臺灣博碩士論文加值系統

本研究為利用奈米鈀金屬粒子作為無電鍍銅觸媒將感光型介電材料(Photoimageable dielectric, PID)進行金屬化，透過二階段改質的手法搭配新式金屬觸媒，試圖改善無電鍍銅於感光型介電材料上鍍不良及附著力不佳的缺點，並且取代現有乾式真空濺鍍的金屬化方式，成為降低成本並且提升生產效能的解決方案，首先使用半導體標準的RCA-SC1流程或氧氣電漿的方式將PID基板進行第一階段親水化處理，並利用末端含有胺基之矽烷化合物進行表面第二階段改質，使矽烷化合物形成自組裝薄膜層(Self-assembly monolayer, SAM)，再利用自行研發之聚乙烯醇保護奈米鈀金屬粒子(Polyvinyl alcohol, PVA-Pd)與矽烷化合物之胺基進行作用，以作為後續無電鍍銅之金屬觸媒並提升其無電鍍銅於PID上之覆蓋率與結合力。
在材料分析的部分，為了確認各階段改質處理對於材料表面的影響以及化學銅的結合力，利用接觸角量測儀(Contact angle measurement)、原子力顯微鏡(Atomic force microscopy, AFM)、掃描式電子顯微鏡(Scanning electron microscopy, SEM)、X射線螢光分析法(X-ray fluorescence analysis, XRF)、X射線光電子能譜儀 (X-ray photoelectron spectroscop, XPS)以及百格刀膠帶測試進行分析。

Electroless-deposition Copper (E’less Cu) is one of most commend technique in electronic package industry. In this work, two step surface modification technique is applied to set up an attachable surface by using RCA-SC1 (standard clean process of semiconductor industry) or radio frequency (RF) power plasma and the 3- 2-(2-aminoethylamino) ethylamino propyl trimethoxysilane (ETAS) for PVA-Pd attach which as the catalyst of E’less deposition. Applying the catalyst agent developed in previous study and synthesized in the laboratory. Using polyvinyl alcohol (PVA) as protective agent of the palladium nanoparticle with well-define size of 2-5nm. [1] The PID surface modification and the adhesion between PID and e’less Cu is evaluated by water contact angle, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscope (AFM), X-ray fluorescence analysis (XRF) and cross cut test.
The results showed that using PVA-Pd as catalyst of E’less Cu on PID had better adhesion than commercial Sn/Pd and applying plasma is more suitable method than RCA-SC1 for organic polymer as the surface hydrophilicity modification method. Based on SEM and AFM analysis, one of the factor to enhance the adhesion is that micro-morphology and roughness occurred after plasma process. The XPS analysis showed many functional groups generated after treatment it might be another factor to enhance adhesion performance of E’less Cu on PID.
In the practical application point of view, this study demonstrate “wet process” alternative for PID metallization and try to resolve the mechanism of surface modification.

目錄
摘要 I
Abstract III
誌謝辭 IV
目錄 V
圖目錄 VII
表目錄 X
第一章　緒論 1
1.1 前言 1
1.2 研究動機與目的 3
第二章　文獻回顧 5
2.1 介電材料的發展及沿革 5
2.1.1 非感光型介電材料 6
2.1.2 感光型介電材料 7
2.2 常見的介電材料銅金屬化製程 10
2.2.1 真空濺鍍 10
2.2.2 蒸鍍 10
2.2.3 銅箔壓合 10
2.2.4 無電鍍 11
2.3 無電鍍銅 11
2.3.1 無電鍍基本原理 11
2.3.2 無電鍍銅的基本原理 12
2.3.3 pH值的影響 14
2.4 鈀金屬觸媒 15
2.4.1 膠體錫鈀(Sn/Pd Colloid) 15
2.4.2 離子鈀 15
2.4.3 奈米鈀 16
2.5 矽烷化合物表面改質 19
2.5.1 常見的矽烷化合物 20
2.5.2 矽烷化合物表面改質機制 20
2.6 感光型介電材料的應用與挑戰 24
第三章　實驗 27
3.1 藥品與材料 27
3.2 設備與儀器 28
3.3 量測原理 29
3.3.1 傅立葉轉換紅外線光譜儀(Fourier transform infrared spectrometer, FTIR) 29
3.3.2 接觸角量測儀 (Contact angle measurement) 30
3.3.3 原子力顯微鏡 (Atomic force microscope, AFM) 31
3.3.4 掃描式電子顯微鏡 (Scanning electron microscope, SEM) 31
3.3.5 X射線光電子能譜儀 (X-ray photoelectron spectroscopy, XPS) 33
3.3.6 X射線螢光分析法(X-ray fluorescence analysis, XRF) 33
3.3.7 附著力測試 (百格刀3M膠帶測試) 34
3.4 實驗方法 36
3.4.1 PID基板製備 36
3.4.2 奈米鈀觸媒(PVA-Pd)之製備 36
3.4.3 表面改質與無電鍍銅之沉積 37
3.4.3.1 RCA方法 37
3.4.3.2 電漿前處理效應 43
第四章　結果與討論 48
4.1 前言 48
4.2 實驗結果 50
4.2.1 RCA方法 50
4.2.1.1 RCA+ETAS改質結果 50
4.2.1.2 AFM及SEM形貌分析 52
4.2.1.3 無電鍍銅 54
4.2.1.4 PID與無電鍍銅結合力驗證 55
4.2.2 電漿前處理效應 57
4.2.2.1 電漿處理時間 58
4.2.2.2 電漿+ETAS改質結果 59
4.2.2.3 AFM及SEM形貌分析 61
4.2.2.4 無電鍍銅 64
4.2.2.5 PID與無電鍍銅結合力驗證 66
4.3 結論與未來展望 70
4.3.1 結論 70
4.3.2 未來展望 71
參考文獻 72

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