臺灣博碩士論文加值系統

本論文分為兩個部分，第一個部分是使用一系列不同鍵結的六種雙極性主體材料 o-, m-, p-NPCz 和 o-, m-, p-NPDa 材料搭配綠色 TADF 分子 4CzIPN 作為客體材料製成有機發光元件，利用不同連接材料的能階和它們共同傳輸的能力使元件有高效率表現。其中元件表現最好的為 NPCz 系列材料之元件，EQE 為 15.5 ~ 18.4 %，沒有滾降現象，放光為綠色；o-, m-, p-NPDa 系列材料元件，EQE 為 3.1 ~ 5.3 %，放光為橘黃色。NPDa 系列作為雙極性主體材料的元件效率表現較不佳以及放光會有紅移產生橘黃色之因素，為 NPDa 材料和客體材料 4CzIPN 會形成 Exciplex 而產生紅移形成橘黃色，且在三重態能量低於 4CzIPN 之三重態能量無法有效的轉移給客體分子，導致元件表現效率不佳。
第二個部分是利用激發複合體共主體材料 Exciplex co-host 製作高效率發光元件，利用 Exciplex 作為共主體材料的最佳優勢在於可以單獨設計 HTM 與 ETM 分子以操控放光層之 HOMO/LUMO 能階。像這樣一個簡單的元件結構不僅具有成本效益，而且元件效率高且有效降低工作電壓。此章節之新興研究領域，將利用縝密的分子設計開發具激發複合體放光特性的共主體材料，將其結合適合的放光體來製作高效率及低效率滾降的 OLED 元件。利用搭配不同的 Donor 及 Acceptor 材料作為 Exciplex 的共主體結構，摻雜昱鐳提供的綠光磷光材料製成高效率綠光元件，最好的組合為 TCP: 3P-T2T: PEG55(5%)，EQE = 21.95 %。再利用昱鐳所提供的 Donor 材料搭配 CN-T2T 當作 co-host 結構。表現最好的 Donor 為 HT-3，最初 CN-T2T 是適用於紅光元件結構，因為我們摻雜的是綠光磷光材料，我們希望搭配出更藍的 Exciplex 放光，所以我們嘗試搭配新的 Acceptor 材料 CN-pympyr 和 CN-pymph 作為 Acceptor 建構適用於綠光摻雜的共主體結構，這邊以 HT-3: CN-pymph: PEG55 (5 %) 的表現最佳，EQE = 21.53 %。

This thesis is composed of two major parts. The first part is to study a series of bipolar host materials by adjusting the linkage topology to evaluate the performance of OLEDs, namely, o-, m-, p-NPCz and o-, m-, p-NPDa. The devices employing these new bipolar hosts with green thermally activated delayed fluorescence (TADF) doped with 4CzIPN. The device with NPCz as bipolar host exhibits the best device performance with external quantum efficiency of 15.5 ~ 18.4% and green emissions. NPDa as bipolar host exhibits performance with external quantum efficiency of 3.1 ~ 5.3% and yellow to orange emissions.However, o-, m-, p-NPDa with lower ET and shallower HOMO levels than 4CzIPN exhibit inferior host to dopant energy transfer. Instead, the Exciplex formation between host and 4CzIPN, which was verified by TRPL, led the resulting EL spectra of the NPDa-based devices broad with yellow to orange emissions.
In the second part, we doing research on the Exciplex co-host system is used to produce high-efficiency light-emitting devices. The advantage of using Exciplex as a cohost is that HTM and ETM molecules can be designed separately to control the HOMO/LUMO energy of the light-emitting layer. This co-host,which is simple structure , is not only cost effective, but also effective in device performance and reducing the operating voltage. In this part, will use the meticulous molecular design to formulate an Exciplex co-host, combining with a suitable dopant aim to create high performance and low efficiency roll-off OLEDs. Exciplex co-host structure is composed of different Donor and Acceptor materials doped with green phosphorescent materials for green PhOLEDs. The best combination tune out to TCP: 3P-T2T: 5% PEG55, EQE = 21.95%. Meanwhile, CN-T2T as acceptor mix with eRay’s donor as co-host structure for green PhOLEDs. The best donor is HT-3，HT-3: CN-T2T: 10% PEG55，EQE = 20.05%. CN-T2T was often applied to red PhOLEDs; however, new Acceptor materials CN-PymPyr and CN-PymPh which is a suitable Acceptors for green PhOLEDs are employed instead. The best result is HT-3: CN-pymph: 5% PEG55 , EQE as high as 21.53%, which reach eRay’s requirement.

致謝 I
摘要 II
Abstract III
目錄 IV
圖目錄 VI
表目錄 IX
第一章 緒論 1
1-1 前言 1
1-2 有機發光二極體原理與結構 1
1-3 有機發光二極體激發複合之介紹 2
1-4 論文架構 4
參考文獻 5
第二章 實驗原理與架構 6
2-1 簡介 6
2-2 有機材料之製備與基本特性量測 6
2-2.1 有機材料之昇華純化 6
2-2.2 基本光物理特性之量測 7
2-2.3 有機材料能階量測 8
2-2.4 載子遷移率量測 8
2-2.5 螢光量子產率 10
2-2.6 時間解析光致發光螢光之量測 10
2-3 有機發光元件製作與量測 12
2-3.1 有機發光元件之製作 12
2-3.2 有機發光元件之量測 12
參考文獻 13
第三章 新型萘啶的雙極性主體材料，利用熱激活延遲螢光應用在有機發光二 極體 14
3-1 緒論 14
3-1.1 有機材料分子結構介紹 14
3-1.2 NPCz與NPDa 系列有機材料介紹 14
3-1.3 有機分子的物理特性 16
3-1.4 學長成果回顧 19
3-2 時間解析光致發光螢光量測與螢光量子產率之表現 21
3-3 載子遷移率 25
3-4 結論 27
參考文獻 28
第四章 利用Exciplex co-host結構應用在綠光磷光元件 29
4-1 緒論 29
4-2 Donor與Acceptor材料之介紹 31
4-3 SimCP：PO-T2T 當作 co-host 之物理特性及元件表現 33
4-3.1 物理特性 33
4-3.2 元件表現 34
4-4 CPTBF：PO-T2T 當作 co-host 之物理特性及元件表現 36
4-4.1 物理特性 36
4-4.2 元件表現 37
4-5 CzSi：3P-T2T 當作 co-host 之物理特性及元件表現 39
4-5.1 物理特性 39
4-5.2 元件表現 40
4-6 m-CBP：3P-T2T 當作 co-host 之物理特性及元件表現 42
4-6.1 物理特性 42
4-6.2 元件表現 43
4-7 TCP：3P-T2T 當作 co-host 之物理特性及元件表現 45
4-7.1 物理特性 45
4-7.2 元件表現 46
4-8 昱鐳提供 Donor 有機材料介紹 48
4-8.1 材料介紹 48
4-9 HT 系列：CN-T2T 當作 co-host 之物理特性及元件表現 50
4-9.1 物理特性 50
4-9.2 元件表現 52
4-10 新的 Donor 有機材料介紹及物理特性 54
4-10.1 材料介紹 54
4-10.2 物理特性 54
4-11 HT-3：CN-PymPyr 當作 co-host 之物理特性及元件表現 56
4-11.1 物理特性 56
4-11.2 元件表現 57
4-12 HT-3：CN-PymPh 當作 co-host 之物理特性及元件表現 59
4-12.1 物理特性 59
4-12.2 元件表現 60
4-13 結論 62
參考文獻 63

[1] Sanchez. S., Sweeney. S., LED vs T5 Technology-The Advantages., Disadvantages. Lumiversal White Paper 2010.
[2] M. Era., C. Adachi., T. Tsutsui., S. Ssito., Chem. Phys. Lett 1991, 178, 488.
[3] J. Kido., M. Kohda., K. Okuyama., K. Nagai., Appl. Phys. Lett 1992, 61, 761.
[4] J. Kido., M. Kimura., K. Nagai., Science 1995, 267, 1332.
[5] M. Pope., H. Kallmann., P. Magnante., J. Chem. Phys. Lett 1963, 38, 2024.
[6] C. W. Tang., S. A. VanSlyke., Appl. Phys. Lett 1987, 51, 913.
[7] C. W. Tang., S. A. VanSlyke., C. H. Chen., J. Appl. Phys. Lett 1989, 65, 3610.
[8] M. A. Baldo, D. F. O’Brien, Y. You, A. Shoustikov, S. Sibley, M. E. Thompson, S. R. Forrest, Nature 1998, 395, 151.
[9] M.-H. Ho., S.-W. Hwang., C.-H. Chen., The Chinese Chem. SOC, Taipei. 2005, 63, 443.
[10] H. Uoyama., K. Goushi., K. Shizu., H. Nomura., C. Adachi., Nature 2012, 492, 234.

[1] J. C. de. Mello., H. F. Wittmann., R. h. Friend., Adv. Mater 1997, 9, 230.
[2] X. Gong, M. R. Robinson, J. C. Ostrowski, D. Moses, G. C. Bazan., A. J. Heeger, Adv. Mater 2001, 14, 581.
[3] M. H. Tsai., H. W. Lin., H. C. Su., T. H. Ke., C. C. Wu., F. C. Fang., Y. L. Liao., K. T. Wongand., C. I. Wu, Adv. Mater 2006, 18, 1216.
[4] C. W. Tang., S. A. VanSlyke., Appl. Phys. Lett 1987, 51, 913.
[5] C. W. Tang., S. A. VanSlyke., C. H. Chen., J. Appl. Phys. Lett 1989, 65, 3610.
[6] E. S. Hung., C. W. Tang., M. G. Mason, Appl. Phys. Lett 1997, 70, 152.
[7] L. O. Pålsson., A. P. Monkman., Adv. Mater 2002, 14, 757.
[8] J. C. Mello., H. F. Wittmann., R. H. Friend., Adv. Mater 1997, 9, 230.
[9] A. Endo., K. Sato., K. Yoshimura., T. Kai., A. Kawada., H. Miyazaki.., C. Adachi., App. Phys. Lett. 2011, 98, 083302.
[10] K. Shizu., H. Tanaka., M. Uejima., T. Sato., K. Tanaka., H. Kaji., C. Adachi., J. Phys. Chem. C. 2015, 119, 1291.
[11] A. Sharma., B. Kippelen., P. J. Hotchkiss., S. R. Marder., Appl. Phys. Lett. 2008, 93, 163308.

[1] T. Serevicius., T. Nakagawa., M. C. Kuo., S. H. Cheng., K. T. Wong, C. H. Chang., R. C. Kwong., S. Xia., C. Adachi., Phys. Chem. Chem. Phys. 2013, 15, 15850.
[2] S. Wu., M. Aonuma, Q. Zhang., S. Huang., T. Nakagawa., K. Kuwabara., C. Adachi., J. Mater. Chem. 2014, 2, 421.
[3] A. Endo., M. Ogasawara., A. Takahashi., D. Yokoyama., Y. Kato., C. Adachi., Adv. Mater. 2009, 21, 4802.
[4] A. Endo., K. Sato, K. Yoshimura., T. Kai., A. Kawada., H. Miyazaki., C. Adachi., Appl. Phys. Lett. 2011, 98, 083302.
[5] Y. Im., J. Y. Lee., Chem. Mater. 2014, 26, 1413.
[6] B. S. Kim., J. Y. Lee., Adv. Funct Mater. 2014, 24, 3970.
[7] R. Ishimatsu., S. Matsunami., K. Shizu., C. Adachi., K. Nakano., T. Imato., J. Phys. Chem. A. 2013, 117, 5607.
[8] T. Ogiwara., Y. Wakikawa., T. Ikoma., J. Phys. Chem. A. 2015, 119, 3415.
[9] J. Lee., K. Shizu., H. Tanaka., H. Nomura., T. Yasuda., C. Adachi., J. Mater. Chem. C. 2013, 1, 4599.
[10] J. Li., T. Nakagawa., J. MacDonald., Q. Zhang., H. Nomura., H. Miyazaki., C. Adachi, Adv Mater. 2013, 25, 3319.
[11] G. Mehes., H. Nomura,, Q. Zhang., T. Nakagawa., C. Adachi., Angewandte Chemie. 2012, 51, 11311.
[12] T. Komino., H. Nomura., T. Koyanagi., C. Adachi, Chem. Mater. 2013, 25, 3038.
[13] T. Nakagawa., S. Y. Ku., K. T. Wong., C. Adachi, Chem. Commun. 2012, 48, 9580.
[14] H. Tanaka., K. Shizu., H. Miyazaki., C. Adachi, Chem. Commun. 2012, 48, 11392.
[15] S. Youn. Lee., T. Yasuda., H. Nomura., C. Adachi., Appl. Phys. Lett. 2012, 101, 093306.
[16] Q. Zhang., J. Li, K. Shizu., S. Huang., S. Hirata., H. Miyazaki., C. Adachi., J. Am. Chem. Soc. 2012, 134, 14706.
[17] H. Uoyama., K. Goushi1., K. Shizu1., H. Nomura., C. Adachi., Nature. 2012, 492, 234.

[1] M. A. Baldo., D. F. O’Brien., Y. You., A. Shoustikov., S. Sibley., M. E. Thompson., S. R. Forrest., Nature. 1998, 395, 151.
[2] C. Adachi., M. A. Baldo., S. R. Forrest., M. E. Thompson., Appl. Phys. Lett. 2000, 77, 904.
[3] T. Noda., H. Ogawa., Y. Shirota., Adv. Mater. 1999, 11, 283
[4] J. Wang., Y. Kawabe., S. E. Shaheen., M. M. Morrell., G. E. Jabbour., P. A. Lee., J. Anderson, N. R. Armstrong, B. Kippelen, E. A. Mash., N. Peyghambarian, Adv. Mater. 1998, 10, 230.
[5] J. H. Lee., S. H. Cheng., S. J. Yoo., H. Shin., J. H. Chang., C. I. Wu., K. T. Wong., J. J. Kim., Adv. Funct. Mater. 2015, 25, 361.
[6] C. H. Chen., C. W. Tang., Chemistry of Functional Dyes, Mita Press, 1992, 2, 536.
[7] W. Y. Hung., G. C. Fang., S. W. Lin., S. H. Cheng., K. T. Wong., T. Y. Kuo., P. T. Chou., Scientific Reports. 2014, 4, 5161.