Anti-counterfeiting material based on multi-mode invisible light fluorescent powder as well as preparation method and application of anti-counterfeiting material

Abstract

The invention provides and discloses an anti-counterfeiting material based on multi-mode invisible light fluorescent powder and a preparation method and application thereof, the fluorescent powder is Mg3Y2Ge3O12: Bi < 3 + > / Pr < 3 + > / Yb < 3 + > / Er < 3 + >, triple independent luminescence is realized through quaternary ion co-doping: 980nm near-infrared excitation green up-conversion luminescence (UCL) and 254nm ultraviolet excitation red down-conversion luminescence (DCL), 328nm deep ultraviolet long afterglow (PersL) is generated after ultraviolet excitation is stopped, and the fluorescent powder can be used for preparing anti-counterfeiting materials. Wherein the ultraviolet PersL needs to be detected by special CCD (Charge Coupled Device) equipment to form an invisible hidden layer; during verification, naked eye observation (UCL / DCL) and equipment reading (PersL) are combined to realize four-stage dynamic anti-counterfeiting. The limitation of dependence on visible light in the prior art is broken through, double anti-counterfeiting logic of visible information and hidden ultraviolet verification is formed, the anti-counterfeiting safety level is remarkably improved, and the material stability is excellent.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of material science and anti-counterfeiting technology, and particularly relates to an anti-counterfeiting material based on a multi-mode non-visible light fluorescent powder and a preparation method and application thereof, high security verification is realized through visible light and non-visible light response cooperation.

BACKGROUND

[0002] Drug counterfeiting is a global public health problem, especially in high-value drugs. To address this challenge, various anti-counterfeiting technologies, including luminescent markers, magnetic codes, etc., have been developed and applied. Among them, color luminescence technology is of great concern due to its flexible design, high visibility, cost-effectiveness, and scalability. Luminescent materials based on different luminescence mechanisms (down-conversion luminescence (DCL), up-conversion luminescence (UCL), and persistent luminescence (PersL)) have been used for anti-counterfeiting, but single luminescence mode is difficult to meet the high security requirements and is easily imitated.

[0003] To improve security, luminescent materials with dual-mode or multi-mode emission characteristics have been developed, which produce different optical responses under different excitation stimuli, increasing the difficulty of cracking anti-counterfeiting information. For example, CN117511546A discloses an anti-counterfeiting material with dual-mode orthogonal three-color luminescence, which is composed of a core-shell up-conversion nanoparticle with three shell layers. It can produce up-conversion and down-conversion luminescence under near-infrared and ultraviolet excitation, respectively, realizing dual-mode three-color fluorescent two-dimensional code information display and increasing the difficulty of cracking anti-counterfeiting information. However, the luminescence modes are both in the visible light range (up / down conversion, i.e., 980 nm near-infrared excitation up-conversion blue / green light, 254 nm ultraviolet excitation down-conversion red light), and the anti-counterfeiting information can be directly observed by different light sources, posing a risk of trial-and-error cracking. Meanwhile, the synthesis of its core-shell structure (NaGdF4:Yb / Tm@NaGdF4:Ce / Eu@NaErF4@NaYF4) requires a multi-layer coating process, which is complex.

[0004] For another example, CN118256241A (germanate fluorescent powder) provides a tunable dual-mode luminescent fluorescent powder with a chemical formula of LiIn 1-x-y+xy Sc x-xy GeO4:yBi 3+ Under ultraviolet excitation, adjusting the Sc / In ratio in the composition can achieve color tuning from 484 nm to 580 nm under ultraviolet excitation, and the persistent luminescence time can also be adjusted, further improving the anti-counterfeiting performance. However, the dual-mode mechanism of'steady-state luminescence + persistent luminescence' only realizes the change of visible light color and persistent time by adjusting the Sc / In ratio, and the luminescence mode is tunable dual-mode luminescence (orange-yellow light to blue light, persistent time 0-10 s). The luminescence is in the visible light range, and the persistent luminescence can be observed by the naked eye, making it easy for counterfeiters to crack by observing different light sources with the naked eye.

[0005] It can be seen that these prior arts have key defects: their optical responses mainly rely on luminescence in the visible light range, leading to the fact that the anti-counterfeiting information is easy to be directly observed by the human eye, and then the decryption can be performed through trial and error experiments (trying different light sources), which seriously restricts the improvement of the anti-counterfeiting security level. Therefore, it is urgent to develop a multi-mode synergistic material with non-visible light response capability (especially ultraviolet afterglow luminescence) to break through the security bottleneck through the dual mechanism of “visible authentication + hidden verification”.

SUMMARY

[0006] One of the technical problems to be solved by the present application is to provide an anti-counterfeiting material based on multi-mode non-visible light fluorescent powder and a preparation method thereof. The material integrates three independent luminescence mechanisms of near-infrared UCL, ultraviolet DCL and deep ultraviolet PersL, constructs a four-level dynamic verification chain, forms a dual anti-counterfeiting logic of “visible information + hidden ultraviolet verification”, and significantly improves the anti-counterfeiting security level.

[0007] The present application is to solve one of the above technical problems in the following way:

[0008] An anti-counterfeiting material based on multi-mode non-visible light fluorescent powder, the chemical formula of the fluorescent powder is Mg3Y2Ge3O 12 :Bi 3+ / Pr 3+ / Yb 3+ / Er 3+ ; wherein the molar percentage of the doping ions is:

[0009] Bi 3+ : 0.1-1 mol%;

[0010] Pr 3+ : 0.2-2 mol%;

[0011] Yb 3+ : 0.25-2 mol%;

[0012] Er 3+ : 0.25-2 mol%;

[0013] The fluorescent powder has three luminescence modes.

[0014] Further, the molar percentage of the doping ions is:

[0015] Bi 3+ : 0.5 mol%; Pr 3+ : 0.25 mol%; Yb 3+ : 2 mol%; Er 3+ : 0.5 mol%.

[0016] Further, the three luminescence modes of the fluorescent powder are as follows:

[0017] Upconversion emission (UCL): Green upconversion emission (Er) under 980nm near-infrared excitation 3+ : 4 S3 / 2→ 4 I 15 / 2);

[0018] Downconversion emission (DCL): Red downconversion emission (Pr) under 254nm UV excitation 3+ : 3 P0→ 3 H4);

[0019] PersL (Pers-L): Bi after UV excitation stops 3 + Generates a deep ultraviolet long afterglow with a center wavelength of 328nm and an afterglow time of ≥24h.

[0020] Furthermore, the ultraviolet afterglow emission (PersL) is detected by a 310-330nm bandpass filter combined with a CCD imaging device.

[0021] Furthermore, a method for preparing an anti-counterfeiting material based on multi-mode non-visible light phosphor, the method comprising the following steps:

[0022] Weigh the matrix raw materials MgO, Y2O3, and GeO2, as well as the dopant sources Bi(NO3)3·5H2O, Pr(NO3)3·6H2O, Yb(NO3)3·5H2O, and Er(NO3)3·6H2O according to the stoichiometric ratio.

[0023] Add ethanol and wet grind for 25-45 minutes;

[0024] Then, under air atmosphere, the temperature is increased to 1400±10℃ at 5℃ / min and sintered for 4±0.5h.

[0025] Finally, cooling and grinding yielded the phosphor Mg3Y2Ge3O. 12 :Bi 3+ / Pr 3+ / Yb 3+ / Er 3+ The molar percentage of doped ions is: Bi 3+ 0.1–1 mol%; Pr 3+ 0.2–2 mol%; Yb 3+ 0.25–2 mol%; Er 3+ 0.25–2 mol%.

[0026] The second technical problem to be solved by this invention is to provide an application of anti-counterfeiting material based on multi-mode non-visible light phosphor. This material integrates three independent luminescence mechanisms, namely near-infrared UCL, ultraviolet DCL and deep ultraviolet PersL, to construct a four-level dynamic verification chain, forming a dual anti-counterfeiting logic of "visible information + concealed ultraviolet verification", which significantly improves the level of anti-counterfeiting security.

[0027] The present invention achieves the second technical problem mentioned above in the following way:

[0028] An anti-counterfeiting label, comprising a substrate and a printing layer;

[0029] The printed layer contains the aforementioned phosphor;

[0030] The substrate is pharmaceutical packaging filter paper with a thickness of 0.1–0.3 mm;

[0031] The phosphor is dispersed in an aqueous solution of polyvinyl alcohol (PVA) to form a slurry, wherein the mass fraction of PVA is 5–10%.

[0032] The paste is printed onto pharmaceutical packaging filter paper to form a predetermined pattern.

[0033] Furthermore, a multi-level dynamic anti-counterfeiting verification method includes the aforementioned anti-counterfeiting label; the method is as follows:

[0034] Preliminary verification: Irradiation with a 254nm ultraviolet lamp, visual observation of Pr 3+ The red DCL pattern; the red DCL pattern continues to glow for at least 2 minutes after illumination stops;

[0035] Secondary verification: Switch to 980nm laser irradiation to identify Er. 3+ The green UCL pattern;

[0036] Covert verification: After 60 seconds of UV pre-irradiation, the excitation source was turned off, and Bi was captured using a CCD device with a 310-330nm filter. 3+ UV PersL image.

[0037] Furthermore, in the covert verification, the ultraviolet PersL pattern and the visible light pattern form complementary information, thus forming an anti-counterfeiting logic of "visible authentication + covert verification".

[0038] Furthermore, the aforementioned anti-counterfeiting material based on multi-mode non-visible light fluorescent powder can be applied in the fields of pharmaceutical anti-counterfeiting, luxury goods anti-counterfeiting, document encryption, or food packaging.

[0039] The present invention has the following advantages:

[0040] 1. Invisible anti-counterfeiting achieved through deep ultraviolet long afterglow: This invention utilizes Mg3Y2Ge3O 12Precise doping of 0.5 mol% Bi in the matrix 3+ It generates a deep ultraviolet long afterglow (PersL) with a center wavelength of 328nm. This band is beyond the range of human vision and can only be detected by CCD equipment coupled with a 310-330nm bandpass filter, forming an "invisible cover layer" that completely blocks the visible light trial and error decryption path.

[0041] Meanwhile, the ultraviolet PersL of the present invention remains detectable for more than 24 hours after the 254nm excitation is stopped, and its intensity decays by less than 5% after multiple excitation cycles, thus exhibiting strong stability.

[0042] 2. A multi-level dynamic verification chain is constructed using a triple-emission mode to enhance the technical barrier against counterfeiting: This invention utilizes Bi... 3+ / Pr 3+ / Yb 3+ / Er 3+ Ion co-doping enables a triple independent emission mechanism: green upconversion luminescence excited at 980 nm (Er 3+ : 4 S 3 / 2 → 4 I 15 / 2 ), 254nm ultraviolet-excited red downconversion luminescence (Pr) 3+ : 3 P0→ 3 H4), UV-Vis long afterglow after UV excitation stops. This can form a four-level verification mechanism: 980nm excitation only shows Er... 3+ Green UCL pattern, 254nm UV excitation display Pr 3+ The red DCL pattern, after excitation stops, Pr 3+ The red PersL was maintained for at least 2 minutes, and the CCD, in conjunction with the filter, captured Bi. 3+ The ultraviolet PersL images provide a more complex verification dimension.

[0043] It is evident that the triplet mode of this invention depends on transitions between different ion energy levels (such as Bi). 3+ UV PersL, Er 3+ upconversion, Pr 3+ (Downconversion), counterfeiters need to simultaneously replicate three emission spectra and the ultraviolet PersL decay curve, which is a significantly higher technical barrier than single-matrix tunable systems.

[0044] 3. High-stability material system and solid-state synthesis process ensure industrialization feasibility: This invention adopts a cubic garnet structure (Ia3ˉd space group) and synthesizes it using Bi... 3+ In Y 3+Site-specific solid solution optimization, combined with a solid-state reaction method at 1400℃ for 4 hours, yields a product with phase purity exceeding 99% and uniform elemental distribution. This invention's solid-state process is easier to scale up for production and exhibits excellent lattice stability (PersL decay <5% after multiple excitations). The garnet structure fundamentally ensures persistent luminescence, solving the problem of long-term luminescence decay in existing technologies, making it suitable for the anti-counterfeiting requirements of long-term verification in pharmaceutical distribution.

[0045] 4. Collaborative design of non-visible light and visible light anti-counterfeiting to achieve "dual security protection": This invention combines invisible ultraviolet PersL with UCL and DCL in the visible light range to form a composite system of "visible authentication (UCL / DCL) + covert verification (ultraviolet PersL)". The anti-counterfeiting label can only obtain part of the visible light information with the naked eye. The complete anti-counterfeiting information requires special equipment to read the ultraviolet PersL for verification. This breaks through the limitations of the existing "human eye recognition" and raises the difficulty of counterfeiting from "copying visible light patterns" to "overcoming non-visible light emission and special detection technology", thus significantly improving the level of anti-counterfeiting. [Attached Image Description]

[0046] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0047] Figure 1 The diagram shows the microstructure characterization of the phosphor, including (a) the XRD pattern of MYGB, (b) the crystal structure of MYGB, (c) the EDS spectrum of MYGB, and (d) the elemental mapping images of Mg, Y, Ge, O and Bi (scale bar: 5 μm).

[0048] Figure 2 These are the PL and PersL emission spectra of MYGB.

[0049] Figure 3 This is the PersL emission spectrum of MYGBP.

[0050] Figure 4 The PersL decay curves of MYGBP were monitored at wavelengths of 328 nm and 609 nm.

[0051] Figure 5 This is the UCL emission spectrum of MYGBP-Yb / Er.

[0052] Figure 6 The diagram shows the pattern design and multi-level verification effect ("390" dynamic display) of the anti-counterfeiting label, including (a) a schematic diagram of the anti-counterfeiting system for pharmaceuticals, (b) an anti-counterfeiting pattern composed of MTGBP, MYGBP-Yb / Er and MYGP-Yb / Er, and (c) optical information images under different excitation conditions.

Detailed Implementation Methods

[0053] The following will be combined with the appendix Figures 1-6 The technical solution of the present invention will be clearly and completely described in detail with specific embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0054] Example 1

[0055] Synthesis of phosphors:

[0056] The preparation of the phosphor was carried out in the following steps: First, the matrix raw materials MgO, Y2O3, GeO2 and the dopant sources Bi(NO3)3·5H2O, Pr(NO3)3·6H2O, Yb(NO3)3·5H2O and Er(NO3)3·6H2O were accurately weighed according to the stoichiometric ratio; then, the mixed powder was placed in an agate mortar, and ethanol solvent was added for wet grinding for 30 min to ensure thorough mixing of the raw materials; next, the powder was transferred to an alumina crucible, and the temperature was increased to 1400℃ at a programmed rate of 5℃ / min under air atmosphere, and sintered at a constant temperature for 4 h; finally, the sintered product was naturally cooled and ground into fine powder to obtain the target product Mg3Y2Ge3O 12 :Bi 3+ / Pr 3+ / Yb 3+ / Er 3+ (abbreviated as MYGBP-Yb / Er), the molar percentage of doped ions is: Bi 3+ 0.5 mol%; Pr 3+ 0.25 mol%; Yb 3+ 2 mol%; Er 3+ 0.5 mol%.

[0057] The phosphor prepared by this invention has a cubic garnet structure (space group Ia3ˉd), with a phase purity exceeding 99% and uniform elemental distribution. The ultraviolet PersL of the phosphor of this invention remains detectable for over 24 hours after cessation of 254nm excitation, and its PersL intensity decays by less than 5% after multiple excitation cycles.

[0058] See Figure 1 Because the electronic configuration is [Xe]4f 14 5d 10 6s 2 Bi 3+ It exhibits tunable emission from the near-infrared to the ultraviolet region. This is achieved by adding Bi to a suitable matrix. 3+Ions can achieve ultraviolet PersL emission without visible light. First, Mg3Y2Ge3O2 is selected. 12 As a matrix material for synthesizing phosphors. Figure 1 a shows Mg3Y2Ge3O 12 :Bi 3+ X-ray diffraction (XRD) pattern of Mg3Y2Ge3O (MYGB). All observed diffraction peaks are associated with Mg3Y2Ge3O. 12 The sample was completely identical to the reference pattern (PDF#89-6603), confirming the phase purity of the synthesized sample. The results showed that the MYGB crystal exhibited an antigarnet cubic structure with space group Ia3d. Figure 1 As shown in b, the crystal structure includes two distinct Mg atoms. 2+ Site, two Ge 4+ locus and a Y 3+ Site. Mg 2+ With six O 2- Ion coordination forms MgO6 octahedrons; Ge 4+ With four equivalent O 2- Ionic bonding forms GeO4 tetrahedra; Y 3+ It adopts a body-centered cubic geometry structure, with eight O 2- Ion coordination. Considering ionic radius and charge state, Bi is expected to... 3+ Ions preferentially occupy the Y atoms in the crystal lattice 3+ Ions. Furthermore, energy-dispersive X-ray spectroscopy (EDS)... Figure 1 c) and elemental spectral images ( Figure 1 d) The uniform distribution of Mg, Y, Ge, O and Bi in MYGB and their successful synthesis were confirmed.

[0059] Figure 2 The graph shows the PL and PersL emission spectra of MYGB. The continuous emission (PersL) spectrum of MYGB after excitation by a 254nm UV lamp shows an ultraviolet emission band from 280 to 400nm. The PersL and PL emission spectra show almost identical curves, confirming that the PersL emission also originates from Bi. 3+ of 3 P1→ 1 S0 transition.

[0060] Figure 3 This is the PersL emission spectrum of MYGBP. The figure shows the PersL spectrum of MYGBP after excitation at 254 nm. The ultraviolet emission band is attributed to the emitter Bi. 3+ of 3 P1→ 1 S0 transition, which is related to MYGB ( Figure 2 Consistent with this, the visible emission band from 450 to 680 nanometers is attributed to the transition (3 P0→ 3 H4, 3 P0→ 3 H5, 3 P1→ 3 H5, 3 P0→ 3 H6, 1 D2→ 3 H4, and 3 P0→ 3 F2).

[0061] Figure 4 yes Figure 4 The PersL decay curves of MYGBP were monitored at wavelengths of 328 nm and 609 nm. The figures show that monitoring the Bi... 3+ Emitter (328nm) and Pr 3+ The emitter (612nm) can find persistent PersL after a 254nm UV lamp.

[0062] Figure 5 This is the UCL emission spectrum of MYGBP-Yb / Er. As can be seen from the figure, MYGBP-Yb / Er exhibits green UCL, originating from Er. 3+ change( 2 F 11 / 2 → 4 I 15 / 2 , 4 S 3 / 2 → 4 I 15 / 2 and 4 F 9 / 2 → 4 I 15 / 2 These dopants successfully endowed MYGBP-Yb / Er UCL with capability while retaining the inherent characteristics of PersL.

[0063] Example 2

[0064] Anti-counterfeiting label production method:

[0065] The production of the anti-counterfeiting pattern involves parallel processes: on one hand, MYGBP-Yb / Er fluorescent powder is dispersed in an aqueous solution containing 7wt% polyvinyl alcohol (PVA) and stirred to form a homogeneous slurry; on the other hand, 0.2mm thick pharmaceutical packaging filter paper is selected as the substrate. The slurry is printed onto the substrate through a 200-mesh screen to form the predetermined pattern, and then dried and cured at room temperature to obtain a composite anti-counterfeiting label.

[0066] Example 3

[0067] The multi-level dynamic anti-counterfeiting verification method is implemented according to the following process:

[0068] 1) Primary visible light verification: Illuminate the label with a 254nm ultraviolet lamp (6W) and observe the red DCL pattern with the human eye; after stopping the illumination, continue to observe the Pr. 3+ The resulting red afterglow emission lasts for at least 2 minutes.

[0069] 2) Secondary near-infrared verification: Switching to a 980nm semiconductor laser (power density 1W / cm²) 2 Irradiation, identification of Er 3+ The green UCL feature pattern is excited.

[0070] 3) Professional verification of the covert layer: Using a CCD imaging device (Tano 4600SF model), the following operations were performed: First, the tag was pre-irradiated with a 254nm ultraviolet lamp for 60 seconds; after turning off the excitation source, ultraviolet PersL images were captured using a CCD with a 310-330nm bandpass filter, at which point only Bi... 3+ The material region shows a 328nm characteristic emission.

[0071] Example 4

[0072] Applications of anti-counterfeiting labels in pharmaceutical packaging:

[0073] To demonstrate the superior anti-counterfeiting and encryption capabilities of the multi-mode phosphor MYGBP-Yb / Er, this embodiment designs a sophisticated anti-counterfeiting system using composite patterns. (See also...) Figure 6 An anti-counterfeiting digital pattern is set in the sealed label of the pharmaceutical packaging box. The digital pattern "390" is composed of Mg3Y2Ge3O 12 :Bi 3+ / Pr 3+ (abbreviated as MTGBP), MYGBP-Yb / Er and Mg3Y2Ge3O 12 :Pr 3+ / Yb 3+ / Er 3+ (abbreviated as MYGP-Yb / Er) consists of ( Figure 6 a). This design enables dynamic optical response under different conditions. Figure 6 b). For example Figure 6As shown in Figure c, under 980nm laser excitation, a green "90" appears because the "3" portion composed of MYGBP lacks UCL emission capability. Under 254nm UV lamp excitation, the complete red "390" pattern becomes clearly visible. After the UV light stops, the continuous red emission maintains the "390" pattern. When detected using a CCD device, the "390" pattern reappears. However, because the "0" portion composed of MYGP-Yb / Er cannot emit light in the UVB PersL range, adding an additional filter causes the "390" to become "39". It is evident that this dynamic response mechanism achieves multi-level anti-counterfeiting through the intrinsic optical properties of the material, without relying on computer programs or algorithmic rules. This multi-level optical response demonstrates the great potential for advanced anti-counterfeiting applications, providing multiple verification stages with different authentication mechanisms.

[0074] While specific embodiments of the present invention have been described above, those skilled in the art should understand that the specific embodiments described are merely illustrative and not intended to limit the scope of the present invention. Equivalent modifications and variations made by those skilled in the art in accordance with the spirit of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. An anti-counterfeiting material based on multi-mode non-visible light phosphor, characterized in that: The chemical formula of the phosphor is Mg3Y2Ge3O 12 Bi 3+ / Pr 3+ / Yb 3+ / Er 3+ The molar percentage of doped ions is: Would 3+ :0.1~1mol%; Pr 3+ :0.2~2mol%; Yb 3+ :0.25~2mol%; Is 3+ :0.25~2mol%; The phosphor has a triple emission mode.

2. The anti-counterfeiting material based on multi-mode non-visible light phosphor according to claim 1, characterized in that: The molar percentage of doped ions is: Bi 3+ :0.5mol;Pr 3+ :0.25mol%;Yb 3+ :2mol%;Er 3+ :0.5 mol%) 3. The anti-counterfeiting material based on multi-mode non-visible light phosphor according to claim 1, characterized in that: The phosphor's triple emission modes are as follows: Upconversion emission (UCL): Green upconversion emission (Er) under 980nm near-infrared excitation 3+ : 4 S3 / 2→ 4 I 15 / 2); Downconversion emission (DCL): Red downconversion emission (Pr) under 254nm UV excitation 3+ : 3 P0→ 3 H4); PersL (Pers-L): Bi after UV excitation stops 3+ It produces a deep ultraviolet long afterglow with a center wavelength of 328nm and an afterglow time of ≥24h.

4. The anti-counterfeiting material based on multi-mode non-visible light phosphor according to claim 1, characterized in that: The ultraviolet afterglow emission (PersL) is detected by a 310-330nm bandpass filter combined with a CCD imaging device.

5. A method for preparing anti-counterfeiting materials based on multi-mode non-visible light phosphors, characterized in that: The method steps are as follows: Weigh the matrix raw materials MgO, Y2O3, and GeO2, as well as the dopant sources Bi(NO3)3·5H2O, Pr(NO3)3·6H2O, Yb(NO3)3·5H2O, and Er(NO3)3·6H2O according to the stoichiometric ratio. Add ethanol and wet grind for 25-45 minutes; Then, under air atmosphere, the temperature is increased to 1400±10℃ at 5℃ / min and sintered for 4±0.5h. Finally, cooling and grinding yielded the phosphor Mg3Y2Ge3O. 12 Bi 3+ / Pr 3+ / Yb 3+ / Er 3+ The molar percentage of doped ions is: Bi 3+ 0.1–1 mol%; Pr 3+ 0.2–2 mol%; Yb 3+ 0.25–2 mol%; Er 3+ 0.25–2 mol%.

6. An anti-counterfeiting label, characterized in that: Including the substrate and the printed layer; The printed layer comprises the phosphor according to any one of claims 1 to 4; The substrate is pharmaceutical packaging filter paper with a thickness of 0.1–0.3 mm; The phosphor is dispersed in an aqueous solution of polyvinyl alcohol (PVA) to form a slurry, wherein the mass fraction of PVA is 5–10%. The paste is printed onto pharmaceutical packaging filter paper to form a predetermined pattern.

7. A multi-level dynamic anti-counterfeiting verification method, characterized in that: Including an anti-counterfeiting label as described in claim 6; the method is as follows: Preliminary verification: Irradiation with a 254nm ultraviolet lamp, visual observation of Pr 3+ The red DCL pattern; the red DCL pattern continues to glow for at least 2 minutes after illumination stops; Secondary verification: Switch to 980nm laser irradiation to identify Er. 3+ The green UCL pattern; Covert verification: After 60 seconds of UV pre-irradiation, the excitation source was turned off, and Bi was captured using a CCD device with a 310-330nm filter. 3+ UV PersL image.

8. The multi-level dynamic anti-counterfeiting verification method as described in claim 7, characterized in that: In the covert verification, the ultraviolet PersL pattern and the visible light pattern form complementary information, thus forming an anti-counterfeiting logic of "visible authentication + covert verification".

9. The application of a multi-mode non-visible light fluorescent anti-counterfeiting material according to any one of claims 1-4 in the fields of pharmaceutical anti-counterfeiting, luxury goods anti-counterfeiting, document encryption, or food packaging.

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