CN113897666A - A kind of intrinsically luminescent halide scintillation crystal and its preparation method and application - Google Patents
A kind of intrinsically luminescent halide scintillation crystal and its preparation method and application Download PDFInfo
- Publication number
- CN113897666A CN113897666A CN202010573954.7A CN202010573954A CN113897666A CN 113897666 A CN113897666 A CN 113897666A CN 202010573954 A CN202010573954 A CN 202010573954A CN 113897666 A CN113897666 A CN 113897666A
- Authority
- CN
- China
- Prior art keywords
- scintillation crystal
- crucible
- halide
- crystal
- halide scintillation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
- C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Measurement Of Radiation (AREA)
Abstract
本发明涉及一种本征发光的卤化物闪烁晶体及其制备方法和应用，所述本征发光的卤化物闪烁晶体的组成通式为：AB2X3、A2BX3和A3B2X5；其中A=Li、Na、K、Rb、Cs、In和Tl中的至少一种；B=Cu、Ag和Au中的至少一种；X=F、Cl、Br和I中的至少一种。
The present invention relates to an intrinsically luminescent halide scintillation crystal and a preparation method and application thereof. The general composition formula of the intrinsically luminescent halide scintillation crystal is: AB 2 X 3 , A 2 BX 3 and A 3 B 2 X 5 ; wherein A=at least one of Li, Na, K, Rb, Cs, In and Tl; B=at least one of Cu, Ag and Au; X=at least one of F, Cl, Br and I A sort of.
Description
Technical Field
The invention relates to an intrinsically luminous halide scintillation crystal, a preparation method and application thereof, in particular to an intrinsically luminous AB2X3、A2BX3And A3B2X5A scintillation crystal and a preparation method and application thereof, belonging to the technical field of scintillation materials.
Background
The scintillator is a material capable of converting high-energy rays or particles into visible light or ultraviolet light, and has wide application in the field of radiation detection. With the continuous improvement of the performance requirements of radiation detection materials in the application fields of homeland security, nuclear medicine imaging, high-energy physics and the like, a novel high-performance scintillator needs to be developed urgently.
Scintillators currently used internationally in the field of security inspection are doped with thallium sodium iodide (NaI: Tl)+) Mainly, the material is used as a widely commercial scintillating material, has the advantages of high light output (-40000 photons/MeV), low cost and the like, but has poor energy resolution (-7% @662keV), limits the application of the material in high-resolution nuclide detection, is deliquesced in air and needs to be used after packaging.
To overcome these disadvantages, a number of new scintillators have been developed internationally in recent years, predominantly cerium-doped lanthanum bromide (LaBr) being the predominant property3:Ce3+) And europium-doped strontium iodide (SrI)2:Eu2+). Both materials achieve high energy resolution of 2.6% @662keV, while having higher light output than NaI: Tl. However, LaBr3In the presence of Ce material138The background of La radioactivity affects the performance of the La radioactive background in identifying weak radiation sources, while SrI2The Eu material has a strong self-absorption effect, and the scintillation property is remarkably reduced when the crystal size is larger. In addition, similar to NaI and Tl, the two materials have strong deliquescence and are unstable in the atmospheric environment, so that the preparation cost and the application difficulty are greatly increased.
Several of the above-mentioned scintillation materials suffer from the widespread disadvantage of deliquescing the halide scintillator in air, due to which the halide scintillation crystals often need to be tightly packed before they can be used, which has a significant impact on the cost of material storage and application. Currently, the non (or weak) deliquescent halide scintillator with wider application is mainly thallium doped cesium iodide (CsI: Tl)+) The material has high light output equivalent to NaI Tl, is low in price, and has a long afterglow which limits the application of the material in high-resolution imaging. Tl crystal also has a problem of luminescence nonuniformity due to Tl+The ions are non-uniformly distributed throughout the crystal due to constituent segregation, resulting in non-uniformity in the scintillation properties of the crystal. This drawback is common to all doped luminescent scintillation crystals and inevitably reduces the final energy resolution of the material.
Disclosure of Invention
In response to the above-mentioned problems and needs in the art, the present invention is directed to an AB having intrinsic luminescence2X3、A2BX3And A3B2X5The scintillation crystal has the advantages of high energy resolution, high light output, non-deliquescence, high uniformity, low afterglow and the like, and can be widely applied to the field of radiation detection.
In one aspect, the present invention provides an intrinsically luminescent halide scintillation crystal having a general compositional formula: AB2X3、A2BX3And A3B2X5(ii) a Wherein a is at least one of Li, Na, K, Rb, Cs, In and Tl; b ═ at least one of Cu, Ag, and Au; x ═ at least one of F, Cl, Br, and I.
The light emitting mechanism of the three scintillation crystals is self-trapping exciton recombination light emission. Self-trapped exciton recombination luminescence (STEs) are excited-state transient defects. When the material is excited by illumination, a strong coupling effect is generated between electrons and phonons so as to induce transient distortion of an excited state crystal lattice and further capture photogenerated electrons, namely self-trapped crystal lattice (self-trapped). The trapped photo-generated electrons then release energy through recombination luminescence, thereby exhibiting broad-spectrum emission behavior.
Preferably, the halide scintillation crystal has a general composition formula: (A)1-xA’x)(B1-yB’y)2(X1-zX’z)3、(A1- xA’x)2(B1-yB’y)(X1-zX’z)3And (A)1-xA’x)3(B1-yB’y)2(X1-zX’z)5(ii) a A. A ═ two or more of Li, Na, K, Rb, Cs, In, and Tl; B. b ═ two or more of Cu, Ag, and Au; x, X ═ two of F, Cl, Br, and I; x is more than 0 and less than 1, y is more than 0 and less than 1, and z is more than 0 and less than 1.
On the other hand, the invention also provides a preparation method of the intrinsic luminous halide scintillation crystal, and the halide scintillation crystal is prepared by adopting a Bridgman-Stockbarge method.
Preferably, the method comprises the following steps:
(1) weighing AX and BX as raw materials according to the general formula of the halide scintillation crystal, mixing, placing in a crucible in an inert gas, nitrogen gas or anhydrous dry environment, vacuumizing, and sealing by welding;
(2) placing the welded and sealed crucible in a crucible descending furnace, heating to a temperature 50-100 ℃ higher than the melting point of the raw materials to completely melt the raw materials, adjusting the furnace temperature to reduce the temperature of the bottom of the crucible to the melting point of halide scintillation crystals, and starting the growth of the crystals at a descending speed of 0.1-10.0 mm/h;
(3) and after the crystal growth is finished, cooling to room temperature to obtain the halide scintillation crystal.
Preferably, the crucible is a quartz crucible with a conical bottom or a capillary bottom at the bottom.
Preferably, the purity of the raw materials is more than or equal to 99.9%.
Preferably, the inert gas is argon.
In still another aspect, the invention further provides an application of the halide scintillation crystal in the fields of neutron detection, X-ray detection and gamma-ray detection, such as medical imaging, security inspection, petroleum exploration, industrial inspection and the like.
In yet another aspect, the present invention also provides a radiation detector comprising the halide scintillation crystal described above.
Has the advantages that:
in the invention, the halide scintillation crystal (or named as intrinsic halide scintillation crystal) with intrinsic luminescence has the advantages of intrinsic luminescence, high energy resolution, high light output, low afterglow and nondeliquescence and the like, and meanwhile, the crystal is easy to prepare in large size. Compared with a polycrystalline film scintillator, the single crystal scintillator has higher lattice integrity and crystal quality, so that the single crystal scintillator with the same composition has higher scintillation luminous efficiency. In addition, polycrystalline thin film scintillators can only be used for X-ray detection because they are limited by the thickness of the film, which is not capable of depositing high energy rays and particles. The single crystal scintillator as a block material can detect not only X-rays, but also high-energy rays and particles.
Drawings
FIG. 1 is a photograph of ingots and samples of intrinsic halide scintillation crystals of different compositions;
FIG. 2 is an X-ray excitation emission spectrum of an intrinsic halide scintillation crystal at different compositions;
FIG. 3 is a graph of intrinsic halide scintillation crystals at different compositions137(ii) pulse height spectrum excited by the Cs radioactive source;
FIG. 4 is a graph of scintillation decay time for intrinsic halide scintillation crystals at different compositions;
fig. 5 is a schematic structural view of a radiation detector.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The present disclosure provides a novel intrinsic halide scintillator with non-deliquescence, high energy resolution, high light output, and short decay time, which is of great value in the radiation detection field.
The novel intrinsic luminous halide scintillation crystal has a polycrystalline or single crystal structure and has the following composition general formula:
(A1-xA’x)(B1-yB’y)2(X1-zX’z)3、(A1-xA’x)2(B1-yB’y)(X1-zX’z)3、(A1-xA’x)3(B1-yB’y)2(X1- zX’z)5；
wherein: A. a' ═ Li, Na, K, Rb, Cs, In, and Tl; B. b ═ Cu, Ag, and Au; x, X' ═ F, Cl, Br, and I; x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, and z is more than 0 and less than or equal to 1.
In one embodiment of the invention, a halide scintillation crystal is prepared using a Bridgman method. The growth process of the halide scintillation crystal is exemplarily illustrated below.
And (4) selecting a crucible lowering furnace. The crucible descending furnace consists of three sections, namely a high-temperature zone, a low-temperature zone and a crystallization zone.
And (3) mixing materials. According to the general formula: (A)1-xA’x)(B1-yB’y)2(X1-zX’z)3、(A1-xA’x)2(B1-yB’y)(X1-zX’z)3Or (A)1-xA’x)3(B1-yB’y)2(X1-zX’z)5Weighing and mixing the raw materials to obtain a mixed material. The selected raw materials can be one or more of AX and BX, wherein: a ═ Li, Na, K, Rb, Cs, In, and Tl; b ═ Cu, Ag, and Au; x ═ F, Cl, Br, and I. The purity of all raw materials is above 99.9%. As a further preferable scheme, the raw materials need to be subjected to vacuum drying treatment before being weighed and proportioned, and the drying temperature is less than or equal to 180 ℃.
And (4) charging. The mixture is placed in a quartz crucible with a sharp bottom (conical bottom) or a capillary bottom in a dry atmosphere of inert gas, nitrogen gas or anhydrous. Then the crucible is evacuated and sealed by welding. The inert gas environment is a glove box filled with argon. The nitrogen atmosphere was a glove box filled with nitrogen. The vacuum degree of the vacuum pumping is better than (less than) 10-2Pa。
And (4) melting. And vertically placing the sealed quartz crucible in a high-temperature area of a crystal growth furnace, heating the crystal growth furnace to enable the temperature to exceed the melting point temperature of the raw materials by 50-100 ℃, and completely melting and uniformly mixing the raw materials.
And (4) descending growth. And then adjusting the position of the crucible and the temperature of the furnace to reduce the temperature of the bottom of the crucible to the melting point of the halide scintillation crystal, and then reducing the quartz crucible in the furnace at a reduction speed of 0.1-10.0 mm/h, so that the crystal starts to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified. And then cooling at the speed of 5-50 ℃/h until the temperature is reduced to the room temperature. And finally, taking out the prepared halide scintillation crystal from the quartz crucible.
In the invention, the obtained intrinsic halide scintillation crystal has the advantages of nondeliquescence, high energy resolution, high light output and short decay time, and has good application prospects in the fields of neutron detection, X-ray detection or gamma-ray detection and the like. For example, the structure of a radiation detector composed of the intrinsic halide scintillation crystal and the light detection device provided by the invention is shown in fig. 5. When high-energy particles and rays are irradiated on the intrinsic halide scintillation crystal, a pulse light signal is formed based on the intrinsic luminescence characteristics of the high-energy particles and the rays and transmitted to a light detector, and data of the high-energy particles and the rays can be directly read out at the rear end.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1:
the intrinsic halide scintillation crystal proposed in this example 1 has the composition formula CsCu2I3I.e. with (A)1-xA’x)(B1- yB’y)2(X1-zX’z)3Is shown in the general formula (II); a ═ Cs; b is Cu; x ═ I; x, y, z, 0.
The rare earth halide mixed scintillation crystal is prepared by adopting a Bridgman-Stockbarge method, and comprises the following steps:
a) preparation on demandThe intrinsic halide scintillator composition formula CsCu2I3Weighing the raw materials. In specific operation, according to CsCu2I3Weighing high-purity raw materials CsI and CuI with the purity of 99.99 percent according to the molar ratio;
b) placing the raw materials in a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is evacuated and sealed by welding. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
c) vertically placing the welded and sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to reach 650 ℃ (± 30 ℃) until the raw materials are completely melted and uniformly mixed; adjusting the position of the crucible and the temperature of the furnace to reduce the temperature of the bottom of the crucible to about 380 ℃ (± 30 ℃), and then reducing the quartz crucible in the furnace body at a reducing speed of 0.4mm/h, so that crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified; then cooling at the speed of 10 ℃/h until the temperature is reduced to the room temperature; and finally, taking the prepared halide scintillation crystal out of the quartz crucible in a dry environment and processing the halide scintillation crystal.
The intrinsic halide scintillation crystal is applied to the fields of neutron detection, X-ray detection or gamma-ray detection.
The test result of X-ray excitation emission spectrum shows that CsCu2I3Strong X-ray excitation luminescence exists in the scintillation crystal; the gamma ray pulse height spectrum test result shows that CsCu2I3The scintillation crystal has good gamma ray response at137Under the excitation of a Cs radioactive source, an all energy peak at 662keV exists.
Example 2:
the intrinsic halide scintillation crystal proposed in this example 2 has a composition of formula Cs3Cu2I5I.e. with (A)1-xA’x)3(B1- yB’y)2(X1-zX’z)5Is shown in the general formula (II); a ═ Cs; b is Cu; x ═ I; x, y, z, 0.
The rare earth halide mixed scintillation crystal is prepared by adopting a Bridgman-Stockbarge method, and comprises the following steps:
a) on-demand preparation of intrinsic halide scintillator composition of formula Cs3Cu2I5Weighing the raw materials. In specific operation, according to CsCu2I3Weighing high-purity raw materials CsI and CuI with the purity of 99.99 percent according to the molar ratio;
b) placing the raw materials in a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is evacuated and sealed by welding. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
c) vertically placing the welded and sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to reach 650 ℃ (± 30 ℃) until the raw materials are completely melted and uniformly mixed; adjusting the position of the crucible and the temperature of the furnace to reduce the temperature of the bottom of the crucible to about 390 ℃ (± 30 ℃), and then reducing the quartz crucible in the furnace body at a reducing speed of 0.4mm/h, so that crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified; then cooling at the speed of 12 ℃/h until the temperature is reduced to the room temperature; and finally, taking the prepared halide scintillation crystal out of the quartz crucible in a dry environment and processing the halide scintillation crystal.
The intrinsic halide scintillation crystal is applied to the fields of neutron detection, X-ray detection or gamma-ray detection.
The test result of the X-ray excitation emission spectrum shows that the Cs3Cu2I5The existence of very strong X-ray excited luminescence of the scintillation crystal; the gamma-ray pulse height spectrum test result shows that Cs is3Cu2I5Scintillation crystal in137The full energy peak exists at 662keV under the excitation of a Cs radioactive source, and has a ratio CsCu2I3Better energy resolution and light output.
Example 3:
the intrinsic halide scintillation crystal provided by the embodiment has a composition chemical formula of CsCu2Br3I.e. with (A)1-xA’x)(B1- yB’y)2(X1-zX’z)3Is shown in the general formula (II); a ═ Cs; b is Cu; x ═ Br; x, y, z, 0.
The rare earth halide mixed scintillation crystal is prepared by adopting a Bridgman-Stockbarge method, and comprises the following steps:
a) on-demand preparation of intrinsic halide scintillator composition of formula CsCu2Br3Weighing the raw materials. In specific operation, according to CsCu2Br3Weighing high-purity raw materials CsBr and CuBr with the purity of 99.99 percent according to the molar ratio;
b) placing the raw materials in a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is evacuated and sealed by welding. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
c) vertically placing the welded and sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to reach about 660 ℃ (± 30 ℃) until the raw materials are completely melted and uniformly mixed; adjusting the position of the crucible and the temperature of the furnace to reduce the temperature of the bottom of the crucible to about 360 ℃ (± 30 ℃), and then reducing the quartz crucible in the furnace body at a reducing speed of 0.5mm/h, so that crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified; then cooling at the speed of 15 ℃/h until the temperature is reduced to the room temperature; and finally, taking the prepared halide scintillation crystal out of the quartz crucible in a dry environment and processing the halide scintillation crystal.
The intrinsic halide scintillation crystal is applied to the fields of neutron detection, X-ray detection or gamma-ray detection.
The test result of X-ray excitation emission spectrum shows that CsCu2Br3The existence of weaker X-ray excited luminescence of the crystal; the gamma ray pulse height spectrum test result shows that CsCu2Br3The crystal is in137There was no apparent response from Cs radiation source excitation.
Example 4
The intrinsic halide scintillation crystal proposed in this example 4 has the composition formula (Cs)0.99Li0.01)3(Cu0.997Ag0.003)2I5I.e. with (A)1-xA’x)(B1-yB’y)2(X1-zX’z)3Is shown in the general formula (II); a ═ Cs; a' ═ Li;B＝Cu；B’＝Ag；X＝I；x＝0.01；y＝0.003；z＝0。
the rare earth halide mixed scintillation crystal is prepared by adopting a Bridgman-Stockbarge method, and comprises the following steps:
a) intrinsic halide scintillator composition formula (Cs) prepared on demand0.99Li0.01)3(Cu0.997Ag0.003)2I5Weighing the raw materials. In particular operation, according to (Cs)0.99Li0.01)3(Cu0.997Ag0.003)2I5Weighing high-purity raw materials CsI, LiI, CuI and AgI with the purity of 99.99 percent according to the molar ratio;
b) placing the raw materials in a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is evacuated and sealed by welding. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
c) vertically placing the welded and sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to reach 650 ℃ (± 30 ℃) until the raw materials are completely melted and uniformly mixed; adjusting the position of the crucible and the temperature of the furnace to reduce the temperature of the bottom of the crucible to about 400 ℃ (± 30 ℃), and then reducing the quartz crucible in the furnace body at a reducing speed of 0.8mm/h, so that crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified; then cooling at the speed of 8 ℃/h until the temperature is reduced to the room temperature; and finally, taking the prepared halide scintillation crystal out of the quartz crucible in a dry environment and processing the halide scintillation crystal.
The intrinsic halide scintillation crystal is applied to the fields of neutron detection, X-ray detection or gamma-ray detection.
Example 5
The intrinsic halide scintillation crystal proposed in this example 5 has a composition of formula Cs3(Cu0.99Ag0.01)2(I0.996Br0.004)5I.e. with (A)1-xA’x)(B1-yB’y)2(X1-zX’z)3Is shown in the general formula (II); a ═ Cs; b is Cu; b ═ Ag; x ═ I; x' ═ Br; x is 0;y＝0.01；z＝0.004。
the rare earth halide mixed scintillation crystal is prepared by adopting a Bridgman-Stockbarge method, and comprises the following steps:
a) on-demand preparation of intrinsic halide scintillator composition of formula Cs3(Cu0.99Ag0.01)2(I0.996Br0.004)5Weighing the raw materials. In specific operation, according to Cs3(Cu0.99Ag0.01)2(I0.996Br0.004)5Weighing high-purity raw materials CsI, CuI and AgBr with the purity of 99.99 percent according to the molar ratio;
b) placing the raw materials in a quartz crucible with a capillary bottom in an inert gas environment; then the crucible is evacuated and sealed by welding. In this embodiment, the inert gas environment is a glove box filled with argon or nitrogen;
c) vertically placing the welded and sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to reach 650 ℃ (± 30 ℃) until the raw materials are completely melted and uniformly mixed; adjusting the position of the crucible and the temperature of the furnace to reduce the temperature of the bottom of the crucible to about 400 ℃ (± 30 ℃), and then reducing the quartz crucible in the furnace body at a reducing speed of 0.8mm/h, so that crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified; then cooling at the rate of 18 ℃/h until the temperature is reduced to the room temperature; and finally, taking the prepared halide scintillation crystal out of the quartz crucible in a dry environment and processing the halide scintillation crystal.
The intrinsic halide scintillation crystal is applied to the fields of neutron detection, X-ray detection or gamma-ray detection.
Fig. 1 a to c are photographs of crystal ingots and samples of intrinsic halide scintillation crystals provided by the present invention with different compositions. In the figure 1, the crystal component in a is CsCu2I3(ii) a In the figure 1, the crystal component b is CsCu2Br3(ii) a In the figure 1, the crystal component in c is Cs3Cu2I5. All three crystals in FIG. 1 had a diameter of 7mm and the length of the constant diameter portion was 15 mm. As can be seen from figure 1, the high-quality single crystal which is complete and does not crack and is free of inclusion can be grown under the three components. Taking out in ingotsA small sample is taken out for performance testing, and the sample size is 4 multiplied by 2mm in sequence3、5×2×1mm3、Φ7×2mm3As shown in fig. 1.
In fig. 2, a to c are X-ray excitation emission spectra of intrinsic halide scintillation crystals provided by the present invention at different compositions. In FIG. 2, a shows, CsCu2I3Has an X-ray excitation emission peak at 529 nm. In FIG. 2 b shows CsCu2Br3The X-ray excitation emission peak of (2) is located at 456 nm. In FIG. 2 c shows that Cs3Cu2I5The X-ray excitation emission peak of (2) is located at 443 nm.
In FIG. 3, a-b show the scintillation crystal of intrinsic halide provided by the invention under different compositions137Pulse height spectrum excited by Cs radioactive source. In the case of a in FIG. 3, the photomultiplier tube (PMT) used for the test was Hamamatsu R6231, and the molding time was selected to be 10. mu.s, under which the CsCu was calibrated2I3The light output of (2) is 13400ph/MeV, and the energy resolution of the omnipotent peak at 662keV is approximately 8%. In fig. 3 b, the photomultiplier tube (PMT) used for the test is Hamamatsu R6231, with a forming time of 10 μ s selected, under which Cs is calibrated3Cu2I5The light output of (2) is 40700ph/MeV, and the energy resolution of the full energy peak at 662keV is about 5%.
Fig. 4, a-b, are scintillation decay times for different compositions of intrinsic halide scintillation crystals provided by the present invention. In FIG. 4, a shows, CsCu2I3The scintillation decay time of the crystal sample can be well fitted by a double-exponential function, and the fast component of the decay time is 158ns, accounting for 80%; the slow component was 2554ns, accounting for 20%. In FIG. 4 b shows, CsCu3I5The scintillation decay time of the crystal sample can be well fitted by a double-exponential function, and the fast component of the decay time is 326ns, accounting for 8%; the slow component is 1026ns, 92%. Here, it should be noted that CsCu2Br3The sample is at137The Cs source has no obvious response under irradiation, so the scintillation decay time of the Cs source cannot be tested.
Finally, it must be said here that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adaptations made by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention.
Claims (9)
1. An intrinsically luminescent halide scintillation crystal, characterized in that the halide scintillation crystal has the general composition formula:
AB2X3、A2BX3and A3B2X5(ii) a Wherein a = at least one of Li, Na, K, Rb, Cs, In and Tl; b = at least one of Cu, Ag and Au; x = at least one of F, Cl, Br and I.
2. The halide scintillation crystal of claim 1, wherein the halide scintillation crystal has a general composition formula: (A)1-xA’x)(B1-yB’y)2(X1-zX’z)3、(A1-xA’x)2(B1-yB’y)(X1-zX’z)3And (A)1-xA’x)3(B1-yB’y)2(X1-zX’z)5(ii) a A. A' = at least two of Li, Na, K, Rb, Cs, In, and Tl; B. b' = at least two of Cu, Ag, and Au; x, X' = at least two of F, Cl, Br, and I; x is more than 0 and less than 1, y is more than 0 and less than 1, and z is more than 0 and less than 1.
3. A method of preparing an intrinsically luminescent halide scintillation crystal as claimed in claim 1 or 2, characterized in that the halide scintillation crystal is prepared by means of a crucible descent method.
4. The method of claim 3, comprising:
(1) weighing AX and BX as raw materials according to the general formula of the halide scintillation crystal, mixing, placing in a crucible in an inert gas, nitrogen gas or anhydrous dry environment, vacuumizing, and sealing by welding;
(2) placing the welded and sealed crucible in a crucible descending furnace, heating to a temperature 50-100 ℃ higher than the melting point of the raw materials to completely melt the raw materials, adjusting the temperature of the bottom of the crucible to be reduced to the melting point of a halide scintillation crystal, and starting the growth of the crystal at a descending speed of 0.1-10.0 mm/h;
(3) and after the crystal growth is finished, cooling to room temperature to obtain the halide scintillation crystal.
5. A method according to claim 4, wherein the crucible is a quartz crucible having a bottom with a tapered or capillary bottom.
6. The method according to claim 4 or 5, wherein the purity of the raw material is 99.9% or more.
7. The method of any one of claims 4-6, wherein the inert gas is argon.
8. Use of a halide scintillation crystal according to claim 1 or 2 in the fields of neutron detection, X-ray detection and gamma-ray detection.
9. A radiation detector comprising the halide scintillation crystal of claim 1 or 2.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010573954.7A CN113897666A (en) | 2020-06-22 | 2020-06-22 | A kind of intrinsically luminescent halide scintillation crystal and its preparation method and application |
| PCT/CN2021/099440 WO2021259074A1 (en) | 2020-06-22 | 2021-06-10 | Low-dimensional perovskite-structured metal halide, preparation method therefor, and application thereof |
| EP21829035.1A EP4170002A4 (en) | 2020-06-22 | 2021-06-10 | METAL HALIDES WITH LOW-DIMENSIONAL PEROVSKITE STRUCTURE, ASSOCIATED PREPARATION PROCESS AND CORRESPONDING APPLICATION |
| US18/001,748 US20230235219A1 (en) | 2020-06-22 | 2021-06-10 | Low-dimensional perovskite-structured metal halide and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010573954.7A CN113897666A (en) | 2020-06-22 | 2020-06-22 | A kind of intrinsically luminescent halide scintillation crystal and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113897666A true CN113897666A (en) | 2022-01-07 |
Family
ID=79186290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010573954.7A Pending CN113897666A (en) | 2020-06-22 | 2020-06-22 | A kind of intrinsically luminescent halide scintillation crystal and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113897666A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477267A (en) * | 2022-03-01 | 2022-05-13 | 重庆大学 | A kind of preparation method of lead-free halogen microcrystalline and its product and application |
| CN115852480A (en) * | 2022-11-25 | 2023-03-28 | 中国科学院上海硅酸盐研究所 | Luminescent metal halide scintillator, preparation method and application |
| CN117071070A (en) * | 2023-10-12 | 2023-11-17 | 中国科学院上海硅酸盐研究所 | Transition metal-doped sodium-based halogen scintillation crystal and its preparation method and application |
| CN117552106A (en) * | 2024-01-10 | 2024-02-13 | 江苏先进无机材料研究院 | Rare earth-based zero-dimensional perovskite halide scintillation monocrystal as well as preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199105A (en) * | 1996-06-14 | 1998-11-18 | 中国科学院上海硅酸盐研究所 | Growth technology of thallium doped cesium iodide crystal by antivacuum fall |
| US20130327945A1 (en) * | 2012-06-06 | 2013-12-12 | Canon Kabushiki Kaisha | Compound, scintillator, and radiation detector |
| US20140264044A1 (en) * | 2011-06-06 | 2014-09-18 | Canon Kabushiki Kaisha | Scintillator material and radiation detector using same |
| CN108531988A (en) * | 2018-05-09 | 2018-09-14 | 宁波大学 | A kind of preparation method of rare earth halide scintillation crystal and application |
| CN109943322A (en) * | 2019-03-26 | 2019-06-28 | 华中科技大学 | Application of a compound as scintillator material and preparation method thereof |
-
2020
- 2020-06-22 CN CN202010573954.7A patent/CN113897666A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199105A (en) * | 1996-06-14 | 1998-11-18 | 中国科学院上海硅酸盐研究所 | Growth technology of thallium doped cesium iodide crystal by antivacuum fall |
| US20140264044A1 (en) * | 2011-06-06 | 2014-09-18 | Canon Kabushiki Kaisha | Scintillator material and radiation detector using same |
| US20130327945A1 (en) * | 2012-06-06 | 2013-12-12 | Canon Kabushiki Kaisha | Compound, scintillator, and radiation detector |
| CN108531988A (en) * | 2018-05-09 | 2018-09-14 | 宁波大学 | A kind of preparation method of rare earth halide scintillation crystal and application |
| CN109943322A (en) * | 2019-03-26 | 2019-06-28 | 华中科技大学 | Application of a compound as scintillator material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477267A (en) * | 2022-03-01 | 2022-05-13 | 重庆大学 | A kind of preparation method of lead-free halogen microcrystalline and its product and application |
| CN115852480A (en) * | 2022-11-25 | 2023-03-28 | 中国科学院上海硅酸盐研究所 | Luminescent metal halide scintillator, preparation method and application |
| CN117071070A (en) * | 2023-10-12 | 2023-11-17 | 中国科学院上海硅酸盐研究所 | Transition metal-doped sodium-based halogen scintillation crystal and its preparation method and application |
| CN117071070B (en) * | 2023-10-12 | 2023-12-26 | 中国科学院上海硅酸盐研究所 | Transition metal doped sodium-based halogen scintillation crystal and preparation method and application thereof |
| CN117552106A (en) * | 2024-01-10 | 2024-02-13 | 江苏先进无机材料研究院 | Rare earth-based zero-dimensional perovskite halide scintillation monocrystal as well as preparation method and application thereof |
| CN117552106B (en) * | 2024-01-10 | 2024-04-05 | 江苏先进无机材料研究院 | Rare earth-based zero-dimensional perovskite halide scintillating single crystal and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021259074A1 (en) | Low-dimensional perovskite-structured metal halide, preparation method therefor, and application thereof | |
| US7692153B2 (en) | Scintillator crystal and radiation detector | |
| Van Loef et al. | High-energy-resolution scintillator: Ce 3+ activated LaBr 3 | |
| RU2638158C2 (en) | Scintillator composition, radiation detector device and high-energy radiation recording method | |
| JP5378356B2 (en) | Neutron detection scintillator and neutron detector | |
| CN113897666A (en) | A kind of intrinsically luminescent halide scintillation crystal and its preparation method and application | |
| JP5096005B2 (en) | Bright and fast neutron scintillator | |
| CN101200639A (en) | Scintillator composition and its preparation method | |
| JPWO2006049284A1 (en) | Single crystal for scintillator containing Pr, manufacturing method thereof, radiation detector and inspection apparatus | |
| Wilson et al. | Strontium iodide scintillators for high energy resolution gamma ray spectroscopy | |
| CN114411252B (en) | Novel perovskite-like structure scintillator for neutron detection, and preparation method and application thereof | |
| CN113957386A (en) | Exciton emission type halide scintillator, thin film, single crystal, preparation method and application | |
| CN115852480A (en) | Luminescent metal halide scintillator, preparation method and application | |
| Chewpraditkul et al. | Scintillation properties of Gd3 (Al5-xGax) O12: Ce (x= 2.3, 2.6, 3.0) single crystals | |
| WO2012137738A1 (en) | Scintillator, radiation detector, and method for detecting radiation | |
| CN115506007B (en) | Near infrared luminous metal halide scintillation crystal and preparation method and application thereof | |
| Raja et al. | Difficulties and improvement in growth of Europium doped Strontium Iodide (SrI2: Eu2+) scintillator single crystal for radiation detection applications | |
| JP2013040274A (en) | Garnet type crystal for scintillator and radiation detector using the same | |
| CN101084329A (en) | Pr-containing single crystal for scintillator, process for producing the same, radiation detector and inspection apparatus | |
| JP5737978B2 (en) | Neutron detection scintillator and neutron beam detector | |
| Roos | Scintillation Detectors | |
| Yang et al. | Synthesis and scintillation properties of CsGd2Cl7: Ce3+ for gamma ray and neutron detection | |
| Shah et al. | High Resolution Sensor for Nuclear Waste Characterization | |
| Kim et al. | Crystal Growth and Scintillation Properties of ${\hbox {Rb}} _ {2}{\hbox {CeBr}} _ {5} $ | |
| JP2012162596A (en) | Scintillator for neutron detection and neutron beam detector |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220107 |
|
| WD01 | Invention patent application deemed withdrawn after publication |