CN115367767A - Lithium sodium yttrium borate, cerium doped compound and crystal thereof, and preparation method and application thereof - Google Patents
Lithium sodium yttrium borate, cerium doped compound and crystal thereof, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses lithium sodium yttrium borate, a cerium doped compound and a crystal thereof, and a preparation method and application thereof 2 NaY(BO 3 ) 2 The chemical general formula of the cerium doped compound of lithium sodium yttrium borate is Li 2 NaY 1‑x Ce x (BO 3 ) 2 Wherein x is more than 0 and less than or equal to 0.5, is cheap and easy to obtain, is simple and convenient to synthesize, has stable physicochemical properties, is not deliquesced, has good scintillation and fluorescence properties, and can be used as a scintillation material as a neutron detection material or as blue fluorescent powder for LED illuminationThe method has important economic and scientific research values in the fields of high-energy physical particle detection, light illumination and the like.
Description
The technical field is as follows:
the invention relates to the technical field of scintillating materials, in particular to lithium sodium yttrium borate, a cerium doped compound and a crystal thereof, and a preparation method and application thereof.
The background art comprises the following steps:
neutrons have strong penetrating power, can identify light elements, particularly elements such as hydrogen, lithium and the like, and the spin S =1/2 of the neutrons can magnetically interact with atoms/ions with unpaired electrons so as to detect magnetic moments, so that the utilization of neutron diffraction/scattering is a powerful means for researching the crystal structure, the superstructure and the magnetic structure of materials at present. Neutrons are uncharged particles different from X-rays and alpha-rays, so that they cannot directly cause ionization of scintillation materials to be observed, and therefore, how to effectively and accurately detect neutrons is one of important research contents of current high-energy particle detection.
The utilization of the scintillation crystal is an important technical scheme at present, and the scintillation crystal-based scintillator detector has a wider application range, environmental adaptability and higher detection efficiency compared with other detectors. Existing rare earth elpasolite family crystals Cs 2 LiYCl 6 ：Ce 3+ 、Cs 2 LiLuBr 6 ：Ce 3+ 、Rb 2 LiYBr 6 ：Ce 3+ The scintillation material has the advantages of high light yield, fast attenuation, high energy resolution, capability of realizing n-gamma double detection and the like, and is considered to be an ideal neutron detection scintillation material. YCl of the type of crystalline material grown however 3 、LuBr 3 、YBr 3 The raw materials are expensive, the raw materials are required to be packaged in a quartz crucible under the anhydrous and oxygen-free conditions, and the prepared crystal is extremely easy to deliquesce in the air, so that the cost and the difficulty of crystal growth, processing and packaging are greatly increased, and a novel scintillation material which is stable in physical and chemical properties, not deliquescent, cheap and easy to obtain needs to be further explored.
The invention content is as follows:
the invention aims to provide lithium sodium yttrium borate, a cerium doped compound and a crystal thereof, and a preparation method and application thereof, which are cheap and easy to obtain, stable in physicochemical property, free from deliquescence, good in scintillation/fluorescence performance, and expected to be used in the fields of high-energy particle detection and LED illumination to solve the problems of high cost and unstable property in the prior art.
The invention is realized by the following technical scheme:
a lithium sodium yttrium borate compound of the formula Li 2 NaY(BO 3 ) 2 And molecular weight 243.39.
Lithium sodium yttrium borate crystal of formula Li 2 NaY(BO 3 ) 2 Belongs to the monoclinic system, and the space group is P2 1 N, unit cell parameter of
α＝90°，β＝103.278，γ＝90°，
Z＝4。
The cerium doped compound of lithium sodium yttrium borate has the chemical general formula of Li 2 NaY 1-x Ce x (BO 3 ) 2 Wherein x is more than 0 and less than or equal to 0.5.
The cerium doped crystal of lithium sodium yttrium borate has the chemical general formula of Li 2 NaY 1-x Ce x (BO 3 ) 2 Wherein x is more than 0 and less than or equal to 0.5, belongs to monoclinic system, and has space group P2 1 N, unit cell parameters in the range of
α＝90°，β＝102.729(2)-103.889(1)°，γ＝90°，
Z＝4。
The asymmetric unit of the unit cell comprises 1 Na, 2 Li and 1Y 1-x Ce x (x is more than or equal to 0 and less than or equal to 0.5), 2 crystallographically independent sites of B and 6O. Na forms an octadentate with O, both Li forms a tetradentate with O, both B forms a tridentate with O, Y 1-x Ce x (x is more than or equal to 0 and less than or equal to 0.5) and O form heptacoordination. The three-dimensional space structure is based on NaO 8 Dodecahedral, isolated BO 3 Planar triangular, liO 4 Tetrahedron and (Y) 1-x Ce x )O 7 The pentagonal bipyramids are mutually linked. NaO 8 The dodecahedrons are connected with each other at the same side and point to form a one-dimensional Na-O chain, (Y) 1-x Ce x )O 7 The pentagonal bipyramids are connected in pairs to form (Y) 1-x Ce x ) 2 O 12 Dimer, (Y) 1-x Ce x ) 2 O 12 Dimer and Na-O chain and BO 3 The plane triangle forms the main crystal structure skeleton, and two crystallographically independent LiO 4 Formation of tetrahedral common edge junctions [ LiO 2 ]The one-dimensional chain penetrates through the framework of the crystal along the direction of the b axis.
The invention also discloses a preparation method of the lithium sodium yttrium borate compound, which comprises the following steps:
mixing a sodium-containing compound, an yttrium-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: yttrium: lithium: the molar ratio of boron elements is 1:1:2:2, then putting the mixture into a crucible, putting the mixture into a muffle furnace, heating to 400-550 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out the mixture, putting the mixture into the muffle furnace after the second grinding, introducing hydrogen, heating to 550-700 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out the mixture, putting the mixture into the muffle furnace after the third grinding, introducing hydrogen, heating to 700-800 ℃, keeping the temperature for 12-48 hours, taking out the mixture, and grinding the mixture to obtain the lithium sodium yttrium borate compound. 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 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 provides a preparation method of the cerium doped compound of lithium sodium yttrium borate, which comprises the following steps:
mixing a sodium-containing compound, an yttrium-containing compound, a cerium-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: (yttrium + cerium): 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 400-550 ℃, 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 550-700 ℃, 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 700-800 ℃, 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 、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); comprisesThe compound of 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 。
A method of preparing lithium sodium yttrium borate crystals, the method comprising the steps of: mixing a sodium-containing compound, an yttrium-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: yttrium: lithium: the molar ratio of boron elements is 1-8:1:5-13:5-15, placing the mixture into a crucible, heating the mixture to 700-1050 ℃ at a heating rate of 1-30 ℃/h to obtain high-temperature melt, preserving the heat for 12-60h, and then cooling the mixture to room temperature at a speed of 1-15 ℃/h to obtain the lithium sodium yttrium borate 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 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 cerium doped crystals of lithium sodium yttrium borate, the method comprising the steps of: mixing a sodium-containing compound, an yttrium-containing compound, a cerium-containing compound, a lithium-containing compound and a boron-containing compound according to the following ratio of sodium: (yttrium + cerium): lithium: the molar ratio of boron elements is 1-8:1:5-13:5-15, placing the mixture into a crucible, placing the crucible into a molten salt furnace, introducing hydrogen, heating the mixture to 700-1050 ℃ at a heating rate of 1-30 ℃/h to obtain high-temperature melt, preserving the heat for 12-60h, and then mixing and grinding the mixtureAnd cooling to room temperature at the speed of 1-15 ℃/h to obtain the lithium sodium yttrium borate 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 ·4H 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 。
A method of preparing cerium doped crystals of lithium sodium yttrium borate, the method comprising the steps of: mixing a sodium-containing compound, an yttrium-containing compound, a cerium-containing compound, a lithium-containing compound and a boron-containing compound according to the following ratio of sodium: (yttrium + cerium): lithium: the boron molar ratio is 1-5:1:1-5:1-8, 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 saturation point temperature, then putting a platinum or iridium rod from the growth furnace to contact the surface of the melt, keeping the temperature for 2-12 hours, then reducing the temperature to the saturation point temperature 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 away from the liquid level, then quickly reducing the temperature to the room temperature at the speed of 10-100 ℃/h, and finally obtaining the cerium doped crystal of the lithium sodium yttrium borate. 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 ·4H 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 protects the application of the cerium doped compound or crystal of the lithium sodium yttrium borate, and the cerium doped compound or crystal of the lithium sodium yttrium borate is stable in air and does not deliquesce, and can be used as a scintillation material as a neutron detection material or as an optical functional material such as blue fluorescent powder for LED illumination.
The invention has the following beneficial effects: the cerium doped compound or the crystal of the lithium sodium yttrium borate has stable physicochemical property, is not deliquescent, has good flickering and fluorescent properties, can be used as a flickering material to be used as a neutron detection material or as blue fluorescent powder for LED illumination, and has important economic and scientific research values in the fields of high-energy physical particle detection, light illumination and the like.
Description of the drawings:
FIG. 1 shows the lithium sodium yttrium Li borate prepared in example 5 of the present invention 2 NaY(BO 3 ) 2 A schematic crystal structure of a single crystal along the b-axis and c-axis;
FIG. 2 is Li prepared in example 5 2 NaY(BO 3 ) 2 A theoretical band structure diagram of the crystal;
FIG. 3 is a block diagramLi prepared in example 1 2 NaY(BO 3 ) 2 Compound, li prepared in example 2 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 Compound, li prepared in example 3 2 NaY 0.7 Ce 0.3 (BO 3 ) 2 A powder XRD spectrum of the compound;
FIG. 4 is Li prepared in example 7 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 Scintillation properties of the crystal;
FIG. 5 is Li prepared in example 8 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 Scintillation properties of the crystal;
FIG. 6 is Li prepared in example 4 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 Fluorescence emission spectra of the compounds;
FIG. 7 is Li prepared in example 4 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 Fluorescent CIE chromaticity coordinates of the compound;
FIG. 8 is Li prepared in example 6 2 NaY 0.6 Ce 0.4 (BO 3 ) 2 Fluorescence decay curve under ultraviolet light excitation after crystal grinding.
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 Yttrium Compound Li 2 NaY(BO 3 ) 2 Compound (I)
Raw materials used (analytical purity): y is 2 O 3 0.1mol、H 3 BO 3 0.4mol、Na 2 CO 3 0.1mol、Li 2 CO 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
Putting the corundum crucible into a muffle furnace, heating to 500 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the second time, and then putting the corundum crucible into a furnacePutting the mixture into a muffle furnace, heating to 600 ℃, 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 700 ℃, keeping the temperature for 24 hours, taking out, and grinding to obtain the Li of the invention 2 NaY(BO 3 ) Compound (I) 2 。
Example 2: synthesis of 0.5% cerium-doped sodium yttrium lithium borate Li 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 Compound (I)
Raw materials used (analytical pure): y is 2 O 3 0.995mol、CeO 2 0.01mol、B 2 O 3 2.0mol、Na 2 CO 3 1.0mol、Li 2 CO 3 2.0mol。
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
Putting the platinum crucible into a tubular furnace, introducing hydrogen, heating to 450 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, putting the platinum crucible into a muffle furnace after the second grinding, introducing hydrogen, heating to 630 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, putting the platinum crucible into the muffle furnace after the third grinding, introducing hydrogen, heating to 730 ℃, keeping the temperature constant for 24 hours, taking out, and grinding to obtain the Li of the invention 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 A compound is provided.
Example 3: synthesis of 30% cerium-doped lithium sodium yttrium Li borate 2 NaY 0.7 Ce 0.3 (BO 3 ) 2 A compound:
raw materials used (analytical pure): y (NO) 3 ) 3 ·6H 2 O 0.07mol、Ce(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 materialsPlacing into agate mortar, carefully mixing and grinding, and then filling into
Putting the platinum crucible into a muffle furnace, putting the platinum crucible into a tubular furnace, introducing hydrogen, heating to 500 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the second time, putting the platinum crucible into the muffle furnace, grinding for the second time, introducing hydrogen 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 platinum crucible into the muffle furnace, introducing hydrogen, heating to 730 ℃, keeping the temperature for 24 hours, taking out, and grinding to obtain the Li of the invention 2 NaY 0.7 Ce 0.3 (BO 3 ) 2 A compound is provided.
Example 4: synthesis of 50% cerium-doped lithium sodium yttrium Li borate 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 Compound (I)
Raw materials used (analytical purity): y (NO) 3 ) 3 ·6H 2 O 0.75mol、Ce 2 O 3 0.375mol、B 2 O 3 1.5mol、Na 2 C 2 O 4 0.75mol、LiOH 3.0mol。
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
Putting the corundum crucible into a muffle furnace, introducing hydrogen, 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, introducing hydrogen, 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, introducing hydrogen, heating to 750 ℃, keeping the temperature for 24 hours, taking out, and grinding to obtain the Li of the invention 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 A compound is provided.
Example 5: preparation of lithium sodium yttrium Li borate 2 NaY(BO 3 ) 2 Crystal
Raw materials used (analytical pure): na (Na) 2 CO 3 0.015mol、Y 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
Putting the platinum crucible into a molten salt furnace, heating the platinum crucible to 950 ℃ at a speed of 20 ℃/h to completely melt the raw materials, preserving the heat for 12 hours, and then slowly cooling the platinum crucible at a speed of 2 ℃/h to obtain the platinum crucible with the size of 0.3 multiplied by 0.1mm 3 Lithium sodium yttrium lithium borate (Li) 2 NaY(BO 3 ) 2 And (4) crystals.
Example 6: preparation of 20% cerium-doped lithium sodium yttrium Li borate 2 NaY 0.8 Ce 0.2 (BO 3 ) 2 Crystal
Raw materials used (analytical pure): na (Na) 2 B 4 O 7 ·10H 2 O 0.9mol、Y(OH) 3 0.48mol、CeO 2 0.12mol、Li 2 CO 3 2.25mol、B 2 O 3 0.9mol。
The method comprises the following specific steps: weighing the above raw materials, mixing and grinding in mortar, and packaging
Putting the platinum crucible into a molten salt furnace, introducing hydrogen, heating to 965 ℃ at a speed of 10 ℃/h to completely melt the raw materials, preserving the heat for 36 hours, and then slowly cooling at a speed of 5 ℃/h to obtain the platinum crucible with the size of 0.38 multiplied by 0.23 multiplied by 0.17mm 3 Li of (2) 2 NaY 0.8 Ce 0.2 (BO 3 ) 2 And (4) crystals.
Example 7: preparation of 35% cerium doped lithium sodium yttrium Li borate 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 Crystal
Raw materials used (analytical purity): naHCO 2 3 0.4mol、Y 2 O 3 0.065mol、CeO 2 0.07mol、Li 2 CO 3 0.8mol、H 3 BO 3 1.8mol
The method comprises the following specific steps: weighing the above raw materials, mixing and grinding in mortar, and packaging
Putting the platinum crucible into a molten salt furnace, and introducing Ar/H 2 Heating to 980 deg.C at 15 deg.C/h for completely melting raw materials, maintaining for 12 hr, and slowly cooling at 5 deg.C/h to obtain a product with size of 0.21 × 0.12 × 0.08mm 3 Li of (2) 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 And (4) crystals.
Example 8: preparation of 10% cerium-doped lithium sodium yttrium Li borate 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 Crystal
Raw materials used (analytical pure): naBO 2 4H 2 O 1.0mol、Y 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
Putting the platinum crucible into a medium-frequency pulling furnace, and introducing high-purity N 2 /H 2 Heating the mixed gas to be completely melted, stirring for 24 hours, when the temperature of the melt 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 the 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 the room temperature at the speed of 50 ℃/h to obtain the crystal with the size of 3.2 DEG×2.3×1.5mm 3 Li of (2) 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 And (4) crystals.
Example 9: characterization of lithium sodium yttrium borate and its cerium-doped compounds and crystals
The lithium sodium borate yttrium Li prepared in the embodiment 5 of the invention 2 NaY(BO 3 ) 2 The single crystal adopts an X-ray single crystal diffraction method to carry out cell structure determination, the cell structure is shown in figure 1 and can be obtained from figure 1, and the lithium sodium yttrium borate crystal Li 2 NaY(BO 3 ) 2 Belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
α＝90°，β＝103.278，γ＝90°，
Z =4. The 10% cerium-doped lithium sodium yttrium borate Li prepared in example 8 of the invention 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 The single crystal is subjected to cell structure determination by an X-ray single crystal diffraction method, and the Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 Belongs to the monoclinic system, and the space group is P2 1 N, unit cell parameter of
α＝90°，β＝103.362，γ＝90°，
Z＝4。
Li prepared in the examples 1, 2 and 3 of the present invention 2 NaY(BO 3 ) 2 、Li 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 And Li 2 NaY 0.7 Ce 0.3 (BO 3 ) 2 The compound is carefully ground and then irradiated by X-rayThe normal temperature XRD test of the linear powder diffractometer is carried out, as shown in figure 3, the result shows that the prepared compound belongs to a pure phase and no other impure phases are generated.
Li prepared in inventive example 7 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 The X-ray scintillation spectrum of the crystal is shown in figure 4, and the crystal has scintillation detection performance in a visible light band, which proves that Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 Has better use value.
Li prepared in the invention of example 8 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 The X-ray scintillation spectrum of the crystal is shown in figure 5, and the crystal has scintillation detection performance in a visible light band, which proves that Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 Has better use value.
Li prepared in inventive example 4 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 After being carefully ground, the compound emits characteristic blue light under the excitation of ultraviolet light, the fluorescence emission spectrum of the compound is shown in figure 6, and the CIE chromaticity coordinates (0.155, 0.143 and 0.702) of the compound are marked in figure 7, so that the compound is proved to have good use value as blue fluorescent powder for LEDs.
Li prepared in inventive example 4 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 After being carefully ground, the compound emits characteristic blue light under the excitation of ultraviolet light, the fluorescence emission spectrum of the compound is shown in figure 6, and the CIE chromaticity coordinates (0.155, 0.143 and 0.702) of the compound are marked in figure 7, so that the compound is proved to have good use value as blue fluorescent powder for LEDs.
Li prepared in inventive example 6 2 NaY 0.6 Ce 0.4 (BO 3 ) 2 After the crystal is carefully ground and excited by ultraviolet light, the fluorescence attenuation curve of the crystal is shown in figure 8, the attenuation is fast to nanosecond level, and the crystal has good use value.
Claims (10)
1. Has a chemical formula of Li 2 NaY(BO 3 ) 2 The lithium sodium yttrium borate compound of (1).
2. Lithium sodium yttrium borate crystal characterized by having the chemical formula of Li 2 NaY(BO 3 ) 2 Monoclinic system, space group is P2 1 N, unit cell parameter of
α＝90°，β＝103.278，γ＝90°，
Z＝4。
3. The cerium doped compound of lithium sodium yttrium borate is characterized in that the chemical general formula is Li 2 NaY 1-x Ce x (BO 3 ) 2 Wherein x is more than 0 and less than or equal to 0.5.
4. The cerium doped crystal of lithium sodium yttrium borate is characterized in that the chemical general formula is Li 2 NaY 1-x Ce x (BO 3 ) 2 Wherein x is more than 0 and less than or equal to 0.5, monoclinic system, and space group is P2 1 N, unit cell parameters in the range of
α＝90°，β＝102.729(2)-103.889(1)°，γ＝90°，
Z＝4。
5. A method of preparing a lithium sodium yttrium borate compound of claim 1 comprising the steps of:
mixing a sodium-containing compound, an yttrium-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: yttrium: lithium: the molar ratio of boron elements is 1:1:2:2, uniformly putting the mixture into a mortar, fully mixing and grinding the mixture, then putting the mixture into a crucible, putting the crucible into a muffle furnace, heating the mixture to 400-550 ℃, keeping the temperature for 12-48 hours, cooling the mixture to room temperature, taking out the mixture, putting the mixture into the muffle furnace after the second grinding, introducing hydrogen, heating the mixture to 550-700 ℃, keeping the temperature for 12-48 hours, cooling the mixture to room temperature, taking out the mixture, putting the mixture into the muffle furnace after the third grinding, introducing hydrogen, heating the mixture to 700-800 ℃, keeping the temperature for 12-48 hours, taking out the mixture, and grinding the mixture to obtain a lithium sodium yttrium borate compound; 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 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 of preparing a cerium doped compound of lithium sodium yttrium borate according to claim 3, comprising the steps of:
mixing a sodium-containing compound, an yttrium-containing compound, a cerium-containing compound, a lithium-containing compound and a boron-containing compound according to the following ratio of sodium: (yttrium + cerium): lithium: the molar ratio of boron elements is 1:1:2:2, then putting the mixture into a crucible, putting the mixture into a muffle furnace, introducing hydrogen, heating to 400-550 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out the mixture, putting the mixture into the muffle furnace after the second grinding, introducing hydrogen, heating to 550-700 ℃, keeping the temperature for 12-48 hours, cooling to room temperature,taking out, grinding for the third time, putting into a muffle furnace, introducing hydrogen, heating to 700-800 ℃, keeping the temperature for 12-48 hours, taking out, and grinding to obtain a 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 、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) to (b); the compound containing cerium being CeO 2 、Ce 2 O 3 、Ce(NO 3 ) 3 ·6H 2 O、Ce 2 (SO 4 ) 3 ·4H 2 Any one of O; the compound containing lithium 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 yttrium lithium sodium borate crystals, comprising the steps of: mixing a sodium-containing compound, an yttrium-containing compound, a lithium-containing compound and a boron-containing compound according to the ratio of sodium: yttrium: lithium: the molar ratio of boron elements is 1-8:1:5-13:5-15, putting the mixture into a crucible, heating the mixture to 700-1050 ℃ at a heating rate of 1-30 ℃/h to obtain high-temperature melt, keeping the temperature for 12-60h, and cooling the solution to room temperature at a speed of 1-15 ℃/h to obtain lithium sodium yttrium borate crystals; 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 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 。
8. A method of preparing cerium doped crystals of lithium sodium yttrium borate, comprising the steps of: mixing a sodium-containing compound, an yttrium-containing compound, a cerium-containing compound, a lithium-containing compound and a boron-containing compound according to the following ratio of sodium: (yttrium + cerium): lithium: the molar ratio of boron elements is 1-8:1:5-13:5-15, uniformly mixing and grinding, placing into a crucible, placing into a molten salt furnace, introducing hydrogen, heating to 700-1050 ℃ at a heating rate of 1-30 ℃/h to obtain a high-temperature melt, keeping the temperature for 12-60h, and cooling to room temperature at a speed of 1-15 ℃/h to obtain lithium sodium yttrium borate crystals; 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) to (b); the compound containing cerium being CeO 2 、Ce 2 O 3 、Ce(NO 3 ) 3 ·6H 2 O、Ce 2 (SO 4 ) 3 ·4H 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 。
9. A method of preparing cerium doped crystals of lithium sodium yttrium borate, comprisingThe method comprises the following steps: mixing a sodium-containing compound, an yttrium-containing compound, a cerium-containing compound, a lithium-containing compound and a boron-containing compound according to the following ratio of sodium: (yttrium + cerium): lithium: the boron molar ratio is 1-5:1:1-5:1-8, 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 a growth furnace, contacting the platinum or iridium rod with 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 cerium-doped crystal of the lithium sodium yttrium borate; 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 ·4H 2 Any one of O; the compound containing lithium being Li 2 CO 3 、LiNO 3 Or LiOH; the boron-containing compound is H 3 BO 3 Or B 2 O 3 。
10. Use of cerium doped compounds or crystals of lithium sodium yttrium borate as scintillating material as neutron detecting material or as blue phosphor for LED illumination.
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