基于蒽基电子传输材料设计及蓝光钙钛矿QLED性能研究

doi:10.6023/A24090272

化学学报 ›› 2025, Vol. 83 ›› Issue (1): 1-9.DOI: 10.6023/A24090272 上一篇下一篇

研究论文

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

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摘要/Abstract

钙钛矿量子点发光二极管(Pe-QLEDs)具有色纯度高、色域宽、多功能发光特性和低成本溶液加工能力等特点, 因此在高清柔性显示中具有巨大的应用潜力. 然而, 在常用的多层“三明治”电致发光器件结构中, 载流子传输层之间的传输能力的差异限制了其发展. 在本研究中, 设计并定制合成了两种以蒽骨架为核心的新型电子传输材料, 分别命名为B1和B3. 得益于电子迁移率的显著提高, 基于B3制备的天蓝光Pe-QLED器件实现了高效的载流子复合, 最终表现出8.82%的外量子效率(EQE)和2.40 V低启亮电压. 相比之下, 基于1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TPBi)制备器件的EQE仅为6.11%, 启亮电压高达3.20 V. 本研究验证了载流子平衡传输在提高器件效率方面的重要作用, 并为蓝光Pe-QLEDs中设计高电子迁移率的电子传输材料提供了参考思路.

关键词: 钙钛矿量子点发光二极管, 电子传输材料, 结构调控, 载流子传输平衡, 蒽骨架

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

引用此文

谭可莹, 方平, 丁杜鹏, 袁诗晨, 刘辰, 杨诗羽, 魏昌庭, 徐勃. 基于蒽基电子传输材料设计及蓝光钙钛矿QLED性能研究[J]. 化学学报, 2025, 83(1): 1-9.

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.

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图/表 6

图1. (a) B1和(b) B3分子的化学结构式、分子前沿轨道和分子表面静电势的分布

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

图2. (a) B1和B3的紫外-可见吸收光谱和光致发光光谱; 三种电子传输材料的(b)热重分析曲线和(c) B1和B3的差示扫描量热曲线; (d)通过紫外光电子能谱测量的B1和B3的二次电子截止边和起始边; (e)基于不同ETMs的单电子器件中的电流密度-电压曲线; 以及(f) ETMs在不同电场下的电子迁移率, 插图数据为三种ETMs的零场迁移率

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

表1. 三种ETMs的热力学性能和电学性能总结

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

图3. 本研究中使用的天蓝光Pe-QLEDs的(a)器件结构以及(b)各功能层的相应能级分布; (c)基于不同ETMs制备的Pe-QLEDs在5 V驱动电压下的EL光谱, 插图为基于B1制备的Pe-QLEDs在器件运行期间的EL发光照片; 基于不同ETMs制备的Pe-QLEDs器件的(d)电流密度-电压特性曲线和(e)外量子效率-电流密度特性曲线; (f) 20个独立器件的最大外量子效率箱式分布图

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

表2. 基于三种ETMs制备的天蓝光Pe-QLED器件性能的关键参数总结

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

图4. 蓝光Pe-QLEDs器件内部载流子动力学行为研究. (a)基于不同ETMs的量子点薄膜的PL衰减曲线; (b)基于不同ETMs制备的Pe-QLEDs器件的瞬态电致发光曲线; (c)基于不同ETMs制备的Pe-QLEDs在3.50 V驱动电压下的阻抗谱奈奎斯特图及其拟合曲线, 插图显示了器件的等效电路图; (d, e)基于TPBi和B3的器件内部的载流子注入、传输和复合过程示意图

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

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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

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