奈米鈀金屬活化液之製備及其在化學鍍銅製程之應用

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研究生：	彭超 Peng Chao
論文名稱：	奈米鈀金屬活化液之製備及其在化學鍍銅製程之應用 The Study of Pd Nanoparticles and Its Application to Electroless Copper Deposition
指導教授：	王詠雲 Yung-Yun Wang 萬其超 Chi-Chao Wan
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2006
畢業學年度：	94
語文別：	英文
論文頁數：	95
中文關鍵詞：	奈米粒子、鈀、無電鍍銅
外文關鍵詞：	nanoparticle, palladium, electroless copper deposition
相關次數：	點閱：2 下載：0
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本論文主要探討奈米鈀粒子的製備及其在印刷電路板中作為無電鍍銅活化液的應用，奈米鈀粒子由PVP保護，本研究所選用的分散劑有水相及乙二醇相，目前兩種分散劑中合成出的奈米鈀粒子經過穿透式電子顯微鏡鑑定，都介於2至7奈米之間，且對於無電鍍銅的催化都達到一定的效果。
乙二醇系統的優點在於合成時不用外加還原劑，而是利用以二醇本身在鹼性環境之下能夠脫水形成具有還原力的乙醛，藉以還原鈀的前趨鹽使其成為奈米粒子，但是前趨鹽對乙二醇溶解度不好，合成時間不易控制，本研究首先針對其製備過程作改良，但是發現其所轉化出來的乙醛濃度不能固定，這時原本已經成熟的水相奈米鈀系統便納入考量，水相系統具有製備方便、較高的催化活性。
本研究的另一項重點就是克服奈米鈀系統經過微蝕之後背光不良的問題，我們試著由不同的微蝕配方找出影響背光的原因，並同時從如何提高活化液本身催化能力著手，最後發現在活化液中加入磷酸並控制酸鹼值在2.2可以克服此問題，由極譜儀的測量結果可以發現，乙二醇系統中的奈米鈀粒子很容易被酸所氧化，相對水相系統的奈米鈀粒子對酸具有較好的穩定度。
由奈米鈀所催化的銅層，藉由X光粉末繞射儀以及掃描式電子顯微鏡的觀察，發現其和工業上錫鈀膠體所催化的銅層性質相似，如果能夠提升催化活性，對於取代錫鈀膠體將更有成效。
本研究也針對其吸附機制作探討，藉由X光電子能譜儀找出PVP所包覆的奈米鈀粒子吸附在基板上的原因，相信對於未來增加鈀吸附量和提升催化活性有幫助。

Pd nanoparticles stabilized by poly(vinylpyrrolidone) (PVP) have been synthesized in ethylene glycol (Pd/PVP/EG) and in water (Pd/PVP). The PVP-stabilized Pd nanoparticles (Pd-based activators) were found to hold strong potential to replace conventional activator Pd/Sn colloid for electroless copper deposition.
However, Pd-based activators led to poor back-light performance with SPS process. Adding phosphoric acid to adjust pH of the activator would improve back-light performance with SPS process for both Pd/PVP and Pd/PVP/EG. We measured the copper deposition rate and palladium adsorption amount by inductively coupled plasma (ICP-MS). The back-light performance of FR-4 substrates with through holes was measured with optical microscope (OM). Zeta potential and X-ray photoelectron spectroscopy (XPS) results confirmed the adsorptive mechanism of Pd-based activators. We found that Pd/PVP added with acid was more easily prepared than Pd/PVP/EG. Furthermore, Pd/PVP added with acid led to higher specific activity and stability than Pd/PVP/EG even though both of them led to qualified back-light performance and similar copper deposition rate. The Pd consumption of Pd/PVP/EG was much more than that of Pd/PVP. We considered that Pd/PVP was more likely to be a candidate than Pd/PVP/EG to compete with Pd/Sn colloid. We also found aeration caused serious oxidation of Pd for acid added Pd/PVP.

Chapter 1 Introduction    1
Chapter 2 Literature Review    3
1 Direct Plating    3
1.1 Pd Colloid    3
1.2 Carbon Black/Graphite    4
1.3 Conductive Polymer    5
2 Electroless Copper Deposition    6
1.1 Pd/Sn Colloid    6
2.2 Pd ion    9
2.3 Pd-based Activators    10
3 Synthesis of Palladium Nanoparticles in EG    13
3.1 Synthesis Noble Metal Compounds in EG    14
3.2 Synthesis Metal Particles with Polyol Method    15
3.3 Synthesis Parameters of Pd Particles in EG    17
4 The PVP Protective Mechanism for Silver Particles    19
5 Mechanism of Electroless Copper Deposition    21
Chapter 3 Experimental Sections    24
1 Materials    24
2 Experimental Instruments    25
3 Principle of Analytical Instruments    26
3.1 Ultraviolet-Visible Absorption Spectrometry (UV-vis)    26
3.2 Fourier Transform Infrared Spectrometry (FT-IR)    27
3.3 Transmission Electron Microscopy (TEM)    29
3.4 Polarography    30
3.5 Zeta Potential    31
3.6 X-ray Photoelectron Spectroscopy (XPS)    34
4 Pd-based Activator in EG System    35
4.1 Preparation of Pd/PVP/EG Nanoparticles    35
4.2 Synthesis of Pd/PVP/EG    35
4.3 Improve Pd/PVP/EG System    36
4.4 Pd/PVP/EG as Activator for Electroless Copper Deposition    36
5 Pd-based Activator in Aqueous System    38
5.1 Synthesis of Pd/PVP    38
5.2 Pd/PVP as Activator for Electroless Copper Deposition    38
6 Pd-based Activators Kept pH 2.2 by Adding H3PO4    39
7 Procedure for Conventional Pd/Sn Colloidal Activator    40
8 Copper Layer Analysis    41
9 Stability of Activators    41
10 Adsorption Mechanism    42
11 The Anions and Stability of Pd-based Activators    42
Chapter 4 Results and Discussions    43
1 Improve EG System    43
1.1 UV-vis Spectra Analysis    44
1.2 Particles Size Analysis    46
1.3 Activity of Pd/PVP/EG for Electroless Copper Deposition    48
1.4 The Back-light Performance Analysis    51
1.5 To Improve Back-light Performance with SPS Process    53
2 Evaluation of Pd/PVP/EG and Pd/PVP    55
2.1 Pd and Cu Amount of Pd/PVP/EG and Pd/PVP    59
2.2 Copper Deposition Rate    62
2.3 Stability of Pd/PVP/EG and Pd/PVP    65
2.4 The Consumption of Activstors    67
3 The Analyses of Pd/PVP    69
3.1 The Amount of Pd Adsorption of Various Conditioners    69
3.2 Stability with Aeration    71
3.3 SEM Images of Pd/PVP and Pd/Sn Colloid    74
3.4 XRD Analysis of Copper Layer    77
4 Adsorption Mechanism of Pd-based Activators    78
4.1 XPS (X-ray Photoelectron Spectroscopy) Spectra    78
4.2 Zeta Potential Analysis    82
4.3 Different Conditioning Situations    83
4.4 FTIR Characterization    86
5 Different Precursors for Pd-based Activators    87
Chapter 5 Conclusions    89
Chapter 6 Future Work    91
Chapter 7 References    92

                                

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