臺灣博碩士論文加值系統

在有機發光元件中（OLEDs），元件的外部量子效率由於受到有機層和玻璃基板等高折射率材料的影響，如何提高元件的出光率一直是研究團隊中相當重視的一個領域。
本論文將藉由金屬的高散射特性，利用奈米金屬顆粒做為元件散射的介質，並針對奈米金屬顆粒在有機層中及ITO玻璃基板上對元件外部量子效率的影響做詳細探討，奈米金屬結構的製作是以金屬薄膜在玻璃基板上的除潤效應（dewetting）為主要方法，此技術有兩項優點：（1）奈米金屬結構的製程簡單且不需要高價位的製程設備（2）容易大面積製造；這兩項優勢對於用電子束微影（electron beam lithography）製作的金屬結構而言是遙不可及。
我們成功利用金屬除潤效應（dewetting）的技術，找出金、銀薄膜最佳散射條件的除潤厚度，將金屬結構製作在ITO正向四周，元件的外部量子效率可提升~13.6 %；更進一步，將結構製作在ITO背向四周，可避免元件漏電流和穿透率的問題，外部量子效率可提升~25 %。

The external quantum efficiency of the organic light-emitting diodes (OLEDs) is influenced by high refracting rate materials in organic layer and ITO glass substrate, etc. How improve the devices coupling-out efficiency is an important issue to study first field that pay much attention in the group.
In this thesis, through metallic high scattering characteristics, we utilize monolayer of gold nanoparticles as a scattering medium and evaporate nanoparticles in organic layer or deposited on ITO glass, and make the detailed discussion on external quantum efficiency of devices.
The alternative to enhance the extraction is to fabricate gold/silver nano-islands with the dewetting process. As the main part of the research topic, this technology has two advantages: (1) The metallic nanostructures do not increase the fabrication cost (2) It is apt to produce on the structure large-scale devices. Because of these two strengths, the nanostructures are distinguished from the pattern fabricated with the electron beam lithography.
We succeed in utilizing metal thin film dewetting technology, and achieve optimum of gold/silver dewetting thickness as the best scattering medium. With metallic nanostructures in peripheral area of emitting region on the ITO glass substrate, external quantum efficiency of devices enhances by about 13.6 %. In addition, fabricating metallic structures on the reverse side of ITO glass substrate can prevent leak current and transmission issue, quantum efficiency can improve about 25 %.

摘要...........................................................................................................I
Abstract...................................................................................................II
致謝.........................................................................................................III
目錄..........................................................................................................V
圖目錄....................................................................................................IX
表目錄.................................................................................................XVI
第一章 序論...........................................................................................1
1-1 前言.............................................................................................1
1-2 有機發光二極體的歷史發展.....................................................2
1-3 元件的發光原理和基本構造.....................................................5
1-4 有機發光二極體全彩化技術.....................................................9
1-5 有機發光二極體的效率...........................................................11
1-6 增強元件出光率的方法...........................................................12
1-6.1 減少不發光模式............................................................14
1-6.2 減少全反射....................................................................14
1-6.3 減少波導效應................................................................17
1-7 研究動機...................................................................................19
第二章 理論基礎................................................................................20
2-1 光與奈米顆粒的散射與吸收...................................................20
2-2 金屬粒子的表面電漿共振.......................................................23
2-2.1 電磁波在物質中傳播的特性........................................23
2-2.2 金屬顆粒的表面電漿共振............................................24
2-3 金屬薄膜的除潤效應...............................................................31
2-3.1 異質成核（heterogeneous nuleation）.........................33
2-3.2 Spinodal dewetting..........................................................34
第三章 實驗步驟與方法..................................................................35
3-1 製程前準備...............................................................................35
3-1.1 基板清潔........................................................................35
3-1.2 金屬薄膜除潤基板製作................................................36
3-1.3 ITO蝕刻與奈米金屬結構製作......................................37
3-2 製程設備介紹...........................................................................42
3-2.1 高溫爐管（Tube Furnace）..........................................42
3-2.2 濺鍍機（Sputter Coater）.............................................42
3-2.3 高真空熱蒸鍍系統（High Vacuum Deposition System）...................................................................................................43
3-3 蒸鍍速率之測定與校正...........................................................44
3-4 元件結構...................................................................................45
3-5 元件量測...................................................................................46
3-5.1 基板散射效率量測........................................................46
3-5.2 穿透率量測....................................................................48
3-5.3 電致發光光譜（Electroluminescent spectra）量測....48
3-5.4 電流、電壓與亮度特性量測........................................49
3-5.5 發光效率之計算............................................................49
第四章 結果與討論............................................................................50
4-1 Amino groups修飾奈米金顆粒對元件的影響.........................50
4-1.1 奈米金顆粒修飾在玻璃基板之SEM影像....................50
4-1.2 奈米金顆粒在基板背側對元件的影響........................52
4-2 不同溫度對ITO玻璃的影響....................................................54
4-3 奈米金屬薄膜厚度及除潤溫度對除潤效應的影響...............58
4-3.1不同厚度及溫度對金薄膜的除潤效應之SEM影像....59
4-3.2不同厚度及溫度對銀薄膜的除潤效應之SEM影像....61
4-4 金薄膜的除潤效應在發光區域上對元件的影響...................65
4-5 奈米金屬顆粒在有機層中對元件的影響...............................67
4-6金屬薄膜的除潤效應在發光區域四周對元件的影響............72
4-7 模擬金、銀薄膜除潤效應對元件散射效率的影響...............79
4-8 銀薄膜的除潤效應在基板背側對元件的影響.......................86
4-8.1 奈米金屬結構覆蓋發光區域........................................86
4-8.2 奈米金屬結構未覆蓋發光區域....................................90
4-9 多層膜的金屬除潤效應對基板穿透率及散射效率的影響...92
第五章 總結.........................................................................................95
參考文獻................................................................................................97

[1]P. Pope, H. P. Kallmann, and P. J. Magnante, Chem. Phys. 1963, 38,
2042.
[2]W. Helfrich andW. G. Schneider, Phys. Rev. Lett. 1965, 14, 229.
[3]W. Helfrich andW. G. Schneider, J. Chem. Phys. 1966, 44, 2902.
[4]D. F. Williams and M. Schadt, Proc. IEEE. 1970, 58, 476.
[5]P. S. Vincett, W. A. Barlow, R. A. Hann, and G. G. Robert, Thin Solid
Films. 1982, 94, 171.
[6]R. H. Patridge, Polymer. 1983, 24, 733.
[7]C.W. Tang, and S. A. VanSlyke, Appl. Phys. Lett. 1987, 51, 913.
[8]S. A. VanSlyke, C. W. Tang, and L. C. Robert, US. Pat. 1988, No.
4,720,432.
[9]C. W. Tang, S. A. VanSlyke, and C. H. Chen, J. Appl. Phys. 1989, 65,
3610.
[10]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.
[11]R. H. Friend, J. H. Burroughes, and D. D. Bradley, US. Pat. 1993, No.
5,247,190.
[12]A. Dodabalapur, B. lab., Solid State Comm. 1993, 102, 259.
[13]M. A. Baldo, D. F. O'Brien, Y. You, A. Shoustikov, S. Sibley, M. E.
Thompson, S. R. Forrest, Nature. 1998, 395, 151.
[14]S. M. Kelly, Flat Panel Displays Advanced Organic Materials. 2000,
TheRoyal Society of Chemistry, Cambridge.
[15]C. Adachi, S. Tokito, T. Tsutsui, S. Saito, J. Appl. Phys. 1998, 27, 713.
[16]B. W. D'Andrade, M. E. Thompson, S. R. Forrest, Adv. Mater. 2002,
14, 147.
[17]R. S. Deshpande, V. Bilovic, S. R. Forrest, Appl. Phys. Lett. 1999, 75,
888.
[18]M. Strukelj, R. H. Jordan, A. Dodabalapur, J. Am. Chem. Soc. 1996,
118,1213.
[19]J. Kido, M. Kimura, K. Nagai, Science. 1995, 267, 1332.
[20]C. Hosokawa, Synth. Met. 1997, 35, 3.
[21]M. Arai, K. Nakaya, O. Onitsuka, T. Inoue, M. Codama, Synth. Met.
1997, 35, 21.
[22]N. C. Greenham, R. H. Friend, D. D. C Brandly, Adv. Mater. 1944, 6,
491.
[23]V. Bulovic, V. B. Khalfin, G. Gu, P. E. Burrows, Phys. Rev. B. 1998, 58,
3730.
[24] T. Yamasaki, K. Sumioka, T. Tsutsui, Appl. Phys. Lett. 2000, 76, 10.
[25]S. Moller, S. R. Forrest, J. Appl. Phys. 2002, 91, 3324.
[26]Y. H. Cheng, J. L. Wu, C. H. Cheng, K. C. Syao, M. C. Lee, Appl.
Phys. Lett. 2007, 90, 091102.
[27]T. Tsutsui, M. Yahiro, H. Yokogawa, K. Kawano, M. Yokoyama, Adv.
Mater. 2001, 13, 1149.
[28]Y. R. Do, Y. C. Kim, Y.-W. Song, C.-O. Cho, H. Jeon, Y.-J. Lee, S.-H
Kim, Y.-H. Lee, Adv. Mater. 2003, 15, 1214.
[29]S. Y. Hsu, M. C. Lee, K. L. Lee, P. K. Wei, Appl. Phys. Lett. 2008, 92,
013303.
[30] R. Jin, Y Cao, C. A. Mirkin, K. L. Kelly, G. C. Schatz, J. G. Zheng,
Ssience. 2001, 294, 5548.
[31] W. L. Barnes, A. Dereux, T. W. Ebbesen, Nature. 2003, 424.
[32] K. L. Kelly, E. Coronado, L. L. Zhao, G. C. Schatz, J. Phys. Chem. B.
2003, 107.
[33] C. J. V. OSS, M. CHAUDHURY, R. J. GOOD, J. Chem. Rev. 1988,
88.
[34] J. M. di Meglio, D. Quere, P. G. de Gennes, Langmuir. 1991, 7, 335.
[35] R. Seemann, S. Herminghaus, K. Jacobs, Phys. Rev. Lett. 2001, 86,
5534.
[36] G. Reiter, A. Sharma, A. Casoli, M. O. David, R. Khanna, P. Auroy,
Langmuir. 1999, 15, 2551.
[37] A. Sharma, R. Khanna, Phys. Rev. Lett. 1998, 81, 3463.
[38] G. Reiter, Langmuir. 1993, 9, 1344.
[39] J. Bischof, D. Scherer, S. Herminghaus, P. Leiderer, Phys. Rev. Lett.
1996, 77, 8.
[40] J. Becker, R. Seemann, H. Mantz, K. Jacobs, K. Mecke, R. Blossey,
Nature Materials. 2003, 2 , 59.