空间限域铅离子与钙钛矿纳米晶间的可逆转换与信息存储应用

doi:10.15541/jim20210270

无机材料学报 ›› 2022, Vol. 37 ›› Issue (4): 445-451.DOI: 10.15541/jim20210270

所属专题：【能源环境】金属有机框架材料；【能源环境】钙钛矿

空间限域铅离子与钙钛矿纳米晶间的可逆转换与信息存储应用

张国庆¹^,²(), 秦鹏¹(), 黄富强¹^,²^,³()

1.中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050
2.上海科技大学物理科学与技术学院, 上海 201210
3.北京大学化学与分子工程学院, 稀土材料化学及应用国家重点实验室, 北京 100871

收稿日期:2021-04-26 修回日期:2021-06-29 出版日期:2022-04-20 网络出版日期:2021-07-12
通讯作者: 秦鹏, 副研究员. E-mail: qinpeng@mail.sic.ac.cn;
黄富强, 研究员. E-mail: huangfq@mail.sic.ac.cn
作者简介:张国庆(1992–), 男, 博士研究生. E-mail: zgq201209@foxmail.com

Reversible Conversion between Space-confined Lead Ions and Perovskite Nanocrystals for Confidential Information Storage

ZHANG Guoqing¹^,²(), QIN Peng¹(), HUANG Fuqiang¹^,²^,³()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
3. State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Received:2021-04-26 Revised:2021-06-29 Published:2022-04-20 Online:2021-07-12
Contact: QIN Peng, associate professor. E-mail: qinpeng@mail.sic.ac.cn;
HUANG Fuqiang, professor. E-mail: huangfq@mail.sic.ac.cn
About author:ZHANG Guoqing (1992–), male, PhD candidate. E-mail: zgq201209@foxmail.com
Supported by:
National Natural Science Foundation of China(21871008);National Natural Science Foundation of China(51872315);Key Research Program of Frontier Science, Chinese Academy of Sciences(QYZDJ-SSW-JSC013)

摘要/Abstract

摘要：

发光材料在机密信息保护与防伪领域中发挥着重要作用。钙钛矿纳米晶作为一类高效低成本发光材料可通过两步法原位转换获得, 使其在信息加密、解密领域极具应用前景。本研究探索了“不可见”铅有机框架和发光MAPbBr₃钙钛矿纳米晶间的可逆转换, 以及它们在荧光打印信息存储中的应用。通过铅离子与2-甲基咪唑配位构建新型金属有机框架, 实现铅离子限域分布, 在此基础上通过与甲胺溴原位反应生成钙钛矿纳米晶。利用金属有机框架在可见/紫外光下无光响应的特性, 通过墨水打印对信息进行加密存储。加密信息经甲胺溴喷雾处理, 引发原位反应生成钙钛矿纳米晶, 在紫外光下表现出强光致发光特性, 实现信息解密。利用甲胺溴和水作为解密和加密试剂可实现荧光的多次循环显示与消除。

关键词: 钙钛矿纳米晶, 光致发光, 墨水打印, 信息存储

Abstract:

Luminescent materials have been widely used in confidential information protection and anticounterfeiting. Luminescent lead halide perovskite nanocrystals, which can be converted from the lead source through a two-step method, are attractive candidates for information encryption and decryption. Herein, the reversible conversion between the invisible lead-organic framework and the luminescent MAPbBr₃ nanocrystals is achieved, together with their further application on information storage by inkjet printing technology. The lead ions are embedded into the metal-organic frameworks through coordination with the 2-methylimidazole linkers. The inherent confined distribution of lead ions facilitates the in-situ growth of perovskite nanocrystals in the second step without the assistance of external bulky ligands. The recorded information was firstly encrypted by the lead organic frameworks, which is invisible under ambient and UV light. After reacting with methylammonium bromide, the perovskite nanocrystals are in-situ formed, and the information becomes readable under UV light. Using methylammonium bromide and water as the decryption and encryption reagents could also switch on/off the luminescence, therefore, realizing the confidential information storage.

Key words: perovskite nanocrystals, photoluminescence, inkjet printing, information storage

中图分类号:

TQ424

张国庆, 秦鹏, 黄富强. 空间限域铅离子与钙钛矿纳米晶间的可逆转换与信息存储应用[J]. 无机材料学报, 2022, 37(4): 445-451.

ZHANG Guoqing, QIN Peng, HUANG Fuqiang. Reversible Conversion between Space-confined Lead Ions and Perovskite Nanocrystals for Confidential Information Storage[J]. Journal of Inorganic Materials, 2022, 37(4): 445-451.

图/表 11

Fig. 1 Schematic diagram of in-situ growth of MAPbBr3 NCs from Pb-ZIF framework and optical images of Pb-ZIF (left under ambient light), and MAPbBr3 NCs@Pb-ZIF (right under UV light)

Fig. 2 (a) TEM image and (b) SAED pattern of Pb-ZIF powders SEM images of (c, d) Pb-ZIF and (e) MAPbBr3 NCs@Pb-ZIF powders, and (f) Elemental mappings of MAPbBr3 NCs@Pb-ZIF powder

Fig. 3 XPS spectra of Pb-ZIF and MAPbBr3 NCs@Pb-ZIF samples (a) Survey XPS spectra; (b) Pb4f XPS spectra (The offset of Pb 4f peaks marked by an arrow); (c) Br3d XPS spectra of Pb-ZIF and MAPbBr3 NCs@Pb-ZIF samples; (d) Br3d XPS spectrum of MAPbBr3 NCs@Pb-ZIF sample after etching

Fig. 4 (a) Absorption and (b) steady-state PL spectra of Pb-ZIF and MAPbBr3 NCs@Pb-ZIF samples; (c) PL decay kinetics of MAPbBr3 NCs@Pb-ZIF sample; (d) Schematic confidential information encryption and decryption process based on Pb-ZIF and MAPbBr3 NCs@Pb-ZIF; (e) Optical images of the printed Pb-ZIF and MAPbBr3 NCs@Pb-ZIF patterns under UV excitation

Fig. 5 SEM images of (a) pristine commercial paper, (b) commercial paper after printed with Pb-ZIF ink, (c) commercial paper with MAPbBr3 NCs@Pb-ZIF NCs, (d) representative information encryption and decryption procedure, and (e) PL intensity of the printed MAPbBr3 NCs@Pb-ZIF patterns in the five cycles of encryption and decryption measurement

Fig. S1 X-ray diffraction patterns of Pb-ZIF and MAPbBr3 NCs@Pb-ZIF powders The ideal diffraction peaks of MAPbBr3 were presented as red vertical line

Fig. S2 Additional optical images of the obtained MAPbBr3 NCs@Pb-ZIF patterns on paper under UV excitation

Fig. S3 Enlarged SEM images and corresponding Br and Pb mappings of the commercial paper with MAPbBr3 NCs@Pb-ZIF NCs

Fig. S4 (a) UV-Vis absorption spectra of the printed Pb-ZIF and MAPbBr3 NCs@Pb-ZIF patterns, (b) steady-state PL spectra and (c) PL decay kinetics of the printed MAPbBr3 NCs@Pb-ZIF patterns

Fig. S5 Thermogravimetric curve of the obtained Pb-ZIF powders

Table S1 PL lifetime for MAPbBr3 NCs@Pb-ZIF powders

	τ₁/ns	f₁	τ₂/ns	f₂	τ_avg/ns
Powder	4.0	82.7%	16.3	17.3%	6.1

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空间限域铅离子与钙钛矿纳米晶间的可逆转换与信息存储应用

Reversible Conversion between Space-confined Lead Ions and Perovskite Nanocrystals for Confidential Information Storage

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