CN-122012085-A - Copper-based halide scintillator and preparation method thereof

CN122012085ACN 122012085 ACN122012085 ACN 122012085ACN-122012085-A

Abstract

The invention discloses a copper-based halide scintillator and a preparation method thereof, comprising the steps of dissolving a cesium source, a copper source and an optional doping element source in a mixed solvent consisting of a polar aprotic solvent and an organic carboxylic acid according to the volume ratio of (95:5) - (85:15) to prepare a clear precursor solution, placing the solution in a rotary evaporator, performing rotary evaporation for 30-180min at the water bath temperature of 80-120 ℃ and the rotation speed of 2-10rpm, directly crystallizing in a bottle to obtain a solid product, and washing and drying to obtain the copper-based halide scintillator. The method has the advantages of simple process, mild condition, and recyclable solvent, and is suitable for mass preparation. The obtained scintillator crystal structure is A 3 Cu 2 X 5 :M (wherein A is Cs + , X is one or more of Cl ‑ 、Br ‑ 、I ‑ , and M is a doping element), and has good scintillation performance.

Inventors

YANG CHENGZHANG
WANG CHUJIE
LI XIAOMING
WANG ZHICHENG

Assignees

杭州钛光科技有限公司

Dates

Publication Date: 20260512
Application Date: 20251231

Claims (10)

1. A method of making a copper-based halide scintillator comprising the steps of: s1, preparing a precursor solution, namely dissolving a cesium source, a copper source and optionally one or more doping element sources into a mixed solvent to obtain a clear and transparent precursor solution, wherein the mixed solvent consists of a polar aprotic solvent and an organic carboxylic acid according to the volume ratio of (95:5) - (85:15); s2, rotary evaporation crystallization, namely placing the precursor solution into a rotary evaporation bottle of a rotary evaporator, setting the water bath temperature to be 80-120 ℃ and the rotation speed to be 2-10 rpm, and carrying out rotary evaporation to obtain a solid scintillator product in the bottle, wherein the rotation speed is 30-180 min; S3, collecting and post-processing the product, namely taking out the solid scintillator product from a rotary steaming bottle, and washing and drying the solid scintillator product by using an organic solvent to obtain the copper-based halide scintillator.
2. The method for producing a copper-based halide scintillator according to claim 1, wherein the cesium source is one or more of cesium iodide, cesium bromide, and cesium chloride, and the copper source is one or more of cuprous iodide, cuprous bromide, and cuprous chloride.
3. The method for producing a copper-based halide scintillator according to claim 1, wherein the doping element M is one or more selected from Na, zn, pb, mn, ag, in, sb, tl, tb, pr, ce, yb, gd, nd and Lu.
4. The method for producing a copper-based halide scintillator according to claim 1, wherein the polar aprotic solvent is N, N-dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone, and the organic carboxylic acid is formic acid or acetic acid.
5. The method for producing a copper-based halide scintillator according to claim 1, wherein in the rotary evaporation process of step S2, the evaporated solvent vapor is recovered after condensation, and the recovered mixed solvent can be directly used for preparing the precursor solution again, and the number of recycling is not less than 5.
6. The method of producing a copper-based halide scintillator according to claim 1, wherein in step S2, the water bath temperature is 100±2 ℃ and the rotation speed is 5 rpm.
7. The copper-based halide scintillator prepared by the process according to any one of claims 1 to 6, having a crystal structure of a 3 Cu 2 X 5 , wherein a is Cs + and X is one or more of Cl - 、Br - 、I - .
8. A copper-based halide scintillator film, which is produced by mixing the copper-based halide scintillator as claimed in claim 7 as a light-emitting material with a highly transparent polymer resin and coating the mixture on a substrate.
9. A method for preparing a copper-based halide scintillator film, comprising the steps of: t1. the copper-based halide scintillator is prepared by the method of any one of claims 1 to 6; T2, mixing the scintillator with an organic solvent and a high-transparency polymer resin to form slurry; and T3, coating the slurry on an optically transparent substrate, and drying or annealing to form the scintillator film.
10. A radiation detector comprising the copper-based halide scintillator film of claim 8.

Description

Copper-based halide scintillator and preparation method thereof Technical Field The invention belongs to the technical field of scintillator materials, and particularly relates to a copper-based halide scintillator and a preparation method thereof. Background In recent years, all-inorganic halide perovskite and its derivatives have become a research hotspot for scintillator materials due to their excellent photoelectric properties, solution processability and cost advantages. The newly discovered copper-based halide scintillators, such as Cs 3Cu2X5 (X=Cl, br, I) and CsCu 2I3, are used as low-toxicity environment-friendly scintillator materials, show excellent characteristics of high light yield, quick decay time, low self absorption and the like, and have great application potential in the field of X-ray imaging. However, the preparation of the current copper-based halide scintillator material mainly adopts a high-temperature solid phase method and an anti-solvent crystallization method, the high-temperature solid phase method needs to be sintered at high temperature for a long time under inert atmosphere, the energy consumption is high, the anti-solvent method is used for inducing crystallization by rapidly adding an anti-solvent into a precursor solution, but the problems of uncontrollable crystallization process, uneven product morphology, poor repeatability and the like exist, and more serious, the use amount of an organic solvent is large and cannot be effectively recovered, so that the environment pollution and the cost are increased. Therefore, the development of a novel preparation method which can realize serialization, solvent recovery, controllable product and is suitable for large-area film formation has great significance for promoting the practical process of the copper-based halide scintillator material. Disclosure of Invention In a first aspect, the invention discloses a method for preparing a copper-based halide scintillator, comprising the steps of: S1, preparing a precursor solution, namely dissolving a cesium source, a copper source and optionally one or more doping element sources into a mixed solvent to obtain a clear and transparent precursor solution, wherein the mixed solvent consists of a polar aprotic solvent and an organic carboxylic acid according to the volume ratio of (95:5) to (85:15); s2, rotary evaporation crystallization, namely placing the precursor solution into a rotary evaporation bottle of a rotary evaporator, setting the water bath temperature to be 80-120 ℃ and the rotation speed to be 2-10 rpm, and carrying out rotary evaporation to obtain a solid scintillator product in the bottle, wherein the rotation speed is 30-180 min; S3, collecting and post-processing the product, namely taking out the solid scintillator product from a rotary steaming bottle, and washing and drying the solid scintillator product by using an organic solvent to obtain the copper-based halide scintillator. In one embodiment, the cesium source is one or more of cesium iodide, cesium bromide and cesium chloride, and the copper source is one or more of cuprous iodide, cuprous bromide and cuprous chloride. In one embodiment, the doping element M is selected from one or more of Na, zn, pb, mn, ag, in, sb, tl, tb, pr, ce, yb, gd, nd or Lu. In one embodiment, the polar aprotic solvent is N, N-Dimethylformamide (DMF), dimethylsulfoxide, or N-methylpyrrolidone, and the organic carboxylic acid is formic acid or acetic acid. In one embodiment, in the rotary evaporation process of step S2, the evaporated solvent vapor is recovered after condensation, and the recovered mixed solvent can be directly used for preparing the precursor solution again, and the cycle use frequency is more than or equal to 5 times. In one embodiment, in step S2, the water bath temperature is 100±2 ℃ and the rotation speed is 5 rpm. In another aspect, the invention provides a copper-based halide scintillator prepared by any of the methods described above, having a crystal structure of a 3Cu2X5, wherein a is Cs + and X is one or more of Cl -、Br-、I-. In another aspect, the present invention provides a copper-based halide scintillator film prepared by mixing the above copper-based halide scintillator as a light-emitting material with a highly transparent polymer resin and coating the mixture on a substrate. In another aspect, the present invention provides a method of preparing a copper-based halide scintillator film, comprising the steps of: T1, preparing a copper-based halide scintillator by adopting the method; T2, mixing the scintillator with an organic solvent and a high-transparency polymer resin to form slurry; and T3, coating the slurry on an optically transparent substrate, and drying or annealing to form the scintillator film. In another aspect, the present invention provides a radiation detector comprising the copper-based halide scintillator film described above. Compared with the prior art, the application has at least the