以共軛高分子為主的高分子發光二極體(Polymer Light Emitting Diode, PLED) 已經被科學家廣泛的研究，藉由從陽極、陰極注入的電洞及電子在發光層中再結合，進而發出不同的光色，因此電荷的注入及傳遞速率之平衡對發光效率有非常大之影響。大部分PLED高分子電洞傳遞速率大於電子，所以可利用多層結構導入電子注入/傳遞層、摻混電子注入/傳遞分子，或是利用化學合成改變分子結構，來提升電子注入及傳遞的能力。
本研究利用Suzuki聚合反應，將親電子性含雙溴官能基的芴酮 (Fluorenone) 和雙硼酯官能基的芴 (Fluorene) 合成一系列主鏈含高比例芴酮之高分子，PF-33、PF-40、PF-40、PF-48、PF-50、PF-52、PF-60 ，探討隨著fluorenone含量增加，對高分子的熱性質、光學性質、電化學性質與元件效能有何差異，同時以掺混的方式將PF-33導入PF內製程元件。在熱性質方面，高分子PF-33~PF-60並沒有發現熔點 (Tm) 出現，而熱裂解溫度 (Td) 皆在430 ℃才有明顯的裂解，PF-33、PF-40、PF-52玻璃轉移溫度 (Tg) 87~95℃，顯示PF-33~PF-60 皆具有高熱穩定性。在光學性質方面，PF-33~PF-60薄膜態的最大UV/Vis 吸收及螢光光譜 (PL) 波長分別在373~382nm 及566~568 nm。在電化學性質方面，利用氧化和還原起始電位分別求出高分子HOMO和LUMO能階，因電子傳遞基團fluorenone的導入，使高分子LUMO能階都有明顯下降，約在-3.17~-3.23 eV，表示改善了電子注入的能力。元件方面，PF-33、PF-40、PF-48雙層元件的其起始電壓分別為6.8V、6.2 V、5.2 V，而大亮度分別為709 cd/m2、313 cd/m2、119 cd/m2，CIE 1931座標皆在 (0.45, 0.52) 。此外我們將PF-33以不同比例 ( 0.02、0.5、1、5 wt% ) 掺混至PF製作成雙層元件，最大亮度分別為610cd/m2、720 cd/m2、3821 cd/m2、4400 cd/m2，流明效率由0.45增加到1.52 cd/A，CIE 1931座標也由 (0.45, 0.52) 轉變到 (0.39, 0.54) 。

Polymer light emitting diode (PLED) based on conjugated polymers has been extensively investigated by many scientists. However, most EL polymers are p-doped devices, the mobility of holes is usually much greater than electrons. An optimized PLED should have efficient and balanced charge injection/transport between anode and cathode. In order to achieve balanced charge injection, introducing electron transporting units in polymer backbone can also be employed to balance charge injection.
In this work, we prepared a series of 9,9-dihexylfluorenone-co-fluorenone (M1) random copolymers, named as PF-33 and PF-40, and alternating copolymers, named as PF-40~PF-60 by Suzuki coupling reaction. These copolymers exhibited good thermal stability with 5% weight loss temperature above 430℃ in nitrogen atmosphere. The LUMO level of these polymers located in -3.23 eV were lowered due to the introduction of fluorenone units. Both electrochemical results and MNDO semi-empirical calculations suggested that reduction started from fluorenone sites. In double layer LED devices of PF-33, PF-40 and PF-48, the turn-on voltages were 6.8, 6.2 and 5.2 V with maximum luminance of 709, 313 and 119cd/m2 and the corresponding C.I.E. coordinate is (0.45, 0.52). Furthermore, we incorporated various contents (0.02, 0.5, 1 and 5 wt %) of PF-33 into PF as emission layer for device fabrication, the maximum luminance were 610, 720, 3821 and 4400 cd/m2 and the luminance efficiency increased from 0.45 to 1.52 cd/A. The better luminance efficiencies were probably due to improved electron injection and carrier transporting as well as efficient charge trapping and recombination at fluorenone sites.

[ 1] Pope, M.; H. Kallmann, P.; Magnante. J. Chem. Phys. 1963, 38, 2042.
[ 2] C. W. Tang.; S. A.Vanslyke. Appl. Phys. Lett. 1987, 51, 913.
[ 3] J. H. Burroughes, D. D. C. Bradly, A. R. Brovn, R. N. Morks, K. Mackay, R. H. Friend, P. L. Burmond, A. B. Holmes, Nature. 1990, 374, 539.
[ 4] 段啟聖；化工資訊與商情，第26期，P.40，民國94年8月.
[ 5] 郭昭輝；塑膠資訊雜誌，民國91年10月.
[ 6] D. A. Skoog, E. J. Holler, T. A. Nieman, Principles of Instrumental
Analysis, 5th edition, Saunders College Publishing. 1997.
[ 7] 黃孝文， 陳雲；化工資訊月刊，第15卷第3期，P.8，2001.
[ 8] 葉昆明，陳雲；科學發展，第385期，P.58，2005年1月.
[ 9] 陳信宏，陳雲；中工高雄會刊，第3期，P.72，2006年.
[10] 楊素華；光訊雜誌，第98 期，P.29，2002 年10 月.
[ 11] M. Wohlgenannt, K. Tandon, S. Mazumdar, S. Ramasesha, Z. V. Vardeny,Nature. 2001, 409, 494.
[12] 陳金鑫；光訊雜誌，第65期，P.12，民86年4月.
[13] J. L. Segura, Acta Polym., 1998, 49, 319.
[14] Halls, J. J.M.; Walsh, C. A.; Greenham, N. C.; Greenham, N. C.; Marseglia, E. A.; Friend, R. H.; Moratti, S. C.. Nature. 1995, 376, 498.
[15] Yang, Y.; Hegger, A. J.. Nature. 1990, 374, 539.
[16] van Mullekom, H. A.M.; Vekemans, J. A. J. M.; Havinga, E. E.; Meijer, E. W.. Mater. Sci. Eng . 2001, 32, 1.
[17] J. Gmeiner, S.; Karg, M. M; W. Rieß, P.; Strohriegl, M. S. Acta. Polym. 1993, 44, 201.
[18] Gustafsson, G.; Cao, Y.; Treacy, G. M.; Klavetter, N. C.; Hegger, A. J. Nature. 1992, 357, 477.
[19] Hughes, G.; Bryce, M. R. J. Mater. Chem. 2005, 15, 94.
[20] Kulkarni, P. A.; Tonzola, C. J.; Babel. A.; Jenekhe, S. A. J. Mater. Chem. 2004, 16, 4556.
[21] Adachi, C.; Tsutsui, T.; Saito, S. Appl. Phys. Lett. 1989, 55, 1489.
[22] Adachi, C.; Tsutsui, T.; Saito, S. Appl. Phys. Lett. 1990, 56, 799.
[23] Antoniadis, H.; Inbasekaran, M.; Woo, E. P. Appl. Phys. Lett. 1998, 73, 3055.
[24] Tokuhisa, H.; Era, M.; Tsutsui, T. Adv. Mater. 1998, 10, 404.
[25] Ahn, J. H.; Wang, C.; Pearson. C.; Bryce, M. R.; Petty, M. C. Appl. Phys. Lett. 2004, 85, 1283.
[26] Tonzola, C. J.; Alam, M. M.; Bean, B. A.; Jenekhe, S. A. Macromolecules 1999, 37, 3554.
[27] Karastatiris, P.; Mikroyannidis, J. A.; Spiliopoulos, I. K.; Kulkarni, A. P.; Jenekhe, S. A. Macromolecules 2004, 37, 7867.
[28] Jandke, M.; Strohriegl, P.; Berleb, S.; Werner, E.; Brutting, W. Macromolecules 1998, 31, 6434.
[29] Wang, C.; Kilitziraki, M.; MacBride, J. A. H.; Bryce, M. R.; Horsburgh, L. E.; Sheridan,A. K.; Monkman,A. P.; Samuel, I. D. W. Adv. Mater. 2000, 12, 217.
[30] Uckert, F.; Tak, Y. H.; Müllen, K.; Bässler, H. Adv Mater. 2000, 12, 905.
[31] Uckert, F.; Setayesh, S.; Müllen, K. Macromolecules 1999, 32, 4519.
[32] Virgili, T.; Lidzey, D. G.; Bradley, D. D. C. Adv Mater. 2000, 12, 58.
[33] Scherf, U.; List, E.J.W. Adv Mater. 2002, 14, 477.
[34] Kulkarni, A. P.; Zhu, Y.; Jenekhe, S. A. Macromolecules 2005, 38, 1553.
[35] Gross, M.; Müller, D. C.; Nothofer, H.G.; Scherf, U.; Neher, D.; Bräuchle, C.; Meerholz, K. Nature. 2000, 405, 661.
[36]Graice, A. W.; Bradley, D. D. C.; Bernius, M. T.;Inbasekaran, M.;Wu, W. W.;Woo, E. P. Appl. Phys. Lett. 1998, 73, 629.
[37] Grell, M.; Knoll, W.; Lupo, D.; Meisel, A.; Miteva, T.; Neher, D.; Nothofer, H. G.; Scherf, U.; Yasuda, A. Adv. Mater. 2000, 11, 671.
[38] Lemmer, U.; Heun, S.; Mahrt, R. F.; Sgherf, U.; Hopmeier, M.; Siegner, U.; Gobel, E. O.; Mullen, K.; Bassler, H. Chem. Phy. Lett. 1995, 240, 373.
[39] Bliznyuk, V. N.; Carter, S. A.; Scott, J. C.; Klarner, G.; Miller, R. D.; Miller, D. C. Macromolecules 1999, 32, 361.
[40] Zeng, G.; Yu, W.-L.; Chua, S.-J.; Huang, W. Macromolecules 2002, 35, 6907.
[41] List, E. J. W.; R. Guentner, P. Scanducci de Freitas, Scherf, U. Adv. Mater. 2002, 14, 374.
[42] Gaal, M.; List, E. J. W.; Scherf, U. Macromolecules 2003, 36, 4236.
[43] Böhme, O.; Spetz, A. L.; Lundström, I.; Schmeißer, D. Adv. Mater. 2001, 13, 597.
[44] Zhao, W.; Cao, T.; White, J. M. Adv. Funct. Mater. 2004, 14, 783.
[45] Panozzo, S.; Vial, Y.; Stephan, O. J. Appl. Phys. 2002, 92, 3495.
[46] Kulkarni, A. P.; Kong, X.; Jenekhe, S. A. J. Phys. Chem. B. 2004, 108, 8689.
[47] Zhou, X. H.; Zhang, Y.; Xie, Y. Q.; Cao, Y.; Pei, J. Macromolecules 2006, 39, 3830.
[48] Gong, X.; Moses, D.; Heeger, A. J.; Xiao, S. J. Phys. Chem. B. 2004, 108, 8601.
[49] Sun, Q. J; Fan, B. H.; Tan, Z. A.; Li, Y. F.; Yang, Y. Appl. Phys. Lett. 2006, 88, 163510.
[50] Rusling, J. F.; Suib, S. L. Adv. Mater. 1994, 6, 922.
[51] Miyaura, N.; Yanagi, T.; Suzuki, A. Synth. Commun. 1981, 11, 513.
[52] Miyaura, N.; Yamada, K.; Suginome, H.; Suzuki, A. J. Am. Chem. Soc. 1985, 107, 972.
[53] Martin, A. R.; Yang, Y. Acta Chem. Scand. 1993, 47,221.
[54] Maxime, R.; Mario L. Macromolecules 1999, 32, 3306.
[55] John, K. S.; Kreisler, S. Y. L. Acc. Chem. Res. 1977, 10, 434.
[56] Dieter, N. J. Macro. Rap. Comm. 2001, 22, 1365.
[57] Egbert, Z.; Alexander, P.; Emmanuelle, H.;David, B.; Jean-Luc, B.; Patricia, S. F.; Ullrich, S.; List, E. J. W. J. Chem. Phys. 2002, 117, 6794.
[58] Chi, C. Y.; Im, C.; Enkelmann, V.; Ziegler, A.; Lieser, G.; Wegner, G. Chem. Eur. J. 2005, 11, 6833.
[59] Biczok, L.; Berces, T.; Linschitz, H. J. Am. Chem. Soc. 1997, 119, 11071.
[60] Samant, V.; Singh, A. K.; Ramakrishna, G.; Ghosh, H. N.; Ghanty, T. K.; Palit, D. K. J. Phys. Chem. A. 2005, 109, 8693.