A zero-dimensional organic-inorganic manganese-based halide scintillation material, its preparation method and application

Abstract

The present invention relates to the technical field of luminescent materials, and particularly to a zero-dimensional organic-inorganic manganese-based halide scintillation material, a preparation method thereof and an application thereof. The method comprises the following steps: mixing manganese bromide and diisopropylammonium bromide and dissolving them in a mixed solvent, heating and stirring to obtain a precursor solution; filtering and then heating, and holding the temperature at 60-100 °C for crystallization to precipitate yellow crystals; washing the yellow crystals with isopropanol, performing suction filtration and then drying to obtain the zero-dimensional organic-inorganic manganese-based halide scintillation material. By adopting the above-mentioned zero-dimensional organic-inorganic manganese-based halide scintillation material, preparation method thereof and application thereof, the obtained scintillation material emits bright green light under X-ray excitation, and the detection limit is far lower than the standard dose of X-ray diagnosis, and it has broad application prospects in the fields of high-energy physics, security inspection, medical detection, etc.

Description

Technical Field

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

[0002] A scintillator is an energy conversion luminescent material with the characteristic of scintillation luminescence. As the core part of a ray detection system, it plays an important role in fields such as medical imaging, high-energy physics, environmental monitoring, and security inspection. Traditional inorganic scintillators such as Y3Al5O 12 :Ce (YAG:Ce), Gd2O3:Eu, CsI:Tl, Bi4Ge3O 12 (BGO) and other inorganic crystals are already quite mature, but there are problems such as high growth energy consumption, difficult processing, and high cost. Pb-based halides such as CsPbBr3 have excellent X-ray absorption ability and can be grown by a low-cost solution method, but there are fundamental problems of the toxicity of Pb elements and environmental protection, which restrict their commercial application potential.

[0003] Organic-inorganic hybrid metal halides have the advantages of high light yield and adjustable emission spectrum by introducing large-volume organic cations to replace smaller alkali metal ions, and have currently become hot materials in the field of scintillators. Among them, Mn-based organic-inorganic hybrid halides can well avoid the toxicity problem of Pb-based ones, but at present, most of the solution growth of Mn-based organic-inorganic hybrid halides uses DMF, dichloromethane, γ-butyrolactone, etc., which are highly toxic and costly at the same time.

[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 method for growing scintillation materials to achieve the greening and environmental protection of material growth and the material itself, and at the same time the material has 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 scintillation material, a preparation method thereof, and an application thereof. The obtained zero-dimensional organic-inorganic manganese-based halide scintillation material emits bright green light under X-rays, and has a low X-ray dose detection limit. When preparing, deionized water is added as a solvent to the mixed solution for growth, which has low cost and good environmental protection, and can be used to solve the problems of high cost and strong toxicity of organic solvents in the growth of conventional halides in solution.

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

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

[0008] Preferably, the single crystal space group of the zero-dimensional organic-inorganic manganese-based halide scintillation material is C1c1, and 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 V = 4521.4(5) Å 3 , and the crystal structure belongs to the monoclinic system.

[0009] The preparation method of the above-mentioned zero-dimensional organic-inorganic manganese-based halide scintillation material includes the following steps:

[0010] S1. Mix manganese bromide and diisopropylammonium bromide and dissolve them in a mixed solvent, heat and stir to obtain a precursor solution;

[0011] S2. Filter the precursor solution in S1 and then heat it, and keep it at 60 - 100 °C for crystallization to precipitate yellow crystals;

[0012] S3. Wash the yellow crystals obtained in S2 with isopropanol, filter by suction and dry to obtain the zero-dimensional organic-inorganic manganese-based halide scintillation material.

[0013] Preferably, in S1, the molar ratio of manganese bromide to diisopropylammonium bromide is 1:1 - 2.

[0014] More preferably, the concentration of manganese bromide in the precursor solution is 0.83 - 1.25 M.

[0015] Preferably, in S1, the mixed solvent is obtained by mixing deionized water and hydrobromic acid aqueous solution in a volume ratio of 4:1.

[0016] More preferably, in S1, the resistivity of deionized water is 18.25 MΩ•cm.

[0017] Preferably, in S1, the temperature of heating and stirring is 40 - 60 °C, and the time of heating and stirring is 0.5 - 1 h.

[0018] Preferably, in S2, the heating equipment is a hot stage or an oven, and the crystallization time is 1 - 3 d.

[0019] Preferably, in S2, the filtration is carried out using a syringe and a water-based filter head.

[0020] The application of the above zero-dimensional organic-inorganic manganese-based halide scintillation material is in high-energy particle detection, imaging or dose monitoring.

[0021] Therefore, the present invention adopts the above-mentioned zero-dimensional organic-inorganic manganese-based halide scintillation material, its preparation method and application, and the beneficial effects are as follows:

[0022] 1. The zero-dimensional organic-inorganic manganese-based halide scintillation material provided by the present invention has excellent scintillation performance under X-ray excitation with different doses, and has broad application prospects in the fields of high-energy physics, security inspection, medical detection, etc. The X-ray dose detection limit is 25.23 nGy air s -1 , which is 1 / 218 of the standard dose rate (5.5 μGy air s -1 ) of the conventional medical diagnosis dose standard;

[0023] 2. The preparation method provided by the present invention and the mixed solvent used are green and environmentally friendly, non-toxic, low-cost, the whole preparation process has mild conditions, simple operation, does not involve highly toxic, highly polluting, highly volatile organic reagents, and has a high yield and good crystallinity, which solves to a certain extent the problems of high cost and difficult preparation of the current X-ray scintillator materials.

[0024] The technical solutions of the present invention will be further described in detail below through the drawings and examples. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is the crystal structure diagram of the zero-dimensional organic-inorganic manganese-based halide scintillation material in Example 1 of the present invention;

[0026] Figure 2 is the powder XRD and single crystal simulated XRD diagrams of the zero-dimensional organic-inorganic manganese-based halide scintillation material in Example 1 of the present invention;

[0027] Figure 3 is the photoluminescence spectrum and lifetime decay curve diagram of the zero-dimensional organic-inorganic manganese-based halide scintillation material in Example 1 of the present invention,

[0028] wherein, Figure 3 a in Figure 3 is the photoluminescence spectrum diagram,

[0029] Figure 4 is the X-ray luminescence spectrum and the linear curve diagram of the X-ray dose rate at low dose of the zero-dimensional organic-inorganic manganese-based halide scintillation material in Example 2 of the present invention,

[0030] wherein, Figure 4 a in Figure 4 is the X-ray luminescence spectrum diagram, DETAILED DESCRIPTION OF THE INVENTION

[0031] 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.

[0032] 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).

[0033] Example 1

[0034] A method for preparing a zero-dimensional organic-inorganic manganese-based halide scintillating material comprises the following steps:

[0035] 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;

[0036] S2. Filter the precursor solution in S1 and heat it in an oven at 80°C for 1 day to crystallize yellow crystals.

[0037] 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.

[0038] Example 2

[0039] A method for preparing a zero-dimensional organic-inorganic manganese-based halide scintillating material comprises the following steps:

[0040] 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;

[0041] S2, filter the precursor solution in S1 and heat it in an oven at 66°C for 3 days to crystallize yellow crystals;

[0042] 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.

[0043] Test Example 1

[0044] a, X-ray single crystal diffraction test

[0045] The zero-dimensional organic-inorganic manganese-based halide scintillation 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) type single crystal diffractometer, with Cu target at 50 kV and 11 mA. The results are as Figure 1 shown. The crystal space group is C1c1, and 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 V = 4521.4(5) Å 3 , and the crystal structure belongs to the monoclinic system.

[0046] b, Powder XRD test

[0047] The zero-dimensional organic-inorganic manganese-based halide scintillation material in Example 1 was subjected to powder XRD test (Rigaku SmartLab SE, Japan), and the results are as Figure 2 shown. It can be seen that the crystal plane diffraction peaks of the zero-dimensional organic-inorganic manganese-based halide scintillation material in Example 1 can be compared with the simulated data results of single crystal XRD.

[0048] c, Photoluminescence spectroscopy test and time-resolved photoluminescence spectroscopy test

[0049] The zero-dimensional organic-inorganic manganese-based halide scintillation material in Example 1 was subjected to photoluminescence spectroscopy test and time-resolved photoluminescence spectroscopy test (FLS 980). As shown in Figure 3 a, the excitation light source is 375 nm, the photoluminescence peak position is at 526 nm (green), and the full width at half maximum is 68 nm. As shown in Figure 3 b, the time-resolved photoluminescence spectrum uses single exponential fitting, and the decay time is 315.94 μs.

[0050] d, X-ray scintillation performance test

[0051] The zero-dimensional organic-inorganic manganese-based halide scintillation material in Example 2 was subjected to X-ray scintillation performance test (MOXTEK MAGPRO TUB00154-9I-06). As shown in Figure 4 a, the emission peak position under X-ray is at 525 nm, and the full width at half maximum is 62 nm. As shown in Figure 4 b, at 458 nGy air s -1 、458 nGy air s -1 、343.5 nGyair s -1 、229 nGy air s -1 、114 nGy air s -1 、57 nGy air s -1 exhibit good linear responses at five low doses, and the measured detection limit is 25.23 nGy air s -1 , far lower than the standard dose rate of conventional medical diagnostic doses (5.5 μGy air s -1 ).

[0052] Therefore, the present invention adopts the above-mentioned zero-dimensional organic-inorganic manganese-based halide scintillation material, its preparation method and application, which have excellent scintillation performance under X-ray excitation at different doses, and have broad application prospects in the fields of high-energy physics, security inspection, medical detection, etc.

[0053] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that they can still modify or equivalently replace the technical solutions of the present invention, and these modifications or equivalent replacements cannot make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A zero-dimensional organic-inorganic manganese-based halide scintillation material, characterized in that: The chemical formula of the zero-dimensional organic-inorganic manganese-based halide scintillation material is (C6H 16 N)2MnBr4; The crystal space group is C1c1, and 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 V = 4521.4(5) Å 3 , and the crystal structure belongs to the monoclinic system; The preparation method of the above-mentioned zero-dimensional organic-inorganic manganese-based halide scintillation material comprises the following steps: S1. Mix manganese bromide and diisopropylammonium bromide and dissolve them in a mixed solvent, then heat and stir to obtain a precursor solution; In S1, the molar ratio of manganese bromide to diisopropylammonium bromide is 1:1 - 2; In S1, the mixed solvent is obtained by mixing deionized water and hydrobromic acid aqueous solution according to a volume ratio of 4:1; S2. Filter the precursor solution in S1 and then heat it, and keep it at 60 - 100 °C for crystallization to precipitate yellow crystals; S3. Wash the yellow crystals obtained in S2 with isopropanol, filter by suction and then dry to obtain the zero-dimensional organic-inorganic manganese-based halide scintillation material.

2. The zero-dimensional organic-inorganic manganese-based halide scintillation material according to claim 1, wherein: In S1, the temperature of heating and stirring is 40 - 60 °C, and the time of heating and stirring is 0.5 - 1 h.

3. A zero-dimensional organic-inorganic manganese-based halide scintillation material according to claim 1, characterized in that: In S2, the heating equipment is a hot stage or an oven, and the crystallization time is 1 - 3 d.

4. A zero-dimensional organic-inorganic manganese-based halide scintillation material according to claim 1, characterized in that: In S2, the filtration is carried out using a syringe and a water-based filter head.

5. Use of a zero-dimensional organic-inorganic manganese-based halide scintillation material as described in claim 1, characterized in that: Applied in high-energy particle detection, imaging or dose monitoring, and the application is for non-therapeutic and non-diagnostic purposes.

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