有機薄膜電晶體材料四甲基硫醚基雙噻吩蒽及苯三併環噻吩衍生物之開發

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研究生：	梁有志 You-jhih Liang
論文名稱：	有機薄膜電晶體材料四甲基硫醚基雙噻吩蒽及苯三併環噻吩衍生物之開發
指導教授：	陳銘洲 Ming-Chou Chen
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
畢業學年度：	97
語文別：	中文
論文頁數：	117
中文關鍵詞：	有機半導體
外文關鍵詞：	OTFT
相關次數：	點閱：7 下載：0
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在antradithiophene (ADT) 之2,3,7,8 號位置接上四個甲基硫醚
基，並在ADT 的5, 11 號位置接上苯乙炔基，以增加其穩定度，可溶
性的BPE-TMSADT 已開發得到。利用”one-pot” reaction 苯三併環噻
吩(BDTT) 可以簡單的製備，其衍生物P-BDTT (3)、FP-BDTT (4)、
BT-BDTT (5)、BBDTT (6) 也已開發得到，其中P-BDTT，為一P 型
半導體材料，載子移動率可達0.24 cm2V-1s-1，BBDTT 亦為P 型半導
體材料，也有不錯的載子移動率，可高達0.12 cm2V-1s-1。

Soluble BPE-TMSADT had been developed by attaching four
methylsulfanyl group at 2,3,7,8 position and two phenylethynyl group at
5,11 position. By using ”one-pot” reaction BDTT was synthesized, and
its derivatives, P-BDTT, FP-BDTT, BT-BDTT, BBDTT have been
developed. All of the materials are P-type semiconductors. P-BDTT
exhibited excellent TFT performance with mobility as high as 0.24
cm2V-1s-1. BBDTT also demonstrated good TFT performance with
mobility as high as 0.12 cm2V-1s-1.

摘 要 ......................................................................................................... I
Abstract ...................................................................................................... II
謝 誌 ....................................................................................................... III
目 錄 ...................................................................................................... IV
附錄 ......................................................................................................... VII
Equation ................................................................................................. VIII
Figure ....................................................................................................... IX
Scheme ..................................................................................................... XI
Table ....................................................................................................... XIII
附錄目錄 ............................................................................................... XIV
第一章 緒論............................................................................................... 1
1-1 前言 .............................................................................................. 2
1-2 有機場效電晶體導論 .................................................................. 3
1-3 有機薄膜電晶體結構 .................................................................. 6
1-5 有機半導體載子移動率影響因素 ............................................ 10
1-5-1 分子設計 ............................................................................. 10
1-5-2 分子排列模式 ..................................................................... 11
V
1-5-3 介電層表面 ......................................................................... 13
1-6 有機薄膜的製備方式 ................................................................ 15
1-6-1 氣相沈積 ............................................................................. 15
1-6-2 液相沈積 ............................................................................. 16
1-7 有機半導體材料 ........................................................................ 18
1-7-1 P-type 有機半導體材料 ...................................................... 19
1-7-2 N-type 有機半導體材料 ..................................................... 20
1-7-3 Ambipolar 有機半導體材料 ............................................... 22
1-8 載子移動率之計算 .................................................................... 23
1-9 研究目的與動機 ........................................................................ 25
第二章 實驗部分 .................................................................................... 31
2-1 化合物名稱對照表 .................................................................... 32
2-2 實驗藥品 .................................................................................... 33
2-2-1 實驗所用之化學物品 ......................................................... 33
2-2-1 實驗所用之溶劑除水方式 ................................................ 34
2-3 實驗儀器 .................................................................................... 35
2-3-1 核磁共振光譜儀 ................................................................. 35
2-3-2 紫外光/可見光吸收光譜儀 ............................................... 35
2-3-3 示差熱掃描卡計 ................................................................. 35
VI
2-3-4 高解析質譜儀 ..................................................................... 36
2-3-5 熱重分析儀 ......................................................................... 37
2-3-6 電化學裝置 ......................................................................... 37
2-4 合成步驟 .................................................................................... 38
2-4-1 2,3,8,9-Tetrakismethylsulfanyl-1,7-dithiadicyclopenta[
b,i]anthracene-5,11-dione (TMSADT-5,11-
-dione; 13) 之合成 .............................................................. 38
2-4-2 2,3,8,9-Tetrakismethylsulfanyl-5,11-bisphenylethynyl-
1,7-dithiadicyclopenta[b,i]anthracene (1)
之合成 .................................................................................. 44
2-4-3 Benzodithieno[3,2-b:2’,3’-d]thiophene (BDTT; 2)
之”one-pot”合成步驟 .......................................................... 45
2-4-4 2-Phenylbenzodithieno[3,2-b:2’,3’-d]thiophene
(P-BDTT; 3) 之合成 .......................................................... 48
2-4-5 2-Pentafluorophenylbenzodithieno[3,2-b:2’,3’-d]thiophene
(FP-BDTT; 4) 之合成方法一 ............................................ 49
2-4-6 2-Pentafluorophenylbenzodithieno[3,2-b:2’,3’-d]thiophene
(FP-BDTT; 4) 之合成方法二 ............................................ 50
2-4-7 2-Bromobenzodithieno[3,2-b:2’,3’-d]thiophene
(2-BrBDTT; 15) 之合成方法 ............................................ 50
2-4-8 2-Benzothiophenylbenzodithieno[3,2-b:2’,3’-d]-
thiophene (BT-BDTT; 5) ..................................................... 51
VII
2-4-9 [2, 2’]Bi[benzodithieno[3,2-b:2’,3’-d]thiophenyl]
(BBDTT; 6) 之合成 ........................................................... 52
2-4-10 Dibenzo[d,d’]thieno[3,2-b;4,5-b’]dithiophene
(DBTDT) 之合成 ............................................................. 53
第三章 結果與討論 ................................................................................ 55
3-1 有機半導體分子之合成探討 .................................................... 56
3-1-1 BDTT (2) 之合成探討 ....................................................... 56
3-1-2 P-BDTT (3) 與FP-BDTT (4) 合成探討 ......................... 59
3-1-3 BT-BDTT (5) 合成探討 ..................................................... 59
3-1-4 BBDTT (6) 合成探討 ........................................................ 61
3-1-5 DBTDT 合成探討 ............................................................... 62
3-2 有機半導體之光學性質探討 .................................................... 63
3-2-1 UV 光學性質探討 ............................................................... 63
3-2-2 DPV 光學性質探討 ............................................................. 67
3-3 熱穩定性探討 ............................................................................ 69
3-4 有機半導體之載子移動率探討 ................................................ 71
第四章 結論............................................................................................. 77
參考文獻 ................................................................................................... 79
附錄……………………………………………………………………..83
VIII
Equation
Equation 1-1. 載子移動率於線性區之計算公式……………………..23
Equation 1-2. 載子移動率於飽和區之計算公式……………………..24
Equation 1-3. 由Equation 1-2 轉換之計算公式…………………...... 24
Equation 1-4. 電容計算公式…………………………………………..25
IX
Figure
Figure 1-1. OTFT 應用於可撓曲顯示器的實例 .................................... 4
Figure 1-2. 場效電晶體結構示意圖 ........................................................ 6
Figure 1-3. 常見有機場效電晶體之結構 ................................................ 7
Figure 1-4. P 型與N 型通道FET 與其電流方向 .................................. 9
Fiqure 1-5. 半導體分子間排列方式與電子傳遞關係示意圖 ............. 11
Figure 1-6. 電荷在有機半導體間的傳遞 .............................................. 12
Fiqure 1-7. 半導體分子排列方式 .......................................................... 13
Figure 1-8. 介電層表面官能基與electron trapping 能力關係圖 ........ 14
Figure 1-9. 真空蒸鍍法與氣相沈積法示意圖 ...................................... 16
Figure 1-10. 溶液製程示意圖 ................................................................ 18
Figure 3-1. 副產物之NMR 300 MHz 光譜圖 ..................................... 58
Figure 3-2. BPE-TMSADT UV 吸收之時間變化圖 ............................ 63
Figure 3-3. BPE-TMSADT (1) 最大吸收峰UV 吸收變化圖 ............ 64
Figure 3-4. BPE-TMSADT (1) 衰減速率變化圖 ................................ 64
Figure 3-5. BPE-TMSADT (1) 在遮光下的UV 吸收度變化 ............ 66
Figure 3-6. BDTT 系列UV 吸收圖 ...................................................... 66
Figure 3-7. FP-BDTT (4) 光穩定度測試圖 ......................................... 67
Figure 3-8. BPE-TMSADT 與BPE-ADT、BPE-TBADT 之能階圖 . 68
X
Figure 3-9. BDTT 系列之能階圖 .......................................................... 69
Figure 3-10. BPE-TMSADT (a) TGA 曲線(b) DSC 曲線 ................... 70
Figure 3-11. BBDTT 之電性圖 ............................................................. 73
Figure 3-12. log ID-VG 曲線圖 ................................................................ 74
XI
Scheme
Scheme 1-1. 文獻上之P-type 有機半導體材料 .................................... 20
Scheme 1-2. 文獻上之N-type 有機半導體材料 ................................... 21
Scheme 1-3. 文獻上之Ambipolar 有機半導體材料 ............................. 22
Scheme 1-4. 文獻上之pentacene precursor ........................................... 26
Scheme 1-5. Howard E. Katz 發表之半導體材料 ................................. 27
Scheme 1-6. John E. Anthony 發表之半導體材料 ................................ 27
Scheme 1-7. 本計劃預定開發的噻吩蔥 (ADT) ................................... 28
Scheme 1-8. 文獻中的有機半導體材料 ................................................ 29
Scheme 1-9. 本計劃預定開發的苯三併環噻吩 (BDTT) .................... 30
Scheme 2-1. TMSADT-5, 11-dione (13) 的合成 .................................. 38
Scheme 2-2. BPE-TMSADT (1) 之合成 .............................................. 44
Scheme 2-3. BDTT (2) 之合成步驟流程圖 .......................................... 45
Scheme 2-4. P-BDTT (3) 之合成步驟流程圖 ...................................... 48
Scheme 2-5. FP-BDTT (4) 之合成方法之一 ....................................... 49
Scheme 2-6. FP-BDTT (3) 之合成方法之二 ....................................... 50
Scheme 2-7. 2-BrBDTT (15) 之合成方法 ............................................ 50
Scheme 2-8. BT-BDTT (5) 之合成方法 ............................................... 51
XII
Scheme 2-9. BBDTT (6) 之合成方法 ................................................... 52
Scheme 2-10. DBTDT 之合成方法 ...................................................... 53
Scheme 3-1. DTT 之合成討論 ............................................................... 57
Scheme 3-2. BDTT (2) 之合成 .............................................................. 58
Scheme 3-3. FP-BDTT (4) 之合成方法 ............................................... 59
Scheme 3-4. BT-BDTT (5) 之合成方法 ............................................... 60
Scheme 3-5. 文獻上BNT 之合成方法 .................................................. 61
Scheme 3-6. BBDTT (6) 之合成方法 ................................................... 61
Scheme 3-7. DBTDT 之合成 ................................................................. 62
Scheme 3-8. pentacene 可能的decomposed 機制 ................................. 65
XIII
Table
Table 1-1. 傳統TFT 與OTFT 的比較 ................................................... 5
Table 1-2. 真空蒸鍍法與液相製程之比較 ............................................ 18
Table 3-1. BDTT 系列熔點及裂解溫度 ................................................ 71
Table 3-2. 有機半導體之OTFT 元件效能 ........................................... 75
XIV
附錄目錄
附錄1. 3-bromo-2-methylsulfanylthiophene (7)
之1H NMR (CDCl3) 圖譜……………………………………84
附錄2. 3-bromo-2-methylsulfanylthiophene (7)
之13C NMR (CDCl3) 圖譜…………………………………...84
附錄3. 2,3-bismethylsulfanylthiophene (8)
之1H NMR (CDCl3) 圖譜…………………………………....85
附錄4. 2,3-bismethylsulfanylthiophene (8)
之13C NMR (CDCl3) 圖譜…………………………………...85
附錄5. 5-bromo-2,3-bismethylsulfanylthiophene (9)
之1H NMR (CDCl3) 圖譜……………………………………86
附錄6. 5-bromo-2,3-bismethylsulfanylthiophene (9)
之13C NMR (CDCl3) 圖譜…………………………………...86
附錄7. 3-bromo-4,5-bismethylsulfanylthiophene-2-carbaldehyde (10)
之1H NMR (CDCl3) 圖譜……………………………………87
附錄8. 2-(3-bromo-4,5-bismethylsulfanylthiophen-2-yl)-[1,3]dioxolane
(11) 之1H NMR (CDCl3) 圖譜 ………..…………......87
附錄9. 4,5-bismethylsulfanylthiophene-2,3-dicarbaldehyde (12)
XV
之1H NMR (CDCl3) 圖譜…………………………………...88
附錄10. 4,5-bismethylsulfanylthiophene-2,3-dicarbaldehyde (12)
之13C NMR (CDCl3) 圖譜…………………………………88
附錄11. TMSADT-5,11-dione (13) 之1H NMR (CDCl3) 圖譜…….89
附錄12. BPE-TMSADT (1) 之1H NMR (CDCl3) 圖譜……….......89
附錄13. 3-bromobenzo[b]thiophene (14)
之1H NMR (CDCl3) 圖譜…………………………….........90
附錄14. 3-bromobenzo[b]thiophene (14)
之13C NMR (CDCl3) 圖譜…………………………..……..90
附錄15. BDTT (2) 之1H NMR (CDCl3) 圖譜…………………......91
附錄16. BDTT (2) 之13C NMR (CDCl3) 圖譜………………….…91
附錄17. P-BDTT (3) 之1H NMR (CDCl3) 圖譜…………………...92
附錄18. P-BDTT (3) 之13C NMR (CDCl3) 圖譜…………………..92
附錄19. FP-BDTT (4) 之1H NMR (CDCl3) 圖譜……………........93
附錄20. FP-BDTT (4) 之19F NMR (CDCl3) 圖譜……………........93
附錄21. 2-BrBDTT (15) 之1H NMR (CDCl3) 圖譜…………….....94
附錄22. 2-BrBDTT (15) 之13C NMR (CDCl3) 圖譜………………94
附錄23. BT-BDTT (5) 之1H NMR (CD2Cl2) 圖譜…………….......95
附錄24. DBTDT 之1H NMR (CDCl3) 圖譜……………………..…95
XVI
附錄25. BPE-TMSADT 氧化電位DPV 曲線圖…………………..96
附錄26. BPE-TMSADT 還原電位DPV 曲線圖…………………..96
附錄27. BDTT 系列氧化電位DPV 曲線圖………………………..97
附錄27. BDTT 系列還原電位DPV 曲線圖………………………..97

                                

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