨建成a 张 平b

  

  1. (a天津工业大学机械电子学院 天津 300160)
    (b中国科学院长春光学精密机械与物理研究所 长春 130033)

  • 投稿日期:2008-02-28 修回日期:2008-06-20 发布日期:2008-11-14
  • 通讯作者: 张涛

Effects of N’,N’-Diethylthiourea on Electrochemical Behavior of Copper Micro-electrodeposition

ZHANG, Tao *,a WU, Yi-Hui b YANG, Jian-Cheng a ZHANG, Ping b   

  1. (a School of Mechanical and Electric Engineering, Tianjin Polytechnic University, Tianjin 300160)
    (b Changchun Institute of Optics, Fine Mechanics and Physics (CIOMP), Chinese Academy of Sciences, Changchun 130033)
  • Received:2008-02-28 Revised:2008-06-20 Published:2008-11-14
  • Contact: ZHANG, Tao

为了研究N’,N’-二乙基硫脲添加剂在微沉积工艺中对铜金属孔洞填充能力的影响, 采用线性伏安法(LSV)、循环伏安法(CV)、SEM测量法分析比较了无添加剂、含硫脲和含N’,N’-二乙基硫脲添加剂时微沉积铜工艺中的电化学行为, 并借助塔菲尔方程, 分析比较此三种情况下电镀反应过程中的电极动力学参数. 结果显示: 当铜微沉积工艺中加入N’,N’ -二乙基硫脲添加剂时, 产生活性极化, 该活性极化效应降低铜离子的放电速度, 抑制孔洞边缘部分沉积较快区域的过快生长; 同时活性极化提高, 将导致成核点的增加, 沉积膜的晶粒较小, 镀膜也较平滑细致, 实验测得铜离子的平滑能力比没有添加剂时提高约50%. 最后通过微沉积工艺成功地将金属铜填充入宽为10 μm, 深宽比为4∶1的微型凹槽中, 且镀层内没有空洞、空隙以及细缝等缺陷.

关键词: 微沉积工艺, N’,N’-二乙基硫脲, 活性极化, 电化学行为

In order to investigate the copper gap-filling during micro electroplating process with additive (N’,N’-diethylthiourea), the electrochemical behavior of different electrolyte (without additive, with thiourea or N’,N’-diethylthiourea additive) were studied by LSV, CV and SEM, and the electrode kinetics parameters was studied by the Tafei equation. The results show that when N’,N’-diethylthiourea was used during the micro electroplating copper process, activation polarization was generated; metal ion discharge rate was lowered, the overgrowth of fast plating area such as micro-trench edges was restrained; at the same time, activation polarization was increased, thus the crystal nucleus molding speed on the electrode was accelerated; the crystal growth speed was decreased, the plating became flat, and the leveling ability was increased about 50% than that without additive. Furthermore, some micro trenches in the silicon wafer, and the width of 10 μm and aspect ratio of 4∶1, were filled by the micro electroplating process with the additive N’,N’-diethylthiourea, however, the electroplating layer had no voids or seams.

Key words: micro-electrodeposition process, N’,N’-diethylthiourea, activation polarization, electrochemical behavior