Zero-dimensional organic-inorganic manganese-based halide scintillating material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of luminescent materials, in particular to a zero-dimensional organic-inorganic manganese-based halide scintillating material and a preparation method and application thereof.The preparation method comprises the following steps that manganese bromide and diisopropyl ammonium bromide are mixed and then dissolved in a mixed solvent, heating and stirring are conducted, and a precursor solution is obtained; heating after filtering, preserving heat at 60-100 DEG C, and crystallizing to separate out yellow crystals; and washing the yellow crystal with isopropanol, carrying out suction filtration, and drying to obtain the zero-dimensional organic-inorganic manganese-based halide scintillating material. According to the zero-dimensional organic-inorganic manganese-based halide scintillation material and the preparation method and application thereof, the obtained scintillation material emits bright green light under X-ray excitation, the detection limit is far lower than the standard dosage of X-ray diagnosis, and the zero-dimensional organic-inorganic manganese-based halide scintillation material has wide application prospects in the fields of high-energy physics, security inspection, medical detection and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and in particular to a zero-dimensional organic-inorganic manganese-based halide scintillation material and a preparation method and application thereof. Background Art

[0002] Scintillator is a kind of energy conversion luminescent material with the characteristics of scintillation and luminescence. As the core part of the radiation detection system, it plays an important role in medical imaging, high energy physics, environmental monitoring and security inspection. 12 :Ce(YAG:Ce)、Gd2O3:Eu、CsI:Tl、Bi4Ge3O 12 Inorganic crystals such as BGO are already quite mature, but they have problems such as high energy consumption for growth, difficulty in processing and high cost. Pb-based halides such as CsPbBr3 have excellent X-ray absorption ability and can be grown by low-cost solution methods, but the toxicity and environmental protection issues of the Pb element fundamentally restrict its commercial application potential.

[0003] Organic-inorganic hybrid metal halides have the advantages of high light yield and adjustable emission spectrum by introducing large organic cations to replace smaller alkali metal ions. They have become a hot material in the field of scintillators. Among them, Mn-based organic-inorganic hybrid halides can well avoid the toxicity problem of Pb-based halides. However, most of the Mn-based organic-inorganic hybrid halides are currently grown by solution method using DMF, dichloromethane, γ-butyrolactone, etc., which are highly toxic and costly.

[0004] Therefore, it is of great significance to develop a new type of environmentally friendly organic-inorganic manganese-based halide material and a corresponding new scintillating material growth method to achieve green material growth and the material itself, while being environmentally friendly and having good scintillation ability for high-energy radiation such as X-rays. Summary of the invention

[0005] The purpose of the present invention is to provide a zero-dimensional organic-inorganic manganese-based halide scintillating material and a preparation method and application thereof. The obtained zero-dimensional organic-inorganic manganese-based halide scintillating material emits bright green light under X-rays and has a low X-ray dose detection limit. Deionized water is added to the mixed solution as a solvent for growth during preparation, which has low cost and good environmental protection. It can be used to solve the problems of high cost and strong toxicity of organic solvents in conventional halide solution growth.

[0006] To achieve the above object, the present invention provides a zero-dimensional organic-inorganic manganese-based halide scintillating material, the chemical formula of which is (C6H 16 N)2MnBr4.

[0007] Preferably, the zero-dimensional organic inorganic manganese-based halide scintillation material is a bulk single crystal or a solid powder.

[0008] Preferably, the zero-dimensional organic-inorganic manganese-based halide scintillator single crystal has a space group of C1c1, unit cell parameters a=29.0299(19) Å, b=14.5711(9) Å, c=11.6005(7) Å, α= 90°, β=112.864(2)°, γ=90°, unit cell volume V =4521.4(5)Å 3 , the crystal structure belongs to monoclinic system.

[0009] The above-mentioned preparation method of a zero-dimensional organic inorganic manganese-based halide scintillation material includes the following steps: S1. Mix manganese bromide and diisopropyl ammonium bromide and dissolve in a mixed solvent, heat and stir to obtain a precursor solution; S2. The precursor solution in S1 is filtered and heated, and the yellow crystal is precipitated by insulated crystals at 60-100°C; S3. The yellow crystal obtained in S2 was washed with isopropanol, dried after suction filtration, and obtained a zero-dimensional organic inorganic manganese-based halide scintillation material.

[0010] Preferably, in S1, the molar ratio of manganese bromide and diisopropyl ammonium bromide is 1:1-2.

[0011] More preferably, the concentration of manganese bromide in the precursor solution is 0.83-1.25M.

[0012] Preferably, in S1, the mixed solvent is obtained by mixing deionized water and hydrobromic acid aqueous solution in a volume ratio of 4:1.

[0013] More preferably, in S1, the deionized water resistivity is 18.25 MΩ•cm.

[0014] Preferably, in S1, the temperature of heating and stirring is 40-60°C, and the time of heating and stirring is 0.5-1h.

[0015] Preferably, in S2, the heating device is a heat table or an oven, and the crystallization time is 1-3d.

[0016] Preferably, in S2, the filtration is performed using a needle tube and an aqueous filter head.

[0017] The above-mentioned zero-dimensional organic inorganic manganese-based halide scintillation materials are used in high-energy particle detection, imaging imaging or dose monitoring.

[0018] Therefore, the present invention adopts the above-mentioned zero-dimensional organic inorganic manganese-based halide scintillation material and its preparation method and application, and its beneficial effects are: 1. The zero-dimensional organic-inorganic manganese-based halide scintillating material provided by the present invention has excellent scintillation performance under different doses of X-ray excitation, and has broad application prospects in the fields of high-energy physics, security inspection, medical testing, etc. The detection limit of X-ray dose is determined to be 25.23nGy. air s -1 , which is the standard dose rate for routine medical diagnostic doses (5.5μGy air s -1 ) 1 / 218; 2. The preparation method provided by the present invention and the mixed solvent used are green and environmentally friendly, non-toxic, and inexpensive. The entire preparation process has mild conditions and simple operation, does not involve highly toxic, highly polluting, and highly volatile organic reagents, and has a high yield and good crystallinity. To a certain extent, it solves the current problems of high cost and difficult preparation of X-ray scintillator materials.

[0019] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 is a crystal structure diagram of the zero-dimensional organic-inorganic manganese-based halide scintillating material in Example 1 of the present invention; Figure 2 The powder XRD and single crystal simulated XRD patterns of the zero-dimensional organic-inorganic manganese-based halide scintillating material in Example 1 of the present invention; Figure 3 is a photoluminescence spectrum and lifetime decay curve of the zero-dimensional organic-inorganic manganese-based halide scintillating material in Example 1 of the present invention, in, Figure 3 a in the figure is the photoluminescence spectrum. Figure 3 b in the figure is the life attenuation curve; Figure 4 is a linear curve diagram of the X-ray luminescence spectrum of the zero-dimensional organic-inorganic manganese-based halide scintillating material and the X-ray dose rate at a low dose in Example 2 of the present invention, in, Figure 4 a in the figure is the X-ray luminescence spectrum. Figure 4 b in FIG. 1 is a linear curve of the X-ray dose rate at low dose. DETAILED DESCRIPTION

[0021] The present invention is further described below in conjunction with the accompanying drawings and embodiments. Unless otherwise defined, the technical terms or scientific terms used in the present invention should be the common meanings understood by people with ordinary skills in the field to which the present invention belongs. The above-mentioned features or features mentioned in the specific examples mentioned in the present invention can be combined arbitrarily, and these specific embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0022] Unless otherwise specified, the raw materials in each example of this application were purchased through commercial channels, among which diisopropylammonium bromide, manganese bromide, and 48 wt.% hydrobromic acid aqueous solution were purchased from the official website of Aladdin Platform Reagents; deionized water was prepared using a laboratory-grade deionized water purifier (Shanghai Zhiang).

[0023] Example 1 A method for preparing a zero-dimensional organic-inorganic manganese-based halide scintillating material comprises the following steps: S1. Mix 1.074 g of manganese bromide and 0.9106 g of diisopropylammonium bromide, dissolve in 5 mL of a mixed solvent (deionized water and 48 wt.% hydrobromic acid aqueous solution mixed in a volume ratio of 4:1), heat and stir at 40° C. for 1 h to obtain a precursor solution; S2. Filter the precursor solution in S1 and heat it in an oven at 80°C for 1 day to crystallize yellow crystals.

[0024] S3. Wash the yellow crystals obtained in S2 with isopropanol, filter and dry in a vacuum drying oven at 40° C. for 12 h to obtain a zero-dimensional organic-inorganic manganese-based halide scintillating material.

[0025] Example 2 A method for preparing a zero-dimensional organic-inorganic manganese-based halide scintillating material comprises the following steps: S1. Mix 1.074 g of manganese bromide and 1.8212 g of diisopropylammonium bromide, dissolve in 6.25 mL of a mixed solvent (deionized water and 48 wt.% hydrobromic acid aqueous solution mixed in a volume ratio of 4:1), heat and stir at 40° C. for 1 h to obtain a precursor solution; S2, filter the precursor solution in S1 and heat it in an oven at 66°C for 3 days to crystallize yellow crystals; S3. Wash the yellow crystals obtained in S2 with isopropanol, filter and dry to obtain a zero-dimensional organic-inorganic manganese-based halide scintillating material.

[0026] Test Example 1 a. X-ray single crystal diffraction test The zero-dimensional organic-inorganic manganese-based halide scintillating material in Example 1 was subjected to X-ray single crystal diffraction test on a Bruker D8 Venture with luS Diamond (Mo) and luS 3.0 (Cu) single crystal diffractometer, with a Cu target at 50 kV and 11 mA. The results are shown in FIG. Figure 1As shown, the crystal space group is C1c1, the unit cell parameters are a=29.0299(19)Å, b=14.5711(9)Å, c=11.6005(7)Å, α=90°, β=112.864(2)°, γ=90°, and the unit cell volume is V=4521.4(5)Å 3 , the crystal structure belongs to monoclinic system.

[0027] b. Powder XRD test The zero-dimensional organic-inorganic manganese-based halide scintillating material in Example 1 was subjected to powder XRD testing (RigakuSmartLab SE, Japan). The results are as follows: Figure 2 As shown, it can be seen that the crystal plane diffraction peak of the zero-dimensional organic-inorganic manganese-based halide scintillating material in Example 1 can be compared with the single crystal XRD simulation data results.

[0028] c. Photoluminescence spectrum test and time-resolved photoluminescence spectrum test The zero-dimensional organic-inorganic manganese-based halide scintillating material in Example 1 was subjected to a photoluminescence spectrum test and a time-resolved photoluminescence spectrum test (FLS 980). Figure 3 As shown in a, the excitation light source is 375nm, the photoluminescence peak is at 526nm (green), and the half-height width is 68nm. Figure 3 As shown in (b), the time-resolved photoluminescence spectrum was fitted using a single exponential, and the decay time was 315.94 μs.

[0029] d. X-ray scintillation performance test The zero-dimensional organic-inorganic manganese-based halide scintillating material in Example 2 was tested for its X-ray scintillation performance (MOXTEK MAGPRO TUB00154-9I-06). Figure 4 As shown in a in Figure 1, the luminescence peak under X-ray is at 525nm and the half-height width is 62nm. Figure 4 As shown in b, at 458nGy air s -1 , 458nGy air s -1 , 343.5nGy air s -1 , 229nGy air s -1 , 114nGy air s -1 , 57nGy air s -1 The five low doses showed good linear response and the detection limit was 25.23 nGy. air s -1 , which is much lower than the standard dose rate of conventional medical diagnosis dose (5.5μGy airs -1 ).

[0030] Therefore, the present invention adopts the above-mentioned zero-dimensional organic-inorganic manganese-based halide scintillating material and its preparation method and application, which has excellent scintillation performance under different doses of X-ray excitation and has broad application prospects in the fields of high-energy physics, security inspection, medical testing, etc.

[0031] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A zero-dimensional organic-inorganic manganese-based halide scintillating material, characterized in that: The chemical formula of the zero-dimensional organic-inorganic manganese-based halide scintillating material is (C6H 16 N)2MnBr4.

2. A method for preparing the zero-dimensional organic-inorganic manganese-based halide scintillating material according to claim 1, characterized in that: The following steps are involved: S1, mixing manganese bromide and diisopropylammonium bromide and dissolving them in a mixed solvent, heating and stirring to obtain a precursor solution; S2, filtering the precursor solution in S1 and heating it, keeping it warm at 60-100°C to crystallize yellow crystals; S3. Wash the yellow crystals obtained in S2 with isopropanol, filter and dry to obtain a zero-dimensional organic-inorganic manganese-based halide scintillating material.

3. The method for preparing a zero-dimensional organic-inorganic manganese-based halide scintillating material according to claim 2, characterized in that: In S1, the molar ratio of manganese bromide to diisopropylammonium bromide is 1:1-2.

4. The method for preparing a zero-dimensional organic-inorganic manganese-based halide scintillating material according to claim 2, characterized in that: In S1, the mixed solvent is obtained by mixing deionized water and hydrobromic acid aqueous solution in a volume ratio of 4:

1.

5. The method for preparing a zero-dimensional organic-inorganic manganese-based halide scintillating material according to claim 2, characterized in that: In S1, the temperature of heating and stirring is 40-60°C, and the time of heating and stirring is 0.5-1h.

6. The method for preparing a zero-dimensional organic-inorganic manganese-based halide scintillating material according to claim 2, characterized in that: In S2, the heating device is a hot table or an oven, and the crystallization time is 1-3 days.

7. The method for preparing a zero-dimensional organic-inorganic manganese-based halide scintillating material according to claim 2, characterized in that: In S2, filtration is performed using a syringe and a water filter tip.

8. An application of the zero-dimensional organic-inorganic manganese-based halide scintillating material as claimed in claim 1, characterized in that: Applications include high energy particle detection, imaging or dose monitoring.

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