Metal cation doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator materials, methods of making and applications thereof

Abstract

The application discloses a kind of metal cation doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator materials, by doping Mn 2+ Or Sb 3+ In NPPZnBr4 (wherein NPP is N-phenylpiperazine) in organic-inorganic hybrid zinc-based halide scintillator, realize the conversion of blue light to green light, red light. Wherein, divalent manganese ion doped zinc-based halide scintillator material, realizes the high efficiency green light emission with quantum efficiency of 87.67%. The application also discloses a preparation method of zinc-based halide scintillator material, which has the advantages of simple process, low cost, green and pollution-free, and can realize large-scale industrial production. The application also discloses a scintillator film containing zinc-based halide material and its preparation and application, with a minimum detection limit of 1.1285 μGy air / s, the scintillation intensity is about 24748 ph MeV ‑1 , imaging resolution is about 16 lp / mm, low toxicity, excellent water stability, can be effectively applied to X-ray medical imaging, nondestructive testing, industrial flaw detection and other fields.

Description

Technical Field

[0001] This invention relates to the field of scintillator materials technology, specifically to a zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material doped with metal cations, its preparation method, and its application. Background Technology

[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 been gradually applied to fields such as medical imaging and industrial inspection due to their high energy conversion efficiency and good light output.

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

[0004] As the performance requirements for scintillators increase, researchers have begun to explore other materials. Among them, metal halides have gradually become a focus due to their excellent properties. Our team's research found that metal halide scintillators have a larger band gap, which can more effectively convert X-ray energy into visible light, enhancing the sensitivity of detectors. Furthermore, they can respond quickly to X-ray radiation, making them suitable for dynamic imaging. Therefore, we studied different metal halide scintillators and successively applied for Chinese patents (CN119020020A) for a zero-dimensional organic zinc halide scintillator material and its preparation method and application; (CN119019260A) for an organic-inorganic hybrid zirconium halide scintillator material and its preparation method and application; and (CN119349644A) for a cadmium-based metal halide nanocrystalline scintillator material doped with divalent manganese ions and its preparation method and application.

[0005] As the research progressed, we discovered that among metal halide scintillators, environmentally friendly lead-free zinc-based metal halides possess excellent physical properties and luminescence performance, such as non-hygroscopicity, 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 yield is not ideal. Therefore, we conducted more in-depth research based on our previously filed (CN119020020A) report on a zero-dimensional organic zinc-based halide scintillator material, its preparation method, and its applications.

[0007] We discovered the transition metal Mn 2+The more dispersed d orbitals of the ions, and their sensitivity to the coordination environment, make it possible to control the emission wavelength and afterglow performance by altering the crystal microstructure environment. Sb 3+ The ions possess chemical activity in the ns 2 The outer electron structure enables hybrid halides to exhibit efficient luminescence with a short lifetime. Based on this, we propose a zero-dimensional organic-inorganic hybrid zinc halide scintillator material doped with metal cations, along with its preparation method and applications. Summary of the Invention

[0008] The first objective of this invention is to provide a zero-dimensional organic-inorganic hybrid zinc halide scintillator material doped with metal cations, in order to expand the types of scintillator materials and to propose a zinc halide scintillator material with good stability and excellent performance.

[0009] A second objective of this invention is to provide a method for preparing the aforementioned scintillator material.

[0010] A third objective of the present invention is to provide a film material made from the above-mentioned scintillator material, and a method for preparing the scintillator film material.

[0011] A fourth object of the present invention is to provide uses for the above-described scintillator material.

[0012] I. Scintillator Materials A zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material doped with metal cations, wherein the scintillator material has the general chemical formula NPPZnBr4: x%Mn 2+ or x%Sb 3+ The compound in which Zn is a divalent zinc ion Zn 2+ 0 <x≤100。

[0013] As a preferred option, x%Mn 2+ In the case of 50≤x≤80, x%Sb 3+ In the case of 0 ≤ x ≤ 40.

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

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

[0016] II. Preparation methods of scintillator materials A method for preparing a zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material doped with metal cations, specifically comprising the following steps: (1) The weighed piperazine compound and bromide are added to a mixed solution containing anhydrous ethanol and hydrobromic acid, and stirred thoroughly at room temperature to dissolve them, so as to obtain a saturated precursor solution. The piperazine compound is N-phenylpiperazine, and the bromide includes zinc bromide, and also includes one of manganese bromide or antimony bromide. (2) The precursor solution obtained in step (1) was allowed to stand at room temperature for reaction, filtered, centrifuged and washed, and dried to obtain the chemical formula NPPZnBr4: x%Mn 2+ or x%Sb 3+ Zero-dimensional organic-inorganic hybrid zinc-based halide scintillator microcrystals doped with metal cations.

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

[0018] III. A scintillator thin film and its preparation method A scintillator film material is prepared by forming a thin film from the above-mentioned zero-dimensional organic-inorganic hybrid zinc halide scintillator material doped with metal cations.

[0019] A method for preparing a scintillator film material, specifically comprising the following steps: (1) The zero-dimensional organic-inorganic hybrid zinc halide scintillator microcrystals doped with metal cations are washed clean and dried, and then dispersed in an organic solvent to form a scintillator dispersion. (2) Dissolve the polymer in an organic solvent to obtain a polymer solution. Mix the scintillator dispersion obtained in step (1) with the polymer solution and stir evenly. Coat the solution onto a substrate and dry it to obtain a transparent scintillator film.

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

[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), a scintillator film is prepared by drop coating.

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

[0026] IV. Applications of Scintillator Materials The above-mentioned zero-dimensional organic-inorganic hybrid zinc halide scintillator materials doped with metal cations are applied to X-ray medical imaging, non-destructive testing, and industrial flaw detection.

[0027] In the scintillator material of this invention, [ZnBr4] 2- It has a tetrahedral spatial coordination configuration and is NPP 2+ Spatial isolation, incorporation of different concentrations of Sb 3+ or Mn 2+ To replace part of the original Zn 2+ Ions form a zero-dimensional molecular structure. By introducing organic cations, a zero-dimensional structure of metal cation-doped zinc-based halide clusters is formed. After sufficient reaction in a room-temperature solvent method followed by drying, metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator microcrystals are obtained. Compared with existing technologies, this effectively compensates for the lack of types of zero-dimensional halide scintillator materials and has the advantages of simple preparation process, low cost, good stability, non-toxicity, and the ability to achieve large-scale industrial production. It also features high fluorescence quantum yield, high efficiency in green / red light emission, and excellent water stability. The electron-hole pairs generated by photoexcitation are localized within zinc halide tetrahedral or manganese halide tetrahedral clusters, exhibiting high radiative recombination efficiency and no self-absorption phenomenon. In this invention, the metal cation-doped zero-dimensional organic-inorganic hybrid zinc-based halide scintillator is combined with organic materials such as polystyrene to successfully prepare NPPZnBr4:x%Mn with uniform area and good stability. 2+ and NPPZnBr4: x%Sb 3+ 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. This invention provides a zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material doped with metal cations, [ZnBr4]. 2- It has a tetrahedral spatial coordination configuration and is NPP 2+ Spatial isolation, incorporation of different concentrations of Sb 3+ or Mn 2+ To replace part of the original Zn 2+Ions, forming a zero-dimensional structure in the molecular structure, doped with Mn 2+ ions or Sb 3+ Ions enable the conversion of blue light into green or red light, and thus, with the addition of Mn doping... 2+ Highly efficient green light emission with a quantum efficiency of 87.67% was achieved in the ions. Compared with the existing zinc-based halide scintillator materials, the quantum efficiency of this invention is significantly improved, which can effectively make up for the lack of zero-dimensional halide scintillator materials, and has excellent water-stable X-ray scintillation performance (the prepared film has high resolution).

[0029] 2. The method for preparing a zero-dimensional organic-inorganic hybrid zinc halide scintillator material doped with metal cations provided by this invention is low in cost, green and pollution-free, and has a short synthesis cycle, enabling large-scale industrial production.

[0030] 3. In this invention, a zero-dimensional organic-inorganic hybrid zinc halide scintillator doped with metal cations is composited with organic materials such as polystyrene to successfully prepare NPPZnBr4:x%Mn with uniform area, tunable flexibility, and good stability. 2+ and NPPZnBr4: x%Sb 3+ The composite film has a scintillation intensity of approximately 24748 ph MeV. -1 The limit of detection is 1.1285 μGy. air With an imaging resolution of approximately 16 lp / mm, it features high light yield, high spatial resolution, and low detection limit, making it effective for applications in X-ray medical imaging, non-destructive testing, and industrial flaw detection. Attached Figure Description

[0031] Figure 1 The divalent manganese ion-doped zinc-based halide scintillator microcrystals NPPZnBr4: 75%Mn prepared in Example 13 of this invention are shown. 2+ A schematic diagram of the crystal structure, NPPZnBr4: 75% Mn 2+ It belongs to the triclinic crystal system and has a space group P1 structure.

[0032] Figure 2 Simulated XRD of single-crystal NPPZnBr4 zinc-based halide scintillator and microcrystalline NPPZnBr4 divalent manganese ion-doped zinc-based halide scintillator prepared in Examples 1-16: x%Mn 2+ The test XRD pattern (simulated XRD pattern is generated from the CIF card obtained by single crystal structure analysis; the test XRD is NPPZnBr4: x%Mn) 2+ (Obtained by powder XRD testing).

[0033] Figure 3Simulated XRD of single-crystal NPPZnBr4 zinc-based halide scintillator compared with trivalent antimony ion-doped zinc-based halide scintillator microcrystals NPPZnBr4 prepared in Examples 1 and 17-21: x%Sb 3+ The test XRD pattern (simulated XRD pattern is generated from the CIF card obtained by single crystal structure analysis; the test XRD is NPPZnBr4: x%Sb) 3+ (Obtained by powder XRD testing).

[0034] Figure 4 The zinc-based halide scintillator NPPZnBr4 (x%Mn) doped with divalent manganese ions prepared in Examples 1-16 2+ The excitation spectrum PLE diagram, including the optimal emission wavelength.

[0035] Figure 5 The zinc-based halide scintillator NPPZnBr4 (x%Mn) doped with divalent manganese ions prepared in Examples 1-16 2+ The emission spectrum PL diagram, including the optimal excitation wavelength.

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

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

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

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

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

[0041] Figure 11The zinc-based halide scintillator NPPZnBr4 (75% Mn) doped with divalent manganese ions was prepared in Example 13. 2+ Fluorescence quantum efficiency.

[0042] Figure 12 The zinc-based halide scintillator NPPZnBr4 (75% Mn) doped with divalent manganese ions was prepared in Example 13. 2+ Time-resolved fluorescence spectra.

[0043] Figure 13 The zinc-based halide scintillator NPPZnBr4 (75% Mn) doped with divalent manganese ions was prepared in Example 13. 2+ Thermogravimetric analysis (TGA) spectrum.

[0044] Figure 14 The zinc-based halide scintillator NPPZnBr4 (75% Mn) doped with divalent manganese ions was prepared in Example 13. 2+ The scanning electron microscope (SEM) image.

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

[0046] Figure 16 This is a luminescence pattern of the zinc-based halide scintillator NPPZnBr4 prepared in Example 1 under 365 nm ultraviolet light irradiation, which is a test of its water stability.

[0047] Figure 17 The zinc-based halide scintillator NPPZnBr4 (75% Mn) doped with divalent manganese ions was prepared in Example 13. 2+ Luminescence pattern of water stability test under 365 nm ultraviolet light irradiation.

[0048] Figure 18 The zinc-based halide scintillator NPPZnBr4 (75% Mn) doped with divalent manganese ions was prepared in Example 13. 2+ Emission spectrum (PL) plot for water stability testing.

[0049] Figure 19 The zinc-based halide scintillator NPPZnBr4 (75% Mn) doped with divalent manganese ions prepared in Example 22 is described. 2+ The lowest detection limit for X-ray dose detection of transparent films.

[0050] Figure 20 The zinc-based halide scintillator NPPZnBr4 (75% Mn) doped with divalent manganese ions obtained in Example 22 is described. 2+Radiation stability of transparent films under continuous X-ray irradiation.

[0051] Figure 21 The zinc-based halide scintillator NPPZnBr4 (75% Mn) doped with divalent manganese ions prepared in Example 22 is described. 2+ X-ray scintillation emission pattern of the transparent thin film, compared with bismuth germanate (BGO) wafer.

[0052] Figure 22 The zinc-based halide scintillator NPPZnBr4 (75% Mn) doped with divalent manganese ions prepared in Example 22 is described. 2+ A real-world image of a chip used in high-resolution X-ray imaging with a transparent thin film.

[0053] Figure 23 The zinc-based halide scintillator NPPZnBr4 (75% Mn) doped with divalent manganese ions prepared in Example 22 is described. 2+ An image of a lead plate at standard X-ray resolution using a transparent thin film.

[0054] Figure 24 The trivalent antimony ion-doped zinc-based halide scintillator NPPZnBr4: 30%Sb prepared in Example 23 is shown. 3+ An X-ray image of the capsule. Detailed Implementation

[0055] The present invention will now be described in further detail with reference to the accompanying drawings, so that those skilled in the art can implement it based on the description.

[0056] It should be noted that, unless otherwise specified, the experimental methods described in the following implementation plan are all conventional methods, and the reagents and materials described are all commercially available unless otherwise specified.

[0057] In this 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 Lianyungang Bohua (Tianjin) Pharmaceutical Chemical 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 the molar ratio, add them to a mixture of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid, and stir the mixture thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

[0060] (3) The zero-dimensional organic zinc halide scintillator microcrystals obtained in step (2) are rinsed with n-hexane and air-dried to obtain clean zinc 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

[0063] (3) The divalent manganese ion-doped zero-dimensional organozinc halide scintillator microcrystals obtained in step (2) were rinsed with n-hexane and air-dried to obtain clean zinc 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25°C for 1 hour to obtain a clear precursor solution.

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

[0066] (3) The divalent manganese ion-doped zero-dimensional organozinc halide scintillator microcrystals obtained in step (2) were rinsed with n-hexane and air-dried to obtain clean zinc 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

[0069] (3) The divalent manganese ion-doped zero-dimensional organozinc halide scintillator microcrystals obtained in step (2) were rinsed with n-hexane and air-dried to obtain clean zinc 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

[0072] (3) The divalent manganese ion-doped zero-dimensional organozinc halide scintillator microcrystals obtained in step (2) were rinsed with n-hexane and air-dried to obtain clean zinc 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25°C for 1 hour to obtain a clear precursor solution.

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

[0075] (3) The divalent manganese ion-doped zero-dimensional organozinc halide scintillator microcrystals obtained in step (2) were rinsed with n-hexane and air-dried to obtain clean zinc 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

[0078] (3) The divalent manganese ion-doped zero-dimensional organozinc halide scintillator microcrystals obtained in step (2) were rinsed with n-hexane and air-dried to obtain clean zinc 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 0.3221 g of manganese bromide powder according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide mixed powder according to the doping ratio, respectively, and add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution. Stir the mixture thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

[0081] (3) The divalent manganese ion-doped zero-dimensional organozinc halide scintillator microcrystals obtained in step (2) were rinsed with n-hexane and air-dried to obtain clean zinc 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

[0084] (3) The divalent manganese ion-doped zero-dimensional organozinc halide scintillator microcrystals obtained in step (2) were rinsed with n-hexane and air-dried to obtain clean zinc 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

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

[0088] Example 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, and add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution. Stir the mixture thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

[0090] (3) The divalent manganese ion-doped zero-dimensional organozinc halide scintillator microcrystals obtained in step (2) were rinsed with n-hexane and air-dried to obtain clean zinc 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25°C for 1 hour to obtain a clear precursor solution.

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

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

[0094] Example 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25°C for 1 hour to obtain a clear precursor solution.

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

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

[0097] Example 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25°C for 1 hour to obtain a clear precursor solution.

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

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

[0100] Example 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25°C for 1 hour to obtain a clear precursor solution.

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

[0102] (3) The divalent manganese ion-doped zero-dimensional organozinc halide scintillator microcrystals obtained in step (2) were rinsed with n-hexane and air-dried to obtain clean zinc 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 the molar ratio of the N-phenylpiperazine solution and the mixed powder of zinc bromide and manganese bromide according to the doping ratio, respectively, and add them to a mixed solution of 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid. Stir the mixture thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

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

[0106] Example 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 powder according to the doping ratio, respectively, and add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution. Stir the mixture thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

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

[0109] Example 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 powder according to the doping ratio, respectively, and add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixture. Stir the mixture thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

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

[0112] Example 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 powder according to the doping ratio, respectively, and add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixture. Stir the mixture thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

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

[0115] Example 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 powder according to the doping ratio, respectively, and add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixture. Stir the mixture thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

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

[0118] Example 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 powder according to the doping ratio, respectively, and add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixture. Stir the mixture thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

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

[0121] Example 22 NPPZnBr4: 75%Mn 2+ Scintillator Thin Films 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 according to the molar ratio of N-phenylpiperazine solution and zinc bromide and manganese bromide powder respectively, add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixed solution, and stir the reaction thoroughly at 25°C for 1 hour to obtain a clear precursor solution.

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

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

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

[0125] (5) Mix the scintillator dispersion obtained in step (3) with the polymer solution obtained in step (4) until homogeneous. Take 540 μL of the mixed liquid and drop it onto a smooth 2.45 cm * 2.45 cm glass substrate. Then place the substrate in a glove box and let it dry naturally until the solvent evaporates to obtain a flexible scintillator film.

[0126] Example 23 NPPZnBr4: 30%Sb 3+ Scintillator Thin Films 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 powder according to the doping ratio, respectively, and add them to 50 ml of anhydrous ethanol and 5 ml of hydrobromic acid mixture. Stir the mixture thoroughly at 25 °C for 1 hour to obtain a clear precursor solution.

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

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

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

[0130] (5) Mix the scintillator dispersion obtained in step (3) with the polymer solution obtained in step (4) until homogeneous. Take 540 μL of the mixed liquid and drop it onto a smooth 2.45 cm * 2.45 cm glass substrate. Then place the substrate in a glove box and let it dry naturally until the solvent evaporates to obtain a flexible scintillator film.

[0131] Example 24 Testing and Experimentation of Scintillator Materials and Applications in X-ray Imaging Structural characterization of samples from Examples 1-21 X-ray powder diffraction (XRD) phase analysis of the ground samples was performed on a Bruker D8 Advance X-ray small-angle powder diffractometer using a Cu target. The test results are as follows: Figure 2 , Figure 3 As shown. A comparison is made between the theoretical XRD diffraction pattern obtained by X-ray single-crystal diffraction fitting and the XRD diffraction pattern obtained by X-ray powder diffraction phase analysis. Figure 2 , Figure 3 As shown, the XRD diffraction pattern obtained by fitting single-crystal data is highly consistent with the experimentally measured XRD diffraction pattern, proving that the obtained sample is a high-purity and high-crystallinity sample.

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

[0133] Test Example 13 Thermal Stability Test Experiment The thermal stability of the sample was measured in air using a PE TGA 4000 from the USA. Figure 13 As shown, the sample exhibits good thermal stability. NPPZnBr4: 75%Mn 2+Maintaining structural integrity at 299 ℃ and exhibiting excellent performance in high-temperature environments helps broaden its application in various complex situations in the field of X-ray imaging.

[0134] Test Examples 1-16: Photoluminescence and Fluorescence Lifetime Testing Experiments The photoluminescence properties of the samples were measured using the Edinburgh FS5 integrated steady-state and transient fluorescence spectrometer, manufactured by Edinburgh Company in the UK. The excitation source was a Xe lamp, with a filtering system allowing selection of specific excitation wavelengths of ultraviolet light. The excitation slit was 1.5 μm, and the receiving slit was 1.5 mm. The experimental photoluminescence spectrum is shown below. Figure 4 , Figure 5 , Figure 7 , Figure 8 , Figure 18 As shown. The scintillator of this invention, NPPZnBr4: 75%Mn 2+ Under optimal ultraviolet light excitation at 266 nm, it exhibits green light emission at 523 nm; NPPZnBr4: 30% Sb 3+ Under optimal ultraviolet light excitation at 422 nm, it exhibits red light emission at 696 nm; and NPPZnBr4: 75%Mn 2+ Exhibiting excellent water stability, the sample retains good photoluminescence properties even after being stored in water for over 7 days. Its 255 nm Stokes shift allows it to maintain superior performance even in humid environments, broadening its application in various complex situations within X-ray imaging. The larger Stokes shift reduces absorption during propagation of the scintillator material in the medium, thus minimizing self-absorption and increasing fluorescence yield. The experimental fluorescence lifetime spectrum is shown below. Figure 12 As shown, the excitation source used was a μF2 microsecond pulsed xenon lamp, with NPPZnBr4: 75% Mn 2+ Under optimal ultraviolet light excitation at 266 nm, it exhibits a fluorescence lifetime of 355.108 μs. The fitting model used to calculate the fluorescence lifetime was ExpDec1, with a coefficient of determination (COD) greater than 0.999.

[0135] Test Example 13: Quantum Efficiency Experiment The quantum efficiency (PLQY) of the samples was obtained using an Edinburgh FLS-1000 steady-state / transient fluorescence spectrometer equipped with a Xe lamp. A 266 nm excitation source was used during the test. The formula for calculating PLQY is: η QE = I S / (E R -E S ), where I S E represents the emission spectrum of the sample. RE is the excitation spectrum from the empty integrating sphere (excluding the sample). S For the excitation spectrum of the sample, see [link / reference]. Figure 11 The fluorescence quantum efficiency (PLQY) is 87.67%.

[0136] Test Examples 13 and 19: Field Emission Scanning Electron Microscopy (SEM) Experiments Field emission scanning electron microscopy (SEM) images of the samples were acquired using a Thermo Fisher Scientific Apreo 2C field emission scanning electron microscope from Thermo Fisher Scientific (China) Co., Ltd. NPPZnBr4: 75%Mn 2+ See the results Figure 14 This shows that NPPZnBr4: 75%Mn 2+ It exhibits a blocky morphology, with particle sizes ranging from submicron to tens of micrometers, and a wide particle size distribution. NPPZnBr4: 30%Sb 3+ The results are as follows Figure 15 It exhibits a flocculent cluster morphology, with most of its size being less than 20 μm. This morphology may originate from the crystallization process during crystal synthesis.

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

[0138] Experimental detection of X-ray dose, such as Figure 19 As shown, the X-ray dose can be controlled by fixing the tube voltage of the X-ray tube and changing the tube current. The actual detected dose is calibrated using a RAMION radiation dosimeter. The detection limit is also a crucial parameter of X-ray detectors, determining the minimum detectable dose. The International Union of Applied Chemistry (IU-PAC) defines the detection limit as the equivalent dose rate that produces a signal greater than three times the noise level (signal-to-noise ratio [SNR] = 3). Therefore, the sample NPPZnBr4: 75%Mn 2+ The detection limit is 1.1285 µGy. air / s, lower than the standard medical diagnostic dose of 5.50 µGy air / s. This indicates that the sample has sensitive X-ray detection capability. The scintillator material prepared in this invention emits bright visible light under X-ray excitation; therefore, the flexible scintillator film prepared in this invention also has good imaging effect for X-ray imaging.

[0139] The zinc-based halide scintillator films of Examples 22 and 23 are applied to high-resolution X-ray imaging, such as... Figure 22 , Figure 23 , Figure 24 As shown, under X-ray irradiation (20-50 keV, 4W), the test results indicate that the NPPZnBr4 obtained in Example 22 of this invention contains 75% Mn. 2+ Scintillator thin films can display chip patterns ( Figure 22 ), standard lead plate ( Figure 23 ) and capsules ( Figure 24 Clear imaging of three types of objects is achieved by... Figure 22 It can be seen that NPPZnBr4: 75%Mn 2+ The imaging resolution of the scintillator thin film reaches 16 line pairs per millimeter (lp / mm). From Figure 21 It can be seen that, under the same test conditions, the NPPZnBr4: 75%Mn obtained in Example 22 of this invention... 2+ The light yield of the scintillator thin film is 24,748 photons MeV. -1 (Specific values ​​are obtained through comparison of integrated areas. Bismuth germanate (BGO) is used as a commercial standard comparison sample, with a default photoyield of 8,000 photons MeV.) -1 The NPPZnBr4 obtained in Example 22: 75% Mn 2+ The light yield of the scintillator thin film is 8000 * 3.0935 = 24748 photonsMeV. -1 ).

[0140] The radiation stability of zinc-based halide scintillator thin films under continuous X-ray irradiation is as follows: Figure 20 As shown, after 30 cycles of continuous X-ray irradiation for 30 seconds each, the normalized intensity of the thin film under X-ray irradiation changes very little. Therefore, the flexible scintillator thin film prepared by this invention exhibits excellent radiation stability under continuous X-ray irradiation.

[0141] Comparative Example 1 (CN119020020A): A zero-dimensional organozinc-based halide scintillator material; Comparative Example 2 (CN119019260A): An organic-inorganic hybrid zirconium halide scintillator material, its preparation method and application; Comparative Example 3 (CN119349644A): Cadmium-based metal halide nanocrystalline scintillator material doped with divalent manganese ions, its preparation method and application; The scintillator material of the present invention is compared with the scintillator material for which our team has filed patents, as shown in Table 1: Table 1 quantum efficiency 87.67% 13.18% 13.5% 20.6% Through comparison, we found that the scintillator material of the present invention has a significantly higher quantum efficiency 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 lifespan of the device and making it more energy-efficient in practical applications.

[0142] Summarize Highly quantum-efficient luminescent materials play a crucial role in display technology, lighting, bioimaging, energy conversion, photocatalysis, and sensing by enhancing luminescence performance, reducing energy consumption, and improving device sensitivity and stability. This characteristic makes them indispensable key materials in modern technological development.

[0143] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material doped with metal cations, characterized in that, The scintillator material has the chemical formula NPPZnBr4 : x%Mn 2+ The compound in which NPP is N-phenylpiperazine and Zn is divalent zinc ion Zn 2+ ; x%Mn 2+ x=75; The scintillator material of NPPZnBr4:75%Mn²⁺ is triclinic and has a P1 space group structure.

2. A method for preparing a zero-dimensional organic-inorganic hybrid zinc halide scintillator material doped with metal cations as described in claim 1, characterized in that, Includes the following steps: (1) The weighed piperazine compound and bromide are added to a mixed solution containing anhydrous ethanol and hydrobromic acid, and stirred thoroughly at room temperature to dissolve them, so as to obtain a saturated precursor solution. The piperazine compound is N-phenylpiperazine, and the bromide includes zinc bromide and manganese bromide. (2) The precursor solution obtained in step (1) was allowed to react at room temperature, filtered, centrifuged, washed, and dried to obtain the product with the general chemical formula NPPZnBr4: x %Mn 2+ Zero-dimensional organic-inorganic hybrid zinc-based halide scintillator microcrystals doped with metal cations.

3. The method for preparing the zero-dimensional organic-inorganic hybrid zinc-based halide scintillator material doped with metal cations as described in claim 2, characterized in that, In step (1), the molar ratio of the piperazine compound to the bromide is 3:1 to 1:1, the volume ratio of anhydrous ethanol to hydrobromic acid in the mixed solution is 5:1 to 20:1, the concentration of the hydrobromic acid is 68.85 wt%, and the total concentration of the mixture of piperazine compound and bromide in the precursor solution is 0.05 to 4 mol / L.

4. A scintillator film material, wherein the zero-dimensional organic-inorganic hybrid zinc halide scintillator material doped with metal cations as described in claim 1 is formed into a thin film.

5. A method for preparing a scintillator film material, used to prepare the scintillator film material as described in claim 4, characterized in that, Includes the following steps: (1) The zero-dimensional organic-inorganic hybrid zinc halide scintillator microcrystals doped with metal cations are washed clean and dried, and then dispersed in an organic solvent to form a scintillator dispersion. (2) Dissolve the polymer in an organic solvent to obtain a polymer solution. The polymer is one of polystyrene, polyvinylidene fluoride or polymethyl methacrylate. 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. Mix the scintillator dispersion obtained in step (1) with the polymer solution and stir evenly. Coat the mixture on a substrate and dry it to obtain a transparent scintillator film.

6. The method for preparing the scintillator film material as described in claim 5, characterized in that, In step (1), the solvent used to rinse the scintillator microcrystals is a mixed solution of any one or more of dimethyl sulfoxide, N,N-dimethylformamide, n-hexane, and anhydrous ethanol, and the organic solvent used to disperse the scintillator microcrystals is toluene.

7. The application of the zero-dimensional organic-inorganic hybrid zinc halide scintillator material doped with metal cations as described in claim 1 in X-ray medical imaging, non-destructive testing and industrial flaw detection.

Images