本論文主要以本實驗室所合成出三種新型聚芳香醚藍光高分子，包含唑(Carbazole)，蒽(Anthracene)、聯蒽(BiAnthracene)和芘(pyrene)的衍生物，成功應用於高分子有機發光二極體，透過高分子薄膜特性分析，包含材料的吸收、放光、熱穩定性以及能階，在三種材料CzAn、CzBAn、CzPy中以CzBAn具有良好的立體障礙性及熱穩定性T¬d5%高達500ｏC，而玻璃轉移溫度Tg為230ｏC，三種高分子材料皆具有良好藍光光色，其理論CIE座標的y軸小於0.15，高分子CzAn和CzBAn的相對量子效率皆大於標準品材料PFO。
三款材料的HOMO能階介於5.71eV至5.78eV之間，因材料本身的非共軛型態導致傳輸能力不佳，為了改善此問題，增加電子傳輸材料TPBi，因其具有較深之HOMO能階，同時兼具電洞阻擋效果，另一種方法是將有機發光層進行物理摻雜的方式，進而提升材料之導電特性，提高元件效率，且有效降低元件驅動電壓。
在此研究，所使用的摻雜藍光高分子有機發光二極體元件結構分別為ITO/ PEDOT:PSS/ CzBAn: PFO/ LiF/ Al及ITO/ PEDOT: PSS/ CzBAn: PVK/ LiF/ Al，分別得到最小驅動電壓4.5V最大亮度2030 cd/m2、最大電流效率 2.5 cd/A、外部量子效率1.4% 和最小驅動電壓6V最大亮度522 cd/m2、最大電流效率4.87 cd/A、外部量子效率2.89%，元件壽命方面，以CzBAn:PVK的摻雜作為發光層，具有最佳之元件壽命。

In this thesis, Three new novel blue light Emitting poly(arylene ether)s containing carbazole、Anthracene、Bianthracene and Pyrene derivatives has been successfully for PLED application. Through the polymers thin film characteristic analyzed, including absorption, light emission, thermal stability, and energy levels. The obtained polymers have high steric hindrance and good thermal stabilities, such as Tg range from 221ｏC to 230¬ｏC, and Td5% range from 438ｏC to 500ｏC. All polymers have lower value in CIE coordinates y < 0.15. The relative quantum efficiency of polymers, CzAn and CzBAn, are better than the standard material PFO.
Due to the structure of the polymers with non-conjugated, the HOMO energy levels were ranged from 5.71eV to 5.78eV. Herein, these two methods had been improved this phenomenon, one method is adding the electron transport layer material TPBi and have hole-blocking layer effect because it HOMO energy level up to 6.3eV, and the other method is physically doping in organic light-emitting layer, thereby improving the conductive properties of the material, increasing the efficiency of device, and effectively reduce the turn on voltage.
The optimized PLED structure of ITO/ PEDOT: PSS/ CzBAn: PFO/ TPBi/ Al, exhibited the turn on voltage is 4.5V, the maximum luminance of 2030 cd/m2, current efficiency of 2.5 cd/A, EQE of 1.4%. The other optimized PLED structure of ITO/ PEDOT:PSS/ CzBAn: PVK/ TPBi/ Al, exhibited the turn on voltage is 6V, the Maximum luminance of 522 cd/m2, the current efficiency of 4.87 cd/A, EQE of 2.89%.
The lifetime of the PLED device of CzBAn: PVK as emitting layer had the best result.

論文審定書 i
中文摘要 ii
Abstract iii
目錄 iv
圖目錄 vii
表目錄 xi
第一章 序論 1
1.1 前言 1
1.2 有機發光二極體之發展 2
1.3 有機發光二極體原理 6
1.4 有機發光二極體能量轉移機制 8
1.4.1 輻射能量轉移 9
1.4.2 非輻射能量轉移 9
1.5 有機發光二極體OLED和PLED之比較 11
1.6 量子效率 12
1.7 濃度淬熄效應 13
1.8 元件基本光學特性 13
1.9 CIE座標 14
1.10 文獻回顧 16
1.11 研究動機 26
第二章 實驗儀器介紹與原理 27
2.1 製程儀器 27
2.1.1 超音波清洗機(Ultrasonic Cleaner) 27
2.1.2 旋轉塗佈機(Spin Coater) 28
2.1.3 磁式旋轉加熱盤(hot plate) 29
2.1.4 電子天秤 29
2.1.5 紫外光臭氧清洗機(UV Ozone) 30
2.1.6 三聯式手套箱系統(Glove Box) 31
2.1.7 蒸鍍機(Evaporator) 32
2.2 量測儀器 33
2.2.1 紫外-可見光光譜儀(UV-visible Spectrophotometer) 33
2.2.2 螢光光譜儀(Fluorescence Spectrophotometer) 34
2.2.3 光電子能譜分析儀(Photo-Electron Spectroscopy in Air，PESA) 35
2.2.4 表面輪廓儀(Surface profiler) 36
2.2.5 光電特性量測系統 37
2.2.6 元件壽命量測系統(Lifetime) 38
第三章 實驗 39
3.1實驗藥品 39
3.2實驗規劃 44
3.3元件製程 45
3.4元件封裝 48
第四章 結果與討論 49
4.1 CzAn、CzBAn、CzPy高分子有機發光二極體材料特性分析 49
4.1.1 吸光特性分析 49
4.1.2 放光特性分析 51
4.1.3 CzAn、CzBAn、CzPy 材料薄膜能階分析 52
4.2 CzAn、CzBAn、CzPy、PFO高分子有機發光二極體之基本元件 54
4.3 以TPBi應用於高分子有機發光二極體元件 59
4.4 以CzBAn與PFO不同比例摻雜 64
4.5 以CzBAn與PVK不同比例摻雜 68
4.6 元件壽命 72
4.6.1 參數設定 72
4.6.2 元件壽命量測 73
第五章 結論 76
參考文獻 77

[1] M. Pope, and P. J. Mangante, Electroluminescence in Organic Crystals, Chem. Phys., 38, 2042-2043 (1963).
[2] N. V. Vityuk, and V. V. Mikho, Electroluminescence of anthracene excited by shaped -voltage pulse, Sov. Phys. Semicond., 6, 1479 (1973).
[3] G. G. Roberts, M. McGinnity, P. S. Vincett, and W. A. Barlow, Electroluminescence, photoluminescence and electroabsorption of a lightly substituted anthracene langmuir film, Solid State Commun., 32, 683-686 (1979).
[4] C. W. Tang, and S. A. Vanslyke, Organic electroluminescent diodes, Appl. Phys. Lett., 51, 913-915 (1987).
[5] J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, and A. B. Holmes, Light-emitting diodes based on conjugated polymers, Nature, 347, 539-541 (1990).
[6] N. C. Greenham, S. C. Moratti, D. D. C. Bradley, R. H. Friend, and A. B. Holmes, Efficient light-emitting diodes based on polymers with high electron affinities, Nature, 365, 628-630 (1993).
[7] Y. Yang, E. Westerweele, C. Zhang, P. Smith, and A. J. Heeger, Enhanced performance of polymer light‐emitting diodes using high‐surface area polyaniline network electrodes, J Appl. Phys. Lett., 77, 694-698 (1995).
[8] A. Kraft, A. Grimsdale, and A. B. Holmes, Electroluminescent Conjugated Polymers—Seeing Polymers in a New Light, Angew. Chem. Int. Ed., 37, 402-428 (1998).
[9] G. Gustafson, Y. Cao, Traecy, G. M. F. Klavetter, N. Colaneri, and A. J. Heeger, Flexible light-emitting diodes made from soluble conducting polymers, Nature, 357, 477-479 (1992).
[10] 陳金鑫，黃孝文著，夢幻顯示器OLED材料與元件，五南圖書出版股份有限公司 (2012) 。
[11] T. Förster, Zwischenmolekulare Energiewanderung und Fluoreszenz, Ann. Phys., 6, 55-75 (1948).
[12] L. Dexter, A Theory of Sensitized Luminescence in Solids, J. Chem. Phys., 21, 836-850 (1953).
[13] M. Klessinger, and J. Michl, Excited States and Photochemistry of Organic Molecules, VCH Publishers, New York (1995).
[14] 劉威廷，新穎發藍光材料與利用質子化製備可調變是光源應用於有機高分子發光二極體，國立中山大學光電工程學系博士論文 (2013)。
[15] K. Sugiyama, D. Yoshimura, T. Miyamae, T. Miyazaki, H.Ishii, Y. Ouchi, and K. Seki, Electronic structures of organic molecular materials for organic electroluminescent devices studied by ultraviolet photoemission spectroscopy, Appl. Phys., 83, 4928-4938 (1998).
[16] X. W. Chen, W. C. H. Choy, C. J. Liang, P. K. A. Wai, and S. He, Modifications of the exciton lifetime and internal quantum efficiency for organic light-emitting devices with a weak/strong microcavity, Appl. Phys. Lett., 91, 221112 (2007).


[17] Y. Yang, S. C. Chang, J. Bharathan, and J. Liu, Organic/polymeric electroluminescent devices processed by hybrid ink-jet printing, J. Mater Sci. Mater. Electron., 11, 89-96 (2000).
[18] 陳柏志，芳香取代吡咯雙極子螢光分子的合成及螢光特性，國立高雄大學應用化學系碩士論文 (2011)。
[19] 陳志強著，OLED有機發光二極體顯示器技術，全華圖書股份有限公司 (2013) 。
[20] C. C. Wu, Y. T. Lin, H. H. Chiang, T. Y. Cho, C. W. Chen, K. T. Wong, Y. L. Liao, G. H. Lee, and S. M. Peng, Highly bright blue organic light-emitting devices using spirobifluorene-cored conjugated compounds, Appl. Phys. Lett., 81, 577-579 (2002).
[21] Z. Zhao, J. H. Li, P. Lu, and Y. Yang, Fluorescent, Carrier-Trapping Dopants for Highly Efficient Single-Layer Polyfluorene LEDs, Adv. Funct. Mater., 17, 2203-2210 (2007).
[22] S. R. Tseng, H. F. Meng, K. C. Lee, and S. F. Horng, Multilayer polymer light-emitting diodes by blade coating method, Appl Phys Lett., 93, 153308 (2008).
[23] Z. Liu, J. Zou, J. Chen, L. Huang, J. Peng, and Y. Cao, Largely enhanced LED efficiency of carbazole–fluorene–silole copolymers by using TPBI hole blocking layer, Polymer., 49, 1604-1610 (2008)
[24] M. U. Hassan, Y. C. Liu, K. U. Hasan, H. Butt, J. F. Chang, and R. H. Friend, Charge trap assisted high efficiency in new polymer-blend based light emitting diodes, Nano Energy., 21, 62-70 (2016).

[25] C. W. Huang, C. L. Tsai, C. Y. Liu, T. H. Jen, N. J. Yang, and S. A. Chen, Design of deep blue electroluminescent spiro-polyfluorenes with high efficiency by facilitating the injection of charge carriers through incorporation of multiple charge transport moieties, Macromolecules, 45, 1281-1287 (2012).
[26] 張銘賢，新穎發藍光聚芳香醚高分子之合成及其在發光二極體上之應用研究，國立中山大學光電工程學系碩士論文 (2012)。
[27] 洪資程，多環藍光芳香烴之聚芳香醚高分子應用於有機發光二極體之合成及應用，國立中山大學光電工程學系碩士論文 (2016)。
[28] P. Wellman, M. Hofmann, O. Zeika, A. Werner, J. Birnstock, R. Meerheim, G. He, K. Walzer, M. Pfeiffer, and K. Leo, High-efficiency p-i-n organic light-emitting diodes with long lifetime, J Soc Inf Display., 13(5), 393-397 (2005).
[29] Y. Kijima, N. Asai, and S. I. Tamura, A Blue Organic Light Emitting Diode, Jpn. J. Appl. Phys., 38, 5274-5277 (1999).
[30] S. K. Kim, B. Yang, Y. Ma, J. H. Lee, and J. W. Park, Exceedingly efficient deep-blue electroluminescence from new anthracenes obtained using rational molecular design, J. Mater. Chem., 18, 3376-3384 (2008).
[31] S. Tao, Z. Hong, Z. Peng, W. Ju, X. Zhang, P. Wan, S. Wu, and S. Lee, Anthracene derivative for a non-doped blue-emitting organic electroluminescence device with both excellent color purity and high efficiency, Chemical Physics Letters., 397, 1-4 (2004).
[32] Y. Yu, Z. Wu, Z. Li, B. Jiao, L. Li, L. Ma, D. Wang, G. Zhou, and X. Hou, Highly efficient deep-blue organic electroluminescent devices (CIEy ≈ 0.08) doped with fluorinated 9,9’-bianthracene derivatives (fluorophores), J Mater Chem C., 1, 8117-8127 (2013).
[33] C. H. Yang, T. F. Guo, and I. W. Sun, Highly efficient greenish blue-emitting organic diodes based on pyrene derivatives, J. Lumin., 124, 93-98 (2007).
[34] S. Tokito, T. Iijima, T. Tsuzuki, and F. Sato, High-efficiency white phosphorescent organic light-emitting devices with greenish-blue and red-emitting layers, Appl Phys Lett., 83, 2459-2461 (2003).
[35] Ossila Ltd, "Spin Coating: A Guide to Theory and Techniques". (2016).
[36] M. Klessinger, Angewandte Chemie-International Edition in English 34, 549 (1995).
[37] M. H. Ho, Y. S. Wu, S. W. Wen, M. T Lee, and T. M. Chen, Highly efficient
deep blue organic electroluminescent device based on 1-methyl-9,10-di(1-naphthyl)anthracene, Appl. Phys. Lett., 89, 252903 (2006).
[38] T. Zhang, H. Dai, and J. Li, Novel carbazole/anthracene hybids for efficient blue organic light-emitting diodes, Displays, 34, 447-451 (2013)
[39] S. L. Lai, Q. X. Tong, M. Y. Chan, T. W. Ng, M. F. Lo, C. C. Ko, S. T. Lee, and C. S. Lee, Carbazole–pyrene derivatives for undoped organic light-emitting devices, Organic Electronics, 12, 541-546 (2011).
[40] C. J. Brabec, S. E. Shaheen, C. Winder, and N. S. Sariciftci, Effect of LiF/metal electrodes on the performance of plastic solar cells, Appl. Phys. Lett., 80, 1288-1290 (2002).
[41] J. H. Jou, S. Kummar, P. H. Fang, A. Venkateswararao, K. R. Justin Thomas, J. J. Shyue, Y. C. Wang, T. H. Lia, and H. H. Yua, Highly efficient ultra-deep blue organic light-emitting diodes with a wet- and dry-process feasible cyanofluorene acetylene based emitter, J. Mater. Chem., 3, 2182-2194 (2015).