Abstract
Afterglow luminescent materials display an unusual phenomenon of delayed emission, primarily due to electron or hole traps. A lot of pioneering work on green and blue emitting afterglow luminescent materials have been reported, however, a handful of lattices are known to exhibit red emission. Red-emanating afterglow luminescent materials are desirable for tactical defence applications due to their lower sensitivity, particularly in dark conditions. A series of red-emanating CaTiO3: Pr3+ phosphor materials were prepared and the role of Zn ions in escalating the photoluminescence (PL) properties was studied. Detailed characterization of the as-synthesized phosphors revealed orthorhombic structure and contraction in unit cell volume was observed upon zinc incorporation. Broad excitation spectrum and sharp peak at 618 nm (red emission) due to transition from 1D2 - 3H4 were observed at room temperature. Ca(0.9),Zn(0.1)TiO3: 0.25 mol% Pr3+ phosphor was found to emit enhanced PL intensity with an afterglow duration of 12 min. At 373 K, the optimized phosphor retained 76% of its initial emission intensity which indicates excellent thermal stability. The development of luminescent security ink followed by deposition onto various substrates was also discussed. The aqueous stability of the deposited patterns was tested on a time scale of more than 10 days. Security ink can be used for anti-counterfeiting applications such as safeguarding important documents and consumable-driven goods.
Similar content being viewed by others
Data availability
All data that support the findings of this study are included in the article.
References
L. Yang, S. Gai, H. Ding, D. Yang, L. Feng, P. Yang, Recent progress in inorganic afterglow materials: mechanisms, persistent luminescent properties, modulating methods, and bioimaging applications. Adv. Opt. Mater. 11(11), 2202382 (2023). https://doi.org/10.1002/ADOM.202202382
J. Wang et al., Multi-modal anti-counterfeiting and encryption enabled through silicon-based materials featuring pH-responsive fluorescence and room-temperature phosphorescence. Nano Res. 13(6), 1614–1619 (2020). https://doi.org/10.1007/S12274-020-2781-1/METRICS
J. Xu, S. Tanabe, Persistent luminescence instead of phosphorescence: History, mechanism, and perspective. J. Lumin. 205, 581–620 (2019). https://doi.org/10.1016/J.JLUMIN.2018.09.047
M.S. Abdelrahman, H. Ahmed, T.A. Khattab, Optical and luminescent properties of Lanthanide-Doped Strontium aluminates. Progress Opt. Sci. Photonics. 25, 333–354 (2023). https://doi.org/10.1007/978-981-99-4145-2_13/COVER
J. Kong, A. Meijerink, Identification and Quantification of Charge Transfer in CaAl2O4:Eu2+,Nd3 + Persistent Phosphor. Adv. Opt. Mater. 11, 2203004 (2023). https://doi.org/10.1002/ADOM.202203004
D. Poelman, N. Avci, P.F. Smet, Measured luminance and visual appearance of multi-color persistent phosphors. Opt. Express 17(1), 358 (2009). https://doi.org/10.1364/OE.17.000358
M. Lastusaari et al., Wavelength-sensitive energy storage in Sr3MgSi2O8:Eu2+,Dy3+. J. Therm. Anal. Calorim. 121(1), 29–35 (2015). https://doi.org/10.1007/S10973-015-4571-7
Y. Wang, H. Guo, Research Advances on Human-Eye-Sensitive Long Persistent Luminescence Materials. Front. Chem. 9, 654347 (2021). https://doi.org/10.3389/FCHEM.2021.654347/BIBTEX
X. Wang, Y. Mao, Recent advances in Pr3+-activated persistent phosphors. J. Mater. Chem. C Mater. 10(10), 3626–3646 (2022). https://doi.org/10.1039/D2TC00208F
K. Lu et al., Effects of praseodymium doping on the electrical properties and aging effect of InZnO thin-film transistor. J. Mater. Sci. 54(24), 14778–14786 (2019). https://doi.org/10.1007/S10853-019-03941-7/METRICS
E.G. Hilario et al., Red emitting CaTiO3: Pr3 + nanophosphors for rapid identification of high contrast latent fingerprints. Nanotechnology 31(36), 364007 (2020). https://doi.org/10.1088/1361-6528/AB93EE
B. Wang et al., Design, Preparation, and Characterization of a Novel Red Long-Persistent Perovskite Phosphor: Ca3Ti2O7:Pr3+. Inorg. Chem. 54(23), 11299–11306 (2015). https://doi.org/10.1021/ACS.INORGCHEM.5B01894/SUPPL_FILE/IC5B01894_SI_001.PDF
E. Pinel, P. Boutinaud, R. Mahiou, What makes the luminescence of Pr3 + different in CaTiO3 and CaZrO3 ? J. Alloys Compd. 380, 1–2 (2004). https://doi.org/10.1016/J.JALLCOM.2004.03.048
B. Kahouadji, L. Guerbous, D.J. Jovanović, M.D. Dramićanin, Temperature dependence of red emission in YPO4:Pr3 + nanopowders. J. Lumin. 241, 118499 (2022). https://doi.org/10.1016/J.JLUMIN.2021.118499
D.V. Sunitha et al., CdSiO3:Pr3+ nanophosphor: Synthesis, characterization and thermoluminescence studies. Spectrochim Acta A Mol Biomol Spectrosc 99, 279–287 (2012). https://doi.org/10.1016/J.SAA.2012.08.057
S. Liu et al., Photoluminescence and afterglow behavior of orange-reddish Pr3+-activated Sr3Al2O6 phosphor. J. Solid State Chem. 294, 121861 (2021). https://doi.org/10.1016/J.JSSC.2020.121861
M. Ju et al., Insights into the Microstructures and Energy Levels of Pr3+-Doped YAlO3Scintillating Crystals. Inorg. Chem. 60(7), 5107–5113 (2021). https://doi.org/10.1021/ACS.INORGCHEM.1C00021/
X. Yang et al., Low-temperature red long-persistent luminescence of Pr3+ doped NaNbO3 with a perovskite structure. J. Lumin. 208, 290–295 (2019). https://doi.org/10.1016/J.JLUMIN.2018.12.066
Y. Jin, Y. Hu, L. Chen, X. Wang, G. Ju, Luminescent properties of a red afterglow phosphor Ca2SnO4:Pr3+. Opt. Mater. 35(7), 1378–1384 (2013). https://doi.org/10.1016/J.OPTMAT.2013.02.008
P. Yang et al., Tailoring lanthanide doping in perovskite CaTiO3 for luminescence applications. Phys. Chem. Chem. Phys. 19(24), 16189–16197 (2017). https://doi.org/10.1039/C7CP01953J
Q. Kuang, X. Hou, C. Du, X. Wang, D. Gao, Recent advances in the anti-counterfeiting applications of long persistent phosphors. Phys. Chem. Chem. Phys. 25(27), 17759–17768 (2023). https://doi.org/10.1039/D3CP01818K
A. Zhu, J. Wang, Y. Du, D. Zhao, Q. Gao, Effects of Zn impurities on the electronic properties of Pr doped CaTiO3. Phys. B Condens. Matter 407(5), 849–854 (2012). https://doi.org/10.1016/J.PHYSB.2011.12.096
R. Chen, Y. Gao, Y. Gao, Synthesis and luminescence properties of CaTiO3:Pr3+, Ni2 + red phosphor. Solid State Sci. 89, 161–166 (2019). https://doi.org/10.1016/J.SOLIDSTATESCIENCES.2019.01.006
G. Swati et al., Novel flux-assisted synthesis for enhanced afterglow properties of (Ca,Zn)TiO3:Pr3+ phosphor. J. Alloys Compd. 698, 930–937 (2017). https://doi.org/10.1016/J.JALLCOM.2016.12.316
B.N. Swathi et al., Designing vivid green Sr9Al6O18:Er3 + phosphor for information encryption and nUV excitable cool-white LED applications. J. Lumin. 257, 119618 (2023). https://doi.org/10.1016/J.JLUMIN.2022.119618
V. Butticè, F. Caviggioli, C. Franzoni, G. Scellato, P. Stryszowski, N. Thumm, Counterfeiting in digital technologies: An empirical analysis of the economic performance and innovative activities of affected companies. Res. Policy 49(5), 103959 (2020). https://doi.org/10.1016/J.RESPOL.2020.103959
W. Ren, G. Lin, C. Clarke, J. Zhou, D. Jin, Optical Nanomaterials and Enabling Technologies for High-Security-Level Anticounterfeiting. Adv. Mater. 32, 1901430 (2020). https://doi.org/10.1002/ADMA.201901430
E. Moretti et al., Luminescent Eu-doped GdVO4 nanocrystals as optical markers for anti-counterfeiting purposes. Chem. Pap. 71(1), 149–159 (2017). https://doi.org/10.1007/S11696-016-0081-8/METRICS
M.R. Carro-Temboury, R. Arppe, T. Vosch, T.J. Sørensen, An optical authentication system based on imaging of excitation-selected lanthanide luminescence. Sci. Adv. (2018). https://doi.org/10.1126/SCIADV.1701384
J. Andres, R.D. Hersch, J.E. Moser, A.S. Chauvin, A New Anti-Counterfeiting Feature Relying on Invisible Luminescent Full Color Images Printed with Lanthanide-Based Inks. Adv. Funct. Mater. 24(32), 5029–5036 (2014). https://doi.org/10.1002/ADFM.201400298
S. Vaidyanathan, Recent progress on lanthanide-based long persistent phosphors: an overview. J. Mater. Chem. C Mater. 11(26), 8649–8687 (2023). https://doi.org/10.1039/D2TC05243A
P. Singh, R.S. Yadav, S.B. Rai, Enhanced photoluminescence in a Eu3 + doped CaTiO3 perovskite phosphor via incorporation of alkali ions for white LEDs. J. Phys. Chem. Solids 151, 109916 (2021). https://doi.org/10.1016/J.JPCS.2020.109916
U. Mizutani, H. Sato, T.B. Massalski, The original concepts of the Hume-Rothery rule extended to alloys and compounds whose bonding is metallic, ionic, or covalent, or a changing mixture of these. Prog Mater Sci 120, 100719 (2021). https://doi.org/10.1016/J.PMATSCI.2020.100719
J. Goethals, A. Bedidi, C. Fourdrin, M. Tarrida, S. Rossano, Experimental study of trivalent rare-earth element incorporation in CaTiO3 perovskite: evidence for a new substitution mechanism. Phys. Chem. Miner. 46(10), 1003–1015 (2019). https://doi.org/10.1007/S00269-019-01058-6/METRICS
Q. Dong, C. Huang, X. Huang, L. He, Multicolor luminescence from CaZnOS: Bi3+, Eu3 + for stress sensing and multimode anti-counterfeiting. J. Alloys Compd. 967, 171687 (2023). https://doi.org/10.1016/J.JALLCOM.2023.171687
Y.C. Lin, M. Bettinelli, S.K. Sharma, B. Redlich, A. Speghini, M. Karlsson, Unraveling the impact of different thermal quenching routes on the luminescence efficiency of the Y3Al5O12:Ce3+ phosphor for white light emitting diodes. J. Mater. Chem. C Mater. 8(40), 14015–14027 (2020). https://doi.org/10.1039/D0TC03821K
Red Luminescence in, Pr3+-Doped Calcium Titanates - Diallo – 1997 - physica status solidi (a) - Wiley Online Library. Accessed: Sep. 18, 2023. [Online]. Available: https://onlinelibrary.wiley.com/doi/epdf/10.1002/1521-396X%28199703%29160%3A1%3C255%3A%3AAID-PSSA255%3E3.0.CO%3B2-Y
S. thapa, G. Adhikari, H. Zhu, A. Grigoriev, Zhu, Zn-Alloyed All-inorganic Halide perovskite-Based White Light-emitting Diodes with Superior color Quality. Sci. Rep. (2019). https://doi.org/10.1038/s41598-019-55228-1
A. Kumar et al., Improvement in upconversion/downshifting luminescence of Gd2O3:Ho3+/Yb3 + phosphor through Ca2+ / Zn2 + incorporation and optical thermometry studies. Mater. Res. Bull. 112, 28–37 (2019). https://doi.org/10.1016/J.MATERRESBULL.2018.11.031
J. Zhang, Y. Fan, Z. Chen, J. Wang, P. Zhao, B. Hao, Enhancing the photoluminescence intensity of CaTiO3:Eu3 + red phosphors with magnesium. J. Rare Earths 33(10), 1036–1039 (2015). https://doi.org/10.1016/S1002-0721(14)60523-8
Y. Inaguma et al., Temperature dependence of luminescence properties of praseodymium-doped perovskite CaTiO3:Pr3+. Thermochim Acta 532, 168–171 (2012). https://doi.org/10.1016/J.TCA.2011.02.036
Z. Barandiarán, M. Bettinelli, L. Seijo, Color control of Pr3+ luminescence by electron-hole recombination energy transfer in CaTiO3 and CaZrO3. J. Phys. Chem. Lett. 8(13), 3095–3100 (2017). https://doi.org/10.1021/ACS.JPCLETT.7B01158/SUPPL_FILE/JZ7B01158_SI_001.PDF
S.M. Chung et al., The effects of zinc on the characteristics of (Zn,Ca)TiO3:Pr3+ phosphors. J. Cryst. Growth 326(1), 94–97 (2011). https://doi.org/10.1016/J.JCRYSGRO.2011.01.060
G. Jyothi, L.S. Kumari, K.G. Gopchandran, Site selective substitution and its influence on photoluminescence properties of Sr0.8Li0.2Ti0.8Nb0.2O3:Eu3 + phosphors. RSC Adv. 7(45), 28438–28451 (2017). https://doi.org/10.1039/C7RA03598E
M.F. García-Mendoza et al., CaTiO3 perovskite synthetized by chemical route at low temperatures for application as a photocatalyst for the degradation of methylene blue. J. Mater. Sci. 34(10), 1–11 (2023). https://doi.org/10.1007/S10854-023-10309-W/METRICS
H.W. Eng, P.W. Barnes, B.M. Auer, P.M. Woodward, Investigations of the electronic structure of d0 transition metal oxides belonging to the perovskite family. J. Solid State Chem. 175(1), 94–109 (2003). https://doi.org/10.1016/S0022-4596(03)00289-5
H. Cheng, Y. Feng, Y. Fu, Y. Zheng, Y. Shao, Y. Bai, Understanding and minimizing non-radiative recombination losses in perovskite light-emitting diodes. J. Mater. Chem. C Mater. 10(37), 13590–13610 (2022). https://doi.org/10.1039/D2TC01869A
R. Dangi et al., Effect of oxygen vacancy on the crystallinity and optical band gap in tin oxide thin film. Energies 16(6), 2653 (2023). https://doi.org/10.3390/EN16062653
S. Sasidharan, G. Jyothi, K.G. Gopchandran, Solution combustion synthesis and luminescence dynamics of CaTiO3: Eu3+, Y3 + nanophosphors. J. Lumin. (2021). https://doi.org/10.1016/j.jlumin.2021.118048
X. Liu et al., Effect of ZnO on structure and luminescence properties of Ce3+-Yb3 + co-doped Na2O–CaO–SiO2–Al2O3 glasses for solar panel applications. Opt. Mater. 142, 113996 (2023). https://doi.org/10.1016/J.OPTMAT.2023.113996
P. Singh, H. Mishra, P.C. Pandey, S.B. Rai, Structure, photoluminescence properties, and energy transfer phenomenon in Sm3+/Eu3+ co-doped CaTiO3 phosphors. New J. Chem. 47(3), 1460–1471 (2023). https://doi.org/10.1039/D2NJ05774C
S. Sasidharan, G. Jyothi, S. Sameera, K.G. Gopchandran, Perovskite titanates at the nanoscale: Tunable luminescence by energy transfer and enhanced emission with Li + co-doping. J. Solid State Chem. (2020). https://doi.org/10.1016/j.jssc.2020.121449
H. Takahashi, M. Hagiwara, S. Fujihara, Redox-induced dual optical switching of CaTiO3:Pr3+ phosphor nanoparticles synthesized by sol–gel method. J Solgel Sci Technol 104(3), 694–701 (2022). https://doi.org/10.1007/S10971-022-05791-3/METRICS
P. Boutinaud, L. Sarakha, E. Cavalli, M. Bettinelli, P. Dorenbos, R. Mahiou, About red afterglow in Pr3 + doped titanate perovskites. J. Phys. D Appl. Phys. 42(4), 045106 (2009). https://doi.org/10.1088/0022-3727/42/4/045106
W. Jia, D. Jia, T. Rodriguez, D.R. Evans, R.S. Meltzer, W.M. Yen, UV excitation and trapping centers in CaTiO3:Pr3+. J. Lumin. 119–120, 13–18 (2006). https://doi.org/10.1016/J.JLUMIN.2005.12.067
P. Wang, X. Xu, D. Zhou, X. Yu, J. Qiu, Sunlight activated long-lasting luminescence from Ba5Si8O21: Eu2+,Dy3 + phosphor. Inorg. Chem. 54(4), 1690–1697 (2015). https://doi.org/10.1021/IC5026312/ASSET/
S. Jana, A. Mondal, J. Manam, S. Das, Pr3 + doped BaNb2O6 reddish orange emitting phosphor for solid state lighting and optical thermometry applications. J. Alloys Compd. (2020). https://doi.org/10.1016/j.jallcom.2019.153342
D. Haranath et al., Rare-earth free yellow-green emitting NaZnPO4:Mn phosphor for lighting applications. Appl. Phys. Lett. (2012). https://doi.org/10.1063/1.4768214/128674
G. Swati, D. Bidwai, D. Haranath, Red emitting CaTiO3: Pr3+ nanophosphors for rapid identification of high contrast latent fingerprints. Nanotechnology (2020) iopscience.iop.org, Accessed: Sep. 05, 2023. [Online]. Available: https://iopscience.iop.org/article/10.1088/1361-6528/ab93ee/meta
P.J. Dereń, R. Pazik, W. Strek, P. Boutinaud, R. Mahiou, Synthesis and spectroscopic properties of CaTiO3 nanocrystals doped with Pr3 + ions. J Alloys Compd 451(1–2), 595–599 (2008). https://doi.org/10.1016/J.JALLCOM.2007.04.197
S. Li, X. Liang, Preparation and luminescent properties of CaTiO 3: Pr 3+, Al 3 + persistent phosphors by nitrate-citric acid combustion method. J. Mater. Sci.: Mater. Electron. 19(12), 1147–1152 (2008). https://doi.org/10.1007/S10854-007-9502-3/FIGURES/7
J. Mu, J. Liu, L. Gao, Upconversion fluorescence modulation of CaTiO3: Yb3+/Er3 + nanocubes via Zn2 + introduction. Optoelectron. Lett. 18(3), 129–134 (2022). https://doi.org/10.1007/S11801-022-1125-7/METRICS
G. Kim, S.J. Lee, Y.J. Kim, The effects of zinc on the structural and luminescent properties of Ca1 – xZnxTiO3:Pr3 + phosphors. Opt. Mater. 34(11), 1860–1864 (2012). https://doi.org/10.1016/J.OPTMAT.2012.05.012
D. Bidwai, Y.R. Parauha, M.K. Sahu, S.J. Dhoble, M. Jayasimhadri, G. Swati, Synthesis and luminescence characterization of aqueous stable Sr3MgSi2O8: Eu2+, Dy3 + long afterglow nanophosphor for low light illumination. J. Solid State Chem. 310, 123089 (2022). https://doi.org/10.1016/J.JSSC.2022.123089
G.V. Kanmani, V. Ponnusamy, G. Rajkumar, S.M.M. Kennedy, A new Eu3+-activated milarite-type potassium magnesium zinc silicate red-emitting phosphor for forensic applications. J. Mater. Sci.: Mater. Electron. 34(8), 1–25 (2023). https://doi.org/10.1007/S10854-023-10087-5/TABLES/9
A.M. Achari, V. Perumalsamy, G. Swati, A. Khare, SrAl2O4:Eu2+,Dy3+ Long Afterglow Phosphor and Its Flexible Film for Optomechanical Sensing Application. ACS Omega 8(48), 45483–45494 (2023). https://doi.org/10.1021/ACSOMEGA.3C05222/SUPPL_FILE/AO3C05222_SI_001.PDF
Funding
We acknowledge DST SERB for providing financial support under the scheme SRG project fellowship (Sanction order no. SRG/2021/001109) to carry out this work.
Author information
Authors and Affiliations
Contributions
PV: Conceptualization, Methodology, Investigation, Data curation, Writing–original draft. GS: Conceptualization, Supervision, Writing–review & editing, Project administration.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Vanishree, P., Swati, G. Enhanced photoluminescence in (Ca, Zn)TiO3: Pr3+ afterglow phosphor for anti-counterfeiting application. J Mater Sci: Mater Electron 35, 597 (2024). https://doi.org/10.1007/s10854-024-12350-9
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s10854-024-12350-9