Self-activated long-afterglow material with multi-mode luminescence and preparation method and application of self-activated long-afterglow material

Abstract

The invention discloses a self-activated long-afterglow material with multi-mode luminescence, a preparation method and application, which can realize effective regulation and control of the multi-mode luminescence performance of fluorescent powder and can be applied to the fields of information encryption, anti-counterfeiting and the like. Based on the defect-rich matrix CaGa4O7, the defect state concentration and depth in the matrix are regulated and controlled by simply doping and replacing Ca < 2 + > with Pb < 2 + >, so that the multi-mode optical characteristics such as the afterglow intensity and decay time of the Ca1-xGa4O7: xPb < 2 + > fluorescent powder, the photochromic degree and the excitation time dependent on fluorescence are effectively regulated and controlled; through combination of multi-mode optical characteristics, the problem that a traditional encryption and anti-counterfeiting technology is single in mode is solved, and the method has great application value in the fields of information encryption, anti-counterfeiting and the like.

Description

Technical Field

[0001] The invention relates to a self-activated long afterglow material with multi-mode luminescence and a preparation method and application thereof, belonging to the technical field of inorganic luminescence. Background Art

[0002] With the rapid development of social economy and science and technology, the emergence of counterfeit and shoddy goods has not only seriously disrupted the order of the market, but also seriously damaged the image of enterprises and the interests of consumers. Therefore, in order to solve the long-standing anti-counterfeiting problem in the world, it is urgent to develop advanced anti-counterfeiting means. Researchers have successively developed fluorescent information anti-counterfeiting encryption technology based on rare earth element doped inorganic phosphors, organic small molecules, quantum dots, and metal organic frameworks. Among them, due to the excellent optical properties of inorganic phosphor materials (rich luminescent colors, narrow emission peaks, high brightness, etc.), they play a vital role in the field of anti-counterfeiting. Unfortunately, most of these fluorescent materials are single-mode information decoding in anti-counterfeiting applications, that is, under fixed excitation, their emission color remains unchanged, so their anti-counterfeiting level depends largely on the scarcity of the stimulation mode or emission type. However, with the increase in the exposure time of these technologies, materials with similar properties are constantly being developed, and the risk of being counterfeited has also increased dramatically.

[0003] In response to the above problems, traditional single-mode luminescent materials are being upgraded to dynamic multi-mode single-component luminescent materials, achieving a high level of anti-counterfeiting in spatial and temporal dimensions. For example, Professor Xu Yan of Northeastern University introduced Bi into the self-activated matrix MgGa2O4. 3+ , through the deep defect engineering, the dynamic transformation from green or near-infrared to blue-white luminescence is achieved, which is successfully applied to anti-counterfeiting and information encryption. Professor Chen Baojiu of Dalian Maritime University prepared Cr 3+ Doped Zn3Ga2Ge2O 10 Self-activated long afterglow material, doped with Cr 3+ Not only did it achieve the tuning of visible light from green, light pink to deep red, it also changed the afterglow color from yellow to red, successfully drawing up an anti-counterfeiting scheme for smartphone recognition. Therefore, dynamic multi-mode luminescence can hide confidential information in the same set of labels, such as real-time changing patterns, multi-color anti-counterfeiting QR codes and dynamic digital codes, etc. This anti-counterfeiting method has extremely high security and flexibility and has broad application prospects. However, there are relatively few reports on self-activated long afterglow materials and the regulation of luminescence properties. Summary of the invention

[0004] The purpose of the present invention is to provide a self-activated long afterglow material with multi-mode luminescence, a preparation method and an application. 2+ Doping can regulate the defect concentration and depth of CaGa4O7 matrix to achieve Ca1-x Ga4O7:xPb 2+ The effective regulation of multi-mode optical properties such as phosphor afterglow intensity and decay time, photochromism degree and excitation time-dependent fluorescence, and the combination of multi-mode optical properties overcome the problem of single mode of traditional encryption and anti-counterfeiting technology, so that it can be applied in fields such as information encryption and anti-counterfeiting.

[0005] The technical solution adopted by the present invention is:

[0006] The present invention provides a self-activated long afterglow luminescent material with multi-mode luminescence, the chemical formula of which is Ca 1-x Ga4O7:xPb 2+ Where 0≤x≤0.1; the Ca 1-x Ga4O7:xPb 2+ Based on the monoclinic C2 / c space group of CaGa4O7, Ga 3+ Site and Ca 2 + The sites are respectively associated with 4 and 5 O 2- The atoms combine to form a GaO4 triangular pyramid and a CaO5 triangular bipyramid, and the GaO4 triangular pyramid and the CaO5 triangular bipyramid are connected by sharing an angle. Based on the crystal structure of CaGa4O7, there are two different coordination environments of the GaO4 triangular pyramid and the CaO5 triangular bipyramid and oxygen vacancy defects. 2+ Different concentrations of Pb were introduced into the 2+ , forming different luminescent sites and defect types.

[0007] Preferably, after stopping the 254nm light source excitation, the afterglow color of the material is sky blue: when Pb 2+ When the doping amount is 0≤x≤0.0.5, the intensity and decay time of the afterglow increase with the increase of Pb 2+ The doping amount increases; when Pb 2+ When the doping amount is 0.05≤x≤0.1, the intensity and decay time of the afterglow increase with the increase of Pb 2+ The adjustable afterglow decay time can produce dynamic patterns that change over time, laying the foundation for dynamic anti-counterfeiting.

[0008] Preferably, the luminous intensity of the material increases with the extension of the excitation time of the 254nm light source. The fluorescence property dependent on the excitation time lays the foundation for the preparation of dynamically changing anti-counterfeiting patterns.

[0009] Preferably, when the material is irradiated with a 254nm light source, the intrinsic powder color of the powder gradually changes from white to brown; when irradiated with a 365nm light source, the brown color gradually bleaches and changes to white, and the above-mentioned photochromic change is reversible.

[0010] The present invention also provides a method for preparing a self-activated long afterglow luminescent material with multi-mode luminescence, comprising the following steps:

[0011] (1) According to Ca 1-x Ga4O7:xPb 2+ The raw materials CaO, Ga2O3 and PbO are weighed in a stoichiometric ratio, and the molar ratio of CaO, Ga2O3 and PbO is 1-x:2:x, and the range of x is 0≤x≤0.1;

[0012] (2) Grinding the weighed raw materials evenly;

[0013] (3) The ground raw material powder is transferred to a crucible, and sintered at 1300-1400° C. in air as a sintering atmosphere for 4-6 hours, and a self-activated long afterglow luminescent material is obtained after cooling.

[0014] The present invention also provides an application of a self-activated long afterglow material with multi-mode luminescence in information security, comprising the following steps:

[0015] Using CaGa4O7, Ca 0.95 Ga4O7:0.05Pb 2+ and Ca 0.9 Ga4O7:0.1Pb 2+ The three materials are processed into particles respectively, and the obtained three particles are recorded as A, B, and C respectively. A, B, and C are used as pixels and arranged into a pixel matrix in a preset manner;

[0016] After irradiating the pixel matrix with 254nm ultraviolet light, the pixel matrix is ​​placed in a dark environment. Among the A, B, and C pixel points, the C pixel point disappears quickly, and a pixel matrix pattern 1 is obtained. The pixel matrix pattern 1 is used to store the first confidential information. After 180s, the A pixel point disappears next, and a pixel matrix pattern 2 is obtained. The pixel matrix pattern 2 is used to store the second confidential information.

[0017] When the pixel matrix is ​​placed in a daylight environment, the color of the A and B pixels changes from white to brown, and a pixel matrix pattern 3 is obtained. The pixel matrix pattern 3 is used to store the third confidential information. The pixel matrix pattern 1, the pixel matrix pattern 2, and the pixel matrix pattern 3 are combined according to preset rules to realize the confidentiality of multiple information.

[0018] The present invention also provides an application of a self-activated long afterglow material with multi-mode luminescence in product anti-counterfeiting, comprising the following steps:

[0019] Using CaGa4O7, Ca 0.95 Ga4O7:0.05Pb 2+ and Ca 0.9Ga4O7:0.1Pb 2+ The three materials were processed into coatings, and the three coatings obtained were recorded as D, E, and F respectively;

[0020] An anti-counterfeiting pattern is provided on the product, wherein the anti-counterfeiting pattern includes three sub-patterns.

[0021] Use D, E and F to coat the three sub-patterns respectively to obtain coated anti-counterfeiting patterns;

[0022] The coated anti-counterfeiting pattern is irradiated with 254nm ultraviolet light, and the sub-patterns become brighter in the following preset order due to the fluorescence enhancement phenomenon: the sub-pattern coated with F, the sub-pattern coated with D, and the sub-pattern coated with E;

[0023] The 254nm ultraviolet light irradiation is removed, and the coated anti-counterfeiting pattern is placed in a dark environment. The sub-patterns darken in sequence due to the long afterglow effect in the following preset order: the sub-pattern coated with F, the sub-pattern coated with E, and the sub-pattern coated with D; product anti-counterfeiting is performed by the preset order of brightening and darkening.

[0024] Beneficial effects of the present invention:

[0025] Compared with the prior art, the beneficial effects of the present invention are: through a simple transition metal ion Pb 2+ Doping and high-temperature solid-phase method were used to synthesize multi-mode luminescence self-activated long afterglow materials. By regulating the defect state concentration and depth of the CGO matrix, the multi-mode optical properties such as the afterglow intensity and decay time of the phosphor, the degree of photochromism, and the excitation time-dependent fluorescence were effectively regulated. The combination of multi-mode optical properties overcomes the problem of the single mode of traditional encryption and anti-counterfeiting technology, making it applicable to fields such as information encryption and anti-counterfeiting. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is Ca 1-x Ga4O7:xPb 2+ XRD pattern of

[0027] Figure 2 The diffuse reflection spectra and photos of CaGa4O7 material after being irradiated with 254nm ultraviolet light for different time periods; in the attached drawings of the present invention, Ca 1-x Ga4O7:xPb 2+ Phosphor is abbreviated as CGO:xPb 2+ ;

[0028] Figure 3 It is the excitation time-dependent fluorescence spectrum and afterglow spectrum of CaGa4O7 material and the corresponding luminescence photograph;

[0029] Figure 4 Ca0.95 Ga4O7:0.05Pb 2+ Excitation time-dependent fluorescence spectra and afterglow spectra of materials and corresponding luminescence photographs;

[0030] Figure 5 It is Ca 0.9 Ga4O7:0.1Pb 2+ Diffuse reflectance spectra and photos of materials after being irradiated with 254nm UV light for different times;

[0031] Figure 6 It is Ca 0.9 Ga4O7:0.1Pb 2+ Excitation time-dependent fluorescence spectra and afterglow spectra of materials and corresponding luminescence photographs;

[0032] Figure 7 It is a schematic diagram of digital anti-counterfeiting technology made using three materials;

[0033] Figure 8 It is a schematic diagram of anti-counterfeiting technology using three materials to prepare rose patterns;

[0034] Fig. 9 It is a schematic diagram of information encryption application prepared using three materials; DETAILED DESCRIPTION

[0035] The invention discloses a self-activated long afterglow material Ca with multi-mode luminescence 1-x Ga4O7:xPb 2+ The preparation method and application of the invention comprise the following steps:

[0036] (1) weighing CaO, Ga2O3 and PbO with a purity greater than 99.9% according to a stoichiometric ratio, wherein the molar ratio of the materials is 1-x:2:x, and the molar ratio range of x is 0-0.1;

[0037] (2) Mix the weighed samples and place them in an agate mortar, add 5-10 ml of anhydrous ethanol and grind for 5-10 minutes;

[0038] (3) The ground powder is transferred to an alumina crucible, and then sintered in a high-temperature muffle furnace at 1300-1400° C. with air as the sintering atmosphere for 4-6 hours. After naturally cooling to room temperature, a self-activated long afterglow material with multi-mode luminescence is obtained.

[0039] (4) Prepare Ca 1-x Ga4O7:xPb 2+ After being ground into powder, it is mixed with epoxy resin glue and prepared into patterns through screen printing and other methods, and the differences in multi-mode optical properties are used for information encryption and anti-counterfeiting applications.

[0040] CaGa4O7 belongs to the monoclinic C2 / c space group and is composed of Ga 3+ Site and Ca 2+ The sites are respectively associated with 4 and 5 O 2- The atoms combine to form a GaO4 triangular pyramid and a CaO5 triangular bipyramid, which are connected by sharing an angle. 1- x Ga4O7:xPb 2+ Based on the existence of two different coordination environments and abundant oxygen vacancy defects in the CaGa4O7 crystal structure, rare earth ions or transition metal ions are introduced at the A or B site to form a variety of different luminescent sites and defect types, further enriching the luminescent properties of the material and laying the foundation for achieving multi-mode dynamic luminescence.

[0041] The present invention will be further described below with reference to the embodiments.

[0042] Example 1

[0043] A preparation method and application of a self-activated long afterglow material CaGa4O7 with multi-mode luminescence, comprising the following steps:

[0044] (1) weighing CaO and Ga2O3 with a purity greater than 99.9% according to a stoichiometric ratio, wherein the molar ratio of the materials is 1:2;

[0045] (2) The weighed samples were mixed and placed in an agate mortar, 5 ml of anhydrous ethanol was added and ground for 10 minutes;

[0046] (3) The ground powder was transferred to an alumina crucible, and then sintered in a high-temperature muffle furnace at 1350°C with air as the sintering atmosphere for 4 hours. After naturally cooling to room temperature, a self-activated long afterglow material with multi-mode luminescence was obtained.

[0047] The XRD test results of CaGa4O7 are as follows Figure 1 As shown, compared with the CaGa4O7 standard card, no obvious impurity peaks and phase changes were observed, proving that the material prepared in Example 1 is pure phase.

[0048] The photochromic curve of CaGa4O7 is as follows Figure 2 As shown, under the irradiation of 254nm light source, the color of the powder gradually changes from white to brown, and under the irradiation of 365nm light source, the brown gradually bleaches to white, and has the characteristics of recycling.

[0049] The excitation time-dependent fluorescence spectrum and afterglow spectrum of CaGa4O7 are shown in Figure 3 As shown, the luminescence intensity of the material increases with the extension of the excitation time of the 254nm light source, and there is a sky blue afterglow phenomenon after the excitation stops.

[0050] Example 2

[0051] A self-activated long afterglow material Ca with multi-mode luminescence 0.95 Ga4O7:0.05Pb 2+ The preparation method and application of the invention comprise the following steps:

[0052] (1) weighing CaO, Ga2O3 and PbO with a purity greater than 99.9% according to a stoichiometric ratio, wherein the molar ratio of the materials is 0.95:2:0.05;

[0053] (2) The weighed samples were mixed and placed in an agate mortar, 5 ml of anhydrous ethanol was added and ground for 10 minutes;

[0054] (3) The ground powder was transferred to an alumina crucible, and then sintered in a high-temperature muffle furnace at 1350°C with air as the sintering atmosphere for 4 hours. After naturally cooling to room temperature, a self-activated long afterglow material with multi-mode luminescence was obtained.

[0055] Ca 0.95 Ga4O7:0.05Pb 2+ The XRD test results are as follows Figure 1 As shown, compared with the CaGa4O7 standard card, no obvious impurity peaks and phase changes were observed, proving that the material prepared in Example 2 is pure phase.

[0056] Ca 0.95 Ga4O7:0.05Pb 2+ The excitation time-dependent fluorescence spectrum and afterglow spectrum are as follows Figure 4 As shown, the luminous intensity of the material increases with the extension of the excitation time of the 254nm light source, and the increasing speed is faster than that of CaGa4O7 in Example 1. At the same time, the afterglow performance is improved compared with CaGa4O7.

[0057] Example 3

[0058] A self-activated long afterglow material Ca with multi-mode luminescence 0.9 Ga4O7:0.1Pb 2+ The preparation method and application of the invention comprise the following steps:

[0059] (1) weighing CaO, Ga2O3 and PbO with a purity greater than 99.9% according to a stoichiometric ratio, wherein the molar ratio of the materials is 0.9:2:0.1;

[0060] (2) The weighed samples were mixed and placed in an agate mortar, 5 ml of anhydrous ethanol was added and ground for 10 minutes;

[0061] (3) The ground powder was transferred to an alumina crucible, and then sintered in a high-temperature muffle furnace at 1350°C with air as the sintering atmosphere for 4 hours. After naturally cooling to room temperature, a self-activated long afterglow material with multi-mode luminescence was obtained.

[0062] Ca 0.9 Ga4O7:0.1Pb 2+ The XRD test results are as follows Figure 1 As shown, compared with the CaGa4O7 standard card, no obvious impurity peaks and phase changes were observed, proving that the material prepared in Example 3 is pure phase.

[0063] Ca 0.9 Ga4O7:0.1Pb 2+ The photochromic curve of Figure 5 As shown, under the irradiation of 254nm light source, the diffuse reflectance curve of the material did not change significantly and the powder remained white.

[0064] Ca 0.9 Ga4O7:0.1Pb 2+ The excitation time-dependent fluorescence spectrum and afterglow spectrum are as follows Figure 6 As shown, the excitation time-dependent fluorescence spectrum of the material shows that Ca 0.9 Ga4O7:0.1Pb 2+ The change process is faster than that of the materials in Examples 1 and 2. However, the afterglow performance of the material is significantly reduced.

[0065] Example 4

[0066] An application form of a self-activated long afterglow material with multi-mode luminescence in information confidentiality includes the following steps:

[0067] like Figure 7 As shown, the materials obtained in Examples 1, 2 and 3 are fully ground and added to circular containers respectively, and the circular containers containing the three materials are arranged in a dot matrix as shown in the schematic diagram. The prepared "888" pattern undergoes photochromic change after being irradiated with a 254nm ultraviolet lamp in a daylight environment, and "888" is transformed into "906", obtaining encrypted information 1. In a dark environment, after the obtained "888" pattern is irradiated with a 254nm ultraviolet lamp, "888" is first transformed into "906", obtaining encrypted information 2. After 180s, "906" is transformed into "475", obtaining encrypted information 3. By arranging and combining encrypted information 1, encrypted information 2, and encrypted information 3, more complex encrypted information can be obtained based on the dynamic changes in the dot matrix color. Therefore, by combining photochromic and long afterglow performance, the disadvantage of the single traditional long afterglow encryption mode is overcome, and a dynamic multi-mode anti-counterfeiting technology is realized.

[0068] Example 5

[0069] An anti-counterfeiting application form of a self-activated long afterglow material with multi-mode luminescence, comprising the following steps:

[0070] like Figure 8 As shown, the materials obtained in Examples 1, 2 and 3 are fully ground and mixed with epoxy resin glue, and then the rose pattern shown in the schematic diagram is prepared by screen printing. In a dark environment, the "flower", "stem" and "leaf" parts of the rose pattern undergo fluorescence enhancement at different rates under the irradiation of a 254nm ultraviolet lamp, and the leaves, flowers and stem parts are displayed in sequence. After turning off the 254nm ultraviolet lamp, the leaves, stems and flowers of the rose pattern disappear in sequence, thereby achieving real-time pattern changes. The pattern similar to the rose pattern in this embodiment can be combined with any non-anti-counterfeiting pattern on the surface of the product, and it has a decorative effect in itself. When used as an anti-counterfeiting label, it is not easy for counterfeiters to find anti-counterfeiting labels mixed with non-anti-counterfeiting patterns, which significantly increases the difficulty of counterfeiting, further increases the anti-counterfeiting effect of this anti-counterfeiting application, and has the application potential of dynamic anti-counterfeiting. Compared with the traditional single long afterglow encryption mode, the technical means in the present invention realizes more modes of pattern change forms, forming a richer anti-counterfeiting pattern.

[0071] In addition, in the preparation formulas of Examples 1 to 3 of the present invention, the value of x is slightly changed, and other preparation processes are the same, so that self-activated long afterglow materials with different chemical formulas can be prepared and countless anti-counterfeiting pattern combinations can be printed.

[0072] Example 6

[0073] An information encryption application form of a self-activated long afterglow material with multi-mode luminescence, comprising the following steps:

[0074] like Fig. 9 As shown, the materials obtained in Examples 1, 2 and 3 are fully ground and added to a circular container, and the three materials are arranged as shown in the schematic diagram. In a dark environment, after the prepared matrix pattern is irradiated with a 254nm ultraviolet lamp, an arrow to the right first appears, indicating an error message. After 180s, the direction of the arrow changes from right to left, indicating the correct information. Therefore, by using the different afterglow properties of the materials, information encryption is achieved.

[0075] The above description shows and describes several preferred embodiments of the invention, but as mentioned above, it should be understood that the invention is not limited to the form disclosed herein, and should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be modified within the scope of the invention concept described herein through the above teachings or the technology or knowledge of the relevant field. Changes and modifications made by those skilled in the art should be within the scope of protection of the claims attached to the invention without departing from the spirit and scope of the invention.

Claims

1. A self-activated long afterglow luminescent material with multi-mode luminescence, characterized in that : The chemical formula is Ca 1-x Ga4O7:xPb 2+ Where 0≤x≤0.1; The Ca 1-x Ga4O7:xPb 2+ Based on the monoclinic C2 / c space group of CaGa4O7, Ga 3+ Site and Ca 2+ The sites are respectively associated with 4 and 5 O 2- The atoms combine to form a GaO4 triangular pyramid and a CaO5 triangular bipyramid, and the GaO4 triangular pyramid and the CaO5 triangular bipyramid are connected by sharing an angle. Based on the crystal structure of CaGa4O7, there are two different coordination environments of the GaO4 triangular pyramid and the CaO5 triangular bipyramid and oxygen vacancy defects. 2+ Different concentrations of Pb were introduced into the 2+ , forming different luminescent sites and defect types.

2. The self-activated long afterglow luminescent material with multi-mode luminescence according to claim 1, characterized in that : After the self-activated long afterglow luminescent material is excited by a 254nm light source, the afterglow color of the material is sky blue: when Pb 2+ When the doping amount is 0≤x≤0.0.5, the intensity and decay time of the afterglow increase with the increase of Pb 2+ The doping amount increases; when Pb 2+ When the doping amount is 0.05≤x≤0.1, the intensity and decay time of the afterglow increase with the increase of Pb 2+ decreases with the increase of doping amount.

3. The self-activated long afterglow luminescent material with multi-mode luminescence according to claim 1, characterized in that The luminescence intensity of the material increases with the extension of the excitation time of the 254nm light source.

4. The self-activated long afterglow luminescent material with multi-mode luminescence according to claim 1, characterized in that When the material is irradiated with a 254nm light source, the intrinsic powder color of the powder gradually changes from white to brown; when irradiated with a 365nm light source, the brown color gradually bleaches and turns into white. The above-mentioned photochromic change is reversible.

5. A method for preparing a self-activated long afterglow luminescent material with multi-mode luminescence according to claim 1, characterized in that : It includes the following steps: (1) According to Ca 1-x Ga4O7:xPb 2+ The raw materials CaO, Ga2O3 and PbO are weighed in a stoichiometric ratio, and the molar ratio of CaO, Ga2O3 and PbO is 1-x:2:x, and the range of x is 0≤x≤0.1; (2) Grinding the weighed raw materials uniformly; (3) The ground raw material powder is transferred to a crucible, and sintered at 1300-1400° C. for 4-6 hours in air as a sintering atmosphere, and a self-activated long afterglow luminescent material is obtained after cooling.

6. Application of a self-activated long afterglow material with multi-mode luminescence in information security, characterized in that: The following steps are involved: Using CaGa4O7, Ca 0.95 Ga4O7:0.05Pb 2+ and Ca 0.9 Ga4O7:0.1Pb 2+ The three materials are processed into particles respectively, and the obtained three particles are recorded as A, B, and C respectively. A, B, and C are used as pixels and arranged into a pixel matrix in a preset manner; After irradiating the pixel matrix with 254nm ultraviolet light, the pixel matrix is ​​placed in a dark environment. Among the A, B, and C pixel points, the C pixel point disappears quickly, and a pixel matrix pattern 1 is obtained. The pixel matrix pattern 1 is used to store the first confidential information. After 180s, the A pixel point disappears next, and a pixel matrix pattern 2 is obtained. The pixel matrix pattern 2 is used to store the second confidential information. When the pixel matrix is ​​placed in a daylight environment, the colors of the A and B pixels change from white to brown, thereby obtaining a pixel matrix pattern 3, wherein the pixel matrix pattern 3 is used to store the third confidential information; The pixel dot matrix pattern 1, the pixel dot matrix pattern 2 and the pixel dot matrix pattern 3 are combined according to preset rules to realize multiple information confidentiality.

7. Application of a self-activated long afterglow material with multi-mode luminescence in product anti-counterfeiting, characterized in that: The following steps are involved: Using CaGa4O7, Ca 0.95 Ga4O7:0.05Pb 2+ and Ca 0.9 Ga4O7:0.1Pb 2+ The three materials were processed into coatings, and the three coatings obtained were recorded as D, E, and F respectively; An anti-counterfeiting pattern is provided on the product, wherein the anti-counterfeiting pattern includes three sub-patterns. Use D, E and F to coat the three sub-patterns respectively to obtain coated anti-counterfeiting patterns; The coated anti-counterfeiting pattern is irradiated with 254nm ultraviolet light, and the sub-patterns become brighter in the following preset order due to the fluorescence enhancement phenomenon: the sub-pattern coated with F, the sub-pattern coated with D, and the sub-pattern coated with E; The 254nm ultraviolet light irradiation is removed, and the coated anti-counterfeiting pattern is placed in a dark environment, and the sub-patterns are darkened in sequence due to the long afterglow effect in the following preset order: the sub-pattern coated with F, the sub-pattern coated with E, and the sub-pattern coated with D; Product anti-counterfeiting through preset sequences of lightening and darkening.

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