Zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material doped with metal cations as well as preparation method and application of zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material

Abstract

The invention discloses a metal cation doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material, which is characterized in that Mn < 2 + > or Sb < 3 + > is doped in NPPZnBr4 (wherein NPP is N-phenylpiperazine) to form an organic-inorganic hybrid zinc-based halide scintillator, and conversion from blue light to green light and red light is realized. According to the zinc-based halide scintillator material doped with the divalent manganese ions, efficient green light emission with the quantum efficiency of 87.67% is achieved. The invention further discloses a preparation method of the zinc-based halide scintillator material. The preparation method has the advantages of being simple in process, low in cost, green, free of pollution and capable of achieving large-scale industrial production. The invention further discloses a scintillator film containing the zinc-based halide material and preparation and application of the scintillator film, the lowest detection limit is 1.1285 microGyair / s, the scintillation intensity is about 24748 ph MeV <-1 >, the imaging resolution is about 16 lp / mm, and the scintillator film is low in toxicity, excellent in water stability and capable of being effectively applied to the fields of X-ray medical imaging, nondestructive testing, industrial flaw detection and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of scintillator materials, and in particular to a metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material and a preparation method and application thereof. Background Art

[0002] The development of metal halide scintillators in the field of X-ray imaging can be traced back to the mid-20th century. With the development of X-ray imaging technology and detectors, metal halide scintillators have gradually been used in medical imaging, industrial detection and other fields due to their high energy conversion efficiency and good light output.

[0003] Although traditional scintillator materials, such as cesium iodide (CsI: Tl) and gallium germanium oxide (GSO: Ce), dominate the field of X-ray detection, they have some limitations, such as low luminescence efficiency, poor water stability, and high cost.

[0004] As the requirements for scintillator performance increase, researchers began to explore other materials. Among them, metal halides have gradually become the focus due to their excellent performance. Our team found that metal halide scintillators have a large band gap, which can more effectively convert the energy of X-rays into visible light and enhance the sensitivity of the detector. And it can respond quickly to X-ray radiation and is suitable for dynamic imaging. Therefore, we studied different metal halide scintillators and applied for Chinese patents (CN119020020A) for a zero-dimensional organic zinc-based halide scintillator material and its preparation method and application; Chinese patent (CN119019260A) for an organic-inorganic hybrid zirconium-based halide scintillator material and its preparation method and application; Chinese patent (CN119349644A) for divalent manganese ion-doped cadmium-based metal halide nanocrystalline scintillator material and its preparation method and application.

[0005] As the research deepened, we found that among metal halide scintillators, environmentally friendly lead-free zinc-based metal halides have excellent physical properties and luminescence performance such as non-deliquescent, high stability, no self-absorption, and high luminescence quantum efficiency, and have great application potential in the field of X-ray imaging.

[0006] However, due to the low fluorescence quantum yield of zinc-based halides, their light output value is not ideal. Therefore, we have conducted more in-depth research on a zero-dimensional organic zinc-based halide scintillator material and its preparation method and application based on the already declared (CN119020020A).

[0007] We found that the transition metal Mn 2+The d orbitals of the ions are more dispersed and sensitive to the coordination environment, making it possible to adjust the emission wavelength and afterglow performance by changing the crystal microstructure environment. 3+ Ions exist in chemically active ns 2 The outer electron structure makes the hybrid halide show short-life high-efficiency luminescence. Based on this, we propose a metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material and its preparation method and application. Summary of the invention

[0008] The first object of the present invention is to provide a metal cation doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material to expand the types of scintillator materials and to propose a zinc-based halide scintillator material with good stability and excellent performance.

[0009] The second object of the present invention is to provide a method for preparing the above scintillator material.

[0010] The third object of the present invention is to provide a film material made of the above scintillator material, and a method for preparing the scintillator film material.

[0011] A fourth object of the present invention is to provide use of the above scintillator material.

[0012] 1. Scintillator Materials A metal cation doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material, the scintillator material having a chemical formula of NPPZnBr4: x%Mn 2+ or x%Sb 3+ A compound wherein Zn is a divalent zinc ion Zn 2+ , 0 <x≤100。

[0013] As a preferred, x%Mn 2+ 50≤x≤80, x%Sb 3+ Where 0≤x≤40.

[0014] As a preferred, x%Mn 2+ Where x=75.

[0015] As a preferred embodiment, x%Sb 3+ Where x=30.

[0016] 2. Preparation method of scintillator materials A method for preparing a metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material, which is used to prepare the above zinc-based halide scintillator material, specifically comprises the following steps: (1) adding weighed piperazine compound and bromide to a mixed solution containing anhydrous ethanol and hydrobromic acid, and stirring and dissolving them at room temperature to obtain a saturated precursor solution, wherein the piperazine compound is N-phenylpiperazine, and the bromide includes zinc bromide and one of manganese bromide or antimony bromide; (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged, washed, and dried to obtain a product having a general chemical formula of NPPZnBr4: x%Mn 2+ or x%Sb 3+ Metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator microcrystals.

[0017] Preferably, in step (1), the molar ratio of the piperazine compound to the bromide is 3:1-1:1, the volume ratio of anhydrous ethanol to hydrobromic acid in the mixed solution is 5:1-20:1, the concentration of hydrobromic acid is 68.85wt%, and the total concentration of the mixture of the piperazine compound and the bromide in the precursor solution is 0.05-4mol / L.

[0018] 3. A scintillator film and a method for preparing the same A scintillator film material is prepared by making the above metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material into a film.

[0019] A method for preparing a scintillator film material is used to prepare the above scintillator film material, specifically comprising the following steps: (1) washing and drying the metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator microcrystals, and then dispersing them in an organic solvent to form a scintillator dispersion; (2) dissolving the polymer in an organic solvent to obtain a polymer solution, mixing the scintillator dispersion obtained in step (1) with the polymer solution and stirring them evenly, coating them on a substrate, and drying them to obtain a transparent scintillator film.

[0020] Preferably, in step (1), the solvent used to wash the scintillator microcrystals is any one of dimethyl sulfoxide, N,N-dimethylformamide, n-hexane, and anhydrous ethanol, or a mixed solution of two or more thereof.

[0021] Preferably, in step (1), the organic solvent used to disperse the scintillator microcrystals is toluene.

[0022] Preferably, in step (2), the polymer is one of polystyrene, polyvinylidene fluoride or polymethyl methacrylate.

[0023] Preferably, in step (2), the organic solvent used to dissolve the polymer is toluene.

[0024] Preferably, in step (2), the scintillator thin film is prepared by a drop coating method.

[0025] Preferably, in step (2), the mass ratio of the scintillator microcrystals in the scintillator dispersion to the polymer in the polymer solution is 3:5.

[0026] 4. Application of scintillator materials The above-mentioned metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator materials are applied to X-ray medical imaging, nondestructive testing and industrial flaw detection.

[0027] In the scintillator material of the present invention, [ZnBr4] 2- It is a tetrahedral spatial coordination configuration and is NPP 2+ Spatial isolation, doping with different concentrations of Sb 3+ or Mn 2+ To replace part of the existing Zn 2+ ions, forming a zero-dimensional structure on the molecular structure, and forming a zero-dimensional structure of a metal cation-doped zinc-based halide cluster by introducing organic cations. The metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator microcrystals are obtained by fully reacting with a room temperature solvent method and then drying. Compared with the prior art, the invention can effectively make up for the shortage of zero-dimensional halide scintillator material types, and has the advantages of simple preparation process, low cost, good stability, non-toxicity, large-scale industrial production, high efficiency green light / red light emission with high fluorescence quantum yield, excellent water stability, etc.; the electron-hole pairs generated by light excitation are localized in the zinc halide tetrahedron or manganese halide tetrahedron cluster, have high radiation recombination efficiency, and no self-absorption phenomenon; the metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator in the present invention is composited with organic substances such as polystyrene to successfully prepare NPPZnBr4: x%Mn with uniform area and good stability 2+ and NPPZnBr4: x%Sb 3+ The composite film, the flexible composite film prepared based on the present invention has the characteristics of high light yield, high spatial resolution and low detection limit, and can be effectively applied to many fields such as non-destructive testing and medical digital radiography.

[0028] Beneficial effects: 1. The present invention provides a metal cation doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material, [ZnBr4] 2- It is a tetrahedral spatial coordination configuration and is NPP 2+ Spatial isolation, doping with different concentrations of Sb 3+ or Mn 2+ To replace part of the existing Zn 2+ions, forming a zero-dimensional structure on the molecular structure, doped with Mn 2+ Ion or Sb 3+ ions realize the conversion of blue light into green or red light, and then doping Mn 2+ The ions achieved efficient green light emission with a quantum efficiency of 87.67%. Compared with the existing zinc-based halide scintillator materials, the quantum efficiency of the present invention is significantly improved, which can effectively make up for the shortage of zero-dimensional halide scintillator materials and has excellent water-stable X-ray scintillation performance (the prepared film has high resolution).

[0029] 2. The preparation method of a metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material provided by the present invention is low-cost, green and pollution-free, has a short synthesis cycle, and can realize large-scale industrial production.

[0030] 3. The metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator in the present invention is compounded with organic matter such as polystyrene to successfully prepare NPPZnBr4: x%Mn with uniform area, adjustable flexibility and good stability. 2+ and NPPZnBr4: x%Sb 3+ Composite film, its scintillation intensity is about 24748 ph MeV -1 , the minimum detection limit is 1.1285 μGy air / s, and the imaging resolution is about 16 lp / mm. It has the characteristics of high light yield, high spatial resolution and low detection limit, and can be effectively applied to X-ray medical imaging, nondestructive testing, industrial flaw detection and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The divalent manganese ion-doped zinc-based halide scintillator microcrystals NPPZnBr4 prepared in Example 13 of the present invention: 75% Mn 2+ Schematic diagram of the crystal structure of NPPZnBr4: 75%Mn 2+ It is a triclinic crystal system with a P1 space group structure.

[0032] Figure 2 The simulated XRD of the zinc-based halide scintillator single crystal NPPZnBr4 and the divalent manganese ion-doped zinc-based halide scintillator microcrystals NPPZnBr4 prepared in Examples 1 to 16: x%Mn 2+ The test XRD spectrum (simulated XRD spectrum is made according to the CIF card obtained by single crystal structure analysis, the test XRD is NPPZnBr4: x%Mn 2+ Powder test PowderXRD obtained).

[0033] Figure 3The simulated XRD of the zinc-based halide scintillator single crystal NPPZnBr4 and the trivalent antimony ion-doped zinc-based halide scintillator microcrystals NPPZnBr4 prepared in Example 1 and Example 17 to Example 21: x%Sb 3+ The test XRD spectrum (simulated XRD spectrum is made according to the CIF card obtained by single crystal structure analysis, the test XRD is NPPZnBr4: x%Sb 3+ Powder test Powder XRD obtained).

[0034] Figure 4 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4: x%Mn prepared in Example 1 to Example 16 2+ PLE diagram of the excitation spectrum, including the optimal emission wavelength.

[0035] Figure 5 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4: x%Mn prepared in Example 1 to Example 16 2+ PL diagram of the emission spectrum, including the optimal excitation wavelength.

[0036] Figure 6 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 13: 75% Mn 2+ CIE chromaticity diagram.

[0037] Figure 7 The trivalent antimony ion-doped zinc-based halide scintillator NPPZnBr4: x%Sb prepared in Example 1 and Example 17-Example 21 3+ PLE diagram of the excitation spectrum, including the optimal emission wavelength.

[0038] Figure 8 The trivalent antimony ion-doped zinc-based halide scintillator NPPZnBr4: x%Sb prepared in Example 1 and Example 17-Example 21 3+ PL diagram of the emission spectrum, including the optimal excitation wavelength.

[0039] Fig. 9 The trivalent antimony ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 21: 30% Sb 3+ CIE chromaticity diagram.

[0040] Fig.10 This is the CIE chromaticity diagram of the zinc-based halide scintillator NPPZnBr4 prepared in Example 1.

[0041] Fig.11The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 13: 75% Mn 2+ The fluorescence quantum efficiency.

[0042] Fig.12 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 13: 75% Mn 2+ Time-resolved fluorescence spectroscopy.

[0043] Fig.13 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 13: 75% Mn 2+ Thermogravimetric spectrum.

[0044] Fig.14 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 13: 75% Mn 2+ Scanning electron microscope (SEM) image.

[0045] Fig.15 The trivalent antimony ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 21: 30% Sb 3+ Scanning electron microscope (SEM) image.

[0046] Fig.16 This is a luminescence image of the water stability test of the zinc-based halide scintillator NPPZnBr4 prepared in Example 1 under 365 nm ultraviolet light.

[0047] Fig.17 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 13: 75% Mn 2+ Luminescence image of water stability test under 365 nm UV light.

[0048] Fig.18 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 13: 75% Mn 2+ Emission spectrum PL diagram of water stability test.

[0049] Fig.19 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 22: 75% Mn 2+ The lowest detection limit for X-ray dose detection of transparent films.

[0050] Fig. 20 The zinc-based halide scintillator NPPZnBr4 doped with divalent manganese ions obtained in Example 22: 75% Mn 2+Radiation stability of transparent films to continuous X-ray irradiation.

[0051] Fig.21 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 22: 75% Mn 2+ X-ray scintillation luminescence spectrum of the transparent film and comparison with bismuth germanium oxide (BGO) wafer.

[0052] Fig. 22 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 22: 75% Mn 2+ Actual image of a chip using transparent film for high-resolution X-ray imaging.

[0053] Fig.23 The divalent manganese ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 22: 75% Mn 2+ Image of a transparent film against a standard X-ray resolution lead plate.

[0054] Fig.24 The trivalent antimony ion-doped zinc-based halide scintillator NPPZnBr4 prepared in Example 23: 30% Sb 3+ Actual imaging of the capsule under X-ray. DETAILED DESCRIPTION

[0055] The present invention is further described in detail below in conjunction with the accompanying drawings so that those skilled in the art can implement the invention with reference to the description.

[0056] It should be noted that the experimental methods described in the following embodiments are conventional methods unless otherwise specified, and the reagents and materials can be obtained from commercial channels unless otherwise specified.

[0057] In the present invention, N-phenylpiperazine, zinc bromide, manganese bromide, antimony bromide, and hydrobromic acid were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., toluene was purchased from Sinopharm Group, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), n-hexane, and anhydrous ethanol were purchased from Lianlong Bohua (Tianjin) Pharmaceutical Chemistry Co., Ltd., and polystyrene (PS) was purchased from Thermo Fisher Scientific (China) Co., Ltd.

[0058] Example 1 NPPZnBr4 scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 1.125 g of zinc bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0059] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0060] (3) The zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4.

[0061] Example 2 NPPZnBr4: 5%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 1.0697 g of zinc bromide powder and 0.0537 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0062] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0063] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 5%Mn 2+ .

[0064] Example 3 NPPZnBr4: 8%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 1.0359 g of zinc bromide powder and 0.0859 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0065] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0066] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 8%Mn 2+ .

[0067] Example 4 NPPZnBr4: 10%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 1.0134 g of zinc bromide powder and 0.1074 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0068] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0069] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 10%Mn 2+ .

[0070] Example 5 NPPZnBr4: 12%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.9909 g of zinc bromide powder and 0.1289 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0071] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0072] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 12%Mn 2+ .

[0073] Example 6 NPPZnBr4: 15%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.9571 g of zinc bromide powder and 0.1611 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0074] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0075] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 15%Mn 2+ .

[0076] Example 7 NPPZnBr4: 20%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.9008 g of zinc bromide powder and 0.2148 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0077] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0078] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 20%Mn 2+ .

[0079] Example 8 NPPZnBr4: 30%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.7882 g of zinc bromide powder and 0.3.221 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0080] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0081] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 30%Mn 2+ .

[0082] Example 9 NPPZnBr4: 40%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.6756 g of zinc bromide powder and 0.4295 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0083] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0084] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 40%Mn 2+ .

[0085] Example 10 NPPZnBr4: 50%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.563 g of zinc bromide powder and 0.5369 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0086] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0087] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 50%Mn 2+ .

[0088] Embodiment 11 NPPZnBr4: 60%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.4504 g of zinc bromide powder and 0.6443 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0089] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0090] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 60%Mn 2+ .

[0091] Example 12 NPPZnBr4: 70%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.3378 g of zinc bromide powder and 0.7516 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0092] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0093] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 70%Mn 2+ .

[0094] Embodiment 13 NPPZnBr4: 75%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.2815 g of zinc bromide powder and 0.8053 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0095] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0096] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 75%Mn 2+ .

[0097] Embodiment 14 NPPZnBr4: 80%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.2252 g of zinc bromide powder and 0.859 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0098] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0099] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 80%Mn 2+ .

[0100] Embodiment 15 NPPZnBr4: 90%Mn 2+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.1126 g of zinc bromide powder and 0.9664 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0101] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0102] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 90%Mn 2+ .

[0103] Example 16 NPPMnBr4 scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 1.0738 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0104] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0105] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPMnBr4.

[0106] Embodiment 17 NPPZnBr4: 5%Sb 3+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 1.0697 g of zinc bromide powder and 0.0903 g of antimony bromide in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0107] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0108] (3) The trivalent antimony ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 5%Sb 3+ .

[0109] Embodiment 18 NPPZnBr4: 8%Sb 3+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 1.0359 g of zinc bromide powder and 0.1444 g of antimony bromide in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0110] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0111] (3) The trivalent antimony ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 8%Sb 3+ .

[0112] Embodiment 19 NPPZnBr4: 10%Sb 3+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 1.0134 g of zinc bromide powder and 0.1805 g of antimony bromide in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0113] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0114] (3) The trivalent antimony ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 10%Sb 3+ .

[0115] Embodiment 20 NPPZnBr4: 20%Sb 3+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.9008 g of zinc bromide powder and 0.361 g of antimony bromide in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0116] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0117] (3) The trivalent antimony ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 20%Sb 3+ .

[0118] Embodiment 21 NPPZnBr4: 30%Sb 3+ Scintillator microcrystals and their preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.7882 g of zinc bromide powder and 0.5415 g of antimony bromide in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0119] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0120] (3) The trivalent antimony ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 30%Sb 3+ .

[0121] Embodiment 22 NPPZnBr4: 75%Mn 2+ Scintillator thin film and its preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 0.2815 g of zinc bromide powder and 0.8053 g of manganese bromide powder in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0122] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0123] (3) The divalent manganese ion-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 75%Mn 2+ ; Then 3 g of the rinsed scintillator microcrystals were dispersed in 20 mL of toluene to form a uniform scintillator dispersion.

[0124] (4) Dissolve 5 g of polystyrene in 20 mL of toluene solvent to obtain a polymer solution.

[0125] (5) The scintillator dispersion obtained in step (3) and the polymer solution obtained in step (4) are mixed and stirred evenly, 540 μL of the mixed liquid is taken and drop-coated on a smooth 2.45 cm*2.45 cm glass substrate, and then the substrate is placed in a glove box and naturally dried until the solvent evaporates to obtain a flexible scintillator film.

[0126] Embodiment 23 NPPZnBr4: 30%Sb 3+ Scintillator thin film and its preparation (1) Weigh 770 μL of N-phenylpiperazine solution and 1.0134 g of zinc bromide powder and 0.1805 g of antimony bromide in a molar ratio, add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir well at 25°C for 1 hour to obtain a clear precursor solution.

[0127] (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals.

[0128] (3) The metal cation-doped zero-dimensional organic zinc-based halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and naturally dried to obtain clean zinc-based halide scintillator microcrystals NPPZnBr4: 30%Sb 3+ ; Then 3 g of the rinsed scintillator microcrystals were dispersed in 20 mL of toluene to form a uniform scintillator dispersion.

[0129] (4) Dissolve 5 g of polystyrene in 20 mL of toluene solvent to obtain a polymer solution.

[0130] (5) The scintillator dispersion obtained in step (3) and the polymer solution obtained in step (4) are mixed and stirred evenly, 540 μL of the mixed liquid is taken and drop-coated on a smooth 2.45 cm*2.45 cm glass substrate, and then the substrate is placed in a glove box and naturally dried until the solvent evaporates to obtain a flexible scintillator film.

[0131] Embodiment 24 Testing of scintillator materials and applications in X-ray imaging Structural Characterization of Samples of Test Examples 1 to 21 The X-ray powder diffraction phase analysis (XRD) of the ground samples was performed on a Bruker D8Advance X-RAY small-angle powder diffractometer from Bruker, Germany, using a Cu target. The test results are shown in Figure 2 , Figure 3 The XRD diffraction theoretical pattern obtained by X-ray single crystal diffraction fitting is compared with the XRD diffraction pattern measured by X-ray powder diffraction phase analysis. Figure 2 , Figure 3 As shown, it can be seen that the XRD diffraction pattern obtained by fitting the single crystal data is highly consistent with the XRD diffraction pattern measured experimentally, proving that the obtained sample is a sample of high purity and high crystallinity.

[0132] X-ray powder diffraction and X-ray single crystal diffraction results are shown in Figure 2 , Figure 3 , the structure shows that: The scintillator material NPPZnBr4: 75%Mn 2+ It is a triclinic crystal system with a P1 space group structure.

[0133] Test Example 13 Thermal Stability Test Experiment The thermal stability of the samples was measured by TGA 4000 of PE Company in the United States in air atmosphere. Fig.13 As shown, the sample has good thermal stability, NPPZnBr4: 75%Mn 2+It maintains structural integrity at 299°C and maintains excellent performance in high-temperature environments, which helps broaden its application in a variety of complex situations in the field of X-ray imaging.

[0134] Test Example 1-Example 16 Photoluminescence and Fluorescence Lifetime Test Experiment The photoluminescence performance of the sample was measured by the Edinburgh FS5 integrated steady-state transient fluorescence spectrometer of the Edinburgh company in the UK. The excitation light source is a Xe lamp, and the ultraviolet light of a specific excitation band can be selected through the filtering system. The excitation slit is 1.5m and the receiving slit is 1.5mm. The experimental spectrum of photoluminescence is shown in Figure 4 , Figure 5 , Figure 7 , Figure 8 , Fig.18 As shown. The scintillator NPPZnBr4 of the present invention: 75%Mn 2+ Under the optimal wavelength excitation of ultraviolet light 266nm, it exhibits green light emission at 523nm; NPPZnBr4: 30%Sb 3+ Under the optimal wavelength excitation of ultraviolet light 422nm, it exhibits red light emission of 696nm; and NPPZnBr4: 75%Mn 2+ It has good water stability and still has good photoluminescence performance after being stored in water for more than 7 days. With a Stokes shift of 255 nm, the sample can maintain excellent performance in a humid environment, which helps to broaden its application in a variety of complex situations in the field of X-ray imaging. The larger Stokes shift can reduce the absorption received by the scintillator material of the present invention when it propagates in the medium, which helps to reduce the self-absorption of light and increase the fluorescence yield. The experimental spectrum of fluorescence lifetime is shown in Fig.12 As shown, the excitation light source used is μF2 microsecond pulse xenon lamp, NPPZnBr4: 75%Mn 2+ Under the optimal wavelength excitation of ultraviolet light 266nm, the fluorescence lifetime is 355.108μs. The fitting model used in calculating the fluorescence lifetime is ExpDec1, and the fitting coefficient of determination (COD) is above 0.999.

[0135] Test Example 13 Quantum Efficiency Experiment The quantum efficiency (PLQY) of the sample was obtained using a fluorescence spectrometer (FLS-1000) equipped with a Xe lamp from Edinburgh, UK. The excitation light source was 266 nm. The calculation formula for PLQY is: QE = I S / (E R -E S ), where I S is the luminescence emission spectrum of the sample, E Ris the excitation light spectrum from an empty integrating sphere (without sample), E S is the excitation spectrum of the sample, see Fig.11 , fluorescence quantum efficiency (PLQY) = 87.67%.

[0136] Field Emission Scanning Electron Microscope (SEM) Experiments of Test Example 13 and Example 19 Field emission scanning electron microscopy (SEM) images of the samples were taken using a Thermo Fisher Scientific (China) Co., Ltd. Thermo Fisher Apreo 2C field emission scanning electron microscope. NPPZnBr4: 75%Mn 2+ The results are shown in Fig.14 , showing that NPPZnBr4: 75%Mn 2+ The particle size varies from submicron to tens of microns, and the particle size distribution is wide. NPPZnBr4: 30%Sb 3+ The results are as follows Fig.15 , which presents a flocculent cluster morphology, most of which are less than 20 μm in size. This morphology may originate from the crystallization process in crystal synthesis.

[0137] Test Example 22, Example 23 X-ray scintillation performance test experiment The X-ray scintillation performance of the sample was measured by the photodetector spectral response measurement system HVC 1800 of Beijing Zhuoli Hanguang Instrument Co., Ltd. The X-ray source used was the Monoblock source of Moxtek (USA). The tube voltage of the X-ray tube was 70 kV, the tube current of the X-ray tube was 170 mA, and the distance between the sample and the X-ray tube was 5 cm.

[0138] Experimental testing of X-ray doses Fig.19 As shown, the X-ray dose can be achieved by fixing the tube voltage of the X-ray tube and changing the tube current of the X-ray tube. The actual detected dose is calibrated by the RAMION radiation dosimeter. The detection limit is also an important parameter of the X-ray detector, which determines the minimum detection dose of the X-ray detector. The International Union of Applied Chemistry (IU-PAC) defines the detection limit as the equivalent dose rate that produces a signal greater than 3 times the noise level (signal-to-noise ratio [SNR] = 3), so the sample NPPZnBr4: 75%Mn 2+ The detection limit is 1.1285 µGy air / s, lower than the conventional medical diagnostic dose standard of 5.50 µGy air / s. This shows that the sample has sensitive X-ray detection capability. The scintillator material prepared by the present invention emits bright visible light under X-ray excitation. Therefore, the flexible scintillator film prepared by the present invention also has good imaging effect when used for X-ray imaging.

[0139] The zinc-based halide scintillator films of Example 22 and Example 23 are applied to high-resolution X-ray imaging of real objects. Fig. 22 , Fig.23 , Fig.24 As shown, under X-ray (20-50keV, 4W) irradiation, it can be seen from the test results that NPPZnBr4 obtained in Example 22 of the present invention: 75%Mn 2+ Scintillator film can turn chip pattern ( Fig. 22 )、Standard lead plate( Fig.23 ) and capsules ( Fig.24 ) Clear imaging of three types of objects, by Fig. 22 It can be seen that NPPZnBr4: 75%Mn 2+ The imaging resolution of the scintillator film reaches 16 line pairs per millimeter (lp / mm). Fig.21 It can be seen that under the same test conditions, the NPPZnBr4 obtained in Example 22 of the present invention: 75%Mn 2+ The light yield of the scintillator film is 24748 photons MeV -1 (The specific value is based on the comparison of the integrated area. Bismuth germanium oxide (BGO) is a commercial standard comparison sample, and the default light yield is 8,000 photons MeV -1 , NPPZnBr4 obtained in Example 22: 75%Mn 2+ The light yield of the scintillator film is 8000*3.0935 = 24748 photonsMeV -1 ).

[0140] The radiation stability of zinc-based halide scintillator films under continuous X-ray irradiation is shown in Fig. 20 As shown in the figure, after 30 cycles of continuous X-ray irradiation for 30 seconds, the normalized intensity of the film under X-ray irradiation changes very little. Therefore, the flexible scintillator film prepared by the present invention has excellent radiation stability under continuous X-ray irradiation.

[0141] Comparative Example 1 (CN119020020A) A zero-dimensional organic zinc-based halide scintillator material; Comparative Example 2 (CN119019260A) An organic-inorganic hybrid zirconium-based halide scintillator material and its preparation method and application; Comparative Example 3 (CN119349644A) Cadmium-based metal halide nanocrystalline scintillator material doped with divalent manganese ions and preparation method and application thereof; The scintillator material of the present invention is compared with the scintillator material for which the team has applied for a patent, as shown in Table 1: Table 1 The present invention Comparative Example 1 Comparative Example 2 Comparative Example 3 Quantum efficiency 87.67% 13.18% 13.5% 20.6% By comparison, we found that the quantum efficiency of the scintillator material of the present invention is significantly higher than that of comparative examples 1, 2, and 3. The higher quantum efficiency not only improves the luminous intensity and brightness, but also reduces energy loss, thereby extending the service life of the device and making it more energy-efficient in practical applications.

[0142] Summarize Luminescent materials with high quantum efficiency play an important role in display technology, lighting, bio-imaging, energy conversion, photocatalysis and sensing by improving luminescence performance, reducing energy consumption, and enhancing device sensitivity and stability. This characteristic makes it an indispensable key material in the development of modern science and technology.

[0143] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention is described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A metal cation doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material, characterized in that: The scintillator material has a chemical formula of NPPZnBr4: x%Mn 2+ or x%Sb 3+ A compound wherein NPP is N-phenylpiperazine and Zn is a divalent zinc ion Zn 2+ , 0<x≤100.

2. The metal cation doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material according to claim 1, characterized in that: x%Mn 2+ 50≤x≤80, x%Sb 3+ Where 0≤x≤30.

3. The divalent manganese ion-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material according to claim 2, characterized in that: x%Mn 2+ Where x=75.

4. The divalent manganese ion-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material according to claim 2, characterized in that: x%Sb 3+ Where x=30.

5. A method for preparing the metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material as claimed in any one of claims 2 to 4, characterized in that: The steps include: (1) adding weighed piperazine compound and bromide to a mixed solution containing anhydrous ethanol and hydrobromic acid, and stirring and dissolving them at room temperature to obtain a saturated precursor solution, wherein the piperazine compound is N-phenylpiperazine, and the bromide includes zinc bromide and one of manganese bromide or antimony bromide; (2) The precursor solution obtained in step (1) is allowed to stand at room temperature for reaction, filtered, centrifuged, washed, and dried to obtain a product having a general chemical formula of NPPZnBr4: x%Mn 2+ or x%Sb 3+ Metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator microcrystals.

6. The method for preparing the metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material according to claim 5, characterized in that: In step (1), the molar ratio of the piperazine compound to the bromide is 3:1-1:1, the volume ratio of anhydrous ethanol to hydrobromic acid in the mixed solution is 5:1-20:1, the concentration of hydrobromic acid is 68.85wt%, and the total concentration of the mixture of the piperazine compound and the bromide in the precursor solution is 0.05-4mol / L.

7. A scintillator film material, wherein the metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material according to any one of claims 1 to 4 is made into a thin film.

8. A method for preparing a scintillator film material, for preparing the scintillator film material according to claim 7, characterized in that: The steps include: (1) washing and drying the metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator microcrystals, and then dispersing them in an organic solvent to form a scintillator dispersion; (2) dissolving a polymer in an organic solvent to obtain a polymer solution, wherein the polymer is one of polystyrene, polyvinylidene fluoride or polymethyl methacrylate, and the organic solvent is toluene. The mass ratio of the scintillator microcrystals in the scintillator dispersion to the polymer in the polymer solution is 3:

5. The scintillator dispersion obtained in step (1) is mixed with the polymer solution and stirred evenly, and then coated on a substrate. After drying, a transparent scintillator film can be obtained.

9. The method for preparing a scintillator film material according to claim 8, characterized in that: In step (1), the solvent used to rinse the scintillator microcrystals is any one of dimethyl sulfoxide, N,N-dimethylformamide, n-hexane, and anhydrous ethanol, or a mixed solution of two or more thereof, and the organic solvent used to disperse the scintillator microcrystals is toluene.

10. Application of the metal cation doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material according to claim 1 in X-ray medical imaging, nondestructive testing and industrial flaw detection.

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