CN118360058A - Potassium cryolite type rare earth scintillation material, preparation method thereof and detection equipment - Google Patents
Potassium cryolite type rare earth scintillation material, preparation method thereof and detection equipment Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 42
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 42
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910001610 cryolite Inorganic materials 0.000 title claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 8
- 239000011591 potassium Substances 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000001514 detection method Methods 0.000 title abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 73
- 239000000126 substance Substances 0.000 claims abstract description 15
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 5
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 5
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 5
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 5
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 27
- 239000010453 quartz Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 238000001228 spectrum Methods 0.000 claims description 16
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 230000005251 gamma ray Effects 0.000 claims description 8
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 3
- 238000003384 imaging method Methods 0.000 claims description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 239000002994 raw material Substances 0.000 description 14
- 229910019328 PrCl3 Inorganic materials 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000004020 luminiscence type Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910003317 GdCl3 Inorganic materials 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- 229910018057 ScCl3 Inorganic materials 0.000 description 1
- 229910009523 YCl3 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- AEDROEGYZIARPU-UHFFFAOYSA-K lutetium(iii) chloride Chemical compound Cl[Lu](Cl)Cl AEDROEGYZIARPU-UHFFFAOYSA-K 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000009206 nuclear medicine Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 1
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Abstract
The invention discloses a potassium cryolite type rare earth scintillation material, a preparation method and detection equipment thereof, wherein the chemical general formula of the potassium cryolite type rare earth scintillation material is Cs 2LiRE1‑x‑yPrxCeyCl6, RE is one or more of scandium, yttrium, lanthanum, gadolinium and lutetium, wherein x is more than 0 and less than or equal to 0.05, and y is more than 0 and less than or equal to 0.1. The elpasolite type rare earth scintillation material can obtain a new neutron/gamma dual-mode detection material with more excellent comprehensive properties such as light yield, energy resolution, neutron/gamma discrimination capability and the like by improving the performance of Cs 2LiYCl6:Pr crystals, in particular the light yield and energy resolution.
Description
Technical Field
The invention relates to the field of inorganic scintillating materials, in particular to an elpasolite type rare earth scintillating material, a preparation method thereof and detection equipment.
Background
The scintillating material can be used for detecting radioactive particles such as alpha rays, beta rays, X rays, gamma rays, neutrons and the like, and has wide application in the fields of nuclear medicine, high-energy physics, safety inspection, petroleum logging and the like. Since neutrons are not themselves charged, electrons in and through the mass do not act in most cases, and ionization cannot be directly caused, the scintillation material for neutron detection needs to contain elements having a large cross section to act on neutrons. 3He、10B、6 The nuclides such as Li can react with thermal neutrons to generate secondary particles that can cause ionization, so these three nuclides are often used to detect thermal neutrons. In a neutron detection scenario, there is typically an accompanying presence of gamma rays, so the detector needs to have neutron and gamma ray discrimination capabilities, which place demands on the particle discrimination performance of the scintillation material.
The traditional thermal neutron detection material is 3 He gas, but the application is limited due to the shortage of resources, high price and high price. The Li-containing rare earth scintillating material with the elpasolite structure is an inorganic scintillating material capable of realizing thermal neutron and gamma ray dual-mode detection. Two scintillators currently being commercialized are Cs 2LiLaBr6:Ce (CLLB:Ce) and Cs 2LiYCl6:Ce (CLYC: ce). Generally, scintillation materials require high light yield, short decay times, and high energy resolution. Scintillation materials for detecting neutrons are also required to have as high a neutron/gamma discrimination capability as possible. The CLYC: ce is considered as the thermal neutron/gamma dual-mode detection material with the best performance at present because the thermal neutron/gamma discrimination capability of CLYC: ce is stronger, although the light yield and energy resolution of CLYC: ce are slightly inferior to CLLB: ce.
The CLYC-Ce can greatly improve the thermal neutron detection efficiency by adopting the raw material enriched with 6 Li. In addition, the nuclear reaction 35Cl(n,p)35 S of Cl element in CLYC: ce and fast neutrons can be used for fast neutron detection, and the raw material enriched with 7 Li can be used for reducing the reaction cross section of the thermal neutrons. Therefore, CLYC: ce is also considered as a scintillation material capable of three-mode detection of gamma rays, thermal neutrons, and fast neutrons. CLYC: ce has an ultrafast component of core-to-valence luminescence (CVL) luminescence of 1 to 4ns under gamma ray excitation, whereas neutron-excited luminescence does not have this fast component, which is a physical mechanism that CLYC: ce has excellent neutron/gamma discrimination capability. However, the activated ion Ce 3+ absorbs the CVL luminescence, and as the crystal size increases, the more pronounced the absorption effect, so that the neutron/gamma discrimination capability of the large-size Ce 3+ activated elpasolite type scintillation crystal decreases. A scintillation crystal Cs 2LiYCl6:0.2%Pr was reported in 2005 by E.V.D.van Loef et al in paper "Optical and scintillation properties of Cs2LiYCl6:Ce3+and Cs2LiYCl6:Pr3+crystals", the light output was only half of CLYC: ce, the energy resolution was 15%, the neutron/gamma discrimination capability was not evaluated, and the overall performance was far worse than that of CLYC: ce.
Disclosure of Invention
The embodiment of the invention aims to provide an elpasolite type rare earth scintillation material, which improves the performance of Cs 2LiYCl6:Pr crystals, in particular the light yield and the energy resolution thereof, so as to obtain a new neutron/gamma dual-mode detection material with more excellent comprehensive performances such as light yield, energy resolution, neutron/gamma discrimination capability and the like.
In order to solve the technical problems, a first aspect of the embodiment of the invention provides an elpasolite type rare earth scintillation material, wherein the elpasolite type rare earth scintillation material has a chemical formula of Cs 2LiRE1-x-yPrxCeyCl6, RE is one or more of scandium, yttrium, lanthanum, gadolinium and lutetium, wherein x is more than 0 and less than or equal to 0.05, and y is more than 0 and less than or equal to 0.1.
Further, the RE material is yttrium element or lanthanum element.
Further, the data range of x is 0 < x.ltoreq.0.05, and the preferred range is 0.0001 < x.ltoreq.0.005; the value of y is more than 0 and less than or equal to 0.1, and the preferable range is more than 0.0001 and less than or equal to 0.01.
Further, the elpasolite type rare earth scintillation material is in a single crystal form.
Accordingly, a second aspect of the embodiments of the present invention provides a method for preparing an elpasolite-type rare earth scintillation material, comprising the steps of:
Weighing cesium chloride, lithium chloride, yttrium chloride, cerium chloride and praseodymium chloride in preset proportions, mixing uniformly, and filling into a quartz crucible;
The quartz crucible is connected into a vacuum system for vacuumizing, and when the vacuum degree reaches a preset pressure value, the sealing is melted;
Placing the quartz crucible in a Bridgman crystal path for single crystal growth, wherein a high temperature region is a first preset temperature value, a low temperature region is a second preset temperature value, a temperature gradient in a gradient region is a third preset value, and the descending rate of the quartz crucible is a fourth preset value;
and after the growth is finished, the temperature is reduced to room temperature according to the fifth preset value.
Further, the numerical range of the first preset temperature value is 600-750 ℃;
the numerical range of the second preset temperature value is 30-300 ℃;
The numerical range of the third preset numerical value is 20 ℃/cm-35 ℃/cm;
the value range of the fourth preset value is 0.1mm/h-1mm/h.
Further, the fifth preset value is in a range of 5 ℃/h to 20 ℃/h.
Accordingly, a third aspect of the embodiments of the present invention provides a scintillation detector comprising any one of the above-described elpasolite-type rare earth scintillation materials.
Accordingly, a fourth aspect of the embodiments of the present invention provides a measurement system comprising any of the elpasolite-type rare earth scintillating materials described herein for measuring neutrons, gamma ray counts, dose, energy spectrum, imaging, particle identification.
Accordingly, a fifth aspect of an embodiment of the present invention provides a lithology scanning imager comprising any one of the above-described elpasolite-type rare earth scintillating materials.
The technical scheme provided by the embodiment of the invention has the following beneficial technical effects:
the performance of Cs 2LiYCl6 Pr crystal, especially the light yield and energy resolution thereof, is improved, so that a new neutron/gamma dual-mode detection material with more excellent comprehensive performances such as light yield, energy resolution, neutron/gamma discrimination capability and the like is obtained.
Drawings
FIG. 1 is a flow chart of a method for preparing an elpasolite-type rare earth scintillation material according to an embodiment of the present invention;
FIG. 2a is a graph showing the excitation and emission spectra of Ce 3+ -activated ions in example 1 provided by the present invention;
FIG. 2b is a graph showing the excitation and emission spectra of Pr 3+ activated ions in example 1 provided by the present invention;
FIG. 3 is a schematic diagram of the energy spectrum of the 137 Cs gamma radiation source of the scintillation crystal of example 2 provided by the present invention;
FIG. 4 is a graph of pulse waveforms of the scintillation crystal of example 1 provided by the present invention under neutron and gamma ray irradiation;
Fig. 5 is a waveform resolution scatter plot of the scintillation crystal of example 1 provided by the present invention under neutron and gamma ray irradiation.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
The first aspect of the embodiment of the invention provides a potassium cryolite type rare earth scintillation material, wherein the chemical formula of the potassium cryolite type rare earth scintillation material is Cs 2LiRE1-x-yPrxCeyCl6, RE is one or more of scandium, yttrium, lanthanum, gadolinium and lutetium, x is more than 0 and less than or equal to 0.05, and y is more than 0 and less than or equal to 0.1.
By optimizing the Pr 3+ content in the Cs 2LiYCl6:Pr crystal, the scintillation performance of Cs 2LiYCl6:Pr can be significantly improved, wherein the sub/gamma resolution is even better than that of CLYC:Ce. However, cs 2LiYCl6: pr crystals have no advantage in light yield and energy resolution over CLYC: ce.
Further, the RE material is yttrium element or lanthanum element.
When RE is yttrium element, the elpasolite type rare earth scintillation material is Cs 2LiYCl6:Pr, ce crystal; when RE is lanthanum, the elpasolite type rare earth scintillation material is Cs 2LiLaCl6:Pr, ce crystal.
Optionally, x is more than 0 and less than or equal to 0.05, and the preferable range is more than 0.0001 and less than or equal to 0.005; y is in the range of 0 < y.ltoreq.0.1, preferably in the range of 0.0001 < x.ltoreq.0.01.
Li is selected from one of natural Li (containing about 7.5% 6 Li, with the remainder being 7 Li), enriched 6 Li (e.g., 95% enriched), enriched 7 Li (e.g., 99% enriched). The crystal growth is carried out by adopting the melt with excessive Li element and non-stoichiometric proportion, so as to reduce the generation of secondary phases, improve the yield of the crystal and obtain high-quality crystal. The Li excess range is not more than 80% of the stoichiometric ratio.
Further, the above-mentioned elpasolite type rare earth scintillating material may be a powder, a ceramic or a single crystal, but is preferably applied in a single crystal form, and the single crystal can be obtained by growth by the Bridgman method.
The elpasolite type rare earth scintillation material provided by the invention contains two activating ions Pr 3+ and Ce 3+. In Cs 2LiYCl6: pr, 4f5d-4f luminescence of Pr 3+ provides excellent neutron/gamma discrimination performance, but there is also an energy transfer process from self-limiting excitons (STE) to activated ions Pr 3+ in the material, which shows 4f-4f luminescence of Pr 3+, and the luminescent component does not contribute to light yield and energy resolution performance due to wavelength mismatch with the photoelectric conversion device, resulting in Cs 2LiYCl6: pr light yield being lower and energy resolution being poor. The doping of Ce 3+ increases the channel for transmitting energy from STE to Ce 3+, reduces the probability of Pr 3+ obtaining energy from STE, thereby increasing the luminescence of Ce 3+ and simultaneously reducing the 4f-4f luminescence of Pr 3+, so that the effective luminescence is increased, and the light yield and the energy resolution are improved obviously. By utilizing the synergistic effect of the Pr 3+ and the Ce 3+, the comprehensive performance of the elpasolite type rare earth scintillating material is effectively improved.
The elpasolite type rare earth scintillating material has high light yield, excellent energy resolution and ultrahigh neutron/gamma discrimination capability, simultaneously has ultrafast fast component decay time and optimized slow component, and neutron and gamma waveforms show obvious difference, and the ultrahigh neutron/gamma discrimination capability can be realized by adopting a waveform resolution technology (PSD), and the FOM value can reach 5.73. As a scintillation material for neutron detection, the comprehensive performance is obviously better than that of a scintillation material of CLYC, ce and CLYC, pr.
Accordingly, referring to fig. 1, a second aspect of the embodiment of the present invention provides a method for preparing a rare earth scintillating material of elpasolite type, which includes the following steps:
Step 1: weighing cesium chloride, lithium chloride, yttrium chloride, cerium chloride and praseodymium chloride in preset proportions, mixing uniformly, and loading into a quartz crucible.
Step 2: and (3) connecting the quartz crucible into a vacuum system for vacuumizing, and burning and sealing when the vacuum degree reaches a preset pressure value.
Step 3: and placing the quartz crucible in a Bridgman crystal path for single crystal growth, wherein the high temperature region is a first preset temperature value, the low temperature region is a second preset temperature value, the temperature gradient of the gradient region is a third preset value, and the descending rate of the quartz crucible is a fourth preset value.
Step 4: and after the growth is finished, the temperature is reduced to room temperature according to the fifth preset value.
Further, the first preset temperature value has a value range of 600-750 ℃;
the value range of the second preset temperature value is 30-300 ℃;
the value range of the third preset value is 20 ℃/cm-35 ℃/cm;
the fourth preset value is in the range of 0.1mm/h-1mm/h.
Further, the fifth preset value is in the range of 5 ℃/h to 20 ℃/h.
The following describes the above preparation process in detail in several examples and comparative examples:
first, in the following, the raw materials used in each of the comparative examples and examples include CsCl、LiCl、ScCl3、YCl3、LaCl3、GdCl3、LuCl3、PrCl3、CeCl3, having a purity of not less than 99.99%, and ultra-dry anhydrous. Wherein the LiCl dosage is in excess of 50% of the stoichiometric ratio.
Comparative example 1: cs (cells) 2LiY0.995Ce0.005Cl6
46.8776G of CsCl, 8.8531g of LiCl, 27.0488gYCl 3、0.1716g CeCl3 and other raw materials are weighed in an argon-filled glove box, are mixed uniformly, are put into a quartz crucible with the diameter of 25mm, are connected into a vacuum system for vacuumizing, and are fused and sealed when the vacuum degree reaches 1X 10 -4 Pa. The crucible was placed in a Bridgman crystal furnace for single crystal growth. The temperature of the high temperature area is 700 ℃, the temperature of the low temperature area is 250 ℃, the temperature gradient of the gradient area is 25 ℃/cm, the descending speed of the crucible is 0.5mm/h, the temperature is reduced to room temperature at the cooling speed of 10 ℃/h after the growth is finished, and the obtained crystal is complete, transparent and defect-free. The crystals were cut into 3mm thick sheet samples in a glove box and polished, followed by performance testing for multi-channel energy spectrum, decay time, energy resolution, neutron/gamma discrimination, etc.
Comparative example 2: cs (cells) 2LiY0.9992Pr0.0008Cl6
In an argon-filled glove box, raw materials of 46.8951g CsCl, 8.8564gLiCl, 27.1731g YCl 3、0.0275g PrCl3 and the like are weighed according to the chemical formula proportion, are mixed uniformly, are put into a quartz crucible with the diameter of 25mm, are connected into a vacuum system for vacuumizing, and are fused and sealed when the vacuum degree reaches 1X 10 -4 Pa. The crucible was placed in a Bridgman crystal furnace for single crystal growth. The temperature of the high temperature area is 720 ℃, the temperature of the low temperature area is 300 ℃, the temperature gradient of the gradient area is 30 ℃/cm, the descending speed of the crucible is 0.4mm/h, the temperature is reduced to room temperature at the cooling speed of 15 ℃/h after the growth is finished, and the obtained crystal is complete, transparent and defect-free. The crystals were cut into 3mm thick sheet samples in a glove box and polished, followed by performance testing for multi-channel energy spectrum, decay time, energy resolution, neutron/gamma discrimination, etc.
The above-mentioned comparative examples 1 and 2 are not intended to be the scope of the present invention, but are merely intended to be used for comparison with the technical effects obtained by the technical solutions of the present invention.
Example 1: cs (cells) 2LiY0.995Pr0.001Ce0.004Cl6
In an argon-filled glove box, raw materials of 46.0000g CsCl, 8.6874gLiCl, 26.2831g YCl 3、0.1347g CeCl3、0.0338g PrCl3 and the like are weighed according to the chemical formula proportion, are mixed uniformly, are put into a quartz crucible with the diameter of 25mm, are connected into a vacuum system for vacuumizing, and are fused and sealed when the vacuum degree reaches 1X 10 -4 Pa. The crucible was placed in a Bridgman crystal furnace for single crystal growth. The temperature of the high temperature area is 680 ℃, the temperature of the low temperature area is 200 ℃, the temperature gradient of the gradient area is 27 ℃/cm, the descending speed of the crucible is 0.8mm/h, the temperature is reduced to room temperature at the cooling speed of 5 ℃/h after the growth is finished, and the obtained crystal is complete, transparent and defect-free. The crystals were cut into 3mm thick sheet samples in a glove box and polished, followed by performance testing for multi-channel energy spectrum, decay time, energy resolution, neutron/gamma discrimination, etc.
Example 2: cs (cells) 2LiY0.895Pr0.005Ce0.1Cl6
In an argon-filled glove box, raw materials of 46.0000g CsCl, 8.6874gLiCl, 23.8748g YCl 3、3.3672g CeCl3、0.1689g PrCl3 and the like are weighed according to the chemical formula proportion, are mixed uniformly, are put into a quartz crucible with the diameter of 25mm, are connected into a vacuum system for vacuumizing, and are fused and sealed when the vacuum degree reaches 1X 10 -4 Pa. The crucible was placed in a Bridgman crystal furnace for single crystal growth. The temperature of the high temperature area is 730 ℃, the temperature of the low temperature area is 150 ℃, the temperature gradient of the gradient area is 32 ℃/cm, the descending speed of the crucible is 1mm/h, the temperature is reduced to room temperature at the cooling speed of 10 ℃/h after the growth is finished, and the obtained crystal is complete, transparent and defect-free. The crystals were cut into 3mm thick sheet samples in a glove box and polished, followed by performance testing for multi-channel energy spectrum, decay time, energy resolution, neutron/gamma discrimination, etc.
Example 3: cs (cells) 2LiY0.96Pr0.02Ce0.02Cl6
In an argon-filled glove box, raw materials of 46.0000g CsCl, 8.6874gLiCl, 25.6087g YCl 3、0.6734g CeCl3、0.6756g PrCl3 and the like are weighed according to the chemical formula proportion, are mixed uniformly, are put into a quartz crucible with the diameter of 25mm, are connected into a vacuum system for vacuumizing, and are fused and sealed when the vacuum degree reaches 1X 10 -4 Pa. The crucible was placed in a Bridgman crystal furnace for single crystal growth. The temperature of the high temperature area is 740 ℃, the temperature of the low temperature area is 280 ℃, the temperature gradient of the gradient area is 33 ℃/cm, the descending speed of the crucible is 0.9mm/h, the temperature is reduced to room temperature at the cooling speed of 18 ℃/h after the growth is finished, and the obtained crystal is complete, transparent and defect-free. The crystals were cut into 3mm thick sheet samples in a glove box and polished, followed by performance testing for multi-channel energy spectrum, decay time, energy resolution, neutron/gamma discrimination, etc.
Example 4: cs (cells) 2LiY0.94Pr0.05Ce0.01Cl6
In an argon-filled glove box, raw materials of 46.0000g CsCl, 8.6874gLiCl, 25.8755g YCl 3、0.6734g CeCl3、0.3378g PrCl3 and the like are weighed according to the chemical formula proportion, are mixed uniformly, are put into a quartz crucible with the diameter of 25mm, are connected into a vacuum system for vacuumizing, and are fused and sealed when the vacuum degree reaches 1X 10 -4 Pa. The crucible was placed in a Bridgman crystal furnace for single crystal growth. The temperature of the high temperature area is 710 ℃, the temperature of the low temperature area is 280 ℃, the temperature gradient of the gradient area is 28 ℃/cm, the crucible descending speed is 0.6mm/h, the temperature is reduced to room temperature at the cooling speed of 8 ℃/h after the growth is finished, and the obtained crystal is complete, transparent and defect-free. The crystals were cut into 3mm thick sheet samples in a glove box and polished, followed by performance testing for multi-channel energy spectrum, decay time, energy resolution, neutron/gamma discrimination, etc.
Example 5: cs (cells) 2LiSc0.994Pr0.002Ce0.004Cl6
46.0000G of CsCl, 8.6874gLiCl g of 20.5476g of ScCl 3、0.1347g CeCl3、0.0676g PrCl3 and other raw materials are weighed according to the chemical formula ratio in an argon-filled glove box, are mixed uniformly, are put into a quartz crucible with the diameter of 25mm, are connected into a vacuum system for vacuumizing, and are fused and sealed when the vacuum degree reaches 1X10 -4 Pa. The crucible was placed in a Bridgman crystal furnace for single crystal growth. The temperature of the high temperature area is 750 ℃, the temperature of the low temperature area is 100 ℃, the temperature gradient of the gradient area is 35 ℃/cm, the descending speed of the crucible is 0.4mm/h, the temperature is reduced to room temperature at the cooling speed of 10 ℃/h after the growth is finished, and the obtained crystal is complete, transparent and defect-free. The crystals were cut into 3mm thick sheet samples in a glove box and polished, followed by performance testing for multi-channel energy spectrum, decay time, energy resolution, neutron/gamma discrimination, etc.
Example 6: cs (cells) 2LiLa0.99Pr0.005Ce0.005Cl6
46.0000G of CsCl, 8.6874gLiCl g of 33.1713g of LaCl 3、0.1684g CeCl3、0.1689g PrCl3 and other raw materials are weighed according to the chemical formula ratio in an argon-filled glove box, are mixed uniformly, are put into a quartz crucible with the diameter of 25mm, are connected into a vacuum system for vacuumizing, and are fused and sealed when the vacuum degree reaches 1X 10 -4 Pa. The crucible was placed in a Bridgman crystal furnace for single crystal growth. The temperature of the high temperature area is 600 ℃, the temperature of the low temperature area is 30 ℃, the temperature gradient of the gradient area is 20 ℃/cm, the descending speed of the crucible is 0.1mm/h, the temperature is reduced to room temperature at the cooling speed of 20 ℃/h after the growth is finished, and the obtained crystal is complete, transparent and defect-free. The crystals were cut into 3mm thick sheet samples in a glove box and polished, followed by performance testing for multi-channel energy spectrum, decay time, energy resolution, neutron/gamma discrimination, etc.
Example 7: cs (cells) 2LiGd0.997Pr0.001Ce0.002Cl6
In an argon-filled glove box, raw materials of 46.0000g CsCl, 8.6874gLiCl g, 35.9044g GdCl 3、0.0673g CeCl3、0.0338g PrCl3 and the like are weighed according to chemical formula proportion, are mixed uniformly, are put into a quartz crucible with the diameter of 25mm, are connected into a vacuum system for vacuumizing, and are fused and sealed when the vacuum degree reaches 1X 10 -4 Pa. The crucible was placed in a Bridgman crystal furnace for single crystal growth. The temperature of the high temperature area is 620 ℃, the temperature of the low temperature area is 50 ℃, the temperature gradient of the gradient area is 22 ℃/cm, the descending speed of the crucible is 0.3mm/h, the temperature is reduced to room temperature at the cooling speed of 16 ℃/h after the growth is finished, and the obtained crystal is complete, transparent and defect-free. The crystals were cut into 3mm thick sheet samples in a glove box and polished, followed by performance testing for multi-channel energy spectrum, decay time, energy resolution, neutron/gamma discrimination, etc.
Example 8: cs (cells) 2LiLu0.99Pr0.003Ce0.007Cl6
In an argon-filled glove box, raw materials of 46.0000g CsCl, 8.6874gLiCl g, 38.0485g GdCl 3、0.2357g CeCl3、0.1013g PrCl3 and the like are weighed according to chemical formula proportion, are mixed uniformly, are put into a quartz crucible with the diameter of 25mm, are connected into a vacuum system for vacuumizing, and are fused and sealed when the vacuum degree reaches 1X 10 -4 Pa. The crucible was placed in a Bridgman crystal furnace for single crystal growth. The temperature of the high temperature area is 660 ℃, the temperature of the low temperature area is 50 ℃, the temperature gradient of the gradient area is 24 ℃/cm, the descending speed of the crucible is 0.5mm/h, the temperature is reduced to room temperature at the cooling speed of 10 ℃/h after the growth is finished, and the obtained crystal is complete, transparent and defect-free. The crystals were cut into 3mm thick sheet samples in a glove box and polished, followed by performance testing for multi-channel energy spectrum, decay time, energy resolution, neutron/gamma discrimination, etc.
Example 9: cs (cells) 2LiY0.6La0.394Pr0.001Ce0.005Cl6
And weighing 46.0000g CsCl、8.6874gLiCl、16.0055g YCl3、13.2015g LaCl3、0.1684g CeCl3、0.0338g PrCl3 and other raw materials according to the chemical formula ratio in an argon-filled glove box, uniformly mixing, loading into a quartz crucible with the diameter of 25mm, introducing into a vacuum system for vacuumizing, and burning and sealing when the vacuum degree reaches 1X 10 -4 Pa. The crucible was placed in a Bridgman crystal furnace for single crystal growth. The temperature of the high temperature area is 680 ℃, the temperature of the low temperature area is 100 ℃, the temperature gradient of the gradient area is 29 ℃/cm, the descending speed of the crucible is 0.6mm/h, the temperature is reduced to room temperature at the cooling speed of 10 ℃/h after the growth is finished, and the obtained crystal is complete, transparent and defect-free. The crystals were cut into 3mm thick sheet samples in a glove box and polished, followed by performance testing for multi-channel energy spectrum, decay time, energy resolution, neutron/gamma discrimination, etc.
The detailed properties of all comparative examples and examples are shown in Table 1.
TABLE 1
As can be seen from Table 1, the scintillation material provided by the invention has an ultra-high neutron/gamma discrimination capability, excellent light output and energy resolution, and an ultra-fast decay component. As a scintillation material for neutron detection, the scintillation material provided by the invention has the comprehensive performance obviously superior to commercial CLYC: ce and CLYC: pr scintillation materials reported in the literature.
Fig. 2a and 2b show excitation and emission spectral characteristics of example 1 of the elpasolite type scintillation material co-doped with two active ions, pr 3+ and Ce 3+, provided by the present invention. Among them, fig. 2a shows the excitation and emission spectrum of Ce 3+, and fig. 2b shows the excitation and emission spectrum of Pr 3+.
Referring to fig. 3, the energy spectrum of the 137 Cs gamma radiation source of example 2 of the elpasolite type scintillation material co-doped with two active ions, pr 3+ and Ce 3+, provided by the invention, is fitted and calculated to obtain an energy resolution of 3.80% at 662 keV.
Referring to fig. 4, the present invention provides a neutron and gamma amplitude normalization waveform for two ion-activated elpasolite scintillators, pr 3+ and Ce 3+, example 1. Wherein the gamma waveform has an ultrafast decay component, and the decay time of the neutron waveform is slower, the two waveforms show significant differences, which is a physical mechanism to achieve neutron/gamma discrimination.
Referring to fig. 5, a two-dimensional scatter diagram of neutron/gamma discrimination of example 1 obtained by using a waveform resolution technique (PSD) is shown that neutron and gamma cases are clearly separated, which indicates that this example has an ultra-high neutron/gamma discrimination capability, and specifically, the discrimination effect FOM value can reach 5.73.
Accordingly, a third aspect of embodiments of the present invention provides a scintillation detector comprising any one of the above-described elpasolite-type rare earth scintillation materials.
Accordingly, a fourth aspect of the present invention provides a measurement system comprising any elpasolite type rare earth scintillation material, the measurement system being configured to measure neutrons, gamma ray counts, dose, energy spectrum, imaging, particle identification.
Accordingly, a fifth aspect of an embodiment of the present invention provides a lithology scanning imager comprising any one of the above-described elpasolite-type rare earth scintillating materials.
The embodiment of the invention aims to protect an elpasolite type rare earth scintillation material, a preparation method and detection equipment thereof, wherein the chemical general formula of the elpasolite type rare earth scintillation material is Cs 2LiRE1-x-yPrxCeyCl6, RE is one or more of scandium, yttrium, lanthanum, gadolinium and lutetium, wherein x is more than 0 and less than or equal to 0.05, and y is more than 0 and less than or equal to 0.1. The technical scheme has the following effects:
the performance of Cs 2LiYCl6 Pr crystal, especially the light yield and energy resolution thereof, is improved, so that a new neutron/gamma dual-mode detection material with more excellent comprehensive performances such as light yield, energy resolution, neutron/gamma discrimination capability and the like is obtained.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (10)
1. The potassium cryolite type rare earth scintillation material is characterized in that the chemical general formula of the potassium cryolite type rare earth scintillation material is Cs 2LiRE1-x-yPrxCeyCl6, RE is one or more of scandium, yttrium, lanthanum, gadolinium and lutetium, wherein x is more than 0 and less than or equal to 0.05, and y is more than 0 and less than or equal to 0.1.
2. The elpasolite type rare earth scintillation material according to claim 1, wherein,
The RE material is yttrium element or lanthanum element.
3. The elpasolite type rare earth scintillation material according to claim 1, wherein,
The data range of x is more than 0 and less than or equal to 0.05; the preferable range is 0.0001 < x.ltoreq.0.005.
The numerical range of y is more than 0 and less than or equal to 0.1; the preferable range is 0.0001 < x.ltoreq.0.01.
4. The elpasolite type rare earth scintillation material according to claim 1, wherein,
The elpasolite type rare earth scintillation material is in a single crystal form.
5. The preparation method of the elpasolite type rare earth scintillation material is characterized by comprising the following steps of:
Weighing cesium chloride, lithium chloride, yttrium chloride, cerium chloride and praseodymium chloride in preset proportions, mixing uniformly, and filling into a quartz crucible;
The quartz crucible is connected into a vacuum system for vacuumizing, and when the vacuum degree reaches a preset pressure value, the sealing is melted;
Placing the quartz crucible in a Bridgman crystal path for single crystal growth, wherein a high temperature region is a first preset temperature value, a low temperature region is a second preset temperature value, a temperature gradient in a gradient region is a third preset value, and the descending rate of the quartz crucible is a fourth preset value;
and after the growth is finished, the temperature is reduced to room temperature according to the fifth preset value.
6. The method for preparing the elpasolite type rare earth scintillation material as claimed in claim 5, wherein,
The numerical range of the first preset temperature value is 600-750 ℃;
the numerical range of the second preset temperature value is 30-300 ℃;
The numerical range of the third preset numerical value is 20 ℃/cm-35 ℃/cm;
the value range of the fourth preset value is 0.1mm/h-1mm/h.
7. The method for preparing the elpasolite type rare earth scintillation material as claimed in claim 5, wherein,
The numerical range of the fifth preset numerical value is 5 ℃/h to 20 ℃/h.
8. A scintillation detector comprising a elpasolite type rare earth scintillation material as claimed in any one of claims 1 to 4.
9. A measurement system comprising the elpasolite type rare earth scintillation material of any one of claims 1 to 4, said measurement system being used for measuring neutrons, gamma ray counts, doses, energy spectra, imaging, particle identification.
10. A lithology scanning imager comprising a elpasolite type rare earth scintillation material as claimed in any one of claims 1 to 4.
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