固態照明是現代社會不可或缺的一部分，它為人類的生活方式帶來巨大變化，使文明得以快速發展，一高品質照明光源不僅應具備節能的優點，更要對人體友善，因其光色及亮度對人體生理時鐘與晝夜節律有異常重大影響。
現今市面上的照明光源大多富含藍光，而許多研究證實，入夜後，光源中藍紫光會強烈抑制褪黑激素分泌，造成失眠、二類型糖尿病、肥胖及心血管疾病，長期下來，將導致乳癌與攝護腺癌罹患率攀升，故黃昏後應使用低色溫、無藍害之照明，而長期未照射藍光又會引發憂鬱症、導致自殺率提升；因此，製作一高效率光源，其色溫可在無藍光的低色溫及少量藍光的中低色溫間調節，不僅可滿足人們對於人體友善光源之需求，也能減少能源的損耗。
本研究使用供體材料 9,9'-Diphenyl-9H,9'H-3,3'-bicarbazole (BCzPh)及受體材料 2,4,6-tris(2-(1H-pyrazol-1-yl)phenyl)-1,3,5-triazine [3P-T2T] 組成複合激子共主體，並加入2.5 wt%紅光客體 Bis(2-(3,5-dimethylphenyl)quinoline-C2,N')(acetylacetonato)iridium(III) [Ir(mphq)2acac]與5 wt%綠光客體 Tris(2-phenylpyridine)iridium(III) [Ir(ppy)3] 作為第一發光層，並使用供體材料 Tris(4-carbazoyl-9-ylphenyl)amine [TCTA]與受體材料 1,3,5-Tri(m-pyridin-3-ylphenyl)benzene [TmPyPB] 組成另一複合激子共主體，並加入0.05 wt%綠光客體 Tris(2-phenylpyridine)iridium(III) [Ir(ppy)3]與8.0 wt%藍光客體 (FIrPic)作為第二發光層，製作出一高效率色溫可調有機發光二極體，在100 cd/m2下，能量效率為25 lm/W，外部量子效率為15 %；其光色在 CIE 1931色彩空間上可呈現日落前20至1分鐘之夕陽光色軌跡；元件效率高可歸因如下：(1)良好的元件結構設計，使電子及電洞有較低的注入能障，再加上發光層中良好的載子平衡；(2)供體、受體間最高填滿分子軌域及最低未填滿分子軌域的能階差異大，使電子、電洞可以累積在同一介面，有利複合激子的形成；而色溫完全貼合黑體輻射軌跡可歸因於：(1)使用了三種可包圍黑體輻射軌跡之色域的黑體輻射互補性染料；(2)電壓增加後，較多激子注入能階較大的藍光客體，使得紅、綠及藍光的相對強度有所改變。

Solid-state lighting is an indispensable part of modern society. It brings great changes to human life and accelerates the development of civilization. A high-quality lighting source should be energy saving and friendly to human body, because its light color and brightness have significant impacts on human body's biological clock and circadian rhythm.
Nowadays most of the lighting sources on the market are rich in blue light, and according to several researches, blue-violet light at night strongly suppresses the secretion of melatonin, causing insomnia, cardiovascular disease, obesity and type 2 diabetes, and long term consequences of that will lead to breast cancer, and rise rates of prostate cancer. Therefore, blue light-less lighting with low color temperature should be used after dusk. In addition, long-term non-exposure to blue light will cause depression and increase the suicide rate. Therefore, a high-efficiency light source whose color temperature can be adjusted between a low color temperature with no blue light and a medium and low color temperature with a small amount of blue light can not only meet people's needs for a human-friendly light source, but also reduce energy consumption.
In this study, donor material 9,9'-Diphenyl-9H,9'H-3,3'-bicarbazole (BCzPh) and acceptor material 2,4,6-tris(2-(1H-pyrazol-1-yl )phenyl)-1,3,5-triazine [3P-T2T] were combined to form the first emissive layer (as exciplex co-host) via doping 2.5 wt% red dye Bis(2-(3,5-dimethylphenyl)quinoline-C2,N')(acetylacetonato)iridium(III) [Ir(mphq)2acac] and 5 wt% green dye Tris(2-phenylpyridine) iridium(III) [Ir(ppy)3]. Donor material 1,3,5-Tri(m-pyridin-3-ylphenyl)benzene [TmPyPB] and acceptor material Tris(4-carbazoyl-9-ylphenyl)amine [TCTA] were combined to form the second emissive layer (also as exciplex co-host) via doping 0.05 wt% green dye Tris(2-phenylpyridine) iridium(III) [Ir(ppy)3] and 8.0 wt% blue dye (FIrPic). At 100 nits, the manufactured high-efficiency device has a power efficacy of 25 lm/W and an external quantum efficiency of 11 %. Its light color can present the sunset light color trajectory 20 to 1 minute before sunset on the CIE 1931 xy coordinates. the high efficiency of it was due to the following reasons: (1) Good device structure design that makes electrons and holes to have a lower injection barrier, and good carrier balance within the emissive layer. (2) The energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of donor and acceptor are large, so that holes and electrons can accumulate at the same interface, which is beneficial to the formation of exciplexes. The color temperature is completely matched the blackbody radiation locus can be due to: (1) the application of three blackbody radiation complementary dyes that can encompass the color gamut of the blackbody radiation locus; (2) after the voltage is increased, more excitons are injected into the blue light guest which has a larger band gap, so the relative intensity of red, green, and blue light changes.

摘要…………………………………………………………………………….............I
Abstract……………………………………………………………………………….III
致謝…………………………………………………………………………………...VI
目錄…………………………………………………………………………………...XI
表目錄……………………………………………………………………………….XV
圖目錄………………………………………………………………………………XVI
壹、 緒論.…………………………………………………………………………...1
貳、 文獻回顧.……………………………………………………………………...3
2-1、OLED的發展歷史………………………………………………………..3
2-2、OLED的發光原理………………………………………………………13
2-3、OLED的基本結構………………………………………………………17
2-4、OLED的能量傳遞機制…………………………………………………18
2-5、OLED的元件效率計算…………………………………………………21
2-6、OLED材料發展…………………………………………………………23
2-6-1、基板材料………………………………………………………………23
2-6-2、陽極材料………………………………………………………………24
2-6-3、電洞注入材料…………………………………………………………24
2-6-4、電洞傳輸材料…………………………………………………………25
2-6-5、發光層…………………………………………………………………25
2-6-6、電子傳輸材料…………………………………………………………26
2-6-6、電子注入材料…………………………………………………………26
2-6-8、陰極材料………………………………………………………………27
2-7、光色及色溫的定義……………………………………………………...27
參、 理論背景…………………………………………………………………….29
3-1、自然光譜相似性指數…………………………………………………...29
肆、 光色可調有機發光二極體………………………………………………….30
4-1、達成光色可調有機發光二極體之方式………………………………...30
4-2、光色可調有機發光二極體回顧………………………………………...30
伍、 複合激子有機發光二極體………………………………………………….33
5-1、複合激子有機發光二極體介紹………………………………………...33
5-1-1、複合激子形成機制…………………………………………………....33
5-1-2、複合激子之能量傳遞方式……………………………………………34
5-2、複合激子有機發光二極體回顧………………………………………...36
陸、 實驗方法…………………………………………………………………….40
6-1、使用之材料……………………………………………………………...40
6-1-1、材料之簡稱、全名及功能……………………………………………40
6-1-2、材料之化學結構………………………………………………………42
6-2、材料特性量測及分析…………………………………………………...46
6-2-1、光激發光(Photoluminescence)光譜之量測…………………………..46
6-3、元件設計與製備………………………………………………………...47
6-3-1、ITO玻璃基板電路設計………………………………………………47
6-3-2、ITO玻璃基板清潔……………………………………………………48
6-3-3、發光層(EML)之製備………………………………………………….49
6-3-4、真空熱蒸鍍機裝置……………………………………………………49
6-3-5、鍍膜速率測定…………………………………………………………50
6-3-6、複合激子類夕陽光OLED製備……………………………………...51
6-3-7、元件之光電性質量測及發光效率計算……………………………....52
柒、 結果與討論………………………………………………………………….55
7-1、元件結構及材料選擇…………………………………………………...55
7-2、材料之光學特性………………………………………………………...57
7-2-1、常溫下的光激發光光譜………………………………………………57
7-2-2、超低溫下的光激發光光譜……………………………………………59
7-3、客體濃度及發光層厚度對於元件的影響……………………………...61
7-4、其他影響元件效率之因素……………………………………………...74
捌、 結論………………………………………………………………………….78
玖、 參考資料…………………………………………………………………….79
附錄一、 個人著作目錄..………………………………………………………...85

[1] Kyba, Christopher. "Is light pollution getting better or worse?." Nature Astronomy 2.4 (2018): 267-269.
[2] BAJYA, MAMTA, et al. "Effect of artificial light on plant ecology and physiology: A review." The Indian Journal of Agricultural Sciences 92.2.
[3] Chaney, William R. "Does night lighting harm trees." Purdue University, Forestry and Natural Resources, FAQ 17 (2002): 1-4.
[4] Tosini, Gianluca, Ian Ferguson, and Kazuo Tsubota. "Effects of blue light on the circadian system and eye physiology." Molecular vision 22 (2016): 61.
[5] Ouyang, X. I. N. L. I., et al. "Mechanisms of blue light-induced eye hazard and protective measures: A review." Biomedicine & Pharmacotherapy 130 (2020): 110577.
[6] Godley, Bernard F., et al. "Blue light induces mitochondrial DNA damage and free radical production in epithelial cells." Journal of Biological Chemistry 280.22 (2005): 21061-21066.
[7] Algvere, Peep V., John Marshall, and Stefan Seregard. "Age‐related maculopathy and the impact of blue light hazard." Acta Ophthalmologica Scandinavica 84.1 (2006): 4-15.
[8] Park, Sung Jun, Hyun Kyoung Yang, and Byung Kee Moon. "Ultraviolet to blue blocking and wavelength convertible films using carbon dots for interrupting eye damage caused by general lighting." Nano Energy 60 (2019): 87-94.
[9] Sparrow, Janet R., Koji Nakanishi, and Craig A. Parish. "The lipofuscin fluorophore A2E mediates blue light–induced damage to retinal pigmented epithelial cells." Investigative ophthalmology & visual science 41.7 (2000): 1981-1989.
[10] West, Kathleen E., et al. "Blue light from light-emitting diodes elicits a dose-dependent suppression of melatonin in humans." Journal of applied physiology (2011).
[11] Figueiro, Mariana G., Barbara Plitnick, and Mark S. Rea. "Pulsing blue light through closed eyelids: effects on acute melatonin suppression and phase shifting of dim light melatonin onset." Nature and Science of Sleep 6 (2014): 149.
[12] Wood, Brittany, et al. "Light level and duration of exposure determine the impact of self-luminous tablets on melatonin suppression." Applied ergonomics 44.2 (2013): 237-240.
[13] Wahl, Siegfried, et al. "The inner clock—Blue light sets the human rhythm." Journal of biophotonics 12.12 (2019): e201900102.
[14] Figueiro, Mariana G., and Mark S. Rea. "The effects of red and blue lights on circadian variations in cortisol, alpha amylase, and melatonin." International journal of endocrinology 2010 (2010).
[15] Figueiro, Mariana G., Andrew Bierman, and Mark S. Rea. "A train of blue light pulses delivered through closed eyelids suppresses melatonin and phase shifts the human circadian system." Nature and Science of Sleep 5 (2013): 133.
[16] Shechter, Ari, et al. "Blocking nocturnal blue light for insomnia: A randomized controlled trial." Journal of psychiatric research 96 (2018): 196-202.
[17] Janků, Karolina, et al. "Block the light and sleep well: Evening blue light filtration as a part of cognitive behavioral therapy for insomnia." Chronobiology international 37.2 (2020): 248-259.
[18] Hatori, Megumi, et al. "Global rise of potential health hazards caused by blue light-induced circadian disruption in modern aging societies." npj Aging and Mechanisms of Disease 3.1 (2017): 1-3.
[19] Park, Yong-Moon Mark, et al. "Association of exposure to artificial light at night while sleeping with risk of obesity in women." JAMA internal medicine 179.8 (2019): 1061-1071.
[20] Mineshita, Yui, et al. "Screen time duration and timing: effects on obesity, physical activity, dry eyes, and learning ability in elementary school children." BMC Public Health 21.1 (2021): 1-11.

[21] Holzman, David C. "What’s in a color? The unique human health effects of blue light." (2010): A22-A27.
[22] Stevens, Richard G., et al. "Breast cancer and circadian disruption from electric lighting in the modern world." CA: a cancer journal for clinicians 64.3 (2014): 207-218.
[23] Barker, Emma, Kairi Kolves, and Diego De Leo. "Rail‐suicide prevention: Systematic literature review of evidence‐based activities." Asia‐Pacific Psychiatry 9.3 (2017): e12246.
[24] Bennett, Shoshana, et al. "Use of modified spectacles and light bulbs to block blue light at night may prevent postpartum depression." Medical hypotheses 73.2 (2009): 251-253.
[25] Patel, Bhrijesh N., and Mrugesh M. Prajapati. "OLED: A modern display technology." International Journal of Scientific and Research Publications 4.6 (2014): 1-5.
[26] Renard, G., and J. Leid. "The dangers of blue light: True story!." Journal francais d'ophtalmologie 39.5 (2016): 483-488.
[27] Bernanose, Andre, Marcel Comte, and Paul Vouaux. "Sur un nouveau mode d'émission lumineuse chez certains composés organiques." Journal de Chimie Physique 50 (1953): 64-68.
[28] Pope, Martin, H. P. Kallmann, and P. J. Magnante. "Electroluminescence in organic crystals." The Journal of Chemical Physics 38.8 (1963): 2042-2043.
[29] Helfrich, W., and W. G. Schneider. "Recombination radiation in anthracene crystals." Physical Review Letters 14.7 (1965): 229.
[30] Vincett, P. S., et al. "Electrical conduction and low voltage blue electroluminescence in vacuum-deposited organic films." Thin solid films 94.2 (1982): 171-183.
[31] Tang, Ching W., and Steven A. VanSlyke. "Organic electroluminescent diodes." Applied physics letters 51.12 (1987): 913-915.
[32] Tang, Ching Wan, Steven A. VanSlyke, and Chin H. Chen. "Electroluminescence of doped organic thin films." Journal of applied physics 65.9 (1989): 3610-3616.
[33] Burroughes, Jeremy H., et al. "Light-emitting diodes based on conjugated polymers." nature 347.6293 (1990): 539-541.
[34] Era, Masanao, et al. "Double-heterostructure electroluminescent device with cyanine-dye bimolecular layer as an emitter." Chemical physics letters 178.5-6 (1991): 488-490.
[35] Jabbour, G. E., et al. "Aluminum based cathode structure for enhanced electron injection in electroluminescent organic devices." Applied physics letters 73.9 (1998): 1185-1187.
[36] Baldo, Marc A., et al. "Highly efficient phosphorescent emission from organic electroluminescent devices." Nature 395.6698 (1998): 151-154.
[37] Huang, Jingsong, et al. "Low-voltage organic electroluminescent devices using pin structures." Applied Physics Letters 80.1 (2002): 139-141.
[38] Matsumoto, Toshio, et al. "27.5 L: late‐news paper: multiphoton organic EL device having charge generation layer." SID Symposium Digest of Technical Papers. Vol. 34. No. 1. Oxford, UK: Blackwell Publishing Ltd, 2003.
[39] Shao, Yan, and Yang Yang. "White organic light-emitting diodes prepared by a fused organic solid solution method." Applied Physics Letters 86.7 (2005): 073510.
[40] Sun, Yiru, and Stephen R. Forrest. "Enhanced light out-coupling of organic light-emitting devices using embedded low-index grids." Nature photonics 2.8 (2008): 483-487.
[41] Uoyama, Hiroki, et al. "Highly efficient organic light-emitting diodes from delayed fluorescence." Nature 492.7428 (2012): 234-238.
[42] J. H. Jou, OLED Introduction. 2015
[43] Thompson, Linda G., and S. E. Webber. "External heavy atom effect on the phosphorescence spectra of some halonaphthalenes." The Journal of Physical Chemistry 76.2 (1972): 221-224.
[44] Förster, Th. "Zwischenmolekulare energiewanderung und fluoreszenz." Annalen der physik 437.1-2 (1948): 55-75.
[45] Dexter, David L. "A theory of sensitized luminescence in solids." The journal of chemical physics 21.5 (1953): 836-850.
[46] P. Vandersteegen et al., Employing a 2D surface grating to improve light out coupling of a substrate emitting organic LED (Integrated Optoelectronic Devices 2007). SPIE, 2007.
[47] K.-H. Kim and S.-Y. Park, "Enhancing light-extraction efficiency of OLEDs with high- and low-refractive-index organic–inorganic hybrid materials," Organic Electronics, vol. 36, pp. 103-112, 2016/09/01/ 2016.
[48] J. R. Vig, "UV/ozone cleaning of surfaces," Journal of Vacuum Science &Technology A, vol. 3, no. 3, pp. 1027-1034, 1985.
[49] C. C. Wu, C. I. Wu, J. C. Sturm, and A. Kahn, "Surface modification of indium tin oxide by plasma treatment: An effective method to improve the efficiency, brightness, and reliability of organic light emitting devices," Applied Physics Letters, vol. 70, no. 11, pp. 1348-1350, 1997.
[50] Solution-processed hexaazatriphenylene hexacarbonitrile as a universal hole-injection layer for organic light-emitting diodes, H. Lin et al., Org. Electronics 14, 1204–1210 (2013)
[51] X. Fan et al., "PEDOT:PSS for Flexible and Stretchable Electronics: Modifications, Strategies, and Applications," Advanced Science, vol. 6, no. 84, p. 1900813, 2019.
[52] E. Tutis, D. Berner, and L. Zuppiroli, The mechanism of lifetime extension
due to CuPc injection layer in organic light-emitting diodes (Photonics Europe). SPIE, 2004.
[53] T.-C. Li and R.-C. Chang, "Improving the performance of ITO thin films by coating PEDOT:PSS," International Journal of Precision Engineering and Manufacturing-Green Technology, vol. 1, no. 4, pp. 329-334, 2014/10/01 2014.
[54] S.-C. Dong, L. Xu, and C. W. Tang, "Chemical degradation mechanism of TAPC as hole transport layer in blue phosphorescent OLED," Organic Electronics, vol. 42, pp. 379-386, 2017/03/01/ 2017.
[55] T. Smith and J. Guild, "The C.I.E. colorimetric standards and their use," Transactions of the Optical Society, vol. 33, no. 3, pp. 73-134, 1931/01/01 1931.
[56] Jou, Jwo-Huei, et al. "A universal, easy-to-apply light-quality index based on natural light spectrum resemblance." Applied Physics Letters 104.20 (2014): 76_1.
[57] Erdmann, Dick, and GE Specification Engineer. "Color rendering index (CRI)." General Electric (GE) (2010).
[58] CIE 17.4-1987 International Lighting Vocabulary.
[59] Burrows, P. E., et al. "Achieving full-color organic light-emitting devices for lightweight, flat-panel displays." IEEE Transactions on electron devices 44.8 (1997): 1188-1203.
[60] Reyes, Reynaldo, et al. "Voltage color tunable OLED with (Sm, Eu)-β-diketonate complex blend." Chemical Physics Letters 396.1-3 (2004): 54-58.
[61] Zheng, Tianhang, and Wallace CH Choy. "An effective intermediate Al/Au electrode for stacked color-tunable organic light emitting devices." Applied Physics A 91.3 (2008): 501-506.
[62] Zhang, H. M., and Wallace CH Choy. "Real-time color-tunable electroluminescence from stacked organic LEDs using independently addressable middle electrode." IEEE Photonics Technology Letters 20.13 (2008): 1154-1156.
[63] Jou, Jwo-Huei, et al. "Sunlight-style color-temperature tunable organic light-emitting diode." Applied Physics Letters 95.1 (2009): 184.
[64] Jou, Jwo‐Huei, et al. "Pseudo‐natural Light for Displays and Lighting." Advanced Optical Materials 3.1 (2015): 95-102.
[65] Fröbel, Markus, et al. "Get it white: color-tunable AC/DC OLEDs." Light: Science & Applications 4.2 (2015): e247-e247.
[66] Ying, Shian, et al. "High efficiency color-tunable organic light-emitting diodes with ultra-thin emissive layers in blue phosphor doped exciplex." Applied Physics Letters 114.3 (2019): 033501.
[67] Shih, Sheng-Hsu, et al. "High efficiency color-temperature tunable organic light-emitting diode." Journal of Materials Chemistry C 7.48 (2019): 15322-15334.
[68] Wang, Qiang, et al. "High-efficiency organic light-emitting diodes with exciplex hosts." Journal of Materials Chemistry C 7.37 (2019): 11329-11360.
[69] Lee, Jeong‐Hwan, et al. "Langevin and trap‐assisted recombination in phosphorescent organic light emitting diodes." Advanced Functional Materials 24.29 (2014): 4681-4688.
[70] Jenekhe, Samson A., and John A. Osaheni. "Excimers and exciplexes of conjugated polymers." Science 265.5173 (1994): 765-768.
[71] Matsumoto, Naoki, Masakazu Nishiyama, and Chihaya Adachi. "Exciplex formations between tris (8-hydoxyquinolate) aluminum and hole transport materials and their photoluminescence and electroluminescence characteristics." The Journal of Physical Chemistry C 112.20 (2008): 7735-7741.
[72] Goushi, Kenichi, and Chihaya Adachi. "Efficient organic light-emitting diodes through up-conversion from triplet to singlet excited states of exciplexes." Applied Physics Letters 101.2 (2012): 023306.
[73] Hung, Wen-Yi, et al. "Highly efficient bilayer interface exciplex for yellow organic light-emitting diode." ACS applied materials & interfaces 5.15 (2013): 6826-6831.
[74] Kim, Kwon-Hyeon, et al. "Phosphorescent dye-based supramolecules for high-efficiency organic light-emitting diodes." Nature communications 5.1 (2014): 1-8.
[75] Lee, Jeong‐Hwan, et al. "An exciplex forming host for highly efficient blue organic light emitting diodes with low driving voltage." Advanced Functional Materials 25.3 (2015): 361-366.
[76] Hung, Wen-Yi, et al. "The first tandem, all-exciplex-based WOLED." Scientific reports 4.1 (2014): 1-6.
[77] Zhu, Liping, et al. "High efficiency yellow fluorescent organic light emitting diodes based on m-MTDATA/BPhen exciplex." Frontiers of Optoelectronics 8.4 (2015): 439-444.
[78] Hung, Wen-Yi, et al. "Balance the carrier mobility to achieve high performance exciplex OLED using a triazine-based acceptor." ACS Applied Materials & Interfaces 8.7 (2016): 4811-4818.
[79] Sych, Galyna, et al. "Dual interface exciplex emission of quinoline and carbazole derivatives for simplified nondoped white OLEDs." The Journal of Physical Chemistry C 123.4 (2019): 2386-2397.
[80] Zhang, Tianmu, et al. "Highly efficient and low efficiency roll-off organic light-emitting diodes with double-exciplex forming co-hosts." Journal of Materials Chemistry C 9.18 (2021): 6062-6067.