CN115321580B - Long afterglow material of rare earth element doped fluoride, preparation method and application thereof - Google Patents
Long afterglow material of rare earth element doped fluoride, preparation method and application thereof Download PDFInfo
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- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
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Abstract
The invention belongs to the technical field of luminescent materials, and in particular relates to a rare earth element doped fluoride long afterglow material with adjustable size, and a mass preparation method and application thereof, wherein the preparation method comprises the following steps: mixing rare earth salt, sodium fluoride and ammonium fluoride with water under the condition of no ligand, regulating the pH value of the solution to be neutral, adding an alcohol solvent for hydrothermal reaction to obtain beta-NaReF 4 A long afterglow material; wherein, re is at least one selected from yttrium, scandium, lanthanum, cerium, neodymium, samarium, europium, gadolinium, promethium, dysprosium, holmium, erbium, thulium, ytterbium, praseodymium, lutetium and terbium; the molar ratio of the sodium fluoride to the ammonium fluoride is 1: (0-9). The preparation method of the rare earth element doped fluoride long afterglow material provided by the invention is suitable for mass production, the single production product can reach 26g, and the yield is about 95%.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a rare earth element doped fluoride long afterglow material with adjustable size, and a mass preparation method and application thereof.
Background
The 7 electron orbits of the lanthanide rare earth ion 4f layer endow 1600 electron energy levels and more than 20 energy level transitions, and the light-emitting device is a huge light-emitting treasury. Rare earth ions can be used as a luminescent center to be doped into a matrix, and have the excellent performances of narrow emission spectrum, large Stokes shift, long luminescent life and tunable luminescent wavelength in an ultraviolet light to infrared light region. Currently, the matrix of the luminescent material is of the types of oxides, sulfides, nitrides, fluorides and the like. Wherein the fluoride matrix has lower phonon vibration energy<350cm -1 ) There may beThe energy loss caused by non-radiative relaxation transition is effectively reduced, and the luminescent efficiency is good, so that the luminescent material has great potential in biomedical, photoelectric devices, anti-counterfeiting fields and the like.
By AReF 4 (A is an alkali metal element and Re is a rare earth element) as a representative, and the rare earth doped fluoride micro-nano material is widely paid attention to and developed. Recent researches show that the rare earth doped fluoride material has excellent long afterglow luminescence property under the action of X rays, so that the rare earth doped fluoride material has a large application space in the fields of biomedical imaging, industrial flaw detection and the like. The mass preparation of rare earth doped fluoride materials is an important link for promoting the further productive conversion.
Most laboratory-level synthesis methods can only perform small-scale synthesis, and the single yield is less than one gram, so that the industrial requirement cannot be met. The most commonly used synthesis methods in the laboratory at present mainly comprise a coprecipitation method, a hydrothermal method, a high-temperature thermal decomposition method and the like. The coprecipitation method has low yield, long time consumption, high cost and large exhaust emission, and limits the industrial application of the coprecipitation method; the trifluoroacetate serving as a raw material of the high-temperature thermal decomposition method generates a large amount of hydrofluoric acid toxic gas at high temperature, and the required anhydrous and anaerobic severe reaction conditions at high temperature are unfavorable for production safety. Therefore, the problems of low yield, high cost, serious pollution and the like of the two synthesis methods need to be solved. The rare earth luminescent material synthesized by the hydrothermal method has the advantages of high purity, good crystal form and good monodispersity, the reaction temperature is low, and the size and the morphology of the product are easy to control. In addition, the hydrothermal method is very suitable for industrialized mass production due to the characteristics of simple operation, simple instrument, high yield, environmental friendliness and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, the technical problems to be solved by the invention are as follows: provides a preparation method of a long afterglow material capable of producing rare earth element doped fluoride in a large scale, the long afterglow material prepared by the preparation method and application thereof.
In order to solve the technical problems, the invention provides a rare earth element doped fluorideThe preparation method of the bright material comprises the steps of mixing rare earth salt, sodium fluoride and ammonium fluoride with water under the condition of not containing any ligand, adjusting the pH value of the solution to be neutral, adding alcohol solvent for hydrothermal reaction to obtain beta-NaReF 4 A long afterglow material;
wherein, re is at least one selected from yttrium, scandium, lanthanum, cerium, neodymium, samarium, europium, gadolinium, promethium, dysprosium, holmium, erbium, thulium, ytterbium, praseodymium, lutetium and terbium;
the molar ratio of the sodium fluoride to the ammonium fluoride is 1: (0-9).
Further provides the rare earth element doped fluoride long afterglow material prepared by the preparation method.
And the application of the rare earth element doped fluoride long afterglow material in biological marking, X-ray detection, display and imaging.
The invention has the beneficial effects that: the preparation method of the rare earth element doped fluoride long afterglow material provided by the invention can not only obtain beta-NaReF with excellent luminous performance by adjusting the proportion between sodium fluoride and ammonium fluoride under the condition of not adding any ligand 4 The long afterglow material has no ligand system, can reduce the material amount, raise the yield, lower material cost and simplify the synthesis process, and is one key technological problem from laboratory synthesis stage to industrial mass production. Meanwhile, the use of the traditional ligand is abandoned, so that the growth limit of the product can be effectively improved, the size of the product is increased to a micron level to a certain extent, and the luminous performance of the long afterglow material is further improved. In addition, the long afterglow material is synthesized under the condition of no ligand, namely, the product is not subjected to ligand modification, so that the direct in-situ modification can be realized without an additional ligand removal step in the application process of the product, the application process is greatly simplified, and the product loss in the ligand removal process is reduced.
Drawings
FIG. 1 shows a micron-sized NaLuF obtained in example 1 of the present invention 4 X-ray powder derivatives of TbShooting;
FIG. 2 shows the micron-sized NaLuF obtained in example 1 of the present invention 4 Tb scanning electron microscope image;
FIG. 3 shows the micron-sized NaLuF obtained in example 1 of the present invention 4 Tb product photograph;
FIG. 4 shows the micron-sized NaLuF obtained in example 1 of the present invention 4 Tb X-ray excitation luminescence spectrum;
FIG. 5 shows the micron-sized NaLuF obtained in example 1 of the present invention 4 Tb is an X-ray afterglow attenuation curve graph;
FIG. 6 shows NaLuF obtained in example 2 of the present invention with different raw material ratios 4 Tb transmission electron microscopy images (scale bar is 2 microns);
FIG. 7 shows NaLuF obtained in example 2 of the present invention with different raw material ratios 4 Tb X-ray excitation luminescence spectrum;
FIG. 8 shows NaLuF obtained in example 2 of the present invention with different raw material ratios 4 Tb X-ray excitation luminescence spectrum;
FIG. 9 shows NaLuF obtained in example 2 of the present invention with different raw material ratios 4 Tb is an X-ray afterglow attenuation curve graph;
FIG. 10 shows NaLuF obtained in example 2 of the present invention with different raw material ratios 4 Tb is an X-ray afterglow attenuation curve graph;
FIG. 11 shows NaLuF obtained in example 3 of the present invention with different doping concentrations of rare earth elements and co-doping of rare earth elements 4 Tb and NaLuF 4 Gd, tb transmission electron microscope pictures (scale bar is 2 microns);
FIG. 12 shows NaLuF obtained in example 3 of the present invention with different doping concentrations of rare earth elements and co-doping of rare earth elements 4 Tb and NaLuF 4 Gd, tb X-ray excitation luminescence spectrogram;
FIG. 13 shows NaLuF obtained in example 3 of the present invention with different doping concentrations of rare earth elements and co-doping of rare earth elements 4 Tb and NaLuF 4 Gd, tb X-ray afterglow attenuation curve graph;
FIG. 14 is a graph showing the result of comparative example 1 of the present inventionEDTA-2Na and CitNa respectively 3 NaLuF with PEG and OA as ligands 4 Tb transmission electron microscopy images (scale bar is 2 microns);
FIG. 15 shows the results of comparative example 1 of the present invention with EDTA-2Na and CitNa, respectively 3 NaLuF with PEG and OA as ligands 4 Tb X-ray excitation luminescence spectrum;
FIG. 16 shows the results of comparative example 1 of the present invention with EDTA-2Na and CitNa, respectively 3 NaLuF with PEG and OA as ligands 4 Tb is an X-ray afterglow attenuation curve graph;
FIG. 17 shows NaLuF obtained in example 4 of the present invention at various reaction times 4 Tb transmission electron microscopy images (scale bar is 2 microns);
FIG. 18 shows NaLuF obtained in example 4 of the present invention at various reaction times 4 Tb X-ray excitation luminescence spectrum;
FIG. 19 shows NaLuF obtained in example 4 of the present invention at various reaction times 4 Tb is an X-ray afterglow attenuation curve graph;
FIG. 20 shows NaLuF at different reaction temperatures obtained in example 5 of the present invention 4 Tb transmission electron microscopy images (scale bar is 2 microns);
FIG. 21 shows NaLuF at different reaction temperatures obtained in example 5 of the present invention 4 Tb X-ray excitation luminescence spectrum;
FIG. 22 shows NaLuF at different reaction temperatures obtained in example 5 of the present invention 4 Tb is an X-ray afterglow attenuation curve graph;
FIG. 23 shows NaLuF obtained in example 6 of the present invention at various sodium hydroxide concentrations 4 Tb transmission electron microscopy images (scale bar is 2 microns);
FIG. 24 shows NaLuF with different sodium hydroxide concentrations obtained in example 6 of the present invention 4 Tb X-ray excitation luminescence spectrum;
FIG. 25 shows NaLuF with different sodium hydroxide concentrations obtained in example 6 of the present invention 4 Tb is an X-ray afterglow attenuation curve graph;
FIG. 26 shows the rare earth elements obtained in example 7 of the present inventionPlain doped NaLuF 4 Transmission electron microscope pictures of Pr/Nd/Sm/Tb/Dy/Ho/Er/Tm (the scale bars are all 2 micrometers);
FIG. 27 shows the different rare earth doped NaLuF obtained in example 7 of the present invention 4 An X-ray excitation luminescence spectrum chart of Pr/Nd/Sm/Tb/Dy/Ho/Er/Tm;
FIG. 28 shows the different rare earth doped NaLuF obtained in example 7 of the present invention 4 An X-ray afterglow attenuation curve graph of Pr/Nd/Sm/Tb/Dy/Ho/Er/Tm;
FIG. 29 shows a NaLuF prepared by a high temperature co-precipitation method obtained in comparative example 2 of the present invention 4 Tb transmission electron microscopy (scale bar 50 nm);
FIG. 30 shows the preparation of NaLuF by high temperature co-precipitation in comparative example 2 of the present invention and the preparation of NaLuF by ligand-free concentrated hydrothermal method in this patent 4 Tb X-ray excitation luminescence spectrum;
FIG. 31 shows the preparation of NaLuF by high temperature co-precipitation in comparative example 2 of the present invention and the preparation of NaLuF by ligand-free concentrated hydrothermal method in this patent 4 Tb X-ray afterglow attenuation curve graph.
Detailed Description
In order to describe the technical contents, the achieved objects and effects of the present invention in detail, the following description will be made with reference to the embodiments in conjunction with the accompanying drawings.
The preparation process of long afterglow material with RE doped fluoride includes mixing RE salt, sodium fluoride and ammonium fluoride with water and regulating pH value to neutrality, and adding alcohol solvent to perform hydrothermal reaction to obtain beta-NaReF 4 type long afterglow material; wherein, re is at least one selected from yttrium, scandium, lanthanum, cerium, neodymium, samarium, europium, gadolinium, promethium, dysprosium, holmium, erbium, thulium, ytterbium, praseodymium, lutetium and terbium; the molar ratio of the sodium fluoride to the ammonium fluoride is 1: (0-9).
Wherein the ligand is selected from at least one of an organic additive, a surfactant, and a functional ligand. For example, sodium citrate as described in CN111876154A, oleic acid, polyethyleneimine, ethylenediamine tetraacetic acid, cetyltrimethylammonium bromide and the like as described in the prior artOrganic additives or surfactants for controlling nanocrystal size, phase and morphology, and functional ligands for surface modification of long afterglow materials, such as EDTA-2Na, citNa 3 PEG, OA, and the like.
In one embodiment, the rare earth salt is preferably mixed with water before being mixed with sodium fluoride and ammonium fluoride. The rare earth salt is at least one selected from nitrate, chloride and acetate of rare earth. Illustratively, the rare earth salt is a rare earth nitrate, rare earth chloride or rare earth acetate; or a combination of rare earth nitrate and rare earth chloride salt, or a combination of rare earth nitrate and rare earth acetate salt, or a combination of rare earth chloride salt or rare earth acetate salt, or a combination of rare earth nitrate, rare earth chloride salt and rare earth acetate salt. The salt form selection for a particular rare earth element may be considered in terms of its water solubility. The rare earth element in the present invention may be any rare earth element known to those skilled in the art, and is not particularly limited. Preferably, the rare earth element is selected from at least one of yttrium, scandium, lanthanum, cerium, neodymium, samarium, europium, gadolinium, promethium, dysprosium, holmium, erbium, thulium, ytterbium, praseodymium, lutetium, and terbium. More preferably, the rare earth element comprises at least lutetium or terbium, more preferably the rare earth element is lutetium and terbium. In one embodiment, when terbium is contained in the rare earth element, the molar content of terbium is preferably 0.5 to 50%, more preferably 0.5 to 40%, still more preferably 5 to 30%, still more preferably 5 to 25%, most preferably 5 to 20%, and illustratively the molar content of terbium is 0.5%, 5%, 10%, 15%, 20%, 25%. In another embodiment, when lutetium and terbium are contained in the rare earth element, the molar ratio of lutetium to terbium is preferably (3 to 200): 1, more preferably (3 to 100): 1, more preferably (4 to 20): 1, most preferably (4 to 6): 1, illustratively, the molar ratio of lutetium to terbium is 4: 1. 99.5:0.5, 95: 5. 90: 10. 85: 15. 80:20 or 75:25.
wherein deionized water is preferably used as the water. The mixing preferably employs ultrasonic mixing to facilitate dissolution of the rare earth salt in water by ultrasonic mixing. The mixing time is preferably 3 to 10 minutes.
The rare earth salt concentration in the mixed solution is preferably 0.5 to 10mol/L, more preferably 0.5 to 8mol/L, still more preferably 0.5 to 6mol/L, still more preferably 0.8 to 4mol/L, most preferably 0.8 to 2mol/L, and the rare earth salt concentration in the mixed solution is 1.25mol/L or 1mol/L, for example.
The inventor finds that the ratio between sodium fluoride and ammonium fluoride is critical to the influence on the luminous performance of the long afterglow material in a synthetic system lacking other ligands, and the ratio between ammonium fluoride, sodium fluoride and rare earth elements also determines the quality of the long afterglow luminous performance. Preferably, the molar ratio of the rare earth salt to the sodium fluoride is 1: (1-6); more preferably 1: (1-2.5), most preferably 1:1; the molar ratio of the rare earth salt to the ammonium fluoride is 1: (0 to 9), more preferably 1: (2 to 6), and more preferably 1: (3-5), most preferably 1:4. wherein the sodium fluoride and ammonium fluoride are both mixed in the form of an aqueous solution thereof. Wherein, the concentration of the aqueous solution of sodium fluoride is preferably 0.1-1 mol/L, and most preferably 0.5-1 mol/L; the concentration of the aqueous solution of ammonium fluoride is preferably 0.5 to 15mol/L, more preferably 2 to 15mol/L, still more preferably 2 to 10mol/L, still more preferably 3 to 8mol/L, and most preferably 4 to 5mol/L.
In one embodiment, the aqueous solution of sodium fluoride is preferably added dropwise under stirring, and the aqueous solution of ammonium fluoride is stirred after the addition is completed and then added dropwise after the completion of the stirring. Wherein, the white turbid solution can be obtained by dripping sodium fluoride. Preferably, the stirring is performed for 10 to 40 minutes, more preferably 20 to 30 minutes after the addition of sodium fluoride. After the ammonium fluoride aqueous solution is added dropwise, the solution is gel, preferably stirred for 20-60 min, more preferably 30-50 min, and still more preferably 30-40 min; the rotation speed of stirring at this time is preferably 600 to 1000r/min, more preferably 800 to 900r/min.
However, the inventors found that when the pH value of the solution is adjusted, the problem that the luminous performance of the long afterglow material is reduced due to the too high or too low pH value is caused. Therefore, it is necessary to ensure that the pH of the solution is neutral after thorough mixing. The solution pH can thus be adjusted to neutral by adding a pH adjuster. In order to avoid the introduction of impurities during the pH adjustment, it is preferable to carry out the pH adjustment by using an aqueous sodium hydroxide solution having a concentration of 10 to 20 mol/L. Of course, this step of adjusting the pH to neutral may be omitted in some embodiments, since the pH of the solution itself is near neutral (7) after the components are thoroughly mixed.
After the pH of the solution is adjusted to neutral, the solution is preferably stirred and then the alcoholic solvent is added, and the stirring time is preferably 10 to 30 minutes, more preferably 10 to 20 minutes. The pressure of the synthesis system during high-temperature reaction is increased by introducing an alcohol solvent so as to improve the synthesis condition of high-temperature and high-pressure of the hydrothermal reaction. The alcohol solvent may be any alcohol solvent known to those skilled in the art, and is not limited herein. Ethanol is preferred. The alcohol solvent is preferably added in the form of a drop. The volume ratio of the solution mixed with each component after the pH adjustment to the alcohol solvent is (2-5): 1, more preferably (2 to 4): 1, most preferably (3 to 4): 1. the hydrothermal reaction is preferably carried out after the addition of the alcohol solvent and stirring. The stirring is preferably 10 to 40 minutes, more preferably 20 to 30 minutes.
The existing rare earth element doped fluoride mainly comprises AB 3 (e.g. YF) 3 ：Tb 3+ ) And ABX 4 (NaLuF) 4 ：Tb 3+ ). In one aspect, AB 3 Rare earth doped fluorides compared to ABX 4 The rare earth doped fluoride has softer lattice rigidity and slightly larger phonon vibration, so that the energy loss caused by non-radiative relaxation transition is also increased. AB, on the other hand 3 The density of luminescent centers of the rare earth element doped fluoride is larger, so that the probability of non-radiative relaxation transition between luminescent ions is also greatly increased, and the luminescent performance is reduced. I.e. AB as a whole 3 Rare earth doped fluoride has poor luminescence property, poor afterglow or no afterglow. And for ABX 4 The rare earth element doped fluoride has an alpha type and a beta type, and the beta type has better luminescence performance compared with the alpha type. Therefore, the invention avoids the preferential synthesis of alpha-rare earth element doped fluoride with more stable kinetics under the low-temperature condition by increasing the reaction temperature of the hydrothermal reaction. Meanwhile, the high temperature condition is also favorable for improving the crystallinity of the crystal, and the improvement of the crystallinity can further enhance the luminous performance of the long afterglow material.
In particular, the hydrothermal reaction is preferably carried out in a reaction vessel. The volume of the reaction system solution of the hydrothermal reaction is preferably 10% -80%, more preferably 30% -80%, still more preferably 50% -80%, still more preferably 60% -80% and most preferably 70% -80% of the volume of the reaction kettle; the temperature of the hydrothermal reaction is preferably 160 to 230 ℃, more preferably 180 to 230 ℃, and still more preferably 200 to 210 ℃. Illustratively, the temperature of the hydrothermal reaction is 200 ℃, 210 ℃, or 220 ℃. The reaction time of the hydrothermal reaction is preferably 2 to 24 hours, more preferably 4 to 20 hours, still more preferably 6 to 18 hours, and most preferably 6 to 12 hours. Illustratively, the reaction time of the hydrothermal reaction is 2h, 4h, 6h, 8h, 10h, 12h, or 16h.
After the hydrothermal reaction, the suspension particles are preferably centrifuged, washed and dried to obtain the rare earth doped fluoride long afterglow material with adjustable size from nano level to micron level; the washing is preferably performed by using one or more of redistilled water, ethanol and toluene; the drying temperature is preferably 50 to 100 ℃, more preferably 50 to 80 ℃, and most preferably 60 to 70 ℃.
A long afterglow material of rare earth element doped fluoride is prepared by the preparation method. Wherein the particle size of the prepared long afterglow material is adjustable within the range of 0.1-10 mu m, namely the long afterglow material can be nano-scale or micro-scale material, and more preferably, the particle size of the long afterglow material is 1-10 mu m. The crystal structure of the long afterglow material is hexagonal phase. The long afterglow material has fluorescence and long afterglow luminescence phenomena under the excitation of X rays, and the rest of the glow time can last for more than 30 days.
The long afterglow material provided by the invention has excellent luminous performance and size advantages, and meanwhile, the long afterglow material is prepared in a water-ethanol system, so that the long afterglow material has better water solubility, and even if the long afterglow material does not carry out additional ligand surface modification such as PEG, the long afterglow material still has great advantages in the application of biological marking, X-ray detection, display and imaging.
Example 1
Example 1:100mmol micron-sized NaLuF 4 Preparation of Tb
1.1 mixing 80mmol lutetium nitrate and 20mmol terbium nitrate powder, dissolving in deionized water to 80mL, and dissolving with ultrasound to obtain 1.25 mol.L -1 Rare earth nitrate solution.
1.2 dropwise adding 100mL of sodium fluoride solution to the solution in step 1.1, wherein the concentration of the sodium fluoride solution is 1 mol.L -1 A white turbid solution was obtained and stirring was continued for 20min.
1.3 drop-adding 80mL of ammonium fluoride solution to the solution in step 1.2, wherein the concentration of the ammonium fluoride solution is 5 mol.L -1 The solution becomes gel, and the stirring speed is increased to 800 r.min -1 Stirring was continued for 30min.
1.4 slowly dropwise adding sodium hydroxide solution to the solution in step 1.3 to ph=7, wherein the concentration of the sodium hydroxide solution is 20mol·l -1 Stirring was continued for 10min.
1.5 drop 100mL absolute ethanol into the solution in step 1.4 and continue stirring for 20min.
1.6 transferring the mixed solution obtained in the step 1.5 into a 500mL reaction kettle, and performing hydrothermal reaction at 200 ℃ for 12 hours to obtain a white product. After centrifugation, washing the product with twice distilled water and ethanol for 3 times to obtain micron-sized NaLuF 4 Tb white powder was dried at 60℃for 6h.
The micron-sized NaLuF obtained in example 1 was subjected to X-ray diffraction 4 Tb white powder was analyzed to obtain its X-ray powder diffraction pattern as shown in FIG. 1. As can be seen from FIG. 1, the diffraction peak positions are the same as those of the hexagonal phase of beta-NaLuF 4 PDF standard card with crystal structure (NaLuF) 4 : JCDF No. 27-0726) is consistent, is a pure hexagonal phase structure and has no impurity phase. In addition, the high temperature is more conducive to the improvement of the crystal crystallinity, which in turn can effectively enhance the luminescence property, and it can be demonstrated that the product has good crystallinity from the sharp and high-intensity diffraction peaks in fig. 1.
The micron-sized NaLuF obtained in example 1 was subjected to a scanning electron microscope 4 Tb white powder was analyzed to obtain a scanning electron microscope image thereof, as shown in FIG. 2. As can be seen from FIG. 2, the shape is a bar with a length of 2-5 mum。
FIG. 3 shows the micron-sized NaLuF obtained in example 1 4 Tb white powder product plot with a single yield of about 26g and a yield of about 95%.
The micron-sized NaLuF obtained in example 1 was subjected to excitation luminescence spectrum by X-ray 4 Tb white powder is analyzed to obtain an X-ray excitation luminescence spectrum chart of the Tb white powder, as shown in figure 4. FIG. 4 is a NaLuF 4 Fluorescent emission pattern of Tb material corresponding to Tb 3+ Is characterized by four characteristic emission peaks 5 D 4 → 7 F 6 ， 5 D 4 → 7 F 6 ， 5 D 4 → 7 F 6 And 5 D 4 → 7 F 6 wherein the upper right hand corner of FIG. 4 is NaLuF 4 Fluorescent photograph of Tb powder in excited state.
FIG. 5 is a NaLuF of example 1 4 X-ray afterglow attenuation curve graph of Tb material, and long afterglow material is excited for 3min under 50kv and 80mA silver target. It can be seen that the long afterglow intensity is maintained to be more than 1000 times of the baseline after the excitation is finished for 10min, which proves that the fluorescent powder has excellent and durable long afterglow luminescence property.
Example 2: 100mmol NaLuF with different raw material ratios 4 Preparation of Tb
2.1 mixing 80mmol lutetium nitrate and 20mmol terbium nitrate powder, dissolving in deionized water to constant volume to 100mL, and dissolving with ultrasound to obtain 1 mol.L -1 Rare earth nitrate solution.
2.2 dropwise adding 100mL of the sodium fluoride solution in the step 2.1, wherein the concentration of the sodium fluoride solution is 1 mol.L -1 A white turbid solution was obtained and stirring was continued for 20min.
2.3 dropwise adding 60mL of the ammonium fluoride solution to the solution in step 2.2, wherein the concentration of the ammonium fluoride solution is 15 mol.L -1 The solution becomes gel, and the stirring speed is increased to 800 r.min -1 Stirring was continued for 30min.
2.4 slowly dropwise adding sodium hydroxide solution to the solution in step 2.3 to ph=7, wherein the concentration of the sodium hydroxide solution is 20mol·l -1 Stirring was continued for 10min.
2.5 drop 100mL absolute ethanol into the solution in step 2.4 and continue stirring for 20min.
2.6 transferring the mixed solution obtained in the step 2.5 into a 500mL reaction kettle, and performing hydrothermal reaction at 200 ℃ for 12 hours to obtain a white product. After centrifugation, the product is washed 3 times with distilled water and ethanol to obtain NaLuF 4 Tb white powder was dried at 60℃for 6h.
2.7, comparing the performances of products with different raw material ratios to obtain the optimal performance ratio: repeating the steps 2.1-2.6, wherein the rest conditions are all completed under the same condition except that the molar ratio of the sodium fluoride to the ammonium fluoride is adjusted. Namely, under the condition of keeping the total amount of the rare earth salt to be constant, the optimal proportion of the rare earth salt to the sodium fluoride and the ammonium fluoride is determined by adjusting the amount of the sodium fluoride or the ammonium fluoride in the step 2.2 or the step 2.3. The final products with different molar ratios of sodium fluoride to ammonium fluoride are respectively (molar mass ratio, sodium fluoride: ammonium fluoride): a-1:3; b-1:4; c-1:5; d-1:6; e-1:7; f-1:9; g-4:0; h-2:4; i-3:3; j-3:4; k-4:2; l-5:1; m-5:4; n-6:0.
NaLuF obtained in example 2 was subjected to a transmission electron microscope to obtain NaLuF having different ratios of raw materials 4 Tb is analyzed respectively to obtain a transmission electron microscope image of Tb, as shown in FIG. 6. As can be seen from FIG. 6, naLuF has a molar ratio of sodium fluoride to ammonium fluoride of 1:3 4 Tb is limited in growth possibly due to less fluorine source and poor solubility of ammonium fluoride in ethanol, so that the morphology of the Tb is about 100 nanometers, the morphologies of the rest experimental groups with different proportions are all irregular rods, and the length is between 1 and 6 mu m. Wherein, the molar ratio of sodium fluoride to ammonium fluoride with optimal luminous performance is NaLuF of 1:4 4 Tb is in a short bar shape and has a length of 2-5 mu m.
NaLuF obtained in example 2 and having different ratios of raw materials by using X-ray excitation luminescence spectrum 4 Tb is respectively analyzed to obtain X-ray excitation luminescence spectrograms, as shown in fig. 7 and 8 (the luminescence intensity of different raw material ratios listed in the figures gradually increases from bottom to top). As can be seen from FIGS. 7 and 8, all the above proportionsIn (2), when the molar ratio of sodium fluoride to ammonium fluoride is 1:4, the fluorescence intensity has an optimal value, and the same ratio is improved by 3 times (when the molar ratio of sodium fluoride to ammonium fluoride is 1:3, the fluorescence intensity is the lowest value).
FIGS. 9 and 10 (the afterglow intensity of the different ratios of the raw materials shown in the drawing gradually increases from bottom to top) show NaLuF at the different ratios of the raw materials in example 2 4 X-ray afterglow attenuation curve graph of Tb material, and long afterglow material is excited by rays under 50kv and 80mA silver target for 3min. It can be seen that in all the above ratios, when the molar ratio of sodium fluoride to ammonium fluoride is 1:4, the afterglow performance of the material is optimal, and the same ratio is improved by 13 times (when the molar ratio of sodium fluoride to ammonium fluoride is 1:3, the afterglow performance is the lowest).
Example 3: rare earth element different doping concentration and 100mmol NaLuF co-doped with different rare earth elements 4 Tb and NaLuF 4 Gd, tb preparation
3.1 mixing and dissolving 99.5mmol lutetium nitrate and 0.5mmol terbium nitrate powder in deionized water to 80mL, and ultrasonically dissolving to obtain 1.25 mol.L -1 Rare earth nitrate solution.
3.2 dropwise adding 100mL of sodium fluoride solution to the solution in step 3.1, wherein the concentration of the sodium fluoride solution is 1 mol.L -1 A white turbid solution was obtained and stirring was continued for 20min.
3.3 drop-adding 80mL of ammonium fluoride solution to the solution in step 3.2, wherein the concentration of the ammonium fluoride solution is 5 mol.L -1 The solution becomes gel, and the stirring speed is increased to 800 r.min -1 Stirring was continued for 30min.
3.4 slowly dropwise adding sodium hydroxide solution to the solution in step 3.3 to ph=7, wherein the concentration of the sodium hydroxide solution is 20mol·l -1 Stirring was continued for 10min.
3.5 drop 100mL absolute ethanol into the solution in step 3.4, and continue stirring for 20min.
3.6 transferring the mixed solution obtained in the step 3.5 into a 500mL reaction kettle, and performing hydrothermal reaction for 12h at 200 ℃ to obtain a white product. After centrifugation, the product is washed 3 times with distilled water and ethanol to obtain NaLuF 4 Tb white powder was dried at 60℃for 6h.
3.7, comparing the performances of products co-doped with different rare earth elements at different doping concentrations to obtain the optimal doping concentration of Tb: changing the mole ratio of the rare earth salt added in the step 3.1, repeating the steps 3.2-3.6 to finally obtain the rare earth element with different doping concentrations (mole concentrations) and the products of co-doping of different rare earth elements, wherein the products are respectively as follows: a-0.5% Tb; b-5% tb; c-10% Tb; d-15% Tb; e-20% Tb; f-25% Tb; g-5% Gd-15% Tb; h-5% Gd-20% Tb; i-10% Gd-20% Tb.
The rare earth element different doping concentrations and the products of different rare earth element co-doping obtained in example 3 were analyzed by transmission electron microscopy, respectively, to obtain a transmission electron microscopy image thereof, as shown in fig. 11. Wherein, except the product b-5% Tb with the shape and size of 200-500 nm, the shape and size of the rest products are irregular bars, and the length is between 1 and 8 mu m. Wherein, the Tb doping concentration with the optimal luminescence performance is 15-20%, the shape is a short bar shape, and the length is 2-6 mu m.
The rare earth element different doping concentrations and the products co-doped with different rare earth elements obtained in example 3 were respectively analyzed by using an X-ray excitation luminescence spectrum to obtain an X-ray excitation luminescence spectrum chart thereof, as shown in fig. 12. In all the doping concentrations, when the molar ratio of lutetium nitrate to terbium nitrate is 1 (4-6), naLuF 4 Tb (15% -20%), the fluorescence intensity of which has the best value.
FIG. 13 is an X-ray afterglow attenuation curve of the rare earth element doped at different concentrations and co-doped products of the rare earth element obtained in example 3, wherein the long afterglow materials are all excited by rays for 3min under a silver target of 50kv and 80 mA. It can be seen that in all the doping concentrations mentioned above, when the molar ratio of lutetium nitrate to terbium nitrate is 1 (4-6), i.e. NaLuF 4 Tb (15% -20%), the afterglow performance of the material has an optimal value.
Comparative example 1:100mmol of NaLuF modified by different ligands 4 Preparation of Tb
1.1 mixing 80mmol lutetium nitrate, 20mmol terbium nitrate with 40mmol EDTA-2Na (disodium edetate) powder, 200mmol CitNa, respectively 3 (citric acid)Sodium) powder and 5mmol PEG (polyethylene glycol-2000) powder are mixed and dissolved in deionized water to 80mL, and ultrasonic dissolution is carried out to obtain 1.25 mol.L -1 Rare earth nitrate solution. In addition, for the OA (oleic acid) ligand, 3g of sodium hydroxide solid was added to the dissolved rare earth nitrate solution and 100mL of absolute ethanol from step 1.5 was added in advance, followed by 40mL of OA ligand.
1.2 dropwise adding 100mL of sodium fluoride solution to the solution in step 1.1, wherein the concentration of the sodium fluoride solution is 1 mol.L -1 A white turbid solution was obtained and stirring was continued for 20min.
1.3 drop-adding 80mL of ammonium fluoride solution to the solution in step 1.2, wherein the concentration of the ammonium fluoride solution is 5 mol.L -1 The solution becomes gel, and the stirring speed is increased to 800 r.min -1 Stirring was continued for 30min.
1.4 slowly dropwise adding sodium hydroxide solution to the solution in step 1.3 to ph=7, wherein the concentration of the sodium hydroxide solution is 20mol·l -1 Stirring was continued for 10min.
1.5 drop 100mL absolute ethanol into the solution in step 1.4 and continue stirring for 20min.
1.6 transferring the mixed solution obtained in the step 1.5 into a 500mL reaction kettle, and performing hydrothermal reaction at 200 ℃ for 12 hours to obtain a white product. After centrifugation, the product is washed 3 times with distilled water and ethanol to obtain NaLuF 4 Tb white powder was dried at 60℃for 6h.
The NaLuF obtained in comparative example 1 was subjected to a transmission electron microscope 4 Tb was analyzed to obtain a transmission electron micrograph thereof as shown in FIG. 14. First, EDTA-2Na ligand product is bar-shaped and has length of 2-3 microns. The reason for this phenomenon is mainly that the ligand is adsorbed on the crystal surface, which changes the growth rate of the crystal and limits the growth of the crystal to a certain extent, thereby generating a phenomenon that affects the morphology growth. In addition, EDTA-2Na ligand is more selective to the growth of the crystal on the c-axis (100) crystal plane due to the different preference of different ligands for the growth orientation of different crystal planes of the crystal, so the morphology is in a rod shape. Second, citNa 3 The shape of the ligand product is short flat six-edgeThe size of the column is 1-3 μm. The morphology of the polymer is different from EDTA-2Na ligand, and the polymer is changed into a short hexagonal prism from a rod shape, and the main reason for the phenomenon is that the surface adsorbs CitNa 3 The crystal growth orientation of the ligand is more preferable to the a-axis (001) crystal plane, so that the morphology thereof is represented by a short flat hexagonal prism. Thirdly, the morphology of the PEG ligand product and the OA ligand product is bar-shaped, and the size is 2-4 mu m. The main reason for this phenomenon is that the adsorption tendency of the ligand on the crystal side decreases the surface energy of the crystal side, resulting in a decrease in the growth rate thereof, and finally, it appears as a rod.
The NaLuF obtained in comparative example 1 was subjected to excitation luminescence spectrum by X-ray 4 Tb is analyzed to obtain an X-ray excitation luminescence spectrum chart of Tb, as shown in figure 15. It can be seen that the NaLuF with the added ligand 4 The fluorescent intensity of Tb material is significantly lower than that of ligand-free material.
FIG. 16 is a NaLuF of comparative example 1 4 X-ray afterglow attenuation curve graph of Tb material, and long afterglow material is excited for 3min under 50kv and 80mA silver target. It can be seen that the NaLuF with the added ligand 4 The afterglow performance of Tb material is obviously lower than that of ligand-free material.
Example 4: 100mmol of NaLuF with different reaction times 4 Preparation of Tb
4.1 mixing 80mmol lutetium nitrate and 20mmol terbium nitrate powder, dissolving in deionized water to 80mL, and dissolving with ultrasound to obtain 1.25 mol.L -1 Rare earth nitrate solution.
4.2 dropwise adding 100mL of sodium fluoride solution to the solution in step 4.1, wherein the concentration of the sodium fluoride solution is 1 mol.L -1 A white turbid solution was obtained and stirring was continued for 20min.
4.3 drop-adding 80mL of ammonium fluoride solution to the solution in step 4.2, wherein the concentration of the ammonium fluoride solution is 5 mol.L -1 The solution becomes gel, and the stirring speed is increased to 800 r.min -1 Stirring was continued for 30min.
4.4 slowly dropwise adding sodium hydroxide solution to the solution in step 4.3 to ph=7, wherein the concentration of the sodium hydroxide solution is 20mol·l -1 Stirring was continued for 10min.
4.5 drop 100mL absolute ethanol into the solution in step 4.4, and continue stirring for 20min.
4.6 transferring the mixed solution obtained in the step 4.5 into a 500mL reaction kettle, and respectively carrying out hydrothermal reactions at 200 ℃ for 2h, 4h, 6h, 8h, 10h, 12h and 16h to obtain white products. After centrifugation, the product is washed 3 times with distilled water and ethanol to obtain NaLuF 4 Tb white powder was dried at 60℃for 6h.
The products of different reaction times obtained in example 4 were analyzed separately by transmission electron microscopy to obtain a transmission electron microscopy image thereof, as shown in fig. 17. Wherein, the products of the reaction time of 2h and 4h have more nano-scale small particles, which may be that the crystals do not grow completely due to insufficient reaction time. The product with the reaction time between 6 and 16 hours is in the shape and the size of irregular bars with the shape and the size of 1 to 6 mu m.
The different reaction time products obtained in example 4 were each analyzed by using an X-ray excitation luminescence spectrum to obtain an X-ray excitation luminescence spectrum thereof, as shown in fig. 18. When the reaction time is 6 to 12 hours, the fluorescence intensity has an optimum value, and when the reaction time is less than 4 hours, the fluorescence intensity is greatly reduced due to incomplete reaction.
FIG. 19 is a graph showing the decay of the X-ray afterglow of the products obtained in example 4 at different reaction times, the long afterglow materials were each irradiated for 3min at a silver target of 50kv and 80 mA. It can be seen that when the reaction time is 6-12 hours, the afterglow performance of the material has an optimal value, and when the reaction time is less than 4 hours, the residual glow performance is greatly reduced due to incomplete reaction.
Example 5: 100mmol of NaLuF with different reaction temperatures 4 Preparation of Tb
5.1 mixing 80mmol lutetium nitrate and 20mmol terbium nitrate powder, dissolving in deionized water to 80mL, and dissolving with ultrasound to obtain 1.25 mol.L -1 Rare earth nitrate solution.
5.2 dropwise adding 100mL of the sodium fluoride solution in the step 5.1, wherein the concentration of the sodium fluoride solution is 1 mol.L -1 A white turbid solution was obtained and stirring was continued for 20min.
5.3 drop-adding 80mL of ammonium fluoride solution to the solution in step 5.2, wherein the concentration of the ammonium fluoride solution is 5 mol.L -1 The solution becomes gel, and the stirring speed is increased to 800 r.min -1 Stirring was continued for 30min.
5.4 slowly dropwise adding sodium hydroxide solution to the solution in step 5.3 to ph=7, wherein the concentration of the sodium hydroxide solution is 20mol·l -1 Stirring was continued for 10min.
5.5 drop 100mL absolute ethanol into the solution in step 5.4 and continue stirring for 20min.
5.6 transferring the mixed solution obtained in the step 5.5 into a 500mL reaction kettle, and respectively carrying out hydrothermal reaction at 180 ℃, 200 ℃, 210 ℃ and 220 ℃ for 12 hours to obtain a white product. After centrifugation, the product is washed 3 times with distilled water and ethanol to obtain NaLuF 4 Tb white powder was dried at 60℃for 6h.
The products of different reaction temperatures obtained in example 5 were analyzed by a transmission electron microscope, respectively, to obtain a transmission electron microscope image thereof, as shown in fig. 20, in which irregular bars having a morphology size of 2 to 6 μm were formed.
The products of different reaction temperatures obtained in example 5 were analyzed by using the X-ray excitation luminescence spectrum, respectively, to obtain an X-ray excitation luminescence spectrum chart thereof, as shown in fig. 21, and when the reaction temperature was 200 c, the fluorescence intensity had an optimum value.
FIG. 22 is a graph showing the attenuation of the afterglow of X-rays for products of different reaction temperatures obtained in example 5, wherein the long afterglow materials were each irradiated for 3min at a silver target of 50kv and 80 mA. It can be seen that the afterglow properties of the material are optimal at a reaction temperature of 200 ℃.
Example 6: 100mmol of NaLuF with different sodium hydroxide concentrations 4 Preparation of Tb
6.1 mixing 80mmol lutetium nitrate and 20mmol terbium nitrate powder, dissolving in deionized water to 80mL, and dissolving with ultrasound to obtain 1.25 mol.L -1 Rare earth nitrate solution.
6.2 dropwise adding 100mL of sodium fluoride solution to the solution in step 6.1, wherein the concentration of the sodium fluoride solutionIs 1 mol.L -1 A white turbid solution was obtained and stirring was continued for 20min.
6.3 drop-adding 80mL of ammonium fluoride solution to the solution in step 6.2, wherein the concentration of the ammonium fluoride solution is 5 mol.L -1 The solution becomes gel, and the stirring speed is increased to 800 r.min -1 Stirring was continued for 30min.
6.4 slowly dropwise adding sodium hydroxide solution to the solution in step 6.3 to a pH=7 and adding 0.3g and 0.6g of sodium hydroxide solid, respectively, wherein the concentration of the sodium hydroxide solution is 20 mol.L -1 Stirring was continued for 10min.
6.5 drop-adding 100mL absolute ethanol into the solution in the step 6.4, and stirring for 20min.
6.6 transferring the mixed solution obtained in the step 6.5 into a 500mL reaction kettle, and performing hydrothermal reaction at 200 ℃ for 12 hours to obtain a white product. After centrifugation, the product is washed 3 times with distilled water and ethanol to obtain NaLuF 4 Tb white powder was dried at 60℃for 6h.
The products of different sodium hydroxide concentrations obtained in example 6 were analyzed by transmission electron microscopy, respectively, to obtain a transmission electron microscopy image thereof, as shown in fig. 23, in which irregular bars having a morphology size of 2 to 6 μm were formed. The different pH values have certain influence on the morphology and the luminous performance of the reaction system, and along with the increase of the concentration of NaOH, the morphology of the NaOH gradually shows a slender line shape.
The products of example 6 were each analyzed by X-ray excitation luminescence spectrum to obtain an X-ray excitation luminescence spectrum, as shown in fig. 24, with the fluorescence intensity having an optimum value when the reaction ph=7.
FIG. 25 is an X-ray afterglow decay graph of the products of different sodium hydroxide concentrations obtained in example 6, long afterglow materials were each excited to radiation for 3min at a 50kv, 80mA silver target. It can be seen that when the reaction ph=7, the afterglow performance of the material has an optimum value.
Example 7: 100mmol NaLuF doped with different rare earth elements 4 Re preparation
7.1 to 99.5mmol lutetium nitrate and 0.5mmol praseodymium nitrateMixing the powder and dissolving in deionized water to 80mL, and dissolving by ultrasonic to obtain 1.25 mol.L -1 Rare earth nitrate solution.
7.2 dropwise adding 100mL of the sodium fluoride solution to the solution in step 7.1, wherein the concentration of the sodium fluoride solution is 1 mol.L -1 A white turbid solution was obtained and stirring was continued for 20min.
7.3 drop-adding 80mL of ammonium fluoride solution to the solution in step 7.2, wherein the concentration of the ammonium fluoride solution is 5 mol.L -1 The solution becomes gel, and the stirring speed is increased to 800 r.min -1 Stirring was continued for 30min.
7.4 slowly dropwise adding sodium hydroxide solution to the solution in step 7.3 to ph=7, wherein the concentration of the sodium hydroxide solution is 20mol·l -1 Stirring was continued for 10min.
7.5 drop 100mL absolute ethanol into the solution in step 7.4 and continue stirring for 20min.
7.6 transferring the mixed solution obtained in the step 7.5 into a 500mL reaction kettle, and performing hydrothermal reaction at 200 ℃ for 12 hours to obtain a white product. After centrifugation, the product is washed 3 times with distilled water and ethanol to obtain NaLuF 4 Tb white powder was dried at 60℃for 6h.
7.7 changing the types of the rare earth salt added in the step 7.1, and repeating the steps 7.2 to 7.6 to finally obtain the products doped with different rare earth elements, wherein the products are respectively as follows: a-NaLuF 4 :0.5％Pr；b-NaLuF 4 :1％Nd；c-NaLuF 4 :0.5％Sm；d-NaLuF 4 :20％Tb；e-NaLuF 4 :0.5％Dy；f-NaLuF 4 :1％Ho；g-NaLuF 4 :1％Er；h-NaLuF 4 :1％Tm。
The different rare earth element doped products obtained in example 7 were analyzed separately by transmission electron microscopy to obtain a transmission electron microscopy image thereof, as shown in fig. 26. The shape and the size of the product doped with the other rare earth elements are irregular bars with the shape and the size of 1-8 mu m except the size of the product doped with Pr in the nanometer level.
The products doped with different rare earth elements obtained in example 7 were respectively analyzed by using an X-ray excitation luminescence spectrum, and an X-ray excitation luminescence spectrum chart thereof was obtained as shown in fig. 27. In the figure, the Tb doped emission curve is scaled down by a factor of 0.2 compared to the source Tb curve. From the graph, the fluorescence intensity of Tb doping is far greater than that of other rare earth elements.
FIG. 28 is a graph showing the attenuation of the afterglow of X-rays for different rare earth doped products obtained in example 7, wherein the long afterglow materials were each excited to a radiation of 50kv and 80mA under a silver target for 3min. It can be seen that the afterglow performance of the Tb doping is far better than that of other rare earth elements.
Comparative example 2: high-temperature coprecipitation method for preparing NaLuF 4 :Tb
2.1 into a 25mL double neck round bottom flask was added 0.34mmol lutetium acetate, 0.06mmol terbium acetate, 4mL oleic acid, and 6mL octadecene in sequence.
2.2 vacuum was applied and heated to 130℃with stirring.
2.3 after the liquid level was bubble free, 1mmol of sodium hydroxide solid was added rapidly to the flask and immediately evacuated to maintain 130 ℃.
2.4 after the liquid level was bubble free, 1.6mmol of ammonium fluoride solid was added quickly to the flask and immediately evacuated to maintain 130 ℃.
2.5 after the liquid surface is bubble free, nitrogen is introduced into the flask, and the temperature is raised to 300 ℃ and maintained for 1h.
2.6 naturally cooling to room temperature, washing the product with cyclohexane and ethanol for 3 times respectively, and obtaining NaLuF 4 Tb white powder was dried at 60℃for 6h.
The NaLuF obtained in comparative example 2 was subjected to a transmission electron microscope 4 Tb is analyzed to obtain a transmission electron microscope image, and as shown in FIG. 29, the Tb has a hexagonal shape of about 24nm, uniform shape and good dispersibility.
The NaLuF obtained in comparative example 2 was subjected to excitation luminescence spectrum by X-ray 4 Tb and NaLuF obtained by ligand-free concentrated hydrothermal method in this patent 4 Tb is analyzed to obtain an X-ray excitation luminescence spectrum chart of the Tb, as shown in figure 30. It can be seen that the NaLuF obtained by the ligand-free concentrated hydrothermal method used in this patent 4 Tb, its fluorescence intensityIs significantly higher than NaLuF prepared by a high-temperature coprecipitation method 4 :Tb。
FIG. 31 is a NaLuF obtained in comparative example 2 4 Tb and NaLuF obtained by ligand-free concentrated hydrothermal method in this patent 4 X-ray afterglow attenuation curve graph of Tb, and long afterglow material is excited for 3min under the condition of 50kv and 80mA silver target. It can be seen that the NaLuF obtained by the ligand-free concentrated hydrothermal method used in this patent 4 Tb has afterglow performance obviously superior to that of NaLuF prepared by high temperature coprecipitation method 4 :Tb。
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent changes made by the specification and drawings of the present invention, or direct or indirect application in the relevant art, are included in the scope of the present invention.
Claims (8)
1. A process for preparing the long-afterglow material doped with rare-earth element and fluoride includes such steps as mixing rare-earth salt, sodium fluoride and ammonium fluoride with water, regulating pH value to neutral, adding alcohol solvent, and hydrothermal reaction to obtain beta-NaReF 4 A long afterglow material;
wherein, re is at least one selected from yttrium, scandium, lanthanum, cerium, neodymium, samarium, europium, gadolinium, promethium, dysprosium, holmium, erbium, thulium, ytterbium, praseodymium, lutetium and terbium;
the molar ratio of the sodium fluoride to the ammonium fluoride is 1: (0-9);
the long afterglow material has fluorescence and long afterglow luminescence under the excitation of X rays;
the reaction temperature of the hydrothermal reaction is 160-230 ℃ and the reaction time is 2-24 h.
2. The method according to claim 1, wherein the rare earth salt is at least one selected from the group consisting of nitrate, chloride and acetate of rare earth.
3. The method according to claim 2, wherein the rare earth salt comprises at least nitrate, chloride or acetate of lutetium and/or terbium.
4. The method of claim 1, wherein the molar ratio of the rare earth salt to the sodium fluoride is 1: (1-6); the molar ratio of the rare earth salt to the ammonium fluoride is 1: (0-9).
5. The preparation method according to claim 1, wherein the volume ratio of the solution after pH adjustment to the alcohol solvent is (2-5): 1.
6. a rare earth element doped fluoride long afterglow material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 5.
7. The long-afterglow material of claim 6, characterized in that the particle size of the long-afterglow material is 0.1 to 10 μm.
8. Use of the long persistence material of claim 6 or 7 in biomarkers, X-ray detection, visualization, and imaging.
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