CN115367766A - Lithium sodium lutetium borate, rare earth doped compound and crystal thereof, and preparation method and application thereof - Google Patents

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

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CN115367766A
CN115367766A CN202210938320.6A CN202210938320A CN115367766A CN 115367766 A CN115367766 A CN 115367766A CN 202210938320 A CN202210938320 A CN 202210938320A CN 115367766 A CN115367766 A CN 115367766A
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lutetium
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CN115367766B (en
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陈鹏允
林利添
杨鸣名
匡猛
倪海勇
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Institute of Resource Utilization and Rare Earth Development of Guangdong Academy of Sciences
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Abstract

The invention discloses a novel lithium sodium lutetium borate, a rare earth doped compound or crystal thereof and a preparation method thereof, wherein the chemical formula of the lithium sodium lutetium borate is Li 2 NaLuB 2 O 6 The general formula of the rare earth doped compound of lithium sodium lutetium borate is Li 2 NaLu 1‑x RE x B 2 O 6 Wherein x is more than 0 and less than or equal to 0.5, RE is rare earth element, is cheap and easy to obtain, is simple and convenient to synthesize, has stable physicochemical properties, has good scintillation and fluorescence properties of the rare earth doped compound of lithium sodium lutetium borate, can be used as a scintillation material or as fluorescent powder for LED illumination, and has important economic and scientific research values in the fields of nuclear medicine imaging, high-energy physical particle detection, light illumination and the like。

Description

Lithium sodium lutetium borate, rare earth doped compound and crystal thereof, and preparation method and application thereof
The technical field is as follows:
the invention relates to the technical field of scintillating materials, in particular to lithium borate sodium lutetium, a rare earth doped compound and a crystal thereof, and a preparation method and application thereof.
The background art comprises the following steps:
the scintillation crystal is an object capable of emitting pulsed light under the action of high-energy particles or rays (such as X-rays and gamma rays), and is widely used in the fields of high-energy physics, nuclear physics, space physics, nuclear medicine, geological exploration, safety inspection, national defense industry and the like. The PET/CT nuclear medicine imaging technology of high-end medical equipment is an important way for carrying out accurate disease diagnosis in modern medicine. At present, the method is widely applied to the fields of early diagnosis of tumors, nervous system diseases and cardiovascular and cerebrovascular diseases, pathological research of diseases, evaluation of tumor treatment effects, research and development of medicines and the like in clinic.
At present, the rare earth scintillation crystal material is a core component of high-end medical equipment imaging, and is a core key material influencing the resolution and image quality of PET/CT imaging. In recent years, third generation PET, especially for multi-modality imaging systems based on depth and time of flight (TOF) capabilities, has placed higher technical demands on high blocking capability, high spatial resolution and energy resolution of scintillating crystals. Existing rare earth scintillation crystal materials, e.g. (Lu, Y) 2 SiO 5 :Ce 3+ 、LaBr 3 :Ce 3+ And the like have various excellent performances such as high light yield, fast attenuation, high energy resolution and the like, and are considered to be scintillation crystal materials which are relatively suitable for TOF-PET systems in the field of nuclear medicine imaging. However, (Lu, Y) 2 SiO 5 :Ce 3+ The melting point of the crystal is extremely high (2050-2100 ℃), which has severe requirements on the heat resistance of crystal growth equipment, and the crystal growth needs to use an expensive iraurita crucible, which greatly increases the cost and the period of the crystal growth. And for LaBr 3 :Ce 3+ Since there are problems of easy deliquescence and expensive raw materials, there is a need to search for a new scintillator material with a low melting point and stable physicochemical propertiesAnd (5) feeding.
The invention content is as follows:
the invention aims to provide lithium sodium lutetium borate, a rare earth doped compound and crystal thereof, a preparation method and application thereof, and the lithium sodium lutetium borate, the rare earth doped compound and crystal thereof are easy to prepare, stable in physicochemical property, difficult to deliquesce in air and good in scintillation/fluorescence performance, and are expected to be used as scintillation materials and fluorescent powder for LEDs.
The invention is realized by the following technical scheme:
lithium sodium lutetium borate compound with the chemical formula of Li 2 NaLuB 2 O 6 。
Lithium sodium lutetium borate crystal with the chemical formula of Li 2 NaLuB 2 O 6 Belongs to the monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003784389600000021
Figure BDA0003784389600000022
α＝90°，β＝102.729°，γ＝90°，
Figure BDA0003784389600000023
Z＝4。
The rare earth doped compound of lithium sodium lutetium borate has the chemical general formula of Li 2 NaLu 1 -xRE x B 2 O 6 Wherein x is more than 0 and less than or equal to 0.5, RE is a rare earth element selected from one or more of Ce, pr, nd, eu, tb, ho, er, tm and Yb.
The chemical general formula of the rare earth doped crystal of lithium sodium lutetium borate is Li 2 NaLu 1-x RE x B 2 O 6 Wherein x is more than 0 and less than or equal to 0.5, RE is a rare earth element selected from one or more of Ce, pr, nd, eu, tb, ho, er, tm and Yb, and belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameters in the range of
Figure BDA0003784389600000024
α＝90°，β＝102.729-103.889°，γ＝90°，
Figure BDA0003784389600000025
Z＝4。
The three-dimensional space structure is based on NaO 8 Dodecahedral, isolated BO 3 Planar triangular, liO 4 Tetrahedron sum (Lu) 1- x RE x )O 7 (x is more than 0 and less than or equal to 0.5) the pentagonal bipyramids are mutually linked, and RE is one or more of Ce, pr, nd, eu, tb, ho, er, tm and Yb of rare earth elements. Wherein, naO 8 The dodecahedrons are connected with each other at the same side and point to form a one-dimensional Na-O zigzag chain (Lu) 1-x RE x )O 7 The pentagonal bipyramids are connected in pairs to form (Lu) 1-x RE x ) 2 O 12 Dimer, (Lu) 1-x RE x ) 2 O 12 Dimer and Na-Ozigzag chain and BO 3 The plane triangle forms the main skeleton of the crystal structure, and two crystallographically independent LiO 4 Formation of tetrahedral common edge junctions [ LiO 2 ]One-dimensional chain along [010]The direction runs through the framework of the crystal.
The invention also provides a preparation method of the lithium borate sodium lutetium compound, which comprises the following steps:
mixing a sodium-containing compound, a lutetium-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: lutetium: lithium: the molar ratio of boron elements is 1:1:2:2, then placing the mixture into a crucible, placing the crucible into a muffle furnace, heating to 400-500 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, placing the muffle furnace into which hydrogen is introduced after the second grinding, heating to 600-700 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, placing the muffle furnace into which hydrogen is introduced after the third grinding, heating to 700-750 ℃, keeping the temperature for 12-48 hours, taking out, and grinding to obtain the lithium sodium lutetium borate compound. Wherein the sodium-containing compound is 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 Lu 2 O 3 、Lu(NO 3 ) 3 ·6H 2 Any one of O; the lithium-containing compound being Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound is H 3 BO 3 Or B 2 O 3 。
The invention also discloses a preparation method of the rare earth doped compound of lithium sodium lutetium borate, which comprises the following steps:
mixing a sodium-containing compound, a lutetium-containing compound, a rare earth-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: (lutetium + rare earth): lithium: the molar ratio of boron elements is 1:1:2:2, then placing the mixture into a crucible, placing the mixture into a muffle furnace, introducing hydrogen, heating to 400-500 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out the mixture, placing the mixture into the muffle furnace after the second grinding, introducing hydrogen, heating to 600-700 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out the mixture, placing the mixture into the muffle furnace after the third grinding, introducing hydrogen, heating to 700-750 ℃, keeping the temperature for 12-48 hours, taking out the mixture, and grinding the mixture to obtain the cerium doped compound of lithium sodium yttrium borate.
Wherein the sodium-containing compound is 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 Lu 2 O 3 、Lu(NO 3 ) 3 ·6H 2 Any one of O; the rare earth-containing compound being 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 Any of O, the lithium-containing compound being Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound is H 3 BO 3 Or B 2 O 3 。
A method of preparing lithium sodium lutetium borate crystals, the method comprising the steps of: mixing a sodium-containing compound, a lutetium-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: lutetium: lithium: the molar ratio of boron elements is 1-3:1:5-8:5-10, placing the mixture into a crucible, heating the mixture to 800-1000 ℃ at a heating rate of 5-20 ℃/h to obtain high-temperature melt, preserving the heat for 12-48h, and then cooling the melt to room temperature at a speed of 1-10 ℃/h to obtain the lithium sodium lutetium borate crystal. Wherein the sodium-containing compound is 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 Any one of O; the lutetium-containing compound is Lu 2 O 3 、Lu(NO 3 ) 3 ·6H 2 Any one of O; the lithium-containing compound being Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound is H 3 BO 3 Or B 2 O 3 。
Particularly, when the lithium borate sodium lutetium crystal is prepared, a cosolvent is also added, and the fluxing agents are PbO and PbO 2 、PbF 2 Any one of KF and KCl.
A method for preparing lithium sodium lutetium rare earth borate doped crystal comprises the following steps: mixing a sodium-containing compound, a lutetium-containing compound, a rare earth-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: (lutetium + rare earth): lithium: the molar ratio of boron elements is 1-3:1:5-8:5-10, mixing and grinding, and placing into a crucibleHeating to 800-1000 ℃ at a heating rate of 5-20 ℃/h to obtain high-temperature melt, preserving heat for 12-48h, and then cooling to room temperature at a speed of 1-10 ℃/h to obtain the lithium sodium lutetium rare earth doped crystal. Wherein the sodium-containing compound is 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 Any one of O; the lutetium-containing compound is Lu 2 O 3 、Lu(NO 3 ) 3 ·6H 2 Any one of O; the compound containing rare earth 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 Any of O, the lithium-containing compound being Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound is H 3 BO 3 Or B 2 O 3 。
Specifically, lithium sodium lutetium rare earth doped crystal is prepared, a cosolvent is also added, and a sodium-containing compound, a lutetium-containing compound, a rare earth-containing compound, a lithium-containing compound, a boron-containing compound and the cosolvent are mixed according to the weight ratio of sodium: (lutetium + rare earth): the mass ratio of lithium to boron to flux is 1-3:1:2-3:2-5:1-10, mixing and grinding, placing into a crucible, heating to 800-1000 deg.C at a heating rate of 5-50 deg.C/h to obtain high temperature solution, maintaining for 12-48h, and mixingCooling to room temperature at the speed of 1-20 ℃/h to obtain the lithium sodium lutetium borate and the rare earth doped crystal thereof. The fluxing agent is PbO or PbO 2 、PbF 2 KF or KCl.
A method for preparing lithium sodium lutetium rare earth metal doped crystals, which comprises the following steps: mixing a sodium-containing compound, a lutetium-containing compound, a rare earth-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: (lutetium + rare earth): lithium: the molar ratio of boron is 1-3:1:2-5:1-8, placing the mixture into a crucible, placing the crucible into a medium-frequency pulling furnace, and introducing high-purity N 2 /H 2 Heating to completely melt the/Ar gas, stirring for 12-24 hours, when the temperature of the melt is 0.1-3 ℃ higher than the temperature of the saturation point, putting a platinum or iridium rod from the growth furnace, enabling the platinum or iridium rod to contact the surface of the melt, keeping the temperature for 2-12 hours, reducing the temperature to the temperature of the saturation point at 0.1-10 ℃/h, setting the rotating speed of the platinum or iridium rod to be 2-25r/min, then slowly reducing the temperature at the speed of 0.05-10 ℃/h, pulling at the pulling speed of 0.05-0.75mm/h, when the crystal grows to a certain size, pulling the crystal off the liquid level, and quickly reducing the temperature to the room temperature at the speed of 10-100 ℃/h to finally obtain the lithium sodium lutetium rare earth doped crystal. Wherein the sodium-containing compound is 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、NaBO 2 ·4H 2 Any one of O; the yttrium-containing compound being Y 2 O 3 、Y(NO 3 ) 3 ·6H 2 O、Y(OH) 3 、Y 2 (CO 3 ) 3 、Y 2 (SO 4 ) 3 Any one of (a); the compound containing cerium being CeO 2 、Ce 2 O 3 、Ce(NO 3 ) 3 ·6H 2 O、Ce 2 (SO 4 ) 3 Any of 4H 2O; the lithium-containing compound being Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound is H 3 BO 3 Or B 2 O 3 。
The invention also protects the application of the lithium sodium lutetium borate compound or crystal or the lithium sodium lutetium rare earth borate doped compound or crystal, and the lithium sodium lutetium rare earth borate doped compound or crystal is used as a scintillation material as a high-energy ray detection material or as an optical function material such as fluorescent powder for LED illumination; the lithium sodium lutetium borate compound or crystal is used as an optical lens material or an optical prism material for a large-aperture wide-field photographic objective lens, a long-focal-length zoom lens, a high-power microscope and the like.
The invention has the following beneficial effects: the invention provides a novel lithium sodium lutetium borate, a rare earth doped compound or crystal thereof and a preparation method thereof, wherein the novel lithium sodium lutetium borate, the rare earth doped compound or crystal thereof is cheap and easy to obtain, simple and convenient to synthesize and stable in physicochemical property, and the lithium sodium lutetium rare earth doped compound or crystal has good scintillation and fluorescence properties, can be used as a scintillation material for detecting high-energy particles such as X rays and the like, or used as fluorescent powder for LED illumination, and has important economic and scientific research values in the fields of nuclear medicine imaging, high-energy physical particle detection, illumination and the like; the lithium sodium lutetium borate compound or crystal is used as an optical lens material or an optical prism material for a large-aperture wide-field photographic objective lens, a long-focal-length zoom lens, a high-power microscope and the like.
Description of the drawings:
FIG. 1 shows lithium sodium lutetium Li borate prepared in example 7 of the present invention 2 NaLu(BO 3 ) 2 A schematic crystal structure of a single crystal along the b-axis and c-axis;
FIG. 2 is lithium sodium lutetium Li borate prepared in example 7 of the present invention 2 NaLu(BO 3 ) 2 The dispersive refractive index of a single crystal;
FIG. 3 shows lithium sodium lutetium Li borate prepared in example 1 of the present invention 2 NaLu(BO 3 ) 2 (ii) a diffuse reflectance spectrum of the compound;
FIG. 4 is Li of the present invention 2 NaLu(BO 3 ) 2 Powder XRD diffractogram of compound;
FIG. 5 is Li 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 Powder XRD diffractogram of compound;
FIG. 6 is Li 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 Powder XRD diffractogram of compound;
FIG. 7 is Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 The scintillation properties of the crystal;
FIG. 8 is Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 Fluorescence emission spectra of the crystals;
FIG. 9 is Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 Fluorescence emission spectra of the compounds;
FIG. 10 is Li 2 NaLu 0.8 Tb 0.4 (BO 3 ) 2 Fluorescence emission spectra of the compounds;
FIG. 11 is Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 Crystals, li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 Compound, li 2 NaLu 0.8 Tb 0.4 (BO 3 ) 2 CIE chromaticity coordinates of the compounds.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1: synthesis of lithium sodium borate lutetium compound Li 2 NaLu(BO 3 ) 2 Compound (I)
Raw materials used (analytical purity): lu (Lu) 2 O 3 0.05mol、H 3 BO 3 0.2mol、Na 2 CO 3 0.05mol、Li 2 CO 3 0.05mol. The method comprises the following specific steps: weighing the above raw materials, placing into an agate mortar, carefully mixing and grinding, and then filling into a container
Figure BDA0003784389600000071
Putting the corundum crucible into a muffle furnace, heating to 500 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, putting the corundum crucible into the muffle furnace after the second grinding, heating to 600 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, putting the corundum crucible into the muffle furnace after the third grindingRaising the temperature to 700 ℃, keeping the temperature for 24 hours, taking out, and grinding to obtain the lithium sodium lutetium Li borate 2 NaLu(BO 3 ) 2 A compound is provided.
Example 2: 0.5% cerium doped Li for synthesizing lithium sodium lutetium borate 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 Compound (I)
Raw materials used (analytical purity): lu (light emitting diode) 2 O 3 0.04975mol、CeO 2 0.0005mol、H 3 BO 3 0.2mol、Na 2 CO 3 0.05mol、Li 2 CO 3 0.1mol。
The method comprises the following specific steps: weighing the above raw materials, placing into an agate mortar, carefully mixing and grinding, and then filling into a container
Figure BDA0003784389600000072
Putting the corundum crucible with the diameter of mm multiplied by 10mm into a tubular furnace, introducing hydrogen atmosphere, heating to 450 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the second time, putting the corundum crucible into a muffle furnace, introducing hydrogen atmosphere, heating to 630 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the third time, putting the corundum crucible into the muffle furnace, introducing hydrogen atmosphere, heating to 730 ℃, keeping the temperature for 24 hours, taking out, and grinding to obtain the Li 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 A compound is provided.
Example 3: 30% neodymium-doped Li for synthesizing lithium sodium lutetium borate 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 Compound (I)
Raw materials used (analytical purity): 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。
The method comprises the following specific steps: weighing the above raw materials, placing into an agate mortar, carefully mixing and grinding, and then filling into a container
Figure BDA0003784389600000081
In a platinum crucible with mm multiplied by 15mm,putting the mixture into a muffle furnace, heating to 500 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the second time, putting the mixture into the muffle furnace, heating to 680 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the third time, putting the mixture into the muffle furnace, heating to 730 ℃, keeping the temperature for 24 hours, taking out, and grinding to obtain the Li of the invention 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 A compound is provided.
Example 4: 20% europium-doped Li for synthesizing lithium sodium lutetium borate 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 Compound (I)
Raw materials used (analytical pure): lu (Lu) 2 O 3 0.004mol、Eu 2 O 3 0.001mol、B 2 O 3 0.01mol、NaHCO 3 0.01mol、Li 2 CO 3 0.01mol。
The method comprises the following specific steps: weighing the above raw materials, placing into an agate mortar, carefully mixing and grinding, and then filling into a container
Figure BDA0003784389600000082
Putting a platinum crucible with the size of mm multiplied by 15mm into a muffle furnace, heating to 480 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, putting the crucible into the muffle furnace after the second grinding, heating to 660 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, putting the crucible into the muffle furnace after the third grinding, heating to 750 ℃, keeping the temperature for 24 hours, taking out, and grinding to obtain the europium-doped Li of the invention 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 Compound (I)
Example 5: 40% terbium-doped Li for synthesizing lithium sodium lutetium borate 2 NaLu 0.6 Tb 0.4 (BO 3 ) 2 Compound (I)
Raw materials used (analytical purity): lu (light emitting diode) 2 O 3 0.009mol、Tb 4 O 7 0.003mol、B 2 O 3 0.03mol、NaHCO 3 0.03mol、Li 2 CO 3 0.03mol。
The method comprises the following specific steps: the raw materials are weighed and then put into an agate mortar for careful mixing and grinding,then is filled in
Figure BDA0003784389600000091
Putting a platinum crucible with the diameter of mm multiplied by 15mm into a muffle furnace, heating to 500 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, putting the crucible furnace after the second grinding, heating to 650 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, putting the crucible furnace after the third grinding, heating to 730 ℃, keeping the temperature for 24 hours, taking out, and grinding to obtain the Li of the invention 2 NaLu 0.6 Tb 0.4 (BO 3 ) 2 A compound is provided.
Example 6: 50% ytterbium doped Li for synthesizing lithium sodium lutetium borate 2 NaLu 0.5 Yb 0.5 (BO 3 ) 2 Compound (I)
Raw materials used (analytical purity): 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。
The method comprises the following specific steps: weighing the above raw materials, placing into an agate mortar, carefully mixing, grinding, and filling into a container
Figure BDA0003784389600000092
Figure BDA0003784389600000093
Putting the corundum crucible into a muffle furnace, heating to 480 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, putting the corundum crucible into the muffle furnace after the second grinding, heating to 660 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, putting the corundum crucible into the muffle furnace after the third grinding, heating to 750 ℃, keeping the temperature for 24 hours, taking out, and grinding to obtain the Li of the invention 2 NaLu 0.5 Yb 0.5 (BO 3 ) 2 A compound is provided.
Example 7: preparation of lithium sodium lutetium Li borate by self-help solvent method 2 NaLu(BO 3 ) 2 Raw materials for crystals (analytical pure): na (Na) 2 CO 3 0.015mol、Lu 2 O 3 0.005mol、Li 2 CO 3 0.04mol、H 3 BO 3 0.1mol。
The method comprises the following specific steps: weighing the above raw materials, mixing and grinding in mortar, and packaging
Figure BDA0003784389600000094
Putting the platinum crucible into a molten salt furnace, heating the platinum crucible to 950 ℃ at a speed of 20 ℃/h for completely melting the raw materials, preserving the heat for 12 hours, and then slowly cooling the platinum crucible at a speed of 2 ℃/hour to obtain the platinum crucible with the size of 0.37 multiplied by 0.32 multiplied by 0.16mm 3 Li of (2) 2 NaLu(BO 3 ) 2 And (4) crystals.
Example 8: 20% neodymium-doped Li for preparing lithium sodium lutetium borate by self-help solvent method 2 NaLu 0.8 Nd 0.2 (BO 3 ) 2 Crystal
Raw materials used (analytical pure): na (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。
The method comprises the following specific steps: weighing the above raw materials, mixing and grinding in mortar, and packaging
Figure BDA0003784389600000101
Putting the platinum crucible into a molten salt furnace, heating to 965 ℃ at a rate of 10 ℃/h to completely melt the raw materials, preserving the heat for 36 hours, and then slowly cooling at a rate of 5 ℃/hour to obtain the product with the size of 0.25 multiplied by 0.2 multiplied by 0.13mm 3 Li of (2) 2 NaLu 0.8 Nd 0.2 (BO 3 ) 2 And (4) crystals.
Example 9: 35% thulium doped Li of lithium sodium lutetium borate prepared by self-help solvent method 2 NaLu 0.65 Tm 0.35 (BO 3 ) 2 Crystal
Raw materials used (analytical purity): naHCO 2 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
The method comprises the following specific steps: weighing the above raw materials, mixing and grinding in mortar, and packaging
Figure BDA0003784389600000102
Putting the platinum crucible into a molten salt furnace, heating the platinum crucible to 980 ℃ at a speed of 15 ℃/h to completely melt the raw material, preserving the heat for 12 hours, and then slowly cooling the platinum crucible at a speed of 5 ℃/hour to obtain the platinum crucible with the size of 0.17 multiplied by 0.13 multiplied by 0.1mm 3 Li of (2) 2 NaLu 0.65 Tm 0.35 (BO 3 ) 2 And (4) crystals.
Example 10: method for preparing lithium sodium lutetium Li borate by cosolvent method 2 NaLu(BO 3 ) 2 Crystal
Raw materials used (analytical purity): naHCO 2 3 0.1mol、Lu 2 O 3 0.05mol、Li 2 CO 3 0.2mol、H 3 BO 3 0.2mol、PbO 0.5mol。
The method comprises the following specific steps: weighing the above raw materials, mixing and grinding in mortar, and packaging
Figure BDA0003784389600000103
Placing into a muffle furnace, heating at 5 deg.C/h to 900 deg.C for completely melting raw materials, maintaining for 12 hr, and slowly cooling at 3 deg.C/hr to obtain a product with size of 0.52 × 0.37 × 0.12mm 3 Li of (2) 2 NaLu(BO 3 ) 2 And (4) crystals.
Example 11: 10% cerium doped Li for preparing lithium sodium lutetium borate by cosolvent method 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 Crystal
Raw materials used (analytical purity): naNO 3 1.5mol、Lu 2 O 3 0.45mol、CeO 2 ·0.1mol、LiOH 2.5mol、H 3 BO 3 3.0mol、PbF 2 10mol。
The method comprises the following specific steps: weighing the above raw materials, mixing and grinding in mortar, and packaging
Figure BDA0003784389600000111
GoldPutting the crucible into a muffle furnace, heating to 950 ℃ at a speed of 5 ℃/h for completely melting the raw materials, preserving the heat for 12 hours, and then slowly cooling at a speed of 2 ℃/h to obtain the product with the thickness of 0.27 multiplied by 0.16 multiplied by 0.11mm 3 Li of (2) 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 And (4) crystals.
Example 12: 15% praseodymium-doped Li for preparing lithium sodium lutetium borate by cosolvent method 2 NaLu 0.85 Pr 0.15 (BO 3 ) 2 Crystal
Raw materials used (analytical purity): na (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。
The method comprises the following specific steps: weighing the above raw materials, mixing and grinding in mortar, and packaging
Figure BDA0003784389600000112
Putting the platinum crucible into a muffle furnace, heating to 1000 ℃ at a speed of 25 ℃/h for completely melting the raw materials, preserving the heat for 12 hours, and then slowly cooling at a speed of 2 ℃/hour to obtain the product with the thickness of 0.57 multiplied by 0.46 multiplied by 0.21mm 3 Li of (2) 2 NaLu 0.85 Pr 0.15 (BO 3 ) 2 And (4) crystals.
Example 13: 10% cerium-doped Li for preparing lithium sodium lutetium borate by pulling method 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 Crystal
Raw materials used (analytical pure): naBO 2 4H 2 O 1.0mol、Lu 2 O 3 0.45mol、CeO 2 ·0.1mol、Li 2 CO 3 0.4mol、H 3 BO 3 1.0mol。
The method comprises the following specific steps: weighing the above raw materials, mixing and grinding in mortar, and packaging
Figure BDA0003784389600000113
Putting the platinum crucible into a medium-frequency pulling furnace, and introducing high-purity N 2 /H 2 Mixed gas, addHeating to completely melt, stirring for 24 hours, when the melt temperature is higher than the saturation point temperature by 0.5 ℃, putting a platinum rod from the growth furnace to contact the surface of the melt, keeping the temperature for 2 hours, reducing the temperature to the saturation point temperature at 0.25 ℃/h, setting the rotating speed of the platinum rod to be 10r/min, then slowly reducing the temperature at 0.05 ℃/h, pulling at a pulling speed of 0.1mm/h, pulling the crystal off the liquid level when the crystal grows to a certain size, and finally quickly reducing the temperature to room temperature at a speed of 50 ℃/h to obtain the crystal with the size of 5.2 multiplied by 4.3 multiplied by 1.7mm 3 Li of (2) 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 And (4) crystals.
Example 14: 30 percent holmium-doped Li for preparing lithium sodium lutetium borate by pulling method 2 NaLu 0.7 Ho 0.3 (BO 3 ) 2 Crystal
Raw materials used (analytical purity): na (Na) 2 CO 3 0.5mol、Lu 2 O 3 0.35mol、Ho 2 O 3 ·0.15mol、Li 2 CO 3 0.4mol、B 2 O 3 0.5mol。
The method comprises the following specific steps: weighing the above raw materials, mixing and grinding in mortar, and packaging
Figure BDA0003784389600000121
Putting the platinum crucible into a medium-frequency pulling furnace, and introducing high-purity N 2 Heating to completely melt, stirring for 16 hours, when the melt temperature is higher than the saturation point temperature by 1.5 ℃, putting a platinum rod from the growth furnace to contact the surface of the melt, keeping the temperature for 2 hours, reducing the temperature to the saturation point temperature at 0.75 ℃/h, setting the rotating speed of the platinum rod to be 15r/min, then slowly reducing the temperature at 0.55 ℃/h, pulling at a pulling speed of 0.3mm/h, pulling the crystal off the liquid level when the crystal grows to a certain size, and finally quickly reducing the temperature to the room temperature at a speed of 30 ℃/h to obtain the crystal with the size of 5.3 multiplied by 3.3 multiplied by 2.2mm 3 Li of (2) 2 NaLu 0.7 Ho 0.3 (BO 3 ) 2 And (4) crystals.
Example 15: 5 percent erbium-doped Li for preparing lithium sodium lutetium borate by pulling method 2 NaLu 0.95 Er 0.05 (BO 3 ) 2 Crystal
Raw materials used (analytical purity): 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 method comprises the following specific steps: weighing the above raw materials, mixing and grinding in mortar, and packaging
Figure BDA0003784389600000122
Putting the platinum crucible into an intermediate frequency pulling furnace, introducing high-purity Ar gas, heating to completely melt the platinum crucible, stirring for 18 hours, when the temperature of a melt is 2.5 ℃ higher than the saturation point, putting a platinum rod into the growth furnace to contact the surface of the melt, keeping the temperature for 2 hours, reducing the temperature to the saturation point at 1.25 ℃/h, setting the rotating speed of the platinum rod to 15r/min, slowly reducing the temperature at the speed of 0.55 ℃/h, pulling at the pulling speed of 0.5mm/h, pulling the crystal away from the liquid level when the crystal grows to a certain size, and finally quickly reducing the temperature to the room temperature at the speed of 70 ℃/h to obtain the crystal with the size of 2.3 multiplied by 1.6 multiplied by 1.2mm 3 Li of (2) 2 NaLu 0.95 Er 0.05 (BO 3 ) 2 And (4) crystals.
Example 16: lithium sodium lutetium borate and characteristic test of rare earth doped compound and crystal thereof
The lithium sodium lutetium Li borate prepared in the embodiment 7 of the invention 2 NaLu(BO 3 ) 2 The single crystal is subjected to cell structure determination by an X-ray single crystal diffraction method, the cell structure is shown in figure 1 and can be obtained from figure 1, and the lithium sodium lutetium borate crystal Li 2 NaLu(BO 3 ) 2 Belongs to the monoclinic system, and the space group is P2 1 The unit cell parameters are:
Figure BDA0003784389600000131
α＝90°，β＝102.729°，γ＝90°，
Figure BDA0003784389600000132
Z＝4。
20 percent of neodymium-doped Li of the lithium sodium lutetium borate prepared in the embodiment 8 of the invention 2 NaLu 0.8 Nd 0.2 (BO 3 ) 2 The crystal cell structure of the single crystal is determined by X-ray single crystal diffraction method, and Li is measured 2 NaLu 0.8 Nd 0.2 (BO 3 ) 2 The crystal belongs to monoclinic system, and the space group is P2 1 The unit cell parameters are:
Figure BDA0003784389600000133
α＝90°，β＝102.957°，γ＝90°，
Figure BDA0003784389600000134
Figure BDA0003784389600000135
Z＝4。
lithium sodium lutetium Li borate prepared in example 7 of the invention 2 NaLu(BO 3 ) 2 The single crystal passed the dispersion refractive index test, and the result is shown in fig. 2, and it has better refractive index and lower dispersion in the test range, proving that it has the use of optical prism material.
Lithium sodium lutetium Li borate prepared in the embodiment 1 of the invention 2 NaLu(BO 3 ) 2 The result of the diffuse reflection test of the compound is shown in figure 3, and the compound has better transmission performance in the range of 400-800nm and can be used as an optical material.
Li prepared in the examples 1, 2 and 3 of the present invention 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 After the compound is carefully ground, an X-ray powder diffractometer is used for carrying out normal-temperature XRD test, as shown in figures 4-6, the result shows that the prepared compound belongs to a pure phase and no other impure phases are generated.
Li prepared in inventive example 11 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 The crystal, excited by X-ray (Ag target), has a scintillation spectrum shown in FIG. 7, li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 The scintillation detection performance of the material is obviously superior to that of Bi under the same test conditions 4 Ge 3 O 12 (BGO) reference crystals, proving Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 Has good use value.
Li prepared in inventive example 13 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 The crystal, after being carefully grinded, emits characteristic blue light under the excitation of ultraviolet light, the fluorescence emission spectrum of the crystal is shown in figure 8, the CIE chromaticity coordinates (0.157, 0.154 and 0.690) of the crystal are marked in figure 11, and the blue fluorescent powder for the LED has good use value.
Li prepared in inventive example 4 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 The compound, after being carefully ground, emits characteristic red light under the excitation of ultraviolet or visible light, the fluorescence emission spectrum of the compound is shown in figure 9, the CIE chromaticity coordinates (0.615, 0.384 and 0.001) of the compound are marked in figure 11, and the red fluorescent powder for the LED has good use value.
Li prepared in inventive example 5 2 NaLu 0.6 Tb 0.4 (BO 3 ) 2 The compound, after being carefully ground, emits characteristic green light under the excitation of ultraviolet light, the fluorescence emission spectrum of the compound is shown in figure 10, the CIE chromaticity coordinates (0.345, 0.535 and 0.121) of the compound are marked in figure 11, and the green fluorescent powder for the LED has good use value.

Claims (10)

1. Has a chemical formula of Li 2 NaLuB 2 O 6 The lithium sodium borate lutetium compound of (1).
2. Lithium sodium lutetium borate crystal is characterized in that the chemical formula is Li 2 NaLuB 2 O 6 Monoclinic system, space group is P2 1 N, cell parameter of
Figure FDA0003784389590000011
α＝90°，β＝102.729°，γ＝90°，
Figure FDA0003784389590000012
Figure FDA0003784389590000013
Z＝4。
3. The rare earth doped compound of lithium sodium lutetium borate is characterized in that the chemical general formula is Li 2 NaLu 1-x RE x B 2 O 6 Wherein x is more than 0 and less than or equal to 0.5, RE is a rare earth element selected from one or more of Ce, pr, nd, eu, tb, ho, er, tm and Yb.
4. The rare earth doped crystal of lithium sodium lutetium borate is characterized in that the chemical general formula is Li 2 NaLu 1-x RE x B 2 O 6 Wherein x is more than 0 and less than or equal to 0.5, RE is a rare earth element selected from one or more of Ce, pr, nd, eu, tb, ho, er, tm and Yb, and belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameters in the range of
Figure FDA0003784389590000014
Figure FDA0003784389590000015
α＝90°，β＝102.729-103.889°，γ＝90°，
Figure FDA0003784389590000016
Z＝4。
5. A method of preparing the lithium sodium lutetium borate compound of claim 1, comprising the steps of: mixing a sodium-containing compound, a lutetium-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: lutetium: lithium: the molar ratio of boron elements is 1:1:2:2, then placing the mixture into a crucible, placing the crucible into a muffle furnace, heating to 400-500 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, and passing through a second furnaceAfter the secondary grinding, putting the mixture into a muffle furnace, introducing hydrogen, heating to 600-700 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, grinding for the third time, putting the mixture into the muffle furnace, introducing hydrogen, heating to 700-750 ℃, keeping the temperature for 12-48 hours, taking out, and grinding to obtain a lithium sodium lutetium borate compound; the sodium-containing compound is 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 Lu 2 O 3 、Lu(NO 3 ) 3 ·6H 2 Any one of O; the lithium-containing compound being Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound is H 3 BO 3 Or B 2 O 3 。
6. A method for preparing a rare earth doped compound of lithium sodium lutetium borate of claim 3, comprising the steps of: mixing a sodium-containing compound, a lutetium-containing compound, a rare earth-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: (lutetium + rare earth): lithium: the molar ratio of boron elements is 1:1:2:2, uniformly putting the mixture into a mortar for fully mixing and grinding, then putting the mixture into a crucible, putting the mixture into a muffle furnace, introducing hydrogen, heating to 400-500 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, putting the mixture into the muffle furnace after secondary grinding, introducing hydrogen, heating to 600-700 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, putting the mixture into the muffle furnace after third grinding, introducing hydrogen, heating to 700-750 ℃, keeping the temperature for 12-48 hours, taking out, and grinding to obtain a cerium doped compound of lithium sodium yttrium borate; the sodium-containing compound is 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 Lu 2 O 3 、Lu(NO 3 ) 3 ·6H 2 Any one of O; the rare earth-containing compound being 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 Any of O, the lithium-containing compound being Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound is H 3 BO 3 Or B 2 O 3 。
7. A method of preparing the lithium sodium lutetium borate crystal of claim 2, comprising the steps of: mixing a sodium-containing compound, a lutetium-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: lutetium: lithium: the molar ratio of boron elements is 1-3:1:5-8:5-10, uniformly mixing and grinding, putting into a crucible, heating to 800-1000 ℃ at a heating rate of 5-20 ℃/h to obtain high-temperature melt, keeping the temperature for 12-48h, and cooling to room temperature at a speed of 1-10 ℃/h to obtain lithium sodium lutetium borate crystals; wherein the sodium-containing compound is 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 Any one of O; the lutetium-containing compound is Lu 2 O 3 、Lu(NO 3 ) 3 ·6H 2 Any one of O; lithium-containing compoundIs Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound is H 3 BO 3 Or B 2 O 3 。
8. The method for preparing lithium sodium lutetium borate crystals as claimed in claim 7, wherein a cosolvent comprising PbO and PbO is added during the preparation of lithium sodium lutetium borate crystals 2 、PbF 2 KF or KCl.
9. A method of making the lithium sodium lutetium rare earth borate doped crystal of claim 4, comprising the steps of: mixing a sodium-containing compound, a lutetium-containing compound, a rare earth-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: (lutetium + rare earth): lithium: the molar ratio of boron elements is 1-3:1:5-8:5-10, uniformly mixing and grinding, putting into a crucible, heating to 800-1000 ℃ at a heating rate of 5-20 ℃/h to obtain high-temperature melt, keeping the temperature for 12-48h, and cooling to room temperature at a speed of 1-10 ℃/h to obtain lithium sodium lutetium borate rare earth doped crystal; wherein the sodium-containing compound is 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 Any one of O; the lutetium-containing compound is Lu 2 O 3 、Lu(NO 3 ) 3 ·6H 2 Any one of O; the rare earth-containing compound being 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 Any of O, the lithium-containing compound being Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound is H 3 BO 3 Or B 2 O 3 ；
Or, the method comprises the steps of: mixing a sodium-containing compound, a lutetium-containing compound, a rare earth-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: (lutetium + rare earth): lithium: the boron molar ratio is 1-3:1:2-5:1-8, placing the mixture into a crucible, placing the crucible into a medium-frequency pulling furnace, and introducing high-purity N 2 /H 2 Heating to completely melt the/Ar gas, stirring for 12-24 hours, when the temperature of a melt is 0.1-3 ℃ higher than the temperature of a saturation point, putting a platinum or iridium rod from the growing furnace, enabling the platinum or iridium rod to contact the surface of the melt, keeping the temperature for 2-12 hours, reducing the temperature to the temperature of the saturation point at 0.1-10 ℃/h, setting the rotating speed of the platinum or iridium rod to be 2-25r/min, then slowly reducing the temperature at the speed of 0.05-10 ℃/h, pulling at the pulling speed of 0.05-0.75mm/h, when a crystal grows to a certain size, pulling the crystal off the liquid level, quickly reducing the temperature to room temperature at the speed of 10-100 ℃/h, and finally obtaining the lithium sodium lutetium rare earth doped crystal; wherein the sodium-containing compound is 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、NaBO 2 ·4H 2 Any one of O; the yttrium-containing compound being Y 2 O 3 、Y(NO 3 ) 3 ·6H 2 O、Y(OH) 3 、Y 2 (CO 3 ) 3 、Y 2 (SO 4 ) 3 Any one of (a); the compound containing cerium being CeO 2 、Ce 2 O 3 、Ce(NO 3 ) 3 ·6H 2 O、Ce 2 (SO 4 ) 3 Any of 4H 2O; the lithium-containing compound being Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound is H 3 BO 3 Or B 2 O 3 。
10. The lithium borate sodium lutetium compound or crystal or the lithium borate sodium lutetium rare earth doped compound or crystal is used as a scintillation material to be used as a high-energy ray detection material or as fluorescent powder for LED illumination; the lithium sodium lutetium borate compound or crystal is used as an optical lens or an optical prism material.
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