臺灣博碩士論文加值系統

摘要
本論文利用旋轉塗佈技術製作RR-P3HT薄膜，首先探討其分子結構，接著探討利用此薄膜當有機半導體層製作有機二極體元件及有機薄膜電晶體元件之特性。分子結構部份，利用廣角X-ray繞射(WXRD)、紫外光-可見光光譜(UV-VIS)、與拉曼光譜(Raman Spectroscopy)探討其結構，發現RR-P3HT溶液濃度愈高，旋轉塗佈轉速愈慢，製作RR-P3HT薄膜之結構序次性愈佳，有效共軛長度愈長，片狀結構愈明顯。有機二極體元件部份，元件結構以電極沈積於有機層之上的特性較好，此外，與RR-P3HT為歐姆接觸的ITO電極為較佳選擇。有機薄膜電晶體部份，使用濃度0.88wt%與2wt% 之RR-P3HT 溶液製作之元件，具有明顯的電晶體特性，載子遷移率皆在10-3 cm2/Vs等級。然而使用較稀濃度0.05wt% 製作的元件，並未觀察到電晶體特性。

Abstract
In this study, Regioregular Poly(3-hexylthiophene) (RR-P3HT) films were prepared by using spin-coating technique. The molecular structure of these films was discussed and the characteristics of the organic diodes and thin film transistors made by these films were investigated.
The molecular structure of these organic films was characterized by wide angle X-ray diffraction, UV-VIS absorption spectroscopy, and raman spectroscopy. As the concentration of RR-P3HT solution is increased and spinning speed is lowered，the structure order of RR-P3HT films will be better and the effective conjugate length will be longer and lamellar structures will increase. For the organic diode, the performance of device structure will be better as the electrodes were deposited upon the organic layer. ITO was the better material for electrodes.
For the organic thin film transistor, the transistor work obviously as it was fabricated by using 0.88wt% and 2wt% of RR-P3HT solution, and the mobility in the order of 10-3 cm2/Vs. There was no transistor performance as the device was fabricated using 0.05wt% of RR-P3HT solution.

目錄
誌謝………………………………………………………………………I
中文摘要…………………………………………………………………Ⅱ
英文摘要……………………………………………………………….Ⅲ
目錄…………………………………………………………………Ⅳ
表索引……………………………………………………………Ⅶ
圖形索引………………………………………………………………Ⅷ
第一章 緒論及文獻回顧…………………………………………1
1-1 前言………………………………………………………………1
1-2 有機二極體………………………………………………………2
1-3 有機薄膜電晶體………………………………………………2
1-3-1 有機薄膜電晶體的基本原理與構造…………………3
1-3-2 有機薄膜電晶體的基本公式及特性…………………5
1-3-3 有機薄膜的製程方法…..………………………………6
1-3-4 有機半導體材料…..……………………………………6
1-4 本論文目的與組織架構…………………………………………8
本章圖表………………………………………………………………9
第二章 實驗方法…………………………………………………16
2-1 有機材料…………………………………………………………16
2-1-1 Regioregular Poly(3-hexylthiophene)…………………16
2-1-2 Poly(methyl methacrylate)………………………………16
2-1-3 薄膜製備…………………………………………………16
2-2 電極材料與製備…………………………………………………17
2-2-1 鋁(Aluminum﹔Al)電極…………………………………17
2-2-2 鉻(Chromium﹔Cr)電極…………………………………17
2-2-3 金(Golden﹔Au)電極……………………………………17
2-2-4 氧化銦錫(Indium Tin Oxide)電極…………………… 17
2-3 元件結構…………………………………………………………17
2-3-1 金屬-半導體-金屬二極體……………………………17
2-3-2 有機薄膜電晶體…………………………………………18
2-4 特性分析…………………………………………………………18
2-4-1 表面型態…………………………………………………18
2-4-2 膜厚量測…………………………………………………18
2-4-3 熱分析……………………………………………………19
2-4-4 X-ray結構分析…………………………………………19
2-4-5 紫外光-可見光光譜分析…………………………………19
2-4-6 拉曼分析…………………………………………………19
2-4-7 電性分析…………………………………………………20
本章圖表………………………………………………………………21
第三章 結果與討論………………………………………………...25
3-1 Regioregular Poly(3-hexylthiophene)鍍膜之物性分析…………25
3-1-1 表面型態…..……..………………………………………..25
3-1-2 熱分析…..……..……………………………………….….25
3-1-3 X-ray結構分析…..……..………………………………..25
3-1-4 紫外光-可見光光譜分析…..……..………………………26
3-1-5 拉曼分析…..……..………………………………………..27
3-2 金屬-半導體-金屬二極體電性分析及探討……………………..28
3-2-1 金屬效應…..……..…………………………………….….28
3-2-2 結構效應…..……..…………………………………….….29
3-2-3有機半導體層及通道效應…………….…………………..30
3-3 有機薄膜電晶體電性分析及探討………………………………..31
3-3-1 絕緣層效應…..……..……………………………………..31
3-3-2 RR-P3HT薄膜製程條件效應…..……..…………………32
本章圖表………………………………………………….……………34
第四章 結論…………………………….………..……………………73
參考文獻…………………………………………………….…………75

表索引
表1-1各種薄膜電晶體之載子移動速率比較…………...………….…9
表1-2 一般有機薄膜的沉積方法………………………...…………..10
表2-1 MSM Diode試片分類……………………………….…………21
表3-1 RR-P3HT在不同濃度及不同轉速下之偏極化紫外光-可見光光譜分析……………...……………………………………………34
表3-2 RR-P3HT在不同濃度及不同轉速下之拉曼光譜分析……….35
表3-3四種電極材料與RR-P3HT之接面電阻……………………….36
表3-4 PMMA在不同濃度及不同轉速下之漏電流比較…………….37
表3-5 RR-P3HT在不同濃度及不同轉速下之電晶體特性比較…….38







圖形索引
圖1-1常見的共軛高分子化學結構。….………………………………11
圖1-2 1, 3-丁二烯(1, 3-butadiene)分子結構。….……………………..12
圖1-3 OTFT元件結構示意圖。….…………………………………….13
圖1-4 OTFT電性圖，(a) IDS vs. VDS﹔(b) IDS1/2 vs. VG。….…………...14圖1-5 有機半導體材料(a) 高分子﹔(b) 共軛性寡聚體﹔(c) 富含電子分子。….…………………………………………………….15
圖2-1 (a) RR-P3HT化學結構﹔(b) PMMA化學結構。….…………...22
圖2-2 MSM Diode元件結構示意圖，(a) 結構一﹔(b) 結構二﹔(c) 結構三。….…………………………………………………………23
圖2-3 上閘極式(Top Gate)電晶體示意圖。….……………………….24
圖3-1 RR-P3HT在不同濃度及不同轉速下之AFM(2D)。….………..39
圖3-2 RR-P3HT在不同濃度及不同轉速下之AFM(3D)。….………..40
圖3-3 RR-P3HT之DSC Curve，(a) Powder﹔(b) Film。….…………..41
圖3-4 RR-P3HT Powder之TGA Curve。….…………………………..42
圖3-5 RR-P3HT薄膜之微觀結構，(a) RR-P3HT化學結構﹔(b) 片狀(Lamellae)結構。….……………………………………………..43
圖3-6 RR-P3HT在不同濃度及不同轉速下之X-ray繞射圖譜。…….44
圖3-7 RR-P3HT在不同濃度及不同轉速下之Non-Polarization UV-Vis圖譜。….…………………………………………………………45
圖3-8 RR-P3HT在不同濃度及不同轉速下之P-Polarization UV-Vis圖譜。….……………………………………………………………46
圖3-9 RR-P3HT在不同濃度及不同轉速下之S-Polarization UV-Vis圖譜。….……………………………………………………………47
圖3-10 RR-P3HT在不同濃度及不同轉速下之Raman圖譜。….……48
圖3-11 RR-P3HT在Raman圖譜下之分子鍵結及振動模式。….……49
圖3-12 四種電極材料:Al、Cr、Au及ITO和RR-P3HT的界面能帶圖。….………………………………………………………….50
圖3-13 四種電極材料:Al、Cr、Au及ITO和RR-P3HT(0.88wt％，1400rpm)的MSM Diode(結構一，導電通道為50μm)電流-電壓關係曲線圖。….…………………………………………….51
圖3-14 結構二與結構一之MSM Diode電流-電壓關係曲線圖，(a) Al / RR-P3HT / Al﹔(b) Au / RR-P3HT / Au，其中RR-P3HT為0.88wt％，1400rpm，導電通道為50μm。….…………………..52
圖3-15 結構三Al / RR-P3HT / Al之MSM Diode電流-電壓關係曲線圖。….………………………………………………………….53
圖3-16 結構三Al / RR-P3HT / Au之MSM Diode電流-電壓關係曲線圖。….……………………………………………………….54
圖3-17 結構三Au / RR-P3HT / Au之MSM Diode電流-電壓關係曲線圖。….……………………………………………………….55
圖3-18 結構三Cr / RR-P3HT / Al之MSM Diode電流-電壓關係曲線圖。….………………………………………………………….56
圖3-19 結構三Cr / RR-P3HT / Au之MSM Diode電流-電壓關係曲線圖。….……………………………………………………….57
圖3-20 結構三ITO / RR-P3HT / Al之MSM Diode電流-電壓關係曲線圖。….……………………………………………………….58
圖3-21 結構三ITO / RR-P3HT / Au之MSM Diode電流-電壓關係曲線圖。….……………………………………………………….59
圖3-22 RR-P3HT(0.88wt％)在不同轉速下之MSM Diode(結構一，導電通道為50μm)電流-電壓關係曲線圖。…………………….60
圖3-23 RR-P3HT(1400rpm)在不同濃度下之MSM Diode(結構一，導電通道為50μm)電流-電壓關係曲線圖。….…………….….61
圖3-24 RR-P3HT在不同厚度下之MSM Diode(結構一，導電通道為50μm)電流-電壓關係曲線圖。….………...………………….62
圖3-25 RR-P3HT(0.88wt％，1400rpm)在不同導電通道長度下之MSM Diode電流-電壓關係曲線圖，(a) Cr / RR-P3HT / Cr﹔(b) ITO / RR-P3HT / ITO。….………………………………………….63
圖3-26 PMMA在不同濃度及不同轉速下之MIM Diode漏電流-厚度關係曲線圖。….……………………………………………….64
圖3-27 PMMA在不同濃度及不同轉速下之MIM Diode漏電流-轉速關係曲線圖。….……………………………………………….65
圖3-28 RR-P3HT(0.88wt％，700rpm)之OTFT電流-電壓關係曲線圖。….………………………………………………………….66
圖3-29 RR-P3HT(0.88wt％，1400rpm)之OTFT電流-電壓關係曲線圖。….………………………………………………………….67
圖3-30 RR-P3HT(0.88wt％，2100rpm)之OTFT電流-電壓關係曲線圖。….………………………………………………………….68
圖3-31 RR-P3HT(2wt％，700rpm)之OTFT電流-電壓關係曲線圖。….………………………………………………………….69
圖3-32 RR-P3HT(2wt％，1400rpm)之OTFT電流-電壓關係曲線圖。….………………………………………………………….70
圖3-33 RR-P3HT(2wt％，2100rpm)之OTFT電流-電壓關係曲線圖。….………………………………………………………….71
圖3-34 有無PMMA之ITO / RR-P3HT / ITO MSM Diode的電性比較，(a) 無PMMA﹔(b) 有PMMA﹔(c) 電流-電壓關係曲線圖。….………………………………………………………….72

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