臺灣博碩士論文加值系統

本研究以天藍色染料，製備出紫藍色有機發光二極體。將位於CIExy (0.190, 0.241) 之天藍色染料1-((9,9-diethyl-9H-fluoren-2-yl)ethynyl)
pyrene摻雜於主體4,4’-bis(9-carbazolyl)-biphenyl時，能放出CIExy (0.155, 0.063) 的紫藍光色，並將色飽和度提昇至100%以上；效率表現上，在亮度為 100 cd/m2 時，外部量子效率為3.5%，能量效率為 1.2 lm/W。
顯著的深藍位移可歸因為： ㄧ、低的摻雜濃度可以避免因染料過度聚集而產生的紅位移；二、搭配一與客體極性相匹配的主體可進一步分散染料；三、好的主客體能階搭配可以使激子在主體上產生，進而驅動高能量的放光；四、選擇有能力放出短波長，驅動更高能量激子的主體。
獲得高效率的原因為：ㄧ、低的摻雜濃度可避免染料聚集，因能量焠息(quenching)所導致的效率滾降(roll-off)；二、好的能階結構搭配，使激子在主體上產生，讓主至客體間效率有效地傳遞；三、具有良好主-客體間能量傳遞特性之主體。
更值得注意的是，此方法同時適用於不具有立體空間障礙的淡藍光染料，可以調整其光色使更飽和。

We reveal in this communication a new finding regarding the use of a sky-blue emitter to generate purplish-blue emission from organic light emitting diodes (OLEDs) with a polarity matching and high-energy exciton generating host. The resulting device exhibits CIExy coordinates of (0.155, 0.063) and a 3.5% external quantum efficiency with a 1.2 lm/W power efficiency at 100 cd/m2 as a sky-blue emitter, 1-((9,9-diethyl-9H-fluoren-2-yl)ethynyl)pyrene, with CIExy of (0.19, 0.24) is doped into a host of 4,4’-bis(9-carbazolyl)-biphenyl for example. The resulting purplish-blue emission enables a greater than 100% color saturation. The extraordinarily marked blue-shift may be resulted from a low doping concentration to prevent bathochromic shift due to emitter segregation, a polarity matching host to further disperse the emitter, and a proper host and guest energy level paring that enables exciton to generate on host to trigger short wavelength emission. Furthermore, the host is capable of generating excitons with higher energy to facilitate triggering emission with a shorter wavelength. The high efficiency may be attributed to the low doping concentration preventing concentration-quenching caused efficiency roll-off, the exciton generated on host facilitating the occurrence of the efficiency effective host-to-guest energy transfer, and the employed host possessing an effective host-to-guest energy transfer effect. Notably, the new approach also works for other light-blue emitters in yielding a highly desirable deep-blue light provided whose molecular structure is free of steric hindrance.

目錄
摘要 I
誌謝 III
目錄 V
壹、緒論 1
貳、文獻回顧 3
2-1、有機發光二極體的歷史發展 3
2-2、發光原理 13
2-3、能量傳遞機制 19
2-4、出光效率 22
2-5、有機發光二極體材料之發展 24
2-5-1、陽極材料 24
2-5-2、電洞傳輸材料 25
2-5-3、電子傳輸材料 26
2-5-4、電子注入材料 27
2-5-5、陰極材料 28
2-6、螢光深藍光有機發光二極體之發展 28




參、實驗方法 33
3-1、材料 33
3-2、蒸鍍裝置 36
3-3、蒸鍍速率之測定與校正 37
3-4、元件之電路設計 37
3-5、基材清洗 38
3-6、旋轉塗布 38
3-7、真空熱蒸鍍薄膜 39
3-8、元件光電特性量測及效率計算 39
肆、結果與討論 41
4-1、OLED元件結構 41
4-2、發光材料特性 42
4-3、紫藍光OLED元件效率 43
4-3-1、摻雜濃度對元件效率的影響 43
4-3-2、能階結構對元件效率的影響 45
4-3-3、能量傳遞 47
4-4、紫藍光OLED元件光色 48
4-4-1、摻雜濃度對元件光色的影響 48
4-4-2、固溶效應 51
4-4-3、能階結構搭配及主體材料選擇 52
4-5、立體障礙對材料堆疊的影響 53
4-6、紫藍光OLED元件之效率與光色 54
伍、結論 55
陸、參考資料 56
附錄、個人著作目錄 61




圖目錄
圖一、美國柯達公司於1987年首創的採用異質介面雙層元件 (a)結構及 (b)能階示意圖 5
圖二、日本九州大學Saito教授研究群提出載子再結合區域位於具電洞傳輸功能之發光層的OLED元件結構 6
圖三、日本九州大學Saito教授研究群提出之三層式OLED元件結構 7
圖四、英國劍橋大學Calvendish實驗室利用共軛高分子所發表的單層PLED結構圖 8
圖五、1992年日本山形大學Kido教授提出載子再結合區域分別具電洞與電子傳輸功能之發光層的OLED元件結構 8
圖六、2002年德國Dresden大學Leo教授研究團隊發表p-i-n結構之OLED元件能階示意圖 10
圖七、溶劑預混法置備蒸鍍源示意圖 11
圖八、2006年美國密西根大學Forrest教授研究團隊發表螢磷光混合型白光OLED (a)元件結構與 (b)能量傳遞示意圖 12
圖九、OLED之 (a)元件結構及 (b)能階示意圖 14
圖十、Jablonski能階圖 17
圖十一、電子、電洞再結合所產生的激發態分布示意圖 18
圖十二、輻射能量傳遞之示意圖 20
圖十三、單Förster energy trnasfer和Dexter energy transfer之示意圖 21
圖十四、光在OLED元件中產生折射與全反射之示意圖 23
圖十五、國際照明標準委員會（Commission International de L’ Eclairage）色座標圖 32
圖十六、電洞傳輸材料、電子傳輸材料及螢光藍光染料結構式 34
圖十七、主體材料結構式 35
圖十八、真空熱真蒸鍍系統示意圖 36
圖十九、OLED元件電路設計圖 37
圖二十、旋轉塗佈法示意圖 39
圖二十一、OLED元件之電流-電壓-亮度及CIE色座標量測示意圖 40
圖二十二、深藍光元件結構圖 41
圖二十三、深藍光OLED能階結構圖 45
圖二十四、使用不同主體對元件效率之影響 46
圖二十五、於THF中，主體光激發光光譜和客體吸收光譜 47
圖二十六、客體摻雜濃度對電激發光光譜的影響 48




圖二十七、以 (a) CBP (b) Spiro-2CBP (c) SimCP2 (d) TCTA 作為主體，降低摻雜濃度對光色在CIE色座標的影響，和最佳的色彩飽和度表現 50
圖二十八、PA-1客體以3wt%摻雜於不同主體之電激發光光譜 52
圖二十九、文中所使用之螢光藍光染料立體分子結構式 53
圖三十、深藍光元件之光色與效率比較圖 54


表目錄
表一、本研究使用之材料，其用途、命名和簡稱 33
表二、PA-1之電化學及物理性質 42
表三、PA-1於不同狀態之光學性質 43
表四、PA-1依不同濃度摻雜於不同主體之元件效能比較 44
表五、以Gaussian 03模擬之主、客體偶極距 51

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