White organic light-emitting devices based on phosphor-sensitized fluorescence

ZOU Wenjing; ZHAO Yukang; WU Youzhi; ZHANG Cairong

doi:10.7498/aps.74.20241294

Abstract

Although phosphorescent organic light-emitting devices (OLEDs) can have an internal quantum efficiency (IQE) of 100%, the IQE usually decays at high current densities due to triplet-triplet annihilation. Phosphor-sensitized fluorescence can realize the energy transfer between phosphorescent emitter and fluorescent emitter, and can be used to suppress the efficiency fluctuations and adjust the color of the device. With this in mind, white light emission including different colors of phosphorescent emitter and fluorescent emitter can be expected. Herein, phosphor-sensitized fluorescent white OLEDs are fabricated by combining ultra-thin layer insertion and doping, in which laser dyes DCM (4-(Dicyanomethylene)-2-methyl-6-(4-dimethyl-aminostyryl)-4H-pyran), iridium complexes Ir(ppy)₃ (tris(2-phenylpyridine)iridium), and biphenyl ethylene derivatives BCzVB (1,4-bis[2- (3-N-ethylcarbazoryl)vinyl]benzene) are used as red, green and blue emitters, respectively. By adjusting the doping concentration of Ir(ppy)₃ phosphorescent green emitter in CBP (4,4’-N,N’-dicarbazole-biphyenyl) host, with ultra-thin layers of BCzVB fluorescent blue emitter on both sides of CBP:Ir(ppy)₃ doping system and with ultra-thin layer of DCM fluorescent red emitter inserting in CBP:Ir(ppy)₃ layer, the three colors can be balanced. White emissions are obtained in the device, the highest external quantum efficiency is 2.5% (current efficiency of 5.1 cd/A), the maximum brightness is 12400 cd/m², and Commission Internationale de l'Eclairage (CIE) co-ordinates can reach the ideal white light equilibrium point (0.33, 0.33) at a current density of 1 mA/cm². The acquisition of white light is attributed to the appropriate doping ratio of Ir(ppy)₃ and the position of DCM, which effectively balances the emission ratio of three primary colors: red, green, and blue. The results indicate that the partially energy transfer of triplet excitons to singlet excitons by phosphor-sensitized fluorescence scheme can be used to realize high-efficiency white organic electroluminescent devices, thereby reducing energy consumption and providing more room for promoting OLED applications.

Keywords:

Authors and contacts

1.
School of Materials Science & Engineering, Lanzhou University of Technology, Lanzhou 730050, China
2.
School of Science, Lanzhou University of Technology, Lanzhou 730050, China

Corresponding author: WU Youzhi, youzhiwu@163.com

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11964016).

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References

[1]	Kido J, Hongawa K, Okuyama K 1994 Appl. Phys. Lett. 64 815 Google Scholar
[2]	吴雨廷, 朱洪强, 魏福贤, 王辉耀, 陈敬, 宁亚茹, 吴凤娇, 陈晓莉, 熊祖洪 2022 物理学报 71 227201 Google Scholar Wu Y T, Zhu H Q, Wei F X, Wang H Y, Chen J, Ning Y R, Wu F J, Chen X L, Xiong Z H 2022 Acta Phys. Sin. 71 227201 Google Scholar
[3]	Hwang J, Choi H K, Moon J, Kim T Y, Shin J W, Joo C W, Han J H, Cho D H, Huh J W, Choi S Y, Lee J I, Chu H Y 2012 Appl. Phys. Lett. 100 133304 Google Scholar
[4]	Cho J T, Kim D H, Koh E I, Kim T W 2014 Thin Solid Films 570 63 Google Scholar
[5]	Chen Y W, Yang D Z, Qiao X F, Dai Y F, Sun Q, Ma D G 2020 J. Mater. Chem. C 8 6577 Google Scholar
[6]	Rosenow T C, Furno M, Reineke S, Olthof S, Lüssem B, Leo K 2010 J. Appl. Phys. 108 113113 Google Scholar
[7]	Wang Q, Ding J Q, Ma D G, Cheng Y X, Wang L X, Jing X B, Wang F S 2009 Adv. Funct. Mater. 19 84 Google Scholar
[8]	Sun Y, Forrest S R 2007 Appl. Phys. Lett. 91 263503 Google Scholar
[9]	Reineke S, Schwartz G, Walzer K, Falke M, Leo K 2009 Appl. Phys. Lett. 94 163305 Google Scholar
[10]	Gao Z X, Wang F F, Guo K P, Wang H, Wei B, Xu B S 2014 Opt. Laser Technol. 56 20 Google Scholar
[11]	Murawski C, Leo K, Gather M C 2013 Adv. Mater. 25 6801 Google Scholar
[12]	Reineke S, Schwartz G, Walzer K, Leo K 2007 Appl. Phys. Lett. 91 123508 Google Scholar
[13]	Baldo M A, Thompson M E, Forrest S R 2000 Nature 403 750 Google Scholar
[14]	Heimel P, Mondal A, May F, Kowalsky W, Lennartz C, Andrienko D, Lovrincic R 2018 Nat. Commun. 9 4990 Google Scholar
[15]	D’Andrade B W, Baldo M A, Adachi C, Brooks J, Thompson M E, Forrest S R 2001 Appl. Phys. Lett. 79 1045 Google Scholar
[16]	Chen X, Huang Y, Luo D, Chang C, Lu C, Su H 2023 Chem. Eur. J. 29 e202300034 Google Scholar
[17]	Baek S, Park J Y, Woo S, Lee W, Kim W, Cheon H, Kim Y, Lee J 2024 Small Struct. 5 2300564 Google Scholar
[18]	Cheong K, Han S W, Lee J Y 2024 Small Methods 8 2301710
[19]	Liang N, Zhao Y K, Wu Y Z, Zhang C R, Shao M 2021 Appl. Phys. Lett. 119 053301 Google Scholar
[20]	Zhou Y, Gao H, Wang J, Yeung F S Y, Lin S H, Li X B, Liao S L, Luo D X, Kwok H S, Liu B Q 2023 Electronics 12 3164 Google Scholar
[21]	Meyer J, Hamwi S, Kröger M, Kowalsky W, Riedl T, Kahn A 2012 Adv. Mater. 24 5408 Google Scholar
[22]	Vipin C K, Shukla A, Rajeev K, Hasan M, Lo S C, Namdas E B, Ajayaghosh A, Unni K N N 2021 J. Phys. Chem. C 125 22809 Google Scholar
[23]	Yang S H, Huang S F, Chang C H, Chung C H 2011 J. Lumin. 131 2106 Google Scholar
[24]	Ko C W, Tao Y T, Lin J T, Justin Thomas K R 2002 Chem. Mater. 14 357 Google Scholar
[25]	Petrova P K, Ivanov P I, Tomova R L 2014 J. Phys. : Conf. Ser. 558 012028 Google Scholar
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[28]	Gulbinas V, Zaushitsyn Y, Sundström V, Hertel D, Bässler H, Yartsev A 2002 Phys. Rev. Lett. 89 107401 Google Scholar
[29]	Liu Z G, Chen Z J, Gong H Q 2005 Chinese Phys. Lett. 22 1536 Google Scholar

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图 1 有机材料的化学结构

Figure 1. The chemical structure of organic materials.

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图 2 (a) OLED器件结构示意图; (b) OLED器件能级结构示意图

Figure 2. Schematic diagram of (a) device structure and (b) the corresponding energy level of the OLED.

DownLoad: Full-Size Img PowerPoint

图 3 不同Ir(ppy)₃掺杂浓度(6%, 3%, 1%, 0.7%和0.4%)器件的EL光谱图(@20 mA/cm²)

Figure 3. EL spectra (@20 mA/cm²) of devices with different Ir(ppy)₃ doping concentrations (6%, 3%, 1%, 0.7%, 0.4%).

DownLoad: Full-Size Img PowerPoint

图 4 BCzVB/CBP:Ir(ppy)₃结构能量传递原理图

Figure 4. Schematic diagram of the energy transfer with the structure of BCzVB/ CBP:Ir(ppy)₃.

DownLoad: Full-Size Img PowerPoint

图 5 不同Ir(ppy)₃掺杂浓度(6%, 3%, 1%, 0.7%, 0.4%)器件的电流效率-电流密度-亮度特性曲线

Figure 5. Current efficiency-current density-brightness characteristics of devices with different Ir(ppy)₃ doping concentrations (6%, 3%, 1%, 0.7%, 0.4%).

DownLoad: Full-Size Img PowerPoint

图 6 在0.7% Ir(ppy)₃掺杂浓度条件下两侧蒸镀和单侧蒸镀BCzVB器件EL光谱(@20 mA/cm²)比较

Figure 6. Comparison of EL spectra (@ 20 mA/cm²) of devices with BCzVB deposited on both and one sides at a doping concentration of 0.7% Ir(ppy)₃.

DownLoad: Full-Size Img PowerPoint

图 7 CBP (20 nm), CBP:Ir(ppy)₃ (0.7%, 20 nm)和BCzVB (0.3 nm)/CBP:Ir(ppy)₃(0.7%, 20 nm)/BCzVB (0.3 nm)薄膜的激发和光致发光光谱

Figure 7. Excitation and Photoluminescence spectra of CBP (20 nm), CBP:Ir(ppy)₃ (0.7%, 20 nm) and BCzVB (0.3 nm)/CBP:Ir(ppy)₃ (0.7%, 20 nm)/BCzVB (0.3 nm) film.

DownLoad: Full-Size Img PowerPoint

图 8 DCM超薄层在CBP:Ir(ppy)₃中离(+)BCzVB/CBP:Ir(ppy)₃阳极侧界面距离分别为y = 10, 12, 14, 16 nm器件的EL光谱(@20 mA/cm²)

Figure 8. EL spectra (@20 mA/cm²) of devices with ultra-thin DCM layer in CBP:Ir(ppy)₃ at distances of y = 10, 12, 14, 16 nm, respectively, from the (+) BCzVB/CBP:Ir (ppy)₃ interface at anode side.

DownLoad: Full-Size Img PowerPoint

图 9 BCzVB/CBP:Ir(ppy)₃/DCM/CBP:Ir(ppy)₃/BCzVB结构能量传递原理图

Figure 9. Schematic diagram of the energy transfer with the structure of BCzVB/CBP:Ir(ppy)₃/DCM/CBP:Ir(ppy)₃/BCzVB.

DownLoad: Full-Size Img PowerPoint

图 10 DCM超薄层在CBP:Ir(ppy)₃中离(+)BCzVB/CBP:Ir(ppy)₃阳极侧界面距离分别为y = 10, 12, 14, 16 nm器件的　(a)电流密度-电压特性曲线; (b)电流效率-电流密度-亮度特性曲线

Figure 10. Current density-voltage (a) and current efficiency-current density-brightness (b) characteristics of devices with ultra-thin DCM layer in CBP:Ir(ppy)₃ at distances of y = 10, 12, 14, 16 nm, respectively, from the (+) BCzVB/CBP:Ir(ppy)₃ interface at anode side.

DownLoad: Full-Size Img PowerPoint

图 11 y = 12 nm器件在不同电流密度(电压)下的EL光谱图

Figure 11. EL spectra of the device with y = 12 nm at different current density (voltage).

DownLoad: Full-Size Img PowerPoint

表 1 对应y = 10, 12, 14, 16 nm器件的CIE色坐标变化范围(@0.2—200 mA/cm²)

Table 1. Variation of CIE color coordinates of devices with y = 10, 12, 14, 16 nm (@0.2–200 mA/cm²)

器件	CIE色坐标变化范围
B1 (y = 10)	(0.28—0.22, 0.32—0.21)
B2 (y = 12)	(0.34—0.23, 0.36—0.23)
B3 (y = 14)	(0.41—0.25, 0.40—0.26)
B4 (y = 16)	(0.46—0.27, 0.43—0.31)

DownLoad: CSV

表 2 OLED器件性能总结

Table 2. Summary of the EL performances of the OLED.

器件	最大电流效率/(cd·A^–1)	最高亮度/(cd·m^–2)
A0 (x = 0.7)	9.53	23760
A1 (x = 6)	54.9	104900
A2 (x = 3)	52.1	111276
A3 (x = 1)	45.4	82830
A4 (x = 0.7)	34.9	39072
A5 (x = 0.4)	28.2	35046
B1 (y = 10)	5.1	12400
B2 (y = 12)	4.4	11900
B3 (y = 14)	3.6	11500
B4 (y = 16)	2.85	10800

DownLoad: CSV

[1]	Kido J, Hongawa K, Okuyama K 1994 Appl. Phys. Lett. 64 815 Google Scholar
[2]	吴雨廷, 朱洪强, 魏福贤, 王辉耀, 陈敬, 宁亚茹, 吴凤娇, 陈晓莉, 熊祖洪 2022 物理学报 71 227201 Google Scholar Wu Y T, Zhu H Q, Wei F X, Wang H Y, Chen J, Ning Y R, Wu F J, Chen X L, Xiong Z H 2022 Acta Phys. Sin. 71 227201 Google Scholar
[3]	Hwang J, Choi H K, Moon J, Kim T Y, Shin J W, Joo C W, Han J H, Cho D H, Huh J W, Choi S Y, Lee J I, Chu H Y 2012 Appl. Phys. Lett. 100 133304 Google Scholar
[4]	Cho J T, Kim D H, Koh E I, Kim T W 2014 Thin Solid Films 570 63 Google Scholar
[5]	Chen Y W, Yang D Z, Qiao X F, Dai Y F, Sun Q, Ma D G 2020 J. Mater. Chem. C 8 6577 Google Scholar
[6]	Rosenow T C, Furno M, Reineke S, Olthof S, Lüssem B, Leo K 2010 J. Appl. Phys. 108 113113 Google Scholar
[7]	Wang Q, Ding J Q, Ma D G, Cheng Y X, Wang L X, Jing X B, Wang F S 2009 Adv. Funct. Mater. 19 84 Google Scholar
[8]	Sun Y, Forrest S R 2007 Appl. Phys. Lett. 91 263503 Google Scholar
[9]	Reineke S, Schwartz G, Walzer K, Falke M, Leo K 2009 Appl. Phys. Lett. 94 163305 Google Scholar
[10]	Gao Z X, Wang F F, Guo K P, Wang H, Wei B, Xu B S 2014 Opt. Laser Technol. 56 20 Google Scholar
[11]	Murawski C, Leo K, Gather M C 2013 Adv. Mater. 25 6801 Google Scholar
[12]	Reineke S, Schwartz G, Walzer K, Leo K 2007 Appl. Phys. Lett. 91 123508 Google Scholar
[13]	Baldo M A, Thompson M E, Forrest S R 2000 Nature 403 750 Google Scholar
[14]	Heimel P, Mondal A, May F, Kowalsky W, Lennartz C, Andrienko D, Lovrincic R 2018 Nat. Commun. 9 4990 Google Scholar
[15]	D’Andrade B W, Baldo M A, Adachi C, Brooks J, Thompson M E, Forrest S R 2001 Appl. Phys. Lett. 79 1045 Google Scholar
[16]	Chen X, Huang Y, Luo D, Chang C, Lu C, Su H 2023 Chem. Eur. J. 29 e202300034 Google Scholar
[17]	Baek S, Park J Y, Woo S, Lee W, Kim W, Cheon H, Kim Y, Lee J 2024 Small Struct. 5 2300564 Google Scholar
[18]	Cheong K, Han S W, Lee J Y 2024 Small Methods 8 2301710
[19]	Liang N, Zhao Y K, Wu Y Z, Zhang C R, Shao M 2021 Appl. Phys. Lett. 119 053301 Google Scholar
[20]	Zhou Y, Gao H, Wang J, Yeung F S Y, Lin S H, Li X B, Liao S L, Luo D X, Kwok H S, Liu B Q 2023 Electronics 12 3164 Google Scholar
[21]	Meyer J, Hamwi S, Kröger M, Kowalsky W, Riedl T, Kahn A 2012 Adv. Mater. 24 5408 Google Scholar
[22]	Vipin C K, Shukla A, Rajeev K, Hasan M, Lo S C, Namdas E B, Ajayaghosh A, Unni K N N 2021 J. Phys. Chem. C 125 22809 Google Scholar
[23]	Yang S H, Huang S F, Chang C H, Chung C H 2011 J. Lumin. 131 2106 Google Scholar
[24]	Ko C W, Tao Y T, Lin J T, Justin Thomas K R 2002 Chem. Mater. 14 357 Google Scholar
[25]	Petrova P K, Ivanov P I, Tomova R L 2014 J. Phys. : Conf. Ser. 558 012028 Google Scholar
[26]	Miao Y Q, Du X G, Wang H, Liu H H, Jia H S, Xu B S, Hao Y Y, Liu X G, Li W L, Huang W 2014 RSC Adv. 5 4261 Google Scholar
[27]	邹文静, 吴有智, 张材荣 2024 兰州理工大学学报 50 21 Zou W J, Wu Y Z, Zhang C R 2024 J. Lanzhou Univ. Tech. 50 21 Zou W J, Wu Y Z, Zhang C R 2024 J. Lanzhou Univ. Tech. 50 21
[28]	Gulbinas V, Zaushitsyn Y, Sundström V, Hertel D, Bässler H, Yartsev A 2002 Phys. Rev. Lett. 89 107401 Google Scholar
[29]	Liu Z G, Chen Z J, Gong H Q 2005 Chinese Phys. Lett. 22 1536 Google Scholar

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