硅酸盐学报

Zr⁴⁺掺杂CsPbI₃钙钛矿量子点玻璃的光学性能

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许周速 ¹ , 王鹏 ¹ , 杨伊健 ¹ , 郑国君 ² , 满涛 ³ , 王阳明 ⁴ , 刘小峰 ⁵ , 邱建荣 ³

硅酸盐学报 | 钙钛矿掺杂玻璃的基础和应用专题—研究论文 2024,52(8): 2606-2614

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硅酸盐学报 |钙钛矿掺杂玻璃的基础和应用专题—研究论文 2024 , 52 (8) : 2606 -2614

Zr⁴⁺掺杂CsPbI₃钙钛矿量子点玻璃的光学性能

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许周速¹, 王鹏¹, 杨伊健¹, 郑国君², 满涛³, 王阳明⁴, 刘小峰⁵, 邱建荣³

作者信息

^1．浙江工业大学光电子智能化技术研究所，杭州 310023

^2．宁波大学信息科学与工程学院，浙江宁波 315211

^3．浙江大学光电科学与工程学院，杭州 310027

^4．浙江工业大学计算机科学与技术学院，杭州 310023

^5．浙江大学材料科学与工程学院，杭州 310027

通讯作者:

刘小峰（1982—），男，博士，副教授。

作者简介:

许周速（1981—），男，博士，副教授。

Optical Properties of Zr⁴⁺ Doped CsPbI₃ Perovskite Quantum Dots Glass

Zhousu XU¹, Peng WANG¹, Yijian YANG¹, Guojun ZHENG², Tao MAN³, Yangming WANG⁴, Xiaofeng LIU⁵, Jianrong QIU³

Affiliations

^1.Institute of Intelligent Optoelectronic Technology, Zhejiang University of Technology, Hangzhou 310023, China

^2.College of Electrical Engineering and Computer Sciences, Ningbo University, Ningbo 315211, Zhejiang, China

^3.College of Optical Science and Engineering, Zhejiang University, Hangzhou 310027, China

^4.College of Computer Science and Technology, Zhejiang University of Technology, Hangzhou 310023, China

^5.School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China

Corresponding Author:

LIU Xiaofeng (1982-), male, Ph.D., Associate Professor. E-mail: xfliu@zju.edu.cn

XU Zhousu (1981-), male, Ph.D., Associate Professor. E-mail: xuzhousu@zjut.edu.cn

出版时间: 2024-08-20 doi: 10.14062/j.issn.0454-5648.20240108

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摘要

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钙钛矿量子点具有优异的光电性能，有望应用于显示、光伏和光电探测等领域，然而，较差的稳定性限制其应用，将钙钛矿量子点嵌入到玻璃中可以有效地提升其稳定性。采用高温熔融-热处理方法制备了Zr⁴⁺掺杂CsPbI₃量子点硼硅酸盐玻璃。结果表明：CsPbI₃量子点在玻璃内部析出，并且随着ZrO₂含量增加，由于较小直径的Zr⁴⁺取代了较大直径的Pb²⁺，（200）晶面的衍射峰向大角度偏移；随着ZrO₂含量的增加，发光峰和吸收边均出现蓝移，荧光强度和量子效率先增大后减小，荧光寿命逐渐减小；随着ZrO₂含量增加，玻璃中［BO₄］和［SiO₄］四面体网络结构增加，导致玻璃三维网络结构增加，从而抑制了CsPbI₃量子点的析晶。本工作表明所制备的玻璃具有良好的热稳定性，能够应用于显示、照明等领域。

关键词

锆离子 / 量子点 / 硼硅酸盐玻璃 / 析晶

Abstract

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Introduction

In recent years, all-inorganic halide perovskite (CsPbX₃, X=Cl, Br, I) quantum dots (QDs) have attracted widespread attention due to their excellent optical and electrical properties. They exhibit high photoluminescence (PL) efficiency, narrow emission bandwidth and tunable emission energy at a wide spectral range. However, the poor stability of CsPbX₃ QDs under ambient conditions strongly limit their applications. In this work, CsPbI₃ QD-doped borosilicate glasses were prepared by high-temperature melting-quenching followed by heat treatment. ZrO₂ is employed as the network modifier, which effectively modifies the local network structure of glass. By optimizing the concentration of ZrO₂ and the heat treatment temperature or time, the PL efficiency of the glass can be effectively improved. PL intensity of the QDs glass sample demonstrates high stability, which is almost unchanged after multiple heating and cooling cycles between 293 K and 373 K.

Methods

The CsPbI₃ QD-doped glasses were prepared by high-temperature melting-quenching followed by heat treatment. All raw materials with the designed ratios were accurately weighed and mixed in an agate mortar for 20 min. After the raw materials were thoroughly mixed, they were placed in a covered alumina crucible and transferred to a muffle furnace for melting at 1200 ℃ for 20 min. Afterwards, the glass melt was quenched onto a steel plate and pressed into a glass plate. Finally, the precursor glass were heat-treated at different temperatures (520-550 ℃) for 4 h and at 530 ℃ for different times (2-12 h) to precipitate the CsPbI₃ QDs.

PL spectra, PL decay curves and thermal stability of glass samples were examined with a FLS 980 fluorescence spectrometer. Optical absorption spectra were recorded by using a UV-3600UV-Vis-NIR spectrometer. X-ray diffraction patterns were recorded by using an X'Pert PRO powder diffractometer. The network structure of glass was analyzed by using a Nicolet 6700 spectrometer and an InVia Reflex Raman spectrometer. The photoluminescence quantum yield (PLQY) was measured with an absolute PLQY measurement system.

Results and discussion

From the XRD results, as the heat treatment time increases, two diffraction peaks at angles (2θ) of 28.5° and 35.5° become stronger in intensity, corresponding to the (200) and (211) planes of CsPbI₃ QDs, respectively. With increasing the ZrO₂ concentration, the diffraction peak of (200) crystal plane shifts to a larger angle, which is attributed to the replacement of larger Pb²⁺ ions by smaller Zr⁴⁺. Based on FTIR and Raman spectra characterizations, the network structure of glass is mainly composed of [BO₄], [SiO₄] and [BO₃] units. As the ZrO₂ concentration increases, the fraction of tetrahedral network structure formed by [BO₄] and [SiO₄] units in the glass increases, leading to an increase in the fraction of the three-dimensional network structure of the glass, therefore inhibiting the crystallization of CsPbI₃ QDs and reducing the size of QDs. This results in the blue shift of the absorption edge and emission peak wavelength. From the emission spectra, with increasing the ZrO₂ concentration, the PL intensity of the glass samples first increases and then decreases. Both the absorption edge and emission peak wavelength show a clear redshift with increasing the heat treatment temperature or time, which is mainly attributed to the increased size of QDs. According to the PL decay curves, as the ZrO₂ concentration increases, the PL lifetime of glass gradually decreases; as the heat treatment temperature increases, the PL lifetime of glass gradually increases. Finally, after multiple heating and cooling cycles at 293-373 K, there was no significant decrease in the PL intensity of the glass.

Conclusions

The CsPbI₃ QD-doped borosilicate glass was prepared successfully by high-temperature melting-quenching followed by heat treatment. X-ray diffraction shows that CsPbI₃ QDs are precipitated in the glass. With increasing the ZrO₂ concentration, the PL intensity of the glass samples first increases and then decreases, and the highest PLQY reaches 32.6%. In addition, the emission peak wavelength and absorption edge show a blue shift, which is attributed to the increased fraction of tetrahedral network structures formed by [BO₄] and [SiO₄] units in the glass at higher ZrO₂ concentrations. Consequently, the increase in the fraction of the three-dimensional network structures of the glass impedes the movement of Cs⁺, Pb²⁺ and I^-, inhibiting the crystallization of CsPbI₃ QDs. After multiple heating and cooling cycles at 293-373 K, there was no significant decrease in the PL intensity of the glass, indicating that Zr⁴⁺ doped CsPbI₃ perovskite QDs glass has good thermal stability, which may find applications in display, lighting and other fields.

Key words

zirconium ions / quantum dots / borosilicate glass / crystallization

引用本文

许周速, 王鹏, 杨伊健, 郑国君, 满涛, 王阳明, 刘小峰, 邱建荣. Zr⁴⁺掺杂CsPbI₃钙钛矿量子点玻璃的光学性能. 硅酸盐学报, 2024 , 52 (8) : 2606 -2614 . DOI: 10.14062/j.issn.0454-5648.20240108

Zhousu XU, Peng WANG, Yijian YANG, Guojun ZHENG, Tao MAN, Yangming WANG, Xiaofeng LIU, Jianrong QIU. Optical Properties of Zr⁴⁺ Doped CsPbI₃ Perovskite Quantum Dots Glass[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (8) : 2606 -2614 . DOI: 10.14062/j.issn.0454-5648.20240108

基金

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浙江省自然科学基金(LZ24F050009; LR21E020005)
国家自然科学基金(12304443; 62175210; U20A20211)
区域光纤通信网与新型光通信系统国家重点实验室开放基金(上海交通大学; 2023GZKF016)

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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.0454-5648.20240108

接收时间：2024-02-02
首发时间：2026-10-22
出版时间：2024-08-20

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收稿日期：2024-02-02
修回日期：2024-02-28

基金

浙江省自然科学基金(LZ24F050009; LR21E020005)

国家自然科学基金(12304443; 62175210; U20A20211)

区域光纤通信网与新型光通信系统国家重点实验室开放基金(上海交通大学; 2023GZKF016)

作者信息

^1．浙江工业大学光电子智能化技术研究所，杭州 310023

^2．宁波大学信息科学与工程学院，浙江宁波 315211

^3．浙江大学光电科学与工程学院，杭州 310027

^4．浙江工业大学计算机科学与技术学院，杭州 310023

^5．浙江大学材料科学与工程学院，杭州 310027

通讯作者:

刘小峰（1982—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240108

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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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