Luminescence Property of the Multicolor Persistent Luminescence Materials for Dynamic Anti-counterfeiting Applications

doi:10.15541/jim20210043

Abstract

Abstract:

Luminescent anti-counterfeiting has characteristics of visibility and convenience, which is a popular method in many anti-counterfeiting technologies. However, this anti-counterfeiting luminescent materials have the shortcomings of single emission color and static anti-counterfeiting pattern, leading to easy imitablity. It is urgent to develop new luminescent materials that can achieve dynamic and more reliable anti-counterfeiting performance. In this research, the multicolor persistent luminescence material, chromium doped zinc gallogermanate, was prepared by hydrothermal method. Its persistent luminescence property and dynamic anti-counterfeiting application potential were investigated. Experimental results show that the emission intensity in blue-green and red light regions can be adjusted by changing the raw materials ratio of gallium to germanium. Under the excitation of 254 and 365 nm UV light, a series of samples are observed to be white and red, respectively, indicating multi-mode luminescence characteristics. Furthermore, the decay rate of blue, green and red components in white afterglow is different, so the afterglow color can change dynamically over time. Anti-counterfeiting patterns, designed based on this multicolor afterglow features, improves the security through dynamic change of afterglow color in the time dimension, demonstrating the potential application in dynamic anti-counterfeiting.

Key words: persistent luminescence, multicolor afterglow, dynamic anti-counterfeiting

CLC Number:

O433

ZHANG Cong, LI Yurou, SHAO Kang, LIN Jing, WANG Kai, PAN Zaifa. Luminescence Property of the Multicolor Persistent Luminescence Materials for Dynamic Anti-counterfeiting Applications[J]. Journal of Inorganic Materials, 2021, 36(12): 1256-1262.

Figures/Tables 8

Fig. 1 XRD patterns of (1-x)ZnGa2O4-xZn2GeO4(x=0.5, 0.6, 0.7, 0.8, 0.9)

Fig. 2 TEM images of (1-x)ZnGa2O4-xZn2GeO4 (a) x=0.5; (b) x=0.6; (c) x=0.7; (d) x=0.8; (e) x=0.9

Fig. 3 Normalized emission spectra of ZGGO : Cr series samples under 273 nm excitation (a), and comparison of luminescence intensity of ZGGO : Cr series samples in blue-green and NIR region (b) The inset in (b) shows the I696 nm/I500 nm changing with x

Fig. 4 Normalized excitation spectra of ZGGO : Cr (x=0.7) (a), and emission spectra of ZGGO : Cr (x=0.7) under 254 nm and 365 nm excitation (b) Insets in (b) show the photographic images of the sample under 254 and 365 nm irradiation

Fig. 5 Persistent luminescence decay curves of ZGGO : Cr with Xenon lamp pre-charged for 5 min (a) 460 nm; (b) 540 nm; (c) 696 nm Colourful figures are available on website

Fig. 6 Emission spectra of ZGGO : Cr (x=0.7) samples before and after high temperature treatment (a) and persistent luminescence decay curves of ZGGO : Cr after high temperature treatment with Xenon lamp pre-charged for 5 min (b)

Fig. 7 Normalized emission spectra of Zn2GaO4, Zn2GeO4, Zn2GeO4 : Cr3+, and Zn2GaO4 : Cr3+ (λex=254 nm)

Fig. 8 Manufacturing principle of anti-counterfeiting pattern (a), images of the luminescent pattern under 254 nm UV lamp and different decay time (b), and images of the luminescent pattern under 365 nm UV lamp and different decay time (c)

References 25

[1]	ARPPE R, SØRENSEN T J. Physical unclonable functions generated through chemical methods for anti-counterfeiting. Nature Reviews Chemistry, 2017, 1(4): 0031. DOI URL
[2]	LIM K T P, LIU H, LIU Y, et al. Holographic colour prints for enhanced optical security by combined phase and amplitude control. Nature Communications, 2019, 10(1): 25-32. DOI URL
[3]	ZHU S, MENG Q, WANG L, et al. Highly photoluminescent carbon dots for multicolor patterning, sensors, and bioimaging. Angewandte Chemie International Edition, 2013, 52(14): 3953-3957. DOI URL
[4]	ZHOU W, ZHUANG J, LI W, et al. Towards efficient dual-emissive carbon dots through sulfur and nitrogen co-doped. Journal of Materials Chemistry C, 2017, 5(32): 8014-8021. DOI URL
[5]	WANG L, TAN W H. Multicolor FRET silica nanoparticles by single wavelength excitation. Nano Letters, 2006, 6(1): 84-88. DOI URL
[6]	KRUTZIK P, NOLAN G. Fluorescent cell barcoding in flow cytometry allows high-throughput drug screening and signaling profiling. Nature Methods, 2006, 3: 361-368. DOI URL
[7]	ZHOU B, HUANG J, YAN L, et al. Probing energy migration through precise control of interfacial energy transfer in nanostructure. Advanced Materials, 2019, 31: 1806308.
[8]	YAO W, TIAN Q, TIAN B, et al. Dual upconversion nanophotoswitch for security encoding. Science China Materials, 2019, 62(3): 368-378. DOI URL
[9]	ZHAO S, WANG Z, MA Z, et al. Achieving multimodal emission in Zn₄B₆O₁₃ : Tb³⁺, Yb³⁺ for information encryption and anti- counterfeiting. Inorganic Chemistry, 2020, 59(21): 15681-15689. DOI URL
[10]	WANG J, MA Q, ZHENG W, et al. One-dimensional luminous nanorods featuring tunable persistent luminescence for autofluorescence-free biosensing. ACS Nano, 2017, 11(8): 8185-8191. DOI URL
[11]	GU L, SHI H, GU M, et al. Dynamic ultralong organic phosphorescence by photoactivation. Angewandte Chemie International Edition, 2018, 57(28): 8425-8431. DOI URL
[12]	KALININ Y V, PANDEY S, HONG J, et al. A chemical display: generating animations by controlled diffusion from porous voxels. Advanced Functional Materials, 2015, 25(26): 3998-4004. DOI URL
[13]	ZHANG Y, HUANG R, LI H, et al. Triple-mode emissions with invisible near-infrared after-glow from Cr³⁺-doped zinc aluminum germanium nanoparticles for advanced anti-counterfeiting applications. Small, 2020, 16(35): 2003121. DOI URL
[14]	GANGWAR A K, KANIKA K, KEDAWAT G, et al. Single excitable dual emissive novel luminescent pigment to generate advanced security features for anti-counterfeiting applications. Journal of Materials Chemistry C, 2019, 7(44): 13867-13877. DOI URL
[15]	PAN Z, LU Y, LIU F. Sunlight-activated long-persistent luminescence in the near-infrared from Cr³⁺-doped zinc gallogermanates. Nature Materials, 2012, 11(1): 58-63. DOI URL
[16]	LI J Y, YAN X P. Synthesis of functionalized triple-doped zinc gallogermanate nanoparticles with superlong near-infrared persistent luminescence for long-term orally administrated bioimaging. Nanoscale, 2016, 8: 14965-14970. DOI URL
[17]	LI L, PAN F, TANNER P A, et al. Tunable dual visible and near- infrared persistent luminescence in doped zinc gallogermanate nanoparticles for simultaneous photosensitization and bioimaging. ACS Applied Nano Materials, 2020, 3(2): 1961-1971. DOI URL
[18]	BAI Q, LI P, WANG Z, et al. Inducing tunable host luminescence in Zn₂GeO₄ tetrahedral materials via doping Cr³⁺. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2018, 199: 179-188. DOI URL
[19]	ZHOU Z H, ZHENG W, KONG J T, et al. Rechargeable and LED- activated ZnGa₂O₄ : Cr³⁺near-infrared persistent luminescence nanoprobes for background-free biodetection. Nanoscale, 2017, 9: 6846-6853. DOI URL
[20]	WANG K, YAN L P, SHAO K, et al. Near-infrared afterglow enhancement and trap distribution analysis of silicon-chromium co-doped persistent luminescence materials Zn₁₊_xGa_2-2_xSi_xO₄:Cr³⁺. Journal of Inorganic Materials, 2019, 34(9): 983-990.
[21]	LI Y, GECEVICIUS M, QIU J R. Long persistent phosphors-from fundamentals to applications. Chemical Society Reviews, 2016, 45(8): 2090-2136. DOI URL
[22]	ZHANG Y, WU Z, GENG D, et al. Full color emission in ZnGa₂O₄: simultaneous control of the spherical morphology, luminescent, and electric properties via hydrothermal approach. Advanced Functional Materials, 2014, 24(42): 6581-6593. DOI URL
[23]	LIU Z, JING X, WANG L. Luminescence of native defects in Zn₂GeO₄. Journal of the Electrochemical Society, 2007, 154(6): H500-H506. DOI URL
[24]	CHI F F, WEI X T, JIANG B, et al. Luminescence properties and the thermal quenching mechanism of Mn²⁺ doped Zn₂GeO₄ long persistent phosphors. Dalton Transactions, 2018, 47(4): 1303-1311. DOI URL
[25]	HE H, ZHANG Y, PAN Q, et al. Controllable synthesis of Zn₂GeO₄ : Eu nanocrystals with multi-color emission for white light-emitting diodes. Journal of Materials Chemistry C, 2015, 3(21): 5419-5429. DOI URL