本論文為合成聚芳香醚高分子並應用於藍光高分子有機發光二極體，使用螺二芴 (Spirobifluorene)的二氟及二醇衍生物為主體，芘(Pyrene)的二氟衍生物為客體，聚合成一主客體摻雜的高分子。許多文獻以Spirobifluorene為主體材料，接上其他基團形成衍生物，就是想要利用Spirobifluorene的立體障礙性大、結構較為剛硬的優點，來增加衍生物的熱穩定性以及薄膜型態。芘(Pyrene)是一種常見的藍光材料，具有高效率、優異的電子傳輸能力以及良好光色的優點，其缺點為其共平面結構，造成在薄膜態時容易結晶，成膜時會有表面不平均及不穩定的問題，其熱穩定性也不佳。
　　Spirobifluorene衍生物的放光光譜與Pyrene衍生物的吸收光譜有很大的重疊區域，主體可以利用Förster energy transfer 的方式轉移能量至客體，因此會有良好的發光效率。藉由縮和聚合的方式，讓材料能保有小分子的發光特性及高效率，又有高分子的高熱穩定性、良好的薄膜表面形態以及易加工的特性。同時在主客體分子之間增加分子來增加分子間距，藉此減少濃度淬熄效應。
　　本論文利用不同比例的Spirobifluorene衍生物、Pyrene衍生物以及4,4'-Dihydroxybiphenyl聚合出兩個系列的高分子，所有高分子的熱烈解溫度都有提升至550℃以上，其中以P0系列摻雜客體10%有最佳的量子效率。

In this study, a series of poly(arylene ether)s polymer are synthized and applied in blue organic light-emitting diodes. Using Spirobifluorene of difluoro and glycol derivatives as the host material and Pyrene of difluoro derivatives as the guest material to form a host-guest doping system polymer. Many papers are using Spirobifluorene derivatives as host material and synthizing other assembly. Due to Spirobifluorene derivatives’ large steric hindrance and the more rigid structure, materials’ thermal stability and film morphological will be improved. Pyrene is a common blue-light material which has high efficiency、excellent eletron transmission ability and good emitting color. However, Pyrene easily crystallize when it is solid state, because of it’s structure. Pyrene also has some problems on thermal
stability.
　　Spirobifluorene derivatives’ PL spectras have a great overlap with Pyrene derivative’s absorption spectra, therefore, the host materials can transfer energy to the guest material by Förster energy transfer. By using condensation polymerization to synthesize polymer, the emitting material can keep light-emitting characteristics and hight efficiency of the small molecule material, and have hight thermal stability and nice film morphological of the polymer material at the same time.
　　We use different ratios of the Spirobifluorene derivatives、4,4'-Dihydroxybiphenyl and Pyrene derivatives to synthesize two series of blue polymers. All polymers have great thermal stability and their pyrolysis temperature are higher than 550℃. On solid state, the polymer of P0 series has the best quantum efficiency when the guest material’s doping ratios comes to 10%.

中文審定書 i
英文審定書 ii
誌謝 iii
中文摘要 iv
Abstract v
目錄 vii
圖目錄 x
表目錄 xiv
附錄目錄 xv
第一章 緒論 1
1-1 前言 1
1-2 有機發光二極體之發展歷史 2
1-3 有機發光二極體原理 4
1-4 有機電激發光元件掺雜技術 6
1-5 能量轉移機制 7
1-5-1 Förster能量轉移 7
1-5-2 Dexter能量轉移 8
1-6 濃度淬熄效應 8
1-7 文獻回顧 9
1-8 研究動機 14
第二章 實驗材料及實驗儀器介紹 16
2-1 實驗材料 16
2-2 熱分析儀器 16
2-2-1熱重分析儀(Thermogravimetric analyzer，TGA) 16
2-2-2 熱示差掃描卡量計(Differential scanning calorimetry，DSC) 17
2-3 光學分析儀器 18
2-3-1 紫外光與可見光光譜儀(UV-Vis Spectrometer，UV-Vis) 18
2-3-2 螢光光譜儀(Fluorescence spectrometer，PL) 19
2-3-3 光電子光譜分析儀(Photoelectron spectroscopy in air，PESA) 20
2-4 材料鑑定分析儀器 21
2-4-1凝膠滲透分析儀(Gel Permeation Chromatograph，GPC) 21
2-4-2 核磁共振光譜儀(Nuclear Magnetic Resonance，NMR) 22
第三章 實驗 24
3-1 材料製備流程 24
3-1-1 Spirobifluorene衍生物材料製備流程 24
3-1-2 Pyrene衍生物(Py)材料製備流程 25
3-2 Spirobifluorene衍生物 26
3-3 Pyrene 衍生物 32
3-4 藍光高分子合成(P2) 34
3-4-1 高分子P2-000之合成 34
3-4-2 高分子P2-001之合成 36
3-4-3 高分子P2-005之合成 38
3-4-3 高分子P2-010之合成 40
3-4-4 高分子P2-050之合成 42
3-5 藍光高分子合成(P0) 44
3-5-1 高分子P0-000之合成 44
3-5-2 高分子P0-001之合成 46
3-5-3 高分子P0-005之合成 48
3-5-4 高分子P0-010之合成 50
第四章 結果與討論 52
4-1 單體之合成及量測 52
4-1-1 單體之熱穩定性量測 52
4-1-2 單體之光學分析 53
4-2 藍光高分子之合成及量測(P2) 56
4-2-1 高分子之熱穩定性分析 57
4-2-2 高分子之光學分析 59
4-2-3 高分子能階分析 65
4-2-4 高分子量子效率 67
4-3 藍光高分子之合成及量測(P0) 70
4-3-1 高分子之熱穩定性分析 72
4-3-2 高分子之光學分析 74
4-3-3 高分子能階分析 80
4-3-4 高分子量子效率 82
第五章 結論 84
參考文獻 86
附錄 89

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