Te-doped double perovskite Cs2Zr 1-x Sn x Cl6 solid solution materials, their preparation methods and applications

Abstract

This invention discloses a Te-doped double perovskite Cs2Zr 1‑ x Sn x Cl6 solid solution materials, their preparation methods and applications, including this Te-doped double perovskite Cs2Zr 1‑x Sn x The general chemical formula for Cl6 solid solution materials is Cs₂Zr. 1‑x Sn x Cl6:yTe 4+ , where 0 < x < 1, 0 < y < 0.2, can be prepared by solvothermal reaction under relatively low reaction conditions, has high hygroscopic resistance, chemical stability and X-ray induced charge carrier storage capacity, and the charge carrier storage temperature covers an ultra-wide temperature range from 100K to 400K.

Description

Technical Field

[0001] This invention belongs to the field of optical storage materials technology, specifically relating to a Te-doped double perovskite Cs2Zr 1-x Sn x Cl6 solid solution materials, their preparation methods, and applications. Background Technology

[0002] With the rapid development of society and technology, the amount of data generated continues to rise, and how to efficiently store and access this data has become a major concern. The development of novel optical storage materials is a key approach to solving this challenge. These materials are typically composed of inorganic compounds, mainly consisting of a crystal matrix, electron trapping regions, and hole trapping regions. When irradiated by high-energy radiation (such as X-rays), optical storage materials can generate free charge carriers (electrons and holes). Some of these free charge carriers are trapped in the trapping centers of electrons and holes. External physical stimuli, such as mechanical force or heat, can release the electrons or holes stored in the trapping centers. When electrons and holes recombine, the released energy causes the recombination center to transition from the ground state to an excited state. Subsequently, when the recombination center returns from the excited state to the ground state, it emits photons. It is precisely because of this unique luminescent property that optical storage materials have been widely used in fields such as X-ray imaging and information storage. Therefore, continued research and development of novel optical storage materials has significant scientific research value and practical application potential for improving data storage.

[0003] BaFBr(I):Eu 2+ BaFBr(I) is a common alkaline earth halide optical storage material, mainly used in X-ray detectors, imaging systems (such as computed tomography CT), and fluorescence analysis. However, at low temperatures, its excited-state Eu2+ is difficult to radiatively recombine effectively, leading to a decrease in luminescence brightness, making it unsuitable for applications in extremely low-temperature environments (such as aerospace equipment or polar probes). BaFBr(I) is a hygroscopic material, easily hydrolyzed or degraded in humid environments, resulting in decreased optical performance or material failure. This necessitates sealed operation or handling in a dry environment, increasing application difficulty. Furthermore, prolonged use or exposure to strong light can cause BaFBr(I):Eu 2+ The efficiency may decrease, which is related to the migration of Eu2+ ions or energy level changes in the crystal. Preparation of BaFBr(I):Eu 2+The process conditions are harsh, requiring ultra-high temperatures (>1000℃) and a reducing atmosphere (H2), as well as strict control of raw material purity. In particular, preventing material oxidation is crucial during the addition of iodine (I-) and optimization of Eu2+ doping concentration, leading to high production costs for BaFBr(I)2+. In summary, although BaFBr(I)2+ has advantages in certain imaging and detection fields, its poor performance at low temperatures, hygroscopicity, and slow response limit its applications. If use under low-temperature or humid conditions is required, new alternative materials urgently need to be developed. Summary of the Invention

[0004] The purpose of this invention is to provide a Te-doped double perovskite Cs2Zr 1-x Sn x Cl6 solid solution materials, their preparation methods and applications, including this Te-doped double perovskite Cs2Zr 1-x Sn x Cl6 solid solution materials possess high moisture resistance, chemical stability, and X-ray induced charge carrier storage capacity, and the charge carrier storage temperature covers an ultra-wide temperature range from 100K to 400K.

[0005] The technical solution of the present invention is as follows:

[0006] A Te-doped double perovskite Cs2Zr 1-x Sn x Cl6 solid solution materials have the general chemical formula Cs2Zr 1-x Sn x Cl6:yTe 4+ , where 0 < x < 1, 0 < y < 0.2.

[0007] In some possible implementations, its crystal structure is cubic, and its space group is [missing information].

[0008] In some possible implementations, it is obtained by heat treatment of cesium-containing compounds, zirconium-containing compounds, tin-containing compounds, chlorine-containing compounds and tellurium-containing compounds, wherein the heat treatment temperature is 170-200°C and the heat treatment time is 0.5-24 hours.

[0009] In some possible implementations, the cesium-containing compound is cesium chloride and / or cesium carbonate, the zirconium-containing compound is zirconium chloride, the tin-containing compound is at least one of tin tetrachloride, tin dioxide and stannous oxide, the chlorine-containing compound is hydrochloric acid, and the tellurium-containing compound is tellurium dioxide and / or tellurium tetrachloride.

[0010] A Te-doped double perovskite Cs2Zr 1-x Sn xA method for preparing Cl6 solid solution materials, the general chemical formula of which is Cs2Zr-doped double perovskite solid solution material. 1-x Sn x Cl6:yTe 4+ Where 0 < x < 1, 0 < y < 0.2, the preparation method includes the following steps:

[0011] (1) Weigh out cesium-containing compounds, zirconium-containing compounds, tin-containing compounds, chlorine-containing compounds and tellurium-containing compounds with a molar ratio of 2:1-x:x:6:y;

[0012] (2) Mix the cesium-containing compound, zirconium-containing compound, tin-containing compound, chlorine-containing compound and tellurium-containing compound and place them in a sealed reaction vessel. Heat treat at 170-200°C for 0.5-24 hours and cool to obtain the product.

[0013] In some possible implementations, the heat treatment is carried out as follows: the temperature is raised from room temperature to 170-200°C at a heating rate of 1-3°C / min, held for 0.5-24 hours, and then cooled to room temperature at a cooling rate of 2-20°C / hour. After cooling, the solids are separated and retained, thus obtaining the product.

[0014] In some possible implementations, the cesium-containing compound is cesium chloride and / or cesium carbonate, the zirconium-containing compound is zirconium chloride, the tin-containing compound is at least one of tin tetrachloride, tin dioxide and stannous oxide, the chlorine-containing compound is hydrochloric acid, and the tellurium-containing compound is tellurium dioxide and / or tellurium tetrachloride.

[0015] In some possible implementations, after separating and retaining the solids, the following steps are also included: washing and drying the solids. For example, in this instance, ethanol is used as the washing reagent.

[0016] In some possible implementations, the cesium-containing compound, zirconium-containing compound, and tin-containing compound in step (1) are weighed in a protective atmosphere. The tellurium-containing compound and the chlorine-containing compound may be weighed together in a protective atmosphere or directly in air. As in the example, the protective atmosphere may be a nitrogen atmosphere or a rare gas atmosphere.

[0017] In some possible implementations, step (2) is carried out in a closed air atmosphere.

[0018] The above-mentioned Te-doped double perovskite Cs2Zr 1-x Sn x Application of Cl6 solid solution materials in the preparation of optical storage materials.

[0019] An optical storage material, the raw material of which includes the above-mentioned Te-doped double perovskite Cs2Zr 1-x Sn x Cl6 solid solution material.

[0020] The present invention has at least the following beneficial effects:

[0021] (1) The Te-doped double perovskite Cs2Zr of the present invention 1-x Sn x Cl6 solid solution materials exhibit high moisture resistance and chemical stability, and can be effectively excited by X-ray high-energy photons to generate high carrier storage. 4+ Not only does it serve as an effective hole trapping and luminescent recombination center, but Te 4+ In Cs2Zr 1-x Sn x Doping Cl6 can induce a large number of electron trap centers with electron-trapping properties. Furthermore, by adjusting the Sn content, the thermoluminescence peak position can be tuned over a wide temperature range from 100K to 400K. The material can be applied to ultra-wide temperature-range X-ray imaging and structural detection.

[0022] (2) Te-doped double perovskite Cs2Zr 1-x Sn x In Cl6 solid solution materials, only Te is used. 4+ Highly efficient X-ray optical storage materials can be obtained by doping individual ions. Compared with traditional optical storage materials co-doped with multiple rare-earth luminescent ions, Cs2Zr... 1-x Sn x Cl6:Te 4+ Solid solution optical storage materials exhibit highly repeatable luminescent properties and have low production costs.

[0023] (3) This invention employs a solvothermal reaction method, which can generate Te-doped double perovskite Cs2Zr with high crystallinity and carrier storage at 170–200℃. 1-x Sn x Compared to the harsh conditions of ultra-high temperatures (>1000 degrees Celsius) and reducing atmospheres (H2) required for traditional optical storage materials, Cl6 solid solution materials offer simpler reaction conditions and operations, resulting in lower production costs. Furthermore, the equipment required for this method is mature and simple in structure, facilitating large-scale production. Attached Figure Description

[0024] Figure 1 The Te-doped double perovskite Cs2Zr prepared in Examples 1-3 1-x Sn x X-ray diffraction pattern of Cl6 solid solution material;

[0025] Figure 2 The Te-doped double perovskite solid solution Cs2Zr prepared in Examples 1-3 1-x Sn xThe pyroelectric spectrum of Cl6 material after X-ray excitation, and the Te-doped double perovskite Cs2Zr prepared in Example 1. 1-x Sn x Comparison of Cl6 solid solution materials under sunlight and after being excited by X-ray light;

[0026] Figure 3 The Te-doped double perovskite Cs2Zr prepared in Example 1 1-x Sn x Thermoluminescence emission spectrum of Cl6 solid solution material after X-ray excitation;

[0027] Figure 4 The Te-doped double perovskite Cs2Zr prepared in Example 1 1-x Sn x The relationship between the absolute afterglow intensity of Cl6 solid solution material at room temperature and time after X-ray excitation;

[0028] Figure 5 The Te-doped double perovskite Cs2Zr prepared in Example 2 1-x Sn x Thermoluminescence emission spectrum of Cl6 solid solution material after X-ray excitation;

[0029] Figure 6 The Te-doped double perovskite Cs2Zr prepared in Example 2 1-x Sn x Comparison of afterglow emission spectra of Cl6 solid solution material after X-ray excitation at 140K (Kelvin);

[0030] Figure 7 The Te-doped double perovskite Cs2Zr prepared in Example 3 1-x Sn x Thermoluminescence emission spectrum of Cl6 solid solution material after X-ray excitation;

[0031] Figure 8 The Te-doped double perovskite Cs2Zr prepared in Example 4 1-x Sn x Thermoluminescence emission spectrum of Cl6 solid solution material after X-ray excitation. Detailed Implementation

[0032] The technical solution of the present invention will be further explained and described below through specific embodiments.

[0033] In the following embodiments, the water used can be one or more of distilled water, purified water, and drinking water; unless otherwise specified, the detection methods in the following embodiments are conventional detection methods; unless otherwise specified, the reagents in the following embodiments are all purchased from commercial channels.

[0034] Example 1

[0035] Te-doped double perovskite Cs2Zr in Example 1 1-x Sn x The Cl6 solid solution material is Cs2Zr. 0.75 Sn 0.25 Cl6:0.01Te 4 + Solid solution materials, based on this chemical formula, calculate the preparation method of Cs₂Zr. 0.75 Sn 0.25 Cl6:0.01Te 4+ The chemical raw materials required for the solid solution material are: 0.3367 g of cesium chloride (CsCl), 0.1748 g of zirconium chloride (ZrCl4), 0.0651 g of tin chloride (SnCl4), 0.00159 g of tellurium dioxide (TeO2) and 8 mL of 12 mol / L hydrochloric acid (HCl) solution.

[0036] Its preparation method includes the following steps:

[0037] (1) Accurately weigh 0.3367 g of cesium chloride, 0.1748 g of zirconium chloride and 0.0651 g of tin chloride in a glove box filled with nitrogen, and accurately weigh 0.00159 g of tellurium dioxide in an air atmosphere. Place these four compound raw materials in a small glass bottle, and then add 8 mL of hydrochloric acid solution with a concentration of 12 mol / L.

[0038] (2) After the raw materials in the small glass container are mixed evenly, they are transferred to the lining of a hydrothermal reactor. The hydrothermal reactor is placed in a high-temperature furnace for heat treatment. The sample is heated from room temperature to 180°C over 1 hour, held at 180°C for 12 hours, and then cooled to room temperature at a rate of 2.5°C / hour. After the sample cools to room temperature, the solution in the reactor lining is poured out, the crystals in the lining are washed with ethanol, and then dried at 60°C for 0.5 hours to obtain Cs₂Zr. 0.75 Sn 0.25 Cl6:0.01Te 4+ Solid solution materials.

[0039] To verify the crystal structure of the synthesized sample, Figure 1 The Cs2Zr prepared in Example 1 is given. 0.75 Sn 0.25 Cl6:0.01Te 4+ X-ray diffraction pattern of the solid solution material. The pattern was obtained using a Bruker D8 Advance instrument, with the X-ray tube voltage set to 40 kV and the current set to 30 mA. Figure 1 The X-ray spectra show that the Cs2Zr in Example 10.75 Sn 0.25 Cl6:0.01Te 4+ The solid solution material has the same crystal structure as Cs₂ZrCl₆ (PDF#74-0505). 4 + The doping did not lead to the formation of new impurity phases.

[0040] Figure 2 The Cs2Zr of Example 1 is given. 0.75 Sn 0.25 Cl6:0.01Te 4+ Thermoluminescence curve of the solid solution material. The thermoluminescence curve testing procedure was as follows: the sample was cooled to 100K, excited with X-rays for 70 seconds, and then the sample was heated at a rate of 1K / s while monitoring the change in luminescence intensity with temperature. The X-ray dose was approximately 6.94 mGy. To ensure comparability of luminescence intensity, Figure 2 The sample mass and X-ray excitation time were calibrated. From Figure 2 It can be seen that Cs2Zr 0.75 Sn 0.25 Cl6:0.01Te 4+ The thermoluminescence curve mainly consists of two thermoluminescence bands with peaks at 158 ​​K and 228 K. The thermoluminescence curve covers a temperature range from 100 K to 400 K. (Cs₂Zr) 0.75 Sn 0.25 Cl6:0.01Te 4+ The integral thermoluminescence intensity is that of commercial long afterglow materials Y2O2S:Eu 3+ 15.8 times that. Furthermore, Figure 2 The Cs2Zr of Example 1 is also given. 0.75 Sn 0.25 Cl6:0.01Te 4+ Room temperature photographs of solid solution materials and room temperature afterglow photographs after X-ray excitation. Cs₂Zr after X-ray excitation stops. 0.75 Sn 0.25 Cl6:0.01Te 4+ The room temperature afterglow intensity can reach 220 mcd / m 2 .

[0041] Figure 3 Cs2Zr as in Example 1 0.75 Sn 0.25 Cl6:0.01Te 4+Thermoluminescent emission spectrum of solid solution material. The sample was first cooled to 100 K, then excited with X-ray for 500 seconds, and the relationship between its emission spectrum and temperature was measured. The X-ray tube settings were 45 kV, 70 μA, and 3.15 W. The heating rate for the thermoluminescent emission spectrum was 1 K / s. Figure 3 It can be seen that at a low temperature of 169 K, its thermoluminescent emission spectrum consists of a peak at ~582 nm and a shoulder-shaped broad emission band with a peak at ~750 nm. The entire emission spectrum covers a wavelength range from 450 to 1000 nm. At a relatively high temperature of 239 K, the thermoluminescent emission spectrum consists of a Te band with a peak at ~582 nm. 4+ It consists of a launch belt.

[0042] Figure 4 Cs2Zr as in Example 1 0.75 Sn 0.25 Cl6:0.01Te 4+ Absolute decay curve of room-temperature afterglow luminescence for solid solution materials. Before testing absolute afterglow luminescence, the sample was excited by X-rays at room temperature (295 K) for 500 seconds. The X-ray tube settings were 58 kV, 190 μA, and 11 W. From... Figure 4 It can be seen that Cs2Zr in Example 1 0.75 Sn 0.25 Cl6:0.01Te 4+ The room temperature afterglow of the solid solution material exceeded 1.1 hours. After 1.1 hours of decay, Cs₂Zr 0.75 Sn 0.25 Cl6:0.01Te 4+ The afterglow intensity is 4687 times that of the background signal. This indicates that the Cs2Zr in Example 1... 0.75 Sn 0.25 Cl6:0.01Te 4+ Solid solution materials have high X-ray induced carrier storage properties.

[0043] Example 2

[0044] Te-doped double perovskite Cs2Zr in Example 2 1-x Sn x The Cl6 solid solution material is Cs2Zr. 0.5 Sn 0.5 Cl6:0.01Te 4+ Solid solution materials. Based on this chemical formula, the preparation of Cs₂Zr was calculated. 0.5 Sn 0.5 Cl6:0.01Te 4+The chemical raw materials required for the solid solution material are: 0.3367 g of cesium chloride (CsCl), 0.1165 g of zirconium chloride (ZrCl4), 0.1303 g of tin chloride (SnCl4), and 0.00159 g of tellurium dioxide (TeO2) and 10 mL of 12 mol / L hydrochloric acid (HCl) solution.

[0045] Its preparation method includes the following steps:

[0046] (1) Accurately measure 0.3367 g of cesium chloride, 0.1165 g of zirconium chloride, and 0.1303 g of tin chloride in a nitrogen-protected glove box, and accurately weigh 0.00159 g of tellurium dioxide in air. Place these four compound raw materials in a small glass bottle, and then add 10 mL of 12 mol / L hydrochloric acid solution.

[0047] (2) Stir the chemical raw materials in the small glass bottle with a glass rod to ensure uniform mixing, then transfer them to the liner of the reaction vessel for heat treatment. The sample was heated from room temperature to 185°C over 2 hours and held at 185°C for 10 hours, then cooled to room temperature at a rate of 2.5°C / hour. The reaction vessel was opened, the liner was removed, and excess solution was poured out to obtain the Cs₂Zr from Example 2. 0.5 Sn 0.5 Cl6:0.01Te 4+ Solid solution materials.

[0048] Figure 1 Cs2Zr of Example 2 is given. 0.5 Sn 0.5 Cl6:0.01Te 4+ X-ray diffraction pattern of the solid solution material. Its diffraction peaks are similar to those of the standard substances Cs₂SnCl₆ (PDF#70-2413) and Cs₂ZrCl₆ (PDF#74-0505). This indicates that the Cs₂Zr in Example 2... 0.5 Sn 0.5 Cl6:0.01Te 4+ The solid solution material has a similar crystal structure to the standard substances Cs₂SnCl₆ (PDF#70-2413) and Cs₂ZrCl₆ (PDF#74-0505). 4+ The doping did not induce a significant impurity phase.

[0049] Figure 2 Cs2Zr of Example 2 is given. 0.5 Sn 0.5 Cl6:0.01Te 4+Thermoluminescence curve of the solid solution material after X-ray excitation. The thermoluminescence curve mainly consists of two bands with peaks at ~150K and ~210K. The thermoluminescence curve covers a temperature range of 100K to 350K. Example 2: Cs₂Zr 0.5 Sn 0.5 Cl6:0.01Te 4+ The integrated thermoluminescence intensity of solid solution materials is the highest among commercially available long-afterglow materials, such as Y₂O₂S:Eu. 3+ 15.9 times. This indicates that Cs2Zr 0.5 Sn 0.5 Cl6:0.01Te 4+ It has high carrier storage capacity.

[0050] Figure 5 Cs2Zr of Example 2 is given. 0.5 Sn 0.5 Cl6:0.01Te 4+ Thermoluminescence emission spectrum of solid solution material after X-ray excitation. (Cs₂Zr) 0.5 Sn 0.5 Cl6:0.01Te 4+ The emission spectrum of solid solution materials is temperature-dependent. At low temperatures, such as 150 K, in addition to the Te spectrum exhibiting a peak at ~582 nm, [the following is a separate, unrelated point:] 4+ The characteristic emission band of the thermoluminescence spectrum also included a shoulder-shaped emission band with a peak at approximately 750 nm. As the temperature increased, for example at 209 K and 295 K, the thermoluminescent emission spectrum was mainly composed of Te emission bands with peaks around 582 nm. 4+ It consists of characteristic light-emitting bands.

[0051] Figure 6 Cs2Zr of Example 2 is given. 0.5 Sn 0.5 Cl6:0.01Te 4+ Afterglow emission spectrum of solid solution material at 140 K after 300 seconds of X-ray excitation. The X-ray tube setup was 45 kV, 70 μA, and 3.15 W. From... Figure 6 It can be seen that Cs2Zr in Example 2 0.5 Sn 0.5 Cl6:0.01Te 4+ Solid solution materials can emit ultra-wideband afterglow light of 500nm to 1000nm for more than 60 seconds, which indicates that they have high current carrying capacity.

[0052] Example 3

[0053] Example 3: Te-doped double perovskite Cs2Zr 1-x Sn x The Cl6 solid solution material is Cs2Zr.0.25 Sn 0.75 Cl6:0.01Te 4 + Solid solution materials, based on this chemical formula, calculate the preparation method of Cs₂Zr. 0.25 Sn 0.75 Cl6:0.01Te 4+ The required chemical raw materials are: 0.3367 g cesium chloride (CsCl), 0.0583 g zirconium chloride (ZrCl4), 0.1954 g tin chloride (SnCl4), 0.00159 g tellurium dioxide (TeO2) and 12 mL of 12 mol / L hydrochloric acid (HCl) solution.

[0054] Its preparation method includes the following steps:

[0055] (1) Accurately weigh the required amounts of 0.3367 g of cesium chloride, 0.0583 g of zirconium chloride, 0.1954 g of tin chloride (SnCl4), and 0.00159 g of tellurium dioxide (TeO2) in a nitrogen-protected glove box, and transfer the raw materials to a small glass bottle. Place the small glass bottle in an air atmosphere and quickly add 12 mL of a 12 mol / L hydrochloric acid solution.

[0056] (2) The raw materials in the small glass container were mixed evenly and then transferred to the lining of a high-temperature reactor. A polytetrafluoroethylene (PTFE) inner cover was added to the lining to create a closed environment for the reactants. The reactor was uniformly heated from room temperature to 200°C over 2 hours and held at 200°C for 24 hours. Finally, it was cooled to room temperature at a rate of 5°C / hour. The PTFE lining was removed, and the excess solution was poured out to obtain Cs₂Zr. 0.25 Sn 0.75 Cl6:0.01Te 4+ Solid solution materials.

[0057] Figure 1 Cs2Zr of Example 3 is given. 0.25 Sn 0.75 Cl6:0.01Te 4+ X-ray diffraction patterns of solid solution materials. From Figure 1 It can be seen that its X-ray diffraction pattern is similar to that of the standard substance Cs₂SnCl₆ (PDF#70-2413). This indicates that the Cs₂Zr in Example 3... 0.25 Sn 0.75 Cl6:0.01Te 4+ The solid solution material has the same crystal structure as Cs₂SnCl₆. Te 4+ The doping did not introduce impurity phases.

[0058] Figure 2 Cs2Zr of Example 3 is given.0.25 Sn 0.75 Cl6:0.01Te 4+ Thermoluminescence curve of the solid solution material after X-ray excitation. Its thermoluminescence spectrum mainly consists of two pyroluminescent bands with temperature peaks at ~142K and ~203K. The thermoluminescence spectrum covers a wide temperature range from 100K to 350K. Example 3: Cs₂Zr 0.25 Sn 0.75 Cl6:0.01Te 4+ The integrated thermoluminescence intensity of solid solution materials is the commercial Y2O2S:Eu 3+ 12.8 times. This indicates that the Cs2Zr in Example 3 is 12.8 times higher. 0.25 Sn 0.75 Cl6:0.01Te 4 + Solid solution materials have high X-ray induced charge carrier storage properties.

[0059] Figure 7 Cs2Zr of Example 3 is given. 0.25 Sn 0.75 Cl6:0.01Te 4+ Thermoluminescence emission spectrum of solid solution optical storage material after X-ray excitation. At 147 K, its emission spectrum consists of Te peaks at ~582 nm. 4+ The emission spectrum consists of a characteristic emission band and a shoulder-shaped emission band with a peak at ~750 nm. At 210 K, the emission spectrum is mainly composed of Te peaks at ~582 nm. 4+ Characteristic emission components.

[0060] Example 4

[0061] Example 4: Te-doped double perovskite Cs2Zr 1-x Sn x The Cl6 solid solution material is Cs2Zr. 0.75 Sn 0.25 Cl6:0.1Te 4 + Based on its chemical formula, the synthesis of Cs₂Zr was calculated. 0.75 Sn 0.25 Cl6:0.1Te 4+ The required chemical raw materials are: 0.3367 g cesium chloride (CsCl), 0.1768 g zirconium chloride (ZrCl4), 0.0651 g tin chloride (SnCl4), 0.01596 g tellurium dioxide (TeO2) and 8 mL of hydrochloric acid with a concentration of 12 mol / L.

[0062] Its preparation method includes the following steps:

[0063] (1) Accurately weigh the required amounts of 0.3367 g of cesium chloride (CsCl), 0.1768 g of zirconium chloride (ZrCl4), 0.0651 g of tin chloride (SnCl4), and 0.01596 g of tellurium dioxide (TeO2) in a glove box under nitrogen protection. Place the above chemical raw materials into a small glass bottle and quickly add 8 mL of 12 mol / L hydrochloric acid in air.

[0064] (2) The raw materials in the glass bottle were first thoroughly mixed. Then, they were transferred to the lining of a hydrothermal reactor. The reactor was placed in a high-temperature oven for heat treatment. The oven temperature was set as follows: after 1 hour, the oven temperature was raised from room temperature to 180 degrees Celsius, held at 180 degrees Celsius for 10 hours, and then cooled from 180 degrees Celsius to room temperature for 10 hours. The polytetrafluoroethylene lining was removed, and the excess solution was poured out to obtain Cs₂Zr. 0.75 Sn 0.25 Cl6:0.1Te 4+ Solid solution materials.

[0065] Figure 8 Cs2Zr is given 0.75 Sn 0.25 Cl6:0.1Te 4+ Thermoluminescent emission spectrum of solid solution materials. The method for measuring thermoluminescent emission spectrum is as follows: [The text abruptly ends here, likely due to an incomplete sentence or missing information.] 0.75 Sn 0.25 Cl6:0.1Te 4+ The solid solution material was ground and pressed into a thin sheet with a mass of approximately 0.1 g; the sample was cooled to 100 Kelvin and excited with X-rays for 500 seconds; the sample was then gradually heated to 500 Kelvin at a heating rate of 1 Kelvin per second; the emission spectrum of the sample was recorded during the heating process. Figure 8 It can be seen that the emission spectrum of the sample consists of a broadband emission band with a peak wavelength of 582 nm. The thermoluminescence curve covers a temperature range from 100 Kelvin to 400 Kelvin. The thermoluminescent spectrum is a broadband spectrum with a peak at approximately 190 Kelvin.

[0066] The above description is merely a preferred embodiment of the present invention, and therefore should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made in accordance with the scope of the patent and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A Te-doped double perovskite Cs₂Zr 1-x Sn x The method for preparing Cl6 solid solution materials is characterized by... The general chemical formula of the Te-doped double perovskite solid solution material is Cs₂Zr. 1-x Sn x Cl6:yTe 4+ Where 0 < x < 1, 0 < y < 0.2, the preparation method includes the following steps: (1) Weigh out cesium-containing compounds, zirconium-containing compounds, tin-containing compounds, chlorine-containing compounds and tellurium-containing compounds with a molar ratio of 2:1-x:x:6:y; (2) Mix the cesium-containing compound, the zirconium-containing compound, the tin-containing compound, the chlorine-containing compound and the tellurium-containing compound and place them in a sealed reaction vessel. Heat treat at 170~200 °C for 0.5~24 hours. After cooling, separate and retain the solids to obtain the product.

2. The preparation method according to claim 1, characterized in that, The specific operation of the heat treatment is as follows: the temperature is increased from room temperature to 170-200 ℃ at a heating rate of 1-3 ℃ / min, held at the temperature for 0.5-24 hours, and then cooled down to room temperature at a cooling rate of 2-20 ℃ / hour.

3. The preparation method according to claim 1 or 2, characterized in that, The cesium-containing compound is cesium chloride and / or cesium carbonate, the zirconium-containing compound is zirconium chloride, the tin-containing compound is at least one of tin tetrachloride, tin dioxide, and stannous oxide, the chlorine-containing compound is hydrochloric acid, and the tellurium-containing compound is tellurium dioxide and / or tellurium tetrachloride.

4. The preparation method according to claim 1 or 2, characterized in that, The cesium-containing compound, the zirconium-containing compound, and the tin-containing compound in step (1) are weighed in a protective nitrogen atmosphere.

5. A Te-doped double perovskite Cs₂Zr prepared by the preparation method according to any one of claims 1 to 4 1- x Sn x Cl6 solid solution material.

6. The Te-doped double perovskite Cs₂Zr as described in claim 5 1-x Sn x Cl6 solid solution material, characterized in that... Its crystal structure is cubic, and its space group is .

7. The Te-doped double perovskite Cs₂Zr as described in claim 5 or 6 1-x Sn x Application of Cl6 solid solution materials in the preparation of optical storage materials.

8. An optical storage material, characterized in that, Its raw materials include the Te-doped double perovskite Cs₂Zr as described in claim 5 or 6. 1-x Sn x Cl6 solid solution material.

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