WO2024027106A1 - Lithium sodium lutetium borate, rare earth doped compound and crystal thereof, preparation method therefor, and use thereof - Google Patents

Lithium sodium lutetium borate, rare earth doped compound and crystal thereof, preparation method therefor, and use thereof Download PDF

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WO2024027106A1
WO2024027106A1 PCT/CN2023/070436 CN2023070436W WO2024027106A1 WO 2024027106 A1 WO2024027106 A1 WO 2024027106A1 CN 2023070436 W CN2023070436 W CN 2023070436W WO 2024027106 A1 WO2024027106 A1 WO 2024027106A1
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lutetium
sodium
lithium
rare earth
borate
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French (fr)
Chinese (zh)
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陈鹏允
林利添
杨鸣名
匡猛
倪海勇
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广东省科学院资源利用与稀土开发研究所
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/12—Borates
    • C01B35/128—Borates containing plural metal or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/003—Heating or cooling of the melt or the crystallised material
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/04—Prisms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of scintillation materials, and specifically relates to lithium sodium lutetium borate and its rare earth doped compounds and crystals as well as their preparation methods and uses.
  • Scintillation crystal refers to an object that can emit pulsed light under the action of high-energy particles or rays (such as X-rays, ⁇ -rays, etc.). It is widely used in high-energy physics, nuclear physics, space physics, nuclear medicine, geological exploration, safety inspection, and Defense industry and other fields. High-end medical equipment PET/CT nuclear medicine imaging technology is an important way for modern medicine to accurately diagnose diseases. At present, it has been widely used in clinical fields such as early diagnosis of tumors, neurological diseases, and cardiovascular and cerebrovascular diseases, research on disease pathology, evaluation of tumor treatment effects, and drug development.
  • rare earth scintillation crystal materials are core components of high-end medical equipment imaging and are key materials that affect the resolution and image quality of PET/CT imaging.
  • TOF time-of-flight
  • existing rare earth scintillation crystal materials such as (Lu, Y) 2 SiO 5 : Ce 3+ , LaBr 3 : Ce 3+ , etc. have many excellent properties such as high light yield, fast attenuation and high energy resolution, and are considered to be nuclear candidates.
  • the purpose of the present invention is to provide lithium sodium lutetium borate and its rare earth doped compounds and crystals and their preparation methods and uses, which are easy to prepare, have stable physical and chemical properties, are not easy to deliquesce in the air and have good scintillation/fluorescence properties, and are expected to be used as scintillation materials and LEDs. Use fluorescent powder.
  • Lithium sodium lutetium borate compound has the chemical formula Li 2 NaLuB 2 O 6 .
  • Rare earth doped compound of lithium sodium lutetium borate the general chemical formula is: Li 2 NaLu 1-x RE x B 2 O 6 , where 0 ⁇ x ⁇ 0.5, RE is a rare earth element selected from Ce, Pr, Nd, Eu , Tb, Ho, Er, Tm, Yb one or more.
  • RE is One or more of the rare earth elements Ce, Pr, Nd, Eu, Tb, Ho, Er, Tm and Yb.
  • the NaO 8 dodecahedrons are connected by common edges and points to form a one-dimensional Na-O zigzag chain
  • the (Lu 1-x RE x )O 7 pentagonal bipyramids are connected by common edges to form (Lu 1- x RE _ _ _ _ _ _ LiO 4 tetrahedrons form edge-sharing connections to form [LiO 2 ] one-dimensional chains that run through the skeleton of the crystal along the [010] direction.
  • the present invention also protects the preparation method of lithium sodium lutetium borate compound, which includes the following steps:
  • the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , NaNO 3 , NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H 2 O, NaBO 2 ⁇ 4H 2 Any one of O;
  • the lutetium-containing compound is any one of Lu 2 O 3 , Lu(NO 3 ) 3 ⁇ 6H 2 O;
  • the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH
  • the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  • the present invention also protects the preparation method of the rare earth doped compound of lithium sodium lutetium borate, which includes the following steps:
  • the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , NaNO 3 , NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H 2 O, NaBO 2 ⁇ 4H 2 O Any one of them;
  • the lutetium-containing compound is any one of Lu 2 O 3 and Lu(NO 3 ) 3 ⁇ 6H 2 O;
  • the rare earth-containing compound is selected from CeO 2 , Pr 2 O 3 , Pr 6 O 11 , Nd 2 O 3 , Eu 2 O 3 , Tb 2 O 3 , Tb 4 O 7 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Ce(NO 3 ) 3 ⁇ 6H 2 O, Pr(NO 3 ) 3 ⁇ 6H 2 O, Nd(NO 3 ) 3 ⁇ 6H 2 O, Eu(NO 3 ) 3 ⁇ 6H 2 O, Tb(NO 3 ) 3 ⁇ 6H 2
  • a method for preparing lithium sodium lutetium borate crystal includes the following steps: adding sodium-containing compounds, lutetium-containing compounds, lithium-containing compounds, and boron-containing compounds according to the molar ratio of sodium:lutetium:lithium:boron element to 1 -Mix and grind evenly in the ratio of 3:1:5-8:5-10, put it into a crucible, heat it to a temperature of 800-1000°C at a heating rate of 5-20°C/h, and then obtain a high-temperature melt, and keep it warm for 12-48h , and then lowered to room temperature at a rate of 1-10°C/h to obtain lithium sodium lutetium borate crystals.
  • the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , NaNO 3 , NaF, NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H 2 O, NaBO 2 ⁇ Any one of 4H 2 O;
  • the compound containing lutetium is any one of Lu 2 O 3 , Lu(NO 3 ) 3 ⁇ 6H 2 O;
  • the compound containing lithium is any one of Li 2 CO 3 , LiNO 3 or LiOH Any of them;
  • the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  • a flux is also added, and the flux is any one of PbO, PbO 2 , PbF 2 , KF or KCl.
  • a method for preparing sodium lithium borate and lutetium rare earth doped crystals includes the following steps: adding sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, and boron-containing compounds according to sodium: (lutetium + rare earth): lithium: boron element molar ratio is 1-3: 1: 5-8: 5-10, evenly mixed and ground, put into a crucible, heated to a temperature of 800-800 with a heating rate of 5-20°C/h After reaching 1000°C, a high-temperature melt is obtained, kept for 12-48h, and then lowered to room temperature at a rate of 1-10°C/h to obtain lithium sodium borate and lutetium rare earth doped crystals.
  • the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , NaNO 3 , NaF, NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H 2 O, NaBO 2 ⁇ Any one of 4H 2 O;
  • the lutetium-containing compound is any one of Lu 2 O 3 and Lu(NO 3 ) 3 ⁇ 6H 2 O;
  • the rare earth-containing compound is selected from CeO 2 , Pr 2 O 3 , Pr 6 O 11 , Nd 2 O 3 , Eu 2 O 3 , Tb 2 O 3 , Tb 4 O 7 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Ce(NO 3 ) 3 ⁇ 6H 2 O, Pr(NO 3 ) 3 ⁇ 6H 2 O, Nd(NO 3 ) 3 ⁇ 6H 2 O, Eu(NO 3 ) 3 ⁇ 6H 2 O, Tb(NO 3 ) 3 ⁇ 6
  • lithium sodium borate and lutetium rare earth doped crystals are prepared, and a cosolvent is added.
  • the sodium-containing compound, the lutetium-containing compound, the rare earth-containing compound, the lithium-containing compound, the boron-containing compound, and the flux are calculated according to sodium: ( Lutetium + rare earth):lithium:boron:flux are evenly mixed and ground in a ratio of 1-3:1:2-3:2-5:1-10, put into a crucible, and heated at 5-50°C/ After heating to a temperature of 800-1000°C at a heating rate of h, a high-temperature solution is obtained, kept for 12-48h, and then lowered to room temperature at a rate of 1-20°C/h to obtain lithium sodium lutetium borate and its rare earth doped crystals.
  • the flux is any one of PbO, PbO 2 , PbF 2 , KF or KCl.
  • a method for preparing lithium sodium borate and lutetium rare earth metal doped crystals includes the following steps: adding sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, and boron-containing compounds according to sodium: ( Lutetium + rare earth):lithium:boron molar ratio is 1-3:1:2-5:1-8, evenly mixed and ground, put into a crucible, then put into a medium frequency pulling furnace, and high-purity N 2 /H 2 /Ar gas, heat until completely melted, stir for 12-24 hours, when the melt temperature is 0.1-3°C higher than the saturation point, then put a platinum or iridium rod from the growth furnace to contact the melt surface, and keep it for 2-12 hours, then reduce the temperature to the saturation point temperature at 0.1-10°C/h, and set the rotation speed of the platinum or iridium rod to 2-25r/min, and then set the speed of the platinum or iridium rod to 0.05-10°C/ h slowly
  • the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H 2 O, Any of NaBO 2 ⁇ 4H 2 O;
  • yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ⁇ 6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 ( Any one of SO 4 ) 3 ;
  • the cerium-containing compound is any one of CeO 2 , Ce 2 O 3 , Ce(NO 3 ) 3 ⁇ 6H 2 O, and Ce 2 (SO 4 ) 3 ⁇ 4H 2 O ;
  • Lithium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H
  • the present invention also protects the use of the lithium sodium lutetium borate compound or crystal or the lithium sodium lutetium borate rare earth doped compound or crystal.
  • the lithium sodium sodium lutetium borate rare earth doped compound or crystal is used as a scintillation material for high-energy ray detection materials. Or used as optical functional materials such as phosphors for LED lighting; the lithium sodium lutetium borate compound or crystal is used as an optical lens material, or used in large aperture, wide field of view photography objectives, long focal length, zoom lens and high power microscopes, etc.
  • Optical prism materials are used.
  • the beneficial effects of the present invention are as follows:
  • the present invention provides a new type of lithium sodium lutetium borate and its rare earth doped compounds or crystals and their preparation methods, which are cheap and easy to obtain, simple to synthesize, and have stable physical and chemical properties.
  • the described lithium sodium lutetium borate rare earth Doped compounds or crystals have good scintillation and fluorescence properties and can be used as scintillation materials to detect high-energy particles such as X-rays, or as phosphors for LED lighting. They have important economic and scientific research in the fields of nuclear medicine imaging, high-energy physics particle detection, and light illumination. Value;
  • the lithium sodium lutetium borate compound or crystal is used as an optical lens material, or an optical prism material for large aperture, wide field of view photographic objectives, long focal length, zoom lens, high power microscope, etc.;.
  • Figure 1 is a schematic diagram of the crystal structure along the b-axis and c-axis of the lithium sodium lutetium borate Li 2 NaLu(BO 3 ) 2 single crystal prepared in Example 7 of the present invention
  • Figure 2 is the dispersion refractive index of the lithium sodium lutetium borate Li 2 NaLu (BO 3 ) 2 single crystal prepared in Example 7 of the present invention
  • Figure 3 is the diffuse reflection spectrum of the lithium sodium lutetium borate Li 2 NaLu (BO 3 ) 2 compound prepared in Example 1 of the present invention
  • Figure 4 is a powder XRD diffraction pattern of the Li 2 NaLu (BO 3 ) 2 compound of the present invention
  • Figure 5 is the powder XRD diffraction pattern of Li 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 compound
  • Figure 6 is a powder XRD diffraction pattern of Li 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 compound
  • Figure 7 is the scintillation performance of Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal
  • Figure 8 is the fluorescence emission spectrum of Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal
  • Figure 9 is the fluorescence emission spectrum of Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 compound
  • Figure 10 is the fluorescence emission spectrum of Li 2 NaLu 0.8 Tb 0.4 (BO 3 ) 2 compound
  • Figure 11 shows the CIE chromaticity coordinates of Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal, Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 compound, and Li 2 NaLu 0.8 Tb 0.4 (BO 3 ) 2 compound.
  • Raw materials used (analytically pure): Lu 2 O 3 0.05 mol, H 3 BO 3 0.2 mol, Na 2 CO 3 0.05 mol, Li 2 CO 3 0.05 mol.
  • the specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into Put the corundum crucible into a muffle furnace, raise the temperature to 500°C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the second time, put it into the muffle furnace, raise the temperature to 600°C, and keep the temperature constant for 24 hours.
  • Raw materials used (analytically pure): Lu 2 O 3 0.04975 mol, CeO 2 0.0005 mol, H 3 BO 3 0.2 mol, Na 2 CO 3 0.05 mol, Li 2 CO 3 0.1 mol.
  • Raw materials used (analytically pure): Lu(NO 3 ) 3 ⁇ 6H 2 O, 0.07mol, Nd(NO 3 ) 3 ⁇ 6H 2 O 0.03mol, H 3 BO 3 0.2mol, NaNO 3 0.1mol, LiNO 3 0.2mol .
  • Example 4 Synthesis of 20% Europium-doped Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 compound of lithium sodium lutetium borate
  • Raw materials used (analytically pure): Lu 2 O 3 0.004 mol, Eu 2 O 3 0.001 mol, B 2 O 3 0.01 mol, NaHCO 3 0.01 mol, Li 2 CO 3 0.01 mol.
  • Raw materials used (analytically pure): Lu 2 O 3 0.009 mol, Tb 4 O 7 0.003 mol, B 2 O 3 0.03 mol, NaHCO 3 0.03 mol, Li 2 CO 3 0.03 mol.
  • Raw materials used (analytically pure): Lu(NO 3 ) 3 ⁇ 6H 2 O 0.25mol, Yb 2 O 3 0.125mol, B 2 O 3 0.5mol, Na 2 C 2 O 4 0.25mol, LiOH 1.0mol.
  • Example 7 Preparation of lithium sodium lutetium borate Li 2 NaLu (BO 3 ) 2 crystal by self-service solvent method.
  • Raw materials used (analytically pure): Na 2 CO 3 0.015 mol, Lu 2 O 3 0.005 mol, Li 2 CO 3 0.04 mol, H 3 BO 3 0.1mol.
  • Example 8 Preparation of 20% neodymium-doped Li 2 NaLu 0.8 Nd 0.2 (BO 3 ) 2 crystal of lithium sodium lutetium borate by self-service solvent method
  • Raw materials used (analytically pure): Na 2 B 4 O 7 10H 2 O 0.3mol, Lu 2 O 3 0.08mol, Nd 2 O 3 0.02mol, Li 2 CO 3 0.75mol, B 2 O 3 0.3mol.
  • Example 9 35% thulium-doped Li 2 NaLu 0.65 Tm 0.35 (BO 3 ) 2 crystal of lithium sodium lutetium borate prepared by self-service solvent method
  • Example 10 Preparation of lithium sodium lutetium borate Li 2 NaLu(BO 3 ) 2 crystal by cosolvent method
  • Raw materials used (analytically pure): NaHCO 3 0.1 mol, Lu 2 O 3 0.05 mol, Li 2 CO 3 0.2 mol, H 3 BO 3 0.2 mol, PbO 0.5 mol.
  • Example 11 Preparation of 10% cerium-doped Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal of lithium sodium lutetium borate by cosolvent method
  • Raw materials used (analytically pure): NaNO 3 1.5 mol, Lu 2 O 3 0.45 mol, CeO 2 ⁇ 0.1 mol, LiOH 2.5 mol, H 3 BO 3 3.0 mol, PbF 2 10 mol.
  • Example 12 Preparation of 15% praseodymium-doped Li 2 NaLu 0.85 Pr 0.15 (BO 3 ) 2 crystal of lithium sodium lutetium borate by cosolvent method
  • Raw materials used (analytically pure): Na 2 C 2 O 4 1.25mol, Lu(NO 3 ) 3 ⁇ 6H 2 O 0.85mol, Pr 6 O 11 ⁇ 0.025mol, LiNO 3 2.5mol, B 2 O 3 2.5mol, KF 8mol.
  • Example 13 Preparation of 10% cerium-doped Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal of lithium sodium lutetium borate by Czochralski method
  • Raw materials used (analytically pure): NaBO 2 4H 2 O 1.0 mol, Lu 2 O 3 0.45 mol, CeO 2 ⁇ 0.1 mol, Li 2 CO 3 0.4 mol, H 3 BO 3 1.0 mol.
  • the specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into Platinum crucible, then put it into the medium frequency pulling furnace, pass in high-purity N 2 /H 2 mixed gas, heat until completely melted, stir for 24 hours, when the melt temperature is 0.5°C higher than the saturation point, then remove it from the growth furnace Put a platinum rod into it and let it contact the surface of the melt and keep it for 2 hours. Then reduce the temperature to the saturation point temperature at 0.25°C/h, and set the rotation speed of the platinum rod to 10r/min, and then set it to 0.05°C/h. The temperature is slowly lowered at a rate of h, and pulled at a pulling speed of 0.1mm/h.
  • the crystal When the crystal grows to a certain size, the crystal is lifted off the liquid surface and finally dropped to room temperature at a rate of 50°C/h to obtain the size. It is a 5.2 ⁇ 4.3 ⁇ 1.7mm 3 Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal.
  • Example 14 Preparation of 30% holmium-doped Li 2 NaLu 0.7 Ho 0.3 (BO 3 ) 2 crystal of lithium sodium lutetium borate by Czochralski method
  • Raw materials used (analytically pure): Na 2 CO 3 0.5 mol, Lu 2 O 3 0.35 mol, Ho 2 O 3 ⁇ 0.15 mol, Li 2 CO 3 0.4 mol, B 2 O 3 0.5 mol.
  • the specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into Put the platinum crucible into a medium frequency pulling furnace, pass in high-purity N2 gas, heat it until it is completely melted, and stir for 16 hours. When the melt temperature is 1.5°C higher than the saturation point, put platinum into the growth furnace. Rod, let it contact the surface of the melt, keep it for 2 hours, then lower the temperature to the saturation point temperature at 0.75°C/h, and set the rotation speed of the platinum rod to 15r/min, and then slowly reduce the temperature to 0.55°C/h. Cool down and pull at a pulling speed of 0.3mm/h.
  • Example 15 Preparation of 5% Erbium-doped Li 2 NaLu 0.95 Er 0.05 (BO 3 ) 2 crystal of lithium sodium lutetium borate by Czochralski method
  • Raw materials used (analytically pure): NaOH 1.5mol, Lu(NO 3 ) 3 ⁇ 6H 2 O 0.95mol, Er(NO 3 ) 3 ⁇ 6H 2 O 0.05mol, LiF 1.6mol, B 2 O 3 1.75mol.
  • the specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into Platinum crucible, then put it into the medium frequency pulling furnace, pass in high-purity Ar gas, heat it until it is completely melted, and stir for 18 hours.
  • the melt temperature is 2.5°C higher than the saturation point
  • put the platinum rod from the growth furnace. let it contact the surface of the melt and keep it for 2 hours, then lower the temperature to the saturation point temperature at 1.25°C/h, set the rotation speed of the platinum rod to 15r/min, and then slowly cool down at a rate of 0.55°C/h , pull at a pulling speed of 0.5mm/h.
  • Example 16 Characteristics testing of lithium sodium lutetium borate and its rare earth doped compounds and crystals
  • the unit cell structure of the lithium sodium lutetium borate Li 2 NaLu(BO 3 ) 2 single crystal prepared in Example 7 of the present invention was measured using the X-ray single crystal diffraction method.
  • Nd 0.2 (BO 3 ) 2 single crystal prepared in Example 8 of the present invention was measured using the X-ray single crystal diffraction method to determine the unit cell structure, and Li 2 NaLu 0.8 was measured.
  • the lithium sodium lutetium borate Li 2 NaLu(BO 3 ) 2 single crystal prepared in Example 7 of the present invention passed the dispersion refractive index test. The results are shown in Figure 2. It has a good refractive index and low dispersion in the test range, proving that It has uses as optical prism material.
  • the lithium sodium lutetium borate Li 2 NaLu(BO 3 ) 2 compound prepared in Example 1 of the present invention was tested through diffuse reflection. The results are shown in Figure 3. It has good transmission performance in the range of 400-800 nm and can be used as an optical Material.
  • an X-ray powder diffractometer was used to perform XRD testing at room temperature, as shown in Figure 4-6. The results showed that the prepared compound was a pure phase and no other impurity phases were generated.
  • Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal prepared in Example 11 of the present invention is excited under X-rays (Ag target), and its scintillation spectrum is as shown in Figure 7.
  • Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 's scintillation detection performance is significantly better than the Bi 4 Ge 3 O 12 (BGO) reference crystal under the same test conditions, proving that Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 has good use value.
  • the Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal prepared in Example 13 of the present invention emits characteristic blue light under ultraviolet light excitation. Its fluorescence emission spectrum is shown in Figure 8, and its CIE chromaticity The coordinates (0.157, 0.154, 0.690) are marked in Figure 11. Blue phosphors have good use value in LEDs.
  • Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 compound prepared in Example 4 of the present invention emits characteristic red light under ultraviolet or visible light excitation. Its fluorescence emission spectrum is shown in Figure 9, and its CIE The chromaticity coordinates (0.615, 0.384, 0.001) are marked in Figure 11. Red phosphors have good use value in LEDs.
  • Li 2 NaLu 0.6 Tb 0.4 (BO 3 ) 2 compound prepared in Example 5 of the present invention emits characteristic green light under ultraviolet light excitation. Its fluorescence emission spectrum is shown in Figure 10, and its CIE color The degree coordinates (0.345, 0.535, 0.121) are marked in Figure 11. Green phosphors have good use value in LEDs.

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Abstract

Lithium sodium lutetium borate, a rare earth doped compound and crystal thereof, and a preparation method therefor. The chemical formula of the lithium sodium lutetium borate is Li2NaLuB2O6, and the general formula of the rare earth doped compound of the lithium sodium lutetium borate is Li2NaLu1 - xRExB2O6, wherein 0<x≤0.5, and RE is a rare earth element. The present invention is cheap and easy to obtain and simple and convenient to synthesize, and has stable physicochemical properties; the rare earth doped compound of the lithium sodium lutetium borate has good scintillation and fluorescence properties, can be used as a scintillation material or used as phosphor powder for LED lighting, and has important economic and scientific research values in the fields of nuclear medicine imaging, high-energy physical particle detection, lighting, and the like.

Description

硼酸锂钠镥及其稀土掺杂化合物和晶体及其制备方法与用途Lithium sodium lutetium borate and its rare earth doped compounds and crystals and their preparation methods and uses 技术领域：Technical areas:
本发明涉及闪烁材料技术领域，具体涉及一种硼酸锂钠镥及其稀土掺杂化合物和晶体及其制备方法与用途。The invention relates to the technical field of scintillation materials, and specifically relates to lithium sodium lutetium borate and its rare earth doped compounds and crystals as well as their preparation methods and uses.
背景技术：Background technique:
闪烁晶体是指在高能粒子或射线(如X射线、γ射线等)的作用下能够发出脉冲光的物体，被广泛用于高能物理、核物理、空间物理、核医学、地质勘探、安全检查以及国防工业等领域。高端医疗设备PET/CT核医学成像技术是现代医学进行精准疾病诊断的重要途径。目前临床已经广泛应用于肿瘤，神经系统疾病和心脑血管疾病的早期诊断，对疾病病理学研究，肿瘤治疗效果评估和药物研发等领域。Scintillation crystal refers to an object that can emit pulsed light under the action of high-energy particles or rays (such as X-rays, γ-rays, etc.). It is widely used in high-energy physics, nuclear physics, space physics, nuclear medicine, geological exploration, safety inspection, and Defense industry and other fields. High-end medical equipment PET/CT nuclear medicine imaging technology is an important way for modern medicine to accurately diagnose diseases. At present, it has been widely used in clinical fields such as early diagnosis of tumors, neurological diseases, and cardiovascular and cerebrovascular diseases, research on disease pathology, evaluation of tumor treatment effects, and drug development.
目前而言，稀土闪烁晶体材料是高端医疗设备成像核心部件，是影响PET/CT成像的分辨率和图像质量核心关键材料。近年来，特别是基于深度和飞行时间(TOF)性能多模态成像系统的第三代PET，对闪烁晶体高阻断能力、高空间分辨率和能量分辨率提出更高技术要求。现有的稀土闪烁晶体材料例如(Lu，Y) 2SiO 5：Ce 3+、LaBr 3：Ce 3+等具备高光产额、快衰减和高能量分辨率等多种优异性能，被认为是核医学成像领域中比较适合TOF-PET系统的闪烁晶体材料。然而，(Lu，Y) 2SiO 5：Ce 3+晶体的熔点极高(2050-2100℃)，这对于晶体生长设备的耐热性能要求十分严苛，而且晶体生长需要使用价格昂贵的铱金坩埚，这些都极大地增加了晶体生长的成本和周期。而对于LaBr 3：Ce 3+，存在着极易潮解、原料昂贵等问题，因此亟需探索熔点低、理化性质稳定的新型闪烁材料。 At present, rare earth scintillation crystal materials are core components of high-end medical equipment imaging and are key materials that affect the resolution and image quality of PET/CT imaging. In recent years, especially the third generation of PET based on multi-modal imaging systems with depth and time-of-flight (TOF) performance, higher technical requirements have been placed on scintillation crystals with high blocking capabilities, high spatial resolution and energy resolution. Existing rare earth scintillation crystal materials such as (Lu, Y) 2 SiO 5 : Ce 3+ , LaBr 3 : Ce 3+ , etc. have many excellent properties such as high light yield, fast attenuation and high energy resolution, and are considered to be nuclear candidates. Scintillation crystal materials that are more suitable for TOF-PET systems in the field of medical imaging. However, the melting point of (Lu, Y) 2 SiO 5 : Ce 3+ crystal is extremely high (2050-2100°C), which imposes strict requirements on the heat resistance of crystal growth equipment, and crystal growth requires the use of expensive iridium. Crucibles, these greatly increase the cost and cycle of crystal growth. As for LaBr 3 : Ce 3+ , there are problems such as being easily deliquesced and expensive raw materials. Therefore, there is an urgent need to explore new scintillation materials with low melting points and stable physical and chemical properties.
发明内容：Contents of the invention:
本发明的目的是提供硼酸锂钠镥及其稀土掺杂化合物和晶体及其制备方法与用途，易制备、理化性质稳定、在空气中不易潮解且闪烁/荧光性能良好，有望作为闪烁材料和LED用荧光粉。The purpose of the present invention is to provide lithium sodium lutetium borate and its rare earth doped compounds and crystals and their preparation methods and uses, which are easy to prepare, have stable physical and chemical properties, are not easy to deliquesce in the air and have good scintillation/fluorescence properties, and are expected to be used as scintillation materials and LEDs. Use fluorescent powder.
本发明是通过以下技术方案予以实现的：The present invention is realized through the following technical solutions:
硼酸锂钠镥化合物，化学式为Li 2NaLuB 2O 6。 Lithium sodium lutetium borate compound has the chemical formula Li 2 NaLuB 2 O 6 .
硼酸锂钠镥晶体，化学式为Li 2NaLuB 2O 6，属单斜晶系，空间群为P2 1/n，晶胞参数为
Figure PCTCN2023070436-appb-000001
Figure PCTCN2023070436-appb-000002
α＝90°，β＝102.729°，γ＝90°，
Figure PCTCN2023070436-appb-000003
Z＝4。 Lithium sodium lutetium borate crystal, the chemical formula is Li 2 NaLuB 2 O 6 , belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are
Figure PCTCN2023070436-appb-000001
Figure PCTCN2023070436-appb-000002
α=90°, β=102.729°, γ=90°,
Figure PCTCN2023070436-appb-000003
Z=4.
硼酸锂钠镥的稀土掺杂化合物，化学通式为：Li 2NaLu 1-xRE xB 2O 6，其中，0＜x≤0.5，RE为稀土元素，选自Ce、Pr、Nd、Eu、Tb、Ho、Er、Tm、Yb的一种或几种。 Rare earth doped compound of lithium sodium lutetium borate, the general chemical formula is: Li 2 NaLu 1-x RE x B 2 O 6 , where 0＜x≤0.5, RE is a rare earth element selected from Ce, Pr, Nd, Eu , Tb, Ho, Er, Tm, Yb one or more.
硼酸锂钠镥的稀土掺杂晶体，化学通式为：Li 2NaLu 1-xRE xB 2O 6，其中0＜x≤0.5，RE为稀土元素，选自Ce、Pr、Nd、Eu、Tb、Ho、Er、Tm、Yb的一种或几种，属单斜晶系，空间群为P2 1/n，晶胞参数的范围为
Figure PCTCN2023070436-appb-000004
α＝90°，β＝102.729-103.889°，γ＝90°，
Figure PCTCN2023070436-appb-000005
Z＝4。 Rare earth doped crystal of lithium sodium lutetium borate, the general chemical formula is: Li 2 NaLu 1-x RE x B 2 O 6 , where 0＜x≤0.5, RE is a rare earth element, selected from Ce, Pr, Nd, Eu, One or more of Tb, Ho, Er, Tm and Yb, belonging to the monoclinic crystal system, the space group is P2 1 /n, and the range of unit cell parameters is
Figure PCTCN2023070436-appb-000004
α=90°, β=102.729-103.889°, γ=90°,
Figure PCTCN2023070436-appb-000005
Z=4.
其三维空间结构是基于NaO 8十二面体、孤立BO 3平面三角形、LiO 4四面体和(Lu 1-xRE x)O 7(0＜x≤0.5)五角双锥相互链接而成，RE为稀土元素的Ce、Pr、Nd、Eu、Tb、Ho、Er、Tm、Yb的一种或几种。其中，NaO 8十二面体之间共边及共点相连形成一维的Na-O zigzag链，而(Lu 1-xRE x)O 7五角双锥两两共边相连，形成(Lu 1-xRE x) 2O 12二聚体，(Lu 1-xRE x) 2O 12二聚体和Na-O zigzag链以及BO 3平面三角形构成了晶体结构的主要骨架，两种晶体学独立的LiO 4四面体共边连接的形成[LiO 2]一维链沿着[010]方向贯穿于晶体的骨架中。 Its three-dimensional space structure is based on NaO 8 dodecahedron, isolated BO 3 planar triangle, LiO 4 tetrahedron and (Lu 1-x RE x )O 7 (0＜x≤0.5) pentagonal bipyramid linked to each other, RE is One or more of the rare earth elements Ce, Pr, Nd, Eu, Tb, Ho, Er, Tm and Yb. Among them, the NaO 8 dodecahedrons are connected by common edges and points to form a one-dimensional Na-O zigzag chain, while the (Lu 1-x RE x )O 7 pentagonal bipyramids are connected by common edges to form (Lu 1- x RE _ _ _ _ _ _ _ LiO 4 tetrahedrons form edge-sharing connections to form [LiO 2 ] one-dimensional chains that run through the skeleton of the crystal along the [010] direction.
本发明还保护硼酸锂钠镥化合物的制备方法，包括如下步骤：The present invention also protects the preparation method of lithium sodium lutetium borate compound, which includes the following steps:
将含钠的化合物、含镥的化合物、含锂的化合物、含硼的化合物按照钠∶镥∶锂∶硼元素摩尔比为1∶1∶2∶2的比例均匀放入研钵中充分混合研磨，然后装入坩埚中，放入马弗炉中，升温至400-500℃，恒温12-48小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中通入氢气，再升温至600-700℃，恒温12-48小时，冷却至室温，取出，经第三次研磨后放入马弗炉中通入氢气，再升700-750℃，恒温12-48小时，取出，经研磨得到硼酸锂钠镥化合物。其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、NaNO 3、NaOH、Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含镥的化合物为Lu 2O 3、Lu(NO 3) 3·6H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 Evenly put the sodium-containing compound, the lutetium-containing compound, the lithium-containing compound, and the boron-containing compound into a mortar and thoroughly mix and grind them in a ratio of sodium:lutetium:lithium:boron element molar ratio of 1:1:2:2. , then put it into a crucible, put it into a muffle furnace, raise the temperature to 400-500°C, keep the temperature constant for 12-48 hours, cool to room temperature, take it out, grind it for the second time, put it into the muffle furnace and pass in hydrogen, and then Raise the temperature to 600-700°C, keep the temperature constant for 12-48 hours, cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace and pass in hydrogen, then raise it to 700-750°C, keep the temperature constant for 12-48 hours, take it out. After grinding, the lithium sodium borate compound is obtained. Among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , NaNO 3 , NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, NaBO 2 ·4H 2 Any one of O; the lutetium-containing compound is any one of Lu 2 O 3 , Lu(NO 3 ) 3 ·6H 2 O; the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH One kind; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
本发明还保护硼酸锂钠镥的稀土掺杂化合物的制备方法，包括如下步骤：The present invention also protects the preparation method of the rare earth doped compound of lithium sodium lutetium borate, which includes the following steps:
将含钠的化合物、含镥的化合物、含稀土的化合物、含锂的化合物、含硼的化合物按照钠∶(镥+稀土)∶锂∶硼元素摩尔比为1∶1∶2∶2的比例均匀放入研钵中充分混合研磨，然后装入坩埚中，放入马弗炉中通入氢气，升温至400-500℃，恒温12-48小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中通入氢气，再升温至600-700℃，恒温12-48小时，冷却至室温，取出，经第三次研磨后放入马弗炉中通入氢气，再升700-750℃，恒温12-48小时，取出，经研磨得到硼酸锂钠钇的铈掺杂化合物。Mix sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, and boron-containing compounds in a molar ratio of sodium: (lutetium + rare earth): lithium: boron element of 1:1:2:2 Evenly put it into a mortar and mix thoroughly, then put it into a crucible, put it into a muffle furnace and pass in hydrogen, raise the temperature to 400-500°C, keep it constant for 12-48 hours, cool it to room temperature, take it out, and grind it for the second time. Then put it into a muffle furnace and pass in hydrogen, then raise the temperature to 600-700°C, keep the temperature constant for 12-48 hours, cool to room temperature, take it out, grind it for the third time, put it into the muffle furnace and pass in hydrogen, and then raise it to 700°C. -750°C, constant temperature for 12-48 hours, take out, and grind to obtain a cerium-doped compound of lithium sodium yttrium borate.
其中含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、NaNO 3、NaOH、Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含镥的化合物为Lu 2O 3、Lu(NO 3) 3·6H 2O中的任一种；含稀土的化合物选自CeO 2、Pr 2O 3、Pr 6O 11、Nd 2O 3、Eu 2O 3、Tb 2O 3、Tb 4O 7、Ho 2O 3、Er 2O 3、Tm 2O 3、Yb 2O 3、Ce(NO 3) 3·6H 2O、Pr(NO 3) 3·6H 2O、Nd(NO 3) 3·6H 2O、Eu(NO 3) 3·6H 2O、 Tb(NO 3) 3·6H 2O、Ho(NO 3) 3·5H 2O、Ho(NO 3) 3·6H 2O、Er(NO 3) 3·6H 2O、Tm(NO 3) 3·5H 2O中的任一种，含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 The sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , NaNO 3 , NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, NaBO 2 ·4H 2 O Any one of them; the lutetium-containing compound is any one of Lu 2 O 3 and Lu(NO 3 ) 3 ·6H 2 O; the rare earth-containing compound is selected from CeO 2 , Pr 2 O 3 , Pr 6 O 11 , Nd 2 O 3 , Eu 2 O 3 , Tb 2 O 3 , Tb 4 O 7 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Ce(NO 3 ) 3 ·6H 2 O, Pr(NO 3 ) 3 ·6H 2 O, Nd(NO 3 ) 3 ·6H 2 O, Eu(NO 3 ) 3 ·6H 2 O, Tb(NO 3 ) 3 ·6H 2 O, Ho(NO 3 ) 3 ·5H 2 O, Ho(NO 3 ) 3 ·6H 2 O, Er(NO 3 ) 3 ·6H 2 O, Tm(NO 3 ) 3 ·5H 2 O, and the lithium-containing compound is Any of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
一种制备硼酸锂钠镥晶体的方法，该方法包括以下步骤：将含钠的化合物、含镥的化合物、含锂的化合物、含硼的化合物按照钠∶镥∶锂∶硼元素摩尔比为1-3∶1∶5-8∶5-10的比例均匀混合研磨，装入坩埚中，以5-20℃/h的升温速率加热至温度800-1000℃后得到高温熔液，保温12-48h，然后以1-10℃/h的速度降至室温，得到硼酸锂钠镥晶体。其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、NaNO 3、NaF、NaOH、Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含镥的化合物为Lu 2O 3、Lu(NO 3) 3·6H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 A method for preparing lithium sodium lutetium borate crystal. The method includes the following steps: adding sodium-containing compounds, lutetium-containing compounds, lithium-containing compounds, and boron-containing compounds according to the molar ratio of sodium:lutetium:lithium:boron element to 1 -Mix and grind evenly in the ratio of 3:1:5-8:5-10, put it into a crucible, heat it to a temperature of 800-1000°C at a heating rate of 5-20°C/h, and then obtain a high-temperature melt, and keep it warm for 12-48h , and then lowered to room temperature at a rate of 1-10°C/h to obtain lithium sodium lutetium borate crystals. Among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , NaNO 3 , NaF, NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, NaBO 2 · Any one of 4H 2 O; the compound containing lutetium is any one of Lu 2 O 3 , Lu(NO 3 ) 3 ·6H 2 O; the compound containing lithium is any one of Li 2 CO 3 , LiNO 3 or LiOH Any of them; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
特别地，制备硼酸锂钠镥晶体时，还加入助溶剂，助熔剂为PbO、PbO 2、PbF 2、KF或KCl中的任一种。 In particular, when preparing lithium sodium lutetium borate crystal, a flux is also added, and the flux is any one of PbO, PbO 2 , PbF 2 , KF or KCl.
一种制备硼酸锂钠镥稀土掺杂晶体的方法，该方法包括以下步骤：将含钠的化合物、含镥的化合物、含稀土的化合物、含锂的化合物、含硼的化合物按照钠∶(镥+稀土)∶锂∶硼元素摩尔比为1-3∶1∶5-8∶5-10的比例均匀混合研磨，装入坩埚中，以5-20℃/h的升温速率加热至温度800-1000℃后得到高温熔液，保温12-48h，然后以1-10℃/h的速度降至室温，得到硼酸锂钠镥稀土掺杂晶体。其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、NaNO 3、NaF、NaOH、Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含镥的化合物为Lu 2O 3、Lu(NO 3) 3·6H 2O中的任一种；含稀土的化合物选自CeO 2、Pr 2O 3、Pr 6O 11、Nd 2O 3、Eu 2O 3、Tb 2O 3、Tb 4O 7、Ho 2O 3、Er 2O 3、Tm 2O 3、Yb 2O 3、Ce(NO 3) 3·6H 2O、Pr(NO 3) 3·6H 2O、Nd(NO 3) 3·6H 2O、Eu(NO 3) 3·6H 2O、Tb(NO 3) 3·6H 2O、Ho(NO 3) 3·5H 2O、Ho(NO 3) 3·6H 2O、Er(NO 3) 3·6H 2O、 Tm(NO 3) 3·5H 2O中的任一种，含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 A method for preparing sodium lithium borate and lutetium rare earth doped crystals. The method includes the following steps: adding sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, and boron-containing compounds according to sodium: (lutetium + rare earth): lithium: boron element molar ratio is 1-3: 1: 5-8: 5-10, evenly mixed and ground, put into a crucible, heated to a temperature of 800-800 with a heating rate of 5-20°C/h After reaching 1000°C, a high-temperature melt is obtained, kept for 12-48h, and then lowered to room temperature at a rate of 1-10°C/h to obtain lithium sodium borate and lutetium rare earth doped crystals. Among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , NaNO 3 , NaF, NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, NaBO 2 · Any one of 4H 2 O; the lutetium-containing compound is any one of Lu 2 O 3 and Lu(NO 3 ) 3 ·6H 2 O; the rare earth-containing compound is selected from CeO 2 , Pr 2 O 3 , Pr 6 O 11 , Nd 2 O 3 , Eu 2 O 3 , Tb 2 O 3 , Tb 4 O 7 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Ce(NO 3 ) 3 ·6H 2 O, Pr(NO 3 ) 3 ·6H 2 O, Nd(NO 3 ) 3 ·6H 2 O, Eu(NO 3 ) 3 ·6H 2 O, Tb(NO 3 ) 3 ·6H 2 O, Ho Any of (NO 3 ) 3 ·5H 2 O, Ho(NO 3 ) 3 ·6H 2 O, Er(NO 3 ) 3 ·6H 2 O, Tm(NO 3 ) 3 ·5H 2 O, containing lithium The compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
特别地，制备硼酸锂钠镥稀土掺杂晶体，还加入助溶剂，将含钠的化合物、含镥的化合物、含稀土的化合物、含锂的化合物、含硼的化合物、助熔剂按照钠∶(镥+稀土)∶锂∶硼∶助熔剂的物质的量比为1-3∶1∶2-3∶2-5∶1-10的比例均匀混合研磨，装入坩埚，以5-50℃/h的升温速率加热至温度800-1000℃后得到高温溶液，保温12-48h，然后以1-20℃/h的速度降至室温，得到硼酸锂钠镥及其稀土掺杂晶体。助熔剂为PbO、PbO 2、PbF 2、KF或KCl中的任一种。 In particular, lithium sodium borate and lutetium rare earth doped crystals are prepared, and a cosolvent is added. The sodium-containing compound, the lutetium-containing compound, the rare earth-containing compound, the lithium-containing compound, the boron-containing compound, and the flux are calculated according to sodium: ( Lutetium + rare earth):lithium:boron:flux are evenly mixed and ground in a ratio of 1-3:1:2-3:2-5:1-10, put into a crucible, and heated at 5-50°C/ After heating to a temperature of 800-1000°C at a heating rate of h, a high-temperature solution is obtained, kept for 12-48h, and then lowered to room temperature at a rate of 1-20°C/h to obtain lithium sodium lutetium borate and its rare earth doped crystals. The flux is any one of PbO, PbO 2 , PbF 2 , KF or KCl.
一种制备硼酸锂钠镥稀土金属掺杂晶体的方法，该方法包括以下步骤：将含钠的化合物、含镥的化合物、含稀土的化合物、含锂的化合物、含硼的化合物按照钠∶(镥+稀土)∶锂∶硼摩尔比为1-3∶1∶2-5∶1-8的比例均匀混合研磨，装入坩埚中，再放入中频提拉炉中，通入高纯N 2/H 2/Ar气，加热至完全融化，搅拌12-24小时，熔体温度高于饱和点温度0.1-3℃时，再从生长炉内放入铂金或铱金杆，使其接触熔液表面，并保持2-12小时，再将温度以0.1-10℃/h降至饱和点温度后，并将铂金或铱金杆的转速设置为2-25r/min，然后以0.05-10℃/h的速率缓慢降温，并以0.05-0.75mm/h的提拉速度提拉，待晶体长到一定尺寸时，将晶体提离液面拉脱，再以10-100℃/h的速率快速降至室温，最后得到硼酸锂钠镥稀土掺杂晶体。其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3中的任一种；含铈的化合物为CeO 2、Ce 2O 3、Ce(NO 3) 3·6H 2O、Ce 2(SO 4) 3·4H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH；含硼的化合物为H 3BO 3或B 2O 3。 A method for preparing lithium sodium borate and lutetium rare earth metal doped crystals. The method includes the following steps: adding sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, and boron-containing compounds according to sodium: ( Lutetium + rare earth):lithium:boron molar ratio is 1-3:1:2-5:1-8, evenly mixed and ground, put into a crucible, then put into a medium frequency pulling furnace, and high-purity N 2 /H 2 /Ar gas, heat until completely melted, stir for 12-24 hours, when the melt temperature is 0.1-3°C higher than the saturation point, then put a platinum or iridium rod from the growth furnace to contact the melt surface, and keep it for 2-12 hours, then reduce the temperature to the saturation point temperature at 0.1-10℃/h, and set the rotation speed of the platinum or iridium rod to 2-25r/min, and then set the speed of the platinum or iridium rod to 0.05-10℃/ h slowly cool down at a rate of 0.05-0.75mm/h, and pull it up at a pulling speed of 0.05-0.75mm/h. When the crystal grows to a certain size, lift the crystal away from the liquid surface, and then rapidly drop it at a rate of 10-100℃/h. to room temperature, and finally obtain lithium sodium borate lutetium rare earth doped crystal. Among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, Any of NaBO 2 ·4H 2 O; yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ·6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 ( Any one of SO 4 ) 3 ; the cerium-containing compound is any one of CeO 2 , Ce 2 O 3 , Ce(NO 3 ) 3 ·6H 2 O, and Ce 2 (SO 4 ) 3 ·4H 2 O ; Lithium-containing compounds are Li 2 CO 3 , LiNO 3 or LiOH; boron-containing compounds are H 3 BO 3 or B 2 O 3 .
本发明还保护所述硼酸锂钠镥化合物或晶体或硼酸锂钠镥稀土掺杂化合物或晶体的用途，所述的硼酸锂钠镥稀土掺杂化合物或晶体作为闪烁材料用作高能射线探测材料，或用作LED照明用荧光粉等光功能材料；所述的硼酸锂钠镥化合物或晶体作为光学透镜材料，或用于大孔径、宽视场摄影物镜、长焦距、变焦距镜头以及高倍显微镜等的光学棱镜材料。The present invention also protects the use of the lithium sodium lutetium borate compound or crystal or the lithium sodium lutetium borate rare earth doped compound or crystal. The lithium sodium sodium lutetium borate rare earth doped compound or crystal is used as a scintillation material for high-energy ray detection materials. Or used as optical functional materials such as phosphors for LED lighting; the lithium sodium lutetium borate compound or crystal is used as an optical lens material, or used in large aperture, wide field of view photography objectives, long focal length, zoom lens and high power microscopes, etc. Optical prism materials.
本发明的有益效果如下：本发明提供了一类新型硼酸锂钠镥及其稀土掺杂化合物或晶体及其制备方法，廉价易得、合成简便，理化性质稳定，所述的硼酸锂钠镥稀土掺杂化合物或晶体闪烁和荧光性能良好，可以作为闪烁材料探测X射线等高能粒子，或用作LED照明用荧光粉，在核医学成像、高能物理粒子探测和光照明等领域具有重要的经济和科研价值；所述的硼酸锂钠镥化合物或晶体作为光学透镜材料，或用于大孔径、宽视场摄影物镜、长焦距、变焦距镜头以及高倍显微镜等的光学棱镜材料；。The beneficial effects of the present invention are as follows: The present invention provides a new type of lithium sodium lutetium borate and its rare earth doped compounds or crystals and their preparation methods, which are cheap and easy to obtain, simple to synthesize, and have stable physical and chemical properties. The described lithium sodium lutetium borate rare earth Doped compounds or crystals have good scintillation and fluorescence properties and can be used as scintillation materials to detect high-energy particles such as X-rays, or as phosphors for LED lighting. They have important economic and scientific research in the fields of nuclear medicine imaging, high-energy physics particle detection, and light illumination. Value; The lithium sodium lutetium borate compound or crystal is used as an optical lens material, or an optical prism material for large aperture, wide field of view photographic objectives, long focal length, zoom lens, high power microscope, etc.;.
附图说明：Picture description:
图1是本发明实施例7制备得到的硼酸锂钠镥Li 2NaLu(BO 3) 2单晶沿b轴和c轴的的晶体结构示意图； Figure 1 is a schematic diagram of the crystal structure along the b-axis and c-axis of the lithium sodium lutetium borate Li 2 NaLu(BO 3 ) 2 single crystal prepared in Example 7 of the present invention;
图2是本发明实施例7制备得到的硼酸锂钠镥Li 2NaLu(BO 3) 2单晶的色散折射率； Figure 2 is the dispersion refractive index of the lithium sodium lutetium borate Li 2 NaLu (BO 3 ) 2 single crystal prepared in Example 7 of the present invention;
图3是本发明实施例1制备得到的硼酸锂钠镥Li 2NaLu(BO 3) 2化合物的漫反射光谱； Figure 3 is the diffuse reflection spectrum of the lithium sodium lutetium borate Li 2 NaLu (BO 3 ) 2 compound prepared in Example 1 of the present invention;
图4是本发明的Li 2NaLu(BO 3) 2化合物的粉末XRD衍射图； Figure 4 is a powder XRD diffraction pattern of the Li 2 NaLu (BO 3 ) 2 compound of the present invention;
图5是Li 2NaLu 0.995Ce 0.005(BO 3) 2化合物的粉末XRD衍射图； Figure 5 is the powder XRD diffraction pattern of Li 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 compound;
图6是Li 2NaLu 0.7Nd 0.3(BO 3) 2化合物的粉末XRD衍射图； Figure 6 is a powder XRD diffraction pattern of Li 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 compound;
图7是Li 2NaLu 0.9Ce 0.1(BO 3) 2晶体的闪烁性能； Figure 7 is the scintillation performance of Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal;
图8是Li 2NaLu 0.9Ce 0.1(BO 3) 2晶体的荧光发射光谱； Figure 8 is the fluorescence emission spectrum of Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal;
图9是Li 2NaLu 0.8Eu 0.2(BO 3) 2化合物的荧光发射光谱； Figure 9 is the fluorescence emission spectrum of Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 compound;
图10是Li 2NaLu 0.8Tb 0.4(BO 3) 2化合物的荧光发射光谱； Figure 10 is the fluorescence emission spectrum of Li 2 NaLu 0.8 Tb 0.4 (BO 3 ) 2 compound;
图11是Li 2NaLu 0.9Ce 0.1(BO 3) 2晶体、Li 2NaLu 0.8Eu 0.2(BO 3) 2化合物、Li 2NaLu 0.8Tb 0.4(BO 3) 2化合物的CIE色度坐标。 Figure 11 shows the CIE chromaticity coordinates of Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal, Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 compound, and Li 2 NaLu 0.8 Tb 0.4 (BO 3 ) 2 compound.
具体实施方式：Detailed ways:
以下是对本发明的进一步说明，而不是对本发明的限制。The following is a further description of the present invention, rather than a limitation of the present invention.
实施例1：合成硼酸锂钠镥化合物Li 2NaLu(BO 3) 2化合物 Example 1: Synthesis of Lithium Sodium Lutetium Borate Compound Li 2 NaLu (BO 3 ) 2 Compound
所用原料(分析纯)：Lu 2O 30.05mol、H 3BO 30.2mol、Na 2CO 30.05mol、Li 2CO 30.05mol。具体步骤如下：将上述原料称量好后，放入玛瑙研钵中仔细混合研磨，然后装入
Figure PCTCN2023070436-appb-000006
的刚玉坩埚中，放入马弗炉中，升温至500℃，恒温24小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中，再升温至600℃，恒温24小时，冷却至室温，取出，经第三次研磨后放入马弗炉中，再升700℃，恒温24小时，取出，经研磨得到本发明的硼酸锂钠镥Li 2NaLu(BO 3) 2化合物。 Raw materials used (analytically pure): Lu 2 O 3 0.05 mol, H 3 BO 3 0.2 mol, Na 2 CO 3 0.05 mol, Li 2 CO 3 0.05 mol. The specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into
Figure PCTCN2023070436-appb-000006
Put the corundum crucible into a muffle furnace, raise the temperature to 500°C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the second time, put it into the muffle furnace, raise the temperature to 600°C, and keep the temperature constant for 24 hours. Cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace, raise it to 700°C, keep the temperature constant for 24 hours, take it out, and grind it to obtain the lithium sodium lutetium borate Li 2 NaLu (BO 3 ) 2 compound of the present invention.
实施例2：合成硼酸锂钠镥的0.5％铈掺杂Li 2NaLu 0.995Ce 0.005(BO 3) 2化合物 Example 2: Synthesis of lithium sodium lutetium borate 0.5% cerium doped Li 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 compound
所用原料(分析纯)：Lu 2O 30.04975mol、CeO 20.0005mol、H 3BO 30.2mol、Na 2CO 30.05mol、Li 2CO 30.1mol。 Raw materials used (analytically pure): Lu 2 O 3 0.04975 mol, CeO 2 0.0005 mol, H 3 BO 3 0.2 mol, Na 2 CO 3 0.05 mol, Li 2 CO 3 0.1 mol.
具体步骤如下：将上述原料称量好后，放入玛瑙研钵中仔细混合研磨，然后装入
Figure PCTCN2023070436-appb-000007
Figure PCTCN2023070436-appb-000008
的刚玉坩埚中，放入管式炉中并通入氢气氛，升温至450℃，恒温24小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中通入氢气氛，再升温至630℃，恒温24小时， 冷却至室温，取出，经第三次研磨后放入马弗炉中通入氢气氛，再升730℃，恒温24小时，取出，经研磨得到本发明的Li 2NaLu 0.995Ce 0.005(BO 3) 2化合物。 The specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into
Figure PCTCN2023070436-appb-000007
Figure PCTCN2023070436-appb-000008
Put it into a corundum crucible, put it into a tube furnace and introduce a hydrogen atmosphere, heat it to 450°C, keep it constant for 24 hours, cool it to room temperature, take it out, grind it for the second time, put it into a muffle furnace and introduce a hydrogen atmosphere, and then Raise the temperature to 630°C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace and pass in a hydrogen atmosphere, raise it to 730°C again, keep the temperature constant for 24 hours, take it out, and grind it to obtain Li of the present invention. 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 compound.
实施例3：合成硼酸锂钠镥的30％钕掺杂Li 2NaLu 0.7Nd 0.3(BO 3) 2化合物 Example 3: Synthesis of lithium sodium lutetium borate 30% neodymium doped Li 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 compound
所用原料(分析纯)：Lu(NO 3) 3·6H 2O、0.07mol、Nd(NO 3) 3·6H 2O 0.03mol、H 3BO 30.2mol、NaNO 30.1mol、LiNO 30.2mol。 Raw materials used (analytically pure): Lu(NO 3 ) 3 ·6H 2 O, 0.07mol, Nd(NO 3 ) 3 ·6H 2 O 0.03mol, H 3 BO 3 0.2mol, NaNO 3 0.1mol, LiNO 3 0.2mol .
具体步骤如下：将上述原料称量好后，放入玛瑙研钵中仔细混合研磨，然后装入
Figure PCTCN2023070436-appb-000009
Figure PCTCN2023070436-appb-000010
的铂金坩埚中，放入马弗炉中，升温至500℃，恒温24小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中，再升温至680℃，恒温24小时，冷却至室温，取出，经第三次研磨后放入马弗炉中，再升730℃，恒温24小时，取出，经研磨得到本发明的Li 2NaLu 0.7Nd 0.3(BO 3) 2化合物。 The specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into
Figure PCTCN2023070436-appb-000009
Figure PCTCN2023070436-appb-000010
Put it into a platinum crucible, put it into a muffle furnace, raise the temperature to 500°C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the second time, put it into the muffle furnace, raise the temperature to 680°C, and keep the temperature constant for 24 hours. Cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace, raise it to 730°C, keep the temperature constant for 24 hours, take it out, and grind it to obtain the Li 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 compound of the present invention.
实施例4：合成硼酸锂钠镥的20％铕掺杂Li 2NaLu 0.8Eu 0.2(BO 3) 2化合物 Example 4: Synthesis of 20% Europium-doped Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 compound of lithium sodium lutetium borate
所用原料(分析纯)：Lu 2O 30.004mol、Eu 2O 30.001mol、B 2O 30.01mol、NaHCO 30.01mol、Li 2CO 30.01mol。 Raw materials used (analytically pure): Lu 2 O 3 0.004 mol, Eu 2 O 3 0.001 mol, B 2 O 3 0.01 mol, NaHCO 3 0.01 mol, Li 2 CO 3 0.01 mol.
具体步骤如下：将上述原料称量好后，放入玛瑙研钵中仔细混合研磨，然后装入
Figure PCTCN2023070436-appb-000011
Figure PCTCN2023070436-appb-000012
的铂金坩埚中，放入马弗炉中，升温至480℃，恒温24小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中，再升温至660℃，恒温24小时，冷却至室温，取出，经第三次研磨后放入马弗炉中，再升750℃，恒温24小时，取出，经研磨得到本发明的铕掺杂Li 2NaLu 0.8Eu 0.2(BO 3) 2化合物 The specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into
Figure PCTCN2023070436-appb-000011
Figure PCTCN2023070436-appb-000012
into a platinum crucible, put it into a muffle furnace, raise the temperature to 480°C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the second time and put it into the muffle furnace, then raise the temperature to 660°C, keep the temperature constant for 24 hours. Cool to room temperature, take it out, put it into a muffle furnace after grinding for the third time, then raise it to 750°C, keep the temperature constant for 24 hours, take it out, and grind it to obtain the europium-doped Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 of the present invention. compound
实施例5：合成硼酸锂钠镥的40％铽掺杂Li 2NaLu 0.6Tb 0.4(BO 3) 2化合物 Example 5: Synthesis of Lithium Sodium Lutetium Borate 40% Terbium Doped Li 2 NaLu 0.6 Tb 0.4 (BO 3 ) 2 Compound
所用原料(分析纯)：Lu 2O 30.009mol、Tb 4O 70.003mol、B 2O 30.03mol、NaHCO 30.03mol、Li 2CO 30.03mol。 Raw materials used (analytically pure): Lu 2 O 3 0.009 mol, Tb 4 O 7 0.003 mol, B 2 O 3 0.03 mol, NaHCO 3 0.03 mol, Li 2 CO 3 0.03 mol.
具体步骤如下：将上述原料称量好后，放入玛瑙研钵中仔细混合研磨，然后装入
Figure PCTCN2023070436-appb-000013
Figure PCTCN2023070436-appb-000014
的铂金坩埚中，放入马弗炉中，升温至500℃，恒温24小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中，再升温至650℃，恒温24小时，冷却至室温，取出，经第三次研磨后放入马弗炉中，再升730℃，恒温24小时，取出，经研磨得到本发明的Li 2NaLu 0.6Tb 0.4(BO 3) 2化合物。 The specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into
Figure PCTCN2023070436-appb-000013
Figure PCTCN2023070436-appb-000014
Put it into a platinum crucible, put it into a muffle furnace, raise the temperature to 500°C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the second time, put it into the muffle furnace, raise the temperature to 650°C, and keep the temperature constant for 24 hours. Cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace, raise it to 730°C, keep the temperature constant for 24 hours, take it out, and grind it to obtain the Li 2 NaLu 0.6 Tb 0.4 (BO 3 ) 2 compound of the present invention.
实施例6：合成硼酸锂钠镥的50％镱掺杂Li 2NaLu 0.5Yb 0.5(BO 3) 2化合物 Example 6: Synthesis of lithium sodium lutetium borate 50% ytterbium doped Li 2 NaLu 0.5 Yb 0.5 (BO 3 ) 2 compound
所用原料(分析纯)：Lu(NO 3) 3·6H 2O 0.25mol、Yb 2O 30.125mol、B 2O 30.5mol、Na 2C 2O 40.25mol、LiOH 1.0mol。 Raw materials used (analytically pure): Lu(NO 3 ) 3 ·6H 2 O 0.25mol, Yb 2 O 3 0.125mol, B 2 O 3 0.5mol, Na 2 C 2 O 4 0.25mol, LiOH 1.0mol.
具体步骤如下：将上述原料称量好后，放入玛瑙研钵中仔细混合研磨，然后装入
Figure PCTCN2023070436-appb-000015
Figure PCTCN2023070436-appb-000016
的刚玉坩埚中，放入马弗炉中，升温至480℃，恒温24小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中，再升温至660℃，恒温24小时，冷却至室温，取出，经第三次研磨后放入马弗炉中，再升750℃，恒温24小时，取出，经研磨得到本发明的Li 2NaLu 0.5Yb 0.5(BO 3) 2化合物。 The specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into
Figure PCTCN2023070436-appb-000015
Figure PCTCN2023070436-appb-000016
Put the corundum crucible into a muffle furnace, raise the temperature to 480°C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the second time and put it into the muffle furnace, then raise the temperature to 660°C, keep the temperature constant for 24 hours. Cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace, raise it to 750°C, keep the temperature constant for 24 hours, take it out, and grind it to obtain the Li 2 NaLu 0.5 Yb 0.5 (BO 3 ) 2 compound of the present invention.
实施例7：自助溶剂法制备硼酸锂钠镥Li 2NaLu(BO 3) 2晶体所用原料(分析纯)：Na 2CO 30.015mol、Lu 2O 30.005mol、Li 2CO 30.04mol、H 3BO 30.1mol。 Example 7: Preparation of lithium sodium lutetium borate Li 2 NaLu (BO 3 ) 2 crystal by self-service solvent method. Raw materials used (analytically pure): Na 2 CO 3 0.015 mol, Lu 2 O 3 0.005 mol, Li 2 CO 3 0.04 mol, H 3 BO 3 0.1mol.
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070436-appb-000017
铂金坩埚中，再放入熔盐炉中，以20℃/h加热至950℃原料完全熔化，保温12小时，然后2℃/小时的速率缓慢降温，得到尺寸为0.37×0.32×0.16mm 3的Li 2NaLu(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070436-appb-000017
Put it into a platinum crucible, then put it into a molten salt furnace, heat it at 20°C/h until the raw material is completely melted at 950°C, keep it warm for 12 hours, and then slowly cool it down at a rate of 2°C/hour to obtain a 0.37 × 0.32 × 0.16mm 3 Li 2 NaLu(BO 3 ) 2 crystal.
实施例8：自助溶剂法制备硼酸锂钠镥的20％钕掺杂Li 2NaLu 0.8Nd 0.2(BO 3) 2晶体 Example 8: Preparation of 20% neodymium-doped Li 2 NaLu 0.8 Nd 0.2 (BO 3 ) 2 crystal of lithium sodium lutetium borate by self-service solvent method
所用原料(分析纯)：Na 2B 4O 710H 2O 0.3mol、Lu 2O 30.08mol、Nd 2O 30.02mol、Li 2CO 30.75mol、B 2O 30.3mol。 Raw materials used (analytically pure): Na 2 B 4 O 7 10H 2 O 0.3mol, Lu 2 O 3 0.08mol, Nd 2 O 3 0.02mol, Li 2 CO 3 0.75mol, B 2 O 3 0.3mol.
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070436-appb-000018
铂金坩埚中，再放入熔盐炉中，以10℃/h加热至965℃原料完全熔化，保温36小时，然后5℃/小时的速率缓慢降温，得到尺寸为0.25×0.2×0.13mm 3的Li 2NaLu 0.8Nd 0.2(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070436-appb-000018
Put it into a platinum crucible, then put it into a molten salt furnace, heat it at 10°C/h until the raw material is completely melted at 965°C, keep it warm for 36 hours, and then slowly cool it down at a rate of 5°C/hour to obtain a 0.25×0.2×0.13mm 3 Li 2 NaLu 0.8 Nd 0.2 (BO 3 ) 2 crystal.
实施例9：自助溶剂法制备的硼酸锂钠镥的35％铥掺杂Li 2NaLu 0.65Tm 0.35(BO 3) 2晶体 Example 9: 35% thulium-doped Li 2 NaLu 0.65 Tm 0.35 (BO 3 ) 2 crystal of lithium sodium lutetium borate prepared by self-service solvent method
所用原料(分析纯)：NaHCO 30.2mol、Lu 2O 30.0325mol、Tm 2O 30.0175mol、Li 2CO 30.4mol、H 3BO 30.9mol Raw materials used (analytically pure): NaHCO 3 0.2mol, Lu 2 O 3 0.0325mol, Tm 2 O 3 0.0175mol, Li 2 CO 3 0.4mol, H 3 BO 3 0.9mol
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070436-appb-000019
铂金坩埚中，再放入熔盐炉中，以15℃/h加热至980℃原料完全熔化，保温12小时，然后5℃/小时的速率缓慢降温，得到尺寸为0.17×0.13×0.1mm 3的Li 2NaLu 0.65Tm 0.35(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070436-appb-000019
Put it into a platinum crucible, then put it into a molten salt furnace, heat it at 15°C/h until the raw material is completely melted at 980°C, keep it warm for 12 hours, and then slowly cool it down at a rate of 5°C/hour to obtain a 0.17 × 0.13 × 0.1mm 3 Li 2 NaLu 0.65 Tm 0.35 (BO 3 ) 2 crystal.
实施例10：助溶剂法制备硼酸锂钠镥Li 2NaLu(BO 3) 2晶体 Example 10: Preparation of lithium sodium lutetium borate Li 2 NaLu(BO 3 ) 2 crystal by cosolvent method
所用原料(分析纯)：NaHCO 30.1mol、Lu 2O 30.05mol、Li 2CO 30.2mol、H 3BO 30.2mol、PbO0.5mol。 Raw materials used (analytically pure): NaHCO 3 0.1 mol, Lu 2 O 3 0.05 mol, Li 2 CO 3 0.2 mol, H 3 BO 3 0.2 mol, PbO 0.5 mol.
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070436-appb-000020
黄金坩埚中，再放入马弗炉中，以5℃/h加热至900℃原料完全熔化，保温12小时，然后3℃/小时的速率缓慢降温，得到尺寸为0.52×0.37×0.12mm 3的Li 2NaLu(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070436-appb-000020
Put the gold crucible into a muffle furnace, heat it at 5°C/h until the raw material is completely melted at 900°C, keep it warm for 12 hours, and then slowly cool it down at a rate of 3°C/hour to obtain a 0.52×0.37×0.12mm 3 Li 2 NaLu(BO 3 ) 2 crystal.
实施例11：助溶剂法制备硼酸锂钠镥的10％铈掺杂Li 2NaLu 0.9Ce 0.1(BO 3) 2晶体 Example 11: Preparation of 10% cerium-doped Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal of lithium sodium lutetium borate by cosolvent method
所用原料(分析纯)：NaNO 31.5mol、Lu 2O 30.45mol、CeO 2·0.1mol、LiOH 2.5mol、H 3BO 33.0mol、PbF 210mol。 Raw materials used (analytically pure): NaNO 3 1.5 mol, Lu 2 O 3 0.45 mol, CeO 2 ·0.1 mol, LiOH 2.5 mol, H 3 BO 3 3.0 mol, PbF 2 10 mol.
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070436-appb-000021
黄金坩埚中，再放入马弗炉中，以5℃/h加热至950℃原料完全熔化，保温12小时，然后2℃/小时的速率缓慢降温，得到0.27×0.16×0.11mm 3的Li 2NaLu 0.9Ce 0.1(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070436-appb-000021
Put the gold crucible into a muffle furnace, heat it at 5℃/h until the raw material is completely melted at 950℃, keep it warm for 12 hours, and then slowly cool it down at a rate of 2℃/hour to obtain 0.27×0.16×0.11mm 3 Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal.
实施例12：助溶剂法制备硼酸锂钠镥的15％镨掺杂Li 2NaLu 0.85Pr 0.15(BO 3) 2晶体 Example 12: Preparation of 15% praseodymium-doped Li 2 NaLu 0.85 Pr 0.15 (BO 3 ) 2 crystal of lithium sodium lutetium borate by cosolvent method
所用原料(分析纯)：Na 2C 2O 41.25mol、Lu(NO 3) 3·6H 2O 0.85mol、Pr 6O 11·0.025mol、LiNO 32.5mol、B 2O 32.5mol、KF 8mol。 Raw materials used (analytically pure): Na 2 C 2 O 4 1.25mol, Lu(NO 3 ) 3 ·6H 2 O 0.85mol, Pr 6 O 11 ·0.025mol, LiNO 3 2.5mol, B 2 O 3 2.5mol, KF 8mol.
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070436-appb-000022
铂金坩埚中，再放入马弗炉中，以25℃/h加热至1000℃原料完全熔化，保温12小时，然后2℃/小时的速率缓慢降温，得到0.57×0.46×0.21mm 3的Li 2NaLu 0.85Pr 0.15(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070436-appb-000022
Put it into a platinum crucible, then put it into a muffle furnace, heat it at 25℃/h until the raw material is completely melted at 1000℃, keep it warm for 12 hours, and then slowly cool it down at a rate of 2℃/hour to obtain 0.57×0.46×0.21mm 3 Li 2 NaLu 0.85 Pr 0.15 (BO 3 ) 2 crystal.
实施例13：提拉法制备硼酸锂钠镥的10％铈掺杂Li 2NaLu 0.9Ce 0.1(BO 3) 2晶体 Example 13: Preparation of 10% cerium-doped Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal of lithium sodium lutetium borate by Czochralski method
所用原料(分析纯)：NaBO 24H 2O 1.0mol、Lu 2O 30.45mol、CeO 2·0.1mol、Li 2CO 30.4mol、H 3BO 31.0mol。 Raw materials used (analytically pure): NaBO 2 4H 2 O 1.0 mol, Lu 2 O 3 0.45 mol, CeO 2 ·0.1 mol, Li 2 CO 3 0.4 mol, H 3 BO 3 1.0 mol.
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070436-appb-000023
铂金坩埚中，再放入中频提拉炉中，通入高纯N 2/H 2混合气，加热至完全融化，搅拌24小时，熔体温度高于饱和点温度0.5℃时，再从生长炉内放入铂金杆，使其接触熔液表面，并保持2小时，再将温度以0.25℃/h降至饱和点温度后，并将铂金杆的转速设置为10r/min，然后以0.05℃/h的速率缓慢降温，以0.1mm/h的提拉速度提拉，待晶体长到一定尺寸时，将晶体提 离液面拉脱，最后以50℃/h的速率快速降至室温，得到尺寸为5.2×4.3×1.7mm 3的Li 2NaLu 0.9Ce 0.1(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070436-appb-000023
Platinum crucible, then put it into the medium frequency pulling furnace, pass in high-purity N 2 /H 2 mixed gas, heat until completely melted, stir for 24 hours, when the melt temperature is 0.5°C higher than the saturation point, then remove it from the growth furnace Put a platinum rod into it and let it contact the surface of the melt and keep it for 2 hours. Then reduce the temperature to the saturation point temperature at 0.25℃/h, and set the rotation speed of the platinum rod to 10r/min, and then set it to 0.05℃/h. The temperature is slowly lowered at a rate of h, and pulled at a pulling speed of 0.1mm/h. When the crystal grows to a certain size, the crystal is lifted off the liquid surface and finally dropped to room temperature at a rate of 50°C/h to obtain the size. It is a 5.2×4.3×1.7mm 3 Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal.
实施例14：提拉法制备硼酸锂钠镥的30％钬掺杂Li 2NaLu 0.7Ho 0.3(BO 3) 2晶体 Example 14: Preparation of 30% holmium-doped Li 2 NaLu 0.7 Ho 0.3 (BO 3 ) 2 crystal of lithium sodium lutetium borate by Czochralski method
所用原料(分析纯)：Na 2CO 30.5mol、Lu 2O 30.35mol、Ho 2O 3·0.15mol、Li 2CO 30.4mol、B 2O 30.5mol。 Raw materials used (analytically pure): Na 2 CO 3 0.5 mol, Lu 2 O 3 0.35 mol, Ho 2 O 3 ·0.15 mol, Li 2 CO 3 0.4 mol, B 2 O 3 0.5 mol.
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070436-appb-000024
铂金坩埚中，再放入中频提拉炉中，通入高纯N 2气，加热至完全融化，搅拌16小时，熔体温度高于饱和点温度1.5℃时，再从生长炉内放入铂金杆，使其接触熔液表面，并保持2小时，再将温度以0.75℃/h降至饱和点温度后，并将铂金杆的转速设置为15r/min，然后以0.55℃/h的速率缓慢降温，以0.3mm/h的提拉速度提拉，待晶体长到一定尺寸时，将晶体提离液面拉脱，最后以30℃/h的速率快速降至室温，得到尺寸为5.3×3.3×2.2mm 3的Li 2NaLu 0.7Ho 0.3(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070436-appb-000024
Put the platinum crucible into a medium frequency pulling furnace, pass in high-purity N2 gas, heat it until it is completely melted, and stir for 16 hours. When the melt temperature is 1.5°C higher than the saturation point, put platinum into the growth furnace. Rod, let it contact the surface of the melt, keep it for 2 hours, then lower the temperature to the saturation point temperature at 0.75°C/h, and set the rotation speed of the platinum rod to 15r/min, and then slowly reduce the temperature to 0.55°C/h. Cool down and pull at a pulling speed of 0.3mm/h. When the crystal grows to a certain size, lift the crystal away from the liquid surface and finally drop it to room temperature quickly at a rate of 30°C/h to obtain a size of 5.3×3.3 ×2.2mm 3 Li 2 NaLu 0.7 Ho 0.3 (BO 3 ) 2 crystal.
实施例15：提拉法制备硼酸锂钠镥的5％铒掺杂Li 2NaLu 0.95Er 0.05(BO 3) 2晶体 Example 15: Preparation of 5% Erbium-doped Li 2 NaLu 0.95 Er 0.05 (BO 3 ) 2 crystal of lithium sodium lutetium borate by Czochralski method
所用原料(分析纯)：NaOH 1.5mol、Lu(NO 3) 3·6H 2O 0.95mol、Er(NO 3) 3·6H 2O 0.05mol、LiF 1.6mol、B 2O 31.75mol。 Raw materials used (analytically pure): NaOH 1.5mol, Lu(NO 3 ) 3 ·6H 2 O 0.95mol, Er(NO 3 ) 3 ·6H 2 O 0.05mol, LiF 1.6mol, B 2 O 3 1.75mol.
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070436-appb-000025
铂金坩埚中，再放入中频提拉炉中，通入高纯Ar气，加热至完全融化，搅拌18小时，熔体温度高于饱和点温度2.5℃时，再从生长炉内放入铂金杆，使其接触熔液表面，并保持2小时，再将温度以1.25℃/h降至饱和点温度后，并将铂金杆的转速设置为15r/min，然后以0.55℃/h 的速率缓慢降温，以0.5mm/h的提拉速度提拉，待晶体长到一定尺寸时，将晶体提离液面拉脱，最后以70℃/h的速率快速降至室温，得到尺寸为2.3×1.6×1.2mm 3的Li 2NaLu 0.95Er 0.05(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070436-appb-000025
Platinum crucible, then put it into the medium frequency pulling furnace, pass in high-purity Ar gas, heat it until it is completely melted, and stir for 18 hours. When the melt temperature is 2.5°C higher than the saturation point, put the platinum rod from the growth furnace. , let it contact the surface of the melt and keep it for 2 hours, then lower the temperature to the saturation point temperature at 1.25℃/h, set the rotation speed of the platinum rod to 15r/min, and then slowly cool down at a rate of 0.55℃/h , pull at a pulling speed of 0.5mm/h. When the crystal grows to a certain size, lift the crystal away from the liquid surface and finally drop it to room temperature quickly at a rate of 70°C/h to obtain a size of 2.3×1.6× 1.2mm 3 of Li 2 NaLu 0.95 Er 0.05 (BO 3 ) 2 crystal.
实施例16：硼酸锂钠镥及其稀土掺杂化合物和晶体的特性测试Example 16: Characteristics testing of lithium sodium lutetium borate and its rare earth doped compounds and crystals
将本发明实施例7制备得到的硼酸锂钠镥Li 2NaLu(BO 3) 2单晶采用X射线单晶衍射法进行晶胞结构测定，其晶胞结构如图1所示，由图1可以得出，所述硼酸锂钠镥晶体Li 2NaLu(BO 3) 2属单斜晶系，空间群是P2 1/n，晶胞参数为：
Figure PCTCN2023070436-appb-000026
α＝90°，β＝102.729°，γ＝90°，
Figure PCTCN2023070436-appb-000027
Z＝4。 The unit cell structure of the lithium sodium lutetium borate Li 2 NaLu(BO 3 ) 2 single crystal prepared in Example 7 of the present invention was measured using the X-ray single crystal diffraction method. The unit cell structure is shown in Figure 1. It can be seen from Figure 1 It is concluded that the lithium sodium lutetium borate crystal Li 2 NaLu(BO 3 ) 2 belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are:
Figure PCTCN2023070436-appb-000026
α=90°, β=102.729°, γ=90°,
Figure PCTCN2023070436-appb-000027
Z=4.
将本发明实施例8制备得到硼酸锂钠镥的20％钕掺杂Li 2NaLu 0.8Nd 0.2(BO 3) 2单晶采用X射线单晶衍射法进行晶胞结构测定，测得Li 2NaLu 0.8Nd 0.2(BO 3) 2晶体属单斜晶系，空间群是P2 1/n，晶胞参数为：
Figure PCTCN2023070436-appb-000028
α＝90°，β＝102.957°，γ＝90°，
Figure PCTCN2023070436-appb-000029
Figure PCTCN2023070436-appb-000030
Z＝4。 The 20% neodymium-doped Li 2 NaLu 0.8 Nd 0.2 (BO 3 ) 2 single crystal prepared in Example 8 of the present invention was measured using the X-ray single crystal diffraction method to determine the unit cell structure, and Li 2 NaLu 0.8 was measured. Nd 0.2 (BO 3 ) 2 crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are:
Figure PCTCN2023070436-appb-000028
α=90°, β=102.957°, γ=90°,
Figure PCTCN2023070436-appb-000029
Figure PCTCN2023070436-appb-000030
Z=4.
将本发明实施例7制备的硼酸锂钠镥Li 2NaLu(BO 3) 2单晶通过色散折射率测试，结果如图2所示，其在测试范围具有较好折射率且色散较低，证明其具有光学棱镜材料的用途。 The lithium sodium lutetium borate Li 2 NaLu(BO 3 ) 2 single crystal prepared in Example 7 of the present invention passed the dispersion refractive index test. The results are shown in Figure 2. It has a good refractive index and low dispersion in the test range, proving that It has uses as optical prism material.
将本发明实施例1制备的硼酸锂钠镥Li 2NaLu(BO 3) 2化合物通过漫反射测试，结果如图3所示，其在400-800nm范围具有较好的透过性能，可作为光学材料。 The lithium sodium lutetium borate Li 2 NaLu(BO 3 ) 2 compound prepared in Example 1 of the present invention was tested through diffuse reflection. The results are shown in Figure 3. It has good transmission performance in the range of 400-800 nm and can be used as an optical Material.
将本发明实施例1、实施例2和实施例3制备得到的Li 2NaLu(BO 3) 2、Li 2NaLu 0.995Ce 0.005(BO 3) 2和Li 2NaLu 0.7Nd 0.3(BO 3) 2化合物仔细研磨后采用X射线粉末衍射仪进行常温XRD测试，如图4-6所示，结果表明所制备得到的化合物属于纯相，并无其他杂相生成。 Li 2 NaLu (BO 3 ) 2 , Li 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 and Li 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 compounds prepared in Example 1, Example 2 and Example 3 of the present invention After careful grinding, an X-ray powder diffractometer was used to perform XRD testing at room temperature, as shown in Figure 4-6. The results showed that the prepared compound was a pure phase and no other impurity phases were generated.
将本发明实施例11制备得到的Li 2NaLu 0.9Ce 0.1(BO 3) 2晶体，在X射线(Ag靶)下激发，其闪烁光谱如图7所示，Li 2NaLu 0.9Ce 0.1(BO 3) 2的闪烁探测性能明显优于同等测试条件的Bi 4Ge 3O 12(BGO)参比晶体，证明Li 2NaLu 0.9Ce 0.1(BO 3) 2有良好的使用价值。 The Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal prepared in Example 11 of the present invention is excited under X-rays (Ag target), and its scintillation spectrum is as shown in Figure 7. Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 's scintillation detection performance is significantly better than the Bi 4 Ge 3 O 12 (BGO) reference crystal under the same test conditions, proving that Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 has good use value.
将本发明实施例13制备得到的Li 2NaLu 0.9Ce 0.1(BO 3) 2晶体，仔细研磨后，在紫外光激发下，发出特征蓝光，其荧光发射光谱如图8所示，其CIE色度坐标(0.157、0.154、0.690)在图11标出，在LED用蓝色荧光粉有良好的使用价值。 After careful grinding, the Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 crystal prepared in Example 13 of the present invention emits characteristic blue light under ultraviolet light excitation. Its fluorescence emission spectrum is shown in Figure 8, and its CIE chromaticity The coordinates (0.157, 0.154, 0.690) are marked in Figure 11. Blue phosphors have good use value in LEDs.
将本发明实施例4制备得到的Li 2NaLu 0.8Eu 0.2(BO 3) 2化合物，仔细研磨后，在紫外或可见光激发下，发出特征红光，其荧光发射光谱如图9所示，其CIE色度坐标(0.615、0.384、0.001)在图11标出，在LED用红色荧光粉有良好的使用价值。 After careful grinding, the Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 compound prepared in Example 4 of the present invention emits characteristic red light under ultraviolet or visible light excitation. Its fluorescence emission spectrum is shown in Figure 9, and its CIE The chromaticity coordinates (0.615, 0.384, 0.001) are marked in Figure 11. Red phosphors have good use value in LEDs.
将本发明实施例5制备得到的Li 2NaLu 0.6Tb 0.4(BO 3) 2化合物，仔细研磨后，在紫外光激发下，发出特征绿光，其荧光发射光谱如图10所示，其CIE色度坐标(0.345、0.535、0.121)在图11标出，在LED用绿色荧光粉有良好的使用价值。 After careful grinding, the Li 2 NaLu 0.6 Tb 0.4 (BO 3 ) 2 compound prepared in Example 5 of the present invention emits characteristic green light under ultraviolet light excitation. Its fluorescence emission spectrum is shown in Figure 10, and its CIE color The degree coordinates (0.345, 0.535, 0.121) are marked in Figure 11. Green phosphors have good use value in LEDs.

Claims (10)

  1. 化学式为Li 2NaLuB 2O 6的硼酸锂钠镥化合物。 Lithium sodium lutetium borate compound with the chemical formula Li 2 NaLuB 2 O 6 .
  2. 硼酸锂钠镥晶体，其特征在于，化学式为Li 2NaLuB 2O 6，单斜晶系，空间群为P2 1/n，晶胞参数为
    Figure PCTCN2023070436-appb-100001
    α＝90°，β＝102.729°，γ＝90°，
    Figure PCTCN2023070436-appb-100002
    Figure PCTCN2023070436-appb-100003
    Z＝4。     Lithium sodium lutetium borate crystal is characterized by having a chemical formula of Li 2 NaLuB 2 O 6 , a monoclinic crystal system, a space group of P2 1 /n, and a unit cell parameter of
    Figure PCTCN2023070436-appb-100001
    α=90°, β=102.729°, γ=90°,
    Figure PCTCN2023070436-appb-100002
    Figure PCTCN2023070436-appb-100003
    Z=4.
  3. 硼酸锂钠镥的稀土掺杂化合物，其特征在于，化学通式为：Li 2NaLu 1-xRE xB 2O 6，其中，0＜x≤0.5，RE为稀土元素，选自Ce、Pr、Nd、Eu、Tb、Ho、Er、Tm、Yb的一种或几种。 The rare earth doped compound of lithium sodium lutetium borate is characterized in that the general chemical formula is: Li 2 NaLu 1-x RE x B 2 O 6 , where 0＜x≤0.5, RE is a rare earth element selected from Ce, Pr , one or more of Nd, Eu, Tb, Ho, Er, Tm, Yb.
  4. 硼酸锂钠镥的稀土掺杂晶体，其特征在于，化学通式为：Li 2NaLu 1-xRE xB 2O 6，其中0＜x≤0.5，RE为稀土元素，选自Ce、Pr、Nd、Eu、Tb、Ho、Er、Tm、Yb的一种或几种，属单斜晶系，空间群为P2 1/n，晶胞参数的范围为
    Figure PCTCN2023070436-appb-100004
    Figure PCTCN2023070436-appb-100005
    α＝90°，β＝102.729-103.889°，γ＝90°，
    Figure PCTCN2023070436-appb-100006
    Z＝4。     The rare earth doped crystal of lithium sodium lutetium borate is characterized in that the general chemical formula is: Li 2 NaLu 1-x RE x B 2 O 6 , where 0＜x≤0.5, RE is a rare earth element selected from Ce, Pr, One or more of Nd, Eu, Tb, Ho, Er, Tm, Yb, belonging to the monoclinic crystal system, the space group is P2 1 /n, and the range of unit cell parameters is
    Figure PCTCN2023070436-appb-100004
    Figure PCTCN2023070436-appb-100005
    α=90°, β=102.729-103.889°, γ=90°,
    Figure PCTCN2023070436-appb-100006
    Z=4.
  5. 一种权利要求1所述硼酸锂钠镥化合物的制备方法，其特征在于，包括以下步骤：将含钠的化合物、含镥的化合物、含锂的化合物、含硼的化合物按照钠∶镥∶锂∶硼元素摩尔比为1∶1∶2∶2的比例均匀放入研钵中充分混合研磨，然后装入坩埚中，放入马弗炉中，升温至400-500℃，恒温12-48小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中通入氢气，再升温至600-700℃，恒温12-48小时，冷却至室温，取出，经第三次研磨后放入马弗炉中通入氢气，再升700-750℃，恒温12-48小时，取出，经研磨得到硼酸锂钠镥化合物；含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、NaNO 3、NaOH、Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含镥的化合物为Lu 2O 3、Lu(NO 3) 3·6H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼 的化合物为H 3BO 3或B 2O 3 A method for preparing the lithium sodium lutetium borate compound of claim 1, characterized in that it includes the following steps: adding sodium-containing compounds, lutetium-containing compounds, lithium-containing compounds, and boron-containing compounds according to sodium: lutetium: lithium ∶ The molar ratio of boron element is 1:1:2:2, put it evenly into the mortar, mix and grind thoroughly, then put it into the crucible, put it into the muffle furnace, raise the temperature to 400-500℃, and keep the temperature constant for 12-48 hours , cool to room temperature, take it out, grind it for the second time, put it into a muffle furnace and pass in hydrogen, then heat it up to 600-700°C, keep it constant for 12-48 hours, cool it to room temperature, take it out, grind it for the third time and put it in the furnace. Pour hydrogen into the muffle furnace, then raise it to 700-750°C, keep the temperature constant for 12-48 hours, take it out, and grind it to obtain the lithium sodium lutetium borate compound; the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , and Na 2 C 2 Any one of O 4 , NaNO 3 , NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, NaBO 2 ·4H 2 O; compounds containing lutetium are Lu 2 O 3 , Lu ( Any one of NO 3 ) 3 ·6H 2 O; the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3
  6. 一种权利要求3所述硼酸锂钠镥的稀土掺杂化合物的制备方法，其特征在于，包括如下步骤：将含钠的化合物、含镥的化合物、含稀土的化合物、含锂的化合物、含硼的化合物按照钠∶(镥+稀土)∶锂∶硼元素摩尔比为1∶1∶2∶2的比例均匀放入研钵中充分混合研磨，然后装入坩埚中，放入马弗炉中通入氢气，升温至400-500℃，恒温12-48小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中通入氢气，再升温至600-700℃，恒温12-48小时，冷却至室温，取出，经第三次研磨后放入马弗炉中通入氢气，再升700-750℃，恒温12-48小时，取出，经研磨得到硼酸锂钠钇的铈掺杂化合物；含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、NaNO 3、NaOH、Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含镥的化合物为Lu 2O 3、Lu(NO 3) 3·6H 2O中的任一种；含稀土的化合物选自CeO 2、Pr 2O 3、Pr 6O 11、Nd 2O 3、Eu 2O 3、Tb 2O 3、Tb 4O 7、Ho 2O 3、Er 2O 3、Tm 2O 3、Yb 2O 3、Ce(NO 3) 3·6H 2O、Pr(NO 3) 3·6H 2O、Nd(NO 3) 3·6H 2O、Eu(NO 3) 3·6H 2O、Tb(NO 3) 3·6H 2O、Ho(NO 3) 3·5H 2O、Ho(NO 3) 3·6H 2O、Er(NO 3) 3·6H 2O、Tm(NO 3) 3·5H 2O中的任一种，含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 A method for preparing a rare earth doped compound of lithium sodium lutetium borate according to claim 3, characterized in that it includes the following steps: adding sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, and The boron compound is evenly put into a mortar and thoroughly mixed and ground in a molar ratio of sodium: (lutetium + rare earth): lithium: boron element of 1:1:2:2, then put into a crucible and put into a muffle furnace Pour in hydrogen gas, raise the temperature to 400-500°C, keep the temperature constant for 12-48 hours, cool to room temperature, take it out, grind it for the second time and put it into a muffle furnace. Pour in hydrogen gas, then raise the temperature to 600-700°C, and keep the temperature constant for 12-48 hours. 48 hours, cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace and pass in hydrogen, then raise it to 700-750°C, keep the temperature constant for 12-48 hours, take it out, and grind it to obtain cerium-doped lithium sodium yttrium borate. Miscellaneous compounds; sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , NaNO 3 , NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, NaBO 2 ·4H Any one of 2 O; the lutetium-containing compound is any one of Lu 2 O 3 and Lu(NO 3 ) 3 ·6H 2 O; the rare earth-containing compound is selected from CeO 2 , Pr 2 O 3 , Pr 6 O 11 , Nd 2 O 3 , Eu 2 O 3 , Tb 2 O 3 , Tb 4 O 7 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Ce(NO 3 ) 3 · 6H 2 O, Pr(NO 3 ) 3 ·6H 2 O, Nd(NO 3 ) 3 ·6H 2 O, Eu(NO 3 ) 3 ·6H 2 O, Tb(NO 3 ) 3 ·6H 2 O, Ho( Any of NO 3 ) 3 ·5H 2 O, Ho(NO 3 ) 3 ·6H 2 O, Er(NO 3 ) 3 ·6H 2 O, Tm(NO 3 ) 3 ·5H 2 O, containing lithium The compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  7. 一种制备权利要求2所述硼酸锂钠镥晶体的方法，其特征在于，该方法包括以下步骤：将含钠的化合物、含镥的化合物、含锂的化合物、含硼的化合物按照钠∶镥∶锂∶硼元素摩尔比为1-3∶1∶5-8∶5-10的比例均匀混合研磨，装入坩埚中，以5-20℃/h的升温速率加热至温度800-1000℃后得到高温熔液，保温12-48h，然后以1-10℃/h的速度降至室温，得到硼酸锂钠镥晶体；其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、NaNO 3、NaF、NaOH、Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含镥的化合物为Lu 2O 3、 Lu(NO 3) 3·6H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 A method for preparing the lithium sodium lutetium borate crystal of claim 2, characterized in that the method includes the following steps: adding sodium-containing compounds, lutetium-containing compounds, lithium-containing compounds, and boron-containing compounds according to sodium: lutetium ∶ Lithium: Boron element molar ratio is 1-3: 1: 5-8: 5-10. Mix and grind evenly, put it into a crucible, and heat it to a temperature of 800-1000°C at a heating rate of 5-20°C/h. Obtain a high-temperature melt, keep it warm for 12-48h, and then lower it to room temperature at a rate of 1-10°C/h to obtain lithium sodium lutetium borate crystals; among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , and Na 2 C 2 Any one of O 4 , NaNO 3 , NaF, NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, NaBO 2 ·4H 2 O; compounds containing lutetium are Lu 2 O 3 , Any one of Lu(NO 3 ) 3 ·6H 2 O; the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  8. 根据权利要求7所述制备硼酸锂钠镥晶体的方法，其特征在于，制备硼酸锂钠镥晶体时，还加入助溶剂，助熔剂为PbO、PbO 2、PbF 2、KF或KCl中的任一种。 The method for preparing lithium sodium lutetium borate crystal according to claim 7, characterized in that when preparing lithium sodium lutetium borate crystal, a flux is also added, and the flux is any one of PbO, PbO 2 , PbF 2 , KF or KCl kind.
  9. 一种制备权利要求4所述硼酸锂钠镥稀土掺杂晶体的方法，其特征在于，该方法包括以下步骤：将含钠的化合物、含镥的化合物、含稀土的化合物、含锂的化合物、含硼的化合物按照钠∶(镥+稀土)∶锂∶硼元素摩尔比为1-3∶1∶5-8∶5-10的比例均匀混合研磨，装入坩埚中，以5-20℃/h的升温速率加热至温度800-1000℃后得到高温熔液，保温12-48h，然后以1-10℃/h的速度降至室温，得到硼酸锂钠镥稀土掺杂晶体；其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、NaNO 3、NaF、NaOH、Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含镥的化合物为Lu 2O 3、Lu(NO 3) 3·6H 2O中的任一种；含稀土的化合物选自CeO 2、Pr 2O 3、Pr 6O 11、Nd 2O 3、Eu 2O 3、Tb 2O 3、Tb 4O 7、Ho 2O 3、Er 2O 3、Tm 2O 3、Yb 2O 3、Ce(NO 3) 3·6H 2O、Pr(NO 3) 3·6H 2O、Nd(NO 3) 3·6H 2O、Eu(NO 3) 3·6H 2O、Tb(NO 3) 3·6H 2O、Ho(NO 3) 3·5H 2O、Ho(NO 3) 3·6H 2O、Er(NO 3) 3·6H 2O、Tm(NO 3) 3·5H 2O中的任一种，含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3； A method for preparing the lithium sodium borate lutetium rare earth doped crystal of claim 4, characterized in that the method includes the following steps: adding a sodium-containing compound, a lutetium-containing compound, a rare earth-containing compound, a lithium-containing compound, The boron-containing compounds are uniformly mixed and ground according to the molar ratio of sodium: (lutetium + rare earth): lithium: boron element of 1-3:1:5-8:5-10, put into a crucible, and heated at 5-20℃/ After heating to a temperature of 800-1000°C at a heating rate of h, a high-temperature melt is obtained, kept for 12-48h, and then lowered to room temperature at a rate of 1-10°C/h to obtain a lithium sodium borate lutetium rare earth doped crystal; which contains sodium The compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , NaNO 3 , NaF, NaOH, Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, NaBO 2 ·4H 2 O Any of; the lutetium-containing compound is any of Lu 2 O 3 and Lu(NO 3 ) 3 ·6H 2 O; the rare earth-containing compound is selected from CeO 2 , Pr 2 O 3 , Pr 6 O 11 , Nd 2 O 3 , Eu 2 O 3 , Tb 2 O 3 , Tb 4 O 7 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Ce(NO 3 ) 3 ·6H 2 O , Pr(NO 3 ) 3 ·6H 2 O, Nd(NO 3 ) 3 ·6H 2 O, Eu(NO 3 ) 3 ·6H 2 O, Tb(NO 3 ) 3 ·6H 2 O, Ho(NO 3 ) Any of 3 ·5H 2 O, Ho(NO 3 ) 3 ·6H 2 O, Er(NO 3 ) 3 ·6H 2 O, Tm(NO 3 ) 3 ·5H 2 O, and the lithium-containing compound is Li Any one of 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 ;
    或，该方法包括以下步骤：将含钠的化合物、含镥的化合物、含稀土的化合物、含锂的化合物、含硼的化合物按照钠∶(镥+稀土)∶锂∶硼摩尔比为1-3∶1∶2-5∶1-8的比例均匀混合研磨，装入坩埚中，再放入中频提拉炉中，通入高纯N 2/H 2/Ar气，加热至完全融化，搅拌12-24小时，熔体温度高于饱和点温度0.1-3℃时，再从生长炉内放入铂金或铱金杆，使其接触熔液表面，并保持2-12小时，再将温度以0.1-10℃/h降至饱和点温度后， 并将铂金或铱金杆的转速设置为2-25r/min，然后以0.05-10℃/h的速率缓慢降温，并以0.05-0.75mm/h的提拉速度提拉，待晶体长到一定尺寸时，将晶体提离液面拉脱，再以10-100℃/h的速率快速降至室温，最后得到硼酸锂钠镥稀土掺杂晶体；其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3中的任一种；含铈的化合物为CeO 2、Ce 2O 3、Ce(NO 3) 3·6H 2O、Ce 2(SO 4) 3·4H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH；含硼的化合物为H 3BO 3或B 2O 3。 Or, the method includes the following steps: adding a sodium-containing compound, a lutetium-containing compound, a rare earth-containing compound, a lithium-containing compound, and a boron-containing compound according to a sodium:(lutetium+rare earth):lithium:boron molar ratio of 1- Mix and grind evenly in the ratio of 3:1:2-5:1-8, put it into a crucible, and then put it into a medium frequency pulling furnace, pass in high-purity N 2 /H 2 /Ar gas, heat it until it is completely melted, and stir 12-24 hours, when the melt temperature is 0.1-3°C higher than the saturation point temperature, put a platinum or iridium rod from the growth furnace, let it contact the melt surface, and keep it for 2-12 hours, and then increase the temperature to After cooling down to the saturation point temperature at 0.1-10°C/h, set the rotation speed of the platinum or iridium rod to 2-25r/min, then slowly cool down at a rate of 0.05-10°C/h, and cool down at a rate of 0.05-0.75mm/ Pull the crystal at a pulling speed of h. When the crystal grows to a certain size, lift the crystal away from the liquid surface and then quickly drop it to room temperature at a rate of 10-100°C/h. Finally, the lithium sodium borate lutetium rare earth doped crystal is obtained. ; Among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O , any one of NaBO 2 ·4H 2 O; the yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ·6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 Any one of (SO 4 ) 3 ; the cerium-containing compound is any one of CeO 2 , Ce 2 O 3 , Ce(NO 3 ) 3 ·6H 2 O, and Ce 2 (SO 4 ) 3 ·4H 2 O species; lithium-containing compounds are Li 2 CO 3 , LiNO 3 or LiOH; boron-containing compounds are H 3 BO 3 or B 2 O 3 .
  10. 硼酸锂钠镥化合物或晶体或硼酸锂钠镥稀土掺杂化合物或晶体的用途，其特征在于，所述的硼酸锂钠镥稀土掺杂化合物或晶体作为闪烁材料用作高能射线探测材料，或用作LED照明用荧光粉；所述的硼酸锂钠镥化合物或晶体作为光学透镜或光学棱镜材料。The use of lithium sodium lutetium borate compounds or crystals or lithium sodium lutetium borate rare earth doped compounds or crystals, characterized in that the lithium sodium sodium lutetium borate rare earth doped compounds or crystals are used as scintillation materials as high-energy ray detection materials, or as Used as phosphor for LED lighting; the lithium sodium lutetium borate compound or crystal can be used as optical lens or optical prism material.
PCT/CN2023/070436 2022-08-05 2023-01-04 Lithium sodium lutetium borate, rare earth doped compound and crystal thereof, preparation method therefor, and use thereof WO2024027106A1 (en)

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