為了提高有機發光二極體(OLED)元件的出光效率，本研究以聚醯亞胺/二氧化矽複合物為出發點分別製備具有物理混摻方式(A系列)、化學共價鍵結方式(B系列)和含有中空奈米粒子(C系列)的三種光取出薄膜。A系列是由聚醯胺酸(Polyamic acid, PAA)和矽酸四甲酯(Tetramethyl orthosilicate, TMOS)，利用溶膠-凝膠法和熱閉環醯亞胺化製備；B系列使用3-氨基丙基三乙氧基矽烷(3-Aminopropyltriethoxysilane, APTES)作為矽烷偶合劑將矽分子與聚醯亞胺進行共價鍵結所形成之複合材料；C系列是加入由陽離子界面活性劑(Hexadecyltrimethylammonium chloride, CTAC)和非離子界面活性劑(Pluronic® F-127)製備出的中空二氧化矽奈米粒子並與聚醯亞胺進行共價鍵結形成含有中空材之複合材料。
我們針對不同二氧化矽含量，探討三個系列之熱性質、光學性質、型態和光電特性，其中隨著二氧化矽含量增加，玻璃轉移溫度(Glass transition temperature; Tg) 隨之增加，且所有複合材料在5 wt%的熱裂解溫度(Thermal decomposition temperature, Td)均維持500 oC以上，顯示此材料擁有極佳的熱性質。光學性質上，使用UV-vis量測塗佈於玻璃基板上的薄膜透射率，PI薄膜於波長為400-100 nm間其穿透率達99 %，並搭配橢圓偏光儀測量其折射率為1.61，當添加二氧化矽粒子時，隨著二氧化矽含量增加，直穿透率下降，但搭配積分球再進行一次量測，發現總穿透率明顯改善，表示二氧化矽粒子達到散射效果且透過積分球可成功收集到散射的光。此外，經由掃描式電子顯微鏡(Scanning electron microscope, SEM) 觀察二氧化矽粒子分散的情形，並使用動態光散射粒徑分析儀(Dynamic light scattering, DLS)分析其平均粒徑大小的趨勢，發現B系列的二氧化矽粒子比A系列分佈均勻且粒徑較小，於C系列中，我們亦以穿透式電子顯微鏡(Transmission electron microscope; TEM)觀察中空二氧化矽奈米粒子已被成功製備出來。
最後，將上述複合薄膜應用於OLED元件中以增強光取出效果，通過增加複合材料當作散射層，並不會影響OLED元件原本的出光顏色，而散射層合成方式與矽含量皆會影響光電效率，隨著矽含量越高光電效率越好，與原元件相比，三系列中最佳之光電特型之電流效率從49.0提升至64.6 cd/A，而發光功率效率也從64.1提升至87.8 lm/w，對光提取最主要參考數據EQE也成功從14.4%提升至18.7 %，最後，透過光場分佈可觀察散射效果C > B > A。

In order to enhance light outcoupling efficiency of organic light emitting diodes (OLED) devices, we prepared three polyimides/silica composites with physical blending (A1-A3), covalent bonds (B1 and B2) and contain hollow nanoparticles (C1 and C2) characteristics. A series were prepared from the corresponding poly(amic acid) (PAA) and tetramethyl orthosilicate (TMOS) through thermal imidization and sol-gel process to form non-covalent bonding polyimide/silica composites. B series were prepared using 3-aminopropyltriethoxysilane (APTES) as coupling agent to form covalent bonding polyimide/silica composites. C series were prepared the covalent bonding polyimide/silica composites but the hollow silica nanoparticles.
Their optical, thermal, morphology were investigated. As the silica content increased the thermal properties increasing. In addition, the scattering properties increasing as well.
In addition, B series hybrid films showed better well-dispersed behavior than the A series under similar silica content through the SEM and DLS results. For C series, hollow nanoparticles had been prepared successfully through TEM image.
Finally, whole hybrid films were applied into OLED devices for optical measurement. Under similar silica content, the EQE performance was in the trend of C > B > A = pure polyimide = reference. In addition, the C2 based as light extraction film exhibited the best device performance than others, the current efficiency, power efficiency and EQE vale of this device was at 64.6 cd/A, 87.8 lm/w and 18.7 %. The EQE value reached 30 % that of a reference device (EQE = 14.4 %) fabricated and measured under similar conditions.

摘要 I
Abstract IV
誌謝 VI
目錄 VII
表目錄 XII
圖目錄 XIII
第一章 緒論 1
1-1 前言 1
1-2 有機發光二極體發展歷史與特點 2
1-3 有機發光二極體工作原理 3
1-4 有機發光二極體基本特性參數 5
第二章 文獻回顧與研究動機 7
2-1 表面等離子模式(surface plasmonic mode) 7
2-2 光取出薄膜 7
2-2-1內取出層 8
2-2-1-1引入圖案化的透明電極 8
2-2-1-2微腔效應調整 9
2-2-1-3引入光子晶體 10
2-2-1-4插入散射介質 11
2-2-2 外取出層 12
2-2-2-1基材表面粗糙化 12
2-2-2-2微型陣列 14
2-2-2-3表面圖案化 16
2-2-2-4表面散射介質 17
2-2-3 其他 20
2-3 聚醯亞胺/二氧化矽複合材料及衍生光取出層 21
2-3-1聚醯亞胺之簡介 21
2-3-2二氧化矽之簡介 27
2-4 研究動機 30
第三章 實驗方法 31
3-1 實驗架構 31
3-2 實驗藥品 32
3-4 儀器設備 38
3-5 實驗流程 41
3-5-1 聚醯亞胺之合成 41
3-5-2非共價鍵結之聚醯亞胺/二氧化矽合成 (A系列) 42
3-5-3共價鍵結之聚醯亞胺/二氧化矽合成 (B系列) 43
3-5-4奈米中空二氧化矽粒子合成 44
3-5-5共價鍵結之聚醯亞胺/奈米中空二氧化矽合成 (C系列) 45
3-5-6 OLED元件製備 46
3-6 分析儀器量測 48
3-6-1 傅立葉轉換紅外線光譜儀(FT-IR) 48
3-6-2 熱性質-熱重分析儀(TGA) 48
3-6-3 熱性質-示差熱掃描分析儀(DSC) 48
3-6-4 型態性質-高解析度場發射掃描式電子顯微鏡(FE-SEM) 49
3-6-5 型態性質-穿透式電子顯微鏡(TEM) 49
3-6-6 光學性質-動態光散射粒徑分析儀(DLS) 50
3-6-7 光學性質-橢圓偏光儀 50
3-6-8 光學性質-紫外光/可見光/近紅外光分光光譜儀 (UV-Vis-NIR) 50
3-6-9 光電特性 51
第四章 結果與討論 52
4-1 高分子複合材料之FT-IR鑑定分析 52
4-1-1 聚醯亞胺結構之鑑定分析 53
4-1-2 聚醯亞胺/二氧化矽複合材料之鑑定分析 54
4-2 TGA之熱性質分析 56
4-3 DSC之熱性質分析 61
4-4 SEM/TEM之型態與DLS之光學性質分析 64
4-5 UV-Vis之光學性質分析 68
4-6 OLED光電特性分析 72
4-6-1 I-V-L curve 73
4-6-2 發光效率 75
4-6-3 外部量子效率 (EQE) 77
4-6-4 光場分佈 80
4-6-5 EL光譜及元件點亮圖 82
第五章 結論 85
第六章 參考文獻 87
附錄 A 98

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