An anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence and its application

Abstract

The invention discloses an anti-counterfeiting material with dual-mode orthogonal three-primary-color luminescence and application thereof, belonging to the technical field of nano fluorescent anti-counterfeiting materials. The anti-counterfeiting material is composed of a core-shell upconversion nanoparticle with one core and three shells, wherein the core-shell upconversion nanoparticle comprises, from the inside to the outside, an upconversion blue light emitting core, a downconversion red light emitting first shell, an upconversion green light emitting second shell and an inert third shell; the upconversion blue light emitting core is used to absorb 980nm near-infrared excitation light and generate upconversion blue light emission, the downconversion red light emitting first shell emits downconversion red light by absorbing 254nm ultraviolet light, the upconversion green light emitting second shell absorbs 808nm near-infrared excitation light and generates upconversion green light emission by self-sensitization, and the inert third shell is used to reduce fluorescence quenching caused by surface defects; thereby, independent dual-mode orthogonal three-primary-color luminescence is realized in a single nanoparticle based on the three-layer core-shell structure of NaGdF4:Yb / Tm@NaGdF4:Ce / Eu@NaErF4@NaYF4.

Description

Technical Field

[0001] The invention belongs to the technical field of nano fluorescent anti-counterfeiting materials, and specifically relates to an anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence and application thereof. Background Art

[0002] Fluorescent materials with light stimulus response can change their luminescent color or luminescent state under the irradiation of light of different wavelengths, showing great application prospects in the fields of information coding, data encryption, fingerprint recognition, security and anti-counterfeiting. Compared with traditional fluorescent anti-counterfeiting materials, fluorescent materials with stimulus response characteristics can provide additional anti-counterfeiting features in terms of anti-counterfeiting because they can produce dynamic optical output, thereby significantly improving the level of security and anti-counterfeiting.

[0003] At present, various fluorescent materials with stimulus-responsive properties, including metal organic frameworks, organic dyes, polymer quantum dots, lanthanide ion-doped upconversion nanoparticles, perovskites, etc., are widely used in fields such as information security protection and anti-counterfeiting. However, most stimulus-responsive fluorescent materials can usually only respond to fixed stimulation modes (specific excitation wavelengths), produce monotonous luminescent color changes (monochromatic fluorescence switching or two-color fluorescence conversion) and irreversible fluorescence response behaviors, resulting in unsatisfactory anti-counterfeiting effects and lack of effective protection of anti-counterfeiting information, which greatly limits the development of stimulus-responsive fluorescent materials in practical security and anti-counterfeiting applications. In addition, the luminescence of these materials in response to stimuli is usually based on a single mode, which is contrary to the development requirements of advanced anti-counterfeiting technology.

[0004] Therefore, there is an urgent need to develop a dual-mode multicolor fluorescent material that responds to multiple stimuli to achieve advanced anti-counterfeiting applications with a higher level of security. Summary of the invention

[0005] In view of the problems of existing fluorescent anti-counterfeiting materials such as simple luminescence mode and low anti-counterfeiting security performance, the present invention provides an anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence and its application. The anti-counterfeiting two-dimensional code pattern obtained by inkjet printing of the anti-counterfeiting material can produce anti-counterfeiting characteristics with up / down conversion dual-mode orthogonal three-primary color luminescence, realizing the application of advanced anti-counterfeiting.

[0006] The principle of the anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence of the present invention is as follows:

[0007] Benefiting from the rich energy level structure and long-lived excited state energy level of lanthanide ions, it can achieve multi-band emission covering ultraviolet, visible to near-infrared light based on optical frequency up-conversion or down-conversion. Hexagonal-NaGdF4 is selected as the matrix material of the up-conversion luminescent layer (core) because its lower phonon energy helps to enhance the up-conversion luminescence efficiency. Hexagonal-NaGdF4 is selected as the matrix material of the down-conversion luminescent layer because Gd 3+ The energy migration characteristics of ions can effectively improve down-conversion luminescence. 3+ 、Ce 3+ , Er 3+ The ions act as sensitizers to absorb 980nm, 254nm, and 808nm excitation light. 3+ 、Eu 3+ , Er 3+ The ions act as luminescence centers to generate up-conversion and down-conversion dual-mode three-primary color luminescence. It should be noted that the three luminescent regions are spatially isolated from the up-conversion blue light emitting core and the up-conversion green light emitting layer through the design of the sandwich structure NaGdF4:Yb / Tm@NaGdF4:Ce / Eu@NaErF4, cleverly avoiding the mutual interference of the two up-conversion luminescence processes, thereby realizing independent dual-mode orthogonal three-primary color luminescence in a single nanoparticle based on the three-layer core-shell structure of NaGdF4:Yb / Tm@NaGdF4:Ce / Eu@NaErF4@NaYF4.

[0008] The present invention is achieved through the following technical solutions:

[0009] A anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence is composed of a core-shell upconversion nanoparticle with one core and three shells, wherein the core-shell upconversion nanoparticle comprises, from the inside to the outside, an upconversion blue light emitting core, a downconversion red light emitting first shell, an upconversion green light emitting second shell and an inert third shell; wherein the upconversion blue light emitting core is used to absorb 980nm near-infrared excitation light and generate upconversion blue light emission, the downconversion red light emitting first shell emits downconversion red light by absorbing 254nm ultraviolet light, the upconversion green light emitting second shell absorbs 808nm near-infrared excitation light and generates upconversion green light emission by self-sensitization, and the inert third shell is used to reduce fluorescence quenching caused by surface defects.

[0010] Furthermore, the main matrix material of the up-conversion blue light emitting core and the up-conversion green light emitting second shell layer is NaGdF4, NaErF4, NaYF4, NaLuF4, NaScF4, NaYbF4 or LiYF4, KYF4.

[0011] Furthermore, the main matrix material of the first shell layer of the down-conversion red light emission is NaGdF4.

[0012] Furthermore, the one-core-three-shell core-shell upconversion nanoparticles are doped with a sensitizer and an activator, wherein the sensitizer includes Yb 3+ 、Ce 3+ , Er 3+ ions, the molar percentage of the sensitizer is 5% to 50%; the activator includes Tm 3+ 、Eu 3+ , Er 3+ ions, the molar percentage of the activator doped is 0.01% to 10%; Yb 3+ Ions act as sensitizers to absorb the energy of 980nm near-infrared light and transfer it to the activator Tm 3+ Ions emit upconverted blue light; Ce 3+ Ions are used as sensitizers to absorb the energy of 254nm ultraviolet light and transmit it to the Gd 3+ The energy migration of ions transfers energy to the co-doped activator Eu 3+ Ions emit down-converted red light; Er 3+ The ions are used as sensitizers to absorb the energy of 808nm near-infrared light and generate upconversion green light through self-sensitization.

[0013] Furthermore, the material of the up-conversion blue light emitting core is NaGdF4:Yb / Tm, the down-conversion red light emitting first shell is NaGdF4:Ce / Eu, the material of the up-conversion green light emitting second shell is NaErF4, and the material of the inert third shell is NaYF4; the up-conversion blue light emitting core NaGdF4:Yb / Tm is used to absorb 980nm near-infrared excitation light and generate up-conversion blue light emission, the down-conversion red light emitting first shell NaGdF4:Ce / Eu emits down-conversion red light by absorbing 254nm ultraviolet light, the up-conversion green light emitting second shell NaErF4 absorbs 808nm near-infrared excitation light and generates up-conversion green light emission by self-sensitization, and the inert third shell NaYF4 is used to reduce fluorescence quenching caused by surface defects.

[0014] On the other hand, the present invention also provides an application of an anti-counterfeiting material having dual-mode orthogonal three-primary-color luminescence in anti-counterfeiting, which specifically includes the following contents:

[0015] The anti-counterfeiting two-dimensional code pattern obtained by inkjet printing of the anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence is used to realize up / down conversion dual-mode three-primary color fluorescent two-dimensional code information display.

[0016] Furthermore, under the irradiation of 980nm and 808nm near-infrared light, the obtained two-dimensional code pattern displays the two-dimensional code information of up-conversion blue fluorescence and green fluorescence respectively; under the irradiation of 254nm ultraviolet light, the two-dimensional code information of down-conversion red fluorescence can be displayed.

[0017] Compared with the prior art, the advantages of the present invention are as follows:

[0018] The anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence of the present invention has up / down conversion dual-mode luminescence characteristics. Compared with single-mode fluorescent anti-counterfeiting materials, it not only increases the complexity of the material preparation process and the difficulty of material replacement, but also adds additional fluorescent anti-counterfeiting characteristics, thereby improving the level of security and anti-counterfeiting. In addition, the dual-mode orthogonal three-primary color luminescence anti-counterfeiting material can produce red, green, and blue multi-color information display in terms of information security protection. Compared with single-color or two-color fluorescent anti-counterfeiting materials, it not only realizes multiple protection of information and improves the security of information protection, but also can realize complex full-color and colorful information display, making it have important application prospects in the fields of multi-color coding and advanced anti-counterfeiting. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following is a brief introduction to the drawings required for the specific embodiments or the description of the prior art. In all the drawings, similar elements or parts are generally identified by similar reference numerals. In the drawings, the elements or parts are not necessarily drawn according to the actual scale.

[0020] Figure 1 :Schematic diagram of the structure of a dual-mode orthogonal three-primary color luminescent anti-counterfeiting material based on the three-layer core-shell structure of NaGdF4:Yb / Tm@NaGdF4:Ce / Eu@NaErF4@NaYF4;

[0021] Figure 2 :Schematic diagram of the up-conversion blue luminescence mechanism of the dual-mode orthogonal tri-color luminescent anti-counterfeiting material based on the core-shell structure under 980nm wavelength excitation;

[0022] Figure 3 :Schematic diagram of the up-conversion green luminescence mechanism of the dual-mode orthogonal tri-color luminescent anti-counterfeiting material based on the core-shell structure under 808nm wavelength excitation;

[0023] Figure 4 :Schematic diagram of the down-conversion red luminescence mechanism of the dual-mode orthogonal tri-color luminescent anti-counterfeiting material based on the core-shell structure under 254nm wavelength excitation;

[0024] Figure 5 : Transmission electron microscope (TEM) photo of the dual-mode orthogonal tri-color luminescent anti-counterfeiting material based on the three-layer core-shell structure;

[0025] Figure 6 : Particle size distribution diagram of dual-mode orthogonal three-primary color luminescent anti-counterfeiting material based on the three-layer core-shell structure;

[0026] Figure 7 : X-ray diffraction pattern of the dual-mode orthogonal three-primary color luminescent anti-counterfeiting material based on the core-shell structure;

[0027] Figure 8 : Up / down conversion dual-mode emission spectra of the dual-mode orthogonal tri-primary color luminescent anti-counterfeiting material based on the core-shell structure under different wavelength excitations of 980nm, 808nm and 254nm;

[0028] Fig. 9 : A photo of the anti-counterfeiting QR code pattern under natural light obtained by inkjet printing of the dual-mode orthogonal three-primary color luminescent anti-counterfeiting material based on the core-shell structure. DETAILED DESCRIPTION

[0029] In order to clearly and completely describe the technical solution and its specific working process of the present invention, the specific implementation methods of the present invention are as follows in conjunction with the accompanying drawings of the specification:

[0030] Example 1

[0031] like Figure 1 As shown, this embodiment provides an anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence, the material is composed of core-shell upconversion nanoparticles with one core and three shells, the core-shell upconversion nanoparticles include, from the inside to the outside, an upconversion blue light emitting core NaGdF4:Yb / Tm, a downconversion red light emitting first shell NaGdF4:Ce / Eu, an upconversion green light emitting second shell NaErF4 and an inert third shell NaYF4; the upconversion blue light emitting core NaGdF4:Yb / Tm is used to absorb 980nm near-infrared excitation light and generate upconversion blue light emission, the downconversion red light emitting first shell NaGdF4:Ce / Eu emits downconversion red light by absorbing 254nm ultraviolet light, the upconversion green light emitting second shell NaErF4 absorbs 808nm near-infrared excitation light and generates upconversion green light emission by self-sensitization, and the inert third shell NaYF4 is used to reduce fluorescence quenching caused by surface defects.

[0032] like Figure 8 As shown, the luminescent anti-counterfeiting material generates blue light emission under the excitation of 980nm near-infrared light, generates green light emission under the excitation of 808nm near-infrared light, and generates red light emission under the excitation of 254nm ultraviolet light.

[0033] like Figure 5As shown, the three-layer core-shell structured nanoparticles are monodisperse, hexagonal nanoparticles with uniform morphology; Figure 6 As shown, the average size of the three-layer core-shell nanoparticles is 57 nm. Figure 7 As shown, the core and core-single-layer shell nanoparticles are pure NaGdF4 nanocrystals, the core-double-layer shell nanoparticles are pure NaErF4 nanocrystals, and the core-triple-layer shell nanoparticles are pure NaYF4 nanocrystals.

[0034] like Figure 2-Figure 4 As shown, the light emitting principle of the anti-counterfeiting material with dual-mode orthogonal three-primary color light emission in this embodiment is as follows:

[0035] Core doped Yb 3+ The ions first absorb the 980nm near-infrared excitation light and then transfer the energy to the co-doped Tm through a three-photon / four-photon process. 3+ ions, producing upconversion blue light emission, such as Figure 2 As shown. The first shell layer is doped with Ce 3+ The ions first absorb ultraviolet light with a wavelength of 254nm, and then transfer the energy to the Gd 3+ Ions transferred to co-doped Eu 3+ ions, producing down-converted red emission, such as Figure 4 Compared with Ce 3+ →Eu 3+ , by constructing Ce 3+ →Gd 3+ →Eu 3+ The energy transfer path of ions can reduce energy loss, thereby effectively improving down-conversion luminescence. 3+ ions, absorbing 808nm near-infrared excitation light, produce upconversion green light emission by self-sensitization, such as Figure 3 As shown. The third shell is an inert shell, which is used to reduce fluorescence quenching caused by surface defects. In order to prevent unnecessary energy transfer and cross relaxation between the doped ions in the two up-conversion luminescent cores (layers), the two are spatially isolated by embedding a down-conversion red light emitting layer between them.

[0036] The NaGdF4:Yb / Tm@NaGdF4:Ce / Eu@NaErF4@NaYF4 core-shell structured anti-counterfeiting material with dual-mode orthogonal tri-primary color luminescence described in this embodiment is prepared by the following method:

[0037] (1) Preparation of NaGdF4:Yb / Tm core nanoparticles: Rare earth salts Gd(CH3COO)3 (0.236 mmol), Yb(CH3COO)3 (0.16 mmol) and Tm(CH3COO)3 (0.004 mmol) were added to a mixed solvent of 3 mL of oleic acid (OA) and 7 mL of 1-octadecene (ODE) in a predetermined ratio, and the mixture was heated to 150°C for 90 minutes to obtain a Gd / Yb / Tm-OA rare earth oleic acid complex. After cooling to room temperature, a methanol solution of NH4F (1.6 mmol) and NaOH (1.0 mmol) was added. After the methanol evaporated, the mixture was heated to 290°C under inert gas protection for 90 minutes to obtain core nanoparticles.

[0038] (2) Preparation of shell precursors: 0.4 mmol of rare earth salt required for the shell coating is added to a mixed solvent of 3 mL of oleic acid (OA) and 7 mL of 1-octadecene (ODE) in a predetermined ratio, and the mixture is heated to 150 °C and reacted for 60 minutes to obtain the Gd / Ce / Eu-OA, Er-OA, and Y-OA rare earth oleic acid complexes required for the first shell, the second shell, and the third shell, respectively.

[0039] (3) Preparation of NaGdF4:Yb / Tm@NaGdF4:Ce / Eu core-shell structured nanoparticles. The prepared NaGdF4:Yb / Tm core nanoparticles were added as seeds to the shell precursor Gd / Ce / Eu-OA rare earth oleic acid complex solution, and a methanol solution of NH4F (1.6 mmol) and NaOH (1.0 mmol) was added. After the methanol evaporated, the mixture was heated to 290°C under inert gas protection for 90 minutes to obtain core-shell structured nanoparticles.

[0040] (4) Preparation of NaGdF4:Yb / Tm@NaGdF4:Ce / Eu@NaErF4 double-layer core-shell structured nanoparticles. The prepared NaGdF4:Yb / Tm@NaGdF4:Ce / Eu core-shell structured nanoparticles were added as seeds to the shell precursor Er-OA rare earth oleic acid complex solution, and a methanol solution of NH4F (1.6 mmol) and NaOH (1.0 mmol) was added. After the methanol evaporated, the mixture was heated to 290°C under inert gas protection for 90 minutes to obtain double-layer core-shell structured nanoparticles.

[0041] (5) Preparation of NaGdF4:Yb / Tm@NaGdF4:Ce / Eu@NaErF4@NaYF4 three-layer core-shell structure nanoparticles. The prepared NaGdF4:Yb / Tm@NaGdF4:Ce / Eu@NaErF4 double-layer core-shell structure nanoparticles were added as seeds to the shell precursor Y-OA rare earth oleic acid complex solution, and a methanol solution of NH4F (1.6 mmol) and NaOH (1.0 mmol) was added. After the methanol evaporated, the mixture was heated to 290°C under inert gas protection for 90 minutes to obtain three-layer core-shell structure nanoparticles.

[0042] Example 2

[0043] The NaYF4:Yb / Tm@NaGdF4:Ce / Tb@NaYF4:Er / Ho@NaYF4 core-shell structured anti-counterfeiting material with dual-mode orthogonal tri-primary color luminescence described in this embodiment is prepared by the following method:

[0044] (1) Preparation of NaYF4:Yb / Tm core nanoparticles: Rare earth salts Y(CH3COO)3 (0.236 mmol), Yb(CH3COO)3 (0.16 mmol) and Tm(CH3COO)3 (0.004 mmol) were added to a mixed solvent of 3 mL of oleic acid (OA) and 7 mL of 1-octadecene (ODE) in a predetermined ratio, and the mixture was heated to 150°C for 90 minutes to obtain a Y / Yb / Tm-OA rare earth oleic acid complex. After cooling to room temperature, a methanol solution of NH4F (1.6 mmol) and NaOH (1.0 mmol) was added. After the methanol evaporated, the mixture was heated to 290°C under inert gas protection for 90 minutes to obtain core nanoparticles.

[0045] (2) Preparation of shell precursors: 0.4 mmol of rare earth salt required for the shell coating is added to a mixed solvent of 3 mL of oleic acid (OA) and 7 mL of 1-octadecene (ODE) in a predetermined ratio, and the mixture is heated to 150°C and reacted for 60 minutes to obtain the Gd / Ce / Tb-OA, Y / Er / Ho-OA, and Y-OA rare earth oleic acid complexes required for the first shell, the second shell, and the third shell, respectively.

[0046] (3) Preparation of NaYF4:Yb / Tm@NaGdF4:Ce / Tb core-shell structured nanoparticles. The prepared NaYF4:Yb / Tm core nanoparticles were added as seeds to the shell precursor Gd / Ce / Tb-OA rare earth oleic acid complex solution, and a methanol solution of NH4F (1.6 mmol) and NaOH (1.0 mmol) was added. After the methanol evaporated, the mixture was heated to 290°C under inert gas protection for 90 minutes to obtain core-shell structured nanoparticles.

[0047] (4) Preparation of NaYF4:Yb / Tm@NaGdF4:Ce / Tb@NaYF4:Er / Ho double-layer core-shell structure nanoparticles. The prepared NaYF4:Yb / Tm@NaGdF4:Ce / Tb core-shell structure nanoparticles were added as seeds to the shell precursor Y / Er / Ho-OA rare earth oleic acid complex solution, and a methanol solution of NH4F (1.6 mmol) and NaOH (1.0 mmol) was added. After the methanol evaporated, the mixture was heated to 290°C under inert gas protection and reacted for 90 minutes to obtain double-layer core-shell structure nanoparticles.

[0048] (5) Preparation of NaYF4:Yb / Tm@NaGdF4:Ce / Tb@NaYF4:Er / Ho@NaYF4 three-layer core-shell structure nanoparticles. The prepared NaYF4:Yb / Tm@NaGdF4:Ce / Tb@NaYF4:Er / Ho double-layer core-shell structure nanoparticles were added as seeds to the shell precursor Y-OA rare earth oleic acid complex solution, and a methanol solution of NH4F (1.6 mmol) and NaOH (1.0 mmol) was added. After the methanol evaporated, the mixture was heated to 290°C under inert gas protection for 90 minutes to obtain three-layer core-shell structure nanoparticles.

[0049] The luminescence principle of an anti-counterfeiting material with dual-mode orthogonal three-primary-color luminescence in the embodiment is as follows:

[0050] Core doped Yb 3+ The ions first absorb the 980nm near-infrared excitation light and then transfer the energy to the co-doped Tm through a three-photon / four-photon process. 3+ ions, producing upconversion blue light emission. The first shell doped Ce 3+ The ions first absorb ultraviolet light with a wavelength of 254nm, and then transfer the energy to the Gd 3+ Ion transfer to co-doped Tb 3+ ions, producing down-converted green emission. The second shell doped Er 3+ ions absorb 1560nm near-infrared excitation light and transfer energy to the co-doped Ho 3+ ions, producing up-conversion red light emission. The third shell is an inert shell, which is used to reduce fluorescence quenching caused by surface defects. In order to prevent unnecessary energy transfer and cross relaxation between the doped ions in the two up-conversion luminescent cores (layers), the two are spatially isolated by embedding a down-conversion green light emitting layer between them.

[0051] Example 3

[0052] like Fig. 9As shown, the present embodiment provides an application of an anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence in anti-counterfeiting, and the anti-counterfeiting two-dimensional code pattern obtained by inkjet printing of the anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence is used to realize up / down conversion dual-mode three-primary color fluorescence two-dimensional code information display. Since the anti-counterfeiting material is colorless and transparent, the two-dimensional code pattern it produces is invisible under natural light, and the invisible state makes the two-dimensional code information hidden. However, under the irradiation of 980nm and 808nm near-infrared light, the hidden pattern can respectively display the two-dimensional code information of up-conversion blue fluorescence and up-conversion green fluorescence. And under the irradiation of 254nm ultraviolet light, the hidden pattern can display the two-dimensional code information of down-conversion red fluorescence. This anti-counterfeiting two-dimensional code with up / down conversion dual-mode three-primary color fluorescence display significantly increases the difficulty of being forged and improves the security level of anti-counterfeiting.

[0053] Specifically, in this embodiment, the three-layer core-shell structure nanoparticles obtained in Example 1 are protonated with hydrochloric acid to treat the oleic acid ligands on the surface, and the obtained dual-mode orthogonal tri-primary color luminescent anti-counterfeiting material based on the aqueous solution of the nanoparticles is added to the ink cartridge of the printer through a syringe, and an anti-counterfeiting two-dimensional code pattern is obtained by inkjet printing. The two-dimensional code pattern generated by the anti-counterfeiting material cannot be seen under natural light, but using an optical lens under the irradiation of 980nm and 808nm near-infrared light, the two-dimensional code information display of up-conversion blue and green fluorescence can be seen respectively, and under the irradiation of 254nm ultraviolet light, the two-dimensional code information display of down-conversion red fluorescence can be seen.

[0054] The preferred embodiments of the present invention are described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0055] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0056] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. An anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence, characterized in that: The nanoparticle is composed of a core-shell upconversion nanoparticle with one core and three shells, wherein the core-shell upconversion nanoparticle includes, from the inside to the outside, an upconversion blue light emitting core, a downconversion red light emitting first shell, an upconversion green light emitting second shell and an inert third shell; The material of the up-conversion blue light emitting core is NaGdF4:Yb / Tm, Yb 3+ Ions act as sensitizers to absorb the energy of 980nm near-infrared light and transfer it to the activator Tm 3+ Ions emit upconversion blue light; downconversion red light emission The first shell is NaGdF4:Ce / Eu, Ce 3+ Ions are used as sensitizers to absorb the energy of 254nm ultraviolet light and transmit it to the Gd 3+ The energy migration of ions transfers energy to the co-doped activator Eu 3+ Ions emit down-converted red light; up-converted green light emission The second shell material is NaErF4, Er 3+ The ions are used as sensitizers to absorb the energy of 808nm near-infrared light and generate up-conversion green light through self-sensitization. The material of the inert third shell is NaYF4, which is used to reduce the fluorescence quenching caused by surface defects. The molar percentage of the sensitizer is 5% to 50%; the molar percentage of the activator is 0.01% to 10%.

2. The application of the anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence in anti-counterfeiting as claimed in claim 1, characterized in that: The specific contents include the following: The anti-counterfeiting two-dimensional code pattern obtained by inkjet printing of the anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence is used to realize up / down conversion dual-mode three-primary color fluorescent two-dimensional code information display.

3. The application of the anti-counterfeiting material with dual-mode orthogonal three-primary color luminescence in anti-counterfeiting as claimed in claim 1, characterized in that: Under the irradiation of 980nm and 808nm near-infrared light, the obtained QR code pattern displays the QR code information of up-conversion blue fluorescence and green fluorescence respectively; under the irradiation of 254nm ultraviolet light, the QR code information of down-conversion red fluorescence can be displayed.

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