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博碩士論文 etd-0726111-161645 詳細資訊
Title page for etd-0726111-161645
論文名稱
Title
電沉積法製備類鑽碳薄膜摻雜金屬之研究
Study on the electrodeposition of metal-doped DLC thin film
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
108
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2011-07-21
繳交日期
Date of Submission
2011-07-26
關鍵字
Keywords
光能隙、場發射、金屬摻雜、類鑽碳、電沉積
field emission, optical band gap, electrodeposition, DLC, metal-doped
統計
Statistics
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中文摘要
類鑽碳(DLC)薄膜具有許多類似鑽石的特性,如硬度高、化學穩定性佳、及高熱傳導性等,在近年來引起相當多的研究討論,被視為極有潛力的材料之一,但由於薄膜內應力過高且與基板附著性不佳使DLC之發展應用受到限制。由許多研究發現在薄膜中摻雜金屬粒子能有效釋放應力並可增強與基板之附著性,並提出許多Me-DLC之製備方式,然而製程皆為汽相沉積,需要高真空設備且製程控制繁雜,相較於液相電沉積系統則具有相當多的優勢,例如成本低、製程簡單、且能在不規則之大面積基板上成膜。本研究嘗試以液相電沉積的方式在ITO透明導電膜上沉積非晶質銅/類鑽碳(Cu-DLC)複合薄膜,並探討工作環境對薄膜組成結構及特性影響。
由I-t圖形之末端電流觀察薄膜之阻抗變化,Cu-DLC能有效降低電子在膜內之傳輸阻抗,並由AFM觀察其表面形貌呈尖錐狀,可增強電子場發射之特性,並經由Raman分析發現,銅金屬的加入,薄膜sp2鍵結量增加,使其ID/IG比值提高趨於石墨化,而由於膜內壓應力獲得釋放,造成G-peak往低波數偏移。ESCA分析結果薄膜中沒有銅碳化合物形成,而sp2/(sp2+sp3)比值隨著溶液pH值提高而增加,並得知Cu-DLC在酸性環境條件,或以[Cu(NH3)n]2+銅氨錯離子之形式摻雜,薄膜中金屬銅含量較高,較利於銅金屬成長,並由n&k analyzer量測推導出其具有最低的光能隙值;而在文章最後,將針對薄膜之成長機制及在電子場發射之特性應用作為探討。

Abstract
Recently, synthesis of Diamond-Like Carbon (DLC) films has received considerable interest. Owing to their similar characteristics of diamonds, such as extreme hardness, chemical stability, and high heat conductivity etc, DLC films are regarded as one of the most promising materials. But the practical applications have been limited due to their high internal stress and insufficient adhesion at the interface between DLC film and substrate. Several methods used to the deposition of Me-DLC films have been proposed. Studies have shown that the internal stress was released and the adhesion also improved by doping metallic element into DLC films. Conventionally, metal incorporation in DLC films were prepared by vapor deposition. The requirement of high vacuum equipment makes the process complicated. Besides, there are many merits in electrodeposition, such as low cost, simplicity of experimental set up, and availability for deposition on complex shapes substrate in large area. In this study, electrodepositing technique was used to synthesize the amorphous Cu-DLC films deposited on ITO substrate, in which the pH value of electrolyte varied, to study the characteristics and the composition of DLC films.
According to the I-t curves of deposition, the end of current density was used for the impedance comparison of films. With the addition of Cu, the resistance of the electron transportation in Cu-DLC was reduced, and the awl-shaped surface morphology was observed by AFM measurement, which could enhance the electron field emission properties of thin films. For Raman analysis, the effect of Cu addition would promote the sp2 bonding; this result corresponds with the increasing ID/IG value. It indicates that film becomes graphitization due to the addition of Cu and leads the shift of G-peak position toward lower wavenumber. ESCA spectra of C1s and
Cu2p indicate no obvious evidence of Cu-C formation. The sp2/(sp2+sp3) ratio increases with the pH value. In addition, we found that Cu-DLC in acidic environmental condition, or doping as [Cu(NH3)n]2+ complex is more conducive to the growth of copper metal in DLC films, and has the lowest optical band gap value deduced by n&k analyzer. Finally, we discussed the thin film growth mechanisms and the characteristic of electron field emission for the applications in the future.

目次 Table of Contents
國立中山大學研究生學位論文審定書 i
致 謝 ii
摘 要 iii
Abstract iv
表目錄 xiii
第一章 緒 論 1
1-1 前言 1
1-2 研究目的 2
1-3 論文架構 2
第二章 理論背景及文獻回顧 3
2-1 碳材料簡介 3
2-2 類鑽碳膜之分類及定義 4
2-3 類鑽碳膜之製備方法 5
2-4 電沉積製備類鑽碳膜之選擇碳源準則 6
2-5 類鑽碳膜之成長與反應機制 9
2-6 類鑽碳膜存在的問題與解決方法 11
2-7 液相電沉積原理與方法 12
2-8 液相電沉積法製備Cu-DLC 13
第三章實驗方法與儀器設備 15
3-1 實驗流程 15
3-2 實驗材料與儀器設備 15
3-2 實驗材料與儀器設備 16
3-2-1 實驗材料 16
3-2-2 儀器設備 16
3-3 實驗操作步驟 16
3-3-1 基板前置處理 16
3-3-2 電解液的泡製 17
3-3-3 電沉積之操作步驟 18
3-4 量測儀器與其原理 18
3-4-1掃瞄式電子顯微鏡 (Scanning Electron Microscopy) 18
3-4-2 X光光電子能譜儀 ( X-ray Photoelectron Spectroscopy ) 19
3-4-3 拉曼光譜 (Raman spectra) 20
3-4-4 薄膜特性分析儀 (N & K analyzer) 22
3-4-5 原子力顯微鏡 (Atomic Force Microscope, AFM) 24
第四章 結果與討論 25
4-1 Cu-DLC高電壓製程之影響 25
4-2 Cu-DLC低電壓製程之影響 27
4-2-1 pH值對沉積速率影響 28
4-2-2 pH值對薄膜阻抗之影響 28
4-2-3 pH值對阻抗影響的機制探討 29
4-2-4 鹼性摻雜溶液加入氨水之影響 31
4-3 SEM表面形貌分析 32
4-3-1 酸性環境 32
4-3-2中性環境 32
4-3-3 鹼性環境 33
4-4 鍵結形態分析 33
4-4-1 Raman光譜分析 33
4-4-2 XPS鍵結形態分析 35
4-5 光學能隙分析 38
4-5-1 光學能隙的推導 38
4-5-2 光學能隙與膜厚探討 39
4-6 薄膜成長機制與特性應用 40
4-6-1化學反應機制 40
4-6-2 Cu-DLC之場發射特性 41
第五章 總結 43
參考文獻 88
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