CN115367766B - 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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CN115367766B
CN115367766B CN202210938320.6A CN202210938320A CN115367766B CN 115367766 B CN115367766 B CN 115367766B CN 202210938320 A CN202210938320 A CN 202210938320A CN 115367766 B CN115367766 B CN 115367766B
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lutetium
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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 and 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 a rare earth element, is low in cost and easy to obtain, simple and convenient to synthesize, stable in physicochemical property, good in scintillation and fluorescence performance of rare earth doped compound of lithium sodium lutetium borate, can be used as a scintillation material 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, light illumination and the like.

Description

Lithium sodium lutetium borate, rare earth doped compound and crystal thereof, and preparation method and application thereof
Technical field:
the invention relates to the technical field of scintillation materials, in particular to lithium sodium lutetium borate, a rare earth doped compound and a crystal thereof, and a preparation method and application thereof.
The background technology is as follows:
the scintillation crystal is an object capable of emitting pulse light under the action of high-energy particles or rays (such as X rays, gamma rays and the like), and is widely used in the fields of high-energy physics, nuclear physics, space physics, nuclear medicine, geological exploration, security 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. The clinical application of the kit is widely applied to the fields of early diagnosis of tumors, nervous system diseases and cardiovascular and cerebrovascular diseases, research on disease pathology, evaluation of tumor treatment effect, drug development and the like.
At present, the rare earth scintillation crystal material is a high-end medical equipment imaging core component and is a core key material affecting the resolution and image quality of PET/CT imaging. In recent years, particularly third generation PET based on depth and time of flight (TOF) performance multi-modality imaging systems, higher technical requirements are placed on high blocking capability, high spatial resolution and energy resolution of scintillation crystals. Existing rare earth scintillation crystal materials such as (Lu, Y) 2 SiO 5 :Ce 3+ 、LaBr 3 :Ce 3+ The material has various excellent performances such as high light yield, rapid attenuation, high energy resolution and the like, and is considered to be a scintillation crystal material which is more suitable for a TOF-PET system in the field of nuclear medicine imaging. However, (Lu, Y) 2 SiO 5 :Ce 3+ The crystal has an extremely high melting point (2050-2100 deg.c), which is very demanding for the heat resistance of the crystal growth apparatus, and the crystal growth requires the use of an expensive iridium crucible, which greatly increases the cost and cycle time of the crystal growth. And for LaBr 3 :Ce 3+ There are problems such as extremely deliquescent property and expensive raw materials, and therefore, there is a need to search for a novel scintillating material having a low melting point and stable physicochemical properties.
The invention comprises the following steps:
the invention aims to provide lithium sodium lutetium borate, a rare earth doped compound and crystal thereof, and a preparation method and application thereof, wherein the lithium sodium lutetium borate, the rare earth doped compound and crystal are easy to prepare, stable in physicochemical property, not easy to deliquesce in air, good in scintillation/fluorescence performance and expected to be used as a scintillation material and fluorescent powder for LEDs.
The invention is realized by the following technical scheme:
lithium sodium lutetium borate compound with chemical formula of Li 2 NaLuB 2 O 6 。
Lithium sodium lutetium borate crystal with chemical formula of Li 2 NaLuB 2 O 6 Belongs to monoclinic system, and the space group is P2 1 N, unit cell parameters are
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 and is selected from one or more than one of Ce, pr, nd, eu, tb, ho, er, tm, yb.
Rare earth doped crystal of lithium sodium lutetium borate, 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 and is one or more selected from Ce, pr, nd, eu, tb, ho, er, tm, yb, the rare earth element belongs to monoclinic system, and the space group is P2 1 The range of unit cell parameters is/n
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 Dodecahedron, isolated BO 3 Plane triangle, liO 4 Tetrahedral sum (Lu) 1- x RE x )O 7 (x is more than 0 and less than or equal to 0.5) pentagonal bipyramid are mutually linked, and RE is one or more than one of Ce, pr, nd, eu, tb, ho, er, tm, yb of rare earth elements. Wherein NaO is 8 The dodecahedron bodies are connected together at the same edge and the same point to form a one-dimensional Na-O zigzag chain, while (Lu) 1-x RE x )O 7 The pentagonal bipyramid is connected two by two in a common edge to form (Lu) 1-x RE x ) 2 O 12 Dimer, (Lu) 1-x RE x ) 2 O 12 Dimer and Na-ozizag chain and BO 3 The plane triangle forms the main framework of the crystal structure, and two kinds of crystallographically independent LiO 4 Formation of tetrahedral co-edge connection [ LiO ] 2 ]One-dimensional chain along [010 ]]The direction penetrates through the framework of the crystal.
The invention also provides a preparation method of the lithium sodium lutetium borate compound, which comprises the following steps:
sodium-containing compounds, lutetium-containing compounds, lithium-containing compounds, boron-containing compounds are prepared as sodium: lutetium: lithium: the molar ratio of boron element is 1:1:2:2, then placing the materials into a crucible, heating to 400-500 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, placing the materials 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, placing the materials into the muffle furnace after tertiary grinding, introducing hydrogen, raising the temperature 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 is Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound being H 3 BO 3 Or B is a 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:
sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, boron-containing compounds are prepared according to sodium: (lutetium + rare earth): lithium: the molar ratio of boron element is 1:1:2:2, then placing the materials into a crucible, placing the crucible into a muffle furnace, introducing hydrogen, heating to 400-500 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, placing the materials 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, placing the materials into the muffle furnace after tertiary grinding, introducing hydrogen, raising the temperature to 700-750 ℃, keeping the temperature for 12-48 hours, taking out, and grinding 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 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 is any one of the compounds containing lithium, li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound being H 3 BO 3 Or B is a 2 O 3 。
A method of preparing lithium sodium lutetium borate crystals, the method comprising the steps of: sodium-containing compounds, lutetium-containing compounds, lithium-containing compounds, boron-containing compounds are prepared as sodium: lutetium: lithium: the molar ratio of boron element is 1-3:1:5-8: mixing and grinding at a ratio of 5-10, loading into crucible, and heating at 5-20deg.C/hrHeating to 800-1000 ℃ at a speed to obtain high Wen Rongye, preserving heat for 12-48h, and then 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; the lithium-containing compound is Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound being H 3 BO 3 Or B is a 2 O 3 。
In particular, when preparing lithium sodium lutetium borate crystal, cosolvent is also added, and the fluxing agent is PbO and PbO 2 、PbF 2 Any one of KF or KCl.
A method for preparing lithium sodium lutetium borate rare earth doped crystals, the method comprising the steps of: sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, boron-containing compounds are prepared according to sodium: (lutetium + rare earth): lithium: the molar ratio of boron element is 1-3:1:5-8: mixing and grinding uniformly in proportion of 5-10, loading into a crucible, heating to the temperature of 800-1000 ℃ at the heating rate of 5-20 ℃/h to obtain high Wen Rongye, preserving heat for 12-48h, and then cooling to room temperature at the speed of 1-10 ℃/h to obtain lithium sodium lutetium rare earth borate 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 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 is any one of the compounds containing lithium, li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound being H 3 BO 3 Or B is a 2 O 3 。
In particular, preparing lithium sodium lutetium rare earth doped crystal, adding cosolvent, mixing sodium-containing compound, lutetium-containing compound, rare earth-containing compound, lithium-containing compound, boron-containing compound, and fluxing agent according to sodium: (lutetium + rare earth): the mass ratio of the substances of the boron and the fluxing agent is 1-3:1:2-3: mixing and grinding uniformly in a ratio of 2-5:1-10, loading into a crucible, heating to a temperature of 800-1000 ℃ at a heating rate of 5-50 ℃/h to obtain a high-temperature solution, preserving heat for 12-48h, and then cooling to room temperature at a speed of 1-20 ℃/h to obtain lithium sodium lutetium borate and rare earth doped crystals thereof. The fluxing agent is PbO, pbO 2 、PbF 2 Any one of KF or KCl.
A method of preparing lithium sodium lutetium borate rare earth metal doped crystals, the method comprising the steps of: sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, boron-containing compounds are prepared according to sodium: (lutetium + rare earth): lithium: the molar ratio of boron is 1-3:1:2-5:1-8, charging into crucible, charging into intermediate frequency pulling furnace, charging high purity N 2 /H 2 Heating Ar gas to completely melt, stirring for 12-24 hr, and placing platinum or iridium rod into the growth furnace to make it contact with the surface of molten liquid, and keeping the temperature of molten liquid at 2-12 deg.C when the temperature of molten liquid is above saturation point temperature by 0.1-3deg.CAnd (3) after the temperature is reduced to the saturation point temperature at 0.1-10 ℃/h, setting the rotating speed of a platinum or iridium rod to 2-25r/min, then slowly reducing the temperature at the speed of 0.05-10 ℃/h, and carrying out pulling at the pulling speed of 0.05-0.75mm/h, when the crystal grows to a certain size, carrying out pulling-off on the crystal from the liquid level, and then quickly reducing the temperature to room temperature at the speed of 10-100 ℃/h, thus 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; y being an yttrium-containing compound 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 them; the cerium-containing compound is CeO 2 、Ce 2 O 3 、Ce(NO 3 ) 3 ·6H 2 O、Ce 2 (SO 4 ) 3 Any one of 4H 2O; the lithium-containing compound is Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound being H 3 BO 3 Or B is a 2 O 3 。
The invention also protects the application of the lithium sodium lutetium borate compound or crystal or lithium sodium lutetium rare earth doped compound or crystal, wherein the lithium 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 used as a light functional 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-focus zoom lens, a high-power microscope and the like.
The beneficial effects of the invention are as follows: the invention provides a novel lithium sodium lutetium borate and rare earth doped compound or crystal thereof and a preparation method thereof, which are low in cost, easy to obtain, simple and convenient to synthesize and stable in physicochemical property, and the lithium sodium lutetium borate 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 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, light 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-focus zoom lens, a high-power microscope and the like.
Description of the drawings:
FIG. 1 is a lithium sodium lutetium Li borate prepared in example 7 of the present invention 2 NaLu(BO 3 ) 2 Schematic of the crystal structure of the single crystal along the b-axis and the c-axis;
FIG. 2 is a lithium sodium lutetium Li borate prepared in example 7 of the present invention 2 NaLu(BO 3 ) 2 Dispersive refractive index of single crystal;
FIG. 3 is a lithium sodium lutetium Li borate prepared in example 1 of the present invention 2 NaLu(BO 3 ) 2 Diffuse reflectance spectrum of the compound;
FIG. 4 is Li of the present invention 2 NaLu(BO 3 ) 2 Powder XRD diffractogram of the compound;
FIG. 5 is Li 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 Powder XRD diffractogram of the compound;
FIG. 6 is Li 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 Powder XRD diffractogram of the compound;
FIG. 7 is Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 The scintillation property of the crystal;
FIG. 8 is Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 Fluorescence emission spectrum of the crystal;
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. 11Is Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 Crystals, li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 Compounds, li 2 NaLu 0.8 Tb 0.4 (BO 3 ) 2 CIE chromaticity coordinates of the compounds.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1: synthesis of lithium sodium lutetium borate Compound Li 2 NaLu(BO 3 ) 2 Compounds of formula (I)
Raw materials used (analytically pure): 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 materials, placing into agate mortar, mixing, grinding, and loading into
Figure BDA0003784389600000071
The corundum crucible is placed into a muffle furnace, heated to 500 ℃, kept at constant temperature for 24 hours, cooled to room temperature, taken out, placed into the muffle furnace after being ground for the second time, heated to 600 ℃, kept at constant temperature for 24 hours, cooled to room temperature, taken out, placed into the muffle furnace after being ground for the third time, heated to 700 ℃ again, kept at constant temperature for 24 hours, taken out, and ground to obtain the lithium sodium lutetium Li borate 2 NaLu(BO 3 ) 2 A compound.
Example 2: synthesis of lithium sodium lutetium borate 0.5% cerium doped Li 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 Compounds of formula (I)
Raw materials used (analytically pure): lu (Lu) 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 materials, placing into agate mortar, mixing, grinding, and loading into
Figure BDA0003784389600000072
Placing the corundum crucible with the thickness of mm multiplied by 10mm into a tubular furnace, introducing hydrogen atmosphere, heating to 450 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing the corundum crucible into a muffle furnace after secondary grinding, introducing hydrogen atmosphere, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing the corundum crucible into the muffle furnace after tertiary grinding, introducing hydrogen atmosphere, keeping the temperature constant for 24 hours at 730 ℃, taking out, and grinding to obtain the Li 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 A compound.
Example 3: synthesis of lithium sodium lutetium borate 30% Neodymium doped Li 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 Compounds of formula (I)
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。
The method comprises the following specific steps: weighing the above materials, placing into agate mortar, mixing, grinding, and loading into
Figure BDA0003784389600000081
Placing the mixture into a platinum crucible with the thickness of mm multiplied by 15mm, heating to 500 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing the mixture into the muffle after secondary grinding, heating to 680 ℃ again, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing the mixture into the muffle after tertiary grinding, keeping the temperature constant for 24 hours again at 730 ℃, taking out, and grinding to obtain the Li 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 A compound.
Example 4: synthesis of lithium sodium lutetium borate 20% europium doped Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 Compounds of formula (I)
Raw materials used (analytically 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 materials, placing into agate mortar, mixing, grinding, and loading into
Figure BDA0003784389600000082
Placing the mixture into a platinum crucible with the thickness of mm multiplied by 15mm, heating to 480 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing the mixture into the muffle after secondary grinding, heating to 660 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing the mixture into the muffle after tertiary grinding, keeping the temperature constant for 24 hours, taking out, and grinding to obtain the europium-doped Li 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 Compounds of formula (I)
Example 5: synthesis of lithium sodium lutetium borate 40% terbium doped Li 2 NaLu 0.6 Tb 0.4 (BO 3 ) 2 Compounds of formula (I)
Raw materials used (analytically pure): lu (Lu) 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: weighing the above materials, placing into agate mortar, mixing, grinding, and loading into
Figure BDA0003784389600000091
Placing the mixture into a platinum crucible with the thickness of mm multiplied by 15mm, heating to 500 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing the mixture into the muffle after secondary grinding, heating to 650 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing the mixture into the muffle after tertiary grinding, keeping the temperature constant for 24 hours, taking out, and grinding to obtain the Li 2 NaLu 0.6 Tb 0.4 (BO 3 ) 2 A compound.
Example 6: synthesis of lithium sodium lutetium borate 50% ytterbium doped Li 2 NaLu 0.5 Yb 0.5 (BO 3 ) 2 Compounds of formula (I)
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。
The method comprises the following specific steps: weighing the above materials, placing into agate mortar, mixing, grinding, and loading into
Figure BDA0003784389600000092
Figure BDA0003784389600000093
Is put into a muffle furnace, heated to 480 ℃, kept at constant temperature for 24 hours, cooled to room temperature, taken out, put into the muffle furnace after being ground for the second time, heated to 660 ℃, kept at constant temperature for 24 hours, cooled to room temperature, taken out, put into the muffle furnace after being ground for the third time, heated to 750 ℃ and kept at constant temperature for 24 hours, taken out, and ground to obtain the Li 2 NaLu 0.5 Yb 0.5 (BO 3 ) 2 A compound.
Example 7: self-help solvent method for preparing lithium sodium lutetium Li borate 2 NaLu(BO 3 ) 2 Raw materials for crystals (analytically 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 materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784389600000094
Putting the platinum crucible into a molten salt furnace, heating to 950 ℃ at 20 ℃/h, fully melting the raw materials, preserving heat for 12 hours, and then slowly cooling at the rate of 2 ℃/h to obtain the alloy with the size of 0.37 multiplied by 0.32 multiplied by 0.16mm 3 Li of (2) 2 NaLu(BO 3 ) 2 And (5) a crystal.
Example 8: self-help solvent method for preparing 20% neodymium doped Li of lithium sodium lutetium borate 2 NaLu 0.8 Nd 0.2 (BO 3 ) 2 Crystal body
Raw materials used (analytically 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 materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784389600000101
Putting into a platinum crucible, putting into a molten salt furnace, heating to 965 ℃ at a speed of 10 ℃ per hour, fully melting the raw materials, preserving heat for 36 hours, and slowly cooling at a speed of 5 ℃ per hour to obtain the alloy 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 (5) a crystal.
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 body
Raw materials used (analytically pure): naHCO (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
The method comprises the following specific steps: weighing the above materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784389600000102
Putting into a platinum crucible, putting into a molten salt furnace, heating to 980 ℃ at 15 ℃/h, fully melting the raw materials, preserving heat for 12 hours, and slowly cooling at a rate of 5 ℃/h to obtain the alloy 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 (5) a crystal. />
Example 10: cosolvent method for preparing lithium sodium lutetium Li borate 2 NaLu(BO 3 ) 2 Crystal body
Raw materials used (analytically pure): naHCO (NaHCO) 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 materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784389600000103
Putting the gold crucible into a muffle furnace, heating to 900 ℃ at 5 ℃ per hour to completely melt the raw materials, preserving heat for 12 hours, and then slowly cooling at the rate of 3 ℃ per hour to obtain the alloy with the size of 0.52 multiplied by 0.37 multiplied by 0.12mm 3 Li of (2) 2 NaLu(BO 3 ) 2 And (5) a crystal.
Example 11: co-solvent method for preparing 10% cerium doped Li of lithium sodium lutetium borate 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 Crystal body
Raw materials used (analytically pure): 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 materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784389600000111
Putting the gold crucible into a muffle furnace, heating to 950 ℃ at 5 ℃ per hour to completely melt the raw materials, preserving heat for 12 hours, and then slowly cooling at the rate of 2 ℃ per hour to obtain 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 (5) a crystal.
Example 12: 15% praseodymium-doped Li of lithium sodium lutetium borate prepared by cosolvent method 2 NaLu 0.85 Pr 0.15 (BO 3 ) 2 Crystal body
Raw materials used (analytically pure): 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 materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784389600000112
Putting into a platinum crucible, putting into a muffle furnace, heating to 1000deg.C at 25deg.C/hr to melt the raw materials completely, maintaining the temperature for 12 hr, and slowly cooling at 2deg.C/hr to obtain 0.57X10.46X 0.21mm 3 Li of (2) 2 NaLu 0.85 Pr 0.15 (BO 3 ) 2 And (5) a crystal.
Example 13: preparation of lithium sodium lutetium borate by Czochralski method with 10% cerium doped Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 Crystal body
Raw materials used (analytically 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 materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784389600000113
Putting the platinum crucible into an intermediate frequency pulling furnace, and introducing high-purity N 2 /H 2 Heating the mixed gas to completely melt, stirring for 24 hours, putting a platinum rod from a growth furnace when the temperature of the melt is 0.5 ℃ higher than the saturation point temperature, enabling the platinum rod 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 10r/min, slowly reducing the temperature at the speed of 0.05 ℃/h, carrying out pulling at the pulling speed of 0.1mm/h, carrying out pulling-off of the crystal from the liquid surface when the crystal grows to a certain size, and finally rapidly reducing the temperature to the room temperature at the speed of 50 ℃/h to obtain the crystal with the size of 5.2X4.3X1.7 mm 3 Li of (2) 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 And (5) a crystal.
Example 14: 30% holmium doped Li for preparing lithium sodium lutetium borate by Czochralski method 2 NaLu 0.7 Ho 0.3 (BO 3 ) 2 Crystal body
Raw materials used (analytically pure): 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 materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784389600000121
Putting the platinum crucible into an intermediate frequency pulling furnace, and introducing high-purity N 2 Heating to completely melt, stirring for 16 hr, placing platinum rod into the growth furnace to make it contact with the surface of molten liquid, holding for 2 hr, cooling the temperature to saturation point at 0.75deg.C/hr, setting the rotation speed of platinum rod to 15r/min, slowly cooling at 0.55deg.C/hr, pulling the crystal from liquid surface when the crystal grows to a certain size, and quickly cooling to room temperature at 30 deg.C/hr to obtain crystal with size of 5.3X13.3X12.2 mm 3 Li of (2) 2 NaLu 0.7 Ho 0.3 (BO 3 ) 2 And (5) a crystal.
Example 15: 5% erbium-doped Li for preparing lithium sodium lutetium borate by Czochralski method 2 NaLu 0.95 Er 0.05 (BO 3 ) 2 Crystal body
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 method comprises the following specific steps: weighing the above materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784389600000122
Putting into a platinum crucible, putting into an intermediate frequency pulling furnace, introducing high-purity Ar gas, heating to completely melt, stirring for 18 hours, and putting into a platinum rod from the growth furnace when the temperature of the melt is 2.5 ℃ higher than the saturation point temperature to make contactMaintaining the surface of the molten liquid for 2 hours, reducing the temperature to the saturation point temperature at 1.25 ℃/h, setting the rotating speed of a platinum rod to 15r/min, slowly reducing the temperature at 0.55 ℃/h, pulling at a pulling speed of 0.5mm/h, pulling the crystal off the liquid surface when the crystal grows to a certain size, and finally rapidly reducing the temperature to the room temperature at a speed of 70 ℃/h to obtain the crystal with the size of 2.3X1.6X1.2 mm 3 Li of (2) 2 NaLu 0.95 Er 0.05 (BO 3 ) 2 And (5) a crystal.
Example 16: lithium sodium lutetium borate and rare earth doped compound and characteristic test of crystal thereof
Lithium sodium lutetium Li borate prepared in example 7 of the present invention 2 NaLu(BO 3 ) 2 The single crystal adopts X-ray single crystal diffraction method to measure the unit cell structure, the unit cell structure is shown in figure 1, and can be obtained from figure 1, the lithium sodium lutetium borate crystal Li 2 NaLu(BO 3 ) 2 Belonging to monoclinic system, the space group is P2 1 And/n, the unit cell parameters are:
Figure BDA0003784389600000131
α＝90°，β＝102.729°，γ＝90°，/>
Figure BDA0003784389600000132
Z＝4。
20% neodymium doped Li of lithium sodium lutetium borate prepared in example 8 of the invention 2 NaLu 0.8 Nd 0.2 (BO 3 ) 2 The single crystal adopts an X-ray single crystal diffraction method to measure the unit cell structure, 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 And/n, 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 present invention 2 NaLu(BO 3 ) 2 The single crystal passed the dispersive refractive index test, and the result is shown in fig. 2, which shows that the single crystal has a better refractive index and lower dispersion in the test range, and the single crystal has the application of an optical prism material.
Lithium sodium lutetium Li borate prepared in example 1 of the present 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 example 1, example 2 and example 3 of the present invention 2 NaLu(BO 3 ) 2 、Li 2 NaLu 0.995 Ce 0.005 (BO 3 ) 2 And Li (lithium) 2 NaLu 0.7 Nd 0.3 (BO 3 ) 2 The compound is carefully ground and then subjected to normal temperature XRD test by an X-ray powder diffractometer, as shown in figures 4-6, and the result shows that the prepared compound belongs to a pure phase and no other impurity phase is generated.
Li prepared in example 11 of the present invention 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 The crystal, excited by X-rays (Ag target), has a scintillation spectrum as shown in FIG. 7, li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 The scintillation detection performance of the fluorescent probe is obviously superior to Bi under the same test condition 4 Ge 3 O 12 (BGO) reference Crystal, demonstrating Li 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 Has good use value.
Li prepared in example 13 of the present invention 2 NaLu 0.9 Ce 0.1 (BO 3 ) 2 After the crystal is carefully ground, characteristic blue light is emitted under ultraviolet excitation, the fluorescence emission spectrum is shown in fig. 8, the CIE chromaticity coordinates (0.157, 0.154 and 0.690) are shown in fig. 11, and the blue fluorescent powder for the LED has good use value.
The preparation of example 4 of the present inventionLi 2 NaLu 0.8 Eu 0.2 (BO 3 ) 2 After the compound is carefully ground, characteristic red light is emitted under ultraviolet or visible light excitation, the fluorescence emission spectrum is shown in fig. 9, the CIE chromaticity coordinates (0.615, 0.384 and 0.001) of the compound are shown in fig. 11, and the compound has good use value in red fluorescent powder for LEDs.
Li prepared in example 5 of the present invention 2 NaLu 0.6 Tb 0.4 (BO 3 ) 2 After the compound is carefully ground, characteristic green light is emitted under ultraviolet excitation, the fluorescence emission spectrum is shown in fig. 10, the CIE chromaticity coordinates (0.345, 0.535 and 0.121) are shown in fig. 11, and the compound has good use value in green fluorescent powder for LEDs.

Claims (10)

1. The chemical formula is Li 2 NaLuB 2 O 6 The preparation method of the lithium sodium lutetium borate compound is characterized by comprising the following steps: sodium-containing compounds, lutetium-containing compounds, lithium-containing compounds, boron-containing compounds are prepared as sodium: lutetium: lithium: the molar ratio of boron element is 1:1:2:2, then placing the materials into a crucible, heating to 400-500 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, placing the materials 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, placing the materials into the muffle furnace after tertiary grinding, introducing hydrogen, heating to 700-750 ℃, keeping the temperature for 12-48 hours, taking out, and grinding to obtain the lithium sodium lutetium borate compound.
2. A lithium sodium lutetium borate compound according to claim 1, 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 is Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound being H 3 BO 3 Or B is a 2 O 3 。
3. Lithium sodium lutetium borate crystal characterized by the chemical formula Li 2 NaLuB 2 O 6 Monoclinic system with space group ofP2 1 /nThe unit cell parameters area =6.5571 Å, b= 9.0338 Å, c= 8.7765 Å, α= 90 °，β=102.729 °，γ= 90 °，V= 507.1036 Å 3 ，Z= 4。
4. The rare earth doped compound of lithium sodium lutetium borate is characterized by having a chemical general formula of 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 and is selected from one or more than one of Ce, pr, nd, eu, tb, ho, er, tm, yb; the preparation method comprises the following steps: sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, boron-containing compounds are prepared according to sodium: (lutetium + rare earth): lithium: the molar ratio of boron element is 1:1:2:2, then placing the materials into a crucible, placing the crucible into a muffle furnace, introducing hydrogen, heating to 400-500 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, placing the materials 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, placing the materials into the muffle furnace after tertiary grinding, introducing hydrogen, heating to 700-750 ℃, keeping the temperature for 12-48 hours, taking out, grinding to obtain the rare earth doped compound of lithium sodium lutetium borate.
5. A rare earth doped compound of lithium sodium lutetium borate according to claim 4, 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 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 is any one of the compounds containing lithium, li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound being H 3 BO 3 Or B is a 2 O 3。
6. The rare earth doped crystal of lithium sodium lutetium borate is characterized by having a chemical general formula of 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 and is one or more selected from Ce, pr, nd, eu, tb, ho, er, tm, yb, belonging to monoclinic system, and the space group isP2 1 /nThe unit cell parameters range froma = 6.5571-6.6648 Å, b= 9.0338-9.2417 Å, c= 8.7765-8.9273 Å, α= 90°，β=102.729-103.889 °，γ= 90 °，V= 507.1036-533.792 Å 3 ，Z= 4。
7. A method of preparing lithium sodium lutetium borate crystals according to claim 3, comprising the steps of: the sodium-containing compound and the lutetium-containing compoundLithium-containing compounds, boron-containing compounds according to sodium: lutetium: lithium: the molar ratio of boron element is 1-3:1:5-8: mixing and grinding uniformly in a proportion of 5-10, loading into a crucible, heating to a temperature of 800-1000 ℃ at a heating rate of 5-20 ℃/h to obtain high Wen Rongye, preserving heat for 12-48h, and then 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; the lithium-containing compound is Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound being H 3 BO 3 Or B is a 2 O 3 。
8. The method for preparing lithium sodium lutetium borate crystal according to claim 7, wherein a cosolvent is added during the preparation of the lithium sodium lutetium borate crystal, and the fluxing agent is PbO or PbO 2 、PbF 2 Any one of KF or KCl.
9. A method of preparing the lithium sodium lutetium sodium borate rare earth doped crystal of claim 6, comprising the steps of: sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, boron-containing compounds are prepared according to sodium: (lutetium + rare earth): lithium: the molar ratio of boron element is 1-3:1:5-8: mixing and grinding uniformly in a proportion of 5-10, loading into a crucible, heating to a temperature of 800-1000 ℃ at a heating rate of 5-20 ℃/h to obtain high Wen Rongye, preserving heat for 12-48h, and then cooling to room temperature at a speed of 1-10 ℃/h to obtain lithium sodium lutetium rare earth borate doped 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; 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 is any one of the compounds containing lithium, li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound being H 3 BO 3 Or B is a 2 O 3 ；
Or, the method comprises the following steps: sodium-containing compounds, lutetium-containing compounds, rare earth-containing compounds, lithium-containing compounds, boron-containing compounds are prepared according to sodium: (lutetium + rare earth): lithium: the molar ratio of boron is 1-3:1:2-5:1-8, charging into crucible, charging into intermediate frequency pulling furnace, charging high purity N 2 /H 2 Ar gas, heating to completely melt, stirring for 12-24 hr, when the melt temperature is 0.1-3deg.C higher than saturation point temperature, placing platinum or iridium rod into growth furnace, making it contact with the surface of molten liquid, holding for 2-12 hr, reducing temperature to saturation point temperature at 0.1-10deg.C/h, setting rotating speed of platinum or iridium rod to 2-25r/min, slowly reducing temperature at 0.05-10deg.C/h, pulling at 0.05-0.75mm/h, and when crystal grows to a certain size, pulling the crystal from liquid surface, and removing at 10-100deg.C/hThe rate of the crystal is quickly reduced to room temperature, and finally lithium sodium lutetium rare earth doped crystal is obtained; 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 lutetium-containing compound is Lu 2 O 3 、Lu(NO 3 ) 3 ·6H 2 Any one of 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 Any one of O; the lithium-containing compound is Li 2 CO 3 、LiNO 3 Or LiOH, the boron-containing compound being H 3 BO 3 Or B is a 2 O 3 。
10. Use of a lithium sodium lutetium borate compound as defined in claim 1 or a lithium sodium lutetium borate crystal as defined in claim 3 or a lithium sodium lutetium borate rare earth doped compound as defined in claim 4 or a lithium sodium lutetium rare earth doped crystal as defined in claim 6, characterized in that the lithium sodium lutetium borate rare earth doped compound or crystal is used as a scintillation material as a high energy radiation detection material or as a phosphor for LED illumination; the lithium sodium lutetium borate compound or crystal is used as an optical lens or optical prism material.
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