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

doi:10.15541/jim20210270

Abstract

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

CLC Number:

TQ424

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.

Figures/Tables 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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