以PEDOT:PSS混合石墨烯對光電特性之影響

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姓名

蘇昱綾(Yu-Ling Su) 查詢紙本館藏

畢業系所

機械工程學系

論文名稱

以PEDOT:PSS混合石墨烯對光電特性之影響
(The effects of graphene additives on optoelectronic properties of PEDOT:PSS)

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摘要(中)

透明導電薄膜即是透明且可導電的薄膜，應用相當廣泛，包含觸控面板、太陽能電池、可撓性之LCD及OLED，導電高分子是新型透明導電薄膜的一種，以聚二氧乙基?吩:聚苯乙烯磺酸化合物Poly(3,4-ethylenedioxythiophene): poly(styrene-4-sulfonate)，PEDOT:PSS為代表材料。本研究以簡易的製備方式，將電化學剝離石墨烯(Electrochemical exfoliated graphene，ECG)混合PEDOT:PSS製成複合薄膜，以探討添加石墨烯後的透明導電薄膜之光電特性。電化學剝離石墨烯製備過程不須複雜的化學變化，產率高且成本低。將電化學剝離之石墨烯摻雜在PEDOT:PSS中，PEDOT分子與石墨烯以π-π鍵鍵結，而PSS鏈與石墨烯的微量官能基鍵結，降低PEDOT與PSS間庫倫引力，使PEDOT與PSS分離且PEDOT產生構象變化，且石墨烯與PEDOT形成導電網絡，以利於導電，其片電阻由0.36 kΩ/□降至0.18 kΩ/□。PEDOT:PSS穩定性差，其透明導電薄膜放置約60天後無法測量到片電阻值，從不同天數量測之ATR-FTIR譜圖中可觀察到，C-H及O-H發生明顯變化。而PEDOT:PSS/ECG透明導電薄膜經270天依然可測量到片電阻值，且不同天數量測之ATR-FTIR譜圖之譜線無劇烈變化，故推測PEDOT:PSS中的C-H及O-H鍵結改變使整體結構不穩定導致裂化。PEDOT:PSS混合石墨烯不只可提升導電性，也可提升穩定度耐久性，本實驗將探討PEDOT:PSS劣化原因以及添加石墨烯後改善之處。

摘要(英)

Transparent conductive films (TC films), which have good properties of optically transparent and electrically conductive, are widely used in touch screen, solar cell, flexible LCD and OLED. The conductive polymer is used as TC films, such as Poly(3,4-ethylenedioxythiophene): poly(styrene-4-sulfonate) (PEDOT:PSS). In this study, we used an easier method to mix the electrochemical exfoliated graphene (ECG) into PEDOT:PSS. The effects of graphene additives on optoelectronic properties of PEDOT:PSS were investigated. Electrochemical exfoliation method is widely applied due to high scalability and low production cost, especially it does not need complicatedly chemical reactions. We mixed the ECG powders into PEDOT:PSS. In this way, PEDOT molecular and ECG sheet were combined with π-π bond, and PSS chains bond on the functional group of ECG. These reactions decrease the Coulombic interaction between PEDOT and PSS, which induced phase separation and conformational change of PEDOT. It improved the conductivity of TC films so that the sheet resistance decreased from 0.36 kΩ/□ to 0.18 kΩ/□. In the electrical stability measurement, the sheet resistance of PEDOT:PSS TC films could not be measured after 60 days. The ATR-FTIR spectrum for PEDOT:PSS TC films were employed, where the C-H and O-H peaks were observed changed after 40 days. However, the sheet resistance of PEDOT:PSS/ECG can be measured after 270 days. The ATR-FTIR spectrum for PEDOT:PSS/ECG TC films showed no huge variation. We suppose that the changes of C-H and O-H are the key that makes PEDOT:PSS damaged. In conclusion, the effects of graphene additives promote the conductivity and stability of PEDOT:PSS.

關鍵字(中)

★ 電化學剝離石墨烯
★ 穩定性

關鍵字(英)

★ Electrochemical exfoliated graphene
★ PEDOT:PSS
★ Stability

論文目次

摘要 I
Abstract II
誌謝 III
總目錄 IV
圖目錄 VII
表目錄 XI
第一章緒論 1
1-1 石墨烯簡介 1
1-2 石墨烯製備方式 3
1-2-2 微機械剝離法 (Micromechanical exfoliation) 3
1-2-3 化學氣相沉積法 (Chemical vapor deposition，CVD) 5
1-2-4 化學剝離法 (Chemical exfoliation) 7
1-2-5 電化學剝離法 (Electrochemical exfoliation) 8
第二章研究背景與文獻回顧 10
2-1 透明導電薄膜 10
2-1-2 PEDOT:PSS 11
2-2 PEDOT:PSS 改質方法 13
2-2-1 添加有機溶劑 13
2-2-2 加熱退火 16
2-3 石墨烯混摻PEDOT:PSS 19
2-3-1 氧化石墨烯混摻PEDOT:PSS 19
2-3-2 氧化石墨烯混摻PSS再聚合PEDOT 23
2-3-3 還原氧化石墨烯混摻PEDOT:PSS 25
2-3-4 還原氧化石墨烯混摻PSS再聚合PEDOT 26
2-3-5 電化學剝離石墨烯混摻PEDOT:PSS 28
2-4 實驗動機 29
第三章實驗步驟與檢測方式 30
3-1 實驗架構 30
3-2 玻璃基板清洗 31
3-3 製備電化學剝離石墨烯 33
3-4 調配複合材料溶液 33
3-4-1 PEDOT:PSS/ECG溶液配置 33
3-4-2 參考樣品: 本質PEDOT:PSS溶液配置 34
3-5 製作透明導電薄膜 35
3-5-2 不鏽鋼線棒及鐵氟龍棒塗佈 36
3-5-3 噴塗法 36
3-6 材料特性檢測 37
3-6-1 表面輪廓儀(Alpha-Step) 37
3-6-2 接觸角量測儀(Contact angle meter) 37
3-6-3 光學顯微鏡(Optical microscope，OM) 37
3-6-4 原子力顯微鏡(Atomic force microscope，AFM) 38
3-7 光電特性檢測 38
3-7-1 四點探針量測儀(Four-point probe tester) 38
3-7-2 可見光紫外光分光光譜儀(Ultraviolet-visible spectroscopy) 39
3-8 材料分析檢測 39
3-8-1 拉曼光譜儀(Raman spectroscopy) 39
3-8-2 X射線光電子能譜儀(X-ray photoelectron spectroscopy，XPS) 40
3-8-3 霍氏轉換紅外光譜儀(Fourier-transform infrared spectrometer，FTIR) 42
第四章結果與討論 43
4-1 PEDOT:PSS/ECG 材料特性分析 43
4-1-1 電化學剝離石墨烯在PEDOT:PSS溶液中分散性 43
4-1-2 表面形貌觀察 44
4-2 透明導電薄膜塗佈方式比較 47
4-2-1 不鏽鋼線棒及鐵氟龍棒塗佈 47
4-2-2 噴塗法 51
4-3 PEDOT:PSS/ECG透明導電薄膜片電阻量測與分析 55
4-3-1 透明導電薄膜加熱溫度對片電阻之影響 55
4-3-2 透明導電薄膜加熱時間對片電阻之影響 58
4-3-3 透明導電薄膜之石墨烯調配濃度最佳化 60
4-4 PEDOT:PSS/ECG與PEDOT:PSS透明導電薄膜之比較 63
4-4-1 光電特性比較 63
4-4-2 時效耐久性比較 66
第五章結論 81
參考文獻 82

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指導教授

蘇清源(Ching-Yuan Su)

審核日期

2017-1-25

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