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研究生: 黃鐙毅
Deng-Yi Huang
論文名稱: 利用溶液製程製作不同次結構之併環噻吩小分子高效能有機場效應電晶體
Solution-Processable Tetrathienoacene (TTA) Based Small Molecules with Different Substructure For Organic Field Effect Transistor (OFET) Application
指導教授: 劉振良
Cheng-Liang Liu
口試委員:
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程與材料工程學系
Department of Chemical & Materials Engineering
論文出版年: 2016
畢業學年度: 104
語文別: 中文
論文頁數: 108
中文關鍵詞: 場效應電晶體溶液製程有機小分子半導體材料併環噻吩
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  • 以接上側鏈增加溶解度之四併環噻吩(3,7-dipentadecyltetrathienoacene;TTAR)為核心並在兩側接上三種不同數目併環噻吩構成之次結構: (1) 2,6-di(thiophen-2yl) DT、(2) 2,6-di(thieno[3,2-b]- thiophen-2yl) DTT,(3) 2,6-di(dithieno[3,2-b;2’,3’-d]thiophen-2yl) DDTT,來合成實驗中使用的TTAR系列p型有機小分子半導體材料(DT-TTAR、DTT-TTAR、DDTT-TTAR)。
    透過剪切力塗佈之溶液製程,由TTAR系列製成之場效應電晶體隨著次結構上併環噻吩數目增加,其載子遷移率從DT-TTAR的0.03 cm2V-1s-1,增加至DTT-TTAR的0.13 cm2V-1s-1和DDTT-TTAR的0.81 cm2V-1s-1;從UV-vis吸收光譜、AFM表面形貌分析與低掠角X光繞射對有機半導體薄膜之分析,可以觀察到透過增加併環噻吩數量之次結構,使得TTAR系列有著更明顯的分子間硫-硫(S-S)作用力使得分子形成更有序之排列,降低分子內TTAR核心與次結構之間不共平面所造成之影響,形成更有序之分子排列;TTAR系列小分子隨著結構上併環噻吩數量增加,由電性量測得到載子遷移率增加之結果可以觀察到透過改變TTAR核心連接之不同次結構,能夠增強分子間作用力,並對載子遷移率的增加有著正面的影響。


    New synthesis organic semiconductor (OSC) materials with the core of 3,7-dipentadecyltetrathienoacene (TTAR , R = C15H29) combining with three different thiophene-based end-capping groups on both side of TTAR core. These substructures are: (1) 2,6-di(thiophen-2yl) DT, (2) 2,6-di(thieno[3,2-b]- thiophen-2yl) DTT, (3) 2,6-di(dithieno[3,2-b;2’,3’-d]thiophen-2yl) DDTT. Combining with these substructures and TTAR core to form the p-type OSC materials (DT-TTAR, DTT-TTAR and DDTT-TTAR) for organic filed effect transistor (OFET) application.
    By solution shearing process, the mobility of TTAR series OFET increases from 0.03 cm2V-1s-1 (DT-TTAR) to 0.81 cm2V-1s-1 (DDTT-TTAR) with the same trend of increasing number of fused thieophene end-capping groups. With the result analysis from UV-vis absorption spectroscopy, AFM topography and graze incident x-ray diffraction (GIXRD). We can observe the bathochromic shift on UV-vis spectroscopy resulted from stronger intermolecular interaction which is caused by increasing number of fused thiophene end-capping groups by. AFM topography shows that larger domain size with the same trend of increasing number of fused thiophene end-capping group on the both sides of TTAR core. On the analysis result of GIXRD, the azimuthal swing of (0,0,2) diffraction peak reduced by stronger intermolecular interaction induced by end-capping groups. With the aid of stronger intermolecular interaction, the reduction of azimuthal swing shows that more uniform molecular packing along with the qz direction. By the analysis results of UV-vis spectroscopy, AFM topography and GIXRD, the increasing number of fused thiophene end-capping groups provide stronger intermolecular interaction to reduce the effect of non-coplanarity between the TTAR core and end-capping groups. The results show that increasing number of fused thiophene end-capping groups have positive effect on higher charge carrier mobility and more order molecular packing.

    摘要 i Abstract ii 致謝 iv 目錄 v 圖目錄 ix 表目錄 xiv 第一章緒論 1 1-1 前言 1 1-1-2有機場效應電晶體簡介 2 1-2 元件結構與組成 3 1-3 有機場效應電晶體特徵曲線及電性參數 11 1-4 有機半導體材料 16 1-4-1有機小分子半導體材料 17 1-4-2有機高分子半導體材料 22 1-5 有機半導體製程 28 1-5-1 真空熱蒸鍍製程(vacuum thermal deposition) 28 1-5-2 溶液製程(solution process) 30 1-5-2-1液滴塗佈法(drop-casting) 31 1-5-2-2旋轉塗佈製程(spin-coating) 34 1-5-2-3印刷法製程(printing) 36 1-5-2-4半月型塗佈法(meniscus-guided coating)-剪切力塗佈法(solution-shearing) 38 1-6 研究動機 41 第二章 實驗 42 2-1 實驗藥品 42 2-2 實驗設備與裝置 43 2-3 實驗方法 44 2-3-1 基板表面處理與表面修飾層 44 2-3-2 元件製備 45 2-4 實驗分析 46 2-4-1 電性量測 46 2-4-2 紫外光至可見光波段光譜儀(UV-Vis) 47 2-4-3偏光光學顯微鏡(POM) 47 2-4-4原子力學顯微鏡(AFM) 47 2-4-5低掠角X光繞射 (GIWXRD) 48 2-4-6分子模擬計算 48 第三章 結果與討論 49 3-1 有機場效應電晶體元件電性分析 49 3-2 有機小分子半導體材料性質鑑定 52 3-3 溶液製程表面形貌分析 59 3-3-1剪切力塗佈法在光學顯微鏡下表面形貌 59 3-3-2剪切力塗佈法在原子力學顯微鏡下表面形貌 61 3-4 有機小分子材料半導體薄膜微結構分析 64 第四章 結論和未來展望 69 參考文獻 72 附錄 76 分子結構 77 DDPP系列 79 DDTTR 系列 82 DCAT 系列 86 DDTT-BST(b8) 88

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