硅酸盐学报

钙钛矿纳米晶复合硫系玻璃析晶机理及性能

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范培宽 ¹^,² , 周港杰 ¹^,² , 康世亮 ¹^,² , 林常规 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): 2634-2642

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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) : 2634 -2642

钙钛矿纳米晶复合硫系玻璃析晶机理及性能

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范培宽¹^,², 周港杰¹^,², 康世亮¹^,², 林常规¹^,²

作者信息

^1．宁波大学红外材料及器件实验室，浙江宁波 315211

^2．先进红外光电材料与器件浙江省工程研究中心，浙江宁波 315211

通讯作者:

林常规（1984—），男，博士，研究员。

作者简介:

范培宽（1998—），男，硕士研究生。

Crystallization Mechanism and Properties of Perovskite Nanocrystalline Embedded Chalcogenide Glass

Peikuan FAN¹^,², Gangjie ZHOU¹^,², Shiliang KANG¹^,², Changgui LIN¹^,²

Affiliations

^1.Laboratory of infrared Materials and Devices, Ningbo University, Ningbo 315211, Zhejiang, China

^2.Engineering Research Center for Advanced Infrared Photoelectric Materials and Devices, Ningbo 315211, Zhejiang, China

Corresponding Author:

LIN Changgui (1984-), male, Ph.D., Professor. E-mail: linchanggui@nbu.edu.cn

FAN Peikuan (1998-), male, Master candidate. E-mail: fpeikuan@163.com

出版时间: 2024-08-20 doi: 10.14062/j.issn.0454-5648.20230984

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摘要

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钙钛矿纳米晶因其优异的可调发光和光电性能，在各光电应用领域广受关注。本文综述了硫系玻璃中金属卤化物钙钛矿纳米晶的研究进展，介绍了玻璃熔体法制备钙钛矿纳米晶复合硫系玻璃及其性能，并以无铅钙钛矿材料CsSnBr₃为例探讨了硫系玻璃中钙钛矿纳米晶析晶机理，并总结了目前钙钛矿纳米晶复合硫系玻璃的研究现状及发展趋势。

关键词

钙钛矿纳米晶 / 硫系玻璃 / 熟化 / 卤化锡 / 卤化铅

Abstract

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Inorganic perovskite nanocrystals exhibit superior thermal stability and higher quantum yields compared to organic-inorganic hybrid perovskites. Additionally, perovskite nanocrystals have gained significant attention in fields such as solar cells, low-threshold lasers, light-emitting diodes (LEDs), and photodetectors, owing to their excellent tunable luminescent and optoelectronic properties.

As a kind of nanocrystal with excellent photoelectric properties, CsPbX₃ can achieve tunable emission in the whole visible spectral region by means of compositional alloying and quantum size effect. However, all-inorganic CsPbX₃ perovskite nanocrystal still faces challenges in terms of poor stability and the toxicity of lead, which limits its application. Various strategies have been proposed to improve its resistance against environmental erosion, including surface modification, polymer encapsulation, and in-situ crystallization within inert glass matrices. Among them, embedding nanocrystals into inert glass matrices has been proposed to enhance their stability and demonstrate excellent heat resistance and resistance to intense light irradiation. However, traditional oxide glass is prepared under high-temperature open environments, leading to the volatilization of some glass components and the decomposition of perovskite nanocrystals. It results in unclear composition of the prepared glass and poor sample reproducibility. On the other hand, in response to the environmental toxicity of lead-based perovskites, non-toxic metals such as Sn, Bi, and Ge were employed for the substitution for Pb. Tin-based perovskites, in particular, have similar crystal and electronic structures to lead-based perovskites and exhibit fascinating near-infrared luminescence. By controlling the composition and quantum size, the emission spectra of CsSnX₃ perovskites can be tuned from visible light to approximately 1 μm in the near-infrared spectral region, which can not be achieved in lead-based perovskite materials. However, due to the high sensitivity and easy oxidation of metastable Sn²⁺, the synthesis of CsSnX₃ perovskite usually requires more stringent conditions, making the preparation procedure more difficult.

Chalcogenide glassy flux method is introduced by using chalcogenide-based materials with good glass-forming ability, such as GeS₂ and Sb₂S₃, as fluxes. Metal halides like CsX, SnX₂, or PbX₂ are dissolved in such chalcogenide fluxes, and the resulting mixture is melted and rapidly cooled to form glass. Subsequent heat treatment is applied to achieve controllable precipitation of the dissolved metal halides. This method allows for the formation of perovskite nanocrystals with arbitrary halide compositions within the transparent glass matrix, and meanwhile prevents the loss of metal halide precursors, therefore improving the reproducibility. The controllable crystallization mechanism of chalcogenide glass-ceramics with the composition of 79.2GeS₂-15.8Sb₂S₃-5CsSnBr₃ was investigated. The base samples were subjected to thermal treatments at 290 ℃ for 13, 20, 60 h, and 100 h. The variation of particle size and quantity of precipitated CsSnBr₃ nanocrystals was observed by SEM and plotted as a function of the heat-treatment conditions. It was found that it exhibited power-law variations with time, following the Lifshitz-Slyozov-Wagner (LSW) theory. The phenomenon of increasing crystal size and decreasing crystal quantity during the heat treatment process was explained using Ostwald ripening theory. As the heat treatment progresses, the continuous growth of larger crystals consumes at the expense of smaller crystals. Eventually, when all crystal sizes became similar, this dissolution-growth behavior reach equilibrium.

Summary and prospects

Inorganic perovskite nanocrystals have attracted significant attention due to their tunable emission wavelength and excellent optoelectronic properties. By utilizing glass flux method, controlled precipitation of perovskite nanocrystals such as CsPbX₃ and CsSnX₃ has been successfully achieved in sulfur-based glass. Tunable photoluminescence ranging from visible to near-infrared has been realized. The crystallization behavior of these perovskite nanocrystals in sulfur-based glass was revealed to follow the Ostwald ripening mechanism, allowing for controllability of nanocrystal size, crystal phase, and crystallinity. However, further research is required to investigate the characteristics of perovskite nanocrystals in sulfur-based glass, e.g., the relationship between their size, luminescence intensity, composition variations, and luminescence efficiency. Additionally, as a semiconductor material, sulfur-based glass holds potential application in electroluminescence compared to other substrate materials.

Key words

perovskite nanocrystals / chalcogenide glasses / ripening / cesium tin halide / cesium lead halide

引用本文

范培宽, 周港杰, 康世亮, 林常规. 钙钛矿纳米晶复合硫系玻璃析晶机理及性能. 硅酸盐学报, 2024 , 52 (8) : 2634 -2642 . DOI: 10.14062/j.issn.0454-5648.20230984

Peikuan FAN, Gangjie ZHOU, Shiliang KANG, Changgui LIN. Crystallization Mechanism and Properties of Perovskite Nanocrystalline Embedded Chalcogenide Glass[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (8) : 2634 -2642 . DOI: 10.14062/j.issn.0454-5648.20230984

基金

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国家自然科学基金(62122039)

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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.0454-5648.20230984

接收时间：2023-12-22
首发时间：2026-10-22
出版时间：2024-08-20

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收稿日期：2023-12-22
修回日期：2024-01-08

基金

国家自然科学基金(62122039)

作者信息

^1．宁波大学红外材料及器件实验室，浙江宁波 315211

^2．先进红外光电材料与器件浙江省工程研究中心，浙江宁波 315211

通讯作者:

林常规（1984—），男，博士，研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230984

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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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