A composite doped aluminate optical information storage material and preparation method thereof

Abstract

The present invention provides a composite doped aluminate optical information storage material and a preparation method thereof. The chemical formula of the optical information storage material is Lu 3‑x Al 5‑‑y O 12 : xR, yM, R is selected from at least one element selected from Dy, Pr, Eu, Ba, Yb, Gd, Ta, Hf, Sr, Ce, Tb, Er, Tm, and Nd; M is selected from at least one element selected from Fe, Mn, Ti, Ca, Cr, V, Sc, and Mg, wherein 0≤x≤3 and 0≤y≤1. The material prepared by the present invention has great application prospects in optical storage, anti-counterfeiting, emergency display, and optical information processing.

Description

Technical Field

[0001] The invention relates to an aluminate-doped optical information storage material and a preparation method thereof, belonging to the field of inorganic optical storage materials. Background Art

[0002] Optical information storage materials, also known as electron-trapping materials, utilize light or thermal excitation to trap and release electrons within the material, enabling the reading, writing, and erasing of optical information. These materials offer advantages such as fast access speeds, repeatable read / write / erase capabilities, high storage density, short infrared response times, and high quantum conversion efficiency. Therefore, these materials hold great promise for applications in optical storage, emergency displays, and optical information processing.

[0003] The electron-trapping materials currently under research still have many shortcomings, such as sulfides (CaSrS), halides (BaFCl) and nitrides. They have poor physical, chemical and thermal stability and can cause environmental pollution. Therefore, these materials are not the best choice for optical storage materials.

[0004] CN109704585A discloses a BaSi2O5:Eu for optical information storage 2+ , Nd 3+ Glass ceramics have simple processes and low costs, and can achieve ultraviolet light storage and near-infrared laser excitation reading. However, the physical stability of this glass material is poor, and whether it can enter the application field requires comprehensive analysis; CN1837142A discloses a rare earth doped lutetium aluminum garnet (Lu3Al5O 12 :Ce) structure scintillating ceramic material, this material has high absorption efficiency in the near-ultraviolet and visible light regions, can excite a large number of carriers, and has a fast light response. It is mainly used in scintillation detection, solid-state laser and other fields. However, due to the shallow trap depth and few trap energy levels in this material, it cannot be used in the field of optical information storage.

[0005] In the present invention, lutetium aluminum garnet (Lu3Al5O 12 ) is used as the matrix material, and by selecting suitable rare earth ions or transition ions for doping, a large number of deep defect traps are introduced into the matrix material using "trap engineering" to achieve its optical information storage characteristics. Summary of the Invention

[0006] In order to overcome the stability and environmental protection problems of current organic optical information storage materials and inorganic halogen / sulfide optical information storage materials, the present invention provides an optical information storage material of aluminate doped with amphoteric metals, transition elements and rare earth elements and a secondary solid-phase reaction synthesis method thereof, with the aim of preparing a material with good physicochemical stability and good optical information storage properties.

[0007] On the one hand, the present invention provides a composite doped aluminate optical information storage material, characterized in that the chemical formula of the optical information storage material is Lu 3-x Al 5--y O 12 : xR, yM, R is selected from at least one element of Dy, Pr, Eu, Ba, Yb, Gd, Ta, Hf, Sr, Ce, Tb, Er, Tm, and Nd; M is selected from at least one element of Fe, Mn, Ti, Ca, Cr, V, Sc, and Mg, wherein 0≤x≤3 and 0≤y≤1.

[0008] The optical information storage material, a composite of aluminates doped with amphoteric metals, transition metals, and rare earth elements, is provided. When the powdered material is irradiated with 254-nanometer ultraviolet light, some carriers within the material absorb energy, are excited into trap levels, and are stored, completing optical information writing. After the light source is removed, the sample is stimulated with 808-nanometer light, releasing the trapped carriers and causing them to emit light again, completing optical information readout.

[0009] The Lu-doping elements introduce luminescence centers into the material, and the Al-doping elements cooperate to create deep trap defects.

[0010] Preferably, x / y=1-10, and controlling the doping molar ratio to be 1-10 can effectively introduce luminescence centers and trap centers, create deeper defect traps, and prevent concentration quenching.

[0011] On the other hand, the present invention provides a method for preparing the composite doped aluminate optical information storage material, comprising the following steps: 3-x Al 5--y O 12 : xR, yM, respectively weigh the compounds of each element, grind and mix them once; pre-calculate the obtained mixture at 600-1200°C for 1-10 hours to perform a solid-phase reaction to form a pre-calcinated powder; the obtained pre-calcinated powder is grinded a second time and then heat-treated at 1300-2000°C for 3-12 hours to perform a secondary solid-phase reaction to obtain the composite doped aluminate optical information storage material.

[0012] The present invention uses a secondary solid-phase synthesis method and controls the temperature and time of the primary solid-phase reaction and the secondary solid-phase reaction to effectively regulate the writing and reading luminescence intensity of the material. The obtained optical information storage material can ideally realize the writing and reading of optical information.

[0013] Preferably, the total time of the first solid-phase reaction and the second solid-phase reaction is more than 11 hours, which is conducive to the generation and growth of compound crystals and the synthesis of pure phase compounds.

[0014] Preferably, the primary solid phase reaction temperature is 800-1000° C., and the reaction time is 3-6 hours.

[0015] Preferably, the secondary solid phase reaction temperature is 1400-1800° C., and the reaction time is 8-10 hours.

[0016] Preferably, the grinding medium used in the primary grinding and / or secondary grinding is anhydrous ethanol, and the ratio of the volume of anhydrous ethanol to the volume of the powder to be ground is 1:1.

[0017] Preferably, the first grinding and / or second grinding is for 0.5 to 1 hour.

[0018] The material requires a specific light source to excite and read the stored optical information, and can be used as a confidentiality storage system.

[0019] The invention has the characteristics of: relating to an optical information storage material of aluminate composite doped with amphoteric metal, transition metal and rare earth element and a secondary solid phase reaction synthesis method thereof.

[0020] 1) In the present invention, by selecting appropriate doping elements and incorporating them into the matrix material, external defects such as Schottky defects, Frenkel defects, and vacancy defects can be generated. In addition, high-temperature treatment during the material synthesis process can introduce intrinsic defects, that is, local defect energy levels are introduced into the matrix band gap. Light stimulation causes carriers in the ground state or valence band to undergo stimulated transitions, and some carriers are captured and stored in the above-mentioned trap energy levels. Under the stimulation of longer wavelength light, the material absorbs energy, causing the trapped carriers to be released into the conduction band / valence band until they are recaptured by other recombination centers, achieving electron-hole recombination luminescence.

[0021] 2) In addition, the concentration of the composite doping ions cannot be too little or too much. Too little will result in fewer defect energy levels inside the matrix material, which cannot meet the requirements of optical information storage; too much will cause "concentration quenching" and also affect the optical information storage performance.

[0022] The composite doped aluminate optical information storage material of the present invention has good optical information storage properties, good chemical and thermal stability, is easy to prepare, and has low cost. It has broad application prospects in the fields of biological molecule fluorescence labeling, infrared detection, anti-counterfeiting and optical information storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 These are the XRD phase analysis spectra of the optical information storage materials prepared in Examples 1, 2 and 3.

[0024] Figure 2 These are the thermoluminescence curves of the optical information storage materials prepared in Examples 1, 2 and 3.

[0025] Figure 3These are the XRD phase analysis spectra of the optical information storage materials prepared in Examples 4, 5 and 6.

[0026] Figure 4 These are the XRD phase analysis spectra of the optical information storage materials prepared in Examples 7, 8 and 9. DETAILED DESCRIPTION

[0027] The following examples are further given to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. The specific process parameters and the like in the following examples are only examples within a suitable range, and those skilled in the art can make selections within a suitable range based on the description herein, and are not intended to be limited to the specific values exemplified below.

[0028] The following shows a method for preparing the optical information storage material of aluminate doped with amphoteric metals, transition metals and rare earth elements.

[0029] First, according to the chemical formula Lu 3-x Al 5--y O 12 :xR,yM Select the raw materials, then weigh and mix and grind them once. After adding anhydrous ethanol and mixing thoroughly, the grinding time is preferably 0.5 to 1 hour to thoroughly mix the raw materials and shorten the experimental period. The ratio of the added anhydrous ethanol volume to the total raw material volume is 1:1.

[0030] Then, a solid-phase reaction synthesis is carried out. The ground powder is subjected to a solid-phase reaction in air. The heating rate can be 3-5°C / min, the reaction temperature is 800-1000°C, and the reaction time is 3-6 hours. If the temperature of a solid-phase reaction is too high or the time is too long, it will not be conducive to the formation of the required crystal phase and increase production costs; if the temperature is too low or the time is too short, it may not be possible to generate crystal nuclei and grow into grains. Then the temperature is cooled to room temperature in the furnace to make a pre-fired powder. The purpose of this process is to thermally decompose the raw materials, preliminarily synthesize a part of the main phase crystal phase of the compound, and remove organic impurities such as alcohol.

[0031] Subsequently, a secondary mixing and grinding process is performed. After the pre-calcined powder is added to anhydrous ethanol and mixed evenly, the volume ratio of anhydrous ethanol to powder volume is 1:1. The secondary grinding time is preferably 0.5 to 1 hour, until the anhydrous ethanol is completely evaporated. This ensures that the crystal nuclei and grains in the pre-calcined powder are evenly dispersed, which facilitates phase formation during the secondary solid-phase sintering.

[0032] Next, a secondary solid-phase reaction synthesis is performed. The powder obtained from the secondary grinding is subjected to a secondary solid-phase reaction in air at a heating rate of 3-5°C / min, a reaction temperature of 1400-1800°C, and a reaction time of 8-10 hours. Too high a reaction temperature can easily overheat the sample, while too long a reaction time can affect the material's luminescence intensity. Too low a temperature or too short a reaction time is also detrimental to the synthesis of the crystalline phase. The material is then cooled to room temperature in the furnace to obtain a composite-doped aluminate optical information storage material.

[0033] Table 1 is a list of formulas for all samples prepared in the experimental design

[0034] Table 1

[0035] Example formula Doping element 1 Doping element 2 Example 1 <![CDATA[Lu 2.985 Al 4.998 O 12 :0.015Ce 3+ ,0.002V 3+ ]]> <![CDATA[0.015Ce 3+ ]]> <![CDATA[0.002V 3+ ]]> Example 2 <![CDATA[Lu 2.985 Al 4.996 O 12 :0.015Ce 3+ ,0.004V 3+ ]]> <![CDATA[0.015Ce 3+ ]]> <![CDATA[0.004V 3+ ]]> Example 3 <![CDATA[Lu 2.985 the 4.994 A 12 :0.015Ce 3+ ,0.006V 3+ ]]> <![CDATA[0.015Ce 3+ ]]> <![CDATA[0.006V 3+ ]]> Example 4 <![CDATA[Lu 2.999 Al5O 12 :0.001Tb 3+ ]]> <![CDATA[0.001Tb 3+ ]]> Example 5 <![CDATA[Lu 2.999 Al 4.9995 The 12 :0.001Tb 3+ ,0.0005Ti 3+ ]]> <![CDATA[0.001Tb 3+ ]]> <![CDATA[0.0005Ti 3+ ]]> Example 6 <![CDATA[Lu 2.999 Al 4.999 The 12 :0.001Tb 3+ ,0.001Ti 3+ ]]> <![CDATA[0.001Tb 3+ ]]> <![CDATA[0.001Ti 3+ ]]> Example 7 <![CDATA[Lu 2.995 Al5O 12 :0.005Pr 3+ ]]> <![CDATA[0.005Pr 3+ ]]> Example 8 <![CDATA[Lu 2.995 the 4.9985 A 12 :0.005Pr 3+ ,0.0015Ti 3+ ]]> <![CDATA[0.005Pr 3+ ]]> <![CDATA[0.0015Ti 3+ ]]> Example 9 <![CDATA[Lu 2.995 the 4.997 A 12 :0.005Pr 3+ ,0.003Ti 3+ ]]> <![CDATA[0.005Pr 3+ ]]> <![CDATA[0.003Ti 3+ ]]>

[0036] Example 1

[0037] Synthesis of Lu by Secondary Solid-Phase Reaction 2.985 Al 4.998 O 12 :0.015Ce 3+ ,0.002V 3+ Phosphor: Lutetium oxide (Lu2O3, 99.999%), aluminum oxide (Al2O3, 99.999%), cerium dioxide (CeO2, 99.99%), and vanadium pentoxide (V2O5, 99.99%) are used as raw materials. The raw materials are weighed according to the stoichiometric ratio, placed in a mortar, and evenly mixed with anhydrous ethanol as a solvent. The volume ratio of anhydrous ethanol added to the volume of the sample powder is 1:1. The powder is ground once for 0.5 to 1 hour and dried at 120°C. The obtained powder is placed in a corundum crucible and placed in a muffle furnace for a solid-phase reaction in air. The reaction temperature is 800°C, the heating rate is 5°C / min, the temperature is maintained for 4 hours, and the powder is naturally cooled to obtain a pre-fired powder. Then put the pre-calcined powder into a mortar and add anhydrous ethanol. The volume ratio of the added anhydrous ethanol to the sample powder is 1:1. Grind it again until the anhydrous ethanol is ground dry. Dry it at 120℃. Finally, place the ceramic body in a muffle furnace with a heating rate of 5℃ / min. Perform a secondary solid-phase reaction at 1750℃ for 10 hours. After cooling to room temperature, turn off the power and cool it down to obtain the synthesized material. The XRD pattern of the prepared optical storage material and the standard PDF card are as follows: Figure 1 As shown in the figure, the analysis found that the crystal phase of the product synthesized by the secondary solid phase reaction is Lu3Al5O 12 phase, and some miscellaneous peaks, belonging to the Al2O3 phase. But overall it is consistent with the PDF standard card (JCPD-73-1368), which shows that high-purity Lu3Al5O 12 In the matrix phase, the doping elements enter the crystal lattice to form a solid solution without significantly changing the phase formation of the material. Its thermoluminescence spectrum is as follows: Figure 2As shown in the figure, the specific steps of this testing method are to first irradiate the material with 254nm ultraviolet light for 5-10 minutes, then let it stand for a certain period of time, and then use a thermoluminescence spectrometer to collect data from room temperature to high temperature. This method is one of the effective methods for verifying the optical storage properties of a material. From the peak position in the figure and using the Urbach empirical formula (E = Tm / 500), it can be determined that the trap depth is approximately 1.0eV, indicating that it has good optical information storage properties. For electron-trapping optical storage materials, the trap energy level plays a crucial role. The trap depth and trap density are closely related to the optical information storage capacity. The intensity of the thermoluminescence curve is related to the number of carriers trapped by the trap energy level, and the peak position is related to the trap depth. Therefore, in the field of inorganic optical storage materials, the optical information storage properties of the sample are verified by measuring the thermoluminescence curve.

[0038] Example 2

[0039] The process of Example 1 was adopted, but the concentration of the doping element V was increased. Synthesis of Lu by Secondary Solid Phase Reaction Method 2.985 Al 4.996 O 12 :0.015Ce 3+ ,0.004V 3+ Phosphor: Lutetium oxide (Lu2O3, 99.999%), aluminum oxide (Al2O3, 99.999%), cerium dioxide (CeO2, 99.99%), and vanadium pentoxide (V2O5, 99.99%) are used as raw materials. The raw materials are weighed according to the stoichiometric ratio, placed in a mortar, and evenly mixed with anhydrous ethanol as a solvent. The volume ratio of anhydrous ethanol added to the volume of the sample powder is 1:1. The powder is ground once for 0.5 to 1 hour and dried at 120°C. The obtained powder is placed in a corundum crucible and placed in a muffle furnace for a solid-phase reaction in air. The reaction temperature is 800°C, the heating rate is 5°C / min, the temperature is maintained for 4 hours, and the powder is naturally cooled to obtain a pre-fired powder. Then put the pre-calcined powder into a mortar and add anhydrous ethanol. The volume ratio of the added anhydrous ethanol to the sample powder is 1:1. Grind it twice until the anhydrous ethanol is ground dry. Dry it at 120℃. Finally, place the ceramic body in a muffle furnace with a heating rate of 5℃ / min and perform a secondary solid-phase reaction at 1750℃ for 10 hours. After cooling to room temperature, turn off the power and cool it down to obtain the synthesized material. The XRD spectrum of the prepared optical storage material is shown in Figure 2. Figure 1 As shown, high-purity Lu3Al5O 12 In the matrix phase, the doping elements enter the crystal lattice to form a solid solution without significantly changing the phase formation of the material. Figure 2 As shown in the figure, the peak position and the Urbach empirical formula (E = T m / 500), E is the trap depth (eV); T mThe peak position of the thermoluminescence spectrum shows that the trap depth is about 1.0 eV, confirming the optical information storage properties of the sample.

[0040] Example 3

[0041] The process of Example 1 was adopted, but the concentration of the doping element V was continued to be increased. Synthesis of Lu by Secondary Solid Phase Reaction Method 2.985 Al 4.994 O 12 :0.015Ce 3+ ,0.006V 3+ Phosphor: Lutetium oxide (Lu2O3, 99.999%), aluminum oxide (Al2O3, 99.999%), cerium dioxide (CeO2, 99.99%), and vanadium pentoxide (V2O5, 99.99%) are used as raw materials. The raw materials are weighed according to the stoichiometric ratio, placed in a mortar, and evenly mixed with anhydrous ethanol as a solvent. The volume ratio of anhydrous ethanol added to the volume of the sample powder is 1:1. The powder is ground once for 0.5 to 1 hour and dried at 120°C. The obtained powder is placed in a corundum crucible and placed in a muffle furnace for a solid-phase reaction in air. The reaction temperature is 800°C, the heating rate is 5°C / min, the temperature is maintained for 4 hours, and the powder is naturally cooled to obtain a pre-fired powder. Then put the pre-calcined powder into a mortar and add anhydrous ethanol. The volume ratio of the added anhydrous ethanol to the sample powder is 1:1. Grind it twice until the anhydrous ethanol is ground dry. Dry it at 120℃. Finally, place the ceramic body in a muffle furnace with a heating rate of 5℃ / min and perform a secondary solid-phase reaction at 1750℃ for 10 hours. After cooling to room temperature, turn off the power and cool it down to obtain the synthesized material. The XRD spectrum of the prepared optical storage material is shown in Figure 2. Figure 1 As shown, high-purity Lu3Al5O 12 In the matrix phase, the doping elements enter the crystal lattice to form a solid solution without significantly changing the phase formation of the material. Figure 2 As shown in the figure, the peak position and the Urbach empirical formula (E = T m / 500), E is the trap depth (eV); T m It is the peak position of the thermoluminescent spectrum, and it can be seen that its trap depth is about 1.0eV, which confirms the optical information storage characteristics of the sample.

[0042] Example 4

[0043] Synthesis of Lu by Secondary Solid-Phase Reaction 2.999 Al5O 12 :0.001Tb 3+Phosphor: Lutetium oxide (Lu2O3, 99.999%), aluminum oxide (Al2O3, 99.999%), and terbium oxide (Tb4O7, 99.99%) are used as raw materials. The raw materials are weighed according to the stoichiometric ratio, placed in a mortar, and evenly mixed with anhydrous ethanol as a solvent. The volume ratio of anhydrous ethanol added to the volume of the sample powder is 1:1. The powder is ground once for 0.5 to 1 hour and dried at 120°C. The obtained powder is placed in a corundum crucible and placed in a muffle furnace for a solid-phase reaction in air. The reaction temperature is 800°C, the heating rate is 5°C / min, the temperature is maintained for 4 hours, and the powder is naturally cooled to obtain a pre-fired powder. Then put the pre-calcined powder into a mortar and add anhydrous ethanol. The volume ratio of the added anhydrous ethanol to the sample powder is 1:1. Grind it again until the anhydrous ethanol is ground dry. Dry it at 120℃. Finally, place the ceramic body in a muffle furnace with a heating rate of 5℃ / min. Perform a secondary solid-phase reaction at 1750℃ for 10 hours. After cooling to room temperature, turn off the power and cool it down to obtain the synthesized material. The XRD pattern of the prepared optical storage material and the standard PDF card are as follows: Figure 3 As shown in the figure, the analysis found that the crystal phase of the product synthesized by the secondary solid phase reaction is Lu3Al5O 12 phase, which is consistent with the PDF standard card (JCPD-73-1368), indicating that high-purity Lu3Al5O 12 In the matrix phase, the doping elements enter the crystal lattice to form a solid solution without significantly changing the phase formation of the material.

[0044] Example 5

[0045] Synthesis of Lu by Secondary Solid-Phase Reaction 2.999 Al 4.9995 O 12 :0.001Tb 3+ ,0.0005Ti 3+Phosphor: Lutetium oxide (Lu2O3, 99.999%), aluminum oxide (Al2O3, 99.999%), terbium oxide (Tb4O7, 99.99%) and titanium dioxide (TiO2, 99.99%) are used as raw materials. The raw materials are weighed according to the stoichiometric ratio, placed in a mortar, and evenly mixed with anhydrous ethanol as a solvent. The volume ratio of anhydrous ethanol added to the volume of the sample powder is 1:1. The powder is ground for 0.5 to 1 hour at a time and dried at 120°C. The obtained powder is placed in a corundum crucible and placed in a muffle furnace for a solid-phase reaction in air at a reaction temperature of 800°C, a heating rate of 5°C / min, and kept warm for 4 hours. The powder is naturally cooled to obtain a pre-fired powder. Then put the pre-calcined powder into a mortar and add anhydrous ethanol. The volume ratio of the added anhydrous ethanol to the sample powder is 1:1. Grind it again until the anhydrous ethanol is ground dry. Dry it at 120℃. Finally, place the ceramic body in a muffle furnace with a heating rate of 5℃ / min. Perform a secondary solid-phase reaction at 1750℃ for 10 hours. After cooling to room temperature, turn off the power and cool it down to obtain the synthesized material. The XRD pattern of the prepared optical storage material and the standard PDF card are as follows: Figure 3 As shown in the figure, the analysis found that the crystal phase of the product synthesized by the secondary solid phase reaction is Lu3Al5O 12 phase, which is consistent with the PDF standard card (JCPD-73-1368), indicating that high-purity Lu3Al5O 12 In the matrix phase, the doping elements enter the crystal lattice to form a solid solution without significantly changing the phase formation of the material.

[0046] Example 6

[0047] Synthesis of Lu by Secondary Solid-Phase Reaction 2.999 Al 4.999 O 12 :0.001Tb 3+ ,0.001Ti 3+Phosphor: Lutetium oxide (Lu2O3, 99.999%), aluminum oxide (Al2O3, 99.999%), terbium oxide (Tb4O7, 99.99%) and titanium dioxide (TiO2, 99.99%) are used as raw materials. The raw materials are weighed according to the stoichiometric ratio, placed in a mortar, and evenly mixed with anhydrous ethanol as a solvent. The volume ratio of anhydrous ethanol added to the volume of the sample powder is 1:1. The powder is ground for 0.5 to 1 hour at a time and dried at 120°C. The obtained powder is placed in a corundum crucible and placed in a muffle furnace for a solid-phase reaction in air at a reaction temperature of 800°C, a heating rate of 5°C / min, and kept warm for 4 hours. The powder is naturally cooled to obtain a pre-fired powder. Then put the pre-calcined powder into a mortar and add anhydrous ethanol. The volume ratio of the added anhydrous ethanol to the sample powder is 1:1. Grind it again until the anhydrous ethanol is ground dry. Dry it at 120℃. Finally, place the ceramic body in a muffle furnace with a heating rate of 5℃ / min. Perform a secondary solid-phase reaction at 1750℃ for 10 hours. After cooling to room temperature, turn off the power and cool it down to obtain the synthesized material. The XRD pattern of the prepared optical storage material and the standard PDF card are as follows: Figure 3 As shown in the figure, the analysis found that the crystal phase of the product synthesized by the secondary solid phase reaction is Lu3Al5O 12 phase, which is consistent with the PDF standard card (JCPD-73-1368), indicating that high-purity Lu3Al5O 12 In the matrix phase, the doping elements enter the crystal lattice to form a solid solution without significantly changing the phase formation of the material.

[0048] Example 7

[0049] Synthesis of Lu by Secondary Solid-Phase Reaction 2.995 Al5O 12 :0.005Pr 3+ Phosphor: Lutetium oxide (Lu2O3, 99.999%), aluminum oxide (Al2O3, 99.999%), praseodymium oxide (Pr6O 11, 99.9%) as raw materials, weigh the raw materials according to the stoichiometric ratio, put them into a mortar, mix them evenly with anhydrous ethanol as the solvent, add anhydrous ethanol and the volume ratio of sample powder is 1:1, grind for 0.5 to 1 hour, and dry the powder at 120℃; put the obtained powder into a corundum crucible and place it in a muffle furnace for a solid phase reaction in the air, the reaction temperature is 800℃, the heating rate is 5℃ / min, keep warm for 4 hours, and cool naturally to obtain a pre-burned powder. Then put the pre-burned powder into a mortar and add anhydrous ethanol, the volume ratio of anhydrous ethanol added is 1:1 to the volume ratio of sample powder, grind it a second time until the anhydrous ethanol is dry, dry it at 120℃, finally place the ceramic body in a muffle furnace, heat up at a rate of 5℃ / min, and carry out a second solid phase reaction at 1750℃ for 10 hours. After cooling to room temperature, turn off the power and cool it to obtain the synthesized material. The XRD spectrum of the prepared optical storage material and the standard PDF card are as follows Figure 4 As shown in the figure, the analysis found that the crystal phase of the product synthesized by the secondary solid phase reaction is Lu3Al5O 12 phase, which is consistent with the PDF standard card (JCPD-73-1368), indicating that high-purity Lu3Al5O 12 In the matrix phase, the doping elements enter the crystal lattice to form a solid solution without significantly changing the phase formation of the material.

[0050] Example 8

[0051] Synthesis of Lu by Secondary Solid-Phase Reaction 2.995 Al 4.9985 O 12 :0.005Pr 3+ ,0.0015Ti 3+ Phosphor: Lutetium oxide (Lu2O3, 99.999%), aluminum oxide (Al2O3, 99.999%), praseodymium oxide (Pr6O 11 ,99.9%) and titanium dioxide (TiO2,99.99%) are used as raw materials. The raw materials are weighed according to the stoichiometric ratio, placed in a mortar, and evenly mixed with anhydrous ethanol as a solvent. The volume ratio of anhydrous ethanol added to the sample powder is 1:1. Grind once for 0.5 to 1 hour, and dry the powder at 120°C. The obtained powder is placed in a corundum crucible and placed in a muffle furnace for a solid-phase reaction in air. The reaction temperature is 800°C, the heating rate is 5°C / min, and the temperature is kept for 4 hours. It is then naturally cooled to obtain a pre-fired powder. Then the pre-fired powder is placed in a mortar and anhydrous ethanol is added. The volume ratio of anhydrous ethanol added to the sample powder is 1:1. Grind twice until the anhydrous ethanol is dry, dry at 120°C, and finally place the ceramic body in a muffle furnace with a heating rate of 5°C / min. A second solid-phase reaction is carried out at 1750°C for 10 hours. After cooling to room temperature, the power is turned off and cooled to obtain the synthesized material. The XRD spectrum of the prepared optical storage material and the standard PDF card are as follows: Figure 4 As shown in the figure, the analysis found that the crystal phase of the product synthesized by the secondary solid phase reaction is Lu3Al5O 12 phase, which is consistent with the PDF standard card (JCPD-73-1368), indicating that high-purity Lu3Al5O 12 In the matrix phase, the doping elements enter the crystal lattice to form a solid solution without significantly changing the phase formation of the material.

[0052] Example 9

[0053] Synthesis of Lu by Secondary Solid-Phase Reaction 2.995 Al 4.997 O 12 :0.005Pr 3+ ,0.003Ti 3+ Phosphor: Lutetium oxide (Lu2O3, 99.999%), aluminum oxide (Al2O3, 99.999%), praseodymium oxide (Pr6O 11 ,99.9%) and titanium dioxide (TiO2,99.99%) are used as raw materials. The raw materials are weighed according to the stoichiometric ratio, placed in a mortar, and evenly mixed with anhydrous ethanol as a solvent. The volume ratio of anhydrous ethanol added to the sample powder is 1:1. Grind once for 0.5 to 1 hour, and dry the powder at 120°C. The obtained powder is placed in a corundum crucible and placed in a muffle furnace for a solid-phase reaction in air. The reaction temperature is 800°C, the heating rate is 5°C / min, and the temperature is kept for 4 hours. It is then naturally cooled to obtain a pre-fired powder. Then the pre-fired powder is placed in a mortar and anhydrous ethanol is added. The volume ratio of anhydrous ethanol added to the sample powder is 1:1. Grind twice until the anhydrous ethanol is dry, dry at 120°C, and finally place the ceramic body in a muffle furnace with a heating rate of 5°C / min. A second solid-phase reaction is carried out at 1750°C for 10 hours. After cooling to room temperature, the power is turned off and cooled to obtain the synthesized material. The XRD spectrum of the prepared optical storage material and the standard PDF card are as follows: Figure 4 As shown in the figure, the analysis found that the crystal phase of the product synthesized by the secondary solid phase reaction is Lu3Al5O 12 phase, which is consistent with the PDF standard card (JCPD-73-1368), indicating that high-purity Lu3Al5O 12 In the matrix phase, the doping elements enter the crystal lattice to form a solid solution without significantly changing the phase formation of the material.

Claims

1. A composite doped aluminate optical information storage material, characterized in that: The chemical formula of the optical information storage material is Lu 3-x Al 5--y O 12 : xR, yM, R is selected from at least one element of Dy, Pr, Eu, Ba, Yb, Gd, Ta, Hf, Sr, Ce, Tb, Er, Tm, and Nd; M is selected from at least one element of Fe, Mn, Ti, Ca, Cr, V, Sc, and Mg, wherein 0≤x≤3, 0≤y≤1; The preparation method of the composite doped aluminate optical information storage material comprises: 3-x Al 5-- y O 12 : xR, yM are respectively weighed, and the compounds of each element are ground and mixed once; the obtained mixture is pre-fired at 800-1000 ° C for 3 to 6 hours to perform a solid-phase reaction to form a pre-fired powder; the obtained pre-fired powder is ground twice and then heat-treated at 1400-1800 ° C for 8 to 10 hours to perform a secondary solid-phase reaction to obtain the composite doped aluminate optical information storage material.

2. The composite doped aluminate optical information storage material according to claim 1, characterized in that x / y=1~10.

3. The composite doped aluminate optical information storage material according to claim 1, characterized in that: The total time of the first solid phase reaction and the second solid phase reaction is more than 11 hours.

4. The optical information storage material method of composite doped aluminate according to any one of claims 1 to 3, characterized in that: The grinding medium used in the primary grinding and / or secondary grinding is anhydrous ethanol, and the volume ratio of the anhydrous ethanol to the volume of the powder to be ground is 1:

1.

5. The composite doped aluminate optical information storage material according to any one of claims 1 to 3, characterized in that: The primary grinding and / or secondary grinding is performed for 0.5 to 1 hour.

6. The composite doped aluminate optical information storage material according to any one of claims 1 to 3, characterized in that: Use ultraviolet light with a wavelength of 254 nanometers to irradiate the material to complete the writing of optical information; then use laser with a wavelength of 808 nanometers to irradiate the material to complete the reading of information; and then use high-power laser to irradiate the material to complete the erasure of information, thereby realizing the repeated reading / writing of optical information.

7. Use of the composite doped aluminate optical information storage material according to any one of claims 1 to 6 in emergency display, anti-counterfeiting and optical information storage.

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