臺灣博碩士論文加值系統

本研究選用共軛高分子Poly(fluorene)當做host材料，磷光Ir complex作為dopant材料，在phosphorescent light emitting diodes (PHOLEDs)的應用上，利用Suzuki Cross Coupling方法，將綠光和紅光的Ir complex以化學鍵結共軛高分子Polyfluorene，利用UV-vis和PL比較化學鍵結和摻合樣品，在THF、Toluene、chloroform溶劑中，濃度0.0001~1wt%探討溶劑及濃度效應，及Toluene溶液所形成固體膜，光電性質的變化。
比較Electrophosphorescent Polymers無定形均勻的固體膜，與摻雜共軛高分子與磷光Ir complex具有相分離的固體膜，光電性質的差異性，利用POM(偏光顯微鏡)，觀察兩種固體膜相分離的情形，與固體膜PL光譜圖比較，可知兩種材料內部能量傳遞的差異。
於Electrophosphorescent Polymers合成部分，有別於以往的研究，Ir complex鍵結在Poly(fluorene)C-9位置取代基碳鏈的末端，本研究利用具有dibromo官能基的Ir complex，以Suzuki Cross Coupling方法，鍵結在高分子共軛主鏈上，由GPC分子量分佈的分析，可以確認Ir complex與共軛高分子鍵結一起。
紅光Ir complex R鍵結共軛高分子PFO，在溶液態時Ir complex R的特性峰出現在505nm地方，同樣成份摻雜的樣品Ir complex R特性峰出現在520nm地方，兩者的固體膜，Ir complex R特性峰分別出現在619nm和608nm位置，前者為無定形均勻固體膜，後者為相分離嚴重的固體膜。
紅光Electrophosphorescent Polymers固體膜可以觀察到紅光Ir complex R的特性峰，綠光Electrophosphorescent Polymers固體膜卻觀察不到Ir complex G的特性峰，顯然兩者能量傳遞路徑有相當的差異。

This research to synthesize the phosphorescent light emitting diodes (PHOLEDs) by the host conjugate polymers polyfluorene and the dopant phosphorescent Ir complex using Suzuki Cross coupling reaction. First we synthesize the green or red Ir complex and the conjugate polymer polyfluorene bonding by the chemical bond, then we utilize Ultraviolet and Visible Light Spectroscopy (UV), and Photoluminescent Spectroscopy (PL) to investigate the solvent and concentration effect of the resulting polymers dissolvent in THF, toluene and chloroformthe, and solid film from toluene theirs differences of photophysical properties with blend system.
After compared the photophysical properties of the electrophosphorescent polymers amorphous solid film with the blend system which has phase separates, then utilize POM (polarizing microscope), observes situation which two kind of solid membranes separates, compares with the solid membrane PL light spectrogram, may know two kind of materials interior energy transfer the difference.
In synthesis electrophosphorescent polymers, different to the previously research, Ir complex functions group bonding in Poly (fluorene) the C-9 position substituting group carbon chain terminal. This research use the dibromo function group and Ir complex bonding in the conjugate polymer main chain by Suzuki Cross Coupling reaction. By the GPC molecular weight distribution analysis, may confirm the electrophosphorescent polymer were successful synthesized.
The PL spectra of red electrophosphorescent polymers and blend system have emission maximum at 505, 520nm in solution, respectively. Those solid film have emission maximum at 619, 608nm, respectively. Former has the amorphous solid film, latter has the serious shape separates solid film.
The red electrophosphorescent polymers solid film may observe the characteristic-peak of Ir complex R, but the green electrophosphorescent polymers solid film actually out-of-sight the characteristic peak of Ir complex G, obviously two energy-transfer way has the suitable difference.

目 錄
摘要…………………………………………………………………………………..I
Abstract………………………………………………………………………………III
目錄………………………………………………………………………………….IV
圖目錄……………………………………………………………………………….VI
表目率……………………………………………………………………………….IX

第一章 緒 論……………………………………………………………………….1
1.1、研究背景…………………………………………………………………1
1.2、文獻回顧…………………………………………………………………5
1.2.1、有機共軛高分子………………………………………………….5
1.2.2、磷光過渡金屬錯和物…………………………………………….8

第二章 實驗內容………………………………………………………………….13
2.1、實驗藥品………………………………………………………………..13
2.2、Poly(9,9-dioctylfluorene)………………………………………………..14
2.2.1、9,9-dioctylfluorene(1)…………………………………………….14
2.2.2、2,7-Dibromo-9,9-dioctylfluorene(2)…………………………15
2.2.3、9,9-dioctylfluorene-2,7-Diboronic acid(3)………………15
2.2.4、Poly(9,9-dioctylfluorene) (4)…………………………………16
2.3、Iridium(III) Bis(2-(1-(4-bromonaphthalene))pyridine-C2’,N) (acetyl acetonate)…………..…………………………………………………… 17
2.3.1、1,4-dibromonaphthalene (5)………………………………………17
2.3.2、1-bromonaphthalene-4-boronic acid (6)………………………17
2.3.3、2-(1-(4-bromonaphthalene))pyridine (7)……………………18
2.3.4、μ-chloro-bridged dimmer (8)…………………………………….19
2.3.5、Iridium(III) Bis(2-(1-(4-bromonaphthalene))pyridine-C2’,N)(acetyl acetonate) (9)……………………….…………………………….19
2.4、Iridium(III) Bis(2-(1-(4-bromophenyl))pyridine-C2’,N)(acetyl acetonate)………………………………………………………………...20
2.4.1、1-bromobenzene-4-boronic acid (10)…………………………20
2.4.2、2-(1-(4-bromophenyl))pyridine (11)…………………………21
2.4.3、μ-chloro-bridged dimmer (12)……………………………………21
2.4.4、Iridium(III) Bis(2-(1-(4-bromonaphthalene))pyridine-C2’,N)(acetyl acetonate) (13)…………………………………………….......22
2.5、Poly(9,9-dioctylfluorene)-α,ω- Diboronic acid……………………22
2.6、α,ω-dipyridine- poly(9,9-dioctylfluorene)…………………………23
2.7、Electrophosphorescent Polymers………………………………………..24

第三章 結果與討論……………………………………………………………….26
3.1、單體的合成與鑑定………………………………………………………26
3.2、Poly(9,9-dioctylfluorene)-α,ω- Diboronic acid的合成與鑑定…………28
3.3、α,ω-dipyridine- poly(9,9-dioctylfluorene)的合成與鑑定……………….30
3.4、Iridium complex的合成與鑑定………………………………………….32
3.5、PL光譜分析…………………………………………………………….36
THF溶液部分…………………………………………………………...38
Toluene溶液部分………………………………………………………..46
Chloroform溶液部分……………………………………………………52
固體膜部分……………………………………………………………...59
3.6、UV-vis光譜分析………………………………………………………..62
3.7、GPC分析………………………………………………………………..64
3.8、偏光顯微鏡(POM)分析…………………………………………………71

第四章 結論……………………………………………………………………….79

參考文獻………………………………….………………………………………82

附錄………………………………………………………………………………87

1. Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks, R. N.; Mackay, K.; Friend, R. H.; Burns, P. L.; Holmes, A. B. Nature (London) 1990, 347, 539.

2. S. Setayesh, D. Marsitzky, and K. Mu1 llen, Macromolecules 2000, 33, 2016.

3. Sirringhaus, H.; Wilson, R. J.; Friend, R. H.; Inbasekaran, M.; Wu, W.; Woo, E. P.; Grell, M.; Bradley, D. D. C. Appl. Phys. Lett. 2000, 77, 406.

4. Nelson, A.; Markiewicz, D.; Scott, J. C.; Miller, R. D. Chem.Mater. 1999, 11, 1800. (b) Lee, J. I.; Kla¨rner, G.; Miller, R.D. Chem. Mater. 1999, 11, 1083. (c) Setayesh, S.; Grimsdale, A. C.; Weil, T.; Enkelmann, V.; Mu¨ llen, K.; Meghdadi, F.; List, E. J. W.; Leising, G. J. Am. Chem. Soc. 2001, 123, 946.

5. X. Cong et al., Adv. Funct. Mater ., 13, 325 (2003).

6. Miteva, T.; Meisel, A.; Knoll, W.; Nothofer, H. G.; Scherf, U.;Mu¨ ller, K.; Meerholz, K.; Yasuda, A.; Neher, D. Adv. Mater. 2001, 13, 565.

7. Surin, M.; Hennebicq, E.; Ego, C.; Marsitzky, D.; Grimsdale, A. C.; Mu¨ llen, K.; Bre´das, J.-L.; Lazzaroni, R.; Lecle`re, P. Chem. Mater. 2004, 16, 994.

8. Brown, T. M.; Kim, J. S.; Friend, R. H.; Cacialli, F.; Daik, R.;Feast, W. J. Appl. Phys. Lett. 1999, 75, 1679

9. (a) Donat-Bouillud, A.; Le´vesque, I.; Tao, Y.; D’Iorio, M. Chem. Mater. 2000, 12, 1931.(b) Ego, C.; Grimsdale, A. C.; Weil, T.; Enkelmann, V.; Mu¨ llen,K. Adv. Mater. 2002, 14, 809.(c) Leclerc, M. J. Polym. Sci., Part A: Polym. Chem. 2001, 22, 1365.

10. Wai-Yeung Wong, Li Liu, Dongmui Cui, Louis M. Leung, Chin-Fai Kwong, Tik-Ho Lee, and Ho-Fung Ng, Macromolecules, 2005, 38, 4970.

11. Andressa M. Assaka, Paula C. Rodrigues, Alfredo R.M. de Oliveira, Liming Ding, Bin Hu, Frank E. Karasz, Leni Akcelrud, Polymer 45 (2004) 7071–7081.

12. Fangzhong Shen, Hong Xia, Chengbo Zhang, Dong Lin, Lin He, and Yuguang Ma, J. Phys. Chem. B 2004, 108, 1014-1019.

13. Tae-Hyuk Kwon, Hyo Soon Cho, Myoung Ki Kim, Ji-Whan Kim, Jang-Joo Kim, Kwan Hee Lee, Su Jin Park, Ik-Soo Shin,† Hasuck Kim, Dong Mok Shin, Young Keun Chung, and Jong-In Hong, Organometallics 2005, 24, 1578-1585.

14. Baldo, M. A.; O’Brien, D. F.; Thompson, M. E.; Forrest, S. R. Phys. ReV. B 1999, 60, 14422.

15. (a) Baldo, M. A.; O’Brien, D. F.; You, Y.; Shoustikov, A.; Sibley, S.; Thompson, M. E.; Forrest, S. R. Nature 1998, 395, 151-154. (b) Baldo, M A.; Lamansky, S.; Burrows, P. E.; Thompson, M. E.; Forrest, S. R. Appl. Phys. Lett. 1999, 75, 4-6. (c) Thompson, M. E.; Burrows, P. E.; Forrest, S. R. Curr. Opin. Solid State Mater. Sci. 1999, 4, 369.

16. Adachi, C.; Baldo, M. A.; Forrest, S. R.; Thompson, M. E. Appl. Phys. Lett. 2000, 78, 1704.
17. (a) Gross, M.; Nuller, D. C.; Nothofer, H.-G.; Scherf, U.; Neher, D.; Brauchle, C.; Meerholz, K. Nature 2000, 405, 661-665. (b) Chen, X.; Liao, J.-L.; Liang, Y.; Ahmed, M. O.; Tseng, H.-E.; Chen, S.-C. J. Am. Chem. Soc. 2003, 125, 636-637. (c) Higgins, R. W. T.; Monkman, A. P.; Nothofer, H.-G.; Scherf, U. J. Appl. Phys. 2002, 91, 99-105. (d) Zhu, W.; Liu, C.; Su, L.; Yang, W.; Yuan, M.; Cao, Y. J. Mater. Chem. 2003, 13, 50-55. (e) Chen, F.-C.; Yang, Y.; Thompson, M. E.; Kido, J. Appl. Phys. Lett. 2002, 80, 2308-2310.

18. Vaeth, K. M.; Tang, C. W. J. Appl. Phys. 2002, 92, 3447-3453.

19. Madhusoodhanan Sudhakar, Peter I. Djurovich, Thieo E. Hogen-Esch, and Mark E. Thompson, J. AM. CHEM. SOC. 2003, 125, 7796-7797.

20. (a)Bin Liu, Wang-Lin Yu, Yee-Hing Lai, and Wei Huang, Macromolecules 2000, 33, 8945-8952. (b) Taek Ahn, Seung-Yong Song, and Hong-Ku Shim, Macromolecules 2000, 33, 6764-6771. (c) Yuning Li, Jianfu Ding, Michael Day, Ye Tao, Jianping Lu, and Marie D’iorio, Chem. Mater.(d) D. Mikael Johansson, Mathias Theander, Thomas Granlund, Olle Ingana1 s, andMats R. Andersson, Macromolecules 2001, 34, 1981-1986.(e) Qiang Peng, Zhi-Yun Lu, Yan Huang, Ming-Gui Xie, Shao-Hu Han, Jun-Biao Peng, and Yong Cao. (f) Wei Yang, Jian Huang, Chuanzhen Liu, Yuhua Niu, Qiong Hou, Renqiang Yang, Yong Cao, Polymer 45 (2004) 865–872. (g) Xiaowei Zhan, Yunqi Liu, Xia Wu, Shuai Wang, and Daoben Zhu, Macromolecules 2002, 35, 2529-2537.

21. (a)Sergey Lamansky, Peter Djurovich, Drew Murphy, Feras Abdel-Razzaq, Hae-Eun Lee, Chihaya Adachi, Paul E. Burrows, Stephen R. Forrest, and Mark E. Thompson, J. Am. Chem. Soc. 2001, 123, 4304-4312. (b) Inamur R. Laskar, Shih-Feng Hsu, Teng-Ming Chen, Polyhedron 24 (2005) 189–200. (c) Wei-Chieh Chang , Andrew Teh Hu , Jiun-Pey Duan , Dinesh Kumar Rayabarapu , Chien-Hong Cheng, Journal of Organometallic Chemistry 689 (2004) 4882–4888. (d) Wen Liang Huang , Mei Ching Tseng, Jen Rong Lee, Xue Yu Chen, Inorganica Chimica Acta 349 (2003) 97–/103.