硅酸盐学报

铯铅卤钙钛矿量子点玻璃的稳定性研究进展

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牛璐玥 ¹^,² , 孙永昊 ¹^,² , 王慈 ¹^,² , 任晶 ¹^,²

硅酸盐学报 | 钙钛矿掺杂玻璃的基础和应用专题—综合评述 2024,52(8): 2623-2633

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硅酸盐学报 |钙钛矿掺杂玻璃的基础和应用专题—综合评述 2024 , 52 (8) : 2623 -2633

铯铅卤钙钛矿量子点玻璃的稳定性研究进展

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牛璐玥¹^,², 孙永昊¹^,², 王慈¹^,², 任晶¹^,²

作者信息

^1．哈尔滨工程大学物理与光电工程学院，纤维集成光学教育部重点实验室，哈尔滨 150001

^2．哈尔滨工程大学物理与光电工程学院，海洋光子材料与器件物理工业与信息化部重点实验室，哈尔滨 150001

通讯作者:

王慈（1991—），女，博士，讲师。

任晶（1981—），男，博士，教授。

作者简介:

牛璐玥（1994—），女，博士研究生。

Research Progress on Stability of Cesium Lead Halide Perovskite Quantum Dots Glass

Luyue NIU¹^,², Yonghao SUN¹^,², Ci WANG¹^,², Jing REN¹^,²

Affiliations

^1.Key Laboratory of In-Fiber Integrated Optics of Ministry of Education, College of Physics and Optoelectronic Engineering, Harbin Engineering University, Harbin 150001, China

^2.Key Laboratory of Photonic Materials and Devices Physics for Oceanic Applications, Ministry of Industry and Information Technology of China, College of Physics and Optoelectronic Engineering, Harbin Engineering University, Harbin 150001, China

Corresponding Author:

WANG Ci (1991-), female, Ph.D., Lecturer. E-mail: 2520210429@hrbeu.edu.cn;

REN Jing (1981-), male, Ph.D., Professor. ren.jing@hrbeu.edu.cn

NIU Luyue (1994-), female, Doctoral candidate. E-mail: luyueniu@hrbeu.edu.cn

出版时间: 2024-08-20 doi: 10.14062/j.issn.0454-5648.20230919

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摘要

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铯铅卤（CsPbX₃）钙钛矿量子点（PQDs）在光电领域取得了突破性进展，然而其在实际应用中一直受到稳定性差的困扰。将PQDs嵌入到结构紧密、性能稳定的惰性无机玻璃基体中，形成“量子点玻璃”复合材料，在保留PQDs优异发光性能的同时，不但巧妙地解决PQDs稳定性差的“致命”缺点，而且有望进一步挖掘玻璃的优势，如拉制光纤，制备新型光电功能材料，在开发综合性能优异的光电器件方面具有很好的潜力。本文综述了目前CsPbX₃ PQDs玻璃的制备方法、析晶和发光机理，重点介绍了量子点玻璃在实际应用中面临的稳定性问题，包括在温度、光照和湿度等环境条件下的稳定性及重要研究进展，并对其未来研究中应重点关注的问题提出了展望。

关键词

钙钛矿 / 铯铅卤 / 量子点玻璃 / 发光

Abstract

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Cesium lead halide perovskite quantum dots (CsPbX₃) have emerged as pivotal materials in the realm of optoelectronics, owing to their exceptional properties. However, traditional synthesis methods often yield quantum dots (QDs) with poor durability, rendering them susceptible to degradation under various environmental impact such as light, oxygen, humidity, and high temperatures. This inherent instability hampers their long-term viability across diverse applications.

1) Stability Challenges and Solutions When exposed to adverse conditions, colloidal CsPbX₃ QDs swiftly deteriorate, leading to a decline in their photoluminescence (PL) emission performance. To mitigate this issue, diverse strategies have been devised, focusing on enhancing the long-term durability of QDs. Such as surface ligand modification, mesoporous structure encapsulation, core-shell structures, and composition engineering:

Despite these advancements, challenges persist, particularly regarding the efficacy of surface protective layers. Existing methods often yield structures with insufficient density, leading to compromised long-term protection. Additionally, the stability of silicon dioxide, commonly utilized in wet chemical methods, remains a concern. The protective layer structure formed by these methods on the surface of PQDs is not dense, and the silicon dioxide prepared by wet chemical methods is also unstable, making the long-term protection of PQDs insufficient against external environmental factors.

2) Quantum Dots Glass: A Solution for Long-Term Stability Inorganic glass is considered an excellent medium to prevent QDs degradation and improve their thermal stability. For example, there have been reports on the growth of II-VI and IV-VI QDs in glass, such as ZnO, ZnS, ZnSe, CdS, CdSe, PbS, and PbSe. Studies have found that glass has chemical and physical stability, as well as high mechanical strength, high temperature resistance, and chemical corrosion resistance. Glasses can prevent QDs from being eroded by the surrounding environment, allowing QDs to be evenly distributed in the glass matrix without aggregation, and the size of QDs embedded in glass is easy to control. Hence, a novel approach to address the stability issues of CsPbX₃ QDs involves embedding them within a structurally dense and performance-stable inert glass matrix, creating what is known as "quantum dots glass." This innovative composite material effectively circumvents the drawbacks associated with poor stability in standalone QDs while preserving their exceptional performance characteristics.

3) Expanding Horizons with Quantum Dots Glass Quantum dots glass not only offers enhanced stability but unlocks new possibilities in optoelectronic applications as well. Beyond addressing stability concerns, quantum dots glass holds promise for diverse applications, including:

Optical Fiber Fabrication: Leveraging the properties of quantum dots glass opens avenues for the fabrication of high-performance optical fibers, facilitating advancements in telecommunications and photonics.

Optoelectronic Functional Materials: By integrating quantum dots glass into optoelectronic devices, novel functionalities and performance enhancements can be achieved, paving the way for next-generation technologies.

Summary and prospects

In this paper, we delve into the preparation methods, crystallization, and emission mechanisms of cesium lead halide quantum dots glass. Emphasis is placed on the stability challenges encountered in practical applications, including temperature variations, light exposure, and humidity. Significant strides in addressing these challenges are highlighted, offering insights into potential avenues for future research endeavors.

At the same time, quantum dots glass retains the excellent optical performance of CsPbX₃ PQDs. Studies have shown that enhancing the rigidity of the glass network structure, such as replacing GeO₄ tetrahedra with SiO₄ tetrahedra, helps enhancing the water resistance of quantum dots glass. Additionally, using tellurite-based glasses with a higher density to encapsulate QDs or doping with high atomic number rare earth ions, such as Gd³⁺ and Lu³⁺, contributes to improve the material's radiation resistance. However, the understanding of the damage mechanism of PQDs glass under high energy beam irradiation, the thermal erasure mechanism, and the PL quenching mechanism of quantum dots glass at high temperatures is not deep enough at present. There is an urgent need for more direct experimental and theoretical research.

The development of quantum dots glass represents a significant leap forward in enhancing the long-term stability of CsPbX₃ QDs. With the in-depth study of the synthesis process of quantum dots glass, by designing rational glass compositions and regulating the precipitation process of CsPbX₃ PQDs, comprehensive optimization of optical performance can be achieved. By harnessing the unique properties of both QDs and glass matrices, this composite material not only overcomes stability limitations but also opens new frontiers in optoelectronics. It provides new perspectives for improving the current state of quantum dots glass and is expected to play a crucial role in various optical fields. Moving forward, continued research and innovation in this field hold immense potential for revolutionizing optoelectronic device design and functionality.

Key words

perovskite / cesium lead halide / quantum dots glass / luminous

引用本文

牛璐玥, 孙永昊, 王慈, 任晶. 铯铅卤钙钛矿量子点玻璃的稳定性研究进展. 硅酸盐学报, 2024 , 52 (8) : 2623 -2633 . DOI: 10.14062/j.issn.0454-5648.20230919

Luyue NIU, Yonghao SUN, Ci WANG, Jing REN. Research Progress on Stability of Cesium Lead Halide Perovskite Quantum Dots Glass[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (8) : 2623 -2633 . DOI: 10.14062/j.issn.0454-5648.20230919

基金

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国家自然科学基金面上项目(52372003; 52201008)
核探测与核电子学国家重点实验室开放课题(SKLPDE-KF-202205)
黑龙江省自然科学基金重点项目(ZD2023E004)

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2024年第52卷第8期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230919

接收时间：2023-11-28
首发时间：2026-10-22
出版时间：2024-08-20

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出版历史

收稿日期：2023-11-28
修回日期：2023-12-30

基金

国家自然科学基金面上项目(52372003; 52201008)

核探测与核电子学国家重点实验室开放课题(SKLPDE-KF-202205)

黑龙江省自然科学基金重点项目(ZD2023E004)

作者信息

^1．哈尔滨工程大学物理与光电工程学院，纤维集成光学教育部重点实验室，哈尔滨 150001

^2．哈尔滨工程大学物理与光电工程学院，海洋光子材料与器件物理工业与信息化部重点实验室，哈尔滨 150001

通讯作者:

王慈（1991—），女，博士，讲师。

任晶（1981—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230919

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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