臺灣博碩士論文加值系統

本研究利用 1,4-dibromo-2-nitrobenzene 作為起始物，經過烏耳曼反應、還原
反應、施蒂勒反應及溴化反應製備成新型單體 3,8-bis(5-bromo-4-decylthiophen-2-
yl)benzo[c]cinnoline (M1)；並利用 1,4-dibromo-2-fluorobenzene 作為起始物，經過
硝化反應、烏耳曼反應、施蒂勒反應及還原反應後製備成新型含氟化合物 2,9-
difluoro-3,8-bis(4-decylthiophen-2-yl)benzo[c]cinnoline (10)。以新型單體 (M1) 與
2,5-bis(trimethylstannyl)-thieno[3,2-b]thiophene 進行施蒂勒微波聚合反應出新型
共軛高分子 BZCTT。BZCTT 之數目平均分子量為 24.2 KDa。BZCTT 之熱裂
解溫度 Td5 %為 376 ℃，並展現出良好的熱穩定性。BZCTT 薄膜之紫外光可見光
吸收波長為 478 nm，相較於本實驗室已發表之高分子 BZCTVT，BZCTT 展現
出較藍位移之吸收波長以及較大之光學能隙。於循環伏安法測試中，BZCTT 之
測得結果 (HOMO= -5.80 eV, LUMO= -3.43 eV, Egelec = 2.37 eV) 相較於 BZCTVT
(HOMO= -5.63 eV, LUMO= -3.47 eV, Egelec = 2.16 eV) 展現出較低之 HOMO 能階
以及較大之能隙，可推測 BZCTT 有較佳之大氣穩定性。BZCTT 以 BGTC 形式
製成 OFET 元件進行測試， BZCTT 展現出 p 型半導體之性質。經過 150 ℃熱
退火後之電洞遷移率為 6.02 × 10-5，其電流開關比為 106；170 ℃熱退火後之電
洞遷移率為 9.01 × 10-5，其電流開關比則為 107。最後進行低掠角 X 光繞射測試，
BZCTT 薄膜表現出較傾向 edge-on 之排列方式，並可證實經熱退火後可影響其
結晶性。

A novel monomer, 3,8-bis(5-bromo-4-decylthiophen-2-yl)benzo[c]cinnoline
(M1), and a novel compound, 2,9-difluoro-3,8-bis(4-decylthiophen-2-yl)benzo[c]cinnoline (10), were synthesized via several synthetic steps from 1,4-
dibromo-2-nitrobenzene and 1,4-dibromo-2-fluorobenzene. Novel conjugated polymer
BZCTT was prepared from monomer (M1) and 2,5-bis(trimethylstannyl)-thieno[3,2-
b]thiophene by using Stille coupling polymerization in microwave reactor. The
structure of BZCTT was characterized by 1H-NMR. The number molecular weight of
BZCTT, measured in THF was 24.2 KDa, The decomposition temperature at 5 %
weight loss (T d5 %) of BZCTT was 376 ℃, exhibiting outstanding thermal stabilities.
The optical and electrochemical properties of BZCTT were investigated by UV-vis
spectroscopy and cyclic voltammetry. For BZCTT, absorption peak at 478 nm was
observed, showing hypsochromic shift compared with our previous research, BZCTVT.
The cyclic voltammertric studies revealed that BZCTT exhibited almost same LUMO
(-3.43 and -3.47 eV) and lower HOMO (-5.80 and -5.63 eV) energy levels compared
with BZCTVT. A bottom-gate, top-contact OFET based on BZCTT exhibited p-
channel behavior with hole mobilities of 6.02 × 10-5 and 9.01 × 10-5 cm2 V-1 S-1 and on/off ratio greater than 106 after 150 ℃ and 170 ℃ thermal annealing. Grazing incidence X-ray diffraction result suggest that thin film of BZCTT was prefered edge-on orientation and can be significantly influenced through thermal annealing process.

摘要 I
Abstract II
目錄 III
Figure 索引 IV
Table 索引 IX
一、 緒論 1
1.1 前言 1
1.2 共軛高分子 1
1.3 能帶理論 3
1.4 載子傳遞方式 4
1.5 有機場效電晶體 5
1.5.1 有機場效電晶體之簡介與發展歷史 5
1.5.2 有機場效電晶體之元件結構 6
1.5.3 有機場效電晶體之運作原理 8
1.5.4 有機場效電晶體之基本參數與特性 10
1.5.5 有機場效電晶體之分子堆疊情形 12
二、文獻回顧 13
2.1 高分子有機半導體材料簡介 13
2.1.1 施體材料 (Donor) 13
2.1.2 受體材料 (Acceptor) 15
2.2 導入氟原子取代基對共軛高分子之影響 17
2.3 Thieno[3,2-b]thiophene施體結構在共軛高分子上的應用 24
2.4 高載子遷移率之共軛高分子案例 27
2.5 Benzo[c]cinnoline及其衍生物在共軛高分子上的應用 33
2.6 研究動機 40
三、實驗 42
3.1 實驗所需藥品 42
3.2 實驗設備及儀器 43
3.3 單體合成 44
銅粉活化 44
4,4'-dibromo-2,2'-dinitrobiphenyl (2) 44
3,8-dibromobenzo[c]cinnoline (3) 45
3,8-bis(4-decylthiophen-2-yl)benzo[c]cinnoline (5) 45
3,8-bis(5-bromo-4-decylthiophen-2-yl)benzo[c]cinnoline (M1) 46
1,4-dibromo-2-fluoro-5-nitrobenzene (7) 47
4,4'-dibromo-5,5’-difluoro-2,2'-dinitrobiphenyl (8) 48
4,4’-bis(4-decylthiophen-2-yl)- 5,5’-difluoro-2,2’-dinitrobiphenyl (9) 48
2,9-difluoro-3,8-bis(4-decylthiophen-2-yl)benzo[c]cinnoline (10) 49
3.4 高分子聚合 51
四、結果與討論 52
4.1 單體與高分子的合成 52
4.1.1 合成反應 52
4.1.2 單體之合成與性質表徵 55
4.1.3 高分子之合成與性質表徵 71
4.2 高分子分子量與溶解度研究 72
4.3 高分子熱學性質分析 74
4.4 高分子光學性質 77
4.5 高分子電性質分析 80
4.6 高分子構型模擬與能階分佈 83
4.7 元件特性分析 84
4.8 高分子結構分析 88
五、結論 94
參考文獻 95

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