臺灣博碩士論文加值系統

本研究係以具拉電子特性之丙二腈衍生物(2,6-Dimethyl-yran-4-ylidene-malononitrile)與茀(Fluorene) 或噻吩(Thiophene) 透過Suzuki Coupling進行共聚合反應，並以對溴甲苯進行分子鏈端末端終止反應(End Capping)，合成出含茀與噻吩之主鏈型共聚合高分子MPFM與MPTM；再以具拉電子特性之三氮井(Triazine) 基團作為分枝單元(Branching unit)，合成出含茀與噻吩之多分枝型共聚合高分子HPFM與HPTM。四種高分子於薄膜態之紫外光-可見光最大吸收與最大放光波長分別為：448、457、427、447 nm 與572、562、585、575 nm。經由熱處理程序後，發現四種高分子光學特性產生不同變化，本研究即運用熱處理後光學特性之改變，進行有機高分子發光二極體之製作與探討。
在有機高分子發光二極體之研究中，以 HPFM 為發光層並經80 ℃熱處理後所製得之元件，其亮度為 1031 cd/m2、發光效率為 1.97 cd/A、色度座標 CIE 為(0.48, 0.56)，為四種高分子中亮度效率表現最佳之材料；HPTM 經 160 ℃ 熱處理後所製得之元件，其亮度為213 cd/m2、發光效率為0.11 cd/A、色度座標CIE 為 (0.64, 0.36)，為最接近紅光光色之表現。隨後以多分枝型藍光高分子材料－ PTFA10分別摻混3 wt. %、6 wt. %、8 wt. % 之HPFM，經80 ℃熱處理後所製得之白光發光元件其亮度分別為3523、3252、4173 cd/m2、發光效率分別為2.19、3.30、4.69 cd/A、色度座標 CIE 值為 (0.21, 0.34)、(0.28, 0.49)、(0.23, 0.39)，是為接近白光之光色。

A series of main chain polymers were synthesized by the Suzuki coupling reaction with malononitrile derivative and fluorine, or malononitrile derivative and Thiophene. Moreover, the hyperbranched polymers were synthesized by the same way with electron-withdrawing group triazine as molecular cores. All the polymers were end-capped with p-brombo-toluene. Four red light emitting polymers (LEPs) namely MPFM, HPFM, MPTM and HPTM were synthesized in this study. The maximal UV-Vis absorption and the PL emission of four polymers in solid film were 448, 457, 427, 447 nm and 572, 562, 585, 575 nm, respectively. After thermal annealing, the optical properties were changed with the morphology modification. The thermal annealing effect on electroluminescence properties of the polymer light emitting diodes are discussed.
After annealing at 80 ℃ for 1 hr, the brightness, current efficiency, and Commission Internation de L’Eclairage CIE of HPFM were 1031 cd/m2, 1.97 cd/A, and CIE (0.48, 0.56), which was the best performance of four polymers. Then after annealing at 160 ℃ for 1hr , the brightness, current efficiency, and CIE of HPTM were 213 cd/m2, 0.11 cd/A and　CIE (0.64, 0.36). Deep red emission was observed. In this study, blue light emitting hyperbranched conjugated polymer PTFA10 was blended with 3 wt. %, 6 wt.% and 8 wt.% HPFM to fabricate white polymer light emitting diodes (WPLEDs). After annealing at 80 ℃ for 1 hr, the brightness, current efficiency, and CIE of the EPLEDs were 3523, 3252, 4173 cd/m2, and 2.19, 3.30, 4.69 cd/A, and (0.21, 0.34), (0.28, 0.49), and (0.23, 0.39).

目錄
中文摘要...............................................I
英文摘要...............................................II
誌謝...................................................IV
目錄...................................................V
表目錄.................................................VII
圖目錄.................................................VIII
附錄...................................................XI

第一章 緒論.............................................01
1-1共軛高分子...........................................01
1-2有機發光二極體.......................................02
1-2-1 螢光理論.......................................04
1-2-2 發光理論.......................................05
1-3高分子電激發光元件...................................06
1-3-1 單層電激發光元件結構...........................06
1-3-2 多層電激發光元件結構...........................06
1-3-3 元件發光效率..................................07
1-3-4 電極之選擇.....................................07
第二章 文獻回顧.........................................09
2-1化學結構對發光材料之特性影響.........................09
2-1-1 小分子紅光材料................................09
2-1-2 高分子紅光材料................................09
2-2 多分枝型材料結構之影響...............................11
2-3 熱處理效應...........................................13
2-4 研就動機.............................................14
第三章 實驗部分........................................17
3-1 化學藥品.............................................17
3-1-1 合成所需化學藥品..............................17
3-1-2 元件製作所需材料..............................18
3-2 溶劑之前處理.........................................18
3-3單體之製備............................................18
3-4 高分子材料之聚合.....................................20
3-5 基本物性與光電特性檢測...............................24
3-6元件製作..............................................27
第四章 結果與討論.......................................28
4-1高分子材料之特性分析..................................28
4-1-1 結構鑑定分析..................................28
4-1-2 高分子之分子量分析.............................30
4-1-3 高分子之溶解性測試............................30
4-2熱重分析儀(TGA)和微差熱掃描卡計(DSC)之熱性質分析.....31
4-3 高分子光學性質分析...................................34
4-3-1紫外光-可見光光譜(UV-vis) 分析...................34
4-3-2 螢光光譜(PL)分析................................36
4-4高分子之電化學特性之分析..............................38
4-5 高分子之光學熱穩定性分析.............................41
4-5-1 熱處理後之紫外光-可見光光譜....................41
4-5-2 熱處理後之螢光光譜.............................43
4-6 高分子之光電特性分析.................................46
4-6-1 發光層膜厚測試.................................46
4-6-2 電激發光光譜分析...............................46
4-6-3 高分子電激發光元件之電激發光特性分析...........48
4-7 掺混藍光材料之白光電激發光元件.......................55
4-7-1 紫外光－可見光吸收與螢光放光光譜...............55
4-7-2 白光電激發光光譜分析...........................56
4-7-3 白光電激發光元件之電激發光特性分析.............59
第五章 結論.............................................64
第六章 參考文獻..........................................65
附錄.....................................................68
表目錄
表 1.1 OLED 與 PLED 的比較............................03
表 1.2 常見電極材料之公作函數............................08
表4.1 高分子材料之分子量及其分子量分佈...................30
表4.2 高分子之溶解性測試.................................31
表4.3 高分子之紫外光-可見光吸收最大波峰及螢光放光最大波峰.........37
表4.4 經由循環伏安計量儀所量測高分子HOMO及LUMO值....41
表4.5 紫外光-可見光吸收光譜、螢光光譜薄膜態經熱處理後之最大值.......46
表4.6不同溫度下處理之高分子電激發光元件特性..............48
表 4.7高分子電激發光元件膜厚、最大亮度、電流密度及效率值..52
表 4.8高分子薄膜表面粗糙度...............................55
表 4.9 不同溫度下處理之白光電激發光元件特性..............59
表4.10白光電激發光元件驅動電壓、最大亮度、電流密度及效率
值.................................................63
圖目錄
圖1.1 常見共軛高分子圖...................................01
圖 1.2 絕緣體、半導體及導體共價帶與導帶的能階分佈..........02
圖1.3 發光能階示意圖.....................................04
圖1.4 光激發光示意圖.....................................05
圖1.5 電激發光示意圖.....................................05
圖1.6 單層電激發光元件結構...............................06
圖1.7 多層電激發光元件結構...............................07
圖2.1 DCM 衍生物之分子結構.............................09
圖2.2 PM-PPV結構......................................10
圖2.3 含PPV衍生物之高分子材料..........................10
圖2.4 PF-DCM結構......................................11
圖2.5 PF-PZB結構.......................................11
圖2.6 多分枝型聚茀高分子之化學結構圖....................12
圖2.7 Hongli Wangw 所合成之高分子結構...................12
圖2.8 TRZ-F(MB)3、TRZ-F(MB)5分子結構...................13
圖2.9 PDOFBSF 分子結構................................14
圖2.10 PFx-DPVF 分子結構...............................14
圖2.11 MPFM, HPFM, MPTM及HPTM之高分子結構圖.......15
圖2.12 PAFA10之結構式..................................16
圖3.1 PEDOT/PSS之結構式...............................18
圖3.2 單體製備流程.......................................22
圖3.3 MPFM高分子聚合流程..............................23
圖3.4 HPFM高分子聚合流程..............................23
圖3.5 MPTM高分子聚合流程..............................24
圖3.6 HPTM高分子聚合流程..............................24
圖4.1 四種高分子材料之TGA圖...........................32
圖4.2 MPFM 之DSC圖...................................32
圖4.3 HPFM 之DSC圖...................................33
圖4.4 MPTM 之DSC圖...................................33
圖4.5 HPTM 之DSC圖...................................34
圖4.6 高分子溶液態之紫外光-可見光吸收光譜圖.............35
圖4.7 高分子薄膜態之紫外光-可見光吸收光譜圖.............36
圖4.8 高分子溶液態之螢光光譜圖..........................37
圖4.9 高分子薄膜態之螢光光譜圖..........................37
圖4.10 參考物Ferrocene經由循環伏安計量儀量測之CV圖......39
圖4.11 MPFM經由循環伏安計量儀量測之CV圖...............39
圖4.12 HPFM經由循環伏安計量儀量測之CV圖...............40
圖4.13 MPTM經由循環伏安計量儀量測之CV圖...............40
圖4.14 HPTM經由循環伏安計量儀量測之CV圖...............41
圖4.15 MPFM於不同溫下之紫外光-可見光光譜圖.............42
圖4.16 HPFM於不同溫下之紫外光-可見光光譜圖..............42
圖4.17 MPTM於不同溫下之紫外光-可見光光譜圖.............43
圖4.18 HPTM於不同溫下之紫外光-可見光光譜圖.............43
圖4.19 MPFM於不同溫下之螢光光譜圖......................44
圖4.20 HPFM於不同溫下之螢光光譜圖......................44
圖4.21 MPTM於不同溫下之螢光光譜圖......................45
圖4.22 HPTM於不同溫下之螢光光譜圖......................45
圖4.23 高分子發光元件之電激發光光譜圖(80℃)...............47
圖4.24 高分子發光元件之電激發光光譜圖(120℃)..............47
圖4.25 高分子發光元件之電激發光光譜圖(160℃)..............48
圖4.26 電激發光元件之亮度、電流密度對電壓變化圖(80℃) .....49
圖4.27 電激發光元件之亮度、電流密度對電壓變化圖(120℃) ....50
圖4.28 電激發光元件之亮度、電流密度對電壓變化圖(160℃) ....50
圖4.29 高分子電激發光元件之效率對電壓變化圖(80℃).........51
圖4.30 高分子電激發光元件之效率對電壓變化圖(120℃)........51
圖4.31 高分子電激發光元件之效率對電壓變化圖(160℃)........52
圖4.32 PEDOT/MPFM(15mg/mL)，經不同溫度處理後之AFM圖...53
圖4.33 PEDOT/MPFM(15mg/mL)，經不同溫度處理後之AFM圖...53
圖4.34 PEDOT/MPFM(15mg/mL)，經不同溫度處理後之AFM圖...54
圖4.35 PEDOT/MPFM(15mg/mL)，經不同溫度處理後之AFM圖...54
圖4.36 PTFA10、HPFM 及PTFA10/HPFM 複合薄膜之紫外光-可見光吸收光譜圖.............................................56
圖4.37 PTFA10、HPFM及PTFA10/HPFM 複合薄膜之螢光光譜圖.......................................................56
圖4.38 PTFA10掺混3wt.% HPFM 之白光電激發光光譜圖.......57
圖4.39 PTFA10掺混6wt.% HPFM 之白光電激發光光譜圖........58
圖4.40 PTFA10掺混8 wt.% HPFM 之白光電激發光光譜圖.......58
圖4.41 PTFA/HPFM 掺混之白光電激發光元件之亮度、電流密度對電壓變化圖(80 ℃).........................................60
圖4.42 PTFA10/HPFM 掺混之白光電激發光元件之亮度、電流密度對電壓變化圖(120 ℃)......................................60
圖4.43 PTFA10/HPFM 掺混之白光電激發光元件之亮度、電流密度對電壓變化圖(120 ℃)......................................61
圖4.44 PTFA10/HPFM 掺混之白光電激發光元件之效率對電壓變化圖(80 ℃).................................................61
圖4.45 PTFA10/HPFM 掺混之白光電激發光元件之效率對電壓變化圖(120 ℃)................................................62
圖4.46 PTFA10/HPFM 掺混之白光電激發光元件之效率對電壓變化圖(160 ℃)................................................62
附錄
附錄一 Compound 1 1H-NMR圖...........................68
附錄二 Compound 2 1H-NMR圖...........................68
附錄三 Compound 3 1H-NMR圖...........................69
附錄四 Compound 4 1H-NMR圖...........................69
附錄五 MPFM 1H-NMR圖................................70
附錄六 HPFM 1H-NMR圖................................70
附錄七 MPTM 1H-NMR圖...............................71
附錄八 HPTM 1H-NMR圖................................71

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