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Acta Metall Sin  2017, Vol. 53 Issue (4): 487-493    DOI: 10.11900/0412.1961.2016.00388
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Preparation and Activation Mechanism of Pd Colloid with High Concentration and Performance
Shuoshuo QU1,2,Qingsheng ZHU2(),Yadong GONG1,Yuying YANG1,Caifu LI2,Shian GAO2
1 School of Mechanical Engineering & Automation, Northeastern University, Shenyang 110819, China
2 Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
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Shuoshuo QU,Qingsheng ZHU,Yadong GONG,Yuying YANG,Caifu LI,Shian GAO. Preparation and Activation Mechanism of Pd Colloid with High Concentration and Performance. Acta Metall Sin, 2017, 53(4): 487-493.

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Abstract  

The non-conductive substrate is often metallized through electroless plating method. Prior to the electroless plating, the substrate surfaces need to be firstly Pd activation pre-treated. The traditional "two-step" activation process, i.e., sensitization-activation, has been gradually obsoleted because of poor controllability and uniformity. A "one-step" activation process using Pd colloid has been widely used in industry, especially for the microvia metallization treatment in printed circuit board (PCB) fabrication. The bottleneck problem of this technology is the preparation of the Pd colloid solution with high concentration and excellent catalytic activity. The aim of this work is to develop a preparation method of the Pd colloid with high concentration and high quality. Pd colloid was prepared by a continuous reduction reaction with minor content. By mean of this process, the Pd concentration of the prepared colloid can exceed 2%. The morphology, microstructure and composition of the Pd colloid were characterized by SEM, TEM, XRD and XPS, respectively. The activate ability of the Pd colloid was examined by electroless Cu and electrochemical test. It was found that the average diameter of the Pd particles was less than 4 nm. Even if the concentration of Pd was less than 25 mg/L, this Pd colloid still had good activation ability for electro less Cu. The result demonstrated that the shell structure of the Pd micelle played a key role for the activation ability. The shell of Pd micelle was consisted of Sn2+, Sn4+ and Cl-, and generally formed two structures, [PdSn2]Cl6 and [PdSn3]Cl8. For the structure of [PdSn3]Cl8, the failure of the hydrolysis could lead to the loss of activation. The preparation method in this work can effectively avoid the occurrence of [PdSn3]Cl8, which greatly improved the activation ability of the Pd colloid.

Key words:  Pd colloidal      electroless Cu      activation     
Received:  26 August 2016     
Fund: Supported by National Natural Science Foundation of China (No.51471180) and Science and Technology Program of Shenyang (No.F16-205-1-18)

URL: 

https://www.ams.org.cn/EN/10.11900/0412.1961.2016.00388     OR     https://www.ams.org.cn/EN/Y2017/V53/I4/487

Fig.1  Schematic of preparing Pd colloid (1—funnel, 2—SnCl2 solution, 3—PdCl2 solution, 4—valve, 5—U bend, 6—glass tube, 7—bracket, 8—Pd colloid)
Fig.2  TEM (a) and HRTEM images (b) and size distribution (c) of prepared Pd nanoparticles (Insets in Figs.2a and b show the corresponding electron diffraction pattern and Fourier transform, respectively)
Fig.3  XRD spectrum of Pd colloid
Fig.4  Mixed potential (E)-time (t) curves of samples treated using Pd colloid with different concentrations
Fig.5  Surface SEM images before (a) and after electroless plating for 5 s (b), 30 s (c) and 2 min (d)
Fig.6  Cross-section SEM images of electroless Cu film after electroless plating
(a) overall pattern (b) details pattern
Fig.7  XPS survey scan of the electroless surface of Pd colloid (a), and XPS core-level spectra of Pd 3d (b) and Sn 3d (c)
Fig.8  TEM (a) and HRTEM (b) images of Pd particle in prepared Pd colloid with dark-green color (Insets in Figs.8a and b show the corresponding electron diffraction pattern and Fourier transform, respectively)
Fig.9  Model schematic of the shell structure evolution after acceleration of Pd colloid with (a) and wihtout (b) excellent activation ability
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