本研究主要以雙載子傳輸特性CC-MP系列材料，作為紅色磷光元件的主體材料。首先根據每一款材料的光物理特性去設計元件結構，搭配適合的客體材料、電子傳輸層及電洞傳輸層，幫助載子注入使元件中載子平衡，且有效的將激子侷限在發光層中；接著調整元件各層有機層厚度，改變複合區位置，減少激子在有機介面的淬熄；最後改變不同的摻雜濃度，探討各主體材料在發光層中扮演的角色，及其能量轉移釋放機制。
CC-MP系列主體材料經由不同元件參數探討後，在CC-MP2、CC-MP3、CC-MP4、CC-MP6、CC-MP7及CC-MP8元件主要以主客體能量轉移為主要的放光途徑，而CC-MP2、CC-MP6、CC-MP8客體吸收放光頻譜重疊較高且CC-MP2（ET=2.28eV）、CC-MP6（ET=2.35eV）、CC-MP8（ET=2.34eV）的三重態能階較高，以上幾點讓CC-MP2（Device2，EQE=12.2%）、CC-MP6（Device6，EQE=13.2%）、CC-MP8（Device8，EQE=15.5%）有優異的元件特性表現。CC-MP系列材料中以CC-MP8為主體所製造的元件，EQE可達15.5%、最大亮度19200 cd/m2，由此雙載子傳輸特性CC-MP系列材料成功製作出效率優異的深紅光元件。

關鍵字：有機發光二極體、雙載子傳輸特性材料、紅色磷光元件、載子捕捉、主客體能量轉移

In this study, bipolar transporting materials, CC-MP series, were used as host in phosphorescence devices. Suitable guest-emitting, electron-transporting and hole transporting material for CC-MP series were chosen according to the photophysical properties of CC-MP series. The thickness of those organic layers were adjusted to help carrier inject and reach a balance for effective excitons recombination. Doping concentration was also discussed as a parameter which affect energy transfer mechanism in the devices.
According to the dependence of doping concentration on both the current density-voltage characteristics and device efficiency, the main route of emission mechanism would be through energy transfer between host and guest rather than through carrier trapping by guest. CC-MP8 showed the maximum EQE of 15.5% among all the materials, attributed by the high triplet energy and large overlap between PL spectrum of CC-MP8 and absorption of the guest. Thus, bipolar transporting materials, CC-MP series, successfully produced excellent efficiency the deep red devices.

Keywords: Organic Light-Emitting Diode, bipolar transporting materials, red phosphorescence devices, carrier rapping, host-guest energy transfer

目錄
中文論文審定書 i
英文論文審定書 ii
摘要 iii
Abstract iv
目錄 v
圖目錄 vii
表目錄 ix
第一章 緒論 1
1-1 前言 1
1-2 有機發光二極體（OLED）的發展及文獻回顧 2
1-3 研究動機與目的 3
1-4 各章提要 4
第二章 基礎理論 5
2-1 影響OLED發光效率的因子 5
2-2 有機電激發光（Organic Electroluminescence，OEL)原理 6
2-2-1 電激發光（OEL）原理 6
2-2-2 螢光與磷光發光原理 8
2-2-3 主客體發光系統 10
2-3 有機發光二極體（OLED）材料的選擇 13
2-3-1 陰極 13
2-3-2 陽極 14
2-3-3 電子注入（EIL）/傳輸層（ETL）材料 14
2-3-4 電洞注入（HIL）/傳輸層材料（HTL） 15
2-3-5 主客體發光材料 16
第三章 實驗設備與元件製程 18
3-1 實驗流程 18
3-2 實驗設備介紹 19
3-2-1 超音波震盪機（Ultrasonic Cleaner） 19
3-2-2 純化系統-管式高溫爐（Tube-Furnace） 19
3-2-3 紫外光／可見光光譜（UV／Vis spectrophotometer）、螢光光譜儀（Fluorimeter）與光激量子效率量測系統（Photoluminescence quantum yield measurement system) 20
3-2-4 橢圓偏光儀（Ellipsometer） 20
3-2-5 紫外光臭氧清洗機（UV-Ozone） 20
3-2-6 真空熱蒸鍍系統（Vacuum Evaporation Deposition System） 21
3-2-7 手套箱（Glove Box） 22
3-2-8 量測系統 22
3-3 元件製程與量測 23
3-3-1 基板清潔 23
3-3-2 基板表面處理 23
3-3-3 元件蒸鍍 23
3-3-4 元件量測 24
第四章 結果與討論 25
4-1 簡介 25
4-2 主體材料的光物理特性比較 25
4-3 元件的電激發光性質分析 31
4-3-1 CC-MP1 31
4-3-2 CC-MP2 35
4-3-3 CC-MP3 37
4-3-4 CC-MP4 39
4-3-5 CC-MP5 41
4-3-6 CC-MP6 45
4-3-7 CC-MP7 47
4-3-8 CC-MP8 50
4-4 最佳化元件之比較 53
第五章 結論 56
參考文獻 57

[1] M. Pope, H. P. Kallmann and P. Magnante "Electroluminescence in organic crystals." The Journal of Chemical Physics 38.8 (1963): 2042-2043.
[2] C. W. Tang and S. A. VanSlyke "Organic electroluminescent diodes." Applied physics letters 51.12 (1987): 913-915.
[3] J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Fried, P. L. Burns and A. B. Holmes "Light-emitting diodes based on conjugated polymers." Nature 347.6293 (1990): 539-541.
[4] M. A. Baldo, D. F. O'Brien1, Y. You, A. Shoustikov, S. Sibley, M. E. Thompson and S. R. Forrest "Highly efficient phosphorescent emission from organic electroluminescent devices." Nature 395.6698 (1998): 151-154.
[5] K. S. Yook, J. Y. Lee "Bipolar host materials for organic light‐emitting diodes." The Chemical Record 16.1 (2016): 159-172.
[6] M. J. Cho, S. J. Kim, S. H. Yoon, J. Shin, T. R. Hong, H. J. Kim, Y. H. Son, J. S. Kang, H. A. Um, T. W. Lee, J. K. Bin, B. S. Lee, J. H. Yang, G. S. Chae, J. H. Kwon, and D. H. Choi "New bipolar host materials for realizing blue phosphorescent organic light-emitting diodes with high efficiency at 1000 cd/m2." ACS Applied Materials & Interfaces 6.22 (2014): 19808-19815.
[7] D. Ammermann, A. Böhler, S. Dirr, H. H. Johannes, W. Kowalsky "Multilayer organic light emitting diodes for flat panel displays." International Journal of Electronics and Communications 50 (1996): 327-333.
[8] A. Köhler, J. S. Wilson, R. H. Friend "Fluorescence and phosphorescence in organic materials." Advanced Engineering Materials 4.7 (2002): 453-459.
[9] E. Orselli, R. Q. Albuquerque, P. M. Fransen, R. Fröhlich, H. M. Janssenc and L. D. Cola "1, 2, 3-Triazolyl-pyridine derivatives as chelating ligands for blue iridium (III) complexes. Photophysics and electroluminescent devices." Journal of Materials Chemistry 18.38 (2008): 4579-4590.
[10] 陳金鑫, and 黃孝文. OLED: 有機電激發光材料與元件. 五南圖書出版股份有限公司, 2005.
[11] C. Adachi1, M. A. Baldo1, S. R. Forrest1 and M. E. Thompson "High-efficiency organic electrophosphorescent devices with tris (2-phenylpyridine) iridium doped into electron-transporting materials." Applied Physics Letters 77.6 (2000): 904.
[12] T. Förster "Zwischenmolekulare energiewanderung und fluoreszenz." Annalen Der Physik 437.1‐2 (1948): 55-75.
[13] D. L. Dexter "A theory of sensitized luminescence in solids." The Journal of Chemical Physics 21.5 (1953): 836-850.
[14] H. Suzuki1 and S. Hoshino "Effects of doping dyes on the electroluminescent characteristics of multilayer organic light‐emitting diodes." Journal of Applied Physics 79.11 (1996): 8816-8822.
[15] A. C. A. Chen, S. W. Culligan, Y. Geng, S. H. Chen, K. P. Klubek, K. M. Vaeth, C. W. Tang "Organic Polarized Light‐Emitting Diodes via Förster Energy Transfer Using Monodisperse Conjugated Oligomers." Advanced Materials 16.9‐10 (2004): 783-788.
[16] T. Wakimoto, Y. Fukuda, K. Nagayama, A. Yokoi, H. Nakada, M. Tsuchida "Organic EL cells using alkaline metal compounds as electron injection materials." IEEE Transactions on Electron Devices 44.8 (1997): 1245-1248.
[17] J. C. D. Mello, H. F. Wittmann, and R. Friend "An improved experimental determination of external photoluminescence quantum efficiency." Advanced Materials 9.3 (1997): 230-232.
[18] J. R. Vig "UV/ozone cleaning of surfaces." Journal of Vacuum Science & Technology A 3.3 (1985): 1027-1034.
[19] 林松澂.具三甲基苯硼與吩噻嗪基團化合物之載子傳輸特性研究.中山大學.碩士論文, 2016.
[20] H. Lee, S. W. Cho, K. Han, P. E. Jeon, C. N. Whang, K. Jeong, K. Cho and Y. Yi "The origin of the hole injection improvements at indium tin oxide/molybdenum trioxide/N, N'-bis (1-naphthyl)-N, N'-diphenyl-1, 1'-biphen-yl-4, 4'-diamine interfaces." Applied Physics Letters 93.4 (2008): 43308-43308
[21] S. Möller and S. R. Forrest "Improved light out-coupling in organic light emitting diodes employing ordered microlens arrays." Journal of Applied Physics 91.5 (2002): 3324-3327.
[22] P. T Chou, Y. Chi "Osmium‐and Ruthenium‐Based Phosphorescent Materials: Design, Photophysics, and Utilization in OLED Fabrication." European Journal of Inorganic Chemistry 2006.17 (2006): 3319-3332.
[23] M. A. Baldo, C. Adachi, and S. R. Forrest "Transient analysis of organic electrophosphorescence. II. Transient analysis of triplet-triplet annihilation." Physical Review B 62.16 (2000): 10967- 10977.
[24] 許芳銘. 設計與合成雙性磷光主體材料與其高效率藍光及紅光元件製作.交通大學.博士論文,2009.
[25] 程裕仁.以對稱三甲苯啡噻為中心之雙極性發光材料.中正大學.碩士論文,2015.
[26] S. O. Jeon, K. S. Yook, C. W. Joo, J. Y. Lee "Highly efficient single-layer phosphorescent white organic light-emitting diodes using a spirofluorene-based host material." Optics Letters 34.4 (2009): 407-409.
[27] W. S. Jeona, T. J. Parka, S. Y. Kima, R. Podeb, J. Janga, J. H. Kwona "Ideal host and guest system in phosphorescent OLEDs." Organic Electronics 10.2 (2009): 240-246.
[28] S. O. Jeon, K. S. Yook, C. W. Joo, J. Y. Lee "Theoretical maximum quantum efficiency in red phosphorescent organic light-emitting diodes at a low doping concentration using a spirobenzofluorene type triplet host material." Organic Electronics 11.5 (2010): 881-886.