無電鍍沉積（Electroless Plating）是一項常被應用於印刷電路板（Printed Circuit Board, PCB）產業的技術，此技術具有鍍層較緻密且不需額外提供電流等優勢。在進行無電鍍沉積前，需要先將基板進行活化，鈀觸媒經常被用作此流程必須的活化劑。本研究旨在開發一種具自吸附性質之新型奈米鈀觸媒，並將其作為在有機基材上無電鍍銅之催化劑。
研究中第一部分以聚乙烯醇（Polyvinyl Alcohol, PVA）作為奈米鈀的保護劑，使PVA-Pd奈米粒子能穩定分散在懸浮液中，並以混摻的方式將常用作改質劑之高分子聚乙烯亞胺（Polyethylenimine, PEI）加入PVA-Pd中，使奈米粒子PEI-PVA-Pd能同時具有改質及活化兩種特性。第二部分則由於PEI-PVA-Pd的不穩定性，進一步引入以Jeffamine包覆的奈米鈀觸媒JA-Pd，使觸媒除了有自吸附性質外，還能具有高穩定性以延長觸媒的使用壽命。另外，本研究以氟系高頻基板（Polytetraflouroethylene, PTFE）作為分析所使用的主要材料，後續測試以液晶高分子（Liquid Crystal Polymer, LCP）確認在其他有機材料上應用的可行性。
本研究透過穿透式電子顯微鏡（Transmission Electron Microscope, TEM）以及奈米粒經分析儀（Dynamic Light Scattering, DLS）確認奈米粒子的尺寸大小和粒徑分布，並以感應耦合電漿原子發射光譜儀（Inductively Couple Plasma Optical Emission Spectroscopy, ICP-OES）與電化學分析儀（Autolab）比較觸媒之催化活性。接著透過X射線光電子能譜儀（X-Ray Photoelectron Spectroscopy, XPS）確認奈米鈀觸媒的結構，並將觸媒吸附於PTFE基板上後，以水滴接觸角（Water Contact Angle, WCA）以及XPS表面分析觀察吸附前後的表面變化和確認吸附機制。最後以萬能拉力機（Universal Testing Machine）以及SEM分析無電鍍銅層和基板之間的附著力與撕裂面。

Electroless plating (ELP) is a technique widely applied in the printed circuit board (PCB) industry. Palladium catalysts are often used as the activators process in ELP process. This research aims to develop a novel self-adhesive nano palladium catalyst and utilize it as the activator for ELP on organic substrates.
In the first part of this study, polyvinyl alcohol (PVA) is used as a capping agent for palladium nanoparticles. Polyethylenimine (PEI), commonly used as a modifier, is incorporated into PVA-Pd through blending. The novel Pd nanoparticle PEI-PVA-Pd obtains both modification and activation properties. In the second part, due to the instability of PEI-PVA-Pd, another nano-palladium catalyst capped with Jeffamine (JA-Pd) is synthesized. This catalyst not only exhibits self-adsorbing properties but also offers high stability. The primary material used in this study is polytetrafluoroethylene (PTFE), with additional testing on liquid crystal polymer (LCP) to confirm the feasibility of application on other organic materials.
The study employs transmission electron microscopy (TEM) and dynamic light scattering (DLS) to determine the size and size distribution of the nanoparticles. The activity of the catalysts is compared using inductively coupled plasma optical emission spectroscopy (ICP-OES) and induction time analysis. Subsequently, the catalyst structure was confirmed using X-ray photoelectron spectroscopy (XPS). The catalysts are then adsorbed onto the PTFE substrate, the surface changes are observed using Water Contact Angle (WCA) measurements and XPS surface analysis to confirm the adsorption mechanism. Finally, the adhesion strength and the fracture surface between the electroless copper layer and the substrate were analyzed using a universal testing machine and Scanning Electron Microscopy (SEM).

摘要 i
Abstract ii
致謝辭 iii
目錄 iv
圖目錄 viii
表目錄 xiv
第 一 章 緒論 1
第 二 章 文獻回顧 4
2-1 金屬化製程技術 4
2-2 無電鍍沉積法 4
2-2-1 無電鍍沉積法基本原理 4
2-2-2 無電鍍銅液組成與特性 5
2-2-3 無電鍍銅液反應及觸媒催化機制 7
2-3 鈀觸媒種類及應用 9
2-3-1 錫鈀膠體觸媒（Sn/Pd Colloid） 10
2-3-2 離子鈀觸媒（Pd-ion） 10
2-3-3 奈米鈀觸媒（Pd Nanoparticles） 11
2-4 金屬奈米粒子 11
2-4-1 奈米粒子分散機制 11
2-4-2 奈米粒子保護劑種類 13
2-5 表面改質 14
2-5-1 矽烷化合物改質及其於無電鍍沉積上之應用 15
2-5-2 聚乙烯亞胺改質及其於無電鍍沉積上之應用 17
2-5-3 其他含氮官能基聚合物表面改質其於無電鍍沉積上之應用 20
2-6 Jeffamine聚醚胺 23
2-6-1 Jeffamine聚醚胺簡介 23
2-6-2 Jeffamine聚醚胺種類 24
2-6-3 Jeffamine聚醚胺於表面改質上之應用 25
2-7 奈米鈀搭配表面改質於無電鍍沉積上之應用 26
2-7-1 以ETAS表面改質搭配奈米鈀觸媒PVA-Pd活化 27
2-7-2 以ETAS混摻PVA-Pd之自吸附奈米鈀觸媒ETAS-PVA-Pd 30
2-7-3 以PEI表面改質搭配奈米鈀觸媒PVA-Pd活化 33
2-7-4 以PEI包覆之自吸附奈米鈀觸媒PEI-Pd 35
2-8 印刷電路板之有機基材 37
2-8-1 氟系高頻基板金屬化應用 37
2-8-2 液晶高分子基板金屬化應用 41
2-9 研究目的與動機 46
第 三 章 實驗 48
3-1 實驗藥品 48
3-2 實驗材料 48
3-2-1 氟系高頻基板簡介 48
3-2-2 RO3000系列簡介 50
3-2-3 液晶高分子簡介 50
3-3 設備與儀器 51
3-3-1 奈米粒徑分析儀 (Dynamic Light Scattering, DLS) 52
3-3-2 X射線光電子能譜儀 (X-Ray Photoelectron Spectroscopy, XPS) 52
3-3-3 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) 53
3-3-4 萬能附著力機 (Universal Testing Machine) 55
3-3-5 接觸角量測儀 (Contact Angle) 56
3-3-6 穿透式電子顯微鏡 (Transmission Electron Microscope, TEM) 57
3-3-7 感應耦合電漿原子發射光譜儀 (Inductively Couple Plasma Optical Emission Spectrometry, ICP-OES) 58
3-3-8 電化學分析儀 59
3-3-9 表面輪廓量測儀 (Alpha Step) 61
3-3-10 紫外光-可見光光譜儀 (Ultraviolet–visible Spectrometer, UV-Vis) 63
3-4 實驗流程 64
3-4-1 奈米鈀觸媒PVA-Pd合成 64
3-4-2 奈米鈀觸媒PEI-PVA-Pd合成 65
3-4-3 奈米鈀觸媒JA-Pd合成 66
3-4-4 無電鍍藥水配置以及無電鍍銅沉積 67
3-4-5 電鍍銅藥水配製 68
第 四 章 結果與討論 70
4-1 PEI-PVA-Pd奈米鈀觸媒分析 70
4-1-1 PEI-PVA-Pd粒徑分布及分析 70
4-1-2 PEI-PVA-Pd活性分析 72
4-1-3 PEI-PVA-Pd自吸附於RO3003基板上分析 76
4-1-4 RO3003上無電鍍銅層沉積表面形貌 79
4-1-5 RO3003上無電鍍銅層附著力分析 80
4-1-6 PEI-PVA-Pd觸媒穩定性分析 87
4-2 JA-Pd奈米鈀觸媒分析 89
4-2-1 不同合成比例之JA-Pd比較 89
4-2-2 JA-Pd之粒徑與還原完成度分析 92
4-2-3 JA-Pd、PEI-PVA-Pd及Sn/Pd活性分析 94
4-2-4 JA-Pd包覆穩定機制 95
4-2-5 JA-Pd自吸附於RO3003基板上分析 100
4-2-6 以JA-Pd活化之無電鍍層附著力分析 103
4-2-7 JA-Pd觸媒穩定性分析 107
4-2-8 PEI-PVA-Pd及JA-Pd於LCP基材無電鍍銅附著力結果 110
第 五 章 結論 112
第 六 章 未來展望 114
參考文獻 115

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