製作有機發光二極體(Organic Light Emitting Diode, OLED)常見的方式是利用真空蒸鍍的製程方法，但由於製程環境條件要求嚴苛、材料利用率低及製程設備昂貴等缺點，未來要大量生產大面積OLED想必是更為困難。為了克服此議題，本研究團隊自行研發了連續下料及多點下料刮刀塗佈液態製程技術，此技術不需嚴苛的製程環境且材料使用率較高，使得生產成本下降許多。本論文研究目的是利用此技術製作發光面積約"62×110 " 〖"mm" 〗^"2" 和"57×105 " 〖"mm" 〗^"2" 之大尺寸OLED元件，藉由調變製程參數，提高元件薄膜均勻性及穩定度。
本論文藉由調變刮刀塗佈技術其塗佈速度與利用不同有機層材料及有機溶劑優化薄膜之均勻性；並於單層結構中使用電子傳輸材料EPH409、改變陰極CsF/Al之蒸鍍條件、增加電洞注入層及發光層厚度與蒸鍍絕緣材料SiO材料，進而提升元件穩定性，目前元件測試最佳穩定性已持續點亮約400個小時。而此大面積OLED元件發光面積為"57×105 " 〖"mm" 〗^"2" 。

Organic Light Emitting Diodes(OLEDs) are usually fabricated by vacuum deposition. The vacuum deposition need strict process environmental conditions. This process needs expensive equipment, and the low utilization ratio of material. It is difficult to mass-fabric -ate large-area OLEDs in the future. Our lab developed the liquid process of continuous delivery blade coating and multi-delivery blade coating. This solution-processable blade coating don’t need strict process environmental conditions, and have high utilization ratio of material. The production cost of the OLEDs will be significantly reduced. The main objective of this thesis was using this blade coating to fabricate large-area OLEDs with a size of "62×110 " 〖"mm" 〗^"2" and "57×105 " 〖"mm" 〗^"2" . The thin film uniformity and stability of devices were improved by optimizing the experimental parameters.
Optimizing thin film uniformity by blade coating speed adjustment and changing sol -vent of the organic material solution. Some experimental method can improve devices st -ability include the following: replacing electron transport material of the single layer stru -cture with EPH409, adjusting CsF/Al electrode deposition conditions, hole injection layer and emission layer increase thickness, evaporating SiO on base. ,Devices operated is up to 400 hours.

摘要 III
ABSTRACT IV
誌謝 V
目錄 VI
圖目錄 VIII
表目錄 X
第一章 緒論 1
1.1 前言 1
1.2 有機發光二極體歷史簡介 2
1.3 研究動機與方向 3
1.4論文架構 5
第二章 有機發光二極體基礎理論及有機材料介紹 6
2.1有機材料之能量轉移機制 6
2.1.1螢光與磷光理論 6
2.1.2主客發光體之能量轉換機制 10
2.2 有機發光二極體元件結構與發光原理 12
2.2.1 元件結構 12
2.2.2 元件發光原理 14
2.2.3元件操作電壓與電流機制 15
2.2.4 元件發光效率 17
2.3 有機材料介紹 18
2.3.1 電洞注入材料(Hole injection material) 18
2.3.2 電洞傳輸材料(Hole transport material) 19
2.3.3 主客體發光體材料(Host material and guest material) 20
2.3.4 電子傳輸材料(Electron transport material) 22
第三章 有機發光二極體製作流程 24
3.1 ITO基板蝕刻流程 24
3.2 有機層塗佈-刮刀塗佈技術 29
3.3 蒸鍍陰極金屬 35
3.4 元件封裝 37
3.5 元件量測 39
3.5.1電性量測 39
3.5.2 壽命量測 40
第四章 大面積有機發光二極體製程介紹 42
4.1 連續下料刮刀塗佈液態製程 42
4.1.1 連續下料裝置系統介紹 42
4.1.2 連續下料刮刀塗佈液態製程之流程 45
4.2 多點下料刮刀塗佈液態製程 48
4.2.1 多點下料刮刀塗佈用具介紹 48
4.2.2 多點下料刮刀塗佈液態製程之流程 50
4.3 連續下料及多點下料刮刀塗佈製程之比較 52
第五章 實驗設計與結果討論 53
5.1 大面積OLED元件膜面改善 53
5.1.1 降低刮刀速度 54
5.1.2 有機層材料溶液之混和溶劑 56
5.1.3 有機層材料溶液改以低沸點之溶劑 58
5.2 提升大面積OLED元件穩定性 60
5.2.1單層結構中之電子傳輸材料改換成EPH409 61
5.2.2 改變陰極CsF/Al之蒸鍍條件 63
5.2.3增加電洞注入層與發光層厚度 69
5.2.4 元件周圍蒸鍍SiO材料 73
第六章 結果與未來展望 77
第七章 參考文獻 80

“Continuous blade coating for multi-layer large-area organic light-emitting diode and solar cell“, Chun-Yu Chen, Hao-Wen Chang, Yu-Fan Chang, Bo-Jie Chang, Yuan-Sheng Lin, Pei-Siou Jian, Han-Cheng Yeh, Hung-Ta Chien, En-Chen Chen, Yu-Chiang Chao, Hsin-Fei Meng, Hsiao-Wen Zan, Hao-Wu Lin, Sheng-Fu Horng, Yen-Ju Cheng,Feng-Wen Yen, I-Feng Lin, Hsiu-Yuan Yang, Kuo-Jui Huang, and Mei-Rurng Tseng, J. Appl. Phys., 110, 094501 (2011)
“Current efficiency in organic light-emitting diodes with a hole-injection layer”, Hui Wang, Kevin P. Klubek, and C. W. Tang, Appl. Phys. Lett.93, 093306 (2008)
“Improvement of organic light-emitting diodes performance by the insertion of a 〖Si〗_3 N_4 layer”, Hongjin Jiang, Yan Zhou, Boon Siew Ooi, Yuwen Chen, Terence Wee, Yee Loy Lam, Jingsong Huang, Shiyong Liu, Thin Solid Films 363, 25 (2000).
“Enhancement in brightness and efficiency of organic electroluminescent device using novel N,N-di(9-ethylcarbaz-3-yl)-3-methylaniline as hole injecting and transporting material”, D. Liu, C. G. Zhen, X. S. Wang, D. C. Zou, B. W. Zhang, and Y. Cao, Synth. Met. 146, 85 (2004).
“Blue organic electrophosphorescence using exothermic host–guest energy transfer”, R. J. Holmes, S. R. Forrest, Y. J. Tung, R. C. Kwong, J. J. Brown, S. Garon, and M. E. Thompson, Appl. Phys. Lett. 82, 2422 (2003).
“Influence of the hole injection layer on the luminescent performanceof organic light-emitting diodes”, S. F. Chen and C. W. Wang, Appl. Phys. Lett. 85, 765 (2004).
“Novel Starburst Molecule as a Hole Injecting and Transporting Material for Organic Light-Emitting Devices”, J. Li, C. Ma, J. Tang, C. S. Lee, and S. Lee, Chem. Mater. 17, 615 (2005).
“Improving the performance of blue phosphorescent organic light-emitting devices using a composite emitter”, M. T. Chu, M. T. Lee, C. H. Chen, and M. R. Tseng, Org. Electron. 10, 1158 (2009).
“High-efficiency and low-voltage p‐i‐np‐i‐nelectrophosphorescent organic light-emitting diodes with double-emission layers”, G. He, M. Pfeiffer, K. Leo, M. Hofmann, J. Birnstock, R. Pudzich, and J. Salbeck, Appl. Phys. Lett. 85, 3911 (2004).
“White organic light-emitting diodes with fluorescent tube efficiency”, S. Reineke, F. Lindner, G. Schwartz, N. Seidler, K. Walzer, B. Lüssem, and K. Leo, Nature 459, 234 (2009).
“Multilayer polymer light-emitting diodes by blade coating method”, S. R. Tseng, H. F. Meng, K. C Lee, and S. F Horng, Appl. Phys. Lett. 93, 153308 (2008).
“All-solution-processed blue small molecular organic light-emitting diodes with multilayer device structure”, J. D. You, S. R. Tseng, H. F. Meng, F. W. Yen, I. F Lin, and S. F. Horng, Org. Electron. 10, 1610 (2009).
“Multi-layer organic light-emitting diodes processed from solution using phosphorescent dendrimers in a polymer host”, L. C. Ko, Z. Y. Liu, C. Y. Chen, C. L. Yeh, S. R. Tseng, H. F. Meng, S. C. Lo, P. L. Burn, and S. F. Horng, Org. Electron. 11, 1005 (2010).
“Solution-processed small molecular electron transport layer for multilayer polymer light-emitting diodes”, Z. Y. Liu, S. R. Tseng, Y. C. Chao, C. Y. Chen, H. F. Meng, S. F. Horng, Y. H. Wu, and S. H. Chen, Synth. Met. 161, 426 (2011).
“Highly efficient solution-processed red organic light-emitting diodes with long-side-chained triplet emitter”, Y. C. Chao, S. Y. Huang, C. Y. Chen, Y. F. Chang, H. F. Meng, F. W. Yen, I. F. Lin, H. W. Zan, and S. F. Horng, Synth. Met. 161, 148 (2011).
“Effects of triplet energies and transporting properties of carrier transporting materials on blue phosphorescent organic light emitting devices”, J. Lee, N. Chopra, S. H. Eom, Y. Zheng, J. Xue, F. So, and J. Shi, Appl. Phys. Lett. 93, 123306 (2008).
“Blue polymer electrophosphorescent devices with different electron-transporting oxadiazoles”, X. H. Yang, F. Jaiser, S. Klinger, and D. Neher, Appl. Phys. Lett. 88, 021107 (2006).
“All-small-molecule efficient white organic light-emitting diodes by multi-layer blade coating”, Han-Cheng Yeh, Hsin-Fei Meng, Hao-Wu Lin, Teng-Chih Chao, Mei-Rurng Tseng, Hsiao-Wen Zan, Organic Electronics. 13, 914-918 (2012)
“Highly efficient solution-processed blue-green to red and white light-emitting diodes using cationic iridium complexes as dopants”, Lei He, Lian Duan, Juan Qiao, Deqiang Zhang, Liduo Wang, Yong Qiu, Organic Electronics. 11, 1185-1191 (2010)
“Above 20% external quantum efficiency in green and white phosphorescent organic light-emitting diodes using an electron transport type green host material”, Soon Ok Jeon, Jun Yeob Lee, Organic Electronics. 12, 1893-1898 (2011).
“Soluble processed low-voltage and high efficiency blue phosphorescent organic light-emitting devices using small molecule host systems”, Organic Electronics. 13, 586-592 (2012).
“All-solution-processed blue small molecular organic light-emitting diodes with multilayer device structure“, Jia-Da You, Shin-Rong Tseng, Hsin-Fei Meng, Feng-Wen Yen, I-Feng Lin, Sheng-Fu Horng, Organic Electronics, Vol. 10, Issue 8, 1610-1614 (2009)
“High-efficiency blue multilayer polymer light-emitting diode fabricated by a general liquid buffer method“, Shin-Rong Tseng, Hsin-Fei Meng, Chi-Hung Yeh, Huan-Chung Lai, Sheng-Fu Horng, Hua-Hsien Liao, Chain-Shu Hsu, Li-Chi Lin, Synth. Metal, 158, 130-134 (2008)
“Broad band and white phosphorescent polymer light-emitting diodes in multilayer structure “, Kai-Chin Tang, Shin-Rong Tseng, Wei-Shan Li, Hsin-Fei Meng, Sheng-Fu Horng, Chian-Shu Hsu, Synth. Metal, 158, 287~291 (2008)
“Deep Blue Light-Emitting Diode based on High Molecular Weight Poly(9,9-dioctylfluorene) with High Efficiency and Color Stability“, Shin-Rong Tzeng and Hsin-Fei Meng, Organic Electronics, 9, 279-284(2008)
“Electron traps in organic light emitting diodes“, Min-Jan Tsai and Hsin-Fei Meng, J. Appl. Phys., 97, 114502 (2005)
“Recombination distribution and color tuning of multilayer organic light-emitting diode“, Chia-Hsun Chen and Hsin-Fei Meng, Appl. Phys. Lett., 86, 201102 (2005)
“General application of blade coating to small-molecule hosts for organic light-emitting diode“, Hao-Wen Chang, Yi-Ting Lee, Mei-Rurng Tseng, Meng-Hao Jang, Han-Cheng Yeh, Fang-Tsai Luo, Hsin-Fei Meng, Chin-Ti Chen, Yun Chi, Yong Qiu, Lian Duan, Hao-Wu Lin Sheng-Fu Horng and Hsiao-Wen Zan, Synthetic Metals, 196, 99–109(2014)
“Single-emission-layer white organic light-emitting devices: Chromaticity and colour-rendering consideration“, Chia-Chan Fan, Ming-Hong Huang, Wei-Chieh Lin, Hao-Wu Lin, Yun Chi, Hsin-Fei Meng, Teng-Chih Chao, Mei-Rurng Tseng, Organic Electronics 15,517–523(2014)
“Interface and thickness tuning for blade coated small-molecule organic light-emitting diodes with high power efficiency“, Yu-Fan Chang, Yu-Chian Chiu, Hao-Wen Chang, Yi-Siang Wang, Yi-Lun Shih, Chih-Hao Wu, Yi-Lun Liu, Yu-Sheng Lin, Hsin-Fei Meng, Yun Chi, Heh-Lung Huang, Mei-Rurng Tseng, Hao-Wu Lin, Hsiao-Wen Zan, Sheng-Fu Horng, Jenh-Yih Juang, Journal of Applied Physics,114, 123101, (2013)
“Achieving saturation in vertical organic transistors for organic light-emitting diode driving by nanorod channel geometric control“, Chang-Hung Li, Fabrice Stehlin, Kai-Ruei Wang, Yu-Hsin Lin, Fernand Wieder, Olivier Soppera, Hsiao-Wen Zan, Hsin-Fei Meng, Applied Physics Letters 102, 163305 (2013)
“Unmodified small-molecule organic light-emitting-diodes by blade coating“, Yu-Fan Chang, Yu-Chian Chiu, Han-Cheng Yeh, Hao-Wen Chang, Chun-Yu-Chen, Hsin-Fei Meng, Hao-Wu Lin, Heh-Lung Huang, Teng-Chih Chao, Mei-Rurng Tseng, Hsiao-Wen Zan, and Sheng-Fu Horng, Organic Electronics, vol. 13, pp. 2149-2155, (2012)
“All-small-molecule efficient white organic light-emitting diodes by multi-layer blade coating“, Han-Cheng Yeh, Hsin-Fei Meng, Hao-Wu Lin, Teng-Chih Chao, Mei-Rurng Tseng, Hsiao-Wen Zan, Organic Electronics,13,914 (2012)
“Vacuum-free lamination of low work function cathode for efficient solution-processed organic light-emitting diodes“, Yu-Fan Chang, Chun-Yu Cheng, Fang-Tsai Luo, Yu-Chiang Chao, Hsin-Fei Meng, Hsiao-Wen Zan, Hao-Wu Lin, Sheng-Fu Horng, Han-Cheng Yeh, Mei-Rung Tseng, Organic Electronics, 13, 388 (2012)
“Solution-processed small molecular electron transport layer for multilayer polymer light-emitting diodes“, Zong-You Liu, Shin-Rong Tseng, Yu-Chiang Chao, Chun-YuChen,Hsin-Fei Meng, Sheng-Fu Horng, Yu-Hsun Wu, Su-Hua Chen, Synthetic Metals, 161, pp.426–430 (2011)
“ITO-free large-area top-emission organic light-emitting diode by blade coating” Hao-Wen Chang, Hsin-Fei Meng, Sheng-Fu Horng, Hsiao-Wen Zan, Synthetic Metal, 212, 19024,(2016)
“Efficient hybrid white light-emitting diodes by organic-inorganic materials at different CCT from 3000K to 9000K“, Kuo-Ju Chen, Yi-Chun Lai, Bin-Cheng Lin, Chien-Chung Lin, Sheng-Huan Chiu, Zong-Yi Tu, Min-Hsiung Shih, Peichen Yu, Po-Tsung Lee, Xiuling Li, Hsin-Fei Meng, Gou-Chung Chi, Teng-Ming Chen, Hao-Chung Kuo, Optics Express, 23, A204-A210 (2015)
“Stable solution processed hole injection material for organic light-emitting diodes”, Szuheng Ho, Chaoyu Xiang, Rui Liu, Neetu Chopra, Mathew Mathai, Franky So, Organic Electronics, 15, 2513-2517 (2014)
“Stability of the interface between indium-tin-oxide and poly(3,4-ethylenedi -oxythiophene/poly(styrenesulfonate) in polymer light-emitting diodes”, M. P. de Jong,L. J. van IJzendoorn, and M. J. A. de Voigt, Appl. Phys. Lett. 77, 2255 (2000)
“Organic electroluminescent diodes”, C. W. Tang and S. A. VanSlyke, Appl. Phys. Lett. 51, 913 (1987)
“Lifetime of organic light emitting diodes on polymer anodes”, Karsten Fehse, Rico Meerheim, Karsten Walzer, Karl Leo, Wilfried Lövenich, and Andreas Elschner, Appl. Phys. Lett. 93, 083303 (2008)
“Optimization of driving lifetime durability in organic LED devices using Ir complex”, Teruichi Watanabe, Kenji Nakamura, Shin Kawami, Yoshinori Fukuda, Taishi Tsuji, Takeo Wakimoto, Satoshi Miyaguchi, Proc. SPIE 4105, Organic Light-Emitting Materials and Devices IV, 175 (February 2, 2001)
“Highly efficient and stable sky blue organic light-emitting devices”, Mei-Fang Lin, Lei Wang, Wai-Kwok Wong, Kwok-Wai Cheah, Hoi-Lam Tam, Meng-Ting Lee, and Chin H. Chen, Appl. Phys. Lett. 89, 121913 (2006)
“Large-area non-close-packed nanosphere deposition by blade coating for vertical space-charge-limited transistor”, Yen-Chu Chao, Kai-Ruei Wang, Hsin-Fei Meng, Hsiao-Wen Zan b, Yung-Hsuan Hsu, Organic Electronics, 13, 3177-3182 (2012)
“Role of air exposure in the improvement of injection efficiency of transition metal oxide/organic contact”, C.H. Cheung, W.J. Song, S.K. So Org. Electron., 11, p.89 (2010)
“Stable and efficient blue fluorescent organic light-emitting diode by blade coating with or without electron-transport layer”, Lan-Sheng Yang, Hsin-Fei Meng, Yu-Fan Chang, Cheng-Hsin Lien, Hsiao-Wen Zan, Sheng-Fu Horng, Lian Duan, and Yong Qiu, Organic Electronics, 23 ,June (2017)
“Blade coating of Tris(8-hydroxyquinolinato)aluminum as the electrontransport layer for all-solution blue fluorescent organic light-emitting diodes”, Yu-Fan Chang, Hsin-Fei Meng, Gang-Lun Fan, Ken-Tsung Wong, Hsiao-Wen Zan, Hao-Wu Lin, Heh-Lung Huang, Sheng-Fu Horng, Organic Electronics, 29,99-106 (2016)
“High quantum efficiency in simple blue phosphorescent organic light-emitting diodes without any electron injection layer”, Sang Eok Jang, Chul Woong Joo, Jun Yeob Lee, Thin Solid Films, 519, 906–910 (2010)
陳金鑫，黃孝文，OLED夢幻顯示器-OLED材料與元件，五南書局，台北，2007
李直蔚，降低使用非探性活性金屬極 有機電激發光體之操作電壓，國立交通大學，碩士論文，2011