WO2024082090A1 - Manganese-based scintillation crystalline material, and preparation method therefor and use thereof - Google Patents

Manganese-based scintillation crystalline material, and preparation method therefor and use thereof Download PDF

Info

Publication number
WO2024082090A1
WO2024082090A1 PCT/CN2022/125653 CN2022125653W WO2024082090A1 WO 2024082090 A1 WO2024082090 A1 WO 2024082090A1 CN 2022125653 W CN2022125653 W CN 2022125653W WO 2024082090 A1 WO2024082090 A1 WO 2024082090A1
Authority
WO
WIPO (PCT)
Prior art keywords
manganese
crystalline material
based scintillating
preparation
scintillating crystalline
Prior art date
Application number
PCT/CN2022/125653
Other languages
French (fr)
Chinese (zh)
Inventor
卢健
郑发鲲
郭国聪
高娟
徐忠宁
王文飞
李宝义
Original Assignee
闽都创新实验室
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 闽都创新实验室 filed Critical 闽都创新实验室
Priority to PCT/CN2022/125653 priority Critical patent/WO2024082090A1/en
Publication of WO2024082090A1 publication Critical patent/WO2024082090A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/16—Measuring radiation intensity
    • G01T1/20—Measuring radiation intensity with scintillation detectors
    • G01T1/202—Measuring radiation intensity with scintillation detectors the detector being a crystal

Definitions

  • the present application relates to a manganese-based scintillation crystalline material and a preparation method and application thereof, belonging to the technical field of scintillation materials.
  • Scintillator crystals are a type of material that can emit ultraviolet-visible light after absorbing the energy of high-energy particles (such as ⁇ , ⁇ particles) or high-energy rays (X-rays, ⁇ -rays, neutrons, etc.). They play a very important role in the field of radiation detection. Detection devices based on scintillators are widely used in important fields such as space exploration, industrial non-destructive testing, medical X-CT, oil and mineral exploration, and national defense security inspection.
  • the main commercial scintillator materials include bismuth germanate Bi 4 Ge 3 O 12 (BGO), lead tungstate PbWO 4 (PWO), barium fluoride (BaF 2 ), yttrium lutetium silicate Lux Y 2-x SiO 5 :Ce (LYSO) and other inorganic crystals.
  • BGO bismuth germanate Bi 4 Ge 3 O 12
  • PWO lead tungstate PbWO 4
  • BaF 2 barium fluoride
  • LYSO yttrium lutetium silicate Lux Y 2-x SiO 5 :Ce
  • a manganese-based scintillating crystalline material is provided. Compared with currently commercialized inorganic scintillating materials, this scintillating material has better response capability, low X-ray dose detection limit, high scintillation intensity, and overcomes the high energy consumption disadvantage in the current commercial scintillating material synthesis process. It has important commercial application value in the field of high-performance scintillating materials.
  • a manganese-based scintillating crystalline material the chemical formula of which is: (mtp) 2 MnCl 4 ;
  • MTP is a methyltriphenylphosphine cation.
  • the manganese-based scintillating crystalline material is an organic-inorganic hybrid material.
  • the manganese-based scintillating crystalline material is a block of small single crystals or solid powder.
  • the manganese-based scintillating crystalline material has a zero-dimensional molecular structure.
  • the manganese-based scintillating crystalline material comprises three asymmetric structural units.
  • the asymmetric structural unit contains an inorganic unit of [MnCl 4 ] 2- and an organic unit of methyltriphenylphosphine cation.
  • the asymmetric structural unit comprises 2 mtp + s that are 1/3 occupied, 1 Mn 2+ , 1 Cl - , and 1 Cl - s that are 1/3 occupied.
  • the asymmetric structural unit contains an inorganic unit [MnCl 4 ] 2- , wherein the Mn 2+ ion is a tetrahedral spatial configuration, wherein the Mn-Cl1 bond length is The Mn-Cl2 bond length is The bond lengths of Mn-Cl2#1 and Mn-Cl2#2 are
  • the asymmetric structural unit contains an inorganic unit [MnCl 4 ] 2- , wherein the Mn 2+ ion is a tetrahedral spatial configuration, wherein the Mn-Cl1 bond length is The Mn-Cl2 bond length is The bond lengths of Mn-Cl2#1 and Mn-Cl2#2 are
  • the bond angle of Cl2#1-Mn1-Cl2#2 is 109.63 ⁇ 109.73°
  • the bond angle of Cl2-Mn1-Cl2#2 is 109.63 ⁇ 109.73°
  • the bond angle of Cl2-Mn1-Cl2#1 is 109.63 ⁇ 109.73°
  • the bond angle of Cl1-Mn1-Cl2 is 109.21 ⁇ 109.31°
  • the bond angle of Cl1-Mn1-Cl2#2 is 109.21 ⁇ 109.31°
  • the bond angle of Cl1-Mn1-Cl2#1 is 109.21 ⁇ 109.31°
  • the bond angle of Cl1-Mn1-Cl2#1 is 109.21 ⁇ 109.31°.
  • the bond angle of Cl2#1-Mn1-Cl2#2 is 109.68(5)°
  • the bond angle of Cl2-Mn1-Cl2#2 is 109.68(5)°
  • the bond angle of Cl2-Mn1-Cl2#1 is 109.68(5)°
  • the bond angle of Cl1-Mn1-Cl2 is 109.26(5)°
  • the bond angle of Cl1-Mn1-Cl2#2 is 109.26(5)°
  • the bond angle of Cl1-Mn1-Cl2#1 is 109.26(5)°.
  • the crystal structure of the manganese-based scintillating crystalline material belongs to the cubic crystal system, P2 1 3 space group, has a chiral structure, and a flack factor of -0.028 (19).
  • the unit cell parameters of the manganese-based scintillating crystalline material are the unit cell parameters of the manganese-based scintillating crystalline material.
  • the unit cell parameters of the manganese-based scintillating crystalline material are the unit cell parameters of the manganese-based scintillating crystalline material.
  • the emission peak of the manganese-based scintillating crystalline material under excitation of ultraviolet light with a wavelength of 135 to 420 nm is 506 to 510 nm, which is green light emission.
  • the thermal decomposition temperature of the manganese-based scintillating crystalline material is 393-403°C.
  • the above thermal decomposition temperature indicates that the manganese-based scintillating crystalline material has good thermal stability.
  • the manganese-based scintillating crystalline material has a single crystal-single crystal transformation behavior, and its phase transition point is 206-216°C.
  • a method for preparing the above-mentioned manganese-based scintillating crystalline material comprising the following steps:
  • a mixture containing methyltriphenylphosphine chloride, manganese chloride, a protic solvent and water is reacted and crystallized to obtain the manganese-based scintillating crystalline material.
  • the crystallization comprises:
  • the intermediate product obtained by the reaction is placed in a diffusion atmosphere of a reverse diffusion solvent and crystallized for 72 to 192 hours to obtain a manganese-based scintillating crystalline material, wherein the obtained manganese-based scintillating crystalline material is in a single crystal state;
  • the intermediate product obtained by the reaction is completely evaporated by the solvent to obtain a manganese-based scintillating crystalline material, and the obtained manganese-based scintillating crystalline material is in a powder state.
  • the intermediate product obtained by the reaction is filtered and cooled.
  • the methyltriphenylphosphine chloride is an aromatic ring organic phosphine compound.
  • the molar ratio of the added amount of manganese chloride to methyltriphenylphosphine chloride is 0.1-2.5:1.
  • the molar ratio of the added amount of manganese chloride to methyltriphenylphosphine chloride is any value among 0.1:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, or any range value between any two of them.
  • the molar ratio of the added amount of manganese chloride to methyltriphenylphosphine chloride is 0.33-0.75:1.
  • the molar ratio of the added amount of manganese chloride to methyltriphenylphosphine chloride is any value among 0.33:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.75:1, or any range value between any two of them.
  • the solid-to-liquid ratio of the methyltriphenylphosphine chloride to the protic solvent is 1:1-50.
  • the protic solvent is selected from at least one of ethanol, methanol, tetrahydrofuran and N-methylpyrrolidone.
  • the protic solvent is a mixed solvent of methanol and ethanol, and the volume ratio of methanol to ethanol is 3:1 to 10:1.
  • reaction conditions include: reaction temperature of 80 to 100° C.; reaction time of 12 to 24 hours.
  • the reverse diffusion solvent is selected from at least one of ether, chloroform, dichloromethane and acetone.
  • the high-energy particles include X-rays.
  • the manganese-based scintillating crystalline material provided in the present application has sensitive X-ray detection capability.
  • the X-ray detection limit of the manganese-based scintillating crystalline material is 1.23 ⁇ Gy air /s, which is much lower than the conventional medical diagnostic dose standard of 5.50 ⁇ Gy air /s.
  • the high-performance X-ray detection capability can further improve the spatial resolution of imaging display devices, which is crucial for high-quality imaging. It has important commercial application value in the field of high-energy particle detection and imaging display materials.
  • the manganese-based scintillating crystalline material provided in the present application has good thermal stability and excellent X-ray scintillation performance. Its upper limit of thermal stability is as high as 398°C, and its scintillation intensity is 1.47 to 2 times that of bismuth germanate BGO scintillation crystal, reaching 30 to 50% of the scintillation intensity of yttrium silicate lutetium LYSO scintillation crystal.
  • the method for preparing the manganese-based scintillating crystalline material provided in the present application has simple steps and is green and environmentally friendly.
  • the obtained product has high purity, good crystallinity and high yield. It overcomes the disadvantage of high industrial energy consumption existing in traditional commercial scintillators and is suitable for large-scale industrial production. It has important commercial application value in the field of scintillating materials, and the material does not contain heavy metals such as Pb and Bi.
  • FIG1 is a schematic diagram of the crystal structure of a manganese-based scintillating crystalline material sample 1 prepared in Example 1 of the present application (excluding hydrogen atoms), wherein the upper portion of FIG1 is the spatial coordination configuration of Mn(II), and the lower portion of FIG1 is the spatial configuration of a methyltriphenylphosphine cation;
  • FIG2 is an XRD diffraction theoretical spectrum obtained by fitting the single crystal data of the manganese-based scintillating crystalline material sample 1 prepared in Example 1 of the present application and its experimentally measured XRD diffraction spectrum;
  • FIG3 is a graph showing the thermal stability of a manganese-based scintillating crystalline material sample 1 prepared in Example 1 of the present application;
  • FIG4 is a photoluminescence experimental spectrum of the manganese-based scintillating crystalline material sample 1 prepared in Example 1 of the present application, including the optimal excitation wavelength and the optimal emission wavelength;
  • FIG5 is an X-ray scintillation luminescence experimental spectrum of the manganese-based scintillation crystalline material sample 1 prepared in Example 1 of the present application;
  • FIG6 is a graph showing a comparison of the scintillation performance of the manganese-based scintillation crystalline material sample 1 prepared in Example 1 of the present application;
  • FIG. 7 is an experimental graph showing X-ray dose detection of the manganese-based scintillating crystalline material sample 1 prepared in Example 1 of the present application.
  • the raw materials in the examples of the present application were purchased through commercial channels, among which methyltriphenylphosphine chloride and manganese chloride were purchased from the official website of Shanghai Exploration Platform Reagents; protic solvents such as ethanol and methanol, and solvents such as ether and chloroform were purchased from Sinopharm Group.
  • Example 2 The sample 1 prepared in Example 2 was subjected to X-ray single crystal diffraction test (on a Mercury CCD single crystal diffractometer, Mo target, K ⁇ radiation source). The test temperature is 298K), and the structure is analyzed by Olex 2 1.2. The test results are shown in Figure 1. In the asymmetric unit, there are 2 1/3 occupied mtp + cations, 1 Mn 2+ ion, 1 Cl ion and 1/3 occupied Cl ion; through the symmetrization operation, a Mn 2+ metal ion and four Cl ions form a tetrahedral [MnCl 4 ] 2- inorganic unit.
  • Mn is a tetrahedral geometric configuration with a four-coordinate distortion; the Mn-Cl1 bond length is The Mn-Cl2 bond length is The bond lengths of Mn-Cl2#1 and Mn-Cl2#2 are Taking Mn as the center, the bond angle of Cl2#1-Mn1-Cl2#2 is 109.68(5)°, the bond angle of Cl2-Mn1-Cl2#2 is 109.68(5)°, the bond angle of Cl2-Mn1-Cl2#1 is 109.68(5)°, the bond angle of Cl1-Mn1-Cl2 is 109.26(5)°, the bond angle of Cl1-Mn1-Cl2#2 is 109.26(5)°, and the bond angle of Cl1-Mn1-Cl2#1 is 109.26(5)°, all of which are within the normal numerical range, where #1 represents the symmetric code 1-x, 1/2+y, 1/2-z; #2 represents the symmetric
  • X-ray powder diffraction phase analysis was performed on Sample 1 prepared in Example 2 (on a Rigaku MiniFlex600 X-ray diffractometer, Cu target, K ⁇ radiation source). ), the XRD diffraction theoretical pattern obtained by X-ray single crystal diffraction fitting is compared with the XRD diffraction pattern measured by X-ray powder diffraction phase analysis as shown in Figure 2. It can be seen that the XRD diffraction pattern obtained by single crystal data fitting is highly consistent with the XRD diffraction pattern measured experimentally, proving that the obtained sample is a sample of high purity and high crystallinity.
  • Sample 1 material belongs to the P2 1 3 space group of the cubic system.
  • Example 2 A thermal stability test experiment was carried out on sample 1 prepared in Example 2 (measured on a TGA&DSC METTLER TOLEDO thermogravimetric analyzer in a nitrogen atmosphere). As shown in Figure 3, the manganese-based scintillating crystalline material powder has good thermal stability and still maintains its structural integrity at 398°C.
  • Sample 1 also exhibits single crystal-to-single crystal transformation behavior, and its phase transition point is about 212°C.
  • the X-ray scintillation performance test experiment was carried out on the sample 1 prepared in Example 2, and lead tungstate PWO, barium fluoride BaF2 , bismuth germanate BGO and yttrium lutetium silicate LYSO purchased from Xiamen Zhongshuo Optoelectronics Technology Co., Ltd. were used as reference standards.
  • test samples were first screened by the photoluminescence performance test under ultraviolet light excitation (the selected instrument was Edinburgh FLS920 for photoluminescence performance test, in which the excitation light source was a Xe lamp, and the ultraviolet light of a specific excitation band could be selected through the filtering system, the excitation slit was 1 mm, and the receiving slit was 1 mm.), and the experimental spectrum of photoluminescence is shown in Figure 4. Under the optimal wavelength excitation of 280 nm, the optimal photoluminescence peak of sample 1 was at 508 ⁇ 2 nm, which was green light emission.
  • the experimental spectrum of X-ray scintillation performance is shown in Figure 5.
  • the scintillation light of sample 1 is also at 508 ⁇ 2nm.
  • sample 1 shows a scintillation signal at 508 ⁇ 2nm; with the change of X-ray dose, the scintillation intensity of sample 1 changes linearly.
  • the tube voltage is fixed at 50kV and the tube current is gradually reduced from 100 ⁇ A to 50 ⁇ A, the X-ray scintillation performance decreases successively.
  • the comparative experimental spectrum of scintillation performance is shown in Figure 6.
  • the tube voltage of the X-ray tube is 50kV
  • the tube current of the X-ray tube is 100 ⁇ A
  • the distance between the sample and the X-ray tube is 5cm
  • the weight of the test sample is 100mg.
  • the experimental determination of the scintillation intensity of sample 1 is about 1.47 times that of bismuth germanate BGO scintillation crystal and 0.34 times that of yttrium lutetium silicate LYSO. Its scintillation performance is much stronger than lead tungstate PWO and barium fluoride BaF2 .
  • the experimental detection of X-ray dose is shown in FIG7 , where the X-ray dose can be achieved by fixing the tube voltage of the X-ray tube and changing the tube current of the X-ray tube, and the dose detected by the reagent is calibrated by the RAMION radiation dosimeter.
  • the linear slope of the curve represents the detection sensitivity of the scintillating crystalline material to high-energy X-rays.
  • the dose detection limit of X-rays is 3 ⁇ , where ⁇ is the ratio of the standard deviation of instrument noise to the slope of the X-ray dose detection curve

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Molecular Biology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Luminescent Compositions (AREA)

Abstract

Disclosed in the present application are a manganese-based scintillation crystalline material, and a preparation method therefor and the use thereof. The chemical formula of the manganese-based scintillation crystalline material is: (mtp) 2MnCl4, wherein mtp is a methyl triphenylphosphine cation. Further disclosed in the present application is a preparation method for the manganese-based scintillation crystalline material. The preparation method comprises: reacting a mixture containing methyl triphenylphosphine chloride, manganese chloride, a protonic solvent and water; and crystallizing the product so as to obtain the manganese-based scintillation crystalline material. The manganese-based scintillation crystalline material provided in the present application has sensitive X-ray detection capability, good thermal stability and good X-ray scintillation performance; the provided preparation method for the manganese-based scintillation crystalline material involves simple steps, and is green and environmentally friendly; and the obtained product has a high purity, good crystallinity and a high yield, and overcomes the defect of the industrial energy consumption in a traditional commercial scintillator being high, such that the manganese-based scintillation crystalline material is suitable for large-scale industrial production and has important commercial application value in the field of scintillating materials.

Description

一种锰基闪烁晶态材料及其制备方法和应用A manganese-based scintillating crystalline material and its preparation method and application 技术领域Technical Field
本申请涉及一种锰基闪烁晶态材料及其制备方法和应用，属于闪烁材料技术领域。The present application relates to a manganese-based scintillation crystalline material and a preparation method and application thereof, belonging to the technical field of scintillation materials.
背景技术Background technique
闪烁晶体是一类能够吸收高能粒子(如α、β粒子)或高能射线(X射线、γ射线、中子等)的能量后发出紫外-可见光的材料，在辐射探测领域发挥着十分重要的作用，基于闪烁体的探测器件广泛应用于宇宙探测、工业无损探伤、医用X-CT、石油矿石勘探以及国防安检等重要领域。目前商业化的闪烁体材料主要有锗酸铋Bi 4Ge 3O 12(BGO)、钨酸铅PbWO 4(PWO)、氟化钡(BaF 2)、硅酸钇镥Lu xY 2-xSiO 5:Ce(LYSO)等无机晶体。这些闪烁材料在工业生产中耗能极高，而且在提拉法/布里奇曼传统高温单晶生长中，微小散射颗粒的存在、激活剂离子的沉积等也易带来性能上的巨大差异。 Scintillator crystals are a type of material that can emit ultraviolet-visible light after absorbing the energy of high-energy particles (such as α, β particles) or high-energy rays (X-rays, γ-rays, neutrons, etc.). They play a very important role in the field of radiation detection. Detection devices based on scintillators are widely used in important fields such as space exploration, industrial non-destructive testing, medical X-CT, oil and mineral exploration, and national defense security inspection. Currently, the main commercial scintillator materials include bismuth germanate Bi 4 Ge 3 O 12 (BGO), lead tungstate PbWO 4 (PWO), barium fluoride (BaF 2 ), yttrium lutetium silicate Lux Y 2-x SiO 5 :Ce (LYSO) and other inorganic crystals. These scintillator materials consume extremely high energy in industrial production, and in the traditional high-temperature single crystal growth of Czochralski method/Bridgman method, the presence of tiny scattering particles and the deposition of activator ions can also easily lead to huge differences in performance.
同时，随着医学诊疗手段的提高，需要性能更加优异闪烁材料，以确保医学高分辨精准成像的基础上，同时减少患者在X射线下的曝露剂量。因此，提升闪烁探测器对X射线的检测能力，是开展新型闪烁体的重要研究方向。At the same time, with the improvement of medical diagnosis and treatment methods, scintillation materials with better performance are needed to ensure high-resolution and accurate medical imaging while reducing the patient's exposure to X-rays. Therefore, improving the detection capability of scintillation detectors for X-rays is an important research direction for developing new scintillators.
发明内容Summary of the invention
根据本申请的一个方面，提供了一种锰基闪烁晶态材料，该闪烁材料与目前商业化的无机闪烁材料相比，具有更好的响应能力，X射线剂量检测极限低，闪烁强度高，并且克服了目前商业闪烁材料合成过程中高耗能缺点，在高性能闪烁材料领域具有重要商业应用价值。According to one aspect of the present application, a manganese-based scintillating crystalline material is provided. Compared with currently commercialized inorganic scintillating materials, this scintillating material has better response capability, low X-ray dose detection limit, high scintillation intensity, and overcomes the high energy consumption disadvantage in the current commercial scintillating material synthesis process. It has important commercial application value in the field of high-performance scintillating materials.
本申请采用如下技术方案：This application adopts the following technical solutions:
一种锰基闪烁晶态材料，化学式为：(mtp) 2MnCl 4； A manganese-based scintillating crystalline material, the chemical formula of which is: (mtp) 2 MnCl 4 ;
其中mtp为甲基三苯基膦阳离子。Wherein MTP is a methyltriphenylphosphine cation.
可选地，所述锰基闪烁晶态材料为所述闪烁晶态材料为有机无机 杂化材料。Optionally, the manganese-based scintillating crystalline material is an organic-inorganic hybrid material.
可选地，所述锰基闪烁晶态材料为块状小单晶或固体粉末。Optionally, the manganese-based scintillating crystalline material is a block of small single crystals or solid powder.
可选地，所述锰基闪烁晶态材料为零维分子结构。Optionally, the manganese-based scintillating crystalline material has a zero-dimensional molecular structure.
可选地，所述锰基闪烁晶态材料包含三个不对称结构单元。Optionally, the manganese-based scintillating crystalline material comprises three asymmetric structural units.
可选地，所述不对称结构单元中含有[MnCl 4] 2-无机基元和甲基三苯基膦阳离子有机基元。 Optionally, the asymmetric structural unit contains an inorganic unit of [MnCl 4 ] 2- and an organic unit of methyltriphenylphosphine cation.
可选地，所述不对称结构单元包含2个1/3占据的mtp +、1个Mn 2+、1个Cl -、1个1/3占据的Cl -。 Optionally, the asymmetric structural unit comprises 2 mtp + s that are 1/3 occupied, 1 Mn 2+ , 1 Cl - , and 1 Cl - s that are 1/3 occupied.
可选地，所述不对称结构单元中含有[MnCl 4] 2-无机基元，其中Mn 2+离子为四面体空间构型，其中Mn-Cl1键长为
Figure PCTCN2022125653-appb-000001
Mn-Cl2键长为
Figure PCTCN2022125653-appb-000002
Mn-Cl2#1和Mn-Cl2#2的键长为
Figure PCTCN2022125653-appb-000003
Optionally, the asymmetric structural unit contains an inorganic unit [MnCl 4 ] 2- , wherein the Mn 2+ ion is a tetrahedral spatial configuration, wherein the Mn-Cl1 bond length is
Figure PCTCN2022125653-appb-000001
The Mn-Cl2 bond length is
Figure PCTCN2022125653-appb-000002
The bond lengths of Mn-Cl2#1 and Mn-Cl2#2 are
Figure PCTCN2022125653-appb-000003
可选地，所述不对称结构单元中含有[MnCl 4] 2-无机基元，其中Mn 2+离子为四面体空间构型，其中Mn-Cl1键长为
Figure PCTCN2022125653-appb-000004
Mn-Cl2键长为
Figure PCTCN2022125653-appb-000005
Mn-Cl2#1和Mn-Cl2#2的键长为
Figure PCTCN2022125653-appb-000006
Optionally, the asymmetric structural unit contains an inorganic unit [MnCl 4 ] 2- , wherein the Mn 2+ ion is a tetrahedral spatial configuration, wherein the Mn-Cl1 bond length is
Figure PCTCN2022125653-appb-000004
The Mn-Cl2 bond length is
Figure PCTCN2022125653-appb-000005
The bond lengths of Mn-Cl2#1 and Mn-Cl2#2 are
Figure PCTCN2022125653-appb-000006
可选地，所述[MnCl 4] 2-无机基元中，以Mn为中心时，Cl2#1-Mn1-Cl2#2键角为109.63～109.73°，Cl2-Mn1-Cl2#2键角为109.63～109.73°，Cl2-Mn1-Cl2#1键角为109.63～109.73°，Cl1-Mn1-Cl2键角为109.21～109.31°，Cl1-Mn1-Cl2#2键角为109.21～109.31°，Cl1-Mn1-Cl2#1键角为109.21～109.31°。 Optionally, in the [MnCl 4 ] 2- inorganic unit, with Mn as the center, the bond angle of Cl2#1-Mn1-Cl2#2 is 109.63~109.73°, the bond angle of Cl2-Mn1-Cl2#2 is 109.63~109.73°, the bond angle of Cl2-Mn1-Cl2#1 is 109.63~109.73°, the bond angle of Cl1-Mn1-Cl2 is 109.21~109.31°, the bond angle of Cl1-Mn1-Cl2#2 is 109.21~109.31°, and the bond angle of Cl1-Mn1-Cl2#1 is 109.21~109.31°.
可选地，所述[MnCl 4] 2-无机基元中，以Mn为中心时，Cl2#1-Mn1-Cl2#2键角为109.68(5)°，Cl2-Mn1-Cl2#2键角为109.68(5)°，Cl2-Mn1-Cl2#1键角为109.68(5)°，Cl1-Mn1-Cl2键角为109.26(5)°，Cl1-Mn1-Cl2#2键角为109.26(5)°，Cl1-Mn1-Cl2#1键角为109.26(5)°。 Optionally, in the [MnCl 4 ] 2- inorganic unit, with Mn as the center, the bond angle of Cl2#1-Mn1-Cl2#2 is 109.68(5)°, the bond angle of Cl2-Mn1-Cl2#2 is 109.68(5)°, the bond angle of Cl2-Mn1-Cl2#1 is 109.68(5)°, the bond angle of Cl1-Mn1-Cl2 is 109.26(5)°, the bond angle of Cl1-Mn1-Cl2#2 is 109.26(5)°, and the bond angle of Cl1-Mn1-Cl2#1 is 109.26(5)°.
上述键角均在正常数值范围内，其中#1表示对称码1-x，1/2+y，1/2-z；#2表示对称码-1/2+x，1/2-y，1-z。The above bond angles are all within the normal value range, where #1 represents the symmetric code 1-x, 1/2+y, 1/2-z; #2 represents the symmetric code -1/2+x, 1/2-y, 1-z.
可选地，所述锰基闪烁晶态材料的晶体结构属于立方晶系，P2 13空间群，具有手性结构，flack因子为-0.028(19)。 Optionally, the crystal structure of the manganese-based scintillating crystalline material belongs to the cubic crystal system, P2 1 3 space group, has a chiral structure, and a flack factor of -0.028 (19).
可选地，所述锰基闪烁晶态材料的晶胞参数中，晶胞参数为
Figure PCTCN2022125653-appb-000007
Optionally, in the unit cell parameters of the manganese-based scintillating crystalline material, the unit cell parameters are
Figure PCTCN2022125653-appb-000007
可选地，所述锰基闪烁晶态材料的晶胞参数中，晶胞参数为
Figure PCTCN2022125653-appb-000008
Optionally, in the unit cell parameters of the manganese-based scintillating crystalline material, the unit cell parameters are
Figure PCTCN2022125653-appb-000008
可选地，所述锰基闪烁晶态材料的晶胞参数中，α＝90°，β＝90°，γ＝90°，Z＝4。Optionally, in the unit cell parameters of the manganese-based scintillating crystalline material, α=90°, β=90°, γ=90°, and Z=4.
可选地，所述锰基闪烁晶态材料在135～420nm波长紫外光激发下的发射峰为506～510nm，为绿光发射。Optionally, the emission peak of the manganese-based scintillating crystalline material under excitation of ultraviolet light with a wavelength of 135 to 420 nm is 506 to 510 nm, which is green light emission.
可选地，所述锰基闪烁晶态材料的热分解温度为393～403℃。Optionally, the thermal decomposition temperature of the manganese-based scintillating crystalline material is 393-403°C.
上述热分解温度说明锰基闪烁晶态材料具有良好的热稳定性。The above thermal decomposition temperature indicates that the manganese-based scintillating crystalline material has good thermal stability.
可选地，所述锰基闪烁晶态材料具有单晶-单晶转变行为，其相变点为206～216℃。Optionally, the manganese-based scintillating crystalline material has a single crystal-single crystal transformation behavior, and its phase transition point is 206-216°C.
根据本申请的另一方面，提供了一种上述锰基闪烁晶态材料的制备方法，包括如下步骤：According to another aspect of the present application, a method for preparing the above-mentioned manganese-based scintillating crystalline material is provided, comprising the following steps:
将含有甲基三苯基氯化膦、氯化锰、质子性溶剂、水的混合物，反应，结晶，得到所述锰基闪烁晶态材料。A mixture containing methyltriphenylphosphine chloride, manganese chloride, a protic solvent and water is reacted and crystallized to obtain the manganese-based scintillating crystalline material.
可选地，所述结晶包括：Optionally, the crystallization comprises:
将反应得到的中间产物置于反向扩散溶剂的扩散气氛中，结晶72～192h，得到锰基闪烁晶态材料，所制得的锰基闪烁晶态材料为单晶状态；The intermediate product obtained by the reaction is placed in a diffusion atmosphere of a reverse diffusion solvent and crystallized for 72 to 192 hours to obtain a manganese-based scintillating crystalline material, wherein the obtained manganese-based scintillating crystalline material is in a single crystal state;
或将反应得到的中间产物经溶剂挥发完全，得到锰基闪烁晶态材料，所制得的锰基闪烁晶态材料为粉末状态。Or the intermediate product obtained by the reaction is completely evaporated by the solvent to obtain a manganese-based scintillating crystalline material, and the obtained manganese-based scintillating crystalline material is in a powder state.
上述结晶过程均为自主装反应得到晶态材料。The above crystallization processes are all self-assembly reactions to obtain crystalline materials.
可选地，所述反应后还包括对反应得到的中间产物进行过滤和冷却。Optionally, after the reaction, the intermediate product obtained by the reaction is filtered and cooled.
所述甲基三苯基氯化膦为芳香环有机膦化合物。The methyltriphenylphosphine chloride is an aromatic ring organic phosphine compound.
可选地，所述氯化锰与甲基三苯基氯化膦的添加量的摩尔比为0.1～2.5：1。Optionally, the molar ratio of the added amount of manganese chloride to methyltriphenylphosphine chloride is 0.1-2.5:1.
可选地，所述氯化锰与甲基三苯基氯化膦的添加量的摩尔比为0.1：1、0.5：1、1：1、1.5：1、2：1、2.5：1中的任意值，或任意两者之间的范围值。Optionally, the molar ratio of the added amount of manganese chloride to methyltriphenylphosphine chloride is any value among 0.1:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, or any range value between any two of them.
可选地，所述氯化锰与甲基三苯基氯化膦的添加量的摩尔比为 0.33～0.75：1。Optionally, the molar ratio of the added amount of manganese chloride to methyltriphenylphosphine chloride is 0.33-0.75:1.
可选地，所述氯化锰与甲基三苯基氯化膦的添加量的摩尔比为0.33：1、0.4：1、0.5：1、0.6：1、0.7：1、0.75：1中的任意值，或任意两者之间的范围值。Optionally, the molar ratio of the added amount of manganese chloride to methyltriphenylphosphine chloride is any value among 0.33:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.75:1, or any range value between any two of them.
可选地，所述甲基三苯基氯化膦与质子性溶剂的固液比为1：1～50。Optionally, the solid-to-liquid ratio of the methyltriphenylphosphine chloride to the protic solvent is 1:1-50.
可选地，所述质子性溶剂选自乙醇、甲醇、四氢呋喃、N-甲基吡咯烷酮中的至少一种。Optionally, the protic solvent is selected from at least one of ethanol, methanol, tetrahydrofuran and N-methylpyrrolidone.
可选地，所述质子性溶剂为甲醇、乙醇的混合溶剂，所述甲醇与乙醇的体积比为3：1～10：1。Optionally, the protic solvent is a mixed solvent of methanol and ethanol, and the volume ratio of methanol to ethanol is 3:1 to 10:1.
可选地，所述反应的条件包括：反应温度为80～100℃；反应时间为12～24小时。Optionally, the reaction conditions include: reaction temperature of 80 to 100° C.; reaction time of 12 to 24 hours.
可选地，所述反向扩散溶剂选自乙醚、氯仿、二氯甲烷、丙酮中的至少一种。Optionally, the reverse diffusion solvent is selected from at least one of ether, chloroform, dichloromethane and acetone.
根据本申请另一方面，提供一种上述锰基闪烁晶态材料、上述制备方法制备得到的锰基闪烁晶态材料在高能粒子探测、成像显像或剂量监测方中的应用。According to another aspect of the present application, there is provided an application of the above-mentioned manganese-based scintillating crystalline material and the manganese-based scintillating crystalline material prepared by the above-mentioned preparation method in high-energy particle detection, imaging or dose monitoring.
可选地，所述高能粒子包括X射线。Optionally, the high-energy particles include X-rays.
本申请能产生的有益效果包括：The beneficial effects of this application include:
(1)本申请所提供的锰基闪烁晶态材料具有灵敏的X射线检测能力，所述锰基闪烁晶态材料的X射线检测极限为1.23μGy air/s，远低于常规医疗诊断剂量标准5.50μGy air/s，高性能的X射线检测能力可进一步提高成像显示器件的空间分辨率，对于高质量显像至关重要，在高能粒子探测与成像显示材料领域具有重要商业应用价值。 (1) The manganese-based scintillating crystalline material provided in the present application has sensitive X-ray detection capability. The X-ray detection limit of the manganese-based scintillating crystalline material is 1.23 μGy air /s, which is much lower than the conventional medical diagnostic dose standard of 5.50 μGy air /s. The high-performance X-ray detection capability can further improve the spatial resolution of imaging display devices, which is crucial for high-quality imaging. It has important commercial application value in the field of high-energy particle detection and imaging display materials.
(2)本申请所提供的锰基闪烁晶态材料具有良好的热稳定性和优异的X射线闪烁性能，其热稳定上限高达398℃，闪烁强度为锗酸铋BGO闪烁晶体的1.47～2倍，达到了硅酸钇镥LYSO闪烁晶体的30～50％的闪烁强度。(2) The manganese-based scintillating crystalline material provided in the present application has good thermal stability and excellent X-ray scintillation performance. Its upper limit of thermal stability is as high as 398°C, and its scintillation intensity is 1.47 to 2 times that of bismuth germanate BGO scintillation crystal, reaching 30 to 50% of the scintillation intensity of yttrium silicate lutetium LYSO scintillation crystal.
(3)本申请所提供的锰基闪烁晶态材料制备方法步骤简单、绿色环保，所得产品纯度高、结晶度好、收率高，且克服了传统商业闪烁体中存在的工业高耗能的缺点，适合大规模工业化生产，在闪烁材料领域具有重要商业应用价值，且材料中不含有Pb、Bi等重金属。(3) The method for preparing the manganese-based scintillating crystalline material provided in the present application has simple steps and is green and environmentally friendly. The obtained product has high purity, good crystallinity and high yield. It overcomes the disadvantage of high industrial energy consumption existing in traditional commercial scintillators and is suitable for large-scale industrial production. It has important commercial application value in the field of scintillating materials, and the material does not contain heavy metals such as Pb and Bi.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本申请实施例1中制备的锰基闪烁晶态材料样品1的晶体结构示意图(不含氢原子)，其中图1上部分为Mn(II)的空间配位构型，图1下部分为甲基三苯基膦阳离子的空间构型；FIG1 is a schematic diagram of the crystal structure of a manganese-based scintillating crystalline material sample 1 prepared in Example 1 of the present application (excluding hydrogen atoms), wherein the upper portion of FIG1 is the spatial coordination configuration of Mn(II), and the lower portion of FIG1 is the spatial configuration of a methyltriphenylphosphine cation;
图2为本申请实施例1中制备的锰基闪烁晶态材料样品1单晶数据拟合得到的XRD衍射理论图谱与其实验测得的XRD衍射图谱；FIG2 is an XRD diffraction theoretical spectrum obtained by fitting the single crystal data of the manganese-based scintillating crystalline material sample 1 prepared in Example 1 of the present application and its experimentally measured XRD diffraction spectrum;
图3为本申请实施例1中制备的锰基闪烁晶态材料样品1的热稳定性实验图谱；FIG3 is a graph showing the thermal stability of a manganese-based scintillating crystalline material sample 1 prepared in Example 1 of the present application;
图4为本申请实施例1中制备的锰基闪烁晶态材料样品1的光致发光实验图谱，包括最佳激发波长和最佳发射波长；FIG4 is a photoluminescence experimental spectrum of the manganese-based scintillating crystalline material sample 1 prepared in Example 1 of the present application, including the optimal excitation wavelength and the optimal emission wavelength;
图5为本申请实施例1中制备的锰基闪烁晶态材料样品1的X射线闪烁发光实验图谱；FIG5 is an X-ray scintillation luminescence experimental spectrum of the manganese-based scintillation crystalline material sample 1 prepared in Example 1 of the present application;
图6为本申请实施例1中制备的锰基闪烁晶态材料样品1的闪烁性能实验比较图谱；FIG6 is a graph showing a comparison of the scintillation performance of the manganese-based scintillation crystalline material sample 1 prepared in Example 1 of the present application;
图7为本申请实施例1中制备的锰基闪烁晶态材料样品1对X射线剂量检测的实验图谱。FIG. 7 is an experimental graph showing X-ray dose detection of the manganese-based scintillating crystalline material sample 1 prepared in Example 1 of the present application.
具体实施方式Detailed ways
下面结合实施例详述本申请，但本申请并不局限于这些实施例。The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.
如无特别说明，本申请的实施例中的原料均通过商业途径购买，其中甲基三苯基氯化磷、氯化锰购自于上海探索平台试剂官网；乙醇、甲醇等质子性溶剂以及乙醚、氯仿等溶剂购自于国药集团。Unless otherwise specified, the raw materials in the examples of the present application were purchased through commercial channels, among which methyltriphenylphosphine chloride and manganese chloride were purchased from the official website of Shanghai Exploration Platform Reagents; protic solvents such as ethanol and methanol, and solvents such as ether and chloroform were purchased from Sinopharm Group.
实施例1Example 1
将6mmol甲基三苯基氯化膦和3mmol金属盐MnCl 2加入到16mL 乙醇和4mL去离子水中，在100℃的反应温度下加热溶解24小时，冷却后使溶剂自然挥发进行结晶，直到得到锰基闪烁晶态材料晶态粉末，晶体化学式为(mtp) 2MnCl 4，标记为样品1。 6mmol of methyltriphenylphosphine chloride and 3mmol of metal salt MnCl 2 were added to 16mL of ethanol and 4mL of deionized water, and heated to dissolve at a reaction temperature of 100°C for 24 hours. After cooling, the solvent was naturally evaporated for crystallization until a crystalline powder of a manganese-based scintillating crystalline material was obtained, the crystal chemical formula of which was (mtp) 2 MnCl 4 , marked as sample 1.
实施例2Example 2
将6mmol甲基三苯基氯化膦和3mmol金属盐MnCl 2加入到16mL乙醇和4mL去离子水中，在100℃的反应温度下加热溶解24小时；冷却后过滤掉反应中生产的MnO 2沉淀，滤液置于乙醚气氛中一周左右析出锰基闪烁晶态材料晶体，收率为57％(基于MnCl 2)，晶体化学式为(mtp) 2MnCl 4，标记为样品2。经测试样品2与实施例1中的样品1结构与性能均一致。 6mmol of methyltriphenylphosphine chloride and 3mmol of metal salt MnCl2 were added to 16mL of ethanol and 4mL of deionized water, and heated to dissolve at a reaction temperature of 100°C for 24 hours; after cooling, the MnO2 precipitate produced in the reaction was filtered out, and the filtrate was placed in an ether atmosphere for about a week to precipitate manganese-based scintillating crystalline material crystals, with a yield of 57% (based on MnCl2 ), and the crystal chemical formula was (mtp) 2MnCl4 , marked as sample 2. The structure and performance of sample 2 were consistent with those of sample 1 in Example 1 after testing.
测试例1Test Example 1
对实施例2所制备的样品1进行X-射线单晶衍射测试(在MercuryCCD型单晶衍射仪上进行，Mo靶，Kα辐射源
Figure PCTCN2022125653-appb-000009
测试温度298K)，并通过Olex 21.2对进行结构解析。测试结果如图1图所示，在不对称单元中，2个1/3占据的mtp +阳离子，1个Mn 2+离子、一个Cl离子以及一个1/3占据的Cl离子；通过对称化操作，一个Mn 2+金属离子与四个Cl离子形成四面体构型的[MnCl 4] 2-无机基元，可以看出，Mn为四配位畸变的四面体几何构型；Mn-Cl1键长为
Figure PCTCN2022125653-appb-000010
Mn-Cl2键长为
Figure PCTCN2022125653-appb-000011
Mn-Cl2#1和Mn-Cl2#2的键长为
Figure PCTCN2022125653-appb-000012
以Mn为中心，Cl2#1-Mn1-Cl2#2键角为109.68(5)°，Cl2-Mn1-Cl2#2键角为109.68(5)°，Cl2-Mn1-Cl2#1键角为109.68(5)°，Cl1-Mn1-Cl2键角为109.26(5)°，Cl1-Mn1-Cl2#2键角为109.26(5)°，Cl1-Mn1-Cl2#1键角为109.26(5)°，均在正常数值范围内，其中#1表示对称码1-x，1/2+y，1/2-z；#2表示对称码-1/2+x，1/2-y，1-z。 The sample 1 prepared in Example 2 was subjected to X-ray single crystal diffraction test (on a Mercury CCD single crystal diffractometer, Mo target, Kα radiation source).
Figure PCTCN2022125653-appb-000009
The test temperature is 298K), and the structure is analyzed by Olex 2 1.2. The test results are shown in Figure 1. In the asymmetric unit, there are 2 1/3 occupied mtp + cations, 1 Mn 2+ ion, 1 Cl ion and 1/3 occupied Cl ion; through the symmetrization operation, a Mn 2+ metal ion and four Cl ions form a tetrahedral [MnCl 4 ] 2- inorganic unit. It can be seen that Mn is a tetrahedral geometric configuration with a four-coordinate distortion; the Mn-Cl1 bond length is
Figure PCTCN2022125653-appb-000010
The Mn-Cl2 bond length is
Figure PCTCN2022125653-appb-000011
The bond lengths of Mn-Cl2#1 and Mn-Cl2#2 are
Figure PCTCN2022125653-appb-000012
Taking Mn as the center, the bond angle of Cl2#1-Mn1-Cl2#2 is 109.68(5)°, the bond angle of Cl2-Mn1-Cl2#2 is 109.68(5)°, the bond angle of Cl2-Mn1-Cl2#1 is 109.68(5)°, the bond angle of Cl1-Mn1-Cl2 is 109.26(5)°, the bond angle of Cl1-Mn1-Cl2#2 is 109.26(5)°, and the bond angle of Cl1-Mn1-Cl2#1 is 109.26(5)°, all of which are within the normal numerical range, where #1 represents the symmetric code 1-x, 1/2+y, 1/2-z; #2 represents the symmetric code -1/2+x, 1/2-y, 1-z.
对实施例2所制备的样品1进行X-射线粉末衍射物相分析(在Rigaku公司的MiniFlex600型X射线衍射仪上进行，Cu靶，Kα辐射源
Figure PCTCN2022125653-appb-000013
)，通过X-射线单晶衍射拟合得到的XRD衍射理论图谱与其X-射线粉末衍射物相分析测得的XRD衍射图谱比较如图2 所示，可以看出，通过单晶数据拟合得到的XRD衍射图谱与其实验测得的XRD衍射图谱高度一致，证明所得样品为高纯度和高结晶度的样品。 X-ray powder diffraction phase analysis was performed on Sample 1 prepared in Example 2 (on a Rigaku MiniFlex600 X-ray diffractometer, Cu target, Kα radiation source).
Figure PCTCN2022125653-appb-000013
), the XRD diffraction theoretical pattern obtained by X-ray single crystal diffraction fitting is compared with the XRD diffraction pattern measured by X-ray powder diffraction phase analysis as shown in Figure 2. It can be seen that the XRD diffraction pattern obtained by single crystal data fitting is highly consistent with the XRD diffraction pattern measured experimentally, proving that the obtained sample is a sample of high purity and high crystallinity.
X-射线粉末衍射和X-射线单晶衍射结果表明：X-ray powder diffraction and X-ray single crystal diffraction results show that:
样品1材料属于立方晶系的P2 13空间群。 Sample 1 material belongs to the P2 1 3 space group of the cubic system.
晶胞参数为
Figure PCTCN2022125653-appb-000014
α＝β＝γ＝90°，Z＝4。 The unit cell parameters are
Figure PCTCN2022125653-appb-000014
α＝β＝γ＝90°, Z＝4.
测试例2Test Example 2
对实施例2所制备的样品1进行热稳定性测试实验(在TGA&DSC METTLER TOLEDO热重分析仪，在氮气气氛中测得)，如图3所示，锰基闪烁晶态材料晶体粉末具有良好的热稳定性，在398℃下依然保持结构的完整性。A thermal stability test experiment was carried out on sample 1 prepared in Example 2 (measured on a TGA&DSC METTLER TOLEDO thermogravimetric analyzer in a nitrogen atmosphere). As shown in Figure 3, the manganese-based scintillating crystalline material powder has good thermal stability and still maintains its structural integrity at 398°C.
样品1还具有单晶-单晶转变行为，其相变点约为212℃。 Sample 1 also exhibits single crystal-to-single crystal transformation behavior, and its phase transition point is about 212°C.
测试例3Test Example 3
对实施例2所制备的样品1进行X-射线闪烁性能测试实验，使用购自于厦门中烁光电科技有限公司的钨酸铅PWO、氟化钡BaF 2、锗酸铋BGO和硅酸钇镥LYSO作为参考标样。所有测试样品均先经过紫外光激发下的光致发光性能测试的筛选(所选仪器为光致发光性能测试的爱丁堡FLS920，其中激发光源为Xe灯，经过滤波系统可选择特定的激发波段的紫外光，激发狭缝为1mm，接收狭缝为1mm。)，光致发光的实验谱图如图4所示。在280nm最佳波长激发下，样品1的最佳光致发光峰在508±2nm，为绿光发射。 The X-ray scintillation performance test experiment was carried out on the sample 1 prepared in Example 2, and lead tungstate PWO, barium fluoride BaF2 , bismuth germanate BGO and yttrium lutetium silicate LYSO purchased from Xiamen Zhongshuo Optoelectronics Technology Co., Ltd. were used as reference standards. All test samples were first screened by the photoluminescence performance test under ultraviolet light excitation (the selected instrument was Edinburgh FLS920 for photoluminescence performance test, in which the excitation light source was a Xe lamp, and the ultraviolet light of a specific excitation band could be selected through the filtering system, the excitation slit was 1 mm, and the receiving slit was 1 mm.), and the experimental spectrum of photoluminescence is shown in Figure 4. Under the optimal wavelength excitation of 280 nm, the optimal photoluminescence peak of sample 1 was at 508±2 nm, which was green light emission.
X-射线闪烁性能的实验谱图如图5所示。样品1的闪烁发光也在508±2nm。且固定X射线光管的管电压，改变X射线光管的管电流时，样品1均在508±2nm处表现出闪烁信号；随X射线剂量的变化，样品1的闪烁强度随之线性变化。当管电压固定为50kV，管电流的从100μA逐步降低到50μA，X-射线闪烁性能依次降低。The experimental spectrum of X-ray scintillation performance is shown in Figure 5. The scintillation light of sample 1 is also at 508±2nm. When the tube voltage of the X-ray tube is fixed and the tube current of the X-ray tube is changed, sample 1 shows a scintillation signal at 508±2nm; with the change of X-ray dose, the scintillation intensity of sample 1 changes linearly. When the tube voltage is fixed at 50kV and the tube current is gradually reduced from 100μA to 50μA, the X-ray scintillation performance decreases successively.
闪烁性能的对比实验谱图如图6所示。当X射线光管的管电压为50kV，X射线光管的管电流为100μA，样品与X-射线光管的距离 为5cm，测试样品重量为100mg。可以看出，在相同测试条件下，实验测定样品1的闪烁强度约为锗酸铋BGO闪烁晶体的1.47倍，为硅酸钇镥LYSO的0.34倍，其闪烁性能远强于钨酸铅PWO，氟化钡BaF 2。与目前商业化的闪烁材料相比，PWO<BaF 2<BGO<1<LYSO，本申请所述闪烁晶态材料的性能比商用的闪烁材料BGO优异，然而合成却更加低廉，有着极大的优势条件。 The comparative experimental spectrum of scintillation performance is shown in Figure 6. When the tube voltage of the X-ray tube is 50kV, the tube current of the X-ray tube is 100μA, the distance between the sample and the X-ray tube is 5cm, and the weight of the test sample is 100mg. It can be seen that under the same test conditions, the experimental determination of the scintillation intensity of sample 1 is about 1.47 times that of bismuth germanate BGO scintillation crystal and 0.34 times that of yttrium lutetium silicate LYSO. Its scintillation performance is much stronger than lead tungstate PWO and barium fluoride BaF2 . Compared with the currently commercialized scintillation materials, PWO< BaF2 <BGO<1<LYSO, the performance of the scintillation crystalline material described in this application is better than the commercial scintillation material BGO, but the synthesis is cheaper, with great advantages.
X-射线剂量的实验检测如图7所示，其中X-射线的剂量可以通过固定X射线光管的管电压，改变X射线光管的管电流实现，试剂探测的剂量经过RAMION辐射剂量仪校正。曲线的线性斜率表示该闪烁晶态材料对高能X-射线的检测灵敏度。根据国际纯粹化学和应用化学联合会规定，X-射线的剂量检出限为3σ，σ为仪器噪音标准差与X-射线剂量检测曲线斜率|k|的比值，仪器噪音的标准差为0.97，因此，可分别求出样品1检测限为1.23μGy air/s，低于常规医疗诊断剂量标准5.50μGy air/s。这表明，样品1具有灵敏的X-射线检测能力。 The experimental detection of X-ray dose is shown in FIG7 , where the X-ray dose can be achieved by fixing the tube voltage of the X-ray tube and changing the tube current of the X-ray tube, and the dose detected by the reagent is calibrated by the RAMION radiation dosimeter. The linear slope of the curve represents the detection sensitivity of the scintillating crystalline material to high-energy X-rays. According to the provisions of the International Union of Pure and Applied Chemistry, the dose detection limit of X-rays is 3σ, where σ is the ratio of the standard deviation of instrument noise to the slope of the X-ray dose detection curve |k|, and the standard deviation of instrument noise is 0.97. Therefore, the detection limit of sample 1 can be calculated to be 1.23μGy air /s, which is lower than the conventional medical diagnostic dose standard of 5.50μGy air /s. This shows that sample 1 has sensitive X-ray detection capabilities.
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the above disclosed technical content to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims (19)

  1. 一种锰基闪烁晶态材料，其特征在于，所述锰基闪烁晶态材料的化学式为(mtp) 2MnCl 4； A manganese-based scintillating crystalline material, characterized in that the chemical formula of the manganese-based scintillating crystalline material is (mtp) 2 MnCl 4 ;
    其中mtp为甲基三苯基膦阳离子。Wherein MTP is a methyltriphenylphosphine cation.
  2. 根据权利要求1所述的锰基闪烁晶态材料，其特征在于，所述锰基闪烁晶态材料包含三个不对称结构单元；The manganese-based scintillating crystalline material according to claim 1, characterized in that the manganese-based scintillating crystalline material comprises three asymmetric structural units;
    所述不对称结构单元中含有[MnCl 4] 2-无机基元，其中Mn 2+离子为四面体空间构型。 The asymmetric structural unit contains [MnCl 4 ] 2- inorganic unit, wherein the Mn 2+ ion is in a tetrahedral spatial configuration.
  3. 根据权利要求1所述的锰基闪烁晶态材料，其特征在于，所述不对称结构单元包含2个1/3占据的mtp +、1个Mn 2+、1个Cl -、1个1/3占据的Cl -。 The manganese-based scintillating crystalline material according to claim 1, characterized in that the asymmetric structural unit comprises 2 mtp + s that are occupied by 1/3, 1 Mn 2+ , 1 Cl - , and 1 Cl - s that are occupied by 1/3.
  4. 根据权利要求1所述的锰基闪烁晶态材料，其特征在于，所述[MnCl 4] 2-无机基元中Mn-Cl1键长为
    Figure PCTCN2022125653-appb-100001
    Mn-Cl2键长为
    Figure PCTCN2022125653-appb-100002
    Mn-Cl2#1和Mn-Cl2#2的键长为
    Figure PCTCN2022125653-appb-100003
    The manganese-based scintillating crystalline material according to claim 1, characterized in that the Mn-Cl1 bond length in the [MnCl 4 ] 2- inorganic unit is
    Figure PCTCN2022125653-appb-100001
    The Mn-Cl2 bond length is
    Figure PCTCN2022125653-appb-100002
    The bond lengths of Mn-Cl2#1 and Mn-Cl2#2 are
    Figure PCTCN2022125653-appb-100003
  5. 根据权利要求1所述的锰基闪烁晶态材料，其特征在于，所述[MnCl 4] 2-无机基元中，以Mn为中心时，Cl2#1-Mn1-Cl2#2键角为109.63～109.73°，Cl2-Mn1-Cl2#2键角为109.63～109.73°，Cl2-Mn1-Cl2#1键角为109.63～109.73°，Cl1-Mn1-Cl2键角为109.21～109.31°，Cl1-Mn1-Cl2#2键角为109.21～109.31°，Cl1-Mn1-Cl2#1键角为109.21～109.31°； The manganese-based scintillating crystalline material according to claim 1 is characterized in that, in the [MnCl 4 ] 2- inorganic unit, with Mn as the center, the bond angle of Cl2#1-Mn1-Cl2#2 is 109.63-109.73°, the bond angle of Cl2-Mn1-Cl2#2 is 109.63-109.73°, the bond angle of Cl2-Mn1-Cl2#1 is 109.63-109.73°, the bond angle of Cl1-Mn1-Cl2 is 109.21-109.31°, the bond angle of Cl1-Mn1-Cl2#2 is 109.21-109.31°, and the bond angle of Cl1-Mn1-Cl2#1 is 109.21-109.31°;
    其中#1表示对称码1-x，1/2+y，1/2-z；#2表示对称码-1/2+x，1/2-y，1-z。Among them, #1 represents the symmetric code 1-x, 1/2+y, 1/2-z; #2 represents the symmetric code -1/2+x, 1/2-y, 1-z.
  6. 根据权利要求1所述的锰基闪烁晶态材料，其特征在于，所述锰基闪烁晶态材料的晶体结构属于立方晶系，P2 13空间群，具有 手性结构，flack因子为-0.028(19)。 The manganese-based scintillating crystalline material according to claim 1 is characterized in that the crystal structure of the manganese-based scintillating crystalline material belongs to the cubic crystal system, the P2 1 3 space group, has a chiral structure, and the flack factor is -0.028 (19).
  7. 根据权利要求1所述的锰基闪烁晶态材料，其特征在于，所述锰基闪烁晶态材料的晶胞参数为
    Figure PCTCN2022125653-appb-100004
    α＝90°，β＝90°，γ＝90°，Z＝4。     The manganese-based scintillating crystalline material according to claim 1, characterized in that the unit cell parameters of the manganese-based scintillating crystalline material are
    Figure PCTCN2022125653-appb-100004
    α=90°, β=90°, γ=90°, Z=4.
  8. 根据权利要求1所述的锰基闪烁晶态材料，其特征在于，所述锰基闪烁晶态材料在135～420nm波长紫外光激发下的发射峰为506～510nm。The manganese-based scintillating crystalline material according to claim 1 is characterized in that the emission peak of the manganese-based scintillating crystalline material under excitation of ultraviolet light with a wavelength of 135 to 420 nm is 506 to 510 nm.
  9. 根据权利要求1所述的锰基闪烁晶态材料，其特征在于，所述锰基闪烁晶态材料的热分解温度为393～403℃。The manganese-based scintillating crystalline material according to claim 1, characterized in that the thermal decomposition temperature of the manganese-based scintillating crystalline material is 393-403°C.
  10. 根据权利要求1所述的锰基闪烁晶态材料，其特征在于，所述锰基闪烁晶态材料具有单晶-单晶转变行为，其相变点为206～216℃。The manganese-based scintillating crystalline material according to claim 1 is characterized in that the manganese-based scintillating crystalline material has a single crystal-single crystal transformation behavior, and its phase transition point is 206-216°C.
  11. 一种根据权利要求1～10任意一项所述锰基闪烁晶态材料的制备方法，其特征在于，包括如下步骤：A method for preparing the manganese-based scintillating crystalline material according to any one of claims 1 to 10, characterized in that it comprises the following steps:
    将含有甲基三苯基氯化膦、氯化锰、质子性溶剂、水的混合物，反应，结晶，得到所述锰基闪烁晶态材料。A mixture containing methyltriphenylphosphine chloride, manganese chloride, a protic solvent and water is reacted and crystallized to obtain the manganese-based scintillating crystalline material.
  12. 根据权利要求11所述的制备方法，其特征在于，所述氯化锰与甲基三苯基氯化膦的摩尔比为0.1～2.5：1。The preparation method according to claim 11, characterized in that the molar ratio of manganese chloride to methyltriphenylphosphine chloride is 0.1 to 2.5:1.
  13. 根据权利要求11所述的制备方法，其特征在于，所述氯化锰与甲基三苯基氯化膦的摩尔比为0.33～0.75：1。The preparation method according to claim 11, characterized in that the molar ratio of manganese chloride to methyltriphenylphosphine chloride is 0.33-0.75:1.
  14. 根据权利要求11所述的制备方法，其特征在于，所述甲基三苯基氯化膦与质子性溶剂的固液比为1：1～50。The preparation method according to claim 11 is characterized in that the solid-liquid ratio of the methyltriphenylphosphine chloride to the protic solvent is 1:1 to 50.
  15. 根据权利要求11所述的制备方法，其特征在于，所述反应的条件包括：反应温度为80～100℃；反应时间为12～24小时。The preparation method according to claim 11 is characterized in that the reaction conditions include: reaction temperature of 80 to 100° C.; reaction time of 12 to 24 hours.
  16. 根据权利要求11所述的制备方法，其特征在于，所述结晶包括：The preparation method according to claim 11, characterized in that the crystallization comprises:
    将反应得到的中间产物置于反向扩散溶剂的扩散气氛中，结晶72～192h，得到锰基闪烁晶态材料；placing the intermediate product obtained by the reaction in a diffusion atmosphere of a reverse diffusion solvent and crystallizing for 72 to 192 hours to obtain a manganese-based scintillating crystalline material;
    或将反应得到的中间产物经溶剂挥发完全，得到锰基闪烁晶态材料。Alternatively, the intermediate product obtained by the reaction is completely evaporated by the solvent to obtain a manganese-based scintillating crystalline material.
  17. 根据权利要求11所述的制备方法，其特征在于，所述质子性溶剂选自乙醇、甲醇、四氢呋喃、N-甲基吡咯烷酮中的至少一种。The preparation method according to claim 11, characterized in that the protic solvent is selected from at least one of ethanol, methanol, tetrahydrofuran, and N-methylpyrrolidone.
  18. 根据权利要求11所述的制备方法，其特征在于，所述反向扩散溶剂选自乙醚、氯仿、二氯甲烷、丙酮中的至少一种。The preparation method according to claim 11, characterized in that the reverse diffusion solvent is selected from at least one of ether, chloroform, dichloromethane and acetone.
  19. 权利要求1～10任意一项所述的锰基闪烁晶态材料、根据权利要求11～18任意一项所述制备方法制备得到的锰基闪烁晶态材料在高能射线粒子探测、成像显像或剂量监测方中的应用。Use of the manganese-based scintillating crystalline material according to any one of claims 1 to 10, or the manganese-based scintillating crystalline material prepared according to the preparation method according to any one of claims 11 to 18 in high-energy ray particle detection, imaging or dose monitoring.
PCT/CN2022/125653 2022-10-17 2022-10-17 Manganese-based scintillation crystalline material, and preparation method therefor and use thereof WO2024082090A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2022/125653 WO2024082090A1 (en) 2022-10-17 2022-10-17 Manganese-based scintillation crystalline material, and preparation method therefor and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2022/125653 WO2024082090A1 (en) 2022-10-17 2022-10-17 Manganese-based scintillation crystalline material, and preparation method therefor and use thereof

Publications (1)

Publication Number Publication Date
WO2024082090A1 true WO2024082090A1 (en) 2024-04-25

Family

ID=90736537

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/125653 WO2024082090A1 (en) 2022-10-17 2022-10-17 Manganese-based scintillation crystalline material, and preparation method therefor and use thereof

Country Status (1)

Country Link
WO (1) WO2024082090A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115651027A (en) * 2022-10-17 2023-01-31 闽都创新实验室 Manganese-based scintillation crystalline material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113720866A (en) * 2021-08-31 2021-11-30 南京邮电大学 Method for realizing X-ray detection and imaging by utilizing organic-inorganic hybrid metal manganese halide
CN113801165A (en) * 2021-09-01 2021-12-17 中国科学院福建物质结构研究所 Scintillation material and preparation method and application thereof
CN114180845A (en) * 2021-11-22 2022-03-15 东北大学 Metal halide scintillator microcrystalline glass material, preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113720866A (en) * 2021-08-31 2021-11-30 南京邮电大学 Method for realizing X-ray detection and imaging by utilizing organic-inorganic hybrid metal manganese halide
CN113801165A (en) * 2021-09-01 2021-12-17 中国科学院福建物质结构研究所 Scintillation material and preparation method and application thereof
CN114180845A (en) * 2021-11-22 2022-03-15 东北大学 Metal halide scintillator microcrystalline glass material, preparation method and application thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
B P CHANDRA, MEERA RAMRAKHIANI, M H ANSARI, S TIWARI : "A search for mechanoluminophors capable of pressure-induced thermal population of excited states", PRAMANA, SPRINGER INDIA, NEW DELHI, vol. 36, no. 4, 1 April 1991 (1991-04-01), New Delhi, pages 407 - 421, XP093162756, ISSN: 0304-4289, DOI: 10.1007/BF02847214 *
CHANDRA B. P. ET AL.: "Tetrahedral manganese (II) Complexes - Intense and Unique Type of Mechanoluminophors", PRAMANA, vol. 29, no. 4, 31 October 1987 (1987-10-31), XP000650218, ISSN: 0304-4289 *
COTTON F. ALBERT ET AL.: "Correlation of Structure and Triboluminescence for Tetrahedral Manganese(II) Compounds", INORGANIC CHEMISTRY, vol. 40, no. 14, 5 June 2001 (2001-06-05), XP055653047, ISSN: 0020-1669, DOI: 10.1021/ic0101836 *
F. ALBERT COTTON, DAVID M. L. GOODGAME, MARGARET GOODGAME: "Absorption Spectra and Electronic Structures of Some Tetrahedral Manganese(II) Complexes", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 84, 1 January 1962 (1962-01-01), pages 167 - 172, XP093162759, DOI: 10.1021/ja00861a008 *
M F MOSTAFA, A S ATALLAH: "Permittivity and AC Conductivity Study of The Layered Perovskite [(CH3)(C6H5)3P]2MnCl4 Showing Evidence of Phase Transition", PHYSICS LETTERS A, vol. 264, no. 2-3, 20 December 1999 (1999-12-20), pages 242 - 248, XP093162751, DOI: 10.1016/S0375-9601(99)00682-9 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115651027A (en) * 2022-10-17 2023-01-31 闽都创新实验室 Manganese-based scintillation crystalline material and preparation method and application thereof

Similar Documents

Publication Publication Date Title
WO2023029683A1 (en) Scintillating material and preparation method therefor and application thereof
Yanagida et al. Comparative study of ceramic and single crystal Ce: GAGG scintillator
CN102286286B (en) The muriate scintillator of radiation detection
KR20170088374A (en) Novel thallium doped sodium, cesium or lithium iodide scintillators
Su et al. Mn 2+-doped Cs 2 ZnBr 4 scintillator for X-ray imaging
WO2024082090A1 (en) Manganese-based scintillation crystalline material, and preparation method therefor and use thereof
CN101665696A (en) Preparation method of Eu&lt;3+&gt; doped yttrium lanthanum oxide fluorescent powder and transparent scintillating ceramic
Zhou et al. Compositional engineering of doped zero-dimensional zinc halide blue emitters for efficient X-ray scintillation
CN102277170A (en) Iodide scintillator for radiation detection
WO2023201870A1 (en) Crystal, method for preparing same, and use thereof as blue fluorescent scintillation material
CN114561704A (en) Flux growth method and application of large-size bismuth tungstate crystal
Grippa et al. Scintillation properties of CaBr2 crystals doped with Eu2+ ions
Liu et al. Fabrication of Gd2O2S: Pr scintillation ceramics from water-bath synthesized nanopowders
Totsuka et al. Investigations of optical and scintillation properties of Tm3+-doped YAlO3
Chen et al. Low temperature luminescence and scintillation properties of NaLa (MoO4) 2 crystal grown by the vertical Bridgman method
US20110147595A1 (en) Tungstate-based scintillating materials for detecting radiation
WO2023169120A1 (en) Divalent europium sulfide near-infrared scintillator and preparation method therefor
Zhang et al. Improved growth technique for high-quality trans-stilbene single crystals achieving a record PSD performance
CN112625061B (en) Green fluorescent scintillating material and preparation method and application thereof
CN115651027A (en) Manganese-based scintillation crystalline material and preparation method and application thereof
CN115894256A (en) Zero-dimensional manganese-based metal halide, preparation method thereof and application thereof in high-resolution flexible X-ray scintillator imaging
Shah et al. Structural differences in the luminescence properties of lanthanide doped orthorhombic and monoclinic phases of Y 2 GeO 5
RU2682554C1 (en) Poly-crystalline scintillation materials in the form of powders production method
Gerasymov et al. Impact of codoping on structure, optical and scintillation properties of Gd₂Si₂O₇-based crystals
Tomaszewicz et al. New cadmium and rare-earth metal molybdato–tungstates with scheelite-type structure

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22962288

Country of ref document: EP

Kind code of ref document: A1