臺灣博碩士論文加值系統

利用薄層元件結構、適當之元件能階設計、選用高發光效率之紅、藍綠光染料，及能量轉移效率極佳之藍光主體材料，以溶劑預溶混合均勻之主、客發光材料混合物為源蒸鍍，我們製備了一系列高效率、高光色安定性螢光白光有機電致發光二極體（White Organic Light- Emitting Diode, WOLED）；所用主體材料為1,4-bis(2,2-diphenylvinyl)biphenyl、1-tert-butyl-9,10-bis(2-naphtyl)anthracene、藍綠光染料di(tri-phenylamine)-1,4-divinylna-phthalene、綠光染料10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-(1)benzopyrano(6,7,8-l,j)quinolizine-11-one、紅光染料4-(dicyanomethylene)-2-methyl-6-(julolidin-4-yl-vinyl)-4H-pyran；所搭配的電洞傳輸材料為N,N’-bis-(1-naphthy)-N,N’diphenyl-1,1’-biphenyl4-4’-diamine，電子傳輸材料為1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene；所得元件結構使電子、電洞容易進入發光層中，更可藉由高能量轉移效率的主體材料，將激態能量有效轉移至客發光分子，而得高發光效率；另外，所得摻雜染料分佈均勻之單一發光層，加上前述適當之元件結構，使電子、電洞容易被侷限在此發光層中再結合發光，不易因施加電壓變化而偏移至其他非發光層，故可得高光色安定性；所得三波長WOLEDs元件中，最大發光效率可達16 lm/W或19.2 cd/A，在元件亮度為100 cd/m2時，其1931國際照明標準委員會（Commission International de L’Eclairage，CIE）色座標為（0.359, 0.427），此元件最大發光亮度可達56,000 cd/m2；所得雙波長純白光WOLEDs元件中，發光效率最高者，可達6.6 lm/W或9.6 cd/A，在元件亮度為100 cd/m2時，其CIE色座標為（0.346, 0.343）；所得三波長純白光WOLEDs元件中，效率最高者達5.9 lm/W或8.5 cd/A，在元件亮度為100 cd/m2時，其CIE色座標為（0.339, 0.359）；所得各式白光或純白光WOLED元件，在亮度從100 cd/m2變化至10,000 cd/m2時，其所得CIE色座標變化，均小於（0.03, 0.03）。

獻………………………………………………………………Ⅰ
摘要……………………………………………………………Ⅱ
致謝……………………………………………………………Ⅲ
目錄……………………………………………………………Ⅶ
表目錄………………………………………………………ⅩⅡ
圖目錄………………………………………………………ⅩⅢ
壹、緒論 ………………………………………………………1
貳、文獻回顧 …………………………………………………4
2-1、有機發光二極體的歷史發展……………………………4
2-2、發光原理…………………………………………………8
2-3、有機發光材料……………………………………………14
2-4、白光有機發光二極體之發展……………………………16
2-4-1、單層發光白光元件 …………………………………17
2-4-2、積層發光白光元件 …………………………………20
2-5、研究構想…………………………………………………24
參、實驗方法 …………………………………………………26
3-1、材料 ……………………………………………………26
3-2、蒸鍍裝置…………………………………………………26
3-3、蒸鍍速率之測定與校正…………………………………27
3-4、蒸鍍源之製備……………………………………………27
3-5、基材清洗 ………………………………………………28
3-6、元件之電路設計…………………………………………29
3-7、負電極之製備……………………………………………29
3-8、元件電流、電壓與亮度特性量測………………………29
3-9、發光效率之計算…………………………………………30
3-10、電致發光光譜量測…………………………………… 30
3-11、光激發光光譜量測…………………………………… 31
3-12、紫外光吸收光譜量測………………………………… 31
3-13、最高已填滿分子軌域及最低未填滿分子軌域量測 …31
肆、結果與討論 ………………………………………………33
4-1、溶劑預混法製備蒸鍍源對OLED元件之影響……………33
4-1-1、以共蒸鍍法製作之紅、藍、綠光OLED元件…………33
4-1-2、以溶劑預混法製作之紅、藍、綠光OLED元件………34
4-1-3、溶劑預混法與共蒸鍍法之比較………………………35
4-2、元件結構對WOLED元件之影響 …………………………36
4-2-1、元件結構及鍍膜參數…………………………………36
4-2-2、電洞傳輸層厚度對元件發光效能之影響……………37
4-2-3、發光層厚度對元件發光效能之影響…………………38
4-2-4、電子傳輸層厚度對元件發光效能之影響……………40
4-3、紅光染料DCM2濃度對雙波長WOLED元件之影響 ………41
4-3-1、元件結構及鍍膜參數…………………………………41
4-3-2、元件之亮度-電壓-電流密度關係……………………42
4-3-3、元件發光效率…………………………………………43
4-3-4、元件之電致發光光譜…………………………………46
4-3-5、元件之CIE色座標 ……………………………………47
4-3-6、元件光色安定性………………………………………48
4-4、綠光染料C545T濃度對三波長WOLED元件之影響 ……49
4-4-1、元件結構及鍍膜參數…………………………………49
4-4-2、元件之亮度-電壓-電流密度關係……………………50
4-4-3、元件發光效率…………………………………………51
4-4-4、元件之電致發光光譜…………………………………53
4-4-5、元件之CIE色座標 ……………………………………53
4-4-6、元件光色安定性………………………………………54
4-5、主體材料對雙波長WOLED元件之影響 …………………55
4-5-1、元件結構及鍍膜參數…………………………………55
4-5-2、元件之亮度-電壓-電流密度關係……………………55
4-5-3、元件發光效率…………………………………………56
4-5-4、元件之CIE色座標 ……………………………………58
4-6、電子傳輸層材料對雙波長WOLED元件之影響 …………59
4-6-1、元件結構及鍍膜參數…………………………………59
4-6-2、元件之亮度-電壓-電流密度關係……………………59
4-6-3、元件發光效率…………………………………………60
4-6-4、元件之電致發光光譜…………………………………61
4-6-5、元件之之CIE色座標及光色安定性 …………………62
4-7、高效率藍綠光OLED元件…………………………………63
4-7-1、元件結構及鍍膜參數…………………………………63
4-7-2、元件之亮度-電壓-電流密度關係……………………63
4-7-3、元件發光效率…………………………………………64
4-7-4、元件之電致發光光譜…………………………………67
4-7-5、元件CIE色座標 ………………………………………68
4-8、高效率三波長WOLED元件 ………………………………68
4-8-1、元件結構及鍍膜參數…………………………………68
4-8-2、元件之亮度-電壓-電流密度關係……………………69
4-8-3、元件發光效率…………………………………………70
4-8-4、元件之電致發光光譜…………………………………73
4-8-5、元件CIE色座標 ………………………………………74
4-8-6、元件光色安定性………………………………………74
伍、結論 ………………………………………………………76
陸、參考資料 …………………………………………………80
柒、表與圖 ……………………………………………………81
捌、發表著作…………………………………………………191

[1] K. Ziemelis, Nature. 1999, 399, 408.
[2] C. W. Tang, and S. A. VanSlyke, Appl. Phys. Lette. 1987, 51, 913.
[3] J. H. Burroughs, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burn, and A. B. Holmes, Nature 1990, 347, 539.
[4] O. Prache, Displays. 2001, 22, 49.
[5] J. Y. Lee, J. H. Kwon, H. K. Chung, Organic Electronics, 2003, 4, 143.
[6] H. Lim, W. J. Cho, C. S. Ha, S. Ando, Y. K. Kim, C. H. Park, K. Lee, Adv. Mater. 2002, 14, 1275.
[7] J. Lewis, S. Grego, B. Chalamala, E. Vick, D. Temple, Appl. Phys. Lette. 2004, 85, 3450.
[8] J. Kido, M. Kimura, K. Nagai, Science 1995, 267, 1332.
[9] Z. Shen, P. E. Burrows, V. Bulović, S. R. Forrest, M. E. Thompson, Science 1997, 276, 2009.
[10] M. Ricks, M. Boroson, J. Ludwicki, A. Arnold, Society for Information Display 2005, Boston, USA, 2005, p. 826.
[11] A. R. Duggal, J. J. Shiang, C. M. Heller, D. F. Foust, Appl. Phys. Lett. 2002, 80, 3470.
[12] B. W. D’Andrade, R. J. Holmes, S. R. Forrest, Adv. Mater. 2004, 16, 624.
[13] B. W. D’Andrade, S. R. Forrest, Adv. Mater. 2004, 16, 1585.
[14] S. R. Forrest, Organic Electronics, 2003, 4, 45.
[15] R. C. Kwong, S. Lamansky, M. E. Thompson, Adv. Mater. 2000, 12, 1134.
[16] M. Ikai, S. Tokito, Y. Sakamoto, T. Suzuki, Y. Taga, Appl. Phys. Lett. 2001, 79, 156.
[17] Z. Y. Xie, L. S. Hung, S. T. Lee, Appl. Phys. Lett. 2001, 79, 1048.
[18] F. Nüesch, D. Berner, E. Tutiš, M. Schaer, C. Ma, X. Wang, B. Zhang, L. Zuppiroli, Adv. Funct. Mater. 2005, 15, 323.
[19] M. Pope, C. E. Swenberg, Electronic Process in Organic Crystals and Polymers, Second Edition, Oxford University Press, New York, 1999.
[20] R. H. Young, C. W. Tang, A. P. Marchetti, Appl. Phys. Lett. 2002, 80, 874.
[21] T. H. Liu, C. Y. Iou, C. H. Chen, Appl. Phys. Lett. 2003, 83, 5241.
[22] G. Li, and J. Shinar, Appl. Phys. Lett. 2003, 83, 5359.
[23] C. H. Chuen, Y. T. Tao, Appl. Phys. Lett. 2002, 81, 4499.
[24] C. H. Chuen, Y. T. Tao, F. I. Wu, and C. F. Shu, Appl. Phys. Lett. 2004, 85, 4609.
[25] Y. Shao and Y. Yang, Appl. Phy. Lett. 2005, 86, 073510.
[26] Bernanose, M. Conet, P. Vouauzx, J. Chem. Phys. 1953, 50, 64.
[27] P. Pope, H. P. Kallmann, and P. J. Magnante, Chem. Phys. 1963, 38, 2042.
[28] W. Helfrich, W. G. Schneider, Phys. Rev. Lett. 1965, 14, 229.
[29] W. Helfrich, W. G. Schneider, J. Chem. Phys. 1966, 44, 2902.
[30] P. S. Vincett, W. A. Barlow, R. A. Hann, G. G. Robert, Solid Thin Films 1982, 94, 171.
[31] R. H. Patridge, Polymer 1983, 24, 733.
[32] S. A. VanSlyke, C. W. Tang, and L. C. Robert, US. Pat. 1988, No. 4,720,432.
[33] W. Tang, S. A. VanSlyke, and C. H. Chen, J. Appl. Phys. 1989, 65, 3610.
[34] R. H. Friend, J. H. Burroughes, and D. D. Bradley, US. Pat. 1993, No. 5,247,190.
[35] Adachi, S. Tokito, T. Tsutsui, S. Saito, Jpn. J. Appl. Phys. 1988, 27, 713.
[36] M. Era, C. Adachi, T. Tsutsui, S. Saito, Chem. Phys. Lett. 1991, 178, 488.
[37] J. Kido, M. Kohda, K. Okuyama, K. Nagai, Appl. Phys. Lett. 1992, 61, 761.
[38] J. Kido, K. Hongawa, K. Okuyama, K. Nagai, Appl. Phys. Lett. 1994, 64, 815.
[39] J. Kido, H. Shionoya, K. Nagai, Appl. Phys. Lett. 1995, 67, 2281.
[40] Dodabalapur, Bell Lab., Solid State Com. 1997, 102, 259.
[41] S. Miyata, H. S. Nalwa, Organic Electroluminescent Materials and Devices, Gordon and Breach Science Publishers, 1997, Chap 1.
[42] K. Sugiyama, D. Yoshimura, T. Miyamae, T. Miyazaki, H. Ishii, Y. Ouchi, K. Seki, J. Appl. Phys. 1998, 83, 4928.
[43] T. Förster, Ann. Phys. 1948, 6, 55.
[44] L. Dexter, J. Chem. Phys. 1953, 21, 836.
[45] M. A. Lampert, P. Mark, Current Injection in Solids 1970, New York, Academic Press.
[46] S. Miyata, H. S. Nalwa, Organic Electroluminescent Materials and Devices, Gordon and Breach Science Publishers, 1997, Chap 8.
[47] S. Miyata, H. S. Nalwa, Organic Electroluminescent Materials and Devices, Gordon and Breach Science Publishers, 1997, Chap 9.
[48] J. Yang, J. Shen, J. Appl. Phys. 1998, 84, 2105.
[49] Z. Liu, J. Pinto, J. Soaves, E. Pereira, Synth. Metals 2001, 122, 177.
[50] K. A. Higginson, X. Zhang, F. Padaimitrakoppulos, Chem. Mater. 1998, 10, 1017.
[51] S. A. VanSlyke, C. H. Chen, C. W. Tang, Appl. Phys. Lett. 1996, 69, 2160.
[52] Sakamoto, C. Adachi, T. Koyama, Y. Taniguchi, C. D. Merritt, H. Murata, Z. H. Kafafi, Appl. Phys. Lett. 1999, 75, 766.
[53] C. Giebeler, H. Antoniadis, D. D. C. Bradley, Y. Shirota, J. Appl. Phys. 1999, 85, 608.
[54] L. S. Hung, and C. W. Tang, US. Pat. 1997, No. 5,677,572.
[55] M. A. Baldo, D. F. Brlen, and S. R. Forrect, US. Pat. 2000, No. 6,097,147.
[56] Commission Internationale de L’eclairage (CIE), Colorimetry, Publication Report No. 15.2, 1986.
[57] J. H. Jou, Y. S. Chiu, R. Y. Wang, C. P. Wang, Y. C. Huang, C. S. Lin, C. H. Cheng, C. I. Chao, “White Organic Light Emitting Diodes with Phosphore- scent Iridium Complexes Co-doped in One Single Emission Layer”, 2005 IDMC International Display Manufacturing Conference and Exhibition, Taipei, 2005.
[58] S. Naka, K. Shinno, and H. Anada, Electron. Trans. IEICE. 1997, 80, 1114.
[59] 林瑋哲, 碩士論文, 國立清華大學材料科學與工程研究所, 2004.
[60] G. Lei, L. Wang, and Y. Qiu, Appl. Phys. Lett. 2004, 85, 5403.
[61] R. H. Jordan, A. Dodabalapur, M. Strukelj, and T. M. Miller, Appl. Phys. Lett. 1996, 68, 1192.
[62] S. R. Forrest, R. S. Desphande, and V. Bulovic, Appl. Phys. Lett. 1999, 75, 888.
[63] Y. S. Huang, J. H. Jou, W. K. Weng, and J. M. Liu, Appl. Phys. Lett. 2002, 80, 2782.
[64] G. Cheng, F. Li, Y. Duan, J. Feng, S. Liu, S. Qiu, D. Lin, Y. Ma, and S. T. Lee, Appl. Phys. Lett. 2003, 82, 4224.
[65] Y. F. Zhang, G Cheng, Y. Zhao, J. Y. Hou, and S. Y. Liu, Appl. Phys. Lett. 2005, 86, 011112.
[66] Kido, Organic Electroluminescence Material and Display, 2001, Chap17.
[67] Kido, Organic Electroluminescence Material and Display, 2001, Chap23.
[68] S. Tokito, T. Iijima, T. Tsuzuki, and F. Sato, Appl. Phys. Lett. 2003, 83, 2459.
[69] T. S. Liu, Y. S. Wu, M. T. Lee, H. H. Chen, C. H. Liao, and C. H. Chen, Appl. Phys. Lett. 2004, 85, 4304
[70] S. Janietz, D. D. C. Bradley, M. Grell, C. Giebeler, M. Inbasekaran, E. P. Woo, Appl. Phys. Lett. 1998, 73, 2453.
[71] H. Nakamura, H. Ikeda, H. Kawamura, H. Higashi, H. Tokailin, K. Fukuoka, C. Hosokawa, and T. Kusumoto, SID 1999 Digest, 1999, 446.
[72] E. I. Haskal, Synth. Met. 1997, 91, 187.
[73] J. Kalinowski, P. Di Marco, M. Cocchi, V. Fattori, N. Camaioni, Appl. Phys. Lett. 1996, 68, 2317.
[74] K. R. J. Thomas, J. T. Lin, Y. T. Tao, C. W. Ko, J. Am. Chem. Soc. 2001, 123, 9404.
[75] Y. T. Tao, C. W. Ko, E. Balasubramaniam, Thin Solid Films, 2002, 417, 61.
[76] F. Nüesch, D. Berner, E. Tutiš, M. Schaer, C. Ma, X. Wang, B. Zhang, L. Zuppiroli, Adv. Funct. Mater. 2005, 15, 323.
[77] V. Bulovic, A. Shoustikov, M. A. Baldo, E. Bose, V. G.Kozlov, M. E. Thompson, and S. R. Forrest, Chem. Phys. Lett. 1998, 287, 455.
[78] 劉醇炘, 碩士論文, 國立交通大學應用化學研究所, 2002.
[79] V. Bulovic, R. Deshpande, M. E. Thompson, and S. R. Forrest, Chem. Phys. Lett. 1999, 308, 317.
[80] C. H. Chen, C. W. Tang, Appl. Phys. Lette. 2001, 79, 3711.