CN109943322B - Application of compound as scintillator material and preparation method thereof - Google Patents
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Abstract
The present invention belongs to a high-performance scintillator material and high-energy ray detectionThe field discloses an application of a compound as a scintillator material and a preparation method thereof, wherein the compound satisfies a chemical general formula AB2X3Wherein A represents a monovalent alkali metal cation, B represents a monovalent transition metal cation, and X represents a monovalent halogen anion. The preparation method specifically uses AX and BX with a molar ratio of 1:2 as raw materials, and prepares the compound with a chemical general formula of AB based on an anti-solvent crystallization method, a cooling crystallization method, a molten salt mixing method or a Czochralski method2X3The compound of (1). The invention obtains the chemical general formula satisfying AB by regulating and controlling the components of the compound2X3The novel scintillator material has the characteristics of no toxicity, stability, simple preparation method and high light yield. As a novel scintillator, the material disclosed by the invention has huge potential in the field of high-energy detection, and shows an application prospect of large-scale industrial production.
Description
Technical Field
The invention belongs to the field of high-performance scintillator materials and high-energy ray detection, and particularly relates to application of a compound as a scintillator material and a preparation method thereof.
Background
A scintillator is a material that absorbs the energy of high-energy particles and releases photons. For solid scintillators, organic scintillators and inorganic scintillators are mainly included. Compared with organic scintillators, inorganic scintillators have the advantages of high density, large atomic number, stable physicochemical property and the like, are widely applied to the fields of medical imaging, nuclear physics, high-energy physics, industrial detection and the like at present, and become one of the most important parts for detecting high-energy rays.
The scintillator materials which are mainstream in the market at present comprise CsI/NaI, Tl and PbWO4、Bi4Ge3O12(BGO), and the like. However, they still have some gap from the ideal scintillator. As for CsI/NaI: Tl materials, the light yield of the CsI/NaI: Tl materials is very high and can reach 50000 photons/MeV, the price of the CsI/NaI: Tl materials is low, and the crystal manufacturing process is very simple. However, the compounds contain virulent Tl elements, and have great hidden danger to the environment and the human body; in addition, the material has poor stability and needs to be completely sealed and packaged; long decay life (230 ns); low mechanical strength, and the like, thereby limiting the further development of the application of the detector. For PbWO4Material, its density is very high (8.28 g/cm)3) The scintillation crystal has the advantages of fast decay time (3-5 ns), shortest radiation length (0.9cm) in the currently known scintillation crystal, and excellent radiation resistance. However, the light yield of this material is very low, only 1% of CsI/NaI: Tl. For Bi4Ge3O12(BGO) crystals, which are star materials in oxide scintillator crystals due to their high density/atomic number, high energy conversion efficiency, high stability, high mechanical strength, and simple large-size crystal preparation process. However, it is expensive, radiation resistant, and prone to produce impurities during crystal production. Therefore, the development of the scintillating material which is nontoxic, low in price, high in light yield, good in stability and short in decay life has great research significance.
Disclosure of Invention
In view of the above-mentioned drawbacks or needs of the prior art, it is an object of the present invention to provide a method for preparing a scintillator material using a compound whose chemical formula satisfies AB by controlling the composition of the compound2X3Wherein a represents a monovalent alkali metal cation, B represents a monovalent transition metal cation, and X represents a monovalent halogen anion. The scintillator material has the characteristics of no toxicity, stability, simple preparation method and high light yield. As a novel scintillator, the material disclosed by the invention has great potential in the field of high-energy detection and shows the application of large-scale industrial productionAnd (5) landscape.
To achieve the above object, the present invention provides a use of a compound as a scintillator material, characterized in that the compound satisfies the general formula AB2X3Wherein A represents a monovalent alkali metal cation, B represents a monovalent transition metal cation, and X represents a monovalent halogen anion.
As a further preferred aspect of the present invention, A is Rb+、Cs+Either one or a combination of both.
In a further preferred embodiment of the present invention, B is Cu+、Ag+Any one of them.
As a further preferred aspect of the present invention, X is Cl-、Br-、I-Any one or a combination of several of them.
According to another aspect of the present invention, there is provided a process for preparing a compound of the formula AB2X3The method is characterized in that AX and BX with the molar ratio of 1:2 are used as raw materials, and the compound is prepared by an anti-solvent crystallization method, a cooling crystallization method, a molten salt mixing method or a Czochralski method to obtain a chemical general formula satisfying AB2X3A compound of (1); wherein A represents a monovalent alkali metal cation, B represents a monovalent transition metal cation, and X represents a monovalent halogen anion.
According to a further aspect of the present invention, the present invention provides the use of the above-described novel scintillator material as a scintillator material.
Through the technical scheme of the invention, compared with the prior art, the AB is generally used in the invention2X3A novel scintillator-like material having the following properties: 1) no toxicity and low price; 2) the preparation method is simple and can be synthesized in large batch; 3) the self-absorption is weak, and the light yield is high; 4) the absorption coefficient is large, the density is high, and the atomic number is large; 5) strong radiation resistance and good light/heat/water stability; 6) high mechanical strength and can be used for preparing flexible films.
The invention discovers AB for the first time2X3New use of the material as a scintillator by passing the material through AB2X3Group A ofControlled to be monovalent alkali metal cations (e.g. Rb)+、Cs+) The B component is controlled to be a monovalent transition metal cation (e.g., Cu)+、Ag+) The X component is controlled to be monovalent halogen anion (such as Cl)-、Br-、I-) The combined effect of the three components is utilized to ensure that the AB is2X3The material can be used as a scintillator and has high light yield. Based on the AB2X3The material can be further developed to obtain a high-energy detector, and has high sensitivity and good stability.
Also, the prior art lacks A as a monovalent alkali metal cation (e.g., Rb)+、Cs+) B is a monovalent transition metal cation (e.g., Cu)+、Ag+) And X is a monovalent halide anion (e.g., Cl)-、Br-、 I-) AB of2X3In view of the relevant research of the compound preparation method, the invention also provides a corresponding preparation method, the preparation method is simple to operate and low in cost, only AX and BX with the molar ratio satisfying 1:2 are used as raw materials, and the compound can be prepared based on an anti-solvent crystallization method, a cooling crystallization method, a molten salt mixing method or a pulling method, and the preparation method is simple and can be synthesized in a large scale.
In summary, the above solution conceived by the present invention has great advantages in cost, performance and manufacturing process compared to existing materials and technologies. Therefore, the method has great potential in the field of high-energy detection, shows the application prospect of large-scale industrial production, can be used as a scintillator material, and has good application prospect.
Drawings
FIG. 1 is AB2X3Crystal structure of type material. As can be seen from the figure, AB2X3The structure of the material mainly comprises [ CuI4]A double-stranded structure formed by tetrahedrons.
Fig. 2A is a graph of the theoretically calculated absorption coefficient of different materials for different photon energies, and fig. 2B is a graph of the theoretically calculated absorption versus thickness of different materials for 50KeV energy rays. With CsCu2I3For example, it can be seen from the figure that CsCu of the present invention2I3The material has larger average atomic number, so that the material can have absorption coefficient which is comparable to that of the CsI material which is mainstream in the market; and CsCu for an X-ray photon energy of 50KeV2I3Only a thickness of about 850um is required to absorb 99% of the X-ray photons.
FIG. 3 is CsCu prepared according to the present invention2I3Thermogram of (c). As can be seen from the figure, the melting point is 375 ℃. And since the material is a pure inorganic material, thermal stability is good. The weight loss phenomenon starts to appear at 500 ℃ and then is accompanied by CsCu2I3→ CsI +2CuI decomposition process.
FIG. 4 is CsCu prepared according to the present invention2I3Fluorescence spectrum and absorption spectrum of (a). As can be seen from the fluorescence spectrogram, CsCu2I3The emission peak position of (A) was 553nm, and the half-peak width was 79 nm. As can be seen from the absorption spectrum, CsCu2I3The band edge absorption of (a) is 426nm, and by fitting, we calculate that the material is a direct band gap material with a forbidden band width of 2.9 eV. Combining the absorption spectra and the fluorescence spectra, we calculated CsCu2I3The stokes shift of the material is large, about 127nm, and therefore self-absorption is weak. The reason for this is mainly that excitons are mainly confined to [ CuI ]4]In a double-stranded structure composed of tetrahedrons, the light-emitting mechanism is thus attributed to self-confined exciton (STE) emission.
FIG. 5 is CsAg prepared according to the present invention2I3、RbCu2I3、CsCu2Cl3、CsCu2Br3And CsCu2I3XRD pattern of (a).
FIGS. 6-10 are CsCu prepared according to the present invention2Cl3、CsCu2Br3、CsCu2I3、RbCu2Br3And RbCu2I3The scintillator response performance map of (1). As can be seen, the responses were approximately 78.06 mV, 636.97mV, 1.31V, 834.22mV, 406.88mV, respectively.
FIG. 11 is a graph of the response obtained with LYSO at a light yield of 27000 photons/MeV as a reference. FromAs can be seen, the response of the reference sample is 1.20V. Based on FIGS. 6-11, CsCu can be calculated2Cl3、CsCu2Br3、CsCu2I3、RbCu2Br3And RbCu2I31755, 14310, 29430, 18900 and 9155 photons/MeV, respectively.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
CsCu was prepared by the following antisolvent crystallization method2X3The powder is exemplified and described in detail.
Example one
The novel scintillator material is prepared by the following specific steps:
step 1: weighing 1.8187g of cesium iodide (CsI) and 2.6667g of cuprous iodide (CuI) in a mortar, mixing and grinding uniformly, pouring into a centrifuge tube, adding 10mL of dimethyl sulfoxide (DMSO) into the centrifuge tube, and shaking and dissolving in a glove box to obtain a precursor solution;
step 2: adding an anti-solvent, namely dichloromethane of 30mL, into the obtained precursor solution, and oscillating to fully mix and react the anti-solvent and the precursor solution;
and step 3: after the white powder was completely precipitated, the tube was placed in a centrifuge and centrifuged at 7000rpm/min for 10 minutes to remove the supernatant.
And 4, step 4: the precipitate was washed dropwise with 5mL of dichloromethane, centrifuged at 5500rpm/min for 5 minutes, the supernatant removed, and repeated 1 more time.
And 5: placing the precipitate in a drying tower for pumping to obtain white CsCu2I3And (3) powder.
Example two
The novel scintillator material is prepared by the following specific steps:
step 1: weighing 1.4897g of cesium bromide (CsBr) and 1.0042g of cuprous bromide (CuBr) in a mortar, mixing and grinding uniformly, pouring into a centrifuge tube, adding 12mL of dimethyl sulfoxide (DMSO) into the centrifuge tube, and shaking and dissolving in a glove box to obtain a precursor solution;
step 2: adding an anti-solvent, namely 40mL of dichloromethane, into the obtained precursor solution, and oscillating to fully mix and react the anti-solvent and the precursor solution;
and step 3: after the yellow powder had completely precipitated, the tube was placed in a centrifuge and centrifuged at 7000rpm/min for 10 minutes to remove the supernatant.
And 4, step 4: the precipitate was washed dropwise with 6mL of dichloromethane, centrifuged at 5500rpm/min for 5 minutes, the supernatant removed, and repeated 1 more time.
And 5: placing the precipitate in a drying tower for pumping to obtain yellow CsCu2Br3And (3) powder.
EXAMPLE III
The novel scintillator material is prepared by the following specific steps:
step 1: weighing 1.1785g of cesium chloride (CsCl) and 0.6930g of cuprous chloride (CuCl) in a mortar, mixing and grinding uniformly, pouring into a centrifuge tube, adding 10mL of dimethyl sulfoxide (DMSO) into the centrifuge tube, and shaking and dissolving in a glove box to obtain a precursor solution;
step 2: adding an anti-solvent, namely dichloromethane of 30mL, into the obtained precursor solution, and oscillating to fully mix and react the anti-solvent and the precursor solution;
and step 3: after the white powder was completely precipitated, the tube was placed in a centrifuge and centrifuged at 7000rpm/min for 10 minutes to remove the supernatant.
And 4, step 4: the precipitate was washed dropwise with 5mL of dichloromethane, centrifuged at 5500rpm/min for 5 minutes, the supernatant removed, and repeated 1 more time.
And 5: placing the precipitate in a drying tower for pumping to obtain white CsCu2Cl3And (3) powder. The temperature-reducing crystallization method is used for preparing AB2X3The powder is exemplified and described in detail.
Example four
Step 1: 0.2124g of rubidium iodide (RbI) and 0.3809g of cuprous iodide (CuI) are weighed into a mortar, mixed and ground uniformly, and then poured into a hydrothermal kettle.
Step 2: adding 10mL of hydroiodic acid into the hydrothermal kettle;
and step 3: screwing down the hydrothermal kettle and placing the hydrothermal kettle in a muffle furnace.
And 4, step 4: the reaction kettle program was set up and first warmed from room temperature to 150 ℃ for 30 minutes. Then incubated at 150 ℃ for 10 hours. Finally, slowly cooling from 150 ℃ to room temperature at a cooling rate of 2 ℃/h.
And 5: and starting a muffle furnace program, and taking out the hydrothermal kettle after the operation is finished.
Step 6: opening the hydrothermal kettle, removing residual hydroiodic acid, and taking out the obtained RbCu2I3And (3) powder.
EXAMPLE five
Step 1: 0.2598g of cesium iodide (CsI) and 0.4695g of silver iodide (AgI) were weighed into a mortar, mixed and ground uniformly, and then poured into a hydrothermal kettle.
Step 2: adding 10mL of hydroiodic acid into the hydrothermal kettle;
and step 3: screwing down the hydrothermal kettle and placing the hydrothermal kettle in a muffle furnace.
And 4, step 4: the reaction kettle program was set up and first warmed from room temperature to 150 ℃ for 30 minutes. Then incubated at 150 ℃ for 10 hours. Finally, slowly cooling from 150 ℃ to room temperature at a cooling rate of 2 ℃/h.
And 5: and starting a muffle furnace program, and taking out the hydrothermal kettle after the operation is finished.
Step 6: opening the hydrothermal kettle, removing the residual hydroiodic acid, and taking out the obtained CsAg2I3And (3) powder.
EXAMPLE six
The novel scintillator material is prepared by the following specific steps:
step 1: weighing 1.1576g of rubidium bromide (RbBr) and 1.004g of cuprous bromide (CuBr) in a mortar, mixing and grinding uniformly, pouring into a centrifuge tube, adding 10mL of dimethyl sulfoxide (DMSO) into the centrifuge tube, and shaking and dissolving in a glove box to obtain a precursor solution;
step 2: adding an anti-solvent, namely dichloromethane of 30mL, into the obtained precursor solution, and oscillating to fully mix and react the anti-solvent and the precursor solution;
and step 3: after the white powder was completely precipitated, the tube was placed in a centrifuge and centrifuged at 7000rpm/min for 10 minutes to remove the supernatant.
And 4, step 4: the precipitate was washed dropwise with 5mL of dichloromethane, centrifuged at 5500rpm/min for 5 minutes, the supernatant removed, and repeated 1 more time.
And 5: the precipitate is placed in a drying tower for pumping and drying, and finally white RbCu is obtained2Br3And (3) powder.
CsCu obtained based on the above-described embodiment2Cl3、CsCu2Br3、CsCu2I3、RbCu2Br3And RbCu2I3The results of the unit cell information and the values of density and effective atomic number are shown in Table 1.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. The application of the compound as a scintillator material is characterized in that the compound satisfies the chemical general formula AB2X3Wherein A represents a monovalent alkali metal cation, B represents a monovalent transition metal cation, and X represents a monovalent halogen anion.
2. The use of claim 1, wherein a is Rb+、Cs+Either one or a combination of both.
3. The use according to claim 1, wherein B is Cu+、Ag+Any one of them.
4. The use according to claim 1, wherein X is Cl-、Br-、I-Any one or a combination of several of them.
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| CN115010166A (en) * | 2022-05-31 | 2022-09-06 | 桂林电子科技大学 | Preparation method of lead-free copper-based perovskite powder and scintillation film and application of film |
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