硅酸盐学报

CsPb（Cl/Br）₃钙钛矿量子点玻璃的载流子动力学

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陈荣华 ¹ , 林继栋 ¹ , 陈树鑫 ¹ , 牛伟帆 ¹ , 林世盛 ¹ , 陈大钦 ¹^,²

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): 2587-2597

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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) : 2587 -2597

CsPb（Cl/Br）₃钙钛矿量子点玻璃的载流子动力学

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陈荣华¹, 林继栋¹, 陈树鑫¹, 牛伟帆¹, 林世盛¹, 陈大钦¹^,²

作者信息

^1．福建师范大学物理与能源学院，福州 350117

^2．福建省先进高温超导材料工程研究中心，福州 350117

通讯作者:

陈大钦（1978—），男，博士，教授。

作者简介:

陈荣华（1998—），男，硕士研究生。

Carrier Dynamics in CsPb(Cl/Br)₃ Perovskite Quantum Dot Glasses

Ronghua CHEN¹, Jidong LIN¹, Shuxin CHEN¹, Weifan NIU¹, Shisheng LIN¹, Daqin CHEN¹^,²

Affiliations

^1.College of Physics and Energy, Fujian Normal University, Fuzhou 350117, China

^2.Fujian Province Engineering Research Center for Advanced High-temperature Superconducting Materials, Fuzhou 350117, China

Corresponding Author:

CHEN Daqin (1978-), male, Ph.D., Professor. E-mail: dqchen@fjnu.edu.cn

CHEN Ronghua (1998-), male, Master candidate. E-mail: crh.fjnu@foxmail.com

出版时间: 2024-08-20 doi: 10.14062/j.issn.0454-5648.20230915

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摘要

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全无机钙钛矿量子点因其卓越光电特性受到广泛关注，但较差的稳定性限制其实际应用。近年来，致密无机玻璃网络中原位析出钙钛矿量子点（CsPbX₃@glass）具有优异稳定性，然而大部分研究致力于优化钙钛矿量子点玻璃的光学性能，对其载流子动力学的研究较为匮乏。由此，本工作借助飞秒激光超快瞬态吸收光谱（fs-TAS）探索了由于晶化温度改变导致的缺陷变化与卤素比例变化对CsPb（Cl/Br）₃@glass载流子动力学的影响。研究发现，随着热处理温度升高，更多Br^-从玻璃网络中扩散进入量子点晶格，导致CsPb（Cl/Br）₃量子点电声耦合强度减弱，热载流子弛豫时间逐渐从140 fs增加至210 fs；当经历较高温度热处理（520 ℃）时，fs-TAS的基态漂白红侧（长波长方向）出现随时间衰减的负信号，证明新缺陷态存在，导致CsPb（Cl/Br）₃@glass呈现特别长的荧光寿命。

关键词

钙钛矿 / 量子点 / 玻璃 / 超快瞬态吸收光谱 / 热载流子弛豫 / 发光材料

Abstract

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Introduction

Inorganic perovskite quantum dots have attracted extensive attention due to their excellent optoelectronic properties, but the poor stability limits their practical applications. In recent years, perovskite quantum dots in situ crystallization inside robust inorganic glass network (CsPbX₃@glass, X=Cl, Br, I) have been evidenced to have superior stability. However, most studies have focused on optimizing the optical properties, while few investigations aiming at carrier dynamics. What's more, we don't know if interesting phenomenon will happen to the carrier dynamics of perovskite quantum dot glasses, which obtain rare study of mechanism of carrier dynamics, and no halogen mixing are involved before. In this work, the influence of defects and halogen ratios induced by the elevation of crystallization temperature on the carrier dynamics of CsPb(Cl/Br)₃@glass nanocomposites are investigated by means of femtosecond laser ultrafast transient absorption spectroscopy (fs-TAS).

Methods

We synthesized perovskite quantum dot glass by high temperature melting-heat treatment, showing final composition with proportions of (%, in mole) 30SiO-25B₂O₃-5Al₂O₃-5ZnO-5CaF₂-2PbBr₂-4PbCl₂-5NaBr-10NaCl-9Cs₂CO₃. The raw materials are silica (SiO₂, Bodie, analytical grade), alumina (Al₂O₃, Hengxing, 99%), calcium fluoride (CaF₂, McLean, 99%), boron oxide (B₂O₃, McLean, 98%), zinc oxide (ZnO, McLean, 99%), cesium carbonate (Cs₂CO₃, McLean, 98%), sodium bromide (NaBr, McLean, 99%) and sodium iodide (NaCl, McLean, 99.5%), which are used as raw materials to weigh, mix and grind in agate mortar. The resulting mixture was then placed in a sealed alumina crucible and melted at 1 200 ℃ for 30 min in ambient atmosphere. Subsequently, the glass melt was poured into a copper mold at room temperature. Finally, the obtained bulk glass was treated at 480, 500 ℃ and 520 ℃ respectively for 10 h to induce the precipitation of perovskite quantum dots in the glass, thus obtaining glass ceramics containing perovskite quantum dots.

Results and discussion

TEM shows that perovskite quantum dots are precipitated in glass. With the increase of temperature of thermal treatment, XRD appears attenuated diffraction peak of perovskite quantum dots and shifts to a small angle, while PL spectrum and absorption peak red shift, which prove that Br^- has entered into the lattice. Subsequently, PLQY proved that high thermal treatment temperature could weaken radiation recombination, and the fluorescence attenuation curve shows an unusually long life. The transient absorption spectrum explores the whole carrier dynamics process. First, it is obtained that the hot carrier relaxation lifetimes of perovskite quantum dot glasses treated at 480, 500 ℃ and 520℃ are 140, 190 fs and 210 fs, respectively. The temperature related spectrum proves that the hot carrier relaxation becomes slower due to the weakening of electro-acoustic coupling. In the following process of exciton recombination, a new defect state can be observed on the transient absorption spectrum, which may be the reason of the abnormal life of high thermal treatment temperature.

Conclusions

In summary, with the increase of thermal treatment temperature, the electro-acoustic coupling strength decreases due to the entry of Br^- into the lattice. Meanwhile, the hot carrier relaxation takes longer period of time. In addition, due to the high treatment temperature, new shallow level defects that can capture electrons appear, and some electrons can be released back to the conduction band for radiation recombination. This eventually leads to a great improvement of fluorescence lifetime. Understanding these internal mechanisms may provide new guidance for synthesis and application of the investigated material.

Key words

perovskite / quantum dot / glass / ultrafast transient absorption spectroscopy / hot carrier relaxation / luminescent materials

引用本文

陈荣华, 林继栋, 陈树鑫, 牛伟帆, 林世盛, 陈大钦. CsPb（Cl/Br）₃钙钛矿量子点玻璃的载流子动力学. 硅酸盐学报, 2024 , 52 (8) : 2587 -2597 . DOI: 10.14062/j.issn.0454-5648.20230915

Ronghua CHEN, Jidong LIN, Shuxin CHEN, Weifan NIU, Shisheng LIN, Daqin CHEN. Carrier Dynamics in CsPb(Cl/Br)₃ Perovskite Quantum Dot Glasses[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (8) : 2587 -2597 . DOI: 10.14062/j.issn.0454-5648.20230915

基金

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国家自然科学基金(52272141; 51972060; 12074068; 52102159; 22103013; 12304442)
福建省自然科学基金(2022J05091; 2020J02017; 2021J06021; 2021J01190; 2020J01931; 2020H0026)

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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.0454-5648.20230915

接收时间：2023-11-27
首发时间：2026-10-22
出版时间：2024-08-20

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收稿日期：2023-11-27
修回日期：2023-12-09

基金

国家自然科学基金(52272141; 51972060; 12074068; 52102159; 22103013; 12304442)

福建省自然科学基金(2022J05091; 2020J02017; 2021J06021; 2021J01190; 2020J01931; 2020H0026)

作者信息

^1．福建师范大学物理与能源学院，福州 350117

^2．福建省先进高温超导材料工程研究中心，福州 350117

通讯作者:

陈大钦（1978—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230915

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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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