阅读说明：本技术 利用有机-无机杂化金属锰卤化物实现x射线检测与成像的方法 (Method for realizing X-ray detection and imaging by utilizing organic-inorganic hybrid metal manganese halide ) 是由 刘淑娟 孟海星 赵强 黄维 于 2021-08-31 设计创作，主要内容包括：本发明公开了利用有机-无机杂化金属锰卤化物实现X射线检测与成像的方法,该方法的实现是基于一类锰卤化物对X射线具有响应性的特殊性质,利用该特性可以该类锰卤化物为原料制备成闪烁体,所得闪烁体薄膜在日光下不发光,利用紫外线或X射线照射后,闪烁体薄膜会显示出绿色发光效果,因而可将其应用于X射线检测与成像领域；同时,该类化合物还具有优良的光物理性能,固态下发射绿光,其可作为绿色发光材料应用在白光LED制备中；本申请公开的方法拓宽了有机-无机杂化金属锰卤化物的常规应用场景,进一步挖掘了此类材料的潜在性能,无论是对理论研究还是实践应用都具有重要意义。(The invention discloses a method for realizing X-ray detection and imaging by utilizing organic-inorganic hybrid metal manganese halide, which is realized based on the special property that a class of manganese halide has responsiveness to X-rays, the class of manganese halide can be used as a raw material to prepare a scintillator by utilizing the characteristic, the obtained scintillator film does not emit light under sunlight, and after the radiation of ultraviolet rays or X-rays, the scintillator film can show a green light-emitting effect, so that the method can be applied to the field of X-ray detection and imaging; meanwhile, the compound also has excellent photophysical properties, emits green light in a solid state, and can be used as a green luminescent material to be applied to the preparation of a white light LED; the method disclosed by the application widens the conventional application scene of the organic-inorganic hybrid metal manganese halide, further excavates the potential performance of the material, and has important significance for theoretical research and practical application.)

1. The method for realizing X-ray detection and imaging by utilizing the organic-inorganic hybrid metal manganese halide is characterized by comprising the following steps of:

1) dissolving organic-inorganic hybrid metal manganese halide by organic dissolution;

2) adding polyethylene glycol 10000 or polymethyl methacrylate into the organic solvent in the step 1) to obtain a mixed solution;

3) stirring the mixed solution obtained in the step 2) for 2-6 hours, then dripping the mixed solution into a mold, and volatilizing the solvent to obtain a scintillator film;

4) the scintillator film obtained in the step 3) does not emit light under sunlight, and shows a green light emitting effect after being irradiated by X rays or excited by ultraviolet rays of 200nm-500 nm;

wherein, the structural general formula of the organic-inorganic hybrid metal manganese halide in the step 1) is as follows:

wherein the content of the first and second substances,

x ═ Br or Cl;

wherein the content of the first and second substances,

n＝0，1，2_…；

a＝1，2；

r ═ F or Br.

2. The method for realizing X-ray detection and imaging by using organic-inorganic hybrid metal manganese halide according to claim 1, wherein the organic solvent in step 1) is ethanol, methanol, dichloromethane, benzene or toluene.

3. The method for realizing X-ray detection and imaging by utilizing organic-inorganic hybrid metal manganese halide according to claim 1, wherein the concentration of the polyethylene glycol 10000 or polymethyl methacrylate after being mixed into the organic solvent in the step 2) is 50mg/mL-200 mg/L.

4. The method for realizing X-ray detection and imaging by using the organic-inorganic hybrid metal manganese halide as claimed in claim 1, wherein the organic-inorganic hybrid metal manganese halide in the step 1) is prepared by a one-pot method, and the specific synthetic route is as follows:

5. the method for realizing X-ray detection and imaging by using the organic-inorganic hybrid metal manganese halide according to claim 4, wherein the step of synthesizing the organic-inorganic hybrid metal manganese halide in the step 1) comprises the following steps: firstly weighing triphenylphosphine salt ligand, placing the triphenylphosphine salt ligand in a reaction bottle, fully dissolving the triphenylphosphine salt ligand by using dichloromethane, adding the weighed manganese bromide tetrahydrate/manganese chloride tetrahydrate into the reaction bottle, injecting 5-10mL of ethanol solution, stirring for 6 hours, volatilizing the solution, and obtaining light green crystals after one week.

6. The method for X-ray detection and imaging using organic-inorganic hybrid metal manganese halides according to claim 5, wherein the mass ratio of triphenylphosphine salt ligand to manganese bromide tetrahydrate/manganese chloride tetrahydrate is 2: 1.

Technical Field

The invention belongs to the technical field of photoluminescent materials, and particularly relates to a method for realizing X-ray detection and imaging by using organic-inorganic hybrid metal manganese halide.

Background

In recent years, X-ray detection and imaging have been widely used in the fields of medical diagnosis, environmental monitoring, industrial inspection, safety inspection, astronomical observation, and the like, and have attracted extensive attention and research of researchers. Currently, implementations of X-ray detectors can be roughly classified into a direct type and an indirect type. The former directly absorbs incident X-rays, generates electronic signals through semiconductors or guides chemical signals through thin films, directly converts the X-rays into visible light, and this implementation form is limited by the problems of high cost and low efficiency; the latter is to convert the X-ray into light by the scintillator to realize detection imaging.

Scintillator materials are widely studied as a key element in X-ray detection imaging. Perovskite materials are common scintillator preparation materials, but N-H bonds of amino groups in the existing various perovskite materials can form weak hydrogen bonds with water molecules in the air, and the water molecules are introduced into a crystal structure to cause degradation of perovskite, so that the stability of the perovskite materials is weakened; meanwhile, the conditions for preparing the device by the perovskite material are severe, so that the practical application of the perovskite material is limited to a certain extent. Therefore, non-amino-stable perovskite-like materials are yet to be developed.

The hybrid lead halide is a non-amino stable perovskite-like material with large light absorption coefficient, high quantum efficiency, high photoelectric conversion efficiency and excellent semiconductor characteristics. However, the biotoxicity of lead greatly limits its practical application.

In recent years, environmental-friendly, efficient and low-toxicity manganese halide materials are reported successively, compared with other noble metal elements, manganese has the advantages of rich resources, environmental friendliness, low price, multiple valences and multiple coordination types, and the self property of manganese enables the hybrid manganese halide to have rich photophysical properties. For example, tsukudani professor tsukudani of Qingdao science and technology university, Yangli university Yan\26104professor of Zhejiang university, Jiangjiang MingShi and the like are designed and synthesized into two halide perovskite single crystal materials C based on metal manganese₄H₁₂NMnCl₃And (C)₈H₂₀N)₂MnBr₄Mn due to the specificity of the crystal structures of the two materials²⁺The luminous quantum efficiency reaches 93.1 percent and 85.1 percent, and the superiority of the complex is proved in the X-ray imaging and white light LED manufacturing field; meanwhile, the luminous efficiency of the white light LED manufactured by doping the two materials reaches 96lm W^-1The minimum detection limit of X-ray imaging reaches 36.9nGy_airs^-1、24.2nGy_air s^-1。

The quaternary phosphonium salt ions are used as organic-inorganic hybrid manganese halides synthesized by organic counter cations and are also an important part of manganese halide materials, various phosphonium salt manganese halide compounds are also prepared in recent years in succession, and the phosphonium salt manganese halide compounds have the advantages of environmental protection, low toxicity and low cost. However, the research on the existing phosphonium manganese halide compounds has mainly focused on their photoluminescence and mechanoluminescence characteristics, such as the presently disclosed [ MPP ]]₂[MnBr₄]、[EPP]₂[MnBr₄]、[TPP]₂[MnBr₄]And [ BPP ]]₂[MnBr₄]The average value of photoluminescence efficiency (PLQY) of the materials can reach more than 80%, but no relevant report is found for the research of the substances in the field of X-ray detection and imaging, so that the application scenes of the substances are severely limited, and the potential efficacy of the substances cannot be fully exerted.

Disclosure of Invention

The invention aims to solve the defects in the prior art and discloses a method for realizing X-ray detection and imaging by utilizing organic-inorganic hybrid metal manganese halide.

The technical scheme of the invention is as follows: the method for realizing X-ray detection and imaging by utilizing the organic-inorganic hybrid metal manganese halide comprises the following steps:

1) dissolving organic-inorganic hybrid metal manganese halide by organic dissolution;

2) adding polyethylene glycol 10000 or polymethyl methacrylate into the organic solvent prepared in the step 1) to obtain a mixed solution;

3) stirring the mixed solution obtained in the step 2) for 2-6 hours, then dripping the mixed solution into a mold, and volatilizing the solvent to obtain a scintillator film;

4) the scintillator film obtained in the step 3) does not emit light under sunlight, and shows a green light emitting effect after being irradiated by X rays or excited by ultraviolet rays of 200nm-500 nm;

wherein, the structural general formula of the organic-inorganic hybrid metal manganese halide in the step 1) is as follows:

wherein the content of the first and second substances,

x ═ Br or Cl;

wherein the content of the first and second substances,

wherein the content of the first and second substances,

n＝0，1，2…；

a＝1，2；

r ═ F or Br.

Further, the organic solvent in step 1) is ethanol, methanol, dichloromethane, benzene or toluene.

Further, in the step 2), the concentration of the polyethylene glycol 10000 or the polymethyl methacrylate after being mixed into the organic solvent is 50mg/mL-200 mg/L.

Further, the organic-inorganic hybrid metal manganese halide in the step 1) is prepared by a one-pot method, and the specific synthetic route is as follows:

the method comprises the following specific steps: firstly weighing triphenylphosphine salt ligand, placing the triphenylphosphine salt ligand in a reaction bottle, fully dissolving the triphenylphosphine salt ligand by using dichloromethane, adding the weighed manganese bromide tetrahydrate/manganese chloride tetrahydrate into the reaction bottle, injecting 5-10mL of ethanol solution, stirring for 6 hours, volatilizing the solution, and obtaining light green crystals after one week.

Further, the ratio of the amounts of triphenylphosphine salt ligand to manganese bromide tetrahydrate/manganese chloride tetrahydrate material was 2: 1.

The invention has the beneficial effects that:

1. the application discloses an organic-inorganic hybrid metal manganese halide which is prepared by reacting triphenylphosphine salt organic counter cation with [ MnX₄]^2-The ion type luminous manganese complex formed by the action of tetrahedron (X ═ Cl or Br) has responsiveness to X-rays, can be prepared into a scintillator, the obtained scintillator film does not emit light under sunlight, and after the excitation of 200-500nm ultraviolet rays or the irradiation of the X-rays, the scintillator film shows a green luminous effect, so that the material can be applied to the field of X-ray detection and imaging;

2. the organic-inorganic hybrid metal manganese halide disclosed by the application has excellent photophysical properties, emits green light in a solid state, can be used as a green luminescent material, is combined with the existing red fluorescent powder, and can obtain a white light LED device under the excitation of blue light;

3. based on the characteristics that the organic-inorganic hybrid metal manganese halide disclosed by the application has responsiveness to ultraviolet rays and X rays and can show good green light emission effect under corresponding stimulation, the compound can be prepared into anti-counterfeiting ink and has good application prospect in the field of anti-counterfeiting printing;

4. the organic-inorganic hybrid metal manganese halide disclosed by the application is synthesized by a one-pot method, is simple to prepare, has the characteristics of low cost and low toxicity, can be produced and applied in a large area, and is expected to become a next-generation emerging material in the fields of X-ray detection and biological imaging.

Drawings

FIG. 1 is a normalized excitation-emission spectrum of manganese halide structures 1-6 prepared in example 1;

FIG. 2 is a CIE 1931 chromaticity diagram of manganese halide structures 1-6 prepared in example 1;

FIG. 3 is a spectrum of X-ray responsiveness of manganese halide structures 1-6 prepared in example 1;

FIG. 4 is a spectrum of the linear response of manganese halide structures 1-6 prepared in example 1 to X-rays;

FIG. 5 is a graph of a thin film scintillator and an image produced with the manganese halide structure 6 produced in example 1;

Detailed Description

The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.

Example 1: synthesis of organic-inorganic hybrid manganese halide

The specific synthesis method comprises the following steps:

the synthesis steps are as follows: the manganese halides are prepared by a one-pot method; firstly, weighing an organic ligand, placing the organic ligand in a reaction bottle, fully dissolving the organic ligand in dichloromethane, weighing manganese bromide tetrahydrate/manganese chloride tetrahydrate according to the mass ratio of substances (ligand: manganese bromide tetrahydrate/manganese chloride tetrahydrate is 2:1), adding the weighed manganese bromide tetrahydrate/manganese chloride tetrahydrate into the reaction bottle, injecting 5-10mL of ethanol solution, and stirring for 6 hours; by the solution evaporation method, after one week, pale green crystals were obtained.

Property testing of manganese halide structures 1-6

Test 1: acquiring a normalized solid state excitation-emission spectrum (structures 1-6 correspond to (a) - (f) minimaps in sequence) and a CIE 1931 chromaticity diagram of the manganese halide with the structures 1-6; as shown in FIG. 1 and FIG. 2, the emission characteristic peaks of the manganese halides are respectively found in the interval of 506nm-514nm, which is consistent with green light emission.

And (3) testing 2: according to FIG. 3 (structures 1-6 followSequences corresponding to (a) - (f) panels), X-ray dose rates from 2.99 μ Gy_air s^-1Increased to 41.8 μ Gy_airs^-1The irradiation spectrum (RL spectrum) of the manganese halide is shown in FIG. 4 (structures 1 to 6 correspond to panels (a) to (f) in this order). Under the irradiation of X-rays with different dose rates, the irradiation intensity and the X-ray dose rate have a certain linear relation, and the result shows that the manganese halide has certain linear responsiveness to the X-rays. The light yield of the manganese halide is 29500, 28600, 20020, 26180, 27060 and 31900photons/MeV respectively.

Based on the unique green light emission and high photoluminescence quantum efficiency characteristics of the organic-inorganic hybrid manganese halide, the organic-inorganic hybrid manganese halide is applied to the field of X-ray imaging.

The process of manufacturing the scintillator comprises the following steps: taking the manganese halide structure 6 as an example, 40mg of manganese complex is dissolved in 1mL of organic solvent such as ethanol/methanol/dichloromethane/benzene/toluene, doped with polyethylene glycol 10000 (PEG)/polymethyl methacrylate (PMMA), stirred for 4 hours, the mixed liquid is dropped into a mold, and the scintillator film is obtained after 12 hours of volatilization. The scintillator does not emit light under sunlight, only shows white PEG/PMMA film, and emits green light (the luminous color of the complex) under the irradiation of ultraviolet rays and X rays;

as shown in fig. 5, the left image in fig. 5 is a scintillator made by doping manganese halide with PMMA to the structure 6, and emits green light under ultraviolet; based on the characteristic that different metals have different absorbances on X-rays, the scintillator is different in spatial saturation, so that optical imaging is performed, and the internal structure of the chip can be clearly observed, as shown in the right diagram of FIG. 5.

The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.