臺灣博碩士論文加值系統

本研究是以高分子摻雜小分子的方式，製作單層高分子電激發光元件。利用本實驗室合成的小分子材料HBT (2-(2-hydroxyphenyl)benzothiazole)為雜摻料，在製程上以陰極金屬、發光層及旋轉塗佈時轉速控制等參數設定，探討元件光電性質影響。此外，我們選擇不同高分子基材如PVK、MEH-PPV，添加螢光材料 Nile red 或DCJTB製作三種摻混系列之元件，我們得到兩個有趣的現象，其一是HBT小分子的摻合，會提升發光的強度，其二是PVK摻合HBT小分子操作電壓在12 V時，會得到放光波峰為420、530與600nm的白光元件。
在本論文的另一部份，我們嘗試利用溶劑參與染料擴散熱轉印方法運用在雜摻的發光元件上，觀察其發光特性。

In this study, single-layer polymer light-emitting devices using dye dispersed in polymer matrix are fabricated. 2-(2-Hydroxyphenyl) benzothiazole, HBT, is synthesized and used as the dopant in emissive polymer layer. Three types of polymer matrix are used, including MEH-PPV, PVK with DCJTB or Nile red. The devices have been fabricated in varied conditions on the metal cathode deposition, single or double layered device configuration, and varied spinning rates of polymer film deposition.
The results of our experiments indicate a few interesting phenomena. Firstly, the electroluminescent intensity of PLED has been enhanced by the addition of HBT material. Secondly, HBT is found able to fabricate white-light EL devices while using PVK as polymer matrix. The polymer blended EL device has relatively low driving voltage at 8 Volts. The EL spectrum exhibits three emission peaks at 420, 530 and 600 nm, which represent deep blue, green and red light respectively.
In the final part of this dissertation, the different approach to form dye dispersed polymer film is presented via the method of solvent-assisted dye-diffusion thermal transfer. The EL devices fabricated from this process have lower turn-on voltage than the devices from polymer blending system.

中文摘要 i
英文摘要 ii
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
第一章 序論 1
第二章 相關理論及文獻回顧 3
2.1有機電激發光原理及元件構造 3
2.1.1 光激發光原理 3
2.1.2 電激發光之原理 4
2.1.3 電激發光之雙層元件結構 6
2.2螢光的能量轉移 7
2.3摻混／摻雜系統 8
2.3.1 高分子摻合小分子系統 8
2.3.2 高分子摻高分子系統 9
2.4雜摻材料之回顧 ……10
2.4.1 藍光 10
2.4.2 紅光 12
2.4.3 綠光 14
2.4螢光分子的ESIPT ……16
第三章 發光元件之製作與特性量測 18
3.1元件製作流程 18
3.1.1 高分子摻合小分子溶液之藥品備製 19
3.1.1.1 實驗藥品 19
3.1.1.2 材料物性量測 20
3.1.2 透明電極基板圖形化 21
3.1.2.1 ITO玻璃之蝕刻 21
3.1.2.2 玻璃基板之清洗 22
3.1.3 高分子成膜 23
3.1.4 陰極蒸鍍 25
3.1.5 PLED光電量測 28
第四章 結果與討論 29
4.1 HBT小分子材料能階之推估 30
4.2 以PVK 、MEH-PPV為主發光體摻混HBT電激發光元件之光電性…………………………………………………………………..32
4.2.1 PVK摻合HBT 32
4.2.2 MEH-PPV摻合HBT 39
4.3以PVK、HBT為主發光體分別摻合DCJTB與Nile red之電激發光元件光電性質 43
4.3.1 PVK、DCJTB摻合HBT 43
4.3.2 PVK、Nile red摻合HBT 47
4.4元件效能的提昇 50
4.4.1 陰極金屬不同蒸鍍方式對電激發光元件光電性質影響 50
4.4.2 電洞傳輸層PEDOT對於電激發光元件光電性質之影響 51
4.4.3 發光層在旋轉塗佈時，轉速對於EL元件光電性質之影響
53
第五章 利用溶劑參與染料擴散熱轉印法製作電激發光元件 54
5.1溶劑參與染料擴散熱轉印法之簡介………………………...……54
5.2溶劑參與染料擴散熱轉印時，製程溫度下降原理 55
5.3溶劑參與染料擴散熱轉印製程步驟 56
5.4以溶劑參與染料擴散熱轉印製程步驟而得之電激發光元件光電性質的量測 58
第六章 結論 60
參考文獻 61

1. J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, A. B. Holmes, "Light-emitting diodes based on conjugated polymers, " Nature, Vol. 347, 1990, pp. 539-341.
2. A. R. Brown, D. D. C. Bradley, J. H. Burroughes, R. H. Friend, N. C. Greenham, P. L. Burn, A. B. Holmes and A. Kraft,” Poly(p-phenylenevinylenes) light-emitting diodes: enhanced electroluminescent efficiency through charge carrier confinement,” Appl. Phys. Lett., Vol. 61, 1992, pp. 2793-2795.
3. (a) N. J. Turro, D. M. West, F. J. Holler, "Modern Molecular Photochemistry, " Sausalito, California, University Science Books, 1991.(b) R. P. Wayne, Principles and Applications of Photochemistry, Oxford University Press: Oxford, 1988.
4. M. Uchida, Y. Ohmori, and K. Yoshono, "Color-variable light-emitting diode utilizing conducting polymer containing fluorescent dye, " Jpn. J. Appl. Phys., Vol. 32, 1993, pp. L921-L924.
5. G. Yu, H. Nishino, A. J. Heeger, T. A Chen, and R. d. Rieke, "Enhanced electroluminescence from semiconducting polymer blends, " Synth. Met., Vol. 72, 1995, pp. 249-252.
6. B. Hu, Z. Yang, and F. E. Karasz, "Electroluminescence of pure poly(n-vinylcarbazole) and its blends with a multiblock copolymer, " J. Appl. Phys., Vol. 76, 1994, pp. 2419-2422.
7. U. Scherf and K. Mullen, "Poly(arylene)s and poly(arylene-vinylene)s . 11. a modified 2-step route to soluble phenylene-type ladder polymers, " Macromolecules, Vol. 25, 1992, pp. 3546-3548.
8. I. N. Kang, D. H. Hwang, H. H. Shim, T. Zyung, and J. J. Kim, "Highly improved quantum efficiency in blend polymer LEDs, " Macromolecules, Vol. 29, 1996, pp. 165-169.
9. Y. Cao, G. Yu, and A. J. heeger, " Efficient, low operating voltage polymer LEDs with aluminum as the cathode material, " Adv Matert., Vol. 10, 1998, pp. 917-920
10. D. Wang, Z. Hong, S. L., N. Minami, K. Yase and F. Wang, "Luminescence enhancement by blending PVK with blue PPV copolymer, " Synth. Met., Vol. 102, 1999, pp. 1132-1133.
11. J. Chung, B. Choi and H. H. Lee, "Polyaniline and poly(N-vinylcarbazole) blends as anode for blue light-emitting diodes, " Appl. Phys. Lett., Vol. 74, 1999, pp. 3645-3647.
12. S. Y. Song, M. S. Jang, H. K. Shim, I. S. Song and W. H. Kim, " New soluble light-emitting diode polymer containing oxadiazole unit, "Synth. Met., Vol. 102, 1999, pp. 1116-1117.
13. E. J. W. List, L. Holzer, S. Tasch, G. Leising, U. Scherf and S. Luzzati, "Efficient single-layer yellow-light emitting-diodes with ladder-type poly(p-phenylene)/ poly(decyl-thiophene) blends, " Solid State Communications, Vol. 109 1999, pp. 455-459.
14. 黃春輝，光電功能超薄膜，大陸：北京大學出版社，2001，第267頁。
15. 顧鴻壽，光電有機電激發光顯示器，台北：新文京開發出版有限公司，2001，第96頁。
16. C. Hosokawa, H. Higashi, H. Nakamura, and T. Kusumoto, "Highly efficient blue electroluminescence from a distyrylarylene emitting layer with a new dopant, " Appl. Phys. Lett., Vol. 67, 1995, pp. 3853-3855.
17. Y. Kim, J. G. Lee, D. K. Choi, Y. Y. Jung, B. Park, J. H. Keum, and C. S. Ha, " Red electroluminescent devices utilizing dye-dispersed soluble polyimide thin film as an emission layer, " Synth. Met., Vol. 91, 1997, pp. 329-330.
18. C. M. Bouche, P. L. Barny, H. Facoetti, and P. Robin, "Ultrafast generation of blue light by efficient second-harmonic generation in periodically-poled bulk and waveguide potassium titanyl phosphate, " Appl. Phys. Lett., Vol. 73 1998, pp. 873-875.
19. Y. Hamada, H. Kanno, T. Tsujioka, and H. Takahashi, " Red organic light-emitting diodes using an emitting assist dopant, " Appl. Phys. Lett., Vol. 75, 1999, pp. 1682-1684.
20. C. H. Chen, C. W. Tang, J. Shi, and K. P. Klubek, "Recent developments in the synthesis of red dopants for Alq3 hosted electroluminescence, " Thin Solid Films, Vol. 363, 2000, pp. 327-341..
21. C. C. Wu, J. C. Sturm, R. A. Register, J. Tian, E. P. Dana, and M. E. Thompson, "Efficient organic electroluminescent devices using single-layer doped polymer thin films with bipolar carrier transport abilities, " IEEE Trans. Electron Devices, Vol. 44, 1997, pp. 1269-1281.
22. Y. Sakakibara, T. Tani, S. Okutsu and T. Enokkia, "Red organic electroluminescence devices with a reduced porphyrin compound, tetraphenylchlorin, " Appl. Phys. Lett., Vol. 74, 1999, pp. 2587-2589.
23. Y. Sakakibara, S. Okutsu, T. Enokida, and T. Tani, "Red electroluminescence and photoluminescence properties of a reduced porphyrin compound, tetraphenylchlorin, " Thin Solid Films, Vol. 363, 2000, pp. 29-32.
24. Y. Ohmori, H. Kajii, T. Sawatani, H. Ueta, K. Yoshino, "Enhancement of electroluminescence utilizing confined energy transfer for red light emission, " Thin Solid Films, Vol. 393, 2001, pp. 407-411.
25. I. Sequy, P. Destruel, and H. Bock, "An all-columnar bilayer light-emitting diode, " Synth. Met., Vol. 111-112, 2000, pp. 15-18
26. I. Sequy, P. Jolinat, P. Destruel, J. Farenc, R. Mamy, H. Bock, J. Ip, and T. P. Nquyen, "Red organic light emitting device made from triphenylene hexaester and perylene tetraester, " J. Appl. Phys., Vol. 89, 2001, pp. 5442-5448.
27. M. Mitsuya, T. Suzuki, T. Koyama, H. Shiral, Y. Taniguchi, M. Satsuki, and S. Suga, "Bright red organic light-emitting diodes doped with a fluorescent dye, " Appl. Phys. Lett., Vol. 77, 2000, pp. 3272-3274.
28. C. W. Tang, S. A. VanSlyke, and C. H. Chen, "Electroluminescence of doped organic thin films, " Appl. Phys. Lett., Vol. 65, 1989, pp. 3610-3616.
29. 黃春輝，光電功能超薄膜，大陸：北京大學出版社，2001，第263頁。
30. L. G. Denis, K. Vladimir, R. Wolfgang, "Excited-state intramolecular proton transfer (ESIPT) in 2-(2’-hydroxyphenyl)pyridine and some carbon-bridged derivatives, " J. Photochemistry and Photobiology A: Chemistry, Vol. 117, 1998, pp. 209-216.
31. I. Rodrigo S., G.. Paulo F.; L. Paolo R., "Semi-empirical study of a set of 2-(2′-hydroxyphenyl)benzazoles using the polarizable continuum model, " Chem. Phys. Lett., Vol. 327, 2000, pp. 23-28.
32. F. Liang, L. Wang, D. Ma, X. Jing, and F. Wang, "Oxadiazole-containing material with intense blue phosphorescence emission for organic light-emitting diodes, " Appl. Phys. Lett., Vol. 81 2002, pp. 4-6.
33. R. G. Brown, A. B. Simon, S. M. Ormson, "Ultrafast measurements of excited state intramolecular proton transfer (ESIPT) in room temperature solutions of 3-hydroxyflavone and derivatives, " J. Phys. Chem. A, Vol. 105, 2001, pp. 3709-3718.
34. J. K. Kim, J. W. Yu, J. M. Hong, H. N. Cho, D. Y. Kim, and C. Y. Kim, "An alternating copolymer consisting of light emitting and electron transporting units, " J. Mater. Chem., Vol. 9, 1999, pp. 2171-2176.
35. 薛各良，側鏈型螢光高分之活性聚合及PVK摻雜2-(2’-羰基苯)苯駢塞唑電激發光元件，碩士論文，國立臺北科技大學有機高分子研究所，台北，2002。
36. C. C. Wu, S. W. Lin, C. W. Chen, and J. H. Hsu, " Solvent-assisted dye-diffusion thermal transfer for electronic imaging applications, " Appl. Phys. Let., Vol. 80, 2002, pp. 1117-1119.
37. 陳俊發，高分子發光元件之製作，碩士論文，國立臺北科技大學有機高分子研究所，台北，2001。
38. 范家豪，利用摻雜小分子染料的方式製作紅光高分子電激發光元件，碩士論文，國立臺北科技大學有機高分子研究所，台北，2002。
39. 林耕竹，在不同基板上利用DP6-PPV及MEH-PPV之共聚物製作可調色高分子發光元件，碩士論文，國立臺北科技大學光電工程研究所，台北，2002。