Organic-inorganic hybrid zero-dimensional antimony-based halide scintillator and preparation method thereof

Abstract

The present application relates to an organic-inorganic hybrid zero-dimensional antimony-based halide scintillator and a preparation method thereof, and provides an organic-inorganic hybrid zero-dimensional antimony-based halide scintillator having the following general composition formula: A2SbX5·DMF, wherein: A=PPh4 + ; X=Br; DMF is N,N-dimethylformamide, PPh4 + The scintillator is a tetraphenylphosphine cation, wherein the scintillator is a single crystal material. The scintillator composition has a significant solvation effect and has excellent photoluminescence and irradiation luminescence properties, showing important application prospects in X-ray imaging fields such as anti-counterfeiting, medical imaging, and security inspection equipment.

Description

Technical Field

[0001] The present application belongs to the field of photoluminescence and radiation detection technology, and relates to the composition, preparation method and application of a novel organic-inorganic hybrid zero-dimensional antimony-based halide scintillator, and specifically to the composition, preparation method and application of an organic-inorganic hybrid zero-dimensional antimony-based halide scintillator with X-ray response. Background Art

[0002] Scintillators absorb high-energy X-rays and gamma-rays and convert the absorbed energy into low-energy visible light. They are widely used in medical diagnosis, quality and safety inspections, and other fields. Currently, commercially available X-ray scintillators include thallium-doped cesium iodide (CsI:Tl) crystals / thin films, gadolinium oxysulfide (Gd2O2S:Pr), and cadmium tungstate (CdWO4) single crystals. While these materials offer high light yields, they still suffer from complex manufacturing processes, high afterglow, high toxicity, and high manufacturing costs.

[0003] Zero-dimensional organic-inorganic hybrid metal halides have gradually attracted attention in the field of X-ray imaging due to their excellent physical and luminescent properties, such as non-deliquescent properties, high stability, lack of self-absorption, and high luminescence quantum efficiency. Environmentally friendly, lead-free metal halide materials such as Sn(II), Cu(I), and Mn(II) have attracted significant attention as an emerging class of luminescent materials due to their excellent optical properties, including near-100% photoluminescence quantum efficiency, large Stokes shift, and reversible photoluminescence. However, Sn(II) is easily oxidized to Sn(IV), resulting in poor stability of these materials. The luminescence of manganese complexes typically originates from inherently spin-orbit-forbidden dd transitions, resulting in luminescence lifetimes of up to several milliseconds, which cannot meet the requirements of fast X-ray scintillation response.

[0004] In recent years, organic-inorganic hybrid antimony-based halides have been widely studied in the field of optoelectronic devices such as light-emitting displays. 2+ Outer electron structure, hybrid antimony-based halides show short-life high-efficiency luminescence. Sb 3+ Typically formed in zero-dimensional structures: [SbX5] 2- Pyramid and [SbX6] 3- Octahedral. Currently, research on organic-inorganic hybrid antimony-based materials is limited, with most focusing on optical properties, lighting, and light-emitting diodes, while research on their radiation detection properties is limited. The preparation and study of organic-inorganic hybrid antimony-based halide single crystals with X-ray response is of great significance in X-ray imaging fields such as medical imaging and security inspection.

[0005] Therefore, there is an urgent need in this field to develop new organic-inorganic hybrid zero-dimensional antimony-based halide scintillators with X-ray response, so as to meet the higher performance requirements put forward in X-ray imaging fields such as medical imaging and security inspection. Summary of the Invention

[0006] The present application provides an organic-inorganic hybrid zero-dimensional antimony-based halide scintillator and a preparation method thereof that can be widely used in X-ray imaging fields such as medical imaging and security inspection, and optimizes its luminescence and scintillation properties through the unique solvation effect of the compound, thereby meeting the higher performance requirements put forward in X-ray imaging fields such as medical imaging and security inspection.

[0007] According to the first aspect of the present application, an organic-inorganic hybrid zero-dimensional antimony-based halide scintillator is provided, which has the following general composition formula:

[0008] A2SbX5·DMF, where:

[0009] A=PPh4 + ;

[0010] X=Br;

[0011] DMF is N,N-dimethylformamide, PPh4 + is a tetraphenylphosphine cation,

[0012] Wherein, the scintillator is a single crystal material.

[0013] In a preferred embodiment, the scintillator has a zero-dimensional halide perovskite crystal structure consisting of isolated antimony halide polyhedra and organic cations.

[0014] According to a second aspect of the present application, a method for preparing the above-mentioned organic-inorganic hybrid zero-dimensional antimony-based halide scintillator is provided, the method comprising the following steps:

[0015] a. According to the general stoichiometric ratio of the composition formula, a mixture of an organic salt AX and an inorganic antimony halide salt SbX3 was added to DMF and heated with stirring until completely dissolved to form a transparent and clear precursor solution;

[0016] b. Diffusing a low-boiling-point, volatile solvent into the precursor solution obtained in step a, the product precipitates from the solution after diffusion to form a single crystal material, collecting the product, washing it, and drying it, wherein the first glass bottle containing the precursor solution is sealed with sealing paper with small holes and placed in a second glass bottle, and the low-boiling-point, volatile solvent is injected into the second glass bottle, and then the second glass bottle is sealed.

[0017] In a preferred embodiment, in step a, heating to 60-75° C. is performed in a glove box with an inert atmosphere.

[0018] In another preferred embodiment, in step a, the inert atmosphere comprises N2 atmosphere, which is heated to 70°C.

[0019] In another preferred embodiment, in step b, the low-boiling-point, volatile solvent includes methyl tert-butyl ether (MTBE), diethyl ether, or acetone; the sealing paper is tin foil; and the volume of the second glass bottle is three times or more than that of the first glass bottle.

[0020] In another preferred embodiment, in step b, the diffusion temperature is 25-35°C.

[0021] In another preferred embodiment, in step b, the product is washed 2-3 times with MTBE, toluene, ethanol, n-hexane or diethyl ether.

[0022] In another preferred embodiment, in step b, the drying comprises natural air drying at a drying temperature of 25-40°C.

[0023] According to a third aspect of the present application, there is provided an application of the above-mentioned organic-inorganic hybrid zero-dimensional antimony-based halide scintillator in X-ray imaging, including applications in anti-counterfeiting, medical imaging and security inspection equipment.

[0024] Beneficial effects: The organic-inorganic hybrid zero-dimensional antimony-based halide scintillator of the present application can be prepared by a low-cost solution method, and its special solvation effect can optimize its luminescence performance by regulating the metal polyhedron configuration by changing the reverse solvent; its luminescence band is closer to infrared luminescence. Due to the lower energy transfer emission, the near-infrared luminophore can use a host material with a smaller band gap, thereby reducing the energy required to generate electron-hole pairs in the scintillation mechanism, thereby reducing the inherent limitation of the scintillation efficiency; it has excellent photoluminescence performance and irradiation luminescence characteristics, and has important application prospects in X-ray imaging fields such as anti-counterfeiting, medical imaging and security equipment.

[0025] These and other features and advantages will become apparent from reading the following detailed description and referring to the associated drawings.It is to be understood that both the foregoing general description and the following detailed description are illustrative only and are not restrictive of the aspects claimed. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a physical picture of the (PPh4)2SbBr5·DMF scintillator prepared in Example 1 of the present application under natural light.

[0027] Figure 2 This is a physical picture of (PPh4)2SbBr5 prepared in Comparative Example 1 of this application under natural light.

[0028] Figure 3 This is a schematic diagram of the crystal structure of the (PPh4)2SbBr5·DMF scintillator prepared in Example 1 of the present application.

[0029] Figure 4 This is a schematic diagram of the crystal structure of the (PPh4)2SbBr5 scintillator prepared in Comparative Example 1 of the present application.

[0030] Figure 5 This is the photoluminescence spectrum of the (PPh4)2SbBr5·DMF scintillator prepared in Example 1 of the present application.

[0031] Figure 6 This is the photoluminescence spectrum of the (PPh4)2SbBr5 scintillator prepared in Comparative Example 1 of the present application.

[0032] Figure 7 This is a comparison of the photoluminescence spectra of the scintillators prepared in Example 1 and Comparative Example 1 of the present application.

[0033] Figure 8 This is the X-ray excitation emission spectrum of the (PPh4)2SbBr5·DMF scintillator prepared in Example 1 of the present application.

[0034] Figure 9 This is the X-ray excitation emission spectrum of the (PPh4)2SbBr5 scintillator prepared in Comparative Example 1 of the present application.

[0035] Figure 10 This is a comparison of the X-ray excitation emission spectra of the scintillators prepared in Example 1 and Comparative Example 1 of the present application. DETAILED DESCRIPTION

[0036] The present application is described in detail below with reference to the accompanying drawings, and the features of the present application will be further revealed in the following specific description.

[0037] " Scope " disclosed herein is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range. The scope limited in this way can be to include end value or not include end value, and can be arbitrarily combined, that is, any lower limit can form a scope with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for a particular parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range value 1 and 2 are listed, and if the maximum range value 3,4 and 5 are listed, then the following range can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range " ab " represents the abbreviation of any real number combination between a and b, wherein a and b are all real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0038] In this application, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution. In this application, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0039] In this application, unless otherwise specified, the terms "include" and "comprising" used herein may be open-ended or closed-ended. For example, "include" and "comprising" may mean that other components not listed may also be included or that only the listed components are included.

[0040] In the description herein, unless otherwise indicated, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0041] In view of the fact that there is still little research on organic-inorganic hybrid antimony-based materials in the existing technology, and most of them focus on the fields of optical properties, lighting and light-emitting diodes, and there is little research on their radiation detection performance, this application uses organic salts and antimony halide inorganic salts as raw materials, and prepares a new type of organic-inorganic hybrid antimony-based halide scintillation crystal with X-ray response through a low-cost solution method, and discovers its unique solvation effect. Starting from the preparation method, by selecting a suitable solvent to change the crystal structure of the product, it has excellent photoluminescence performance and irradiation luminescence characteristics, and has important application prospects in X-ray imaging fields such as anti-counterfeiting, medical imaging and security equipment.

[0042] Organic-inorganic hybrid zero-dimensional antimony-based halide scintillator

[0043] In a first aspect of the present application, an organic-inorganic hybrid zero-dimensional antimony-based halide scintillator is provided, which has the following general composition formula:

[0044] A2SbX5·DMF, where:

[0045] A=PPh4 + ;

[0046] X=Br;

[0047] DMF is N,N-dimethylformamide, PPh4 + is a tetraphenylphosphine cation,

[0048] Wherein, the scintillator is a single crystal material.

[0049] In the present application, the scintillator has a zero-dimensional halide perovskite crystal structure composed of isolated antimony halide polyhedra and organic cations.

[0050] In the present application, the scintillator material belongs to the triclinic crystal system, the P-1 space group, and the metal halide polyhedron in the crystal structure is pyramidal.

[0051] Preparation method of organic-inorganic hybrid zero-dimensional antimony-based halide scintillator

[0052] In a second aspect of the present application, a method for preparing the above-mentioned organic-inorganic hybrid zero-dimensional antimony-based halide scintillator is provided, the method comprising the following steps:

[0053] a. According to the general stoichiometric ratio of the composition formula, a mixture of an organic salt AX and an inorganic antimony halide salt SbX3 was added to DMF and heated with stirring until completely dissolved to form a transparent and clear precursor solution;

[0054] b. Diffusing a low-boiling-point, volatile solvent into the precursor solution obtained in step a, the product precipitates from the solution after diffusion to form a single crystal material, collecting the product, washing it, and drying it, wherein the first glass bottle containing the precursor solution is sealed with sealing paper with small holes and placed in a second glass bottle, and the low-boiling-point, volatile solvent is injected into the second glass bottle, and then the second glass bottle is sealed.

[0055] In the present application, in step a, heating to 60-75° C. is performed in a glove box under an inert atmosphere.

[0056] In the present application, in step a, the inert atmosphere includes N2 atmosphere, which is heated to 70°C.

[0057] In the present application, in step b, the low boiling point, volatile solvent includes methyl tert-butyl ether MTBE, diethyl ether or acetone.

[0058] In the present application, in step b, the sealing paper is tin foil.

[0059] In the present application, in step b, the volume of the second glass bottle is 3 times or more than the volume of the first glass bottle.

[0060] In the present application, in step b, the diffusion temperature is 25-35°C.

[0061] In the present application, in step b, the product is washed 2-3 times with MTBE, toluene, ethanol, n-hexane or diethyl ether.

[0062] In the present application, in step b, the drying includes natural air drying at a drying temperature of 25-40°C.

[0063] In the present application, the solvation effect optimizes the photoluminescence and irradiation luminescence properties of the product.

[0064] Applications of organic-inorganic hybrid zero-dimensional antimony-based halide scintillators

[0065] In a third aspect of the present application, there is provided an application of the above-mentioned organic-inorganic hybrid zero-dimensional antimony-based halide scintillator in X-ray imaging, including applications in anti-counterfeiting, medical imaging and security inspection equipment.

[0066] The present invention will be further described below with reference to specific examples. It should be understood that these examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention.

[0067] Example 1: Preparation of (PPh4)2SbBr5·DMF

[0068] 2 mmol of tetraphenylphosphonium bromide (PPh4Br) and 1 mmol of antimony tribromide (SbBr3) were weighed and mixed according to the stoichiometric ratio of the chemical formula (PPh4)2SbBr5·DMF. The mixture was dissolved in 3 mL of DMF and heated to 70°C in a glove box under an N2 atmosphere. Stirring was performed for 6 hours to form a transparent precursor solution. The clarified precursor solution was then filtered through a 0.22 μm filter to prevent impurities from affecting crystal nucleation. The vial containing the clarified filtrate was sealed with tin foil with small holes and placed in a larger vial with a volume three times that of the vial. 10 mL of MTBE was then injected into the larger vial, sealed, and allowed to stand for one week to produce yellow single crystals. The single crystal was removed, rinsed three times with MTBE, and then dried in a desiccator at 40°C to obtain a (PPh4)2SbBr5·DMF scintillator single crystal. Figure 1 The actual (PPh4)2SbBr5·DMF scintillator single crystal under natural light is shown.

[0069] Comparative Example 1: Preparation of (PPh4)2SbBr5

[0070] According to the stoichiometric ratio of the chemical formula (PPh4)2SbBr5, 2mmol PPh4Br and 1mmol SbBr3 were weighed and mixed, heated to 70°C in a glove box with an N2 atmosphere, and stirred for 6 hours to form a transparent precursor solution. The clarified precursor solution was filtered with a 0.22μm filter to prevent impurities from affecting the formation of crystal nuclei. The open vial containing the filtrate was then placed in a clean large bottle with a volume three times that of the small vial. 10mL of acetone was added to the large bottle, which was sealed and allowed to stand for a week to obtain a single crystal. The single crystal was removed, washed with acetone three times, and then dried in a drying oven at 40°C. Figure 2 The actual (PPh4)2SbBr5 single crystal under natural light is shown.

[0071] Figure 3 This is a schematic diagram of the crystal structure of the (PPh4)2SbBr5·DMF scintillator prepared in Example 1 of the present application. Figure 4 This is a schematic diagram of the crystal structure of the (PPh4)2SbBr5 scintillator prepared in Comparative Example 1 of this application. Figure 3 and Figure 4 It can be seen that the (PPh4)2SbBr5·DMF scintillator prepared in Example 1 has DMF solvent molecules entering the crystal lattice, and the solvation effect changes the metal halide polyhedron.

[0072] Figure 5 This is the photoluminescence spectrum of the (PPh4)2SbBr5·DMF scintillator prepared in Example 1 of the present application. Figure 6This is the photoluminescence spectrum of the (PPh4)2SbBr5 scintillator prepared in Comparative Example 1 of the present application. Figure 7 This is a comparison of the photoluminescence spectra of the scintillators prepared in Example 1 and Comparative Example 1 of the present application. Figure 7 It can be seen that the photoluminescence intensity of the scintillator prepared in Example 1 is higher than that in Comparative Example 1 under the same test conditions.

[0073] Figure 8 This is the X-ray excitation emission spectrum of the (PPh4)2SbBr5·DMF scintillator prepared in Example 1 of the present application. Figure 9 This is the X-ray excitation emission spectrum of the (PPh4)2SbBr5 scintillator prepared in Comparative Example 1 of the present application. Figure 10 This is a comparison of the X-ray excitation emission spectra of the scintillators prepared in Example 1 and Comparative Example 1 of the present application. Figure 10 It can be seen that the X-ray excitation emission intensity of the scintillator prepared in Example 1 is higher than that in Comparative Example 1 under the same test conditions.

[0074] Finally, it is necessary to explain here that the above embodiments are only used to further illustrate the technical solution of the present invention in detail and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by technicians in this field based on the above content of the present invention all fall within the scope of protection of the present invention.

Claims

1. An organic-inorganic hybrid zero-dimensional antimony-based halide scintillator, characterized in that: It has the following general formula: A2SbX5•DMF, where: A = PPh4 + ; X = Br; DMF is N,N -dimethylformamide, PPh4 + is a tetraphenylphosphine cation, The scintillator is a single crystal material, the crystal system to which the scintillator material belongs is the triclinic system, the space group to which it belongs is the P-1 space group, and the metal halide polyhedron in the crystal structure is a pyramid shape.

2. The organic-inorganic hybrid zero-dimensional antimony-based halide scintillator according to claim 1, characterized in that: The scintillator has a zero-dimensional halide perovskite crystal structure composed of isolated antimony halide polyhedra and organic cations.

3. A method for preparing the organic-inorganic hybrid zero-dimensional antimony-based halide scintillator according to claim 1 or 2, characterized in that: The method comprises the following steps: a composition according to the general stoichiometric ratio weighed organic salt AX and antimony halide inorganic salt SbX3 mixture was added to DMF, heated with stirring until completely dissolved to form a transparent clear precursor solution; b. Diffusing a low-boiling, volatile solvent into the precursor solution obtained in step a, the product precipitates from the solution to form a single crystal. The product is collected, washed, and dried. The first glass bottle containing the precursor solution is sealed with a paper sealant punctured with small holes and placed in a second glass bottle. The low-boiling, volatile solvent is then injected into the second glass bottle, and the second glass bottle is then sealed.

4. The method according to claim 3, wherein In step a, heat to 60-75°C in an inert atmosphere glove box.

5. The method according to claim 4, wherein In step a, the inert atmosphere includes N2 atmosphere, which is heated to 70°C.

6. The method according to claim 3, wherein In step b, the low-boiling-point, volatile solvent includes methyl tert-butyl ether (MTBE), diethyl ether, or acetone; the sealing paper is tin foil; and the volume of the second glass bottle is three times or greater than that of the first glass bottle.

7. The method according to claim 3, wherein In step b, the diffusion temperature is 25-35°C.

8. The method according to claim 3, wherein In step b, the product is washed 2-3 times with MTBE, toluene, ethanol, n-hexane or diethyl ether.

9. The method according to claim 3, wherein In step b, the drying includes natural air drying at a drying temperature of 25-40°C.

10. Use of the organic-inorganic hybrid zero-dimensional antimony-based halide scintillator according to claim 1 or 2 in X-ray imaging, characterized in that: The applications include anti-counterfeiting, medical imaging and security inspection equipment, but do not involve applications in disease diagnosis and treatment.

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