利用電漿聚合方法製備賽吩薄膜及其物理化學性質分析

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研究生：	劉修吉 Hsiu-chi Liu
論文名稱：	利用電漿聚合方法製備賽吩薄膜及其物理化學性質分析 Preparations and Characterizations of Plasma Polymerized Thiophene Thin Films
指導教授：	王孟菊 Meng-jiy Wang
口試委員:	陳克紹 Ko-shao Chen 魏大欽 Ta-chin Wei 林昇佃 Shawn D. Lin
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2009
畢業學年度：	97
語文別：	中文
論文頁數：	51
中文關鍵詞：	連續式電漿、電漿聚合、共軛高分子、賽吩、導電性高分子
外文關鍵詞：	continuous plasma, plasma polymerization, conjugated polymer, thiophene, conductive polymer
相關次數：	點閱：432 下載：0
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本研究之目的為利用賽吩單體，以連續式電漿聚合方式，製備賽吩薄膜。對於所製備之賽吩薄膜，將探討電漿聚合時間、電漿功率以及碘蒸氣摻雜的時間對於賽吩薄膜性質之影響。
由實驗結果可以發現，賽吩薄膜的沈積速率與單體沈積時間之關係呈現反比，表示在短時間下，賽吩具有較高的沈積效能，隨著電漿功率的提升，薄膜的沈積速率會上升；薄膜的厚度隨著沈積時間與電漿功率的增加，會有明顯的提升；粗糙度與沈積時間之關係呈現正比的趨勢，但隨著電漿功率的增加，粗糙度卻是先降後升，是因為受到薄膜表面沾附的微粒與表面型態的影響造成；利用霍爾效應量測系統和交流阻抗儀量測薄膜的電學性質，可以發現賽吩薄膜在摻雜後的導電度有明顯的提升，但因為膜厚太薄，四點探針量測儀和電流伏特光度儀皆不適用；比較碘摻雜前後的薄膜結構的變化，由XPS光譜結果顯示，摻雜後，薄膜表面的碘元素確實有增加，表示摻雜反應有進行，因此使得摻雜後的導電度明顯的提升。
共軛高分子與其衍生物，經過適當的處理，能提高共軛高分子本身能導通電荷的效應，將導電度提升，使其能夠應用在廣泛的領域上，加上高分子本身具有高透明度、可彎曲性、質量輕、價格相對較低、易於加工與耐用性等重要特性，可用來取代金屬作為光電工業的替代品。本研究希望利用連續式電漿製備賽吩高分子膜，並選取不同的電漿參數條件，探討不同的電漿參數條件對於賽吩薄膜的性質影響，找出薄膜性質對於應用上較為適用以及能夠提升導電度的實驗條件，期望賽吩薄膜能夠應用於工業上。

The goal of this research is to prepare thiophene thin films by continuous plasma polymerization method. The effect of operational parameters such as effects of doping, deposition time and applied plasma power on the physical-chemical properties of polymerized thin films were evaluated by studying their thickness, deposition rate, surface morphology, conductivity and chemical compositions.
The results shown that the deposition rates were proportional to the applied plasma power and inversely proportional to the deposition time. The thickness of plasma polymerized thiophene thin films was proportional to the deposition time and the applied power. The surface morphology and roughness analyzed by AFM indicated that the thin films prepared by plasma polymerization were pin-hole free, homogeneous and very smooth. The XPS results helped to observe the evolution of thiophene structure which can explain the variation of chemical composition related to thin film conductivity. XPS results also demonstrated that the percentage of iodine element increases with the conductivity value for plasma polymerized thiophene thin films.
The conductivity analyzed by both the Hall effect measurements and AC impedance measurements demonstrated that the thiophene prepared by plasma polymerization were insulator. On the other hand, we have shown that, the iodine doping can effectively increase the conductivity of plasma polymerized thin films.
Although the thiophene thin films prepared by plasma polymerization in this study provide the conductivity in the range of insulator, the conductivity has been promoted comparing with previous literature. Moreover, the prepared thin films showed good adhesion and smooth surfaces which can be used potentially for novel applications. In order to obtain different range of conductivity, experimental parameters and alternative physical-chemical analyses are planned to be explored.

致謝	I
中文摘要	II
Abstract	III
總目錄	IV
圖目錄	VI
表目錄	VII
第一章、緒論	1
1-1研究背景	1
1-2研究動機	2
第二章、文獻回顧	3
2-1有機導電性高分子	3
2-1-1發展歷史	3
2-1-2導電性高分子定義	4
2-1-2-1能帶理論	4
2-1-2-2偏極子、雙偏極子和孤立子	5
2-1-2-3摻雜(Doping)	6
2-1-3文獻整理	7
2-2單體分子簡介	9
2-3導電性高分子的製備	10
2-3-1選擇電漿方法的原因	10
2-4電漿簡介	10
2-4-1電漿定義	10
2-4-2電漿源種類	11
2-4-2-1直流電漿	12
2-4-2-2電容式偶合射頻電漿	12
2-4-3薄膜沈積	13
2-4-4電漿聚合	13
2-5導電性高分子的應用	14
第三章、研究方法與儀器原理	15
3-1研究目的	15
3-2實驗藥品與儀器	16
3-3實驗流程	16
3-3-1初步測試	16
3-3-2實驗設備	17
3-3-3流量校正	19
3-3-4電漿聚合薄膜	20
3-3-4-1基材準備	20
3-3-4-2電漿聚合	20
3-3-4-3腔體清潔	21
3-3-5薄膜摻雜	21
3-3-6物理性質分析	21
3-3-7化學性質分析	22
3-3-8電學性質分析	22
3-4儀器原理	22
3-4-1原子力顯微鏡	22
3-4-2 X射線光電子能譜儀	22
3-4-3掃描式電子顯微鏡	24
3-4-4石英晶體微量天秤	24
3-4-5交流阻抗儀	24
3-4-6四點探針(Four-Point probe)導電度儀	28
3-4-7電流伏特光度測量儀	29
3-4-8霍爾效應量測系統	29
第四章、結果與討論	30
4-1利用電漿聚合製備賽吩薄膜	30
4-2電漿聚合參數對賽吩薄膜性質之影響	30
4-2-1電漿聚合時間與賽吩薄膜性質之關係	30
(i) 薄膜厚度與電漿聚合時間的關聯分析: α-stepper	31
(ii) 沈積速率與聚合時間的關聯分析: QCM	31
(iii) 表面型態分析: AFM	32
4-2-2電漿聚合功率對賽吩薄膜性質之影響	34
(i) 薄膜厚度與電漿功率的關聯分析: α-stepper	34
(ii) 沈積速率與聚合時間的關聯分析: QCM	35
(iii) 表面型態分析: AFM	35
(iv) X射線電子能譜儀分析: XPS	37
4-3電漿聚合賽吩薄膜的導電性質分析	42
4-3-1未摻雜前賽吩薄膜的導電性質	42
4-3-2 摻雜參數對於賽吩薄膜導電性質的影響: AC impedance	42
4-3-2-1摻雜溫度對於賽吩薄膜導電性質的影響	43
4-3-2-2摻雜時間對於賽吩薄膜導電性質的影響	43
4-3-3 電漿參數對於賽吩薄膜導電性質的影響: Hall effect system	44
4-3-3-1電漿聚合時間對於賽吩薄膜導電性質的影響	44
4-3-3-2電漿聚合功率對於賽吩薄膜導電性質的影響	45
4-4電漿聚合賽吩薄膜物化性質與導電性質之關聯	47
4-4-1電漿聚合薄膜和導電性的關係	47
4-4-2摻雜參數和導電性的關係	48
第五章、結論與建議	49
5-1結論	49
5-2建議	50
第六章、未來目標	51
參考文獻	52

                                

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