臺灣博碩士論文加值系統

從1977年被發現以後，導電高分子就成為近三十多年來學界致力於研究與發展的一個課題，本研究採用之物理氣相沉積法-脈衝式雷射濺鍍法（Pulsed Laser deposition ，PLD）來製作有機分子薄膜，主要之目標為了解有機分子材料在低溫薄膜製程中，所產生之物性或化性變化。本研究使用的三種不同雷射波段分別為193 nm深紫外光、532 nm可見光，以及1064 nm近紅外光，所採用材料為導電性高分子聚苯胺(PANI)與導電性小分子8-羥基喹啉鋁(Alq3)。透過薄膜電性、薄膜表面性質、薄膜化學特性以及奈米尺度之機械性質探討其成膜特性，同時也比較基板的晶格配位對於薄膜特性之影響。結果顯示，不同波長雷射沈積後之薄膜分子量會有很大的差異性，從光譜圖上發現使用532 nm雷射可獲得較類似於原本塊材的靶材特性，而其他波段的雷射則會造成嚴重的特性改變，使用193 nm雷射則可以獲得到更強的奈米機械特性；此外，使用波長越短的雷射可以獲得到越佳的表面形貌；對於小分子而言，從光譜圖上發現經由PLD鍍膜後，薄膜的分子特性也有很大的改變，使用193 nm雷射不僅可獲得很強的機械特性，短波長之雷射亦可使薄膜表面較為平整。綜合而言，以PLD所形成的薄膜其電性因分子量的大改變而產生本質性的改變，而以短波長的193 nm雷射所得之薄膜則有良好之機械特性與表面平整度。

Driven by seeking for more easily processible polymers in optoelectronic devices and systems, conducting polymers, since discovered in 1977, have been being a promising research subject that attracts much attention. The main purpose of the present study is to characterize physical properties of thin polyaniline, PANI, and tris-(8-hydroxyquinoline) aluminum, Alq3, films grown by pulsed laser deposition (PLD) technique. Three particular light wavelengths, including short ultraviolet light at 193 nm, visible light at 532 nm, and near infrared light at 1064 nm, were employed for the deposition. The conductivity, surface morphology and mechanical properties of the thin PANI films on substrates of Si (100), Si (110), Si (111) and glass as well as thin Alq3 films on substrates of Si (100) and glass were presented. Results show that both the conductivity and molecular weights of the thin films grown by PLD are remarkably reduced when compared to their corresponding target materials. The film grown by the wavelength at 532 nm has relatively more favorable conductivity than the films grown by the wavelengths at 193 nm and 1064 nm and the shorter the light wavelength the better surface morphology was obtained. It was also found that an incredible hardness was obtained by a nanoindenter tester for both the PANI and Alq3 films grown by the light at 193 nm. In summary, the conductivity, surface morphology, and mechanical properties of the thin PANI and Alq3 films deposited by the PLD technique were fundamentally different from their corresponding properties at buck state because the molecular structures were dramatically changed due to the laser material interactions during the deposition process.
From 1977, conduct polymer became an important subject for the academic circle to study and develope. In this study, for the major purpose to understand the changes of physical and chemical properies in low-temperature thin film processing of organic, pulsed laser deposition (PLD) was used to produce the polymeric thim film.
Three kinds of lasers with different wavelengths, including 193nm UV light, 532nm visivle light and 1064nm near red light, and two types of polymer, conduct polymer PANI and small molecule A1Q3, were the main objects used in our study. The characters of thin films were discussed through electric, surface, chemical nano-scale mecanical properties. Furthermore, the influence for the match effect of the substrate's lattice was also investigated.
For polymer, different lasers produced huge variation of thin films' molecular weight. By means of the optical spectrum and electrical properties anaylsis, it's obvious to find that the molecular weight of thin films by 532nm laser are closed to the original target, others were on the contrary. For small molecule, as shorter as the wavelength, one could get a better surface character. Besides, utilizing 193nm laser, stronger mechanical characters could be measured.
In conclusion, no matter using optical spectrum or electrical properties anaylsis, we found that the characters of thin film produced by PLD have huge changes. In order to get high mechanical property, 193nm laser is the best choice. On the other hand, laser with shorter wavelength will produce a smoother surface topography.

中文摘要 i
英文摘要 ii
謝誌 iv
目錄 IV
圖目錄 VI
表目錄 IX
第一章 序論 1
1.1 前言 1
1.2 研究動機與目的 2
1.3 論文架構 2
第二章 文獻回顧與研究重點 4
2.1 薄膜沉積之介紹 4
2.1.1 薄膜沉積的原理 4
2.1.2 薄膜之沉積技術 7
2.1.2.1 物理氣相沉積 7
2.1.2.2化學氣相沉積 8
2.1.3 高分子薄膜製程 10
2.2 雷射沉積（PLD）之原理、發展與應用 11
2.2.1 PLD之原理與設備架構 11
2.2.2 PLD之發展與歷史 12
2.2.3 PLD於有機物之應用 13
2.2.4 影響薄膜沉積的因素 16
2.3導電性高分子 17
2.3.1 導電高分子簡介 17
2.3.2 導電原理 19
2.4 聚苯胺薄膜之介紹與應用 21
2.4.1 聚苯胺的介紹與摻雜 21
2.4.2 聚苯胺薄膜之應用 24
2.5 8-羥基喹啉鋁(Alq3)之介紹與應用 25
2.5.1 8-羥基喹啉鋁(Alq3)之材料介紹和說明 25
2.5.2 8-羥基喹啉鋁(Alq3)之應用 27
2.6 本研究之承傳與創新 29
第三章 實驗架構、流程及量測原理 30
3.1 實驗設計 30
3.2 實驗架構 31
3.3 實驗流程 33
3.3.1 實驗藥品 34
3.3.2 實驗之儀器 34
3.3.4 靶材之製作 41
3.4 量測儀器及其原理 42
3.4.1 四點探針 42
3.4.2 紫外光／可見光吸收光譜 43
3.4.3 傅立葉轉換紅外光譜 44
3.4.4 掃瞄式電子顯微鏡(SEM) 45
3.4.5 原子力顯微鏡(AFM)與奈米壓痕之原理 45
第四章 結果與討論 49
4.1 高分子聚苯胺(PANI-CSA/PVC) 50
4.1.1 導電度與薄膜製程的關係 50
4.1.2 化學特性與薄膜製程的關係 52
4.1.2.1 紫外光光譜儀（UV-Vis） 52
4.1.2.2 傅立葉轉換紅外光光譜儀（FTIR） 55
4.1.2.3 凝膠滲透層析儀(GPC) 58
4.1.3 奈米尺度下之機械性質與薄膜製程之探討 60
4.1.4 薄膜表面形貌與薄膜製程之探討 63
4.1.4.1 電子顯微鏡(SEM)之分析與探討 64
4.1.4.2 原子力顯微鏡(AFM)之分析與探討 67
4.1.5 長時間放置後之現象 70
4.2 小分子8-羥基喹啉鋁(Alq3) 72
4.2.1導電度與薄膜製程的關係 72
4.2.2 化學特性與薄膜製程的關係 73
4.2.2.1 紫外光光譜儀（UV-Vis） 73
4.2.2.2 傅立葉轉換紅外光光譜儀（FTIR） 75
4.2.2.3 螢光光譜儀（PL） 78
4.2.3 奈米尺度下之機械性質與薄膜製程之探討 79
4.2.4 薄膜表面形貌與薄膜製程之探討 81
4.2.4.1 電子顯微鏡(SEM)之分析與探討 81
4.2.4.2 原子力顯微鏡(AFM)之分析與探討 82
第五章 結論與未來建議事項 85
5.1 結論 85
5.2 未來建議 87
參考文獻 88
附錄 93

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