本研究設計出一系聚雙芴環Poly(spirobifluorene)s (PSFs) 衍生物之深藍光螢光高分子材料，其單體結構中包含以SP3混成軌域的碳原子鍵結創造單分子中雙重π共軛系統，避免芴 (Fluorene) C9位置氧化成酮基所造成發光光譜紅位移的現象，同時增加其結構的剛硬特性，有效提升這一系列聚合物的熱穩定性。為了高效率藍光與良好的成膜性質，本研究更進一步以Suzuki coupling引入含有芘(Pyrene)與三氟甲基等官能基，在整個聚合物系統中創造出施體與受體( Donor and acceptor pairs) 的系統。
然而，在時開發新型材料的設計與合成前，因此若能以電腦先行計算模擬，使用分子動力學(Molecular Dynamics)計算在設定條件下分子在週期內的軌跡、分子內的扭轉，解析材料可能聚備的物理特性，縮短新材料的開發時間與提升模擬的可靠度。
最後成功的以親合性聚縮合反應合成出聚芳香醚高分子(poly(arylene ether)s)。各部份單體以1H-NMR MALDI-TOF MS 與FT-IR證實分子結構， UV-Vis、PL等分析聚合物及其單體吸收與放光光譜特徵與能隙(ΔEg)變化。結果顯示，高分子材料藍光放光 (λmax = 408 nm)。

In this study, poly(spirobifluorene)s (PSFs) alternating copolymer derivatives have been designed. There are incorporating the basic idea of the spiro concept , while retaining their electronic properties is based on the concept of connecting two more or less extended π-systems with identical or different functions (emission, charge transport) via a common sp3-hybridized atom. While increasing its rigid structure characteristics, effectively enhance the thermal stability of polymers in this series. For high efficiency blue and good film-forming properties, the present study further comprising pyrene incorporated in Suzuki coupling and trifluoromethyl and the like functional group, to create a donor and acceptor system.
However, before the development of new materials design and synthesis, so if the computer in advance in order to calculate simulations using molecular dynamics calculations of molecular tracks under set conditions, reversing intramolecular physical characteristics of polyethylene prepared analytical materials may shorten new materials development time.
and pyrene as blue emitter
Finally, successful synthesis of poly-aromatic ether polymer (poly (arylene ether) s) blue light emitting materials. Each part of the monomer 1H-NMR, MALDI-TOF MS and FT-IR confirmed that the molecular structure, UV-Vis, PL analyzed polymer and monomer absorption and emitting spectral characteristics and the energy gap (ΔEg) change. The results showed that the light-emitting polymer materials PL spectrum (λmax = 408 nm).

論文審定書 i
致謝 ii
中文摘要 iii
Abstract iv
目錄 v
圖目錄 viii
表目錄 x
第一章 緒論 1
1-1 前言 1
1-2 有機電激發光二極體的歷史進程與發展 2
1-3 高分子發光二極體PLED簡介 4
1-4 OEL元件之基本結構 6
1-5 OEL元件基本發光原理 8
1-6 有機電激發光的能量轉移機制 11
1-6-1 輻射能量轉移 12
1-6-1 非輻射能量轉移 13
1-7 濃度淬熄效應 15
1-8 有機電激發光元件與材料介紹 16
1-8-1 發光層 16
1-9 OEL 發光效率之定義和測量方法 18
1-10 有機發光二極體色彩鑑定 21
1-11 分子動力模擬 (Molecular Dynamics Simulation) 23
1-11-1 簡介 23
1-11-2 分子動力學基本架構 24
第二章 有機電激發光二極體材料介紹與實驗動機 25
2-1 藍光主發光材料 (emitting materials) 25
2-1-1 二芳香蒽(Diarylanthracene) 衍生物 25
2-1-2 芘 (pyrene) 26
2-2 芴 (Fluorene)與聚芴 (Polyfluorene, PF)衍生物簡介 28
2-3 雙芴環 (9,9-spirobifluorene)衍生物簡介 30
2-4 聚芳香醚 (Poly(arylene ether))s, PAE)衍生物介紹 32
2-5 分子設計理念及研究動機 33
第三章 實驗步驟及實驗架構 34
3-1 實驗架構 34
3-1 分子模擬系統建構方法及參數設定 35
3-1-1 聚芳香醚高分子材料 35
3-1-2 分子數設定 37
3-1-3 模擬系統平台 38
3-1-4 參數設定 39
3-2 合成實驗裝置 41
3-2-1 單頸瓶反應裝置： 41
3-2-2 雙頸瓶反應裝置： 41
3-2-3 減壓濃縮裝置： 41
3-3 量測分析儀器 42
3-3-1 材料結構鑑定儀器 42
3-3-2 光譜特性分析儀器 45
3-3-3 熱性質分析儀器 49
3-4 材料合成 50
3-4-1 藥品總覽 50
3-4-2 單體合成 51
3-4-3 高分子合成 53
第四章 結果與討論 54
4-1 聚芳香醚高分子之模擬分析 54
4-1-1 迴轉半徑 （Radius of gyration） 54
4-1-2 末端距 (End-to-end distance） 54
4-1-3 聚合物整體長鏈的分布情形 55
4-2 聚芳香醚高分子之結構鑑定 57
4-2-1 核磁共振儀 (NMR) 57
4-2-2 基質輔助雷射脫附游離飛行質譜儀 (MALDI-TOF) 59
4-2-3 傅立葉轉換紅外線光譜 (FT-IR) 分析 60
4-1 熱性質分析 62
4-1-1 熱重分析儀(Thermogravimetric analyzer, TGA) 62
4-2 聚芳香醚高分子之光電特性分析 63
4-2-1 材料光學特性的量測 63
第五章 結論 70
參考文獻 71

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