CN117304933B - Rare earth cluster reinforced low-dimensional halide scintillation material and preparation method and application thereof - Google Patents
Rare earth cluster reinforced low-dimensional halide scintillation material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 180
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 124
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 123
- 150000004820 halides Chemical class 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000000126 substance Substances 0.000 claims abstract description 37
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 32
- 238000001514 detection method Methods 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 13
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims description 91
- 239000002994 raw material Substances 0.000 claims description 63
- 239000010453 quartz Substances 0.000 claims description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 238000001704 evaporation Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 230000002787 reinforcement Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 7
- 238000003466 welding Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 230000005251 gamma ray Effects 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 30
- 230000005865 ionizing radiation Effects 0.000 abstract description 26
- 238000004020 luminiscence type Methods 0.000 abstract description 22
- 229910052792 caesium Inorganic materials 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000002059 diagnostic imaging Methods 0.000 abstract description 4
- 238000007689 inspection Methods 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 22
- 239000010949 copper Substances 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 18
- 238000000295 emission spectrum Methods 0.000 description 16
- 238000001748 luminescence spectrum Methods 0.000 description 14
- 239000011261 inert gas Substances 0.000 description 12
- 239000010409 thin film Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 238000001771 vacuum deposition Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 4
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ANDNPYOOQLLLIU-UHFFFAOYSA-N [Y].[Lu] Chemical compound [Y].[Lu] ANDNPYOOQLLLIU-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
- C09K11/7705—Halogenides with alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- 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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/12—Production of homogeneous polycrystalline material with defined structure directly from the gas state
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- 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
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
- G01T1/202—Measuring radiation intensity with scintillation detectors the detector being a crystal
- G01T1/2023—Selection of materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/36—Measuring spectral distribution of X-rays or of nuclear radiation spectrometry
- G01T1/362—Measuring spectral distribution of X-rays or of nuclear radiation spectrometry with scintillation detectors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The invention belongs to the technical field of ionizing radiation detection materials, and particularly relates to a rare earth cluster reinforced low-dimensional halide scintillation material, a preparation method and application thereof. The chemical general formula of the material is A 8 BC 3 X 18 The method comprises the steps of carrying out a first treatment on the surface of the A is at least one of Cs, in and Tl; b is selected from at least one of Cu, ag, au, in and Tl, and the A and B element components are different; c is at least one selected from La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu; x is selected from at least one of F, cl, br and I. The material is easy to prepare into monocrystalline, powder and polycrystalline films, has the advantages of non (weak) deliquescence, high ionization radiation luminous efficiency, no flicker luminescence self-absorption, high light output, low afterglow, high energy resolution and the like, and has important application prospects in the fields of medical imaging, security inspection, petroleum exploration wells, industrial detection and the like.
Description
Technical Field
The invention belongs to the technical field of ionizing radiation detection materials, and particularly relates to a rare earth cluster reinforced low-dimensional halide scintillation material, a preparation method and application thereof.
Background
As one of the ionizing radiation detecting materials, a scintillation material may convert high-energy particles (α, β, γ radiation) or rays incident therein into a low-energy photon beam. With the increasing requirements of high-end medical imaging, security inspection, petroleum exploration wells and high-energy physical fields on the performance of nuclear radiation detectors, development of novel high-performance scintillation materials is urgently needed.
Up to now, the most commonly used commercial scintillation materials are exogenously doped ion activated compounds such as thallium doped sodium iodide (NaI: tl), thallium doped cesium iodide (CsI: tl) and cerium doped lutetium yttrium silicate (Lu) 1.8 Y 0.2 SiO 5 Ce). However, these scintillation materials generally have problems of non-uniformity of luminescence and scintillation detection performance of the crystal due to segregation effect of doped ions during growth, which can cause non-uniform distribution of doped ions when applied in large size, and limit further application development. The self-activated (intrinsic) luminescent scintillating materials have the advantage of good uniformity of luminescence compared to external ion-activated scintillating materials, and can prevent their performance from being degraded when the crystal size is enlarged. So far, several Ce-derived compositions have been found 3+ 、Eu 2+ And Tl + Ion-self-activated high-performance scintillating materials, e.g. CeBr 3 , Cs 4 EuBr 6 And TlMgCl 3 Their light yield at 662 keV gamma rays varies from 30,000 to 78,000photons/MeV, and their energy resolution varies from 3.7% to 4.3%. However, such self-activated scintillation materials often suffer from self-absorption due to the weak electron-phonon coupling associated with electron transitions, making their performance severely degraded in size-enlarging applications.
In recent years, there have been developed highly sensitive scintillating materials such as Cs with intrinsic luminescence emitted from trapped excitons (STE) 3 Cu 2 I 5 ,Cs 2 HfCl 6 And the like, which have intrinsic characteristics such as high exciton binding energy, large stokes shift induced by strong electron-phonon coupling, and the like, so that they have no ionizing radiation luminescence self-absorption effect and exhibit corresponding bright scintillation emission. For example, cs with strong localized exciton emission 2 HfCl 6 The scintillation material has a high light yield of 54,000 photons/MeV and an excellent energy resolution of 3.3% at 662 keV. In addition, some copper-based low-dimensional perovskites are very promisingIntrinsic scintillation material in the way. For example, low-dimensional perovskite Cs 3 Cu 2 I 5 And CsCu 2 I 3 Can be used as sensitive X/gamma ray scintillating material. These materials are stable in air, are superior to other hygroscopic halide scintillation materials, and have great application potential in the field of radiation detection. China is a large country of rare earth, and has the capability of guaranteeing independent and independent large-scale supply of rare earth resources. Therefore, if a rare earth-based STE high-sensitivity scintillation material with independent intellectual property rights can be explored and created, the method has global strategic significance for solving the problem of 'ultra-high performance scintillation detection material for deep sea and deep space', improving the rare earth added value and optimizing the industrial chain.
It should be noted that the information disclosed in the above background section is only for enhancing understanding of the background of the invention and thus may include information that does not form the prior art that is already known to those of ordinary skill in the art.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a rare earth cluster-based reinforced low-dimensional halide scintillation material, and a preparation method and application thereof.
In a first aspect, the present invention provides a rare earth cluster-based enhanced low-dimensional halide scintillation material having the chemical formula A 8 BC 3 X 18 ;
Wherein A is at least one selected from Cs, in and Tl;
b is selected from at least one of Cu, ag, au, in and Tl, and the A and B element components are different;
c is at least one selected from La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu;
x is selected from at least one of F, cl, br and I.
In the invention, the A-site element is selected from the A obtained by Cs, in and Tl elements 8 BC 3 X 18 The stable state scintillation efficiency of the scintillation material can be improved by more than 300 percent compared with that of an Rb-based material; presence of element Rb 87 The natural radioactive background of Rb adopts CsNon-radioactive background A obtained by In and Tl elements 8 BC 3 X 18 The scintillating material has wider application range; because the atomic numbers of Cs, in and Tl are far greater than Rb, A is obtained from elements Cs, in and Tl 8 BC 3 X 18 The scintillation material can greatly reduce the radiation length of the scintillation material, and is beneficial to miniaturization of the detector.
Preferably, the rare earth cluster-based enhanced low-dimensional halide scintillating material has a chemical formula (Cs 1-x D x ) 8 BC 3 X 18 0 < x < 1 (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.9);
wherein D is selected from at least one of Na, K, rb, in and Tl;
b is at least one selected from Cu, ag, au, in and Tl;
c is at least one selected from La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu;
x is selected from at least one of F, cl, br and I.
Preferably, the rare earth cluster-based enhanced low-dimensional halide scintillation material has the chemical formula (In 1-y E y ) 8 BC 3 X 18 0 < y < 1 (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.9);
wherein E is selected from at least one of Na, K, rb, cs and Tl;
b is at least one selected from Cu, ag, au, in and Tl;
c is at least one selected from La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu;
x is selected from at least one of F, cl, br and I.
Preferably, the rare earth cluster-based enhanced low-dimensional halide scintillating material has a chemical formula (Tl) 1-z M z ) 8 BC 3 X 18 0 < z < 1 (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.9);
wherein M is selected from at least one of Na, K, rb, cs and In;
b is at least one selected from Cu, ag, au, in and Tl;
c is at least one selected from La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu;
x is selected from at least one of F, cl, br and I.
Preferably, the rare earth cluster-based enhanced low-dimensional halide scintillation material is in the form of a bulk single crystal, powder, or polycrystalline thin film. The three forms can meet the requirements of application ends on the forms in a targeted manner, wherein the bulk single crystal is more suitable for gamma energy spectrum detection; the powder is more suitable for radiation warning and luminescence; polycrystalline thin films are more suitable for the field of X-ray imaging.
Preferably, the rare earth cluster-based enhanced low-dimensional halide scintillation material is a bulk single crystal having at least one dimension of at least 1mm, preferably at least 2 mm. A certain thickness is beneficial to depositing more rays/particles energy, and is more suitable for gamma energy spectrum detection.
Preferably, when the rare earth cluster-based enhanced low-dimensional halide scintillating material is a powder (solid phase synthesis), the particle size of the powder is 1nm to 20 μm. The proper particle size is convenient for subsequent use in radiation warning lighting or as a precursor material for imaging films/screens.
Preferably, when the rare earth cluster-based enhanced low-dimensional halide scintillation material is a polycrystalline thin film, the thickness of the polycrystalline thin film is 1 μm to 1000 μm. The polycrystalline film with a certain thickness can realize the energy deposition of rays/particles and meet the requirement of high-efficiency imaging.
In a second aspect, the present invention provides a method for preparing a rare earth cluster-based enhanced low-dimensional halide scintillation material having the chemical formula A 8 BC 3 X 18 ;
Wherein A is at least one selected from Cs, in and Tl;
b is selected from at least one of Cu, ag, au, in and Tl, and the A and B element components are different;
c is at least one selected from La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu;
x is selected from at least one of F, cl, br and I.
The low-dimensional halide scintillation material based on rare earth cluster reinforcement is a bulk single crystal, and the preparation method comprises the following steps: the chemical formula of the low-dimensional halide scintillating material based on rare earth cluster enhancement is A 8 BC 3 X 18 Weigh AX powder, BX powder and CX 3 The powder is mixed and then used as raw material powder, and a crucible descent method is adopted to grow the low-dimensional halide scintillating material based on rare earth cluster reinforcement.
Preferably, the purity of the AX powder is more than 99.9%; the purity of the BX powder is more than 99.9%; CX (CX) 3 The purity of the powder is more than 99.9 percent.
Preferably, the steps and parameters of the crucible lowering method are as follows:
(1) Placing the raw material powder into a quartz crucible with a capillary structure, pumping air to vacuum, and performing welding sealing;
(2) Vertically placing the sealed quartz crucible in a crystal growth furnace, then heating to the melting temperature of the raw material with the highest melting point, preserving heat, completely melting and uniformly mixing the raw material powder;
(3) Adjusting the position and/or furnace temperature of the quartz crucible so that the temperature of the bottom of the capillary structure of the quartz crucible is kept between + -10 ℃ based on the melting point of the rare earth cluster-enhanced low-dimensional halide scintillation material;
(4) Controlling the growth temperature gradient of the crystal growth furnace to be 5-50 ℃/cm, then enabling the quartz crucible to descend in the furnace body at the descending speed of 0.01-10.0 mm/h, and starting the growth of crystals;
(5) And after the growth is finished, cooling to room temperature at a cooling rate of 0.5-50 ℃/h.
In a third aspect, the present invention provides a method for preparing a rare earth cluster-based enhanced low-dimensional halide scintillation material having a chemical formula A 8 BC 3 X 18 ;
Wherein A is at least one selected from Cs, in and Tl;
b is selected from at least one of Cu, ag, au, in and Tl, and the A and B element components are different;
c is at least one selected from La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu;
x is selected from at least one of F, cl, br and I.
The low-dimensional halide scintillating material based on rare earth cluster reinforcement is powder, and the preparation method comprises the following steps:
(1) The chemical formula of the low-dimensional halide scintillating material based on rare earth cluster enhancement is A 8 BC 3 X 18 Weigh AX powder, BX powder and CX 3 Mixing the powder as raw material powder, placing the raw material powder into a quartz tube, pumping air to vacuum, and performing welding sealing;
(2) And (3) carrying out heat preservation treatment on the welded quartz tube for 1-10 hours at 400-1100 ℃ to obtain the powdery low-dimensional halide scintillating material based on rare earth cluster reinforcement.
Preferably, the purity of the AX powder is more than 99.9%; the purity of the BX powder is more than 99.9%; CX (CX) 3 The purity of the powder is more than 99.9 percent.
In a fourth aspect, the present invention provides a method for preparing a rare earth cluster-based enhanced low-dimensional halide scintillation material having a chemical formula A 8 BC 3 X 18 ;
Wherein A is at least one selected from Cs, in and Tl;
b is selected from at least one of Cu, ag, au, in and Tl, and the A and B element components are different;
c is at least one selected from La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu;
x is selected from at least one of F, cl, br and I.
The low-dimensional halide scintillation material based on rare earth cluster reinforcement is a polycrystalline film, and the preparation method comprises the following steps:
(1) The chemical formula of the low-dimensional halide scintillating material based on rare earth cluster enhancement is A 8 BC 3 X 18 Weighing AX powderBody, BX powder and CX 3 Mixing the powder as raw material powder, placing the raw material powder into a quartz tube, pumping air to vacuum, and performing welding sealing;
(2) The welded quartz tube is heat-preserved for 1 to 10 hours at the temperature of 400 to 1100 ℃ to obtain A 8 BC 3 X 18 Powder;
(3) A is prepared by a single source evaporation method 8 BC 3 X 18 And (3) coating the powder on the surface of the substrate to obtain the low-dimensional halide scintillation material based on rare earth cluster reinforcement.
Preferably, the purity of the AX powder is more than 99.99%; the purity of the BX powder is more than 99.99 percent; CX (CX) 3 The purity of the powder is more than 99.99 percent.
Preferably, the parameters of the single source evaporation method include: vacuumizing until the vacuum degree is less than or equal to 30 Pa; the temperature of the substrate is 200-300 ℃; will A 8 BC 3 X 18 The powder is heated to a molten state.
Preferably, the substrate is made of quartz or high boron glass.
In a fifth aspect, the present invention provides the use of rare earth cluster-based enhanced low-dimensional halide scintillation materials in X-ray detection, gamma ray detection and particle detection, including medical imaging, security inspection, petroleum exploration wells, and industrial detection.
The beneficial effects are that:
the low-dimensional halide scintillating material based on rare earth cluster enhancement has the advantages of non (weak) deliquescence, high ionization radiation luminous efficiency, no scintillating luminescence self-absorption, high light output, low afterglow, high energy resolution and the like, can be used for detecting rays or particles such as X-rays and gamma rays, and has important application prospects in the fields of medical imaging, security inspection, petroleum exploration wells, industrial detection and the like.
Drawings
FIG. 1 is an ionization radiation emission spectrum of a rare earth cluster-enhanced low-dimensional scintillation material prepared in example 1;
FIG. 2 is an ionizing radiation emission spectrum of the rare earth cluster-enhanced low-dimensional scintillation material prepared in example 2;
FIG. 3 is an ionizing radiation emission spectrum of the rare earth cluster-enhanced low-dimensional scintillation material prepared in example 3;
FIG. 4 is an ionizing radiation emission spectrum of the rare earth cluster-enhanced low-dimensional scintillation material prepared in example 5;
FIG. 5 is an ionizing radiation emission spectrum of the rare earth cluster-enhanced low-dimensional scintillation material prepared in example 6;
FIG. 6 is a graph showing the contrast of the ionizing radiation emission spectra of the rare-earth cluster-enhanced low-dimensional scintillation materials of example 6 and example 3;
FIG. 7 is an ionizing radiation emission spectrum of a rare earth cluster-enhanced low-dimensional scintillation material of comparative example 1;
FIG. 8 is a rare earth cluster-enhanced low-dimensional scintillating material Rb of comparative example 1 8 CuSc 3 Cl 18 Low-dimensional scintillating material Cs reinforced with rare earth clusters in example 2 8 CuSc 3 Cl 18 Is a contrast ionization radiation luminescence spectrum;
FIG. 9 is a rare earth cluster-enhanced low-dimensional scintillation material Rb of comparative example 2 8 CuY 3 Cl 18 Low-dimensional scintillating material Cs reinforced with rare earth clusters in example 1 8 CuY 3 Cl 18 Is a contrast ionization radiation luminescence spectrum;
FIG. 10 shows Cs of the rare earth zero-dimensional structure of comparative example 3 3 YCl 6 Low-dimensional scintillating material Cs reinforced with rare earth clusters in example 1 8 CuY 3 Cl 18 Is a graph of the luminescence spectrum of ionizing radiation.
FIG. 11 shows Cs of the rare earth zero-dimensional structure of comparative example 3 3 YCl 6 Low-dimensional scintillating material Cs reinforced with rare earth clusters in example 1 8 CuY 3 Cl 18 Powder XRD diffractogram of (2).
FIG. 12 shows Cs of the rare earth zero-dimensional structure of comparative example 3 3 YCl 6 Low-dimensional scintillating material Cs reinforced with rare earth clusters in example 1 8 CuY 3 Cl 18 Is a comparative partial crystal structure diagram.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to illustrate the problem and to explain the invention, without limiting it.
In the present disclosure, the rare earth cluster-based enhanced low-dimensional halide scintillation material has the general formula: a is that 8 BC 3 X 18 The method comprises the steps of carrying out a first treatment on the surface of the Wherein: a is selected from one or more elements of Cs, in and Tl, B is selected from one or more elements of Cu, ag, au, in and Tl, and the elements A and B are different; c is selected from one or more rare earth elements of La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu; x is selected from one or more halogen elements of F, cl, br and I. In an alternative embodiment, the morphology of the rare earth cluster-based enhanced low-dimensional halide scintillation material comprises: bulk single crystals, powders and polycrystalline films.
When the rare earth cluster-based reinforced low-dimensional halide scintillation material is a bulk single crystal, the preparation method thereof is exemplarily described below. In the invention, a crucible descending method can be adopted to prepare blocky single crystals. The following will describe in detail the preparation process by selecting only the crucible lowering method as an example, and other crystal preparation methods are also applicable to the present invention.
According to the composition general formula A 8 BC 3 X 18 Weighing the raw materials and fully mixing. Placing the raw materials in a quartz crucible with a capillary structure in an inert dry gas environment; the crucible was evacuated to vacuum (about 10 -2 ~10 -7 Pa) and sealing by welding.
In an alternative embodiment, the starting material is highly pure (. Gtoreq.99.9%), anhydrous AX, BX, CX 3 One or more of the following, wherein: a=cs, in, and Tl; b= Cu, ag, au, in and Tl; c= La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu, x=f, cl, br and I. The inert dry gas environment is a glove box filled with dry argon or nitrogen.
Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to enable the temperature to exceed the melting point temperature of the raw material with the highest melting point, keeping the temperature until the raw material is completely melted and uniformly mixed; adjusting the position and the furnace temperature of the crucible to reduce the temperature at the bottom of the capillary structure of the crucible to about the melting point of the scintillation crystal; ensuring the growth temperature gradient of the growth furnace to be about 5-50 ℃/cm, and enabling the quartz crucible to descend in the furnace body at the descending speed of 0.01-10.0 mm/h; the crystal in the growth furnace starts to nucleate and grow from the bottom end of the crucible capillary structure until the melt is completely solidified.
After the growth is finished, the growth furnace is cooled to room temperature at a cooling rate of 0.5-50 ℃/h; finally, the prepared crystal is taken out from the quartz crucible.
When the rare earth cluster-based reinforced low-dimensional halide scintillating material is a powder, the following exemplifies a preparation method thereof.
According to the composition general formula A 8 BC 3 X 18 Weighing the raw materials and fully mixing. The materials were placed in a quartz tube in an inert dry gas atmosphere, and then the crucible was evacuated and sealed. Heating the crucible to above the melting point of each raw material until the raw materials are completely melted and uniformly mixed, and then cooling to synthesize uniform A 8 BC 3 X 18 And (3) powder.
In an alternative embodiment, the starting material is highly pure (. Gtoreq.99.9%), anhydrous AX, BX, CX 3 One or more of the following, wherein: cs, in and Tl; b= Cu, ag, au, in and Tl; c= La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu, x=f, cl, br and I. The inert dry gas environment is a glove box filled with dry argon or nitrogen.
When the rare earth cluster-based reinforced low-dimensional halide scintillation material is a polycrystalline thin film, the preparation method thereof is exemplarily described below. The invention can prepare the polycrystalline film by adopting a single-source evaporation method. The following only selects the single source evaporation method as an example to describe the preparation process in detail, and other thin film preparation methods are also applicable to the present invention.
According to the composition general formula A 8 BC 3 X 18 Weighing the raw materials and fully mixing. The materials were placed in a quartz tube in an inert dry gas atmosphere, and then the crucible was evacuated and sealed. Heating the crucible to above the melting point of each raw material until the raw material is completeMelting, mixing uniformly, cooling, synthesizing uniform A 8 BC 3 X 18 Polycrystalline compound starting material. In an alternative embodiment, the starting material is highly pure (. Gtoreq.99.9%), anhydrous AX, BX, CX 3 One or more of the following, wherein: a=cs, in, and Tl; b= Cu, ag, au, in and Tl; c= La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu, x=f, cl, br and I. The inert dry gas environment is a glove box filled with dry argon or nitrogen.
Quartz plate or other substrate is washed by deionized water, alcohol and acetone for more than 20 minutes, and dried, and the synthesized polycrystalline compound raw material is grinded into powder or small particles (called plating material).
And (3) mounting the cleaned substrate on a vacuum coating device, weighing the synthesized plating materials, and loading the synthesized plating materials into a tungsten boat or a molybdenum boat with corresponding volume. Wherein, a single source evaporation method, namely, one boat evaporation A is adopted 8 BC 3 X 18 Polycrystalline compound starting material.
Vacuumizing the vacuum coating device to 10 -4 Pa, and heating the substrate to 200-300 ℃ to ensure the growth quality of microcrystals, and starting a coating procedure. The coating raw material is heated to a molten state or a near-molten state by adopting a current heating or other heating modes, and the vacuum degree in the coating device is obviously reduced at the moment, namely, the evaporation of the coating material and the evaporation of A are started 8 BC 3 X 18 Growth of microcrystalline thin films.
When the vacuum degree in the coating device rises to the level before the coating starts again, namely marking the coating end, turning off the heating device, and obtaining A after cooling 8 BC 3 X 18 Microcrystalline thin films.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1:
the rare earth cluster-reinforced low-dimensional scintillation material proposed in the embodiment 1 is in the form of a bulk single crystal with a composition chemical formula of Cs 8 CuY 3 Cl 18 I.e. as A 8 BC 3 X 18 Is of the general formula; a=cs; b=cu; c=y; x=cl. The bulk single crystal is prepared by adopting a crucible descending method, and comprises the following steps:
a) Composition of halide scintillating material prepared on demand chemical formula Cs 8 CuY 3 Cl 18 High-purity raw materials CsCl, cuCl and YCl with 99.9% purity are respectively weighed according to the mole ratio 3 ;
b) Placing the raw materials into a quartz crucible with a round bottom in an inert gas environment; then the crucible is vacuumized and sealed. Wherein the inert gas environment is a glove box filled with argon or nitrogen;
c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 950 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible capillary to about 580 ℃, then descending the quartz crucible in the furnace body at the descending speed of 0.5 mm/h, and starting nucleation and growth of crystals from the bottom of the crucible capillary until the melt is completely solidified; then cooling at a speed of 10 ℃/h until the temperature is reduced to room temperature; finally, the prepared halide scintillation crystal is taken out of the quartz crucible in a dry environment and processed. The obtained halide scintillation crystal can be used for detecting X-rays, gamma-rays and other rays or the particle detection field.
FIG. 1 is an ionization radiation emission spectrum of a rare-earth cluster-enhanced low-dimensional scintillation material of example 1. As shown in FIG. 1, cs 8 CuY 3 Cl 18 Exhibits bright ionizing radiation luminescence under irradiation, with a luminescence main peak at 490 and nm. The spectral line of the ionization radiation luminescence spectrum is smooth and has no burr, which shows that the ionization radiation can generate high-efficiency ionization radiationEmitting light; the main peak is at 490nm, which indicates that it can be matched with the main stream commercial photomultiplier and silicon-based detector.
Example 2:
the rare earth cluster-reinforced low-dimensional scintillation material proposed in the embodiment 2 is in the form of a bulk single crystal with a composition chemical formula of Cs 8 CuSc 3 Cl 18 I.e. as A 8 BC 3 X 18 Is of the general formula; a=cs; b=cu; c=sc; x=cl. The bulk single crystal is prepared by adopting a crucible descending method, and comprises the following steps:
a) Composition of halide scintillating material prepared on demand chemical formula Cs 8 CuSc 3 Cl 18 High-purity raw materials CsCl, cuCl and ScCl having a purity of 99.9% were weighed out respectively 3 ;
b) Placing the raw materials into a quartz crucible with a round bottom in an inert gas environment; then the crucible is vacuumized and sealed. Wherein the inert gas environment is a glove box filled with argon or nitrogen;
c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to about 930 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 550 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 0.6 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at a speed of 11 ℃/h until the temperature is reduced to room temperature; finally, the prepared halide scintillation crystal is taken out of the quartz crucible in a dry environment and processed. The obtained halide scintillation crystal can be used for detecting X-rays, gamma-rays and other rays or the particle detection field.
FIG. 2 is a graph of the emission spectrum of rare-earth cluster-enhanced low-dimensional scintillating material of example 2. As shown in FIG. 2, cs 8 CuSc 3 Cl 18 Exhibits bright luminescence of ionizing radiation under ionizing radiation, and the main luminescence peak is located at 540 and nm. The spectral line of the ionization radiation luminescence spectrum is smooth and has no burr, which indicates that the ionization radiation luminescence spectrum can generate high-efficiency ionization radiation luminescence; the main peak is located at540 nm, it can be matched with the photoelectric devices such as silicon-based detectors and the like which are mainly used in commercial applications.
Example 3:
the rare earth cluster-reinforced low-dimensional scintillation material of example 3 is in the form of a bulk single crystal with a composition chemical formula of Cs 8 CuLu 3 Cl 18 I.e. as A 8 BC 3 X 18 Is of the general formula; a=cs; b=cu; c=lu; x=cl. The bulk single crystal is prepared by adopting a crucible descending method, and comprises the following steps:
a) Composition of halide scintillating material prepared on demand chemical formula Cs 8 CuLu 3 Cl 18 High-purity raw materials CsCl, cuCl and LuCl with purity of 99.9% are respectively weighed out 3 ;
b) Placing the raw materials into a quartz crucible with a round bottom in an inert gas environment; then the crucible is vacuumized and sealed. Wherein the inert gas environment is a glove box filled with argon or nitrogen;
c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 920 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 550 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 0.7 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at a speed of 12 ℃/h until the temperature is reduced to room temperature; finally, the prepared halide scintillation crystal is taken out of the quartz crucible in a dry environment and processed. The obtained halide scintillation crystal can be used for detecting X-rays, gamma-rays and other rays or the particle detection field.
FIG. 3 is an ionization radiation emission spectrum of the rare earth cluster-enhanced low-dimensional scintillation material of example 3. As shown in FIG. 3, cs 8 CuLu 3 Cl 18 Exhibits bright irradiance under irradiation, with a dominant peak at 430 nm. The spectral line of the ionization radiation luminescence spectrum is smooth and has no burr, which indicates that the ionization radiation luminescence spectrum can generate high-efficiency ionization radiation luminescence; the main peak is located at 430 nm, indicating that it can be used in commercial photoelectric power with the main streamThe tube is matched with photoelectric devices such as a silicon-based detector.
Example 4:
the rare earth cluster-reinforced low-dimensional scintillation material proposed in example 4 is in the form of a bulk single crystal with a composition chemical formula of Cs 8 CuSc 3 Br 18 I.e. as A 8 BC 3 X 18 Is of the general formula; a=cs; b=cu; c=sc; x=br. The bulk single crystal is prepared by adopting a crucible descending method, and comprises the following steps:
a) Composition of halide scintillating material prepared on demand chemical formula Cs 8 CuSc 3 Br 18 High-purity raw materials CsBr, cuBr and ScBr with a purity of 99.9% were weighed out respectively in molar proportions 3 ;
b) Placing the raw materials into a quartz crucible with a round bottom in an inert gas environment; then the crucible is vacuumized and sealed. Wherein the inert gas environment is a glove box filled with argon or nitrogen;
c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growing furnace to 915 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 545 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 0.8 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at a speed of 13 ℃/h until the temperature is reduced to room temperature; finally, the prepared halide scintillation crystal is taken out of the quartz crucible in a dry environment and processed. The obtained halide scintillation crystal can be used for detecting X-rays, gamma-rays and other rays or the particle detection field.
Example 5:
the rare earth cluster-reinforced low-dimensional scintillation material proposed in example 5 is in the form of a bulk single crystal with a composition chemical formula of Cs 8 CuLu 3 Br 18 I.e. as A 8 BC 3 X 18 Is of the general formula; a=cs; b=cu; c=lu, x=br. The bulk single crystal is prepared by adopting a crucible descending method, and comprises the following steps:
a) Pressing the buttonComposition of halide scintillation material to be prepared chemical formula Cs 8 CuLu 3 Br 18 High-purity raw materials CsBr, cuBr and LuBr with a purity of 99.9% were weighed respectively in terms of molar ratio 3 ;
b) Placing the raw materials into a quartz crucible with a round bottom in an inert gas environment; then the crucible is vacuumized and sealed. Wherein the inert gas environment is a glove box filled with argon or nitrogen;
c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to about 910 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 560 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 0.8 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at a speed of 14 ℃/h until the temperature is reduced to room temperature; finally, the prepared halide scintillation crystal is taken out of the quartz crucible in a dry environment and processed. The obtained halide scintillation crystal can be used for detecting X-rays, gamma-rays and other rays or the particle detection field.
FIG. 4 is an ionization radiation emission spectrum of the rare earth cluster-enhanced low-dimensional scintillation material of example 5. As shown in FIG. 4, cs 8 CuLu 3 Br 18 Exhibits bright radiant luminescence under irradiation, with a luminescence main peak at 600 nm. The spectral line of the ionization radiation luminescence spectrum is smooth and has no burr, which indicates that the ionization radiation luminescence spectrum can generate high-efficiency ionization radiation luminescence; the main peak is at 600 nm, which shows that the main peak can be matched with the main stream commercial photomultiplier, silicon-based detector and other photoelectric devices.
Example 6:
the rare earth cluster-reinforced low-dimensional scintillation material of example 6 is in the form of a bulk single crystal with a composition formula of Rb 8 CuLu 3 Cl 18 I.e. as A 8 BC 3 X 18 Is of the general formula; a=rb; b=cu; c=lu, x=cl. The bulk single crystal is prepared by adopting a crucible descending method, and comprises the following steps:
a) On-demand halide scintillating materialMaterial composition chemical formula Rb 8 CuLu 3 Cl 18 High-purity raw materials RbCl, cuCl and LuCl with purity of 99.9% are respectively weighed according to the mole ratio 3 ;
b) Placing the raw materials into a quartz crucible with a round bottom in an inert gas environment; then the crucible is vacuumized and sealed. Wherein the inert gas environment is a glove box filled with argon or nitrogen;
c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 940 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 580 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 0.8 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at a speed of 14 ℃/h until the temperature is reduced to room temperature; finally, the prepared halide scintillation crystal is taken out of the quartz crucible in a dry environment and processed. The obtained halide scintillation crystal can be used for detecting X-rays, gamma-rays and other rays or the particle detection field.
The ionizing radiation luminescence spectrum shows that it has a bright ionizing radiation luminescence with a main luminescence peak of 490 nm. By comparison, rb 8 CuLu 3 Cl 18 Exhibit a higher Cs under ionizing radiation 8 CuLu 3 Cl 18 Poor luminous intensity of ionizing radiation, cs 8 CuLu 3 Cl 18 The main peak luminous intensity is about Rb 8 CuLu 3 Cl 18 4.5 times of the total number of the samples, the Cs is more suitable to be used as an A site in the fields of radiation detection and the like than Rb.
FIG. 5 is an ionization radiation emission spectrum of the rare earth cluster-enhanced low-dimensional scintillation material of example 6. As shown in fig. 5, rb 8 CuLu 3 Cl 18 Exhibits bright irradiance under irradiation, with a main luminescence peak at 490 and nm. FIG. 6 is a graph showing the contrast of the ionizing radiation emission spectra of the rare-earth cluster-enhanced low-dimensional scintillation materials of example 6 and example 3. As shown in fig. 6, rb 8 CuLu 3 Cl 18 Exhibit a higher Cs under irradiation 8 CuLu 3 Cl 18 Poor luminous intensity of radiation, cs 8 CuLu 3 Cl 18 The main peak luminous intensity is about Rb 8 CuLu 3 Cl 18 4.5 times of (a).
Example 7:
the rare earth cluster-reinforced low-dimensional scintillation material of example 7 is in the form of a bulk single crystal with a composition formula (Cs 0.6 K 0.4 ) 8 CuY 3 Cl 18 . The bulk single crystal was prepared by the crucible descent method, the specific procedure being as described in example 1, with the only difference that: in step a), the halide scintillation material composition formula (Cs) prepared as desired 0.6 K 0.4 ) 8 CuY 3 Cl 18 High purity raw materials CsCl, KCl, cuCl and YCl having a purity of 99.99% were weighed out respectively in terms of molar proportions 3 。
Example 8:
the rare earth cluster-reinforced low-dimensional scintillation material of example 8 is in the form of a bulk single crystal with a composition chemical formula of Cs 8 (Cu 0.4 Ag 0.6 )Y 3 Cl 18 . The bulk single crystal was prepared by the crucible descent method, the specific procedure being as described in example 1, with the only difference that: in step a), the halide scintillation material composition formula Cs, as prepared on demand 8 (Cu 0.4 Ag 0.6 )Y 3 Cl 18 High purity raw materials CsCl, cuCl, agCl and YCl having a purity of 99.99% were weighed out respectively in terms of molar proportions 3 。
Example 9:
the rare earth cluster-reinforced low-dimensional scintillation material of example 9 is in the form of a bulk single crystal with a composition chemical formula of Cs 8 Cu(Sc 0.5 Y 0.5 ) 3 Cl 18 . The bulk single crystal was prepared by the crucible descent method, the specific procedure being as described in example 1, with the only difference that: in step a), the halide scintillation material composition formula Cs, as prepared on demand 8 Cu(Sc 0.5 Y 0.5 ) 3 Cl 18 High purity raw materials CsCl, cuCl, scCl with 99.99% purity were weighed out separately 3 And YCl 3 。
Example 10:
the rare earth cluster-reinforced low-dimensional scintillation material of example 10 is in the form of a bulk single crystal with a composition chemical formula of Cs 8 CuY 3 (Cl 0.8 Br 0.2 ) 18 . The bulk single crystal was prepared by the crucible descent method, the specific procedure being as described in example 1, with the only difference that: in step a), the halide scintillation material composition formula Cs, as prepared on demand 8 CuY 3 (Cl 0.8 Br 0.2 ) 18 High purity raw materials CsCl, csBr, cuCl, cuBr, YCl with 99.99% purity were weighed out separately 3 And YBa 3 。
Example 11:
the rare earth cluster-reinforced low-dimensional scintillation material of example 11 is in the form of a polycrystalline thin film having a composition chemical formula of Cs 8 CuY 3 Br 18 . The preparation method of the polycrystalline film by adopting the vapor deposition method comprises the following steps:
a) According to the general formula Cs 8 CuY 3 Br 18 Weighing the raw materials and fully mixing. The materials were placed in a quartz tube in an inert dry gas atmosphere, and then the crucible was evacuated and sealed. Heating the crucible to 950 ℃ until the raw materials are completely melted and uniformly mixed, and then cooling to synthesize uniform Cs 8 CuY 3 Br 18 A polycrystalline compound feedstock;
b) Ultrasonic cleaning quartz plate or other substrate with deionized water, alcohol and acetone for 30 min, drying, and grinding into powder or granule;
c) And (3) mounting the cleaned substrate on a vacuum coating device, weighing the synthesized plating materials, and loading the synthesized plating materials into a tungsten boat or a molybdenum boat with corresponding volume. Wherein, a single source evaporation method, i.e. one boat evaporation Cs is adopted 8 CuY 3 Br 18 A polycrystalline compound feedstock;
d) Vacuumizing the vacuum coating device in the step c) to 10 -4 Pa, and heating the substrate to 250 ℃ to ensure the growth quality of microcrystalsAnd starting a coating program. The coating raw material is heated to a molten state or a near-molten state by adopting a current heating or other heating modes, and the vacuum degree in the coating device is obviously reduced at the moment, namely, the evaporation of the coating material and Cs are started 8 CuY 3 Br 18 Growing a microcrystalline film;
e) When the vacuum degree in the coating device rises to the level before the coating starts again, namely marking the end of coating, turning off the heating device, and obtaining Cs after cooling 8 CuY 3 Br 18 Microcrystalline thin films. The obtained halide scintillation film can be used for detecting X-rays, gamma rays and other rays or the particle detection field.
Example 12:
the rare earth cluster-reinforced low-dimensional scintillation material of example 12 is in the form of a polycrystalline thin film having a composition chemical formula of Cs 8 CuSc 3 I 18 . The preparation method of the polycrystalline film by adopting the vapor deposition method comprises the following steps:
a) According to the general formula Cs 8 CuSc 3 I 18 Weighing the raw materials and fully mixing. The materials were placed in a quartz tube in an inert dry gas atmosphere, and then the crucible was evacuated and sealed. Heating the crucible to 920 ℃ until the raw materials are completely melted and uniformly mixed, and then cooling to synthesize uniform Cs 8 CuSc 3 I 18 A polycrystalline compound feedstock;
b) Ultrasonic cleaning quartz plate or other substrate with deionized water, alcohol and acetone for 35 min, drying, and grinding into powder or granule;
c) And (3) mounting the cleaned substrate on a vacuum coating device, weighing the synthesized plating materials, and loading the synthesized plating materials into a tungsten boat or a molybdenum boat with corresponding volume. Wherein, a single source evaporation method, i.e. one boat evaporation Cs is adopted 8 CuSc 3 I 18 A polycrystalline compound feedstock;
d) Vacuumizing the vacuum coating device in the step c) to 10 -4 Pa, and heating the substrate to 260 ℃ to ensure the growth quality of microcrystals, and starting a coating procedure. By electric current heating or the likeThe heating mode heats the coating material to a molten state or a near-molten state, at this time, the vacuum degree in the coating device is obviously reduced, namely, the evaporation of the coating material and Cs are started 8 CuSc 3 I 18 Growing a microcrystalline film;
e) When the vacuum degree in the coating device rises to the level before the coating starts again, namely marking the end of coating, turning off the heating device, and obtaining Cs after cooling 8 CuSc 3 I 18 Microcrystalline thin films. The obtained halide scintillation film can be used for detecting X-rays, gamma rays and other rays or the particle detection field.
Example 13:
the rare earth cluster-reinforced low-dimensional scintillation material of example 13 is in the form of powder and has a chemical formula of Cs 8 CuSc 3 I 18 . The powder is prepared by adopting a solid phase reaction method, and comprises the following steps: according to the general formula Cs 8 CuSc 3 I 18 Weighing the raw materials and fully mixing. The materials were placed in a quartz tube in an inert dry gas atmosphere, and then the crucible was evacuated and sealed. Heating the crucible to 920 ℃ until the raw materials are completely melted and uniformly mixed, and then cooling to synthesize uniform Cs 8 CuSc 3 I 18 Polycrystalline compound starting material. The obtained halide scintillating powder can be used for detecting X-rays, gamma rays and other rays or the particle detection field.
Example 14:
the rare earth cluster-reinforced low-dimensional scintillation material of example 14 is In the form of bulk single crystal with a composition formula of In 8 CuSc 3 Cl 18 . The bulk single crystal was prepared by the crucible descent method, the specific procedure being as described in example 2, with the only difference that: in step a), the halide scintillation material prepared as desired has the composition formula In 8 CuSc 3 Cl 18 High-purity raw materials InCl, cuCl and ScCl with purity of 99.99% are respectively weighed according to the mole ratio 3 。
Example 15:
the rare-earth cluster-reinforced low-dimensional scintillation material of example 15 is in the form of bulk single crystals, and is chemically composedTl is 8 CuSc 3 Cl 18 . The bulk single crystal was prepared by the crucible descent method, the specific procedure being as described in example 2, with the only difference that: in step a), the halide scintillating material prepared on demand has a composition formula Tl 8 CuSc 3 Cl 18 High-purity raw materials TlCl, cuCl and ScCl with purity of 99.99% were weighed respectively 3 。
Example 16:
the rare earth cluster-reinforced low-dimensional scintillation material of example 16 is In the form of a bulk single crystal with a composition formula (In 0.9 Cs 0.1 ) 8 CuSc 3 Cl 18 . The bulk single crystal was prepared by the crucible descent method, the specific procedure being as described in example 2, with the only difference that: in step a), the halide scintillation material composition formula (In) 0.9 Cs 0.1 ) 8 CuSc 3 Cl 18 High purity raw materials CsCl, inCl, cuCl and ScCl having a purity of 99.99% were weighed out respectively 3 。
Example 17:
the rare earth cluster-reinforced low-dimensional scintillation material of example 17 is in the form of a bulk single crystal having a composition formula (Tl 0.8 In 0.2 ) 8 CuSc 3 Cl 18 . The bulk single crystal was prepared by the crucible descent method, the specific procedure being as described in example 2, with the only difference that: in step a), the halide scintillating material prepared as desired has a compositional formula (Tl) 0.8 In 0.2 ) 8 CuSc 3 Cl 18 High purity raw materials TlCl, inCl, cuCl and ScCl having a purity of 99.99% were weighed out respectively 3 。
Comparative example 1
The rare earth scintillating material of comparative example 1 is in the form of a bulk single crystal, and has a composition chemical formula of Rb 8 CuSc 3 Cl 18 . The bulk single crystal was prepared by the crucible descent method, the specific procedure being as described in example 2, with the only difference that: in step a), the as-prepared halide scintillation material has a composition formula Rb 8 CuSc 3 Cl 18 Molar ratio of (3)High-purity raw materials RbCl, cuCl and ScCl with purity of 99.99 percent are respectively weighed 3 。
FIG. 7 is an ionizing radiation emission spectrum of a rare earth cluster-enhanced low-dimensional scintillation material of comparative example 1. Results of the radiation emission spectrum show Rb 8 CuSc 3 Cl 18 It has a bright radiant luminescence with a main luminescence peak of 400 nm.
FIG. 8 is a rare earth cluster-enhanced low-dimensional scintillating material Rb of comparative example 1 8 CuSc 3 Cl 18 Low-dimensional scintillating material Cs reinforced with rare earth clusters in example 2 8 CuSc 3 Cl 18 Is a graph of the luminescence spectrum of ionizing radiation. As shown in fig. 8, rb 8 CuSc 3 Cl 18 Under irradiation compared with Cs 8 CuSc 3 Cl 18 Exhibits poor irradiance, cs 8 CuSc 3 Cl 18 The main peak intensity is about Rb 8 CuSc 3 Cl 18 Is a factor of 5.3 of the total number of the three,
comparative example 2
The rare earth scintillating material of comparative example 2, which is in the form of bulk single crystal, has a composition chemical formula of Rb 8 CuY 3 Cl 18 . The bulk single crystal was prepared by the crucible descent method, the specific procedure being as described in example 1, with the only difference that: in step a), the as-prepared halide scintillation material has a composition formula Rb 8 CuY 3 Cl 18 High-purity raw materials RbCl, cuCl and YCl with 99.99 percent of purity are respectively weighed according to the mole ratio 3 。
FIG. 9 is a rare earth cluster-enhanced low-dimensional scintillation material Rb of comparative example 2 8 CuY 3 Cl 18 Low-dimensional scintillating material Cs reinforced with rare earth clusters in example 1 8 CuY 3 Cl 18 Is a graph of the luminescence spectrum of ionizing radiation. As shown in fig. 9, rb 8 CuY 3 Cl 18 Under irradiation compared with Cs 8 CuY 3 Cl 18 Exhibits poor irradiance, cs 8 CuY 3 Cl 18 The main peak intensity is about Rb 8 CuSc 3 Cl 18 Is 6.1 times that of (c).
Combining comparative example 2, comparative example 1 and example 6Test results, general formula A 8 BC 3 X 18 In the rare earth cluster reinforced low-dimensional scintillation material, rb element is not ideal as A-site element.
Comparative example 3
The rare earth scintillating material of comparative example 3 is in the form of a bulk single crystal, and the chemical formula of the composition is Cs 3 YCl 6 . The bulk single crystal was prepared by the crucible descent method, the specific procedure being as described in example 1, with the only difference that: in step a), the halide scintillation material composition formula Cs, as prepared on demand 3 YCl 6 The high-purity raw materials CsCl and YCl with 99.99% purity are respectively weighed according to the mole ratio of 3 。
FIG. 10 shows Cs of the rare earth zero-dimensional structure of comparative example 3 3 YCl 6 Low-dimensional scintillating material Cs reinforced with rare earth clusters in example 1 8 CuY 3 Cl 18 Is a graph of the luminescence spectrum of ionizing radiation. As shown in FIG. 10, cs 8 CuY 3 Cl 18 Exhibits bright ionizing radiation luminescence under irradiation, and has a main peak intensity of about Cs 3 YCl 6 By comparison, A can be seen to be 7 times 8 BC 3 X 18 The rare earth reinforced low-dimensional scintillation material has great advantages and application potential in the fields of radiation detection and the like.
FIG. 11 shows Cs of the rare earth zero-dimensional structure of comparative example 3 3 YCl 6 Low-dimensional scintillating material Cs reinforced with rare earth clusters in example 1 8 CuY 3 Cl 18 Powder XRD diffractogram of (2). From the powder X-ray diffraction pattern of FIG. 11, a significant difference in diffraction peaks was observed, indicating a significant difference in structure between the two, i.e., cs 8 CuY 3 Cl 18 Is a brand new compound and Cs 3 YCl 6 There is a substantial difference.
FIG. 12 shows Cs of the rare earth zero-dimensional structure of comparative example 3 3 YCl 6 Low-dimensional scintillating material Cs reinforced with rare earth clusters in example 1 8 CuY 3 Cl 18 Is a comparative partial crystal structure diagram. As shown in FIG. 12, cs 8 CuY 3 Cl 18 Having a paddle-like primitive structureThree around [ CX ] connected by two B-bit elements in the center 6 ] 3- Octahedral formation, in particular of Cs 8 CuY 3 Cl 18 Two central Cu's in the material + Connect three [ YCl ] 6 ] 3- Octahedron forms a paddle-like primitive structure. Due to the existence of the paddle-shaped primitive structure, carriers formed by excitation are easier to localize, so that the luminous efficiency of ionizing radiation is effectively enhanced. Whereas Cs 3 YCl 6 Is Cs + Direct separation [ YCl ] 6 ] 3- Octahedron, there is a clear difference in the structure of the two. From this, it can be seen that A 8 BC 3 X 18 The expressed rare earth cluster reinforced low-dimensional scintillation material is a high-sensitivity scintillation material with a brand new structure, and is compared with the prior A 3 BX 6 The STE scintillating material of the type has an essential difference.
In the invention, the following components are added: the resulting low-dimensional halide scintillating material based on rare-earth cluster enhancement was tested for its ionizing radiation emission spectrum using a tungsten target X-ray tube as excitation source and a QEpro spectrometer based on marine optics as detector.
Finally, what is necessary here is: the above embodiments are only for further detailed description of the technical solutions of the present invention, and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments made by those skilled in the art from the above description of the present invention are all within the scope of the present invention.
Claims (10)
1. A rare earth cluster-based enhanced low-dimensional halide scintillation material characterized by: the rare earth cluster-based enhanced low-dimensional halide scintillation material has a chemical formula of A 8 BC 3 X 18 ;
B is at least one selected from Cu, ag, au, in and Tl;
c is at least one selected from La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, sc, Y and Lu;
x is selected from at least one of F, cl, br and I;
wherein,
the a-site element is composed of In and at least one other element different from In;
the rare earth cluster-based enhanced low-dimensional halide scintillation material has a chemical formula (In 1-y E y ) 8 BC 3 X 18 ,0<y<1;
E is selected from at least one of Na, K, rb, cs and Tl;
or,
the A-bit element is composed of Tl and at least one other element different from Tl;
the rare earth cluster-based enhanced low-dimensional halide scintillation material has a chemical formula (Tl) 1-z M z ) 8 BC 3 X 18 ,0<z<1;
M is selected from at least one of Na, K, rb, cs and In.
2. The rare earth cluster-based enhanced low-dimensional halide scintillation material of claim 1, wherein: the rare earth cluster-enhanced low-dimensional halide-based lattice structure has a paddle-like primitive structure composed of two B-site elements in the center and three octahedrons [ CX ] connected around the B-site elements 6 ] 3- The composition is formed.
3. The rare earth cluster-based enhanced low-dimensional halide scintillation material of claim 1, wherein: the low-dimensional halide scintillating material based on rare earth cluster reinforcement is in the form of a bulk single crystal, powder or polycrystalline film.
4. The rare earth cluster-based enhanced low-dimensional halide scintillation material of claim 1, wherein:
the low-dimensional halide scintillation material based on rare earth cluster enhancement is in the form of a bulk single crystal, and the size of the bulk single crystal in at least one dimension is not less than 1mm; or alternatively
The low-dimensional halide scintillation material based on rare earth cluster enhancement is in the form of powder, and the particle size of the powder is in the range of 1 nm-20 mu m; or alternatively
The low-dimensional halide scintillation material based on rare earth cluster reinforcement is in the form of a polycrystalline film, and the thickness of the polycrystalline film is 1-1000 mu m.
5. A method for preparing a rare earth cluster-based enhanced low-dimensional halide scintillation material, which is characterized in that: the material is the low-dimensional halide scintillation material based on rare earth cluster reinforcement as claimed in any one of claims 1 to 4, the morphology of the material is bulk single crystal, and the preparation method comprises the following steps:
(1) According to chemical formula A of a rare earth cluster-based enhanced low-dimensional halide scintillation material 8 BC 3 X 18 Weigh AX powder, BX powder and CX 3 The powder is used as raw material powder, the raw material powder is placed in a quartz crucible with a capillary structure, and the air is pumped until the pressure is less than or equal to 10 -2 Pa, and performing welding sealing;
(2) Vertically placing the sealed quartz crucible in a crystal growth furnace, then heating to the melting temperature of the raw material with the highest melting point, preserving heat, completely melting and uniformly mixing the raw material powder;
(3) Adjusting the position and/or furnace temperature of the quartz crucible so that the temperature of the bottom of the capillary structure of the quartz crucible is kept between + -10 ℃ based on the melting point of the rare earth cluster-enhanced low-dimensional halide scintillation material;
(4) Controlling the growth temperature gradient of the crystal growth furnace to be 5-50 ℃/cm, then enabling the quartz crucible to descend in the furnace body at the descending speed of 0.01-10.0 mm/h, and starting the growth of crystals;
(5) And after the growth is finished, cooling to room temperature at a cooling rate of 0.5-50 ℃/h.
6. A method for preparing a rare earth cluster-based enhanced low-dimensional halide scintillation material, which is characterized in that: the material is the low-dimensional halide scintillating material based on rare earth cluster reinforcement as claimed in any one of claims 1 to 4, the morphology of the material is powder, and the preparation method comprises the following steps:
(1) Chemistry according to rare earth cluster-based enhanced low-dimensional halide scintillation materialsGeneral formula A 8 BC 3 X 18 Weigh AX powder, BX powder and CX 3 The powder is used as raw material powder, and then is placed in a quartz tube for air extraction until the pressure is less than or equal to 10 -2 Pa, and performing welding sealing;
(2) And (3) carrying out heat preservation treatment on the welded quartz tube for 1-10 hours at 400-1100 ℃ until the raw materials are completely melted and uniformly mixed, and cooling to obtain the powdery low-dimensional halide scintillating material based on rare earth cluster reinforcement.
7. A method for preparing a rare earth cluster-based enhanced low-dimensional halide scintillation material, which is characterized in that: the material is the low-dimensional halide scintillating material based on rare earth cluster reinforcement as claimed in any one of claims 1 to 4, the morphology of the material is a polycrystalline film, and the preparation method comprises the following steps:
(1) According to chemical formula A of a rare earth cluster-based enhanced low-dimensional halide scintillation material 8 BC 3 X 18 Weigh AX powder, BX powder and CX 3 Mixing the powder to obtain raw material powder, and placing in quartz tube, and exhausting gas until pressure is less than or equal to 10 -2 Pa, and performing welding sealing;
(2) The welded quartz tube is heat-preserved for 1 to 10 hours at the temperature of 400 to 1100 ℃ to obtain A 8 BC 3 X 18 Powder;
(3) A is prepared by a single source evaporation method 8 BC 3 X 18 And (3) coating the powder on the surface of the substrate to obtain the low-dimensional halide scintillation material based on rare earth cluster reinforcement.
8. The method for preparing a rare earth cluster-based enhanced low-dimensional halide scintillation material as recited in claim 7, wherein: in the operation of the single source evaporation method, A is 8 BC 3 X 18 Heating the powder to a molten state, and vacuumizing to a vacuum degree of less than or equal to 30 Pa by adopting a quartz or high-boron glass substrate; the temperature of the substrate is 200-300 ℃.
9. The rare earth-based cluster according to any one of claims 5 to 7A method of preparing an enhanced low-dimensional halide scintillation material, comprising: according to the chemical formula A 8 BC 3 X 18 The purity of AX powder is above 99.9%, the purity of BX powder is above 99.9%, CX is in the powder 3 The purity of the powder is more than 99.9 percent.
10. Use of a rare earth cluster-based enhanced low-dimensional halide scintillation material characterized by: the material is the rare earth cluster-based enhanced low-dimensional halide scintillation material of claim 1 or 2, which is used in X-ray detection, gamma-ray detection or particle detection.
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