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1.
Fluorescent materials have been widely used for anti-counterfeiting of important documents and currencies, wherein their anti-counterfeit abilities could be improved through multi-mode excitation. Herein, dual-mode-excited double-colour-emitting Er3+doped SrBi4Ti4O15 up-conversion (UC) phosphors (SBTO: Er3+) were synthesised, and their UC spectra included green (2H11/2/4S3/2 → 4I15/2) and red (4F9/2 → 4I15/2) emissions from Er3+ ions under 980 or 1550 nm excitation. However, the green emission colour of phosphors was independent of dopant concentration under 980 nm laser irradiation; whereas the final emission colour was dominated by red emission and significantly affected by contents of Er3+ under 1550 nm excitation. These observations demonstrated potential application in dual-mode double-colour anti-counterfeiting. The possible UC mechanisms and emission characteristics of the phosphors using different 980 and 1550 nm irradiation source were contrastively investigated, and some fluorescent security patterns were also designed to demonstrate the potential applications in anti-counterfeiting and concealing important information.  相似文献   

2.
《Ceramics International》2022,48(9):12578-12584
Rare earth ions doped luminescent materials have drawn considerable attention as they can generate both upconversion and downshifting emissions. Here, the rare earth ions Pr3+/Er3+ codoped perovskite oxide Bi4Ti3O12 is proposed as a dual-mode temperature sensor and anti-counterfeiting material based on its up/down-conversion luminescence. Under 481 nm excitation, the intensity ratio of green emission (~523 nm in Er3+) and red emission (~611 nm in Pr3+) brings about a very high absolute sensitivity (Sa) of 2% K?1 at 568 K and a maximum relative sensitivity (Sr) of 1.03% K?1 at 478 K in the temperature range of 298–568 K. In addition, the upconversion green emissions of Er3+ yield a relatively-high Sr of 1.1% K?1 at 298 K with 980 nm excitation, which can provide self-calibration coupled with down-conversion luminescence temperature sensing mode. Besides, this phosphor also shows tunable luminous colors for the potential application in the anti-counterfeiting field under various excitation wavelengths.  相似文献   

3.
Up-conversion luminescent (UCL) materials are excellent candidate for optical anti-counterfeiting and the exploitation of multi-wavelength NIR light triggered UC phosphors with tunable color emission is essential for reliable anti-counterfeiting technology. Herein, a series of lanthanide ions (Er3+, Er3+–Ho3+, and Yb3+–Tm3+) doped BaTiO3 submicrometer particles are synthesized through a modified hydrothermal procedure. XRD and SEM measurements were carried out to identify the structure and morphology of the samples and their UCL properties under 808, 980, and 1550 nm NIR excitation are investigated. Er3+ singly doped sample exhibits Er3+ concentration-dependent and excitation wavelength-dependent emission color from green to yellow and orange. The corresponding UC mechanisms under three NIR light excitation are clarified. Pure red emission under 1550-nm excitation was obtained by introducing small amount of Ho3+ and the fluorescent lifetime test was used to confirm the energy transfer from Er3+ to Ho3+. In addition, Yb3+–Tm3+ co-doped sample shows intense blue emission from 1G4 → 3H6 transition of Tm3+ under 980-nm excitation. As a proof of concept, the designed pattern using phosphors with red, green, and blue three primary color emissions under 1550, 808, and 980 nm NIR excitation was displayed to demonstrate their anti-counterfeiting application.  相似文献   

4.
《Ceramics International》2023,49(3):4517-4522
Fluorescent anti-counterfeiting technology has become one of the most commonly used anti-counterfeiting technologies because of its simple preparation, low cost and high safety. However, there are still some key technical problems to be solved in developing multi-mode and polychromatic fluorescent materials for high-level anti-counterfeiting. Herein, Yb3+/Er3+ codoped Cs2AgIn0.99Bi0.01Cl6 double perovskite nanocrystals (DPNCs) with dual-mode polychromatic emission were developed. Under the irradiation of 365 nm ultraviolet (UV) light, the DPNCs emitted a bright downshifting (DS) yellow light, which comes from the self-trapping excitons (STEs) recombination. While the DPNCs produced upconversion (UC) green fluorescence under the 980 nm laser excitation, which is attributed to the transitions of 2H11/2 → 4I15/2 and 4S3/2 → 4I15/2 of Er3+ ions. In view of its dual-mode and polychromatic fluorescence characteristics, a high-level anti-counterfeiting based on this fluorescent material is designed. Moreover, the brightness of the anti-counterfeiting pattern based on this material decreases very little after three months. These results indicated that the dual-mode and polychromatic DPNCs reported have potential application in information encryption and identity recognition.  相似文献   

5.
Undoped and Er3+-doped Bi2O3 thin films were sputter-deposited on Si(100) substrates. Sufficiently oxidized Bi2O3 films with refractive indices between 2.17?2.23 were obtained at a wavelength of 633 nm; these values are comparable to those of bulk Bi2O3 crystals. While the film composition was stable for deposition temperatures between room temperature (RT) and 450 °C, the refractive index steeply decreased above 450 °C and reached 1.4 at 600 °C. The lowering of the optical transmittance spectra indicated aggregation of metallic Bi and darkening of the film. All films exhibited X-ray diffraction patterns of α-Bi2O3. The direct and indirect bandgap energies derived from the Tauc plots were 3.4–3.7 eV and 1.9–2.5 eV, respectively, depending on the O2 flow rate and deposition temperature. Upon excitation of Er3+-doped Bi2O3 films at 532 nm, Er3+ emissions peaking at 1537 and 1541 nm appeared, and the photoluminescence spectra included fine structures reflecting crystal-field splitting. Resonant excitation of Er3+ 4f levels and indirect excitation via the defect levels of Bi2O3 followed by energy transfer to Er3+ contributed to the emission. The films deposited at RT with Er concentrations of 2 at.% had the emission intensity of Er3+, but concentration quenching strongly suppressed the Er3+ emission because the doped Er3+ ions stayed inside the Bi2O3 crystals. At deposition temperatures above 400 °C, the concentration quenching was mitigated possibly because out-diffusion of Er3+ ions reduced the effective number of Er3+ ions in the Bi2O3 crystalline domains.  相似文献   

6.
《Ceramics International》2020,46(11):18614-18622
Studies on lanthanide ions doped upconversion nanomaterials are increasing exponentially due to their widespread applications in various fields such as diagnosis, therapy, bio-imaging, anti-counterfeiting, photocatalysis, solar cells and sensors, etc. Here, we are reporting upconversion luminescence properties of NaBi(MoO4)2:Ln3+, Yb3+ (Ln = Er, Ho) nanomaterials synthesized at room temperature by simple co-precipitation method. Diffraction and spectroscopic studies revealed that these nanomaterials are effectively doped with Ln3+ ions in the scheelite lattice. DR UV–vis spectra of these materials exhibit two broad bands in the range of 200–350 nm correspond to MoO42− charge transfer, s-p transition of Bi3+ ions and sharp peaks due to f-f transition of Ln3+ ions. Upconversion luminescence properties of these nanomaterials are investigated under 980 nm excitation. Doping concentration of Er3+ and Yb3+ ions is optimized to obtain best upconversion photoluminescence in NaBi(MoO4)2 nanomaterials and is found to be 5, 10 mol % for Er3+, Yb3+, respectively. NaBi(MoO4)2 nanomaterials co-doped with Er3+, Yb3+ exhibit strong green upconversion luminescence, whereas Ho3+, Yb3+ co-doped materials show strong red emission. Power dependent photoluminescence studies demonstrate that emission intensity increases with increasing pump power. Fluorescence intensity ratio (FIR) and population redistribution ability (PRA) of 2H11/2 → 4I15/2, 4S3/2 → 4I15/2 transitions of Er3+ increases with increasing the Yb3+ concentration. Also, these values increase linearly with increasing the pump power up to 2 W. It reveal that these thermally coupled energy levels are effectively redistributed in co-doped samples due to local heating caused by Yb3+.  相似文献   

7.
《Ceramics International》2023,49(6):9574-9583
Here we adopt trivalent lanthanide (Ln3+ = Er3+, Er3+/Ho3+, and Yb3+/Tm3+) doped Sr2LaNbO6 (SLNO) as novel upconversion luminescence (UCL) materials for achieving UCL and optical temperature sensing under 980 nm excitation. Specifically, Er3+ single doped Sr2LaNbO6 phosphors present bright high-purity green emission under the 980 nm excitation. While co-doping with the Ho3+ ions, the component of red emission from Er3+ ions increases significantly and sample show a remarkable enhancement of luminescent intensity relative to SLNO:Er3+ sample. The above-mentioned phosphors and Yb3+/Tm3+ co-doped phosphor (blue emission) successfully achieve high-purity trichromatic UCL and mixed white light output in the same host. Furthermore, the temperature sensing performance of the SLNO:Er3+/Ho3+ phosphor based on the fluorescence intensity ratio (FIR) is systematically studied for the first time. The temperature sensing based on the non-thermal coupling levels (NTCLs) exhibit higher sensitivity than that based on the thermal coupling levels (TCLs). The maximum absolute and relative sensitivity for 4F9/2/4I9/2 NTCLs reach 0.16803 K?1 at 427 K and 0.01591 K?1 at 641 K, respectively. Interestingly, NIR emission of 4I9/2 → 4I15/2 transition presents a thermal enhancement, while visible emissions show thermal quenching. These results indicate that the Ln3+ doped Sr2LaNbO6 UCL phosphors have potential applications in the fields of non-contact temperature sensors, full-color displays, and anti-counterfeiting.  相似文献   

8.
Er3+,Yb3+ co-doped CaWO4 polycrystalline powders were prepared by a solid-state reaction and their up-conversion (UC) luminescence properties were investigated in detail. Under 980 nm laser excitation, CaWO4: Er3+,Yb3+ powder exhibited green UC emission peaks at 530 and 550 nm, which were due to the transitions of Er3+ (2H11/2)→Er3+ (4I15/2) and Er3+ (4S3/2)→Er3+ (4I15/2), respectively. Effects of Li+ tri-doping into CaWO4: Er3+,Yb3+ were investigated. The introduction of Li+ ions reduced the optimum calcinations temperature about 100 °C by a liquid-phase sintering process and the UC emission intensity was remarkably enhanced by Li+ ions, which could be attributed to the lowering of the symmetry of the crystal field around Er3+ ions.  相似文献   

9.
《Ceramics International》2022,48(7):9640-9650
In the field of advanced anti-counterfeiting research, it is a hot issue to develop a multimodal anti-counterfeiting material with adjustable luminescence characteristics. Here, persistent luminescent materials of BaGa2O4:xBi3+ (x = 0-0.02) and BaGa2O4:0.005Bi3+,yLi+ (y = 0.001–0.02) were synthesized by a solid state reaction at high temperature. BaGa2O4: Bi3+ exhibited a broad blue emission at ~470 nm (transition from [GaO4]) and a sharp NIR emission at ~710 nm (3P11S0 transition of Bi3+), upon UV excitation at 250 nm. Incorporation of Li+ in BGO: 0.005Bi3+ induced the emission color shifting from blue to green. After stoppage of UV excitation, the BGO:0.005Bi3+ exhibited white afterglow with emission peaks at the range of 500–700 nm. However, incorporation of Li+ leaded to a stronger green afterglow and a weaker NIR afterglow. When the afterglow disappeared, the sample outputted afterglow again after heating processing. The prepared samples exhibited time- and temperature-dependent multimode luminescence, so they were used as components, combined with Morse code to realize multi-modal dynamic anti-counterfeiting. The outcomes in this work indicate that the prepared luminescent materials have broad prospects in advanced anti-counterfeit applications.  相似文献   

10.
11.
A conventional high temperature solid state method was utilized to prepare CaO-Y2O3, which is a potential candidate for manufacturing crucible material to melt titanium and titanium alloys with low cost. Meanwhile, Yb3+ ions and Er3+ ions were selected as the sensitizers and activators respectively to dope into CaO-Y2O3, aimed at providing real-time optical thermometry during the preparation process of titanium alloys realized using fluorescence intensity ratio (FIR) technology. The results reveal that a high measurement precision can be acquired by using the Stark sublevels of Er3+ 4F9/2 to measure the temperature with a maximum absolute error of only about 3 K. In addition, by analyzing the dependence of 4I13/2 → 4I15/2 transition on pump power of 980 nm excitation wavelength, it was found that the laser-induced thermal effect has almost no influence on the temperature measurement conducted by using the FIR of the Stark sublevels of Er3+ 4I13/2, which means that a high excitation pump power can be used to obtain strong NIR emission and good signal-to-noise ratio for optical thermometry without the influence of the laser-induced thermal effect. All the results reveal that CaO-Y2O3: Yb3+/Er3+ is an excellent temperature sensing material with high measurement precision.  相似文献   

12.
《Ceramics International》2016,42(5):5635-5641
A series of Yb3+ ions sensitized NaY(WO4)2:Er3+ phosphors were synthesized through a solid-sate reaction method. The X-ray diffraction (XRD), upconversion (UC) emission and cathodoluminescence (CL) measurments were applied to characterize the as-prepared samples. Under the excitation of 980 nm light, bright green UC emissions corresponding to (2H11/2,4S3/2)→4I15/2 transitions of Er3+ ions were observed and the UC emission intensities showed an upward trend with increasing the Yb3+ ion concentration, achieving its optimum value at 25 mol%. Furthermore, the temperature sensing behavior based on the thermally coupled levels (2H11/2,4S3/2) of Er3+ ions was analyzed by a fluorescence intensity ratio technique. It was found that the obtained samples can be operated in a wide temperature range of 133–773 K with a maximum sensitivity of approximately 0.0112 K−1 at 515 K. Ultimately, strong CL properties were observed in NaY(WO4)2:0.01Er3+/0.25Yb3+ phosphors and the CL emission intensity increased gradually with the increment of accelerating voltage and filament current.  相似文献   

13.
《Ceramics International》2022,48(24):36347-36357
Er3+ and/or Cr3+ doped transparent ZnGa2O4 glass-ceramics were successfully obtained by one-step heat treatment. The results showed that Er3+ ions can enrich around ZnGa2O4 crystal to reduce the crystallization activation energy and promote the growth of ZnGa2O4 crystal. Cr3+ ions may successfully occupy the Ga3+ sites in the ZnGa2O4 lattice but will increase crystallization activation energy and inhibit the growth of the ZnGa2O4 crystal. Before and after crystallization, the coordination-field intensity of Cr3+ ions increased from 2.17 to 2.86, resulting in the peak position of its emission spectra moving from 850 to 688 nm. By excitation at 378 nm, the precursor glass co-doped with Er3+ and Cr3+ ions only showed the characteristic emission peaks belonging to Er3+ ions. After heat treatment, the characteristic emission peaks belonging to Er3+ and Cr3+ ions existed simultaneously, and the emission color changed from green to yellow. By excitation at 980 nm, there were only characteristic emission peaks belonging to Er3+ ions of the Er3+/Cr3+ co-doped glasses before and after heat treatment. The results showed that the Er3+ and/or Cr3+ doped ZnGa2O4 glass-ceramics have adjustable luminescence ability and show potential application value in the field of luminescence display.  相似文献   

14.
The color‐tunable up‐conversion (UC) emission and infrared photoluminescence and dielectric relaxation of Er3+/Yb3+ co‐doped Bi2Ti2O7 pyrochlore thin films prepared by a chemical solution deposition method have been investigated. The pyrochlore phase structure of Bi2Ti2O7 can be stabilized by Er3+/Yb3+ co‐doping. Intense color‐tunable UC emission and infrared photoluminescence can be detected on the thin films excited by a 980 nm diode laser. Two UC emission bands centered at 548 and 660 nm in the spectra can be assigned to 2H11/2, 4S3/24I15/2 and 4F9/24I15/2 transitions of Er3+ ions, respectively. A Stokes infrared emission centered at 1530 nm is due to 4I13/24I15/2 transition of Er3+ ions. The dependence of UC emission intensity on pumping power indicates that the UC emission of the thin films is a two‐photon process. The thin films also exhibit a relatively high dielectric constant and a low dissipation factor as well as a good bias voltage stability. Temperature‐ and frequency‐dependent dielectric relaxation has been confirmed. This study suggests that Er3+/Yb3+ co‐doped Bi2Ti2O7 thin films can be applied to new multifunctional photoluminescence dielectric thin‐film devices.  相似文献   

15.
《Ceramics International》2023,49(7):10829-10838
Bi2O3:Yb3+/Er3+ nanoparticles with flower-like morphology were easily synthesized by urea-assisted coprecipitation reactions. The influences of calcination temperature and doping concentration on the crystal phase structures of Bi2O3 and Bi2O3:x%Yb3+/2%Er3+ (x = 0–30) were systematically investigated by XRD analysis. The experimental results revealed that lanthanide doping could effectively improve the thermal stability of Bi2O2CO3 samples, and the monoclinic-to-tetragonal-to-cubic phase transitions of Bi2O3 were implemented by controlling calcination temperatures and introducing smaller lanthanide ions (Ln3+) into the host lattices. Based on the analysis of TG and DSC curves, we found that the fundamental reason for this phase transition was the different stabilities of each crystalline phase under different doping conditions. Upon 980 nm laser excitation, Bi2O3:x%Yb3+/2%Er3+ samples presented near single-band red upconversion emission owing to the efficient energy reabsorption of the Bi2O3 host to Er3+ emission.  相似文献   

16.
The thermal effects of Er/Yb‐doped NaYF4 phosphor induced by 980/1510 nm laser diode irradiation were intuitively and contrastively investigated using an infrared thermal imaging technology with real‐time online monitoring. The Yb3+/Er3+ codoped materials have strong thermal effects and high‐temperature elevation under 980 nm irradiation. However, the severe thermal effects of materials with higher Er3+ ion doping concentration are remarkably attributed to the cross relaxation between the Er3+ ions under 980 nm irradiation. The energy transfer between Er3+ and Yb3+ ions in Er3+/Yb3+‐codoped materials also contributes to the thermal effects under 1510 nm laser diode irradiation. Under the same testing conditions, the temperature elevation ?T of samples induced by 1510 nm laser diode irradiation is lower than that induced by 980 nm laser diode irradiation. The temperature rising rate and elevation ?T value of samples depend on the ion doping concentration and power density of the laser diode excitation. The internal temperature of the samples exhibits deep temperature gradient under 980/1510 nm laser diode irradiation. By comparing the two kinds of thermometry methods, the temperature value calculated by fluorescence intensity ratio is almost similar to that obtained through infrared thermal imaging technology under higher excitation power pumping.  相似文献   

17.
The doping of transition metal ions in the up-conversion (UC) luminescent material doped with Yb3+/Ln3+ is a facile way to increase their UC luminescence intensities and alter their colors. In this study, La2MgTiO6:Yb3+/Mn4+/Ln3+ (Ln3+ = Er3+, Ho3+, and Tm3+) phosphors showing excellent luminescence properties were prepared by a solid-state method. The sensitivity of the La2MgTiO6:Yb3+/Ln3+/Mn4+ phosphor was double that without Mn4+, because Mn4+ affects the UC emissions of Ln3+ via energy transfer between these ions. Moreover, Mn4+ also acts as a down-conversion activator, which can combine with UC ions to achieve multi-mode luminescence at different wavelengths. Under 980 nm excitation, these samples emit green light (from Er3+ and Ho3+) and blue light (from Tm3+). In contrast, under 365 nm excitation, they emit red light (from Mn4+). Further testing revealed that the La2MgTiO6:Yb3+/Mn4+/Ln3+ phosphors have potential applications in temperature sensing and anti-counterfeiting.  相似文献   

18.
In recent years, rare earth ions doped optical materials have been extensively utilized in anticounterfeiting, temperature measurement, and other fields. However, it is difficult for single-mode photoluminescence to meet the increasingly complex anticounterfeiting needs in practice. In this article, Yb3+/Er3+ codoped Y2WO6 multifunctional microparticles have been designed and prepared, which can emit multimode luminescence and are used for anticounterfeiting and temperature measurement. Under excitation at 254, 365, and 980 nm, Y2WO6:Yb3+/Er3+ microparticles can emit blue, green, and yellow-green luminescence, respectively. The multicolor emission is helpful to improve the security of anticounterfeiting in multimode. In addition, the upconversion, downconversion luminescence, and downconversion lifetime attenuation of this material can be used for fast responsive and noncontact temperature measurement. Among the three temperature measurement methods, the material has the highest sensitivity under the downconversion temperature measurement method, which is 1.25 × 10–2 K–1 (at 303 K). The results suggest that the Y2WO6:Yb3+/Er3+ microparticles have excellent applications in the domain of multimode anticounterfeiting and temperature measurement.  相似文献   

19.
《Ceramics International》2023,49(19):31607-31617
Optical information encryption based on luminescence materials have received much attention recently. However, the single luminescence mode of the luminescence materials greatly limits its anti-counterfeiting application with high safety level. Here, a series of luminescence materials of Tb3+ and Bi3+ co-doped ZnGa2O4 phosphors with great correspondence in photoluminescence (PL), persistent luminescence (PersL), and thermoluminescence (TL) modes was synthesized by the conventional solid-phase method for the application in multi-modal anti-counterfeiting fields. Under the excitation of 254 nm, ZnGa1.99O4:0.01 Tb3+, yBi3+ (y = 0.001,0.002) sample exhibited a broad blue emission band (the transition from [GaO6]) at 440 nm and the characteristic emission peaks of Tb3+ at 495 nm, 550 nm, 591 nm and 625 nm, corresponding to the transitions of 5D4-7Fn (n = 6, 5, 4, 3), respectively. Interestingly, the co-doping of Bi3+ ions improve the crystallinity and particle size of the phosphor, subsequently enhanced the PL intensity of Tb3+ to 6 times that of Tb3+ singly doped ZnGa2O4 phosphor. Further, the flexible films with multi-modal luminescence properties have been fabricated through the unique TL and PersL characteristics of ZnGa2O4: Tb3+, Bi3+ phosphors, including “Optical information storage film”, “snowflake and characters” and “QR code”. Moreover, a set of optical information encryption is obtained by combining ZnGa2O4:Tb3+, Bi3+ phosphor and red emitting phosphor. The results indicate that ZnGa2O4:Tb3+, Bi3+ phosphor with multi-modal stimulus response can be expected to be potentially used in the applications of optical information storage and anti-counterfeiting fields.  相似文献   

20.
Fluorescence and absorption spectra at 530 nm (2H11/24I15/2), 560 nm (4S3/24I15/2), 660 nm (4F9/24I15/2), 980 nm (4I11/24I15/2), 1530 nm (4I13/24I15/2), and 2710 nm (4I11/24I13/2) of Er3+ in Gd3Ga5O12 single-crystal codoped with Pr3+ have been measured. Judd-Ofelt analysis yields the intensity parameters Ω2 = (0.68 ± 0.03) × 10−20 cm2, Ω4 = (0.60 ± 0.07) × 10−20 cm2, and Ω6 = (0.90 ± 0.17) × 10−20 cm2. A comparison with previously reported values of Er3+-only doping case shows that Pr3+-codoping causes slight change of both Ω2 and Ω4, while onefold increase of Ω6. From calculated radiative rates and measured fluorescence spectra, Er3+ emission cross-section spectra were calibrated at first. Then, the absorption cross-section spectra were calculated using McCumber relation. In parallel, the absorption cross-section spectra were also obtained from the measured absorption spectrum, and compared with those obtained from the McCumber relation. The comparison shows that both methods give consistent result of absorption cross-section spectrum. Further comparison with Er3+-only doping case shows that Pr3+-codoping causes considerable change of Er3+ cross-section value. In spectrally mixing regions of Er3+ and Pr3+, Pr3+ emission affects little the determination of Er3+ emission cross-section as Pr3+ fluorescence is much weaker than Er3+ fluorescence due to low Pr3+ concentration.  相似文献   

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