CN115367767B - Lithium sodium yttrium borate and cerium doped compound and crystal thereof, and preparation methods and application thereof - Google Patents

Lithium sodium yttrium borate and cerium doped compound and crystal thereof, and preparation methods and application thereof Download PDF

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CN115367767B
CN115367767B CN202210938324.4A CN202210938324A CN115367767B CN 115367767 B CN115367767 B CN 115367767B CN 202210938324 A CN202210938324 A CN 202210938324A CN 115367767 B CN115367767 B CN 115367767B
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陈鹏允
杨鸣名
林利添
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 lithium sodium yttrium borate, a cerium doped compound and crystal thereof, a preparation method and application thereof, and a lithium sodium yttrium borate compound with a chemical formula of Li 2 NaY(BO 3 ) 2 Cerium doped compound of lithium sodium yttrium borate with 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, is cheap and easy to obtain, is simple and convenient to synthesize, has stable physicochemical properties, does not deliquesce, has good scintillation and fluorescence properties, can be used as a scintillation material for neutron detection or 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

Lithium sodium yttrium borate and cerium doped compound and crystal thereof, and preparation methods and application thereof
Technical field:
the invention relates to the technical field of scintillation 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 technology is as follows:
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 moment, so that the utilization of neutron diffraction/scattering is a powerful means for researching the crystal structure, the super structure and the magnetic structure of materials at present. Neutrons are uncharged particles that differ from X-rays and alpha-rays, and therefore cannot be observed by directly causing ionization of scintillation materials, so how to effectively and accurately detect neutrons is one of the important research matters of current high-energy particle detection.
The scintillator detector using the scintillation crystal as a core has wider application range, environmental adaptability and higher detection efficiency compared with other detectors. Existing rare earth potassium cryolite family crystal Cs 2 LiYCl 6 ：Ce 3+ 、Cs 2 LiLuBr 6 ：Ce 3+ 、Rb 2 LiYBr 6 ：Ce 3+ The 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. However, YCl grown by the crystal material 3 、LuBr 3 、YBr 3 The raw materials are expensive, the raw materials are also required to be packaged in a quartz crucible under the anhydrous and anaerobic condition, and the prepared crystal is extremely deliquescent in the air, so that the cost and difficulty in crystal growth, processing and packaging are greatly increased, and therefore, a novel scintillation material which is stable in physicochemical property, free from deliquescence, low in cost and easy to obtain is required to be further explored.
The invention comprises the following steps:
the invention aims to provide lithium sodium yttrium borate and cerium doped compound and crystal thereof, and a preparation method and application thereof, wherein the lithium sodium yttrium borate and cerium doped compound and crystal are low in cost, easy to obtain, stable in physicochemical property, free from deliquescence and good in scintillation/fluorescence performance, and are expected to be used in the fields of high-energy particle detection and LED illumination, so that the problems of high cost and unstable property in the prior art are solved.
The invention is realized by the following technical scheme:
lithium sodium yttrium borate compound with chemical formula of Li 2 NaY(BO 3 ) 2 Molecular weight 243.39.
Lithium sodium yttrium borate crystal with chemical formula of Li 2 NaY(BO 3 ) 2 Belongs to monoclinic system, and the space group is P2 1 N, unit cell parameters are
Figure BDA0003784398540000021
Figure BDA0003784398540000022
α＝90°，β＝103.278，γ＝90°，/>
Figure BDA0003784398540000023
Z＝4。
Cerium doped compound of lithium sodium yttrium borate with 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.
Cerium doped crystal of lithium sodium yttrium borate with 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 the space group is P2 1 The range of unit cell parameters is/n
Figure BDA0003784398540000024
Figure BDA0003784398540000025
α＝90°，β＝102.729(2)-103.889(1)°，γ＝90°，
Figure BDA0003784398540000026
Figure BDA0003784398540000027
Z＝4。
The asymmetric unit of the unit cell comprises 1 Na, 2 Li and 1Y 1-x Ce x (0.ltoreq.x.ltoreq.0.5), 2B and 6O. Na forms eight coordination with O, two Li forms four coordination with O, two B forms three coordination with O, Y 1-x Ce x (0.ltoreq.x.ltoreq.0.5) and O form seven coordination. The three-dimensional space structure is based on NaO 8 Dodecahedron, isolated BO 3 Plane triangle, liO 4 Tetrahedral sum (Y) 1-x Ce x )O 7 The pentagonal bipyramid is formed by interlinking pentagonal bipyramids. NaO (NaO) 8 The dodecahedron bodies are connected together at the same edge and the same point to form a one-dimensional Na-O chain, (Y) 1-x Ce x )O 7 The pentagonal bipyramid is connected in a two-by-two joint way 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 framework, and two kinds of independent crystallography LiO 4 Formation of tetrahedral co-edge connection [ LiO ] 2 ]The one-dimensional chain penetrates through the framework of the crystal along the direction of the b axis.
The invention also provides a preparation method of the lithium sodium yttrium borate compound, which comprises the following steps:
a sodium-containing compound, an yttrium-containing compound, a lithium-containing compound, a boron-containing compound, according to sodium: yttrium: lithium: the molar ratio of boron element is 1:1:2:2, then placing the materials into a crucible, heating to 400-550 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, placing into the muffle furnace after secondary grinding, introducing hydrogen, heating to 550-700 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, placing into the muffle furnace after tertiary grinding, introducing hydrogen, raising to 700-800 ℃, keeping the temperature for 12-48 hours, taking out, and grinding 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; 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 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 cerium doped compound of lithium sodium yttrium borate, which comprises the following steps:
a sodium-containing compound, a yttrium-containing compound, a cerium-containing compound, a lithium-containing compound, a boron-containing compound, according to sodium: (yttrium+cerium): 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 400-550 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, placing the materials 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, placing the materials into the muffle furnace after the third grinding, introducing hydrogen, raising the temperature to 700-800 ℃, 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 、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 。
A method for preparing lithium sodium yttrium borate crystals, the method comprising the steps of: a sodium-containing compound, an yttrium-containing compound, a lithium-containing compound, a boron-containing compound, according to sodium: yttrium: lithium: the molar ratio of boron element is 1-8:1:5-13: mixing and grinding uniformly in proportion of 5-15, loading into a crucible, heating to 700-1050 ℃ at a heating rate of 1-30 ℃/h to obtain high Wen Rongye, preserving heat for 12-60h, and then cooling to room temperature at a speed of 1-15 ℃/h to obtain lithium sodium yttrium borate crystals. Wherein, the liquid crystal display device comprises a liquid crystal display device,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 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 。
A method of preparing a cerium doped crystal of lithium sodium yttrium borate, the method comprising the steps of: a sodium-containing compound, a yttrium-containing compound, a cerium-containing compound, a lithium-containing compound, a boron-containing compound, according to sodium: (yttrium+cerium): lithium: the molar ratio of boron element is 1-8:1:5-13:5-15, 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 high Wen Rongye, preserving heat for 12-60h, and cooling to room temperature at a speed of 1-15 ℃/h to obtain 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; 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 ·4H 2 Any one of O; lithium-containing compoundsIs 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 a cerium doped crystal of lithium sodium yttrium borate, the method comprising the steps of: a sodium-containing compound, a yttrium-containing compound, a cerium-containing compound, a lithium-containing compound, a boron-containing compound, according to sodium: (yttrium+cerium): lithium: the molar ratio of boron is 1-5:1:1-5:1-8, charging into crucible, charging into intermediate frequency pulling furnace, charging high purity N 2 /H 2 Ar gas is heated to be completely melted, stirred for 12-24 hours, when the temperature of the melt is 0.1-3 ℃ higher than the saturation point temperature, a platinum or iridium rod is put into a growth furnace to be contacted with the surface of the melt, the temperature is kept for 2-12 hours, after the temperature is reduced to the saturation point temperature at 0.1-10 ℃/h, the rotating speed of the platinum or iridium rod is set to be 2-25r/min, then the temperature is slowly reduced at the speed of 0.05-10 ℃/h, the temperature is slowly reduced at the lifting speed of 0.05-0.75mm/h, when the crystal grows to a certain size, the crystal is lifted off the liquid level, and then the temperature is quickly reduced to the room temperature at the speed of 10-100 ℃/h, and finally the cerium doped crystal of lithium sodium yttrium borate 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; 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 ·4H 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 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 for neutron detection or used as a light functional material such as blue fluorescent powder for LED illumination.
The beneficial effects of the invention are as follows: the invention provides a novel lithium sodium yttrium borate and cerium doped compound or crystal thereof and a preparation method thereof, and the novel lithium sodium yttrium borate and cerium doped compound or crystal thereof are low in cost, easy to obtain and simple and convenient to synthesize, have stable physicochemical properties, do not deliquesce, have good scintillation and fluorescence properties, can be used as a scintillation material to be used as a neutron detection material or used as blue fluorescent powder for LED illumination, and have 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 is a lithium sodium yttrium borate Li prepared in example 5 of the present invention 2 NaY(BO 3 ) 2 Schematic of the crystal structure of the single crystal along the b-axis and the c-axis;
FIG. 2 is Li prepared in example 5 2 NaY(BO 3 ) 2 Theoretical energy band structure diagram of crystal;
FIG. 3 is Li prepared in example 1 2 NaY(BO 3 ) 2 Compounds, li prepared in example 2 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 Compounds, li prepared in example 3 2 NaY 0.7 Ce 0.3 (BO 3 ) 2 Powder XRD spectrum of the compound;
FIG. 4 is Li prepared in example 7 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 The scintillation property of the crystal;
FIG. 5 is Li prepared in example 8 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 The scintillation property 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 obtained by the preparation of example 6 2 NaY 0.6 Ce 0.4 (BO 3 ) 2 Fluorescence decay curve under ultraviolet excitation after crystal grinding.
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 yttrium borate Compound Li 2 NaY(BO 3 ) 2 Compounds of formula (I)
Raw materials used (analytically pure): y is Y 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 materials, placing into agate mortar, mixing, grinding, and loading into
Figure BDA0003784398540000061
Is put into a muffle furnace, heated to 500 ℃, 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 600 ℃ again, 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 700 ℃ again, kept at constant temperature for 24 hours, taken out, and ground to obtain the Li 2 NaY(BO 3 ) Compounds of formula (I) 2 。
Example 2: synthesis of 0.5% cerium doped lithium sodium yttrium borate Li 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 Compounds of formula (I)
Raw materials used (analytically pure): y is Y 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 materials, placing into agate mortar, mixing, grinding, and loading into
Figure BDA0003784398540000073
Figure BDA0003784398540000074
Placing the platinum crucible into a tube furnace, introducing hydrogen, heating to 450 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing the crucible into a muffle furnace after secondary grinding, introducing hydrogen, heating to 630 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing the crucible into the muffle furnace after tertiary grinding, introducing hydrogen, keeping the temperature constant for 24 hours, taking out, grinding to obtain the Li 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 A compound.
Example 3: synthesis of 30% cerium doped lithium sodium yttrium borate Li 2 NaY 0.7 Ce 0.3 (BO 3 ) 2 A compound:
raw materials used (analytically 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 materials, placing into agate mortar, mixing, grinding, and loading into
Figure BDA0003784398540000071
Figure BDA0003784398540000072
Placing the crucible into a muffle furnace, placing into a tube furnace, introducing hydrogen, heating to 500 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing into the muffle furnace after secondary grinding, introducing hydrogen into the muffle furnace after secondary grinding, heating to 680 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, placing into the muffle furnace after tertiary grinding, introducing hydrogen, keeping the temperature constant for 24 hours at 730 ℃, taking out, and grinding to obtain the Li of the invention 2 NaY 0.7 Ce 0.3 (BO 3 ) 2 Chemical combinationAnd (3) an object.
Example 4: synthesis of 50% cerium doped lithium sodium yttrium borate Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 Compounds of formula (I)
Raw materials used (analytically pure): 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 materials, placing into agate mortar, mixing, grinding, and loading into
Figure BDA0003784398540000075
Figure BDA0003784398540000076
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 secondary 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 tertiary grinding, introducing hydrogen, keeping the temperature for 24 hours, taking out, and grinding to obtain the Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 A compound.
Example 5: preparation of lithium sodium yttrium borate Li 2 NaY(BO 3 ) 2 Crystal body
Raw materials used (analytically 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 materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784398540000082
Putting the platinum crucible into a molten salt furnace, heating to 950 ℃ at 20 ℃/h, fully melting the raw materials, preserving the heat for 12 hours, and then slowly cooling at the rate of 2 ℃/h to obtain the alloy with the size of 0.3×0.3×0.1mm 3 Lithium sodium yttrium borate Li 2 NaY(BO 3 ) 2 And (5) a crystal.
Example 6: preparation of 20% cerium doped lithium sodium yttrium borate Li 2 NaY 0.8 Ce 0.2 (BO 3 ) 2 Crystal body
Raw materials used (analytically 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 materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784398540000083
Putting into a platinum crucible, putting into a molten salt furnace, introducing hydrogen, heating to 965 ℃ at 10 ℃/h, fully melting the raw materials, preserving heat for 36 hours, and slowly cooling at a rate of 5 ℃/h to obtain the alloy 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 (5) a crystal.
Example 7: preparation of 35% cerium doped lithium sodium yttrium borate Li 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 Crystal body
Raw materials used (analytically pure): naHCO (NaHCO) 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 materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784398540000081
Putting the mixture into a platinum crucible, and then putting the mixture into a molten salt furnace to be introduced with Ar/H 2 Heating to 980 deg.C at 15 deg.C/h to melt the raw materials completely, maintaining the temperature for 12 hr, and slowly cooling at 5 deg.C/hr to obtain the final product with a size of 0.21×0.12×0.08mm 3 Li of (2) 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 And (5) a crystal.
Example 8: preparation of 10% cerium doped lithium sodium yttrium borate Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 Crystal body
Raw materials used (analytically 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 materials, mixing in a mortar, grinding, and packaging
Figure BDA0003784398540000096
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 3.2X2.3X1.5 mm 3 Li of (2) 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 And (5) a crystal.
Example 9: lithium sodium yttrium borate and characteristic test of cerium doped compound and crystal thereof
Lithium sodium yttrium lithium borate prepared in example 5 of the present invention 2 NaY(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 the figure 1 can obtain the lithium sodium yttrium borate crystal Li 2 NaY(BO 3 ) 2 Belonging to monoclinic system, the space group is P2 1 N, unit cell parameters are
Figure BDA0003784398540000091
α＝90°，β＝103.278，γ＝90°，/>
Figure BDA0003784398540000092
Z=4. 10% cerium doped lithium sodium yttrium borate Li prepared in example 8 of the present invention 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 Unit cell structure determination of single crystal by X-ray single crystal diffraction method, li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 Belonging to monoclinic system, the space group is P2 1 N, unit cell parameters->
Figure BDA0003784398540000093
Figure BDA0003784398540000094
α＝90°，β＝103.362，γ＝90°，/>
Figure BDA0003784398540000095
Z＝4。
Li prepared in example 1, example 2 and example 3 of the present invention 2 NaY(BO 3 ) 2 、Li 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 And Li (lithium) 2 NaY 0.7 Ce 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 figure 3, and the result shows that the prepared compound belongs to a pure phase and no other impurity phase is generated.
Li prepared in example 7 of the present invention 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 The crystal has X-ray scintillation spectrum shown in figure 4 and scintillation detection performance in visible light band, which proves that Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 Has better use value.
Li prepared in example 8 of the present invention 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 The crystal has X-ray scintillation spectrum shown in figure 5 and scintillation detection performance in visible light band, which proves that Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 Has a relatively high degree ofGood use value.
Li prepared in example 4 of the present invention 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 After the compound is carefully ground, characteristic blue light is emitted under ultraviolet excitation, the fluorescence emission spectrum is shown in fig. 6, and the CIE chromaticity coordinates (0.155, 0.143 and 0.702) are shown in fig. 7, so that the compound has good use value as blue fluorescent powder for LEDs.
Li prepared in example 4 of the present invention 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 After the compound is carefully ground, characteristic blue light is emitted under ultraviolet excitation, the fluorescence emission spectrum is shown in fig. 6, and the CIE chromaticity coordinates (0.155, 0.143 and 0.702) are shown in fig. 7, so that the compound has good use value as blue fluorescent powder for LEDs.
Li prepared in example 6 of the present invention 2 NaY 0.6 Ce 0.4 (BO 3 ) 2 After the crystal is carefully ground, the fluorescence attenuation curve of the crystal is shown in figure 8 under ultraviolet excitation, and the attenuation is faster to nanosecond level, so that the crystal has good use value.

Claims (10)

1. The chemical formula is Li 2 NaY(BO 3 ) 2 The preparation method of the lithium sodium yttrium borate compound is characterized by comprising the following steps:
a sodium-containing compound, an yttrium-containing compound, a lithium-containing compound, a boron-containing compound, according to sodium: yttrium: lithium: the molar ratio of boron element is 1:1:2:2, then placing the materials into a crucible, heating to 400-550 ℃, 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 550-700 ℃, 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 700-800 ℃, keeping the temperature for 12-48 hours, taking out, and grinding to obtain the lithium sodium yttrium borate compound.
2. According to claim 1Wherein the sodium-containing compound is Na 2 CO 3 、NaHCO 3 、Na 2 C 2 O 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 Any one of them; 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. The lithium sodium yttrium borate crystal is characterized in that the chemical formula is Li 2 NaY(BO 3 ) 2 Monoclinic system with space group ofP2 1 /nThe unit cell parameters area =6.6146 Å, b= 9.1303 Å, c= 8.8503 Å, α= 90°，β=103.278，γ= 90°，V= 520.21 Å 3 ，Z= 4。
4. The cerium doped compound of lithium sodium yttrium borate is characterized by having a 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 preparation method comprises the following steps: a sodium-containing compound, a yttrium-containing compound, a cerium-containing compound, a lithium-containing compound, a boron-containing compound, according to sodium: (yttrium+cerium): 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 400-550 ℃, keeping the temperature for 12-48 hours, cooling to room temperature, taking out, placing the materials 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, placing the materials into the muffle furnace after the third grinding, introducing hydrogen, heating to 700-800 ℃, keeping the temperature for 12-48 hours, taking out, grinding to obtain the cerium doped lithium sodium yttrium borateAnd (3) a compound.
5. The cerium doped lithium sodium yttrium borate compound of claim 4, wherein the sodium containing compound is Na 2 CO 3 、NaHCO 3 、Na 2 C 2 O 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 Any one of them; the cerium-containing compound is CeO 2 、Ce 2 O 3 、Ce(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。
6. The cerium doped crystal of lithium sodium yttrium borate is characterized by having a 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 monoclinic system is a space groupP2 1 /nThe unit cell parameters range froma = 6.5571(7)- 6.8648 (1) Å, b= 9.0338(9)- 9.3417(2) Å, c= 8.7765(9)- 9.2273 (2) Å, α= 90°，β=102.729(2)-103.889(1) °，γ= 90°，V= 507.1036-577.792(2) Å 3 ，Z= 4。
7. A process for preparing lithium sodium yttrium borate crystals according to claim 3, characterized in that it comprises the steps of: a sodium-containing compound, an yttrium-containing compound, a lithium-containing compound, a boron-containing compound, according to sodium: yttrium: lithium: the molar ratio of boron element is 1-8:1:5-13: mixing and grinding at 5-15 ratio, loading into crucible, heating to 700-1050 deg.C at 1-30deg.C/hr to obtain high Wen Rongye, maintaining for 12-60 hr, and heating at 1-15deg.C/hrCooling to room temperature to obtain lithium sodium yttrium borate crystal; wherein the sodium-containing compound is Na 2 CO 3 、NaHCO 3 、Na 2 C 2 O 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 Any one of them; 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. A method for preparing the lithium sodium yttrium borate cerium doped crystal of claim 6, comprising the steps of: a sodium-containing compound, a yttrium-containing compound, a cerium-containing compound, a lithium-containing compound, a boron-containing compound, according to sodium: (yttrium+cerium): lithium: the molar ratio of boron element is 1-8:1:5-13:5-15, 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 high Wen Rongye, preserving heat for 12-60h, and cooling to room temperature at a speed of 1-15 ℃/h to obtain lithium sodium yttrium borate crystal; wherein the sodium-containing compound is Na 2 CO 3 、NaHCO 3 、Na 2 C 2 O 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 Any one of them; the cerium-containing compound is CeO 2 、Ce 2 O 3 、Ce(NO 3 ) 3 ·6H 2 Any one of O; the lithium-containing compound is Li 2 CO 3 、LiNO 3 Or Li (lithium)Any one of OH; the boron-containing compound being H 3 BO 3 Or B is a 2 O 3 。
9. A method for preparing the lithium sodium yttrium borate cerium doped crystal of claim 6, comprising the steps of: a sodium-containing compound, a yttrium-containing compound, a cerium-containing compound, a lithium-containing compound, a boron-containing compound, according to sodium: (yttrium+cerium): lithium: the molar ratio of boron is 1-5:1:1-5:1-8, 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 hours, when the temperature of the melt is 0.1-3 ℃ higher than the saturation point temperature, putting a platinum or iridium rod into a growth furnace to enable the platinum or iridium rod to contact the surface of the melt, keeping the temperature for 2-12 hours, 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, slowly reducing the temperature at the speed of 0.05-10 ℃/h, and pulling the crystal 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 surface, and rapidly reducing the temperature to room temperature at the speed of 10-100 ℃/h, thus obtaining the cerium doped crystal 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 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 Any one of them; the cerium-containing compound is CeO 2 、Ce 2 O 3 、Ce(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 。
10. Use of the cerium doped compound of lithium sodium yttrium borate as claimed in claim 4 or the cerium doped crystal of lithium sodium yttrium borate as claimed in claim 6 as a scintillating material for use as a neutron detection material or as a blue phosphor for LED illumination.
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