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研究生:楊政憲
研究生(外文):Cheng-Hsien Yang
論文名稱:含2,3,4,5-四苯基噻吩發光基團之雜環高分子
論文名稱(外文):Light-emitting hetero-cyclic polymers containing 2, 3, 4, 5- tetraphenylthiophene moiety
指導教授:洪金龍
指導教授(外文):Jin-Long Hong
學位類別:碩士
校院名稱:國立中山大學
系所名稱:材料科學研究所
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:82
中文關鍵詞:噁二唑基團發光二極體去鹵化縮合聚合四苯基噻雜環高分子
外文關鍵詞:light-emitting diodestetraphenylthiophenedehalogenation polycondensationhetero-cyclic polymeroxadiazole
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以四苯基噻吩(TP)為單元之雜環高分子可經由不同聚合方式製備而得。首先,2,5-bis(4-bromophenyl)-3,4-diphenylthiophene (TP-Br)可分別與NiCl2/PPh3或n-BuLi行偶合反應得到TP重複單元之高分子(PTP-NiCl2及PTP-BuLi)。高分子PTP-NiCl2及PTP-BuLi均可溶於一般的有機溶劑且其PL最大放射光譜分為488及483 nm。另外,以縮合聚合的方式可將具電洞傳遞性質的TP基團與具電子傳遞性質的噁二唑基團聚合成一p-n態的共聚高分子(PTP-OXD)。高分子PTP-OXD的PL最大放射光譜(=507 nm)比高分子PTP-NiCl2及PTP-BuLi皆高。由循環伏安法的結果顯示,導入1,3,4-噁二唑基團之高分子PTP-OXD較PTP-NiCl2能有效的發揮電子、電洞注入的平衡作用。


Polymers containing bulky tetraphenylthiophene (TP) moieties were prepared by different coupling reactions. Firstly, 2,5-bis(4-bromophenyl)-3,4-diphenylthiophene (TP-Br) was coupled together by either NiCl2/PPh3 or n-BuLi to form polymers with TP as the repeat unit. The resulting polymers (PTP-NiCl2 and PTP-BuLi) are easily soluble in organic solvents and are photoluminescent (PL) materials (□max = 488 and 483 nm, respectively). The other approach combine both the hole- transporting TP and the electron-transporting 2,5-oxadiazole moieties in the copolymer chain by polycondensation reaction. The resulting polymer (PTP-OXD) emits at wavelength (□max = 507 nm) relatively longer than those for PTP-NiCl2 and PTP-BuLi. From CV measurement, PTP-OXD was confirmed to possess better charge injection balance than PTP-NiCl2.


目錄
中文摘要i
Abstractii
目錄iii
流程目錄v
表目錄vi
圖目錄vii
第一章 緒論1
§1.1 前言1
§1.2 共軛導電高分子的簡介及發展1
§1.3 其軛導電高分子的光電特性及應2
§1.4 高分子發光二極體的基本原理及元件構造5
§1.5 高分子發光二極體的未來發展方向6
第二章 文獻回顧12
§2.1 前言12
§2.2 合成部分12
§2.3 物性部分16
§2.4 研究動機19
第三章 實驗部分30
§3.1 實驗裝置及設備30
§3.2 分析儀器31
§3.3 藥品33
§3.4 實驗部分35
第四章 結果與討論42
§4.1 前言42
§4.2 化合物結構之鑑定42
§4.3 化合物之熱性質鑑定46
§4.4 溶解度測試47
§4.5 化合物之光學性質48
§4.6 高分子之電化學性質50
第五章 結論52
參考文獻77
流程目錄
(List of Schemes)
Scheme 1. Synthetic Route to Poly(tetraphenylthiophene) (PTPT).
53
Scheme 2. Synthetic Route to Poly(tetraphenylthiophene-2,5- oxadiazloe-p-phenyl-2,5-oxadiazole) (PTPT-OXD).54
表目錄
(List of Table)
Table 1. The synthetic results of compounds.56
Table 2. GPC results of polymer 4, 557
Table 3. Thermal properties of 1, 2, 4, 5 and 11 obtained by DSC and TGA.
57
Table 4. Solubility of 1, 2, 4, 5 and 11.58
Table 5. The absorption and photoluminescence maxima of 1,
4, 5 and 11 at room temperature.58
Table 6. The Stokes shift of 4, 5 and 11 in liquid and solid states.59
Table 7. Electrochemical and optical data of 4 and 11.59
圖目錄
(List of Figures)
第一章 緒論
Fig. 1-1 Chemical structure of common conjugated polymers.8
Fig. 1-2 The molecular structure of 1,3-butadiene.8
Fig. 1-3 Structures of conjugated polymer: (a) trans-polyacetylene ;(b)
polythiophene; (c) poly(p-phenylene); (d) polypyrrole; (e) poly(p-phenylene vinylene); (f) poly(2,5-thienylene vinylene).9
Fig. 1-4 Slice through a plastic transistor. In the technique used by Drury et al., layers of polymer are cast one by one on a spinning disk, and the electrodes are patterned by ultraviolet light.10
Fig. 1-5 Schematic structure of a polymer LED formed with a single layer of conjugated polymer.11
Fig. 1-6 Engineer band-edge offset between HTL and ETL, so that electrons
in the ETL are trapped at the heterojunction, and capture holes
injected into the HTL capture at heterojuction.11
第二章 文獻回顧
Fig. 2-1 The earliest recommented synthesis method of polythiophene.22
Fig. 2-2 The others synthetic methods of polythiophenes..23
Fig. 2-3 Coupling of dihalobenzenes..24
Fig. 2-4 Structure of thiophene monomers and oligmers investigated in
this study.(49)25
Fig. 2-5 The chemical structures of the materials used in this study.(50)26
Fig. 2-6 Synthetic Route.(53)27
Fig. 2-7 Cyclic of oligoarylenes and polyarylenes. (60a-d)28
Fig. 2-8 (a) Synthetic route of TPT;(b) The 3-D simulate digram of PTPT.29
第四章 結果與討論
Fig. 4-1 1H-NMR spectrum of 1.60
Fig. 4-2 1H-NMR spectrum of 2.61
Fig. 4-3 Differential scanning calorimetric curves of (a) 2;Tm=251℃;
△H=80 J/g (b) Ullmann reaction;Tm=241℃;△H=56 J/g
;at a heating rate of 10℃/min in nitrogen.62
Fig. 4-4 1H-NMR spectrum of 4.63
Fig. 4-5 1H-NMR spectrum of 5.64
Fig. 4-6 1H-NMR spectrum of 6.65
Fig. 4-7 FT-IR spectra of compound of 1, 6 and 7.66
Fig. 4-8 FT-IR spectra of compound of 10 and 11.67
Fig. 4-9 Thermograimetric curves of 1, 2, 4 and 5 with a heating rate of
10℃/min in nitrogen.68
Fig. 4-10 Differential scanning calorimetric curves of (a) TPT;Tm=188℃
;△H=98 J/g;(b) TPT- Br;Tm=251℃;△H=80 J/g at a
heating rate of 10℃/min in nitrogen.69
Fig. 4-11 Differential scanning calorimetric curves of 4;Tg=177℃;△
Cp=1.31 J/g℃, 5;Tg=122℃;△Cp=0.25J/g℃ and 11 ;
Tg=170℃;△Cp=2.01 J/g℃at a heating rate of 10℃/min in
nitrogen.70
Fig. 4-12 UV/Vis absorption spectra of 1, 4 , 5and 11 in solution states at
room temperature.71
Fig. 4-13 UV/Vis absorption spectra of 4 , 5and 11 in film states at room temperature.72
Fig. 4-14 Photoluminescence spectra of 4 , 5and 11 in solution states at room
temperature.73
Fig. 4-15 Photoluminescence spectra of 4 , 5and 11 in film states at room temperature.74
Fig. 4-16 CV of 4 and 11 coated on ITO electrodes in acetonitrile containing
0.1 M n-Bu4NClO4 at a scan rate of 50 mV/s.75
Fig. 4-17 Energy level diagram of 4 and 11 from CV and UV-vis
absorption spectrum.


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