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CN113957386A - Exciton emission type halide scintillator, thin film, single crystal, preparation method and application - Google Patents

Exciton emission type halide scintillator, thin film, single crystal, preparation method and application Download PDF

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Publication number
CN113957386A
CN113957386A CN202111261218.9A CN202111261218A CN113957386A CN 113957386 A CN113957386 A CN 113957386A CN 202111261218 A CN202111261218 A CN 202111261218A CN 113957386 A CN113957386 A CN 113957386A
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exciton
halide scintillator
crucible
halide
single crystal
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吴云涛
王谦
闻学敏
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0694—Halides
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    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
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    • 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
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    • 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
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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    • 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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    • 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
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
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    • 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
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
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    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
    • 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

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Abstract

The invention provides an exciton luminous type halide scintillator, a thin film, a single crystal, a preparation method and application, wherein the exciton luminous type halide scintillator has the following chemical formula: (A)1‑xAx’)5(B1‑yB’y)3(X1‑zX’z)8(ii) a Wherein: a and A' are respectively selected from one of Li, Na, K, Rb, Cs, In and Tl, and 0<x is less than or equal to 1; b and B' are respectively selected from one of Cu, Ag and Au, and 0<y is less than or equal to 1; x and X 'are respectively selected from one of F, Cl, Br and I, X and X' are not the same element, and 0<z<1. The exciton luminous halide scintillator has the advantages of nondeliquescence, high fluorescence quantum efficiency, high light output, low afterglow and the like, can be used for detecting X rays, gamma rays and neutrons, and has important application prospects in the fields of nuclear medicine imaging, security inspection, petroleum exploratory wells, industrial detection and the like.

Description

Exciton luminous halide scintillator, thin film, monocrystal, preparation method and application
Technical Field
The invention relates to the field of ceramic materials and preparation, in particular to a novel exciton luminous halide scintillator, a thin film, a single crystal, a preparation method and application.
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.
The scintillation material widely used internationally at present is thallium-doped sodium iodide (NaI: Tl)+) Mainly, the material has the advantages of high light output (-40000 photons/MeV), low cost and the like, but the material is deliquescent in the air and needs to be used after being packaged. New scintillators developed in recent years, such as cerium-doped lanthanum bromide (LaBr)3:Ce3+) And europium-doped strontium iodide (SrI)2:Eu2+) All have strong deliquescence and are unstable in the atmospheric environment, so that the preparation cost and the application difficulty are greatly increased. Most halide scintillators often require tight packaging before they can be used, which can have 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)+) This material has high light output comparable to NaI Tl and is inexpensive, but its long persistence limits its application to high resolution imaging. Tl crystal also has a problem of luminescence nonuniformity due to Tl+The ion components are segregated and have non-uniform distribution throughout the crystal, resulting in non-uniformity in the scintillation properties of the crystal. In addition, the CsI Tl crystal also needs to be used after packaging to avoid deliquescence in air.
In recent years, metal halide perovskite structure scintillating materials have received great attention, such as CsPbBr3And the like. Further, perovskite system materials having a molecular level low dimensional structure generally have exciton luminescence characteristics characterized by large stokes shift and high luminescence quantum efficiency. Wherein the copper-silver based low-vitamin perovskite is Cs3Cu2I5(zero-dimensional), CsCu2I3(one-dimensional), Rb2CuBr3(one-dimensional) and Rb2AgBr3(one-dimensional), etc., exhibit excellent scintillation properties and are considered a very potential class of scintillators. Taking Cs-Cu-X system as an example, Cs with zero-dimensional perovskite structure3Cu2I5The crystal has the advantages of high physical and chemical stability, no self-absorption, high light output, high energy resolution, ultra-low afterglow and the like, greatly improves the scintillation property after Tl doping, and is expected to realize commercial application; CsCu as another compound of Cs-Cu-I binary system2I3Also has great development potential. In addition, the copper-silver based low-dimensional perovskite can derive a new structural material when a plurality of halogen elements coexist, has excellent luminescence and scintillation performances, and has potential application in the radiation detection field.
It is to be noted that the information disclosed in the above background section is only for enhancement of understanding of the background of the present invention and therefore may include information that does not constitute prior art known to a person of ordinary skill in the art.
Disclosure of Invention
In view of the above problems and needs in the prior art, the present invention provides an exciton luminescent halide scintillator, a thin film, a single crystal, a method for preparing the same, and applications of the exciton luminescent halide scintillator, wherein the exciton luminescent halide scintillator has the advantages of non-deliquescence, high fluorescence quantum efficiency, high light output, low afterglow, and the like.
A first aspect of the invention provides an exciton-emitting halide scintillator having the formula:
(A1-xA’)5(B1-yB’y)3(X1-zX’z)8；
wherein:
a and A' are respectively selected from one of Li, Na, K, Rb, Cs, In and Tl, and x is more than 0 and less than or equal to 1;
b and B' are respectively selected from one of Cu, Ag and Au, and y is more than 0 and less than or equal to 1;
x and X 'are respectively selected from one of F, Cl, Br and I, X and X' are not the same element, and 0< z < 1.
According to an example of the first aspect, a and a ' are Cs, B and B ' are Cu, and X ' are Cl and I, respectively.
According to an example of the first aspect, z is equal to 0.25.
A second aspect of the present invention provides an exciton emission type halide scintillator thin film, which is constituted of the halide scintillator.
According to an example of the second aspect, the exciton emission type halide scintillator thin film is obtained by one of a vacuum evaporation method, a sputtering method or a gel coating method.
According to an example of the second aspect, the exciton emission type halide scintillator film is obtained by a vacuum evaporation method;
the vacuum evaporation method comprises the following steps:
s10: according to the chemical formula (A)1-xA’x)5(B1-yB’y)3(X1-zX’z)8Weighing raw materials of each component;
s20: synthesizing the raw materials of each component into a compound coating raw material by utilizing a high-temperature cooling method or a solid-phase reaction method;
s30: heating the compound coating raw material in the evaporation boat to a molten state in a vacuum coating device to obtain the exciton luminous type halide scintillator film on a substrate; in the evaporation process, the temperature of the substrate is 20-300 ℃; the vacuum of the vacuum coating deviceDegree less than 10-2Pa。
A third aspect of the invention provides an exciton emission type halide scintillator single crystal composed of the halide scintillator.
According to an example of the third aspect, the exciton emission type halide scintillator single crystal is obtained by one of a crucible descent method based on a melt method, a pulling method based on a melt method, a cooling method based on a solution method, an evaporation method based on a solution method, or a hydrothermal method based on a solution method.
A fourth aspect of the present invention provides a production method for producing the exciton emission type halide scintillator single crystal, including the steps of:
s100: according to the chemical formula (A)1-xA’x)5(B1-yB’y)3(X1-zX’z)8Weighing raw materials of each component;
s200: sealing and packaging the raw materials of each component in a crucible under an inert gas or anhydrous dry environment;
s300: vertically placing a crucible sealed and packaged with each component raw material in a crystal growth furnace to grow the exciton luminous halide scintillator single crystal
According to an example of the fourth aspect, the S300 step includes the steps of:
s310: vertically placing a crucible sealed and packaged with each component raw material in the middle of a crystal growth furnace, heating the crystal growth furnace to a temperature higher than the melting point of an exciton luminous halide scintillator, and melting and mixing the component raw materials;
s320: adjusting the position of the crucible, and adjusting the temperature of the crystal growth furnace to reduce the temperature of the bottom of the crucible to the melting point of the exciton luminous halide scintillator;
s330: descending the crucible in the crystal growth furnace at the speed of 0.1-10.0 mm/h until the melt is completely solidified;
s340: the crucible temperature was slowly cooled to room temperature.
The fifth aspect of the invention provides an application of the halide scintillator in neutron detection, X-ray detection or gamma-ray detection; or
Applying the halide scintillator film to neutron detection, X-ray detection or gamma-ray detection; or
The halide scintillator single crystal is applied to neutron detection, X-ray detection or gamma-ray detection.
The exciton luminous halide scintillator has the advantages of nondeliquescence, high fluorescence quantum efficiency, high light output, low afterglow and the like, can be used for detecting X rays, gamma rays and neutrons, and has important application prospects in the fields of nuclear medicine imaging, security inspection, petroleum exploratory wells, industrial detection and the like.
Drawings
Other features, objects, and advantages of the invention will be apparent from the following detailed description of non-limiting embodiments, which proceeds with reference to the accompanying drawings and which is incorporated in and constitutes a part of this specification, illustrating embodiments consistent with the present application and together with the description serve to explain the principles of the application. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a sample photograph of an exciton emission type halide scintillator under natural light and ultraviolet light irradiation according to an embodiment of the present invention;
FIG. 2 is a photo-induced exciton emission spectrum of an exciton-emitting halide scintillator in accordance with one embodiment of the present invention;
FIG. 3 is a graph of fluorescence decay time for an exciton emission halide scintillator in accordance with one embodiment of the present invention;
FIG. 4 is a graph of fluorescence quantum efficiency of an excitonic luminescent halide scintillator according to an embodiment of the present invention;
FIG. 5 is a graph of a radiation exciton emission spectrum for an exciton emission halide scintillator in accordance with one embodiment of the present invention;
FIG. 6 is an X-ray detection limit diagram of an exciton emission halide scintillator in accordance with one embodiment of the present invention;
FIG. 7 is a graph of X-ray scintillation decay time for an exciton-emitting halide scintillator in accordance with an embodiment of the present invention;
FIG. 8 is a graph of steady state X-ray afterglow for an excitonic luminescent halide scintillator of an embodiment of the present invention.
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art. The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
Furthermore, the drawings are merely schematic illustrations of the present disclosure and are not necessarily drawn to scale. The same reference numerals in the drawings denote the same or similar parts, and thus their repetitive description will be omitted. Some of the block diagrams shown in the figures are functional entities and do not necessarily correspond to physically or logically separate entities.
Embodiments of the invention provide an exciton emissive halide scintillator having the following formula:
(A1-xA’)5(B1-yB’y)3(X1-zX’z)8；
wherein:
a and A' are respectively selected from one of Li, Na, K, Rb, Cs, In and Tl, and x is more than 0 and less than or equal to 1;
b and B' are respectively selected from one of Cu, Ag and Au, and y is more than 0 and less than or equal to 1;
x and X 'are respectively selected from one of F, Cl, Br and I, X and X' are not the same element, and 0< z < 1.
The exciton luminous type halide scintillator of the invention is A5B3X8Phase of structure, absence of A in binary phase diagram in view of AX-BX system with only one halogen element5B3X8Article of constructionPhase, therefore, X and X' of the exciton-emitting halide scintillator of the present invention are not the same element, i.e., X8Including at least two or more elements. At X8Under the condition of containing a plurality of elements, a new stable crystal structure is derived, and the exciton luminous type halide scintillator has exciton luminescence of 350-1200 nm under the excitation of high-energy rays (such as X rays and gamma rays), high-energy particles (such as alpha particles, beta particles and neutrons) and ultraviolet light. Preferably, A and A ' are Cs, B and B ' are Cu, and X ' are Cl and I, respectively. Further, when A and A ' are Cs, B and B ' are Cu, and X ' are Cl and I, respectively, preferably z is equal to 0.25.
The exciton luminous halide scintillator has the advantages of nondeliquescence, high fluorescence quantum efficiency, high light output, low afterglow and the like, can be used for detecting X rays, gamma rays and neutrons, and has important application prospects in the fields of nuclear medicine imaging, security inspection, petroleum exploratory wells, industrial detection and the like.
Embodiments of the present invention also provide an exciton emission type halide scintillator thin film, which is composed of the exciton emission type halide scintillator.
The exciton luminous type halide scintillator film can be obtained by adopting one of a vacuum evaporation method, a sputtering method or a gel coating method.
Preferably, the exciton emission type halide scintillator film is obtained by a vacuum evaporation method, and the vacuum evaporation method comprises the following steps:
s10: according to the chemical formula (A)1-xA’x)5(B1-yB’y)3(X1-zX’z)8Weighing raw materials of each component; wherein, Li, Na, K, Rb, Cs, In and Tl, Cu, Ag and Au; and the raw material purity of elements such as F, Cl, Br, I and the like is more than 99.9 percent. Preferably, the raw materials need to be dried in vacuum before being weighed and proportioned, the temperature of the dried materials is less than or equal to 180 ℃, and the vacuum degree is better than 10-2Pa, the above ingredients can be carried out in a drying chamber or in an inert gas atmosphere, such as a glove box filled with argon or nitrogen. It should be noted thatThe starting materials may not be simple substances, but may be compounds, as shown in the following examples.
S20: synthesizing the raw materials of each component into a compound coating raw material by utilizing a high-temperature cooling method or a solid-phase reaction method;
s30: heating the compound coating raw material in the evaporation boat to a molten state in a vacuum coating device to obtain the exciton luminous type halide scintillator film on a substrate; in the evaporation process, the temperature of the substrate is 20-300 ℃; the vacuum degree of the vacuum coating device is lower than 10-2Pa。
Embodiments of the present invention also provide an exciton emission type halide scintillator single crystal composed of the exciton emission type halide scintillator.
The exciton luminous halide scintillator single crystal can be obtained by one of a crucible descent method based on a melt method, a pulling method based on the melt method, a cooling method based on a solution method, an evaporation method based on the solution method or a hydrothermal method based on the solution method.
The embodiment of the invention also provides a preparation method for the exciton luminous type halide scintillator single crystal, which specifically comprises the following steps:
s100: according to the chemical formula (A)1-xA’x)5(B1-yB’y)3(X1-zX’z)8Weighing raw materials of each component; wherein, Li, Na, K, Rb, Cs, In and Tl, Cu, Ag and Au; and the raw material purity of elements such as F, Cl, Br, I and the like is more than 99.9 percent. Preferably, the raw materials need to be dried in vacuum before being weighed and proportioned, the temperature of the dried materials is less than or equal to 180 ℃, and the vacuum degree is better than 10-2Pa, the above ingredients can be carried out in a drying chamber or in an inert gas atmosphere, such as a glove box filled with argon or nitrogen. The above raw materials may not be simple substances, but may be compounds, as shown in the following examples.
S200: sealing and packaging the raw materials of each component in a crucible under an inert gas or anhydrous dry environment; preferably, the crucible is a quartz crucible. The sealing packaging technology of the quartz crucible in an inert gas or anhydrous dry environment is more mature, and the raw materials of each component can be sealed and packaged in the crucible by adopting a welding sealing mode;
s300: vertically placing a crucible sealed by sealing and packaging raw materials of all components in a crystal growth furnace to grow the exciton luminous halide scintillator single crystal;
the step S300 includes the steps of:
s310: vertically placing a crucible sealed and packaged with each component raw material in the middle of a crystal growth furnace, heating the crystal growth furnace to a temperature higher than the melting point of an exciton luminous halide scintillator, and melting and mixing each component raw material;
s320: adjusting the position of the crucible, and adjusting the temperature of the crystal growth furnace to reduce the temperature of the bottom of the crucible to the melting point of the exciton luminous halide scintillator;
s330: descending the crucible in the crystal growth furnace at the speed of 0.1-10.0 mm/h until the melt is completely solidified;
s340: the crucible temperature was slowly cooled to room temperature. Meanwhile, the crystal is easy to prepare in large size.
The embodiment of the invention also provides an application, and the application can be the application of the halide scintillator in neutron detection, X-ray detection or gamma-ray detection, such as the fields of medical imaging, security inspection, petroleum exploration, industrial detection and the like
The application can also be the application of the halide scintillator film in neutron detection, X-ray detection or gamma-ray detection, such as the fields of medical imaging, security inspection, petroleum exploration, industrial detection and the like.
The application can also be the application of the halide scintillator single crystal in neutron detection, X-ray detection or gamma-ray detection, such as the fields of medical imaging, security inspection, petroleum exploration, industrial detection and the like.
The excitonic light-emitting halide scintillator single crystal of the present invention will be further described with reference to specific examples. The exciton emitting halide scintillator crystal in this example has the formula Cs5Cu3Cl6I2I.e. with (A)1-xA’x)5(B1-yB’y)3(X1-zX’z)8Is shown in the general formula, A is Cs; b is Cu; x ═ Cl; x' ═ I; x-y-0; and z is 0.25.
The exciton luminous halide scintillator crystal is prepared by adopting a Bridgman method, and the specific preparation method comprises the following steps:
s100 a: according to Cs5Cu3Cl6I2Weighing raw materials of the components, in the embodiment, the raw materials of simple substances are not adopted, compounds are adopted as raw materials, and the weight ratio of the raw materials is 5: 1: 2 molar ratio of CsCl, CuCl and CuI, high purity raw materials with a purity of 99.99% were weighed.
S200 b: the raw materials of each component are placed in a quartz crucible with a capillary bottom in an inert gas environment, and then the quartz crucible is vacuumized and welded and sealed, wherein the inert gas environment can be a glove operation box filled with argon or nitrogen.
S310 c: vertically placing the welded and sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to 550 ℃ until the raw materials of each component are completely melted and uniformly mixed;
s320 c: adjusting the position of the crucible, and adjusting the temperature of the crystal growth furnace to reduce the temperature of the bottom of the quartz crucible to-300 ℃;
s330 c: when the quartz crucible is descended in the crystal growth furnace at the speed of 0.4mm/h, the crystal starts to nucleate and grow from the capillary bottom of the quartz crucible until the melt is completely solidified;
s340 c: cooling the crystal growth furnace to room temperature at the speed of 10 ℃/h; finally, the prepared halide scintillator single crystal is taken out from the quartz crucible in a dry environment. The above-described Bridgman method can realize the production of a halide scintillator single crystal of large size. The prepared halide scintillator single crystal can be further processed to obtain a halide scintillator element which can be applied to equipment such as neutron detection, X-ray detection or gamma-ray detection.
Fig. 1 is a sample photograph of a cut exciton luminous halide scintillator single crystal wafer under natural light and ultraviolet light irradiation. As can be seen in FIG. 1, under natural light, Cs5Cu3Cl6I2Is colorless and transparent, and under the irradiation of ultraviolet light, the exciton luminous type halide scintillator single crystal has bright bluish light emission.
FIG. 2 is a photoluminescence spectrum, Cs, of the above exciton-emitting halide scintillator single crystal5Cu3Cl6I2With a single peak emission at 470nm, the emission monitored at 470nm has three excitation peaks at 325nm, 300nm and 275nm, respectively. Cs5Cu3Cl6I2Has a single component attenuation characteristic of 37.5us, as shown in fig. 3.
Cs5Cu3Cl6I2The fluorescence quantum efficiency test further proves that the exciton luminous type halide scintillator single crystal has higher fluorescence quantum efficiency and Cs5Cu3Cl6I2The fluorescence quantum efficiency of (2) can reach 70%, as shown in fig. 4. Cs5Cu3Cl6I2The scintillation yield with 44000ph./MeV under X-ray excitation is shown in FIG. 5.
Meanwhile, FIG. 6 is an X-ray detection limit diagram of the above exciton-emitting halide scintillator single crystal, and it can be seen that Cs is5Cu3Cl6I2Has a signal-to-noise ratio of 3 at a radiation dose of 162 nGy/s.
Cs of FIG. 75Cu3Cl6I2The X-ray scintillation decay time plot of (a) shows that there are three components, 0.6 μ s, 30.9 μ s and 57.5 μ s, respectively. In addition, Cs of FIG. 85Cu3Cl6I2Steady state X-ray afterglow curve display Cs5Cu3Cl6I2Has an ultra-low steady-state afterglow. The test result of the X-ray excitation emission spectrum shows that Cs is5Cu3Cl6I2There is a strong X-ray excitation luminescence. In conclusion, the exciton luminous halide scintillator has the advantages of nondeliquescence, high fluorescence quantum efficiency, high light output, low afterglow and the like, and can be applied to the fields of neutron detection, X-ray detection or gamma-ray detection.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. It will be evident to those skilled in the art that the present application is not limited to the details of the foregoing illustrative embodiments, and that the present application may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned. Furthermore, it is obvious that the word "comprising" does not exclude other elements or steps, and the singular does not exclude the plural. A plurality of units or means recited in the apparatus claims may also be implemented by one unit or means in software or hardware. It is to be understood that the terms "lower" or "upper", "downward" or "upward" and the like are used to describe features of the exemplary embodiments with reference to the positions of such features as displayed in the figures; the terms first, second, etc. are used to denote names, but not any particular order.

Claims (10)

1. An exciton-emitting halide scintillator, wherein the exciton-emitting halide scintillator has the formula:
(A1-xAx’)5(B1-yB’y)3(X1-zX’z)8；
wherein:
a and A' are respectively selected from one of Li, Na, K, Rb, Cs, In and Tl, and x is more than 0 and less than or equal to 1;
b and B' are respectively selected from one of Cu, Ag and Au, and y is more than 0 and less than or equal to 1;
x and X 'are respectively selected from one of F, Cl, Br and I, X and X' are not the same element, and 0< z < 1.
2. The exciton emitting halide scintillator of claim 1, wherein a and a ' are Cs, B and B ' are Cu, and X ' are Cl and I, respectively.
3. The exciton emissive halide scintillator in accordance with claim 2, wherein z is equal to 0.25.
4. An exciton emission type halide scintillator thin film, which is formed of the exciton emission type halide scintillator according to claim 1.
5. The exciton emission halide scintillator film of claim 4, wherein the exciton emission halide scintillator film is obtained by one of a vacuum evaporation method, a sputtering method or a gel coating method.
6. The exciton emission halide scintillator film of claim 4, wherein the exciton emission halide scintillator film is obtained by vacuum evaporation;
the vacuum evaporation method comprises the following steps:
s10: according to the chemical formula (A)1-xA’x)5(B1-yB’y)3(X1-zX’z)8Weighing raw materials of each component;
s20: synthesizing the raw materials of each component into a compound coating raw material by utilizing a high-temperature cooling method or a solid-phase reaction method;
s30: heating the compound coating raw material in the evaporation boat to a molten state in a vacuum coating device to obtain the exciton luminous type halide scintillator film on a substrate; in the evaporation process, the temperature of the substrate is 20-300 ℃; the vacuum degree of the vacuum coating device is lower than 10-2Pa。
7. An exciton-emitting halide scintillator single crystal, which is composed of the exciton-emitting halide scintillator according to any one of claims 1 to 3.
8. The exciton emission halide scintillator single crystal according to claim 7, wherein the exciton emission halide scintillator single crystal is obtained by one of a crucible descent method based on a melt method, a czochralski method based on a melt method, a cooling method based on a solution method, an evaporation method based on a solution method, or a hydrothermal method based on a solution method.
9. A production method for producing the exciton-emitting halide scintillator single crystal according to claim 7 or 8, comprising the steps of:
s100: according to the chemical formula (A)1-xA’x)5(B1-yB’y)3(X1-zX’z)8Weighing raw materials of each component;
s200: sealing and packaging the raw materials of each component in a crucible under an inert gas or anhydrous dry environment;
s300: vertically placing a crucible sealed by sealing and packaging raw materials of all components in a crystal growth furnace to grow the exciton luminous halide scintillator single crystal;
the step S300 includes the steps of:
s310: vertically placing a crucible sealed and packaged with each component raw material in the middle of a crystal growth furnace, heating the crystal growth furnace to a temperature higher than the melting point of an exciton luminous halide scintillator, and melting and mixing the component raw materials;
s320: adjusting the position of the crucible, and adjusting the temperature of the crystal growth furnace to reduce the temperature of the bottom of the crucible to the melting point of the exciton luminous halide scintillator;
s330: descending the crucible in the crystal growth furnace at the speed of 0.1-10.0 mm/h until the melt is completely solidified;
s340: the crucible temperature was slowly cooled to room temperature.
10. Use of a halide scintillator according to any one of claims 1 to 3 for neutron detection, X-ray detection or gamma-ray detection; or
Applying the halide scintillator film of any one of claims 4 to 6 for neutron detection, X-ray detection, or gamma ray detection; or
Use of the halide scintillator single crystal of claim 7 or 8 for neutron detection, X-ray detection, or gamma ray detection.
CN202111261218.9A 2021-10-28 2021-10-28 Exciton emission type halide scintillator, thin film, single crystal, preparation method and application Pending CN113957386A (en)

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