Title

三官能化芴衍生物的合成及其光電性質

Translated Titles

Synthesis and Optoelectronic Properties of Trifunctionalized Fluorene Derivative

Authors

吳珮淳

Key Words

芴 ; 混掺 ; 藍光 ; 有機發光二極體 ; OLED ; fluorene ; blend ; blue

PublicationName

成功大學化學工程學系學位論文

Volume or Term/Year and Month of Publication

2008年

Academic Degree Category

碩士

Advisor

陳雲

Content Language

繁體中文

Chinese Abstract

對於有機發光二極體而言,發光材料的合成及其結構為影響發光特性的主要因素之ㄧ,因此可透過分子結構設計來改善發光材料的光電特性。本研究利用Wittig反應和Heck反應合成2,4,7-tris(methylphenylethenyl)-9,9-dihexylfluorene (TF) 以及2,7-dis(methylphenylethenyl)-9,9-dihexylfluorene (DF),以紅外光譜(FT-IR)、核磁共振光譜(1H-NMR)、元素分析儀(EA)來鑑定其結構。 TF碳4位置上的methylphenylethenyl基團和芴平面之間形成不共平面的扭角,阻礙分子堆疊,使得TF具有玻璃轉移溫度,而沒有明顯的熔點。由於DF和TF具有相同的主鏈使其具有相同的共軛長度,因此能帶間隙(Egel分別為2.84及2.83eV)相同。溶液態量子效率分別為ΦDF = 0.45、ΦTF = 0.42,激發能量因TF碳4位置上的methylphenylethenyl基團的振動而損失,使得TF量子效率略小於DF。將TF和PVK混摻製成元件,元件結構為[ITO/PEDOT:PSS/blend layer/Ca(50nm)/Al(100nm)]。隨著TF的重量比例從10%增加至60%,最大電流效率從0.02 cd/A增至0.17 cd/A、最大輝度從70 cd/m2增加至1170 cd/m2,而起始電壓從9.5 V降至4.7 V;CIE 1931色度座標分別為(0.15, 0.08)、(0.15, 0.08)、(0.15, 0.09)、(0.15, 0.09),由於電荷trap在TF中而從TF發光,使得發光顏色皆為純藍色,且EL發光光譜不隨TF含量增加而改變。

English Abstract

In this study, 2,4,7-tris(methylphenylethenyl)-9,9-dihexylfluorene (TF) and 2,7-dis(methylphenylethenyl)-9,9-dihexylfluorene (DF) have been successfully synthesized using the Wittig and Heck reactions. Their structure were well characterized by 1H-NMR, FT-IR and EA. The methylphenylethenyl group at 4 position of TF reveals a twist relative to the fluorene plane, which effectively prevents close packing of the molecules. DSC analysis revealed that the Tg of TF was 15.4 oC, but no obvious Tm was detected. The conjugation length of TF and DF are the same because they possess similar main chain structure. Accordingly, the band gap of TF (Egel= 2.84 eV) and DF (Egel= 2.83 eV) are the same. The PL quantum efficiencies of DF and TF are 0.45 and 0.42, respectively, in CHCl3. Slightly reduced efficiency of TF is probably due to energy dissipation through the additional methylphenylethenyl group at 4-position. The device structure was ITO/PEDOT:PSS/(PVK and TF Blend Layer at different weight ratios)/Ca/Al. When the weight percent of TF increased from 10% to 60%, the turn-on voltage decreased from 9.5 V to 4.7 V, maximum current efficiency increased from 0.02 cd/A to 0.17 cd/A and maximum luminance increased from 70 cd/m2 to 1170 cd/m2. The CIE 1931 chromaticity coordinates of the emission light are (0.15, 0.08), (0.15, 0.08), (0.15, 0.09) and (0.15, 0.09). The emission color are pure blue for all devices which originate exclusively from TF via charge trapping.

Topic Category 工學院 > 化學工程學系
工程學 > 化學工業
Reference
  1. [2] Tang, C. W.; Vanslyke, S. A. Appl. Phys. Lett., 51, 913 (1987).
    連結:
  2. [5] Skoog, D. A.; Holler, E. J.; Nieman, T. A. Principles of Instrumental Analysis, 5th edition, Saunders College Publishing, (1997).
    連結:
  3. [13] Ajn, T.; Song, S. Y.; Ku, H. Macromolecules., 33, 6764 (2000).
    連結:
  4. [19] Neher, D. Macromol. Rapid Commun., 22, 1365 (2001).
    連結:
  5. [23] Zhao, W.; Cao, T.; White, J. M. Adv. Funct. Mater. , 14, 783 (2004).
    連結:
  6. [32] Akcelrud, L. Prog. Polym. Sci., 28, 875 (2003).
    連結:
  7. [33] Barberis, V. P.; Mikroyannidis, J.A. Journal of Polymer Science Part A: Polymer Chemistry, 11, 3556 (2006).
    連結:
  8. [36] Jin, S. G.; Kang, S. Y.; Kim, M. Y.; Chan, Y. U. Macromolecules, 36, 3841 (2003)
    連結:
  9. [38] Xin, Y.; Wen, G. A.; Zeng, W. J.; Zhao, L.; Zhu, X. R.; Fan, Q. L.; Feng, J. C.; Wang, L. H.; Wei, W.; Peng, B.; Cao, Y.; Huang, W. Macromolecules, 38, 6755 (2005).
    連結:
  10. [40] Chou, C. H.; Shu, C. F. Macromolecules, 35, 9673 (2002).
    連結:
  11. [41] Li, J.; Bo, Z. Macromolecules, 37, 2013 (2004).
    連結:
  12. [42] Wu, C. W.; Lin, H. C. Macromolecules, 39, 7232 (2006).
    連結:
  13. [43] Wong, K. T.; Chen, R. T.; Fang, F. C.; Wu, C.; Lin, Y. T. Organic Letters, 10, 1979 (2005).
    連結:
  14. [44] Klaerner, G.; Miller, R. D. Macromolecules, 31, 2007 (1998).
    連結:
  15. [49] Liu, Q. D.; Lu, J.; Ding, J.; Day, M.; Tao, Ye.; Chi, Y. Adv. Funct. Mater., 17, 1028 (2007).
    連結:
  16. [51] Rusling, J. F.; Suib, S. L. Adv. Mater., 12, 922 (1994).
    連結:
  17. [53] (a) Meng, H.; Chen, Z. K.; Liu, X. L.; Lai, Y. H.; Chua, S. J.; Huang, W. Phys. Chem. Chem. Phys., 1, 3123 (1999). (b) Meng, H.; Chen, Z. K.; Yu, W. L.; Pei, J.; Liu, X. L.; Lai, Y. H.; Huang, W. Synth. Met., 100, 297 (1999).
    連結:
  18. [54] Heck, R. F.; Nolley, J. J. Org. Chem., 14, 2320 (1972).
    連結:
  19. [55] Mizoroki, T.; Mori, K.; Ozaki, A. Bull. Chem. Soc. Jap., 44, 581 (1971).
    連結:
  20. [57] Ranger, M.; Leclerc, M. Macromolecules, 32, 3306 (1999).
    連結:
  21. [60] Zhao, W.; Cao, T.; White, J. M. Adv. Funct. Mater., 14, 783 (2004).
    連結:
  22. [1] Pope, M.; Kallmann, H.; Magnante, P. J. Chem. Phys., 38, 2042 (1963).
  23. [3] Burroughes, J. H.; Bradly, D. D. C.; Brovn, A. R.; Morks, R. N.; Mackay, K.; Friend, R. H.; Burmond, P. L.; Holmes, A. B. Nature, 374, 539 (1990).
  24. [4] 郭昭輝;塑膠資訊雜誌,民國91年10月.
  25. [6] 黃孝文, 陳雲;化工資訊月刊,第15卷第3期,P.8,2001.
  26. [7] 葉昆明,陳雲;科學發展,第385期,P.58,2005年1月.
  27. [8] 陳信宏,陳雲;中工高雄會刊,第3期,P.72,2006年.
  28. [9] 楊素華;光訊雜誌,第98 期,P.29,2002 年10 月.
  29. [10] Wohlgenannt, M.; Tandon, K.; Mazumdar, S.; Ramasesha, S.; Vardeny, Z. V. Nature, 409, 494 (2001).
  30. [11] 翁文國;工業材料雜誌,第162期,P.75,,民國89年6月.
  31. [12] Grice, A. W.; Bradley, D. D. C.; Bernius, M. T.; Inbasekaran, M. W.; Wu, W.; Woo, E. P. Appl. Phy. Lett., 73, 629 (1998).
  32. [14] Long, X.; Grell, M.; Malinovski, A.; Bradley, D. D. C. Opt. Mat., 9, 70 (1998).
  33. [15] Meskers, S. C. J.; Hübner, J.; Oestreich, M.; Bässler, H. J. Phys. Chem. B,105, 9139 (2001).
  34. [16] Jenekhe, S. A.; Oasheni, J. A. Science, 265, 765 (1994).
  35. [17] Lemmer, U.; Heun, S.; Mahrt, R. F.; Scherf, U.; Hopmeier, M.; Siegner, U.; Gobel, E.O.; Mullen, K.; Bassler, H. Chem. Phy. Lett., 240, 373 (1995).
  36. [18] Blatchford, J. W.; Jessen, S. W.; Lin, L.-B.; Gustafson, T. L.; Fu, D.-K.; Wang, H.-L.; Swager, T. M.; MacDiarmid, A. G.; Epstein, A. J. Phys. Rev. B, 54, 9180 (1996).
  37. [20]Bliznyuk, V. N.; Carter, S. A.; Scott, J. C.; Klarner, G.; Miller, R. D.; Miller, D. C. Macromolecules, 32, 361(1999).
  38. [21] Romaner, L.; Pogantsch, A.; Scandiucci de Freitas, P.; Scherf, U.; Gaal, Chem. Commun.M.; Zojer, E.; List, E. J. W. Adv. Funct. Mater., 13, 597 (2003).
  39. [22] List, E. J. W.; R. Guentner, P. Scanducci de Freitas, Scherf, U. Adv. Mater., 14, 374 (2002).
  40. [24] Gaal, M.; List, E. J. W.; Scherf, U. Macromolecules, 36, 4236 (2003).
  41. [25] Klarner, G.; Lee, J. I.; Davey, M. H.; Miller, R. D. Adv. Mater., 11, 115(1999).
  42. [26] Setayesh, S.; Grimsdale,A. C.; Weil, T.; Enkelmann, V.; Müllen, K.; Meghdadi, F.; List, E. J. W.; Leising, G. J. Am. Chem. Soc., 123, 946 (2001).
  43. [27] Lee, J. L.; Klaerner, G.; Davey, M. H.; Miller, R. D. Synth. Met., 102, 1087 (1999).
  44. [28] Wu, F. I.; Reddy, S.; Shu, C. F.; Liu, M. S.; Jen, A. K. Chem. Mater., 15, 269 (2003).
  45. [29] Chen, J. P.; Klaerner, G.; Lee, J. I.; Lee, V. Y.; Markiewicz, D.; . Miller, R. D; Scott, J. C. Synth. Met., 107, 129 (1999).
  46. [30] Liu, B.; Yu, W. L.; Lai, Y. H.; Huang, W. Chem. Mater., 13, 1984 (2001).
  47. [31] Taranekar, P.; Abdulbaki, M.; Krishnamoorti, R.; Phanichphant, S.; Waenkaew, P.; Patton, D.; Fulghum, T.; Advincula, R. Macromolecules, 39, 3848 (2006).
  48. [34] Kreyenschmidt, M.; Klärner, G.; Fuhrer, T.; Ashenhurst, J.; Karg, S.; Chen, W. D.; Lee, V. Y.; Scott, J. C.; Miller, R. D. Macromolecules, 31, 1099 (1998).
  49. [35] Klarner,G.; Lee, J. I.; Davey, M. H.; Miller, R. D. Adv. Mater., 110, 993 (1998).
  50. [37] Mitwva, T.; Meisel, A.; Knoll, W.; Nothofer, H. G.; Scherf, U. ; Muller, D. C.; Meerholz, K.; Yasuda, A.; Neher, D. Adv. Mater, 13, 565 (2001).
  51. [39] Ha1ussler, M.; Liu, J.; Zheng, R.; Lam, J. W. Y.; Qin, A.; Tang, B. Z. Macromolecules, 40, 1914 (2007).
  52. [45] Liu, Q.; Liu, W.; Yao, B.; Tian, H.; Xie, Z.; Geng, Y.; Wang, F. Macromolecules, 6, 1851 (2007).
  53. [46] Lee, S. H.; Nakamura, T.; Tsutsui, T. Organic Letters, 13, 2005 (2001).
  54. [47] Katsis, D.; Ou, J. J.; Culligan, S. W.; Chen, S. H.; Rothberg, L. J. Chem. Mater., 14, 1332 (2002).
  55. [48] Li, Y.; Ding, J.; Day, M.; Tao, Y.; Lu, J.; D’iorio, M. Chem. Mater., 15, 4936 (2003).
  56. [50] Kong, Q.; Zhu, D.; Quan, Y.; Chen, Q.; Ding, J.; Lu, J.; Tao, Y. Chem. Mater., 19, 3309 (2007).
  57. [52] Liu, Y.; Liu, M. S.; Jen, A. K. Acta. Polym., 50, 105 (1999).
  58. [56] Ozawa, F.; Kubo, A.; Hayashi, T. Chemistry Lett., 2177 (1992).
  59. [58] Alder, R. W.; Anderson, K. R.; Benjes, P. A.; Butts, C. P.; Koutentis, P. A.; Orpen, A. G. J. Chem. Soc., Chem. Commun., 309 (1998).
  60. [59] Jin, S. H.; Park, H. J.; Kim, J. Y.; Lee, K.; Lee, S. P.; Moon, D. K.; Lee, H. J.; Gal, Y. S. Macromolecules, 35, 7532 (2002).