臺灣博碩士論文加值系統

摘要

高分子發光二極體(Polymer Light Emitting Diode, PLED)始於1990年英國劍橋大學Friend等人的研究，發現共軛高分子可做為發光二極體材料，從此開啟了高分子發光二極體的時代。
聚茀( Polyfluorene)，具有良好的熱安定、化學穩定性，且具有很高的螢光量子效率(Fluorescence Quantum Efficiency)，螢光放射波長涵蓋在400～460 nm(藍光)，很適合作為發藍光的結構。但是Polyfluorene光學穩定性不佳，容易有激發雙體、凝集或是分子因氧化生成酮基(Fluorenone)，而改變發光顏色，降低ΦPL而大大限制其應用性。
Triazole是很好的電子注入傳送材料，藉由Triazole的導入高分子中可以提升電子注入的能力，而改善電荷注入的平衡，增加高分子發光效率。
本研究為了探討Triazole構形對於Polyfluorene的光學穩定性、電化學及元件等的影響，利用Suzuki Reaction，將Fluorene分子與Triazole分子聚合成一系列的高分子。由實驗結果發現，在物理性質方面，P2~P7可以溶於一般的溶劑，如CHCl3、NMP、C2H2Cl4，有利於元件的加工。光學方面，高分子發光主要由Fluorene所貢獻，導入Triazole基團可以改善部分高分子的光學熱穩定性。電化學性質方面，其HOMO與LUMO能階分別為 -5.61, -5.62, -5.61, -5.62, -5.65, -5.62, -5.62eV 與 -2.52, -2.67, -2.70, -2.71, -2.80, -2.82, -2.75 eV。導入Triazole基團之後，可以降低高分子的LUMO能階，使電子注入較容易。但是在電激發光時，高分子的發光依然會有Excimer產生的現象，而使發光光色隨驅動電壓而改變，但隨著Triazole的加入，可以降低Excimer部分的發光，並改善其光色純度。

Abstract

Since the discovery of electroluminescence(EL) in the poly(1,4-phenyl-
enevinylene) (PPV) in 1990, EL conjugated polymers have attracted much interest in recent years because of their potential application in large-area flat panel displays.In the past decade, fluorene-based conjugated polymers (PFs) have emerged as a very promising class of blue-light emitting materials for use in PLEDs because of their high thermal stability, high electroluminescence quantum efficiencies. However, one drawback has limited the application of polyfluorene in blue PLED .For example, excimer , aggregation and fluorenone were observed and the formation of these interaction reduced PL and EL efficiency.
To solve this problem in this study, we prepared a series of fluorine based copolymers with triazole segment aiming to investigate the conformations of copolymers affecting optical stability. The influences of the conformations of triazole on photophysical, electrochemical, and electroluminescent properties of the resulting polymers. The copolymers were soluble in common solvents such as chloroform, NMP, and 1,1,2,2-tetrachloroethane and exhibited good thermal stability with Tds higher than 400℃. The emission of P1~P7 are dominated by the fluorene segment . Furthermore, the HOMO and LUMO energy level of P1~P7 , estimated from electrochemical data, are -5.61, -5.62, -5.61, -5.62, -5.65, -5.62, -5.62eV and -2.52, -2.67, -2.70, -2.71, -2.80, -2.82, -2.75 eV, respectively. It can lower the LUMO energy level . Double-layer light emitting diodes of P1~P7 reveal emission maxima around 480~550 nm. There are still excimer emission and the color changes with the driving voltage . But with the increasing of the triazoles, it can suppress the excimer emission and improve the purity of color.

目 錄

中文摘要……………………………………………………………….……I
英文摘要……………………………………………………...……….…...Ⅱ
誌謝………………………….......………………………………...….……III
目錄……………………………….......…………………………….……...IV
流程目錄………………………….….……………………………………. V
表目錄…………………………………………………………………...... VI
圖目錄………………………………………………………………….... VII


第一章 緒論
1-1 簡介……….…………………….……........……………………....……1
1-2 有機電激發光二極體元件的發光原理與結構……..............................3
1-2-1發光原理...............……..............……......………….………...…....3
1-2-2元件結構.....................….….............................................5
1-2-2-1單層元件.....................….………….........…………...……….5
1-2-2-2 雙層元件及多層元件....….………….........……....….…………....6
1-2-3 發光效率………….........……....…………….........……....…………7
1-3 分子間激發態………….........…………….........……………..........…..8
1-4聚茀之激發雙體(Excimer)改善與分子設計....……………....……….10
1-5 有機發光二極體未來研究方向………………………………………12
1-6 研究動機…………………………………………………………...….13

第二章 文獻回顧
2-1有機發光二極體分子的設計….….……….…………………….......15
2-1-1 高分子有機電致發光材料…......….………………………...........15
2-1-2 電光轉換效率…...……………….………………........................…16
2-2 螢光原理….…………………...............................................................16
2-3 影響螢光的因素……..…...…………………..........…………...........18
2-4 螢光的能量轉移….......……….......………………………………19
2-5聚茀(Polyfluorene)與Triazole.....…………........……….…………..…20

第三章 實驗部份內容
3-1實驗裝置與設備……………….…..........………………………..……24
3-2鑑定儀器…………………….………..…….......………………25
3-3物性及光電特性測量儀器………….…………....………….....26
3-4 藥品及材料……………….………………………….........…..………29
3-5合成步驟與結果……………………………………........…........31
3-5-1單體合成……………………………………….................31
3-5-2高分子合成……………………………….........................34
3-6 聚合反應原理………………….......................……………37
3-6-1有機金屬觸媒……..................…………………………...37
3-6-2 Suzuki Reaction………………………….…................…38
3-7 相對量子產率………………………………………………...………39
3-8 循環伏安法...................................……………………………………39
3-9 元件製作…...………………......................................…………….41
3-9-1 ITO玻璃之清洗…………………...................................41
3-9-2 高分子發光膜的製作…………………............................................42
3-9-3 陰極蒸鍍………………...........………………................................42
3-9-4 元件量測……………...........……………….....................................43
第四章 結果與討論
4-1 單體結構之鑑定…..…………………………….……………………45
4-2高分子結構之鑑定……………………………..…………....46
4-3 高分子3-D分子結構分析...…………………………….……………47
4-4 高分子分子量的測定…................…...…....…………….……………47
4-5 溶解度測試…...........……………………….....……………47
4-6 高分子熱性質分析…………….…………………...............…………48
4-6-1 熱重分析……………………………………….....……..........….…49
4-6-2 微差式掃描熱卡計析........…..……...........………………….…..…49
4-7 高分子光學性質………………..........…………………….……..…...50
4-7-1 高分子在溶液中及薄膜態的光學性質………...….............…...….50
4-7-2高分子在酸性環境下的光學性質......…………...........................…51
4-7-3 光學熱穩定性……………....…………………………………..…..52
4-8 相對量子效率……………...........….......…………………….….……54
4-9 電化學性質探討…………………................................................……55
4-9-1 高分子電化學性質探討…………........................................………56
4-10元件性質討論…………………….....................................………57
4-10-1電流密度(I)-電壓(V)-亮度(L)特性………………………………..57
4-10-2電激發光光譜(Electroluminescence Spectra)…………………...…58
第五章 結論………………………….……………………………………60
參考文獻……………………………….……………...……………......102

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