共沉淀法制备Cs2Ag0.1Na0.9BiCl6:Tm3+双钙钛矿及其近红外发光性能

doi:10.15541/jim20230005

无机材料学报 ›› 2023, Vol. 38 ›› Issue (9): 1083-1088.DOI: 10.15541/jim20230005

所属专题：【能源环境】钙钛矿(202310)

共沉淀法制备Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺双钙钛矿及其近红外发光性能

王马超¹^,²(), 唐扬敏¹^,², 邓明雪¹, 周真真¹, 刘小峰³, 王家成¹^,²(), 刘茜¹()

1.中国科学院上海硅酸盐研究所, 上海 200050
2.中国科学院大学材料科学与光电技术学院, 北京 100864
3.浙江大学材料科学与工程学院, 杭州 310027

收稿日期:2023-01-03 修回日期:2023-03-15 出版日期:2023-09-20 网络出版日期:2023-04-11
通讯作者: 王家成, 研究员. E-mail: jiacheng.wang@mail.sic.ac.cn;
刘茜, 研究员. E-mail: qianliu@mail.sic.ac.cn
作者简介:王马超(1998-), 男, 硕士研究生. E-mail: wangmachao21@mails.ucas.ac.cn
基金资助:
国家自然科学基金(92163117);国家自然科学基金(62175210);上海市自然科学基金(20ZR1465900);上海市自然科学基金(22ZR1472100)

Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺ Double Perovskite: Coprecipitation Preparation and Near-infrared Emission

WANG Machao¹^,²(), TANG Yangmin¹^,², DENG Mingxue¹, ZHOU Zhenzhen¹, LIU Xiaofeng³, WANG Jiacheng¹^,²(), LIU Qian¹()

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Science, Beijing 100864, China
3. School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China

Received:2023-01-03 Revised:2023-03-15 Published:2023-09-20 Online:2023-04-11
Contact: WANG Jiacheng, professor. E-mail: jiacheng.wang@mail.sic.ac.cn;
LIU Qian, professor. E-mail: qianliu@mail.sic.ac.cn
About author:WANG Machao (1998-), male, Master candidate. E-mail: wangmachao21@mails.ucas.ac.cn
Supported by:
National Natural Science Foundation of China(92163117);National Natural Science Foundation of China(62175210);Shanghai Municipal Natural Science Foundation(20ZR1465900);Shanghai Municipal Natural Science Foundation(22ZR1472100)

摘要/Abstract

摘要：

间接带隙的Cs₂NaBiCl₆双钙钛矿材料具有近红外宽波段发射特性, 但低发光效率限制了其在近红外发光领域的应用。本工作通过共沉淀法快速制备微米级尺寸的Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺双钙钛矿晶体, 实现了近红外荧光增强, 并系统研究了其光学吸收、光致发射(PL)、光致激发(PLE)、时间分辨光致发光和荧光量子效率(PLQY)等光学性能。共沉淀法制备的Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺的光学带隙为3.06 eV。在350 nm紫外光激发下, 可以观察到峰值位于680 nm的近红外宽峰发射, 这源于自陷激子发光。通过引入Tm³⁺作为新的发光中心, 实现了810 nm波段的近红外发光增强, 在780~830 nm波段荧光量子效率(PLQY)从1.67%提高到11.77%, 提高了6.05倍。在650~900 nm波段, Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺的近红外PLQY高达25.22%。本研究证明了共沉淀法快速制备的Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺钙钛矿作为新型近红外光源材料的可行性。

关键词: 近红外发光, 自陷激子, 共沉淀, 双钙钛矿, Cs₂Ag_0.1Na_0.9BiCl₆

Abstract:

Cs₂NaBiCl₆ double perovskite with indirect band demonstrates near-infrared (NIR) wide-band emission, but its low efficacy limits its potential applications in the field of NIR. In this work, micron-sized Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺ double perovskites were synthesized via the coprecipitation method, which shows enhanced NIR emission. Their optical absorption, photoluminescence emission (PL) and excitation (PLE), time-resolved photoluminescence, and photoluminescence quantum yield (PLQY) were investigated. The Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺ shows optical bandgap of 3.06 eV and NIR broad emission peaking at 680 nm under 350 nm excitation due to recombination of self-trapped excitons (STEs). Meanwhile, a new emission peak could be observed at 810 nm due to Tm³⁺ doping. The PLQY in the band range of 780-830 nm can be increased by 6.05 times from 1.67% to 11.77% and in the band range of 650-900 nm can reach 25.22%. This study proves the feasibility of Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺ double perovskite as new NIR emission material.

Key words: near-infrared emission, self-trapped excitons, coprecipitation, double perovskite, Cs₂Ag_0.1Na_0.9BiCl₆

中图分类号:

TQ422

王马超, 唐扬敏, 邓明雪, 周真真, 刘小峰, 王家成, 刘茜. 共沉淀法制备Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺双钙钛矿及其近红外发光性能[J]. 无机材料学报, 2023, 38(9): 1083-1088.

WANG Machao, TANG Yangmin, DENG Mingxue, ZHOU Zhenzhen, LIU Xiaofeng, WANG Jiacheng, LIU Qian. Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺ Double Perovskite: Coprecipitation Preparation and Near-infrared Emission[J]. Journal of Inorganic Materials, 2023, 38(9): 1083-1088.

图/表 5

图1 晶体的结构表征

Fig. 1 Microstructure of crystals (a) Crystal structure and (b) XRD patterns of Cs2NaBiCl6, Cs2Ag0.1Na0.9BiCl6, and Cs2Ag0.1Na0.9BiCl6:Tm3+; (c) SEM image (left) and EDS elemental mappings (right) of Cs2Ag0.1Na0.9BiCl6:Tm3+

图2 Cs2NaBiCl6, Cs2Ag0.1Na0.9BiCl6和Cs2Ag0.1Na0.9BiCl6:Tm3+的光学带隙

Fig. 2 Band gaps of Cs2NaBiCl6, Cs2Ag0.1Na0.9BiCl6 and Cs2Ag0.1Na0.9BiCl6:Tm3+ crystals (a) Optical absorption; (b) Tauc plots. Colorful figures are available on the website

图3 晶体的XPS和Raman表征

Fig. 3 XPS and Raman characterizations of crystals (a) Total XPS spectra, and (b) Ag3d, (c) Na1s, (d) Bi4f, and (e) Cl2p high-resolution XPS spectra of Cs2NaBiCl6, Cs2Ag0.1Na0.9BiCl6 and Cs2Ag0.1Na0.9BiCl6:Tm3+; (f) Raman spectra of Cs2Ag0.1Na0.9BiCl6 and Cs2NaBiCl6

图4 晶体的光学性能

Fig. 4 Optical properties of crystals (a) Photoluminescence emission (PL) spectra, (c) integrated NIR emission intensity and (d) photoluminescence quantum yield (PLQY) of Cs2NaBiCl6, Cs2Ag0.1Na0.9BiCl6 and Cs2Ag0.1Na0.9BiCl6:Tm3+; (b) excitation (PLE) spectra and (e) PL decay curves (λem = 680 nm) of Cs2Ag0.1Na0.9BiCl6 and Cs2Ag0.1Na0.9BiCl6:Tm3+; Colorful figures are available on website

图5 Cs2Ag0.1Na0.9BiCl6:Tm3+的发光原理

Fig. 5 Schematic diagram of simplified energy levels for Cs2Ag0.1Na0.9BiCl6:Tm3+

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共沉淀法制备Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺双钙钛矿及其近红外发光性能

Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺ Double Perovskite: Coprecipitation Preparation and Near-infrared Emission

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