臺灣博碩士論文加值系統

本研究利用真空蒸鍍，製備一系列具單一發光層之雙波段螢光白光有機發光二極體（White organic light-emitting diodes，WOLEDs），所製備之WOLEDs，可分為兩部份探討。.
第一部份：高效率雙波段螢光白光有機發光二極體，分別利用三種不同主體材料：di(4-fluoro-phenyl)amino-di(styryl)biphenyl (DSB)、9,10-di-(2-na-phthyl)-anthracene (ADN)與1-tert-butyl-9,10- bis(2-nap-htyl)-anthracene (BANE)，並選用紅光染料4-(dicyano- me-thylene)-2-meth-yl-6-(julolidin-4-yl-vinyl)-4H-pyran (DCM2)，所搭配的電洞傳輸材料為N,N’-bis-(1- naphthy)-N,N’di- phenyl-1,1’- biphenyl4-4’-diamine (NPB)，電子傳輸材料為1,3,5- tris(N-phenyl- benzimidazol-2-yl)benzene (TPBi)；利用溶劑預溶混合主、客體發光材料，再將乾燥所得之混合物作為蒸鍍源，所得WOLEDs元件結構依序為透明導電陽極ITO（1250 Å）/電洞傳輸層NPB（450 Å）/發光層（250 Å）/電子傳輸層TPBi（400 Å）/電子注入層LiF（8 Å）/陰極Al（1500 Å）；當以DSB為主體材料，DCM2摻雜濃度為0.15 wt%時，所得的雙波段泛白光元件中，在亮度為100 cd/m2時，發光效率最大可達14.8 lm/W或15.6 cd/A，其CIE色座標為(0.424, 0.441)，元件最大發光亮度可達24,600 cd/m2；獲此高效率的原因可歸因為：一、高效率藍綠光DSB主體材料之選擇，二、具有高Förster能量轉移效率之主、客體發光系統，可使電子-電洞產生之激態能量，有效轉移給客發光分子；三、能階適當之元件設計，使電洞、電子容易注入發光層，進而被侷限於單一發光層中，增加發光效率。
第二部份：可撓式高效率白光有機發光二極體，選用PES做為可撓式OLEDs基材，這是因為PET之表面粗糙度大於PES，而表面粗糙度是影響元件表現的重要因素，再利用磁控濺鍍法於PES上製備透明導電陽極ITO，並於ITO與PES之間鍍製不同厚度之SiO2薄膜，以降低表面粗糙度，其SiO2薄膜最佳厚度為150 Å，ITO電阻率為3.9 × 10-4 Ω-cm，Rms為14 ± 1 Å。元件結構為PES/SiO2（150Å）/ITO （500Å）/NPB（500 Å）/發光層 （350 Å）/TPBi （400 Å）/LiF （8 Å）/Al （1500 Å），ITO鍍製溫度為200℃，可在廣義白光範圍得到最大亮度為9,000 cd/m2，最大發光效率為13.2 lm/W，在元件亮度為100 cd/m2時，其CIE色座標為（0.391, 0.438）。獲此高效率的原因可歸因為：一、最適化之SiO2薄膜厚度（150 Å）以降低PES表面粗糙度，二、高溫鍍製（200℃）ITO薄膜，具有最佳之導電性質。

目錄
獻…..……………………………………………………………………Ⅰ
摘要.………….…………………………………………………………Ⅱ
致謝.……..…………..…………………………………….……………Ⅲ
目錄…..…………………………………………………………………VI
表目錄.……………….…………………………………………………..Ⅹ
圖目錄.……….…………………………………………………………..ⅩI
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……………………………………………………...10
2-3、有機發光材料之演進…………….…………………………..15
2-4、可撓式基材之發展…………………….…..............................21
2-5、可撓式有機發光二極體…………………….…......................24
2-6、白光有機發光二極體之發展………………………….….....26
2-6-1、單層發光白光元件…………………………………......27
2-6-2、積層發光白光元件…………………………………......32
參、 實驗方法..…………………………………………………………38
3-1、材料……..…..…………………………………….………….38
3-2、透明導電陽極及SiO2薄膜之製備………….………………39
3-3、可撓式基材粗糙度與電性量測………….……………….....40
3-3-1、原子力顯微鏡………….…………………………………..40
3-3-2、霍爾效應量測儀………….………………………………..40
3-4、蒸鍍裝置……………...……………………………..……….41
3-5、蒸鍍速率之測定與校正.….………………………………....41
3-6、蒸鍍源之製備..………………………………………………43
3-7、基材清洗…….....…………….……………………………....43
3-8、元件之電路設計…………….….…………………………....44
3-9、元件電流、電壓與亮度特性量測.………………………....44
3-10、發光效率之計算…….……………………………………....45
3-11、電致發光光譜（electroluminescent spectra）量測….…....46
3-12、光激發光光譜（photoluminescent spectra）量測….……..46
3-13、紫外光吸收光譜（ultraviolet visible, UV-vis）量測….….46
肆、 結果與討論……………………………………………………47
4-1 藍光有機發光二極體…….….……………………………….47
4-1-1主體材料之特性分析……………………………………47
4-1-2、藍光有機發光二極體之製備…………………………...48
4-1-3、元件電壓對電流密度之影響…………………………...49
4-2、雙波段白光有機發光二極體………………………………...49
4-2-1、元件結構及鍍膜參數………………………………….49
4-2-2、主體材料對元件發光效率之影響……………………...50
4-2-3、元件電壓對電流密度之影響…………………………..51
4-2-4、元件之能階……………………………………………...51
4-2-5、Förster能量轉移……………………………………......52
4-2-6、高效率白光OLEDs………………………………….....53
4-2-7、高效率白光OLEDs之電致發光光譜………………….54
4-3、高效率可撓式白光OLEDs…………………………………..55
4-3-1、可撓式基材對OLEDs之影響……………….…………55
4-3-2、可撓式基材粗糙度對透明導電陽極之影響…………...55
4-3-3、SiO2薄膜厚度對可撓式白光有機發光二極體之影響……………………………………………………………….56
4-3-4、ITO鍍製溫度對電性之影響……………………………57
4-3-5、元件結構及鍍膜參數…………………………………...58
4-3-6、元件之亮度-電壓-電流密度關係……………………....59
4-3-7、元件發光效率……………….…………………………60
4-3-8、元件之CIE色座標……………………………………...60
4-3-9、元件之電致發光光譜………………….…….…………61
伍、結論…………………………………………………….…………..62
陸、參考資料……………………………………………………………64
柒、表與圖……………………………………………………………...72

陸、參考資料
[1] H. Lim, W. J. Cho, C. S. Ha, S. Ando, Y. K. Kim, C. H. Park, K. Lee, Adv. Mater. 2002, 14, 1275.
[2] J. Lewis, S. Grego, B. Chalamala, E. Vick, D. Temple, Appl. Phys. Lette. 2004, 85, 3450.
[3] J. Kido, M. Kimura, K. Nagai, Science 1995, 267, 1332.
[4] Z. Shen, P. E. Burrows, V. Bulović, S. R. Forrest, M. E. Thompson, Science 1997, 276, 2009.
[5] M. Ricks, M. Boroson, J. Ludwicki, A. Arnold, Society for Information Display 2005, Boston, USA, 2005, p. 826.
[6] A. R. Duggal, J. J. Shiang, C. M. Heller, D. F. Foust, Appl. Phys. Lett. 2002, 80, 3470.
[7] B. W. D’Andrade, R. J. Holmes, S. R. Forrest, Adv. Mater. 2004, 16, 624.
[8] B. W. D’Andrade, S. R. Forrest, Adv. Mater. 2004, 16, 1585.
[9] S. R. Forrest, Organic Electronics, 2003, 4, 45.
[10] R. C. Kwong, S. Lamansky, M. E. Thompson, Adv. Mater. 2000, 12, 1134.
[11] M. Ikai, S. Tokito, Y. Sakamoto, T. Suzuki, Y. Taga, Appl. Phys. Lett. 2001, 79, 156.
[12] Z. Y. Xie, L. S. Hung, S. T. Lee, Appl. Phys. Lett. 2001, 79, 1048.
[13] F. Nüesch, D. Berner, E. Tutiš, M. Schaer, C. Ma, X. Wang, B. Zhang, L. Zuppiroli, Adv. Funct. Mater. 2005, 15, 323.
[14] M. Pope, C. E. Swenberg, Electronic Process in Organic Crystals and Polymers, Second Edition, Oxford University Press, New York, 1999.
[15] T. C. Gorjanc, D. Leong, and C. Py, D. Roth, Thin Solid Films 2002, 413, 181.
[16] H. Lim, W. J. Cho, C. S. Ha, S. Ando, Y. K. Kim, C. H. Park, and K. Lee, Adv. Mater. 2002, 14, 1275.
[17] A. Bernanose, M. Conet, and P. Vouauzx, J. Chem. Phys. 1953, 50, 64.
[18] P. Pope, H. P. Kallmann, and P. J. Magnante, Chem. Phys. 1963, 38, 2042.
[19] W. Helfrich and W. G. Schneider, Phys. Rev. Lett. 1965, 14, 229.
[20] W. Helfrich and W. G. Schneider, J. Chem. Phys. 1966, 44, 2902.
[21] D. F. Williams and M. Schadt, Proc. IEEE 1970, 58, 476.
[22] P. S. Vincett, W. A. Barlow, R. A. Hann, and G. G. Robert, Thin Solid Films 1982, 94, 171.
[23] R. H. Patridge, Polymer 1983, 24, 733.
[24] C. W. Tang, and S. A. VanSlyke, Appl. Phys. Lett. 1987, 51, 913.
[25] S. A. VanSlyke, C. W. Tang, and L. C. Robert, US. Pat. 1988, No. 4,720,432.
[26] C. W. Tang, S. A. VanSlyke, and C. H. Chen, J. Appl. Phys. 1989, 65, 3610.
[27] 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.
[28] R. H. Friend, J. H. Burroughes, and D. D. Bradley, US. Pat. 1993, No. 5,247,190.
[29] C. Adachi, S. Tokito, T. Tsutsui, and S. Saito, Jpn. J. Appl. Phys. 1988, 27, L713.
[30] M. Era, C. Adachi, T. Tsutsui, and S. Saito, Chem. Phys. Lett. 1991, 178, 488.
[31] J. Kido, M. Kohda, K. Okuyama, and K. Nagai, Appl. Phys. Lett. 1992, 61, 761.
[32] J. Kido, M. Kimura, and K. Nagai, Science 1995, 267, 1332.
[33] J. Kido, H. Shionoya, and K. Nagai, Appl. Phys. Lett. 1995, 67, 2281.
[34] J. Shi and C. W. Tang, Appl. Phys. Lett. 1997, 70, 1665.
[35] G. E. Jabbour, B. Kippelen, N. R. Armstrong, and N. Peyghambarian, Appl. Phy. Lett. 1998, 73, 1185.
[36] J. Kido and T. Mizukami, US. Pat. 2000, No. 6,013,384.
[37] N. C. Greenham, R. H. Friend, A. R. Brown, D. D. C. Bradley, K. Pichler, P. L. Burns, A. Kraft, and A. B. Holmes, Proc. SPIE 1994, 1910, 84.
[38] M. A. Baldo, D. F. O’Brien, Y. You, A. Shoustikov, S. Sibley, M. E. Thompson, and S. R. Forrest, Nature 1998, 395,151.
[39] C. Adachi, M. A. Baldo, M. E. Thompson, and S. R. Forrest, J. Appl. Phys. 2001, 90,5048.
[40] Y. Shao and Y. Yang, Appl. Phy. Lett. 2005, 86, 073510.
[41] A. Dodabalapur and Bell Lab., Solid State Com. 1997, 102, 259.
[42] S. Miyata and H. S. Nalwa, Organic Electroluminescent Materials and Devices, Gordon and Breach Science Publishers, 1997, Chap 1.
[43] K. Sugiyama, D. Yoshimura, T. Miyamae, T. Miyazaki, H. Ishii, Y. Ouchi, and K. Seki, J. Appl. Phys. 1998, 83, 4928.
[44] T. Förster, Ann. Phys. 1948, 6, 55.
[45] D. L. Dexter, J. Chem. Phys. 1953, 21, 836.
[46] M. A. Lampert and P. Mark, Current Injection in Solids 1970, New York, Academic Press.
[47] S. Miyata and H. S. Nalwa, Organic Electroluminescent Materials and Devices, Gordon and Breach Science Publishers 1997, Chap 8.
[48] S. Miyata and H. S. Nalwa, Organic Electroluminescent Materials and Devices, Gordon and Breach Science Publishers 1997, Chap 9.
[49] J. Yang and J. Shen, J. Appl. Phys. 1998, 84, 2105.
[50] Z. Liu and J. Pinto, J. Soaves, E. Pereira, Synth. Metals 2001, 122, 177.
[51] K. A. Higginson, X. Zhang, and F. Padaimitrakoppulos, Chem. Mater. 1998, 10, 1017.
[52] S. A. VanSlyke, C. H. Chen, and C. W. Tang, Appl. Phys. Lett. 1996, 69, 2160.
[53] G. Sakamoto, C. Adachi, T. Koyama, Y. Taniguchi, C. D. Merritt, H. Murata, and Z. H. Kafafi, Appl. Phys. Lett. 1999, 75, 766.
[54] C. Giebeler, H. Antoniadis, D. D. C. Bradley, and Y. Shirota, J. Appl. Phys. 1999, 85, 608.
[55] J. Kido, K. Hongawa, K. Okuyama, and K. Nagai, Appl. Phys. Lett. 1994, 64, 815.
[56] L. Do, E. Ham, N. Yamamoto, and M. Fujihira, Mol. Cryst. Liq.Cryst. 1993, 280, 373.
[57] C. Hosokawa, H. Higashi, and T. Kusumoto, Appl. Phys. Lett. 62, 1993, 3238.
[58] J. Kido, K. Hongawa, K. Okuyama, and K. Nagai, Appl. Phys. Lett. 1993, 63, 2627.
[59] J. Kido, K. Hongawa, K. Okuyama, and K. Nagai, Appl. Phys. Lett. 1994, 64, 815.
[60] S. A. VanSlyke, C. H. Chen, and C. W. Tang, Appl. Phys. Lett. 1996, 69, 2160.
[61] K. Chondroudis and D. B. Mitzi, Appl. Phys. Lett. 2000, 69, 58.
[62] C. H. Chen, Chemistry（The Chinese Chem. Soc., Taipei）1996, 54, 125.
[63] Y. Shirota, Y. Kuwabara, and H. Inada, Appl. Phys. Lett. 1994, 65, 807.
[64] C. Adachi, K. Nagai, and N. Tamoto, Appl. Phys. Lette. 1995, 66, 2679.
[65] Y. Sato, S. Ichinosawa, and H. Kanai, IEEE Journal of Selected Topics in Quantum Electronics 1998, 4, 40.
[66] Y. Hamada, T. Sano, H. Fujii, Y. Nishio, H. Takahashi, and K.Shibata, Appl. Phys. Lett. 1997, 71, 3338.
[67] D. G. Ma, G. Wang, Y. F. Hu, Y. G. Zhang, L. X. Wang, X. B. Jing, and F. S. Wang, Appl. Phys. Lett. 2003, 82, 1296.
[68] L. S. Hung and C. W. Tang, US. Pat. 1997, No. 5,677,572.
[69] M. A. Baldo, D. F. Brlen, and S. R. Forrect, US. Pat. 2000, No. 6,097,147.
[70] F. Li and H. Tang, Appl. Phy. Lett. 1997, 70,1233.
[71] 田宏隆, 電子與材料雜誌, 2004, 21, 50.
[72] F. L. Wong, M. K. Fung, S. W. Tong, C. S. Lee and S. T. Lee, Thin Solid Films, 2004 466, 225.
[73] Y. Yang, Q. Huang, A. W. Metz, J. Ni, S. Jin, T. J. Marks, M. E. Madsen, A. DiVenere, and S. T. Ho, Adv. Mater. 2004, 16, 321.
[74] Y. Li, L. W. Tan, X. T. Hao, K. S. Ong and F. Zhua and L. S. Hung, Appl. Phy. Lett. 2005, 86,153508-1.
[75] A. Mikami, T. Koshiyama and T. Tsubokawa, J. J. Appl. Phys. 2005, 44, 608.
[76] Commission Internationale de L’eclairage （CIE）, Colorimetry, Publication Report No. 15.2, 1986.
[77] B. W. D’Andrade, R. J. Holmes, and S. R. Forrest, Adv. Mater. 2004, 16, 624.
[78] J. H. Jou, Y. S. Chiu, R. Y. Wang, C. P. Wang, Y. C. Huang, C. S. Lin, C. H. Cheng, and C. I. Chao, International Display Manufacturing Conference and Exhibition 2005.
[79] J. H. Jou, Y. S. Chiu, R. Y. Wang, H. C. Hu, C. P. Wang, and H. W. Lin, Organic Electronics 2005, 7, 8.
[80] S. Naka, K. Shinno, and H. Anada, Electron. Trans. IEICE 1997, 80, 1114.
[81] 林瑋哲, 碩士論文, 國立清華大學材料科學工程研究所, 2004.
[82] J. T. Lim, M. J. Lee, N. H. Lee, Y. J. Ahn, C. H. Lee, and D. H. Hwang, Curre. Appl. Phys. 2004, 4, 327-330.
[83] C. H. Chuen, Y. T. Tao, F. I. Wu, and C. F. Shu, Appl. Phys. Lett. 2004, 85, 4609.
[84] G. Lei, L. Wang, and Y. Qiu, Appl. Phys. Lett. 2004, 85, 5403.
[85] J. H. Jou, Y. S. Chiu, C. P. Wang, R. Y. Wang, and H. C. Hu, Appl. Phys. Lett. , 2006, 88, 193501.
[86] R. H. Jordan, A. Dodabalapur, M. Strukelj, and T. M. Miller, Appl. Phys. Lett. 1996, 68, 1192.
[87] S. R. Forrest, R. S. Desphande, and V. Bulovic, Appl. Phys. Lett. 1999, 75, 888.
[88] Y. S. Huang, J. H. Jou, W. K. Weng, and J. M. Liu, Appl. Phys. Lett. 2002, 80, 2782.
[89] 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.
[90] Y. F. Zhang, G Cheng, Y. Zhao, J. Y. Hou, and S. Y. Liu, Appl. Phys. Lett. 2005, 86, 011112.
[91] J. Kido, Organic Electroluminescence Material and Display, 2001, Chap17.
[92] J. Kido, Organic Electroluminescence Material and Display, 2001, Chap 23.
[93] F. Li, G. Cheng, Y. Zhao, J. Feng, S. Liu, M. Zhang, Y. Ma, and J. Shen, Appl. Phys. Lett. 2003, 83, 4716.
[94] G. Li and J. Shinar, Appl. Phys. Lett. 2003, 83, 5359.
[95] S. Tokito, T. Iijima, T. Tsuzuki, and F. Sato, Appl. Phys. Lett. 2003, 83, 2459.
[96] G. Cheng, Y. Zhao, Y. Zhang, S. Liu, F. He, H. Zhang, and Y. Ma, Appl. Phys. Lett. 2004, 84, 4457.
[97] 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
[98] D. Qin and Y. Tao, Appl. Phys. Lett. 2005, 86, 113507.
[99] M. Pope and C. E. Swenberg, Electronic Process in Organic Crystals and Polymers, Second Edition, Oxford University Press, New York, 1999.
[100] W. Tang, S. A. VanSlyke, and C. H. Chen, J. Appl. Phys. 1989, 65, 3610.
[101] 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.
[102] R. Freudenstein, A. Klett, and W. Kulisch, Thin Solid Films 2001, 398, 217.
[103] Y. Hu, X. Diao, C. Wang, W. Hao and T. Wang, J. Vacuum 2004, 75, 183.
[104] 王人仰, 碩士論文, 國立清華大學材料科學與工程研究所, 2005.
[105] 郭俊頡, 碩士論文, 國立中山大學光電工程研究所, 2005.