本研究旨在通過發光層主體材料為熱活化延遲螢光(TADF)材料DIC-TRZ摻雜氘代和無氘代客體材料D-Ir(mppy)3和Ir(mppy)3來延長綠色底部發光有機發光二極管的壽命。氘代和無氘代元件分別由以下元件結構組成，(i) Glass/ITO/PEDOT：PSS/HATCN/TAPC/DIC-TRZ：D-Ir(mppy)3/TPBi/LiF/Al，和(ii) Glass/ITO/PEDOT：PSS/HATCN/TAPC/DIC-TRZ：Ir(mppy)3/TPBi/LiF/Al，進行了氘代和無氘代元件的發光特性與元件壽命結果比較。
發光層主體材料DIC-TRZ摻雜Ir(mppy)3的元件比僅有DIC-TRZ無摻雜元件的電流效率提升了6倍，在6V下電流效率為6.8 cd/A，亮度為1347 cd/m2。實驗中元件出現的燒點問題，我們通過旋塗PEDOT:PSS減少ITO表面粗糙度來改善，降低元件短路的可能性。塗佈一層PEDOT:PSS的元件具有相較於三層PEDOT:PSS元件更高的亮度，且壽命也更長，在定電壓4V下，一層PEDOT:PSS元件的初始亮度為134.3 cd/m2，壽命半衰期為7.2 hr，而三層PEDOT:PSS元件的初始亮度為188.1 cd/m2，壽命半衰期為6.5 hr，顯示出塗佈一層PEDOT:PSS的元件具有較佳的發光特性與壽命。
將Ir(mppy)3替換成氘代D-Ir(mppy)3後，調變了不同發光層摻雜濃度，發現在摻雜濃度為25%時，元件具有最佳的亮度特性，在6V下達到1393 cd/m2，與摻雜濃度為34%和57%的元件相比相差了2.1倍，在定電壓4V下，元件壽命最長，初始亮度為438.8 cd/m2，元件壽命為42.8 hr，且帶有一層PEDOT:PSS的元件比三層PEDOT:PSS的元件顯示出更長的壽命，與Ir(mppy)3元件的結果相符。
最後，我們比較氘代D-Ir(mppy)3與無氘代Ir(mppy)3的發光特性與壽命差異，D-Ir(mppy)3元件之電流密度與亮度較高，且與Ir(mppy)3元件相比更接近綠光，在定電壓4V下，氘代D-Ir(mppy)3元件之初始亮度為438.3 cd/m2，壽命半衰期為42.8 hr，而無氘代Ir(mppy)3元件之初始亮度為188.1 cd/m2，壽命半衰期為7.2 hr，顯示出發光層摻雜氘代D-Ir(mppy)3元件具有延長元件壽命之效果，與無氘代Ir(mppy)3元件相比，壽命延長了5.9倍。

The aim of this study is to extend the lifetime of green bottom-emitting organic light-emitting diodes (OLEDs) by doping deuterated and non-deuterated guest materials, D-Ir(mppy)3 and Ir(mppy)3, into the thermally activated delayed fluorescence (TADF) material DIC-TRZ as the emission layer. Deuterated and non-deuterated devices were fabricated with the following device structures: (i) Glass/ITO/PEDOT:PSS/HATCN/TAPC/DIC-TRZ:D-Ir(mppy)3/TPBi/LiF/Al and (ii) Glass/ITO/PEDOT:PSS/HATCN/TAPC/DIC-TRZ:Ir(mppy)3/TPBi/LiF/Al. The emission characteristics and device lifetime of the deuterated and non-deuterated devices were compared.

The device with the emissive layer material DIC-TRZ doped with Ir(mppy)3 showed a 6 times improvement in current efficiency compared to the device with undoped DIC-TRZ. To address the issue of dark spot observed in the devices, the surface roughness of ITO was reduced by spin-coating PEDOT:PSS, which decreased the likelihood of device shorting. The device coated with a single layer of PEDOT:PSS exhibited higher luminance compared to the device with three layers of PEDOT:PSS and also showed a longer lifetime.

By replacing Ir(mppy)3 with deuterated D-Ir(mppy)3 and varying the doping concentration in the emissive layer, it was found that the device exhibited optimal luminance characteristics at a doping concentration of 25%, which was 2.1 times higher than the devices with doping concentrations of 34% and 57%. Additionally, the device with a single layer of PEDOT:PSS showed a longer lifetime compared to the device with three layers of PEDOT:PSS, consistent with the results obtained for Ir(mppy)3 devices.

Finally, a comparison was made between the emission characteristics and lifetime of devices containing deuterated D-Ir(mppy)3 and non-deuterated Ir(mppy)3. The D-Ir(mppy)3 device exhibited higher current density and luminance compared to the Ir(mppy)3 device, the light emitted by D-Ir(mppy)3 devices is closer to green. At a constant voltage of 4V, the initial luminance of the deuterated D-Ir(mppy)3 device was 438.3 cd/m2 with a lifetime of 42.8 hours, while the initial brightness of the non-deuterated Ir(mppy)3 device was 188.1 cd/m2 with a lifetime of 7.2 hours, demonstrating the effectiveness of deuterated D-Ir(mppy)3 in extending the device lifetime, resulting in a 5.9 times increase compared to the non-deuterated.

摘要......i
Abstract......ii
誌謝......iv
目錄......v
表目錄......vii
圖目錄......viii
第一章、緒論......1
1.1有機發光二極體簡介......1
1.2研究動機......2
1.3文獻探討......3
第二章、有機發光二極體原理......5
2.1有機發光二極體原理......5
2.1.1有機發光二極體發光機制......5
2.1.2電流注入理論......7
2.1.3有機發光二極體各層結構介紹......8
2.2 熱活化延遲螢光材料......10
第三章、實驗方法與步驟......11
3.1實驗流程......11
3.2陽極與陰極圖形製備......12
3.2.1雷射雕刻基板圖形化......12
3.2.2基板清洗......14
3.3有機層之塗佈與熱蒸鍍......15
3.3.1電洞注入層塗佈......15
3.3.2熱蒸鍍有機層操作流程......18
3.3.3熱蒸鍍有機層之材料選用......22
3.4金屬蒸鍍陰極......25
3.5元件封裝......27
3.6 元件發光特性與壽命量測......31
第四章、結果與討論......33
4.1 Ir(mppy)3綠光有機發光二極體之光電特性......33
4.1.1 Ir(mppy)3之綠光元件......33
4.1.2綠光元件燒點問題......38
4.1.3旋塗PEDOT:PSS改善燒點問題......40
4.1.4 PEDOT:PSS對綠光元件發光特性之影響......42
4.1.5 調變PEDOT:PSS厚度對綠光元件之影響......45
4.2 D-Ir(mppy)3綠光有機發光二極體之光電特性......50
4.2.1 D-Ir(mppy)3之綠光元件......50
4.2.2 比較Ir(mppy)3與D-Ir(mppy)3之綠光元件壽命......55
第五章、結論......59
參考文獻......60
Extended Abstract......62

[1] Zhongbin Wu, Dongge Ma, “Recent advances in white organic light-emitting diodes”, Materials Science and Engineering: R: Reports, vol. 107, pp. 1-42, 2016
[2] https://www.samsung.com/tw/smartphones/galaxy-z-fold4/
[3] https://www.corning.com/tw/zh_tw/innovation/corning-emerging-innovations/oled-lighting-corning-emerging-innovations.html
[4] https://www.eurisotop.com/deuterium-oxide-oleds
[5] C. C. T. a. K. C. Hwang, “Enhancement of OLED Efficiencies and High-Voltage Stabilities of Light-Emitting,” Journal of Physical Chemistry , vol. 111, pp. 3490-3494, 2007.
[6] https://deutramed.com/deuterium-application-in-oleds
[7] H. Tsuji, C. Mitsui, and E. Nakamura, “The hydrogen/deuterium isotope effect of the host material on the lifetime of organic light-emitting diodes,” Chem. Commun., vol. 50, pp. 14870–14872, 2014.
[8] X. Liu, C.-Y. Chan, F. Mathevet, M. Mamada, Y. Tsuchiya, Y.-T. Lee, H. Nakanotani, S. Kobayashi, M. Shiochi, and C. Adachi, “Isotope Effect of Host Material on Device Stability of Thermally Activated Delayed Fluorescence Organic Light‐Emitting Diodes,” Small Science, vol. 1, p. 2000057, 2021.
[9] H. J. Bae, J. S. Kim, A. Yakubovich, J. Jeong, S. Park, J. Chwae, S. Ishibe, Y. Jung, V. K. Rai, W. Son, S. Kim, H. Choi, and M. Baik, “Protecting Benzylic C-H Bonds by Deuteration Doubles the Operational Lifetime of Deep‐Blue Ir‐Phenylimidazole Dopants in Phosphorescent OLEDs,” Advanced Optical Materials, vol. 9, p. 2100630, May 2021.
[10] P. Wang, F.-F. Wang, Y. Chen, Q. Niu, L. Lu, H.-M. Wang, X.-C. Gao, B. Wei, H.-W. Wu, X. Cai, and D.-C. Zou, “Synthesis of all-deuterated tris (2-phenylpyridine) iridium for highly stable electrophosphorescence: the ‘deuterium effect,” Journal of Materials Chemistry C, vol. 1, p. 4821, 2013.
[11] https://news.lgdisplay.com/en/2022/09/lg-display-demonstrates-oleds-decade-of-excellence-in-technology-innovation-at-ifa-2022/
[12] 黃奕翔，2009，“微共振腔有機發光二極體元件結構與光學特性之模擬與分析”，國立彰化師範大學光電科技研究所碩士論文。
[13] 黃孝文、陳金鑫，2005，“有機電激發光材料與元件”，五南圖書出版社，pp. 34-36。
[14] https://www.hangjianet.com/v5/topicDetail?id=15293871404730000.
[15] 工業材料雜誌，OLEDs熱活化延遲螢光材料之元件應用, 365, pp. 106-113
[16] X. Huang, Y. Qu, “Ultrathin, lightweight and flexible organic light-emitting devices with a high light outcoupling efficiency”, Organic Electronics, vol. 69, pp.297-300, 2019
[17] S. W. Kang, D. H. Beak, “Green phosphorescent organic light-emitting diode exhibiting highest external quantum efficiency with ultra-thin undoped emission layer”, Scientific Reports, vol. 11, pp. 8436, 2021
[18] P. E. Burrows, V. Bulovic, “Reliability and degradation of organic light emitting devices,” Appl. Phys. Lett. 65, pp. 2922-2924, 1994
[19] X. Fan, W. Y. Fan, “PEDOT:PSS for Flexible and Stretchable Electronics: Modifications, Strategies, and Applications”, Advanced Science, vol. 6, pp. 1900813, 2019