Multi-channel information encryption method based on gallium germanate oxide

Abstract

The invention relates to a multi-channel information encryption method based on gallium germanate oxide, and belongs to the technical field of anti-counterfeiting materials. The chemical formula of the gallium germanate oxide is M (3-x) Ga2Ge3O12: x Ln, M is Ca and Sr, and Ln is Pr < 3 + >, Eu < 3 + > and 0lt; x is less than or equal to 0.09; the gallium germanate oxide M < 3-x > Ga < 2 > Ge < 3 > O < 12: x > L < n > is blue and white in light emission under the excitation of ultraviolet light, and the rest is orange white in light emission; under X-ray excitation, the fluorescent powder emits orange light, and the rest of the fluorescent powder emits orange red light; multi-channel anti-counterfeiting identification is carried out by utilizing different luminescence characteristics of gallium germanate oxide M (3-x) Ga2Ge3O12: x Ln under excitation of ultraviolet light and X-ray energy. The single material gallium germanate oxide responds to double excitation sources (ultraviolet light and X rays) and has the time-resolved afterglow characteristic, and through the double excitation response and the time-resolved afterglow characteristic, the technical bottlenecks that a traditional anti-counterfeiting technology is prone to being copied and single in verification means are effectively solved.

Description

Technical Field

[0001] The invention relates to a multi-channel information encryption method based on gallium germanate oxide, and belongs to the technical field of anti-counterfeiting materials. Background Art

[0002] In the existing technology, many types of luminescent materials have been explored for anti-counterfeiting, such as carbon dots, nanoceramics, metal halide perovskites, transparent glass media, organic polymers and lanthanide / transition metal ion-doped inorganic phosphors. Among them, lanthanide-doped oxide luminescent materials have attracted much attention due to the unique advantages of their material system. This type of material exhibits three core characteristics: distinct color characteristics and visual recognition capabilities, adjustable luminescence lifetime gradients, and multimodal luminescence response mechanisms based on multi-wavelength excitation sources, providing innovative solutions for constructing multi-channel dynamic anti-counterfeiting systems. At present, many oxide materials for multi-channel dynamic anti-counterfeiting have been developed, such as Mg 2+ / Ge 4+ ZnGa2O4, Pb co-doped with Mn 2+ With Tb 3+ Co-doped NaGdGeO4, etc. However, to achieve multifunctionality, these materials often require co-doping with multiple rare earth ions, which increases the complexity of material design and synthesis. More importantly, because these materials often rely on ultraviolet and visible light energy as excitation sources to induce optical signal output, their photoresponse sensitivity and light output identifiability are significantly limited. Summary of the Invention

[0003] In view of the problems that the existing multi-channel dynamic anti-counterfeiting materials rely on ultraviolet and visible light energy as the excitation light source to induce the output of light signals, and the sensitivity of their light response and the identifiability of light output are significantly limited, the present invention proposes a multi-channel information encryption method based on gallium germanate oxide, which utilizes gallium germanate oxide M 3-x Ga2Ge3O 12 :x Ln's distinct luminescence properties under UV and X-ray excitation, respectively, enable multi-channel anti-counterfeiting identification. The single-material gallium germanate oxide of the present invention exhibits high responsiveness to dual excitation sources (UV and X-rays) and time-resolved afterglow characteristics. This property effectively addresses technical bottlenecks of traditional anti-counterfeiting technologies, such as ease of duplication and limited verification methods.

[0004] A multi-channel information encryption method based on gallium germanate oxide, wherein the chemical formula of the gallium germanate oxide is M 3-x Ga2Ge3O 12 :x Ln, where M is Ca, Sr, Mg or Ba, and Ln is Pr 3+ 、Eu 3+ 、Dy 3+, 0 <x≤0.09;

[0005] The gallogermanate oxide M 3-x Ga2Ge3O 12 :x Ln emits blue-white light under ultraviolet excitation, and its afterglow is orange-white; it emits orange light under X-ray excitation, and its afterglow is orange-red; Gallium germanate oxide M 3-x Ga2Ge3O 12 :x Ln emission induced by ultraviolet light or X-ray

[0006] The wavelength of light covers 350nm to 800nm; its luminescence originates from the energy level transition of rare earth ions and self-activated matrix. When thermally excited by ultraviolet light or X-rays, the electrons in the valence band are excited from the ground state to the excited state. Due to their instability, they return from the excited state to the ground state. The energy released in this process is expressed in the form of light radiation.

[0007] Using gallium germanate oxide M 3-x Ga2Ge3O 12 :x Ln uses different luminescence characteristics under ultraviolet light and X-ray energy excitation to perform multi-channel anti-counterfeiting identification.

[0008] The gallogermanate oxide M 3-x Ga2Ge3O 12 :x Ln preparation method, the specific steps are as follows:

[0009] (1) Wet-grinding and mixing the M-containing compound, the gallium-containing compound, the germanium-containing compound, and the Ln-containing compound to obtain a mixed powder;

[0010] (2) The mixed powder of step (1) is placed in an air atmosphere at a temperature of 1200-1300° C. and calcined for 5-6 hours, cooled to room temperature, and ground to obtain gallium germanate oxide M 3-x Ga2Ge3O 12 :x Ln.

[0011] Preferably, the compound containing M in step (1) is a carbonate, nitrate, chloride, oxide, hydroxide, oxalate or acetate.

[0012] Preferably, the gallium-containing compound in step (1) is gallium carbonate, gallium nitrate, gallium chloride, gallium oxide, gallium hydroxide, gallium oxalate or gallium acetate.

[0013] Preferably, the germanium-containing compound in step (1) is germanium carbonate, germanium nitrate, germanium chloride, germanium oxide, germanium hydroxide, germanium oxalate or germanium acetate.

[0014] Preferably, the Ln-containing compound in step (1) is carbonate, nitrate, chloride, oxide, hydroxide, oxalate or acetate.

[0015] Multi-channel anti-counterfeiting principle based on gallium germanate oxide: Taking gallium germanate oxide Ca 3-x Ga2Ge3O 12 :x Pr 3+ (0 < x ≤ 0.09) as an example, gallium germanate oxide Ca 3-x Ga2Ge3O 12 :x Pr 3+ (0 < x ≤ 0.09) belongs to the garnet structure (space group Ia3d), where Ca 2+ occupies the dodecahedral position, Ga 3+ / Ge 4+ occupies the octahedral and tetrahedral positions, and Pr 3+ replaces the Ca 2+ site. For the phenomena of photoluminescence (PL), X-ray irradiation luminescence (RL) and long persistent luminescence (LPL), when excited by ultraviolet light or X-ray, electrons in the valence band are excited from the ground state to the excited state, and free electrons move freely in the conduction band. Some of them will be trapped by shallow and deep traps, and the Pr 3+ ions will be excited to emit light at room temperature or under thermal stimulation. Due to the instability of the excited state, free electrons return to the ground state, and a large amount of energy will be released during this process. Part of the energy is released in the form of phonon vibration energy, and part of the energy is released in the form of light radiation. The energy of this part of light radiation forms the luminescence of Pr 3+ ions. Utilizing the different luminescence characteristics of gallium germanate oxide Ca 3-x Ga2Ge3O 12 :x Pr 3+ (0 < x ≤ 0.09) under ultraviolet light and X-ray energy excitation respectively (showing blue-white luminescence under ultraviolet light excitation and orange-white afterglow; showing orange luminescence under X-ray excitation and orange-red afterglow), multi-channel anti-counterfeiting identification is carried out.

[0016] The beneficial effects of the present invention are as follows:

[0017] (1) The present invention utilizes the different luminescence characteristics of gallium germanate oxide M 3-x Ga2Ge3O 12 :x Ln under ultraviolet light and X-ray energy excitation respectively (showing blue-white luminescence under ultraviolet light excitation and orange-white afterglow; showing orange luminescence under X-ray excitation and orange-red afterglow), and conducts multi-channel anti-counterfeiting identification, which can effectively solve the technical bottlenecks existing in traditional anti-counterfeiting technologies, such as being easily replicated and having a single verification method;

[0018] (2) Gallium germanate oxide M of the present invention 3-x Ga2Ge3O 12 :x Ln has a simple preparation method and can emit light with a wavelength covering 350nm to 800nm ​​under the induction of X-ray energy irradiation and ultraviolet light irradiation, with excellent luminescence performance;

[0019] (3) The present invention uses gallium germanate oxide M 3-x Ga2Ge3O 12 :x Ln excitation conditions and time-resolved luminescence characteristics provide a high-security verification method and can be applied to multi-channel anti-counterfeiting. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 Ca3Ga2Ge3O in Example 1 12 The crystal structure diagram of

[0021] Figure 2 The oxide Ca3Ga2Ge3O of Example 1 12 , Ca 3-x Ga2Ge3O 12 :xPr 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, and 0.090, respectively);

[0022] Figure 3 The oxide Ca3Ga2Ge3O of Example 1 12 , Ca 3-x Ga2Ge3O 12 :xPr 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, and 0.090, respectively) Photographs of luminescence under 254nm ultraviolet light excitation and afterglow after being turned off;

[0023] Figure 4 The oxide Ca3Ga2Ge3O of Example 1 12 , Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ Emission spectrum of

[0024] Figure 5 The oxide Ca3Ga2Ge3O of Example 1 12 , Ca 3-x Ga2Ge3O 12 :xPr 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, and 0.090, respectively);

[0025] Figure 6 Example 1 oxide Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ , Ca 2.91 Ga2Ge3O 12 :0.09Pr 3+ Afterglow spectrum of

[0026] Figure 7 The oxide Ca3Ga2Ge3O of Example 1 12 , Ca 3-x Ga2Ge3O 12 :xPr 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, and 0.090, respectively) photos of the luminescence under X-ray excitation and the afterglow after it is turned off;

[0027] Figure 8 The oxide Ca3Ga2Ge3O of Example 1 12 , Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ RL spectrum under X-ray;

[0028] Figure 9 Example 1Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ Afterglow spectrum under X-ray;

[0029] Figure 10 Example 1Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ CIE diagram of afterglow;

[0030] Figure 11 Example 2 Gallium Germanate Oxide Sr3Ga2Ge3O 12 The crystal structure diagram of

[0031] Figure 12 Example 2 oxide Sr3Ga2Ge3O 12 、Sr 3-x Ga2Ge3O 12 :xEu 3+ (x is 0.010, 0.050, and 0.090, respectively);

[0032] Figure 13 Example 2 oxide Sr3Ga2Ge3O 12 、Sr 3-xGa2Ge3O 12 :xEu 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, and 0.090, respectively) emission spectra and luminescence photographs under 254 nm ultraviolet light excitation;

[0033] Figure 14 Example 2 oxide Sr3Ga2Ge3O 12 、Sr 3-x Ga2Ge3O 12 :xEu 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, 0.090 respectively) CIE diagram of the spectrum at UV = 254 nm;

[0034] Figure 15 Example 2 oxide Sr3Ga2Ge3O 12 、Sr 3-x Ga2Ge3O 12 :xEu 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, and 0.090, respectively) spectra and luminescence photographs under X-rays;

[0035] Figure 16 Example 2 oxide Sr3Ga2Ge3O 12 、Sr 3-x Ga2Ge3O 12 :xEu 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, and 0.090 respectively) CIE diagram of the spectrum under X-ray. DETAILED DESCRIPTION

[0036] The present invention will be further described in detail below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the contents described above.

[0037] Example 1: A multi-channel information encryption method based on gallium germanate oxide, the specific steps are as follows: the chemical formula of the gallium germanate oxide is Ca 3-x Ga2Ge3O 12 :xPr 3+ , x are 0.005, 0.010, 0.030, 0.050, 0.070, and 0.090 respectively;

[0038] Not doped with Pr 3+ Gallium germanate oxide Ca3Ga2Ge3O 12 The preparation method comprises the following specific steps:

[0039] (1) 0.6005 g of Ca2CO3 (purity 99.99%), 0.3749 g of Ga2O3 (purity 99.99%), and 0.6278 g of GeO2 (purity 99.99%) were wet-milled and mixed, and 3 g of anhydrous ethanol was added during the wet-milling process to obtain a mixed powder;

[0040] (2) The mixed powder of step (1) was calcined in an air atmosphere at 1200°C for 6 hours, cooled to room temperature, and ground to obtain gallium germanate oxide Ca3Ga2Ge3O 12 ;

[0041] Not doped with Pr 3+ Gallium germanate oxide Ca3Ga2Ge3O 12 The crystal structure of Figure 1 ,from Figure 1 It can be seen that Ca3Ga2Ge3O 12 It has a cubic crystal structure with a space group of Ia-3d. The structure is composed of [CaO8] dodecahedrons, [GaO6] octahedrons and [GeO4] tetrahedrons arranged in an orderly manner in space.

[0042] The chemical formula of the gallogermanate oxide is Ca 3-x Ga2Ge3O 12 :xPr 3+ The preparation method (x is 0.005, 0.010, 0.030, 0.050, 0.070, and 0.090, respectively) comprises the following steps:

[0043] (1) Ca2CO3 (purity 99.99%) (0.6005 g, 0.5985 g, 0.5945 g, 0.5865 g, 0.5825 g, respectively), Ga2O3 (purity 99.99%) 0.3749 g, GeO2 (purity 99.99%) 0.6278 g, Pr2O3 (purity 99.99%) (0.0016 g, 0.0033 g, 0.0099 g, 0.0165 g, 0.0231 g, 0.0297 g, respectively) were wet-milled and uniformly mixed. 3 g of anhydrous ethanol was added during the wet-milling process to obtain a mixed powder;

[0044] (2) The mixed powder of step (1) was calcined in an air atmosphere at 1200°C for 6 hours, cooled to room temperature, and ground to obtain gallium germanate oxide Ca 2.995 Ga2Ge3O 12 :0.005Pr 3+ , Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ , Ca 2.97 Ga2Ge3O12 :0.03Pr 3+ , Ca 2.95 Ga2Ge3O 12 :0.05Pr 3+ , Ca 2.93 Ga2Ge3O 12 :0.07Pr 3+ , Ca 2.91 Ga2Ge3O 12 :0.09Pr 3+ ;

[0045] Oxide Ca3Ga2Ge3O 12 , Ca 2.995 Ga2Ge3O 12 :0.005Pr 3+ , Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ , Ca 2.97 Ga2Ge3O 12 :0.03Pr 3+ , Ca 2.95 Ga2Ge3O 12 :0.05Pr 3+ , Ca 2.93 Ga2Ge3O 12 :0.07Pr 3+ , Ca 2.91 Ga2Ge3O 12 :0.09Pr 3+ The XRD pattern of Figure 2 ,from Figure 2 It can be seen that the oxide Ca3Ga2Ge3O 12 , Ca 2.995 Ga2Ge3O 12 :0.005Pr 3+ , Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ , Ca 2.97 Ga2Ge3O 12 :0.03Pr 3+ , Ca 2.95 Ga2Ge3O 12 :0.05Pr 3+ , Ca 2.93 Ga2Ge3O 12 :0.07Pr 3+ , Ca 2.91 Ga2Ge3O 12 :0.09Pr 3+The samples were all pure phases without any impurity phases;

[0046] Oxide Ca3Ga2Ge3O 12 , Ca 2.995 Ga2Ge3O 12 :0.005Pr 3+ , Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ , Ca 2.97 Ga2Ge3O 12 :0.03Pr 3+ , Ca 2.95 Ga2Ge3O 12 :0.05Pr 3+ , Ca 2.93 Ga2Ge3O 12 :0.07Pr 3+ , Ca 2.91 Ga2Ge3O 12 :0.09Pr 3+ See the following pictures for the luminescence under UV = 254nm excitation and the afterglow after turning off. Figure 3 , the samples all showed obvious color evolution, CGGO: 0.005Pr 3+ and CGGO: 0.01Pr 3+ It exhibits blue emission during UV excitation, but produces an orange-white to red afterglow after irradiation stops. 3+ At concentrations (x ≥ 0.03), the sample showed a blue-white gradient afterglow;

[0047] Oxide Ca3Ga2Ge3O 12 , Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ The emission spectrum of Figure 4 ,from Figure 4 It can be seen that the PL spectrum of undoped CGGO shows a broad band (350-700 nm) with a peak at 450 nm, which is attributed to self-activated emission. 3+ ions, obvious narrow peaks appeared in the range of 450-750 nm, which were attributed to Pr 3+ Inner shell transitions;

[0048] Oxide Ca3Ga2Ge3O 12 , Ca 2.995 Ga2Ge3O 12 :0.005Pr 3+ , Ca 2.99 Ga2Ge3O 12:0.01Pr 3+ , Ca 2.97 Ga2Ge3O 12 :0.03Pr 3+ , Ca 2.95 Ga2Ge3O 12 :0.05Pr 3+ , Ca 2.93 Ga2Ge3O 12 :0.07Pr 3+ , Ca 2.91 Ga2Ge3O 12 :0.09Pr 3+ The emission spectrum of Figure 5 ,from Figure 5 It can be seen that with the increase of Pr 3+ With the increase of concentration (x = 0, 0.005, 0.01, 0.03, 0.05, 0.07 and 0.09), the host emission intensity gradually decreased, while Pr 3+ The emission is enhanced, indicating that the energy is transferred from the CGGO host to the Pr 3+ ions;

[0049] Oxide Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ , Ca 2.91 Ga2Ge3O 12 :0.09Pr 3+ The afterglow spectrum of Figure 6 ,from Figure 6 It can be seen that the reason for the afterglow color change is the 607nm ( 1 D2→ 3 H4) Changes in intensity;

[0050] Oxide Ca3Ga2Ge3O 12 , Ca 2.995 Ga2Ge3O 12 :0.005Pr 3+ , Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ , Ca 2.97 Ga2Ge3O 12 :0.03Pr 3+ , Ca 2.95 Ga2Ge3O 12 :0.05Pr 3+ , Ca 2.93 Ga2Ge3O 12 :0.07Pr 3+ , Ca 2.91 Ga2Ge3O12 :0.09Pr 3+ The luminescence under X-ray excitation and the afterglow after shutdown are shown in the following pictures. Figure 7 ,from Figure 7 It can be seen that under the excitation of X-rays, they all show orange luminescence and produce orange to red afterglow after the irradiation stops;

[0051] Oxide Ca3Ga2Ge3O 12 , Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ , Ca 2.91 Ga2Ge3O 12 :0.09Pr 3+ The RL spectrum under X-ray is shown in Figure 8 ,from Figure 8 It can be seen that CGGO does not emit light under X-rays and is doped with Pr 3+ The ion shows Pr 3 + luminescence of ions;

[0052] Oxide Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ Afterglow spectrum under X-ray and CIE Figure 9 and Figure 10 ,from Figure 9 and Figure 10 It can be seen that the afterglow color of the sample under x-ray changes from orange to red;

[0053] Therefore, gallium germanate oxide Ca 3-x Ga2Ge3O 12 :xPr 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, 0.090 respectively) It emits blue-white light under ultraviolet excitation, and its afterglow is orange-white; it emits orange light under X-ray excitation, and its afterglow is orange-red; using gallium germanate oxide Ca 3-x Ga2Ge3O 12 :xPr 3+ Multi-channel anti-counterfeiting identification is performed based on the different luminescence characteristics under ultraviolet light and X-ray energy excitation.

[0054] Example 2: A multi-channel information encryption method based on gallium germanate oxide, the specific steps are as follows: the chemical formula of the gallium germanate oxide is Sr 3-x Ga2Ge3O 12 :xEu 3+, x are 0.005, 0.010, 0.030, 0.050, 0.070, and 0.090 respectively;

[0055] Not doped with Eu 3+ Gallium germanate oxide Sr3Ga2Ge3O 12 The preparation method comprises the following specific steps:

[0056] (1) 0.8858 g of Sr2CO3 (purity 99.99%), 0.3749 g of Ga2O3 (purity 99.99%), and 0.6278 g of GeO2 (purity 99.99%) were wet-milled and mixed. 3 g of anhydrous ethanol was added during the wet-milling process to obtain a mixed powder.

[0057] (2) The mixed powder of step (1) was calcined in an air atmosphere at 1250°C for 5.5 hours, cooled to room temperature, and ground to obtain gallium germanate oxide Sr3Ga2Ge3O 12 ;

[0058] Not doped with Eu 3+ Gallium germanate oxide Sr3Ga2Ge3O 12 The crystal structure of Figure 11 ,from Figure 11 It can be seen that Sr3Ga2Ge3O 12 It has a cubic crystal structure with a space group of Ia-3d; the structure is composed of [SrO8] dodecahedrons, [GaO6] octahedrons and [GeO4] tetrahedrons arranged in an orderly manner in space;

[0059] The chemical formula of the gallium germanate oxide is Sr 3-x Ga2Ge3O 12 :xEu 3+ The preparation method (x is 0.005, 0.010, 0.030, 0.050, 0.070, and 0.090, respectively) comprises the following steps:

[0060] (1) Sr2CO3 (purity 99.99%) (0.8843 g, 0.8828 g, 0.8769 g, 0.8710 g, 8651 g, 0.8592 g, respectively), Ga2O3 (purity 99.99%) 0.3749 g, GeO2 (purity 99.99%) 0.6278 g, Eu2O3 (purity 99.99%) (0.0018 g, 0.0035 g, 0.0106 g, 0.0176 g, 0.0246 g, 0.0317 g, respectively) were wet-milled and uniformly mixed, and 3 g of anhydrous ethanol was added during the wet-milling process to obtain a mixed powder;

[0061] (2) The mixed powder of step (1) was calcined in an air atmosphere at 1250°C for 5.5h, cooled to room temperature, and ground to obtain gallium germanate oxide Sr 2.995 Ga2Ge3O 12 :0.005Eu 3+ 、Sr 2.99 Ga2Ge3O 12 :0.01Eu 3+ 、Sr 2.97 Ga2Ge3O 12 :0.03Eu 3+ 、Sr 2.95 Ga2Ge3O 12 :0.05Eu 3+ 、Sr 2.93 Ga2Ge3O 12 :0.07Eu 3+ 、Sr 2.91 Ga2Ge3O 12 :0.09Eu 3+ ;

[0062] oxide Sr3Ga2Ge3O 12 、Sr 2.99 Ga2Ge3O 12 :0.01Eu 3+ 、Sr 2.95 Ga2Ge3O 12 :0.05Eu 3+ 、Sr 2.91 Ga2Ge3O 12 :0.09Eu 3+ The XRD pattern of Figure 12 ,from Figure 12 It can be seen that the oxide Ca3Ga2Ge3O 12 , Ca 2.99 Ga2Ge3O 12 :0.01Pr 3+ , Ca 2.95 Ga2Ge3O 12 :0.05Pr 3+ , Ca 2.91 Ga2Ge3O 12 :0.09Pr 3+ The samples were all pure phases without any impurity phases;

[0063] oxide Sr3Ga2Ge3O 12 、Sr 2.995 Ga2Ge3O 12 :0.005Eu 3+ 、Sr 2.99 Ga2Ge3O12 :0.01Eu 3+ 、Sr 2.97 Ga2Ge3O 12 :0.03Eu 3+ 、Sr 2.95 Ga2Ge3O 12 :0.05Eu 3+ 、Sr 2.93 Ga2Ge3O 12 :0.07Eu 3+ 、Sr 2.91 Ga2Ge3O 12 :0.09Eu 3+ The emission spectrum and photographs are shown in Figure 13 ,from Figure 13 It can be seen that the PL spectrum of undoped SGGO shows a broad band (350-600 nm) with a peak at 450 nm, which is attributed to self-activated emission; when Pr 3+ ions, obvious narrow peaks appeared in the range of 550-700 nm, which were attributed to Eu 3+ inner shell transition; with the Eu 3+ With the increase of concentration (x = 0, 0.005, 0.01, 0.03, 0.05, 0.07 and 0.09), the host emission intensity gradually decreases, while Eu 3+ The emission is enhanced, indicating energy transfer from the SGGO host to Eu 3+ ions and caused the sample color to change from blue to orange;

[0064] The oxide of this embodiment is Sr3Ga2Ge3O 12 、Sr 3-x Ga2Ge3O 12 :xEu 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, 0.090 respectively) The CIE diagram of the spectrum at UV = 254nm is shown in Figure 14 ,from Figure 14 It can be seen that the CIE diagram further proves the change of the sample color from blue to orange;

[0065] The oxide of this embodiment is Sr3Ga2Ge3O 12 、Sr 3-x Ga2Ge3O 12 :xEu 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, 0.090 respectively) The spectrum and luminescence photograph under X-ray are shown in the figure. Figure 15 ,from Figure 15 It can be seen that only Eu exists under X-rays3+ The luminescence of ions changes with the doping concentration. 3+ With the increase of concentration (x = 0, 0.005, 0.01, 0.03, 0.05, 0.07, and 0.09), the color gradually changes from orange to red;

[0066] The oxide of this embodiment is Sr3Ga2Ge3O 12 、Sr 3-x Ga2Ge3O 12 :xEu 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, 0.090 respectively) The CIE diagram of the spectrum under X-ray is shown in Figure 16 ,from Figure 16 It can be seen that the CIE diagram further proves the change of sample color from orange to red;

[0067] Therefore, Sr gallium germanate oxide 3-x Ga2Ge3O 12 :xEu 3+ (x is 0.005, 0.010, 0.030, 0.050, 0.070, 0.090 respectively) It emits blue to orange light under ultraviolet light excitation; it emits orange to red light under X-ray excitation; using gallium germanate oxide Sr 3-x Ga2Ge3O 12 :xEu 3+ Multi-channel anti-counterfeiting identification is performed based on the different luminescence characteristics under ultraviolet light and X-ray energy excitation.

[0068] The above describes the specific embodiments of the present invention in detail, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in this field without departing from the scope of the present invention.

Claims

1. A multi-channel information encryption method based on gallium germanate oxide, characterized in that: The chemical formula of the gallogermanate oxide is M 3-x Ga2Ge3O 12 : x Ln, where M is Ca, Sr, and Ln is Pr 3+ 、Eu 3+ , 0 <x≤0.09; The gallogermanate oxide M 3-x Ga2Ge3O 12 : x Ln emits blue-white light under ultraviolet light excitation, and its afterglow is orange-white; it emits orange light under X-ray excitation, and its afterglow is orange-red; Using gallium germanate oxide M 3-x Ga2Ge3O 12 : The different luminescence characteristics of x Ln under ultraviolet light and X-ray energy excitation are used for multi-channel anti-counterfeiting identification.

2. The multi-channel information encryption method based on gallium germanate oxide according to claim 1, characterized in that: The gallogermanate oxide M 3-x Ga2Ge3O 12 : The preparation method of x Ln, the specific steps are as follows: (1) Wet-grinding and mixing the M-containing compound, the gallium-containing compound, the germanium-containing compound, and the Ln-containing compound to obtain a mixed powder; (2) The mixed powder of step (1) is calcined in an air atmosphere at a temperature of 1200-1300°C for 5-6 hours, cooled to room temperature, and ground to obtain gallium germanate oxide M 3-x Ga2Ge3O 12 : x Ln.

3. The multi-channel information encryption method based on gallium germanate oxide according to claim 2, characterized in that: The compound containing M in step (1) is carbonate, nitrate, chloride, oxide, hydroxide, oxalate or acetate.

4. The multi-channel information encryption method based on gallium germanate oxide according to claim 2, characterized in that: The gallium-containing compound in step (1) is gallium carbonate, gallium nitrate, gallium chloride, gallium oxide, gallium hydroxide, gallium oxalate or gallium acetate.

5. The multi-channel information encryption method based on gallium germanate oxide according to claim 2, characterized in that: The germanium-containing compound in step (1) is germanium carbonate, germanium nitrate, germanium chloride, germanium oxide, germanium hydroxide, germanium oxalate or germanium acetate.

6. The multi-channel information encryption method based on gallium germanate oxide according to claim 2, characterized in that: The Ln-containing compound in step (1) is a carbonate, nitrate, chloride, oxide, hydroxide, oxalate or acetate.

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