臺灣博碩士論文加值系統

本研究為一新方法製備親水性與疏水性貴金屬奈米粒子，利用以苯乙烯寡分子為主含硫酸根基團之寡分子，在不添加還原劑的情況下可還原貴金屬奈米粒子，並可在未添加分散劑的情況下，使奈米粒子穩定分散於有機溶液或水溶液中，其反應的機制可能為：在加熱寡分子與貴金屬離子時，於苯乙烯寡分子鏈端的硫酸根基團，首先熱裂為亞硫酸基團(SO32-)與醇基(Alcohol)，而Alcohol氧化做為還原核點的角色，SO32-用來成長奈米粒子，此外利用Gaussian 98分子模擬軟體來印証苯乙烯寡分子有一步驟還原奈米粒子的能力。 以苯乙烯寡分子所還原之鈀奈米粒子(St/Pd)可做為無電鍍所使用之活化液，其沉積速率較傳統錫鈀(Sn/Pd)膠體來的好，此St/Pd膠體之墨水成功的利用噴墨列印的方式噴印至可繞曲基材上，而金屬鈀所形成之圖案可催化無電鍍反應於低溫下製備金屬導線。
另外為了解決鈀活化液在無電電鍍銅時於基材上的附著力與製備非有機性之鈀活化液，因此使用了具備pH敏感性的甲殼素Chitosan(CS)-co-醋酸乙烯酯poly(Vinyl Acetate) (PVAc)的高分子，來增加鈀粒子在基材上的附著力。在酸性溶液中時Chitosan所含的氨基NH2會產生質子化反應(Protonation)得到質子轉變為NH3+，而NH3+可藉由靜電排斥力使奈米粒子於溶液中穩定分散，而當進入鹼性之銅鍍液裡後，NH3+官能基行去質子化作用(Deprotonation)轉換為NH2官能基，而利用NH2官能基來增加鈀活化液對基材的附著力，從研究結果發現，所還原出來的鈀奈米粒子的粒徑隨PVAc的比例增加而增加，而表面電位結果證實，當溶液從酸性轉換到鹼性時，Chitosan鏈上的NH3+官能基去質子化形成NH2官能基，因此表面電位從正轉變為中性，而穩定鈀奈米粒子靜電斥力也隨著質
子化反應消失，使得粒子吸附於基材上，藉由此反應機制來增加增加墨水與基材之間的附著力。

A novel method for the preparation of hydrophilic or hydrophobic noble metal nanoparticles was developed in this study. The styrene-based oligomers with sulfate end groups, which can be applied for the reduction and stabilization of noble metal nanoparticles, show well dispersion in aqueous or organic solvent without addition of surfactant and reducing agent in the mixture. Based on this study, a possible mechanism is proposed: by heating the aqueous solution in the presence of metal ions and styrene oligomers, the sulfate group which is on the chain end of styrene oligomers decomposes to sulfite (SO32-) firstly and alcohol is synchronously produced. The reduction of metal nuclei could thus take place by means of oxidization of alcohol and the growth of metal nuclei would be succeeded because of the presence of SO32-. The simulated results of Gaussian 98 program were in good agreement with the capabilities of styrene oligomers applied for one-step reduction of nanoparticles. These Pd nanoparticles reduced by styrene (St) can be used as activator for electroless metal deposition. The deposition rate of St/Pd nanoparticles system was higher than that of conventional Sn/Pd colloids. The ink based on St/Pd colloids was successfully ink-jet printed onto a flexible substrate. The formed metallic palladium patterns were subjected to electroless nickel plating, yielding well-defined nickel lines at low temperature.
A pH-sensitive chitosan (CS)-graft- poly(vinyl acetate) (PVAc) copolymer was also utilized to self-reduce Pd nanoparticles. The pH-sensitive chitosan chains not only function as stabilizing agent for noble metal nanoparticles in ink solution but also enhance the adhesion between Pd nanoparticles(PdNPs) and the substrate during the electroless deposition of Cu film. It is interesting to note that the diameter of PdNPs increases with increasing of PVAc contents. By heating the aqueous solution in the presence of metal ions and chitosan-g-PVAc, the metal nuclei reduced within the core. The core diameter increases with increasing PVAc percentages, resulting in formation of bigger Pd nanoparticles. The zeta potential of these copolymer stabilized PdNPs decreases with increasing pH value. Since the amino group in chitosan has a pKa value of ~6.5, thus, chitosan is positively charged (NH3+) in acidic or neutral solution, whereas it turns to neutral in an alkaline solution. The CS-g-0.5PVAc/PdNPs used as the catalyst was ink-jet printed onto flexible FR-4 substrate first, followed by electroless Cu deposition. This process is clean, easy and low-cost for formation of a high resolution patterning.

誌 謝 ii
摘 要 iii
ABSTRACT v
目錄 vii
表目錄 ix
圖目錄 x
1. 緒論 1
1.1 研究背景 1
1.2 研究動機 4
2. 文獻回顧 5
2.1 分子自身還原貴金屬奈米粒子 5
2.2 自由基聚合聚苯乙烯寡分子與聚苯乙烯磺化反應 8
2.3 共聚合反應聚苯乙烯與聚甲基丙烯酸甲酯共聚物 14
2.4 以噴墨列印在可繞性基材上製作金屬導線之研究 18
2.5 電化學沉積金屬技術 24
3. 實驗步驟 33
3.1 實驗藥品 33
3.2 實驗設備 34
3.3 檢測方式 35
3.4 聚苯乙烯寡分子合成與磺酸化反應還原貴金屬奈米粒子 41
3.5 聚苯乙烯與聚甲基丙烯酸甲酯共聚合反應還原貴金屬奈米粒子 42
3.6 噴墨列印與無電鍍製程製作金屬導線之研究 44
3.7 甲殼素共聚聚醋酸乙烯酯反應 46
4. 結果與討論 47
4.1 苯乙烯寡分子與磺酸化苯乙烯寡分子合成與自身還原貴金屬奈米粒子 47
4.1.1 苯乙烯寡分子與磺酸化苯乙烯寡分子之製備與反應機制探討 47
4.1.2 苯乙烯寡分子與磺酸化苯乙烯寡分子自身還原貴金屬奈米粒子之探討 54
4.2 苯乙烯-甲基丙烯酸甲酯共聚物與自身還原貴金屬奈米複合粒子 68
4.2.1 苯乙烯-甲基丙烯酸甲酯共聚物之製備與反應機制探討 68
4.2.2 苯乙烯-甲基丙烯酸甲酯共聚物自身還原貴金屬奈米粒子之探討 72
4.3 苯乙烯-甲基丙烯酸甲酯共聚物製備鈀奈米觸媒墨水應用於噴墨列印金屬化製程 85
4.4 甲殼素接枝聚醋酸乙烯酯聚合物與自身還原鈀奈米粒子 105
5. 結 論 117
未來規劃 118
參考文獻 119
論文發表 136
自傳 142

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