Scintillation material of rare earth orthosilicate doped with strong electron-affinitive element and its preparation method and application thereof

Patent metadata

Field	Value
Publication number	US-11567223-B2
Application number	US-202117454688-A
Country	US
Kind code	B2
Filing date	Nov 12, 2021
Priority date	Nov 16, 2020
Publication date	Jan 31, 2023
Grant date	Jan 31, 2023

Abstract

The invention relates to a scintillation material of rare earth orthosilicate doped with a strong electron-affinitive element and its preparation method and application thereof. The chemical formula of the scintillation material of rare earth orthosilicate doped with the strong electron-affinitive element is: RE 2(1−x−y+δ/2) Ce 2x M (2y−δ) Si (1−δ) M δ O 5 . In the formula, RE is rare earth ions and M is strong electron-affinitive doping elements; the value of x is 0<x≤0.05, the value of y is 0<y≤0.015, and the value of δ is 0≤δ≤10−4; and M is selected from at least one of tungsten, lead, molybdenum, tellurium, antimony, bismuth, mercury, silver, nickel, indium, thallium, niobium, titanium, tantalum, tin, cadmium, technetium, zirconium, rhenium, and gallium Ga.

First claim

The invention claimed is:

1. A scintillation material of rare earth orthosilicate doped with a strong electron-affinitive element, the chemical formula of the scintillation material being:
RE 2(1−x−y+δ/2-a) Ce 2x M (2y−δ) A 2a Si (1−δ) M δ O 5 , wherein
RE is rare earth ions, and M is strong electron-affinitive doping elements,
the value of x is 0<x≤0.05, the value of y is 0<y≤0.015, the value of δ is 0≤δ≤10 −4 , and the value of a is 0≤a≤0.01,
M is selected from at least one of tungsten, lead, molybdenum, tellurium, antimony, bismuth, mercury, silver, nickel, indium, thallium, niobium, titanium, tantalum, tin, cadmium, technetium, zirconium, rhenium, and gallium, and
A is selected from at least one of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, scandium, and copper.

2. The scintillation material according to claim 1 , wherein
when M is selected from at least one of tungsten, lead, molybdenum, tellurium, antimony, bismuth, mercury, silver, nickel, indium, thallium, niobium, tantalum, tin, cadmium, technetium and rhenium, the value of y is 0.000005≤y≤0.015, and
when M is selected from at least one of titanium, zirconium, and gallium, the value of y is 0.0006≤y≤0.015.

3. The scintillation material according to claim 1 , wherein a molar ratio of [CeO 7 ] and [CeO 6 ] in the scintillation material is (4˜100):1.

4. The scintillation material according to claim 1 , wherein RE is selected from at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.

5. The scintillation material according to claim 1 , wherein the value of a is 0<a≤0.01.

6. The scintillation material according to claim 1 , wherein the scintillation material is polycrystalline powders, ceramics, or single crystals.

7. A method for preparing scintillation polycrystalline powder of rare earth orthosilicate doped with a strong electron-affinitive element, the method comprising:
according to the chemical formula of the scintillation polycrystalline powder, weighing at least one of an oxide of A or a carbonate of A, an oxide of M, CeO 2 , SiO 2 , and an oxide of RE, and mixing to obtain a mixture powder, where A is selected from at least one of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, scandium, and copper; and
carrying out a solid-phase reaction on the obtained mixture powder at 1000-2000° C. for 5 to 200 hours to obtain cerium co-doped orthosilicate polycrystalline powder, wherein
the chemical formula of the scintillation polycrystalline powder is:
RE 2(1−x−y+δ/2−a) Ce 2x M (2y−δ) A 2a Si (1−δ) M δ O 5 ,
RE is rare earth ions, and M is strong electron-affinitive doping elements,
the value of x is 0<x≤0.05, the value of y is 0<y≤0.015, the value of δ is 0≤δ≤10 −4 , and the value of a is 0≤a≤0.01,
M is selected from at least one of tungsten, lead, molybdenum, tellurium, antimony, bismuth, mercury, silver, nickel, indium, thallium, niobium, titanium, tantalum, tin, cadmium, technetium, zirconium, rhenium, and gallium, and
A is selected from at least one of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, scandium, and copper.

8. A method for preparing a scintillation ceramic of rare earth orthosilicate doped with a strong electron-affinitive element, the method comprising:
according to the chemical formula of the scintillation ceramic, weighing at least one of an oxide of A or a carbonate of A, an oxide of M, CeO 2 , SiO 2 , and an oxide of RE to obtain a mixture powder, where A is selected from at least one of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, scandium, and copper; and
pressing the obtained mixture powder, and carrying out a solid-phase reaction at 1000-2000° C. for 5 to 200 hours to obtain cerium co-doped orthosilicate scintillation ceramic, the pressure for the press forming being 0.03 to 5 GPa, wherein
the chemical formula of the scintillation ceramic is:
RE 2(1−x−y+δ/2−a) Ce 2x M (2y−δ) A 2a Si (1−δ) M δ O 5 ,
RE is rare earth ions, and M is strong electron-affinitive doping elements,
the value of x is 0<x≤0.05, the value of y is 0<y≤0.015, the value of δ is 0≤δ≤10 −4 , and the value of a is 0≤a≤0.01,
M is selected from at least one of tungsten, lead, molybdenum, tellurium, antimony, bismuth, mercury, silver, nickel, indium, thallium, niobium, titanium, tantalum, tin, cadmium, technetium, zirconium, rhenium, and gallium, and
A is selected from at least one of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, scandium, and copper.

9. A method for preparing a scintillation single crystal of rare earth orthosilicate doped with a strong electron-affinitive element, the method comprising:
according to the chemical formula of the single crystal, weighing at least one of an oxide of A or a carbonate of A, an oxide of M, CeO2, SiO2, and an oxide of RE to obtain a mixture powder, where A is selected from at least one of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, scandium, and copper;
heating the obtained mixture powder to be molten; and
growing the scintillation single crystal by adopting a pulling method, a Bridgman method, a temperature gradient (TGT) method, a heat-exchange method, a Kyropoulos method, a top-seeded solution growth (TSSG) method, a fluxing agent crystal growth method, or a micro pull-down (μ-PD) method, wherein
the chemical formula of the single crystal is:
RE 2(1−x−y+δ/2−a) Ce 2x M (2y−δ) A 2a Si (1−δ) M δ O 5 ,
RE is rare earth ions, and M is strong electron-affinitive doping elements,
the value of x is 0<x≤0.05, the value of y is 0<y≤0.015, the value of δ is 0≤δ≤10 −4 , and the value of a is 0≤a≤0.01,
M is selected from at least one of tungsten, lead, molybdenum, tellurium, antimony, bismuth, mercury, silver, nickel, indium, thallium, niobium, titanium, tantalum, tin, cadmium, technetium, zirconium, rhenium, and gallium, and
A is selected from at least one of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, scandium, and copper.

10. An application of the scintillation material according to claim 1 , in the fields of high-energy physical detection for particle discrimination and fast-responsible nuclear medical imaging.

Assignees

• Shanghai Inst Ceramics Cas

Inventors

• Ding Dongzhou
• Zhao Shuwen
• Yang Fan
• Shi Junjie
• Yuan Chen
• Wang Linwei
• Xue Zhongjun

Classifications

• G01T1/2023 Primary

  Selection of materials · CPC title

• C30B29/22

  Complex oxides · CPC title

• C30B28/02

  directly from the solid state · CPC title

• C04B35/16 Primary

  based on silicates other than clay {(zircon C04B35/48)} · CPC title

• C30B11/00

  Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method (C30B13/00, C30B15/00, C30B17/00, C30B19/00 take precedence; under a protective fluid C30B27/00) · CPC title