銀鈀合金奈米粒子之製備及其在無電鍍沉積之應用

The Study of Ag/Pd Nanoparticles and Its Application to Electroless Deposition

藍若琳(Jo-Lin Lan)

指導教授 ： 萬其超 ； 王詠雲

國立清華大學/工學院/化學工程學系/碩士(2007年)

https://doi.org/10.6843/NTHU.2007.00038

摘要

本論文主要探討銀鈀奈米粒子之製備，以及其在於無電鍍銅沉積之活化催化反應。以PVP作為保護劑、甲醛當作還原劑，成功的合成出銀鈀奈米粒子。此高分子保護之銀鈀奈米粒子除了可以成功地催化無電鍍銅，並顯示出利用此活化程序製備積體電路中銅內連線之可行性。
使用高分子型(PVP)保護劑所合成出的銀鈀奈米粒子，經由穿透式電子顯微鏡，分析奈米粒子的大小，根據紫外光光譜及X光粉末繞射儀的鑑定，可以確定製備出銀鈀合金奈米粒子。並根據電子能譜儀以硫醇官能基之鍵結、ex-situ紫外光光譜及混合電位，分析出此銀鈀奈米粒子為表面鈀成份較多的結構，且銀鈀奈米粒子合金的形式會隨著高分子保護劑PVP的含量不同而有所改變。
在催化活性方面，利用石英晶體微天平(QCM)以及循環伏安法(CV)可知銀鈀奈米粒子的催化活性與純鈀奈米粒子及現今商用錫鈀膠體的催化活性相近。經過鍍通孔製程背光及信賴度測試，均與現今商用錫鈀膠體效果相當，且經過曝氣測試得知，銀鈀奈米粒子不會被氧氣所氧化聚集，有著可使用於水平製程應用的可能性。銀鈀奈米粒子具備著奈米合金優越的催化活性、以部分銀來代替鈀降低原料成本即可使用於水平曝氣製程等優勢。

關鍵字

奈米粒子 ； 鈀 ； 銀 ； 無電鍍銅

並列摘要

Ag/Pd nanoparticles stabilized by poly(vinylpyrrolidone) (PVP) have been synthesized successfully in various molar ratios. The PVP-stabilized Pd and Ag/Pd nanoparticles were found to hold strong potential to replace conventional activator Pd/Sn colloid for electroless copper deposition.
The essential property of Pd-PVP and Ag/Pd-PVP nanoparticles will be discussed, including the TEM images for the particle sizes, the ex-situ UV-vis spectra analysis. XPS data and mixed potential for the growth mechanism of Ag/Pd nanoparticles. The catalytic activity will be measured by QCM and CV.
The application of Pd-PVP and Ag/Pd-PVP nanoparticle is used as the activators in the PTH (plating-through-hole) process. Using Pd-PVP and Ag/Pd-PVP as activators led to poor back-light performance if SPS process in included as in the conventional practice. Adding phosphoric acid to adjust pH of the activator would improve back-light performance with SPS process for both Pd-PVP and Ag/Pd-PVP. However, the stability of Pd-PVP and Ag/Pd-PVP nanoparticles was found to be sensitive. Accordingly, in order to extend the lifetime of activators, adding appropriate additive is necessary.
The back-light performance and the thermal stress test showed that using Ag/Pd-PVP as activators is qualified for replacing the Sn/Pd colloid. Since Ag/Pd-PVP is less subject to oxidize by aerating, and the material cost will reduce by partially replacing palladium by silver, so Ag/Pd-PVP has the potential to become a commercially competitive product.

並列關鍵字

nanoparticles ； palladium ； silver ； electroless copper deposition

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