近年來，有機發光二極體(OLED)為備受期待的平面顯示器，在顯示器中全彩顯示為終極目標，其中藍光更是全彩顯示器中重要的一環，但藍光之能階較深，較為不易製作與合成，因而被廣泛研究，其研究文獻顯示許多有關蒽(Anthracene)、芘(pyrene)或是芴 (fluorene)等有著優異的藍色發光小分子；而在有機發光材料中，咔唑(Carbazole)衍生物的發光及電荷傳輸特性也曾被多次探討，並應用於OLED材料結構中，在本論文將引入上述結構並設計合成。
在此論文之中，開發出四種藍光分子NA、NB、NF、NP，其結構由蒽(Anthracene)、聯蒽(BiAnthracene)、螺二芴 (Spirobifluorene)、芘(pyrene)等四種優異的藍光分子透過合成的方式在其兩端接上咔唑(Carbazole)基團，在本身結構發出不錯藍光的特性下，藉此增加材料的電洞傳輸特性，並提高材料的立體障礙性，以減少堆疊所造成的濃度淬熄。
合成出的結構藉由質譜儀及核磁共振來鑑定結構確定無誤。在熱分析方面，其四種材料皆有不錯的熱穩定性(Td5% > 400°C)，NB及NP玻璃轉移溫度(Tg)為283°C及178°C。在光學特性量測中，以紫外光與可見光光譜儀及螢光光譜儀量測吸收與放光，薄膜吸收範圍在311nm至405nm，薄膜放光波長在430nm至464nm。最後以材料NA製作元件，結構為 ITO/NPB (40nm)/NA (30nm)/TPBi (30nm)/LiF (0.5nm)/Al (100nm)。

In this generation, organic light emitting diodes (OLEDs) have attracted much attention for application in flat-panel display. In full-color display, deep blue emission is very difficult to achieve because its large energy band gap. Many researchers have reported lots of small moleculars as excellent blue emission, such as anthracene, fluorene, and pyrene. Therefore, the synthesis of carbazole derivatives were extensively investigated. Carbazole derivatives possess electronic and charge-transport properties.
Herein, four deep blue materials, namely NA、NB、NF、NP, were synthesized base on anthracene, bianthracene, spirobifluorene, pyrene. Four compounds introduced carbazole side group, improved charge-transport properties, and increased steric effect to avoid quenching in the structure.
Molecular structures of the final compounds were confirmed by 1H NMR, mass spectrometry. The rigid molecular structures with side carbazole groups were beneficial to thermal, as manifest by their Td5% temperature of above 400°C. Optical absorption and PL spectra of materials were shown by solution and thin-film type. Finally, to determine the electroluminescent properties of fluorophores, non-doped device was fabricated. Device with the structure of ITO/NPB(40nm)/NA(30nm)/TPBi(30nm)/LiF(0.5nm) /Al(100nm) was fabricated.

中文審定書 i
英文審定書 ii
摘要 iii
Abstract iv
圖目錄 viii
表目錄 x
第一章 序論 1
1.1前言 1
1.2 有機發光二極體發展 2
1.3 有機發光二極體發光原理 5
1.4 量子效率 7
1.5 濃度淬熄 8
1.6 文獻回顧 9
1.7 分子設計理念與動機 14
第二章 實驗儀器介紹 15
2.1 鑑定分析儀器 15
2.1.1基質輔助雷射脫附游離飛行質譜儀 (MALDI/TOF-TOF ) 15
2.1.2核磁共振光譜儀(Nuclear Magnetic Resonance，NMR) 15
2.1.3高效液相層析儀(High Performance Liquid Chromatography，HPLC) 15
2.2熱分析儀器 16
2.2.1熱重分析儀(Thermogravimetric analyzer，TGA) 16
2.2.2 熱視差掃描卡量計 16
2.3光電特性分析儀器 17
2.3.1紫外光與可見光光譜儀 (UV-Vis spectrometer，UV-Vis) 17
2.3.2螢光光譜儀 (Fluorescence spectrometer，PL) 17
2.3.3光電子光分析儀 (Photoelectron Spectrometer，PESA) 17
2.4元件製作相關儀器 18
2.4.1 真空昇華純化機 18
2.4.2紫外光臭氧清洗機(UV Ozone) 18
2.4.3 手套箱 18
2.4.4 蒸鍍機 19
2.4.5光電特性量測系統 19
第三章 實驗 20
3.1 實驗材料 20
3.2 實驗 22
3.2.1材料合成流程 22
3.2.2材料分析及元件製作流程 23
3.2.3 Suzuki coupling 24
3.2.4 Nucleophilic Aromatic Substitution 28
3.2.5元件製作 32
第四章 結果與討論 33
4.1分子理論模擬 33
4.2 材料鑑定 36
4.3 熱穩定性分析 38
4.3.1 熱重分析儀(Thermogravimetric analyzer，TGA) 38
4.3.2 熱示差掃描卡量計(Differential scanning calorimetry，DSC) 39
4.4 光學分析 41
4.4.1 溶液態光譜分析 41
4.4.2 薄膜態光譜分析 43
4.4.3 理論CIE圖 45
4.5能階分析 46
4.6元件初步測試 48
第五章 結論 51
第六章 參考文獻 52
附錄 57

[1] M. Pope, H. P. Kallmann, and P. Magnante, Electroluminescence in Organic Crystals. The Journal of Chemical Physics, 1963, 38, 2042.
[2] N. V. Vityuk, V. V. Mikho, The asymmetrical electroluminescence of thin films of anthracene. Soviet Physics Journal, 1973, 16, 1629.
[3] G. G. Roberts, M. M. Ginnity, W. A. Barlow and P. S. Vincett, Electroluminescence, photoluminescence and electroabsorption of a lightly substituted anthracene langmuir film. Solid State Communications, 1979, 32, 683.
[4] C. W. Tang, S. A. VanSlyke, Organic electroluminescent diodes. Applied Physics Letters, 1987, 51, 913.
[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 1990, 347, 539.
[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, 1993, 365, 628.
[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. Journal of Applied Physics, 1995, 77, 694.
[8] A. Kraft, A. C. Grimsdale and A. B. Holmes, Electroluminescent Conjugated Polymers—Seeing Polymers in a New Light. Angewandte Chemie International Edition, 1998, 37, 402.
[9] M. A. Baldo, D. F. O'Brien, Y. You, A. Shoustikov, S. Sibley, M. E. Thompson and S. R. Forrest, Highly efficient phosphorescent emission from organic electroluminescent devices. Nature, 1998, 395, 151.
[10] T. L. Wu, M. J. Huang, C. C. Lin, P. Y. Huang, T. Y. Chou, R. Wu C. Cheng, H. W. Lin, R. S. Liu and C. H. Cheng Diboron compound-based organic light-emitting diodes with high efficiency and reduced efficiency roll-off. Nature Photonics, 2018, 12, 235.
[11] K. Sugiyama, D. Yoshimura, Electronic structures of organic molecular materials for organic electroluminescent devices studied by ultraviolet photoemission spectroscopy. Journal of Applied Physics, 1998, 83, 4928.
[12] X. W. Chen, Wallace C. H. Choy and C. J. Liang, Modifications of the exciton lifetime and internal quantum efficiency for organic light-emitting devices with a weak/strong microcavity. Applied Physics Letters, 2007, 91, 221112.
[13] Y. Yang, S. C. Chang, J. Bharathan and Jie Liu, Organic/polymeric electroluminescent devices processed by hybrid ink-jet printing. Journal of Materials Science: Materials in Electronics, 2000, 11, 89.
[14] Y. Yu, Z. Wu, Z. Li, B. Jiao, L. Li, L. Ma, D. Wang, G. Zhou and X. Houa, Highly efficient deep-blue organic electroluminescent devices (CIEy ≈ 0.08) doped with fluorinated 9,9′-bianthracene derivatives (fluorophores). Journal of Materials Chemistry C, 2013, 1, 8117.
[15] Z. Li, B. Jiao, Z. Wu, P. Liu, L. Ma, X. Lei, D. Wang, G. Zhou, H. Hud and X. Houa Fluorinated 9,9′-spirobifluorene derivatives as host materials for highly efficient blue organic light-emitting devices. Journal of Materials Chemistry C, 2013, 1, 2183.
[16] P. Zhang, W. Dou, Z. Ju, L. Yang, X. Tang, W. Liu and Y. Wu A 9,9′-bianthracene-cored molecule enjoying twisted intramolecular charge transfer to enhance radiative-excitons generation for highly efficient deep-blue OLEDs. Organic Electronics, 2013, 14, 915.
[17] C. C. Wu, Y. T. Lin, H. H. Chiang, T. Y. Cho, and C. W. Chen, Highly bright blue organic light-emitting devices using spirobifluorene-cored conjugated compounds. Applied Physics Letters, 2002, 81, 577
[18] 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, 2011, 12, 41.
[19] P. Kotchapradist, N. Prachumrak, R. Tarsang, S. Jungsuttiwong, T. Keawin, T. Sudyoadsuk and V. Promarak, , Pyrene-functionalized carbazole derivatives as non-doped blue emitters for highly efficient blue organic light-emitting diodes. Journal of Materials Chemistry C, 2013, 1, 4916.
[20] 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. 中山大學光電工程研究所學位論文, 2016.
[21] 徐振勛, 合成含咔唑聚芳香高分子應用於藍光有機發光二極體材料之研究. 中山大學光電工程研究所學位論文, 2017.
[22] F. F. Zhang, C. G. Zhou and J. P. Yan, New progress of researches in carbazole compounds. Chinese Journal of Organic Chemistry, 2010, 30, 783.
[23] J. F. Morin, M. Leclerc, D. Ades and A. Siove, , Polycarbazoles: 25 years of progress. Macromolecular Rapid Communications, 2005, 26, 761.
[24] 張銘賢, 新穎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. 中山大學光電工程研究所學位論文, 2012.
[25] C. Lee, W. Yang, and R. G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. PHYSICAL REVIEW B, 1988, 37, 785.
[26] Y. Ataly, D. Avci and A. BaSoglu, Theoretical analysis of vibrational spectra and scaling‐factor of 2‐aryl‐1,3,4‐oxadiazole derivatives. Journal of Quantum Chemistry, 2008, 19, 239.
[27] S. Tang, W. Li, F. Shen, D. Liu, B. Yang and Y. Ma, Highly efficient deep-blue electroluminescence based on the triphenylamine-cored and peripheral blue emitters with segregative HOMO–LUMO characteristics. Journal of Materials Chemistry C, 2012, 22, 4401.
[28] 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-9,10di(1-naphthyl)anthracene. Applied Physics Letters, 2003, 89, 252903.
[29] C. H. Yang, T. F. Guo, I. W. Sun,, Highly efficient greenish blue-emitting organic diodes based on pyrene derivatives. Journal of Luminescence, 2007, 124, 93.
[30] Z. F. Li, W. P. Liu, Y. Yu, X. Lv, C. F. Si, Z. X. Wu, Y. X. Cui, H. Y. Jia, J. S. Yu, H. Wang, F. Shi and Y. Y. Hao, , Effect of fluorocarbon (trifluoromethyl groups) substitution on blue electroluminescent properties of 9,9′-bianthracene derivatives with twisted intramolecular charge-transfer excited states. Dyes and Pigments, 2015, 122, 238.
[31] A. A. Shoustikov, Y. You and M. E. Thompson, Electroluminescence Color Tuning by Dye Doping in Organic Light-Emitting Diodes. IEEE Journal of Selected Topics in Quantum Electronics 1998, 4, 3
[32] K. H. Weinfurtner, H. Fujikawa, S. Tokito and Y. Taga, Highly efficient pure blue electroluminescence from polyfluorene: Influence of the molecular weight distribution on the aggregation tendency. Applied Physics Letters, 2000, 76, 2502.
[33] 溫新宜, 雙芴環衍生物之合成及其於藍光與白光有機發光二極體之應用. 中山大學光電工程研究所博士學位論文, 2013.
[34] 廖久富, 製程條件對雙芴環衍生物之影響及其應用於可調光色有機電激發光二極體. 中山大學光電工程研究所學位論文, 2014.