CsPbBr3@MIL-53纳米复合荧光粉的合成、性能及其白光LEDs应用

doi:10.15541/jim20240141

无机材料学报 ›› 2024, Vol. 39 ›› Issue (9): 1035-1043.DOI: 10.15541/jim20240141

CsPbBr₃@MIL-53纳米复合荧光粉的合成、性能及其白光LEDs应用

瞿牡静¹(), 张淑兰¹, 朱梦梦¹^,², 丁浩杰¹, 段嘉欣¹, 代恒龙¹, 周国红³(), 李会利¹^,²()

1.华东师范大学物理与电子科学学院, 纳光电集成与先进装备教育部工程研究中心, 上海 200241
2.华东师范大学重庆研究院精密光学重庆市重点实验室, 重庆 401120
3.中国科学院上海硅酸盐研究所, 中国科学院透明光功能无机材料重点实验室, 上海 201899

收稿日期:2024-03-22 修回日期:2024-04-30 出版日期:2024-09-20 网络出版日期:2024-05-16
通讯作者: 李会利, 教授. E-mail: hlli@phy.ecnu.edu.cn;
周国红, 研究员. E-mail: sic_zhough@mail.sic.ac.cn
作者简介:瞿牡静(2000-), 女, 硕士研究生. E-mail: mjing2021@163.com
基金资助:
国家自然科学基金(12274136);重庆市自然科学基金(33606015)

CsPbBr₃@MIL-53 Nanocomposite Phosphors: Synthesis, Properties and Applications in White LEDs

QU Mujing¹(), ZHANG Shulan¹, ZHU Mengmeng¹^,², DING Haojie¹, DUAN Jiaxin¹, DAI Henglong¹, ZHOU Guohong³(), LI Huili¹^,²()

1. Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, School of Physics and Electronic Sciences, East China Normal University, Shanghai 200241, China
2. Chongqing Key Laboratory of Precision Optics, Chongqing Institute of East China Normal University, Chongqing 401120, China
3. Key Laboratory of Transparent Opto-functional Inorganic Materials, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China

Received:2024-03-22 Revised:2024-04-30 Published:2024-09-20 Online:2024-05-16
Contact: LI Huili, professor. E-mail: hlli@phy.ecnu.edu.cn;
ZHOU Guohong, professor. E-mail: sic_zhough@mail.sic.ac.cn
About author:QU Mujing (2000-), female, Master candidate. E-mail: mjing2021@163.com
Supported by:
National Natural Science Foundation of China(12274136);Chongqing Municipal Natural Science Foundation(33606015)

摘要/Abstract

摘要：

全无机钙钛矿(CsPbX₃, X = Cl, Br, I)纳米晶因其卓越的光电性能被广泛应用于光电子器件领域, 但稳定性问题仍然是制约其商业化发展的主要因素之一。基于此, 本研究以提高CsPbBr₃纳米晶的稳定性和固态发光性能为研究目标, 选用具有优异疏水性能的多孔MIL-53(Al)金属有机框架(MOFs)作为封装基质, 通过热注射工艺在MIL-53(Al)孔道内原位限域生长CsPbBr₃纳米晶, 成功制备了优异发光性能和稳定性的CsPbBr₃@MIL-53纳米复合荧光粉。MIL-53通过包含的苯环和有机配体与CsPbBr₃纳米晶螯合, 将其稳固地锚定在孔道内, 既保护了CsPbBr₃纳米晶免受外界环境的影响, 又有效防止了纳米晶之间的聚集, 从而避免了固态荧光猝灭。此外, MIL-53中的COO^-官能团与CsPbBr₃纳米晶表面未配对的Pb²⁺结合, 钝化了其表面的缺陷, 抑制了载流子的非辐射复合。MIL-53包含的苯环及有机长链又赋予了纳米复合荧光粉出色的疏水性能。这些因素的协同作用显著提升了CsPbBr₃@MIL-53纳米复合荧光粉的光学性能和水稳定性, 其荧光量子产率(Photoluminescence Quantum Yield, PLQY)为75.4%, 是固态CsPbBr₃纳米晶粉体(33.2%)的2.3倍。将CsPbBr₃@MIL-53纳米复合荧光粉完全浸泡在水中10 h, 其荧光强度仍能维持初始值的75.6%。最后, 将绿光发射的CsPbBr₃@MIL-53纳米复合荧光粉应用于白光发光二极管(Light Emitting Diodes, LEDs)器件, 实现了126% NTSC和85% Rec. 2020的宽色域覆盖面积, 表明其在显示器件领域具有优异的应用前景。

关键词: 全无机钙钛矿, 金属有机框架, CsPbBr₃@MIL-53, 稳定性, 白光LEDs

Abstract:

The all-inorganic CsPbX₃ (X=Cl, Br, I) perovskite nanocrystals have been widely applied in optoelectronic devices due to their excellent optoelectronic properties. However, their poor stability remains one of the main factors restricting their commercial development. This research focuses on improving the stability and solid-state luminescence performance of CsPbBr₃ nanocrystals. The porous MIL-53 (Al) metal-organic frameworks (MOFs) with outstanding hydrophobic properties was chosen as the encapsulation matrix. CsPbBr₃ nanocrystals were grown in situ within the MIL-53 (Al) channels by using a thermal injection process to successfully synthesize CsPbBr₃@MIL-53 nanocomposite phosphors with outstanding solid-state luminescence performance and high stability. MIL-53 chelates with CsPbBr₃ nanocrystals through benzene rings and organic ligands, firmly anchoring nanocrystals in the pores. This not only protects the CsPbBr₃ nanocrystals from external environmental influences but also effectively prevents aggregation between nanocrystals, thereby avoiding quenching of solid-state fluorescence. Additionally, the COO^- functional groups in MIL-53 bind with the unpaired Pb²⁺ on the surface of CsPbBr₃ nanocrystals, passivating the surface defects and suppressing non-radiative carrier recombination. Furthermore, the contained benzene rings and organic long chains endow the nanocomposite phosphors with excellent hydrophobic properties. The synergistic effect of these factors significantly enhances the optical performance and water stability of CsPbBr₃@MIL-53 nanocomposite phosphors. As a result, photoluminescence quantum yield (PLQY) of CsPbBr₃@MIL-53 nanocomposite phosphors reaches 75.4%, which is 2.3 times of that of solid-state CsPbBr₃ nanocrystal powders (33.2%). Even after being completely immersed in water for 10 h, its fluorescence intensity can still maintain 75.6% of the initial value. Finally, the green-emitting CsPbBr₃@MIL-53 nanocomposite phosphors were applied to white LED devices, achieving a wide-color-gamut coverage area of 126% NTSC and 85% Rec. 2020, which demonstrates its application prospects in wide-color-gamut display devices.

Key words: all-inorganic perovskite, metal-organic framework, CsPbBr₃@MIL-53, stability, white LEDs

中图分类号:

TQ174

瞿牡静, 张淑兰, 朱梦梦, 丁浩杰, 段嘉欣, 代恒龙, 周国红, 李会利. CsPbBr₃@MIL-53纳米复合荧光粉的合成、性能及其白光LEDs应用[J]. 无机材料学报, 2024, 39(9): 1035-1043.

QU Mujing, ZHANG Shulan, ZHU Mengmeng, DING Haojie, DUAN Jiaxin, DAI Henglong, ZHOU Guohong, LI Huili. CsPbBr₃@MIL-53 Nanocomposite Phosphors: Synthesis, Properties and Applications in White LEDs[J]. Journal of Inorganic Materials, 2024, 39(9): 1035-1043.

图/表 9

图1 介孔MIL-53(Al)的合成示意图[25]

Fig. 1 Synthesis schematic of mesoporous MIL-53 (Al)[25]

图2 CsPbBr3@MIL-53纳米复合荧光粉的合成示意图

Fig. 2 Schematic diagram of synthesis for CsPbBr3@MIL-53 nanocomposite phosphors

图3 CsPbBr3纳米晶、MIL-53 MOFs和CsPbBr3@MIL-53纳米复合荧光粉的(a, c, d, e)TEM和(b, f)HRTEM照片

Fig. 3 (a, c, d, e) TEM and (b, f) HRTEM images of CsPbBr3 NCs, MIL-53 MOFs and CsPbBr3@MIL-53 nanocomposite phosphors (a, b) CsPbBr3 NCs; (c) MIL-53 MOFs; (d-f) CsPbBr3@MIL-53 nanocomposite phosphors with the inserted histogram in the figure (e) showing the statistical results of the particle size distribution of CsPbBr3 NCs in the composite phosphors

图4 MIL-53和水洗处理前后CsPbBr3@MIL-53纳米复合荧光粉的XRD图谱

Fig. 4 XRD patterns of MIL-53 and CsPbBr3@MIL-53 nanocomposite phosphors before and after water treatment

图5 MIL-53和CsPbBr3@MIL-53的BET比表面积测试

Fig. 5 BET specific surface area testing of MIL-53 and CsPbBr3@MIL-53 (a) N2 adsorption-desorption isotherms; (b) Pore size distribution; Colorful figures are available on website

图6 MIL-53、CsPbBr3及CsPbBr3@MIL-53的XPS谱图

Fig. 6 XPS spectra of MIL-53, CsPbBr3 and CsPbBr3@MIL-53 (a) Total spectra; (b) Pb4f high-resolution spectra; (c) O1s high-resolution spectra

图7 CsPbBr3@MIL-53纳米复合荧光粉的光学性能

Fig. 7 Optical properties of CsPbBr3@MIL-53 nanocomposite phosphors (a) Emission spectra of CsPbBr3@MIL-53 with different weights of MIL-53; (b) Time-resolved photoluminescence (TRPL) curves and PLQYs of the optimized sample as well as CsPbBr3 NCs; Colorful figures are available on website

图8 CsPbBr3纳米晶和CsPbBr3@MIL-53纳米复合荧光粉的热、水稳定性测试

Fig. 8 Thermal- and water-stability of CsPbBr3@MIL-53 nanocomposite phosphors and CsPbBr3 NCs (a, b) Temperature-dependent PL spectra (λex=365 nm); (c) Normalized temperature-dependent PL spectra; (d, e) PL spectra of samples immersed in water for different periods; (f) Normalized time-dependent PL spectra

图9 基于CsPbBr3@MIL-53纳米复合荧光粉封装的白光LED器件性能

Fig. 9 Properties of white LED device fabricated by using green CsPbBr3@MIL-53 nanocomposite phosphors (a) EL spectrum of white LED driven by 2.6 V and 35.0 mA with inset photo showing the lighted white LED device; (b) Color gamut coverage of the white LED in comparison with NTSC and Rec. 2020 standard

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CsPbBr₃@MIL-53纳米复合荧光粉的合成、性能及其白光LEDs应用

CsPbBr₃@MIL-53 Nanocomposite Phosphors: Synthesis, Properties and Applications in White LEDs

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