Molecular Design of Anthracene-Based Electron-Transporting Materials for Efficient Blue Perovskite QLEDs

doi:10.6023/A24090272

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (1): 1-9.DOI: 10.6023/A24090272 Previous Articles Next Articles

Original article

基于蒽基电子传输材料设计及蓝光钙钛矿QLED性能研究

谭可莹^a^,^b, 方平^a^,^b, 丁杜鹏^a^,^b, 袁诗晨^a, 刘辰^a, 杨诗羽^a, 魏昌庭^a^,^*(), 徐勃^a^,^*()

a 南京理工大学材料科学与工程学院新型显示材料与器件工信部重点实验室南京 210094
b 南京理工大学钱学森学院南京 210094

投稿日期:2024-09-10 发布日期:2024-11-19
基金资助:
国家级大学生创新创业训练计划项目(202310288035); 国家自然科学基金(22279059); 国家自然科学基金(62404104); 江苏省自然科学基金(BK20240083); 江苏省自然科学基金(BK20241465); 江苏省卓越博士后计划(2023ZB844); 中国博士后面上项目(2023M731687); 南京理工大学大型仪器开放基金资助

Molecular Design of Anthracene-Based Electron-Transporting Materials for Efficient Blue Perovskite QLEDs

Keying Tan^a^,^b, Ping Fang^a^,^b, Dupeng Ding^a^,^b, Shichen Yuan^a, Chen Liu^a, Shiyu Yang^a, Changting Wei^a(), Bo Xu^a()

a MIIT Key Laboratory of Advanced Display Materials and Devices, School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
b Qian Xuesen College, Nanjing University of Science and Technology, Nanjing 210094, China

Received:2024-09-10 Published:2024-11-19
Contact: *E-mail: ctwei@njust.edu.cn; boxu@njust.edu.cn
Supported by:
National Undergraduate Training Program for Innovation and Entrepreneurship(202310288035); National Natural Science Foundation of China(22279059); National Natural Science Foundation of China(62404104); Natural Science Foundation of Jiangsu Province(BK20240083); Natural Science Foundation of Jiangsu Province(BK20241465); Jiangsu Funding Program for Excellent Postdoctoral Talent(2023ZB844); China Postdoctoral Science Foundation(2023M731687); NJUST Large Instrument Equipment Open Fund

1. .pdf(1377KB)

Abstract

Perovskite quantum dot light-emitting diodes (Pe-QLEDs) hold significant promise for high-definition flexible displays due to their exceptional color purity, wide color gamut, versatile light-emitting properties, and cost-effective solution processing capabilities. However, the varying transport capacities of the carrier-transporting layers in commonly used multilayer ‘sandwich’ electroluminescent device structures pose limitations on their development. In this study, we synthesized two asymmetric anthracene-based compounds, designated as B1 and B3, featuring a large π-conjugated anthracene-based skeleton as their core, which exhibit sufficiently high thermal stability suitable for vacuum thermal deposition method. Additionally, we optimized the group size and push-pull electronic characteristics of the peripheral groups to enhance carrier transport capability. From the measured space-charge-limited current data of electron-only devices, we calculated high electron transport mobilities of 4.78×10⁻⁵ cm²•V⁻¹•s⁻¹ for B1 and 4.13×10⁻⁵ cm²•V⁻¹•s⁻¹ for B3. Based on these impressive physicochemical properties, the external quantum efficiency (EQE) of the sky-blue Pe-QLEDs prepared with B1 and B3 as the electron-transporting layer (ETL) reached 6.32% and 8.82%, respectively, while the maximum brightness was 4631.77 cd•m⁻² and 3585.29 cd•m⁻², respectively. B1- and B3-based Pe-QLEDs devices outperformed the control device using 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi) as the ETL, which exhibited an EQE of 6.11% and brightness of 3041.77 cd•m⁻². Notably, both B1 and B3 also enhance the electron injection capability of the devices and significantly reduce the device turn-on voltage (2.20 V and 2.40 V, respectively), primarily attributed to their more balanced carrier transport within the devices. Ultimately, transient electroluminescence and electrochemical impedance spectroscopy confirmed that B1 and B3 facilitate the rapid establishment of steady-state emission within the device and effectively reduce carrier accumulation at the interfaces. Among these electron-transporting materials (ETMs), B3 enhances the effective recombination ratio, resulting in improved device efficiency. This study highlights the critical role of balanced carrier transport in enhancing device efficiency and provides valuable insights for the design of high electron mobility ETMs aimed at constructing efficient Pe-QLEDs.

Key words: perovskite quantum dot light-emitting diodes, electron-transporting material, structural modulation, carrier transport balance, anthracenyl skeleton

Cite this article

Keying Tan, Ping Fang, Dupeng Ding, Shichen Yuan, Chen Liu, Shiyu Yang, Changting Wei, Bo Xu. Molecular Design of Anthracene-Based Electron-Transporting Materials for Efficient Blue Perovskite QLEDs[J]. Acta Chimica Sinica, 2025, 83(1): 1-9.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

Figure 1. Chemical structures, frontier molecular orbitals, and electrostatic potential (ESP) distributions of (a) B1 and (b) B3

Figure 2. (a) UV-Vis absorption and PL spectra of B1 and B3; (b) TGA curves of the three ETMs, and (c) DSC curves of B1 and B3; (d) the secondary electron cutoff and onset edges of B1 and B3 measured by UPS; (e) current density-voltage curves in electron-only devices based on different ETMs; (f) electron mobilities of the ETMs under varying electric fields, with the interpolated data representing the zero-field mobilities of the ETMs

ETMs	T_d/℃	T_g/℃	E_g/eV	LUMO/eV	HOMO/eV	μ₀/(cm²•V⁻¹•s⁻¹)	β/(cm•V⁻¹)	μ_e^a/(cm²•V⁻¹•s⁻¹)
TPBi	474.00	119.67	3.59	－2.70	－6.29	9.23×10⁻⁶	1.19×10⁻²	1.61×10⁻⁵
B1	512.33	—	2.97	－2.25	－5.22	4.78×10⁻⁵	1.12×10⁻²	6.14×10⁻⁵
B3	507.67	150.33	3.08	－2.39	－5.47	4.13×10⁻⁵	9.72×10⁻³	5.13×10⁻⁵

Table 1. Summary of the thermodynamic properties and electrical properties of these three ETMs

Figure 3. (a) Device structure, and (b) corresponding energy level distributions of each functional layer in the sky blue Pe-QLEDs used in this study; (c) EL spectra of Pe-QLEDs prepared using different ETMs at 5 V driving voltage, with the inset showing the EL images of the Pe-QLEDs prepared with B1 taken during device operation; (d) current density-voltage characteristic curve, and (e) EQE-current density characteristic curve of the Pe-QLED devices based on different ETMs; (f) box plots of the maximum external quantum efficiency of measured from 20 individual devices

ETM	EQE_max/%	L_max/(cd•m⁻²)	V_T^a/V
TPBi	6.11	3041.77	3.20
B1	6.32	4631.77	2.20
B3	8.82	3585.29	2.40

Table 2. Summary of key parameters in the performance of sky blue Pe-QLEDs device prepared using the three ETMs

Figure 4. Investigating the carrier dynamics behavior in blue Pe-QLEDs devices. (a) PL decay curves of QDs films fabricated with the three different ETMs; (b) transient EL curves of Pe-QLEDs prepared utilizing different ETMs; (c) Nyquist plots of the impedance spectra of Pe-QLEDs made with different ETMs under a driving voltage of 3.50 V, accompanied by their fitting curves, with an inset depicting the simplified equivalent circuit; (d, e) a schematic diagram representing the internal carrier injection, transport, and recombination in devices based on TPBi and B3

References 44

[1]	Chan, W. C. W.; Nie, S. Science 1998, 281, 2016. doi: 10.1126/science.281.5385.2016 pmid: 9748158
[2]	Hines, M. A.; Guyot-Sionnest, P. J. Phys. Chem. 1996, 100, 468.
[3]	Murray, C. B.; Norris, D. J.; Bawendi, M. G. J. Am. Chem. Soc. 1993, 115, 8706.
[4]	Cho, H.; Jeong, S.-H.; Park, M.-H.; Kim, Y.-H.; Wolf, C.; Lee, C.-L.; Heo, J. H.; Sadhanala, A.; Myoung, N.; Yoo, S.; Im, S. H.; Friend, R. H.; Lee, T.-W. Science 2015, 350, 1222.
[5]	Protesescu, L.; Yakunin, S.; Bodnarchuk, M. I.; Krieg, F.; Caputo, R.; Hendon, C. H.; Yang, R. X.; Walsh, A.; Kovalenko, M. V. Nano Lett. 2015, 15, 3692. doi: 10.1021/nl5048779 pmid: 25633588
[6]	Song, J.; Li, J.; Li, X.; Xu, L.; Dong, Y.; Zeng, H. Adv. Mater. 2015, 27, 7162.
[7]	Peng, Y.; Zhao, Y.; Yang, J.; Zhang, X.; Cheng, J. Acta Chim. Sinica 2024, 82, 879 (in Chinese).
	( 彭亚晶, 赵雨新, 杨金辉, 仉昕昕, 程佳玲, 化学学报, 2024, 82, 879.) doi: 10.6023/A24030066
[8]	Akkerman, Q. A.; Rainò, G.; Kovalenko, M. V.; Manna, L. Nature Mater. 2018, 17, 394.
[9]	Li, H.; Feng, Y.; Zhu, M.; Yun, G.; Fan, C.; Cui, Q.; Cai, Q.; Yang, K.; He, P.; Dai, X.; Huang, J.; Ye, Z. Nature Nanotech. 2024, 19, 638.
[10]	Wang, J.; Li, M.; Cai, B.; Ren, H.; Fan, W.; Xu, L.; Yao, J.; Wang, S.; Song, J. Angew. Chem. Int. Ed. 2024, 63, e202410689.
[11]	Nong, Y.; Yao, J.; Li, J.; Xu, L.; Yang, Z.; Li, C.; Song, J. Adv. Mater. 2024, 36, 2402325.
[12]	Lim, J.; Bae, W. K.; Kwak, J.; Lee, S.; Lee, C.; Char, K. Opt. Mater. Express 2012, 2, 594.
[13]	Zaiats, G.; Ikeda, S.; Kamat, P. V. NPG Asia Mater. 2020, 12, 57.
[14]	Zhao, L.; Lee, K. M.; Roh, K.; Khan, S. U. Z.; Rand, B. P. Adv. Mater. 2019, 31, 1805836.
[15]	Xu, L.; Li, J.; Cai, B.; Song, J.; Zhang, F.; Fang, T.; Zeng, H. Nat. Commun. 2020, 11, 3902.
[16]	Zou, C.; Liu, Y.; Ginger, D. S.; Lin, L. Y. ACS Nano 2020, 14, 6076.
[17]	Yuan, S.; Zheng, X.; Shen, W.-S.; Liu, J.; Cui, L.-S.; Zhang, C.; Tian, Q.-S.; Wu, J.-J.; Zhou, Y.-H.; Wang, X.-D.; Wang, Z.-K.; Han, P.; Luther, J. M.; Bakr, O. M.; Liao, L.-S. ACS Energy Lett. 2022, 7, 1348.
[18]	Zhang, X.; Lin, H.; Huang, H.; Reckmeier, C.; Zhang, Y.; Choy, W. C. H.; Rogach, A. L. Nano Lett. 2016, 16, 1415.
[19]	Zhang, W.; Smith, J.; Hamilton, R.; Heeney, M.; Kirkpatrick, J.; Song, K.; Watkins, S. E.; Anthopoulos, T.; McCulloch, I. J. Am. Chem. Soc. 2009, 131, 10814.
[20]	Li, J.; Xu, L.; Wang, T.; Song, J.; Chen, J.; Xue, J.; Dong, Y.; Cai, B.; Shan, Q.; Han, B.; Zeng, H. Adv. Mater. 2017, 29, 1603885.
[21]	Yang, F.; Chen, H.; Zhang, R.; Liu, X.; Zhang, W.; Zhang, J.; Gao, F.; Wang, L. Adv. Funct. Mater. 2020, 30, 1908760.
[22]	Jia, J.; Zhu, L.; Wei, Y.; Wu, Z.; Xu, H.; Ding, D.; Chen, R.; Ma, D.; Huang, W. J. Mater. Chem. C 2015, 3, 4890.
[23]	Fang, T.; Wang, T.; Li, X.; Dong, Y.; Bai, S.; Song, J. Sci. Bull. 2021, 66, 2302253.
[24]	Yuan, S.; Fang, T.; Huang, J.; Li, X.; Wei, C.; Zhou, Y.; Li, Y.; Zheng, X.; Huang, J.; Su, J.; Baryshnikov, G.; Choy, W. C. H.; Zeng, H.; Xu, B. ACS Energy Lett. 2023, 8, 818.
[25]	Lin, L.; Zhang, Q.; Ni, Y.; Shang, L.; Zhang, X.; Yan, Z.; Zhao, Q.; Chen, J. Chem 2022, 8, 1822.
[26]	Li, X.-S.; Peng, Y.-Q.; Yang, Q.-S.; Xing, H.-W.; Lu, F.-P. Acta Phys. Sin. 2007, 56, 5441 (in Chinese).
	( 李训栓, 彭应全, 杨青森, 刑宏伟, 路飞平, 物理学报, 2007, 56, 5441.)
[27]	Wang, C.; Dong, H.; Jiang, L.; Hu, W. Chem. Soc. Rev. 2018, 47, 422.
[28]	Ye, S.; Wang, Y.; Guo, R.; Zhang, Q.; Lv, X.; Duan, Y.; Leng, P.; Sun, S.; Wang, L. Chem. Eng. J. 2020, 393, 124694.
[29]	Liu, H.; Kang, L.; Li, J.; Liu, F.; He, X.; Ren, S.; Tang, X.; Lv, C.; Lu, P. J. Mater. Chem. C 2019, 7, 10273.
[30]	Zhang, D.; Song, X.; Li, H.; Cai, M.; Bin, Z.; Huang, T.; Duan, L. Adv. Mater. 2018, 30, 1707590.
[31]	Zhang, D.; Duan, L. J. Phys. Chem. Lett. 2019, 10, 2528.
[32]	Wang, Q.; Chen, Y.; Yan, C.; Zeng, X.; Fu, X.; Pan, L.; Cao, J.; Yang, S.; Li, W.; Chen, X.; Yang, W. ACS Energy Lett. 2023, 8, 3710.
[33]	Gao, D.; Li, R.; Chen, X.; Chen, C.; Wang, C.; Zhang, B.; Li, M.; Shang, X.; Yu, X.; Gong, S.; Pauporté, T.; Yang, H.; Ding, L.; Tang, J.; Chen, J. Adv. Mater. 2023, 35, 2301028.
[34]	Ye, S.; Guo, R.; Xiang, S.; Zhang, Q.; Lv, X.; Liu, W.; Fan, L.; Leng, P.; Sun, S.; Wang, L. Mater. Chem. Front. 2019, 3, 812.
[35]	Jia, M.; Xu, X.; Peng, J.; Zhang, J.; Yao, C.; Li, L. Adv. Opt. Mater. 2016, 4, 1635.
[36]	Pan, J.; Wei, C.; Wang, L.; Zhuang, J.; Huang, Q.; Su, W.; Cui, Z.; Nathan, A.; Lei, W.; Chen, J. Nanoscale 2018, 10, 592.
[37]	Blakesley, J. C.; Castro, F. A.; Kylberg, W.; Dibb, G. F. A.; Arantes, C.; Valaski, R.; Cremona, M.; Kim, J. S.; Kim, J.-S. Org. Electron. 2014, 15, 1263.
[38]	Malliaras, G. G.; Salem, J. R.; Brock, P. J.; Scott, C. Phys. Rev. B 1998, 58, 13411.
[39]	Javaux, C.; Mahler, B.; Dubertret, B.; Shabaev, A.; Rodina, A. V.; Efros, A. L.; Yakovlev, D. R.; Liu, F.; Bayer, M.; Camps, G.; Biadala, L.; Buil, S.; Quelin, X.; Hermier, J. P. Nature Nanotech. 2013, 8, 206.
[40]	Shen, Y.; Hu, X.-M.; Guo, M.-L.; Li, Y.-Q.; Tang, J.-X. J. Phys. Chem. Lett. 2024, 15, 7916.
[41]	Xu, M.; Peng, Q.; Zou, W.; Gu, L.; Xu, L.; Cheng, L.; He, Y.; Yang, M.; Wang, N.; Huang, W.; Wang, J. Appl. Phys. Lett. 2019, 115, 041102.
[42]	Wei, C.; Xu, B.; Zhang, M.; Su, Z.; Gu, J.; Guo, W.; Gao, X.; Su, W.; Cui, Z.; Jeon, S.; Fan, Z.; Zeng, H. eScience 2024, 4, 100227.
[43]	Tang, P.; Xie, L.; Xiong, X.; Wei, C.; Zhao, W.; Chen, M.; Zhuang, J.; Su, W.; Cui, Z. ACS Appl. Mater. Interfaces 2020, 12, 13087.
[44]	Li, X.; Haghshenas, M.; Wang, L.; Huang, J.; Sheibani, E.; Yuan, S.; Luo, X.; Chen, X.; Wei, C.; Xiang, H.; Baryshnikov, G.; Sun, L.; Zeng, H; Xu, B. ACS Energy Lett. 2023, 8, 1445.

基于蒽基电子传输材料设计及蓝光钙钛矿QLED性能研究

Molecular Design of Anthracene-Based Electron-Transporting Materials for Efficient Blue Perovskite QLEDs

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 6

References 44

Related Articles 0

Recommended Articles

Metrics

Comments