WO2024027105A1 - Lithium sodium yttrium borate and cerium-doped compound and crystal thereof, and preparation methods therefor and use thereof - Google Patents

Lithium sodium yttrium borate and cerium-doped compound and crystal thereof, and preparation methods therefor and use thereof Download PDF

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WO2024027105A1
WO2024027105A1 PCT/CN2023/070435 CN2023070435W WO2024027105A1 WO 2024027105 A1 WO2024027105 A1 WO 2024027105A1 CN 2023070435 W CN2023070435 W CN 2023070435W WO 2024027105 A1 WO2024027105 A1 WO 2024027105A1
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lithium
sodium
cerium
yttrium
containing compound
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陈鹏允
杨鸣名
林利添
匡猛
倪海勇
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广东省科学院资源利用与稀土开发研究所
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    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C—CHEMISTRY; METALLURGY
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions

  • the invention relates to the technical field of scintillation materials, and specifically relates to a lithium sodium yttrium borate and its cerium doped compound and crystal, as well as its preparation method and use.
  • the use of scintillation crystals is currently an important technical solution.
  • the scintillator detector with scintillation crystal as the core has a wider adaptability range, environmental adaptability and higher detection efficiency than other detectors.
  • the existing rare earth potassium cryolite group crystals Cs 2 LiYCl 6 : Ce 3+ , Cs 2 LiLuBr 6 : Ce 3+ , Rb 2 LiYBr 6 : Ce 3+ , etc. have high light yield, fast attenuation, high energy resolution and can It has the advantages of realizing n- ⁇ dual detection and is considered to be an ideal scintillation material for neutron detection.
  • the purpose of the invention is to provide lithium sodium yttrium borate and its cerium-doped compounds and crystals and their preparation methods and uses, which are cheap and easy to obtain, have stable physical and chemical properties, are not deliquescent and have good flickering/fluorescence properties, and are expected to be used in high-energy particle detection and LED lighting.
  • Field use solves the problems of high cost and unstable nature of existing technology.
  • Lithium sodium yttrium borate compound has a chemical formula of Li 2 NaY (BO 3 ) 2 and a molecular weight of 243.39.
  • the cerium-doped compound of lithium sodium yttrium borate has a general chemical formula: Li 2 NaY 1-x Ce x (BO 3 ) 2 , where 0 ⁇ x ⁇ 0.5.
  • Cerium-doped crystal of lithium sodium yttrium borate the general chemical formula is: Li 2 NaY 1-x Ce x (BO 3 ) 2 , where 0 ⁇ x ⁇ 0.5, it belongs to the monoclinic crystal system, and the space group is P2 1 /n.
  • Na forms eight coordinations with O
  • two Lis form four coordinations with O
  • two Bs form three coordinations with O
  • Y 1-x Ce x (0 ⁇ x ⁇ 0.5) forms seven coordinations with O.
  • Its three-dimensional space structure is based on NaO 8 dodecahedron, isolated BO 3 planar triangle, LiO 4 tetrahedron and (Y 1-x Ce x )O 7 pentagonal bipyramid linked to each other.
  • NaO 8 dodecahedrons share edges and points to form a one-dimensional Na-O chain
  • (Y 1-x Ce x )O 7 pentagonal bipyramids share edges to form (Y 1-x Ce x ) 2 O 12 dimer
  • the edge connections form [LiO 2 ] one-dimensional chains that run through the skeleton of the crystal along the b-axis direction.
  • the present invention also protects the preparation method of lithium sodium yttrium borate compound, which includes the following steps:
  • the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H 2 O, Any of NaBO 2 ⁇ 4H 2 O; yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ⁇ 6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 ( Any one of SO 4 ) 3 ; the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  • the present invention also protects the preparation method of the cerium doped compound of lithium sodium yttrium borate, which includes the following steps:
  • the sodium-containing compound, the yttrium-containing compound, the cerium-containing compound, the lithium-containing compound, and the boron-containing compound are mixed according to the ratio of sodium: (yttrium + cerium): lithium: boron element molar ratio of 1:1:2:2 Evenly put it into a mortar and mix thoroughly, then put it into a crucible, put it into a muffle furnace and pass in hydrogen, raise the temperature to 400-550°C, keep it constant for 12-48 hours, cool it to room temperature, take it out, and grind it a second time.
  • the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H 2 O, NaBO Any of 2 ⁇ 4H 2 O;
  • the yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ⁇ 6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 (SO 4 ) Any one of 3 ;
  • the cerium-containing compound is any one of CeO 2 , Ce 2 O 3 , Ce(NO 3 ) 3 ⁇ 6H 2 O, and Ce 2 (SO 4 ) 3 ⁇ 4H 2 O;
  • the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH;
  • the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  • a method for preparing lithium sodium yttrium borate crystal includes the following steps: adding sodium-containing compounds, yttrium-containing compounds, lithium-containing compounds, and boron-containing compounds according to the molar ratio of sodium:yttrium:lithium:boron element to 1 -Mix and grind evenly in the ratio of 8:1:5-13:5-15, put it into a crucible, heat it to a temperature of 700-1050°C at a heating rate of 1-30°C/h, and then obtain a high-temperature melt, and keep it warm for 12-60h , and then lowered to room temperature at a rate of 1-15°C/h to obtain lithium sodium yttrium borate crystals.
  • the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H 2 O, Any of NaBO 2 ⁇ 4H 2 O; yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ⁇ 6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 ( Any one of SO 4 ) 3 ; the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  • a method for preparing cerium-doped crystals of lithium sodium yttrium borate includes the following steps: adding sodium-containing compounds, yttrium-containing compounds, cerium-containing compounds, lithium-containing compounds, and boron-containing compounds according to sodium: ( Yttrium + cerium): lithium: boron element molar ratio is 1-8: 1: 5-13: 5-15, evenly mixed and ground, put into a crucible, placed in a molten salt furnace and passed into hydrogen, and then 1 After heating to a temperature of 700-1050°C at a heating rate of -30°C/h, a high-temperature melt is obtained, kept for 12-60h, and then lowered to room temperature at a rate of 1-15°C/h to obtain lithium sodium yttrium borate crystals.
  • the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H 2 O, Any of NaBO 2 ⁇ 4H 2 O; yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ⁇ 6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 ( Any one of SO 4 ) 3 ; the cerium-containing compound is any one of CeO 2 , Ce 2 O 3 , Ce(NO 3 ) 3 ⁇ 6H 2 O, and Ce 2 (SO 4 ) 3 ⁇ 4H 2 O ;
  • the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  • a method for preparing cerium-doped crystals of lithium sodium yttrium borate includes the following steps: adding sodium-containing compounds, yttrium-containing compounds, cerium-containing compounds, lithium-containing compounds, and boron-containing compounds according to sodium: ( Yttrium + cerium): lithium: boron molar ratio is 1-5: 1: 1-5: 1-8, evenly mixed and ground, put into a crucible, then put into a medium frequency pulling furnace, and pass in high-purity N 2 /H 2 /Ar gas, heat until completely melted, stir for 12-24 hours, when the melt temperature is 0.1-3°C higher than the saturation point, then put a platinum or iridium rod from the growth furnace to make it contact with the melt surface, and keep it for 2-12 hours, then reduce the temperature to the saturation point temperature at 0.1-10°C/h, and set the rotation speed of the platinum or iridium rod to 2-25r/min, and then set the speed of the platinum or iridium rod to
  • the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H 2 O, Any of NaBO 2 ⁇ 4H 2 O;
  • yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ⁇ 6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 ( Any one of SO 4 ) 3 ;
  • the cerium-containing compound is any one of CeO 2 , Ce 2 O 3 , Ce(NO 3 ) 3 ⁇ 6H 2 O, and Ce 2 (SO 4 ) 3 ⁇ 4H 2 O
  • the present invention also protects the use of the cerium-doped compound or crystal of lithium sodium yttrium borate.
  • the cerium-doped compound or crystal of lithium sodium yttrium borate is stable in the air, does not deliquesce, and can be used as a scintillation material.
  • Sub-detection materials, or used as light functional materials such as blue phosphor for LED lighting.
  • the beneficial effects of the present invention are as follows:
  • the present invention provides a new type of lithium sodium yttrium borate and its cerium-doped compounds or crystals and preparation methods thereof, which are cheap, easy to obtain, and simple to synthesize.
  • the cerium-doped compounds of the lithium sodium yttrium borate are The compound or crystal has stable physical and chemical properties, does not deliquesce, and has good scintillation and fluorescence properties. It can be used as a scintillation material, a neutron detection material, or a blue phosphor for LED lighting. It has important applications in the fields of high-energy physical particle detection and light illumination. economic and scientific research value.
  • Figure 1 is a schematic diagram of the crystal structure along the b-axis and c-axis of the lithium sodium yttrium borate Li 2 NaY (BO 3 ) 2 single crystal prepared in Example 5 of the present invention
  • Figure 2 is a theoretical energy band structure diagram of the Li 2 NaY (BO 3 ) 2 crystal prepared in Example 5;
  • Figure 3 shows the Li 2 NaY (BO 3 ) 2 compound prepared in Example 1, the Li 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 compound prepared in Example 2, and the Li 2 NaY 0.7 Ce 0.3 (BO 3 ) compound prepared in Example 3. ) Powder XRD spectrum of compound 2 ;
  • Figure 4 is the scintillation performance of the Li 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 crystal prepared in Example 7;
  • Figure 5 is the scintillation performance of the Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 crystal prepared in Example 8;
  • Figure 6 is the fluorescence emission spectrum of the Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 compound prepared in Example 4;
  • Figure 7 is the fluorescence CIE chromaticity coordinate of the Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 compound prepared in Example 4;
  • Figure 8 is a fluorescence decay curve under ultraviolet light excitation after grinding the Li 2 NaY 0.6 Ce 0.4 (BO 3 ) 2 crystal prepared in Example 6.
  • Example 1 Synthesis of lithium sodium yttrium borate compound Li 2 NaY (BO 3 ) 2 compound
  • Raw materials used (analytically pure): Y 2 O 3 0.1 mol, H 3 BO 3 0.4 mol, Na 2 CO 3 0.1 mol, Li 2 CO 3 0.2 mol.
  • the specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into Put the corundum crucible into a muffle furnace, raise the temperature to 500°C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the second time, put it into the muffle furnace, raise the temperature to 600°C, and keep the temperature constant for 24 hours.
  • Example 2 Synthesis of 0.5% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 compound
  • Raw materials used (analytically pure): Y 2 O 3 0.995 mol, CeO 2 0.01 mol, B 2 O 3 2.0 mol, Na 2 CO 3 1.0 mol, Li 2 CO 3 2.0 mol.
  • Example 3 Synthesis of 30% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.7 Ce 0.3 (BO 3 ) 2 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.
  • Example 4 Synthesis of 50% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 compound
  • 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.
  • Example 5 Preparation of lithium sodium yttrium borate Li 2 NaY (BO 3 ) 2 crystal
  • Raw materials used (analytically pure): Na 2 CO 3 0.015 mol, Y 2 O 3 0.005 mol, Li 2 CO 3 0.04 mol, H 3 BO 3 0.1 mol.
  • Example 6 Preparation of 20% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.8 Ce 0.2 (BO 3 ) 2 crystal
  • Raw materials used (analytically pure): 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.
  • Example 7 Preparation of 35% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 crystal
  • Example 8 Preparation of 10% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 crystal
  • Raw materials used (analytically pure): NaBO 2 4H 2 O 1.0 mol, Y 2 O 3 0.45 mol, CeO 2 ⁇ 0.1 mol, Li 2 CO 3 0.4 mol, H 3 BO 3 1.0 mol.
  • the specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into Platinum crucible, then put it into the medium frequency pulling furnace, pass in high-purity N 2 /H 2 mixed gas, heat until completely melted, stir for 24 hours, when the melt temperature is 0.5°C higher than the saturation point, then remove it from the growth furnace Put a platinum rod into it and let it contact the surface of the melt and keep it for 2 hours. Then reduce the temperature to the saturation point temperature at 0.25°C/h, and set the rotation speed of the platinum rod to 10r/min, and then set it to 0.05°C/h. The temperature is slowly lowered at a rate of h, and pulled at a pulling speed of 0.1mm/h.
  • the crystal When the crystal grows to a certain size, the crystal is lifted off the liquid surface and finally dropped to room temperature at a rate of 50°C/h to obtain the size. It is a 3.2 ⁇ 2.3 ⁇ 1.5mm 3 Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 crystal.
  • Example 9 Characteristics testing of lithium sodium yttrium borate and its cerium doped compounds and crystals
  • the unit cell structure of the lithium sodium yttrium borate Li 2 NaY (BO 3 ) 2 single crystal prepared in Example 5 of the present invention was measured using the X-ray single crystal diffraction method.
  • the unit cell structure of the 10% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 single crystal prepared in Example 8 of the present invention was determined using the X-ray single crystal diffraction method.
  • an X-ray powder diffractometer was used to perform XRD testing at room temperature, as shown in Figure 3. The results showed that the prepared compound was a pure phase and no other impurity phases were generated.
  • Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 compound prepared in Example 4 of the present invention emits characteristic blue light under ultraviolet light excitation. Its fluorescence emission spectrum is shown in Figure 6, and its CIE chromaticity The coordinates (0.155, 0.143, 0.702) are marked in Figure 7, which proves that it has good use value as a blue phosphor for LED.
  • Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 compound prepared in Example 4 of the present invention emits characteristic blue light under ultraviolet light excitation. Its fluorescence emission spectrum is shown in Figure 6, and its CIE chromaticity The coordinates (0.155, 0.143, 0.702) are marked in Figure 7, which proves that it has good use value as a blue phosphor for LED.

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Abstract

Disclosed in the present invention are lithium sodium yttrium borate and a cerium-doped compound and crystal thereof, and preparation methods therefor and the use thereof. The lithium sodium yttrium borate compound has a chemical formula of Li2NaY(BO3)2; and the cerium-doped compound of the lithium sodium yttrium borate has a general chemical formula of Li2NaY1-xCex(BO3)2, where 0 < x ≤ 0.5. The cerium-doped compound of lithium sodium yttrium borate is inexpensive and easily available, is simple and convenient to synthesize, stable in terms of physicochemical properties, free of deliquescence and good in terms of scintillating and fluorescent properties, can be used as a scintillating material to serve as a neutron detection material or as a blue fluorescent powder for LED lighting, and has important economic and scientific research values in the fields of high-energy physical particle detection, light illumination, etc.

Description

硼酸锂钠钇及其铈掺杂化合物和晶体及其制备方法与用途Lithium sodium yttrium borate and its cerium doped compounds and crystals and their preparation methods and uses 技术领域：Technical areas:
本发明涉及闪烁材料技术领域，具体涉及一种硼酸锂钠钇及其铈掺杂化合物和晶体及其制备方法与用途。The invention relates to the technical field of scintillation materials, and specifically relates to a lithium sodium yttrium borate and its cerium doped compound and crystal, as well as its preparation method and use.
背景技术：Background technique:
中子具有穿透力强、能识别轻元素特别是氢和锂等元素，而且中子的自旋S＝1/2可以与带有未成对电子的原子/离子发生磁相互作用因而能探测磁矩，因此利用中子衍射/散射是目前研究材料晶体结构、超结构及磁结构的一种强有力手段。中子是不同于X射线和α射线的不带电的粒子，因此它无法直接引起闪烁材料电离而被观测到，故如何对中子进行有效而准确地探测是当前高能粒子检测的一个重要研究内容之一。Neutrons have strong penetrating power and can identify light elements, especially elements such as hydrogen and lithium. Moreover, the spin S=1/2 of neutrons can have magnetic interactions with atoms/ions with unpaired electrons and can detect magnetic fields. moment, so the use of neutron diffraction/scattering is currently a powerful means to study the crystal structure, superstructure and magnetic structure of materials. Neutrons are uncharged particles different from X-rays and α-rays. Therefore, they cannot directly cause ionization of scintillation materials and be observed. Therefore, how to effectively and accurately detect neutrons is an important research content in current high-energy particle detection. one.
利用闪烁晶体是当前的一个重要技术方案，以闪烁晶体为核心的闪烁体探测器相对于其他探测器具有更广的适应范围，环境适应性和较高的探测效率。现有的稀土钾冰晶石族晶体Cs 2LiYCl 6：Ce 3+、Cs 2LiLuBr 6：Ce 3+、Rb 2LiYBr 6：Ce 3+等具备高光产额、快衰减、高能量分辨率且能实现n-γ双探测等优点，被认为是较为理想的中子探测闪烁材料。然而该类晶体材料生长的YCl 3、LuBr 3、YBr 3等原料价格昂贵，这些原料还需在无水无氧的条件下封装在石英坩埚内，而且制备的晶体在空气中极易潮解等，极大地增加了晶体生长、加工、封装的成本和困难，因此需要进一步探索理化性质稳定、不潮解、廉价易得的新型闪烁材料。 The use of scintillation crystals is currently an important technical solution. The scintillator detector with scintillation crystal as the core has a wider adaptability range, environmental adaptability and higher detection efficiency than other detectors. The existing rare earth potassium cryolite group crystals Cs 2 LiYCl 6 : Ce 3+ , Cs 2 LiLuBr 6 : Ce 3+ , Rb 2 LiYBr 6 : Ce 3+ , etc. have high light yield, fast attenuation, high energy resolution and can It has the advantages of realizing n-γ dual detection and is considered to be an ideal scintillation material for neutron detection. However, the raw materials such as YCl 3 , LuBr 3 , and YBr 3 used to grow this type of crystal material are expensive. These raw materials need to be packaged in quartz crucibles under water-free and oxygen-free conditions, and the prepared crystals are easily deliquescent in the air. This greatly increases the cost and difficulty of crystal growth, processing, and packaging. Therefore, it is necessary to further explore new scintillation materials with stable physical and chemical properties, non-deliquescing, cheap and easy to obtain.
发明内容：Contents of the invention:
本发明的目的是提供硼酸锂钠钇及其铈掺杂化合物和晶体及其制备方法与用途，廉价易得、理化性质稳定、不潮解且闪烁/荧光性能良好，有望在高能粒子探测和LED照明领域使 用解决了现有技术成本高、性质不稳定的问题。The purpose of the invention is to provide lithium sodium yttrium borate and its cerium-doped compounds and crystals and their preparation methods and uses, which are cheap and easy to obtain, have stable physical and chemical properties, are not deliquescent and have good flickering/fluorescence properties, and are expected to be used in high-energy particle detection and LED lighting. Field use solves the problems of high cost and unstable nature of existing technology.
本发明是通过以下技术方案予以实现的：The present invention is realized through the following technical solutions:
硼酸锂钠钇化合物，化学式为Li 2NaY(BO 3) 2，分子量243.39。 Lithium sodium yttrium borate compound has a chemical formula of Li 2 NaY (BO 3 ) 2 and a molecular weight of 243.39.
硼酸锂钠钇晶体，化学式为Li 2NaY(BO 3) 2，属单斜晶系，空间群为P2 1/n，晶胞参数为
Figure PCTCN2023070435-appb-000001
Figure PCTCN2023070435-appb-000002
α＝90°，β＝103.278，γ＝90°，
Figure PCTCN2023070435-appb-000003
Z＝4。 Lithium sodium yttrium borate crystal, the chemical formula is Li 2 NaY (BO 3 ) 2 , belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are
Figure PCTCN2023070435-appb-000001
Figure PCTCN2023070435-appb-000002
α=90°, β=103.278, γ=90°,
Figure PCTCN2023070435-appb-000003
Z=4.
硼酸锂钠钇的铈掺杂化合物，化学通式为：Li 2NaY 1-xCe x(BO 3) 2，其中，0＜x≤0.5。 The cerium-doped compound of lithium sodium yttrium borate has a general chemical formula: Li 2 NaY 1-x Ce x (BO 3 ) 2 , where 0＜x≤0.5.
硼酸锂钠钇的铈掺杂晶体，化学通式为：Li 2NaY 1-xCe x(BO 3) 2，其中0＜x≤0.5，属单斜晶系，空间群为P2 1/n，晶胞参数的范围为
Figure PCTCN2023070435-appb-000004
Figure PCTCN2023070435-appb-000005
α＝90°，β＝102.729(2)-103.889(1)°，γ＝90°，
Figure PCTCN2023070435-appb-000006
Figure PCTCN2023070435-appb-000007
Z＝4。 Cerium-doped crystal of lithium sodium yttrium borate, the general chemical formula is: Li 2 NaY 1-x Ce x (BO 3 ) 2 , where 0＜x≤0.5, it belongs to the monoclinic crystal system, and the space group is P2 1 /n. The range of unit cell parameters is
Figure PCTCN2023070435-appb-000004
Figure PCTCN2023070435-appb-000005
α=90°, β=102.729(2)-103.889(1)°, γ=90°,
Figure PCTCN2023070435-appb-000006
Figure PCTCN2023070435-appb-000007
Z=4.
晶胞的不对称单元中有1个Na、2个Li、1个Y 1-xCe x(0≤x≤0.5)、2个B和6个O的晶体学独立位点。Na与O形成八配位，两个Li都与O形成四配位，两个B都与O形成三配位，Y 1-xCe x(0≤x≤0.5)与O形成七配位。其三维空间结构是基于NaO 8十二面体、孤立BO 3平面三角形、LiO 4四面体和(Y 1-xCe x)O 7五角双锥相互链接而成。NaO 8十二面体之间共边及共点相连形成一维的Na-O链，(Y 1-xCe x)O 7五角双锥两两共边相连，形成(Y 1-xCe x) 2O 12二聚体，(Y 1-xCe x) 2O 12二聚体和Na-O链以及BO 3平面三角形构成了主要的晶体结构骨架，两种晶体学独立的LiO 4四面体共边连接的形成[LiO 2]一维链沿着b轴方向贯穿于晶体的骨架中。 There are 1 Na, 2 Li, 1 Y 1-x Ce x (0≤x≤0.5), 2 B and 6 O crystallographically independent sites in the asymmetric unit of the unit cell. Na forms eight coordinations with O, two Lis form four coordinations with O, two Bs form three coordinations with O, and Y 1-x Ce x (0≤x≤0.5) forms seven coordinations with O. Its three-dimensional space structure is based on NaO 8 dodecahedron, isolated BO 3 planar triangle, LiO 4 tetrahedron and (Y 1-x Ce x )O 7 pentagonal bipyramid linked to each other. NaO 8 dodecahedrons share edges and points to form a one-dimensional Na-O chain, (Y 1-x Ce x )O 7 pentagonal bipyramids share edges to form (Y 1-x Ce x ) 2 O 12 dimer, ( Y 1 - x Ce The edge connections form [LiO 2 ] one-dimensional chains that run through the skeleton of the crystal along the b-axis direction.
本发明还保护硼酸锂钠钇化合物的制备方法，包括如下步骤：The present invention also protects the preparation method of lithium sodium yttrium borate compound, which includes the following steps:
将含钠的化合物、含钇的化合物、含锂的化合物、含硼的化合物按照钠∶钇∶锂∶硼元素摩尔比为1∶1∶2∶2的比例均匀放入研钵中充分混合研磨，然后装入坩埚中，放入马弗炉 中，升温至400-550℃，恒温12-48小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中通入氢气，再升温至550-700℃，恒温12-48小时，冷却至室温，取出，经第三次研磨后放入马弗炉中通入氢气，再升700-800℃，恒温12-48小时，取出，经研磨得到硼酸锂钠钇化合物。其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 Evenly put sodium-containing compounds, yttrium-containing compounds, lithium-containing compounds, and boron-containing compounds into a mortar and grind thoroughly in a ratio of sodium:yttrium:lithium:boron element molar ratio of 1:1:2:2. , then put it into a crucible, put it into a muffle furnace, raise the temperature to 400-550°C, keep the temperature constant for 12-48 hours, cool to room temperature, take it out, grind it for the second time, put it into the muffle furnace and pass in hydrogen, and then Raise the temperature to 550-700℃, keep the temperature constant for 12-48 hours, cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace and pass in hydrogen, then raise it to 700-800℃, keep the temperature constant for 12-48 hours, take it out. After grinding, the lithium sodium yttrium borate compound is obtained. Among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, Any of NaBO 2 ·4H 2 O; yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ·6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 ( Any one of SO 4 ) 3 ; the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
本发明还保护硼酸锂钠钇的铈掺杂化合物的制备方法，包括如下步骤：The present invention also protects the preparation method of the cerium doped compound of lithium sodium yttrium borate, which includes the following steps:
将含钠的化合物、含钇的化合物、含铈的化合物、含锂的化合物、含硼的化合物按照钠：(钇+铈)∶锂∶硼元素摩尔比为1∶1∶2∶2的比例均匀放入研钵中充分混合研磨，然后装入坩埚中，放入马弗炉中通入氢气，升温至400-550℃，恒温12-48小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中通入氢气，再升温至550-700℃，恒温12-48小时，冷却至室温，取出，经第三次研磨后放入马弗炉中通入氢气，再升700-800℃，恒温12-48小时，取出，经研磨得到硼酸锂钠钇的铈掺杂化合物。The sodium-containing compound, the yttrium-containing compound, the cerium-containing compound, the lithium-containing compound, and the boron-containing compound are mixed according to the ratio of sodium: (yttrium + cerium): lithium: boron element molar ratio of 1:1:2:2 Evenly put it into a mortar and mix thoroughly, then put it into a crucible, put it into a muffle furnace and pass in hydrogen, raise the temperature to 400-550°C, keep it constant for 12-48 hours, cool it to room temperature, take it out, and grind it a second time. Then put it into a muffle furnace and pass in hydrogen, then raise the temperature to 550-700°C, keep the temperature constant for 12-48 hours, cool to room temperature, take it out, grind it for the third time, put it into the muffle furnace and pass in hydrogen, and then raise it to 700°C. -800°C, constant temperature for 12-48 hours, take out, and grind to obtain a cerium-doped compound of lithium sodium yttrium borate.
其中含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3中的任一种；含铈的化合物为CeO 2、Ce 2O 3、Ce(NO 3) 3·6H 2O、Ce 2(SO 4) 3·4H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 The sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, NaBO Any of 2 ·4H 2 O; the yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ·6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 (SO 4 ) Any one of 3 ; the cerium-containing compound is any one of CeO 2 , Ce 2 O 3 , Ce(NO 3 ) 3 ·6H 2 O, and Ce 2 (SO 4 ) 3 ·4H 2 O; The lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
一种制备硼酸锂钠钇晶体的方法，该方法包括以下步骤：将含钠的化合物、含钇的化合物、含锂的化合物、含硼的化合物按照钠∶钇∶锂∶硼元素摩尔比为1-8∶1∶5-13∶5-15的比例均匀混合研磨，装入坩埚中，以1-30℃/h的升温速率加热至温度700-1050℃后得到高温熔液，保温12-60h，然后以1-15℃/h的速度降至室温，得到硼酸锂钠钇晶体。其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 A method for preparing lithium sodium yttrium borate crystal. The method includes the following steps: adding sodium-containing compounds, yttrium-containing compounds, lithium-containing compounds, and boron-containing compounds according to the molar ratio of sodium:yttrium:lithium:boron element to 1 -Mix and grind evenly in the ratio of 8:1:5-13:5-15, put it into a crucible, heat it to a temperature of 700-1050°C at a heating rate of 1-30°C/h, and then obtain a high-temperature melt, and keep it warm for 12-60h , and then lowered to room temperature at a rate of 1-15°C/h to obtain lithium sodium yttrium borate crystals. Among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, Any of NaBO 2 ·4H 2 O; yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ·6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 ( Any one of SO 4 ) 3 ; the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
一种制备硼酸锂钠钇的铈掺杂晶体的方法，该方法包括以下步骤：将含钠的化合物、含钇的化合物、含铈的化合物、含锂的化合物、含硼的化合物按照钠∶(钇+铈)∶锂∶硼元素摩尔比为1-8∶1∶5-13∶5-15的比例均匀混合研磨，装入坩埚中，放置于熔盐炉中并通入氢气，再以1-30℃/h的升温速率加热至温度700-1050℃后得到高温熔液，保温12-60h，然后以1-15℃/h的速度降至室温，得到硼酸锂钠钇晶体。其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3中的任一种；含铈的化合物为CeO 2、Ce 2O 3、Ce(NO 3) 3·6H 2O、Ce 2(SO 4) 3·4H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 A method for preparing cerium-doped crystals of lithium sodium yttrium borate, the method includes the following steps: adding sodium-containing compounds, yttrium-containing compounds, cerium-containing compounds, lithium-containing compounds, and boron-containing compounds according to sodium: ( Yttrium + cerium): lithium: boron element molar ratio is 1-8: 1: 5-13: 5-15, evenly mixed and ground, put into a crucible, placed in a molten salt furnace and passed into hydrogen, and then 1 After heating to a temperature of 700-1050°C at a heating rate of -30°C/h, a high-temperature melt is obtained, kept for 12-60h, and then lowered to room temperature at a rate of 1-15°C/h to obtain lithium sodium yttrium borate crystals. Among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, Any of NaBO 2 ·4H 2 O; yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ·6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 ( Any one of SO 4 ) 3 ; the cerium-containing compound is any one of CeO 2 , Ce 2 O 3 , Ce(NO 3 ) 3 ·6H 2 O, and Ce 2 (SO 4 ) 3 ·4H 2 O ; The lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
一种制备硼酸锂钠钇的铈掺杂晶体的方法，该方法包括以下步骤：将含钠的化合物、含钇的化合物、含铈的化合物、含锂的化合物、含硼的化合物按照钠∶(钇+铈)∶锂∶硼摩尔比为1-5∶1∶1-5∶1-8的比例均匀混合研磨，装入坩埚中，再放入中频提拉炉中，通入高纯N 2/H 2/Ar 气，加热至完全融化，搅拌12-24小时，熔体温度高于饱和点温度0.1-3℃时，再从生长炉内放入铂金或铱金杆，使其接触熔液表面，并保持2-12小时，再将温度以0.1-10℃/h降至饱和点温度后，并将铂金或铱金杆的转速设置为2-25r/min，然后以0.05-10℃/h的速率缓慢降温，并以0.05-0.75mm/h的提拉速度提拉，待晶体长到一定尺寸时，将晶体提离液面拉脱，再以10-100℃/h的速率快速降至室温，最后得到硼酸锂钠钇的铈掺杂晶体。其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3中的任一种；含铈的化合物为CeO 2、Ce 2O 3、Ce(NO 3) 3·6H 2O、Ce 2(SO 4) 3·4H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH；含硼的化合物为H 3BO 3或B 2O 3。 A method for preparing cerium-doped crystals of lithium sodium yttrium borate, the method includes the following steps: adding sodium-containing compounds, yttrium-containing compounds, cerium-containing compounds, lithium-containing compounds, and boron-containing compounds according to sodium: ( Yttrium + cerium): lithium: boron molar ratio is 1-5: 1: 1-5: 1-8, evenly mixed and ground, put into a crucible, then put into a medium frequency pulling furnace, and pass in high-purity N 2 /H 2 /Ar gas, heat until completely melted, stir for 12-24 hours, when the melt temperature is 0.1-3°C higher than the saturation point, then put a platinum or iridium rod from the growth furnace to make it contact with the melt surface, and keep it for 2-12 hours, then reduce the temperature to the saturation point temperature at 0.1-10℃/h, and set the rotation speed of the platinum or iridium rod to 2-25r/min, and then set the speed of the platinum or iridium rod to 0.05-10℃/ h slowly cool down at a rate of 0.05-0.75mm/h, and pull it up at a pulling speed of 0.05-0.75mm/h. When the crystal grows to a certain size, lift the crystal away from the liquid surface, and then rapidly drop it at a rate of 10-100℃/h. to room temperature, and finally obtain a cerium-doped crystal of lithium sodium yttrium borate. Among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, Any of NaBO 2 ·4H 2 O; yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ·6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 ( Any one of SO 4 ) 3 ; the cerium-containing compound is any one of CeO 2 , Ce 2 O 3 , Ce(NO 3 ) 3 ·6H 2 O, and Ce 2 (SO 4 ) 3 ·4H 2 O ; Lithium-containing compounds are Li 2 CO 3 , LiNO 3 or LiOH; boron-containing compounds are H 3 BO 3 or B 2 O 3 .
本发明还保护所述硼酸锂钠钇的铈掺杂化合物或晶体的用途，所述的硼酸锂钠钇的铈掺杂化合物化合物或晶体在空气中稳定，不潮解，可以作为闪烁材料用作中子探测材料，或用作LED照明用蓝色荧光粉等光功能材料。The present invention also protects the use of the cerium-doped compound or crystal of lithium sodium yttrium borate. The cerium-doped compound or crystal of lithium sodium yttrium borate is stable in the air, does not deliquesce, and can be used as a scintillation material. Sub-detection materials, or used as light functional materials such as blue phosphor for LED lighting.
本发明的有益效果如下：本发明提供了一类新型硼酸锂钠钇及其铈掺杂化合物或晶体及其制备方法，廉价易得、合成简便，所述的硼酸锂钠钇的铈掺杂化合物化合物或晶体理化性质稳定、不潮解且闪烁和荧光性能良好，可以作为闪烁材料用作中子探测材料，或用作LED照明用蓝色荧光粉，在高能物理粒子探测和光照明等领域具有重要的经济和科研价值。The beneficial effects of the present invention are as follows: The present invention provides a new type of lithium sodium yttrium borate and its cerium-doped compounds or crystals and preparation methods thereof, which are cheap, easy to obtain, and simple to synthesize. The cerium-doped compounds of the lithium sodium yttrium borate are The compound or crystal has stable physical and chemical properties, does not deliquesce, and has good scintillation and fluorescence properties. It can be used as a scintillation material, a neutron detection material, or a blue phosphor for LED lighting. It has important applications in the fields of high-energy physical particle detection and light illumination. economic and scientific research value.
附图说明：Picture description:
图1是本发明实施例5制备得到的硼酸锂钠钇Li 2NaY(BO 3) 2单晶沿b轴和c轴的的晶体结构示意图； Figure 1 is a schematic diagram of the crystal structure along the b-axis and c-axis of the lithium sodium yttrium borate Li 2 NaY (BO 3 ) 2 single crystal prepared in Example 5 of the present invention;
图2是实施例5制备的Li 2NaY(BO 3) 2晶体的理论能带结构图； Figure 2 is a theoretical energy band structure diagram of the Li 2 NaY (BO 3 ) 2 crystal prepared in Example 5;
图3是实施例1制备的Li 2NaY(BO 3) 2化合物、实施例2制备的Li 2NaY 0.995Ce 0.005(BO 3) 2化合物、实施例3制备的Li 2NaY 0.7Ce 0.3(BO 3) 2化合物的粉末XRD谱图； Figure 3 shows the Li 2 NaY (BO 3 ) 2 compound prepared in Example 1, the Li 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 compound prepared in Example 2, and the Li 2 NaY 0.7 Ce 0.3 (BO 3 ) compound prepared in Example 3. ) Powder XRD spectrum of compound 2 ;
图4是实施例7制备的Li 2NaY 0.65Ce 0.35(BO 3) 2晶体的闪烁性能； Figure 4 is the scintillation performance of the Li 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 crystal prepared in Example 7;
图5是实施例8制备的Li 2NaY 0.9Ce 0.1(BO 3) 2晶体的闪烁性能； Figure 5 is the scintillation performance of the Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 crystal prepared in Example 8;
图6是实施例4制备的Li 2NaY 0.5Ce 0.5(BO 3) 2化合物的荧光发射光谱； Figure 6 is the fluorescence emission spectrum of the Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 compound prepared in Example 4;
图7是实施例4制备的Li 2NaY 0.5Ce 0.5(BO 3) 2化合物的荧光CIE色度坐标； Figure 7 is the fluorescence CIE chromaticity coordinate of the Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 compound prepared in Example 4;
图8是实施例6制备得到的Li 2NaY 0.6Ce 0.4(BO 3) 2晶体研磨后，紫外光激发下的荧光衰减曲线。 Figure 8 is a fluorescence decay curve under ultraviolet light excitation after grinding the Li 2 NaY 0.6 Ce 0.4 (BO 3 ) 2 crystal prepared in Example 6.
具体实施方式：Detailed ways:
以下是对本发明的进一步说明，而不是对本发明的限制。The following is a further description of the present invention, rather than a limitation of the present invention.
实施例1：合成硼酸锂钠钇化合物Li 2NaY(BO 3) 2化合物 Example 1: Synthesis of lithium sodium yttrium borate compound Li 2 NaY (BO 3 ) 2 compound
所用原料(分析纯)：Y 2O 30.1mol、H 3BO 30.4mol、Na 2CO 30.1mol、Li 2CO 30.2mol。具体步骤如下：将上述原料称量好后，放入玛瑙研钵中仔细混合研磨，然后装入
Figure PCTCN2023070435-appb-000008
的刚玉坩埚中，放入马弗炉中，升温至500℃，恒温24小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中，再升温至600℃，恒温24小时，冷却至室温，取出，经第三次研磨后放入马弗炉中，再升700℃，恒温24小时，取出，经研磨得到本发明的Li 2NaY(BO 3)化合物 2。 Raw materials used (analytically pure): Y 2 O 3 0.1 mol, H 3 BO 3 0.4 mol, Na 2 CO 3 0.1 mol, Li 2 CO 3 0.2 mol. The specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into
Figure PCTCN2023070435-appb-000008
Put the corundum crucible into a muffle furnace, raise the temperature to 500°C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the second time, put it into the muffle furnace, raise the temperature to 600°C, and keep the temperature constant for 24 hours. Cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace, raise it to 700°C, keep the temperature constant for 24 hours, take it out, and grind it to obtain the Li 2 NaY (BO 3 ) compound 2 of the present invention.
实施例2：合成0.5％铈掺杂的硼酸锂钠钇Li 2NaY 0.995Ce 0.005(BO 3) 2化合物 Example 2: Synthesis of 0.5% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.995 Ce 0.005 (BO 3 ) 2 compound
所用原料(分析纯)：Y 2O 30.995mol、CeO 20.01mol、B 2O 32.0mol、Na 2CO 31.0mol、Li 2CO 32.0mol。 Raw materials used (analytically pure): Y 2 O 3 0.995 mol, CeO 2 0.01 mol, B 2 O 3 2.0 mol, Na 2 CO 3 1.0 mol, Li 2 CO 3 2.0 mol.
具体步骤如下：将上述原料称量好后，放入玛瑙研钵中仔细混合研磨，然后装入
Figure PCTCN2023070435-appb-000009
Figure PCTCN2023070435-appb-000010
的铂金坩埚中，放入管式炉中并通入氢气，升温至450℃，恒温24小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中通入氢气，再升温至630℃，恒温24小时，冷却至室温，取出，经第三次研磨后放入马弗炉中通入氢气，再升730℃，恒温24小时，取出，经研磨后得到本发明的Li 2NaY 0.995Ce 0.005(BO 3) 2化合物。 The specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into
Figure PCTCN2023070435-appb-000009
Figure PCTCN2023070435-appb-000010
Put it into a platinum crucible, put it into a tube furnace and pass in hydrogen, heat it to 450°C, keep it constant for 24 hours, cool it to room temperature, take it out, grind it for the second time, put it into a muffle furnace and pass in hydrogen, and then heat it to 630°C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace and pass in hydrogen, then raise it to 730°C, keep the temperature constant for 24 hours, take it out, and grind it to obtain Li 2 NaY of the present invention. 0.995 Ce 0.005 (BO 3 ) 2 compound.
实施例3：合成30％铈掺杂的硼酸锂钠钇Li 2NaY 0.7Ce 0.3(BO 3) 2化合物： Example 3: Synthesis of 30% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.7 Ce 0.3 (BO 3 ) 2 compound:
所用原料(分析纯)：Y(NO 3) 3·6H 2O 0.07mol、Ce(NO 3) 3·6H 2O 0.03mol、H 3BO 30.2mol、NaNO 30.1mol、LiNO 30.2mol。 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.
具体步骤如下：将上述原料称量好后，放入玛瑙研钵中仔细混合研磨，然后装入
Figure PCTCN2023070435-appb-000011
Figure PCTCN2023070435-appb-000012
的铂金坩埚中，放入马弗炉中，放入管式炉中并通入氢气，升温至500℃，恒温24小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中，经第二次研磨之后放入马弗炉中通入氢气，再升温至680℃，恒温24小时，冷却至室温，取出，经第三次研磨后放入马弗炉中通入氢气，再升730℃，恒温24小时，取出，经研磨得到本发明的Li 2NaY 0.7Ce 0.3(BO 3) 2化合物。 The specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into
Figure PCTCN2023070435-appb-000011
Figure PCTCN2023070435-appb-000012
Put it into a platinum crucible, put it into a muffle furnace, put it into a tube furnace and pass in hydrogen, heat it up to 500°C, keep it constant for 24 hours, cool it down to room temperature, take it out, grind it for the second time and put it into the muffle furnace. , after the second grinding, put it into a muffle furnace and pass in hydrogen, then raise the temperature to 680°C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the third time, put it into the muffle furnace and pass in hydrogen, and then Raise to 730°C, keep the temperature constant for 24 hours, take it out, and grind to obtain the Li 2 NaY 0.7 Ce 0.3 (BO 3 ) 2 compound of the present invention.
实施例4：合成50％铈掺杂的硼酸锂钠钇Li 2NaY 0.5Ce 0.5(BO 3) 2化合物 Example 4: Synthesis of 50% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 compound
所用原料(分析纯)：Y(NO 3) 3·6H 2O 0.75mol、Ce 2O 30.375mol、B 2O 31.5mol、Na 2C 2O 40.75mol、LiOH 3.0mol。 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.
具体步骤如下：将上述原料称量好后，放入玛瑙研钵中仔细混合研磨，然后装入
Figure PCTCN2023070435-appb-000013
Figure PCTCN2023070435-appb-000014
的刚玉坩埚中，放入马弗炉中通入氢气，升温至480℃，恒温24小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中通入氢气，再升温至660℃，恒温24小时，冷却至室温，取 出，经第三次研磨后放入马弗炉中通入氢气，再升750℃，恒温24小时，取出，经研磨得到本发明的Li 2NaY 0.5Ce 0.5(BO 3) 2化合物。 The specific steps are as follows: After weighing the above raw materials, put them into an agate mortar, mix and grind carefully, and then put them into
Figure PCTCN2023070435-appb-000013
Figure PCTCN2023070435-appb-000014
Put it into a corundum crucible, put it into a muffle furnace and pass in hydrogen, heat it up to 480°C, keep it constant for 24 hours, cool it to room temperature, take it out, grind it for the second time, put it into a muffle furnace and pass in hydrogen, and then heat it up to 660°C. °C, keep the temperature constant for 24 hours, cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace and pass in hydrogen, then raise it to 750°C, keep the temperature constant for 24 hours, take it out, and grind it to obtain Li 2 NaY 0.5 Ce of the present invention. 0.5 (BO 3 ) 2 compounds.
实施例5：制备硼酸锂钠钇Li 2NaY(BO 3) 2晶体 Example 5: Preparation of lithium sodium yttrium borate Li 2 NaY (BO 3 ) 2 crystal
所用原料(分析纯)：Na 2CO 30.015mol、Y 2O 30.005mol、Li 2CO 30.04mol、H 3BO 30.1mol。 Raw materials used (analytically pure): Na 2 CO 3 0.015 mol, Y 2 O 3 0.005 mol, Li 2 CO 3 0.04 mol, H 3 BO 3 0.1 mol.
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070435-appb-000015
铂金坩埚中，再放入熔盐炉中，以20℃/h加热至950℃原料完全熔化，保温12小时，然后2℃/小时的速率缓慢降温，得到尺寸为0.3×0.3×0.1mm 3的硼酸锂钠钇Li 2NaY(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070435-appb-000015
Put it into a platinum crucible, then put it into a molten salt furnace, heat it at 20°C/h until the raw material is completely melted at 950°C, keep it warm for 12 hours, and then slowly cool it down at a rate of 2°C/hour to obtain a 0.3×0.3×0.1mm 3 Lithium sodium yttrium borate Li 2 NaY (BO 3 ) 2 crystal.
实施例6：制备20％铈掺杂的硼酸锂钠钇Li 2NaY 0.8Ce 0.2(BO 3) 2晶体 Example 6: Preparation of 20% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.8 Ce 0.2 (BO 3 ) 2 crystal
所用原料(分析纯)：Na 2B 4O 7·10H 2O 0.9mol、Y(OH) 30.48mol、CeO 20.12mol、Li 2CO 32.25mol、B 2O 30.9mol。 Raw materials used (analytically pure): 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.
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070435-appb-000016
铂金坩埚中，再放入熔盐炉中并通入氢气，以10℃/h加热至965℃原料完全熔化，保温36小时，然后5℃/小时的速率缓慢降温，得到尺寸为0.38×0.23×0.17mm 3的Li 2NaY 0.8Ce 0.2(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070435-appb-000016
Put the platinum crucible into a molten salt furnace and pass in hydrogen, heat it at 10℃/h until the raw material is completely melted at 965℃, keep it warm for 36 hours, and then slowly cool it down at a rate of 5℃/hour to obtain a size of 0.38×0.23× 0.17mm 3 Li 2 NaY 0.8 Ce 0.2 (BO 3 ) 2 crystal.
实施例7：制备35％铈掺杂的硼酸锂钠钇Li 2NaY 0.65Ce 0.35(BO 3) 2晶体 Example 7: Preparation of 35% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 crystal
所用原料(分析纯)：NaHCO 30.4mol、Y 2O 30.065mol、CeO 20.07mol、Li 2CO 30.8mol、H 3BO 31.8mol Raw materials used (analytically pure): 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
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070435-appb-000017
铂金坩埚中，再放入熔盐炉中通入Ar/H 2，以15℃/h加热至980℃原料完全熔化，保温12 小时，然后5℃/小时的速率缓慢降温，得到尺寸为0.2l×0.12×0.08mm 3的Li 2NaY 0.65Ce 0.35(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070435-appb-000017
Put the platinum crucible into a molten salt furnace and pass in Ar/H 2 , heat it at 15℃/h until the raw material is completely melted at 980℃, keep it warm for 12 hours, and then slowly cool it down at a rate of 5℃/hour to obtain a size of 0.2l ×0.12×0.08mm 3 Li 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 crystal.
实施例8：制备10％铈掺杂的硼酸锂钠钇Li 2NaY 0.9Ce 0.1(BO 3) 2晶体 Example 8: Preparation of 10% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 crystal
所用原料(分析纯)：NaBO 24H 2O 1.0mol、Y 2O 30.45mol、CeO 2·0.1mol、Li 2CO 30.4mol、H 3BO 31.0mol。 Raw materials used (analytically pure): NaBO 2 4H 2 O 1.0 mol, Y 2 O 3 0.45 mol, CeO 2 ·0.1 mol, Li 2 CO 3 0.4 mol, H 3 BO 3 1.0 mol.
具体步骤如下：将上述原料称量好后，放入研钵中混合研磨，然后装入
Figure PCTCN2023070435-appb-000018
铂金坩埚中，再放入中频提拉炉中，通入高纯N 2/H 2混合气，加热至完全融化，搅拌24小时，熔体温度高于饱和点温度0.5℃时，再从生长炉内放入铂金杆，使其接触熔液表面，并保持2小时，再将温度以0.25℃/h降至饱和点温度后，并将铂金杆的转速设置为10r/min，然后以0.05℃/h的速率缓慢降温，以0.1mm/h的提拉速度提拉，待晶体长到一定尺寸时，将晶体提离液面拉脱，最后以50℃/h的速率快速降至室温，得到尺寸为3.2×2.3×1.5mm 3的Li 2NaY 0.9Ce 0.1(BO 3) 2晶体。 The specific steps are as follows: After weighing the above raw materials, mix and grind them in a mortar, and then put them into
Figure PCTCN2023070435-appb-000018
Platinum crucible, then put it into the medium frequency pulling furnace, pass in high-purity N 2 /H 2 mixed gas, heat until completely melted, stir for 24 hours, when the melt temperature is 0.5°C higher than the saturation point, then remove it from the growth furnace Put a platinum rod into it and let it contact the surface of the melt and keep it for 2 hours. Then reduce the temperature to the saturation point temperature at 0.25℃/h, and set the rotation speed of the platinum rod to 10r/min, and then set it to 0.05℃/h. The temperature is slowly lowered at a rate of h, and pulled at a pulling speed of 0.1mm/h. When the crystal grows to a certain size, the crystal is lifted off the liquid surface and finally dropped to room temperature at a rate of 50°C/h to obtain the size. It is a 3.2×2.3×1.5mm 3 Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 crystal.
实施例9：硼酸锂钠钇及其铈掺杂化合物和晶体的特性测试Example 9: Characteristics testing of lithium sodium yttrium borate and its cerium doped compounds and crystals
将本发明实施例5制备得到的硼酸锂钠钇Li 2NaY(BO 3) 2单晶采用X射线单晶衍射法进行晶胞结构测定，其晶胞结构如图1所示，由图1可以得出，所述硼酸锂钠钇晶体Li 2NaY(BO 3) 2属单斜晶系，空间群是P2 1/n，晶胞参数为
Figure PCTCN2023070435-appb-000019
α＝90°，β＝103.278，γ＝90°，
Figure PCTCN2023070435-appb-000020
Z＝4。将本发明实施例8制备得到的10％铈掺杂的硼酸锂钠钇Li 2NaY 0.9Ce 0.1(BO 3) 2单晶采用X射线单晶衍射法进行晶胞结构测定，所述Li 2NaY 0.9Ce 0.1(BO 3) 2属单斜晶系，空间群是P2 1/n，晶胞参数为
Figure PCTCN2023070435-appb-000021
Figure PCTCN2023070435-appb-000022
α＝90°，β＝103.362，γ＝90°，
Figure PCTCN2023070435-appb-000023
Z＝4。 The unit cell structure of the lithium sodium yttrium borate Li 2 NaY (BO 3 ) 2 single crystal prepared in Example 5 of the present invention was measured using the X-ray single crystal diffraction method. The unit cell structure is shown in Figure 1. It can be seen from Figure 1 It is concluded that the lithium sodium yttrium borate crystal Li 2 NaY (BO 3 ) 2 belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are
Figure PCTCN2023070435-appb-000019
α=90°, β=103.278, γ=90°,
Figure PCTCN2023070435-appb-000020
Z=4. The unit cell structure of the 10% cerium-doped lithium sodium yttrium borate Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 single crystal prepared in Example 8 of the present invention was determined using the X-ray single crystal diffraction method. The Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are
Figure PCTCN2023070435-appb-000021
Figure PCTCN2023070435-appb-000022
α=90°, β=103.362, γ=90°,
Figure PCTCN2023070435-appb-000023
Z=4.
将本发明实施例1、实施例2和实施例3制备得到的Li 2NaY(BO 3) 2、Li 2NaY 0.995Ce 0.005(BO 3) 2和Li 2NaY 0.7Ce 0.3(BO 3) 2化合物仔细研磨后采用X射线粉末衍射仪进行常温XRD测试，如图3所示，结果表明所制备得到的化合物属于纯相，并无其他杂相生成。 Li 2 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 compounds prepared in Example 1, Example 2 and Example 3 of the present invention After careful grinding, an X-ray powder diffractometer was used to perform XRD testing at room temperature, as shown in Figure 3. The results showed that the prepared compound was a pure phase and no other impurity phases were generated.
将本发明实施例7制备得到的Li 2NaY 0.65Ce 0.35(BO 3) 2晶体其X射线闪烁光谱如图4所示，其在可见光波段具有闪烁探测性能，证明Li 2NaY 0.5Ce 0.5(BO 3) 2有较好的使用价值。 The X-ray scintillation spectrum of the Li 2 NaY 0.65 Ce 0.35 (BO 3 ) 2 crystal prepared in Example 7 of the present invention is shown in Figure 4. It has scintillation detection performance in the visible light band, proving that Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 has good use value.
将本发明实施例8制备得到的Li 2NaY 0.9Ce 0.1(BO 3) 2晶体其X射线闪烁光谱如图5所示，其在可见光波段具有闪烁探测性能，证明Li 2NaY 0.9Ce 0.1(BO 3) 2有较好的使用价值。 The X-ray scintillation spectrum of the Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 crystal prepared in Example 8 of the present invention is shown in Figure 5. It has scintillation detection performance in the visible light band, proving that Li 2 NaY 0.9 Ce 0.1 (BO 3 ) 2 has good use value.
将本发明实施例4制备得到的Li 2NaY 0.5Ce 0.5(BO 3) 2化合物，仔细研磨后，在紫外光激发下，发出特征蓝光，其荧光发射光谱如图6所示，其CIE色度坐标(0.155、0.143、0.702)在图7标出，证明其作为LED用蓝色荧光粉有良好的使用价值。 After careful grinding, the Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 compound prepared in Example 4 of the present invention emits characteristic blue light under ultraviolet light excitation. Its fluorescence emission spectrum is shown in Figure 6, and its CIE chromaticity The coordinates (0.155, 0.143, 0.702) are marked in Figure 7, which proves that it has good use value as a blue phosphor for LED.
将本发明实施例4制备得到的Li 2NaY 0.5Ce 0.5(BO 3) 2化合物，仔细研磨后，在紫外光激发下，发出特征蓝光，其荧光发射光谱如图6所示，其CIE色度坐标(0.155、0.143、0.702)在图7标出，证明其作为LED用蓝色荧光粉有良好的使用价值。 After careful grinding, the Li 2 NaY 0.5 Ce 0.5 (BO 3 ) 2 compound prepared in Example 4 of the present invention emits characteristic blue light under ultraviolet light excitation. Its fluorescence emission spectrum is shown in Figure 6, and its CIE chromaticity The coordinates (0.155, 0.143, 0.702) are marked in Figure 7, which proves that it has good use value as a blue phosphor for LED.
将本发明实施例6制备得到的Li 2NaY 0.6Ce 0.4(BO 3) 2晶体，仔细研磨后，在紫外光激发下，其荧光衰减曲线如图8所示，其衰减较快至纳秒量级，证明其有良好的使用价值。 After careful grinding of the Li 2 NaY 0.6 Ce 0.4 (BO 3 ) 2 crystal prepared in Example 6 of the present invention, its fluorescence decay curve is shown in Figure 8 under ultraviolet light excitation, and its decay is as fast as nanoseconds. grade, proving its good use value.

Claims (10)

  1. 化学式为Li 2NaY(BO 3) 2的硼酸锂钠钇化合物。 Lithium sodium yttrium borate compound with the chemical formula Li 2 NaY (BO 3 ) 2 .
  2. 硼酸锂钠钇晶体，其特征在于，化学式为Li 2NaY(BO 3) 2，单斜晶系，空间群为P2 1/n，晶胞参数为
    Figure PCTCN2023070435-appb-100001
    α＝90°，β＝103.278，γ＝90°，
    Figure PCTCN2023070435-appb-100002
    Z＝4。     Lithium sodium yttrium borate crystal is characterized by having a chemical formula of Li 2 NaY(BO 3 ) 2 , monoclinic crystal system, space group of P2 1 /n, and unit cell parameters of
    Figure PCTCN2023070435-appb-100001
    α=90°, β=103.278, γ=90°,
    Figure PCTCN2023070435-appb-100002
    Z=4.
  3. 硼酸锂钠钇的铈掺杂化合物，其特征在于，化学通式为：Li 2NaY 1-xCe x(BO 3) 2，其中，0＜x≤0.5。 The cerium-doped compound of lithium sodium yttrium borate is characterized in that the general chemical formula is: Li 2 NaY 1-x Ce x (BO 3 ) 2 , where 0<x≤0.5.
  4. 硼酸锂钠钇的铈掺杂晶体，其特征在于，化学通式为：Li 2NaY 1-xCe x(BO 3) 2，其中0＜x≤0.5，单斜晶系，空间群为P2 1/n，晶胞参数的范围为
    Figure PCTCN2023070435-appb-100003
    Figure PCTCN2023070435-appb-100004
    α＝90°，β＝102.729(2)-103.889(1)°，γ＝90°，
    Figure PCTCN2023070435-appb-100005
    Figure PCTCN2023070435-appb-100006
    Z＝4。     The cerium-doped crystal of lithium sodium yttrium borate is characterized by the general chemical formula: Li 2 NaY 1-x Ce x (BO 3 ) 2 , where 0＜x≤0.5, monoclinic crystal system, and space group P2 1 /n, the range of unit cell parameters is
    Figure PCTCN2023070435-appb-100003
    Figure PCTCN2023070435-appb-100004
    α=90°, β=102.729(2)-103.889(1)°, γ=90°,
    Figure PCTCN2023070435-appb-100005
    Figure PCTCN2023070435-appb-100006
    Z=4.
  5. 一种权利要求1所述硼酸锂钠钇化合物的制备方法，其特征在于，包括以下步骤：A method for preparing the lithium sodium yttrium borate compound of claim 1, characterized in that it includes the following steps:
    将含钠的化合物、含钇的化合物、含锂的化合物、含硼的化合物按照钠∶钇∶锂∶硼元素摩尔比为1∶1∶2∶2的比例均匀放入研钵中充分混合研磨，然后装入坩埚中，放入马弗炉中，升温至400-550℃，恒温12-48小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中通入氢气，再升温至550-700℃，恒温12-48小时，冷却至室温，取出，经第三次研磨后放入马弗炉中通入氢气，再升700-800℃，恒温12-48小时，取出，经研磨得到硼酸锂钠钇化合物；其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 Evenly put sodium-containing compounds, yttrium-containing compounds, lithium-containing compounds, and boron-containing compounds into a mortar and grind thoroughly in a ratio of sodium:yttrium:lithium:boron element molar ratio of 1:1:2:2. , then put it into a crucible, put it into a muffle furnace, raise the temperature to 400-550°C, keep the temperature constant for 12-48 hours, cool to room temperature, take it out, grind it for the second time, put it into the muffle furnace and pass in hydrogen, and then Raise the temperature to 550-700℃, keep the temperature constant for 12-48 hours, cool to room temperature, take it out, grind it for the third time, put it into a muffle furnace and pass in hydrogen, then raise it to 700-800℃, keep the temperature constant for 12-48 hours, take it out. After grinding, the lithium sodium yttrium borate compound is obtained; among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 Any one of B 4 O 7 ·10H 2 O, NaBO 2 ·4H 2 O; yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ·6H 2 O, Y(OH) 3 , Y 2 Any one of (CO 3 ) 3 and Y 2 (SO 4 ) 3 ; the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  6. 一种权利要求3所述硼酸锂钠钇的铈掺杂化合物的制备方法，其特征在于，包括如下步骤：A method for preparing a cerium-doped compound of lithium sodium yttrium borate according to claim 3, characterized in that it includes the following steps:
    将含钠的化合物、含钇的化合物、含铈的化合物、含锂的化合物、含硼的化合物按照钠∶(钇+铈)∶锂∶硼元素摩尔比为1∶1∶2∶2的比例均匀放入研钵中充分混合研磨，然后装入坩埚中，放入马弗炉中通入氢气，升温至400-550℃，恒温12-48小时，冷却至室温，取出，经第二次研磨之后放入马弗炉中通入氢气，再升温至550-700℃，恒温12-48小时，冷却至室温，取出，经第三次研磨后放入马弗炉中通入氢气，再升700-800℃，恒温12-48小时，取出，经研磨得到硼酸锂钠钇的铈掺杂化合物；其中含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3中的任一种；含铈的化合物为CeO 2、Ce 2O 3、Ce(NO 3) 3·6H 2O、Ce 2(SO 4) 3·4H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 The sodium-containing compound, the yttrium-containing compound, the cerium-containing compound, the lithium-containing compound, and the boron-containing compound are mixed according to the ratio of sodium: (yttrium + cerium): lithium: boron element molar ratio of 1:1:2:2 Evenly put it into a mortar and mix thoroughly, then put it into a crucible, put it into a muffle furnace and pass in hydrogen, raise the temperature to 400-550°C, keep it constant for 12-48 hours, cool it to room temperature, take it out, and grind it a second time. Then put it into a muffle furnace and pass in hydrogen, then raise the temperature to 550-700°C, keep the temperature constant for 12-48 hours, cool to room temperature, take it out, grind it for the third time, put it into the muffle furnace and pass in hydrogen, and then raise it to 700°C. -800°C, constant temperature for 12-48 hours, take out, and grind to obtain cerium-doped compounds of lithium sodium yttrium borate; the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , and Na 2 SO 4 , NaNO 3 , NaOH or any one of Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, NaBO 2 ·4H 2 O; Yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ·6H 2 O, any of Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 (SO 4 ) 3 ; cerium-containing compounds are CeO 2 , Ce 2 O 3 , Ce(NO 3 ) Any one of 3 ·6H 2 O, Ce 2 (SO 4 ) 3 ·4H 2 O; the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  7. 一种制备硼酸锂钠钇晶体的方法，其特征在于，该方法包括以下步骤：将含钠的化合物、含钇的化合物、含锂的化合物、含硼的化合物按照钠∶钇∶锂∶硼元素摩尔比为1-8∶1∶5-13∶5-15的比例均匀混合研磨，装入坩埚中，以1-30℃/h的升温速率加热至温度700-1050℃后得到高温熔液，保温12-60h，然后以1-15℃/h的速度降至室温，得到硼酸锂钠钇晶体；其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 A method for preparing lithium sodium yttrium borate crystal, characterized in that the method includes the following steps: adding sodium-containing compounds, yttrium-containing compounds, lithium-containing compounds, and boron-containing compounds according to the elements sodium:yttrium:lithium:boron The molar ratio is 1-8:1:5-13:5-15, evenly mixed and ground, put into a crucible, and heated to a temperature of 700-1050°C at a heating rate of 1-30°C/h to obtain a high-temperature melt. Keep the temperature for 12-60h, and then lower it to room temperature at a rate of 1-15°C/h to obtain lithium sodium yttrium borate crystals; among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 Any one of 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 O; the yttrium-containing compound is Y 2 O 3 , Y ( Any of NO 3 ) 3 ·6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 (SO 4 ) 3 ; the lithium-containing compound is Li 2 CO 3 , LiNO 3 or LiOH Any of them; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  8. 一种制备硼酸锂钠钇的铈掺杂晶体的方法，其特征在于，该方法包括以下步骤：将含钠的化合物、含钇的化合物、含铈的化合物、含锂的化合物、含硼的化合物按照钠∶(钇+铈)∶锂∶硼元素摩尔比为1-8∶1∶5-13∶5-15的比例均匀混合研磨，装入坩埚中，放置于熔盐炉中并通入氢气，再以1-30℃/h的升温速率加热至温度700-1050℃后得到高温熔液，保温12-60h，然后以1-15℃/h的速度降至室温，得到硼酸锂钠钇晶体；其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3中的任一种；含铈的化合物为CeO 2、Ce 2O 3、Ce(NO 3) 3·6H 2O、Ce 2(SO 4) 3·4H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH中的任一种；含硼的化合物为H 3BO 3或B 2O 3。 A method for preparing cerium-doped crystals of lithium sodium yttrium borate, characterized in that the method includes the following steps: adding a sodium-containing compound, an yttrium-containing compound, a cerium-containing compound, a lithium-containing compound, and a boron-containing compound. Mix and grind evenly according to the ratio of sodium: (yttrium + cerium): lithium: boron element molar ratio of 1-8: 1: 5-13: 5-15, put it into a crucible, place it in a molten salt furnace and pass in hydrogen , then heated to a temperature of 700-1050°C at a heating rate of 1-30°C/h to obtain a high-temperature melt, kept for 12-60h, and then lowered to room temperature at a rate of 1-15°C/h to obtain lithium sodium yttrium borate crystals ; Among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH or Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O , any one of NaBO 2 ·4H 2 O; the yttrium-containing compounds are Y 2 O 3 , Y(NO 3 ) 3 ·6H 2 O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 Any one of (SO 4 ) 3 ; the cerium-containing compound is any one of CeO 2 , Ce 2 O 3 , Ce(NO 3 ) 3 ·6H 2 O, and Ce 2 (SO 4 ) 3 ·4H 2 O species; the lithium-containing compound is any one of Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  9. 一种制备硼酸锂钠钇的铈掺杂晶体的方法，其特征在于，该方法包括以下步骤：将含钠的化合物、含钇的化合物、含铈的化合物、含锂的化合物、含硼的化合物按照钠∶(钇+铈)∶锂∶硼摩尔比为1-5∶1∶1-5∶1-8的比例均匀混合研磨，装入坩埚中，再放入中频提拉炉中，通入高纯N 2/H 2/Ar气，加热至完全融化，搅拌12-24小时，熔体温度高于饱和点温度0.1-3℃时，再从生长炉内放入铂金或铱金杆，使其接触熔液表面，并保持2-12小时，再将温度以0.1-10℃/h降至饱和点温度后，并将铂金或铱金杆的转速设置为2-25r/min，然后以0.05-10℃/h的速率缓慢降温，并以0.05-0.75mm/h的提拉速度提拉，待晶体长到一定尺寸时，将晶体提离液面拉脱，再以10-100℃/h的速率快速降至室温，最后得到硼酸锂钠钇的铈掺杂晶体；其中，含钠的化合物为Na 2CO 3、NaHCO 3、Na 2C 2O 4、Na 2SO 4、NaNO 3、NaOH或Na 2B 4O 7、Na 2B 4O 7·10H 2O、NaBO 2·4H 2O中的任一种；含钇的化合物为Y 2O 3、Y(NO 3) 3·6H 2O、Y(OH) 3、Y 2(CO 3) 3、Y 2(SO 4) 3 中的任一种；含铈的化合物为CeO 2、Ce 2O 3、Ce(NO 3) 3·6H 2O、Ce 2(SO 4) 3·4H 2O中的任一种；含锂的化合物为Li 2CO 3、LiNO 3或LiOH；含硼的化合物为H 3BO 3或B 2O 3。 A method for preparing cerium-doped crystals of lithium sodium yttrium borate, characterized in that the method includes the following steps: adding a sodium-containing compound, an yttrium-containing compound, a cerium-containing compound, a lithium-containing compound, and a boron-containing compound. Mix and grind evenly according to the ratio of sodium: (yttrium + cerium): lithium: boron molar ratio of 1-5: 1: 1-5: 1-8, put it into the crucible, then put it into the medium frequency pulling furnace, and pass it through Use high-purity N 2 /H 2 /Ar gas, heat it until it is completely melted, and stir for 12-24 hours. When the melt temperature is 0.1-3°C higher than the saturation point, put a platinum or iridium rod into the growth furnace. It contacts the surface of the melt and keeps it for 2-12 hours, then lowers the temperature to the saturation point temperature at 0.1-10°C/h, and sets the rotation speed of the platinum or iridium rod to 2-25r/min, and then sets the speed to 0.05 Slowly cool down at a rate of -10℃/h, and pull at a pulling speed of 0.05-0.75mm/h. When the crystal grows to a certain size, lift the crystal away from the liquid surface, and then pull it out at a speed of 10-100℃/h. The rate quickly dropped to room temperature, and finally a cerium-doped crystal of lithium sodium yttrium borate was obtained; among them, the sodium-containing compounds are Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , Na 2 SO 4 , NaNO 3 , NaOH Or any one of Na 2 B 4 O 7 , Na 2 B 4 O 7 ·10H 2 O, NaBO 2 ·4H 2 O; the yttrium-containing compound is Y 2 O 3 , Y(NO 3 ) 3 ·6H 2 Any one of O, Y(OH) 3 , Y 2 (CO 3 ) 3 , Y 2 (SO 4 ) 3 ; the cerium-containing compound is CeO 2 , Ce 2 O 3 , Ce(NO 3 ) 3 ·6H Any one of 2 O, Ce 2 (SO 4 ) 3 ·4H 2 O; the lithium-containing compound is Li 2 CO 3 , LiNO 3 or LiOH; the boron-containing compound is H 3 BO 3 or B 2 O 3 .
  10. 硼酸锂钠钇的铈掺杂化合物或晶体的用途，其特征在于，作为闪烁材料用作中子探测材料，或用作LED照明用蓝色荧光粉。The use of cerium-doped compounds or crystals of lithium sodium yttrium borate is characterized by being used as scintillation materials as neutron detection materials or as blue phosphors for LED lighting.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1712490A (en) * 2005-07-01 2005-12-28 中山大学 Red rare-earth luminescent material of PDP and production thereof
CN101768441A (en) * 2010-01-11 2010-07-07 海洋王照明科技股份有限公司 Rare earth borate luminescent material and preparation material thereof
CN102021651A (en) * 2009-09-11 2011-04-20 中国科学院上海硅酸盐研究所 Cerium-doped rare earth borate scintillating crystal and Bridgman preparation method thereof
CN103741217A (en) * 2014-01-20 2014-04-23 中国科学院理化技术研究所 Sodium yttrium borate, sodium yttrium borate nonlinear optical crystal as well as preparation method and application of sodium yttrium borate nonlinear optical crystal
CN108949175A (en) * 2018-09-21 2018-12-07 陕西科技大学 A kind of three strontium yttrium borate base blue colour fluorescent powder of cerium dopping and preparation method thereof
CN115367767A (en) * 2022-08-05 2022-11-22 广东省科学院资源利用与稀土开发研究所 Lithium sodium yttrium borate, cerium doped compound and crystal thereof, and preparation method and application thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5200741B2 (en) * 2007-08-01 2013-06-05 三菱化学株式会社 Crystalline silicon nitride and method for producing the same, and phosphor using the same, phosphor-containing composition, light emitting device, lighting device, image display device, sintered body, and pigment
TWI362413B (en) * 2008-02-25 2012-04-21 Ind Tech Res Inst Borate phosphor and white light illumination device utilizing the same
US20120126172A1 (en) * 2009-07-23 2012-05-24 Ocean's Kinge Lighting Science & Technology Co., L Luminescent borate glass and preparation method therof
CN105038794A (en) * 2015-06-12 2015-11-11 佛山市启正电气有限公司 Photoconversion material for enhancing energy efficiency of solar cells and preparation method thereof
CN106917140B (en) * 2017-03-26 2019-10-15 中国科学院新疆理化技术研究所 Boronic acid compound lithium sodium birefringece crystal and preparation method and purposes
US11291950B2 (en) * 2019-11-07 2022-04-05 Massachusetts Institute Of Technology Treatment of acid gases using molten alkali metal borates and associated methods of separation
CN113846381B (en) * 2020-06-28 2022-11-01 天津理工大学 Compound barium yttrium borate and barium yttrium borate nonlinear optical crystal, and preparation method and application thereof
CN114292648B (en) * 2021-12-29 2023-05-16 广东省科学院资源利用与稀土开发研究所 Cerium and manganese doped magnesia-alumina spinel fluorescent temperature sensing material and application thereof in temperature measurement

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1712490A (en) * 2005-07-01 2005-12-28 中山大学 Red rare-earth luminescent material of PDP and production thereof
CN102021651A (en) * 2009-09-11 2011-04-20 中国科学院上海硅酸盐研究所 Cerium-doped rare earth borate scintillating crystal and Bridgman preparation method thereof
CN101768441A (en) * 2010-01-11 2010-07-07 海洋王照明科技股份有限公司 Rare earth borate luminescent material and preparation material thereof
CN103741217A (en) * 2014-01-20 2014-04-23 中国科学院理化技术研究所 Sodium yttrium borate, sodium yttrium borate nonlinear optical crystal as well as preparation method and application of sodium yttrium borate nonlinear optical crystal
CN108949175A (en) * 2018-09-21 2018-12-07 陕西科技大学 A kind of three strontium yttrium borate base blue colour fluorescent powder of cerium dopping and preparation method thereof
CN115367767A (en) * 2022-08-05 2022-11-22 广东省科学院资源利用与稀土开发研究所 Lithium sodium yttrium borate, cerium doped compound and crystal thereof, and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
S. ASIRI NAIDU ET AL.: "Influence of structural distortions upon photoluminescence properties of Eu3+ and Tb3+ activated Na3Ln(BO3)2 (Ln=Y, Gd) borates", JOURNAL OF SOLID STATE CHEMISTRY, vol. 190, 27 February 2012 (2012-02-27), pages 186 - 190, XP028482746, DOI: 10.1016/j.jssc.2012.02.042 *
ZENG HONGWEI, YOU FANGTIAN, PENG HONGSHANG, HUANG SHIHUA: "Energy transfer from Ce3+ to Tb3+, Dy3+ and Eu3+ in Na3Y(BO3)2", JOURNAL OF RARE EARTHS, ELSEVIER, AMSTERDAM, NL, vol. 33, no. 10, 1 October 2015 (2015-10-01), AMSTERDAM, NL, pages 1051 - 1055, XP093136573, ISSN: 1002-0721, DOI: 10.1016/S1002-0721(14)60525-1 *

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