臺灣博碩士論文加值系統

本篇論文中第一部份為利用常壓化學氣相沉積法以銅箔作為觸媒成長出大面積且均勻之石墨烯薄膜，並探討固定晶格方向之銅箔，其厚度對於石墨烯成長層數的影響。我們並利用拉曼光譜儀分析石墨烯之層數及均勻性、以四點探針量測石墨烯薄膜之片電阻、以紫外線/可見光分光光譜儀量測薄膜之光穿透率，並探討石墨烯之成長機制。我們觀察到，在未刻意固定銅箔晶格方向下成長石墨烯，所呈現之現象皆為當銅箔厚度的厚度越厚，成長出的石墨烯越趨近於多層的石墨烯，因此，我們也嘗試利用改良化學氣相沉積的過程控制銅箔受熱時保持固定晶格方向，在130μm、90μm、40μm銅箔上成長石墨烯之I2D/IG之比值分別為0.9-少層、1.0-雙層、1.4-單層，其薄膜透光率分別約為95%、96%、97%，成功利用銅箔厚度來控制我們需要的石墨烯層數。
此外，我們將石墨烯薄膜應用於大分子有機發光二極體作為陽極，但因石墨烯本質為疏水性，導電高分子PEDOT:PSS及PH1000，兩者材料應用於元件中亦有層間潤濕性的問題，故我們利用硝酸將石墨烯進行摻雜，其一能降低片電阻又不影響透光，其二為增加薄膜表面之潤濕性，硝酸摻雜石墨烯前後之接觸角分別為71∘及98∘，故我們利用IPA摻雜於導電高分子PEDOT:PSS及PH1000並搭配硝酸摻雜之石墨烯薄膜，其接觸角成功從71∘降至約23∘，與PEDOT:PSS於PT-ITO(Plasma Treatment)之接觸角相近，此改質方法的搭配有助於增加導電高分子之成膜均勻性並有助於增加石墨烯於元件中之應用。
緊接著我們再利用表面電位分布(SKPM)及場發射電子顯微鏡(FESEM)進一步證明改質前後之導電高分子於石墨烯薄膜之分布情形及其表面形貌，然而我們可以明顯地觀察到，IPA改質前後之導電高分子於石墨烯薄膜之披覆性亦有得到明顯改善。
最後石墨烯及ITO應用於PLED元件上的特性，在漏電流的部分，石墨烯在電流密度部分 10-4 A/cm2 遠大於在ITO為陽極的元件 10-6 A/cm2，且發光面積不均勻，推測可能由於製備石墨烯薄膜時多次的疊加轉印導致薄膜結構亦不穩定，然而，本身單層石墨烯之薄膜結構不完整故電流流至電阻較大或者流經石墨烯薄膜結構缺陷處，導致電流流失，產生漏電的情形故電洞無法循二極體結構躍遷至發光層與電子進行復合。但是我們證明，經過一連串於石墨烯薄膜及導電高分子的改質後，石墨烯薄膜運用於PLED元件之陽極是具有可行性。

In this study we used copper as the catalyst to grow large-area uniform graphene films by atmospheric-pressure chemical vapor deposition.We also explore the fixed direction of the lattice of copper, the thickness of the graphene layers.
Raman spectroscopy of graphene, four-point probe sheet resistance measurement, and UV/Vis spectrophotometer were used to characterize the properties of graphene. We found that when the Cu foil thickness was increased, the number of graphene layers became larger.
We also explored the application of graphene in polymer light-emitting diode (PLED) devices, and studied the influences of the doping method on the graphene work function, sheet resistance, and contact angle, AFM, FESEM and SPoM. In this study, we used nitric acid (HNO3) to dope graphene film, and we found that transmittance of the film was unaffected.Moreover, the doping methods can effectively raise the graphene work function from 4.6 eV to 4.9 eV. The contact angle between graphene and PEDOT : PSS was also studied. We found that by adding 0.25 wt.% of IPA as a surfactant into the PEDOT : PSS solution in addition to doping the graphene the contact angle was effectively reduced to 23o. Finally, the performance of PLED devices was characterized. The leakage current for PLED with a graphene anode was 10-4 A/cm2 much higher than that with an ITO anode 10-6 A/cm2 and the light-emitting patter was non-uniform.

書名頁……………………………………………………………………...i
論文口試委員審定書…………………………………………………..…ii
授權書…………………………………………………………………….iii
摘要 iii
Abstract vi
誌謝 vii
目錄 ix
表目錄 xiiii
圖目錄 xiiiii
一、緒論 1
1.1 前言 1
1.2 研究動機 6
二、文獻回顧 8
2.1 石墨烯…………………………………………………………....8
2.1.1石墨烯的特性 8
2.1.2石墨烯的應用 10
2.2石墨烯之製備方法……………………………………………...14
2.2.1 膠帶剝離法…………………………………………………...14
2.2.2 氧化還原法…………………………………………………...15
2.2.3化學氣相沉積法 18
2.2.4碳化矽熱裂解磊晶法 19
2.2.5超臨界流體法[28] 20
2.3 化學氣相沉積法之進程 22
2.4 有機發光二極體………………………………………………. 28
三、實驗製備流程及步驟 32
3.1實驗流程圖 32
3.2實驗材料 33
3.2.1石墨烯製備材料 33
3.2.2有機發光二極體製備的設備及材料 34
3.3實驗設備及儀器 35
3.3.1石墨烯之製備 35
3.3.2大分子有機發光二極體之製備 37
3.4元件製作及應用設備 38
3.4.1石墨烯透明導電膜製作 38
3.4.2高分子有機發光二極體元件製作 44
3.5分析與檢測 50
3.5.1拉曼光譜特性檢測 50
3.5.2薄膜透光率分析 51
3.5.3功函數量測 53
3.5.4薄膜片電阻量測 54
3.5.5水接觸角量測 56
3.5.6 PLED元件特性量測 57
四、實驗結果與討論 59
4.1 觸媒金屬銅箔厚度對成長石墨烯層數之研究 59
4.1.1 改變銅箔厚度對石墨烯層數之特性研究 59
4.1.2以電化學蝕刻薄化銅箔對於石墨烯層數之研究 63
4.2 溶液摻雜於導電高分子對石墨烯表面潤濕性之影響 67
4.2.1 溶液摻雜於導電高分子對石墨烯薄膜親疏水性之影響 67
4.2.2溶液摻雜於導電高分子對石墨烯薄膜功函數之影響 69
4.2.3溶液摻雜之導電高分子成膜於石墨烯表面均勻性之探討 73
4.3 石墨烯運用於PLED元件之陽極 80
4.3.1 石墨烯運用於PLED陽極漏電流之分析 80
4.3.2 石墨烯運用於PLED陽極電壓-電流之分析 81
4.3.3 石墨烯運用於PLED陽極發光效率及亮度之分析 82
五、結論 85
六、未來展望 87
參考文獻 89

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