由於高階IC載板在未來的發展趨勢朝向表面低粗糙度邁進，以至於在後續金屬化的製程中容易產生金屬層剝落的問題，因此本論文為改善新式IC載板(Ajinomoto Build-up Film, ABF GX-T37)上無電鍍銅層附著力的研究。研究中利用末端具有三個胺基官能團的矽烷化合物(3-2-(2-aminoethylamino) ethylamino propyl trimethoxysilane, ETAS)對ABF基板表面進行改質，藉由矽烷化合物的水解端與表面氫氧化後的ABF基板表面進行脫水反應，使矽烷化合物以共價鍵的形式與基板結合。經矽烷改質後的基板搭配本實驗室所開發出來的聚乙烯醇包覆奈米鈀粒子(Polyvinyl alcohol capped palladium, PVA-Pd)作為無電鍍銅沉積之觸媒，藉由矽烷化合物結構上的胺基官能團與PVA-Pd觸媒進行交互作用，增強後續無電鍍銅層與ABF基板間的附著力。
實驗的首部分是在於矽烷表面改質之結果分析，比較有無矽烷改質之ABF GX-T37基板表面的差異性。利用水滴接觸角量測及原子力顯微鏡(AFM)觀察矽烷化合物於基板表面的效果與變化，再以X射線光電子能譜儀(XPS)瞭解矽烷化合物在ABF GX-T37基板上的鍵結方式。在矽烷表面改質確立後，接著探討不同改質條件對無電鍍銅層附著力之影響，並利用工業上常使用的T-Peel測試機台進行銅層附著力測試，與目前商業上所使用的Sn/Pd膠體觸媒及Pd-ion觸媒製程相比較。然而在重複附著力測試實驗時，發現不同批次進行除膠渣(Desmear)處理的基板附著力差異甚大，因此後續將對此部分再做更深入的探討。
第二部分則是研究除膠渣程序對於不同型號之ABF基板表面所產生之影響，藉由掃描式電子顯微鏡(SEM)、能量散射光譜儀(EDS)與AFM對基板表面進行材料分析，以及銅層與基板之裂面分析，從中尋找出影響無電鍍銅層與基板間附著力之關鍵因素，並試圖將矽烷表面改質搭配奈米鈀(ETAS+PVA-Pd)的技術套用在目前已商業化的ABF GX-13上。

Traditional electroless copper deposition technology cannot satisfy the requirement of fine linewidth and minimal signal loss, which are the features of advanced circuitry. To meet the feature of fine linewidth and minimal signal loss of advanced circuit, modern substrates are made flat and does not allow massively roughened. In this study, we aim to modify the surface of Ajinomoto Build-up Film (ABF) by the formation of the covalent bond between silane, 3-2-(2-amionethylamino) ethylamino propyl trimethoxysilane (ETAS) and substrate. After ETAS modification, home-made polyvinyl alcohol capped palladium(PVA-Pd) nanoparticles were adsorbed onto ETAS-modified ABF film to catalyze electroless copper plating. To enhance the adhesion by interaction of ETAS with PVA-Pd.
In the first part of this study, we analyze the effect of ETAS modification on ABF GX-T37 by water contact angle, atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). Meanwhile, the adhesion of electroless copper layers prepared using commercial catalyst (Sn/Pd and Pd-ion) were compared. Finally, the relationship between ETAS modification and the adhesion has been connected. Although repeating the adhesion tests, the result show low reproducibility between the ABF GX-T37substrates fabricated by different lots. Therefore, the following analysis of morphology of substrate was carried out to clarify the effect of desmear process on adhesion.
In the second part of this study, we focused on the morphological features of different types of ABF substrate after desmear process using scanning electron microscope (SEM) and Energy-Dispersive Spectroscopy (EDS) and AFM. Moreover, we scrutinized the profile at copper/substrate interface. Finally, we found out the major factor on influencing adhesion between electroless copper layer and ABF substrate. Furthermore, we are looking forward to apply this technic into the commercialized ABF GX-13 substrate.

摘 要 I
Abstract II
致謝詞 III
目 錄 IV
圖目錄 VII
表目錄 XI
第一章 緒 論 1
1.1 前言 1
1.2 研究目的與動機 7
第二章 文獻回顧 8
2.1 IC載板電氣特性 8
2.2 ABF材料 10
2.3 IC載板內導線製程 11
2.3.1 除膠渣製程 11
2.3.2 IC載板表面金屬化 13
2.4無電鍍銅沉積 15
2.4.1 無電鍍沉積基本原理 15
2.4.2 無電鍍銅的發展歷史 16
2.4.3 無電鍍銅的反應機制 16
2.4.4 無電鍍銅鍍液的組成與特性 17
2.5 無電鍍銅觸媒 19
2.5.1 錫鈀膠體觸媒(Sn/Pd Colloid) 19
2.5.2 離子鈀觸媒(Commercial Pd-ion) 20
2.5.3 奈米鈀觸媒(Polyvinyl alcohol capped palladium, PVA-Pd) 21
2.6 矽烷化合物表面改質 23
2.6.1 矽烷化合物的結構及應用 23
2.6.2 矽烷化合物表面改質之機制 26
2.6.3 矽烷化合物於無電鍍金屬沉積之應用 27
第三章 實驗部分 37
3.1 藥品與材料 37
3.1.1 奈米鈀觸媒合成 38
3.1.2 無電鍍銅藥水配置 39
3.1.3 電鍍銅藥水配置 40
3.2 設備與儀器 40
3.3 測量原理 41
3.3.1 奈米粒徑分析儀(Dynamic Light Scattering, DLS) 41
3.3.2 接觸角量測儀(Contact angle measurement) 41
3.3.3 原子力顯微鏡(Atomic force microscope, AFM) 42
3.3.4 表面輪廓量測儀(Alpha-Step) 44
3.3.5 X射線光電子能譜(X-ray photoelectron spectroscopy, XPS) 44
3.3.6 掃描式電子顯微鏡(Scanning electron microscope, SEM) 45
3.3.7 百格膠帶測試 46
3.3.8 萬能拉力機(Universal Testing Machine) 47
3.4 實驗方法 49
3.4.1 ABF基板前處理 49
3.4.2 矽烷表面改質之製程 49
3.4.3 無電鍍銅沉積 51
3.4.4 電鍍銅製程 53
第四章 結果及討論 54
4.1 矽烷表面改質與無電鍍銅層附著力之研究 54
4.1.1 矽烷表面改質之鑑定 55
4.1.2 無電鍍銅層之附著力分析結果 58
4.2 GX-T37基板表面狀況對ETAS改質及後續銅鍍層附著力之影響 63
4.2.1 不同批次GX-T37基板表面形貌 65
4.2.2 無電鍍銅顆粒表面形貌 67
4.2.3 無電鍍銅層與基板間之界面分析 67
4.3 影響無電鍍銅層附著力之因素 70
4.3.1 基板表面形貌分析 71
4.3.2 無機粉體裸露程度 75
4.3.3 無電鍍銅層之附著力探討 76
4.3.4 無電鍍銅層與GX-13基板間之裂面分析 79
4.4 矽烷化合物對有機高分子改質之影響 80
4.4.1 百格測試 80
4.4.2 有機薄膜表面氫氧化測試結果 82
第五章 結 論 84
參考資料 85

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