CN117071070B - Transition metal doped sodium-based halogen scintillation crystal and preparation method and application thereof - Google Patents
Transition metal doped sodium-based halogen scintillation crystal and preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 182
- 239000011734 sodium Substances 0.000 title claims abstract description 121
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 72
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 69
- 150000002367 halogens Chemical class 0.000 title claims abstract description 69
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 68
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 66
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000001514 detection method Methods 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 150000004820 halides Chemical class 0.000 claims description 48
- 239000002994 raw material Substances 0.000 claims description 46
- 239000010453 quartz Substances 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- -1 sodium halide Chemical class 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- 239000011261 inert gas Substances 0.000 claims description 21
- 239000010931 gold Substances 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910052716 thallium Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 abstract description 10
- 230000005855 radiation Effects 0.000 abstract description 6
- DVJXWGUUOPZAMD-UHFFFAOYSA-N lithium thallium Chemical compound [Li].[Tl] DVJXWGUUOPZAMD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 111
- 239000010949 copper Substances 0.000 description 56
- 235000009518 sodium iodide Nutrition 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001816 cooling Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 230000006911 nucleation Effects 0.000 description 9
- 238000010899 nucleation Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 5
- 238000002284 excitation--emission spectrum Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 238000010791 quenching Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000006123 lithium glass Substances 0.000 description 2
- 238000009206 nuclear medicine Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012850 discrimination method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 230000005253 gamme decay Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- 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
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- 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
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
- C09K11/626—Halogenides
- C09K11/628—Halogenides with alkali or alkaline earth metals
-
- 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
- C30B11/02—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method without using solvents
-
- 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
- G01T3/00—Measuring neutron radiation
- G01T3/06—Measuring neutron radiation with scintillation detectors
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- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to a transition metal doped sodium-based halogen scintillation crystal and a preparation method and application thereof, belonging to the field of crystal growth technology and radiation detection. Aiming at the problems of low alpha/beta ratio, poor neutron-gamma discrimination capability and the like of the existing lithium thallium co-doped sodium-based halogen scintillation crystal, the invention provides a transition metal doped sodium-based halogen scintillation crystal, and the composition general formula Na of the transition metal doped sodium-based halogen scintillation crystal 1‑a‑b‑c Li a Tl b M c I 1‑d X d The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is at least one of Cu, ag and Au, X is at least one of F, cl and Br, a is more than 0 and less than or equal to 0.2, b is more than 0 and less than or equal to 0.02,0, c is more than or equal to 0.012,0, and d is more than or equal to 0 and less than or equal to 0.5.
Description
Technical Field
The invention relates to a transition metal doped sodium-based halogen scintillation crystal, a preparation method and application thereof, in particular to a scintillation single crystal which is introduced with a co-dopant and has an alpha/beta ratio of more than 1 during neutron-gamma discrimination, belonging to the fields of crystal growth technology and radiation detection.
Background
Neutron detection is of great importance in the fields of scientific research, neutron imaging, nuclear medicine, nuclear safety detection, environmental radiation detection and the like. The most widely used conventional neutron detection materials are 3 He gas. But is provided with 3 He gas is in shortage, high in price and limited in application range. Therefore, there is a need to find new neutron detection materials. One possible solution is to use 6 The nuclear reaction of Li element and neutrons detects neutrons. For example: lithium glass, 6 LiF/ZnS: ag scintillator, etc., neutron-gamma discrimination can be achieved by pulse waveform discrimination (PSD) or the like. The pulse shape discrimination is to discriminate neutrons and gamma rays by utilizing the pulse shape difference of neutrons-gamma rays, and has the function of utilizing neutron/gamma waveform informationIs one of the common methods for neutron-gamma discrimination. The scintillation crystal neutron-gamma discrimination capability was evaluated using a quality factor (FoM) and an alpha/beta ratio. Wherein the ratio of the number of photons produced by neutrons per MeV energy to the number of photons produced by gamma rays per MeV is referred to as the alpha/beta ratio, with a high alpha/beta contributing to distinguishing neutrons from gamma rays.
Existing technology 6 In the Li-loaded scintillator, the lithium glass has low production cost and short response time, but the light yield is small, and the alpha/beta ratio is low by only 0.35. 6 The light yield of LiF/ZnS: ag scintillators under neutron irradiation is as high as 160,000 photons/neutron, but the response time is long, and the scintillators are difficult to be made into transparent single crystals, the actual neutron detection efficiency is less than 20%, and the alpha/beta ratio is only 0.44. 6 The alpha/beta ratio of the LiI to Eu scintillator is up to 0.87 (the highest value of the existing material), but neutron-gamma discrimination cannot be realized through PSD. In the new high-performance neutron/gamma double-detection scintillation crystal developed in recent years, cs 2 LiYCl 6 Ce crystal has high light output and fast attenuation, the alpha/beta ratio reaches 0.73, and the quality factor FoM reaches 4.55. But Cs 2 LiYCl 6 Ce crystals also face the problems of high raw material cost, low crystal growth yield caused by inconsistent melting, and the like.
2017, san Gobi Inc. Yang et al, france will 6 Li is introduced into a low-cost NaI: tl scintillation crystal in a co-doped form, so that neutron-gamma dual-mode detection is realized. NaI: tl prepared by Bridgman method, 6 the gamma detection performance of the Li crystal performance is equivalent to that of a standard NaI: tl crystal, 2% 6 Neutron-gamma discrimination capability of Li doped crystals and Cs of the same size 2 6 LiYCl 6 The Ce crystal is close. NaI is equal to Tl, and the total content of the catalyst, 6 the Li crystal has low cost of raw materials, simple crystal structure and commercial prospect of large-scale application. However, the crystal α/β is still relatively low (about 0.62), and the FoM value still has room for improvement, which is still further optimized for high-demand neutron-gamma dual detection. Patent document 1 (chinese patent publication No. CN115216840 a) discloses a lithium thallium co-doped sodium iodide scintillation crystal (composition formula (Na) 1-a-b-c 6 Li a Tl b M c )I 1-a-b-c X a+b+cd Wherein M is at least one of Yb, sm, la, gd, Y, lu, sc, hf, zr, bi, X is at least one of halogen elements F, cl, br, I, and 0 < a.ltoreq.0.2, 0 < b.ltoreq. 0.01,0 < c.ltoreq.0.01), and the alpha/beta is at most only 0.6 due to quenching, although the crystal has the advantages of high light output, high energy resolution, excellent neutron-gamma discrimination capability and the like. The lithium thallium co-doped sodium iodide scintillation crystal disclosed in patent document 2 (chinese publication No. CN 115637148A) has a composition formula: (Na) 1-a-b-c 6 Li a Tl b M c ) X is a group; x is one or more of F, cl, br, I; m is Ca, sr, mg or Ba; wherein a is more than 0 and less than or equal to 0.2, b is more than 0 and less than or equal to 0.01,0, c is more than 0.05, and the alpha/beta is only 0.7 at most due to quenching, although the light output, the energy resolution and the neutron-gamma discrimination capability are high.
In summary, all currently reported radiation detection materials have an alpha/beta ratio of less than 1, limiting the ability of the detector to further enhance neutron/gamma ray discrimination. 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 problems of low alpha/beta ratio, poor neutron-gamma discrimination capability and the like of the existing lithium thallium co-doped sodium-based halogen scintillation crystal, the invention provides a transition metal doped sodium-based halogen scintillation crystal with alpha/beta ratio more than 1, and a preparation method and application thereof.
In one aspect, the present invention provides a transition metal doped sodium-based halogen scintillation crystal having a composition formula Na 1-a-b-c Li a Tl b M c I 1-d X d The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is at least one of Cu, ag and Au, X is at least one of F, cl and Br, a is more than 0 and less than or equal to 0.2, b is more than 0 and less than or equal to 0.02,0, c is more than or equal to 0.012,0, and d is more than or equal to 0 and less than or equal to 0.5.
The invention creatively develops the radiation detection crystal material with the alpha/beta ratio larger than 1. The technical core of the invention is as follows: one or more elements of copper, silver and gold ions M (M=Cu, ag and Au) are introduced during the growth of the lithium thallium co-doped crystal, new defects are formed by doping, the alpha/beta ratio of the crystal is optimized, and further the scintillation performance of the co-doped crystal is improved.
Preferably, the transition metal doped sodium-based halogen scintillation crystal is a single crystal.
Preferably, the Li element in the transition metal doped sodium-based halogen scintillation crystal is 6 Li。
Preferably, M is Cu.
Preferably, 0 < c.ltoreq.0.004 or/and d=0.
Preferably, the alpha/beta ratio of the transition metal doped sodium-based halogen scintillation crystal is more than 1; the light yield of the transition metal doped sodium-based halogen scintillation crystal is 8000-20000 photon number/MeV.
In still another aspect, the present invention provides a method for preparing a transition metal doped sodium-based halogen scintillation crystal using a crucible descent method. Preferably, the crucible lowering method includes:
(1) According to the composition general formula Na of transition metal doped sodium-based halogen scintillation crystal 1-a-b-c Li a Tl b M c I 1-d X d Weighing sodium halide, lithium halide, thallium halide, copper halide, silver halide and gold halide as raw materials;
(2) Placing the raw materials into a crucible in an inert gas or anhydrous dry environment, vacuumizing and sealing;
(3) Vertically placing the sealed crucible in the middle of a crystal growth furnace, and melting to completely melt and uniformly mix the raw materials; the melting temperature is more than the melting point of the transition metal doped sodium-based halogen scintillation crystal, and the difference is more than 50 ℃;
(4) Regulating the position of the crucible and the temperature of the crystal growth furnace, reducing the temperature of the bottom of the crucible to the melting point of the transition metal doped sodium-based halogen scintillation crystal, and then reducing the quartz crucible in the crystal growth furnace at the reducing speed of 0.1-10.0 mm/h, wherein the transition metal doped sodium-based halogen scintillation crystal starts to nucleate and grow from the bottom of the crucible until the melt is completely solidified;
(5) And after the crystal growth is finished and the temperature is reduced to the room temperature, obtaining the transition metal doped sodium-based halogen scintillation crystal.
Preferably, the purity of the raw materials is more than or equal to 99%; the weighing environment is a drying chamber or a glove box filled with argon or nitrogen.
Preferably, before weighing, the raw materials are subjected to vacuum drying treatment; the temperature of the material dried by the vacuum drying treatment is less than or equal to 180 ℃, and the vacuum degree is less than or equal to 10 -2 Pa。
In yet another aspect, the invention provides an application of a transition metal doped sodium-based halogen scintillation crystal in the neutron detection field, the gamma detection field, and the neutron-gamma dual-mode detection field, wherein the neutron detection field comprises petroleum exploration wells, homeland security and nuclear power applications.
The invention has the beneficial effects that:
based on a pulse shape discrimination method, the transition metal doped sodium-based halogen scintillation crystal provided by the invention can be prepared by a crucible descent method, and can be applied to neutron detection (especially thermal neutron detection), gamma detection, neutron-gamma dual-mode detection and the like.
The transition metal doped sodium-based halogen scintillation crystal for neutron-gamma dual-mode detection provided by the invention can greatly improve the neutron-gamma discrimination capability by introducing one or more of Cu, ag and Au, has a high alpha/beta ratio larger than 1 and a high neutron-gamma discrimination quality factor, and can be widely applied to the fields of neutron detection, gamma detection, neutron-gamma discrimination and the like, such as scientific research, neutron imaging, nuclear medicine, nuclear safety detection, environmental radiation detection and the like.
Drawings
FIG. 1 is a pictorial view of the halide scintillator of examples 1-4;
FIG. 2 is a schematic diagram of a halide scintillator and undoped NaI of example 1: 6 an X-ray excitation emission spectrum of Li, tl crystals;
FIG. 3 is a schematic diagram of a halide scintillator and a non-halide scintillator of example 1Doping NaI: 6 fluorescence excitation emission spectrum of Li, tl crystal;
FIG. 4 is a schematic diagram of a halide scintillator of example 1 with undoped NaI: 6 gamma energy spectrum of Li, tl crystal;
FIG. 5 is a schematic diagram of a halide scintillator of example 1 with undoped NaI: 6 neutron/gamma/alpha energy spectrum of Li, tl crystal;
FIG. 6 is a schematic diagram of a halide scintillator of example 1 with undoped NaI: 6 a scintillation decay time diagram of the Li, tl crystal;
FIG. 7 is a plot of FoM scatter for the halide scintillator of example 1;
FIG. 8 is a graph of average neutron-gamma pulse waveforms for the halide scintillator of example 1;
FIG. 9 is a graph comparing particle discrimination performance of the example 1 halide scintillator with commercial neutron detection materials;
fig. 10 is a schematic diagram of example 1, example 2 halide scintillators with undoped NaI: 6 gamma energy spectrum of Li, tl crystal;
fig. 11 is a schematic diagram of example 1, example 2 halide scintillators with undoped NaI: 6 neutron/gamma light yield contrast plots for Li, tl crystals;
fig. 12 is a FoM scatter plot of the halide scintillator of comparative example 2.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the present disclosure, the composition formula of the transition metal doped sodium-based halogen scintillation crystal for neutron detection is: na (Na) 1-a-b- c Li a Tl b M c I 1-d X d The method comprises the steps of carrying out a first treatment on the surface of the Wherein X is one or more of F, cl, br, I; m is one or more of Cu (+1 valence), ag (+1 valence) or Au (+1 valence); a is more than 0 and less than or equal to 0.2, b is more than 0 and less than or equal to 0.02,0, c is more than or equal to 0.012 (preferably, c is more than or equal to 0.001 and less than or equal to 0.01), and d is more than or equal to 0 and less than or equal to 0.5.
In the present invention, li is preferably used as 6 Li-enriched raw materials, not natural Li ions of natural abundance. While 6 Li is neutron absorber, rootEnrichment based on neutron-gamma discrimination scatter plot 6 Better neutron detection capability can be obtained in the case of Li. Preferred composition is Na 1-a-b-c Li a Tl b Cu c I, i.e. M is preferably Cu and d is preferably 0. More preferably 0 < c.ltoreq.0.004. The transition metal doped sodium-based halogen scintillation crystal component of the invention contains Cu + Ions by Cu + Doping can improve neutron detection capability and neutron-gamma discrimination capability.
The scintillator of the present invention can be prepared into the scintillator single crystal material of the present invention by the crucible descent method and the Czochralski method.
The growth of the halide scintillation single crystal of the present invention by the crucible descent method is exemplarily described below.
According to the general formula Na 1-a-b-c Li a Tl b M c I 1-d X d Sodium halide, lithium halide, thallium halide, copper halide, silver halide and gold halide were weighed separately. Preferred starting materials are high purity sodium halides, lithium halides, thallium halides, copper halides, silver halides and gold halides, for example NaI, 6 LiX, tlix and MX powders or grains. The purity of all raw materials is above 99%. Furthermore, the preferable raw materials need to be subjected to vacuum drying treatment before weighing and proportioning, the temperature of the dried raw materials is less than or equal to 180 ℃, and the vacuum degree is better than 10 -2 Pa, the batching environment is a drying chamber or a glove box filled with argon or nitrogen. By using 6 Li and Tl ions are used as activators of the transition metal doped sodium-based halogen scintillation crystal, 6 li and Tl ions in the form of halides, e.g 6 LiI and TlI are incorporated into the feedstock. M ions (m=cu, ag, au) are used as dopants for the transition metal doped sodium-based halogen scintillation crystal, the M ions being incorporated into the raw material in the form of halides MX. As an example, the weighing and proportioning is performed according to the following formula: (1-a-b-c) NaI+a 6 LiX+ bTlX+cMXd→Na 1-a-b-c Li a Tl b M c I 1-d X d (a is more than 0 and less than or equal to 0.2, b is more than 0 and less than or equal to 0.02,0, c is more than or equal to 0.01,0 and d is more than or equal to 0.5), and then the mixture is put into a mortar for uniform grinding.
In an inert gas or anhydrous dry environment, each raw material is placed in a quartz crucible or a crucible of other materials, and as an example, a quartz crucible is used. And vacuumizing the crucible and sealing the crucible by welding. Among them, quartz is used as a loading raw material and a crucible material for growing crystals. The crucible shape can be cylindrical, square cylindrical or conical, and the bottom of the crucible is provided with a capillary tube or conical bottom or flat bottom for fixing seed crystals.
Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to maintain the temperature over 50 deg.c to the melting point of the synthesized compound for certain period until the material is completely melted and mixed homogeneously.
And regulating the position and the furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to the melting point of the scintillation crystal, and then enabling the quartz crucible to descend in the furnace body at the descending speed of 0.1-10.0 mm/h, wherein the crystal starts to nucleate and grow from the bottom of the crucible until the melt is completely solidified.
And after the crystal growth is finished, slowly cooling the growth furnace to room temperature, and taking out the quartz crucible to obtain the transition metal doped sodium-based halogen scintillation crystal.
According to the invention, the improvement of gamma energy resolution and neutron-gamma discrimination capability can be realized by introducing one or more of copper, silver and gold ions M (M=Cu, ag and Au). The grown crystal has the advantages of high alpha/beta ratio, high neutron-gamma discrimination capability and the like. The provided application of the transition metal doped sodium-based halogen scintillation crystal comprises the application in the fields of neutron detection, gamma detection, neutron-gamma discrimination and the like.
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 composition of the transition metal doped sodium-based halogen scintillation crystal in this example 1 is Na 0.988 Li 0.01 Tl 0.001 Cu 0.001 I, adopting a crucible descending method, and the corresponding preparation method comprises the following steps:
(1) On-demand intrinsic halide scintillator composition Na 0.988 Li 0.01 Tl 0.001 Cu 0.001 I, weighing high-purity raw materials NaI, tlI, 6 LiI and CuI;
(2) Placing the raw materials into a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is vacuumized and sealed. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
(3) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 750 ℃ 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 300 ℃, then descending the quartz crucible in the furnace body at the descending speed of 0.5mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified;
(4) Then cooling at a speed of 5 ℃/h until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and processed. The obtained intrinsic halide scintillator is applied to the fields of neutron detection, gamma detection, neutron-gamma discrimination and the like.
Example 2:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 2 is Na 0.987 Li 0.01 Tl 0.001 Cu 0.002 I, adopting a crucible descending method, and the corresponding preparation method comprises the following steps:
(1) An on-demand intrinsic halide scintillator having a composition of the formula Na 0.987 Li 0.01 Tl 0.001 Cu 0.002 I, weighing high-purity raw materials NaI, tlI, 6 LiI and CuI;
(2) Placing the raw materials into a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is vacuumized and sealed. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
(3) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 750 ℃ 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 300 ℃, then descending the quartz crucible in the furnace body at the descending speed of 0.5mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified;
(4) Then cooling at a speed of 5 ℃/h until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and processed. The obtained intrinsic halide scintillator is applied to the fields of neutron detection, gamma detection, neutron-gamma discrimination and the like.
Example 3:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 3 is Na 0.985 Li 0.01 Tl 0.001 Cu 0.004 I, the preparation is carried out by the crucible lowering method, and the corresponding preparation method is described in example 1.
Example 4:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 4 is Na 0.983 Li 0.01 Tl 0.001 Cu 0.006 I, the preparation is carried out by the crucible lowering method, and the corresponding preparation method is described in example 1.
Example 5:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 5 is Na 0.981 Li 0.01 Tl 0.001 Cu 0.008 I, the preparation is carried out by the crucible lowering method, and the corresponding preparation method is described in example 1.
Example 6:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 6 is Na 0.979 Li 0.01 Tl 0.001 Cu 0.01 I, descending by cruciblePreparation by the method, corresponding preparation method is described in example 1.
Example 7:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 7 is Na 0.977 Li 0.01 Tl 0.001 Cu 0.012 I, the preparation is carried out by the crucible lowering method, and the corresponding preparation method is described in example 1.
Example 8:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 8 is Na 0.988 Li 0.01 Tl 0.001 Ag 0.001 I, the preparation is carried out by the crucible lowering method, and the corresponding preparation method is described in example 1.
Example 9:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 9 is Na 0.988 Li 0.01 Tl 0.001 Au 0.001 I, the preparation is carried out by the crucible lowering method, and the corresponding preparation method is described in example 1.
Example 10:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 10 is Na 0.983 Li 0.01 Tl 0.001 Cu 0.00 6 I 0.999 F 0.001 The crucible descending method is adopted, and the corresponding preparation method comprises the following steps:
(1) On-demand intrinsic halide scintillator composition Na 0.983 Li 0.01 Tl 0.001 Cu 0.006 I 0.999 F 0.001 Weighing high-purity raw materials NaI, tlF, 6 LiI and Cu;
(2) Placing the raw materials into a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is vacuumized and sealed. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
(3) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 750 ℃ 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 300 ℃, then descending the quartz crucible in the furnace body at the descending speed of 0.3mm/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 5 ℃/h until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and processed. The obtained intrinsic halide scintillator is applied to the fields of neutron detection, gamma detection, neutron-gamma discrimination and the like.
Example 11:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 11 is Na 0.988 Li 0.01 Tl 0.001 Cu 0.00 1 I 0.999 Cl 0.001 The crucible descending method is adopted, and the corresponding preparation method comprises the following steps:
(1) On-demand intrinsic halide scintillator composition Na 0.988 Li 0.01 Tl 0.001 Cu 0.001 I 0.999 Cl 0.001 Weighing high-purity raw materials NaI, tlCl, 6 LiI and CuI;
(2) Placing the raw materials into a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is vacuumized and sealed. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
(3) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 750 ℃ 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 300 ℃, then descending the quartz crucible in the furnace body at the descending speed of 0.5mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified;
(4) Then cooling at a speed of 5 ℃/h until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and processed. The obtained intrinsic halide scintillator is applied to the fields of neutron detection, gamma detection, neutron-gamma discrimination and the like.
Example 12:
the transition metal doped sodium-based halogen scintillation crystal of this example 12 has a composition of Na 0.988 Li 0.01 Tl 0.001 Cu 0.00 1 I 0.999 Br 0.001 The crucible descending method is adopted, and the corresponding preparation method comprises the following steps:
(1) On-demand intrinsic halide scintillator composition Na 0.988 Li 0.01 Tl 0.001 Cu 0.001 I 0.999 Br 0.001 Weighing high-purity raw materials NaI, tlBr, 6 LiI and AgI;
(2) Placing the raw materials into a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is vacuumized and sealed. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
(3) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 750 ℃ 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 300 ℃, then descending the quartz crucible in the furnace body at the descending speed of 0.5mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified;
(4) Then cooling at a speed of 5 ℃/h until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and processed. The intrinsic halide scintillator is applied to the fields of neutron detection, gamma detection, neutron-gamma discrimination and the like.
Example 13:
the chemical composition of the transition metal doped sodium-based halogen scintillation crystal in this example 13 was Na 0.988 Li 0.01 Tl 0.001 Ag 0.001 I 0.999 Cl 0.001 The crucible descending method is adopted, and the corresponding preparation method comprises the following steps:
(1) On-demand intrinsic halide scintillator composition Na 0.988 Li 0.01 Tl 0.001 Ag 0.001 I 0.999 Cl 0.001 Weighing heightPure raw material NaI, tlCl, 6 LiI and AgI;
(2) Placing the raw materials into a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is vacuumized and sealed. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
(3) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 750 ℃ 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 300 ℃, then descending the quartz crucible in the furnace body at the descending speed of 0.5mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified;
(4) Then cooling at a speed of 5 ℃/h until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and processed. The obtained intrinsic halide scintillator is applied to the fields of neutron detection, gamma detection, neutron-gamma discrimination and the like.
Example 14:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 14 is Na 0.988 Li 0.01 Tl 0.001 Ag 0.00 1 I 0.999 F 0.001 The crucible descending method is adopted, and the corresponding preparation method comprises the following steps:
(1) On-demand intrinsic halide scintillator composition Na 0.988 Li 0.01 Tl 0.001 Ag 0.001 I 0.999 F 0.001 Weighing high-purity raw materials NaI, tlCl, 6 LiF and AgI;
(2) Placing the raw materials into a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is vacuumized and sealed. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
(3) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 750 ℃ 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 300 ℃, then descending the quartz crucible in the furnace body at the descending speed of 0.5mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified;
(4) Then cooling at a speed of 5 ℃/h until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and processed. The obtained intrinsic halide scintillator is applied to the fields of neutron detection, gamma detection, neutron-gamma discrimination and the like.
Example 15:
in example 15, the composition of the transition metal doped sodium-based halogen scintillation crystal is Na 0.987 Li 0.01 Tl 0.002 Au 0.00 1 I 0.99 F 0.01 The crucible descending method is adopted, and the corresponding preparation method comprises the following steps:
(1) On-demand intrinsic halide scintillator composition Na 0.987 Li 0.01 Tl 0.002 Au 0.001 I 0.99 F 0.01 Weighing high-purity raw materials NaI, tlI, 6 LiF and AuI;
(2) Placing the raw materials into a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is vacuumized and sealed. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
(3) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 750 ℃ 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 300 ℃, then descending the quartz crucible in the furnace body at the descending speed of 0.5mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified;
(4) Then cooling at a speed of 5 ℃/h until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and processed. The obtained intrinsic halide scintillator is applied to the fields of neutron detection, gamma detection, neutron-gamma discrimination and the like.
Example 16:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this example 16 is Na 0.986 Li 0.01 Tl 0.002 Au 0.00 2 I 0.99 Br 0.01 The crucible descending method is adopted, and the corresponding preparation method comprises the following steps:
(1) On-demand intrinsic halide scintillator composition Na 0.986 Li 0.01 Tl 0.002 Au 0.002 I 0.99 Br 0.01 Weighing high-purity raw materials NaI, tlI, 6 LiBr and AuI;
(2) Placing the raw materials into a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is vacuumized and sealed. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
(3) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 750 ℃ 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 300 ℃, then descending the quartz crucible in the furnace body at the descending speed of 0.5mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified;
(4) Then cooling at a speed of 5 ℃/h until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and processed. The obtained intrinsic halide scintillator is applied to the fields of neutron detection, gamma detection, neutron-gamma discrimination and the like.
Comparative example 1:
the composition of the transition metal doped sodium-based halogen scintillation crystal in the comparative example 1 is Na 0.989 Li 0.01 Tl 0.001 I, the preparation is carried out by the crucible lowering method, and the corresponding preparation method is described in example 1.
Comparative example 2:
the composition of the transition metal doped sodium-based halogen scintillation crystal in the comparative example 2 is Na 0.998 Tl 0.001 Cu 0.001 I, the preparation is carried out by the crucible lowering method, and the corresponding preparation method is described in example 1.
Comparative example 3:
the composition of the transition metal doped sodium-based halogen scintillation crystal in this comparative example 3 is Na 0.989 Li 0.01 Cu 0.001 I, the preparation is carried out by the crucible lowering method, and the corresponding preparation method is described in example 1.
Table 1 shows the composition and properties of the transition metal doped sodium-based halogen scintillation crystals prepared according to the invention:
。
from left to right in FIG. 1 are pictorial representations of the halide scintillators of examples 1-4, respectively; as is clear from FIG. 1, the grown crystal is transparent, has no inclusion, and has good crystal quality.
FIG. 2 is a view of Na of example 1 0.988 Li 0.01 Tl 0.001 Cu 0.001 I crystal with undoped NaI of comparative example 1: 6 an X-ray excitation emission spectrum of Li, tl crystals; as can be seen from FIG. 2, na 0.988 Li 0.01 Tl 0.001 Cu 0.001 The X-ray excitation emission peak of the I crystal is located at 415 nm.
FIG. 3 is a view of Na of example 1 0.988 Li 0.01 Tl 0.001 Cu 0.001 I crystal with undoped NaI of comparative example 1: 6 fluorescence excitation emission spectrum of Li, tl crystal; as can be seen from FIG. 3, na 0.988 Li 0.01 Tl 0.001 Cu 0.001 I crystal compared to undoped NaI of comparative example 1: 6 the Li, tl crystal has a significant blue shift in the 410nm emission peak.
FIG. 4 is a view of Na of example 1 0.988 Li 0.01 Tl 0.001 Cu 0.001 I crystal with undoped NaI of comparative example 1: 6 gamma energy spectrum of Li, tl crystal; as can be seen from FIG. 4, na 0.988 Li 0.01 Tl 0.001 Cu 0.001 Light yield of the I crystal compared to undoped NaI: 6 li, tl crystals are low.
FIG. 5 shows a real objectNa of example 1 0.988 Li 0.01 Tl 0.001 Cu 0.001 I crystal with undoped NaI of comparative example 1: 6 neutron/gamma/alpha energy spectrum of Li, tl crystal, as can be seen from FIG. 5, na 0.988 Li 0.01 Tl 0.001 Cu 0.001 The thermal neutron peak of the I crystal is 6596keV, the alpha/beta ratio is 1.38, and the anti-quenching effect is achieved.
FIG. 6 is a view of Na of example 1 0.988 Li 0.01 Tl 0.001 Cu 0.001 I crystal with undoped NaI of comparative example 1: 6 a scintillation decay time diagram of the Li, tl crystal; as can be seen from fig. 6, the introduction of Cu doping elements can change NaI: 6 the scintillation decay time of the Li, tl crystal affects the neutron detection performance of the crystal.
FIG. 7 is a plot of the FoM scatter plot of the halide scintillator of example 1. From FIG. 7, it can be seen that the crystal neutron/gamma resolution, na 0.988 Li 0.01 Tl 0.001 Cu 0.001 The I scintillator has a high neutron/gamma discrimination figure of merit.
FIG. 8 is a graph of average neutron-gamma pulse waveforms for the halide scintillator of example 1; from fig. 8, it can be seen that the scintillation decay time of the crystal sample can be well fitted by a double exponential function, where the fast component of the sub-decay time is 307 ns, accounting for 78.7%; the slow component is 1270 ns, accounting for 21.3%, the fast component of gamma decay time is 503 ns, accounting for 65.1%; the slow component is 2147. 2147 ns, accounting for 34.9%.
FIG. 9 is a graph comparing particle discrimination performance of the example 1 halide scintillator with commercial neutron detection materials; as can be seen from FIG. 9, na 0.988 Li 0.01 Tl 0.001 Cu 0.001 The I crystal has both a higher FoM value and an alpha/beta ratio greater than 1 than commercial neutron detection materials. Thus, na 0.988 Li 0.01 Tl 0.001 Cu 0.001 The I crystal has excellent neutron-gamma discrimination capability.
FIG. 10 is a view of Na of example 1 0.988 Li 0.01 Tl 0.001 Cu 0.001 I Crystal, na of example 2 0.987 Li 0.01 Tl 0.001 Cu 0.002 I crystal with undoped NaI: 6 gamma energy spectra of Li, tl crystals. The gamma energy spectrum test results can show that the crystal light yield of NaI, tl and Li is reduced compared with that of undoped NaI, tl and Li, and the light yield reduction degree is increased along with the increase of the Cu doping concentration.
FIG. 11 is a view of Na of example 1 0.988 Li 0.01 Tl 0.001 Cu 0.001 I Crystal, na of example 2 0.987 Li 0.01 Tl 0.001 Cu 0.002 I crystal with undoped NaI: 6 neutron/gamma light yield contrast plot for Li, tl crystals. The neutron/gamma light yield test results may exhibit Na 0.988 Li 0.01 Tl 0.001 Cu 0.001 I crystal and Na 0.987 Li 0.01 Tl 0.001 Cu 0.002 I crystal, although compared to undoped NaI: 6 the neutron light yield of Li, tl crystals is reduced, but to a lesser extent compared to gamma light yield. Thus, na prepared in examples 1-2 0.988 Li 0.01 Tl 0.001 Cu 0.001 I crystal and Na 0.987 Li 0.01 Tl 0.001 Cu 0.002 The I crystal has the effect of inhibiting gamma light yield.
FIG. 12 is Na in comparative example 2 0.998 Tl 0.001 Cu 0.001 I crystal at 252 FoM scatter plot under Cf source. As shown in fig. 12, the FoM scatter plot is gamma only without neutrons. As can be seen by comparing with fig. 7, comparative example 2 lacks Li as a neutron absorption section so that the crystal cannot perform neutron detection.
In conclusion, the scintillator provided by the embodiment of the invention has excellent neutron and gamma energy spectrum detection capability, excellent neutron/gamma screening capability and potential application prospects in the fields of nuclear energy utilization, security inspection, petroleum exploration wells and the like.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (11)
1. A transition metal doped sodium-based halogen scintillation crystal is characterized in that the composition general formula Na of the transition metal doped sodium-based halogen scintillation crystal 1-a-b-c Li a Tl b M c I 1-d X d The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is Cu + 、Ag + Or Au (gold) + X is at least one of F, cl and Br, a is more than 0 and less than or equal to 0.2, b is more than 0 and less than or equal to 0.02,0, c is more than or equal to 0.012,0, and d is more than 0 and less than or equal to 0.5; the alpha/beta ratio of the transition metal doped sodium-based halogen scintillation crystal is more than 1.
2. The transition metal doped sodium-based halogen scintillation crystal of claim 1, wherein the transition metal doped sodium-based halogen scintillation crystal is a single crystal.
3. The transition metal doped sodium-based halogen scintillation crystal of claim 1, wherein Li element in the transition metal doped sodium-based halogen scintillation crystal is 6 Li。
4. The transition metal doped sodium-based halogen scintillation crystal of claim 1, wherein M is Cu + 。
5. The transition metal doped sodium-based halogen scintillation crystal of claim 1, wherein 0 < c is less than or equal to 0.004 or/and d = 0.
6. The transition metal doped sodium-based halogen scintillation crystal of any one of claims 1-5, wherein the light yield of the transition metal doped sodium-based halogen scintillation crystal is 8000-20000 photons/MeV.
7. A method of preparing a transition metal doped sodium-based halogen scintillation crystal as recited in any one of claims 1-6, wherein the transition metal doped sodium-based halogen scintillation crystal is prepared using a crucible descent method.
8. The method of preparing according to claim 7, wherein the crucible lowering method comprises:
(1) According to the composition general formula Na of transition metal doped sodium-based halogen scintillation crystal 1-a-b-c Li a Tl b M c I 1-d X d Weighing sodium halide, lithium halide, thallium halide, cuprous halide, silver halide and gold halide as raw materials;
(2) Placing the raw materials into a crucible in an inert gas or anhydrous dry environment, vacuumizing and sealing;
(3) Vertically placing the sealed crucible in the middle of a crystal growth furnace, and melting to completely melt and uniformly mix the raw materials; the melting temperature is more than the melting point of the transition metal doped sodium-based halogen scintillation crystal, and the difference is more than 50 ℃;
(4) Regulating the position of the crucible and the temperature of the crystal growth furnace, reducing the temperature of the bottom of the crucible to the melting point of the transition metal doped sodium-based halogen scintillation crystal, and then reducing the quartz crucible in the crystal growth furnace at the reducing speed of 0.1-10.0 mm/h, wherein the transition metal doped sodium-based halogen scintillation crystal starts to nucleate and grow from the bottom of the crucible until the melt is completely solidified;
(5) And after the crystal growth is finished and the temperature is reduced to the room temperature, obtaining the transition metal doped sodium-based halogen scintillation crystal.
9. The method according to claim 8, wherein the purity of the raw material is not less than 99%; the weighing environment is a drying chamber or a glove box filled with argon or nitrogen.
10. The preparation method according to claim 8 or 9, wherein the raw materials are subjected to vacuum drying treatment before weighing; the temperature of the material dried by the vacuum drying treatment is less than or equal to 180 ℃, and the vacuum degree is less than or equal to 10 -2 Pa。
11. Use of the transition metal doped sodium-based halogen scintillation crystal of any one of claims 1-6 in the neutron detection field, the gamma detection field, the neutron-gamma dual mode detection field, wherein the neutron detection field comprises petroleum exploration wells, homeland security, and nuclear power applications.
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| CN113897666A (en) * | 2020-06-22 | 2022-01-07 | 中国科学院上海硅酸盐研究所 | Intrinsically luminous halide scintillation crystal and preparation method and application thereof |
| CN114411252A (en) * | 2022-01-24 | 2022-04-29 | 中国科学院上海硅酸盐研究所 | Novel perovskite-like structure scintillator for neutron detection and preparation method and application thereof |
| CN115216840A (en) * | 2021-04-14 | 2022-10-21 | 中国科学院上海硅酸盐研究所 | Method for preparing lithium thallium-codoped sodium iodide scintillation crystal by ion compensation method |
| CN115404546A (en) * | 2022-09-01 | 2022-11-29 | 中国科学院上海硅酸盐研究所 | Preparation method of lithium-thallium co-doped sodium iodide scintillation crystal |
| CN115637148A (en) * | 2022-09-09 | 2023-01-24 | 中国科学院上海硅酸盐研究所 | Lithium-thallium co-doped sodium iodide scintillation crystal, and preparation method and application thereof |
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| CN113897666A (en) * | 2020-06-22 | 2022-01-07 | 中国科学院上海硅酸盐研究所 | Intrinsically luminous halide scintillation crystal and preparation method and application thereof |
| CN115216840A (en) * | 2021-04-14 | 2022-10-21 | 中国科学院上海硅酸盐研究所 | Method for preparing lithium thallium-codoped sodium iodide scintillation crystal by ion compensation method |
| CN114411252A (en) * | 2022-01-24 | 2022-04-29 | 中国科学院上海硅酸盐研究所 | Novel perovskite-like structure scintillator for neutron detection and preparation method and application thereof |
| CN115404546A (en) * | 2022-09-01 | 2022-11-29 | 中国科学院上海硅酸盐研究所 | Preparation method of lithium-thallium co-doped sodium iodide scintillation crystal |
| CN115637148A (en) * | 2022-09-09 | 2023-01-24 | 中国科学院上海硅酸盐研究所 | Lithium-thallium co-doped sodium iodide scintillation crystal, and preparation method and application thereof |
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